Preparation method of stibnite and arsenopyrite flotation separation complex collecting agent

Abstract

The invention provides a preparation method of a stibnite and arsenopyrite flotation separation complex collecting agent. The complex collecting agent in the method has molecular structures of A, B and C; the method comprises the steps that an R1OCSSNa (K) collecting agent, an R2OCSSNa (K) or R3NCSSNa (K) collecting agent, an R4NCSSNa (K) or (RO) 2PSSNa (NH2) collecting agent and deionized water are prepared into aqueous solutions with certain solubility; any one or more of the collecting agent water solutions are mixed, and the pH value of the solutions is adjusted; soluble metal salt and deionized water are prepared into an aqueous solution with certain solubility; adjusting the pH value of the solution; the flow of the soluble metal ion aqueous solution and the flow of the collecting agent aqueous solution are controlled through a peristaltic pump, the mixing proportion, the reaction temperature, the pH value and the stirring time of the soluble metal ion aqueous solution and the collecting agent aqueous solution are regulated and controlled, and the A complex collecting agent, the B complex collecting agent or the C complex collecting agent is obtained. The method is simple in synthesis process, low in cost and high in reagent selectivity, floatability difference between antimony and arsenic can be expanded, the stibnite recovery effect is good, and stibnite and arsenopyrite mineral flotation separation can be more efficient.

Description

Technical Field

[0001] The invention relates to the technical field of ore dressing agents, in particular to a method for preparing a collector for flotation separation of stibnite and arsenopyrite. Background Art

[0002] Antimony (Sb) has been developing rapidly in key areas such as photovoltaic glass, microchips and military industry in recent years. In antimony deposits, stibnite often coexists with pyrite and arsenopyrite. Since the physical, chemical and mineral process characteristics of arsenopyrite are similar to those of stibnite, arsenopyrite is often selected into antimony concentrate, resulting in excessive arsenic content in the antimony concentrate, leading to a decline in the quality of smelting products, pollution of the atmosphere and water sources, and affecting ecological balance.

[0003] At present, the separation of stibnite and arsenopyrite is mainly carried out by froth flotation. Collectors, as a typical surfactant, are used to adjust the hydrophobicity of minerals, thereby changing the floatability difference between target minerals and gangue minerals to achieve their effective separation. Xanthochlorates, dialkyl dithiophosphates, aminothiols and their derivatives are widely used as collectors for the flotation of sulfide minerals. Although they show excellent collection effects, their selectivity is limited. The activation energy of metal ions is used to enhance the selective adsorption of collectors on minerals. However, in the case of stibnite and arsenopyrite with similar surface properties, the use of activated Pb 2+ or Cu 2+ , through Pb 2+ or Cu 2+ Its hydroxyl complex is adsorbed on the surface of the mineral, providing active sites for the subsequent collector, which then adsorbs on the active sites to capture the target mineral. Studies have found that it has a good activation effect on both minerals, and sometimes even favors the capture of arsenopyrite instead of stibnite. Therefore, it is necessary to find a new collector to expand the floatability difference between stibnite and arsenopyrite, which is necessary for their selective separation.

[0004] In summary, in the prior art, the use of yellow medicine, black medicine, sulfur-nitrogen flotation collectors in the flotation separation process of antimony and arsenic has the problems of large dosage, poor selectivity, easy environmental pollution, etc., and the single flotation reagent has a poor selection effect on antimony and arsenic, but the arsenic content in the antimony concentrate exceeds the standard. Therefore, the present invention provides a preparation method of a collector for the flotation separation of stibnite and arsenopyrite. Summary of the invention

[0005] In view of the shortcomings of the prior art, the purpose of the present invention is to provide a method for preparing a complex collector for flotation separation of stibnite and arsenopyrite to solve the problems raised in the above-mentioned background technology. The present invention proposes a combined reagent with small dosage, strong adaptability and high selectivity in the flotation separation process of stibnite and arsenopyrite. The combined reagent has not only simple process, low cost, clean and environmental protection, but also strong selectivity for stibnite, and is a complex collector with broad application prospects.

[0006] In order to achieve the above object, the present invention is implemented by the following technical scheme: a method for preparing a collector for flotation separation of stibnite and arsenopyrite, comprising the following steps:

[0007] Step 1: A complex collector has the molecular structures of A, B, and C:

[0008]

[0009] in:

[0010] R1: alkyl with 2 to 6 carbon chains;

[0011] R2: alkyl with 2 to 6 carbon chains;

[0012] R3: alkyl with 2 to 6 carbon chains;

[0013] R4: alkyl with 2 to 6 carbon chains;

[0014] R: phenol group, cresol group, alkane group, aromatic group, etc.;

[0015] M:Pb 2+ , Cu 2+ , Fe 3+ ,La 3+ , Y 3+ 、Zn 2+ etc. metal ions;

[0016] Step 2: R1OCSSNa(K), R2OCSSNa(K) or R3NCSSNa(K), R4NCSSNa(K) or (RO)2PSSNa(NH2) collectors are respectively mixed with deionized water, and an aqueous solution with a certain solubility is obtained after adjusting the mixing ratio;

[0017] Step 3: Mix R1OCSSNa(K), R2OCSSNa(K) or R3NCSSNa(K), R4NCSSNa(K) or (RO)2PSSNa(NH2) collector aqueous solutions, and adjust the pH value of the solution with hydrochloric acid or sodium hydroxide;

[0018] Step 4: prepare a soluble metal salt and deionized water into an aqueous solution of a certain solubility; adjust the solution to a certain pH value with hydrochloric acid or sodium hydroxide;

[0019] Step 5: Use peristaltic pumps to control the flow rates of the soluble metal ion aqueous solution and the collector aqueous solution, respectively, and adjust the mixing ratio of the two agents, the reaction temperature, the pH value, and the stirring time to obtain complex collector A, complex collector B, or complex collector C.

[0020] Furthermore, in step 1, M:Pb 2+ , Cu 2+ , Fe 3+ ,La 3+ , Y 3+ 、Zn 2+ The metal ions are soluble chlorides, nitrates, sulfates, etc.

[0021] Furthermore, M is Pb 2+ , Cu 2+ , Fe 3+ ,La 3+ , Y 3+ 、Zn 2+ Any one or a combination of the following.

[0022] Furthermore, the solubility of the aqueous solution after proportioning in step 2 is 1×10 -6 mol / L~8×10 -3 mol / L.

[0023] Furthermore, the mixing ratio of the collector aqueous solution in step 3 is 5% to 95%, and the certain pH value is 5 to 10. The collector aqueous solution is mixed as any one or a combination of R1OCSSNa(K), R2OCSSNa(K) or R3NCSSNa(K), R4NCSSNa(K) or (RO)2PSSNa(NH2).

[0024] Furthermore, the certain solubility in step 4 is 0.5×10 -6 mol / L~4×10 -4 mol / L, adjust the solution to a pH of 5-10.

[0025] Furthermore, in step 5, a peristaltic pump is used to control the flow rates of the metal ion aqueous solution and the collector aqueous solution to be 6 ml / min-60 ml / min, respectively.

[0026] Furthermore, in step five, the molar ratio of the soluble metal ion aqueous solution to the collector aqueous solution is 1 / 10:1 to 10:1.

[0027] Furthermore, in step 5, the reaction temperature of the soluble metal ion aqueous solution and the collector aqueous solution is 5°C to 60°C; the reaction time is 1 min to 10 h; and the pH value is 5 to 10.

[0028] Beneficial effects of the present invention:

[0029] 1. The preparation method of the flotation separation complex collector of stibnite and arsenopyrite is to prepare the complex collector of three sulfide ore and Pb 2 + , Cu 2+ , Fe 3+ ,La 3+ , Y 3+ 、Zn 2+ The complex collector is prepared by using metal ions in a mild environment. The synthesis process is simple, the cost is low, and the agent selectivity is high.

[0030] 2. The preparation method of the complex collector for flotation separation of stibnite and arsenopyrite adopts a complex collector with high capture selectivity for stibnite and low capture selectivity for arsenopyrite, which is beneficial to expand the floatability difference between antimony and arsenic, thereby resulting in better recovery of stibnite and enabling more efficient flotation separation of stibnite and arsenopyrite.

[0031] 3. The preparation method of the collector for flotation separation of stibnite and arsenopyrite has a green and environmentally friendly preparation process, significant environmental and economic benefits, and is suitable for large-scale industrial production. BRIEF DESCRIPTION OF THE DRAWINGS

[0032] Figure 1 The figure is a process flow chart for preparing the complex collector of the present invention;

[0033] Figure 2 It is the infrared spectrum of the Cu-KBX complex and the Pb-DDTC complex in the present invention;

[0034] Figure 3 This is a diagram showing the influence of different metal ion-KBX collectors on the flotation behavior of stibnite and arsenopyrite in Example 1 of the present invention;

[0035] Figure 4 is Cu in Example 2 of the present invention 2+ The effect of different proportions of KBX on the flotation of stibnite and arsenopyrite;

[0036] Figure 5 is Cu in Example 3 of the present invention 2+ The effect of different reaction temperature conditions with KBX on the flotation of stibnite and arsenopyrite;

[0037] Figure 6This is a diagram showing the influence of different metal ion-DDTC collectors on the flotation behavior of stibnite and arsenopyrite in Example 4 of the present invention;

[0038] Figure 7 is Pb in Example 5 of the present invention 2+ The effect of different proportions of DDTC on the flotation of stibnite and arsenopyrite;

[0039] Figure 8 This is a diagram showing the effect of the metal ion-DDTC complex collector on the flotation of stibnite and arsenopyrite in Example 6 of the present invention;

[0040] Fig. 9 This is a diagram showing the effect of the metal ion-SDD complex collector on the flotation of stibnite and arsenopyrite in Example 7 of the present invention. DETAILED DESCRIPTION

[0041] In order to make the technical means, creative features, objectives and effects achieved by the present invention easy to understand, the present invention is further explained below in conjunction with specific implementation methods.

[0042] See also Figures 1 to 9 , the present invention provides the following technical solutions:

[0043] Example 1

[0044] The ROCSSNa (KBX) collector was mixed with deionized water to a concentration of 8×10 -4 mol / L aqueous solution, adjust the solution pH to 6-7 with hydrochloric acid; 2+ , Cu 2+ , Fe 3+ ,La 3+ , Y 3+ 、Zn 2+ The soluble metal salts were mixed with deionized water to make a concentration of 4×10 -4 mol / L aqueous solution; then a peristaltic pump is used to control a certain flow rate of the soluble metal ion aqueous solution and the collector aqueous solution respectively, and the reaction is stirred at 35°C for 30 minutes under the condition of controlling the ratio of the two agents to be 1:1, to obtain the A molecular structure complex collector M-KBX.

[0045] The mixed ore (stibnite: arsenopyrite = 1:1) sample and 35 mL of deionized water were added to a 40 mL flotation tank and stirred for 3 minutes. The pH of the slurry was adjusted to 6 with H2SO4 and stirred for another 3 minutes. Then, 1 mL of Pb-KBX, Cu-KBX, Fe-KBX, Zn-KBX, Al-KBX, and La-KBX complex collector solution was added and stirred for 3 minutes. Then, 0.45 mL of frother MIBC was added to react with the mineral for 3 minutes. Finally, the foam was scraped for 3 minutes, and the product was dried, weighed, and the grade of Sb was tested and its recovery rate was calculated. Figure 3 The figure shows the influence of different metal ion-KBX collectors on the flotation behavior of stibnite and arsenopyrite in this example.

[0046] Depend on Figure 3 It can be seen that when Cu-KBX complex is used as collector, the grade and recovery rate of antimony concentrate are significantly higher than that of KBX alone, the grade of antimony concentrate is as high as 57.51%, and the recovery rate is as high as 93.17%, while the grade and recovery rate of antimony concentrate when Fe-KBX, Zn-KBX, AL-KBX, and La-KBX complexes are used as collectors are significantly lower than that of KBX alone. This shows that the use of Cu-KBX complex collector can achieve the selective separation of stibnite and arsenopyrite.

[0047] Example 2

[0048] Pure stibnite or arsenopyrite sample and 35 mL of deionized water were added to a 40 mL flotation tank and stirred for 3 min. NaOH or H2SO4 was added to adjust the pH of the slurry to 6 and stirred for 3 min. Then, Cu-KBX collector (Cu 2+ The molar ratio of KBX is 1 / 10:1 to 10:1), the dosage is 1 mL, and it is stirred for 3 minutes; 0.45 mL of foaming agent MIBC is added to react with the mineral for 3 minutes, and finally the foam is manually scraped for 3 minutes.

[0049] Figure 4 In this embodiment, Cu 2+ The influence of different coordination ratios of KBX on the flotation difference between stibnite and arsenopyrite; As can be seen from the figure, Cu 2+ Different from the KBX coordination ratio, it has a greater impact on the floatability of stibnite and arsenopyrite. 2+ When the ratio of Cu to KBX is 1 / 2:1, the recovery rate of stibnite reaches 95.00%, while that of arsenopyrite is only 27.00%. 2+ The molar ratio of KBX to KBX is 1 / 2:1, and the complex collector has a better collection effect on stibnite.

[0050] Example 3

[0051] Stibnite or arsenopyrite sample with purity of more than 98% and 35 mL of deionized water were added to a 40 mL flotation tank and stirred for 3 min. NaOH or H2SO4 was added to adjust the pH of the slurry to 6 and stirred for 3 min. Then, Cu-KBX collector (Cu 2+ Reaction temperature with KBX: 15-65°C), dosage is 1 mL, and the sample is treated for 3 minutes; 0.45 mL of foaming agent MIBC is added to react with the mineral for 3 minutes, and finally the foam is manually scraped for 3 minutes.

[0052] Figure 5 In this embodiment, Cu 2+ The influence of different reaction temperature conditions with KBX on the flotation difference between stibnite and arsenopyrite; Figure 5 It can be seen that the reaction temperature of the Cu-KBX complex formation process has a great influence on the floatability of the mineral. Too low or too high a temperature is not conducive to the performance of the collector. Too low a temperature leads to weak capture of stibnite by the Cu-KBX combination, while too high a temperature leads to the decomposition of KBX, which is not conducive to the formation of the complex. At 35°C, Cu 2+ The reaction effect with KBX is the best. At this time, the recovery rate of stibnite is 92.87%, and the recovery rate of arsenopyrite is only 34.89%. The difference in floatability between the two reaches a maximum of 57.98%, indicating that the Cu-KBX complex collector has a better collection effect on stibnite.

[0053] Example 4

[0054] According to the steps in Example 1, the R2NCSSNa (DDTC) collector aqueous solution and different metal ion aqueous solutions were mixed to prepare the B molecular structure complex collector M-DDTC.

[0055] The mixed ore (stibnite: arsenopyrite = 1:1) sample and 35 mL of deionized water were added to a 40 mL flotation tank and stirred for 3 min. The pH of the slurry was adjusted to 6 with H2SO4 and stirred for 3 min. Then, 1 mL of Pb-DDTC, Cu-DDTC, Fe-DDTC, Zn-DDTC, Al-DDTC, and La-DDTC complex solution were added and stirred for 3 min. Then, 0.45 mL of frother MIBC was added to react with the mineral for 3 min. Finally, the foaming operation was performed for 3 min, and the product was dried, weighed, and the grade of Sb in the concentrate was tested, and its recovery rate was calculated. Figure 6 This is a diagram showing the influence of different metal ion-DDTC collectors on the flotation behavior of stibnite and arsenopyrite in this example.

[0056] Depend on Figure 6It can be seen that when Pb-DDTC complex is used as collector, the grade and recovery rate of antimony concentrate are significantly higher than that of DDTC alone, and the grade of antimony concentrate is as high as 58.41% and the recovery rate is as high as 96.28%. This shows that the use of Pb-DDTC complex collector can achieve the selective separation of stibnite and arsenopyrite.

[0057] Example 5

[0058] Stibnite or arsenopyrite sample with purity above 98% and 35 mL of deionized water were added to a 40 mL flotation tank and stirred for 3 min. NaOH or H2SO4 was added to adjust the slurry pH to 6 and stirred for 3 min. Then Pb-DDTC collector (Pb 2+ The molar ratio of DDTC to DDTC is 1 / 10:1 to 10:1), the amount is 1 mL and the sample is treated for 3 minutes; then 0.45 mL of MIBC is added to react with the mineral for 3 minutes. Finally, the foaming is manually scraped for 3 minutes.

[0059] Figure 7 In this embodiment, Pb 2+ The flotation difference diagram of stibnite and arsenopyrite under different ratio conditions with DDTC; Figure 7 It can be seen that Pb 2+ Different coordination ratios with DDTC have a greater impact on the floatability of stibnite and arsenopyrite, especially when the ratio is 1 / 2:1, the recovery rate of stibnite reaches 97.66%, while that of arsenopyrite is only 22.00%. 2+ The Pb-DDTC complex collector has a better collection effect on stibnite at a molar ratio of 1 / 2:1 to DDTC.

[0060] Example 6

[0061] Pure stibnite or arsenopyrite sample and 35 mL of deionized water were added to a 40 mL flotation tank and stirred for 3 min. NaOH or H2SO4 was added to adjust the pH of the slurry to 6 and stirred for 3 min. Then Pb-DDTC collector (Pb 2+ Reaction with DDTC (pH: 4-10), the dosage is 1 mL, and the sample is treated for 3 minutes; 0.45 mL of foaming agent MIBC is added to react with the mineral for 3 minutes, and finally the foam is manually scraped for 3 minutes.

[0062] Figure 8 In this embodiment, Pb 2+ The effect of different reaction pH with DDTC on the flotation difference between stibnite and arsenopyrite; Figure 8 It can be seen that Pb 2+The pH of the reaction with DDTC is in the range of 4-7. As the pH value increases, the formed complex has a stronger capture effect on stibnite. However, under alkaline conditions, the capture effect on stibnite decreases sharply. 2+ Under alkaline conditions, its active components change and are not conducive to the formation of Pb-DDTC complex. At pH 7, the recovery rate of stibnite is 90.91%, while that of arsenopyrite is only 27.55%. The difference in floatability between the two reaches a maximum of 63.63%, indicating that the Pb-DDTC complex collector has a better collection effect on stibnite.

[0063] Example 7

[0064] According to the steps in Example 1, the (RO)2PSSNa(NH2)(SDD) collector aqueous solution was mixed with different metal ion aqueous solutions to prepare the C molecular structure complex collector M-SDD.

[0065] The mixed ore (stibnite: arsenopyrite = 1:1) sample and 35 mL of deionized water were added to a 40 mL flotation tank and stirred for 3 min. The pH of the slurry was adjusted to 6 with H2SO4 and stirred for 3 min. Then 1 mL of Pb-SDD, Cu-SDD, Fe-SDD, Zn-SDD, Al-SDD, and La-SDD complex solution were added and stirred for 3 min. Then 0.45 mL of frother MIBC was added to react with the mineral for 3 min. Finally, the foaming operation was performed for 3 min, and the product was dried, weighed, and the grade of Sb in the concentrate was tested, and its recovery rate was calculated. Fig. 9 This is a diagram showing the influence of different metal ion-SDD collectors on the flotation behavior of stibnite and arsenopyrite in this example.

[0066] Depend on Fig. 9 It can be seen that when the Fe-SDD complex is used as a collector, the grade and recovery rate of the antimony concentrate are significantly higher than those of the single use of SDD, and the grade of the antimony concentrate is as high as 46.29%, and the recovery rate is as high as 89.03%. This shows that the use of the Fe-SDD complex collector can achieve the selective separation of stibnite and arsenopyrite.

[0067] The basic principles and main features of the present invention and the advantages of the present invention are shown and described above. For those skilled in the art, it is obvious that the present invention is not limited to the details of the above exemplary embodiments, and the present invention can be implemented in other specific forms without departing from the spirit or basic characteristics of the present invention.

[0068] In addition, it should be understood that although the present specification is described according to implementation modes, not every implementation mode contains only one independent technical solution. This description of the specification is only for the sake of clarity. Those skilled in the art should regard the specification as a whole. The technical solutions in each embodiment may also be appropriately combined to form other implementation modes that can be understood by those skilled in the art.

Claims

1. A method for preparing a collector for flotation separation of stibnite and arsenopyrite, characterized in that: The following steps are involved: Step 1: A complex collector has the molecular structures of A, B, and C: in: R1: alkyl with 2 to 6 carbon chains; R2: alkyl with 2 to 6 carbon chains; R3: alkyl with 2 to 6 carbon chains; R4: alkyl with 2 to 6 carbon chains; R: phenol group, cresol group, alkane group, aromatic group, etc.; M:Pb 2+ , Cu 2+ , Fe 3+ ,La 3+ , Y 3+ 、Zn 2+ etc. metal ions; Step 2: R1OCSSNa(K), R2OCSSNa(K) or R3NCSSNa(K), R4NCSSNa(K) or (RO)2PSSNa(NH2) collectors are respectively mixed with deionized water, and an aqueous solution with a certain solubility is obtained after adjusting the mixing ratio; Step 3: Mix R1OCSSNa(K), R2OCSSNa(K) or R3NCSSNa(K), R4NCSSNa(K) or (RO)2PSSNa(NH2) collector aqueous solutions, and adjust the pH value of the solution with hydrochloric acid or sodium hydroxide; Step 4: prepare a soluble metal salt and deionized water into an aqueous solution of a certain solubility; adjust the solution to a certain pH value with hydrochloric acid or sodium hydroxide; Step 5: Use peristaltic pumps to control the flow rates of the soluble metal ion aqueous solution and the collector aqueous solution, respectively, and adjust the mixing ratio of the two agents, the reaction temperature, the pH value, and the stirring time to obtain complex collector A, complex collector B, or complex collector C.

2. The method for preparing a collector for flotation separation of stibnite and arsenopyrite according to claim 1, characterized in that: M in step 1: Pb 2+ , Cu 2+ , Fe 3+ ,La 3+ , Y 3+ 、Zn 2+ The metal ions are soluble chlorides, nitrates, sulfates, etc.

3. The method for preparing a collector for flotation separation of stibnite and arsenopyrite according to claim 2, characterized in that: M is Pb 2+ , Cu 2+ , Fe 3+ ,La 3+ , Y 3+ 、Zn 2+ Any one or a combination of the following.

4. The method for preparing a collector for flotation separation of stibnite and arsenopyrite according to claim 1, characterized in that: The solubility of the aqueous solution after proportioning in step 2 is 1×10 -6 mol / L~8×10 -3 mol / L.

5. The method for preparing a collector for flotation separation of stibnite and arsenopyrite according to claim 1, characterized in that: The mixing ratio of the collector aqueous solution in the step three is 5% to 95%, the certain pH value is 5 to 10, and the collector aqueous solution is mixed into: any one or a combination of R1OCSSNa(K), R2OCSSNa(K) or R3NCSSNa(K), R4NCSSNa(K) or (RO)2PSSNa(NH2).

6. The method for preparing a collector for flotation separation of stibnite and arsenopyrite according to claim 1, characterized in that: The certain solubility in step 4 is 0.5×10 -6 mol / L~4×10 -4 mol / L, adjust the solution to a pH of 5-10.

7. The method for preparing a collector for flotation separation of stibnite and arsenopyrite according to claim 1, characterized in that: In the step 5, a peristaltic pump is used to control the flow rates of the metal ion aqueous solution and the collector aqueous solution to be 6 ml / min-60 ml / min respectively.

8. The method for preparing a collector for flotation separation of stibnite and arsenopyrite according to claim 1, characterized in that: The molar ratio of the soluble metal ion aqueous solution to the collector aqueous solution in step 5 is 1 / 10:1 to 10:

1.

9. The method for preparing a collector for flotation separation of stibnite and arsenopyrite according to claim 1, characterized in that: In the step 5, the reaction temperature of the soluble metal ion aqueous solution and the collector aqueous solution is 5° C. to 60° C.; the reaction time is 1 min to 10 h; and the pH value is 5 to 10.

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