Method for flotation separation of stibnite and arsenopyrite

Abstract

The invention provides a stibnite and arsenopyrite flotation separation method which comprises the following steps: sorting and crushing an ore sample containing stibnite and arsenopyrite, and grinding the ore sample to serve as a flotation sample; stibnite, arsenopyrite and water are mixed into ore pulp, and the pH value is adjusted; adding a certain amount of oxidizing agent into the ore pulp and stirring; adding a certain amount of inhibitor into the ore pulp and stirring; adding a certain amount of collecting agent and foaming agent into the ore pulp, and stirring; the obtained ore pulp is subjected to froth flotation, froth products and tank bottom products obtained after flotation are filtered, dried and tested respectively, and the recovery rate is calculated. The oxidizing agent and the metal ion-organic inhibitor complex solution are used as the combined inhibitor, the combined inhibitor is simple in preparation process and process, low in cost and easy to obtain, the medicament cost is saved, the used medicament is simple, other equipment is not needed, the method is environment-friendly, the economic benefit is remarkable, and the method is suitable for industrial production.

Description

Technical Field

[0001] The invention relates to the technical field of mineral processing, in particular to a flotation separation method for stibnite and arsenopyrite. Background Art

[0002] Antimony can be widely used in pigments, medicines, cultural relics manufacturing, flame retardants, catalysts, etc. Antimony resources are mainly extracted from ores. The main mineral of antimony obtained from ores is stibnite (Sb2S3), and stibnite is generally symbiotic with arsenopyrite, pyrite, gold, silver, copper, lead, zinc, etc. The arsenic element in arsenopyrite is a harmful substance to human health and the environment. Excessive arsenic content in antimony concentrate will also have an adverse effect on subsequent smelting, such as rusting and damaging the melting furnace, shortening the life of the furnace, etc., so it is crucial to effectively reduce the arsenic content in antimony concentrate.

[0003] In the process of separation of stibnite and arsenopyrite, organic depressants are increasingly valued by mineral processing workers because of their environmental protection, non-toxicity, low cost and easy availability. The essence of inhibiting arsenopyrite is to eliminate the free activated ions in the ore pulp. At the same time, there are many functional groups and polar groups on the macromolecular chain, which improves the inhibitor's ability to inhibit arsenopyrite minerals. In the prior art. Since organic depressants contain a large number of different functional groups, which may cause low selectivity, the separation effect of using organic depressants alone is not good. Jin Aihua conducted a floatability test on stibnite and arsenopyrite with lignin sulfonate as depressant at natural pH, butyl xanthate (20 mg / L) as collector, and pine oil (15 mg / L) as foaming agent. It was found that with the increase of the dosage of lignin sulfonate, the recovery rate of stibnite slowly decreased, while the recovery rate of arsenopyrite dropped to less than 20% when the dosage of lignin sulfonate was 10 mg / L.

[0004] In summary, inhibitors for separation of stibnite and arsenopyrite have the following shortcomings: 1) When an oxidant is used to achieve the separation effect, a large amount of oxidant is used, resulting in a high economic cost. At the same time, excessive use will cause the bubbles to not be mineralized; 2) The use of organic inhibitors has poor selectivity, the recovery rate of stibnite is not high, and the target mineral is lost; 3) The use of inorganic inhibitors often requires the addition of activators, which brings environmental pollution problems. Summary of the invention

[0005] In view of the shortcomings of the prior art, the purpose of the present invention is to provide a flotation separation method for stibnite and arsenopyrite to solve the problems raised in the above-mentioned background technology. The preparation process of the present invention is simple, the economic cost is low, and the selectivity is good. It is green and environmentally friendly and has high adaptability to the separation of stibnite and arsenopyrite.

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

[0007] S1. Sorting and crushing the ore samples containing stibnite and arsenopyrite, and grinding them to a particle size range of 0.038-0.074 mm as flotation samples;

[0008] S2, mixing stibnite and arsenopyrite with water to form a slurry, and adjusting the slurry to a certain pH value, wherein the pH adjuster is any one or a combination of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid or lime, sodium carbonate, and sodium hydroxide;

[0009] S3, adding a certain amount of oxidant to the slurry and stirring for a certain period of time;

[0010] S4. Add a certain amount of inhibitor to the slurry and stir for a certain period of time;

[0011] S5, adding a certain amount of collector and frother to the slurry and stirring for a certain time, wherein the collector is any one or a combination of xanthate, ethylthiocyanate and black medicine, and the frother is any one or a combination of pine oil, eucalyptus oil and MIBC;

[0012] S6. The ore pulp obtained in step S5 is subjected to froth flotation, and the froth product and the bottom product after flotation are filtered, dried, and tested respectively, and the recovery rate is calculated.

[0013] Furthermore, the pH value of the ore pulp is adjusted to a certain value in S2, and the pH value of the ore pulp is controlled at 7-13.

[0014] Furthermore, the oxidant in S3 is any one or a combination of potassium permanganate, sodium hypochlorite and sodium persulfate.

[0015] Furthermore, the oxidant is 0-100 mg / L, and the stirring time is 1 min-30 min.

[0016] Furthermore, the inhibitor in S4 is tannic acid, starch, Fe 3+ -Tannic acid and Fe 3+ -Any one or a combination of starch; inhibitor Fe 3+ -Tannic acid and Fe 3+ -Specific preparation process of starch: the molar ratio of iron ion to tannic acid is 1:10-15:1, and the molar ratio of iron ion to starch is 1:10-15:1; the pH value control range is 2-10, the reaction time is 1min-60min, and the reaction temperature is: 0-100°C.

[0017] Furthermore, the certain amount of inhibitor in S4 is: 0-100 mg / L, and the stirring time is 1 min to 10 min.

[0018] Furthermore, the ratio of the oxidant to the inhibitor is 2:1 to 1:20; the preferred oxidant is sodium persulfate and the inhibitor is Fe 3+ -Tannic acid and Fe 3+ -starch.

[0019] Furthermore, the amount of the collector in S5 is 0 to 100 mg / L.

[0020] Furthermore, the dosage of the foaming agent is 0 to 100 mg / L; and the stirring time is 3 to 15 minutes.

[0021] Beneficial effects of the present invention:

[0022] 1. The flotation separation method of stibnite and arsenopyrite adopts the method of directly adding an oxidant and a metal ion-organic inhibitor complex solution as a combined inhibitor. The combined inhibitor has a simple production process, low cost and easy acquisition.

[0023] 2. Compared with the reagent system of using only oxidant to achieve separation, the flotation separation method of stibnite and arsenopyrite greatly reduces the amount of oxidant used, saves reagent costs, and avoids the decrease in stibnite recovery rate caused by oxidant and overoxidation caused by excessive oxidant.

[0024] 3. Compared with the reagent system of using only organic depressants to achieve separation, the flotation separation method of stibnite and arsenopyrite improves the selectivity and has a weaker effect on stibnite while suppressing arsenopyrite.

[0025] 4. The medicine used in the present invention is simple, does not require other equipment, is environmentally friendly, has significant economic benefits, and is suitable for industrial production. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] Figure 1 This is a flotation separation flow chart of stibnite and arsenopyrite according to Example 1 of the present invention;

[0027] Figure 2 This is a diagram showing the effect of potassium permanganate dosage on the separation of stibnite and arsenopyrite in Example 2 of the present invention;

[0028] Figure 3 This is a diagram showing the effect of sodium persulfate dosage on the separation of stibnite and arsenopyrite in Example 3 of the present invention;

[0029] Figure 4 This is a diagram showing the effect of sodium hypochlorite dosage on the separation of stibnite and arsenopyrite in Example 4 of the present invention;

[0030] Figure 5 Example 5Fe of the present invention 3+ - Effect of tannic acid dosage on the separation of stibnite and arsenopyrite;

[0031] Figure 6 Example 6Fe of the present invention 3+ -The effect of starch dosage on the separation of stibnite and arsenopyrite. DETAILED DESCRIPTION

[0032] 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.

[0033] See also Figures 1 to 6 , the present invention provides the following technical solutions:

[0034] Example 1

[0035] Take a mixture of stibnite and arsenopyrite (1:1), add it to a 40mL flotation tank, and use a laboratory hanging tank flotation machine to carry out a flotation test at a speed of 1992PRM. The flotation conditions are: natural pH value (6.5-7), butyl xanthate 30g / t, MIBC dosage 15g / t, the concentrate and tailings products obtained by scraping the foam are placed in an electric heating blast drying oven for drying, and then weighed. Then, the quantitative X-ray diffractometer method is used to determine the arsenic grade in the concentrate through the external standard curve, and then the antimony grade is calculated.

[0036] Table 1 Flotation separation results of stibnite and arsenopyrite without adding inhibitor

[0037]

[0038] It can be seen from Table 1 that when no inhibitor is added, the antimony grade in the antimony concentrate is 45.97%, the antimony recovery rate is 52.43%, the arsenic grade is 14.36%, and the arsenic recovery rate is 25.46%.

[0039] Example 2

[0040] Take a mixture of stibnite and arsenopyrite (1:1), add it to a 40mL flotation tank, and use a laboratory hanging tank flotation machine at a speed of 1992PRM to conduct a flotation test. The flotation conditions are: pH 7, butyl xanthate 30g / t, MIBC dosage 15g / t, oxidant potassium permanganate dosage: 0mg / L, 3mg / L, 5mg / L, 10mg / L, 15mg / L, the concentrate and tailings products obtained by scraping foam are placed in an electric blast drying oven for drying, and then weighed. Then, the quantitative X-ray diffractometer method is used to determine the arsenic grade in the concentrate through the external standard curve, and then the antimony grade is calculated.

[0041] Depend on Figure 2 It can be seen that when the oxidant potassium permanganate is used alone, the arsenic grade in the antimony concentrate is maintained at about 20%, and the antimony recovery rate is not high, so the use of potassium permanganate alone does not achieve a good flotation separation effect.

[0042] Example 3

[0043] Take a mixture of stibnite and arsenopyrite (1:1), add it to a 40mL flotation tank, and use a laboratory hanging tank flotation machine at a speed of 1992PRM to conduct a flotation test. The flotation conditions are: pH 7, the dosage of the oxidant sodium persulfate is: 0mg / L, 3mg / L, 5mg / L, 10mg / L, 15mg / L, the concentrate and tailings products obtained by scraping the foam are placed in an electric blast drying oven for drying, and then weighed. Then, the quantitative X-ray diffractometer method is used to determine the arsenic grade in the concentrate through the external standard curve, and then the antimony grade is calculated.

[0044] Depend on Figure 3 It can be seen that when sodium persulfate is used alone, the arsenic grade in the antimony concentrate is maintained at about 6.7%, but the antimony recovery rate is only about 70%, so it does not achieve a good separation effect when used alone.

[0045] Example 4

[0046] Take a mixture of stibnite and arsenopyrite (1:1), add it to a 40mL flotation tank, and use a laboratory hanging tank flotation machine at a speed of 1992PRM to conduct a flotation test. The flotation conditions are: pH 7, the dosage of the oxidant sodium hypochlorite is: 0mg / L, 3mg / L, 5mg / L, 10mg / L, 15mg / L, the concentrate and tailings products obtained by scraping the foam are placed in an electric blast drying oven for drying, and then weighed. Then, the quantitative X-ray diffractometer method is used to determine the arsenic grade in the concentrate through the external standard curve, and then the antimony grade is calculated.

[0047] Depend on Figure 4 It can be seen that when sodium hypochlorite is used alone, the arsenic grade in the antimony concentrate is maintained at about 15.93%, and the antimony recovery rate is low, only about 20%, so it does not achieve a good separation effect when used alone.

[0048] Example 5

[0049] Take a mixture of stibnite and arsenopyrite (1:1) and add it to a 40mL flotation cell. Use a laboratory hanging cell flotation machine to carry out a flotation test at a speed of 1992PRM. The flotation conditions are: pH 7, Fe 3+ -The dosage of tannic acid is: 1mg / L, 3mg / L, 5mg / L, 10mg / L, 20mg / L, 50mg / L. The concentrate and tailings products obtained by scraping are placed in an electric blast drying oven for drying, and then weighed. The quantitative X-ray diffractometer method is used to determine the arsenic grade in the concentrate through the external standard curve, and then the antimony grade is calculated.

[0050] Depend on Figure 5 It can be seen that in Fe 3+- When tannic acid is used alone, the dosage of tannic acid is 5×10 -5 mol / L, the arsenic grade in the antimony concentrate is about 3.00%, and the antimony recovery rate is about 85.80%. 3+ - Tannic acid can achieve flotation separation of stibnite and arsenopyrite at low dosage.

[0051] Example 6

[0052] Take a mixture of stibnite and arsenopyrite (1:1) and add it to a 40mL flotation cell. Use a laboratory hanging cell flotation machine to carry out a flotation test at a speed of 1992PRM. The flotation conditions are: pH 7, Fe 3+ -The starch dosage is: 1mg / L, 3mg / L, 5mg / L, 10mg / L, 20mg / L, 50mg / L. The concentrate and tailings products obtained by scraping are placed in an electric blast drying oven for drying and then weighed. The quantitative X-ray diffractometer method is then used to determine the arsenic grade in the concentrate through the external standard curve, and then the antimony grade is calculated.

[0053] Depend on Figure 6 It can be seen that in Fe 3+ - The amount of starch is less than 5×10 -5 mol / L, the arsenic grade in the concentrate has been decreasing. When the amount of starch is greater than 5×10 -5 mol / L, the arsenic grade in the concentrate remains stable. 3+ - Starch inhibitor has a strong inhibitory effect on arsenopyrite, but has little inhibitory effect on stibnite. -5 mol / L, the recovery rate of antimony was 93.41%, and the arsenic grade in the concentrate was 5.56%. 3+ - Starch can be used to separate stibnite and arsenopyrite by flotation at low dosage

[0054] This embodiment shows and describes the basic principles and main features of the present invention and the advantages of the present invention. 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 features of the present invention.

[0055] 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 flotation separation method for stibnite and arsenopyrite, characterized in that: The following steps are involved: S1. Sorting and crushing the ore containing stibnite and arsenopyrite, and grinding it to a particle size range of 0.038-0.074 mm as a flotation sample; S2, mixing stibnite and arsenopyrite with water to form a slurry, and adjusting the slurry to a certain pH value, wherein the pH adjuster is any one or a combination of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid or lime, sodium carbonate, and sodium hydroxide; S3, adding a certain amount of oxidant to the slurry and stirring for a certain period of time; S4. Add a certain amount of inhibitor to the slurry and stir for a certain period of time; S5, adding a certain amount of collector and frother to the slurry and stirring for a certain time, wherein the collector is any one or a combination of xanthate, ethylthiocyanate and black medicine, and the frother is any one or a combination of pine oil, eucalyptus oil and MIBC; S6. The ore pulp obtained in step S5 is subjected to froth flotation, and the froth product and the bottom product after flotation are filtered, dried, and tested respectively, and the recovery rate is calculated.

2. The method for flotation separation of stibnite and arsenopyrite according to claim 1, characterized in that: The pH value of the ore pulp is adjusted to a certain value in S2, and the pH value of the ore pulp is controlled at 7-13.

3. The method for flotation separation of stibnite and arsenopyrite according to claim 1, characterized in that: The oxidant in S3 is any one or a combination of potassium permanganate, sodium hypochlorite and sodium persulfate.

4. The method for flotation separation of stibnite and arsenopyrite according to claim 3, characterized in that: The oxidant is 0-100 mg / L, and the stirring time is 1-30 min.

5. The method for flotation separation of stibnite and arsenopyrite according to claim 4, characterized in that: The inhibitor in S4 is tannic acid, starch, Fe 3+ -Tannic acid and Fe 3+ -Any one or combination of starch, inhibitor Fe 3+ -Tannic acid and Fe 3+ -Specific preparation process of starch: the molar ratio of iron ion to tannic acid is 1:10-15:1, and the molar ratio of iron ion to starch is 1:10-15:1; the pH value control range is 2-10, the reaction time is 1min-60min, and the reaction temperature is: 0-100°C.

6. A flotation separation method for stibnite and arsenopyrite according to claim 5, characterized in that: The certain amount of inhibitor in S4 is: 0-100 mg / L, and the certain stirring time is 1 min-10 min.

7. The method for flotation separation of stibnite and arsenopyrite according to claim 1, characterized in that: The ratio of the oxidant to the inhibitor is 2:1 to 1:

20.

8. The method for flotation separation of stibnite and arsenopyrite according to claim 1, characterized in that: The amount of the collector in S5 is 0 to 100 mg / L.

9. The method for flotation separation of stibnite and arsenopyrite according to claim 1, characterized in that: The dosage of the foaming agent is 0-100 mg / L; the stirring time is 3 min-15 min.

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