Flotation preactivator for antimony oxide ore and activation and flotation method thereof

Abstract

The present invention belongs to the field of mineral flotation, and specifically relates to a flotation preactivator for antimony oxide ore, comprising an electrolyte, a tartaric acid source and a sulfiding agent; the electrolyte is a water-soluble inorganic salt; the tartaric acid source is tartaric acid and its water-soluble salt; the sulfiding agent is a water-soluble organic sulfide containing at least one group of HS-, -S-. The present invention also includes a method for activating antimony oxide ore and flotation using the activator. In the present invention, the activator can effectively improve the flotation performance of the antimony oxide ore.

Description

Technical Field

[0001] The invention belongs to the field of flotation, and in particular to the field of antimony oxide ore dressing. Background Art

[0002] my country is the country with the richest reserves of antimony resources in the world. Antimony, as one of the four major strategic metals, is widely used in the fields of physical chemistry, such as flame retardants, catalysts, batteries, etc. With the continuous mining and utilization of antimony resources, antimony ores with good selectivity and high grade are becoming less and less, and are replaced by more and more difficult-to-select antimony ores with low grade and high oxidation rate. The overall development trend of antimony resources is poor, fine and mixed.

[0003] Antimony oxide minerals account for about 15% of the proven antimony resources in my country, and the existing antimony oxide ores in my country account for about 15% of the total antimony resources. Among them, the antimony oxide content in the Feishuiyan deposit of Xikuangshan accounts for 8% to 18%; the antimony oxide content in the Tongjiayuan antimony deposit accounts for 33% to 46%; the antimony oxide content in the Xikuangshan North Concentrator deposit accounts for 57.07%. The recycling of such antimony oxide ores plays an important role in alleviating the shortage of antimony resources in my country. For these difficult-to-select antimony oxide ores, due to their fine particle embedding, easy coexistence and encapsulation with other minerals, good mineral surface wettability, strong hydrophilicity, and highly similar properties to gangue minerals, there is still no very mature and industrially good method to achieve efficient recovery of antimony oxide ores.

[0004] Antimony oxide ores mostly coexist with sulfide ores. Due to the dense symbiosis of antimony and sulfide minerals, after the antimony sulfide ore that is easy to separate is recovered, the antimony oxide ore is recovered by gravity separation. However, in actual production, when using shaking table gravity separation to recover antimony oxide, especially when fine-grained antimony oxide ore is recovered, the gravity separation recovery rate is low, and qualified antimony ore products cannot be obtained, making it difficult to fully utilize antimony oxide resources. For a long time, in order to achieve efficient recovery of antimony oxide ore, researchers have carried out a series of extensive studies on antimony oxide ore, mainly focusing on gravity separation, flotation, magnetic separation and its combined process. At present, positive progress has been made, but the separation indicators are still not ideal and it is difficult to achieve industrial application. It is difficult to obtain high-recovery and high-grade antimony gold ore products by gravity separation and flotation. At present, no new process flow with good adaptability has been found, and there is a lack of research on the flotation behavior of antimony oxide ore. Summary of the invention

[0005] In view of the problem that the flotation effect of existing antimony oxide ore is not ideal, the first purpose of the present invention is to provide a flotation preactivator for antimony oxide ore (also referred to as activator in the present invention), which aims to activate and modify the antimony oxide ore and improve its flotation effect.

[0006] The present invention also provides a method for activating antimony oxide ore using the activator, aiming at activating the antimony oxide ore and improving its flotation separation selectivity.

[0007] The third object of the present invention is to provide a method for activating and flotating antimony oxide ore using the activator, so as to improve the separation selectivity of antimony concentrate.

[0008] A flotation preactivator for antimony oxide ore, comprising an electrolyte, a tartaric acid source and a sulfiding agent;

[0009] The electrolyte is a water-soluble inorganic salt;

[0010] The tartaric acid source is tartaric acid and its water-soluble salts;

[0011] The vulcanizing agent is a water-soluble organic sulfide containing at least one of HS- and -S- groups.

[0012] The present invention studies show that the combination of the electrolyte, tartaric acid source and sulfiding agent can achieve cyclic activation and conversion of antimony oxide ore, and can synergistically improve activation and flotation effects.

[0013] In the present invention, the combined synergy of the electrolyte, tartaric acid source and sulfiding agent is the key to improving the activation and flotation performance of antimony oxide ore.

[0014] In the present invention, the electrolyte is at least one of water-soluble sulfate, chloride, and nitrate; preferably at least one of ammonium sulfate, sodium sulfate, and potassium sulfate.

[0015] In the present invention, the tartaric acid source is at least one of tartaric acid, sodium tartrate, potassium tartrate and ammonium tartrate.

[0016] In the present invention, the vulcanizing agent comprises at least one of the compounds of formula 1 and formula 2:

[0017]

[0018] The R is H, C1-C6 alkyl, C1-C6 alkoxy, nitro, halogen, mercapto or C1-C6 alkylamino;

[0019] The M is H, Na, K or NH 4 ;

[0020] Preferably, the vulcanizing agent is at least one of mercaptobenzothiazole and trimercapto-s-triazine trisodium salt. The present invention has found that the use of mercaptobenzothiazole and trimercapto-s-triazine trisodium salt as the vulcanizing agent is helpful to further cooperate with the tartaric acid source and the electrolyte, which is more conducive to the activation of the antimony oxide ore and the subsequent flotation.

[0021] In the present invention, the weight of the electrolyte is 1000 to 4000 parts, preferably 2000 to 3000 parts;

[0022] The weight portion of the tartaric acid source is 500 to 2000 parts, preferably 1000 to 1500 parts:

[0023] The weight portion of the vulcanizing agent is 2000 to 5000 parts, preferably 3000 to 4000 parts.

[0024] In another preferred embodiment of the present invention, the flotation preactivator further comprises a chelating agent.

[0025] The present invention has found that further adding a chelating agent to the activator can further synergistically improve the cyclic activation effect and further improve the flotation separation selectivity and recovery rate of the activated mineral.

[0026] Preferably, the chelating agent is a hydroxamic acid chelating agent, and more preferably a hydroxamic acid chelating agent having a structure of Formula 1;

[0027]

[0028] The R is phenyl, substituted phenyl, or C5-C9 alkyl; the substituted phenyl is a phenyl with at least one substituent selected from C1-C6 alkyl and hydroxyl groups;

[0029] The M is H, Na, K or NH 4 .

[0030] Preferably, in the flotation preactivating agent, the weight portion of the chelating agent is 200 to 1000 parts, preferably 500 to 800 parts.

[0031] In the present invention, in the flotation preactivator, each component is independent of each other before use, or some or all of the components exist in the form of a mixture.

[0032] The present invention also provides a flotation preactivation method for antimony oxide ore, and the flotation preactivation agent of the present invention is used to activate the antimony oxide ore.

[0033] The activation step of the present invention is, for example, slurrying the antimony oxide ore and the flotation preactivator with water, and then performing activation treatment under mechanical strengthening;

[0034] In the present invention, the solid content of the slurry can be adjusted as required, for example, it can be 30% to 70%.

[0035] In the present invention, the dosage of the flotation preactivator can be adjusted according to the grade of the activated ore. Preferably, the dosage of the flotation preactivator is 3700-12000 g / t, preferably 6500-9500 g / t.

[0036] In the present invention, the components of the flotation preactivator can be added in the form of a mixture of part or all of the components, or each component can be added independently.

[0037] In the present invention, the mechanical strengthening may be a grinding operation.

[0038] The present invention also provides a flotation method for antimony oxide ore, which uses the flotation pre-activation method to activate the antimony oxide ore to obtain activated ore pulp, and then adds flotation reagents to perform flotation to obtain antimony concentrate.

[0039] In the present invention, thanks to the activation process, the flotation effect can be improved.

[0040] In the present invention, the flotation process can be achieved based on existing means.

[0041] For example, in the present invention, the activated slurry can be selectively ground according to the particle size requirements to obtain ore pulp, and then a flotation agent is added to perform flotation.

[0042] Preferably, -0.074 mm of the pulp accounts for 50% to 90%;

[0043] Preferably, the flotation reagent contains a collector;

[0044] Preferably, the collector is at least one of a xanthate collector and a sulfur-nitrogen collector; more preferably, it is at least one of a butyl xanthate, an amyl xanthate, a secondary octyl xanthate, an butyl ammonium black medicine, and an ethyl thiocyanate;

[0045] Preferably, the amount of the collector is 100 g / t to 1000 g / t, more preferably 300 to 500 g / t;

[0046] Preferably, the flotation reagent further comprises an inhibitor, and the inhibitor is preferably at least one of sodium persulfate, sodium hexametaphosphate, and carboxymethyl cellulose (CMC);

[0047] Preferably, the dosage of the inhibitor is 100 g / t to 2000 g / t, and further can be 1000 to 1500 g / t;

[0048] Preferably, a regulator is also added to the flotation reagent;

[0049] Preferably, the adjusting agent is activated carbon;

[0050] Preferably, the amount of the adjusting agent is 200 to 1000 g / t, and further can be 500 to 900 g / t.

[0051] In the present invention, the flotation process can be adjusted as needed. Considering the treatment effect and efficiency, the flotation process can adopt 1 to 2 roughing selections, 1 to 3 scavenging selections, and 1 to 3 fine selections.

[0052] In a more specific embodiment of the present invention, the steps include:

[0053] Step 1: Wet Grinding and Activation of Antimony Oxide Ore

[0054] The crushed antimony oxide ore or fine-grained antimony oxide ore is added to the mill, and a certain grinding concentration is controlled for fine grinding and dissociation; while grinding, an activator is added to the mill to activate it under mechanochemical action; the electrolyte is ammonium sulfate, and its dosage is 1000g / t~4000g / t (referring to the mass of the reagent consumed per ton of ore, the same below). The vulcanizing agent is at least one of sodium sulfide, mercaptobenzothiazole (MBT), and tris-mercapto-s-triazine trisodium salt (TMT), and its dosage is 2000g / t~5000g / t. The tartaric acid (salt) includes tartaric acid, sodium tartrate, and potassium tartrate, and its dosage is 500g / t~2000g / t. The chelating agent is at least one of benzohydroxamic acid, salicylic hydroxamic acid, and alkyl hydroxamic acid (C5~9), and its dosage is 200g / t~3000g / t. The grinding concentration is about 30% to 70%.

[0055] Step 2: Flotation

[0056] The antimony oxide pulp after the first step of activation is added to the flotation machine, and the collector and the frother are added in sequence for flotation to obtain the antimony oxide concentrate product and the flotation tailings. The grinding fineness of the antimony oxide ore is -0.074mm, accounting for 50% to 90%. The collector of the antimony oxide ore is at least one of butyl xanthate, amyl xanthate, sec-octyl xanthate, butyl ammonium black medicine, and ethyl thiocyanate, and the dosage is 100g / t to 1000g / t. The inhibitor is at least one of sodium persulfate, sodium hexametaphosphate, and carboxymethyl cellulose (CMC), and the dosage of the inhibitor is 100g / t to 2000g / t. The flotation process adopts 1 to 2 roughing, 1 to 3 scavenging, and 1 to 3 fine cleaning; the "one roughing-two scavenging-two fine" process is preferred.

[0057] Beneficial Effects

[0058] In the present invention, the electrolyte, tartaric acid source and sulfiding agent are combined to achieve synergy, and can realize efficient and cyclic activation of antimony oxide ore, which is beneficial to subsequent flotation separation.

[0059] In the present invention, in addition to the synergistic combination of the electrolyte, tartaric acid source and sulfiding agent, a chelating agent is further added to further improve the synergy, further improve the activation of the antimony oxide ore, and be more conducive to flotation separation.

[0060] The method of the present invention can obtain an antimony concentrate with a grade greater than 35%, and a recovery rate of fine-grained antimony oxide ore greater than 75%. Compared with the original process, the economic effect is significantly improved.

[0061] The whole method has low-cost beneficiation reagents, a simple reagent system and stable indicators. While recovering the antimony concentrate product, the amount of reagents used in the flotation process is reduced, the separation of antimony oxide ore and gangue minerals is achieved, and the grade and recovery rate of the antimony concentrate are improved. The qualified antimony concentrate obtained by flotation can be directly subjected to pyrometallurgical smelting to extract metallic antimony, with significant economic benefits. BRIEF DESCRIPTION OF THE DRAWINGS

[0062] Figure 1 This is a flow chart of the method provided in Embodiment 1 of the present invention. DETAILED DESCRIPTION

[0063] The following examples are intended to illustrate the present invention rather than to further limit the present invention.

[0064] In the following cases, the dosage of the reagents is measured by weight of the original ore (antimony oxide ore).

[0065] In the present invention, the ratios of collectors, inhibitors and other agents are all by weight.

[0066] Embodiment 1:

[0067] This example uses an antimony mine in Hunan, where the antimony oxide ore contains 1.34% antimony. The specific steps are as follows:

[0068] ① Weigh 500g of antimony oxide ore and 500ml of water, and mix them to obtain a mixed slurry with a slurry concentration of 50%;

[0069] ② Add 6800g / t of pre-activator [containing (NH 4 )SO 4 (electrolyte), tartaric acid (tartaric acid source), MBT (sulfurizing agent) and benzohydroxamic acid (chelating agent)], the mixture was sent to a ball mill for 8 minutes (XMQΦ240×90 conical ball mill, cylinder speed 90r / min, feed particle size <3mm, discharge particle size 0.074mm), and the grinding fineness was -0.074mm accounting for 86%;

[0070] ③ Pour the finely ground antimony oxide slurry into the flotation tank and follow the flotation process of "one roughing - two sweeping - two fine" (see Appendix Figure 1The flotation was carried out as shown in the figure, ethylthiocyanate and butyl xanthate with a weight ratio of 1:2 were selected as collectors (300 g / t for roughing, 100 g / t for scavenging, 40 g / t for scavenging), sodium hexametaphosphate, sodium persulfate and CMC with a weight ratio of 2:1:1 were selected as inhibitors (800 g / t for roughing, 400 g / t for refining, 200 g / t for refining), and activated carbon was used as a regulator (800 g / t);

[0071] ④ The samples obtained by flotation are subjected to flocculation sedimentation, filtration and drying to finally obtain antimony concentrate X and tailings K.

[0072] The grade of the antimony concentrate product obtained by flotation is 36.91%, and the recovery rate is 77.83%.

[0073] Embodiment 2:

[0074] Compared with Example 1, the only difference is that in ②, an equal weight of TMT is used to replace the MBT, and other operations and parameters are the same as in Example 1.

[0075] The grade of the antimony concentrate product obtained by flotation is 34.27% and the recovery rate is 78.14%.

[0076] Embodiment 3:

[0077] Compared with Example 1, the only difference is that, in ②, an equal weight of sodium sulfate is used to replace the ammonium sulfate, and other operations and parameters are the same as in Example 1.

[0078] The grade of the antimony concentrate product obtained by flotation is 35.72% and the recovery rate is 76.92%.

[0079] Embodiment 4:

[0080] Compared with Example 1, the only difference is that, in ②, an equal weight of potassium sulfate is used to replace the ammonium sulfate, and other operations and parameters are the same as in Example 1.

[0081] The grade of the antimony concentrate product obtained by flotation is 35.18%, and the recovery rate is 77.03%.

[0082] Embodiment 5:

[0083] Compared with Example 1, the only difference is that in ②, an equal weight of sodium tartrate is used to replace the tartaric acid, and other operations and parameters are the same as in Example 1.

[0084] The grade of the antimony concentrate product obtained by flotation is 35.84% and the recovery rate is 77.90%.

[0085] Embodiment 6:

[0086] Compared with Example 1, the only difference is that, in ②, an equal weight of potassium tartrate is used to replace the tartaric acid, and other operations and parameters are the same as in Example 1.

[0087] The grade of the antimony concentrate product obtained by flotation is 36.59% and the recovery rate is 78.04%.

[0088] Embodiment 7:

[0089] Compared with Example 1, the only difference is that in ②, an equal weight of salicylic acid is used to replace the benzoic acid, and other operations and parameters are the same as in Example 1.

[0090] The grade of the antimony concentrate product obtained by flotation is 35.79% and the recovery rate is 75.38%.

[0091] Embodiment 8:

[0092] Compared with Example 1, the only difference is that in ②, an equal weight of octyl hydroxamic acid is used to replace the benzohydroxamic acid, and other operations and parameters are the same as in Example 1.

[0093] The grade of the antimony concentrate product obtained by flotation is 35.28%, and the recovery rate is 75.94%.

[0094] Embodiment 9:

[0095] Compared with Example 1, the only difference is that in ②, equal weights of TMT-MBT (1500 g / t each) are used to replace the MBT, and other operations and parameters are the same as in Example 1.

[0096] The grade of the antimony concentrate product obtained by flotation is 37.88% and the recovery rate is 80.95%.

[0097] Example 10

[0098] Compared with Example 1, the only difference is that no benzohydroxamic acid (chelating agent) is added to the activator; the total amount of the activator is the same as that of Example 1.

[0099] The results of the concentrate after flotation were: grade was 26.94% and recovery was 64.93%.

[0100] It can be seen that adding a certain chelating agent to the activator can further synergistically improve the flotation separation selectivity and recovery rate.

[0101] Embodiment 11:

[0102] Compared with Example 1, the only difference is that the preactivator component (NH 4 )SO 4The ratio and total dosage of (electrolyte), tartaric acid (tartaric acid source), MBT (sulfurizing agent) and benzohydroxamic acid (chelating agent) are: (1) 1000:500:2000:200 (3700 g / t); (2) 2000:1000:3000:500 (6500 g / t); (3) 3000:1500:4000:800 (9300 g / t); (4) 4000:2000:5000:1000 (12000 g / t).

[0103] The antimony concentrate product obtained by flotation has (1) a grade of 35.19% and a recovery rate of 75.29%; (2) a grade of 35.19% and a recovery rate of 75.29%; (3) a grade of 35.19% and a recovery rate of 75.29%; and (4) a grade of 35.19% and a recovery rate of 75.29%.

[0104]

[0105] Embodiment 12:

[0106] Compared with Example 1, the only difference is that the flotation collector and the usage ratio are: (1) the collector is ethylthiocyanate and sec-octyl xanthate in a weight ratio of 1:2; (2) the collector is ethylthiocyanate and butyl ammonium black medicine in a weight ratio of 1:2; (3) the collector is ethylthiocyanate and amyl xanthate in a weight ratio of 1:2.

[0107] The properties of the antimony concentrate products obtained by flotation are as follows: (1) grade is 35.71% and the recovery rate is 76.35%; (2) grade is 34.05% and the recovery rate is 74.38%; (3) grade is 33.82% and the recovery rate is 75.61%.

[0108] Comparative Example 1:

[0109] Compared with Example 1, the only difference is that in the activator, (1) no (NH 4 )SO 4 ; The total amount of activator is the same as in Example 1. (2) Tartaric acid is not added; The total amount of activator is the same as in Example 1. (3) MBT is not added; The total amount of activator is the same as in Example 1. (4) No activator is added. Other operating conditions are the same as in Example 1.

[0110] The antimony concentrate products obtained by flotation have a (1) grade of 23.56% and a recovery rate of 63.20%; (2) a grade of 18.39% and a recovery rate of 57.14%; (3) a grade of 15.62% and a recovery rate of 53.61%; and (4) a grade of 13.60% and a recovery rate of 36.18%.

[0111] Comparative Example 2:

[0112] Compared with Example 1, the only difference is that, in ②, an equal weight of sulfuric acid is used to replace the tartaric acid, and other operations and parameters are the same as in Example 1.

[0113] The grade of the antimony concentrate product obtained by flotation is 15.47% and the recovery rate is 54.93%.

[0114] Comparative Example 3:

[0115] Compared with Example 1, the only difference is that in ②, an equal weight of Na 2 S replaces the MBT, and other operations and parameters are the same as in Example 1.

[0116] The grade of the antimony concentrate product obtained by flotation is 21.47% and the recovery rate is 64.83%.

Claims

1. A flotation preactivator for antimony oxide ore, characterized in that: including electrolytes, tartaric acid sources, sulfiding agents, and chelating agents; The electrolyte is at least one of water-soluble ammonium sulfate, sodium sulfate and potassium sulfate; The tartaric acid source is at least one of tartaric acid, sodium tartrate, potassium tartrate and ammonium tartrate; The vulcanizing agent comprises at least one of the compounds of formula 1 and formula 2: Formula 1 Formula 2 In Formula 1 and Formula 2, R is H, C1-C6 alkyl, C1-C6 alkoxy, nitro, halogen, thiol or C1-C6 alkylamino; M is H, Na, K or NH4; The chelating agent is a hydroxamic acid chelating agent having a structure of formula 3; Formula 3 In Formula 3, R is phenyl, substituted phenyl, or C5-C9 alkyl; the substituted phenyl is a phenyl having at least one substituent selected from C1-C6 alkyl and hydroxyl groups; and M is H, Na, K, or NH4.

2. The flotation preactivator of antimony oxide ore according to claim 1, characterized in that: The vulcanizing agent comprises formula 1 and formula 2.

3. The flotation preactivator of antimony oxide ore according to claim 1, characterized in that: The weight of the electrolyte is 1000-4000 parts; The weight portion of the tartaric acid source is 500-2000 parts; The weight portion of the vulcanizing agent is 2000 to 5000 parts; The weight portion of the chelating agent is 200 to 1000 parts.

4. A flotation preactivation method for antimony oxide ore, characterized in that: The antimony oxide ore is activated by using the flotation preactivator described in any one of claims 1 to 3.

5. The flotation preactivation method of antimony oxide ore according to claim 4, characterized in that: The antimony oxide ore and the flotation preactivator are slurried with water and then activated under mechanical strengthening.

6. The flotation preactivation method of antimony oxide ore according to claim 5, characterized in that: The solid content of the slurry is 30%~70%.

7. The flotation preactivation method of antimony oxide ore according to claim 6, characterized in that: The dosage of the flotation preactivator is 3700-12000 g / t.

8. A flotation method for antimony oxide ore, characterized in that: The antimony oxide ore is activated by the flotation pre-activation method according to any one of claims 4 to 7 to obtain activated ore pulp, and then a flotation agent is added to perform flotation to obtain antimony concentrate.

9. The flotation method of antimony oxide ore according to claim 8, characterized in that: -0.074mm accounts for 50%~90% of the slurry.

10. The flotation method of antimony oxide ore according to claim 8, characterized in that: The flotation reagent contains a collector.

11. The flotation method of antimony oxide ore according to claim 10, characterized in that: The collector is at least one of a xanthate collector and a sulfur-nitrogen collector.

12. The flotation method of antimony oxide ore according to claim 11, characterized in that: The collector is at least one of butyl xanthate, pentyl xanthate, sec-octyl xanthate, butyl ammonium black medicine and ethyl thiocyanate.

13. The flotation method of antimony oxide ore according to claim 11, characterized in that: The dosage of collector is 100 g / t~1000 g / t.

14. The flotation method of antimony oxide ore according to claim 8, characterized in that: The flotation reagent further comprises an inhibitor, which is at least one of sodium persulfate, sodium hexametaphosphate and carboxymethyl cellulose; The dosage of inhibitor is 100 g / t ~ 2000 g / t.

15. The flotation method of antimony oxide ore according to claim 8, characterized in that: The flotation reagent is also added with a regulator; The adjusting agent is activated carbon; The dosage of the adjusting agent is 200~1000g / t.

16. The flotation method of antimony oxide ore according to any one of claims 8 to 15, characterized in that: The flotation process includes 1~2 roughing, 1~3 scavenging and 1~3 cleaning.

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