Flotation separation method for high-arsenic antimony sulfide

Abstract

The invention relates to a flotation separation method for high-arsenic antimony sulfide, and belongs to the technical field of mineral processing. Ore grinding operation is conducted, ore is crushed to 10-20 cm, sodium sulfide is added into the ore, ball-milling ore grinding is conducted, the ore grinding concentration is controlled to range from 60% to 80%, the graded overflow fineness is controlled to range from 70% to 80%, and the overflow ore pulp concentration ranges from 25% to 30%; ammonium oxalate is added at an overflow ore pulp outlet; sodium tannate is continuously added into the ore pulp, butyl xanthate and MIBC are added for pulp mixing, and arsenic concentrate and antimony-containing tailings are obtained through arsenic flotation; and lead nitrate or ammonium nitrate is added into the antimony-containing tailings, butyl xanthate and MIBC are added for size mixing, flotation of antimony minerals is carried out, and a high-quality low-arsenic antimony sulfide concentrate product is obtained. The method is technically characterized in that under the action of a combined inhibitor sodium sulfide, ammonium oxalate and sodium tannate, antimony sulfide minerals are effectively inhibited, the arsenopyrite is activated at the same time, reverse flotation is conducted on the arsenopyrite through a collecting agent, and effective separation of the arsenopyrite and antimony sulfide is successfully achieved.

Description

Technical Field

[0001] The invention relates to a method for flotation separation of high-arsenic antimony sulfide, belonging to the technical field of mineral processing. Background Art

[0002] In terms of high-arsenic antimony sulfide beneficiation and separation technology, according to publicly available data, there are three main technical processes: arsenic suppression antimony flotation process, antimony suppression arsenic flotation process, and arsenic-antimony mixed flotation-wet leaching process. Currently, the most researched process in China is the arsenic suppression antimony flotation process, which mainly involves adding oxidants such as bleaching powder, potassium permanganate, hydrogen peroxide, and sodium sulfite under high alkaline conditions to suppress arsenopyrite and positively float antimony sulfide minerals. This process has low antimony recovery rates and high arsenic content in the antimony concentrate, failing to meet the quality requirements of high-quality antimony concentrate (As < 0.4%). Although the arsenic-antimony mixed flotation-wet leaching process can reduce the arsenic content in antimony concentrate to qualified products, it has problems such as high production costs and environmental pollution. Summary of the Invention

[0003] To address the aforementioned problems and shortcomings, the present invention provides a method for flotation separation of high-arsenic antimony sulfide. This method involves suppressing antimony sulfide and flotating the harmful substance arsenopyrite, a reverse flotation process. The key technical aspect of the present invention is that, under the combined action of sodium sulfide, ammonium oxalate, and sodium tannate, the antimony sulfide minerals are effectively suppressed while the arsenopyrite is activated. The arsenopyrite is then reverse-floated using a collector, effectively separating the arsenopyrite from the antimony sulfide.

[0004] In order to achieve the above-mentioned purpose, the present invention adopts the following technical solutions:

[0005] A method for flotation separation of high-arsenic antimony sulfide, comprising the following steps:

[0006] Step S1: Grinding operation, crushing the ore to 10-20 cm, adding sodium sulfide to it, and entering the ball mill for grinding, controlling the grinding concentration to 60%-80%, the classification overflow fineness to be controlled at -200 mesh, accounting for 70%-80%, and the overflow pulp concentration to be 25%-30%; and adding ammonium oxalate at the overflow pulp outlet;

[0007] Step S2: Strengthening the inhibition of stibnite, continuing to add sodium tannate to the slurry, and continuously stirring to obtain a slurry in which stibnite is suppressed;

[0008] Step S3: removing arsenopyrite, adding butyl xanthate and MIBC to the slurry in which the stibnite is suppressed, and obtaining arsenic concentrate and antimony-containing tailings through arsenic flotation;

[0009] Step S4: antimony flotation operation, adding lead nitrate or ammonium nitrate to the antimony-containing tailings, adding butyl xanthate and MIBC to prepare the slurry, and then entering the flotation of antimony minerals to obtain high-quality low-arsenic antimony sulfide concentrate products.

[0010] In step S1, the amount of sodium sulfide added is 200 g / t-400 g / t.

[0011] In step S1, the amount of ammonium oxalate added is 200 g / t-600 g / t, and the pH of the slurry is adjusted to 6-9.

[0012] In step S2, the amount of sodium tannate added is 300 g / t-800 g / t, and stirring is continued for 5-8 minutes.

[0013] In step S3, the arsenic flotation comprises one roughing selection, two cleaning selections and three scavenging selections.

[0014] In the step S3, the roughing is performed by adding 60 g / t-120 g / t of butyl xanthate and 40 g / t-80 g / t of MIBC, stirring for 2 minutes, obtaining an arsenic rough concentrate and entering the arsenic concentration operation, and the arsenic roughing tailings entering the scavenging operation; in the first concentration, 100 g / t of ammonium oxalate, 50 g / t of sodium tannate, 20 g / t of butyl xanthate, and 10 g / t of MIBC are added, and no flotation reagent is added in the second concentration to obtain arsenic concentrate and concentrated middlings, which are returned in sequence; in the scavenging operation I, 50 g / t of ammonium oxalate, 50 g / t of sodium tannate, 30 g / t of butyl xanthate, and 10 g / t of MIBC are added, 20 g / t of butyl xanthate is added in the scavenging operation II, and 10 g / t of butyl xanthate is added in the scavenging operation III, and three arsenic scavenging operations are performed, the scavenged middlings are returned in sequence, and the scavenged tailings enter the antimony concentration operation.

[0015] In step S4, the flotation of antimony ore includes one roughing selection, two cleaning selections and two scavenging selections.

[0016] During the roughing process, 100 g / t-400 g / t of lead nitrate or ammonium nitrate is added, and after stirring for 5-10 minutes, the slurry enters the flotation machine, and 50 g / t-200 g / t of butyl xanthate and 20 g / t-50 g / t of MIBC are added to the flotation machine for antimony flotation roughing. The obtained antimony rough concentrate enters the antimony cleaning operation and the antimony roughing tailings enter the scavenging operation.

[0017] 10 g / t of butyl xanthate was added to the antimony crude concentrate for secondary concentration. No mineral processing agent was added for the second concentration, and the middlings were returned in order.

[0018] In antimony scavenging I, 30 g / t of butyl xanthate and 10 g / t of MIBC were added, and in antimony scavenging II, 20 g / t of butyl xanthate was added for secondary antimony scavenging. The ore from the scavenged antimony was returned in order.

[0019] Compared with the prior art, the present invention provides a high-arsenic antimony sulfide beneficiation method, which can achieve efficient separation of arsenic and antimony. Usually, high-arsenic antimony sulfide ores are all subjected to the method of suppressing arsenopyrite to float antimony sulfide, that is, positive flotation. During the production process, a large amount of lime is often added, which will cause the foam to become sticky, serious entrainment, and blockage of pipelines, resulting in unstable production. At the same time, under high alkalinity (pH>10) conditions, antimony sulfide minerals will also be suppressed, resulting in low antimony recovery rate and low quality of antimony concentrate. Therefore, the present invention breaks with tradition and can achieve efficient separation of arsenic and antimony under low alkalinity conditions, with the following advantages: (1) The reagents used are all commercially available conventional reagents, which are low in price and environmentally friendly; (2) The process structure of the present invention is simple, the sorting effect is good, the return water return process index has little impact, and the obtained antimony sulfide concentrate is of high quality; (3) The technical indicators obtained by the present invention are stable, and the valuable element arsenic can be recovered at the same time. This process has strong adaptability. The technical indicators of antimony sulfide concentrate that can be obtained are usually Sb grade > 55%, arsenic content less than 0.3%, and recovery rate > 90%. The product meets the quality requirements of YS / T385-2019 first-class products. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] Figure 1 It is a schematic flow chart of the present invention. DETAILED DESCRIPTION

[0021] The present invention will be further described below with reference to the accompanying drawings.

[0022] Example 1

[0023] like Figure 1 As shown, the method for flotation separation of high-arsenic antimony sulfide comprises the following steps:

[0024] Step S1: Grinding operation: The ore (the high-arsenic antimony ore has an antimony content of 3.61% and an arsenic content of 2.69%, with antimony mainly existing in the form of stibnite and arsenic mainly existing in the form of arsenopyrite) is crushed to 10-20 cm, 200 g / t of sodium sulfide is added, and the ore is fed into a ball mill for grinding. The grinding concentration is controlled to 60%, the classification overflow fineness is controlled to -200 mesh, accounting for 78%, and the overflow pulp concentration is 28%; and 300 g / t of ammonium oxalate is added at the overflow pulp outlet;

[0025] Step S2: Strengthen the inhibition of stibnite, continue to add 400g / t sodium tannate to the slurry, and continue stirring to obtain a slurry that suppresses stibnite for 5min;

[0026] Step S3: removing arsenopyrite, adding butyl xanthate and MIBC to the slurry in which the stibnite is suppressed, and obtaining arsenic concentrate and antimony-containing tailings through arsenic flotation;

[0027] Arsenic flotation consists of one roughing separation, two cleaning separations and three scavenging separations.

[0028] In step S3, the roughing is performed by adding 120 g / t of butyl xanthate and 50 g / t of MIBC, stirring for 2 minutes, and obtaining arsenic rough concentrate for arsenic concentration operation and arsenic roughing tailings for scavenging operation;

[0029] During the first concentration, 100g / t of ammonium oxalate, 50g / t of sodium tannate, 20g / t of butyl xanthate, and 10g / t of MIBC are added. No flotation reagents are added during the second concentration. Arsenic concentrate and concentrated middlings are obtained, and the concentrated middlings are returned in order.

[0030] In the scavenging process I, 50g / t of ammonium oxalate, 50g / t of sodium tannate, 30g / t of butyl xanthate, and 10g / t of MIBC are added. In the scavenging process II, 20g / t of butyl xanthate is added. In the scavenging process III, 10g / t of butyl xanthate is added. Three arsenic scavenging processes are carried out. The scavenged ore is returned in sequence, and the scavenged tailings are sent to the antimony process.

[0031] Step S4: Antimony flotation operation: add lead nitrate or ammonium nitrate to the antimony-containing tailings, add butyl xanthate and MIBC to mix the slurry, and then enter the flotation of antimony minerals:

[0032] The flotation process of antimony ore is one roughing, two cleaning and two scavenging.

[0033] During the roughing process, 300 g / t of lead nitrate is added, and after stirring for 5 minutes, the slurry enters the flotation machine, and 100 g / t of butyl xanthate and 50 g / t of MIBC are added to the flotation machine for antimony flotation roughing. The obtained antimony rough concentrate enters the antimony cleaning process and the antimony roughing tailings enter the scavenging process;

[0034] 10 g / t of butyl xanthate was added to the antimony crude concentrate for secondary concentration, without adding any mineral processing reagents for the second time, and the middlings were returned in order;

[0035] In the antimony scavenging I operation, 30g / t of butyl xanthate and 10g / t of MIBC are added. In the antimony scavenging II operation, 20g / t of butyl xanthate is added. Secondary antimony scavenging is performed and the scavenged and mined antimony is returned in order.

[0036] Obtain high-quality low-arsenic antimony sulfide concentrate products.

[0037] In this embodiment, the antimony grade of the high-quality low-arsenic antimony sulfide concentrate product obtained is 57.88%, the recovery rate is 88.52%, and the arsenic content is 0.14%. The product meets the first-class quality requirements of YS / T385-2019.

[0038] Example 2

[0039] like Figure 1 As shown, the method for flotation separation of high-arsenic antimony sulfide comprises the following steps:

[0040] Step S1: Grinding operation: The ore (the high-arsenic antimony ore has an antimony content of 2.89% and an arsenic content of 4.37%, with antimony mainly existing in the form of stibnite and arsenic mainly existing in the form of arsenopyrite) is crushed to 10-20 cm, 200 g / t of sodium sulfide is added to the ore, and the ore is fed into a ball mill for grinding. The grinding concentration is controlled to be 60%, the classification overflow fineness is controlled to be -200 mesh, accounting for 74%, and the overflow pulp concentration is 25%; and 350 g / t of ammonium oxalate is added to the overflow pulp outlet;

[0041] Step S2: Strengthen the inhibition of stibnite by adding 450 g / t sodium tannate to the slurry and continuously stirring for 5 min to obtain a slurry that inhibits stibnite;

[0042] Step S3: removing arsenopyrite, adding butyl xanthate and MIBC to the slurry in which the stibnite is suppressed, and obtaining arsenic concentrate and antimony-containing tailings through arsenic flotation;

[0043] Arsenic flotation consists of one roughing separation, two cleaning separations and three scavenging separations.

[0044] In step S3, the roughing is performed by adding 100 g / t of butyl xanthate and 50 g / t of MIBC and stirring for 2 minutes to obtain arsenic rough concentrate for arsenic concentration operation and arsenic roughing tailings for scavenging operation;

[0045] During the first concentration, 100g / t of ammonium oxalate, 50g / t of sodium tannate, 20g / t of butyl xanthate, and 10g / t of MIBC are added. No flotation reagents are added during the second concentration. Arsenic concentrate and concentrated middlings are obtained, and the concentrated middlings are returned in order.

[0046] In the scavenging process I, 50g / t of ammonium oxalate, 50g / t of sodium tannate, 30g / t of butyl xanthate, and 10g / t of MIBC are added. In the scavenging process II, 20g / t of butyl xanthate is added. In the scavenging process III, 10g / t of butyl xanthate is added. Three arsenic scavenging processes are carried out. The scavenged ore is returned in sequence, and the scavenged tailings are sent to the antimony process.

[0047] Step S4: Antimony flotation operation: add lead nitrate or ammonium nitrate to the antimony-containing tailings, add butyl xanthate and MIBC to mix the slurry, and then enter the flotation of antimony minerals:

[0048] The flotation process of antimony ore is one roughing, two cleaning and two scavenging.

[0049] During the roughing process, 250 g / t of lead nitrate is added, and after stirring for 10 minutes, the slurry enters the flotation machine, and 100 g / t of butyl xanthate and 50 g / t of MIBC are added to the flotation machine for antimony flotation roughing. The obtained antimony rough concentrate enters the antimony cleaning process and the antimony roughing tailings enter the scavenging process;

[0050] 10 g / t of butyl xanthate was added to the antimony crude concentrate for secondary concentration, without adding any mineral processing reagents for the second time, and the middlings were returned in order;

[0051] In the antimony scavenging I operation, 30g / t of butyl xanthate and 10g / t of MIBC are added. In the antimony scavenging II operation, 20g / t of butyl xanthate is added. Secondary antimony scavenging is performed and the scavenged and mined antimony is returned in order.

[0052] Obtain high-quality low-arsenic antimony sulfide concentrate products.

[0053] In this embodiment, the antimony grade of the high-quality low-arsenic antimony sulfide concentrate product obtained is 61.42%, the recovery rate is 86.53%, and the arsenic content is 0.11%. The product meets the first-class quality requirements of YS / T385-2019.

[0054] Example 3

[0055] like Figure 1 As shown, the method for flotation separation of high-arsenic antimony sulfide comprises the following steps:

[0056] Step S1: Grinding operation: The ore (the high-arsenic antimony ore has an antimony content of 6.88% and an arsenic content of 10.92%, with antimony mainly existing in the form of stibnite and arsenic mainly existing in the form of arsenopyrite) is crushed to 10-20 cm, 200 g / t of sodium sulfide is added to the ore, and the ore is fed into a ball mill for grinding. The grinding concentration is controlled to be 60%, the classification overflow fineness is controlled to be -200 mesh, accounting for 79%, and the overflow pulp concentration is 26%; and 500 g / t of ammonium oxalate is added at the overflow pulp outlet;

[0057] Step S2: Strengthen the inhibition of stibnite, continue to add 550g / t sodium tannate to the slurry, and continue stirring to obtain a slurry that inhibits stibnite for 8min;

[0058] Step S3: removing arsenopyrite, adding butyl xanthate and MIBC to the slurry in which the stibnite is suppressed, and obtaining arsenic concentrate and antimony-containing tailings through arsenic flotation;

[0059] Arsenic flotation consists of one roughing separation, two cleaning separations and three scavenging separations.

[0060] In step S3, the roughing is performed by adding 120 g / t of butyl xanthate and 50 g / t of MIBC, stirring for 2 minutes, and obtaining arsenic rough concentrate for arsenic concentration operation and arsenic roughing tailings for scavenging operation;

[0061] During the first concentration, 100g / t of ammonium oxalate, 50g / t of sodium tannate, 20g / t of butyl xanthate, and 10g / t of MIBC are added. No flotation reagents are added during the second concentration. Arsenic concentrate and concentrated middlings are obtained, and the concentrated middlings are returned in order.

[0062] In the scavenging process I, 50g / t of ammonium oxalate, 50g / t of sodium tannate, 30g / t of butyl xanthate, and 10g / t of MIBC are added. In the scavenging process II, 20g / t of butyl xanthate is added. In the scavenging process III, 10g / t of butyl xanthate is added. Three arsenic scavenging processes are carried out. The scavenged ore is returned in sequence, and the scavenged tailings are sent to the antimony process.

[0063] Step S4: Antimony flotation operation: add lead nitrate or ammonium nitrate to the antimony-containing tailings, add butyl xanthate and MIBC to mix the slurry, and then enter the flotation of antimony minerals:

[0064] The flotation process of antimony ore is one roughing, two cleaning and two scavenging.

[0065] During the roughing process, 400 g / t of lead nitrate is added, and after stirring for 10 minutes, the slurry enters the flotation machine, and 150 g / t of butyl xanthate and 50 g / t of MIBC are added to the flotation machine for antimony flotation roughing. The obtained antimony rough concentrate enters the antimony cleaning process and the antimony roughing tailings enter the scavenging process;

[0066] 10 g / t of butyl xanthate was added to the antimony crude concentrate for secondary concentration, without adding any mineral processing reagents for the second time, and the middlings were returned in order;

[0067] In the antimony scavenging I operation, 30g / t of butyl xanthate and 10g / t of MIBC are added. In the antimony scavenging II operation, 20g / t of butyl xanthate is added. Secondary antimony scavenging is performed and the scavenged and mined antimony is returned in order.

[0068] Obtain high-quality low-arsenic antimony sulfide concentrate products.

[0069] In this embodiment, the antimony grade of the high-quality low-arsenic antimony sulfide concentrate product obtained is 60.77%, the recovery rate is 83.66%, and the arsenic content is 0.21%. The product meets the first-class quality requirements of YS / T385-2019.

[0070] The above describes the specific embodiments of the present invention in detail with reference to the accompanying drawings. However, the present invention is not limited to the above embodiments. Various changes can be made within the knowledge of ordinary technicians in this field without departing from the scope of the present invention.

Claims

1. A method for flotation separation of high-arsenic antimony sulfide, characterized by the steps of include: Step S1: Grinding operation, crushing the ore to 10-20 cm, adding sodium sulfide to it, and entering the ball mill for grinding, controlling the grinding concentration to 60%-80%, the classification overflow fineness to be controlled at -200 mesh, accounting for 70%-80%, and the overflow pulp concentration to be 25%-30%; and adding ammonium oxalate at the overflow pulp outlet; Step S2: Strengthening the inhibition of stibnite, continuing to add sodium tannate to the slurry, and continuously stirring to obtain a slurry in which stibnite is suppressed; Step S3: removing arsenopyrite, adding butyl xanthate and MIBC to the slurry in which the stibnite is suppressed, and obtaining arsenic concentrate and antimony-containing tailings through arsenic flotation; Step S4: antimony flotation operation, adding lead nitrate or ammonium nitrate to the antimony-containing tailings, adding butyl xanthate and MIBC to prepare the slurry, and then entering the flotation of antimony minerals to obtain high-quality low-arsenic antimony sulfide concentrate products.

2. The method for flotation separation of high-arsenic antimony sulfide according to claim 1, characterized in that: In step S1, the amount of sodium sulfide added is 200 g / t-400 g / t.

3. The method for flotation separation of high-arsenic antimony sulfide according to claim 1, characterized in that: In step S1, the amount of ammonium oxalate added is 200 g / t-600 g / t, and the pH of the slurry is adjusted to 6-9.

4. The method for flotation separation of high-arsenic antimony sulfide according to claim 1, characterized in that: In step S2, the amount of sodium tannate added is 300 g / t-800 g / t, and stirring is continued for 5-8 minutes.

5. The method for flotation separation of high-arsenic antimony sulfide according to claim 1, characterized in that: In step S3, the arsenic flotation comprises one roughing selection, two cleaning selections and three scavenging selections.

6. The method for flotation separation of high-arsenic antimony sulfide according to claim 5, characterized in that: In the step S3, the roughing is performed by adding 60 g / t-120 g / t of butyl xanthate and 40 g / t-80 g / t of MIBC, stirring for 2 minutes, obtaining an arsenic rough concentrate and entering the arsenic concentration operation, and the arsenic roughing tailings entering the scavenging operation; in the first concentration, 100 g / t of ammonium oxalate, 50 g / t of sodium tannate, 20 g / t of butyl xanthate, and 10 g / t of MIBC are added, and no flotation reagent is added in the second concentration to obtain arsenic concentrate and concentrated middlings, which are returned in sequence; in the scavenging operation I, 50 g / t of ammonium oxalate, 50 g / t of sodium tannate, 30 g / t of butyl xanthate, and 10 g / t of MIBC are added, 20 g / t of butyl xanthate is added in the scavenging operation II, and 10 g / t of butyl xanthate is added in the scavenging operation III, and three arsenic scavenging operations are performed, the scavenged middlings are returned in sequence, and the scavenged tailings enter the antimony concentration operation.

7. The method for flotation separation of high-arsenic antimony sulfide according to claim 1, characterized in that: In step S4, the flotation of antimony ore includes one roughing selection, two cleaning selections and two scavenging selections.

8. The method for flotation separation of high-arsenic antimony sulfide according to claim 7, characterized in that: During the roughing process, 100 g / t-400 g / t of lead nitrate or ammonium nitrate is added, and after stirring for 5-10 minutes, the slurry enters the flotation machine, and 50 g / t-200 g / t of butyl xanthate and 20 g / t-50 g / t of MIBC are added to the flotation machine for antimony flotation roughing. The obtained antimony rough concentrate enters the antimony cleaning operation and the antimony roughing tailings enter the scavenging operation.

9. The method for flotation separation of high-arsenic antimony sulfide according to claim 8, characterized in that: 10 g / t of butyl xanthate was added to the antimony crude concentrate for secondary concentration. No mineral processing agent was added for the second concentration, and the middlings were returned in order.

10. The method for flotation separation of high-arsenic antimony sulfide according to claim 9, characterized in that: In antimony scavenging I, 30 g / t of butyl xanthate and 10 g / t of MIBC were added, and in antimony scavenging II, 20 g / t of butyl xanthate was added for secondary antimony scavenging. The ore from the scavenged antimony was returned in order.

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