Regulator for high-arsenic and poor-antimony gold ore and method for recovering antimony by using regulator

Abstract

The invention relates to the technical field of gold and antimony beneficiation, in particular to a high-arsenic and poor-antimony gold ore regulator and a method for recovering antimony by using the regulator. The adjusting agent comprises an adjusting agent A and an adjusting agent B; the regulator A comprises 35-45% of oxalic acid, 35-40% of aluminum sulfate, 10-15% of sodium fluosilicate and 5-10% of ammonium chloride; the regulator B comprises 5-15% of sodium humate, 10-20% of ammonium sulfate, 20-30% of sodium sulfite, 15-20% of calcium chloride and 20-40% of bleaching powder. When the raw ore pulp is subjected to gold-antimony mixed roughing, the regulator A is added, the flotation index equal to that when lead nitrate serves as an antimony activating agent can be obtained, and lead pollution can be eliminated; and a regulator B is added when the gold-antimony mixed pre-concentration ore is subjected to antimony roughing and concentration, poison sand in ore pulp is efficiently inhibited under the condition that the pH value is 5-6.5, then high-gold low-arsenic antimony concentrate with the qualified antimony grade and high-arsenic low-antimony gold concentrate with the antimony grade not exceeding the standard are obtained, and efficient comprehensive recycling of the high-arsenic poor-antimony gold ore is achieved.

Description

Technical Field

[0001] This invention relates to the field of gold and antimony beneficiation technology, specifically to a modifier for high-arsenic, low-antimony gold ore and a method for recovering antimony using the modifier. Background Technology

[0002] Antimony (Sb) is a strategic mineral resource in China, widely used in various fields due to its excellent properties. In the antimony flotation process, lead nitrate is commonly used as an activator to increase the floatability of stibnite (mainly composed of Sb₂S₃) in order to improve antimony recovery. This results in lead ions in the antimony concentrate and beneficiation wastewater, causing heavy metal pollution to the surrounding environment. Therefore, finding an antimony activator that can completely replace lead nitrate without heavy metal pollution is a key issue in antimony flotation.

[0003] In gold-antimony coexisting ores, gold (Au) and stibnite (Sb₂S₃) often coexist as fine-grained inclusions or intergrowths. Both are sulfide minerals with similar surface hydrophobicity, making flotation separation difficult. For gold-antimony coexisting ores, flotation processes generally employ mixed gold-antimony flotation to produce a mixed gold-antimony concentrate, or a sequential gold-antimony flotation process to produce both antimony and gold concentrates. Due to the lack of effective antimony-gold separation inhibitors, the gold / antimony grades in the mixed gold-antimony concentrate are often substandard (residual gold in the antimony concentrate, resulting in substandard gold grade), or the gold concentrate contains excessive antimony, both of which severely impact economic efficiency and represent a pressing problem in gold-antimony flotation.

[0004] The problem of low antimony grade in concentrate is particularly prominent when the antimony grade only meets the average grade requirement for comprehensive recovery of associated elements (0.3%-0.5%). When the antimony grade in gold ore is <0.3%, antimony is not considered a comprehensive recovery element, but rather a harmful element that needs to be eliminated, because it seriously affects the gold leaching rate in subsequent smelting operations.

[0005] The main mineral composition of high-arsenic, low-antimony gold ore includes: (1) gold-bearing minerals: arsenopyrite (FeAsS), pyrite, and gold encapsulated in a small amount of stibnite; (2) interfering minerals: realgar / orpiment (As2S3), and clay minerals (such as kaolinite). High-arsenic, low-antimony gold ore is a difficult-to-process gold-antimony symbiotic ore resource with two characteristics: 1. The main gold-bearing minerals in the ore are arsenopyrite and pyrite, and the content of arsenopyrite is high (usually 5%-30%), which is difficult to suppress during the flotation process, resulting in excessive arsenic in the concentrate and affecting the pricing coefficient; 2. The antimony content in the ore is <0.3%. If it is not suppressed during the flotation process, it will cause excessive antimony in the gold concentrate. If it is suppressed as a harmful element, it will waste antimony resources.

[0006] Given the extremely low antimony grade (typically 0.1-0.5%) in high-arsenic, low-antimony gold ores, it is necessary to develop antimony activators that completely replace lead nitrate and are free from heavy metal pollution, in order to obtain gold-antimony grade concentrates and achieve effective gold and antimony recovery. Simultaneously, considering the high arsenopyrite content in high-arsenic, low-antimony gold ores, it is necessary to develop highly efficient antimony-arsenic separation inhibitors to obtain gold-antimony concentrates with low arsenic content. Therefore, developing effective, stable, environmentally friendly, and economically efficient modifiers (antimony activators and arsenic inhibitors), as well as methods for antimony recovery from high-arsenic, low-antimony gold ores, is a challenging and urgent research project. Summary of the Invention

[0007] (a) Technical problems to be solved

[0008] In view of the above-mentioned shortcomings and deficiencies of the prior art, the present invention provides a modifier for high-arsenic and low-antimony gold ore and a method for recovering antimony using the modifier. It can effectively improve the antimony grade of flotation concentrate of high-arsenic and low-antimony gold ore, and obtain high-gold and low-arsenic antimony concentrate with qualified antimony grade and high-arsenic and low-antimony gold concentrate with antimony grade not exceeding the standard. It realizes the efficient and comprehensive recovery and utilization of high-arsenic and low-antimony gold ore, and has important economic significance, especially for the development and utilization of difficult-to-process gold ore resources with associated antimony grade not exceeding 0.30%.

[0009] (II) Technical Solution

[0010] In a first aspect, the present invention provides a modifier for antimony recovery from high-arsenic, low-antimony gold ore, comprising: modifier A and modifier B.

[0011] The modifier A is used to increase the floatability of stibnite; by mass fraction, the modifier A contains 35%-45% oxalic acid, 35%-40% aluminum sulfate, 10%-15% sodium fluorosilicate and 5%-10% ammonium chloride;

[0012] The modifier B is used to inhibit the buoyancy of arsenopyrite under weakly acidic conditions; by mass fraction, the modifier B contains 5%-15% sodium humate, 10%-20% ammonium sulfate, 20%-30% sodium sulfite, 15%-20% calcium chloride and 20%-40% bleaching powder.

[0013] Secondly, the present invention provides a method for recovering antimony from high-arsenic, low-antimony gold ore, comprising the following steps:

[0014] S1. The ore powder obtained by crushing the high-arsenic and low-antimony gold ore to be selected is wet-milled to obtain the raw ore slurry.

[0015] S2. Add modifier A to the raw ore slurry to adjust the slurry. The dosage of modifier A is 1200-1800g / t to obtain the primary slurry.

[0016] S3. Add roughing reagents to the primary slurry to perform gold-antimony mixed roughing to obtain antimony-containing crude gold concentrate and roughing tailings; the roughing reagents include: 60-100 g / t butyl xanthate, 30-50 g / t butyl ammonium black powder and 10-30 g / t No. 2 oil;

[0017] S4. Add a slime inhibitor to the antimony-containing crude gold concentrate obtained in S3 and perform N rounds of gold-antimony mixed pre-selection to obtain gold-antimony mixed pre-selection concentrate and gold-antimony mixed pre-selection tailings. Among them, the gold-antimony mixed pre-selection tailings generated in each round of gold-antimony mixed pre-selection are returned to the previous step, and the gold-antimony mixed pre-selection concentrate is transferred to the next step of processing. N≥2, and a slime inhibitor is added once for each round of gold-antimony mixed pre-selection. The slime inhibitor contains: 50-200g / t sodium hexametaphosphate and 100-400g / t sodium silicate.

[0018] S5. Add acid and modifier B to the gold-antimony mixed pre-selected concentrate produced by S4. The amount of modifier B is 40-100g / t to obtain a secondary slurry.

[0019] S6. The secondary slurry obtained from S5 is subjected to a primary antimony roughing process to obtain a primary antimony roughing concentrate and a primary antimony roughing tailings. The primary antimony roughing concentrate is treated with modifier B to obtain a primary antimony cleaning process to obtain a primary antimony cleaning concentrate and a primary antimony cleaning tailings. The primary antimony cleaning concentrate is subjected to two or more antimony blank cleaning processes (no new reagents are added during blank cleaning) to obtain the final product of high gold and low arsenic antimony concentrate and tailings from each antimony blank cleaning process. The antimony cleaning tailings, tailings from each antimony blank cleaning process, and antimony roughing tailings are all combined to form a high arsenic and low antimony gold concentrate.

[0020] Preferably, in S1, the high-arsenic, low-antimony gold ore contains 0.60%-1.10% arsenic, 0.20%-0.75% antimony, and 2.20g / t-2.60g / t of gold. Antimony is mainly found in stibnite, and the main gold-bearing minerals are pyrite and arsenopyrite.

[0021] Preferably, in S1, the mass of solid particles in the raw ore slurry accounts for 25-35% of the mass of the raw ore slurry; and the mass of solid particles with a particle size of less than 0.074 mm in the raw ore slurry accounts for 70-75% of the mass of solid particles in the raw ore slurry.

[0022] Preferably, in S4, the gold-antimony mixed pre-selection is performed 2-4 times, i.e., N = 2-4, with the gold grade in the gold-antimony mixed pre-selection concentrate being greater than 24 g / t and the antimony grade being greater than 2.30% as the endpoint.

[0023] Preferably, S4 further includes adding scavenging reagents to the roughing tailings generated in S3 for M rounds of gold-antimony mixed scavenging to obtain scavenged gold-antimony mixed concentrate and scavenged gold-antimony tailings; wherein, the scavenged gold-antimony mixed concentrate generated in each gold-antimony mixed scavenging is returned to the previous step, and the scavenged gold-antimony tailings are transferred to the next step for processing, and the scavenged gold-antimony tailings generated in the last gold-antimony mixed scavenging is the final tailings; M≥2, and scavenging reagents are added once for each gold-antimony mixed scavenging; the scavenging reagents include: 10-50 g / t of butyl xanthate and 5-25 g / t of butylammonium black.

[0024] Preferably, in S4, scavenging reagents are added to the roughing tailings for 2-4 gold-antimony mixed scavenging processes, i.e., M = 2-4, preferably 3.

[0025] Preferably, in S5, the amount of acid added is sufficient to bring the pH of the secondary slurry system to 5.0-6.5, and the acid is sulfuric acid.

[0026] Preferably, in S5, the mass of solid particles in the secondary slurry accounts for 10-20% of the mass of the secondary slurry.

[0027] Preferably, in S6, the amount of modifier B added to the primary antimony roughing concentrate is 40-100 g / t;

[0028] The number of antimony blank selections is 2-5 times, with the endpoint being that the antimony grade in the high gold and low arsenic antimony concentrate is greater than 30%.

[0029] (III) Beneficial Effects

[0030] (1) This invention provides a method for recovering antimony from high-arsenic, low-antimony gold ore, comprising: wet-milling the raw ore slurry of high-arsenic, low-antimony gold ore, adding modifier A to adjust the slurry, then adding roughing reagents to perform gold-antimony mixed roughing to obtain antimony-containing crude gold concentrate and roughing tailings; performing multiple gold-antimony mixed scavenging on the roughing tailings to obtain final tailings; adding slime inhibitors to the antimony-containing crude gold concentrate to perform multiple gold-antimony mixed pre-selection to obtain gold-antimony mixed pre-selection concentrate with a gold grade >24 g / t and an antimony grade >2.30% and gold-antimony mixed pre-selection tailings; adding sulfuric acid and modifier B to the gold-antimony mixed pre-selection concentrate to perform one antimony roughing and multiple antimony selections to obtain the final high-gold, low-arsenic antimony concentrate, and merging the antimony roughing tailings and multiple antimony selection tailings into the final high-arsenic, low-antimony gold concentrate.

[0031] This invention is particularly suitable for processing high-arsenic, low-antimony gold ore with arsenic content of 0.60-1.10%, antimony content of 0.20-0.25%, and gold content of 2.20 g / t-2.60 g / t. It can obtain high-gold, low-arsenic antimony concentrate with antimony grade of 30%-35%, gold grade of 70 g / t-90 g / t, arsenic grade of 2.50%-3.00%, antimony recovery rate of 45%-60%, and gold recovery rate of 10%-20%, as well as high-arsenic, low-antimony gold concentrate with antimony grade of 0.40%-1.00%, gold grade of 20 g / t-25 g / t, arsenic grade of 8.00%-13.00%, antimony recovery rate of 20%-30%, and gold recovery rate of 70%-75%. The overall recovery rate of gold and antimony is about 85%, realizing the comprehensive recovery and efficient separation of gold and antimony elements, and improving the economic benefits of high-arsenic, low-antimony gold ore. Gold-antimony symbiotic ores with an antimony content of 0.60% or higher can further improve the antimony grade and recovery rate in high-gold, low-arsenic antimony concentrates.

[0032] (2) The modifier A of the present invention uses oxalic acid, aluminum sulfate, sodium fluorosilicate and ammonium chloride as raw materials and is used in combination in a specific ratio. This increases the activity of antimony minerals and gold-bearing minerals in the slurry, creates favorable conditions for the recovery of gold and antimony elements, and obtains the same flotation index as using lead nitrate as antimony activator. It can significantly reduce the gold and antimony content in the tailings, improve the gold and antimony recovery rate, and avoid lead pollution.

[0033] (3) The modifier B of the present invention uses sodium humate, ammonium sulfate, sodium sulfite, calcium chloride and bleaching powder as raw materials, and is used in a specific ratio and at a low addition amount (40-100g / t). While not changing the activity of antimony mineral and gold-bearing mineral pyrite, it reduces the activity of gold-bearing mineral arsenopyrite in the slurry. It achieves efficient inhibition of arsenopyrite in the pH range of 5.0-6.5 of the slurry system, optimizes the antimony-arsenic separation index, effectively reduces the arsenic content in antimony concentrate, and greatly improves the gold grade in antimony concentrate.

[0034] (4) The method of the present invention enables gold ore with antimony grade lower than the boundary grade to produce concentrate products with qualified gold and antimony grades, making the flotation recovery of ultra-low grade antimony economical and feasible, effectively solving the problem of the development and utilization of associated and difficult-to-process antimony resources below the boundary grade, and providing a new and effective method and reference for the development and utilization of similar antimony associated gold resources, which is suitable for promotion and application.

[0035] (5) This invention only requires adjusting the amount of adjuster B and the number of antimony blank selections to effectively separate gold and antimony minerals, so that the gold / antimony grade in the gold-antimony mixed concentrate (high gold and low arsenic antimony concentrate) is qualified and the antimony content in the gold concentrate (high arsenic and low antimony gold concentrate) does not exceed the standard, thereby improving the product pricing coefficient and effectively increasing the economic benefits of the enterprise. Attached Figure Description

[0036] Figure 1This is a process flow diagram of the method for recovering antimony from high-arsenic, low-antimony gold ore according to the present invention. Detailed Implementation

[0037] To better explain and facilitate understanding of the present invention, the present invention will be described in detail below with reference to the accompanying drawings and specific embodiments.

[0038] See Figure 1 As shown, the present invention provides a method for recovering antimony from high-arsenic, low-antimony gold ore, comprising the following steps:

[0039] (1) The mineral powder obtained by crushing the high arsenic and low antimony gold ore to be selected is wet-milled to obtain raw ore slurry; wherein, the mass of solid particles in the raw ore slurry accounts for 25-35% of the mass of the raw ore slurry; and the mass of solid particles with a particle size of less than 0.074 mm in the raw ore slurry accounts for 70-75% of the mass of solid particles in the raw ore slurry.

[0040] In some typical embodiments, the high-arsenic, low-antimony gold ore has an arsenic content of 0.60%-1.10%, an antimony content of 0.20%-0.75%, and a gold content of 2.20 g / t-2.60 g / t. The antimony element is mainly found in stibnite, and the main gold-bearing minerals are pyrite and arsenopyrite.

[0041] (2) Add modifier A to the raw ore slurry obtained in step (1) at a rate of 1200-1800 g / t to obtain a primary slurry.

[0042] The composition of modifier A is: 35%-45% oxalic acid, 35%-40% aluminum sulfate, 10%-15% sodium fluorosilicate and 5%-10% ammonium chloride.

[0043] (3) Add roughing reagent to the primary slurry obtained in step (2) to perform gold-antimony mixed roughing to obtain antimony-containing crude gold concentrate and roughing tailings.

[0044] The roughing agent comprises butyl xanthate, butylammonium black powder, and No. 2 oil. Preferably, the addition amounts of each component in the roughing agent are: 60-100 g / t of butyl xanthate, 30-50 g / t of butylammonium black powder, and 10-30 g / t of No. 2 oil.

[0045] (4) Add a slime inhibitor to the antimony-containing crude gold concentrate obtained in step (3) and perform N rounds of gold-antimony mixed pre-selection to obtain gold-antimony mixed pre-selection concentrate and gold-antimony mixed pre-selection tailings. The gold-antimony mixed pre-selection tailings generated in each round are returned to the previous step, and the gold-antimony mixed pre-selection concentrate generated in each round is transferred to the next step. The tailings from the first round of gold-antimony mixed pre-selection are returned to the gold-antimony mixed roughing in step (3). Wherein N≥2. A slime inhibitor is added once for each round of gold-antimony mixed pre-selection. Wherein, the slime inhibitor contains sodium hexametaphosphate and sodium silicate. Preferably, the amount of each component added in the slime inhibitor is: 50-200 g / t sodium hexametaphosphate and 100-400 g / t sodium silicate.

[0046] The roughing tailings produced in step (3) are subjected to M gold-antimony mixed scavenging processes with scavenging reagents to obtain scavenged gold-antimony mixed concentrate and scavenged gold-antimony tailings. The scavenged gold-antimony mixed concentrate produced in each gold-antimony mixed scavenging process is returned to the previous step, and the scavenged gold-antimony tailings produced in each gold-antimony mixed scavenging process are transferred to the next step. The scavenged gold-antimony tailings produced in the last gold-antimony mixed scavenging process are the final tailings. The scavenged gold-antimony mixed concentrate produced in the first gold-antimony mixed scavenging process is returned to the gold-antimony mixed roughing process in step (3). M ≥ 2. Scavenging reagents are added once for each gold-antimony mixed scavenging process. The scavenging reagents include butyl xanthate and butylammonium black. Preferably, the addition amount of each component in the scavenging reagent is 10-50 g / t of butyl xanthate and 5-25 g / t of butylammonium black.

[0047] Preferably, the gold-antimony mixed pre-selection is performed twice, i.e., N=2. The specific steps are as follows: First, add 50-200 g / t sodium hexametaphosphate and 100-400 g / t sodium silicate to the antimony-containing crude gold concentrate obtained in step (3), then perform the first gold-antimony mixed pre-selection to obtain a first-stage gold-antimony mixed pre-selection concentrate and a first-stage gold-antimony mixed pre-selection tailings. Return the first-stage gold-antimony mixed pre-selection tailings to the gold-antimony mixed roughing in step (3). Then, add 50-200 g / t sodium hexametaphosphate and 100-400 g / t sodium silicate to the first-stage gold-antimony mixed pre-selection concentrate to perform the second gold-antimony mixed pre-selection to obtain a second-stage gold-antimony mixed pre-selection concentrate and a second-stage gold-antimony mixed pre-selection tailings. Return the second-stage gold-antimony mixed pre-selection tailings to the first-stage gold-antimony mixed pre-selection. At this point, the obtained second-stage gold-antimony mixed pre-selection concentrate has a gold grade >24 g / t and an antimony grade >2.30%.

[0048] Preferably, the gold-antimony mixed scavenging is performed three times, i.e., M=3. The specific steps are as follows: First, 10-50 g / t of butyl xanthate and 5-25 g / t of butylammonium black are added to the roughing tailings produced in step (3) for the first gold-antimony mixed scavenging, resulting in a first-stage scavenged gold-antimony mixed concentrate and a first-stage scavenged gold-antimony tailings. The first-stage scavenged gold-antimony mixed concentrate is returned to the gold-antimony mixed roughing in step (3). Then, 10-50 g / t of butyl xanthate and 5-25 g / t of butylammonium black are added to the first-stage scavenged gold-antimony tailings for the second gold-antimony mixed scavenging, resulting in a second-stage scavenged gold-antimony mixed concentrate and a second-stage scavenged gold-antimony tailings. The second-stage scavenged gold-antimony mixed concentrate is returned to the first-stage gold-antimony mixed scavenging. Add 10-50 g / t of butyl xanthate and 5-25 g / t of butylammonium black to the gold-antimony tailings from the secondary scavenging process for a third gold-antimony mixed scavenging, yielding a tertiary scavenged gold-antimony mixed concentrate and tertiary scavenged gold-antimony tailings. The tertiary scavenged gold-antimony mixed concentrate is returned to the second gold-antimony mixed scavenging process. The tertiary scavenged gold-antimony tailings are the final tailings.

[0049] (5) Add sulfuric acid and the modifier B of the present invention to the gold-antimony mixed pre-selected concentrate obtained in step (4) to obtain a secondary slurry.

[0050] In one specific embodiment, sulfuric acid is added to the gold-antimony mixed pre-selected concentrate to adjust the pH of the slurry system to 5.0-6.5, and 40-100 g / t of adjuster B is added to obtain a secondary slurry with a solid particle mass accounting for 10-20% of the slurry mass.

[0051] Modifier B contains 5%-15% sodium humate, 10%-20% ammonium sulfate, 20%-30% sodium sulfite, 15%-20% calcium chloride, and 20%-40% bleaching powder.

[0052] (6) The secondary slurry from step (5) is subjected to a primary antimony roughing process to obtain a primary antimony roughing concentrate and a primary antimony roughing tailings. The primary antimony roughing concentrate is then treated with an additive B to obtain a primary antimony cleaning process to obtain a primary antimony cleaning concentrate and a primary antimony cleaning tailings. The primary antimony cleaning concentrate is subjected to multiple antimony blank cleaning processes to obtain the final product, a high-gold, low-arsenic antimony concentrate, and tailings from each antimony blank cleaning process. The antimony cleaning tailings obtained from the multiple antimony cleaning processes (including tailings from each blank cleaning process and tailings from the primary antimony cleaning process) and the antimony roughing tailings are all combined to form a high-arsenic, low-antimony gold concentrate.

[0053] Preferably, the amount of modifier B added to the primary antimony roughing concentrate is 40-100 g / t.

[0054] Preferably, the primary antimony concentrate undergoes three rounds of blank antimony refining without the addition of reagents. The specific process is as follows: the primary antimony concentrate undergoes blank refining to obtain primary antimony blank refined concentrate and primary antimony blank refined tailings. The primary antimony blank refined concentrate undergoes a second antimony blank refined concentrate to obtain a second antimony blank refined concentrate and a second antimony blank refined tailings. The second antimony blank refined concentrate undergoes a third antimony blank refined concentrate to obtain a third antimony blank refined concentrate and a third antimony blank refined tailings. The antimony grade of the third antimony blank refined concentrate is >30%, constituting the final high-gold, low-arsenic antimony concentrate. The aforementioned primary antimony refinement tailings, the primary antimony blank refined tailings from the third antimony blank refined concentrate, the second antimony blank refined tailings, the third antimony blank refined tailings, and the antimony roughing tailings are combined to form the final high-arsenic, low-antimony gold concentrate.

[0055] In this invention, modifier A significantly increases the activity of antimony and gold-bearing minerals in the slurry, creating a favorable slurry environment for the efficient enrichment of gold and antimony. It achieves flotation indicators equivalent to those using lead nitrate as an antimony activator, significantly reducing the gold and antimony content in tailings, improving gold and antimony recovery, and avoiding lead contamination. Modifier B reduces the activity of arsenopyrite, a gold-bearing mineral in the slurry, effectively inhibiting arsenopyrite under weakly acidic conditions and low dosage, significantly reducing the arsenic content in antimony concentrate, increasing the gold grade in the antimony concentrate, and thus obtaining a concentrate product with qualified gold and antimony grades.

[0056] The present invention will be further described below with reference to specific embodiments.

[0057] Example 1

[0058] This embodiment provides a high-arsenic, low-antimony gold ore modifier and a method for recovering antimony from it. The raw ore used is a high-arsenic, low-antimony gold ore with a gold grade of 2.24 g / t, an antimony grade of 0.20%, an arsenic grade of 0.73%, a pyrite content of 4.61 wt%, arsenopyrite content of 1.79 wt%, and stibnite content of 0.24 wt%. The specific steps include:

[0059] (1) The ore powder obtained by crushing high arsenic and low antimony gold ore is wet-milled so that the solid particles with a particle size of less than 0.074 mm account for 75% of the solid particles in the slurry. Water is added so that the solid particles in the slurry account for 33 wt% of the slurry mass, thus obtaining the raw ore slurry.

[0060] (2) Add 1500g / t of modifier A, 90g / t of butyl xanthate, 45g / t of butyl ammonium black powder and 15g / t of No. 2 oil to the raw ore slurry obtained in step (1) to carry out gold-antimony mixed roughing to obtain antimony-containing crude gold concentrate and roughing tailings.

[0061] (3) Add 100g / t sodium hexametaphosphate and 200g / t sodium silicate to the antimony-containing crude gold concentrate obtained in step (2) for the first gold-antimony mixed pre-selection, to obtain the first gold-antimony mixed pre-selection concentrate and the first gold-antimony mixed pre-selection tailings. The first gold-antimony mixed pre-selection tailings are returned to the gold-antimony mixed roughing in step (2). Add 50g / t sodium hexametaphosphate and 100g / t sodium silicate to the first gold-antimony mixed pre-selection concentrate for the second gold-antimony mixed pre-selection, to obtain the second gold-antimony mixed pre-selection concentrate and the second gold-antimony mixed pre-selection tailings. The second gold-antimony mixed pre-selection tailings are returned to the first gold-antimony mixed pre-selection.

[0062] Add 40 g / t of butyl xanthate and 20 g / t of butylammonium black to the roughing tailings obtained in step (2) for the first gold-antimony mixed scavenging, to obtain a first-scavenged gold-antimony mixed concentrate and a first-scavenged gold-antimony tailings. The first-scavenged gold-antimony mixed concentrate is returned to the gold-antimony mixed roughing. Add 30 g / t of butyl xanthate and 15 g / t of butylammonium black to the first-scavenged gold-antimony tailings for the second gold-antimony mixed scavenging, to obtain a second-scavenged gold-antimony mixed concentrate and a second-scavenged gold-antimony tailings. The second-scavenged gold-antimony mixed concentrate is returned to the first gold-antimony mixed scavenging. Add 20 g / t of butyl xanthate and 10 g / t of butylammonium black to the second-scavenged gold-antimony tailings for the third gold-antimony mixed scavenging, to obtain a third-scavenged gold-antimony mixed concentrate and a third-scavenged gold-antimony tailings. The third-scavenged gold-antimony mixed concentrate is returned to the second gold-antimony mixed scavenging. The third-scavenged gold-antimony tailings are the final tailings.

[0063] (4) Add sulfuric acid to the secondary gold-antimony mixed pre-selected concentrate obtained in step (3) to adjust the pH of the slurry system to 5.0, add 80 g / t of adjuster B, and add water to obtain a secondary slurry with a solid particle mass of 13 wt% of the slurry mass.

[0064] (5) The secondary slurry obtained in step (4) is subjected to primary antimony roughing to obtain primary antimony roughing concentrate and primary antimony roughing tailings; 40 g / t of modifier B is added to the primary antimony roughing concentrate for primary antimony cleaning to obtain primary antimony cleaning concentrate and primary antimony cleaning tailings; the primary antimony cleaning concentrate is subjected to a first antimony blank cleaning to obtain primary antimony blank cleaning concentrate and primary antimony blank cleaning tailings; the primary antimony blank cleaning concentrate is subjected to a second antimony blank cleaning to obtain secondary antimony blank cleaning concentrate and secondary antimony blank cleaning tailings; the secondary antimony blank cleaning concentrate is subjected to a third antimony blank cleaning to obtain tertiary antimony blank cleaning concentrate and tertiary antimony blank cleaning tailings. The tertiary antimony blank cleaning concentrate is the final high-gold, low-arsenic antimony concentrate. The antimony blank cleaning tailings generated from the antimony roughing tailings, primary antimony cleaning tailings, and tertiary antimony blank cleaning are combined to form the final high-arsenic, low-antimony gold concentrate.

[0065] The test results obtained in Example 1 are shown in Table 1.

[0066] Table 1:

[0067]

[0068] As shown in Table 1, after processing the raw ore with a gold grade of 2.24 g / t, an antimony grade of 0.20%, and an arsenic grade of 0.73% using the method of the embodiment, high-gold, low-arsenic antimony concentrate with a gold grade of 80.50 g / t and an antimony grade of 30.50% and high-arsenic, low-antimony gold concentrate with a gold grade of 22.60 g / t and an antimony grade of 0.850% were obtained. The overall gold recovery rate reached 83.43%, and the overall antimony recovery rate reached 84.12%.

[0069] Comparative Example 1

[0070] This comparative example uses the same process as Example 1, except that lead nitrate is used as the antimony activator during the roughing of the gold-antimony mixture. The amount of lead nitrate added is 1500 g / t, replacing the modifier A in Example 1. The remaining steps of Comparative Example 1 are the same as in Example 1, and the experimental results are shown in Table 2.

[0071] Table 2:

[0072]

[0073] As shown in Table 2, in the roughing process of gold-antimony mixture in Comparative Example 1, lead nitrate was used as the antimony activator. Compared with Example 1, although the gold recovery rate in the high-gold, low-arsenic antimony concentrate of Comparative Example 1 was 0.93% higher and the antimony recovery rate was 3.70% higher, the gold grade in the high-gold, low-arsenic antimony concentrate of Comparative Example 1 decreased by 4.70 g / t and the antimony grade decreased by 1.60%. Furthermore, the final gold and antimony recoveries of Example 1 and Comparative Example 1 were essentially equivalent. This indicates that the modifier A of the present invention can achieve flotation indicators equivalent to lead nitrate and is more conducive to improving concentrate grade.

[0074] Comparative Example 2

[0075] This comparative example uses the same process as Example 1, except that modifier B was not added during either the initial antimony roughing or the initial antimony cleaning. The remaining steps are the same as in Example 1, and the experimental results are shown in Table 3.

[0076] Table 3:

[0077]

[0078]

[0079] As shown in Table 3, Comparative Example 2 did not add modifier B during either the initial antimony roughing or the initial antimony cleaning. Compared to Example 1, the antimony grade in the high-gold, low-arsenic antimony concentrate obtained in Comparative Example 2 was only 2.58%, which is 27.92% lower than the 30.50% in Example 1. Simultaneously, the gold grade of the high-arsenic, low-antimony gold concentrate in Comparative Example 2 was 18.70 g / t, which is 3.10 g / t lower than the 21.80 g / t in Example 1. Therefore, Comparative Example 2 failed to obtain either a high-gold, low-arsenic antimony concentrate with acceptable gold and antimony grades, or a high-arsenic, low-antimony gold concentrate with acceptable gold grades. This indicates that modifier B of the present invention plays an important role in obtaining high-grade gold-antimony concentrate and gold concentrate with antimony content within acceptable limits. Furthermore, modifier B of the present invention can achieve efficient inhibition of arsenopyrite, obtain more ideal antimony-arsenic separation indicators, and improve the gold grade in the antimony concentrate. The process of this invention is particularly applicable to gold ores with antimony grades below the threshold grade, producing concentrate products with qualified gold and antimony grades, improving the economic benefits of enterprises, and solving the problem of unqualified antimony grade in high-arsenic, low-antimony gold ore concentrates.

[0080] Example 2

[0081] This embodiment provides a high-arsenic, low-antimony gold ore modifier and a method for recovering antimony. The raw ore used is a high-arsenic, low-antimony gold ore with a gold grade of 2.46 g / t, an antimony grade of 0.24%, an arsenic grade of 1.05%, a pyrite content of 4.75 wt%, arsenopyrite content of 1.98 wt%, and stibnite content of 0.30 wt%. Compared with Embodiment 1, the difference lies in the adjustment of the reagent dosage in each step, as detailed below. The remaining steps, unless otherwise specified, are the same as in Embodiment 1 and will not be repeated here.

[0082] (1) See Example 1.

[0083] (2) Add 1800g / t of modifier A, 100g / t of butyl xanthate, 50g / t of butyl ammonium black powder and 20g / t of No. 2 oil to the raw ore slurry in step (1) to carry out gold-antimony mixed roughing to obtain antimony-containing crude gold concentrate and roughing tailings.

[0084] (3) In step (2), 150 g / t sodium hexametaphosphate and 300 g / t sodium silicate are added to the antimony-containing crude gold concentrate for the first gold-antimony mixed pre-selection, resulting in a first gold-antimony mixed pre-selection concentrate and a first gold-antimony mixed pre-selection tailings. The first gold-antimony mixed pre-selection tailings are returned to the gold-antimony mixed roughing process. In the first gold-antimony mixed pre-selection concentrate, 100 g / t sodium hexametaphosphate and 200 g / t sodium silicate are added to the second gold-antimony mixed pre-selection, resulting in a second gold-antimony mixed pre-selection concentrate and a second gold-antimony mixed pre-selection tailings. The second gold-antimony mixed pre-selection tailings are returned to the first gold-antimony mixed pre-selection.

[0085] The dosage of scavenging reagent added to the roughing tailings remains unchanged, and the treatment is carried out in the same manner as in Example 1.

[0086] (4) Add sulfuric acid to the secondary gold-antimony mixed pre-selected concentrate obtained in step (3) to adjust the pH of the slurry system to 5.0, add 90 g / t of adjuster B, and add water to obtain a secondary slurry with a solid particle mass of 13 wt% of the slurry mass.

[0087] (5) The secondary slurry obtained in step (4) is subjected to primary antimony roughing to obtain primary antimony roughing concentrate and primary antimony roughing tailings; 50 g / t of modifier B is added to the primary antimony roughing concentrate for primary antimony cleaning to obtain primary antimony cleaning concentrate and primary antimony cleaning tailings. Then, the primary antimony cleaning concentrate is subjected to three consecutive antimony blank cleanings as described in Example 1, and the final antimony blank cleaning concentrate is the final high-gold, low-arsenic antimony concentrate. The antimony roughing tailings, primary antimony cleaning tailings, and antimony blank cleaning tailings generated from the three antimony blank cleanings are combined to form the final high-arsenic, low-antimony gold concentrate.

[0088] The test results obtained in Example 2 are shown in Table 4.

[0089] Table 4:

[0090]

[0091] As shown in Table 4, the gold and antimony grades and recoveries of the high-gold, low-arsenic antimony concentrate obtained in Example 2 are higher than those of the high-gold, low-arsenic antimony concentrate obtained in Example 1, while the arsenic recovery rate is lower. The gold grade and gold recovery rate of the high-arsenic, low-antimony gold concentrate obtained in Example 2 are higher than those of the high-arsenic, low-antimony gold concentrate obtained in Example 1, and the overall gold and antimony recovery rates of Example 2 are higher than those of Example 1. This is because the overall dosage of modifier A and modifier B was increased in Example 2. Modifier A effectively improves the gold and antimony recovery rates, while modifier B effectively suppresses arsenopyrite and effectively improves the gold and antimony grades of the antimony concentrate.

[0092] Example 3

[0093] This embodiment provides a high-arsenic, low-antimony gold ore conditioning agent and a method for recovering antimony. The raw ore used in this embodiment is a gold-antimony symbiotic ore with a gold grade of 2.56 g / t, an antimony grade of 0.67%, an arsenic grade of 0.60%, a pyrite content of 3.75 wt%, arsenopyrite content of 0.95 wt%, and stibnite content of 0.98 wt%. Compared with Embodiment 1, the difference is that, since the antimony grade in the raw ore meets the requirements for associated grade, the number of antimony blank cleaning times is reduced from 3 to 2, and the dosage of reagents in each step is adjusted as follows; the other steps not specifically described are the same as in Embodiment 1 and will not be repeated here.

[0094] (1) See Example 1.

[0095] (2) Add 1500g / t of modifier A, 90g / t of butyl xanthate, 45g / t of butyl ammonium black powder and 15g / t of No. 2 oil to the raw ore slurry in step (1) for gold-antimony mixed roughing; to obtain antimony-containing crude gold concentrate and roughing tailings.

[0096] (3) In step (2), 100 g / t sodium hexametaphosphate and 200 g / t sodium silicate are added to the antimony-containing crude gold concentrate for a first gold-antimony mixed pre-selection, resulting in a first gold-antimony mixed pre-selection concentrate and a first gold-antimony mixed pre-selection tailings. The first gold-antimony mixed pre-selection tailings are returned to the gold-antimony mixed roughing. 50 g / t sodium hexametaphosphate and 100 g / t sodium silicate are added to the first gold-antimony mixed pre-selection concentrate for a second gold-antimony mixed pre-selection, resulting in a second gold-antimony mixed pre-selection concentrate and a second gold-antimony mixed pre-selection tailings. The second gold-antimony mixed pre-selection tailings are returned to the first gold-antimony mixed pre-selection. The dosage of scavenging reagent added to the roughing tailings remains unchanged; the operating steps are described in Example 1.

[0097] (4) Add sulfuric acid to the secondary gold-antimony mixed pre-selected concentrate obtained in step (3) to adjust the pH of the slurry system to 5.0, add 90 g / t of adjuster B, and add water to obtain a secondary slurry with a solid particle mass of 13 wt% of the slurry mass.

[0098] (5) The secondary slurry obtained in step (4) is subjected to primary antimony roughing to obtain primary antimony roughing concentrate and primary antimony roughing tailings; 50 g / t of modifier B is added to the primary antimony roughing concentrate for primary antimony cleaning; primary antimony cleaning concentrate and primary antimony cleaning tailings are obtained. Then, the primary antimony cleaning concentrate is subjected to two consecutive antimony blank cleanings as described in Example 1. The antimony blank cleaning concentrate from the second cleaning is the final high-gold, low-arsenic antimony concentrate. The antimony roughing tailings, the primary antimony cleaning tailings, and the antimony blank cleaning tailings from the two cleanings are combined to form the final high-arsenic, low-antimony gold concentrate.

[0099] The test results obtained in Example 3 are shown in Table 5.

[0100] Table 5:

[0101]

[0102] As shown in Table 5, Example 3 processes gold-antimony symbiotic ore with antimony grade reaching the associated grade, and can also obtain high gold-low arsenic antimony concentrate and high gold-low arsenic antimony concentrate with qualified gold and antimony grades. Compared with Example 1, the antimony grade and antimony recovery rate in the high gold-low arsenic antimony concentrate are both higher, and the comprehensive recovery rate of gold and antimony is higher than that in Example 1. This is because the gold and antimony grades of the original ore in Example 3 are higher than those in Example 1.

[0103] In summary, using traditional gold-antimony flotation processes for high-arsenic, low-antimony gold ores cannot yield antimony concentrates with acceptable antimony grades or gold concentrates with acceptable antimony grades, severely impacting the economic benefits of high-arsenic, low-antimony gold ores. Furthermore, the commonly used antimony activator, lead nitrate, in flotation easily leads to lead ions in the antimony concentrate and beneficiation wastewater, causing heavy metal pollution to the surrounding environment and hindering the company's development. This invention provides a modifier for high-arsenic, low-antimony gold ore and a method for recovering antimony. When performing mixed gold-antimony roughing on the raw ore slurry, modifier A achieves the same flotation indicators as using lead nitrate as an antimony activator. It completely replaces lead nitrate, significantly reducing the gold and antimony content in tailings, increasing gold and antimony recovery, and eliminating heavy metal pollution caused by lead nitrate. When performing antimony roughing and cleaning on the mixed gold-antimony pre-cleaning ore, modifier B effectively inhibits arsenopyrite within a slurry pH range of 5.0-6.5, thereby obtaining high-gold, low-arsenic antimony concentrate and high-arsenic, low-antimony gold concentrate. This solves the problem of antimony grade in antimony concentrate not meeting marketable standards and the problem of excessive antimony grade in gold concentrate, creating greater economic benefits for enterprises. At the same time, it enables gold ores with antimony grades below the cutoff grade to produce concentrate products with qualified gold and antimony grades, realizing efficient separation and comprehensive recovery of high-arsenic and low-antimony gold ores, making the flotation recovery of ultra-low-grade antimony economically feasible, and effectively solving the problem of developing and utilizing associated and difficult-to-process antimony resources below the cutoff grade.

[0104] Furthermore, this invention is well-suited for gold-antimony symbiotic ores with different antimony grades. Only the dosage of the modifier and the number of antimony blank beneficiation processes need to be adjusted to obtain better gold-antimony separation and beneficiation technical indicators. Therefore, this invention also provides new ideas and methods for the comprehensive recovery of gold-antimony symbiotic ores.

[0105] In summary, this invention, through the modifier and its method for recovering antimony, makes the flotation recovery of ultra-low grade antimony economically feasible, creating more economic benefits for enterprises, effectively solving the problem of developing and utilizing associated and difficult-to-process antimony resources below the boundary grade, and is of great significance for the recovery of low-grade and extremely low-grade associated antimony ores.

[0106] Finally, it should be noted that, in order to avoid obscuring the invention with unnecessary details, only the structures and / or processing steps closely related to the solution of the invention are shown in the accompanying drawings, while other details belonging to conventional operations are omitted.

[0107] For numerical ranges in this invention, it should be understood that each intermediate value between the upper and lower limits of the range is also specifically disclosed. Every smaller range between any stated value or intermediate value within a stated range, and any other stated value or intermediate value within said range, is also included within this invention. The upper and lower limits of these smaller ranges may be independently included or excluded from the range. Unless otherwise stated, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art described herein. While only preferred methods and materials have been described herein, any methods and materials similar to or equivalent to those described herein may be used in the implementation or testing of this invention.

[0108] Additionally, it should be noted that the terms “comprising,” “including,” or any other variations thereof are intended to cover non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such process, method, article, or apparatus.

[0109] The above embodiments are only used to illustrate the technical solutions of the present invention, and are not intended to limit it. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some or all of the technical features. These modifications or substitutions, or combinations of technical features in the above embodiments that do not conflict with each other, can be made in accordance with the manner described in the embodiments. These modifications, substitutions or combinations do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A modifier for antimony recovery from high-arsenic, low-antimony gold ore, characterized in that, include: Modifier A and Modifier B; The modifier A is used to increase the floatability of stibnite; by mass fraction, the modifier A contains 35%-45% oxalic acid, 35%-40% aluminum sulfate, 10%-15% sodium fluorosilicate and 5%-10% ammonium chloride; The modifier B is used to inhibit the buoyancy of arsenopyrite under weakly acidic conditions; by mass fraction, the modifier B contains 5%-15% sodium humate, 10%-20% ammonium sulfate, 20%-30% sodium sulfite, 15%-20% calcium chloride and 20%-40% bleaching powder.

2. A method for recovering antimony from high-arsenic, low-antimony gold ore using the modifier described in claim 1, characterized in that, Includes the following steps: S1. The ore powder obtained by crushing the high-arsenic and low-antimony gold ore to be selected is wet-milled to obtain the raw ore slurry. S2. Add modifier A to the raw ore slurry to adjust the slurry. The dosage of modifier A is 1200-1800g / t to obtain the primary slurry. S3. Add roughing reagents to the primary slurry to perform gold-antimony mixed roughing to obtain antimony-containing crude gold concentrate and roughing tailings; the roughing reagents include: 60-100 g / t butyl xanthate, 30-50 g / t butyl ammonium black powder and 10-30 g / t No. 2 oil; S4. Add a slime inhibitor to the antimony-containing crude gold concentrate obtained in S3 and perform N rounds of gold-antimony mixed pre-selection to obtain gold-antimony mixed pre-selection concentrate and gold-antimony mixed pre-selection tailings. Among them, the gold-antimony mixed pre-selection tailings generated in each round of gold-antimony mixed pre-selection are returned to the previous step, and the gold-antimony mixed pre-selection concentrate is transferred to the next step of processing. N≥2, and a slime inhibitor is added once for each round of gold-antimony mixed pre-selection. The slime inhibitor contains: 50-200g / t sodium hexametaphosphate and 100-400g / t sodium silicate. S5. Add acid and modifier B to the gold-antimony mixed pre-selected concentrate produced by S4. The amount of modifier B is 40-100g / t to obtain a secondary slurry. S6. The secondary slurry obtained from S5 is subjected to a primary antimony roughing process to obtain a primary antimony roughing concentrate and a primary antimony roughing tailings. The primary antimony roughing concentrate is treated with modifier B to obtain a primary antimony cleaning process to obtain a primary antimony cleaning concentrate and a primary antimony cleaning tailings. The primary antimony cleaning concentrate is subjected to two or more antimony blank cleaning processes to obtain the final product, high-gold, low-arsenic antimony concentrate, and tailings from each antimony blank cleaning process. The antimony cleaning tailings, tailings from each antimony blank cleaning process, and antimony roughing tailings are all combined to form a high-arsenic, low-antimony gold concentrate.

3. The method according to claim 2, characterized in that, In S1, the high-arsenic, low-antimony gold ore contains 0.60%-1.10% arsenic, 0.20%-0.75% antimony, and 2.20g / t-2.60g / t of gold. Antimony is mainly found in stibnite, and the main gold-bearing minerals are pyrite and arsenopyrite.

4. The method according to claim 2, characterized in that, In S1, the mass of solid particles in the raw ore slurry accounts for 25-35% of the mass of the raw ore slurry; and the mass of solid particles with a particle size of less than 0.074 mm in the raw ore slurry accounts for 70-75% of the mass of solid particles in the raw ore slurry.

5. The method according to claim 2, characterized in that, In S4, the gold-antimony mixed pre-selection is carried out 2-4 times, i.e., N=2-4, with the gold grade being greater than 24g / t and the antimony grade being greater than 2.30% in the gold-antimony mixed pre-selection concentrate as the endpoint.

6. The method according to claim 2, characterized in that, S4 also includes adding scavenging reagents to the roughing tailings generated in S3 for M rounds of gold-antimony mixed scavenging to obtain scavenged gold-antimony mixed concentrate and scavenged gold-antimony tailings; wherein, the scavenged gold-antimony mixed concentrate generated in each gold-antimony mixed scavenging is returned to the previous step, and the scavenged gold-antimony tailings are transferred to the next step for processing, and the scavenged gold-antimony tailings generated in the last gold-antimony mixed scavenging are the final tailings; M≥2, and scavenging reagents are added once for each gold-antimony mixed scavenging; the scavenging reagents include: 10-50 g / t of butyl xanthate and 5-25 g / t of butyl ammonium black.

7. The method according to claim 6, characterized in that, In S4, scavenging reagents are added to the roughing tailings for 2-4 gold-antimony mixed scavenging processes, i.e., M = 2-4.

8. The method according to claim 2, characterized in that, In S5, the amount of acid added is sufficient to bring the pH of the secondary slurry system to 5.0-6.5, and the acid is sulfuric acid.

9. The method according to claim 2, characterized in that, In S5, the mass of solid particles in the secondary slurry accounts for 10-20% of the total mass of the secondary slurry.

10. The method according to claim 2, characterized in that, In S6, the amount of modifier B added to the antimony roughing concentrate is 40-100 g / t; the number of antimony blank refining processes is 2-5 times, with the antimony grade in the high gold and low arsenic antimony concentrate being greater than 30% as the endpoint.

Images