Method for recovering antimony from gold ore containing arsenic and antimony

Abstract

The invention provides a method for recovering antimony from gold ore containing arsenic and antimony, and relates to the field of non-ferrous metallurgy and environmental protection. The method comprises the following steps: sequentially carrying out oxygen-deficient roasting and oxygen-peroxide roasting on the arsenic and antimony-containing gold ore to obtain gold-containing roasted sand and dust-containing flue gas; oxidizing the dust-containing flue gas and then carrying out first dust collection to obtain arsenic-antimony-rich soot and first dust-removed tail gas; separating the arsenic-antimony-rich soot and then carrying out second dust collection to obtain antimony-rich ash, coarse white arsenic and second dust-removed tail gas; removing arsenic from the antimony-rich ash slag to obtain antimony-rich slag; after the antimony-rich slag is leached, antimony-rich leaching liquid and leaching slag are obtained; and after the antimony-rich leachate is subjected to an electro-deposition reaction, cathode antimony and an electro-deposition barren solution are obtained. According to the method, the separation and enrichment effect of multiple components such as gold, antimony, arsenic and sulfur is remarkable, efficient recovery of the complex and refractory gold ore containing arsenic and antimony is achieved, and the application prospect is wide.

Description

Technical Field

[0001] The present application relates to the fields of nonferrous metal metallurgy and environmental protection, and in particular to a method for recovering antimony from arsenic-antimony gold ore. Background Art

[0002] Arsenic- and antimony-containing gold ores are important components of gold and antimony resources, and are important resources for the development and utilization of gold and antimony. However, gold in this type of mineral is mostly in the form of fine or submicronized particles, included in or impregnated in sulfides. Gold is closely related to arsenopyrite and stibnite, and direct leaching of gold is extremely difficult.

[0003] Arsenic-antimony gold ores usually adopt the pre-oxidation-cyanide leaching process. Among them, the oxygen-enriched roasting pre-oxidation process has always been the mainstream of the industry due to its strong adaptability to ores, simple operation and maintenance, and stable technology. However, most of them are based on roasted sand to recover gold. Arsenic-antimony gold ores are directly roasted in oxygen-enriched calcination, which has a good arsenic removal effect, but the antimony volatilization rate is low, resulting in antimony dispersion in the smoke and roasted sand. After cyanide gold extraction from roasted sand, the tailings and arsenic-antimony smoke are landfilled or harmlessly treated as hazardous waste, and antimony cannot be effectively recovered, which not only wastes resources but also has high potential environmental risks. Summary of the invention

[0004] The purpose of this application is to provide a method for recovering antimony from arsenic-antimony gold ore to solve the above problems.

[0005] To achieve the above objectives, this application adopts the following technical solutions:

[0006] The present application provides a method for recovering antimony from arsenic-antimony gold ore, comprising:

[0007] The arsenic-antimony gold ore is subjected to under-oxygen roasting and over-oxygen roasting in sequence to obtain gold-containing roasted sand and dust-containing flue gas;

[0008] After oxidizing the dust-containing flue gas, a first dust collection is performed to obtain arsenic-antimony-rich ash and a first dust-removed tail gas; after separating the arsenic-antimony-rich ash, a second dust collection is performed to obtain antimony-rich ash, crude white arsenic, and a second dust-removed tail gas;

[0009] The antimony-rich ash is subjected to arsenic removal to obtain antimony-rich slag; the antimony-rich slag is subjected to leaching to obtain antimony-rich leaching solution and leaching slag;

[0010] The antimony-rich leaching solution is subjected to an electrodeposition reaction to obtain cathode antimony and electrodeposition lean solution.

[0011] Optionally, the temperature of the underoxygen calcination is 600-1000° C., and the time is 1-4 h; the temperature of the overoxygen calcination is 600-1000° C., and the time is 0.5-2 h.

[0012] Optionally, the roasting oxygen coefficient in the oxygen-deficient roasting is 0.5-0.9, and the roasting oxygen coefficient in the oxygen-overload roasting is 1.1-1.5.

[0013] Optionally, the oxidation conditions are that the excess coefficient of oxygen in air and / or oxygen-enriched air is 1.05-1.2 and the temperature is 500-900°C.

[0014] Optionally, the separation is low-temperature volatilization separation at a temperature of 200-600°C.

[0015] Optionally, the second dust collection is temperature reduction dust collection at a temperature of 120-200°C.

[0016] Optionally, the arsenic removal is carried out by leaching, the leaching agent includes a dilute sulfuric acid solution, and the pH value of the leaching agent is 1.0-6.5.

[0017] Optionally, the liquid-to-solid ratio during the leaching is 1-10 mL of the leaching agent corresponding to 1 mg of the antimony-rich ash.

[0018] Optionally, the leaching agent comprises hydrochloric acid and / or chloride salt, and satisfies at least one of the following conditions:

[0019] a. The concentration of the hydrochloric acid is 30-70g / L;

[0020] b. The chloride salt includes one or more of NaCl, KCl, CaCl2, and the amount of the chloride salt added is 100-200g / L;

[0021] c. The antimony content in the antimony-rich leaching solution is 40-70 g / L.

[0022] Optionally, the electrodeposition step satisfies at least one of the following conditions:

[0023] d. During the electrodeposition reaction, the cathode current density is 100-300A / m 2 ;

[0024] e. The antimony content in the electrodeposition lean solution is 20-40 g / L;

[0025] f. The electrodeposition barren solution can be recycled as a leaching agent after being supplemented with hydrochloric acid.

[0026] Compared with the prior art, the beneficial effects of this application include:

[0027] The present application provides a method for treating arsenic-antimony-gold ore. The arsenic-antimony-gold ore is roasted in two stages to ensure that Sb and As are volatilized and efficiently separated from Au at a relatively low temperature. The volatilized flue gas / dust is oxidized in a secondary combustion chamber, and dust is collected to obtain arsenic-antimony ash. The arsenic-antimony ash is volatilized and separated at low temperature and dust is collected by cooling to obtain crude white arsenic and antimony-rich ash, thereby achieving efficient separation of Sb and As. The antimony-rich ash is leached and electrolytically deposited to obtain metallic antimony and leaching slag, and the leaching slag and roasted sand enter a gold extraction system to recover gold. The method of the present application has significant separation and enrichment effects of multiple components such as gold, antimony, arsenic, and sulfur, thereby achieving efficient recovery of complex and difficult-to-treat arsenic-antimony-gold ore, and has broad application prospects. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings required for use in the embodiments will be briefly introduced below. It should be understood that the following drawings only show certain embodiments of the present application and therefore should not be regarded as limiting the scope of the present application.

[0029] Figure 1 The present invention is a schematic diagram of the process flow of a method for recovering antimony from arsenic-antimony gold ore provided in an embodiment. DETAILED DESCRIPTION

[0030] As used herein:

[0031] "Prepared from" is synonymous with "comprising." As used herein, the terms "comprising," "including," "having," "containing," or any other variation thereof, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises the listed elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.

[0032] The conjunction "consisting of excludes any unspecified element, step, or component. If used in a claim, this phrase renders the claim closed-ended so that it does not include materials other than those described, except for conventional impurities associated therewith. When the phrase "consisting of" appears in a clause of the body of a claim rather than immediately following the subject matter, it limits only the elements described in that clause; other elements are not excluded from the claim as a whole.

[0033] When an amount, concentration, or other value or parameter is expressed as a range, a preferred range, or a range defined by a series of upper preferred values ​​and lower preferred values, this should be understood as specifically disclosing all ranges formed by any pairing of any range upper limit or preferred value with any range lower limit or preferred value, regardless of whether the range is disclosed separately. For example, when a range of "1 to 5" is disclosed, the described range should be interpreted as including ranges "1 to 4", "1 to 3", "1 to 2", "1 to 2 and 4 to 5", "1 to 3 and 5", etc. When a numerical range is described in this article, unless otherwise stated, the range is intended to include its end values ​​and all integers and fractions within the range.

[0034] In these examples, parts and percentages are by mass unless otherwise indicated.

[0035] "Parts by mass" refers to the basic unit of measurement for expressing the mass ratio of multiple components. 1 part can represent any unit mass, such as 1g or 2.689g. If we say that the mass of component A is a parts and the mass of component B is b parts, it means the ratio of the mass of component A to the mass of component B is a:b. Alternatively, it means that the mass of component A is aK and the mass of component B is bK (K is an arbitrary number, indicating a multiple factor). It should not be misunderstood that, unlike the mass parts, the sum of the mass of all components is not limited to 100 parts.

[0036] "And / or" is used to indicate that one or both of the stated situations may occur, for example, A and / or B includes (A and B) and (A or B).

[0037] In order to better explain the technical solution provided by this application, an overall statement of the technical solution is first made before the embodiments.

[0038] The present application provides a method for recovering antimony from arsenic-antimony gold ore, comprising:

[0039] The arsenic-antimony gold ore is subjected to under-oxygen roasting and over-oxygen roasting in sequence to obtain gold-containing roasted sand and dust-containing flue gas;

[0040] After oxidizing the dust-containing flue gas, a first dust collection is performed to obtain arsenic-antimony-rich ash and a first dust-removed tail gas; after separating the arsenic-antimony-rich ash, a second dust collection is performed to obtain antimony-rich ash, crude white arsenic, and a second dust-removed tail gas;

[0041] The antimony-rich ash is subjected to arsenic removal to obtain antimony-rich slag; the antimony-rich slag is subjected to leaching to obtain antimony-rich leaching solution and leaching slag;

[0042] The antimony-rich leaching solution is subjected to an electrodeposition reaction to obtain cathode antimony and electrodeposition lean solution.

[0043] This application adopts a two-stage roasting, and performs underoxygen roasting and peroxygen roasting in sequence. Under underoxygen conditions, on the one hand, minerals such as arsenopyrite are oxidized and decomposed, part of S enters the flue gas in the form of SO2, arsenic volatilizes as As2S3, As2O3, etc., and antimony volatilizes as Sb2S3 or Sb2O3, while preventing Sb from being peroxidized to Sb2O4, which is difficult to volatilize, to ensure the efficient removal of As and Sb, while reducing the encapsulation of Au in the roasted sand; then peroxygen roasting is performed, so that under peroxygen conditions, the remaining sulfide minerals are completely oxidized and decomposed, and enter the flue gas in the form of SO2, which can further release the encapsulated gold and improve the leaching efficiency of roasted gold; and peroxygen roasting makes the mineral more stable, reduces the interference of harmful impurities on subsequent processes, and avoids the large consumption of reagents in the cyanide / non-cyanide gold leaching process, and the high amount of sodium sulfate wastewater in the gold extraction process.

[0044] The oxidation process is carried out in the secondary combustion chamber. The gas oxidized in the secondary combustion chamber can be used to recover waste heat through a waste heat boiler. The first dust removal tail gas is collected to make acid to recover SO2 in the flue gas. The antimony-rich ash residue is leached and electrolytically deposited to obtain metallic antimony and leached residue. The leached residue and roasted sand enter the gold extraction system to recover gold.

[0045] In an optional embodiment, the temperature of the under-oxygen calcination is 600-1000° C., and the time is 1-4 h; the temperature of the over-oxygen calcination is 600-1000° C., and the time is 0.5-2 h.

[0046] Optionally, the temperature of the underoxygen roasting can be 600°C, 650°C, 700°C, 750°C, 800°C, 850°C, 900°C, 950°C, 1000°C, or any value between 600-1000°C; the time of the underoxygen roasting can be 1h, 2h, 3h, 4h, or any value between 1-4h. Optionally, the temperature of the overoxygen roasting can be 600°C, 650°C, 700°C, 750°C, 800°C, 850°C, 900°C, 950°C, 1000°C, or any value between 600-1000°C; the time of the overoxygen roasting can be 0.5h, 1h, 1.5h, 2h, or any value between 0.5-2h.

[0047] In an optional embodiment, the roasting oxygen coefficient in the oxygen-deficient roasting is 0.5-0.9, and the roasting oxygen coefficient in the oxygen-permeable roasting is 1.1-1.5. The oxygen coefficient is a multiple of the theoretical amount of all substances such as S, As, Sb, Fe, etc. in the raw ore and / or roasted sand being oxidized to the corresponding oxides.

[0048] Optionally, the roasting oxygen coefficient in the oxygen-deficient roasting can be 0.5, 0.6, 0.7, 0.8, 0.9, or any value between 0.5 and 0.9. Optionally, the roasting oxygen coefficient in the oxygen-overload roasting can be 1.1, 1.2, 1.3, 1.4, 1.5, or any value between 1.1 and 1.5.

[0049] In an optional embodiment, the oxidation conditions are that the excess coefficient of oxygen in air and / or enriched oxygen is 1.05-1.2 and the temperature is 500-900° C. Air or enriched oxygen is blown into the dusty flue gas in the secondary combustion chamber to oxidize all the substances such as Sb2S3, As2S2, As2S3, etc. volatilized into the dusty flue gas into corresponding oxides.

[0050] Optionally, the oxygen peroxygen coefficient may be 1.05, 1.06, 1.07, 1.08, 1.09, 1.1, 1.11, 1.12, 1.13, 1.14, 1.15, 1.16, 1.17, 1.18, 1.19, 1.2, or any value between 1.05 and 1.2. Optionally, the temperature of the oxygen in the air and / or oxygen-enriched gas may be 500°C, 600°C, 700°C, 800°C, 900°C, or any value between 500 and 900°C.

[0051] In an optional embodiment, the separation is low-temperature volatilization separation at a temperature of 200-600°C. Arsenic and its compounds (such as As2O3) have high volatility in the range of 200-600°C, while antimony compounds are relatively stable at this temperature. Therefore, low-temperature volatilization can effectively separate arsenic and antimony. The volatilized flue gas is cooled and dusted by quenching to obtain crude white arsenic, which can be further used to prepare products such as elemental arsenic, and the tail gas is absorbed by alkaline solution and then discharged in compliance with the emission standards.

[0052] Optionally, the temperature of the volatilization separation may be 200°C, 250°C, 300°C, 350°C, 400°C, 450°C, 500°C, 550°C, 600°C, or any value between 200-600°C.

[0053] In an optional embodiment, the second dust collection is a cooling dust collection with a temperature of 120-200° C. The first dust collection and the second dust collection each independently include one or more of sedimentation dust collection, cyclone dust collection, electric dust collection, and bag dust collection.

[0054] Optionally, the temperature for cooling and collecting dust can be 120°C, 130°C, 140°C, 150°C, 160°C, 170°C, 180°C, 190°C, 200°C, or any value between 120-200°C.

[0055] In an optional embodiment, the arsenic removal is carried out by leaching, the leaching agent includes a dilute sulfuric acid solution, and the pH value of the leaching agent is 1.0-6.5.

[0056] Optionally, the pH value of the washing machine can be 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, or any value between 1-6.5.

[0057] In an optional embodiment, the liquid-to-solid ratio during the leaching is 1-10 mL of the leaching agent corresponding to 1 mg of the antimony-rich ash.

[0058] Optionally, the liquid-to-solid ratio during leaching can be 1 mL of the leaching agent corresponding to 1 mg of the antimony-rich ash, 2 mL of the leaching agent corresponding to 1 mg of the antimony-rich ash, 3 mL of the leaching agent corresponding to 1 mg of the antimony-rich ash, 4 mL of the leaching agent corresponding to 1 mg of the antimony-rich ash, 5 mL of the leaching agent corresponding to 1 mg of the antimony-rich ash, 6 mL of the leaching agent corresponding to 1 mg of the antimony-rich ash, 7 mL of the leaching agent corresponding to 1 mg of the antimony-rich ash, 8 mL of the leaching agent corresponding to 1 mg of the antimony-rich ash, 9 mL of the leaching agent corresponding to 1 mg of the antimony-rich ash, 10 mL of the leaching agent corresponding to 1 mg of the antimony-rich ash, or any value between 1-10 mL of the leaching agent corresponding to 1 mg of the antimony-rich ash.

[0059] In an optional embodiment, the leaching agent for leaching includes hydrochloric acid and / or chloride salts.

[0060] In an optional embodiment, the concentration of the hydrochloric acid is 30-70 g / L.

[0061] The concentration of the hydrochloric acid can be 30g / L, 35g / L, 40g / L, 45g / L, 50g / L, 55g / L, 60g / L, 65g / L, 70g / L, or any value between 30-70g / L.

[0062] In an optional embodiment, the chloride salt includes one or more of NaCl, KCl, and CaCl2, and the added amount of the chloride salt is 100-200 g / L.

[0063] Optionally, the amount of chloride salt added can be 100 g / L, 110 g / L, 120 g / L, 130 g / L, 140 g / L, 150 g / L, 160 g / L, 170 g / L, 180 g / L, 190 g / L, 200 g / L, or any value between 100-200 g / L.

[0064] In an optional embodiment, the antimony content in the antimony-rich leachate is 40-70 g / L.

[0065] Optionally, the antimony-rich leachate may have a body content of 40 g / L, 45 g / L, 50 g / L, 55 g / L, 60 g / L, 65 g / L, 70 g / L, or any value between 40 and 70 g / L.

[0066] In an optional embodiment, during the electrodeposition reaction, the cathode current density is 100-300 A / m 2 .

[0067] Optionally, the cathode current density can be 100A / m 2 , 110A / m 2 , 120A / m 2 、130A / m 2 , 140A / m 2 , 150A / m 2 、160A / m 2 、170A / m 2 、180A / m 2 、190A / m 2 , 200A / m 2 , 210A / m 2 , 220A / m 2 , 230A / m 2 , 240A / m 2 , 250A / m 2 、260A / m 2 、270A / m 2 、280A / m 2 、290A / m 2 、300A / m 2 , or 100-300A / m 2 Any value in between.

[0068] In an optional embodiment, the antimony content in the electrodeposition lean solution is 20-40 g / L.

[0069] Optionally, the antimony content in the electrodeposition barren solution can be 20g / L, 21g / L, 22g / L, 23g / L, 24g / L, 25g / L, 26g / L, 27g / L, 28g / L, 29g / L, 30g / L, 31g / L, 32g / L, 33g / L, 34g / L, 35g / L, 36g / L, 37g / L, 38g / L, 39g / L, 40g / L, or any value between 20-40g / L.

[0070] In an optional embodiment, the electrodeposition barren solution can be recycled as a leaching agent after being supplemented with hydrochloric acid.

[0071] The embodiments of the present application will be described in detail below in conjunction with specific examples, but it will be appreciated by those skilled in the art that the following examples are only used to illustrate the present application and should not be considered as limiting the scope of the present application. If specific conditions are not specified in the examples, they are carried out according to normal conditions or the conditions recommended by the manufacturer. If the manufacturer is not specified for the reagents or instruments used, they are all conventional products that can be purchased commercially.

[0072] There are many types of arsenic-antimony gold ores with great differences in composition. The method of the present application is applicable to arsenic-antimony gold ores of various components. In order to explain the enrichment and separation effect in detail, a typical difficult-to-treat arsenic-antimony gold ore is used for illustration. The composition of the arsenic-antimony gold ore used in each embodiment and comparative example is shown in Table 1.

[0073] Table 1 Raw materials of arsenic-antimony gold ore / % (Au is g / t)

[0074]

[0075] Example 1

[0076] This embodiment provides a method for recovering antimony from arsenic-antimony gold ore. The process flow is as follows: Figure 1 As shown, the specific steps are as follows:

[0077] 20 kg of arsenic-antimony gold ore was roasted in two stages, one of which was under-oxygen roasting at a temperature of 680°C and an oxygen coefficient of 0.75; the second stage was over-oxygen roasting at a temperature of 950°C and an oxygen coefficient of 1.2; 16.10 kg of gold-containing roasted sand (Au 7.38 g / t, Sb 0.16%, As 0.09%, Fe 10.81%, S 0.40%) and dusty flue gas were obtained.

[0078] The dusty flue gas is oxidized and the waste heat is recovered in the secondary combustion chamber under the conditions of an oxygen excess coefficient of 1.1 and a temperature of 700°C. Then, a cyclone and bag dust collector are used to obtain 2.82 kg of arsenic-antimony rich fly ash (Au 4.68 g / t, Sb 17.45%, As 16.85%, Fe 6.86%, S 0.23%).

[0079] The arsenic-antimony rich fly ash was volatilized and separated at 450°C, and the flue gas was cooled and dusted to obtain 2.16 kg of antimony-rich ash (Au 6.05 g / t, Sb 22.10%, As 0.66%, Fe 8.86%, S 0.28%) and 0.64 kg of crude white arsenic (Au 0.21 g / t, Sb 2.31%, As 72.03%).

[0080] The antimony-rich ash was prepared with a liquid-solid ratio of 2 mL of leaching agent corresponding to 1 mg of antimony-rich ash, and the leaching agent was a dilute sulfuric acid solution with a pH value of 2.0. It was then washed with clean water, filtered and dried to obtain 2.05 kg of antimony-rich slag (Au 6.36 g / t, Sb 23.17%, As 0.03%, Fe 8.87%).

[0081] The antimony-rich slag was added with 16L of electrodeposition lean solution (Sb 30g / L, NaCl 150g / L, HCl 32g / L) for leaching, and hydrochloric acid was added to control the free HCl concentration to 30g / L. The leaching was carried out at room temperature for 2h. After filtering and washing, 1.48kg of leached slag (Au 8.77g / t, Sb0.32%, Fe 11.06%) and 16L of antimony-rich leaching solution (including washing water concentrate) (Sb 59.39g / L, NaCl 150g / L, HCl 33g / L) were obtained.

[0082] Antimony-rich leaching solution at 200A / m 2 Electrodeposition was carried out at a current density of , to obtain 0.471 kg of cathode antimony (Sb 99.80%) and electrodeposition lean solution (Sb 30 g / L, NaCl 150 g / L, HCl 32 g / L).

[0083] The Au recovery rate of the whole process is 99.83% (calculated on the basis of roasted sand and acid leaching residue), the S removal rate is 97% (calculated on the basis of roasted sand), the Sb recovery rate is 90.77% (calculated on the basis of cathode antimony), and the As recovery rate is 94.09% (calculated on the basis of crude white arsenic).

[0084] Example 2

[0085] This embodiment provides a method for recovering antimony from arsenic-antimony gold ore, and the specific steps are as follows:

[0086] 20 kg of arsenic-antimony gold ore was roasted in two stages, one of which was under-oxygen roasting at 880°C and an oxygen coefficient of 0.85; the second stage was over-oxygen roasting at 980°C and an oxygen coefficient of 1.3; 16.15 kg of gold-containing roasted sand (Au 7.36 g / t, Sb 0.22%, As 0.12%, Fe 10.78%, S 0.26%) and dusty flue gas were obtained.

[0087] The dusty flue gas is oxidized and the waste heat is recovered in the secondary combustion chamber under the conditions of an oxygen excess coefficient of 1.15 and a temperature of 800°C. Then, a cyclone and bag dust collector are used to obtain 2.79 kg of arsenic-antimony rich fly ash (Au 4.73 g / t, Sb 17.27%, As 17.03%, Fe 6.93%, S 0.19%).

[0088] The arsenic-antimony rich fly ash was volatilized and separated at 550°C, and the flue gas was cooled and dusted to obtain 2.14 kg of antimony-rich ash (Au 6.11 g / t, Sb 21.39%, As 0.44%, Fe 8.95%, S 0.24%) and 0.65 kg of crude white arsenic (Au 0.20 g / t, Sb 3.70%, As 71.66%).

[0089] The antimony-rich ash was prepared with a liquid-to-solid ratio of 2 mL of leaching agent corresponding to 1 mg of antimony-rich ash, and the leaching agent was a dilute sulfuric acid solution with a pH value of 2.0. It was then washed with clean water, filtered and dried to obtain 2.04 kg of antimony-rich slag (Au 6.39 g / t, Sb 22.32%, As 0.02%, Fe 8.92%).

[0090] The antimony-rich slag was added with 16L of electrodeposition lean solution (Sb 30g / L, NaCl 150g / L, HCl 32g / L) for leaching, and hydrochloric acid was added to control the free HCl concentration to 30g / L. The leaching was carried out at room temperature for 2h. After filtering and washing, 1.47kg of leached slag (Au 8.83g / t, Sb0.31%, Fe 11.36%) and 16L of antimony-rich leaching solution (Sb 58.18g / L, NaCl 150g / L, HCl 33g / L) were obtained.

[0091] Antimony-rich leaching solution at 200A / m 2 Electrodeposition was carried out at a current density of , to obtain 0.452 kg of cathode antimony (Sb 99.80%) and electrodeposition lean solution (Sb 30 g / L, NaCl 150 g / L, HCl 32 g / L).

[0092] The Au recovery rate of the whole process is 99.83% (calculated on the basis of roasted sand and acid leaching residue), the S removal rate is 98% (calculated on the basis of roasted sand), the Sb recovery rate is 87.03% (calculated on the basis of cathode antimony), and the As recovery rate is 95.06% (calculated on the basis of crude white arsenic).

[0093] Example 3

[0094] This embodiment provides a method for recovering antimony from arsenic-antimony gold ore, and the specific steps are as follows:

[0095] 20 kg of arsenic-antimony gold ore was roasted in two stages, one of which was under-oxygen roasting at a temperature of 680°C and an oxygen coefficient of 0.75; the second stage was over-oxygen roasting at a temperature of 950°C and an oxygen coefficient of 1.2; 16.10 kg of gold-containing roasted sand (Au 7.38 g / t, Sb 0.16%, As 0.09%, Fe 10.81%, S 0.40%) and dusty flue gas were obtained.

[0096] The dusty flue gas is oxidized and the waste heat is recovered in the secondary combustion chamber under the conditions of an oxygen excess coefficient of 1.2 and a temperature of 700°C. Then, a cyclone and bag dust collector are used to obtain 2.82 kg of arsenic-antimony rich fly ash (Au 4.68 g / t, Sb 17.45%, As 16.85%, Fe 6.86%, S 0.23%).

[0097] The arsenic-antimony rich fly ash was volatilized and separated at 400°C, and the flue gas was cooled and dusted to obtain 2.2 kg of antimony-rich ash (Au 5.94 g / t, Sb 22.03%, As 1.08%, Fe 8.70%, S 0.28%) and 0.62 kg of crude white arsenic (Au 0.21 g / t, Sb 1.19%, As 72.83%).

[0098] The antimony-rich ash was prepared with a liquid-to-solid ratio of 2 mL of leaching agent corresponding to 1 mg of antimony-rich ash, and the leaching agent was a dilute sulfuric acid solution with a pH value of 2.0. It was then washed with clean water, filtered and dried to obtain 2.1 kg of antimony-rich slag (Au 6.21 g / t, Sb 22.97%, As 0.03%, Fe 8.66%).

[0099] The antimony-rich slag was added with 16L of electrodeposition lean solution (Sb 30g / L, NaCl 150g / L, HCl 32g / L) for leaching, and hydrochloric acid was added to control the free HCl concentration to 30g / L. The leaching was carried out at room temperature for 2h. After filtering and washing, 1.50kg of leached slag (Au 8.65g / t, Sb0.32%, Fe 10.91%) and 16L of antimony-rich leaching solution (Sb 59.84g / L, NaCl 150g / L, HCl 33g / L) were obtained.

[0100] Antimony-rich leaching solution at 200A / m 2 Electrodeposition was carried out at a current density of , to obtain 0.478 kg of cathode antimony (Sb 99.80%) and electrodeposition lean solution (Sb 30 g / L, NaCl 150 g / L, HCl 32 g / L).

[0101] The Au recovery rate of the whole process is 99.83% (calculated on the basis of roasted sand and acid leaching residue), the S removal rate is 97% (calculated on the basis of roasted sand), the Sb recovery rate is 92.18% (calculated on the basis of cathode antimony), and the As recovery rate is 92.15% (calculated on the basis of crude white arsenic).

[0102] Comparative Example 1

[0103] This comparative example provides a method for recovering antimony from arsenic-antimony gold ore, and the specific steps are as follows:

[0104] 20 kg of arsenic-antimony gold ore was subjected to one-stage peroxidation roasting at a temperature of 950°C and an oxygen coefficient of 1.2 to obtain 16.30 kg of gold-containing roasted sand (Au 7.29 g / t, Sb 1.02%, As 0.24%, Fe 10.68%, S0.39%) and dust-containing flue gas.

[0105] The dusty flue gas is oxidized and the waste heat is recovered in the secondary combustion chamber under the conditions of an oxygen excess coefficient of 1.1 and a temperature of 700°C. Then, a cyclone and bag dust collector are used to obtain 2.68 kg of arsenic-antimony rich fly ash (Au 4.93 g / t, Sb 13.14%, As 16.82%, Fe 7.22%, S 0.24%).

[0106] The arsenic-antimony rich fly ash was volatilized and separated at 450°C, and the flue gas was cooled and dusted to obtain 2.08 kg of antimony-rich ash (Au 6.28 g / t, Sb 16.43%, As 0.65%, Fe 9.21%, S 0.29%) and 0.60 kg of crude white arsenic (Au 0.22 g / t, Sb 1.76%, As 72.88%).

[0107] The antimony-rich ash was prepared with a liquid-to-solid ratio of 2 mL of leaching agent corresponding to 1 mg of antimony-rich ash, and the leaching agent was a dilute sulfuric acid solution with a pH value of 2.0. It was then washed with clean water, filtered and dried to obtain 2.02 kg of antimony-rich slag (Au 6.46 g / t, Sb 16.83%, As 0.03%, Fe 9.00%).

[0108] The antimony-rich slag was added with 16L of electrodeposition lean solution (Sb 30g / L, NaCl 150g / L, HCl 32g / L) for leaching, and hydrochloric acid was added to control the free HCl concentration to 30g / L. The leaching was carried out at room temperature for 2h. After filtering and washing, 1.50kg of leached slag (Au 8.65g / t, Sb0.23%, Fe 10.91%) and 16L of antimony-rich leaching solution (Sb 51.04g / L, NaCl 150g / L, HCl 33g / L) were obtained.

[0109] The antimony-rich leaching solution was electrodeposited at a current density of 200 A / m2 to obtain 0.337 kg of cathode antimony (Sb 99.80%) and electrodeposition lean solution (Sb 30 g / L, NaCl 150 g / L, HCl 32 g / L).

[0110] The Au recovery rate of the whole process is 99.83% (calculated on the basis of roasted sand and acid leaching residue), the S removal rate is 97% (calculated on the basis of roasted sand), the Sb recovery rate is 64.97% (calculated on the basis of cathode antimony), and the As recovery rate is 89.24% (calculated on the basis of crude white arsenic).

[0111] Comparative Example 2

[0112] This comparative example provides a method for recovering antimony from arsenic-antimony gold ore, and the specific steps are as follows:

[0113] 20 kg of arsenic-antimony gold ore was roasted under oxygen at 980°C and with an oxygen coefficient of 0.85 to obtain 16.26 kg of gold-containing roasted sand (Au 7.30 g / t, Sb 0.38%, As 0.30%, Fe 10.70%, S1.58%) and dusty flue gas.

[0114] The dusty flue gas is oxidized and the waste heat is recovered in the secondary combustion chamber under the conditions of an oxygen excess coefficient of 1.1 and a temperature of 700°C. Then, a cyclone and bag dust collector are used to obtain 2.71 kg of arsenic-antimony rich fly ash (Au 4.87 g / t, Sb 16.82%, As 16.27%, Fe 7.14%, S 0.24%).

[0115] The arsenic-antimony rich fly ash was volatilized and separated at 450°C, and the flue gas was cooled and dusted to obtain 2.13 kg of antimony-rich ash (Au 6.14 g / t, Sb 20.76%, As 0.62%, Fe 8.99%, S 0.29%) and 0.59 kg of crude white arsenic (Au 0.22 g / t, Sb 2.31%, As 72.50%).

[0116] The antimony-rich ash was prepared with a liquid-to-solid ratio of 2 mL of leaching agent corresponding to 1 mg of antimony-rich ash, and the leaching agent was a dilute sulfuric acid solution with a pH value of 2.0. It was then washed with clean water, filtered and dried to obtain 2.04 kg of antimony-rich slag (Au 6.39 g / t, Sb 21.57%, As 0.03%, Fe 8.92%).

[0117] The antimony-rich slag was added with 16L of electrodeposition lean solution (Sb 30g / L, NaCl 150g / L, HCl 32g / L) for leaching, and hydrochloric acid was supplemented to control the free HCl concentration to 30g / L. The leaching was carried out at room temperature for 2h. After filtering and washing, 1.52kg of leached slag (Au 8.65g / t, Sb0.29%, Fe 10.91%) and 16L of antimony-rich leaching solution (Sb 57.22g / L, NaCl 150g / L, HCl 33g / L) were obtained.

[0118] The antimony-rich leaching solution was electrodeposited at a current density of 200 A / m2 to obtain 0.436 kg of cathode antimony (Sb 99.80%) and electrodeposition lean solution (Sb 30 g / L, NaCl 150 g / L, HCl 32 g / L).

[0119] The Au recovery rate of the whole process is 99.83% (calculated on the basis of roasted sand and acid leaching residue), the S removal rate is 88% (calculated on the basis of roasted sand); the Sb recovery rate is 84.08% (calculated on the basis of cathode antimony), and the As recovery rate is 87.3% (calculated on the basis of crude white arsenic).

[0120] Comparative Example 3

[0121] This comparative example provides a method for recovering antimony from arsenic-antimony gold ore. The difference from Example 1 is that no sulfuric acid leaching is performed. The remaining steps and conditions are the same as those in Example 1. The specific steps are as follows:

[0122] 20 kg of arsenic-antimony gold ore was roasted in two stages, one of which was under-oxygen roasting at a temperature of 680°C and an oxygen coefficient of 0.75; the second stage was over-oxygen roasting at a temperature of 950°C and an oxygen coefficient of 1.2; 16.10 kg of gold-containing roasted sand (Au 7.38 g / t, Sb 0.16%, As 0.09%, Fe 10.81%, S 0.40%) and dusty flue gas were obtained.

[0123] The dusty flue gas is oxidized and the waste heat is recovered in the secondary combustion chamber under the conditions of an oxygen excess coefficient of 1.1 and a temperature of 700°C. Then, a cyclone and bag dust collector are used to obtain 2.82 kg of arsenic-antimony rich fly ash (Au 4.68 g / t, Sb 17.45%, As 16.85%, Fe 6.86%, S 0.23%).

[0124] The arsenic-antimony rich fly ash was volatilized and separated at 450°C, and the flue gas was cooled and dusted to obtain 2.16 kg of antimony-rich ash (Au 6.05 g / t, Sb 22.10%, As 0.66%, Fe 8.86%, S 0.28%) and 0.64 kg of crude white arsenic (Au 0.21 g / t, Sb 2.31%, As 72.03%).

[0125] The antimony-rich slag was added with 16L of electrodeposition lean solution (Sb 30g / L, NaCl 150g / L, HCl 32g / L) for leaching, and hydrochloric acid was added to control the free HCl concentration to 30g / L. The leaching was carried out at room temperature for 2h. After filtering and washing, 1.48kg of leached slag (Au 8.77g / t, Sb0.32%, Fe 11.06%) and 16L of antimony-rich leaching solution (including washing water concentrate) (Sb 59.39g / L, NaCl 150g / L, HCl 33g / L, As 0.88g / L) were obtained.

[0126] Antimony-rich leaching solution at 200A / m 2 Electrodeposition was carried out at a current density of , to obtain 0.472 kg of cathode antimony (Sb 99.62%) and electrodeposition lean solution (Sb 30 g / L, NaCl 150 g / L, HCl 32 g / L, As 0.85 g / L).

[0127] The Au recovery rate of the whole process is 99.83% (calculated on roasted sand and acid leaching residue), the S removal rate is 97% (calculated on roasted sand), the Sb recovery rate is 90.77% (calculated on cathode antimony), and the As recovery rate is 94.09% (calculated on crude white arsenic). It has little effect on the recovery of Au, Sb, and As, but it will affect the grade of cathode antimony, greatly increase the difficulty of purifying antimony electrolyte, and there is a potential risk of arsenic hydrogen in the electrolytic process.

[0128] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present application, rather than to limit it. Although the present application has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or replace some or all of the technical features therein with equivalents. However, these modifications or replacements 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 application.

[0129] In addition, those skilled in the art will appreciate that, although some embodiments herein include certain features included in other embodiments but not other features, the combination of features of different embodiments is meant to be within the scope of the present application and form different embodiments. For example, in the above claims, any one of the claimed embodiments may be used in any combination. The information disclosed in this background technology section is intended only to deepen the understanding of the overall background technology of the present application and should not be regarded as an admission or in any form of implication that the information constitutes prior art known to those skilled in the art.

Claims

1. A method for recovering antimony from arsenic-antimony gold ore, characterized in that: include: The arsenic-antimony gold ore is subjected to under-oxygen roasting and over-oxygen roasting in sequence to obtain gold-containing roasted sand and dust-containing flue gas; After oxidizing the dust-containing flue gas, a first dust collection is performed to obtain arsenic-antimony-rich ash and a first dust-removed tail gas; after separating the arsenic-antimony-rich ash, a second dust collection is performed to obtain antimony-rich ash, crude white arsenic, and a second dust-removed tail gas; The antimony-rich ash is subjected to arsenic removal to obtain antimony-rich slag; the antimony-rich slag is subjected to leaching to obtain antimony-rich leaching solution and leaching slag; The antimony-rich leaching solution is subjected to an electrodeposition reaction to obtain cathode antimony and electrodeposition lean solution.

2. The method for recovering antimony from arsenic-antimony gold ore according to claim 1, characterized in that: The temperature of the under-oxygen roasting is 600-1000° C., and the time is 1-4 hours; the temperature of the over-oxygen roasting is 600-1000° C., and the time is 0.5-2 hours.

3. The method for recovering antimony from arsenic-antimony gold ore according to claim 2, characterized in that: The roasting oxygen coefficient in the oxygen-deficient roasting is 0.5-0.9, and the roasting oxygen coefficient in the oxygen-overload roasting is 1.1-1.

5.

4. The method for recovering antimony from arsenic-antimony gold ore according to claim 1, characterized in that: The oxidation conditions are that the excess coefficient of oxygen in air and / or oxygen-enriched air is 1.05-1.2 and the temperature is 500-900°C.

5. The method for recovering antimony from arsenic-antimony gold ore according to claim 1, characterized in that: The separation is low temperature volatilization separation, and the temperature is 200-600°C.

6. The method for recovering antimony from arsenic-antimony gold ore according to claim 1, characterized in that: The second dust collection is temperature-lowering dust collection, and the temperature is 120-200°C.

7. The method for recovering antimony from arsenic-antimony gold ore according to claim 1, characterized in that: The arsenic removal is carried out by leaching, the leaching agent includes a dilute sulfuric acid solution, and the pH value of the leaching agent is 1.0-6.

5.

8. The method for recovering antimony from arsenic-antimony gold ore according to claim 7, characterized in that: The liquid-to-solid ratio of the leaching is 1-10 mL of the leaching agent corresponding to 1 mg of the antimony-rich ash.

9. The method for recovering antimony from arsenic-antimony gold ore according to claim 1, characterized in that: The leaching agent includes hydrochloric acid and / or chloride salt and satisfies at least one of the following conditions: a. The concentration of the hydrochloric acid is 30-70g / L; b. The chloride salt includes one or more of NaCl, KCl, CaCl2, and the amount of the chloride salt added is 100-200g / L; c. The antimony content in the antimony-rich leaching solution is 40-70 g / L.

10. The method for recovering antimony from arsenic-antimony gold ore according to any one of claims 1 to 9, characterized in that: At least one of the following conditions is met: d. During the electrodeposition reaction, the cathode current density is 100-300A / m 2 ; e. The antimony content in the electrodeposition lean solution is 20-40 g / L; f. The electrodeposition barren solution can be recycled as a leaching agent after being supplemented with hydrochloric acid.

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