CN113511677B - Treatment method of arsenic filter cake - Google Patents
Treatment method of arsenic filter cake Download PDFInfo
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- CN113511677B CN113511677B CN202110778525.8A CN202110778525A CN113511677B CN 113511677 B CN113511677 B CN 113511677B CN 202110778525 A CN202110778525 A CN 202110778525A CN 113511677 B CN113511677 B CN 113511677B
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Abstract
The invention relates to the technical field of chemical industry, in particular to a treatment method of an arsenic filter cake, which comprises the following steps: a) Slurrying the arsenic filter cake with dilute sulfuric acid; b) Stirring and leaching the slurried arsenic filter cake under normal pressure to obtain leaching liquid and leaching slag; c) Removing impurities from the leaching solution by adopting barium-titanium double salt; d) Reducing the impurity removing liquid obtained in the step C) by adopting a reducing agent, and obtaining arsenic trioxide after freezing and crystallizing. The invention can thoroughly solve the problem that the arsenic filter cake cannot be stored and pollutes the environment, realizes the harmless treatment of the arsenic filter cake, and converts the harmful component arsenic of the arsenic filter cake into the product arsenic trioxide; fully recovering valuable components copper and sulfur in the arsenic filter cake solid waste, turning waste into wealth and maximizing resource utilization; effectively solves the production problem of the company and increases the economic benefit for the enterprise.
Description
Technical Field
The invention relates to the technical field of chemical industry, in particular to a treatment method of an arsenic filter cake.
Background
Arsenic is a nonmetallic element with a sulfur-philic property, and exists in nature mainly in the form of sulfide ore, oxide ore, and the like. Elemental arsenic is nontoxic, but many compounds of arsenic have strong toxicity, can enter human bodies through skin, respiratory tract and other ways, damage respiratory systems, digestive systems, nervous systems and the like of people, and can cause cancer and even death in serious cases.
In the nonferrous metal extraction process, arsenic mainly enters smoke or waste water and waste residue in the form of sulfide or salt. The arsenic filter cake is one of typical arsenic-containing solid wastes generated in the copper smelting industry, and the main component of the arsenic filter cake is arsenic trisulfide, and the specific components are shown in table 1. At present, most copper smelting enterprises are difficult to find a proper method for treating an arsenic filter cake, and the arsenic filter cake is mainly piled up, but the piling up can cause great threat to the environment and waste of resources.
TABLE 1 arsenic Filter cake chemical composition Table
Disclosure of Invention
In view of the above, the present invention aims to provide a method for treating an arsenic filter cake, which can convert arsenic in the arsenic filter cake into arsenic trioxide.
The invention provides a treatment method of an arsenic filter cake, which comprises the following steps:
a) Slurrying the arsenic filter cake with dilute sulfuric acid;
b) Stirring and leaching the slurried arsenic filter cake under normal pressure to obtain leaching liquid and leaching slag;
c) Removing impurities from the leaching solution by adopting barium-titanium double salt;
d) Reducing the impurity removing liquid obtained in the step C) by adopting a reducing agent, and obtaining arsenic trioxide after freezing and crystallizing.
Preferably, in the step A), the concentration of the dilute sulfuric acid is 50-100 g/L;
the slurrying liquid-solid ratio is 3-6: 1.
preferably, in the step B), the temperature of the stirring leaching is 85-95 ℃ and the time is 2.5-3.5 h.
Preferably, in the step B), the reagent used for agitation leaching further comprises an oxidizing agent;
the oxidant comprises oxygen or hydrogen peroxide;
the mole ratio of the oxidant to the trivalent arsenic ions in the arsenic filter cake is 2-4: 1.
preferably, in the step C), the removing impurities from the leaching solution by using barium-titanium double salt includes:
stirring and reacting the pulpified barium-titanium double salt with the heated leaching solution;
the temperature of the stirring reaction is 70-90 ℃ and the time is 1.5-2 h.
Preferably, in the step C), the mass ratio of the barium-titanium double salt to bismuth in the leaching solution is 1.0-1.5: 1.
preferably, in step D), the reducing agent comprises sulfur dioxide, sulfurous acid or sodium sulfite;
the molar ratio of the reducing agent to the pentavalent arsenic ions in the impurity removing liquid is 2-4: 1.
preferably, in the step D), the temperature of the reduction is 30-70 ℃ and the time is 2.5-3 h.
Preferably, in the step D), the temperature of the freeze crystallization is-5 to-20 ℃.
Preferably, in step D), after the freeze crystallization, the method further includes:
washing and drying the frozen and crystallized product to obtain arsenic trioxide;
and returning the washed washing liquid and the crystallization mother liquid after freezing and crystallization to the pulping process of the step A).
The invention provides a treatment method of an arsenic filter cake, which comprises the following steps: a) Slurrying the arsenic filter cake with dilute sulfuric acid; b) Stirring and leaching the slurried arsenic filter cake under normal pressure to obtain leaching liquid and leaching slag; c) Removing impurities from the leaching solution by adopting barium-titanium double salt; d) Reducing the impurity removing liquid obtained in the step C) by adopting a reducing agent, and obtaining arsenic trioxide after freezing and crystallizing. The invention can thoroughly solve the problem that the arsenic filter cake cannot be stored and pollutes the environment, realizes the harmless treatment of the arsenic filter cake, and converts the harmful component arsenic of the arsenic filter cake into the product arsenic trioxide; fully recovering valuable components copper and sulfur in the arsenic filter cake solid waste, turning waste into wealth and maximizing resource utilization; effectively solves the production problem of the company and increases the economic benefit for the enterprise.
Drawings
FIG. 1 is a flow chart of a process for treating an arsenic filter cake provided by one embodiment of the invention;
FIG. 2 is an external view showing arsenic trioxide prepared in example 3 of the present invention;
FIG. 3 is an external view showing arsenic trioxide produced in comparative example 1 of the present invention.
Detailed Description
The technical solutions of the present invention will be clearly and completely described in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention provides a treatment method of an arsenic filter cake, which comprises the following steps:
a) Slurrying the arsenic filter cake with dilute sulfuric acid;
b) Stirring and leaching the slurried arsenic filter cake under normal pressure to obtain leaching liquid and leaching slag;
c) Removing impurities from the leaching solution by adopting barium-titanium double salt;
d) Reducing the impurity removing liquid obtained in the step C) by adopting a reducing agent, and obtaining arsenic trioxide after freezing and crystallizing.
In certain embodiments of the invention, the components of the arsenic filter cake are shown in table 1.
In the method for treating the arsenic filter cake, the arsenic filter cake is pulpified by dilute sulfuric acid.
In certain embodiments of the invention, the dilute sulfuric acid has a concentration of 50 to 100g/L. In certain embodiments, the dilute sulfuric acid has a concentration of 100g/L, 60g/L, or 80g/L.
In certain embodiments of the invention, the slurried liquid to solid ratio is 3 to 6:1. in certain embodiments, the slurried liquid to solid ratio is 4:1 or 5:1.
and after the slurrying is finished, stirring and leaching the arsenic filter cake after slurrying under normal pressure to obtain leaching liquid and leaching slag.
In certain embodiments of the invention, the temperature of the agitation leaching is 85 to 95 ℃ for 2.5 to 3.5 hours. In certain embodiments, the temperature of the agitation leaching is 90 ℃, 88 ℃ or 95 ℃. In certain embodiments, the agitation leaching time is 3 hours.
In certain embodiments of the invention, the reagent used in the agitation leaching further comprises an oxidizing agent. In certain embodiments of the invention, the oxidizing agent comprises oxygen or hydrogen peroxide. In some embodiments of the invention, the hydrogen peroxide is present in a mass concentration of 25-35%. In certain embodiments, the hydrogen peroxide is present at a mass concentration of 30%. In certain embodiments of the invention, the molar ratio of the oxidizing agent to trivalent arsenic ions in the arsenic filter cake is from 2 to 4:1. in certain embodiments, the molar ratio of the oxidizing agent to trivalent arsenic ions in the arsenic filter cake is 2:1. 2.5:1 or 3:1. in certain embodiments of the present invention, the method of adding the oxidizing agent comprises: in the process of stirring leaching under normal pressure, hydrogen peroxide is continuously added dropwise.
In some embodiments of the invention, after the agitation leaching, the method further comprises: and (3) carrying out solid-liquid separation to obtain leaching liquid and leaching slag. In certain embodiments of the invention, the method of solid-liquid separation is filtration. The method of the filtration is not particularly limited, and filtration methods well known to those skilled in the art may be employed.
In certain embodiments of the invention, the leach residue is smelted to yield copper and sulfur.
In certain embodiments of the invention, the smelting temperature is 1250-1300 ℃. In certain embodiments, the smelting temperature is 1280 ℃, 1270 ℃, or 1260 ℃.
After smelting, copper is recovered in the form of elemental copper, sulfur is converted into sulfur-containing flue gas, and sulfur is recovered in the form of sulfuric acid in a subsequent acid making process.
The invention adopts barium-titanium double salt to remove impurities from the leaching solution.
In certain embodiments of the invention, the barium titanium double salt is prepared according to the following method:
and (3) stirring the barium hydroxide solution and titanium dioxide in the carbon dioxide atmosphere to react and obtain the barium-titanium double salt.
In certain embodiments of the invention, the barium hydroxide solution has a concentration of 50 to 100g/L. In certain embodiments, the barium hydroxide solution has a concentration of 80g/L or 60g/L. In certain embodiments of the present invention, the solvent of the barium hydroxide solution is water.
In certain embodiments of the invention, the molar ratio of the barium hydroxide to the titanium dioxide is 1:1 to 2. In certain embodiments, the molar ratio of the barium hydroxide to the titanium dioxide is 1:1. 1:1.2.
in certain embodiments of the invention, the temperature of the agitation reaction is between 30 and 60 ℃ for a period of between 2 and 3 hours. In certain embodiments, the temperature of the stirred reaction is 40 ℃ or 60 ℃. In certain embodiments, the stirring reaction is for a period of 2 hours or 2.5 hours.
In certain embodiments of the invention, the rotational speed of the stirring reaction is 300 to 350rpm.
In certain embodiments of the invention, filtration is also included after the stirring reaction. The method of the filtration is not particularly limited, and filtration methods well known to those skilled in the art may be employed.
And (3) after the barium-titanium double salt is obtained, adopting the barium-titanium double salt to remove impurities from the leaching solution.
In certain embodiments of the invention, the leachate is purified using slurried barium titanium double salts.
In certain embodiments of the invention, the slurried barium titanium double salt is prepared according to the following method:
the barium-titanium double salt is slurried with desalted water.
The liquid-solid ratio of the slurry is not particularly limited, and the slurry can be sufficiently slurried. In certain embodiments of the invention, the slurried liquid to solid ratio is from 1 to 3:1. in certain embodiments, the slurried liquid to solid ratio is 2:1 or 2.5:1.
in certain embodiments of the invention, the removing impurities from the leachate using slurried barium titanium double salts comprises:
and stirring and reacting the pulpified barium-titanium double salt with the heated leaching solution.
In certain embodiments of the invention, the temperature of the heated leach solution is between 68 and 85 ℃. In certain embodiments, the temperature of the heated leachate is 70 ℃ or 85 ℃.
In certain embodiments of the invention, the temperature of the agitation reaction is 70-90 ℃ for a period of 1.5-2 hours.
In certain embodiments of the invention, the mass ratio of the barium-titanium double salt to bismuth in the leaching solution is 1.0-1.5: 1. in certain embodiments, the mass ratio of the barium-titanium double salt to bismuth in the leachate is 1.3:1 or 1.2:1.
and (3) reducing the impurity-removed liquid by adopting a reducing agent after the impurity removal is completed, and freezing and crystallizing to obtain the arsenic trioxide.
In certain embodiments of the invention, the reducing agent comprises sulfur dioxide, sulfurous acid, or sodium sulfite.
In certain embodiments of the invention, the molar ratio of the reducing agent to pentavalent arsenic ions in the impurity removing liquid is 2 to 4:1. in certain embodiments, the molar ratio of the reducing agent to pentavalent arsenic ions in the impurity removing liquid is 2:1. 2.5:1 or 3:1.
in certain embodiments of the invention, the reduction is at a temperature of 30 to 70 ℃ for a time of 2.5 to 3 hours. In certain embodiments, the temperature of the reduction is 60 ℃, 50 ℃, or 55 ℃. In certain embodiments, the time of the reduction is 3 hours or 2.5 hours.
In the invention, the concentration of arsenic in the reduced solution is lower than 35g/L, evaporation concentration is carried out until the concentration of arsenic in the reduced solution is not lower than 35g/L, and then freezing crystallization is carried out; and (3) directly freezing and crystallizing if the concentration of arsenic in the reduced solution is not lower than 35 g/L. The method of the present invention is not particularly limited, and the method of the present invention may be any method known to those skilled in the art.
In certain embodiments of the invention, the concentration of arsenic in the solution prior to freeze crystallization is from 35 to 45g/L. In certain embodiments, the concentration of arsenic in the solution prior to freeze crystallization is 40.8g/L, 38.8g/L, or 38.5g/L.
In certain embodiments of the invention, the temperature of the freeze crystallization is from-5 ℃ to-20 ℃. In certain embodiments, the temperature of the freeze crystallization is-15 ℃, -10 ℃, or-12 ℃.
In certain embodiments of the invention, the arsenic crystallization rate is not less than 60% after freeze crystallization. In certain embodiments of the invention, the arsenic crystallization rate after freeze crystallization is 64.4%, 64.5%, or 64.8%.
In some embodiments of the present invention, after the freeze crystallization, the method further comprises:
and washing and drying the frozen and crystallized product to obtain the arsenic trioxide.
In certain embodiments of the invention, the detergent employed in the washing is water. And returning the washed washing liquid and the crystallization mother liquid after freezing and crystallization to the pulping process of the step A).
The drying method is not particularly limited, and a drying method well known to those skilled in the art may be employed.
The source of the raw materials used in the present invention is not particularly limited, and may be generally commercially available.
FIG. 1 is a flow chart of a process for treating an arsenic filter cake according to one embodiment of the invention.
The invention adopts normal pressure low acid leaching. The normal pressure low acid leaching can effectively reduce the impurity concentration of copper, lead, bismuth and the like in the leaching solution, and is beneficial to improving the product quality. Compared with the high-pressure oxidation leaching arsenic filter cake, the normal-pressure low-acid leaching process can effectively reduce the entry of impurities such as copper, lead, bismuth and the like in the arsenic filter cake into the leaching liquid, and can avoid exceeding of the impurities such as copper, lead, bismuth and the like in the subsequent arsenic trioxide products. Compared with the copper sulfate displacement method, the normal pressure low acid leaching process does not need to consume copper sulfate, and can greatly reduce the production cost.
The invention adopts barium-titanium double salt to remove bismuth. The barium-titanium double salt can remove impurities, bismuth in the leaching solution can be effectively removed, and arsenic loss can not be caused; the impurity removal rate is high, and the bismuth content in the leaching solution can be reduced to below 0.005 g/L.
The invention further controls the arsenic content in the liquid before freezing and crystallization to be 35-45 g/L, thereby greatly reducing the evaporation capacity and the production cost.
Compared with normal-temperature water-cooling crystallization, the method has the advantages of high crystallization rate by adopting low-temperature freezing crystallization, high crystallization rate and low arsenic concentration in the crystallized liquid; the prepared arsenic trioxide has finer granularity and whiter color.
The washing liquid is mixed with the crystallization mother liquid and returned to slurrying of the arsenic filter cake, so that the recovery rate of arsenic can be improved, and no waste liquid is generated.
The leached slag is enriched in sulfur and copper, and valuable components of the arsenic filter cake can be recovered after furnace return treatment, so that the resource utilization is maximized.
In order to further illustrate the present invention, the following examples are provided to illustrate a method for treating an arsenic filter cake according to the present invention, but should not be construed as limiting the scope of the present invention.
Example 1
Preparation of barium-titanium double salt:
taking 100mL of solution with the barium hydroxide content of 80g/L, adding 3g of titanium dioxide, wherein the molar ratio of the barium hydroxide to the titanium dioxide is 1:1, simultaneously introducing enough carbon dioxide gas, controlling the stirring rotation speed to 300rpm, reacting the solution at 40 ℃ for 2 hours, and filtering to obtain 12.1g of barium-titanium double salt.
Example 2
Preparation of barium-titanium double salt:
taking 100mL of a solution with the barium hydroxide content of 60g/L, adding 2.3g of titanium dioxide, wherein the molar ratio of the barium hydroxide to the titanium dioxide is 1:1.2, simultaneously introducing enough carbon dioxide gas, controlling the stirring rotation speed to 350rpm, reacting the solution at 50 ℃ for 2.5 hours, and filtering to obtain 9g of barium-titanium double salt.
Example 3
1) 1.5kg of arsenic filter cake (the arsenic content is 15.69wt percent and the copper content is 0.33wt percent) is taken, 6L of dilute sulfuric acid is firstly used for pulping, and the liquid-solid ratio of pulping is 4:1, the concentration of the dilute sulfuric acid is 100g/L. After slurrying, stirring and leaching for 3 hours at 90 ℃ and normal pressure, continuously dropwise adding 1.3L of hydrogen peroxide with the mass concentration of 30% (the molar ratio of the hydrogen peroxide to the trivalent arsenic ions in the arsenic filter cake is 2:1) in the leaching process, and filtering to obtain leaching liquid and leaching slag. The volume of the leaching solution is 5.54L, the arsenic content is 40.5g/L, and the bismuth content is 11.5mg/L. The leached residue was dried and weighed 431.5g, and had 90.7wt% of sulfur, 2.56wt% of arsenic and 1.12wt% of copper.
2) 77mg of the barium-titanium double salt of example 1 (the mass ratio of the barium-titanium double salt to bismuth in the leachate is 1.3: 1) Slurrying with proper amount of desalted water, wherein the liquid-solid ratio of slurrying is 2:1, a step of; and (3) heating the leaching solution to 70 ℃, adding the slurried barium-titanium double salt into the leaching solution, stirring at 70 ℃ for reaction for 100min, and obtaining 5.6L of impurity removing liquid after the reaction is finished, wherein the arsenic content is 40.1g/L, and the bismuth content is less than 0.5mg/L.
3) 5.6L of impurity removing liquid is placed in a reactionIntroducing SO into the kettle at 60 DEG C 2 Reaction for 3h, SO 2 Aeration rate 400mL/min, SO 2 The molar ratio of the pentavalent arsenic ions in the impurity removing liquid is 2:1, a step of; after the reaction is finished, 5.5L of reduced liquid is obtained, the arsenic content is 40.8g/L, and the bismuth content is less than 0.5mg/L.
4) And (3) carrying out freezing crystallization on the reduced solution at the temperature of minus 15 ℃ to obtain crude arsenic trioxide and crystallization mother liquor. After freeze crystallization, the arsenic crystallization rate was 64.4%. After washing with water and drying, 190.7g of arsenic trioxide was obtained. FIG. 2 is an external view of arsenic trioxide prepared in example 3 of the present invention. As can be seen from FIG. 2, the arsenic trioxide prepared in this example is finer in particle size and whiter in color.
The purity of the arsenic trioxide is 99.84%, the contents of copper, bismuth, lead, zinc and iron in the arsenic trioxide are respectively less than 0.0010%, and the total impurity content is not more than 0.16%. The washing water of the crude arsenic trioxide is incorporated into the crystallization mother liquor, and the total volume of the crystallization mother liquor is measured to be 5.97L, the arsenic content to be 5.64g/L and the acid content to be 98.4g/L.
5) The crystallization mother liquor is returned to the pulping process of the step 1). The leached slag produced in the step 1) is returned to a smelting furnace for smelting at 1280 ℃, valuable components such as copper, sulfur and the like are recovered, the recovery rate of copper is 98%, and the recovery rate of sulfur is 98%.
In the whole process, the recovery rate of arsenic= (arsenic content in arsenic filter cake-arsenic content in leaching residue)/arsenic content in arsenic filter cake= (1.5×15.69% ×1000-431.5 ×2.56%)/(1.5×15.69% ×1000) =95.3%; the prepared arsenic trioxide accords with the national standard of GB-26721-2011 arsenic trioxide.
Comparative example 1
The procedure of example 3 was followed except that the freezing crystallization of step 4) in example 3 was changed to normal temperature crystallization, and the rest of the procedure was carried out in accordance with the procedure of example 3 of the present invention, to obtain arsenic trioxide, and the crystallization rate of arsenic after normal temperature crystallization was 50.1%.
FIG. 3 is an external view showing arsenic trioxide produced in comparative example 1 of the present invention. As can be seen from FIG. 3, the prepared arsenic trioxide has obviously coarse granularity, yellow color and poor chromaticity during normal temperature crystallization. Meanwhile, the crystallization rate of arsenic of comparative example 1 is significantly lower than that of arsenic at the time of freeze crystallization.
Example 4
1) 1kg of arsenic filter cake (the arsenic content is 20.66wt percent and the copper content is 0.35wt percent) is taken, 5L of dilute sulfuric acid is firstly used for pulping, and the liquid-solid ratio of pulping is 5:1, the concentration of the dilute sulfuric acid is 60g/L. After slurrying, stirring and leaching for 3 hours at 88 ℃ and normal pressure, continuously dropwise adding 0.9L of hydrogen peroxide with the mass concentration of 30% (the molar ratio of the hydrogen peroxide to the trivalent arsenic ions in the arsenic filter cake is 2.5:1) in the leaching process, and filtering to obtain leaching liquid and leaching residues. The volume of the leaching solution is 5.1L, the arsenic content is 39.2g/L, and the bismuth content is 10.3mg/L. The leached residue was dried and weighed 287.6g, containing 91.3wt% sulfur, 2.34wt% arsenic and 1.23wt% copper.
2) 51mg of the barium-titanium double salt of example 1 (the mass ratio of the barium-titanium double salt to bismuth in the leachate is 1.2: 1) Slurrying with proper amount of desalted water, wherein the liquid-solid ratio of slurrying is 2.5:1, a step of; and (3) heating the leaching solution to 70 ℃, adding the slurried barium-titanium double salt into the leaching solution, stirring at 70 ℃ for reaction for 90min, and obtaining 5.18L of impurity removing liquid containing 38.6g/L of arsenic and less than 0.5mg/L of bismuth after the reaction is finished.
3) 5.18L of impurity removing liquid is placed in a reaction kettle, and SO is introduced at 50 DEG C 2 Reaction for 2.5h, SO 2 Aeration rate 300mL/min, SO 2 The molar ratio of the pentavalent arsenic ions in the impurity removing liquid is 2.5:1, a step of; after the reaction is finished, 5.15L of reduced liquid containing 38.8g/L arsenic and less than 0.5mg/L bismuth is obtained.
4) And (3) freezing and crystallizing the reduced solution at the temperature of minus 10 ℃ to obtain crude arsenic trioxide and crystallization mother liquor. After freeze crystallization, the arsenic crystallization rate was 64.5%. After washing with water and drying, 170.4g of arsenic trioxide was obtained. The purity of the arsenic trioxide is 99.86%, the contents of copper, bismuth, lead, zinc and iron in the arsenic trioxide are respectively less than 0.0010%, and the total impurity content is not more than 0.14%. The washing water of the crude arsenic trioxide is incorporated into the crystallization mother liquor, and the total volume of the crystallization mother liquor is measured to be 6.03L, the arsenic content is 11.76g/L, and the acid content is 44.8g/L.
5) The crystallization mother liquor is returned to the pulping process of the step 1). The leached slag produced in the step 1) is returned to a smelting furnace for smelting at 1270 ℃, valuable components such as copper, sulfur and the like are recovered, the recovery rate of copper is 98%, and the recovery rate of sulfur is 98%.
In the whole process, the recovery rate of arsenic= (arsenic content in arsenic filter cake-arsenic content in leaching residue)/arsenic content in arsenic filter cake= (1.0×20.66% ×1000-287.6×2.34%)/(1.0×20.66% ×1000) =96.7%, and the prepared arsenic trioxide accords with the GB-26721-2011 arsenic trioxide-national standard.
Example 5
1) 2kg of arsenic filter cake (20.59 wt% of arsenic content and 0.34wt% of copper content) is taken, 10L of dilute sulfuric acid is used for pulping, and the liquid-solid ratio of pulping is 5:1, the concentration of dilute sulfuric acid is 80g/L. After slurrying, stirring and leaching for 3 hours at 95 ℃ and normal pressure, continuously dropwise adding 1.8L of hydrogen peroxide with the mass concentration of 30% (the molar ratio of the hydrogen peroxide to the trivalent arsenic ions in the arsenic filter cake is 3:1) in the leaching process, and filtering to obtain leaching liquid and leaching slag. The volume of the leaching solution is 10.6L, the arsenic content is 37.7g/L, and the bismuth content is 10mg/L. The leached residue was dried and weighed 573g, and had 91.5wt% sulfur, 2.11wt% arsenic, and 1.2wt% copper.
2) 102mg of the barium-titanium double salt of example 2 (the mass ratio of the barium-titanium double salt to bismuth in the leachate is 1.3: 1) Slurrying with proper amount of desalted water, wherein the liquid-solid ratio of slurrying is 2:1, a step of; and (3) heating the leaching solution to 85 ℃, adding the slurried barium-titanium double salt into the leaching solution, stirring at 85 ℃ for reaction for 110min, and obtaining 10.65L of impurity removing liquid containing 37.5g/L of arsenic and less than 0.5mg/L of bismuth after the reaction is finished.
3) 10.65L of impurity removing liquid is placed in a reaction kettle, and SO is introduced at 55 DEG C 2 Reaction for 3h, SO 2 Aeration rate 500mL/min, SO 2 The molar ratio of the pentavalent arsenic ions in the impurity removing liquid is 3:1, a step of; after the reaction is finished, 10.36L of reduced liquid is obtained, the arsenic content is 38.5g/L, and the bismuth content is less than 0.5mg/L.
4) And (3) freezing and crystallizing the reduced solution at the temperature of-12 ℃ to obtain crude arsenic trioxide and crystallization mother liquor. After freeze crystallization, the arsenic crystallization rate was 64.8%. After washing with water and drying, 341.8g of arsenic trioxide was obtained. The purity of the arsenic trioxide is 99.87%, the contents of copper, bismuth, lead, zinc and iron in the arsenic trioxide are respectively less than 0.0010%, and the total impurity content is not more than 0.13%. The washing water of the crude arsenic trioxide is incorporated into the crystallization mother liquor, and the total volume of the crystallization mother liquor is measured to be 14.8L, the arsenic content is 9.48g/L, and the acid content is 43.2g/L.
5) The crystallization mother liquor is returned to the pulping process of the step 1). The leached slag produced in the step 1) is returned to a smelting furnace for smelting at 1260 ℃, valuable components such as copper, sulfur and the like are recovered, the recovery rate of copper is 98%, and the recovery rate of sulfur is 98%.
In the whole process, the recovery rate of arsenic= (arsenic content in arsenic filter cake-arsenic content in leaching residue)/arsenic content in arsenic filter cake= (2.0×20.59% ×1000-573×2.11%)/(1.0×20.59% ×1000) =97.1%, and the prepared arsenic trioxide accords with the national standard of GB-26721-2011 arsenic trioxide.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (8)
1. A method for treating arsenic filter cake, comprising the steps of:
a) Slurrying the arsenic filter cake with dilute sulfuric acid;
b) Stirring and leaching the slurried arsenic filter cake under normal pressure to obtain leaching liquid and leaching slag;
c) Removing impurities from the leaching solution by adopting barium-titanium double salt;
the barium-titanium double salt is prepared according to the following method:
stirring barium hydroxide solution and titanium dioxide in the carbon dioxide atmosphere to react and obtain barium-titanium double salt;
after the stirring reaction, filtering is further included;
the concentration of the barium hydroxide solution is 50-100 g/L;
the molar ratio of the barium hydroxide to the titanium dioxide is 1:1-2;
the mass ratio of the barium-titanium double salt to bismuth in the leaching solution is 1.0-1.5: 1, a step of;
d) Reducing the impurity removing liquid obtained in the step C) by adopting a reducing agent, and obtaining arsenic trioxide after freezing and crystallizing;
the temperature of the freezing crystallization is-5 to-20 ℃.
2. The method for treating an arsenic filter cake according to claim 1, wherein in the step a), the concentration of the dilute sulfuric acid is 50 to 100g/L;
the liquid-solid ratio of the pulpifying is 3-6: 1.
3. the method for treating an arsenic filter cake according to claim 1, wherein in the step B), the temperature of the agitation leaching is 85-95 ℃ and the time is 2.5-3.5 hours.
4. The method of treating an arsenic filter cake according to claim 1, wherein in step B), the reagent used for agitation leaching further comprises an oxidizing agent;
the oxidant comprises oxygen or hydrogen peroxide;
the molar ratio of the oxidant to the trivalent arsenic ions in the arsenic filter cake is 2-4: 1.
5. the method for treating an arsenic filter cake according to claim 1, wherein in step C), the removing of impurities from the leachate using a barium-titanium double salt comprises:
stirring and reacting the pulpified barium-titanium double salt with the heated leaching solution;
the temperature of the stirring reaction is 70-90 ℃ and the time is 1.5-2 h.
6. The method of treating an arsenic filter cake according to claim 1, wherein in step D), the reducing agent comprises sulfur dioxide, sulfurous acid or sodium sulfite;
the molar ratio of the reducing agent to the pentavalent arsenic ions in the impurity removing liquid is 2-4: 1.
7. the method for treating an arsenic filter cake according to claim 1, wherein in the step D), the reduction temperature is 30 to 70 ℃ and the time is 2.5 to 3 hours.
8. The method for treating an arsenic filter cake according to claim 1, wherein in step D), after the freeze crystallization, further comprising:
washing and drying the frozen and crystallized product to obtain arsenic trioxide;
and returning the washed washing liquid and the crystallization mother liquid after freezing and crystallization to the pulping process of the step A).
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| CN85104205A (en) * | 1985-05-28 | 1986-05-10 | 沈阳矿冶研究所 | The arsenic filter cake method of comprehensive utilization |
| JP2010059035A (en) * | 2008-09-08 | 2010-03-18 | Sumitomo Metal Mining Co Ltd | Method for producing aqueous arsenous acid solution of high purity from copper removal slime |
| CN109930004A (en) * | 2019-04-12 | 2019-06-25 | 江西铜业股份有限公司 | A kind of method of arsenic filter cake resource utilization |
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| CN85104205A (en) * | 1985-05-28 | 1986-05-10 | 沈阳矿冶研究所 | The arsenic filter cake method of comprehensive utilization |
| JP2010059035A (en) * | 2008-09-08 | 2010-03-18 | Sumitomo Metal Mining Co Ltd | Method for producing aqueous arsenous acid solution of high purity from copper removal slime |
| CN109930004A (en) * | 2019-04-12 | 2019-06-25 | 江西铜业股份有限公司 | A kind of method of arsenic filter cake resource utilization |
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