CN113511677A - Arsenic filter cake treatment method - Google Patents
Arsenic filter cake treatment method Download PDFInfo
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- CN113511677A CN113511677A CN202110778525.8A CN202110778525A CN113511677A CN 113511677 A CN113511677 A CN 113511677A CN 202110778525 A CN202110778525 A CN 202110778525A CN 113511677 A CN113511677 A CN 113511677A
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Abstract
The invention relates to the technical field of chemical industry, in particular to a method for treating 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 at normal pressure to obtain a leaching solution and leaching residues; C) removing impurities from the leachate by using barium-titanium double salt; D) reducing the impurity-removed liquid obtained in the step C) by using a reducing agent, and freezing and crystallizing to obtain arsenic trioxide. The invention can thoroughly solve the problems that the arsenic filter cake can not 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; the valuable components of copper and sulfur in the arsenic filter cake solid waste are fully recovered, so that waste is changed into valuable, and the resource utilization is maximized; 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 method for treating an arsenic filter cake.
Background
Arsenic is a non-metallic element having a thiophilic property, and it exists mainly in the form of sulfide ore, oxide ore, etc. in nature. The simple substance 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 human bodies, and can cause cancer and even die when serious.
In the extraction process of nonferrous metals, arsenic mainly enters flue gas or waste water or waste residues in the form of sulfide or salt. The arsenic filter cake is one of typical arsenic-containing solid wastes produced in the copper smelting industry, 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 arsenic filter cakes, mainly carry out stockpiling treatment, but the stockpiling 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 provides a method for treating an arsenic filter cake, which can convert arsenic in the arsenic filter cake into arsenic trioxide.
The invention provides a method for treating 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 at normal pressure to obtain a leaching solution and leaching residues;
C) removing impurities from the leachate by using barium-titanium double salt;
D) reducing the impurity-removed liquid obtained in the step C) by using a reducing agent, and freezing and crystallizing to obtain arsenic trioxide.
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 agitation leaching is 85-95 ℃ and the time is 2.5-3.5 h.
Preferably, in step B), the reagent 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.
preferably, in the step C), the removing impurities from the leachate by using barium titanium double salt comprises:
stirring and reacting the slurried barium-titanium double salt and the heated leaching solution;
the stirring reaction temperature 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 the 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 pentavalent arsenic ions in the impurity removing solution is 2-4: 1.
preferably, in the step D), the reduction temperature is 30-70 ℃ and the time is 2.5-3 h.
Preferably, in the step D), the temperature of the frozen crystals is-5 to-20 ℃.
Preferably, step D), after the freezing and crystallizing, further comprises:
washing and drying the product after freezing and crystallizing to obtain arsenic trioxide;
the washed washing liquid and the mother liquid of the crystals after the freezing and crystallization are returned to the slurry step of the step A).
The invention provides a method for treating 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 at normal pressure to obtain a leaching solution and leaching residues; C) removing impurities from the leachate by using barium-titanium double salt; D) reducing the impurity-removed liquid obtained in the step C) by using a reducing agent, and freezing and crystallizing to obtain arsenic trioxide. The invention can thoroughly solve the problems that the arsenic filter cake can not 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; the valuable components of copper and sulfur in the arsenic filter cake solid waste are fully recovered, so that waste is changed into valuable, and the resource utilization is maximized; effectively solves the production problem of the company and increases the economic benefit for the enterprise.
Drawings
FIG. 1 is a flow diagram of a process for treating an arsenic filter cake according to one embodiment of the present invention;
FIG. 2 is an appearance diagram of arsenic trioxide prepared in example 3 of the present invention;
FIG. 3 is an appearance view of arsenic trioxide prepared in comparative example 1 of the present invention.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a method for treating 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 at normal pressure to obtain a leaching solution and leaching residues;
C) removing impurities from the leachate by using barium-titanium double salt;
D) reducing the impurity-removed liquid obtained in the step C) by using a reducing agent, and freezing and crystallizing to obtain arsenic trioxide.
In certain embodiments of the invention, the arsenic filter cake has the composition shown in table 1.
In the method for treating the arsenic filter cake, the arsenic filter cake is slurried by dilute sulfuric acid.
In some embodiments of the present invention, the concentration of the dilute sulfuric acid is 50-100 g/L. In certain embodiments, the concentration of the dilute sulfuric acid is 100g/L, 60g/L, or 80 g/L.
In certain embodiments of the present invention, the slurry has a liquid-solid ratio of 3-6: 1. in certain embodiments, the slurried liquid-to-solid ratio is 4: 1 or 5: 1.
and after slurrying is finished, stirring and leaching the slurried arsenic filter cake at normal pressure to obtain leachate and leaching slag.
In some embodiments of the invention, the temperature of the agitation leaching is 85-95 ℃ and the time is 2.5-3.5 h. In certain embodiments, the temperature of the agitation leach is 90 ℃, 88 ℃, or 95 ℃. In certain embodiments, the agitation leaching time is 3 hours.
In certain embodiments of the invention, the agent used for agitation leaching further comprises an oxidizing agent. In certain embodiments of the invention, the oxidant comprises oxygen or hydrogen peroxide. In some embodiments of the invention, the mass concentration of the hydrogen peroxide is 25-35%. In some embodiments, the hydrogen peroxide solution has a mass concentration of 30%. In certain embodiments of the invention, the molar ratio of the oxidizing agent to the trivalent arsenic ions in the arsenic filter cake is 2 to 4: 1. in certain embodiments, the molar ratio of the oxidizing agent to the 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 and leaching under normal pressure, hydrogen peroxide is continuously dripped.
In some embodiments of the present invention, after the agitation leaching, the method further comprises: and carrying out solid-liquid separation to obtain a leaching solution and leaching residues. In certain embodiments of the invention, the method of solid-liquid separation is filtration. The method of filtration is not particularly limited in the present invention, and a filtration method known to those skilled in the art may be used.
In certain embodiments of the invention, the leached slag is smelted to produce copper and sulfur.
In certain embodiments of the invention, the temperature of the melting is 1250 to 1300 ℃. In certain embodiments, the temperature of the melting 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 the subsequent acid making process.
The invention adopts barium-titanium double salt to remove impurities from the leaching solution.
In certain embodiments of the present invention, the barium titanium double salt is prepared according to the following method:
and (3) stirring and reacting the barium hydroxide solution and titanium dioxide in the atmosphere of carbon dioxide to obtain the barium-titanium double salt.
In some embodiments of the invention, the concentration of the barium hydroxide solution is 50-100 g/L. In certain embodiments, the concentration of the barium hydroxide solution is 80g/L or 60 g/L. In certain embodiments of the present invention, the solvent of the barium hydroxide solution is water.
In certain embodiments of the present 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 some embodiments of the invention, the stirring reaction is performed at 30-60 ℃ for 2-3 hours. In certain embodiments, the temperature of the stirred reaction is 40 ℃ or 60 ℃. In certain embodiments, the stirring reaction time is 2 hours or 2.5 hours.
In some embodiments of the present invention, the rotation speed of the stirring reaction is 300 to 350 rpm.
In certain embodiments of the invention, after the stirring reaction, filtration is also included. The method of filtration is not particularly limited in the present invention, and a filtration method known to those skilled in the art may be used.
After the barium-titanium double salt is obtained, the leaching solution is subjected to impurity removal by adopting the barium-titanium double salt.
In some embodiments of the invention, the slurried barium-titanium double salt is used to remove impurities from the leachate.
In certain embodiments of the present invention, the slurried barium titanium double salt is prepared as follows:
the barium titanium double salt is slurried with demineralized water.
The present invention is not limited to the liquid-solid ratio of the slurry, and sufficient slurry can be obtained. In certain embodiments of the present invention, the slurry has a liquid-solid ratio of 1-3: 1. in certain embodiments, the slurried liquid-to-solid ratio is 2: 1 or 2.5: 1.
in some embodiments of the present invention, the removing impurities from the leachate with the slurried barium-titanium double salt comprises:
stirring and reacting the slurried barium-titanium double salt and the heated leaching solution.
In some embodiments of the present invention, the temperature of the heated leachate is 68-85 ℃. In certain embodiments, the temperature of the heated leachate is 70 ℃ or 85 ℃.
In some embodiments of the invention, the stirring reaction is performed at a temperature of 70-90 ℃ for 1.5-2 hours.
In some embodiments of the invention, the mass ratio of the barium-titanium double salt to the bismuth in the leaching solution is 1.0-1.5: 1. in certain embodiments, the mass ratio of the barium-titanium double salt to the bismuth in the leachate is 1.3: 1 or 1.2: 1.
and after the impurity removal is finished, reducing the impurity removal liquid after the impurity removal by adopting a reducing agent, 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 some embodiments of the invention, the molar ratio of the reducing agent to the pentavalent arsenic ions in the impurity removal solution is 2-4: 1. in certain embodiments, the molar ratio of the reducing agent to pentavalent arsenic ions in the reject solution is 2: 1. 2.5: 1 or 3: 1.
in some embodiments of the invention, the temperature of the reduction is 30-70 ℃ and the time is 2.5-3 h. In certain embodiments, the temperature of the reduction is 60 ℃, 50 ℃, or 55 ℃. In certain embodiments, the reduction time is 3 hours or 2.5 hours.
In the invention, when the concentration of arsenic in the reduced solution is lower than 35g/L, evaporation and concentration are 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 (4) directly carrying out freeze crystallization when the concentration of arsenic in the reduced solution is not lower than 35 g/L. The method of evaporation concentration is not particularly limited in the present invention, and any evaporation concentration method known to those skilled in the art may be used.
In some embodiments of the invention, the concentration of arsenic in the solution before freezing and crystallizing is 35-45 g/L. In certain embodiments, the concentration of arsenic in the solution prior to freezing crystallization is 40.8g/L, 38.8g/L, or 38.5 g/L.
In certain embodiments of the invention, the temperature of the freeze crystallization is between-5 and-20 ℃. In certain embodiments, the temperature of the freeze crystallization is-15 ℃, -10 ℃, or-12 ℃.
In certain embodiments of the invention, the arsenic has a percent crystallinity of no less than 60% after freezing crystallization. In certain embodiments of the invention, the arsenic has a crystallization yield of 64.4%, 64.5%, or 64.8% after freezing crystallization.
In certain embodiments of the present invention, after the freezing and crystallizing, further comprising:
and washing and drying the product after freezing and crystallization to obtain arsenic trioxide.
In certain embodiments of the invention, the detergent used for the washing is water. The washed washing liquid and the mother liquid of the crystals after the freezing and crystallization are returned to the slurry step of the step A).
The method of drying is not particularly limited in the present invention, and a drying method known to those skilled in the art may be used.
The source of the above-mentioned raw materials is not particularly limited in the present invention, and may be generally commercially available.
FIG. 1 is a flow diagram of a process for treating arsenic filter cake according to one embodiment of the present invention.
The invention adopts normal pressure low acid leaching. The low-acid leaching under normal pressure can effectively reduce the concentration of impurities such as copper, lead, bismuth and the like in the leaching solution, and is beneficial to improving the product quality. Compared with the arsenic filter cake leached by high-pressure oxidation, the arsenic filter cake leaching method adopts the normal-pressure low-acid leaching process, can effectively reduce the impurities such as copper, lead, bismuth and the like in the arsenic filter cake from entering the leaching solution, and can avoid the impurities such as copper, lead, bismuth and the like in the subsequent arsenic trioxide product from exceeding the standard. Compared with a copper sulfate replacement method, the process of normal-pressure low-acid leaching 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 is used for removing impurities, so that bismuth in the leaching solution can be effectively removed, and the loss of arsenic cannot be caused; the impurity removal rate is high, and the bismuth content in the leaching solution can be reduced to be below 0.005 g/L.
The method further controls the arsenic content in the liquid before freezing crystallization to be 35-45 g/L, so that the evaporation amount can be greatly reduced, and the production cost is reduced.
Compared with normal temperature water cooling crystallization, the method has the advantages that the low-temperature freezing crystallization speed is high, the crystallization rate is high, and the concentration of arsenic in the crystallized liquid is low; the prepared arsenic trioxide has finer granularity and whiter color.
The washing liquid is merged into the crystallization mother liquid and returns to the slurrying of the arsenic filter cake, the recovery rate of arsenic can be improved, and no waste liquid is generated.
The sulfur and copper in the leached slag are enriched, and after the leached slag is returned to the furnace for treatment, the valuable components of the arsenic filter cake can be recovered, so that the resource utilization is maximized.
In order to further illustrate the present invention, the following will describe the method for treating arsenic filter cake in detail with reference to the examples, but it should not be construed as limiting the scope of the present invention.
Example 1
Preparing 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 barium hydroxide to the titanium dioxide is 1: and 1, simultaneously introducing sufficient carbon dioxide gas, controlling the stirring rotation speed to be 300rpm and the solution reaction temperature to be 40 ℃, reacting for 2 hours, and filtering to obtain 12.1g of barium-titanium double salt.
Example 2
Preparing barium-titanium double salt:
taking 100mL of solution with the barium hydroxide content of 60g/L, adding 2.3g of titanium dioxide, wherein the molar ratio of barium hydroxide to the titanium dioxide is 1: 1.2, simultaneously introducing sufficient carbon dioxide gas, controlling the stirring speed to be 350rpm, controlling the solution reaction temperature to be 50 ℃, reacting for 2.5h, and filtering to obtain 9g of barium-titanium double salt.
Example 3
1) Taking 1.5kg of arsenic filter cake (the arsenic content is 15.69 wt%, the copper content is 0.33 wt%), firstly slurrying with 6L of dilute sulfuric acid, wherein the slurrying liquid-solid ratio is 4: 1, the concentration of the dilute sulfuric acid is 100 g/L. After slurrying, stirring and leaching for 3h at 90 ℃ under normal pressure, continuously dropwise adding 1.3L of hydrogen peroxide with the mass concentration of 30% (the molar ratio of hydrogen peroxide to trivalent arsenic ions in the arsenic filter cake is 2: 1) in the leaching process, and filtering to obtain leachate and leaching residues. The measured volume of the leaching solution is 5.54L, the arsenic content is 40.5g/L, and the bismuth content is 11.5 mg/L. The leached residue weighed 431.5g after being dried, and contained 90.7 wt% of sulfur, 2.56 wt% of arsenic and 1.12 wt% 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) pulping with a proper amount of demineralized water, wherein the liquid-solid ratio of the pulping is 2: 1; heating the leachate to 70 ℃, adding the slurried barium-titanium double salt into the leachate, stirring at 70 ℃ for reaction for 100min, and obtaining 5.6L of impurity-removing liquid after the reaction is finished, wherein the impurity-removing liquid contains 40.1g/L of arsenic and less than 0.5mg/L of bismuth.
3) Placing 5.6L of impurity-removing liquid in a reaction kettle, and introducing SO at 60 deg.C2Reaction for 3h, SO2Aeration rate 400mL/min, SO2The mol ratio of the arsenic ions to the pentavalent arsenic ions in the impurity removing solution is 2: 1; after the reaction, 5.5L of reduced solution containing 40.8g/L of arsenic and less than 0.5mg/L of bismuth is obtained.
4) And (4) freezing and crystallizing the reduced solution at-15 ℃ to obtain crude arsenic trioxide and a crystallization mother solution. After freezing crystallization, the arsenic crystallization rate was 64.4%. The crude arsenic trioxide was washed with water and dried to give 190.7g of arsenic trioxide. FIG. 2 is an appearance diagram of arsenic trioxide prepared in example 3 of the present invention. As can be seen from FIG. 2, the arsenic trioxide prepared by the present example has a finer particle size and a whiter 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 amount of impurities is not higher than 0.16%. The washing water of the crude arsenic trioxide is merged into the crystallization mother liquor, and the total volume of the crystallization mother liquor is measured to be 5.97L, the arsenic content is measured to be 5.64g/L, and the acid content is measured to be 98.4 g/L.
5) The crystallization mother liquor is returned to the slurrying procedure in the step 1). And (2) returning the leached slag generated in the step 1) to a smelting furnace for smelting at 1280 ℃, and recovering valuable components such as copper, sulfur and the like, wherein 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 conforms to the GB-26721-2011 arsenic trioxide-national standard.
Comparative example 1
The freezing crystallization in the step 4) in the embodiment 3 is changed into normal temperature crystallization, the rest steps are carried out according to the steps in the embodiment 3 of the invention, the arsenic trioxide is obtained, and the crystallization rate of the arsenic after the normal temperature crystallization is 50.1%.
FIG. 3 is an appearance view of arsenic trioxide prepared in comparative example 1 of the present invention. As can be seen from FIG. 3, the prepared arsenic trioxide is obviously coarse in particle size, yellow in color and poor in chroma when crystallized at normal temperature. Meanwhile, the crystallization rate of arsenic of comparative example 1 was significantly lower than that of arsenic at the time of freezing crystallization.
Example 4
1) Taking 1kg of arsenic filter cake (with arsenic content of 20.66 wt% and copper content of 0.35 wt%), firstly slurrying with 5L of dilute sulfuric acid, wherein the slurrying liquid-solid ratio is 5: 1, the concentration of the dilute sulfuric acid is 60 g/L. After slurrying, stirring and leaching for 3h at 88 ℃ under normal pressure, continuously dropwise adding 0.9L of hydrogen peroxide with the mass concentration of 30% (the molar ratio of hydrogen peroxide to trivalent arsenic ions in the arsenic filter cake is 2.5: 1) in the leaching process, and filtering to obtain leachate and leaching residues. The measured volume of the leaching solution is 5.1L, the arsenic content is 39.2g/L, and the bismuth content is 10.3 mg/L. The leached residue weighed 287.6g after drying, and contained 91.3 wt% of sulfur, 2.34 wt% of arsenic and 1.23 wt% of 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 leaching solution is 1.2: 1) pulping with a proper amount of demineralized water, wherein the liquid-solid ratio of the pulping is 2.5: 1; and heating the leachate to 70 ℃, adding the slurried barium-titanium double salt into the leachate, stirring at 70 ℃ for reaction for 90min, and obtaining 5.18L of impurity-removing liquid after the reaction is finished, wherein the impurity-removing liquid contains 38.6g/L of arsenic and less than 0.5mg/L of bismuth.
3) Placing 5.18L of impurity-removing liquid in a reaction kettle, and introducing SO at 50 deg.C2Reaction for 2.5h, SO2Aeration rate 300mL/min，SO2The mol ratio of the impurity removal solution to pentavalent arsenic ions in the impurity removal solution is 2.5: 1; after the reaction, 5.15L of reduced solution containing 38.8g/L of arsenic and less than 0.5mg/L of bismuth is obtained.
4) And (4) freezing and crystallizing the reduced solution at-10 ℃ to obtain crude arsenic trioxide and a crystallization mother solution. After freezing crystallization, the crystallization rate of arsenic was 64.5%. The crude arsenic trioxide was washed with water and dried to obtain 170.4g of arsenic trioxide. The purity of the arsenic trioxide is 99.86 percent, the contents of copper, bismuth, lead, zinc and iron in the arsenic trioxide are respectively less than 0.0010 percent, and the total amount of impurities is not higher than 0.14 percent. The washing water of the crude arsenic trioxide is merged 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 44.8 g/L.
5) The crystallization mother liquor is returned to the slurrying procedure in the step 1). And (2) returning the leaching slag generated in the step 1) to a smelting furnace for smelting at 1270 ℃, and recovering valuable components such as copper, sulfur and the like, wherein 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 conforms to the national standard GB-26721-.
Example 5
1) Taking 2kg of arsenic filter cake (with arsenic content of 20.59 wt% and copper content of 0.34 wt%), firstly slurrying with 10L of dilute sulfuric acid, wherein the slurrying liquid-solid ratio is 5: 1, the concentration of the dilute sulfuric acid is 80 g/L. After slurrying, stirring and leaching for 3h at 95 ℃ and normal pressure, continuously dropwise adding 1.8L of hydrogen peroxide with the mass concentration of 30% (the molar ratio of hydrogen peroxide to trivalent arsenic ions in the arsenic filter cake is 3: 1) in the leaching process, and filtering to obtain leachate and leaching residues. The measured volume of the leaching solution is 10.6L, the arsenic content is 37.7g/L, and the bismuth content is 10 mg/L. After being dried, the leached slag weighs 573g, and contains 91.5 wt% of sulfur, 2.11 wt% of arsenic and 1.2 wt% of copper.
2) Weighing 102mg of the barium-titanium double salt in the embodiment 2 (the mass ratio of the barium-titanium double salt to bismuth in the leaching solution is 1.3: 1) pulping with a proper amount of demineralized water, wherein the liquid-solid ratio of the pulping is 2: 1; and heating the leachate to 85 ℃, adding the slurried barium-titanium double salt into the leachate, stirring at 85 ℃ for reaction for 110min, and obtaining 10.65L of impurity-removing liquid after the reaction is finished, wherein the impurity-removing liquid contains 37.5g/L of arsenic and less than 0.5mg/L of bismuth.
3) 10.65L of impurity-removing liquid is put into a reaction kettle, and SO is introduced at 55 DEG C2Reaction for 3h, SO2Aeration rate 500mL/min, SO2The mole ratio of the impurity removing solution to pentavalent arsenic ions in the impurity removing solution is 3: 1; after the reaction, 10.36L of reduced solution containing 38.5g/L of arsenic and less than 0.5mg/L of bismuth is obtained.
4) And (4) freezing and crystallizing the reduced solution at-12 ℃ to obtain crude arsenic trioxide and a crystallization mother solution. After freezing crystallization, the crystallization rate of arsenic was 64.8%. The crude arsenic trioxide was washed with water and dried to obtain 341.8g of arsenic trioxide. The purity of the arsenic trioxide is 99.87 percent, the contents of copper, bismuth, lead, zinc and iron in the arsenic trioxide are respectively less than 0.0010 percent, and the total amount of impurities is not higher than 0.13 percent. The washing water of the crude arsenic trioxide is merged 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 43.2 g/L.
5) The crystallization mother liquor is returned to the slurrying procedure in the step 1). And (2) returning the leaching slag generated in the step 1) to a smelting furnace for smelting at 1260 ℃, and recovering valuable components such as copper, sulfur and the like, wherein 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)/the arsenic content in arsenic filter cake (2.0 × 20.59% × 1000-.
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 (10)
1. A method of treating an 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 at normal pressure to obtain a leaching solution and leaching residues;
C) removing impurities from the leachate by using barium-titanium double salt;
D) reducing the impurity-removed liquid obtained in the step C) by using a reducing agent, and freezing and crystallizing to obtain arsenic trioxide.
2. The recovery method according to claim 1, wherein 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.
3. the recycling method 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 h.
4. The recovery method according to claim 1, wherein in step B), the reagents used in agitation leaching further comprise 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 recycling method according to claim 1, wherein the step C) of removing impurities from the leachate by using barium titanium double salt comprises:
stirring and reacting the slurried barium-titanium double salt and the heated leaching solution;
the stirring reaction temperature is 70-90 ℃, and the time is 1.5-2 h.
6. The recovery method according to claim 1, wherein in the step C), the mass ratio of the barium-titanium double salt to the bismuth in the leachate is 1.0-1.5: 1.
7. the recovery method 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 pentavalent arsenic ions in the impurity removing solution is 2-4: 1.
8. the recycling method according to claim 1, wherein in the step D), the temperature of the reduction is 30-70 ℃ and the time is 2.5-3 h.
9. The recovery method according to claim 1, wherein the temperature of the frozen crystals in the step D) is-5 to-20 ℃.
10. The recovery method according to claim 1, further comprising, after the step D), the step of freezing and crystallizing:
washing and drying the product after freezing and crystallizing to obtain arsenic trioxide;
the washed washing liquid and the mother liquid of the crystals after the freezing and crystallization are returned to the slurry step of the step A).
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| CN116065039A (en) * | 2023-01-30 | 2023-05-05 | 白家华 | Method for extracting valuable metals from harmless smelting arsenic-containing waste tailings |
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