CN111926187A - Method for comprehensively recovering selenium, mercury, lead and silver from acid sludge - Google Patents
Method for comprehensively recovering selenium, mercury, lead and silver from acid sludge Download PDFInfo
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- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
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- C22B43/00—Obtaining mercury
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Abstract
The invention relates to a method for comprehensively recovering selenium, mercury, lead and silver from acid mud, belonging to the technical field of metallurgical acid mud treatment, wherein carbonate is added to carry out phase transformation reaction with the acid mud to obtain transformation liquid and transformation slag; adding diluted acid to selectively leach lead in the conversion slag, adding sodium chloride after leaching to respectively obtain a lead-containing leachate and selenium-mercury-silver enriched slag, and realizing separation of lead from selenium-mercury-silver; adding an oxidant and acid to chloridize and leach selenium-mercury enriched slag to obtain selenium-mercury leachate and silver-containing slag; introducing sulfur dioxide into the selenium-mercury leachate for reduction to obtain crude selenium and a mercury-containing solution; adding sulfuric acid into the lead-containing leachate to react to generate lead sulfate and dilute acid to obtain dilute acid and pure lead sulfate, wherein the dilute acid is recycled; adding a vulcanizing agent into the mercury-containing solution for reaction to obtain mercury sulfide and a residual sulfide liquid. The method is used for treating and smelting acid sludge by a full wet method, is low in temperature and environment-friendly, has the mercury yield of more than 99.5%, lead of more than 95.0% and selenium of more than 98.0% in the full process, and relates to mature treatment equipment, easy engineering and good application prospect.
Description
Technical Field
The invention belongs to the technical field of metallurgical acid sludge treatment, and particularly relates to a method for comprehensively recovering selenium, mercury, lead and silver from acid sludge.
Background
In order to effectively control mercury emission, the pyrometallurgical nonferrous smelting enterprises wash flue gas to form mercury-containing acid sludge, the mercury content of the acid sludge produced by smelting different nonferrous metals is different, and one of the obvious and common characteristics is that the acid sludge contains lead, selenium, mercury and the like. If unreasonable technology is adopted to treat the acid sludge, the pollution of mercury to the environment is easily caused, and the waste of mineral resources such as rare and high-price selenium mercury in the acid sludge and the like can also be caused. Therefore, the development of a method which can treat the acid sludge safely and environmentally and can effectively recover rare high-valence metal selenium mercury and heavy metal lead is urgently needed. At present, the method for comprehensively recovering selenium, mercury and lead from acid sludge comprises the following steps:
the patent application No. ZL 201710211864.1) adds the heavy acid mud and hydrochloric acid into water, heats, adds potassium chlorate, reacts at a certain temperature to obtain mixed liquor containing mercuric chloride; adding alkali for neutralization, controlling pH to obtain a mixed solution containing mercuric oxide precipitate and Na2SeO3, performing solid-liquid separation, and introducing the selenium-containing solution into a selenium separation system to recover selenium; and (4) drying the mercuric oxide precipitate obtained by separation in the second step, rectifying by adopting a continuous vacuum rectification method, and condensing and recovering the generated mercury vapor to obtain refined mercury. The method adopts wet process treatment, realizes high-efficiency separation of mercury and selenium, and prepares high-purity mercury products through continuous vacuum rectification, thereby avoiding flue gas pollution caused by direct roasting of acid sludge.
Wangming et al have disclosed a method for recovering selenium, mercury, gold and silver from acid sludge (invention patent application No. 201510259346.8), the steps are to put acid sludge produced in the course of roasting flue gas of sulphide ore to make acid into a tube furnace, carry on roasting treatment under the protective atmosphere condition, get roasting slag and flue gas containing gaseous mercury selenide; cooling the flue gas to cool the gaseous mercury selenide in the flue gas into solid mercury selenide, thereby realizing the recovery of selenium and mercury in the acid sludge; and finally, extracting gold and silver in the roasting slag by adopting a cyanidation method to realize the recovery of the gold and the silver in the acid sludge. The method has the advantages of short process, high added value of products, high purity, high recovery rate of valuable elements and little environmental pollution.
The longevity handle and the handle, etc. disclose a method for recovering mercury from copper smelting lead filter cake (invention patent application number: 201510262880.4), which comprises the steps of mixing and stirring naturally dried copper smelting lead filter cake, crude mercury reducing slag and stabilizer lime; continuously adding the materials mixed in the burdening procedure into a crude demercuration electrothermal rotary distillation furnace in batches for preheating and drying; then heating the crude demercuration electrothermal rotary distillation furnace to 500-600 ℃, and maintaining the pressure in the crude demercuration electrothermal rotary distillation furnace at-50 Pa to-100 Pa for 30-40 min; introducing the reacted tail gas of the crude demercuration electrothermal rotary distillation furnace into a crude demercuration condenser through an induced draft fan, condensing mercury vapor in the tail gas into metal crude mercury, and collecting the metal crude mercury into a mercury collecting tank, wherein the temperature of the tail gas out of the crude demercuration condenser is 30-50 ℃; a lead-removing smelting recovery system for the crude evaporated mercury slag in the crude demercuration electrothermal rotary distillation furnace; adding the obtained crude mercury and a reducing agent into a fine demercuration electrothermal rotary distillation furnace, controlling the temperature in the fine demercuration electrothermal rotary distillation furnace to be 600-; and washing tail gas in the coarse demercuration condenser and the fine demercuration condenser by a filler leaching tower and then emptying. The invention has the characteristics of simple process, high mercury recovery rate, low cost, environmental protection and no secondary pollution.
Xushengming, in volume 2 of "nonferrous metallurgy (smelting section)", 1992, describes the recovery of mercury and selenium from mercury and selenium materials, studies the effective separation and recovery of mercury and selenium from acid sludge by using a method of adding calcium to fix selenium and removing mercury, and examines the influence of temperature, time, acidity and dosage on mercury removal effect when lime is used as mercury removal agent and a small amount of ammonium sulfide is added. The results show that: fully and uniformly mixing the selenium-mercury material and the lime powder according to the proportion of (weight ratio) 100: 55-60, granulating on a granulator of ∅ 1000, controlling the particle size to be 5-15 mm, drying the material particles until the moisture is less than or equal to 8%, controlling the hearth temperature to be about 700 ℃, controlling the temperature in the tank to be 520-560 ℃, maintaining a certain negative pressure in the tank, collecting mercury vapor in a condenser, and separating mercury from smoke dust collected in the condenser to obtain mercury soot according to the following ratio: mixing lime =100: 25-35, granulating, airing, and mixing into a raw material granule furnace, wherein the demercuration rate is 98.97%, and the selenium fixation rate of slag is 98.1%.
The prior art mainly focuses on the recovery of mercury, and relates to the fact that lead and selenium are few, and due to mutual influence among lead, selenium and silver, comprehensive recovery of lead, selenium and silver cannot be achieved, and waste of existing resources is still caused.
Disclosure of Invention
In order to overcome the problems in the prior art, the invention provides a method for comprehensively recovering selenium, mercury, lead and silver from acid sludge, which realizes the separation and comprehensive recovery of selenium, mercury, lead and silver in acid sludge by adopting carbonate conversion, dilute acid dissolution, sulfuric acid precipitation of lead, chlorination leaching of selenium and mercury enrichment slag, sulfur dioxide reduction and sulfide precipitation.
In order to realize the purpose, the invention is realized by the following technical scheme:
the method for comprehensively recovering selenium, mercury, lead and silver from acid sludge comprises the following steps:
(1) adding carbonate and acid mud to perform phase-transition reaction, controlling the addition amount of the carbonate, and filtering and washing after the reaction is finished to obtain a transition liquid and transition slag. Sodium carbonate is added to lead the acid mud to realize phase reconstruction, thereby facilitating the subsequent acid leaching.
(2) Adding diluted acid to selectively leach lead in the conversion slag, adding sodium chloride after leaching is finished, fully stirring, filtering and washing to obtain a lead-containing leachate and selenium-mercury-silver enriched slag respectively, and realizing separation of lead from selenium-mercury-silver;
(3) adding an oxidant and acid to chloridize and leach selenium-mercury enriched slag, and filtering and washing to obtain selenium-mercury leachate and silver-containing slag to realize selenium-mercury and silver;
(4) introducing sulfur dioxide into the selenium-mercury leachate for reduction to obtain selenium powder, and filtering and washing to obtain crude selenium and a mercury-containing solution;
(5) adding sulfuric acid into the lead-containing leachate to react to generate lead sulfate and dilute acid, filtering and washing to obtain dilute acid and pure lead sulfate, and returning the dilute acid to the step (2) for recycling;
(6) adding a vulcanizing agent into the mercury-containing solution for reaction, and filtering and washing to obtain mercury sulfide and a residual sulfide liquid; the mercury yield of the process is more than 99.5%, the lead is more than 95.0% and the selenium is more than 98.0%.
Further, the carbonate in the step (1) is sodium carbonate, ammonium carbonate or potassium carbonate, and the using amount of the carbonate is 0.2-1 time of the weight of the acid sludge.
Further, the washing in the step (1) is mechanical stirring washing or ultrasonic wave radiation washing. Ultrasonic wave is introduced for strengthening washing, so that residual sodium sulfate in the conversion slag can be effectively removed, and the lead recovery rate is improved.
Further, the diluted acid in the step (2) is nitric acid or hydrochloric acid.
Further, the oxidant in the step (3) is one of sodium chlorate and sodium hypochlorite; the acid is hydrochloric acid or sulfuric acid.
Further, the adding amount of the sulfuric acid in the step (5) is the same as the molar amount of the lead.
Further, in the step (6), the vulcanizing agent is one of sodium sulfide, hydrogen sulfide or ammonium sulfide.
The invention has the beneficial effects that:
according to the invention, sodium carbonate is added during acid leaching, so that the acid sludge realizes phase reconstruction, lead, selenium, mercury and silver enter the slag, and a foundation is laid for high-yield recovery of lead, mercury, selenium and silver in the subsequent acid leaching process.
The recovery of silver in the subsequent process is realized by adding sodium chloride after the early acid leaching is finished, and the added sodium chloride does not influence the normal leaching of lead; and ultrasonic wave is introduced in the subsequent working procedures to strengthen washing, so that residual sodium sulfate in the conversion slag is effectively removed, and the lead recovery rate is obviously improved.
The invention has high mercury yield, the dilute acid can be recycled, the cost is effectively reduced, and the output of the waste acid is low.
The separation efficiency of selenium, mercury, silver and lead elements in the acid sludge is high, the comprehensive recovery of all elements is realized, and the value of the acid sludge is improved.
The method has the advantages of full-wet treatment, low temperature, environmental friendliness, high yield of selenium, mercury and lead, mature related treatment equipment, easy engineering and good application prospect.
Drawings
FIG. 1 is a schematic process flow diagram of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, preferred embodiments of the present invention will be described in detail below to facilitate understanding of the skilled person.
Example 1
Mixing 1000g of acid mud and 360g of sodium carbonate, placing the mixture in a reactor for leaching, heating the mixture to 30 ℃, reacting for 3h at the rotating speed of 200rpm, stopping heating after leaching is finished, and filtering and mechanically stirring and washing to respectively obtain sodium sulfate leaching liquid and selenium-containing lead-mercury slag; concentrating and crystallizing the sulfate solution to obtain sulfate; leaching the selenium-containing lead-mercury silver slag and dilute nitric acid in a reactor, heating to 80 ℃, reacting for 2h at the rotating speed of 250rpm, stopping heating after leaching is finished, adding sodium chloride with the same molar weight as silver, fully stirring, filtering and washing to obtain lead leachate and selenium-mercury slag respectively; putting the lead solution and dilute sulfuric acid into a reactor for reaction to generate lead sulfate precipitate and dilute nitric acid, and returning the regenerated dilute nitric acid to continuously leach the lead slag; adding sodium chloride and hydrochloric acid to leach selenium mercury silver slag, heating to 70 ℃, reacting for 3 hours at the rotating speed of 250rpm, stopping heating after leaching is finished, and filtering and washing to obtain leachate and silver-containing slag respectively; introducing sulfur dioxide into the leaching solution to reduce selenium, and filtering to obtain selenium powder and a mercury-containing solution; and adding sodium sulfide into the mercury-containing solution to react to obtain mercury sulfide. The analysis and detection show that the yield of mercury is 99.6%, the yield of lead is 96.1%, the yield of selenium is 98.2% and the yield of silver is 98.12%.
Example 2
Mixing 1000g of acid sludge and 360g of sodium carbonate, placing the mixture in a reactor for leaching, heating the mixture to 30 ℃, reacting for 3h at the rotating speed of 200rpm, stopping heating after leaching is finished, and filtering and washing the mixture by ultrasonic radiation to respectively obtain sodium sulfate leaching liquid and selenium-containing lead-mercury slag; concentrating and crystallizing the sulfate solution to obtain sulfate; placing the selenium-containing lead-mercury-silver slag and dilute nitric acid into a reactor for leaching, heating to 80 ℃, reacting for 2h at the rotating speed of 250rpm, stopping heating after leaching is finished, adding sodium chloride, stirring fully, filtering and washing to obtain lead leachate and selenium-mercury slag respectively; putting the lead solution and dilute sulfuric acid into a reactor for reaction to generate lead sulfate precipitate and dilute nitric acid, and returning the regenerated dilute nitric acid to continuously leach the lead slag; adding sodium hypochlorite and hydrochloric acid to leach selenium-mercury-silver residues, heating to 90 ℃, reacting for 3 hours at the rotating speed of 250rpm, stopping heating after leaching is finished, and filtering and washing to obtain leachate and silver-containing residues respectively; adding sulfur dioxide, introducing into the leachate to reduce selenium, and filtering to obtain selenium powder and a mercury-containing solution; and adding sodium sulfide into the mercury-containing solution to react to obtain mercury sulfide. The mercury yield of the process is 99.6%, the lead yield is 98.4%, the selenium yield is 98.5%, and the silver yield is 98.55%. Ultrasonic wave is added for washing, and compared with the example 1, the lead yield is improved by 2.3 percent.
Example 3
Mixing 1000g of acid sludge and 340g of ammonium carbonate, placing the mixture in a reactor for leaching, heating the mixture to 30 ℃, reacting for 3 hours at the rotating speed of 200rpm, stopping heating after leaching is finished, and filtering and mechanically stirring and washing to respectively obtain ammonium sulfate leachate and selenium-containing lead-mercury slag; concentrating and crystallizing the ammonium sulfate solution to obtain ammonium sulfate; leaching selenium-containing lead-mercury slag and dilute nitric acid in a reactor, heating to 80 ℃, reacting for 2h at the rotating speed of 250rpm, stopping heating after leaching is finished, and filtering and washing to obtain lead leachate and selenium-mercury slag respectively; putting the lead solution and dilute sulfuric acid into a reactor for reaction to generate lead sulfate precipitate and dilute nitric acid, and returning the regenerated dilute nitric acid to continuously leach the lead slag; adding sodium hypochlorite and sulfuric acid to leach selenium, mercury and silver residues, heating to 80 ℃, reacting for 3 hours at the rotating speed of 250rpm, stopping heating after leaching is finished, and filtering and washing to obtain leachate and silver-containing residues respectively; adding sulfur dioxide, introducing into the leachate to reduce selenium, and filtering to obtain selenium powder and a mercury-containing solution; and introducing hydrogen sulfide into the mercury-containing solution to react to obtain the mercury sulfide. The mercury yield of the process was 99.6%, the lead yield 96.9%, the selenium yield 98.3%, and the silver yield 98.71%.
Example 4
Mixing 1000g of acid mud and 380g of potassium carbonate, placing the mixture in a reactor for leaching, heating the mixture to 30 ℃, reacting for 3 hours at the rotating speed of 200rpm, stopping heating after leaching is finished, and filtering and mechanically stirring and washing to respectively obtain potassium sulfate leachate and selenium-containing lead-mercury slag; concentrating and crystallizing the potassium sulfate solution to obtain potassium sulfate; leaching selenium-containing lead-mercury residues and dilute hydrochloric acid in a reactor, heating to 80 ℃, reacting for 2h at the rotating speed of 250rpm, stopping heating after leaching is finished, and filtering and washing to obtain lead leachate and selenium-mercury residues respectively; putting the lead solution and dilute sulfuric acid into a reactor for reaction to generate lead sulfate precipitate and dilute hydrochloric acid, and returning the regenerated dilute hydrochloric acid to continuously leach the lead slag; adding sodium chloride and sulfuric acid to leach selenium, mercury and silver residues, heating to 60 ℃, reacting for 2 hours at a rotating speed of 250rpm, stopping heating after leaching is finished, and filtering and washing to obtain leachate and silver-containing residues respectively; adding sulfur dioxide, introducing into the leachate to reduce selenium, and filtering to obtain selenium powder and a mercury-containing solution; and introducing hydrogen sulfide into the mercury-containing solution to react to obtain the mercury sulfide. The mercury yield of the process is 99.7%, the lead yield is 96.5%, the selenium yield is 98.4%, and the silver yield is 97.85%.
Comparative example 5
Mixing 1000g of acid sludge and 400g of sodium carbonate, placing the mixture in a reactor for leaching, heating the mixture to 30 ℃, reacting for 3h at the rotating speed of 200rpm, stopping heating after leaching is finished, and filtering and washing the mixture by ultrasonic radiation to respectively obtain sodium sulfate leaching liquid and selenium-containing lead-mercury slag; concentrating and crystallizing the sodium sulfate solution to obtain sodium sulfate; leaching selenium-containing lead-mercury slag and dilute nitric acid in a reactor, heating to 80 ℃, reacting for 2 hours at a rotating speed of 250rpm, stopping heating after leaching is finished, adding sodium chloride, stirring fully, filtering and washing to obtain lead leachate and selenium-mercury-silver slag respectively; putting the lead solution and dilute sulfuric acid into a reactor for reaction to generate lead sulfate precipitate and dilute nitric acid, and returning the regenerated dilute hydrochloric acid to continuously leach the lead slag; adding sodium chloride and sulfuric acid to leach selenium, mercury and silver residues, heating to 50 ℃, reacting for 2 hours at a rotating speed of 250rpm, stopping heating after leaching is finished, and filtering and washing to obtain leachate and silver-containing residues respectively; adding sulfur dioxide, introducing into the leachate to reduce selenium, and filtering to obtain selenium powder and a mercury-containing solution; and adding ammonium sulfide into the mercury-containing solution to react to obtain mercury sulfide. The mercury yield of the process is 99.6%, the lead yield is 99.1%, the selenium yield is 98.2%, and the silver yield is 98.04%.
Comparative example 1
Mixing 1000g of acid sludge and 400g of sodium carbonate, placing the mixture in a reactor for leaching, heating the mixture to 30 ℃, reacting for 3h at the rotating speed of 200rpm, stopping heating after leaching is finished, and filtering and washing the mixture by ultrasonic radiation to respectively obtain sodium sulfate leaching liquid and selenium-containing lead-mercury slag; concentrating and crystallizing the sodium sulfate solution to obtain sodium sulfate; leaching selenium-containing lead-mercury slag and dilute nitric acid in a reactor, heating to 80 ℃, reacting for 2h at the rotating speed of 250rpm, stopping heating after leaching is finished, and filtering and washing to obtain lead leachate and selenium-mercury slag respectively; putting the lead solution and dilute sulfuric acid into a reactor for reaction to generate lead sulfate precipitate and dilute nitric acid, and returning the regenerated dilute hydrochloric acid to continuously leach the lead slag; adding ozone and sulfuric acid to leach selenium-mercury residues, heating to 50 ℃, reacting for 2 hours at a rotating speed of 250rpm, stopping heating after leaching is finished, and filtering and washing to obtain leachate and leaching residues respectively; adding sulfur dioxide, introducing into the leachate to reduce selenium, and filtering to obtain selenium powder and a mercury-containing solution; and adding ammonium sulfide into the mercury-containing solution to react to obtain mercury sulfide. The mercury yield of the process is 94.6%, 89.1% lead and 98.2% selenium.
Finally, it is noted that the above-mentioned preferred embodiments illustrate rather than limit the invention, and that, although the invention has been described in detail with reference to the above-mentioned preferred embodiments, it will be understood by those skilled in the art that various changes in form and detail may be made therein without departing from the scope of the invention as defined by the appended claims.
Claims (7)
1. A method for comprehensively recovering selenium, mercury, lead and silver from acid sludge is characterized by comprising the following steps: the method for comprehensively recovering selenium, mercury, lead and silver from acid sludge comprises the following steps:
(1) adding carbonate and acid sludge to perform phase-transition reaction, controlling the addition amount of the carbonate, and filtering and washing after the reaction is finished to obtain a transition liquid and transition slag;
(2) adding diluted acid to selectively leach lead in the conversion slag, adding sodium chloride after leaching is finished, fully stirring, filtering and washing to obtain a lead-containing leachate and selenium-mercury-silver enriched slag respectively, and realizing separation of lead from selenium-mercury-silver;
(3) adding an oxidant and acid to chloridize and leach selenium-mercury enriched slag, and filtering and washing to obtain selenium-mercury leachate and silver-containing slag to realize selenium-mercury and silver;
(4) introducing sulfur dioxide into the selenium-mercury leachate for reduction to obtain selenium powder, and filtering and washing to obtain crude selenium and a mercury-containing solution;
(5) adding sulfuric acid into the lead-containing leachate to react to generate lead sulfate and dilute acid, filtering and washing to obtain dilute acid and pure lead sulfate, and returning the dilute acid to the step (2) for recycling;
(6) adding a vulcanizing agent into the mercury-containing solution for reaction, and filtering and washing to obtain mercury sulfide and a residual sulfide liquid; the mercury yield of the process is more than 99.5%, the lead is more than 95.0% and the selenium is more than 98.0%.
2. The method for comprehensively recovering selenium, mercury, lead and silver from acid sludge according to claim 1, characterized in that: the carbonate in the step (1) is sodium carbonate, ammonium carbonate or potassium carbonate, and the using amount of the carbonate is 0.2-1 time of the weight of the acid sludge.
3. The method for comprehensively recovering selenium, mercury, lead and silver from acid sludge according to claim 1, characterized in that: the washing in the step (1) is mechanical stirring washing or ultrasonic radiation washing.
4. The method for comprehensively recovering selenium, mercury, lead and silver from acid sludge according to claim 1, characterized in that: the dilute acid in the step (2) is nitric acid or hydrochloric acid.
5. The method for comprehensively recovering selenium, mercury, lead and silver from acid sludge according to claim 1, characterized in that: the oxidant in the step (3) is one of sodium chlorate and sodium hypochlorite; the acid is hydrochloric acid or sulfuric acid.
6. The method for comprehensively recovering selenium, mercury, lead and silver from acid sludge according to claim 1, characterized in that: the adding amount of the sulfuric acid in the step (5) is the same as the molar weight of the lead.
7. The method for comprehensively recovering selenium, mercury, lead and silver from acid sludge according to claim 1, characterized in that: and (4) the vulcanizing agent in the step (6) is one of sodium sulfide, hydrogen sulfide or ammonium sulfide.
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| CN115341097A (en) * | 2022-01-30 | 2022-11-15 | 昆明理工大学 | Method for treating high-arsenic low-mercury selenic acid sludge through hydrometallurgy |
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