CN110724824B - Method for extracting valuable heavy metals from jarosite slag through ferrous catalytic conversion - Google Patents

Method for extracting valuable heavy metals from jarosite slag through ferrous catalytic conversion Download PDF

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CN110724824B
CN110724824B CN201911040388.7A CN201911040388A CN110724824B CN 110724824 B CN110724824 B CN 110724824B CN 201911040388 A CN201911040388 A CN 201911040388A CN 110724824 B CN110724824 B CN 110724824B
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slag
solid
catalytic conversion
heavy metals
ferrous
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CN110724824A (en
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颜旭
吴佳蕙
曾伟志
柴立元
史美清
魏杨金
彭俊
刘恢
彭宁
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Central South University
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • 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
    • C22B7/04—Working-up slag
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B13/00—Obtaining lead
    • C22B13/04—Obtaining lead by wet processes
    • C22B13/045—Recovery from waste materials
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B15/00—Obtaining copper
    • C22B15/0063—Hydrometallurgy
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B19/00—Obtaining zinc or zinc oxide
    • C22B19/20—Obtaining zinc otherwise than by distilling
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B19/00—Obtaining zinc or zinc oxide
    • C22B19/30—Obtaining zinc or zinc oxide from metallic residues or scraps
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • 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
    • C22B7/006—Wet processes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Abstract

The invention discloses a method for extracting valuable heavy metals from jarosite slag by ferrous catalytic conversion, which comprises the following steps: 1) and (3) ferrous iron catalytic conversion: mixing iron vitriol slag to be treated with Fe2+Mixing the solutions, adjusting the pH of a reaction system to 6-8 by using a pH regulator, reacting under an anaerobic condition, and carrying out solid-liquid separation to obtain converted solid jarosite slag; 2) acid extraction: mixing the converted solid jarosite slag obtained in the step 1) with acid for reaction, and carrying out solid-liquid separation to obtain supernatant and treated solid jarosite slag. The method provided by the invention can greatly improve the extraction of heavy metals in the jarosite slag, and has remarkable effect; the slag amount of the ferrous iron catalytic conversion method is small, no new impurity is introduced, and the method has the advantages of cleanness, low energy consumption and excellent application prospect.

Description

Method for extracting valuable heavy metals from jarosite slag through ferrous catalytic conversion
Technical Field
The invention relates to the field of hazardous waste recycling treatment, and in particular relates to a method for extracting valuable heavy metals from jarosite slag through ferrous catalytic conversion.
Background
The iron vitriol slag is a purification slag formed in the zinc smelting process, the main component of the iron vitriol slag is the yellow iron vitriol formed in the iron precipitation process, and the iron vitriol slag has the characteristics of high water content, low iron content, large slag amount, strong acidity, high sulfur and heavy metal ion content, poor stability and the like. Wherein, valuable or harmful heavy metal elements such as zinc, cadmium, copper, silver, arsenic and the like can coexist with the jarosite slag in various forms such as adsorption, embedding or mixed crystal and the like. Because of the structural characteristics of jarosite, the heavy metals are easy to dissolve out in the process of stockpiling or landfill and pose a threat to the environment, and according to the national hazardous waste entry published in 2016, 3, 30, the jarosite slag belongs to non-ferrous metal smelting waste, the hazardous waste code 321-005-48, and the hazardous characteristic is toxicity.
At present, the treatment method of the iron vitriol slag generally comprises the step of carrying out acid washing after iron precipitation to wash out heavy metals in a dissolution state, an adsorption state and other weak combination states. However, since a large amount of heavy metals coexist with the jarosite slag in ways of embedding, mixed crystallization and the like, extraction by simple acid washing is difficult, and the efficiency of extracting the heavy metals is not high. Although the wet method, the pyrogenic method and the pyrometallurgical-wet method combined method are adopted to treat the jarosite slag so as to further recover the heavy metals. CN107324358A A method for decomposing iron vitriol slag at low temperature and respectively recovering resources; CN 107254585A is a method for recovering zinc, indium, iron and gallium from jarosite slag; the experimental research on the microwave-assisted leaching of zinc in jarosite slag [ J ] hydrometallurgy, 2017,36(3): 188-. Therefore, at present, a clean and green method for promoting the extraction of metals in the iron vitriol slag is urgently needed to be researched, so that the pollution to the environment is reduced, the metal resources can be recycled, and the method has a practical application value.
Disclosure of Invention
In view of the above, the invention aims to provide a method for extracting valuable heavy metals from iron alum slag through ferrous catalytic conversion, which solves the problem of low extraction efficiency of valuable metals from iron alum slag in the prior art, has low medicament consumption and low energy consumption, effectively reduces the treatment cost, and has high practical application value.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a method for extracting valuable heavy metals from jarosite slag through ferrous catalytic conversion comprises the following steps:
1) and (3) ferrous iron catalytic conversion: mixing iron vitriol slag to be treated with Fe2+Is mixed with the solution of (1), pHAdjusting the pH value of the reaction system to 6-8 by using an adjusting agent, reacting under an anaerobic condition, and carrying out solid-liquid separation to obtain converted solid jarosite slag;
2) acid extraction: mixing the converted solid jarosite slag obtained in the step 1) with acid for reaction, and carrying out solid-liquid separation to obtain supernatant and treated solid jarosite slag.
Preferably, the pH regulator comprises one or a combination of NaOH and KOH.
Preferably, said Fe2+The concentration in the reaction system of step 1) is 5 mM-50 mM.
Preferably, in the reaction system of step 1), the solid-to-liquid ratio is 1: 1-20 g/L.
Preferably, in the step 1), the reaction time is 1-7 days.
Preferably, in step 2), the acid includes one or more of sulfuric acid, nitric acid, acetic acid and hydrochloric acid, but is not limited to the acids listed herein, as long as the reaction system of step 2) can be adjusted to a lower pH.
Preferably, in the reaction system in the step 2), the pH value is 1-3; the solid-liquid ratio is 1: 1 to 50 g/L.
Preferably, in the step 2), the reaction time is 1-24 hours.
Preferably, the jarosite slag to be treated is jarosite slag obtained by wet zinc smelting leaching, iron precipitation and acid washing processes.
Preferably, the valuable heavy metal comprises one or more of copper, zinc, lead, arsenic, indium, manganese, aluminum and bismuth, and can be determined according to the actual composition of the jarosite slag.
The invention has the beneficial effects that:
(1) according to the method provided by the invention, the iron vitriol slag is placed in a ferrous solution, the pH is adjusted to 6-8 at the same time, and catalytic conversion is carried out under an oxygen-free condition, so that various valuable or harmful heavy metal elements coexisting with the iron vitriol slag in various forms such as adsorption, embedding or mixed crystal are internally migrated to the surface of the iron vitriol slag, and thus the extraction of valuable heavy metals in the iron vitriol slag can be greatly improved, and the effect is remarkable; the reduction of the iron vitriol slag is promoted, and the iron resource in the subsequent treatment process of the iron vitriol slag is favorably recycled.
(2) The ferrous solution is used as a catalyst, no new impurity is introduced, and secondary pollution is avoided.
(3) The catalytic conversion reaction is carried out under the neutral condition at normal temperature, so that the energy consumption and the medicament dosage are saved, the treatment cost is low, and the method has higher practical application value.
Detailed Description
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein, but rather should be construed as broadly as the present invention is capable of modification in various respects, all without departing from the spirit and scope of the present invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
In the examples, the used iron alum slag is obtained by leaching, iron precipitation and acid washing processes of zinc hydrometallurgy, XRF detection is performed on the iron alum slag, and the element content in the iron alum slag is analyzed, as shown in table 1 below, it can be known from table 1 that heavy metals in the iron alum slag are mainly Zn, Pb and Cu, and thus the three metals are target elements extracted in the examples.
TABLE 1 elemental contents of iron vitriol slag
Figure BDA0002252669340000041
Comparative examples
In this embodiment, the release of heavy metals in the acid extraction process of iron vitriol slag without ferrous catalytic conversion is studied, and the specific acid extraction conditions are as follows: directly adding acetic acid into the acid-washed jarosite slag, controlling the pH of a reaction system to be 3, and controlling the solid-liquid ratio to be 1 g: 25L, and the reaction time is 24 hours; after the reaction was completed, solid-liquid separation was performed, and the release amount of each heavy metal in the supernatant was measured as shown in table 2 below.
TABLE 2 Release concentration of heavy metals in iron vitriol slag without ferrous catalytic conversion
Figure BDA0002252669340000042
Example 1
This example compares the effect of different ferrous concentrations on the release of heavy metals during the acid extraction process during the ferrous catalytic conversion of iron vitriol slag
Mixing the acid-washed iron vitriol slag with Fe with different concentrations2+Mixing the solutions, adding MOPS buffer solution and NaOH to adjust and control the pH of the reaction system to be 7, the solid-to-liquid ratio to be 20g/L and Fe2+The concentration of (A) is 10mM and 30mM respectively; discharging oxygen of the reaction system, sealing, carrying out 7-day conversion reaction, and carrying out solid-liquid separation after the reaction; adjusting the pH of the rest solid to 3 with acetic acid to extract heavy metals, controlling the solid-liquid ratio to be 25g/L, and reacting for 24 hours. After the reaction is completed, carrying out solid-liquid separation to obtain supernatant and treated solid jarosite slag; the concentrations of heavy metals in the supernatant are shown in Table 3, and a comparison with Table 2 shows that 10mM Fe was used2+After catalytic conversion, the extraction rates of lead and copper can be respectively increased by 16 times and 6 times, and 30mM Fe is adopted2+After catalysis, the extraction rates of lead and copper can be respectively improved by 8 times and 4 times, and the effect is very obvious. The result shows that the addition of the ferrous iron is very beneficial to the extraction of heavy metals in the iron vitriol slag, and the effect is better under the condition of 10mM ferrous iron. After the conversion reaction is carried out by ferrous iron of 10mM and 30mM, the release amount of Zn in the iron vitriol slag in the acid extraction process is similar. This is probably due to the fact that Zn is present in the jarosite slag in the form of relatively stable zinc ferrite, which is difficult to extract.
TABLE 3 concentration of heavy metals released from iron vitriol slag after catalytic conversion with different ferrous iron concentrations
Figure BDA0002252669340000051
Example 2
This example is the effect of different conversion times on the release of heavy metals during the acid extraction process during the ferrous catalytic conversion of iron vitriol slag.
Adding Fe into the acid-washed iron vitriol slag2+Adding MOPS buffer solution and NaOH to adjust and control the pH of a reaction system to 7, wherein the solid-to-liquid ratio is 20g/L, and Fe2+Is 10 mM; namely making Fe2+The pH value of a reaction system formed by the solution, the MOPS buffer solution, the NaOH solution and the acid-washed jarosite slag is 7, the solid-to-liquid ratio is 20g/L, and Fe2+Is 10 mM; then, oxygen in the reaction system was discharged and sealed, and the conversion reaction was carried out for different periods of time (1 day, 3 days), followed by solid-liquid separation, and the remaining solid was adjusted to pH 3 with acetic acid to extract heavy metals so that the solid-liquid ratio was 25g/L and the reaction time was 24 hours. Table 4 shows the release of heavy metals during the acid extraction after 1 day of the ferrous catalytic conversion reaction and 3 days. Compared with the table 2, the extraction rates of lead and copper can be improved by 8 times and 4 times after 1 day of conversion, and the extraction rates of lead and copper can be improved by 10 times and 5 times after 3 days of conversion, so that the effect is very obvious, the addition of ferrous iron is very beneficial to the extraction of heavy metals in the jarosite slag, and the effect is better under the condition of 3 days of conversion.
TABLE 4 heavy metal release concentrations in iron vitriol slag after different conversion times
Figure BDA0002252669340000061
It should be noted that the above specific examples only express several embodiments of the present invention, and the description thereof is more specific and detailed, such as the reaction time in ferrous iron catalytic conversion, the pH value of the system, the solid-to-liquid ratio, and Fe2+The concentration of (c); the reaction time, the pH value of the system, the solid-to-liquid ratio, the pH adjusting agent and the like in the acid extraction step cannot be understood as limiting the scope of the present invention, and the present invention can be implemented in any manner according to the content of the present invention as long as sufficient conversion and sufficient mixing in the ferrous iron catalytic conversion and acid extraction processes can be ensured.
In conclusion, the method provided by the invention can greatly improve the extraction of valuable heavy metals in the jarosite slag, and has remarkable effect; the reduction of the jarosite slag is promoted, and the recycling of iron resources in the subsequent treatment process of the jarosite slag is facilitated; the ferrous solution is used as a catalyst, no new impurity is introduced, and secondary pollution is avoided; and the reaction is carried out under the neutral condition at normal temperature, so that the energy consumption and the medicament dosage are saved, the treatment cost is low, and the method has higher practical application value.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims (5)

1. A method for extracting valuable heavy metals from jarosite slag through catalytic conversion of ferrous iron is characterized by comprising the following steps:
1) and (3) ferrous iron catalytic conversion: mixing iron vitriol slag to be treated with Fe2+The solution of (A) is mixed according to the solid-to-liquid ratio of 1-20 g/L, and the Fe2+The concentration in the reaction system of the step 1) is 5 mM-50 mM; adjusting the pH value of the reaction system to 6-8 by using a pH regulator, reacting under an anaerobic condition, and carrying out solid-liquid separation to obtain converted solid jarosite slag; the iron vitriol slag to be treated is copper-lead-containing iron vitriol slag;
2) acid extraction: mixing the converted solid iron vitriol slag obtained in the step 1) with acid for reaction, wherein the pH value is 1-3, the solid-liquid ratio is 1-50 g/L, the reaction time is 1-24 hours, and performing solid-liquid separation to obtain a supernatant and the treated solid iron vitriol slag.
2. The method for extracting valuable heavy metals from jarosite slag through ferrous catalytic conversion according to claim 1, wherein the pH regulator comprises one or a combination of NaOH and KOH.
3. The method for extracting valuable heavy metals from jarosite slag through ferrous catalytic conversion according to claim 1, wherein the reaction time in the step 1) is 1-7 days.
4. The method for extracting valuable heavy metals from jarosite slag through ferrous catalytic conversion according to claim 1, wherein in the step 2), the acid comprises one or more of sulfuric acid, nitric acid, acetic acid and hydrochloric acid.
5. The method for extracting valuable heavy metals from jarosite slag through ferrous catalytic conversion according to claim 1, wherein the jarosite slag to be treated is jarosite slag obtained through zinc hydrometallurgy leaching, iron precipitation and acid washing processes.
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CN101407355B (en) * 2008-10-31 2010-09-29 东北大学 Method for comprehensively utilizing iron vitriol dreg of yellow sodium
CN102888515A (en) * 2012-10-12 2013-01-23 金川集团股份有限公司 Comprehensive utilization method of amarillite slag
CN105039712B (en) * 2015-08-14 2017-05-17 陕西理工学院 Technology for recycling valuable metal from jarosite slag
CN109607622A (en) * 2019-01-03 2019-04-12 昆明理工大学 A method of iron oxide red product is prepared using the heavy scum of zinc hydrometallurgy hematite process

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