CN111733329A - System and method for preparing metal arsenic from resource utilization of multiple arsenic residues - Google Patents
System and method for preparing metal arsenic from resource utilization of multiple arsenic residues Download PDFInfo
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- CN111733329A CN111733329A CN202010723436.9A CN202010723436A CN111733329A CN 111733329 A CN111733329 A CN 111733329A CN 202010723436 A CN202010723436 A CN 202010723436A CN 111733329 A CN111733329 A CN 111733329A
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- arsenic
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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
- C22B7/001—Dry processes
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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
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/02—Roasting processes
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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
- C22B19/00—Obtaining zinc or zinc oxide
- C22B19/30—Obtaining zinc or zinc oxide from metallic residues or scraps
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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
- C22B19/00—Obtaining zinc or zinc oxide
- C22B19/34—Obtaining zinc oxide
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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
- C22B30/00—Obtaining antimony, arsenic or bismuth
- C22B30/04—Obtaining arsenic
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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
- C22B5/00—General methods of reducing to metals
- C22B5/02—Dry methods smelting of sulfides or formation of mattes
- C22B5/10—Dry methods smelting of sulfides or formation of mattes by solid carbonaceous reducing agents
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- 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 system and a method for preparing metal arsenic from resource utilization of various arsenic slags, wherein the system comprises a volatilization furnace, a waste heat boiler, a cyclone dust collector, a reduction furnace, a condenser, a bag-type dust collector and a desulfurization device; the input end of the volatilization furnace is connected with a mixed arsenic slag hopper, a coke hopper and a biomass hopper; the input end of the waste heat boiler is connected with the flue gas output end of the volatilization furnace; the input end of the cyclone dust collector is connected with the output end of the waste heat boiler; the input end of the reducing furnace is connected with the output end of the cyclone dust collector; the input end of the desulfurization device is connected with the air outlet end of the bag-type dust remover, and the output end of the desulfurization device is connected with a chimney. The method can simultaneously treat various arsenic slag hazardous wastes, solve the problem of difficult treatment of small amount of arsenic slag, effectively recycle high-quality metal arsenic and zinc hypoxide, recycle valuable metals in arsenic-containing waste slag, and maximally improve the resource utilization rate.
Description
Technical Field
The invention relates to the technical field of comprehensive utilization of solid hazardous wastes, in particular to a system and a method for preparing metal arsenic from various arsenic slags by resource utilization.
Background
A large amount of arsenic-containing waste residues are generated in the metallurgical and chemical processes, particularly in Yunnan and Guangxi, and are not properly treated, so that great pressure is brought to enterprises and environmental protection. The arsenic-containing waste residue generally belongs to HW24 or HW48 dangerous waste, and the long-time stacking can pollute the atmosphere and underground water, thereby causing damage to human bodies.
In order to reduce the harm of arsenic, the prior art for treating arsenic-containing waste residues mainly comprises three treatment processes of solidification, fire method and wet method, wherein the fixed-line method mainly aims at the arsenic residues which have low arsenic content and are difficult to recycle, and the arsenic residues are subjected to harmless treatment. The fire method and the wet method mainly aim at recycling arsenic slag with large amount and low arsenic content and taste to extract white arsenic. But at present, various arsenic-containing waste residues with small production amount are difficult to treat simultaneously, so that production enterprises are tricky, and great pressure is brought to environmental protection.
Chinese patent CN 103755169a discloses a method for treating arsenic-containing waste residue by a rotary cement kiln, which is mainly to mix arsenic-containing waste residue with cement raw meal and prepare cement clinker by using the rotary cement kiln. The method is not suitable for treating the arsenic-containing waste residue with high arsenic content, only carries out solidification treatment, and does not recycle arsenic and valuable metals, thereby causing resource waste.
Chinese patent CN 106222398A discloses a method for deep arsenic removal by roasting arsenic-containing materials, which is mainly characterized in that the arsenic-containing materials, a chlorinating agent and water are mixed and granulated, then the mixture is sent into a roasting furnace for roasting, and arsenic is removed in the form of arsenic chloride, thereby the arsenic-containing materials are subjected to deep arsenic removal. However, arsenic chloride is still present in the flue dust after removal, and is not finally disposed of or utilized, or causes environmental pollution.
Disclosure of Invention
In view of the above, the present invention is directed to the defects of the prior art, and the main objective of the present invention is to provide a system and a method for preparing metallic arsenic from various arsenic-containing waste residues, which can treat various arsenic-containing waste residues and extract metallic arsenic by resource utilization.
In order to achieve the purpose, the invention adopts the following technical scheme:
a system for preparing metal arsenic from various arsenic slags by resource utilization comprises a volatilization furnace, a waste heat boiler, a cyclone dust collector, a reduction furnace, a condenser, a bag-type dust collector and a desulfurization device; the input end of the volatilization furnace is connected with a mixed arsenic slag hopper, a coke hopper and a biomass hopper; the input end of the waste heat boiler is connected with the flue gas output end of the volatilization furnace; the input end of the cyclone dust collector is connected with the output end of the waste heat boiler; the input end of the reducing furnace is connected with the output end of the cyclone dust collector; the input end of the condenser is connected with the output end of the reducing furnace; the input end of the bag-type dust collector is connected with the smoke output end of the condenser; the input end of the desulfurization device is connected with the air outlet end of the bag-type dust remover, and the output end of the desulfurization device is connected with a chimney.
As a preferable scheme, the volatilization furnace is a rotary kiln or an oxygen-enriched side-blown furnace, and the temperature in the furnace is 1100-1400 ℃.
Preferably, the reduction furnace is an electric heating furnace with coke in it, and the coke is heated to 700 ℃ during operation.
A method for preparing metallic arsenic from resource utilization of various arsenic residues comprises the following steps:
(1) respectively putting the mixed arsenic slag, the coke and the biomass into a mixed arsenic slag hopper, a coke hopper and a biomass hopper according to a proportion and then mixing to form a mixed material;
(2) the mixed material is sent into a volatilization furnace for high-temperature roasting volatilization;
(3) outputting the arsenic-containing flue gas from the volatilization furnace, feeding the arsenic-containing flue gas into a waste heat boiler, and cooling the arsenic-containing flue gas to 750-;
(4) the flue gas is output from the waste heat boiler and then enters a cyclone dust collector, and primary dust removal is carried out through the cyclone dust collector;
(5) the arsenic-containing flue gas after primary dust removal is output from the cyclone dust collector and then is sent into a reduction furnace for reduction, and arsenic trioxide is reduced into metal arsenic steam;
(6) the flue gas containing the metal arsenic is output from the reduction furnace and enters a condenser, the flue gas containing the metal arsenic is condensed to 100-200 ℃, and the metal arsenic is condensed and collected;
(7) the arsenic-removed flue gas is output from the condenser and enters a bag-type dust collector, and secondary zinc oxide is collected by the bag-type dust collector;
(8) the arsenic-removed flue gas is output from the bag-type dust collector and enters a desulfurization device, and is discharged from a chimney after being purified by the desulfurization device.
As a preferable scheme, the mixed arsenic slag comprises a plurality of arsenic slags, namely arsenic-containing smoke dust, neutralized arsenic slag, arsenic sulfide slag and arsenic alkali slag.
As a preferable scheme, the ratio of the mixed arsenic slag to the coke to the biomass fuel is 27:1: 5.
As a preferable scheme, the biomass is one or more of rice hulls, straws or wood chips.
As a preferable scheme, after the arsenic-removed flue gas is cooled by the bag-type dust collector, if the zinc content in the arsenic slag is high, the smoke dust containing secondary zinc oxide is directly collected, and if the zinc content in the arsenic slag is low, the smoke dust is sent to the volatilization furnace again for enrichment smelting.
Compared with the prior art, the invention has obvious advantages and beneficial effects, and specifically, the technical scheme includes that:
by adopting the system and the method, various arsenic residues can be treated together, the problem that a small amount of arsenic residues are difficult to treat is solved, and the environmental pressure is reduced; the roasted arsenic-containing flue gas is dedusted by the cyclone deduster, the dust content in the dedusted flue gas is reduced, the subsequently obtained metal arsenic and secondary zinc oxide have high taste, the subsequent flue gas purification pressure is reduced, and the dust emission concentration is reduced; the arsenic-containing flue gas is cooled and then directly enters a reduction furnace for reduction, and the arsenic trioxide is directly reduced into metallic arsenic, so that the energy is saved, and meanwhile, the metallic arsenic with higher added value is obtained without secondary refining; in addition, the bag-type dust collector can collect secondary zinc oxide, and valuable metals in arsenic-containing waste residues are recycled, so that the resource utilization rate is improved to the maximum extent.
To more clearly illustrate the structural features and effects of the present invention, the present invention will be described in detail below with reference to the accompanying drawings and specific embodiments.
Drawings
FIG. 1 is a schematic flow chart of a preferred embodiment of the present invention;
FIG. 2 is a system diagram of the preferred embodiment of the present invention.
The attached drawings indicate the following:
11. volatilization furnace 12 and waste heat boiler
13. Cyclone dust collector 14 and reduction furnace
15. Condenser 16 and bag-type dust collector
17. Desulphurization unit 18, chimney
21. Mixed arsenic slag hopper 22 and coke hopper
23. A biomass hopper.
Detailed Description
Referring to fig. 2, a specific structure of a system for producing metallic arsenic from various arsenic slags by resource utilization according to a preferred embodiment of the present invention is shown, which includes a volatilization furnace 11, a waste heat boiler 12, a cyclone dust collector 13, a reduction furnace 14, a condenser 15, a bag-type dust collector 16 and a desulfurization device 17.
The input end of the volatilization furnace 11 is connected with a mixed arsenic slag hopper 21, a coke hopper 22 and a biomass hopper 23; in this embodiment, the volatilization furnace 11 is a rotary kiln or an oxygen-enriched side-blown furnace, and the temperature in the furnace is 1100-. The input end of the waste heat boiler 12 is connected with the flue gas output end of the volatilization furnace 11. The input end of the cyclone dust collector 13 is connected with the output end of the waste heat boiler 12. The input end of the reducing furnace 14 is connected with the output end of the cyclone dust collector 13; the reduction furnace 14 is an electric heating furnace with coke in it, and heats the coke to 700 ℃ during operation. The input end of the condenser 15 is connected to the output end of the reduction furnace 14. The input end of the bag-type dust collector 16 is connected with the flue gas output end of the condenser 15. The input end of the desulfurization device 17 is connected with the air outlet end of the bag-type dust collector 16, and the output end of the desulfurization device 17 is connected with a chimney 18.
The invention also discloses a method for preparing metallic arsenic from the resource utilization of various arsenic slags, and the system for preparing the metallic arsenic from the resource utilization of various arsenic slags comprises the following steps:
(1) the mixed arsenic slag, the coke and the biomass are respectively put into the mixed arsenic slag hopper 21, the coke hopper 22 and the biomass hopper 23 according to the proportion and then mixed to form a mixed material. In this embodiment, the mixed arsenic slag includes a plurality of arsenic slags, which are arsenic-containing smoke dust, neutralized arsenic slag, arsenic sulfide slag, arsenic alkali slag, and the like, the collected arsenic-containing slags are mixed, the arsenic-containing slags are mixed until the arsenic content is more than 8%, the biomass is one or more of rice hulls, straws or wood chips, biomass with high heat value and less impurities is preferably selected as fuel according to different mixing ratios of the arsenic-containing slags and local biomass raw material resources, and the mixing ratio of the mixed arsenic slag, coke and biomass fuel is 27:1: 5.
(2) The mixed material is sent into a volatilization furnace 11 for high-temperature roasting volatilization, the mixed material is smelted and volatilized between 1200 ℃ and 1300 ℃ in the furnace, so that arsenic and zinc in the arsenic-containing waste residue are subjected to reduction oxidation reaction, the arsenic enters the flue gas in the form of arsenic trioxide steam, the zinc enters the flue gas in the form of zinc hypoxide, the arsenic content in the arsenic-containing waste residue is less than 1%, and the arsenic and the zinc in the arsenic-containing waste residue are recovered.
(3) The arsenic-containing flue gas is output from the volatilization furnace 11 and enters the waste heat boiler 12, the temperature of the flue gas is reduced to 750-fold-by-800 ℃ through the waste heat boiler 12, and the waste heat is utilized, so that the flue gas can enter the cyclone dust collector 13 to normally operate, and meanwhile, the flue gas can normally carry out reduction reaction at the temperature.
(4) The flue gas is output from the waste heat boiler 12 and then enters the cyclone dust collector 13, and primary dust removal is carried out through the cyclone dust collector 13, and the step is to obtain high-grade metal arsenic and zinc hypoxide products.
(5) The arsenic-containing flue gas after preliminary dust removal is output from the cyclone dust collector 13 and then sent into the reduction furnace 14 for reduction, arsenic trioxide is reduced into metal arsenic steam, the reduction furnace 14 is an electrothermal reduction furnace, coke is heated to 700 ℃ in the reduction furnace 14, and reduction reaction is carried out on the arsenic trioxide in the flue gas and the coke to form the metal arsenic steam.
(6) The flue gas containing the metal arsenic is output from the reduction furnace 14 and enters a condenser 15, the flue gas containing the metal arsenic is condensed to 100-200 ℃, the metal arsenic is condensed and collected, and the grade of the recovered metal arsenic is more than 95%.
(7) The arsenic-removed flue gas is output from the condenser 15 and enters the bag-type dust collector 16, and secondary zinc oxide is collected by the bag-type dust collector 16. After the arsenic-removed flue gas is cooled by the bag-type dust collector, if the zinc content in the arsenic slag is high and the secondary zinc oxide content in the collected zinc-containing smoke dust is more than 60%, the smoke dust containing the secondary zinc oxide is directly collected, and if the zinc content in the arsenic slag is low, the smoke dust is sent to the volatilization furnace 11 again for enrichment smelting.
(8) The arsenic-removed flue gas is output from the bag-type dust collector 16 and enters the desulfurizer 17, and is purified by the desulfurizer 17 and then discharged from the chimney 18.
The design of the invention is characterized in that: by adopting the system and the method, various arsenic residues can be treated together, the problem that a small amount of arsenic residues are difficult to treat is solved, and the environmental pressure is reduced; the roasted arsenic-containing flue gas is dedusted by the cyclone deduster, the dust content in the dedusted flue gas is reduced, the subsequently obtained metal arsenic and secondary zinc oxide have high taste, the subsequent flue gas purification pressure is reduced, and the dust emission concentration is reduced; the arsenic-containing flue gas is cooled and then directly enters a reduction furnace for reduction, and the arsenic trioxide is directly reduced into metallic arsenic, so that the energy is saved, and meanwhile, the metallic arsenic with higher added value is obtained without secondary refining; in addition, the bag-type dust collector can collect secondary zinc oxide, and valuable metals in arsenic-containing waste residues are recycled, so that the resource utilization rate is improved to the maximum extent.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the technical scope of the present invention, so that any minor modifications, equivalent changes and modifications made to the above embodiment according to the technical spirit of the present invention are within the technical scope of the present invention.
Claims (8)
1. A system for preparing metallic arsenic from resource utilization of various arsenic slags is characterized in that: comprises a volatilization furnace, a waste heat boiler, a cyclone dust collector, a reduction furnace, a condenser, a bag-type dust collector and a desulfurization device; the input end of the volatilization furnace is connected with a mixed arsenic slag hopper, a coke hopper and a biomass hopper; the input end of the waste heat boiler is connected with the flue gas output end of the volatilization furnace; the input end of the cyclone dust collector is connected with the output end of the waste heat boiler; the input end of the reducing furnace is connected with the output end of the cyclone dust collector; the input end of the condenser is connected with the output end of the reducing furnace; the input end of the bag-type dust collector is connected with the smoke output end of the condenser; the input end of the desulfurization device is connected with the air outlet end of the bag-type dust remover, and the output end of the desulfurization device is connected with a chimney.
2. The system for preparing metallic arsenic from resource utilization of various arsenic slags as claimed in claim 1, wherein: the volatilization furnace is a rotary kiln or an oxygen-enriched side-blown furnace, and the temperature in the furnace is 1100-1400 ℃.
3. The system for preparing metallic arsenic from resource utilization of various arsenic slags as claimed in claim 1, wherein: the reducing furnace is an electric heating furnace with coke in the furnace, and the coke is heated to 700 ℃ during operation.
4. The method for preparing metallic arsenic from the resource utilization of various arsenic residues is characterized in that the system for preparing the metallic arsenic from the resource utilization of various arsenic residues, which is disclosed by any one of claims 1 to 3, comprises the following steps:
(1) respectively putting the mixed arsenic slag, the coke and the biomass into a mixed arsenic slag hopper, a coke hopper and a biomass hopper according to a proportion and then mixing to form a mixed material;
(2) the mixed material is sent into a volatilization furnace for high-temperature roasting volatilization;
(3) outputting the arsenic-containing flue gas from the volatilization furnace, feeding the arsenic-containing flue gas into a waste heat boiler, and cooling the arsenic-containing flue gas to 750-;
(4) the flue gas is output from the waste heat boiler and then enters a cyclone dust collector, and primary dust removal is carried out through the cyclone dust collector;
(5) the arsenic-containing flue gas after primary dust removal is output from the cyclone dust collector and then is sent into a reduction furnace for reduction, and arsenic trioxide is reduced into metal arsenic steam;
(6) the flue gas containing the metal arsenic is output from the reduction furnace and enters a condenser, the flue gas containing the metal arsenic is condensed to 100-200 ℃, and the metal arsenic is condensed and collected;
(7) the arsenic-removed flue gas is output from the condenser and enters a bag-type dust collector, and secondary zinc oxide is collected by the bag-type dust collector;
(8) the arsenic-removed flue gas is output from the bag-type dust collector and enters a desulfurization device, and is discharged from a chimney after being purified by the desulfurization device.
5. The method for preparing metallic arsenic from resource utilization of various arsenic slags as claimed in claim 4, wherein the method comprises the following steps: the mixed arsenic slag comprises a plurality of arsenic slags, namely arsenic-containing smoke dust, neutralized arsenic slag, arsenic sulfide slag and arsenic alkali slag.
6. The method for preparing metallic arsenic from resource utilization of various arsenic slags as claimed in claim 4, wherein the method comprises the following steps: the ratio of the mixed arsenic slag to the coke to the biomass fuel is 27:1: 5.
7. The method for preparing metallic arsenic from resource utilization of various arsenic slags as claimed in claim 4, wherein the method comprises the following steps: the biomass is one or more of rice hulls, straws or sawdust.
8. The method for preparing metallic arsenic from resource utilization of various arsenic slags as claimed in claim 4, wherein the method comprises the following steps: after the arsenic-removed flue gas is cooled by the bag-type dust collector, if the zinc content in the arsenic slag is high, the smoke dust containing secondary zinc oxide is directly collected, and if the zinc content in the arsenic slag is low, the smoke dust is sent into the volatilization furnace again for enrichment smelting.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113981247A (en) * | 2021-11-16 | 2022-01-28 | 湖南中大资珑科技有限公司 | Arsenic removal system for arsenic-containing material |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113981247A (en) * | 2021-11-16 | 2022-01-28 | 湖南中大资珑科技有限公司 | Arsenic removal system for arsenic-containing material |
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