CN113528846A - Treatment method for resource utilization of arsenic-containing waste residues - Google Patents
Treatment method for resource utilization of arsenic-containing waste residues Download PDFInfo
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- CN113528846A CN113528846A CN202110676560.9A CN202110676560A CN113528846A CN 113528846 A CN113528846 A CN 113528846A CN 202110676560 A CN202110676560 A CN 202110676560A CN 113528846 A CN113528846 A CN 113528846A
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- 229910052785 arsenic Inorganic materials 0.000 title claims abstract description 103
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 title claims abstract description 103
- 239000002699 waste material Substances 0.000 title claims abstract description 88
- 238000000034 method Methods 0.000 title claims abstract description 41
- 238000002386 leaching Methods 0.000 claims abstract description 53
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 45
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 45
- 239000001301 oxygen Substances 0.000 claims abstract description 45
- 238000006243 chemical reaction Methods 0.000 claims abstract description 38
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910052751 metal Inorganic materials 0.000 claims abstract description 26
- 239000002184 metal Substances 0.000 claims abstract description 26
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 24
- 239000011593 sulfur Substances 0.000 claims abstract description 24
- 238000006477 desulfuration reaction Methods 0.000 claims abstract description 22
- 230000023556 desulfurization Effects 0.000 claims abstract description 22
- 239000007789 gas Substances 0.000 claims abstract description 19
- 150000002739 metals Chemical class 0.000 claims abstract description 18
- 239000000126 substance Substances 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 5
- 238000009833 condensation Methods 0.000 claims abstract description 4
- 230000005494 condensation Effects 0.000 claims abstract description 4
- 239000002893 slag Substances 0.000 claims description 35
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 28
- 239000002253 acid Substances 0.000 claims description 21
- 238000002156 mixing Methods 0.000 claims description 18
- 238000001291 vacuum drying Methods 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 10
- GOLCXWYRSKYTSP-UHFFFAOYSA-N arsenic trioxide Inorganic materials O1[As]2O[As]1O2 GOLCXWYRSKYTSP-UHFFFAOYSA-N 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 8
- 238000000227 grinding Methods 0.000 claims description 7
- 238000002425 crystallisation Methods 0.000 claims description 5
- 230000008025 crystallization Effects 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- 238000003825 pressing Methods 0.000 claims description 4
- 238000001556 precipitation Methods 0.000 claims description 3
- 239000002002 slurry Substances 0.000 claims 2
- 238000004064 recycling Methods 0.000 abstract description 13
- 238000011084 recovery Methods 0.000 abstract description 8
- 229960002594 arsenic trioxide Drugs 0.000 abstract description 6
- 229910000413 arsenic oxide Inorganic materials 0.000 abstract description 2
- 239000005864 Sulphur Substances 0.000 abstract 1
- KTTMEOWBIWLMSE-UHFFFAOYSA-N diarsenic trioxide Chemical compound O1[As](O2)O[As]3O[As]1O[As]2O3 KTTMEOWBIWLMSE-UHFFFAOYSA-N 0.000 abstract 1
- 238000003723 Smelting Methods 0.000 description 6
- IKWTVSLWAPBBKU-UHFFFAOYSA-N a1010_sial Chemical compound O=[As]O[As]=O IKWTVSLWAPBBKU-UHFFFAOYSA-N 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- JOLWHRGJOACGLR-UHFFFAOYSA-N [Re].[As] Chemical compound [Re].[As] JOLWHRGJOACGLR-UHFFFAOYSA-N 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical group [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 239000003546 flue gas Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229910052702 rhenium Inorganic materials 0.000 description 3
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 3
- 238000007711 solidification Methods 0.000 description 3
- 230000008023 solidification Effects 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 239000004568 cement Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000011133 lead Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 238000005065 mining Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000001698 pyrogenic effect Effects 0.000 description 2
- 239000002910 solid waste Substances 0.000 description 2
- 150000003568 thioethers Chemical class 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 238000011085 pressure filtration Methods 0.000 description 1
- 239000002351 wastewater Chemical group 0.000 description 1
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Classifications
-
- 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
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/02—Preparation of sulfur; Purification
- C01B17/06—Preparation of sulfur; Purification from non-gaseous sulfides or materials containing such sulfides, e.g. ores
-
- 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
-
- 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
- C22B15/0002—Preliminary treatment
- C22B15/001—Preliminary treatment with modification of the copper constituent
- C22B15/0013—Preliminary treatment with modification of the copper constituent by roasting
-
- 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
- C22B15/0065—Leaching or slurrying
- C22B15/0067—Leaching or slurrying with acids or salts thereof
- C22B15/0071—Leaching or slurrying with acids or salts thereof containing sulfur
-
- 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
-
- 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
- C22B61/00—Obtaining metals not elsewhere provided for in this subclass
-
- 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
-
- 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
- C22B7/007—Wet processes by acid leaching
-
- 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 treatment method for resource utilization of arsenic-containing waste residues, and belongs to the technical field of recycling of arsenic-containing waste residues. The specific method comprises the steps of drying arsenic-containing waste residues under a vacuum condition, then continuing vacuum desulfurization, and then performing vacuum dearsenification to obtain arsenic oxide and elemental sulfur; then the valuable metals are recycled through oxygen pressure leaching reaction. The invention avoids the reaction of sulfur and oxygen in the air to generate a large amount of SO2Gas, while facilitating the condensation and recovery of sulphur sublimed in vacuumObtaining a simple substance sulfur product with higher purity after collection; before the oxygen pressure leaching reaction, the desulfurization and dearsenification are realized, and harmful gas is prevented from being generated in the subsequent reaction process; the recycling of the arsenic and valuable metals is separated, and the influence and pollution of the arsenic on metal recycling are reduced.
Description
Technical Field
The invention belongs to the technical field of arsenic-containing slag recycling, and particularly relates to a treatment method for resource utilization of arsenic-containing waste slag.
Background
China has abundant and various mineral resources, and nonferrous metal mining and smelting enterprises are in the process of transportation. In the development of lead, zinc, copper and other non-ferrous metal mineral resources, arsenic resources are often associated, and in the smelting process, arsenic enters flue gas, waste water and waste residues in the form of oxides, sulfides and the like, only about 10 percent of arsenic is recycled, and the balance is industrial waste which is complex in components and difficult to treat. Wherein, the arsenic enriched into various smelting slags not only poses serious threat to local ecological environment, but also is not beneficial to the recycling of valuable metals in the smelting slags because of the huge amount and harmfulness of the smelting slags. According to the prediction of the nonferrous metal industry association, the apparent consumption of four metals of copper, lead, zinc and aluminum in China can reach 6530 ten thousand tons in 2020, and the arsenic exposed by the mining and selecting smelting activities can reach 25.1 ten thousand tons. At present, the scale of the existing nonferrous metal enterprises in China is generally small, a part of enterprises still adopt backward process equipment with high energy consumption, low resource recovery rate and serious environmental pollution, the clean production level is low, and the complete consumption and treatment of a large amount of arsenic slag are difficult. The comprehensive utilization capacity of arsenic slag in China is weak, and solid waste disposal enterprises do not have the capacity of efficiently disposing the arsenic slag at low cost.
The existing treatment process of arsenic-containing waste residue mainly comprises the processes of solidification and landfill, pyrogenic roasting, wet leaching and the like. The solidification landfill process is to utilize cement, chemical agents, blast furnace slag, plastic materials and the like to solidify arsenic-containing waste residues, and ensure that the leaching toxicity of the arsenic in the waste residues is lower than the hazardous leaching toxicity concentration; the pyrogenic process roasting process is to add an oxidant to oxidize arsenic in the arsenic-containing waste residue to form arsenic trioxide by roasting under the high temperature condition of 600-; the wet leaching process is to utilize chemical reagent to leach soluble elements, such as arsenic, from the waste residue into solution under normal pressure or high pressure, to separate insoluble matter from soluble matter, to further separate soluble elements, such as arsenic, from the solution, to obtain arsenic trioxide and other elements to obtain corresponding product. The cement solidification landfill is widely applied due to the advantages of low cost, simple operation and the like, but the problems of incapability of recycling, resource waste and the like still exist.
As arsenic and valuable metals in the arsenic-containing slag mostly exist in the form of sulfides, harmful gases such as sulfur dioxide and the like are usually generated during the recovery of the waste arsenic slag, thereby causing harm to the environment. The chinese patent publication No. CN101954370A discloses a method for recycling arsenic-containing waste residues, which treats and recovers arsenic waste residues by an alkaline leaching and pickling method to finally obtain arsenic trioxide powder. Although arsenic oxide powder with good purity can be obtained, recovery of other elements is not taken into consideration.
In view of the above, in order to effectively treat the arsenic-containing waste residue, while the waste residue is treated in a harmless manner, arsenic and valuable metals in the waste residue are effectively recycled, a method for effectively treating the arsenic-containing waste residue is urgently needed, so that the recycling of the arsenic and the valuable metals in the arsenic-containing waste residue is realized.
Disclosure of Invention
In order to solve the technical problems, the invention provides a treatment method for resource utilization of arsenic-containing waste residues, and the adopted vacuum desulfurization can avoid the reaction of sulfur and oxygen in the air to generate a large amount of SO2The gas is simultaneously beneficial to condensing and collecting the sulfur sublimated in the vacuum to obtain an elemental sulfur product with higher purity; before the oxygen pressure leaching reaction, the desulfurization and dearsenification are realized, and harmful gas is prevented from being generated in the subsequent reaction process; the recycling of the arsenic and valuable metals is separated, and the influence and pollution of the arsenic on metal recycling are reduced.
In order to achieve the purpose, the invention provides the following technical scheme:
a treatment method for resource utilization of arsenic-containing waste residues comprises the following steps:
(1) drying the arsenic-containing waste residue at a low temperature of 85-100 ℃ for 3-4 h;
(2) vacuum drying the arsenic-containing waste residue dried in the step (1) at the temperature of 110-;
(3) carrying out vacuum desulfurization on the arsenic-containing waste residue subjected to vacuum drying in the step (2) for 2-4h under the vacuum condition of 280-300 ℃, and simultaneously condensing and settling sulfur steam generated in the desulfurization process to prepare a sulfur simple substance;
(4) dearsenization is carried out on the arsenic-containing waste residue desulfurized in the step (3) for 3-4h under the vacuum condition of 600-650 ℃ to obtain arsenic-containing gas and arsenic-removed waste residue, and the arsenic-containing gas is condensed and settled to obtain arsenic-containing condensed residue;
(5) grinding the waste residue after arsenic removal in the step (4), adding waste acid for size mixing, adding a sulfuric acid solution, mixing uniformly, introducing oxygen, carrying out an oxygen pressure leaching reaction for 2-4h, carrying out filter pressing separation on the mixture after the reaction to obtain a leaching solution and leaching residues, extracting the leaching solution, and carrying out evaporative crystallization treatment on the leaching solution to obtain valuable metals;
(6) adding waste acid into the arsenic-containing condensed slag formed in the step (4) for size mixing, heating to 110-150 ℃, and introducing oxygenCarrying out oxygen pressure leaching reaction on the gas for 2-3h, and filtering and separating the gas into leachate and leaching residues after the reaction is finished; reducing the leachate to obtain As2O3And recovering the leached slag to prepare the elemental sulfur.
Further, the vacuum condition in the step (3) is a vacuum degree of 30-90 kpa.
Further, the vacuum condition in the step (4) is a vacuum degree of 30-90 kpa.
Further, the grinding in the step (5) is carried out until the fineness is-200 meshes and accounts for more than 60 percent.
Further, the pulp mixing is to add waste acid solution into the waste residue according to the solid-to-liquid ratio of 1:4-1: 6.
Further, the waste acid is acid-containing solution left after valuable metals are recovered from leachate obtained after oxygen pressure leaching in each step. The main component is sulfuric acid.
Further, after the sulfuric acid solution is added in the step (5), the sulfuric acid concentration of the mixture is 60-180 g/L.
Further, the reaction temperature of the oxygen pressure leaching reaction in the step (5) is 115 ℃ and 125 ℃, and the oxygen pressure is 700kPa and 800 kPa.
Further, the oxygen pressure of the oxygen pressure leaching reaction in the step (6) is 450-500 kPa.
The invention has the following beneficial effects:
1. in the invention, the reaction of sulfur and oxygen in air to generate a large amount of SO is avoided2The gas is firstly subjected to vacuum desulfurization in the recovery process, so that the sublimed sulfur in vacuum is condensed and collected to obtain a high-purity elemental sulfur product; in addition, the invention completes desulfurization and dearsenification before oxygen pressure leaching reaction, avoids the generation of harmful gas of arsenic and sulfur elements in the subsequent reaction process, and simultaneously can separate arsenic from valuable metals for recycling, and also reduces the influence and pollution of arsenic on metal recycling.
2. The waste acid is utilized to carry out size mixing on the waste residue in the oxygen pressure leaching reaction, so that the waste acid resource is fully utilized, the environmental influence caused by direct discharge is avoided, and the cost is reduced; the waste acid source is the waste acid left after valuable metals are recovered from leachate after oxygen pressure leaching reaction in each step, and the main component is sulfuric acid, which is beneficial to decomposing waste residues and dissolving out the valuable metals in the waste residues.
3. The invention reduces SO in the flue gas to the maximum extent by vacuum desulfurization and dearsenification2The sulfur oxidation rate is less than 0.2 percent under the vacuum condition, the burden of flue gas treatment is lightened, the recovery rate of sulfur is improved, the arsenic removal rate of slag reaches more than 94 percent, and the desulfurization rate is more than 95 percent.
4. The method provided by the invention can be used for fully recovering and extracting the waste arsenic slag to obtain the sulfur simple substance, arsenic trioxide and valuable metal components with higher purity, is simple and convenient to operate, utilizes waste resources in the treatment process, reduces the production cost, is suitable for wide popularization and application, and provides a new direction for recycling solid wastes.
Drawings
FIG. 1 is a process flow diagram of example 3 of the present invention.
Detailed Description
The present invention will be further described with reference to the following examples. The following raw materials used in the present invention were purchased from chemical raw materials.
Example 1
A treatment method for resource utilization of arsenic-containing waste residues comprises the following steps:
(1) drying 300g of arsenic-containing waste residue at a low temperature of 85 ℃ for 3 h;
(2) vacuum drying the arsenic-containing waste residue dried in the step (1) at 120 ℃ for 2 h;
(3) carrying out vacuum desulfurization on the arsenic-containing waste residue subjected to vacuum drying in the step (2) for 2h under the vacuum condition of 280 ℃ and 30kpa of vacuum degree, and simultaneously condensing and settling sulfur steam generated in the desulfurization process to prepare a sulfur simple substance;
(4) dearsenizing the arsenic-containing waste residue desulfurized in the step (3) for 3 hours at 600 ℃ under the vacuum condition of the vacuum degree of 30kpa to obtain arsenic-containing gas and the dearsenized waste residue, and condensing and settling the arsenic-containing gas to obtain arsenic-containing condensed residue;
(5) grinding the waste residue after arsenic removal in the step (4) until the fineness is-200 meshes and accounts for more than 60%, adding waste acid according to a solid-to-liquid ratio of 1:4 to perform size mixing, adding a sulfuric acid solution until the concentration of sulfuric acid in the mixture is 60g/L, uniformly mixing, introducing oxygen, performing oxygen pressure leaching reaction at the temperature of 115 ℃ and the oxygen pressure of 700kPa for 2h, performing filter pressing separation on the mixture after the reaction to obtain a leaching solution and leaching residue, and performing reduction and extraction treatment on the leaching solution to recover valuable metals;
(6) adding waste acid into the arsenic-containing condensed slag formed by condensation and precipitation in the step (4) according to a solid-to-liquid ratio of 1:5, mixing, heating to 110 ℃, introducing oxygen to an oxygen pressure of 450kPa, carrying out oxygen pressure leaching reaction for 2h, and filtering and separating the arsenic-containing condensed slag into leachate and leached slag after the reaction is finished; the leachate is reduced to prepare As2O3And recovering the leached slag to obtain a sulfur simple substance.
Example 2
A treatment method for resource utilization of arsenic-containing waste residues comprises the following steps:
(1) drying 200g of arsenic-containing waste residue at a low temperature of 100 ℃ for 4 h;
(2) vacuum drying the arsenic-containing waste residue dried in the step (1) at 110 ℃ for 4 h;
(3) carrying out vacuum desulfurization on the arsenic-containing waste residue subjected to vacuum drying in the step (2) for 4 hours under the vacuum condition of 300 ℃ and the vacuum degree of 90kpa, and simultaneously condensing and settling sulfur steam generated in the desulfurization process to prepare a sulfur simple substance;
(4) dearsenizing the arsenic-containing waste residue desulfurized in the step (3) for 4 hours at 650 ℃ under the vacuum condition with the vacuum degree of 90kpa to obtain arsenic-containing gas and arsenic-removed waste residue, and condensing and settling the arsenic-containing gas to obtain arsenic-containing condensed residue;
(5) grinding the waste residue after arsenic removal in the step (4) until the fineness is-200 meshes and accounts for more than 60%, adding waste acid according to the solid-to-liquid ratio of 1:6 to perform size mixing, adding a sulfuric acid solution until the concentration of sulfuric acid in the mixture is 180g/L, uniformly mixing, introducing oxygen, performing oxygen pressure leaching reaction at the temperature of 125 ℃ and the oxygen pressure of 800kPa for 4 hours, performing pressure filtration separation on the reaction product to obtain a leaching solution and leaching residue, and performing extraction, evaporation and crystallization treatment on the leaching solution to obtain valuable metals;
(6) condensing and settling the formed arsenic-containing condensed slag in the step (4), and adding the arsenic-containing condensed slag into the arsenic-containing condensed slagAdding waste acid according to a solid-to-liquid ratio of 1:4, mixing, heating to 150 ℃, introducing oxygen to an oxygen pressure of 500kPa, carrying out an oxygen pressure leaching reaction for 3h, and filtering and separating the mixture into a leaching solution and leaching residues after the reaction is finished; reducing the leachate to obtain As2O3And recovering the leached slag to obtain a sulfur simple substance.
Example 3
A treatment method for resource utilization of arsenic-containing waste residues comprises the following steps:
(1) 200g of arsenic-rhenium-containing slag is dried at low temperature of 90 ℃ for 4 h; the main components of the arsenic-rhenium-containing slag are shown in Table 1;
(2) vacuum drying the arsenic-rhenium-containing slag dried in the step (1) at 115 ℃ for 3 h;
(3) performing vacuum desulfurization on the arsenic-rhenium-containing slag subjected to vacuum drying in the step (2) for 2-4h at 290 ℃ under the vacuum condition that the vacuum degree is 50kpa, and simultaneously condensing and settling sulfur steam generated in the desulfurization process to prepare a sulfur simple substance;
(4) dearsenizing the arsenic-containing waste residue desulfurized in the step (3) for 3.5 hours at the temperature of 620 ℃ and under the vacuum condition of the vacuum degree of 50kpa to obtain arsenic-containing gas and 11g of dearsenized waste residue, and condensing and settling the arsenic-containing gas to obtain arsenic-containing condensed residue;
(5) grinding the waste residue after arsenic removal in the step (4) until the fineness is-200 meshes and accounts for more than 60%, adding waste acid according to a solid-to-liquid ratio of 1:5 to perform size mixing, adding a sulfuric acid solution until the sulfuric acid concentration in the mixture is 120g/L, uniformly mixing, introducing oxygen, performing oxygen pressure leaching reaction at the temperature of 120 ℃ and the oxygen pressure of 750kPa for 3 hours, performing filter pressing separation on the mixture after the reaction to obtain a leaching solution and leaching residue, performing extraction and evaporative crystallization treatment on the leaching solution, extracting the leaching solution to recover rhenium, wherein the recovery amount of the rhenium is 166g/t, and performing evaporative crystallization on the leaching solution to recover copper, wherein the recovery amount of the copper is 32 kg/t;
(6) adding waste acid into the arsenic-containing condensed slag formed by condensation and precipitation in the step (4) according to a solid-to-liquid ratio of 1:6, mixing, heating to 140 ℃, introducing oxygen to an oxygen pressure of 480kPa, carrying out oxygen pressure leaching reaction for 2.5h, and filtering and separating the arsenic-containing condensed slag into leachate and leached slag after the reaction is finished; will be provided withThe leachate is reduced to obtain As2O3And recovering the leached slag to obtain a sulfur simple substance.
TABLE 1 raw material main ingredient conditions
TABLE 2 examination result of main elements in the waste residue after vacuum desulfurization and dearsenification
FIG. 1 is a process flow diagram of example 3 of the present invention. As can be seen from the data in FIG. 1, Table 1 and Table 2, the arsenic-containing waste residue before treatment has a mass of 200g, the waste residue after vacuum drying and desulfurization and dearsenification treatment has a mass of only 11g, and the concentration multiple is about 9.45 times, so that the contents of sulfur and arsenic are reduced after vacuum reaction, and the calculated dearsenification rate of the slag is more than 94%, and the desulfurization rate is more than 95%. Finally, the leaching rate of rhenium and the leaching rate of arsenic after oxygen pressure leaching are respectively 96% and 98%. The pretreatment and the vacuum desulfurization and dearsenification process realize the removal of sulfur and arsenic and the enrichment of other metals.
The above embodiments are only exemplary embodiments of the present invention, and are not intended to limit the present invention, and the scope of the present invention is defined by the claims. Various modifications and equivalents may be made thereto by those skilled in the art within the spirit and scope of the present invention, and such modifications and equivalents should be considered as falling within the scope of the present invention.
Claims (9)
1. A treatment method for resource utilization of arsenic-containing waste residue is characterized by comprising the following steps:
(1) drying the arsenic-containing waste residue at a low temperature of 85-100 ℃ for 3-4 h;
(2) vacuum drying the arsenic-containing waste residue dried in the step (1) at the temperature of 110-;
(3) carrying out vacuum desulfurization on the arsenic-containing waste residue subjected to vacuum drying in the step (2) for 2-4h under the vacuum condition of 280-300 ℃, and simultaneously condensing and settling sulfur steam generated in the desulfurization process to prepare a sulfur simple substance;
(4) dearsenization is carried out on the arsenic-containing waste residue desulfurized in the step (3) for 3-4h under the vacuum condition of 600-650 ℃ to obtain arsenic-containing gas and arsenic-removed waste residue, and the arsenic-containing gas is condensed and settled to obtain arsenic-containing condensed residue;
(5) grinding the waste residue after arsenic removal in the step (4), adding waste acid for size mixing, adding a sulfuric acid solution, mixing uniformly, introducing oxygen, carrying out an oxygen pressure leaching reaction for 2-4h, carrying out filter pressing separation on the mixture after the reaction to obtain a leaching solution and leaching residues, extracting the leaching solution, and carrying out evaporative crystallization treatment on the leaching solution to obtain valuable metals;
(6) adding waste acid into the arsenic-containing condensed slag formed by condensation and precipitation in the step (4), mixing the waste acid with slurry, heating to 110-150 ℃, introducing oxygen to carry out oxygen pressure leaching reaction for 2-3h, and filtering and separating the arsenic-containing condensed slag into leachate and leaching slag after the reaction is finished; reducing the leachate to obtain As2O3And recovering the leached slag to prepare the elemental sulfur.
2. The method for treating the arsenic-containing waste residue for resource utilization as claimed in claim 1, wherein the vacuum condition in the step (3) is a vacuum degree of 30-90 kpa.
3. The method for treating the arsenic-containing waste residue for resource utilization as claimed in claim 1, wherein the vacuum condition in the step (4) is a vacuum degree of 30-90 kpa.
4. The method for treating arsenic-containing waste residue for resource utilization as claimed in claim 1, wherein the grinding in step (5) is carried out until the fineness of-200 meshes is more than 60%.
5. The method for treating the arsenic-containing waste residue for resource utilization according to claim 1, wherein the slurry mixing is to add waste acid into the waste residue according to a solid-to-liquid ratio of 1:4-1: 6.
6. The method according to claim 1, wherein the waste acid is an acid-containing solution remaining after valuable metals are recovered from a leachate obtained by oxygen pressure leaching in each step.
7. The method for treating the arsenic-containing waste residue for resource utilization as claimed in claim 1, wherein the sulfuric acid solution is added in the step (5), and the concentration of the sulfuric acid in the mixture is 60-180 g/L.
8. The method as claimed in claim 1, wherein the reaction temperature of the oxygen pressure leaching reaction in step (5) is 115 ℃ and 125 ℃, and the oxygen pressure is 700 ℃ and 800 kPa.
9. The method as claimed in claim 1, wherein the oxygen pressure in the oxygen pressure leaching reaction in step (6) is 450kPa and 500 kPa.
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