CN113528830A - Method for recovering sulfur, copper and bismuth in arsenic filter cake leaching residues - Google Patents
Method for recovering sulfur, copper and bismuth in arsenic filter cake leaching residues Download PDFInfo
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- 238000002386 leaching Methods 0.000 title claims abstract description 130
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 56
- 239000011593 sulfur Substances 0.000 title claims abstract description 56
- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 51
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 229910052785 arsenic Inorganic materials 0.000 title claims abstract description 50
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 239000012065 filter cake Substances 0.000 title claims abstract description 39
- 238000000034 method Methods 0.000 title claims abstract description 33
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 27
- 239000010949 copper Substances 0.000 title claims abstract description 27
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 56
- 238000000926 separation method Methods 0.000 claims abstract description 54
- 239000007788 liquid Substances 0.000 claims abstract description 38
- 239000012454 non-polar solvent Substances 0.000 claims abstract description 32
- 238000003756 stirring Methods 0.000 claims abstract description 30
- 239000002893 slag Substances 0.000 claims abstract description 28
- 239000000110 cooling liquid Substances 0.000 claims abstract description 22
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000001816 cooling Methods 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000003723 Smelting Methods 0.000 claims abstract description 16
- 238000011084 recovery Methods 0.000 claims abstract description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 10
- 239000001301 oxygen Substances 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims description 47
- 239000007787 solid Substances 0.000 claims description 24
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 claims description 23
- 238000003825 pressing Methods 0.000 claims description 20
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 16
- 239000004744 fabric Substances 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 7
- 238000007654 immersion Methods 0.000 claims description 6
- 238000005266 casting Methods 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 238000004064 recycling Methods 0.000 claims 5
- 238000004090 dissolution Methods 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 6
- 238000001914 filtration Methods 0.000 description 5
- 229910001451 bismuth ion Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000011085 pressure filtration Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 210000002345 respiratory system Anatomy 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 239000002910 solid waste Substances 0.000 description 2
- UKUVVAMSXXBMRX-UHFFFAOYSA-N 2,4,5-trithia-1,3-diarsabicyclo[1.1.1]pentane Chemical group S1[As]2S[As]1S2 UKUVVAMSXXBMRX-UHFFFAOYSA-N 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 229940052288 arsenic trisulfide Drugs 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 239000012809 cooling fluid Substances 0.000 description 1
- 210000002249 digestive system Anatomy 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 210000000653 nervous system Anatomy 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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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
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
-
- 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
- C01B17/027—Recovery of sulfur from material containing elemental sulfur, e.g. luxmasses or sulfur containing ores; Purification of the recovered sulfur
- C01B17/033—Recovery of sulfur from material containing elemental sulfur, e.g. luxmasses or sulfur containing ores; Purification of the recovered sulfur using a liquid extractant
-
- 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
- C22B1/11—Removing sulfur, phosphorus or arsenic other than 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
- C22B15/0069—Leaching or slurrying with acids or salts thereof containing halogen
-
- 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
- C22B15/0082—Leaching or slurrying with water
-
- 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
- C22B30/06—Obtaining bismuth
-
- 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
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- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
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Abstract
The invention relates to the technical field of chemical industry, in particular to a method for recovering sulfur, copper and bismuth in arsenic filter cake leaching residues, which comprises the following steps: A) stirring and reacting arsenic filter cake leaching residues with a nonpolar solvent, and performing solid-liquid separation to obtain a separation solution and separation residues; B) cooling the separation liquid, and performing solid-liquid separation to obtain crude sulfur and first cooling liquid; carrying out oxygen pressure water leaching on the separation slag at the temperature of 80-90 ℃ to obtain a first leaching solution and first leaching slag; leaching the first leaching residue at 60-90 ℃ by using hydrochloric acid to obtain a second leaching solution and second leaching residue; mixing the second leaching solution with iron powder, and reacting to obtain crude bismuth; and smelting the second leaching slag to obtain copper. The invention creatively provides a process for recovering sulfur by adopting a non-polar solvent, and further adopts twice dissolution and sulfur resolution, so that the obtained sulfur powder has high purity and high sulfur recovery rate, and simultaneously, bismuth and copper can be effectively recovered.
Description
Technical Field
The invention relates to the technical field of chemical industry, in particular to a method for recovering sulfur, copper and bismuth in arsenic filter cake leaching residues.
Background
Arsenic filter cake is one of typical arsenic-containing solid wastes generated in copper smelting process, and the main component of the arsenic filter cake is arsenic trisulfide, which has strong toxicity. It can enter human body through skin, respiratory tract, etc. to damage respiratory system, digestive system, nervous system, etc. and may cause cancer and even death in serious cases. Most copper smelting enterprises are difficult to find a proper method for treating arsenic filter cakes, mainly carry out stockpiling treatment, but the stockpiling can cause great threat to the environment and waste of resources.
The existing treatment method generally firstly leaches arsenic filter cakes, most of arsenic enters the leachate, and then the leachate is treated. However, the leaching residue of the arsenic filter cake still contains a certain amount of arsenic, still belongs to arsenic-containing solid waste, and needs to be continuously treated. At present, in the subsequent treatment in the industry, some arsenic filter cake leaching residues are returned to the furnace for treatment, and some arsenic filter cake leaching residues are subjected to wet leaching treatment; however, the amount of materials to be treated is large and the cost is high during the return treatment, and the sulfur cannot be effectively recovered during the wet leaching treatment, so that the treatment amount of the materials is also large, and the cost is high.
Disclosure of Invention
In view of this, the technical problem to be solved by the present invention is to provide a method for recovering sulfur, copper and bismuth from arsenic filter cake leaching residues.
The invention provides a method for recovering sulfur, copper and bismuth in arsenic filter cake leaching residues, which comprises the following steps:
A) stirring and reacting arsenic filter cake leaching residues with a nonpolar solvent, and performing solid-liquid separation to obtain a separation solution and separation residues;
B) cooling the separation liquid, and performing solid-liquid separation to obtain crude sulfur and first cooling liquid;
carrying out oxygen pressure water leaching on the separation slag at the temperature of 80-90 ℃ to obtain a first leaching solution and first leaching slag;
leaching the first leaching residue at 60-90 ℃ by using hydrochloric acid to obtain a second leaching solution and second leaching residue;
mixing the second leaching solution with iron powder, and reacting to obtain crude bismuth;
and smelting the second leaching slag to obtain copper.
Preferably, in step a), the non-polar solvent comprises carbon tetrachloride and/or carbon disulphide.
Preferably, in the step A), the temperature of the stirring reaction is 25-38 ℃ and the time is 10-20 min;
the liquid-solid ratio of the stirring reaction is 4-9: 1;
the solid-liquid separation method is filter pressing, and filter cloth with 400 meshes is selected for filter pressing.
Preferably, in the step B), the temperature after cooling is 0-10 ℃;
the cooling rate is 0.4-0.6 ℃/min;
and the first cooling liquid is reused for stirring reaction of the arsenic filter cake leaching residue and the nonpolar solvent.
Preferably, after the crude sulfur is obtained in the step B), stirring the crude sulfur and a nonpolar solvent for reaction, and performing solid-liquid separation to obtain elemental sulfur and a second cooling liquid;
the non-polar solvent comprises carbon tetrachloride and/or carbon disulfide;
the stirring reaction is carried out at the temperature of 25-38 ℃ for 10-20 min;
the liquid-solid ratio of the stirring reaction is 4-9: 1;
the solid-liquid separation method is filter pressing, and 400-mesh filter cloth is selected for filter pressing;
and the second cooling liquid is reused for stirring reaction of the crude sulfur and the nonpolar solvent.
Preferably, in the step B), the liquid-solid ratio of the oxygen-pressurized water immersion is 5-8: 1;
the time of the oxygen pressure water immersion is 2.5-3 h.
Preferably, in the step B), the mass concentration of the hydrochloric acid is 15-25%;
the liquid-solid ratio of hydrochloric acid leaching is 5-8: 1;
the leaching time of the hydrochloric acid is 2.5-3 h.
Preferably, in the step B), the reaction temperature of the second leaching solution and the iron powder is 30-60 ℃, and the reaction time is 2-3 h.
Preferably, after the crude bismuth is obtained in step B), the method further comprises:
and (3) carrying out heat treatment on the crude bismuth at the temperature of 600-650 ℃ for 0.5-1 h, cooling to 450-500 ℃, and casting to obtain a bismuth ingot.
Preferably, in the step B), the smelting temperature is 1250-1300 ℃, and the smelting time is 1-2 h.
The invention provides a method for recovering sulfur, copper and bismuth in arsenic filter cake leaching residues, which comprises the following steps: A) stirring and reacting arsenic filter cake leaching residues with a nonpolar solvent, and performing solid-liquid separation to obtain a separation solution and separation residues; B) cooling the separation liquid, and performing solid-liquid separation to obtain crude sulfur and first cooling liquid; carrying out oxygen pressure water leaching on the separation slag at the temperature of 80-90 ℃ to obtain a first leaching solution and first leaching slag; leaching the first leaching residue at 60-90 ℃ by using hydrochloric acid to obtain a second leaching solution and second leaching residue; mixing the second leaching solution with iron powder, and reacting to obtain crude bismuth; and smelting the second leaching slag to obtain copper. According to the characteristics of high sulfur and high arsenic in arsenic filter cake leaching residue, the invention creatively provides a process for recovering sulfur by adopting a non-polar solvent, and further adopts twice dissolution and sulfur resolution, so that the obtained sulfur powder has high purity and high sulfur recovery rate, and can be directly sold as a product. The leaching slag is treated firstly to recover sulfur, so that the influence on bismuth leaching can be reduced, and the leaching effect of bismuth can be improved; the sulfur is recycled firstly, the material treatment capacity during bismuth leaching can be greatly reduced, and the material treatment capacity is reduced by more than 90%. Meanwhile, the bismuth can be effectively leached by adopting hydrochloric acid, and the leaching rate of the bismuth is very high and can reach more than 99%. The treatment cost of bismuth recovery can be effectively reduced by adopting iron powder replacement. The invention can also recover the valuable component copper in the leaching slag, thereby maximizing the resource utilization.
Drawings
FIG. 1 is a flow chart of a process for recovering sulfur, copper and bismuth from arsenic filter cake leaching residues according to an embodiment of the present invention.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a method for recovering sulfur, copper and bismuth in arsenic filter cake leaching residues, which comprises the following steps:
A) stirring and reacting arsenic filter cake leaching residues with a nonpolar solvent, and performing solid-liquid separation to obtain a separation solution and separation residues;
B) cooling the separation liquid, and performing solid-liquid separation to obtain crude sulfur and first cooling liquid;
carrying out oxygen pressure water leaching on the separation slag at the temperature of 80-90 ℃ to obtain a first leaching solution and first leaching slag;
leaching the first leaching residue at 60-90 ℃ by using hydrochloric acid to obtain a second leaching solution and second leaching residue;
mixing the second leaching solution with iron powder, and reacting to obtain crude bismuth;
and smelting the second leaching slag to obtain copper.
According to the invention, arsenic filter cake leaching residue and a nonpolar solvent are stirred to react, and then solid-liquid separation is carried out, so as to obtain a separation solution and separation residue.
In some embodiments of the invention, the arsenic filter cake leaching residue contains 85 wt% to 91 wt% of sulfur and 4 wt% to 5.5 wt% of arsenic. In certain embodiments, the arsenic filter cake leach residue has a sulfur content of 89.2 wt.% or 89.5 wt.%. In certain embodiments, the arsenic content in the arsenic filter cake leaching residue is 4.8 wt% or 4.6 wt%.
In certain embodiments of the present invention, the non-polar solvent comprises carbon tetrachloride and/or carbon disulfide.
In some embodiments of the invention, the stirring reaction is carried out at a temperature of 25-38 ℃ for 10-20 min. In certain embodiments, the temperature of the stirred reaction is 35 ℃ or 38 ℃. In certain embodiments, the time for the stirring reaction is 15min or 20 min.
In some embodiments of the invention, the liquid-solid ratio of the stirring reaction is 4-9: 1. in certain embodiments, the liquid-to-solid ratio of the stirred reaction is 8: 1 or 7.6: 1.
in some embodiments of the present invention, the solid-liquid separation method is filter pressing, and 400-mesh filter cloth is selected for filter pressing. In certain embodiments of the invention, the pressure filtration device is a filter press.
And after separation liquid and separation slag are obtained, cooling the separation liquid, and after solid-liquid separation, obtaining crude sulfur and a first cooling liquid.
In some embodiments of the present invention, the temperature after cooling is 0 to 10 ℃. In certain embodiments, the temperature after cooling is 5 ℃ or 3 ℃. In some embodiments of the present invention, the cooling rate is 0.4-0.6 ℃/min. In certain embodiments, the rate of cooling is 0.5 ℃/min or 0.6 ℃/min.
The method for solid-liquid separation is not particularly limited, and in certain embodiments of the invention, the method for solid-liquid separation is filter pressing, and the filter cloth with 400 meshes is selected for the filter pressing. In certain embodiments of the invention, the pressure filtration device is a filter press.
In certain embodiments of the invention, the first cooling fluid is reused for the agitation reaction of the arsenic filter cake leaching residue and the nonpolar solvent.
In some embodiments of the present invention, after obtaining the crude sulfur, the crude sulfur is stirred to react with the nonpolar solvent, and then solid-liquid separation is performed to obtain elemental sulfur and the second cooling liquid.
In certain embodiments of the present invention, the non-polar solvent comprises carbon tetrachloride and/or carbon disulfide.
In some embodiments of the invention, the stirring reaction is carried out at a temperature of 25-38 ℃ for 10-20 min. In certain embodiments, the temperature of the stirred reaction is 35 ℃ or 38 ℃. In certain embodiments, the time for the stirring reaction is 15min or 20 min.
In some embodiments of the invention, the liquid-solid ratio of the stirring reaction is 4-9: 1. in certain embodiments, the liquid-to-solid ratio of the stirred reaction is 8: 1 or 7.5: 1.
in some embodiments of the present invention, the solid-liquid separation method is filter pressing, and 400-mesh filter cloth is selected for filter pressing.
In certain embodiments of the invention, the second cooling liquid is reused for the stirred reaction of the crude sulfur with the non-polar solvent.
The separation slag is subjected to oxygen pressure water leaching at the temperature of 80-90 ℃ to obtain a first leaching solution and first leaching slag.
In certain embodiments of the invention, the temperature of the oxygen-pressurized water immersion is 84 ℃ or 88 ℃. In some embodiments of the invention, the liquid-solid ratio of the oxygen-pressurized water leaching is 5-8: 1. in certain embodiments, the liquid-to-solid ratio of the oxygen-pressurized water leach is 5.5: 1 or 5.7: 1. in some embodiments of the present invention, the time of the oxygen-pressure water immersion is 2.5 to 3 hours. In certain embodiments, the time of the oxygen-pressure water immersion is 100min or 110 min.
In certain embodiments of the invention, arsenic may be recovered from the first leach solution.
The first leaching residue is leached by hydrochloric acid at the temperature of 60-90 ℃ to obtain a second leaching solution and a second leaching residue.
In certain embodiments of the invention, the hydrochloric acid has a mass concentration of 15% to 25%. In certain embodiments, the hydrochloric acid has a mass concentration of 20% or 25%.
In some embodiments of the invention, the liquid-solid ratio of the hydrochloric acid leaching is 5-8: 1. in certain embodiments, the hydrochloric acid leach has a liquid-to-solid ratio of 5.8: 1 or 6.4: 1. in certain embodiments of the invention, the temperature of the hydrochloric acid leach is 84 ℃ or 60 ℃. In some embodiments of the invention, the hydrochloric acid leaching time is 2.5-3 h. In certain embodiments, the hydrochloric acid leach is 100 min.
The second leaching solution is mixed with iron powder and reacts to obtain crude bismuth.
In some embodiments of the present invention, before mixing the second leaching solution with the iron powder, the method further includes: and detecting the concentration of bismuth ions in the second leaching solution. In some embodiments of the present invention, the molar ratio of the bismuth ions in the second leaching solution to the iron powder is 0.8 to 1.2: 1.3 to 1.7. In certain embodiments of the present invention, the molar ratio of bismuth ions to the iron powder in the second leaching solution is 1: 1.5.
in some embodiments of the invention, the reaction temperature of the second leaching solution and the iron powder is 30-60 ℃, and the reaction time is 2-3 hours. In certain embodiments, the reaction temperature of the second leach solution with the iron powder is 40 ℃ or 50 ℃. In certain embodiments, the reaction time of the second leach solution with iron powder is 2.5 hours.
In some embodiments of the present invention, after mixing the second leaching solution with the iron powder, the method further includes: and filtering to obtain crude bismuth and replacement liquid.
In certain embodiments of the invention, the displacement fluid is recycled for hydrochloric acid leaching.
In some embodiments of the present invention, after obtaining crude bismuth, the method further comprises:
and (3) carrying out heat treatment on the crude bismuth at the temperature of 600-650 ℃ for 0.5-1 h, cooling to 450-500 ℃, and casting to obtain a bismuth ingot.
The heat treatment is used to remove impurities from the crude bismuth.
In certain embodiments of the invention, the temperature of the heat treatment is 630 ℃ or 640 ℃. In certain embodiments of the invention, the time of the heat treatment is 0.5h or 1 h.
In certain embodiments of the invention, the reduced temperature is 460 ℃ or 480 ℃.
The second leaching slag is smelted to obtain copper.
In some embodiments of the invention, the temperature of the smelting is 1250-1300 ℃, and the time of the smelting is 1-2 h. In certain embodiments, the temperature of the melting is 1270 ℃ or 1275 ℃. In certain embodiments, the time for the smelting is 1.5h or 2 h.
The source of the above-mentioned raw materials is not particularly limited in the present invention, and may be generally commercially available.
FIG. 1 is a flow chart of a process for recovering sulfur, copper and bismuth from arsenic filter cake leaching residues according to an embodiment of the present invention.
According to the characteristics of high sulfur and high arsenic in arsenic filter cake leaching residue, the invention creatively provides a process for recovering sulfur by adopting a non-polar solvent, and further adopts twice dissolution and sulfur resolution, so that the obtained sulfur powder has high purity and high sulfur recovery rate, and can be directly sold as a product.
The leaching slag is treated firstly to recover sulfur, so that the influence on bismuth leaching can be reduced, and the leaching effect of bismuth can be improved; the sulfur is recycled firstly, the material treatment capacity during bismuth leaching can be greatly reduced, and the material treatment capacity is reduced by more than 90%.
The hydrochloric acid can effectively leach bismuth, and the leaching rate of bismuth is very high and can reach more than 99%. The treatment cost of bismuth recovery can be effectively reduced by adopting iron powder replacement.
The invention can also recover the valuable component copper in the leaching slag, thereby maximizing the resource utilization.
In order to further illustrate the present invention, the following will describe the method for recovering sulfur, copper and bismuth from arsenic filter cake leaching residue in detail with reference to the examples, but the scope of the present invention should not be construed as being limited thereto.
Example 1
In the arsenic filter cake leaching residue, the content of sulfur is 89.2 wt%, and the content of arsenic is 4.8 wt%.
1) Taking a nonpolar solvent (carbon tetrachloride) 5m3And (3) placing the mixture into a reaction tank, adding 1t of arsenic filter cake leaching residue into the reaction tank, wherein the liquid-solid ratio is 8: 1. controlling the temperature at 35 ℃, and stirring for reaction for 15 min. After the reaction is finished, filter pressing is carried out by a filter press, filter cloth with 400 meshes is selected for filter pressing, and 5m of separation liquid can be obtained390kg of separated slag.
2) Cooling the separated liquid to 5 deg.C at a rate of 0.5 deg.C/min, press-filtering with a press filter, selecting 400 mesh filter cloth, and performing solid-liquid separation to obtain 880kg crude sulfur and 5m crude sulfur3A first cooling liquid. Take another 4.5m3A nonpolar solvent (Carbon tetrachloride) was placed in a reaction tank, 880kg of crude sulfur was added thereto, and the liquid-solid ratio was 8: 1. controlling the temperature at 35 ℃, and stirring for reaction for 15 min. After the reaction is finished, filter pressing is carried out by a filter press, filter cloth with 400 meshes is selected for filter pressing, and 4.5m of second cooling liquid can be obtained3875kg of elemental sulfur, the recovery rate of the sulfur is 98 percent, and the purity is 99.6 percent.
The first cooling liquid is reused for stirring reaction of arsenic filter cake leaching residues and a nonpolar solvent; and the second cooling liquid is reused for stirring reaction of the crude sulfur and the nonpolar solvent.
3) Adding 90kg of separation slag into 0.5m3In water, the liquid-solid ratio is 5.5: 1, soaking in water under oxygen pressure at 84 deg.C and 0.8MPa for 100min to obtain first leachate with a thickness of 0.51m3And 38kg of first extract residue.
4) Using 38kg of first leaching residue of 0.2m3And the hydrochloric acid with the mass concentration of 20% is stirred and leached for 100min at the temperature of 55 ℃, and the liquid-solid ratio of hydrochloric acid leaching is 5.8: 1, 0.2m was obtained3The second leaching solution and 19.5kg of second leaching residue.
5) To 0.2m3Adding 7.65kg of iron powder into the second leaching solution, and reacting at 40 ℃ for 2.5h to obtain 18.2kg of crude bismuth and a replacement solution; the crude bismuth is heat treated for 0.5h at 630 ℃, and then is cast when the temperature is reduced to 460 ℃, so that 18.1kg of bismuth ingot can be obtained, the recovery rate of bismuth is 96 percent, and the purity is more than 99.99 percent; the replacement liquid is reused for hydrochloric acid leaching.
6) And smelting 19.5kg of second leaching slag at 1270 ℃ for 1.5h, so that 19.2kg of copper can be recovered, the recovery rate of the copper is 98.4%, and the purity is over 99.5%.
Example 2
In the arsenic filter cake leaching residue, the content of sulfur is 89.5 wt%, and the content of arsenic is 4.6 wt%.
1) Taking a nonpolar solvent (carbon disulfide) of 12m3Placing the mixture into a reaction tank, adding arsenic filter cake leaching residues into the reaction tank for 2t, wherein the liquid-solid ratio is 7.6: 1. the temperature is controlled at 38 ℃, and the reaction is stirred for 20 min. After the reaction is finished, filter pressing is carried out by a filter press, filter cloth with 400 meshes is selected for filter pressing, and 12.1m of separation solution can be obtained3175kg of slag was separated.
2) Cooling the separated liquid to 3 deg.C at a rate of 0.6 deg.C/min, and press-filtering with a filter pressFiltering with 400 mesh filter cloth, and performing solid-liquid separation to obtain 1765kg crude sulfur and 12m3A first cooling liquid. Then take 10.5m3A nonpolar solvent (carbon disulfide) is placed in a reaction tank, 1765kg of crude sulfur is added, and the liquid-solid ratio is 7.5: 1. the temperature is controlled at 38 ℃, and the reaction is stirred for 20 min. After the reaction is finished, press filtering is carried out by a press filter, 400-mesh filter cloth is selected for press filtering, and 10.5m of second cooling liquid can be obtained31754kg of elemental sulfur, 98 percent of sulfur recovery rate and 99.8 percent of purity.
The first cooling liquid is reused for stirring reaction of arsenic filter cake leaching residues and a nonpolar solvent; and the second cooling liquid is reused for stirring reaction of the crude sulfur and the nonpolar solvent.
3) 175kg of the separated residue was added to 1m3In water, the liquid-solid ratio is 5.7: 1, soaking in water under oxygen pressure at 88 deg.C and 0.9MPa for 110min to obtain first leachate with a thickness of 1.01m3And 73kg of first extract residue.
4) Using 73kg of the first leaching residue of 0.42m3And hydrochloric acid with the mass concentration of 25% is stirred and leached for 100min at the temperature of 60 ℃, and the liquid-solid ratio of hydrochloric acid leaching is 6.4: 1, 0.42m was obtained3The second leach solution and 37.4kg of second leach residue.
5) To 0.42m3Adding 15.1kg of iron powder into the second leaching solution, and reacting at 50 ℃ for 2.5h to obtain 35.3kg of crude bismuth; after the crude bismuth is subjected to heat treatment at 640 ℃ for 1 hour, the crude bismuth is cooled to 480 ℃ for casting, 35kg of bismuth ingot can be obtained, the recovery rate of the bismuth is 96.5%, and the purity is more than 99.99%; the replacement liquid is reused for hydrochloric acid leaching.
6) And smelting 37.4kg of second leaching slag at 1275 ℃ for 2h, so that 36.5kg of copper can be recovered, the recovery rate of the copper is 97.6%, and the purity is more than 99.5%.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. A method for recovering sulfur, copper and bismuth in arsenic filter cake leaching residues comprises the following steps:
A) stirring and reacting arsenic filter cake leaching residues with a nonpolar solvent, and performing solid-liquid separation to obtain a separation solution and separation residues;
B) cooling the separation liquid, and performing solid-liquid separation to obtain crude sulfur and first cooling liquid;
carrying out oxygen pressure water leaching on the separation slag at the temperature of 80-90 ℃ to obtain a first leaching solution and first leaching slag;
leaching the first leaching residue at 60-90 ℃ by using hydrochloric acid to obtain a second leaching solution and second leaching residue;
mixing the second leaching solution with iron powder, and reacting to obtain crude bismuth;
and smelting the second leaching slag to obtain copper.
2. The recovery method according to claim 1, wherein in step a), the nonpolar solvent comprises carbon tetrachloride and/or carbon disulfide.
3. The recycling method according to claim 1, wherein in the step A), the temperature of the stirring reaction is 25-38 ℃ and the time is 10-20 min;
the liquid-solid ratio of the stirring reaction is 4-9: 1;
the solid-liquid separation method is filter pressing, and filter cloth with 400 meshes is selected for filter pressing.
4. The recycling method according to claim 1, wherein in the step B), the temperature after cooling is 0-10 ℃;
the cooling rate is 0.4-0.6 ℃/min;
and the first cooling liquid is reused for stirring reaction of the arsenic filter cake leaching residue and the nonpolar solvent.
5. The recovery method according to claim 1, wherein in the step B), after crude sulfur is obtained, the crude sulfur is stirred to react with a nonpolar solvent, and then solid-liquid separation is performed to obtain elemental sulfur and a second cooling liquid;
the non-polar solvent comprises carbon tetrachloride and/or carbon disulfide;
the stirring reaction is carried out at the temperature of 25-38 ℃ for 10-20 min;
the liquid-solid ratio of the stirring reaction is 4-9: 1;
the solid-liquid separation method is filter pressing, and 400-mesh filter cloth is selected for filter pressing;
and the second cooling liquid is reused for stirring reaction of the crude sulfur and the nonpolar solvent.
6. The recovery method according to claim 1, wherein in the step B), the liquid-solid ratio of the oxygen-pressure water leaching is 5-8: 1;
the time of the oxygen pressure water immersion is 2.5-3 h.
7. The recovery method according to claim 1, wherein in the step B), the mass concentration of the hydrochloric acid is 15% to 25%;
the liquid-solid ratio of hydrochloric acid leaching is 5-8: 1;
the leaching time of the hydrochloric acid is 2.5-3 h.
8. The recycling method according to claim 1, wherein in the step B), the reaction temperature of the second leaching solution and the iron powder is 30 to 60 ℃ and the reaction time is 2 to 3 hours.
9. The recycling method according to claim 1, wherein the step B) further comprises, after obtaining crude bismuth:
and (3) carrying out heat treatment on the crude bismuth at the temperature of 600-650 ℃ for 0.5-1 h, cooling to 450-500 ℃, and casting to obtain a bismuth ingot.
10. The recycling method according to claim 1, wherein in the step B), the temperature of the smelting is 1250-1300 ℃, and the time of the smelting is 1-2 h.
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| CN116099852A (en) * | 2022-12-21 | 2023-05-12 | 福建省矿投环保科技有限公司 | Harmless treatment and arsenic oxide recovery method for hazardous waste residues containing arsenic oxide and sulfur |
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