CN116287729A - Thallium separation method based on sodium carbonate - Google Patents
Thallium separation method based on sodium carbonate Download PDFInfo
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- CN116287729A CN116287729A CN202310193061.3A CN202310193061A CN116287729A CN 116287729 A CN116287729 A CN 116287729A CN 202310193061 A CN202310193061 A CN 202310193061A CN 116287729 A CN116287729 A CN 116287729A
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- thallium
- sodium carbonate
- solid waste
- separation method
- containing solid
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- 229910052716 thallium Inorganic materials 0.000 title claims abstract description 208
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 title claims abstract description 208
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 title claims abstract description 90
- 229910000029 sodium carbonate Inorganic materials 0.000 title claims abstract description 45
- 238000000926 separation method Methods 0.000 title claims abstract description 34
- 239000002910 solid waste Substances 0.000 claims abstract description 45
- 239000000203 mixture Substances 0.000 claims abstract description 27
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims abstract description 22
- 229910000368 zinc sulfate Inorganic materials 0.000 claims abstract description 21
- 229960001763 zinc sulfate Drugs 0.000 claims abstract description 21
- 239000002893 slag Substances 0.000 claims abstract description 19
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 239000011701 zinc Substances 0.000 claims description 40
- 229910052725 zinc Inorganic materials 0.000 claims description 38
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 37
- 238000000034 method Methods 0.000 claims description 22
- 238000000227 grinding Methods 0.000 claims description 19
- 229910052751 metal Inorganic materials 0.000 claims description 18
- 230000008569 process Effects 0.000 claims description 18
- 239000002184 metal Substances 0.000 claims description 17
- 238000003723 Smelting Methods 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 5
- 239000004071 soot Substances 0.000 claims description 4
- CRFJFTKIQKOVBE-UHFFFAOYSA-N FCl.[Cd] Chemical compound FCl.[Cd] CRFJFTKIQKOVBE-UHFFFAOYSA-N 0.000 claims description 3
- ZUXNUCHLRCDSFU-UHFFFAOYSA-N [Zn].ClF Chemical compound [Zn].ClF ZUXNUCHLRCDSFU-UHFFFAOYSA-N 0.000 claims description 3
- 230000010355 oscillation Effects 0.000 claims description 3
- 239000003517 fume Substances 0.000 claims 1
- 238000004064 recycling Methods 0.000 abstract description 2
- 230000002349 favourable effect Effects 0.000 abstract 1
- 230000001737 promoting effect Effects 0.000 abstract 1
- 239000000428 dust Substances 0.000 description 29
- 230000000052 comparative effect Effects 0.000 description 21
- 239000000047 product Substances 0.000 description 20
- 238000004458 analytical method Methods 0.000 description 17
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 16
- 230000008859 change Effects 0.000 description 15
- 239000000460 chlorine Substances 0.000 description 12
- 239000000779 smoke Substances 0.000 description 12
- 239000000126 substance Substances 0.000 description 12
- 229910052793 cadmium Inorganic materials 0.000 description 11
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 11
- 229910052801 chlorine Inorganic materials 0.000 description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 10
- 239000001301 oxygen Substances 0.000 description 10
- 229910052760 oxygen Inorganic materials 0.000 description 10
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 9
- 239000011737 fluorine Substances 0.000 description 9
- 229910052731 fluorine Inorganic materials 0.000 description 9
- 238000002386 leaching Methods 0.000 description 8
- 239000011787 zinc oxide Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 238000001354 calcination Methods 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 5
- 238000007605 air drying Methods 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 4
- 238000010304 firing Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 230000007423 decrease Effects 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- 239000003039 volatile agent Substances 0.000 description 3
- 239000011592 zinc chloride Substances 0.000 description 3
- 235000005074 zinc chloride Nutrition 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- HXELGNKCCDGMMN-UHFFFAOYSA-N [F].[Cl] Chemical compound [F].[Cl] HXELGNKCCDGMMN-UHFFFAOYSA-N 0.000 description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical group [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000002596 correlated effect Effects 0.000 description 2
- 230000029087 digestion Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- PIJPYDMVFNTHIP-UHFFFAOYSA-L lead sulfate Chemical compound [PbH4+2].[O-]S([O-])(=O)=O PIJPYDMVFNTHIP-UHFFFAOYSA-L 0.000 description 2
- SMBGWMJTOOLQHN-UHFFFAOYSA-N lead;sulfuric acid Chemical compound [Pb].OS(O)(=O)=O SMBGWMJTOOLQHN-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical group Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- QCUOBSQYDGUHHT-UHFFFAOYSA-L cadmium sulfate Chemical compound [Cd+2].[O-]S([O-])(=O)=O QCUOBSQYDGUHHT-UHFFFAOYSA-L 0.000 description 1
- 229910000331 cadmium sulfate Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000010431 corundum Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000016507 interphase Effects 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 229910000464 lead oxide Inorganic materials 0.000 description 1
- JQJCSZOEVBFDKO-UHFFFAOYSA-N lead zinc Chemical compound [Zn].[Pb] JQJCSZOEVBFDKO-UHFFFAOYSA-N 0.000 description 1
- HWSZZLVAJGOAAY-UHFFFAOYSA-L lead(II) chloride Chemical compound Cl[Pb]Cl HWSZZLVAJGOAAY-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 1
- 239000000546 pharmaceutical excipient Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate group Chemical group S(=O)(=O)([O-])[O-] QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 150000003476 thallium compounds Chemical class 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000007306 turnover Effects 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- 235000004416 zinc carbonate Nutrition 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 0.000 description 1
- 235000014692 zinc oxide Nutrition 0.000 description 1
Images
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
- C22B7/02—Working-up flue dust
-
- 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
- C22B61/00—Obtaining metals not elsewhere provided for in this subclass
-
- 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Geochemistry & Mineralogy (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention provides a thallium separation method based on sodium carbonate, comprising the following steps: s1, mixing ground thallium-containing solid waste with sodium carbonate to obtain a mixture to be burned; wherein the thallium-containing solid waste comprises zinc sulfate; s2, roasting the mixture to be roasted to obtain a thallium-containing volatile matter and thallium-removing slag; wherein the temperature of the roasting treatment is 750-850 ℃, and the duration of the roasting treatment is not less than 1h. The invention realizes the separation and enrichment of thallium, and is favorable for promoting the harmlessness and recycling of thallium in thallium-containing solid waste.
Description
Technical Field
The invention relates to treatment of solid waste, in particular to a thallium separation method based on sodium carbonate.
Background
Thallium is a typical rare dispersing element found in nature and is widely found in primary metal minerals. Thallium has various characteristics of improving alloy strength, improving alloy hardness, enhancing alloy corrosion resistance and the like, and thallium-containing alloy has potential application value in the aspects of optical fibers, superconducting materials, infrared optical materials, radiation shielding materials, catalysts and the like. However, the annual global thallium usage is less than 30 tons, which results in a lack of enthusiasm for thallium production enterprises.
Although a large amount of thallium elements exist in thallium-containing solid waste, the separation and enrichment of thallium in the prior art still has defects, and optimization exploration is needed. For example, chinese patent publication No. CN101314823B discloses a method for extracting metallic thallium from thallium-containing slag, which adopts a vacuum metallurgy method to extract thallium from thallium-containing slag, and although the extraction rate of thallium is high, three-stage evaporation separation is required, and problems such as complicated operation steps, high equipment requirements, poor applicability and the like are caused, so that thallium separation from thallium-containing solid waste is difficult.
In view of the above, there is a need to provide a thallium separation method based on sodium carbonate to solve or alleviate the above-mentioned technical drawbacks of the separation of thallium from thallium-containing solid waste.
Disclosure of Invention
The invention mainly aims to provide a thallium separation method based on sodium carbonate, which aims to solve the technical problem that thallium separation from thallium-containing solid waste is difficult.
In order to achieve the above object, the present invention provides a thallium separation method based on sodium carbonate, comprising the steps of:
s1, mixing ground thallium-containing solid waste with sodium carbonate to obtain a mixture to be burned;
wherein the thallium-containing solid waste comprises zinc sulfate;
s2, roasting the mixture to be roasted to obtain a thallium-containing volatile matter and thallium-removing slag;
wherein the temperature of the roasting treatment is 750-850 ℃, and the duration of the roasting treatment is not less than 1h.
Further, the thallium-containing solid waste comprises thallium-containing dust generated in the zinc smelting process.
Further, the thallium-containing dust has a thallium content of 0.5 to 0.7wt%.
Further, the particle size of the thallium-containing solid waste after the grinding is not more than 100 meshes.
Further, the thallium-containing solid waste also comprises valuable metal fluorochloride compounds, wherein the valuable metal fluorochloride compounds comprise one or more of lead fluorochloride compounds, zinc fluorochloride compounds and cadmium fluorochloride compounds.
Further, the mass ratio of the sodium carbonate in the mixture to be burned is not less than 10%.
Further, the step S1 further includes: and drying the thallium-containing solid waste before the grinding of the thallium-containing solid waste.
Further, in the step S1, the mixing process includes: co-grinding the grinding product and the sodium carbonate to obtain a primary mixture; and then, carrying out oscillation treatment on the primary mixture to obtain the mixture to be burned.
Further, the roasting treatment time is 1-3h.
Further, the calcination treatment is performed under an air atmosphere or an inert atmosphere.
Compared with the prior art, the invention has at least the following advantages:
the invention provides a thallium separation method based on sodium carbonate, which realizes the effective separation of thallium in thallium-containing solid waste and the reutilization of thallium resources by utilizing zinc sulfate and valuable metal fluorochloride existing in the thallium-containing solid waste and introducing sodium carbonate; by controlling the roasting temperature, the separation of thallium is further ensured, and the selectivity of thallium separation is improved. Compared with other treatment methods, the treatment cost is lower, and the thallium selective separation efficiency is high; the thallium-removed slag obtained after separation can be returned to a lead-zinc smelting system for secondary use, and the thallium recovery is ensured, and meanwhile, the environmental risk of thallium-containing solid waste is greatly reduced.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and other drawings may be obtained according to the structures shown in these drawings without inventive effort for a person skilled in the art.
FIG. 1 is an XRD pattern of thallium-containing soot in example 1 of the present invention;
FIG. 2 is a graph showing the chemical phase analysis results of the water-soluble zinc and the zinc oxide according to the change of the roasting temperature and the change rule of the thallium volatilization rate in the embodiment 2 of the present invention;
FIG. 3 is a graph showing the results of chemical phase analysis of the change of lead in chloride form, lead in sulfate form and lead in oxide form with the firing temperature and the change of thallium volatilization rate in example 2 of the present invention;
FIG. 4 is a graph showing the chemical phase analysis results of the water-soluble zinc and the zinc oxide according to the oxygen concentration and the thallium volatilization rate in example 3;
FIG. 5 is a graph showing the chemical phase analysis results of the change in the concentration of oxygen and the change in the volatilization rate of thallium of example 3 of the present invention.
The achievement of the object, functional features and advantages of the present invention will be further described with reference to the drawings in connection with the embodiments.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and fully with reference to the accompanying drawings, in which it is evident that the embodiments described are only some, but not all embodiments of the invention. All other embodiments, based on the embodiments of the invention, which are apparent to those of ordinary skill in the art without inventive faculty, are intended to be within the scope of the invention.
Moreover, the technical solutions of the embodiments of the present invention may be combined with each other, but it is necessary to be based on the fact that those skilled in the art can implement the embodiments, and when the technical solutions are contradictory or cannot be implemented, it should be considered that the combination of the technical solutions does not exist, and is not within the scope of protection claimed by the present invention.
At present, smelting enterprises face the problems of large pollution of thallium-containing solid waste, high disposal cost and selective separation and recovery of thallium in slag. The treatment of thallium-containing solid waste in the prior art is not completely suitable for industrial application, and the treatment of the thallium-containing solid waste is not strong in pertinence to specific thallium-containing solid waste (no thallium-containing dust is involved in the existing treatment of thallium-containing waste residues).
Based on the method, in order to realize the selective separation of thallium in thallium-containing solid waste on the premise of being applicable to industrial application and complete the enrichment of thallium and the harmless and recycling of baked materials, the invention provides a thallium separation method based on sodium carbonate, which comprises the following steps:
s1, grinding the thallium-containing solid waste to obtain a grinding product; and mixing the ground thallium-containing solid waste (grinding product) with sodium carbonate to obtain a mixture to be burned.
Wherein the ground product may be granular, and the particle size of the thallium-containing solid waste after the grinding may be not more than 100 mesh, that is, the particle size of the ground product may be not more than 100 mesh, and may specifically be 100-400 mesh.
The thallium-containing solid waste contains thallium element; the thallium-containing solid waste can also contain one or more of lead element, zinc element and cadmium element.
In the specific phase category, the thallium-containing solid waste comprises zinc sulfate, and thallium element is added in the zinc sulfate, namely, the thallium-containing excipient phase comprises or is the zinc sulfate; one or more of lead sulfate and cadmium sulfate can be also included in the thallium-containing solid waste.
Further, the thallium-containing solid waste can also comprise valuable metal fluorochloride; and valuable metal oxides can be also included in the thallium-containing solid waste. The valuable metal in the present invention means a metal other than thallium.
The valuable metal fluorochloride may include or be one or more of lead fluorochloride, zinc fluorochloride, and cadmium fluorochloride; the fluorine-chlorine compound may contain one or both of fluorine and chlorine, or may contain both of fluorine and chlorine. The metal oxide may include or be one or more of lead-based oxides, zinc-based oxides, and cadmium-based oxides.
The thallium-containing solid waste can specifically comprise or be thallium-containing dust generated in the zinc smelting process, the thallium-containing dust can comprise or be thallium-containing high-fluorine chlorine dust, the thallium content in the thallium-containing high-fluorine chlorine dust (thallium-containing dust) can be 0.5 to 0.7wt%, and usually 0.6 to 0.7wt%, the thallium in the thallium-containing high-fluorine chlorine dust is basically contained in zinc sulfate, and the thallium element in the thallium-containing high-fluorine chlorine dust comprises or is monovalent thallium.
It should be noted that, when thallium-containing high fluorine chlorine dust or other wastes contain thallium with other valence states, the implementation of the application is not affected.
In order to facilitate the treatment of the thallium-containing solid waste, the step S1 may further include: drying the thallium-containing solid waste to a constant weight before grinding the thallium-containing solid waste; the temperature of the drying treatment may be 60-100 ℃, such as 80 ℃.
In order to ensure the release of thallium and the conversion of the valuable metals, the mass ratio of sodium carbonate in the to-be-burnt mixture may be not less than 10%, and may be, for example, 10-20%.
In order to ensure adequate contact between the thallium containing solid waste and the sodium carbonate, in the step S2, the mixing process comprises: grinding the grinding product and sodium carbonate together to obtain a primary mixture; and then, carrying out oscillation treatment on the primary mixture to obtain the mixture to be burned. Wherein the particle size of the primary mixture may be consistent with the milled product, and the duration of the shaking may be not less than 0.5 hours, preferably may be 0.5 to 3 hours.
And S3, roasting the mixture to be roasted to obtain separated thallium-containing volatile matters and thallium-removed residues (roasted residues). Specifically, thallium-containing volatiles generated in the calcination process can be collected simultaneously during the calcination process, thereby recovering separated thallium.
The collecting process may be: the volatiles are sent to a condenser tube or other condensing device to condense the volatiles, thereby obtaining a thallium containing recycle.
In order to ensure selective separation of thallium, the temperature of the roasting treatment is 750-850 ℃, preferably 800 ℃, and the duration of the roasting treatment is not less than 1h, preferably 1-3h. In addition, the roasting treatment is generally performed in a furnace body, and both the heating of the mixture to be roasted and the cooling process of the residues can be a mode of heating with the furnace and cooling with the furnace.
In order to ensure that the reaction proceeds during the calcination, the calcination treatment cannot be performed under a reducing atmosphere, and the calcination treatment may be generally performed under an air atmosphere or an inert atmosphere.
The main principle related to the invention comprises:
in order to achieve selective volatilization of thallium, the conditions for volatilization of thallium compounds are thermodynamically and kinetically met, i.e., the critical temperature for volatilization of thallium-containing compounds is reached, while allowing release of thallium present in other compounds. Therefore, the reaction, roasting temperature and roasting time in the thallium-containing smoke must be regulated, and the relevant conditions and parameters are controlled, so as to realize selective volatilization of thallium.
1. The main reasons for determining the additive to be sodium carbonate in the invention include:
1) Thallium in thallium-containing high-fluorine chlorine smoke dust (thallium-containing solid waste) has strong correlation with zinc sulfate, and thallium release and selective volatilization can be realized by destroying the zinc sulfate structure. And sodium carbonate can react with zinc sulfate to be converted into zinc carbonate, zinc oxide and sodium sulfate, so as to realize the release of thallium.
Although other substances are also present in the thallium-containing high-fluorine-chlorine dust, since zinc sulfate has a strong correlation with thallium in the thallium-containing dust (zinc sulfate and thallium), thallium in the thallium-containing high-fluorine-chlorine dust is basically assigned to zinc sulfate, and therefore, conversion to zinc sulfate is required to release thallium efficiently.
2) The volatile point of the valuable metal fluorochloride is low, and sodium carbonate can react with the valuable metal fluorochloride to convert the valuable metal fluorochloride into oxide and carbonate, so that the volatile rate of the valuable metal in the roasting process is reduced.
2. The main reasons for determining the roasting temperature to be about 800 ℃ in the invention include:
1) After adding sodium carbonate, valuable metals such as lead, zinc, cadmium and the like are converted into carbonate, and are partially decomposed into oxides at high temperature, and a large amount of volatilization begins to occur after the temperature is higher than 800 ℃ (the specific volatilization effect is based on the examples and the comparative examples).
2) The reaction degree of sodium carbonate and zinc sulfate is controlled by dynamics, and the reaction is nearly complete at 800 ℃.
To facilitate a detailed understanding of the invention by those skilled in the art, reference will now be made to the accompanying drawings, in which:
example 1
Sampling analysis of thallium-containing soot
And (3) taking thallium-containing high-fluorine chlorine smoke dust (thallium-containing smoke dust) generated in the zinc smelting process, drying (80 ℃ air blast drying box) to constant weight, grinding (grinding to 100-mesh sieve), digesting the ground thallium-containing smoke dust, measuring the element content in the thallium-containing smoke dust, and carrying out phase analysis.
In this example, the thallium content of the thallium-containing soot was measured to be 0.66wt%. The thallium element in the thallium-containing high-fluorine chlorine smoke dust is unevenly distributed, the thallium content of the whole smoke dust is between 0.6 and 0.7 weight percent, and the calculation of the volatilization rate of thallium in the subsequent examples and comparative examples takes the content obtained by digestion as a calculation standard.
The specific analysis results are as follows:
1. referring to fig. 1 and chemical phase analysis, in this example, the phases in which thallium-containing smoke mainly exists include zinc oxide, lead oxide, zinc sulfate (water-soluble zinc), lead sulfate, lead chloride, zinc chloride, and the like, and the existence forms include crystalline and amorphous states.
2. In this example, the mass percentages of the main elements in the thallium-containing smoke are shown in the following table:
| element(s) | Zn | Pb | S | Cd | Fe | F | Tl | Cl | O |
| Content (%) | 38.1 | 17.75 | 6.135 | 1.98 | 3.22 | 0.93 | 0.66 | 4.87 | 22.5 |
As can be seen from the above table, the thallium-containing dust mainly contains valuable metal elements such as Zn and Pb.
3. In this example, the chemical phase analysis results (mass%) of Zn are shown with reference to the following table:
4. in this example, the chemical phase analysis results (mass percent) of Pb are shown with reference to the following table:
example 2
Temperature single factor test
1kg of a sample of thallium-containing dust (same as in example 1) dried (80 ℃ C. Forced air drying oven) to a constant weight was ground (to a 100 mesh sieve) to obtain a ground product.
The ground product was calcined at 600 ℃, 700 ℃,800 ℃, 900 ℃, 1000 ℃ and 1100 ℃ respectively.
The process of each roasting is as follows: 15g of ground product is put into a vertical tube furnace for roasting under the air atmosphere; the temperature of each roasting is controlled to be respectively the above temperatures, the heat preservation time of each roasting is 1h, and the baked slag is cooled to the room temperature along with the furnace after the roasting.
In this example, the results of chemical phase analysis of water-soluble zinc and zinc oxide in the post-baking slag as a function of baking temperature (mass ratio in the post-baking slag), and the law of change in thallium volatilization rate (as a function of baking temperature) are shown in FIG. 2.
The results of chemical phase analysis of the change of the chlorinated lead, the sulfuric acid lead and the oxidized lead with the roasting temperature (the mass ratio in the slag after roasting) and the change rule of the thallium volatilization rate (the change with the roasting temperature) in the slag after roasting are shown in fig. 3.
Example 3
Oxygen concentration single factor experiment
1kg of a sample of thallium-containing dust (same as in example 1) dried (80 ℃ C. Forced air drying oven) to a constant weight was ground (to a 100 mesh sieve) to obtain a ground product.
The ground product was calcined at oxygen concentrations of 0%, 10%, 20%, 30%, 40% and 50%, respectively.
Each roasting process is as follows: taking 15g of ground product and roasting in a vertical tube furnace under the oxygen concentration; the roasting temperature is controlled to be 900 ℃, the heat preservation time of each roasting is 1h, and the slag after roasting is cooled to room temperature along with the furnace.
In this example, the results of chemical phase analysis of water-soluble zinc and zinc oxide in the post-baking slag as a function of oxygen concentration (mass ratio in the post-baking slag), and the law of change in thallium volatilization rate as a function of oxygen concentration are shown in FIG. 4.
The results of chemical phase analysis of the change in oxygen concentration of chlorinated lead, sulfuric acid lead and oxidized lead in the post-baking slag (mass ratio in the post-baking slag), and the change law of thallium volatilization rate (change with oxygen concentration) are shown in fig. 5.
Example 4
Water immersion test
1kg of a sample of thallium-containing dust (same as in example 1) dried (80 ℃ C. Forced air drying oven) to a constant weight was ground (to a 100 mesh sieve) to obtain a ground product.
Weighing 0.2000g of ground product, placing into a centrifuge tube, adding 50ml of deionized water into the centrifuge tube, placing into a water bath shaking table (150 r/min) at normal temperature, oscillating for 2 hours, taking out, centrifuging, separating solid from liquid, and taking supernatant to test thallium and zinc content.
The leaching rate is calculated by combining the two, and the mass leaching rate is shown in the following table:
| thallium leaching Rate (%) | Leaching rate of zinc in water-soluble state (%) |
| 98.61 | 100 |
Analytical example 1
Analysis of thallium-occupiant phases in connection with examples 1-4
1. Referring to fig. 2-5, in the analysis and test results of the two single factor experiments, thallium volatilization rates all show obvious correlation with zinc-containing phases, but have weaker correlation with lead-containing phases, and regularity is not obvious. It is therefore assumed that thallium presence has a certain correlation with zinc phase.
Further, referring specifically to fig. 2, as the temperature increases, the water-soluble zinc phase decreases, the zinc oxide phase increases, and the thallium volatilization rate increases, presumably during the temperature increase, the water-soluble zinc phase converts to the zinc oxide phase and simultaneously releases thallium.
Referring specifically to fig. 4, in the oxygen concentration single factor experiment, the water-soluble zinc phase increases and then decreases, while the oxidation state zinc phase and thallium volatilization rate decrease and then increase, and it is also presumed that the inter-phase transformation between the water-soluble zinc phase and the oxidation state zinc phase results.
As is clear from the data of the water leaching experiment, in the water leaching process, the water-soluble zinc is completely dissolved, and thallium is almost completely dissolved, and analysis shows that the thallium existing in the water leaching process is released due to the destruction of the water-soluble zinc phase structure in the water leaching process, so that the thallium is dissolved simultaneously.
Since the dissolution relationship between water-soluble zinc and thallium and the change law in the roasting process are strongly correlated, the occurrence of thallium is considered to have a strong correlation with the water-soluble zinc phase.
2. In combination with the main elements involved in thallium-containing smoke dust, the water-soluble zinc involved in the invention should be zinc chloride and zinc sulfate. Wherein, the volatilization temperature of the zinc chloride phase is lower (about 500 ℃ is obviously volatilized), and the decomposition temperature of the zinc sulfate phase is higher (about 500-600 ℃ is dissociated and 930 ℃ is dissociated violently).
In the temperature single factor experiment, along with the temperature rise, the water-soluble zinc phase is continuously reduced after the temperature exceeds 500 ℃, the water-soluble zinc phase is obviously reduced in the range of 900-1000 ℃ (the severe dissociation temperature of zinc sulfate), and meanwhile, the thallium volatilization rate is obviously improved.
Therefore, the occurrence of thallium is considered to be correlated with the zinc sulfate phase, and the occurrence phase of thallium in the thallium-containing dust is considered to be zinc sulfate.
Example 5
1kg of a sample of thallium-containing dust (same as in example 1) dried (80 ℃ C. Forced air drying oven) to a constant weight was ground (to a 100 mesh sieve) to obtain a ground product.
13.5g of ground product (thallium-containing smoke dust after grinding) and 1.5g of sodium carbonate are weighed, and the weighed ground product and sodium carbonate are added into a mortar together for grinding and mixing to obtain a primary mixture (the primary mixture can pass through a 100-mesh sieve); placing the primary mixture into a plastic bottle with a cover, and placing on a turnover oscillator (30 r/min) to oscillate for 2h to obtain the mixture to be burned.
The obtained mixture to be burned is put into a corundum crucible and is burned in a vertical tube furnace under the air atmosphere. In the roasting process, the roasting temperature is controlled to be 800 ℃, and the heat preservation time is 1h; after roasting, the slag after roasting is cooled to room temperature along with the furnace.
And (3) digesting the baked slag, and measuring the contents of thallium, lead, zinc and cadmium in the digestion liquid.
Calculated, in this example, the mass volatilization rate of thallium was 97.68%, and the mass volatilization rates of lead, zinc and cadmium were 10.98%, 2.27% and 19.69%, respectively.
Example 6
In this example, the amount of the ground product was adjusted to 12g and the amount of sodium carbonate was adjusted to 3g, as compared with example 5, and the other conditions were kept unchanged.
Calculated, in this example, the mass volatilization rate of thallium was 97.94%, and the mass volatilization rates of lead, zinc and cadmium were 10.26%, 2.13% and 18.69%, respectively.
Comparative example 1
In this comparative example, the firing temperature was adjusted to 900 ℃ alone, and other conditions were kept unchanged as compared with example 5.
Calculated, in the comparative example, the mass volatilization rate of thallium is 99.76%, and the mass volatilization rates of lead, zinc and cadmium are 23.21%, 5.80% and 36.86%, respectively.
Based on comparative example 1, it can be seen that:
when the temperature is too high, the thallium-containing phase is destroyed and thallium is completely released, but under high temperature conditions, valuable metals are severely volatilized, and selective separation of thallium cannot be achieved.
Therefore, ensuring the roasting temperature at about 800 ℃ is critical for destroying the structure of thallium-containing phases and realizing the selective volatilization of thallium.
Comparative example 2
In this comparative example, the firing temperature was adjusted to 700 ℃ alone, and other conditions were kept unchanged as compared with example 5.
Calculated, in the comparative example, the mass volatilization rate of thallium is 75.23%, and the mass volatilization rates of lead, zinc and cadmium are 9.11%, 0.86% and 11.66%, respectively.
Comparative example 3
In this comparative example, the firing temperature was adjusted to 500℃as compared with example 5, and other conditions were kept unchanged.
Calculated, in the comparative example, the mass volatilization rate of thallium is 2.20%, and the mass volatilization rates of lead, zinc and cadmium are respectively 0.25%, 1.83% and 5.20%.
Based on comparative examples 2 to 3, it can be seen that:
when the temperature is too low, the structure of the thallium-containing phase is not destroyed, thallium is not completely released, and the thallium volatilization rate is low.
Therefore, ensuring the roasting temperature at about 800 ℃ is necessary to destroy the structure of thallium-containing phases and to achieve selective volatilization of thallium.
Comparative example 4
In this comparative example, the amount of the ground product was adjusted to 14.5g and the amount of sodium carbonate was adjusted to 0.5g, as compared with example 5, and the other conditions were maintained.
Calculated, in the comparative example, the mass volatilization rate of thallium is 31.55%, and the mass volatilization rates of lead, zinc and cadmium are 15.16%, 3.12% and 25.13%, respectively.
Based on comparative example 4, it can be seen that:
when the addition ratio of sodium carbonate is low, the structure of the thallium-containing phase is not destroyed, thallium is not completely released, and the thallium volatilization rate is low.
Thus, ensuring the sodium carbonate ratio is necessary to destroy the structure of the thallium-containing phase and to achieve selective volatilization of thallium.
Comparative example 5
In this comparative example, the sodium carbonate was replaced with calcium oxide alone, and the other conditions were maintained as compared with example 5.
Calculated, in the comparative example, the mass volatilization rate of thallium is 94.51%, and the mass volatilization rates of lead, zinc and cadmium are 3.79%, 42.12% and 32.53%, respectively.
Based on comparative example 5, it can be seen that:
sodium carbonate has a unique effect in the invention, and when the roasting temperature is 800 ℃, and the sodium carbonate is replaced by calcium oxide, the volatilization rate of valuable metals can be increased, so that the thallium volatilization selectivity can be reduced.
In the above technical solution of the present invention, the above is only a preferred embodiment of the present invention, and therefore, the patent scope of the present invention is not limited thereto, and all the equivalent structural changes made by the content of the present invention under the technical concept of the present invention, or the direct/indirect application in other related technical fields are included in the patent protection scope of the present invention.
Claims (10)
1. A thallium separation method based on sodium carbonate, comprising the steps of:
s1, mixing ground thallium-containing solid waste with sodium carbonate to obtain a mixture to be burned;
wherein the thallium-containing solid waste comprises zinc sulfate;
s2, roasting the mixture to be roasted to obtain a thallium-containing volatile matter and thallium-removing slag;
wherein the temperature of the roasting treatment is 750-850 ℃, and the duration of the roasting treatment is not less than 1h.
2. A sodium carbonate based thallium separation method according to claim 1, wherein the thallium containing solid waste comprises thallium containing fumes generated during zinc smelting.
3. A sodium carbonate based thallium separation method according to claim 2, characterized in that the thallium-containing soot comprises thallium in an amount of 0.5 to 0.7wt%.
4. A sodium carbonate based thallium separation method according to claim 1, wherein the thallium containing solid waste has a particle size of no more than 100 mesh after the grinding.
5. A sodium carbonate based thallium separation method according to claim 1, wherein the thallium containing solid waste further comprises a valuable metal fluorochloride compound comprising one or more of lead fluorochloride, zinc fluorochloride, and cadmium fluorochloride.
6. A thallium separation method based on sodium carbonate according to claim 1, wherein the mass ratio of sodium carbonate in the mixture to be burned is not less than 10%.
7. The sodium carbonate based thallium separation method according to claim 1, wherein the step S1 further comprises: and drying the thallium-containing solid waste before the grinding of the thallium-containing solid waste.
8. A sodium carbonate based thallium separation method according to claim 1, wherein in the step S1, the mixing process comprises: co-grinding the grinding product and the sodium carbonate to obtain a primary mixture; and then, carrying out oscillation treatment on the primary mixture to obtain the mixture to be burned.
9. A sodium carbonate based thallium separation method according to claim 1, wherein the roasting treatment is for a period of 1 to 3 hours.
10. A sodium carbonate based thallium separation method according to any one of claims 1 to 9, characterized in that the roasting treatment is performed under an air atmosphere or an inert atmosphere.
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