CN115418491B - Method for capturing platinum group metals by pyrometallurgy of bismuth base alloy - Google Patents
Method for capturing platinum group metals by pyrometallurgy of bismuth base alloy Download PDFInfo
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- CN115418491B CN115418491B CN202211148615.XA CN202211148615A CN115418491B CN 115418491 B CN115418491 B CN 115418491B CN 202211148615 A CN202211148615 A CN 202211148615A CN 115418491 B CN115418491 B CN 115418491B
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 144
- 239000002184 metal Substances 0.000 title claims abstract description 144
- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 88
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 238000000034 method Methods 0.000 title claims abstract description 65
- -1 platinum group metals Chemical class 0.000 title claims abstract description 64
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 31
- 239000000956 alloy Substances 0.000 title claims abstract description 31
- 238000009853 pyrometallurgy Methods 0.000 title claims abstract description 26
- 238000003723 Smelting Methods 0.000 claims abstract description 82
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 65
- 239000000463 material Substances 0.000 claims abstract description 64
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 51
- 239000002893 slag Substances 0.000 claims abstract description 31
- 229910052718 tin Inorganic materials 0.000 claims abstract description 27
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 26
- 230000008569 process Effects 0.000 claims abstract description 26
- JWVAUCBYEDDGAD-UHFFFAOYSA-N bismuth tin Chemical compound [Sn].[Bi] JWVAUCBYEDDGAD-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910002056 binary alloy Inorganic materials 0.000 claims abstract description 20
- 150000001875 compounds Chemical class 0.000 claims abstract description 16
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- 239000011734 sodium Substances 0.000 claims description 33
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 239000003638 chemical reducing agent Substances 0.000 claims description 17
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- BWOROQSFKKODDR-UHFFFAOYSA-N oxobismuth;hydrochloride Chemical compound Cl.[Bi]=O BWOROQSFKKODDR-UHFFFAOYSA-N 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 7
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- 235000019254 sodium formate Nutrition 0.000 claims description 6
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- 229910052708 sodium Inorganic materials 0.000 claims description 5
- 239000002028 Biomass Substances 0.000 claims description 4
- 229910052791 calcium Inorganic materials 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 230000001698 pyrogenic effect Effects 0.000 claims description 4
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 claims description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- 229910052796 boron Inorganic materials 0.000 claims description 3
- 238000004062 sedimentation Methods 0.000 claims description 3
- 241001669680 Dormitator maculatus Species 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 239000002210 silicon-based material Substances 0.000 claims description 2
- 240000007594 Oryza sativa Species 0.000 claims 1
- 241001062472 Stokellia anisodon Species 0.000 claims 1
- 229910000510 noble metal Inorganic materials 0.000 abstract description 13
- 230000008901 benefit Effects 0.000 abstract description 6
- 231100000252 nontoxic Toxicity 0.000 abstract description 4
- 230000003000 nontoxic effect Effects 0.000 abstract description 4
- 239000003054 catalyst Substances 0.000 description 27
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 23
- 239000002699 waste material Substances 0.000 description 22
- 239000010948 rhodium Substances 0.000 description 19
- 239000000126 substance Substances 0.000 description 17
- 239000002585 base Substances 0.000 description 14
- 229910052703 rhodium Inorganic materials 0.000 description 12
- 229910052763 palladium Inorganic materials 0.000 description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 239000007789 gas Substances 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 230000002378 acidificating effect Effects 0.000 description 8
- 229910052697 platinum Inorganic materials 0.000 description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 238000007599 discharging Methods 0.000 description 5
- 239000010419 fine particle Substances 0.000 description 5
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- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 5
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- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium Chemical compound [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 description 4
- 229910001152 Bi alloy Inorganic materials 0.000 description 3
- 229910006404 SnO 2 Inorganic materials 0.000 description 3
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- 238000007670 refining Methods 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000010953 base metal Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
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- 238000003912 environmental pollution Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910000765 intermetallic Inorganic materials 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 231100000956 nontoxicity Toxicity 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
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- 238000005096 rolling process Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229910016338 Bi—Sn Inorganic materials 0.000 description 1
- 241001391944 Commicarpus scandens Species 0.000 description 1
- 229910000519 Ferrosilicon Inorganic materials 0.000 description 1
- 229910000004 White lead Inorganic materials 0.000 description 1
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- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 229910052878 cordierite Inorganic materials 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 239000009519 fu-yuan Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- RYZCLUQMCYZBJQ-UHFFFAOYSA-H lead(2+);dicarbonate;dihydroxide Chemical compound [OH-].[OH-].[Pb+2].[Pb+2].[Pb+2].[O-]C([O-])=O.[O-]C([O-])=O RYZCLUQMCYZBJQ-UHFFFAOYSA-H 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
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- 239000011148 porous material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000001926 trapping method Methods 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
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
- C22B11/00—Obtaining noble metals
- C22B11/02—Obtaining noble metals by dry processes
- C22B11/021—Recovery of noble metals from waste materials
- C22B11/026—Recovery of noble metals from waste materials from spent catalysts
-
- 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
- C22B1/14—Agglomerating; Briquetting; Binding; Granulating
- C22B1/24—Binding; Briquetting ; Granulating
- C22B1/2406—Binding; Briquetting ; Granulating pelletizing
-
- 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
- C22B25/00—Obtaining tin
- C22B25/02—Obtaining tin by 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
- C22B30/00—Obtaining antimony, arsenic or bismuth
- C22B30/06—Obtaining bismuth
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B5/00—General methods of reducing to metals
- C22B5/02—Dry methods smelting of sulfides or formation of mattes
- C22B5/10—Dry methods smelting of sulfides or formation of mattes by solid carbonaceous reducing agents
-
- 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
- C22B9/00—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals
- C22B9/10—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals with refining or fluxing agents; Use of materials therefor, e.g. slagging or scorifying agents
- C22B9/103—Methods of introduction of solid or liquid refining or fluxing agents
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C12/00—Alloys based on antimony or 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
Abstract
The invention discloses a method for trapping platinum group metals by pyrometallurgy of bismuth-based alloys, and belongs to the technical field of noble metal smelting. According to the method for trapping platinum group metals by pyrometallurgy of bismuth-based alloy, metal bismuth or bismuth-containing compound and metal tin or tin-containing compound are used as trapping agents together, a pyrometallurgy process is adopted to perform smelting trapping on platinum group metal-containing materials, and then cooling and separation are carried out to obtain bismuth-tin binary alloy rich in platinum group metals and smelting slag. The bismuth-tin binary alloy is used as the platinum group metal trapping agent, the trapping rate of the platinum group metal can be effectively improved, and the bismuth-tin binary alloy has the advantages of low smelting temperature, green and nontoxic trapping agent, easiness in processing of binary alloy containing noble metal and the like.
Description
Technical Field
The invention belongs to the technical field of noble metal smelting, and particularly relates to a method for capturing Pd, pt and Rh in waste automobile exhaust catalysts or other platinum group metal-containing waste materials by pyrometallurgy of bismuth-base alloy.
Background
Platinum Group Metals (PGMs) platinum (Pt), palladium (Pd), rhodium (Rh) have excellent physical and chemical properties such as corrosion resistance, high temperature resistance, high catalytic activity, etc., and are widely used in various fields such as electric and electronic, jewelry, thermocouples, automobile exhaust catalysts, petrochemical industry, fuel cells, etc., wherein the amount of the Platinum Group Metals (PGMs) platinum (Pt), palladium (Pd), rhodium (Rh) is more than 1/2 of the total consumption in the field of automobile exhaust catalysts. Because of the limitation of the service life of the fuel automobiles, a large number of fuel automobiles are scrapped, and the waste automobile exhaust catalyst generated by the fuel automobiles becomes a very important platinum group metal secondary resource, and is known as a mobile platinum group metal mine.
The method for separating and enriching the platinum group metals by using the cordierite type waste automobile exhaust catalyst mainly comprises two processes of a fire method and a wet method, wherein the wet method mainly adopts strong acid and strong alkali to leach out the platinum group metals, so that the platinum group metals enter a solution or remain in leaching residues, the separation or enrichment of the platinum group metals is realized, and the fine particle metal palladium and rhodium on the surface layer of the catalyst are gradually changed into oxides insoluble in acid and alkali in the high-temperature use process, so that the metal leaching rate is seriously influenced.
The fire trapping method can be classified into copper trapping, lead trapping, iron trapping, sulfonium trapping, bismuth trapping, etc. according to the trapping agent used. The patent application CN201410407037.6 takes CuO as a trapping agent raw material, traps platinum group metals by reducing and smelting waste automobile exhaust catalysts at 1200-1400 ℃, the trapping rate of copper to the platinum group metals reaches more than 99%, and the total content of platinum, palladium and rhodium in smelting slag is less than 10g/t; zhao Guchun (noble metal, 2018,39 (1): 56-59) adopts CuO as collector raw material, uses dead car catalyst crushed to below 1mm as raw material, and can achieve platinum-palladium-rhodium recovery rate of above 97% under the condition of smelting at 1400 ℃ for 5h. But the smelting temperature of the current copper trapping process is higher, and the process flow of separating and refining platinum group metals from the noble copper electrolytic copper anode slime is longer.
The metal lead is used as a noble metal trapping agent and is mainly applied to the field of pyrometallurgy analysis and detection, and patent application CN201110109986.2 discloses a method for trapping Pt, pd and Rh in a waste automobile catalyst by using lead, and the noble lead can be further highly enriched in platinum group metals by vacuum distillation at 900-1200 ℃, and the total grade of the platinum group metals in smelting slag is less than 1.5g/t; shao Kun (noble metal, 2019,40 (03)) 66-69+83 uses basic lead carbonate as trapping agent, and smelting trace noble metal in ore sample at 1050 deg.C for 30min to obtain noble lead, and then quantitatively enriching noble metal in about 50mg of lead particles by using lead-retaining ash blowing method to obtain ideal detection effect. However, lead and its oxide have high volatility and are liable to cause heavy metal environmental pollution.
Metallic iron is a good collector of platinum group metals, patent application CN201810185054.8 with Fe 3 O 4 The method is characterized in that the method is used as a trapping agent raw material, the trapping of platinum in the waste catalyst is realized at 1600-2000 ℃, the recovery rate is more than 99%, and the platinum content in smelting slag is 5-15g/t; li Yong et al (nonferrous metals (smelting part), 2017 (8): 40-43) are directed to the trapping of platinum group metals in spent automotive exhaust catalysts, in Fe 3 O 4 As a trapping agent raw material, the platinum, palladium and rhodium can be comprehensively recovered to more than 97% after smelting for 4 hours at 1450 ℃. However, iron is used as a trapping agent, the smelting temperature is high, the energy consumption is high, and the subsequent separation of the iron matrix is difficult due to the formation of ferrosilicon alloy in the smelting process. Sulfonium can also be used as a precious metal trapping agent, and patent application CN201710856842.0 uses Ni 3 S 2 The platinum group metal in the waste catalyst is trapped by microwave smelting at 1050-1200 ℃ as trapping agent, the smelting temperature of the sulfonium trapping is lower than the temperature of other metal trapping processes, but the flow of separating and refining the platinum group metal from the sulfonium is longer, SO that the catalyst has SO to a certain extent 2 Environmental risk.
The patent application CN201911196098.1 adopts bismuth as a trapping agent, and the platinum group metals in the waste automobile exhaust catalyst are enriched by the pyrometallurgy reduction smelting, so that the inventor optimally designs the smelting process, and the recovery rate of the platinum group metals is improved; zhang Fuyuan et al (Chinese nonferrous metals journal 2020,30 (09): 2162-2170) adopts metal Bi to trap Pd, pt and Rh in waste automobile catalyst, and selects Na 2 O-SiO 2 -Al 2 O 3 -Bi 2 O 3 Slag is easy to separate, the noble bismuth surface is bright, and the recovery rates of Pd, pt and Rh are 98.90%, 95.02% and 97.00% respectively under the optimized conditions that the alkalinity of slag is 0.71, the metal bismuth is 1.9g, the mass ratio of silicon to boron is 0.94:1 and the smelting is carried out at 1100 ℃ for 10 min. The metal bismuth as the trapping agent can effectively solve the industrial problems of difficult base metal separation, large toxicity, high smelting temperature and the like, is a good trapping agent with good prospect, but the bismuth is trapped by the trapping agentThe obtained bismuth is brittle and fragile, and cannot be slammed in the slag separation process.
Therefore, how to overcome the defects of the prior art for capturing platinum group metals by aiming at the pyrometallurgical waste automobile exhaust catalyst is provided, and the novel process for efficiently enriching Pd, pt and Rh by the pyrometallurgical waste materials containing platinum group metals has important significance.
Disclosure of Invention
1. Problems to be solved
The invention aims to overcome the defects of the conventional platinum group metal pyrogenic process and provides a novel method for capturing platinum group metals by pyrogenic smelting of bismuth base alloy. The bismuth-tin binary alloy is used as the platinum group metal trapping agent, so that the trapping effect of the trapping agent on the platinum group metal is effectively enhanced, and the bismuth-tin binary alloy has the advantages of low smelting temperature, green and nontoxic trapping agent, easiness in processing of noble metal-containing binary alloy and the like.
2. Technical proposal
In order to solve the problems, the technical scheme adopted by the invention is as follows:
the invention relates to a method for capturing platinum group metals by pyrometallurgy of bismuth-based alloy, which takes metallic bismuth or bismuth-containing compound and metallic tin or tin-containing compound as capturing agents, and carries out smelting capturing on platinum group metal-containing materials, and then the bismuth-tin binary alloy and smelting slag which are rich in platinum group metals are obtained through sedimentation, cooling and separation.
The technical principle of the invention is based on Bi-Sn binary alloy phase diagram, when Sn content is 0-57% (wt) and temperature is 139-231.9 ℃, metal bismuth and metal tin can form eutectic, bismuth-tin binary alloy is used as platinum group metal trapping agent, and a novel method for trapping platinum group metals by bismuth-base alloy at low temperature is established. Because the metal tin has better ductility, the mechanical property of the binary alloy can be improved, the binary alloy rich in noble metal has good machining performance, and the metal tin and the platinum group metal can form various intermetallic compounds, so that the trapping effect on the platinum group metal can be improved in the smelting process. Meanwhile, the metal bismuth and tin have the characteristics of low melting point, high density, greenness, no toxicity and the like, and are favorable for reducing the smelting temperature, improving the separation effect of slag phase and alloy phase and realizing the zero-pollution smelting process of heavy metal. Therefore, the invention uses bismuth and tin as the trapping agent, and has the advantages of low smelting temperature, good metal trapping effect, environment-friendly and nontoxic trapping agent, easy processing of binary alloy containing noble metal, and the like.
Further, the total mass of bismuth in the trapping agent is 0.1-1.0 times of the mass of the platinum group metal-containing raw material, and the total mass of tin is 0.1-0.5 times of the total mass of bismuth. The addition ratio of the raw materials containing the platinum group metals is determined according to the total amount of the platinum group metals and the trapping rate of the binary tin-bismuth alloy to the platinum group metals, but the specific requirements are that: the platinum group metal content in the sample is more, the addition of less metal bismuth and tin can lead the platinum group metal grade in the bismuth-tin binary alloy to be higher, but the platinum group metal trapping efficiency can be reduced, the platinum group metal content in the sample is less, the addition of more metal bismuth and tin can lead the platinum group metal trapping to be more complete, but the platinum group metal grade in the bismuth-tin binary alloy is reduced, and the enrichment ratio of the platinum group metal is reduced.
Further, the metallic bismuth or bismuth-containing compound comprises Bi, bi 2 O 3 、BiOCl、Bi 2 O 2 CO 3 、BiCl 3 Bismuth, bismuth bloom, bismuth ore and Bi (OH) 3 One or more of the following is preferably bismuth, biOCl, bi 2 O 2 CO 3 One or more of Bi; the metal tin or tin-containing compound includes Sn, snO 2 、SnCl 4 And Sn (OH) 4 One or a combination of more than one of the above.
Further, the method specifically comprises the following steps:
step one, sample preparation and batching
Putting the crushed platinum group metal-containing material, a fluxing agent, a trapping agent and a reducing agent into a ball mill according to a certain mass ratio, and fully ball-milling and mixing to obtain a mixed material;
step two, pelletizing the raw materials
Pelletizing the mixed material in the first step to obtain pellets with qualified granularity, and drying and dehydrating the pellets;
step three, preheating and smelting catching pellets
The dried pellets are firstly placed into a muffle furnace which is heated to 600-900 ℃ to be preheated for 30-80min, materials in a crucible are rapidly heated, biomass is heated and dehydrated to form fine particle amorphous activated carbon, the nascent state activated carbon reduces metal oxides into simple substances, and the form of the pellets is maintained; after preheating, the temperature is continuously raised to 1000-1200 ℃ for smelting for 30-80min, the pellets are gradually melted to enable platinum group metal microparticles to be gradually exposed in the melt, the fine particle metal simple substance trapping agent is combined with the exposed platinum group metal particles, and the particles start to be settled to the bottom of the crucible after growing up to a certain degree. And taking out the crucible after smelting, rapidly pouring the melt into a mold, slowly cooling, and separating to obtain binary tin-bismuth alloy rich in platinum group metals and smelting slag.
Still further, the flux includes three components, wherein component I is a compound containing sodium, potassium, calcium or bismuth, component II is silicon or a silicon-containing compound, and component III is a boron-containing compound, wherein component I provides an alkaline substance, component II, component III provides an acidic substance, and the acidity of the silicon is adjusted by complexing the alkaline substance with the acidic substance.
Further, the component I is Na 2 CO 3 、NaHCO 3 、NaOH、CH 3 COONa、HCOONa、CH 3 CH 2 COONa、C 3 H 3 O 2 Na、C 7 H 5 NaO 2 、KOH、KCl、K 2 CO 3 、KHCO 3 、K 2 SO 4 、KHSO 4 、CaO、CaCO 3 、Ca(OH) 2 、Bi 2 O 3 、BiOCl、Bi 2 O 2 CO 3 、BiCl 3 Bismuth, bismuth bloom, bismuth ore, bi (OH) 3 One or a combination of more than one of the above; the component II is Si, siO 2 、Na 2 O·nSiO 2 、Na 2 SiO 3 One or more of glass powder; component III is Na 2 O·2B 2 O 3 ·10H 2 O、H 3 BO 3 、NaBO 2 、NaCa(B 5 O 9 )·8H 2 O、Na 2 B 4 O 7 ·4H 2 O、CaB 6 O 11 ·5H 2 O, or a combination of one or more of them.
Furthermore, the alkaline substance in the component I is preferably sodium and calcium-containing substances, can reduce the melting point of slag, reduce the viscosity of slag, is favorable for the sedimentation of bismuth-tin alloy, and is more preferably HCOONa and CaCO 3 、NaOH、Na 2 CO 3 、NaHCO 3 、CH 3 COONa and Ca (OH) 2 One or a combination of more than one of the above; component II is preferably Si, siO 2 One or more of glass powder; component III is preferably Na 2 O·2B 2 O 3 ·10H 2 O、H 3 BO 3 、Na 2 B 4 O 7 ·4H 2 O, or a combination of one or more of them.
Furthermore, the reducing agent adopts biomass such as agricultural and forestry waste (straw, sawdust, bagasse, rice chaff, forestry residues and the like) or household garbage and the like, the granularity of the mixed material obtained after ball milling in the first step is smaller than 200 meshes, and the proportion of the materials is controlled to be 0.5-2.
The smaller sample particle size is more representative, the finer sample particle size is favorable for the even distribution of platinum group metals, the interaction force among particles is enhanced in the pelletizing process, the pellets are not easy to break, the smelting trapping effect is ensured, the smaller particle size increases the ball milling cost, so that the ball milling time is preferably 15min, and the material particle size is more than 99% of-200 meshes.
Further, the reducing agent is preferably one or more of crop straw, sawdust, bagasse and rice chaff; when the silicic acid degree is too low, slag is alkaline, a crucible and refractory materials are easy to corrode, and the high-melting-point refractory materials are introduced to change the silicon acidity of the slag, so that the viscosity of the slag is increased, and the metal trapping is not facilitated; the excessive acidity is that the slag is acidic and the melting point of the slag is raised, so that the proportion of each material in the first step is more preferably controlled to be 0.5-1.5, and more preferably 1.0.
Furthermore, organic matters can be used as the trapping agent and the fluxing agent in the first step, and the organic matters contain carbon elements and are dehydrated at high temperature to form amorphous active carbon, so that the reducibility of the matters is considered when the reducing agent is added, and the use amount of the reducing agent is reduced.
Furthermore, in the second step, a disc pelletizer is adopted for pelletizing, the mixed materials are continuously and evenly added into the disc pelletizer, the inclination angle of the disc is controlled to be 40-50 degrees, the rotating speed is controlled to be 6-10r/min, meanwhile, the mixed materials are continuously sprayed to form mother balls with uniform granularity after rolling and rubbing under the combined action of gravity, centrifugal force and friction force, the mother balls with moist surfaces continuously roll and rub on the fine-granularity materials, and a layer of material with lower wetting degree is easily stuck in the process, so that the mother balls are continuously grown and have certain strength. Different pellets are automatically classified in the disc to move along different tracks (materials in the disc can regularly move according to the particle size of the materials per se in the pelletizing process and all have respective movement tracks, the movement tracks with large particle size are close to the disc edge, the movement tracks of the materials with small particle size or materials without being pelletized are close to the disc bottom and far away from the disc edge, when the ball size reaches the requirement, the balls with small particle size are automatically discharged from the disc edge and continuously roll and grow up close to the disc bottom), the pellets are discharged from the disc after reaching 10-12mm, the size of the pellets is not excessively large due to poor heat conductivity of the green pellets, and the pelletizing difficulty is correspondingly increased when the size is larger. And then drying and dehydrating the pellets for 1-5h at the temperature of 110-150 ℃.
Furthermore, the total amount of water sprayed in the pelletizing process is 40% -50% of the material addition amount, and the following is worth explaining: too much water can cause the material to lose rolling ability and not form a mother ball, too little water can cause the material to adhere, preferably 45%. At the same time, the angle of inclination of the turntable must be greater than the angle of repose of the material, otherwise the material will form a layer of powder that is stationary relative to the base of the turntable, moving in synchronism with the turntable. The rotating speed is set according to the inclination angle, if the rotating speed is too high, the pressure of the material to the disc bottom is reduced, the material is suspended, the disc surface material cannot be fully utilized, and the yield of the disc pelletizer is reduced; the rotating speed is too low, the materials cannot roll and rub, the balls cannot be formed, and the disc inclination angle is preferably 50 degrees, and the rotating speed is preferably 8r/min.
3. Advantageous effects
Compared with the prior art, the invention has the beneficial effects that:
(1) According to the method for capturing platinum group metals by the pyrometallurgy bismuth base alloy, the cooperation of the metal bismuth and the tin or the compound thereof is used as the capturing agent, the metal bismuth and the tin or the compound thereof are easier to be reduced into a metal state in the smelting process compared with other capturing agents, the capturing agent is used for capturing the platinum group metals, the good impurity removal effect is achieved, and meanwhile, the metal bismuth and the metal tin can form low-melting-point binary alloy, so that the smelting temperature is reduced.
(2) The method for trapping platinum group metals by the pyrometallurgy bismuth base alloy has the advantages of low smelting temperature, good metal trapping effect, environment-friendly and nontoxic trapping agent, easiness in processing noble metal-containing alloy, strong raw material applicability, wide application range and the like, can be used for efficiently trapping various catalyst materials and intermediate products in a wide content range, and can be popularized to the smelting trapping of other platinum group metal-containing materials.
(3) The method for capturing platinum group metals by the pyrogenic smelting bismuth base alloy has the advantages of low melting point, high density, greenness and no toxicity of the metal bismuth and tin, larger specific gravity of bismuth-tin binary alloy, contribution to two-phase separation, and capabilities of solving the defects of difficult separation of base metals, large toxicity of capturing agents, high smelting temperature and the like in the traditional process, simultaneously forming binary alloy by the metal bismuth and the metal tin in the smelting process, and avoiding the influence on the subsequent platinum group metal refining caused by the fact that impurities are introduced into the alloy due to reaction with the main components of the catalyst or the flux.
(4) According to the method for trapping platinum group metals by the pyrometallurgy bismuth base alloy, disclosed by the invention, the trapping agent is metal, metal oxide or metal salt, so that the generation of toxic and harmful gases can be effectively avoided in the smelting process, and the method has the advantage of environmental protection; meanwhile, the metal tin has better ductility, so that the alloy rich in noble metal obtained by smelting is easy to process, and the metal tin and platinum group metal form an intermetallic compound to play a role in protecting the platinum group metal.
(5) According to the method for trapping platinum group metals by the pyrometallurgy bismuth base alloy, the platinum group metal-containing materials, the fluxing agent, the trapping agent and the reducing agent are mixed according to the mass ratio, then the pelleting treatment is carried out, and then the smelting trapping is carried out, so that excessive dust and oxidation of the reducing agent generated in the traditional pyrometallurgy process can be effectively avoided, the gas generated by the reaction is discharged in time by micro-voids in the sphere, and the trapping rate of Pd, pt and Rh is improved.
Drawings
Fig. 1 is a process schematic diagram of a method for trapping platinum group metals by pyrometallurgy of bismuth-based alloys according to the invention.
Detailed Description
The invention provides a new method for capturing Pd, pt and Rh in waste automobile exhaust catalyst or other platinum group metal-containing waste materials by using a pyrometallurgy bismuth-based binary alloy. The invention mixes waste automobile exhaust catalyst or other waste containing platinum group metal with fluxing agent, trapping agent and reducing agent according to mass ratio, then carries out pelleting treatment, and then carries out smelting trapping. When smelting and capturing, firstly placing the pellets into a muffle furnace for preheating for 30-80min at 500-900 ℃, and carrying out multiphase reaction inside the pellets in the preheating process, such as heating and dehydrating a biomass reducer to form fine particle amorphous activated carbon, evaporating crystal water, evaporating free water to gasify, decomposing salts and the like, wherein the pellets begin to be bonded, the pores are reduced, the pellets shrink and densify, and the reducing atmosphere is sufficient.
Noteworthy are: the powdery material has larger volume, a large amount of gas generated in the smelting process is easy to take away fine particle materials to form smoke dust, the volume of the material is reduced after pelletizing, and the gas escapes from the micro-voids of the pellets, so that the material loss, the dust amount is greatly reduced, the environmental pollution is reduced, and meanwhile, the rapid temperature rise of the material during charging is avoided, and the material overflows due to excessively violent reaction.
After heat treatment, the temperature is continuously raised to 1000-1200 ℃ for smelting and trapping for 30-80min, the pellets are gradually melted to enable platinum group metal microparticles to be gradually exposed to the melt, and the trapping agent and the exposed platinum group metal are collided, combined, pooled and settled in the melt. When the smelting temperature is lower than 1000 ℃, the pellets are in a semi-molten state, and the reduced metal trapping agent is in incomplete contact with platinum group metal microparticles, so that precious metal trapping is poor; when the smelting temperature is higher than 1200 ℃, the viscosity of slag is reduced, and part of trapping agent metal particles do not sufficiently trap platinum group metals, namely the metal particles begin to gather and settle, so that the smelting cost is increased due to the excessively high temperature. And taking out the crucible after smelting, rapidly pouring the melt into a mould, preserving heat and slowly cooling, so that the binary tin-bismuth alloy containing the platinum group metals is fully settled.
The invention is further described below in connection with specific embodiments. The platinum group metal-containing material of the present invention may be an automobile exhaust catalyst or may be generalized to other platinum group metal-containing materials, but only the automobile exhaust catalyst is used as an example for detailed explanation.
Example 1
Referring to fig. 1, a method for trapping platinum group metals by pyrometallurgical smelting of bismuth-based alloys in this embodiment includes the following steps:
step one: preparation and formulation of samples
Weighing 500.00g of crude crushed and finely crushed automobile waste tail gas catalyst, and adding 18.57g of bismuth and 20.76g of BiOCl and Bi 2 O 2 CO 3 20.32g and SnO 2 6.34g, further HCOONa 384.61g, caCO 3 500.00g and 187.51g of NaOH as alkaline material, na 2 O·2B 2 O 3 ·10H 2 O 243.48、H 3 BO 3 143.94g of acidic substances, 2.70g of crop straw as a reducing agent, 2.80g of sawdust and 3.30g of rice chaff are put into a ball mill for full ball milling for 15min, and the silicon acidity of the material is K=0.5.
Step two: pelletizing raw materials
And (3) continuously and uniformly adding 1.5kg of mixed materials into a YZL-25 disc pelletizer through a belt conveyor, controlling the inclination angle of the disc to be 50 degrees and the rotating speed to be 8r/min, continuously spraying the materials to form a mother ball, automatically classifying the mother ball in the disc after the mother ball is continuously long, running along different tracks, discharging the pellets from the disc after the pellet granularity reaches 10-12mm, and drying and dehydrating the pellets for 2h at 140 ℃.
Step three: pellet preheating and smelting trapping
Placing 200g of dried pellets into a crucible, preheating for 30min in a muffle furnace which is heated to 700 ℃, continuously heating to 1100 ℃ for smelting for 80min after preheating, taking out the crucible after smelting, rapidly pouring the melt into a mold for slow cooling, and separating to obtain binary bismuth-tin alloy (Bi 90%g, sn 9%g) and Na which are rich in platinum group metals after complete cooling 2 O-CaO-B 2 O 3 Slag.
TABLE 1 example 1 results of fire smelting bismuth-based Capture analysis
| Name of the name | Weight/g | Pt g/t | Pd g/t | Rh g/t |
| Pellet mass | 200.00 | 10.33 | 89.55 | 20.55 |
| Tin alloy with noble bismuth | 6.60 | 252 | 2562 | 562 |
| Smelting slag | —— | <2 | <5 | <2 |
Example 2
The method for capturing platinum group metals by pyrometallurgy of bismuth base alloys in the embodiment comprises the following steps:
step one: preparation and formulation of samples
Weighing 500.00g of a waste and tail gas catalyst of a certain domestic automobile after coarse crushing and fine crushing, and respectively adding 103.86g of a platinum group metal trapping agent BiOCl and Bi 2 O 2 CO 3 101.67g, bi 83.33g and SnCl 4 119.79g、Sn(OH) 4 117.96g, adding 187.50g of NaOH and Na 2 CO 3 500.00g、NaHCO 3 394.74g of alkaline substance, na 2 O·2B 2 O 3 ·10H 2 O 269.11g、SiO 2 105.53g of acidic substance, 35.14g of crop straw as a reducing agent and putting the mixture into a ball mill for ball milling for 15min, wherein the silicon acidity of the material is K=1.0.
Step two: pelletizing raw materials
And continuously and uniformly adding 2kg of mixed materials into a YZL-25 disc pelletizer through a belt conveyor, controlling the inclination angle of the disc to be 50 degrees and the rotating speed to be 8r/min, continuously spraying the materials to form a mother ball, automatically classifying the mother ball in the disc after the mother ball is continuously grown, running along different tracks, discharging the pellets from the disc after the pellet granularity reaches 10-12mm, and drying and dehydrating the pellets for 3 hours at 130 ℃.
Step three: pellet preheating and smelting trapping
Placing 200g of dried pellets into a crucible, preheating in a muffle furnace which is heated to 600 ℃ for 50min, continuously heating to 1000 ℃ for smelting for 50min after preheating, taking out the crucible after smelting, rapidly pouring the melt into a mold for slow cooling, and separating to obtain binary bismuth-tin alloy (Bi 76% and Sn) rich in platinum group metals after complete cooling22%) and Na 2 O-SiO 2 -B 2 O 3 Slag of slag
TABLE 2 example 2 results of fire bismuth-based capture analysis
| Name of the name | Weight/g | Pt g/t | Pd g/t | Rh g/t |
| Pellet mass | 200 | 20.33 | 100.50 | 40.85 |
| Tin alloy with noble bismuth | 26.82 | 136 | 712 | 274 |
| Smelting slag | —— | <2 | <5 | <4 |
Example 3
The method for capturing platinum group metals by pyrometallurgy of bismuth base alloys in the embodiment comprises the following steps:
step one: preparation and formulation of samples
Weighing 500.00g of a waste and tail gas catalyst of a certain domestic automobile after coarse crushing and fine crushing, and respectively adding 225.27g of platinum group metal trapping agent bismuth, 207.69g of BiOCl, 166.66g of Bi and SnO 2 105.79g、SnCl 2 133.11g and 83.33g of Sn, then CaCO is added 3 351.56g、CH 3 COONa 281.25g, HCOONa 234.37g and Ca (OH) 2 255.68g of alkaline substance, 211.06g of glass powder and H 3 BO 3 290.69g、Na 2 B 4 O 7 ·4H 2 595.30g of acidic substance, 25.04g of crop straw as a reducing agent and 24.97g of bagasse are added, and the mixture is put into a ball mill for full ball milling for 15min, wherein the silicon acidity of the material is K=1.5.
Step two: pelletizing raw materials
And (3) continuously and uniformly adding 3.5kg of mixed materials into a YZL-25 disc pelletizer through a belt conveyor, controlling the inclination angle of the disc to be 50 degrees and the rotating speed to be 8r/min, continuously spraying the materials to form a mother ball, automatically classifying the mother ball in the disc after the mother ball is continuously long, running along different tracks, discharging the pellets from the disc after the pellet granularity reaches 10-12mm, and drying and dehydrating the pellets for 1h at 150 ℃.
Step three: pellet preheating and smelting trapping
Placing 200g of dried pellets into a crucible, preheating for 80min in a muffle furnace heated to 900 ℃, continuously heating to 1200 ℃ for smelting for 30min after preheating, taking out the crucible after smelting, rapidly pouring the melt into a mold for slow cooling, and separating to obtain binary bismuth-tin alloy (Bi 66%, sn 33%) rich in platinum group metals and Na after complete cooling 2 O-CaO-B 2 O 3 Slag.
TABLE 3 example 3 results of fire smelting bismuth-based Capture analysis
| Name of the name | Weight/g | Pt g/t | Pd g/t | Rh g/t |
| Pellet mass | 200 | 50.90 | 200 | 102.99 |
| Tin alloy with noble bismuth | 40.51 | 246 | 967 | 498 |
| Smelting slag | —— | <1 | <4 | <2 |
Example 4
The method for capturing platinum group metals by pyrometallurgy of bismuth base alloys in the embodiment comprises the following steps:
step one: preparation and formulation of samples
Weighing 500.00g of a waste and tail gas catalyst of a certain domestic automobile after coarse crushing and fine crushing, and respectively adding 55.74g of a platinum group metal trapping agent bismuth and Bi 2 O 2 CO 3 6100g, bi 50g and SnCl 4 15.97g、Sn(OH) 4 15.73g of Sn 10.00g, and CaCO is added 3 468.75g、Na 2 CO 3 500.00g、NaHCO 3 394.74g of alkaline substance, siO 2 182.93g、Na 2 O·2B 2 O 3 ·10H 2 O 498.88g、Na 2 B 4 O 7 ·4H 2 515.92g of acidic substance, 8.10g of crop straw as a reducing agent and 9.40g of rice chaff are added, and the mixture is put into a ball mill for full ball milling for 20min, wherein the silicon acidity of the mixture is K=1.3.
Step two: pelletizing raw materials
And (3) continuously and uniformly adding 3kg of mixed materials into a YZL-25 disc pelletizer through a belt conveyor, controlling the inclination angle of the disc to be 45 degrees and the rotating speed to be 6r/min, continuously spraying the materials to form a mother ball, automatically classifying the mother ball in the disc after the mother ball is continuously grown, running along different tracks, discharging the pellets from the disc after the pellet granularity reaches 10-12mm, and drying and dehydrating the pellets at 110 ℃ for 5h.
Step three: pellet preheating and smelting trapping
Placing 200g of dried pellets into a crucible, preheating in a muffle furnace which is heated to 900 ℃ for 60min, continuously heating to 1100 ℃ for smelting for 30min after preheating, taking out the crucible after smelting, rapidly pouring the melt into a mold for slow cooling, and separating to obtain binary bismuth-tin alloy (Bi 83%, sn 15%) and Na which are rich in platinum group metals after complete cooling 2 O-CaO-B 2 O 3 Slag.
TABLE 4 example 4 results of fire bismuth-based capture analysis
| Name of the name | Weight/g | Pt g/t | Pd g/t | Rh g/t |
| Pellet mass | 200.00 | 30.11 | 263.11 | 122.33 |
| Tin alloy with noble bismuth | 12.97 | 448 | 4010 | 1870 |
| Smelting slag | —— | <1 | <3 | <1 |
Example 5
The method for capturing platinum group metals by pyrometallurgy of bismuth base alloys in the embodiment comprises the following steps:
step one: preparation and formulation of samples
Weighing 500.00g of a waste and tail gas catalyst of a certain domestic automobile after coarse crushing and fine crushing, and respectively adding 148.64g of a platinum group metal trapping agent bismuth and Bi 2 O 2 CO 3 162.68g, bi 133.33g and SnO 2 101.71g and 80g Sn, and Ca (OH) are added 2 347.22、NaOH 187.5g、Na 2 CO 3 150g of alkaline substance, siO 2 281.43g, 351.79g of glass powder and H 3 BO 3 385.56g of acidic material, 46.66g of crop straw as a reducing agent and 52.83g of bagasse are added into a ball millBall milling is carried out for 25min, and the silicon acidity of the material is K=2.0.
Step two: pelletizing raw materials
And (3) continuously and uniformly adding 3kg of mixed materials into a YZL-25 disc pelletizer through a belt conveyor, controlling the inclination angle of the disc to be 40 degrees and the rotating speed to be 10r/min, continuously spraying the materials to form mother balls, automatically classifying the mother balls in the disc after the mother balls are continuously grown, running along different tracks, discharging the pellets from the disc after the pellet granularity reaches 10-12mm, and drying and dehydrating the pellets for 3 hours at 125 ℃.
Step three: pellet preheating and smelting trapping
Placing 200g of dried pellets into a crucible, preheating in a muffle furnace which is heated to 750 ℃ for 45min, continuously heating to 1000 ℃ for smelting for 50min after preheating, taking out the crucible after smelting, rapidly pouring the melt into a mold for slow cooling, and separating to obtain binary bismuth-tin alloy (Bi 70%, sn 27%) rich in platinum group metals and Na after complete cooling 2 O-SiO 2 -B 2 O 3 Slag.
TABLE 5 example 5 results of fire smelting bismuth-based Capture analysis
| Name of the name | Weight/g | Pt g/t | Pd g/t | Rh g/t |
| Pellet mass | 200.00 | 45.22 | 301.11 | 155.26 |
| Tin alloy with noble bismuth | 35.25 | 239.55 | 1691 | 864 |
| Smelting slag | —— | <3 | <3 | <3 |
Claims (8)
1. A method for capturing platinum group metals by using a pyrometallurgy bismuth base alloy is characterized by comprising the following steps: taking metal bismuth or bismuth-containing compound and metal tin or tin-containing compound as trapping agents, adopting a pyrogenic process to smelt and trap platinum group metal-containing materials, and carrying out sedimentation, cooling and separation on melt to obtain bismuth-tin binary alloy rich in platinum group metals and smelting slag; the total mass of tin in the trapping agent is 0.1-0.5 times of the total mass of bismuth, and the smelting trapping temperature is 1000-1200 ℃; the method specifically comprises the following steps:
step one, sample preparation and batching
Putting the crushed platinum group metal-containing material, a fluxing agent, a trapping agent and a reducing agent into a ball mill according to a certain mass ratio, and fully ball-milling and mixing to obtain a mixed material; the fluxing agent comprises three components, wherein the component I is a compound containing sodium, potassium, calcium or bismuth, the component II is silicon or a silicon-containing compound, and the component III is a boron-containing compound;
step two, pelletizing the raw materials
Pelletizing the mixed material in the first step to obtain pellets with qualified granularity and strength, and drying and dehydrating the pellets;
step three, preheating and smelting catching pellets
And (3) firstly placing the dried pellets into a muffle furnace which is heated to 600-900 ℃ to be preheated for 30-80min, continuously heating to 1000-1200 ℃ to be smelted for 30-80min after preheating, taking out a melt after smelting, pouring the melt into a mold to be cooled, and separating after the melt is completely cooled to obtain the binary bismuth tin alloy rich in platinum group metals and smelting slag.
2. The method for trapping platinum group metals by pyrometallurgy of bismuth-based alloys according to claim 1, wherein: the total mass of bismuth in the trapping agent is 0.1-1.0 times of the mass of platinum group metal-containing materials.
3. The method for trapping platinum group metals by pyrometallurgy of bismuth-based alloys according to claim 1 or 2, characterized in that: the metal bismuth or bismuth-containing compound comprises Bi, bi 2 O 3 、BiOCl、Bi 2 O 2 CO 3 、BiCl 3 Bismuth, bismuth bloom, bismuth ore and Bi (OH) 3 One or more of the metal tin or tin-containing compound comprises Sn, snO 2 、SnCl 4 And Sn (OH) 4 One or a combination of more than one of the above.
4. The method for trapping platinum group metals by pyrometallurgy of bismuth-based alloys according to claim 1, wherein: the component I is Na 2 CO 3 、NaHCO 3 、NaOH、CH 3 COONa、HCOONa、CH 3 CH 2 COONa、C 3 H 3 O 2 Na、C 7 H 5 NaO 2 、KOH、KCl、K 2 CO 3 、KHCO 3 、K 2 SO 4 、KHSO 4 、CaO、CaCO 3 、Ca(OH) 2 、Bi 2 O 3 、BiOCl、Bi 2 O 2 CO 3 、BiCl 3 Bismuth, bismuth bloom, bismuth ore, bi (OH) 3 One or a combination of more than one of the above; the component II is Si, siO 2 、Na 2 O·nSiO 2 、Na 2 SiO 3 One or more of glass powder; component III is Na 2 O·2B 2 O 3 ·10H 2 O、H 3 BO 3 、NaBO 2 、NaCa(B 5 O 9 )·8H 2 O、Na 2 B 4 O 7 ·4H 2 O、CaB 6 O 11 ·5H 2 O, or a combination of one or more of them.
5. The method for trapping platinum group metals by pyrometallurgy of bismuth-based alloys according to claim 4, wherein: the component I is HCOONa, caCO 3 、NaOH、Na 2 CO 3 、NaHCO 3 、CH 3 COONa and Ca (OH) 2 One or a combination of more than one of the above; the component II is Si, siO 2 One or more of glass powder; component III is Na 2 O·2B 2 O 3 ·10H 2 O、H 3 BO 3 、Na 2 B 4 O 7 ·4H 2 O, or a combination of one or more of them.
6. The method for trapping platinum group metals from pyrometallurgical bismuth base alloys according to any of claims 1, 2, 4, 5, characterized by: the reducing agent adopts biomass, the granularity of the mixed material obtained after ball milling in the first step is less than 200 meshes, and the proportion of the materials is controlled to be 0.5-2.
7. The method for trapping platinum group metals by pyrometallurgy of bismuth-based alloys according to claim 6, wherein: the reducing agent is one or the combination of more than one of crop straw, sawdust, bagasse and rice chaff, and the proportion of the materials in the first step is controlled to be 0.5-1.5.
8. The method for trapping platinum group metals from pyrometallurgical bismuth base alloys according to any of claims 1, 2, 4, 5, characterized by: and step two, pelletizing by adopting a disc pelletizer, continuously and uniformly adding the mixed materials into the disc pelletizer, controlling the inclination angle of the disc to be 40-50 degrees and the rotating speed to be 6-10r/min, continuously spraying the materials, and pelletizing to control the particle size of pellets to be 10-12mm.
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