CN114990347B - Method for recycling platinum group metals in waste catalysts through pyrometallurgy - Google Patents
Method for recycling platinum group metals in waste catalysts through pyrometallurgy Download PDFInfo
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 124
- 239000002184 metal Substances 0.000 title claims abstract description 124
- -1 platinum group metals Chemical class 0.000 title claims abstract description 82
- 239000003054 catalyst Substances 0.000 title claims abstract description 52
- 238000000034 method Methods 0.000 title claims abstract description 52
- 239000002699 waste material Substances 0.000 title claims abstract description 40
- 238000009853 pyrometallurgy Methods 0.000 title claims abstract description 19
- 238000004064 recycling Methods 0.000 title claims abstract description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 51
- 239000002893 slag Substances 0.000 claims abstract description 48
- TUFZVLHKHTYNTN-UHFFFAOYSA-N antimony;nickel Chemical compound [Sb]#[Ni] TUFZVLHKHTYNTN-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000003723 Smelting Methods 0.000 claims abstract description 38
- 229910000990 Ni alloy Inorganic materials 0.000 claims abstract description 34
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 33
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims abstract description 33
- 238000011084 recovery Methods 0.000 claims abstract description 33
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 25
- 229910000905 alloy phase Inorganic materials 0.000 claims abstract description 24
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 23
- 239000002253 acid Substances 0.000 claims abstract description 14
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 12
- 238000004090 dissolution Methods 0.000 claims abstract description 8
- 238000000926 separation method Methods 0.000 claims abstract description 8
- 238000000746 purification Methods 0.000 claims abstract description 7
- 230000009471 action Effects 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims abstract description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 59
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 20
- 239000012141 concentrate Substances 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 16
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 16
- 238000007670 refining Methods 0.000 claims description 16
- 229910045601 alloy Inorganic materials 0.000 claims description 12
- 239000000956 alloy Substances 0.000 claims description 12
- 238000005342 ion exchange Methods 0.000 claims description 10
- 229910052763 palladium Inorganic materials 0.000 claims description 10
- 229910052697 platinum Inorganic materials 0.000 claims description 10
- 229910052703 rhodium Inorganic materials 0.000 claims description 10
- 239000010948 rhodium Substances 0.000 claims description 10
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims description 8
- 229910021538 borax Inorganic materials 0.000 claims description 8
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 8
- 239000000292 calcium oxide Substances 0.000 claims description 8
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 239000000155 melt Substances 0.000 claims description 8
- 238000005453 pelletization Methods 0.000 claims description 8
- 239000000377 silicon dioxide Substances 0.000 claims description 8
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 8
- 239000004328 sodium tetraborate Substances 0.000 claims description 8
- 235000010339 sodium tetraborate Nutrition 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 6
- 239000000571 coke Substances 0.000 claims description 4
- 235000013312 flour Nutrition 0.000 claims description 4
- 229910002804 graphite Inorganic materials 0.000 claims description 4
- 239000010439 graphite Substances 0.000 claims description 4
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 4
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 4
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 4
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 claims description 4
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 4
- LIYKJALVRPGQTR-UHFFFAOYSA-M oxostibanylium;chloride Chemical compound [Cl-].[Sb+]=O LIYKJALVRPGQTR-UHFFFAOYSA-M 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- 239000002817 coal dust Substances 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 12
- 230000008569 process Effects 0.000 description 21
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 7
- 229910052802 copper Inorganic materials 0.000 description 7
- 239000010949 copper Substances 0.000 description 7
- 238000001514 detection method Methods 0.000 description 7
- 235000012239 silicon dioxide Nutrition 0.000 description 7
- 235000017550 sodium carbonate Nutrition 0.000 description 7
- 229910052797 bismuth Inorganic materials 0.000 description 6
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 6
- 238000002844 melting Methods 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- 229910000519 Ferrosilicon Inorganic materials 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- 238000002386 leaching Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000005265 energy consumption Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- BCIZBNQHDOTGIN-UHFFFAOYSA-N [Fe][Sb][Sn] Chemical compound [Fe][Sb][Sn] BCIZBNQHDOTGIN-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000005457 optimization Methods 0.000 description 3
- 239000002910 solid waste Substances 0.000 description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium Chemical compound [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 description 3
- 229910001245 Sb alloy Inorganic materials 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000002140 antimony alloy Substances 0.000 description 2
- 238000003556 assay Methods 0.000 description 2
- 235000012255 calcium oxide Nutrition 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000010587 phase diagram Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- 229910001152 Bi alloy Inorganic materials 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- 229910001021 Ferroalloy Inorganic materials 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- RDQSSKKUSGYZQB-UHFFFAOYSA-N bismuthanylidyneiron Chemical compound [Fe].[Bi] RDQSSKKUSGYZQB-UHFFFAOYSA-N 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000002241 glass-ceramic Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 230000001698 pyrogenic effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 229910052959 stibnite Inorganic materials 0.000 description 1
- IHBMMJGTJFPEQY-UHFFFAOYSA-N sulfanylidene(sulfanylidenestibanylsulfanyl)stibane Chemical compound S=[Sb]S[Sb]=S IHBMMJGTJFPEQY-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- 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
- C22B11/00—Obtaining noble metals
- C22B11/04—Obtaining noble metals by wet processes
- C22B11/042—Recovery of noble metals from waste materials
- C22B11/048—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
- 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
-
- 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)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Geology (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention discloses a method for recycling platinum group metals in waste catalysts by pyrometallurgy, which takes antimony and nickel as trapping agents, the waste catalysts are evenly mixed, palletized, dried and smelted under the action of slag formers, trapping agents and reducing agents, slag phases and alloy phases are separated after full reaction, and the platinum group metals-enriched antimony-nickel alloy is obtained, and the platinum group metals are obtained after acid dissolution, separation and purification of the antimony-nickel alloy after crushing; the method utilizes the good trapping effect of the antimony and the nickel on the platinum group metals, and the platinum group metals in the waste catalyst are cooperatively trapped, designs the high-activity low-melting-point antimony-nickel alloy, greatly reduces the smelting temperature, improves the recovery rate of the platinum group metals, realizes the short-flow, low-cost, green and high-efficiency recovery of the platinum group metals, and has good industrial application prospect.
Description
Technical Field
The invention relates to the technical field of platinum group metal recovery, in particular to a method for recovering platinum group metals in a waste catalyst by pyrometallurgy.
Background
Currently, methods for recovering platinum group metals from spent catalysts include wet processes and pyrogenic processes. The wet process equipment is relatively simple, the production period is short, but the wastewater treatment capacity is high, the disposal cost is high, the reagent consumption is high, the reagent is easy to volatilize, and the safety of operators and the environment is seriously endangered. The pyrometallurgy process utilizes the special affinity of molten metals such as iron, copper, lead, bismuth, sulfonium and the like to platinum group metals, and the platinum group metals are captured into an alloy phase under the action of a fluxing agent, so that the separation and recovery of the platinum group metals are realized. The existing pyrometallurgy process has heavy metal or smoke pollution in copper trapping, sulfonium trapping and lead trapping, and the bismuth trapping has high cost, long flow and low metal recovery rate.
Chinese patent (CN 102134647A) discloses a method for recovering platinum group metals from waste automobile exhaust gas purifying catalyst by lead trapping, and the alloy obtained by lead smelting trapping is further enriched in platinum group metals by vacuum distillation and lead removal.
Chinese patent (CN 109136532B) discloses a method for cooperatively capturing platinum group metals in waste automobile exhaust catalysts by using waste circuit boards, wherein fluorescent glass ceramics are prepared by casting a mold after glass slag phase heat treatment, copper is recovered from copper alloy through electrolysis, and then the platinum group metals are recovered from anode slime. Although the copper capturing effect is good, electrolytic or pressure oxidation leaching copper removal is needed, and the subsequent process is very complex.
Chinese patent publication (CN 110983028A, CN 105400962A) discloses a method for trapping platinum group metals in waste automobile exhaust gas purifying catalysts by iron matte and nickel matte, which has low smelting temperature but SO 2 And the hidden trouble of pollution caused by overflow. The Chinese patent (CN 110735045B) discloses a method for trapping platinum group metals in waste automobile exhaust purification catalysts by bismuth, which comprises the following process steps of proportioning, primary smelting trapping and secondary smelting trapping, wherein the smelting temperature is 1000-1300 ℃. The method is green and environment-friendly, no dangerous solid waste is generated, but the process flow is complicated, the recovery rate of platinum group metals is low, and the bismuth is high in price and high in cost.
The trapping effect of the plasma smelting iron-making trapping technology is good, but the smelting temperature is higher than 1600 ℃, so that the alkali-resistant ferrosilicon alloy is easy to form, and the refining and purifying difficulty of the platinum group metal is greatly improved. Chinese patent (CN 110184465B) discloses a method for capturing platinum group metals in waste automobile exhaust catalyst by iron, the smelting temperature is 1300-1700 ℃, the recovery rate of platinum, palladium and rhodium is higher than 99%, and the formation of ferrosilicon alloy cannot be avoided, so that the recovery rate of platinum group metals is reduced. The Chinese patent (CN 110835686B) takes iron-tin-antimony as a trapping agent, and the platinum group metals in the waste catalyst are cooperatively trapped at 1200-1300 ℃, so that the formation of ferrosilicon alloy can be effectively avoided, but the ferrosilicon-tin-antimony alloy has strong chemical inertia, difficult dissolution, high hardness, difficult physical crushing and pulverization, and difficult complete removal of tin in the subsequent acid leaching pretreatment process, thereby greatly influencing the refining and purification of the platinum group metals.
Aiming at the problems of large wastewater treatment capacity, high reagent consumption, serious environmental hazard, heavy pollution of sulfonium trapping and lead trapping in the prior waste catalyst in the wet leaching process of platinum group metals, complicated copper trapping flow, long production period, high bismuth trapping cost, long flow, low metal recovery rate, high iron trapping smelting temperature, high energy consumption, easy formation of ferrosilicon alloy, long process flow and the like in the pyrometallurgy process, the development of a green, efficient and low-cost platinum group metal recovery process has important significance.
Disclosure of Invention
Aiming at the technical defects, the invention aims to provide a method for recycling platinum group metals in waste catalysts by pyrometallurgy, which utilizes antimony and nickel to have good trapping effect on the platinum group metals, and cooperatively traps the platinum group metals in the waste catalysts, designs high-activity low-melting-point antimony-nickel alloy, greatly reduces smelting temperature, improves platinum group metal recovery rate, solves the problems of long flow, high cost, environmental pollution, low recovery rate and the like of the platinum group metals, and has good industrial application prospect.
In order to solve the technical problems, the invention adopts the following technical scheme:
the invention provides a method for recovering platinum group metals in waste catalysts by pyrometallurgy, which takes antimony and nickel as trapping agents, the waste catalysts are evenly mixed, palletized, dried and smelted under the action of slag forming agents, trapping agents and reducing agents, slag phases and alloy phases are separated after full reaction, the antimony-nickel alloy enriched with platinum group metals is obtained, the alloy is crushed and then antimony-nickel is removed by acid dissolution, platinum group metal enrichment is obtained, and platinum-palladium-rhodium is separated by ion exchange after the enrichment is dissolved by aqua regia, and then platinum group metal products are obtained by refining.
Preferably, the amount of the trapping agent is 5-30wt% of the waste catalyst, and the mass ratio of antimony to nickel is 1 (0.1-1).
Preferably, the antimony comprises one or more of antimony powder, antimony trioxide, antimony oxychloride, stibnite, and antimony concentrate; the nickel is one or more of nickel powder, nickel oxide, nickel hydroxide, nickel sulfate and nickel concentrate.
Preferably, the waste catalyst is a platinum group metal-containing waste catalyst.
Preferably, the reducing agent comprises any one or more of coke, carbon powder, graphite, coal powder and flour.
Preferably, the slag former comprises one or more of calcium oxide, sodium carbonate, borax and silicon dioxide.
Preferably, the reducing agent is used in an amount of 0 to 10wt% of the spent catalyst, and the slag former is used in an amount of 30 to 200wt% of the spent catalyst.
Preferably, the smelting temperature is 1000-1200 ℃.
Preferably, the method specifically comprises the following steps:
step 1: uniformly mixing the waste catalyst, the slag former, the trapping agent and the reducing agent according to a proportion, adding 5-10wt% of water into the uniformly mixed materials, then performing pelletizing, and then performing surface drying treatment;
step 2: smelting the dried material in the step 1 at 1000-1200 ℃ to fully react until an alloy phase is completely settled to the bottom of a melt, and separating a slag phase and the alloy phase to obtain a brittle iron-bismuth alloy enriched with platinum group metals;
step 3: crushing the antimony-nickel alloy obtained in the step 2, performing acid dissolution to remove antimony-nickel, performing ion exchange to separate platinum, palladium and rhodium, and refining to obtain a platinum group metal product.
Preferably, the method can effectively reduce the grade of platinum group metals in slag, and the recovery rate of the platinum group metals is more than 99.5%.
The invention has the beneficial effects that:
1. the production cost and the energy consumption are low: according to the invention, the low-melting-point antimony-nickel alloy phase is designed and optimized, the low-melting-point slag phase is regulated and controlled, the smelting temperature is effectively reduced to 1000-1200 ℃, the smelting energy consumption and cost are greatly reduced, and the service lives of equipment and equipment are prolonged;
2. the recovery rate is high: according to the invention, the selected antimony and nickel are excellent platinum group metal trapping agents, the characteristic of low melting point of metallic antimony is utilized, the antimony-nickel binary phase diagram is used as a basis, the alloy components are adjusted and optimized, so that the antimony and nickel form a low melting point (800-1000 ℃) alloy phase, the separation effect of a slag phase and the alloy phase is improved through the synergistic trapping effect and the optimization of various technological parameters and material proportions, the platinum group metal grade in slag is effectively reduced, and the platinum group metal recovery rate exceeds 99.5%;
3. green and environment-friendly: the smelting slag does not belong to dangerous solid waste, and the production process does not cause damage to the health of operators;
4. the process flow is short: the platinum group metal in the antimony-nickel alloy obtained by smelting is high in grade and easy to dissolve, which is beneficial to the refining and purification of the follow-up platinum group metal, obviously shortens the process flow and reduces the process cost.
Drawings
In order to more clearly illustrate the embodiments of the 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, it being obvious that the drawings in the following description are only some embodiments of the invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
Fig. 1 is a process flow diagram of a method for recovery of platinum group metals in spent catalysts by pyrometallurgy.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Antimony assay is currently less studied as a noble metal analytical detection technique. Li Ke and platinum group metals from chromite and black shale are enriched by antimony assay (analytical laboratories, 2018,37 (4): 428-431, physical and chemical inspection (chemical division), 2021,57 (2): 156-159); shao Kun an analytical method for determining platinum group elements in vanadium titano-magnetite ores by antimony test-inductively coupled plasma mass spectrometry (ICP-MS) is established (metallurgical analysis, 2018, 38 (5): 18-24). The antimony test has the advantages of low smelting temperature and good separation effect, but is only applied to analysis and detection at present, has strong pertinence to raw materials and poor adaptability, and is difficult to be suitable for enriching and recovering platinum group metals in waste catalysts.
According to the invention, by utilizing the characteristic of low melting point of metallic antimony and taking an antimony-nickel binary phase diagram as a basis, the low melting point (800-1000 ℃) alloy phase is formed by antimony and nickel through adjusting and optimizing alloy components; the metal antimony and nickel are good platinum group metal trapping agents, and can be used for synergistically trapping platinum group metals, so that the recovery rate of the platinum group metals is greatly improved; through slag type optimization and regulation, a slag phase with low melting point (900-1100 ℃) and viscosity and good fluidity is designed, the combination of a trapping agent and platinum group metals and the separation of the trapping agent and the platinum group metals from the slag phase are promoted, and the platinum group metals are trapped and recovered at a low temperature (1000-1200 ℃) with high efficiency.
As shown in fig. 1, the following examples are based on the steps of the process flow diagram shown in fig. 1, and the method for recovering platinum group metals from the spent catalyst by pyrometallurgy comprises the following steps:
step 1: uniformly mixing the waste catalyst, the slag former, the trapping agent and the reducing agent according to a set proportion, adding 5-10wt% of water into the uniformly mixed materials, then pelletizing, and then drying the surface;
step 2: smelting the dried material in the step 1 at 1000-1200 ℃ to fully react until an alloy phase is completely settled to the bottom of a melt, and separating a slag phase and the alloy phase to obtain the antimony-nickel alloy enriched with platinum group metals;
step 3: crushing the antimony-nickel alloy obtained in the step 2, performing acid dissolution to remove antimony-nickel, performing ion exchange to separate platinum, palladium and rhodium, and refining to obtain a platinum group metal product.
Wherein the trapping agent comprises antimony and nickel, and the antimony comprises one or more of antimony powder, antimonous oxide, antimony oxychloride, stibium oxide ore and antimony concentrate; the nickel is one or more of nickel powder, nickel oxide, nickel hydroxide, nickel sulfate and nickel concentrate.
The amount of the trapping agent is 5-30wt% of the waste catalyst, the trapping agent comprises antimony and nickel, and the mass ratio of the antimony to the nickel is 1 (0.1-1).
The waste catalyst is a waste catalyst containing platinum group metals.
The slag former comprises one or more of calcium oxide, sodium carbonate, borax and silicon dioxide.
To achieve complete separation of slag from alloy, the spent catalyst: trapping agent: reducing agent: the mass ratio of the slag former is 100 (5-30) (0-10) (30-200).
The reducing agent comprises one or more of coke, carbon powder, graphite, coal powder and flour.
The method can effectively reduce the grade of platinum group metals in slag, and the recovery rate of the platinum group metals is more than 99.5%.
Example 1
100 parts of platinum group metal-containing waste catalyst, 15 parts of stibium, 10 parts of nickel powder, 6 parts of flour and slag forming agent (52 parts of calcium oxide, 11 parts of sodium carbonate, 29 parts of borax and 22 parts of silicon dioxide) are uniformly mixed, and a proper amount of water is added into the uniformly mixed materials for pelletizing and then drying. And smelting the dried material at 1200 ℃, fully reacting until the alloy phase is completely settled to the bottom of the melt, and separating the slag phase and the alloy phase to obtain the antimony-nickel alloy enriched with platinum group metals. Crushing the antimony-nickel alloy, dissolving the antimony-nickel alloy by acid to remove the antimony-nickel alloy to obtain a platinum group metal concentrate, dissolving the concentrate by aqua regia, separating platinum, palladium and rhodium by ion exchange, and refining to obtain a platinum group metal product. The detection shows that the total grade of the platinum group metals in the smelting slag is 2.5g/t, and the recovery rate of the platinum group metals is 99.84%.
Example 2
100 parts of platinum group metal-containing waste catalyst, 5 parts of antimony oxychloride, 3 parts of nickel oxide, 5 parts of coal dust and a slag former (11 parts of calcium oxide, 34 parts of sodium carbonate, 42 parts of borax and 7 parts of silicon dioxide) are uniformly mixed, and a proper amount of water is added into the uniformly mixed materials for pelletizing and then drying. Smelting the dried material at 1080 ℃, fully reacting until the alloy phase is completely settled to the bottom of the melt, separating the slag phase and the alloy phase, and obtaining the antimony-nickel alloy enriched with platinum group metals. Crushing the antimony-nickel alloy, dissolving the antimony-nickel alloy by acid to remove the antimony-nickel alloy to obtain a platinum group metal concentrate, dissolving the concentrate by aqua regia, separating platinum, palladium and rhodium by ion exchange, and refining to obtain a platinum group metal product. Through detection, the total grade of platinum group metals in the smelting slag is 9.8g/t, and the recovery rate of the platinum group metals is 99.55%.
Example 3
100 parts of platinum group metal-containing waste catalyst, 9 parts of antimony powder, 4 parts of nickel concentrate, 3 parts of coke and a slag former (42 parts of calcium oxide, 37 parts of sodium carbonate, 28 parts of borax and 19 parts of silicon dioxide) are uniformly mixed, and a proper amount of water is added into the uniformly mixed materials for pelletizing and then drying. And smelting the dried material at 1140 ℃, fully reacting until the alloy phase is completely settled to the bottom of the melt, and separating the slag phase and the alloy phase to obtain the antimony-nickel alloy enriched in platinum group metals. Crushing the antimony-nickel alloy, dissolving the antimony-nickel alloy by acid to remove the antimony-nickel alloy to obtain a platinum group metal concentrate, dissolving the concentrate by aqua regia, separating platinum, palladium and rhodium by ion exchange, and refining to obtain a platinum group metal product. The detection shows that the total grade of the platinum group metals in the smelting slag is 5.7g/t, and the recovery rate of the platinum group metals is 99.73%.
Example 4
100 parts of platinum group metal-containing waste catalyst, 15 parts of antimony concentrate, 15 parts of nickel sulfate, 9 parts of graphite and a slag former (9 parts of calcium oxide, 8 parts of sodium carbonate, 6 parts of borax and 18 parts of silicon dioxide) are uniformly mixed, and a proper amount of water is added into the uniformly mixed materials for pelletizing and then drying. Smelting the dried material at 1020 ℃, fully reacting until the alloy phase is completely settled to the bottom of the melt, separating the slag phase and the alloy phase, and obtaining the antimony-nickel alloy enriched with platinum group metals. Crushing the antimony-nickel alloy, dissolving the antimony-nickel alloy by acid to remove the antimony-nickel alloy to obtain a platinum group metal concentrate, dissolving the concentrate by aqua regia, separating platinum, palladium and rhodium by ion exchange, and refining to obtain a platinum group metal product. The detection shows that the total grade of the platinum group metals in the smelting slag is 5.5g/t, and the recovery rate of the platinum group metals is 99.79%.
Example 5
100 parts of platinum group metal-containing waste catalyst, 16 parts of antimonous oxide, 11 parts of nickel hydroxide, 7 parts of carbon powder and a slag former (43 parts of calcium oxide, 27 parts of sodium carbonate, 41 parts of borax and 15 parts of silicon dioxide) are uniformly mixed, and a proper amount of water is added into the uniformly mixed materials for pelletizing and then drying. And smelting the dried material at 1100 ℃, fully reacting until the alloy phase is completely settled to the bottom of the melt, and separating the slag phase and the alloy phase to obtain the antimony-nickel alloy enriched in platinum group metals. Crushing the antimony-nickel alloy, dissolving the antimony-nickel alloy by acid to remove the antimony-nickel alloy to obtain a platinum group metal concentrate, dissolving the concentrate by aqua regia, separating platinum, palladium and rhodium by ion exchange, and refining to obtain a platinum group metal product. The detection shows that the total grade of the platinum group metals in the smelting slag is 8.4g/t, and the recovery rate of the platinum group metals is 99.63%.
The prior art CN 102134647A has large lead toxicity and serious environmental pollution; prior art CN110983028A presents SO 2 The hidden trouble of overflow pollution; compared with the two prior arts, the smelting slag does not belong to dangerous solid waste, and the production process does not damage the health of operators, so that the method is environment-friendly;
in the prior art CN 109136532B, electrolytic or pressure oxidation leaching copper removal is needed, and the subsequent process is very complex; the prior art CN 110735045B has the defects of complicated process flow, low platinum group metal recovery rate, high bismuth price and high cost; in the prior art CN 110835686B, iron-tin-antimony is taken as a trapping agent, the iron-tin-antimony alloy has high hardness, is difficult to physically crush and pulverize, and is difficult to completely remove tin in the subsequent acid leaching pretreatment process, so that the refining and purification of platinum group metals are greatly influenced; compared with the three prior arts, the platinum group metals in the antimony-nickel alloy obtained by smelting are high in grade and easy to dissolve, which is beneficial to the refining and purification of the follow-up platinum group metals, obviously shortens the process flow and reduces the process cost.
Although the trapping effect of the plasma smelting iron-making trapping technology is good, the smelting temperature is higher than 1600 ℃, the prior art CN 110184465B adopts ferroalloy which has strong chemical inertia, is difficult to dissolve, has extremely high hardness and is difficult to break, the smelting temperature is 1300-1700 ℃, and the alloy needs to be pretreated, such as blowing, melting or crushing, and the like before the platinum group metal is recovered; even when the iron trapping temperature reaches more than 1500 ℃, the acid-alkali resistant ferrosilicon alloy is easy to form, the difficulty of refining and purifying the platinum group metal is greatly increased, and the recovery rate of the platinum group metal is reduced; compared with the prior art, the invention effectively reduces the smelting temperature to 1000-1200 ℃, and greatly reduces the smelting energy consumption and the cost; and the recovery rate is high, and the selected antimony and nickel are excellent platinum group metal trapping agents, so that the separation effect of slag phases and alloy phases is improved, the grade of platinum group metals in slag is effectively reduced, and the recovery rate of platinum group metals exceeds 99.5 percent through the synergistic trapping effect and the optimization of various technological parameters and material proportions.
It will be apparent to those skilled in the art that various modifications and variations can be made to the present invention without departing from the spirit or scope of the invention. Thus, it is intended that the present invention also include such modifications and alterations insofar as they come within the scope of the appended claims or the equivalents thereof.
Claims (8)
1. A method for recovering platinum group metals in waste catalysts by pyrometallurgy is characterized in that antimony and nickel are used as trapping agents, waste catalysts are uniformly mixed, palletized, dried and smelted under the action of a slag former, a trapping agent and a reducing agent, slag phases and alloy phases are separated after full reaction, antimony-nickel alloy enriched with platinum group metals is obtained, and then crushed, acid-dissolved, separated and purified to obtain the platinum group metals;
the using amount of the trapping agent is 5-30wt% of the waste catalyst, and the mass ratio of antimony to nickel is 1 (0.1-1);
the acid dissolution and separation purification method comprises the steps of crushing alloy, removing antimony and nickel by acid dissolution to obtain platinum group metal enrichment, dissolving the enrichment by aqua regia, separating platinum, palladium and rhodium by ion exchange, and refining to obtain a platinum group metal product.
2. The method for recovery of platinum group metals from spent catalyst by pyrometallurgy according to claim 1, wherein the antimony comprises one or more of antimony powder, antimony trioxide, antimony oxychloride, stibium oxide ore, antimony concentrate; the nickel is one or more of nickel powder, nickel oxide, nickel hydroxide, nickel sulfate and nickel concentrate.
3. The method for recovery of platinum group metals from a spent catalyst by pyrometallurgy according to claim 1, wherein the spent catalyst is a spent catalyst containing platinum group metals.
4. The method for recovery of platinum group metals from spent catalyst by pyrometallurgy according to claim 1, wherein the reducing agent comprises any one or more of coke, carbon powder, graphite, coal dust, flour, and the slag former comprises one or more of calcium oxide, sodium carbonate, borax, and silica.
5. The method for recycling platinum group metals in a waste catalyst by pyrometallurgy according to claim 1, wherein the reducing agent is used in an amount of 0-10wt% of the waste catalyst, and the slag former is used in an amount of 30-200wt% of the waste catalyst.
6. The method for recovery of platinum group metals from spent catalysts by pyrometallurgy according to claim 1, wherein the smelting temperature is 1000-1200 ℃.
7. The method for recovery of platinum group metals from spent catalysts by pyrometallurgy according to claim 1, characterized in that it comprises in particular the following steps:
step 1: uniformly mixing the waste catalyst, the slag former, the trapping agent and the reducing agent according to a proportion, adding 5-10wt% of water into the uniformly mixed materials, then performing pelletizing, and then performing surface drying treatment;
step 2: smelting the dried material in the step 1 at the temperature of 1000-1200 ℃ to fully react until an alloy phase is completely settled to the bottom of a melt, and separating a slag phase and the alloy phase to obtain the antimony-nickel alloy enriched with platinum group metals;
step 3: crushing the antimony-nickel alloy obtained in the step 2, performing acid dissolution to remove antimony-nickel, performing ion exchange to separate platinum, palladium and rhodium, and refining to obtain a platinum group metal product.
8. The method for recovering platinum group metals in waste catalysts by pyrometallurgy according to any one of claims 1 to 7, which is characterized in that the method can effectively reduce the grade of platinum group metals in slag, and the recovery rate of platinum group metals is more than 99.5%.
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| CN115612859B (en) * | 2022-10-28 | 2024-02-09 | 安徽工业大学 | Method for trapping platinum group metals in waste catalyst by bismuth |
| CN115595452B (en) * | 2022-10-31 | 2024-01-30 | 陕西瑞科新材料股份有限公司 | Method for enriching noble metal palladium from resin |
| CN116144929A (en) * | 2022-12-20 | 2023-05-23 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for capturing and recycling platinum group metals in waste catalysts by semi-molten reinforced reduced iron |
| CN116622999A (en) * | 2023-05-31 | 2023-08-22 | 昆明理工大学 | Method for enriching platinum group metals |
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