CN114107692A - Method for adding nickel sulfate to smelt and capture platinum group metal in spent automobile exhaust catalyst - Google Patents
Method for adding nickel sulfate to smelt and capture platinum group metal in spent automobile exhaust catalyst Download PDFInfo
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- CN114107692A CN114107692A CN202111439154.7A CN202111439154A CN114107692A CN 114107692 A CN114107692 A CN 114107692A CN 202111439154 A CN202111439154 A CN 202111439154A CN 114107692 A CN114107692 A CN 114107692A
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- automobile exhaust
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- 239000003054 catalyst Substances 0.000 title claims abstract description 80
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 53
- 239000002184 metal Substances 0.000 title claims abstract description 53
- 238000000034 method Methods 0.000 title claims abstract description 45
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 title claims abstract description 33
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 title claims abstract description 33
- 241001062472 Stokellia anisodon Species 0.000 title claims abstract description 9
- 238000003723 Smelting Methods 0.000 claims abstract description 54
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 42
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 40
- -1 platinum group metals Chemical class 0.000 claims abstract description 31
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 24
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 23
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 22
- 239000010948 rhodium Substances 0.000 claims abstract description 22
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 20
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical group [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 15
- 239000003795 chemical substances by application Substances 0.000 claims description 13
- 235000019738 Limestone Nutrition 0.000 claims description 9
- 239000006004 Quartz sand Substances 0.000 claims description 9
- 229910021538 borax Inorganic materials 0.000 claims description 9
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims description 9
- 229910001634 calcium fluoride Inorganic materials 0.000 claims description 9
- 239000006028 limestone Substances 0.000 claims description 9
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 9
- 239000004328 sodium tetraborate Substances 0.000 claims description 9
- 235000010339 sodium tetraborate Nutrition 0.000 claims description 9
- 239000003610 charcoal Substances 0.000 claims description 4
- RHZUVFJBSILHOK-UHFFFAOYSA-N anthracen-1-ylmethanolate Chemical compound C1=CC=C2C=C3C(C[O-])=CC=CC3=CC2=C1 RHZUVFJBSILHOK-UHFFFAOYSA-N 0.000 claims description 3
- 239000003830 anthracite Substances 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 239000002802 bituminous coal Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 239000002893 slag Substances 0.000 abstract description 25
- 238000011084 recovery Methods 0.000 abstract description 20
- 230000009467 reduction Effects 0.000 abstract description 5
- 239000010909 process residue Substances 0.000 abstract description 4
- 239000000428 dust Substances 0.000 abstract description 2
- 230000004907 flux Effects 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract 1
- 239000002699 waste material Substances 0.000 description 15
- 238000002386 leaching Methods 0.000 description 11
- 230000008569 process Effects 0.000 description 8
- 239000000956 alloy Substances 0.000 description 7
- 229910045601 alloy Inorganic materials 0.000 description 7
- 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 6
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 238000000498 ball milling Methods 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 229910052681 coesite Inorganic materials 0.000 description 4
- 229910052906 cristobalite Inorganic materials 0.000 description 4
- 229910052761 rare earth metal Inorganic materials 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 229910052682 stishovite Inorganic materials 0.000 description 4
- 229910052905 tridymite Inorganic materials 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000000571 coke Substances 0.000 description 3
- 229910052878 cordierite Inorganic materials 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 150000002910 rare earth metals Chemical class 0.000 description 3
- XFWJKVMFIVXPKK-UHFFFAOYSA-N calcium;oxido(oxo)alumane Chemical compound [Ca+2].[O-][Al]=O.[O-][Al]=O XFWJKVMFIVXPKK-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- DYJOUBLHPAIUEU-UHFFFAOYSA-N nickel(2+) sulfane Chemical compound S.[Ni+2] DYJOUBLHPAIUEU-UHFFFAOYSA-N 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910052596 spinel Inorganic materials 0.000 description 2
- 239000011029 spinel Substances 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium Chemical compound [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 229910014779 CaAl4 Inorganic materials 0.000 description 1
- 241001391944 Commicarpus scandens Species 0.000 description 1
- 229910020068 MgAl Inorganic materials 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 description 1
- 229910052661 anorthite Inorganic materials 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- GWWPLLOVYSCJIO-UHFFFAOYSA-N dialuminum;calcium;disilicate Chemical compound [Al+3].[Al+3].[Ca+2].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] GWWPLLOVYSCJIO-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000002223 garnet Substances 0.000 description 1
- 229910052909 inorganic silicate Inorganic materials 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- YGHCWPXPAHSSNA-UHFFFAOYSA-N nickel subsulfide Chemical compound [Ni].[Ni]=S.[Ni]=S YGHCWPXPAHSSNA-UHFFFAOYSA-N 0.000 description 1
- XSKIUFGOTYHDLC-UHFFFAOYSA-N palladium rhodium Chemical compound [Rh].[Pd] XSKIUFGOTYHDLC-UHFFFAOYSA-N 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- WWNBZGLDODTKEM-UHFFFAOYSA-N sulfanylidenenickel Chemical compound [Ni]=S WWNBZGLDODTKEM-UHFFFAOYSA-N 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
Images
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
- C22B1/005—Preliminary treatment of scrap
-
- 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
-
- 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 adding nickel sulfate to smelt and trap platinum group metals in a spent automobile exhaust catalyst, and belongs to the technical field of platinum group metal recovery. The method comprises the steps of mixing a spent automobile exhaust catalyst containing platinum group metals and wet-process residues thereof, a collector nickel sulfate, a reducing agent, a flux and a slag former, then carrying out reduction to produce nickel matte and smelting at 1250-1350 ℃, and collecting platinum, palladium and rhodium in the spent automobile exhaust catalyst and the wet-process residues thereof to respectively obtain nickel matte and smelting slag. From the raw material to the nickel matte, the recovery rate of platinum is more than 99.5 percent, the recovery rate of palladium is more than 99.3 percent, and the recovery rate of rhodium is more than 98 percent. The method has the advantages of short flow, low cost and high yield of platinum group metals, and the related main smelting and dust collecting equipment is mature, thereby having potential industrialization prospect.
Description
Technical Field
The invention belongs to the technical field of platinum group metal recovery, and relates to a method for adding nickel sulfate to smelt and trap platinum group metal in a spent automobile exhaust catalyst.
Background
The platinum group metal has special physicochemical properties and has unique purification capability for purifying the automobile exhaust. The platinum group metal becomes the main material for extracting the platinum group metal after purifying the automobile exhaust and losing efficacy. In addition, platinum group metals in the failed automobile exhaust catalyst are leached by a traditional wet method, and are embedded in cordierite of the failed automobile exhaust catalyst in a dispersion mode, so that the platinum group metals are difficult to leach completely, and wet leaching residues still contain a certain amount of platinum group metals, so that the recovery value is high. At present, the method for recovering platinum group metals in the spent automobile exhaust catalyst comprises the following steps:
dudu super et al discloses a method for enriching platinum group metals and rare earths in a spent automotive exhaust gas purification catalyst (application publication No. 201910437568.2). The technology comprises the steps of carrying out pressure leaching on a spent catalyst in a sodium hydroxide solution after finely grinding, carrying out acid leaching on produced leaching residues, adding sodium sulfate into an acid leaching solution to recover rare earth elements, and recovering platinum, palladium and rhodium metal from acid insoluble residues. The comprehensive recovery rate of lanthanum and yttrium elements reaches more than 90%, and platinum, palladium and rhodium are enriched by more than 13 times, so that the method is beneficial to the subsequent extraction of noble metals.
Sunpi et al have invented a method for recovering precious metals from spent automotive exhaust catalysts (application publication No. 201811567228.3). The process is to carry out mechanochemical activation treatment on a catalyst and then leach to obtain a noble metal leaching solution. The method has the advantages of relatively mild conditions, relatively simple operation, high total leaching rate of the noble metals up to more than 93%, high leaching rate of the metal palladium up to more than 98%, and good practical application value.
Wangxin et al discloses a method for recovering rare earth and platinum group metals from a spent automobile exhaust gas purification catalyst (application publication No. 201910169618.3). The process comprises the steps of catalyst curing, separation, rare earth recovery, platinum group metal roasting and platinum group metal recovery, the method is simple and easy to implement, the leaching rate of the platinum group metal can reach 99.0%, the chlorination residue can be returned to roasting treatment, and the recovery cost of the recovered rare earth and the recovered platinum group metal is saved.
Fangxingxiang et al have invented a method for enriching platinum group metals from a metal support of a spent automotive exhaust catalyst (application publication No. 201510285196.8). The process comprises the steps of carrying out high-temperature smelting and rapid cooling on the spent automobile exhaust catalyst to form a small platinum group metal-containing alloy which is easy to break, and then carrying out acid leaching and separation of precious base metals, thereby realizing high-efficiency enrichment of the platinum group metals. The method does not need any trapping agent, and the technical carrier is used as the platinum group metal trapping agent, so the method has the advantages of simple operation of the whole process, high platinum yield, high enrichment ratio, environmental protection, low cost and good industrial application prospect.
In summary, the existing method for recovering platinum group metals from the spent automobile exhaust catalyst is a wet process, and has short process flow, low yield and serious environmental pollution of waste water and waste residues; based on the method, the method for adding the nickel sulfate to smelt and trap the platinum group metal in the invalid automobile exhaust catalyst is provided, and low-cost, environment-friendly and efficient trapping is realized. The method is not reported in reference data.
Disclosure of Invention
The invention aims to provide a method for adding nickel sulfate to smelt and trap platinum group metals in a spent automobile exhaust catalyst.
In order to achieve the aim, the invention provides a method for adding nickel sulfate to smelt and trap platinum group metals in a spent automobile exhaust catalyst, which comprises the following steps:
(1) mixing and grinding the spent catalyst containing platinum group metal, a trapping agent, a reducing agent, a slagging agent and a fluxing agent according to a certain proportion;
(2) and reducing the mixed and ground mixture to produce nickel matte, smelting and trapping platinum, palladium and rhodium.
Further, in the step (1), the collector is nickel sulfate, the slagging agent is quartz sand and limestone, the fluxing agent is sodium carbonate, borax and calcium fluoride, and the reducing agent is one of coke powder, anthracite, bituminous coal and charcoal.
Furthermore, the adding amount of the nickel sulfate is 2-5 times of the weight ratio of the ineffective catalyst, the adding amount of the quartz sand is 1.5-2 times of the weight ratio of the ineffective catalyst, the adding amount of the limestone is 0.5-1 time of the weight ratio of the ineffective catalyst, the adding amount of the reducing agent is 20-30% of the weight ratio of the ineffective catalyst, and the adding amount of the sodium carbonate, the borax and the calcium fluoride is 15-30% of the weight ratio of the ineffective catalyst.
Further, in the step (2), nickel matte is used for smelting and trapping platinum, palladium and rhodium, the smelting temperature is 1250-1350 ℃, and the smelting time is 30-60 min.
The invention mixes the invalid automobile exhaust catalyst containing platinum group metal and its residue, collector nickel sulfate, coke, flux and slag former; and smelting and trapping platinum, palladium and rhodium by reducing nickel matte to respectively obtain nickel matte alloy and smelting slag. The recovery rate of platinum is more than 90%, the recovery rate of palladium is more than 91%, and the recovery rate of rhodium is more than 90%. The method has the advantages of short flow, low cost, high yield of platinum group metals, mature main smelting and dust collecting equipment and potential industrialization prospect.
The innovation points of the invention are mainly as follows:
(1) smelting nickel sulfate to produce nickel matte, trapping more than 99% of platinum, palladium and rhodium in the nickel matte, and ensuring that the total recovery rate of platinum group metals is more than 99%;
(2) compared with other iron-adding trapping smelting, the smelting temperature is reduced by 150-200 ℃;
(3) in view of the fact that the main phase in the waste residue of the spent automobile exhaust catalyst leached by the wet method in the traditional method is cordierite Mg2Al4Si5O18Platinum group metals are embedded in silicate, nickel matte is reduced to smelt and destroy cordierite structure, the formed nickel matte can efficiently trap platinum, palladium and rhodium, and the problems of difficult filtration, high reagent consumption and the like in wet-process platinum group metal leaching are avoided,The waste water and the waste liquid are difficult to treat, the cost is high and the like.
In conclusion, the method realizes the high-efficiency trapping of Pt, Pd and Rh, and has the advantages of environmental friendliness, low smelting temperature, low cost and the like. In addition, the trapping agent related by the method is low in price, the main smelting equipment is mature, and industrialization is easy to realize.
Drawings
FIG. 1 is a process flow diagram of a method for the nickel sulfate addition smelting capture of platinum group metals in spent automotive exhaust catalysts;
FIG. 2 is an XRD spectrum of slag from example 1 for the smelting of a spent automobile exhaust catalyst plus nickel sulfate to trap platinum group metals;
FIG. 3 is an XRD spectrum of slag from example 2 for the capture of platinum group metals by the smelting of spent automobile exhaust catalyst plus nickel sulfate;
FIG. 4 is an XRD spectrum of slag from example 3 for the capture of platinum group metals by the smelting of spent automobile exhaust catalyst plus nickel sulfate;
FIG. 5 is an XRD spectrum of slag from example 4 for the capture of platinum group metals by the smelting of spent automobile exhaust catalyst plus nickel sulfate;
FIG. 6 is an XRD spectrum of slag from example 5 for the capture of platinum group metals by the smelting of spent automobile exhaust catalyst plus nickel sulfate;
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention clearer, the following detailed description of the present invention is given with reference to specific examples:
example 1
Weighing 1000g of spent automobile exhaust catalyst, wherein the addition amount of nickel sulfate is 3 times of the weight ratio of the spent catalyst, quartz sand is 1.6 times of the weight ratio of the spent catalyst, limestone is 0.8 times of the weight ratio of the spent catalyst, sodium carbonate, borax and calcium fluoride are 25% of the weight ratio of the spent catalyst, and coke is 20% of the weight ratio of the spent catalyst, performing ball milling and mixing, smelting and trapping Pt, Pd and Rh by using reduction matte, wherein the smelting temperature is 1280 ℃, the smelting time is 60min, obtaining nickel matte alloy and smelting slag after smelting is finished, and the recovery rates of the platinum, the palladium and the rhodium respectively reach 99.63%, 99.54% and 98.01%.
Smelting 60m of spent automobile exhaust catalyst by adding nickel sulfateThe XRD pattern of the slag obtained after in is shown in figure 2. As can be seen from FIG. 2, the slag phase is cordierite (Mg)2Al2Si5O8) Magnesium aluminum garnet (Mg)3Al2(SiO4)3) Calcium aluminate spinel (CaAl)2O4) Calcium aluminate spinel (MgAl)2O4)、SiO2. Indicating that under these conditions, the cordierite structure is not completely destroyed, affecting the release of platinum group metals from the spent catalyst, and various solid solution compounds are formed.
Example 2
Weighing 1500g of waste automobile exhaust catalyst wet-process residue, wherein the adding amount of nickel sulfate is 3.5 times of the weight ratio of the waste catalyst, the adding amount of quartz sand is 2 times of the weight ratio of the waste catalyst, limestone is 1 time of the weight ratio of the waste catalyst, sodium carbonate, borax and calcium fluoride are 25% of the weight ratio of the waste catalyst, and charcoal is 30% of the weight ratio of the waste catalyst, performing ball milling and mixing, smelting and trapping Pt, Pd and Rh by using reduction matte, wherein the smelting temperature is 1350 ℃, the smelting time is 30min, obtaining nickel matte alloy and smelting slag after smelting, and the recovery rates of the platinum, the palladium and the rhodium respectively reach 99.61%, 99.65% and 98.08%.
The XRD pattern of the slag obtained after the spent automobile exhaust catalyst is smelted for 30min by adding nickel sulfate is shown in figure 3. As can be seen from FIG. 3, the slag phase contains four compounds Ni3S2、SiO2、CaAl4O7MgO, and others are not shown. The cordierite structure is destroyed and platinum group metals can be released, but nickel sulfide exists in slag, the nickel sulfate does not produce sulfur and the smelting reaction at high temperature is not sufficient.
Example 3
Weighing 500g of spent automobile exhaust catalyst, wherein the addition of nickel sulfate is 4 times of that of the spent catalyst, quartz sand is 1.4 times of that of the spent catalyst, limestone is 0.8 times of that of the spent catalyst, sodium carbonate, borax and calcium fluoride are 25 weight percent of the spent catalyst, and anthracite is 20 weight percent of that of the spent catalyst, performing ball milling and mixing, smelting and trapping Pt, Pd and Rh by using reduced matte, smelting at the temperature of 1320 ℃, for 50min, respectively obtaining nickel matte alloy and smelting slag after smelting is finished, and the recovery rates of the platinum, the palladium and the rhodium respectively reach 99.85%, 99.55% and 98.21%.
The XRD pattern of the slag obtained after the spent catalyst is smelted by adding nickel sulfate for 50min is shown in figure 4. As can be seen from FIG. 4, the phase in the slag is mainly SiO2And anorthite (CaAl)2Si2O8) Other substances are not present.
Example 4
Weighing 800g of waste automobile exhaust catalyst wet-process residue, wherein the addition of nickel sulfate is 2.5 times of that of a waste catalyst, the addition of quartz sand is 1.2 times of that of the waste catalyst, limestone is 0.8 times of that of the waste catalyst, sodium carbonate, borax and calcium fluoride are 20 weight percent of that of the waste catalyst, and charcoal is 25 weight percent of that of the waste catalyst, performing ball milling and mixing, smelting and trapping Pt, Pd and Rh by using reduction and sulfonium making, smelting at 1330 ℃, for 40min, respectively obtaining nickel sulfonium alloy and smelting slag after smelting is finished, and respectively achieving the recovery rates of the platinum and the palladium rhodium of 99.66%, 99.46% and 99.14%.
The XRD pattern of the slag obtained after the spent catalyst is smelted by adding nickel sulfate for 40min is shown in figure 5. As can be seen from FIG. 5, the main phase of the slag is Al2O3.SiO2、2CaO.SiO2Other materials are not present. The slag former fully completes the slag forming process and the sulfur-making smelting is more complete.
Example 5
Weighing 1000g of spent automobile exhaust catalyst, wherein the addition of nickel sulfate is 2 times of that of the spent catalyst, quartz sand is 1.8 times of that of the spent catalyst, limestone is 0.6 times of that of the spent catalyst, sodium carbonate, borax and calcium fluoride are 20% of that of the spent catalyst, and coke is 20% of that of the spent catalyst, performing ball milling and mixing, smelting and trapping Pt, Pd and Rh by using reduction and sulfonium making, smelting at a temperature of 1310 ℃ for 50min, and respectively obtaining nickel sulfonium alloy and smelting slag after smelting, wherein the recovery rates of the platinum, the palladium and the rhodium respectively reach 99.57%, 99.62% and 99.35%.
The results of analyzing nickel matte by X-ray diffraction are shown in FIG. 6. As can be seen from FIG. 6, the main phase of the nickel matte is Ni3S2And Ni, other materials are not shown. The nickel matte being platinum group goldBelongs to an excellent trapping grade, and the trapping effect of the platinum group metals is good in the examples, so that the recovery rate of the platinum group metals is more than 99.0 percent.
Claims (4)
1. A method for adding nickel sulfate to smelt and trap platinum group metals in a spent automobile exhaust catalyst is characterized by comprising the following steps:
(1) mixing and grinding the spent catalyst containing platinum group metal, a trapping agent, a reducing agent, a slagging agent and a fluxing agent according to a certain proportion;
(2) and reducing the mixed and ground mixture to produce nickel matte, smelting and trapping platinum, palladium and rhodium.
2. The method for smelting and trapping platinum group metals in the spent automobile exhaust catalyst by adding the nickel sulfate according to claim 1, wherein the method comprises the following steps: in the step (1), the collector is nickel sulfate, the slagging agent is quartz sand and limestone, the fluxing agent is sodium carbonate, borax and calcium fluoride, and the reducing agent is one of coke powder, anthracite, bituminous coal and charcoal.
3. The method for smelting and trapping platinum group metals in the spent automobile exhaust catalyst by adding the nickel sulfate according to claim 2, wherein the method comprises the following steps: the adding amount of the nickel sulfate is 2-5 times of the weight ratio of the ineffective catalyst, the adding amount of the quartz sand is 1.5-2 times of the weight ratio of the ineffective catalyst, the adding amount of the limestone is 0.5-1 time of the weight ratio of the ineffective catalyst, the adding amount of the reducing agent is 20-30% of the weight ratio of the ineffective catalyst, and the adding amount of the sodium carbonate, the borax and the calcium fluoride is 15-30% of the weight ratio of the ineffective catalyst.
4. The method for smelting and trapping platinum group metals in the spent automobile exhaust catalyst by adding the nickel sulfate according to claim 1, wherein the method comprises the following steps: and (3) smelting and trapping platinum, palladium and rhodium by using nickel matte in the step (2), wherein the smelting temperature is 1250-1350 ℃, and the smelting time is 30-60 min.
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