CN117778738A - Method for enriching platinum, palladium and rhodium in waste ternary catalyst by pyrogenic process - Google Patents
Method for enriching platinum, palladium and rhodium in waste ternary catalyst by pyrogenic process Download PDFInfo
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 title claims abstract description 183
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 164
- 239000010948 rhodium Substances 0.000 title claims abstract description 89
- 229910052697 platinum Inorganic materials 0.000 title claims abstract description 85
- 229910052703 rhodium Inorganic materials 0.000 title claims abstract description 83
- 229910052763 palladium Inorganic materials 0.000 title claims abstract description 80
- 239000003054 catalyst Substances 0.000 title claims abstract description 77
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 238000000034 method Methods 0.000 title claims abstract description 70
- 239000002699 waste material Substances 0.000 title claims abstract description 55
- 230000008569 process Effects 0.000 title claims abstract description 37
- 230000001698 pyrogenic effect Effects 0.000 title claims abstract description 21
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 194
- 229910052742 iron Inorganic materials 0.000 claims abstract description 90
- 238000003723 Smelting Methods 0.000 claims abstract description 86
- 239000002893 slag Substances 0.000 claims abstract description 27
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 22
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000007885 magnetic separation Methods 0.000 claims abstract description 17
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- 229910000629 Rh alloy Inorganic materials 0.000 claims abstract description 3
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- 239000000203 mixture Substances 0.000 claims description 11
- 239000000292 calcium oxide Substances 0.000 claims description 10
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- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 8
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- UQGFMSUEHSUPRD-UHFFFAOYSA-N disodium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound [Na+].[Na+].O1B([O-])OB2OB([O-])OB1O2 UQGFMSUEHSUPRD-UHFFFAOYSA-N 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 7
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- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 3
- XSKIUFGOTYHDLC-UHFFFAOYSA-N palladium rhodium Chemical compound [Rh].[Pd] XSKIUFGOTYHDLC-UHFFFAOYSA-N 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229910052814 silicon oxide Inorganic materials 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
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- 241001062472 Stokellia anisodon Species 0.000 description 2
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- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229910052878 cordierite Inorganic materials 0.000 description 2
- 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 2
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- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- 229910000640 Fe alloy Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910000905 alloy phase Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- 238000009835 boiling Methods 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
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- XWHPIFXRKKHEKR-UHFFFAOYSA-N iron silicon Chemical compound [Si].[Fe] XWHPIFXRKKHEKR-UHFFFAOYSA-N 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
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
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- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses a method for enriching platinum, palladium and rhodium in a waste ternary catalyst by a pyrogenic process, which comprises the steps of crushing and grinding the waste ternary catalyst, mixing the waste ternary catalyst with a slag former, a reducing agent and an iron-containing collector, briquetting, and smelting the obtained briquettes for one time to obtain noble iron and smelting slag; mixing and briquetting the noble iron, lead powder and carbonaceous reducing agent, carrying out secondary smelting on the obtained briquette, and cooling, cutting and separating the obtained melt to obtain noble lead and iron blocks; and carrying out vacuum blowing lead removal on the noble lead to obtain a platinum-palladium-rhodium alloy and lead-containing smoke dust. The total content of platinum, palladium and rhodium in the noble metal enrichment obtained by the method can be more than 80%, smelting slag produced by smelting in the process is discharged after magnetic separation, the total content of platinum, palladium and rhodium in the magnetic separation glass tailings is less than 10g/t, and the total recovery rate of three noble metals of platinum, palladium and rhodium is more than 99.3% based on the magnetic separation tailings. And iron and lead are used as collecting carriers of noble metals platinum, palladium and rhodium, and the process is in closed cycle without loss and additional addition.
Description
Technical Field
The invention relates to a method for enriching platinum, palladium and rhodium in a waste three-way catalyst by a pyrogenic process, in particular to a method for enriching platinum, palladium and rhodium in a waste three-way catalyst by a two-stage pyrogenic process, belonging to the field of precious metal extraction and separation.
Background
The ternary catalyst containing platinum, palladium and rhodium can convert CO, HC and NO x Conversion to non-toxic CO 2 、H 2 O、N 2 Therefore, platinum group metals are widely used in automobile exhaust gas purifying catalysts. Each ternary catalyst uses 1-2 g of platinum group metal, the ternary catalyst is replaced by about 10 ten thousand kilometers, the current ternary waste catalyst added with the waste car replaced every year exceeds 20000 tons, the platinum, palladium and rhodium are contained by about 40t, and the value is about 200 hundred million yuan. Therefore, the development of the technology for efficiently recovering the noble metal in the three-way catalyst has important economic and social benefits.
At present, precious metals are recovered from three-way catalysts of automobiles, and the two treatment processes can be divided into an all-wet recovery process and a combined process of a pyrogenic humidifying method.
There are reports (Zhou Jun et al, recovering platinum group metals [ J ]. Nonferrous metals from granular automobile waste catalysts: smelting part, 1996 (2): 5.DOI: CNKI: SUN: METE.0.1996-02-008.) using a sulfation roasting-water leaching method, gamma-alumina in the automobile clean gas waste catalysts is converted into soluble aluminum sulfate, and aluminum sulfate is dissolved with water, but most of platinum group metals remain in the residue, the recovery rate of the obtained products is not high, and the solution is difficult to filter, and the produced wastewater is also large.
Chinese patent CN1385545a discloses a method for recovering metals such as platinum, palladium and rhodium from automobile exhaust waste catalyst, which adopts an atmospheric pressure dissolution method to treat the automobile exhaust catalyst, and the treatment flow is as follows: crushing the waste catalyst, dissolving by inorganic acid, ion exchange, ammonifying to separate platinum, complexing to extract palladium, and replacing rhodium by copper powder, wherein the yields of platinum, palladium and rhodium are 96%, 97% and 90% respectively, but the platinum and palladium in the leaching solution are subjected to the traditional precipitation separation process, and repeated precipitation separation for many times is needed, so that the platinum and palladium are dispersed, and the direct yield is affected.
There are also reports of the prior art that precious metals in automobile waste catalysts are leached by pressure alkaline leaching pretreatment and pressure cyanidation, and leaching rates of platinum, palladium and rhodium respectively reach 98%, 99% and 96% for unused defective three-way catalysts. However, leaching is carried out under high pressure, and a large amount of highly toxic cyanide is used, so that a large danger is possibly brought, and the problems of low leaching rate, unstable leaching rate and the like of the used waste catalyst cannot be overcome.
The whole wet treatment process has short flow, but the leaching rate of platinum, palladium and rhodium is low, so that the total recovery rate is low; and the total wet process has large wastewater quantity, a large amount of chlorine radicals are contained in the wastewater and are difficult to treat, and meanwhile, leaching residues are still dangerous wastes and are difficult to treat. Therefore, the main stream technology at present adopts a fire method to smelt and enrich platinum, palladium and rhodium, and then adopts a wet method to dissolve, separate and purify.
Chinese patent CN104073641a discloses a process for recovering noble metals from spent car catalyst by plasma smelting enrichment recovery, which comprises adding magnetite collecting agent, coke as reducing agent, calcium oxide and fluorite as slag forming agent, and smelting at 1500-1600 ℃. In addition, chinese patent CN108441647A discloses a method for recovering noble metal platinum in automobile waste catalyst by a pyrogenic process, which comprises adding ferric oxide as a collector and a large amount of carbon as a reducer in the process of smelting by the pyrogenic process, wherein the smelting temperature is 1600-2000 ℃. There are also reports (Li Yong, he Xiaotang, xiong Qingfeng, et al. Smelting method for recovery of platinum palladium rhodium from spent automotive exhaust catalysts]Nonferrous metals: smelting section, 2017 (8): 40-43 pages)) discloses a method for enriching and recovering platinum, palladium and rhodium from a spent automobile exhaust catalyst by a smelting method, and researches on smelting and enriching platinum group metals and Fe are carried out on the spent automobile three-way catalyst 3 O 4 The comprehensive recovery rate of the metal platinum palladium rhodium can reach more than 97 percent at the smelting temperature of 1450 ℃ by taking the trapping agent, the coke as the reducing agent and the CaO as the slag former.
The above technology for enrichment and recovery of pyrometallurgy is characterized by large enrichment ratio, short flow, high production efficiency and no wastewater pollution. However, when the three-way catalyst of the automobile is treated by the smelting method at present, two problems exist: firstly, the enrichment multiple of noble metal is lower, the addition amount of general iron is about 10% of the raw material amount of the three-way catalyst, and the enrichment of noble metal is about 10 times; and secondly, in the prior art of fire enrichment, iron or ferric oxide is used as a collector, a coke reducer is added, and during high-temperature smelting, the carbon quality of the three-way catalyst and the added coke are easy to reduce silicon dioxide in cordierite into elemental silicon, and the elemental silicon is fused with the iron to generate high-silicon iron, so that the silicon iron and platinum group metal form a new alloy phase, and the alloy has extremely strong acid resistance and alkali resistance, increases the difficulty of subsequent iron leaching and precious metal leaching, and influences the recovery rate of platinum, palladium and rhodium.
Disclosure of Invention
Aiming at the defects that the method for recovering platinum, palladium and rhodium in the waste three-way catalyst in the prior art has low pyrometallurgy enrichment multiple, and the generated ferrosilicon increases the difficulty of subsequent iron leaching and precious metal leaching, and the like, the invention aims to provide a method for enriching platinum, palladium and rhodium in the waste three-way catalyst by using the pyrometallurgy. According to the method, the two-stage smelting enrichment is utilized to realize high-efficiency recovery of platinum, palladium and rhodium, meanwhile, the characteristic of fusion of lead to platinum, palladium and rhodium noble metals is combined in the secondary smelting process, the platinum, palladium and rhodium are transferred into noble lead for enrichment, and then the noble lead is subjected to vacuum blowing and lead removal to obtain a high-grade platinum, palladium and rhodium enrichment, so that the problem of difficult leaching of ferrosilicon alloy is avoided.
In order to achieve the technical aim, the invention provides a method for enriching platinum, palladium and rhodium in a waste three-way catalyst by a pyrogenic process, which comprises the steps of crushing and grinding the waste three-way catalyst, mixing the crushed and ground waste three-way catalyst with a slag former, a reducing agent and an iron-containing collector, briquetting, and smelting the obtained briquette for one time to obtain noble iron and smelting slag; mixing and briquetting the noble iron, lead powder and carbonaceous reducing agent, carrying out secondary smelting on the obtained briquette, and cooling, cutting and separating the obtained melt to obtain noble lead and iron blocks; and carrying out vacuum blowing lead removal on the noble lead to obtain a platinum-palladium-rhodium alloy and lead-containing smoke dust.
The invention is characterized in that a two-stage smelting enrichment process is adopted, firstly, precious iron containing platinum, palladium and rhodium is enriched by about 10 times through a primary smelting process, then, lead powder reduced by a carbonaceous reducing agent is added into the precious iron for secondary smelting, and because of the immiscibility of lead and iron and the stronger fusion property of lead to platinum, palladium and rhodium precious metals, the precious metals in the precious iron are transferred into metallic lead to generate precious lead, silicon impurities remain in iron blocks, and the platinum, palladium and rhodium precious metals are secondarily enriched, wherein the precious metals can be enriched by 3-5 times through the secondary enrichment, and the content is 10-15%. Finally, the noble lead is subjected to vacuum blowing lead removal to obtain platinum-palladium-rhodium concentrate with the grade of 80%, which is an effect which cannot be achieved by complex wet iron removal and noble metal dissolution and replacement enrichment in the current pyrogenic process and wet enrichment process. The lead and lead oxide removed in vacuum can be cooled and collected into dust, and then returned to the noble iron for adding lead and smelting, so that closed cycle utilization of lead is realized.
As a preferable scheme, the waste three-way catalyst is crushed and ground to a particle size of less than 80 meshes. Further preferred is a waste three-way catalyst having a particle size of less than 100 mesh after crushing. According to the invention, the waste three-way catalyst is crushed and ground, so that a large amount of surface energy is generated by grinding, the crystal structure of the waste three-way catalyst is damaged, the number of surface active sites and the reachable area are increased, and the subsequent smelting and enrichment are facilitated. On the other hand, the crushed granularity is controlled, so that the subsequent smelting process is more efficient and stable, the waste three-way catalyst is contacted with the collector, and the grade of the noble metal enrichment is improved.
As a preferable scheme, the mass ratio of the waste three-way catalyst, the slag former, the reducing agent and the iron-containing collector is 10:2-5:0.5-1:1-2. The invention adjusts and selects the mass ratio of the waste ternary catalyst, the slag former, the reducing agent and the iron-containing collector to achieve the best smelting enrichment process effect. As a preferred embodiment, the carbonaceous reducing agent is carbon powder.
As a preferred embodiment, the iron-containing collector is iron powder and/or iron oxide powder.
As a preferred scheme, the slag former is a mixture of silicon dioxide, calcium oxide and anhydrous borax.
As a preferable scheme, the reducing agent in the primary smelting is carbon powder.
As a preferable scheme, the conditions of the primary smelting are as follows: the temperature is 1400-1800 ℃ and the time is 4-6 h; the temperature is further optimized to be 1500-1600 ℃. As a preferable scheme, the mass ratio of the silicon dioxide, the calcium oxide and the anhydrous borax is (3-2.5): (2-1.5): (1-0.5).
As a preferable scheme, the amount of the lead powder is 20-30% of the mass of the noble iron. According to the invention, the content of noble metal in the noble lead can be improved by 3-5 times by adding a small amount of lead powder in secondary smelting, silicon in the noble iron does not enter the noble lead and is remained in the iron, separation from silicon impurities is realized, and if the amount of the lead powder is too high, the yield of the noble metal is not further improved and the grade of the noble metal is reduced. More preferably 20 to 25%.
As a preferred scheme, the dosage of the carbonaceous reducing agent is 5-20% of the mass of the noble iron. The lead oxide existing in a small amount in the lead powder can be reduced into simple substance lead by adding a small amount of carbonaceous reducing agent, so that the effect of enriching noble lead with platinum, palladium and rhodium is ensured.
As a preferable scheme, the secondary smelting conditions are as follows: the temperature is 1400-1500 ℃ and the time is 3-4 h. According to the invention, the enrichment of platinum, palladium and rhodium transferred from noble iron to noble lead can be fully realized by controlling the secondary smelting condition.
As a preferable scheme, the conditions of vacuum converting and lead removing are as follows: the temperature is 850-950 ℃, the time is 5-6 h, and the vacuum degree is 300-400 mmHg. According to the invention, the evaporation loss of lead can be reduced under the vacuum condition, the lead removal efficiency is improved, the oxygen content can be effectively reduced, the oxidation reaction of lead is reduced, and the lead removal effect is improved. The temperature of vacuum converting lead removing has direct influence on the lead removing effect, if the temperature is too high, most of lead is converted into lead oxide to escape, and the proper temperature is controlled to volatilize and escape the mixture of lead and lead oxide, so that the mixture of lead and lead oxide obtained after cooling is more favorable for returning to smelting.
As a preferable scheme, the smelting slag is subjected to magnetic separation to obtain noble iron and vitreous tailings; the noble iron returns to primary smelting; the iron blocks are subjected to water quenching atomization and grinding treatment and then are used as an iron-containing collector for recycling; and cooling and collecting the lead-containing smoke dust to form lead powder, and returning the lead powder to secondary smelting.
The waste ternary catalyst is subjected to two-stage smelting enrichment and vacuum lead removal, so that high-grade noble metal enrichment can be obtained, and the maximum total content of platinum, palladium and rhodium can be more than 80%. And iron and lead are used as collecting carriers of noble metals platinum, palladium and rhodium, and are circulated in a closed circuit in the process, so that no loss and no extra addition are needed. The vitreous tailing produced in the iron smelting process is the only externally discharged tailing in the process, and can be used as common solid waste for building materials. The total content of platinum, palladium and rhodium in the magnetically separated glass tailings is less than 10g/t, and the total recovery rate of three noble metals of platinum, palladium and rhodium is more than 99.3 percent based on the magnetically separated tailings.
The invention provides a method for enriching platinum, palladium and rhodium in a waste ternary catalyst by a pyrogenic process, which specifically comprises the following steps:
1) Crushing and grinding: firstly, crushing and grinding the waste ternary catalyst of the automobile, wherein the granularity of the crushed and ground waste ternary catalyst is smaller than 80 meshes.
2) Preparing materials and briquetting: adding ingredients required in the smelting process, uniformly mixing, pressing into balls, and drying for standby. The collecting agent is simple substance iron powder or ferric oxide powder, and the slag former is SiO 2 CaO and anhydrous borax, and a reducing agent is carbon powder, wherein the proportion of the waste three-way catalyst to the slag former to the C powder to the Fe powder=10: (2-5): (0.5-1): (1-2).
3) And (3) smelting for one time to obtain noble iron: smelting the pellets in the step 2) in an intermediate frequency furnace or an electric arc furnace at 1400-1800 ℃ for 4-6 h, separating glass body scum to obtain an iron alloy melt (called noble iron for short) containing Pt, pd and Rh, quenching and atomizing the noble iron melt, and finally grinding the molten iron to 100-200 meshes. In the step, the platinum, palladium and rhodium in the three-way catalyst are transferred into the noble iron, and preliminary enrichment of about 10 times is obtained, and the total content of the platinum, palladium and rhodium in the noble iron is 2-3%.
4) Crushing and magnetic separation of smelting slag: crushing smelting slag containing calcium oxide, magnesium oxide, aluminum oxide and silicon oxide to 0.5-3 mm through a pair of rollers, magnetically separating the smelting slag through 10000Gs magnetic rollers, and returning the obtained magnetic substances to the step 3) for smelting, wherein the magnetic separation tailings are glass body fine powder and can be used as common solid waste for building materials. The total content of platinum, palladium and rhodium in the magnetically separated glass tailings is less than 10g/t, and the total recovery rate of three noble metals of platinum, palladium and rhodium is more than 99.3 percent based on the magnetically separated tailings.
5) Secondary smelting of noble iron to obtain noble lead: adding the noble iron powder into the lead powder and the carbon powder, mixing, pressing into balls, and carrying out secondary smelting. The addition amount of the lead powder is 20-30% of the noble iron amount, the carbon powder amount of the carbonaceous reducing agent is 5-20% of the noble iron amount, the mixture is uniformly mixed and pressed into balls, the smelting temperature is 1400-1500 ℃, the smelting time is 3-4 hours, the molten iron is poured into a ladle, the ladle is shaken for 60 minutes and then is kept stand, lead is settled, the cooling and cutting separation are carried out, the noble lead and iron blocks are obtained, the iron blocks are subjected to water quenching atomization, the grinding is carried out to 100-200 meshes, and the mixture is returned to the step 2) to be used as a collector. The process utilizes the immiscibility of lead and iron and the stronger fusion property of lead to noble metal, transfers the noble metal in the noble iron into metallic lead to generate noble lead, and the noble metal is secondarily enriched, so that the total content of platinum, palladium and rhodium in the noble lead is improved to 8-15%.
6) Vacuum converting and lead removing: and carrying out vacuum blowing on the noble lead, wherein the blowing temperature is 850-950 ℃, the vacuum degree is 300-400 mmHg, and the blowing time is 5-6 hours, so as to obtain the high-grade noble metal enrichment with the highest total content of platinum, palladium and rhodium being more than 80%. Strictly cooling and dust-collecting gasified lead and lead oxide smoke dust, and returning to the step 5) to smelt noble lead.
Compared with the prior art, the technical scheme of the invention has the beneficial technical effects that:
1) The waste ternary catalyst is subjected to the two-stage smelting enrichment and vacuum lead removal enrichment to obtain the high-grade noble metal enrichment, and the maximum total content of platinum, palladium and rhodium can be more than 80 percent. Iron and lead are used as the collecting carrier of noble metals platinum, palladium and rhodium, and are circulated in a closed circuit in the process, so that no loss is caused and no extra addition is needed. The vitreous tailing produced in the iron smelting process is the only externally discharged tailing in the process, and can be used as common solid waste for building materials. The total content of platinum, palladium and rhodium in the tailings after magnetic separation is less than 10g/t, the total recovery rate of three noble metals of platinum, palladium and rhodium is more than 99.3 percent based on the magnetic separation tailings, and the enrichment of platinum, palladium and rhodium can be almost quantitatively recovered in the subsequent wet separation recovery process without loss.
2) According to the invention, there is no need to worry about reduction of silicon oxide into simple substance silicon, so that more silicon oxide can be added during smelting to change the viscosity of scum, the problem of difficulty in separation of metal melt and scum is solved, the entrainment loss of noble metal in the scum is reduced, and the enrichment recovery rate of pyrometallurgy is improved.
Drawings
FIG. 1 is a process flow diagram of an embodiment of the present invention.
Detailed Description
The following examples are given solely for the purpose of illustrating preferred embodiments of the invention and are not intended to limit the scope of the invention, as modifications, which would be obvious to one of ordinary skill in the art, should be made without departing from the scope of the invention.
Unless otherwise specifically indicated, the various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or may be prepared by existing methods.
Example 1
The waste ternary catalyst adopted in the embodiment is a ternary waste catalyst of a certain automobile, and comprises Pt 0.024%, pd0.176% and Rh 0.018%, and the catalyst is made of cordierite (2MgO.2Al) 2 O 3 ·5SiO 2 ) The catalyst is a carrier, is in a honeycomb cylindrical shape, the surface of the catalyst is coated with an alumina active coating, active components are Pt, pd, rh and transition metal oxides, carbon deposition is attached to the surface of the catalyst, the catalyst is partially sintered, and the component analysis results are shown in Table 1.
TABLE 1 waste three-way catalyst Components
| Composition of the components | Al 2 O 3 | SiO 2 | MgO | CeO 2 | P 2 O 5 | Fe 2 O 3 | ZrO 2 | Pt | Pd | Rh |
| Content% | 40.7 | 28.5 | 8.6 | 4.2 | 1.1 | 0.71 | 0.87 | 0.024 | 0.176 | 0.018 |
1) Crushing and grinding
Firstly, crushing and grinding the waste ternary catalyst of the automobile, wherein the granularity of the crushed and ground waste ternary catalyst is-100 meshes.
2) Preparing materials and briquetting
2000g of ground three-way catalyst is taken and the following mass ratio is adopted: 600g of slag former, 100g of carbon powder and 200g of simple substance iron powder are respectively added into the waste three-way catalyst, slag former, carbon powder and iron powder=10:3:0.5:1, and the slag former is SiO 2 Mixture of CaO and anhydrous borax, specifically 300g of SiO 2 200g of CaO and 100g of anhydrous borax. And uniformly mixing all the materials, pressing the mixture into balls and drying the balls.
3) One-time smelting and enriching to obtain noble iron
And (3) smelting the pellets in the step (2) in an intermediate frequency furnace at a smelting temperature of 1500 ℃ for 5 hours, separating vitreous dross to obtain 178g of noble iron, quenching and atomizing the noble iron, and finally grinding the noble iron into 160 meshes. The content of platinum, palladium and rhodium in the analyzed noble iron is respectively as follows: contains Pt 0.261%, pd 1.916%, rh 0.196%, siO 2 12.5%, the direct recovery rate of the noble metal in the step is 96.9%, and the enrichment multiple is 10.89 times.
4) Crushing and magnetic separation of smelting tailings
Crushing smelting tailings to 0.5-3 mm, carrying out magnetic separation by a 10000Gs magnetic roller to obtain 130g of magnetic concentrate containing 107g/t Pt, 785g/t Pd and 81g/t Rh, and returning to the smelting in the step 3) to recover noble metals; 2450g of magnetic separation tailings, which are slag vitreous fine powder, can be used as common solid waste for building materials. The magnetic separation tailings contain 0.9g/t of Pt, 5.4g/t of Pd, 0.8g/t of Rh and 7.1g/t of total content of platinum, palladium and rhodium, and the recovery rates of the platinum, palladium and rhodium are respectively 99.5% of Pt, 99.6% of Pd and 99.4% of Rh based on the magnetic separation tailings.
5) Secondary smelting to obtain noble lead
178g of noble iron powder is added with 35.6g of lead powder and 17.8g of carbon powder, mixed and pressed into balls, secondary smelting is carried out, the smelting temperature is 1460 ℃, the smelting time is 3 hours, the molten iron is poured into a ladle, the ladle is shaken for 60 minutes, then the molten iron stands still, the lead is settled, the cooling is carried out, the cutting separation is carried out, 176g of noble lead and iron blocks are obtained, 34.8g of noble lead and iron blocks are obtained, the iron blocks are water quenched and atomized, ground into 160 meshes, and the mixture is returned to the step 2) to be used as a collector. The content of platinum, palladium and rhodium in the analyzed noble lead is respectively as follows: pt 1.305%, pd 9.58%, rh 0.98%, and the direct recovery of noble metal is 97.5%. The precious metals are secondarily enriched by smelting the precious lead, and the total content of platinum, palladium and rhodium in the precious lead is increased to 11.865 percent.
6) Vacuum converting lead-removing
34.8g of noble lead is subjected to vacuum blowing in a tube furnace, the blowing temperature is 860 ℃, the vacuum degree is 300mmHg, the blowing time is 5 hours, 5.1g of platinum-palladium-rhodium concentrate is obtained, and the contents of platinum-palladium-rhodium are analyzed as follows: pt 8.9%, pd 65.2%, rh 6.7%, and the balance of lead and iron, with a total content of platinum, palladium and rhodium of 80.8%. The tail gas is cooled and collected with dust to obtain 39.7g of lead ash, and the lead ash can be recycled for secondary smelting.
2000g of ternary catalyst, through twice smelting enrichment and vacuum blowing lead removal of noble iron and noble lead, 5.1g of platinum-palladium-rhodium enrichment is obtained, wherein the content of platinum-palladium-rhodium is respectively Pt 8.9%, pd 65.2% and Rh 6.7%, the direct recovery rate of noble metal is 94.5%, because only tailings produced by smelting noble iron are discharged after magnetic separation, the magnetic separation tailings contain Pt 0.9g/t, pd 5.4g/t and Rh 0.8g/t, the total content of platinum-palladium-rhodium is 7.1g/t, and the recovery rates of platinum-palladium-rhodium are respectively Pt 99.5%, pd 99.6% and Rh 99.4% according to the magnetic separation tailings.
Example 2
The amounts and compositions of the three-way catalyst and steps 1) to 4) in this example are the same as in example 1, except that:
5) Secondary smelting to obtain noble lead
Adding 178g of noble iron powder into 50g of lead powder and 35g of carbon powder, mixing, pressing into balls, carrying out secondary smelting, wherein the smelting temperature is 1410 ℃, the smelting time is 3 hours, pouring molten iron into a ladle, shaking the ladle for 60 minutes, standing, sinking lead, cooling, cutting and separating to obtain 177.3g of 52.5g of noble lead and iron blocks, quenching and atomizing the iron blocks with water, grinding to 160 meshes, and returning to the step 2) to serve as a collector. The content of platinum, palladium and rhodium in the analyzed noble lead is respectively as follows: pt 0.894%, pd 6.56%, rh 0.671%, the direct recovery rate of noble metal is 97.8%, the noble metal is secondarily enriched by smelting noble lead, and the total content of platinum, palladium and rhodium in the noble lead is improved to 8.125%.
Compared with the embodiment 1, the recovery rate of noble metal is improved after the use amount of lead powder is increased, but the increment is not obvious, but the grade of noble metal in noble lead is reduced, so that the direct yield of noble metal can be improved but the grade of noble metal in noble lead is reduced when the use amount of lead is increased during lead smelting enrichment, the treatment capacity and energy consumption for subsequent lead removal are increased, and the use amount of lead needs to be controlled to be at most 30 percent.
6) Vacuum converting lead-removing
Carrying out vacuum lead removal on 52.5g of noble lead in a tube furnace, wherein the lead removal temperature is 920 ℃, the vacuum degree is 380mmHg, the lead removal time is 5 hours, 6.7g of platinum-palladium-rhodium concentrate is obtained, and the contents of the platinum-palladium-rhodium are analyzed as follows: 7.0% of Pt, 51.0% of Pd, 5.3% of Rh, and 63.3% of platinum, palladium and rhodium. And cooling and dust collecting the tail gas to obtain 39.7g of lead ash, and recycling the lead ash for secondary lead-adding enrichment smelting.
Compared with the example 1, the vacuum degree is changed from 300mmHg to 380mmHg, the vacuum degree is reduced, the lead removing temperature is increased from 860 ℃ to 920 ℃, the lead removing time is unchanged, the weight of the obtained concentrate after lead removing is increased from 5.1g to 6.7g, and the lead removing effect can be realized by adjusting the lead removing temperature and the vacuum degree within the scope of the invention.
Comparative example 1
The amount of lead used in step 5) of example 1 was changed from 20% to 15% to give 25.6g of noble lead. The content of platinum, palladium and rhodium in the analyzed noble lead is respectively as follows: pt 1.529%, pd 11.225%, rh 1.148%, and the direct recovery of noble metal is 85.7%.
By this comparative example, it was seen that after the lead usage was reduced from 20% to 15%, the noble metal content in the noble lead was increased, the fold enrichment was increased by an average of 1.172 times, but the noble metal recovery in the noble lead was reduced from 97.5% to 85.7%, although the noble metal that did not enter the noble lead was still present in the iron slag, and could be recycled by returning to a smelting stage as a collector, no loss of noble metal occurred, but the inefficient cycling of noble metal resulted in an increase in energy consumption and an increase in the noble metal recovery period, so that the noble metal recovery during the lead enrichment process should be ensured to a relatively high level to avoid these adverse effects.
Comparative example 2
Changing the vacuum degree in the vacuum blowing lead removal in the step 6) of the example 1 from 300mmHg to 500mmHg, and obtaining 9.6g of platinum-palladium-rhodium concentrate under the same other conditions, wherein the analysis contents of platinum-palladium-rhodium are respectively as follows: pt 5.48%, pd40.23%, rh 4.13% and the balance of lead and iron, the total content of platinum, palladium and rhodium being 49.84%.
From comparison, after the vacuum degree is reduced, the lead volatilization is greatly influenced, the lead volatilization is not thorough, and the total content of platinum, palladium and rhodium in the noble metal enriched product is reduced from 80.8% of the example 1 to 49.84%.
Comparative example 3
In this comparative example, steps 1) to 3) were carried out in the same manner as in example 1, 178g of the same noble iron as in example 1 was produced, and the noble iron components were as follows，Pt 0.261％、Pd 1.916％、Rh 0.196％，SiO 2 12.5%, the direct recovery rate of the noble metal in the step is 96.9%, the enrichment multiple is 10.89 times, and the difference is that:
4) Dissolving iron removal
178g of the noble iron powder, adding 1500ml of 6mol/L HCl to dissolve and remove iron, maintaining the temperature at 90 ℃ and the total reaction time for 6 hours to obtain 50.6g of insoluble matters.
5) Aqua regia soluble noble metal
Dissolving 50.6g of insoluble matters in the step 4) by using aqua regia, preparing 300ml of concentrated aqua regia, adding 100ml of water into 50.6g of insoluble slag, slowly adding the prepared aqua regia, avoiding severe reaction, maintaining the temperature at 80-90 ℃, reacting for 4 hours, filtering and washing to obtain 500ml of leaching solution containing platinum, palladium, rhodium and iron.
6) Substitution enrichment of platinum palladium rhodium
50g of iron sheet and 10g of zinc particles are added into 500ml of leaching solution containing platinum, palladium and rhodium and other impurities, the platinum, palladium and rhodium in the leaching solution are replaced, the replacement temperature is 35 ℃, the time is 48 hours, the initial acidity of the reaction is 1.5mol/L, 1.2mg/L of platinum, 1.5mg/L of palladium and 5.6mg/L of rhodium in the replacement mother liquor are obtained by filtering, the platinum, palladium and rhodium enrichment is obtained by adding 300ml of hydrochloric acid with the concentration of 3mol/L, filtering after 60 minutes of boiling and washing, the enrichment is obtained by 8.8g, the analyzed platinum, palladium and rhodium contents are respectively Pt 4.9%, pd 36.5%, rh 3.6%, the total content of platinum, palladium and rhodium is 45.0%, the direct yield of platinum, palladium and rhodium is Pt 90.1%, pd 90.5% and Rh 87.6%.
Compared with the process of enriching noble iron through subsequent lead smelting and vacuum lead removing in the embodiment 1, the content, grade and direct yield of the noble metal enrichment produced by the process of enriching noble metal through smelting and enriching the noble iron by adopting a conventional wet method for dissolving iron in the comparative example are obviously reduced.
Claims (10)
1. A method for enriching platinum, palladium and rhodium in waste ternary catalyst by adopting a pyrogenic process is characterized by comprising the following steps: crushing and grinding the waste ternary catalyst, mixing the waste ternary catalyst with a slag former, a reducing agent and an iron-containing collector, briquetting, and smelting the obtained briquettes once to obtain noble iron and smelting slag; mixing and briquetting the noble iron, lead powder and carbonaceous reducing agent, carrying out secondary smelting on the obtained briquette, and cooling, cutting and separating the obtained melt to obtain noble lead and iron blocks; and carrying out vacuum blowing lead removal on the noble lead to obtain a platinum-palladium-rhodium alloy and lead-containing smoke dust.
2. The method for the pyrogenic enrichment of platinum, palladium and rhodium in a waste three-way catalyst according to claim 1, which is characterized in that: and crushing and grinding the waste ternary catalyst to a granularity smaller than 80 meshes.
3. The method for the pyrogenic enrichment of platinum, palladium and rhodium in a waste three-way catalyst according to claim 1, which is characterized in that: the mass ratio of the waste ternary catalyst to the slag former to the reducing agent to the iron-containing collecting agent is 10:2-5:0.5-1:1-2.
4. The method for the pyrogenic enrichment of platinum, palladium and rhodium in a waste three-way catalyst according to claim 3, which is characterized in that:
the iron-containing collector is iron powder and/or iron oxide powder;
the slag former is a mixture of silicon dioxide, calcium oxide and anhydrous borax;
the carbonaceous reducing agent is carbon powder.
5. The method for the pyrogenic enrichment of platinum, palladium and rhodium in the waste three-way catalyst according to claim 4, which is characterized in that: the mass ratio of the silicon dioxide to the calcium oxide to the anhydrous borax is (3-2.5): (2-1.5): (1-0.5).
6. The method for the pyrogenic enrichment of platinum, palladium and rhodium in a waste three-way catalyst according to claim 1, which is characterized in that: the conditions of the primary smelting are as follows: the temperature is 1400-1800 ℃ and the time is 4-6 h.
7. The method for the pyrogenic enrichment of platinum, palladium and rhodium in the waste three-way catalyst according to claim 6, which is characterized in that:
the dosage of the lead powder is 20-30% of the mass of the noble iron;
the dosage of the carbonaceous reducing agent is 5-20% of the mass of the noble iron.
8. The method for the pyrogenic enrichment of platinum, palladium and rhodium in a waste three-way catalyst according to claim 7, which is characterized in that: the secondary smelting conditions are as follows: the temperature is 1400-1500 ℃ and the time is 3-4 h.
9. The method for the pyrogenic enrichment of platinum, palladium and rhodium in a waste three-way catalyst according to claim 1, which is characterized in that: the conditions of vacuum converting and lead removing are as follows: the temperature is 850-950 ℃, the time is 5-6 h, and the vacuum degree is 300-400 mmHg.
10. The method for the pyrogenic enrichment of platinum, palladium and rhodium in a waste three-way catalyst according to any one of claims 1 to 9, which is characterized in that:
the smelting slag is subjected to magnetic separation to obtain noble iron and vitreous tailing; the noble iron returns to primary smelting;
the iron blocks are subjected to water quenching atomization and grinding treatment and then are used as an iron-containing collector for recycling;
and cooling and collecting the lead-containing smoke dust to form lead powder, and returning the lead powder to secondary smelting.
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