CN117947280A - Method for recycling platinum, palladium and rhodium in automobile three-way catalyst by full wet method - Google Patents
Method for recycling platinum, palladium and rhodium in automobile three-way catalyst by full wet method Download PDFInfo
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 254
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 title claims abstract description 220
- 229910052763 palladium Inorganic materials 0.000 title claims abstract description 130
- 229910052697 platinum Inorganic materials 0.000 title claims abstract description 106
- 239000010948 rhodium Substances 0.000 title claims abstract description 71
- 229910052703 rhodium Inorganic materials 0.000 title claims abstract description 71
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 238000000034 method Methods 0.000 title claims abstract description 67
- 239000003054 catalyst Substances 0.000 title claims abstract description 66
- 238000004064 recycling Methods 0.000 title claims abstract description 20
- 238000002386 leaching Methods 0.000 claims abstract description 86
- 238000000605 extraction Methods 0.000 claims abstract description 28
- 239000007788 liquid Substances 0.000 claims abstract description 24
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- 229920005989 resin Polymers 0.000 claims abstract description 21
- 238000001179 sorption measurement Methods 0.000 claims abstract description 21
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 19
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- 238000001556 precipitation Methods 0.000 claims abstract description 14
- 238000000926 separation method Methods 0.000 claims abstract description 13
- 239000002699 waste material Substances 0.000 claims abstract description 13
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims abstract description 12
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- 229910052799 carbon Inorganic materials 0.000 claims abstract description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 8
- 235000019270 ammonium chloride Nutrition 0.000 claims abstract description 6
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- 239000002994 raw material Substances 0.000 claims description 15
- -1 ammonium nitrosorhodium Chemical compound 0.000 claims description 14
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- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 7
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
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- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 4
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- 125000003386 piperidinyl group Chemical group 0.000 claims description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical group COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical group O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
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- 230000001502 supplementing effect Effects 0.000 claims description 3
- 238000011084 recovery Methods 0.000 abstract description 24
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- 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 5
- 238000006073 displacement reaction Methods 0.000 description 5
- 238000005342 ion exchange Methods 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 4
- 239000003638 chemical reducing agent Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- XWHPIFXRKKHEKR-UHFFFAOYSA-N iron silicon Chemical compound [Si].[Fe] XWHPIFXRKKHEKR-UHFFFAOYSA-N 0.000 description 4
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- 150000002739 metals Chemical class 0.000 description 3
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- 229910000640 Fe alloy Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 2
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- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 230000001698 pyrogenic effect Effects 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- 101001050287 Mus musculus Transcription factor Jun Proteins 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- AUZRORBINHVFFD-UHFFFAOYSA-N [Rh]N=O Chemical compound [Rh]N=O AUZRORBINHVFFD-UHFFFAOYSA-N 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910000905 alloy phase Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
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- 239000000295 fuel oil Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
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- 239000012535 impurity Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
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- 150000007522 mineralic acids Chemical class 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
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- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
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Classifications
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- 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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- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention relates to the field of precious metal extraction and separation, in particular to a method for recycling platinum, palladium and rhodium in an automobile three-way catalyst by an all-wet method. The method comprises the following steps: roasting the three-way catalyst to remove carbon deposition and organic matters; crushing, grinding and mechanically activating the decarbonized three-way catalyst, and simultaneously adding an activating agent to convert the noble metal in an oxidation state into an elemental state; two-stage countercurrent leaching of platinum, palladium and rhodium in the waste catalyst; adsorbing platinum, palladium and rhodium in the leaching liquid by using the resin, and keeping rhodium in the adsorption tail liquid; rhodium is recovered by a displacement method; adsorbing saturated resin column to wash platinum and palladium; extracting palladium and platinum from the leaching solution, and allowing the platinum to enter raffinate; back extracting palladium, precipitating palladium in the back extraction liquid and reducing to obtain sponge palladium; adding platinum in the ammonium chloride precipitation raffinate, and carrying out precipitation reduction on ammonium chloroplatinate to obtain a platinum sponge product. The invention has the advantages of short process, low recovery cost and high noble metal yield.
Description
Technical Field
The invention relates to the field of precious metal extraction and separation, in particular to a method for recycling platinum, palladium and rhodium in an automobile three-way catalyst by an all-wet method.
Background
The eight metals of platinum, palladium, rhodium, osmium, iridium, ruthenium, gold and silver are collectively called noble metals, the first six metals are called platinum group metals (Platium-group metals, abbreviated as PGMS), which have a number of unique physicochemical properties and have very wide and important applications in the national economy and the high and new technology industry, called "modern industrial vitamins" as early as the 60 s of the 20 th century. In the last two decades, with the development and development of high and new technologies and industries thereof, the application field of platinum group metals is continuously expanded, and many fields cannot be replaced by other materials, and the important position is continuously reflected in the technological development of the 21 st century.
The ternary catalyst containing platinum, palladium and rhodium can convert CO, HC and NO x into nontoxic CO 2、H2O、N2, so that the platinum group metal is widely applied to automobile exhaust purification catalysts. Each ternary catalyst uses 1-2 g of platinum group metal, the ternary catalyst is replaced by about 10 ten thousand km, the current ternary waste catalyst added with the waste car is replaced every year by about 10000 tons, the platinum, palladium and rhodium are contained by about 20t, and the value is 100 hundred million yuan. By 2025, the amount of fuel oil China car would be expected to hold more than 4 hundred million, 16000 tons of deactivated car catalyst per year, about 30 tons of platinum group metal, and about 160 hundred million yuan worth. At present, 60% of deactivated automobile catalysts flow abroad, mainly in the United states, germany, japan, korea and Belgium, so that the technology for recovering noble metals in three-way catalysts is developed, and the recovery of platinum group metals from the technology has important economic and social benefits.
The method for recovering platinum group metals from automotive catalysts can be summarized in the following treatment processes: (1) Carrier complete dissolution method. This process is used to treat early gamma-alumina composed particulate and columnar catalysts. Firstly, grinding the catalyst to-200 meshes, then, dissolving the carrier by sulfuric acid, adding hydrochloric acid and chlorine into insoluble slag to leach out platinum group metals, and precipitating and recovering the platinum group metals in the leaching solution by using sulfur dioxide. The recovery rate of this method is 88-94% of platinum, 88-96% of palladium and 84-88% of rhodium. (2) a carrier insolubilization method. This method is used for recovering platinum group metals from cordierite-supported catalysts. It dissolves only the alumina coating containing the catalyst and the cordierite support is substantially free of erosion. The catalyst is crushed into one inch of fragments, gamma-Al 2O3 on the surface of the carrier is dissolved by dilute sulfuric acid, then the catalyst is washed by decantation, the dissolved platinum group metals can be quantitatively recovered by three-stage decantation washing, and then sulfur dioxide is used as a reducing precipitator and Te is used as a trapping agent. The recovery rate of the method is respectively as follows: 85-92% of platinum, 85-93% of palladium and 78-85% of rhodium. (3) plasma enrichment method. The high temperature generated by plasma can reach more than 2000 ℃, aluminum oxide and cordierite are directly melted without adding flux, platinum group metals enter high silicon iron alloy slag, after spray granulation, the silicon iron alloy is dissolved with sulfuric acid and air to dissolve impurities, and leaching slag containing platinum group metals is produced. And recovering platinum group metals from the slag. The method has the problems of lead pollution, high electricity consumption and difficult alloy dissolution, so that the recovery rate of the metal is low and the cost is high. (4) copper smelting cooperative recovery method. During the pyrometallurgical copper smelting, a catalyst is added thereto so that PGMS is introduced into matte and blister copper, and PGMS is introduced into copper anode slime during electrolysis of blister copper, and then PGMS is recovered from the copper anode slime. Therefore, the recovery rate of copper in the smelting process determines the recovery rate of PGMS, and the recovery rates of platinum, palladium and rhodium are generally higher and more than 90 percent, but the production period is long and the recovery rate must be treated in cooperation with copper smelting enterprises.
Zhou Jun A sulfating roasting-water leaching method is adopted to treat an automobile catalyst with a gamma-alumina matrix, the recovery rate of the obtained PGMS is not very high, the solution is difficult to filter, the produced wastewater is also very large, and no proposal is made on how to recover and separate the PGMS from the leaching solution.
Zhang Fangyu et al (CN 1385545A) adopts an atmospheric pressure dissolution method to treat an automobile exhaust catalyst, and the process 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.
Chen Jingdi out of the process of pressure alkaline leaching pretreatment and pressure cyanidation leaching of noble metals in the automobile waste catalyst, leaching rates of platinum, palladium and rhodium respectively reach 98%, 99% and 96% for unused defective three-way catalyst, and pressure cyanidation reduces corrosion to equipment, but a large amount of use of highly toxic cyanide possibly brings about a large danger, and the problems of low leaching rate, unstable leaching rate and the like for used waste catalyst cannot be overcome.
He Xiaotang researches a plasma smelting enrichment recovery process (CN 104073641A), but the slag generated by cordierite has high viscosity, and the metal and the slag are difficult to separate; and secondly, at the smelting temperature of 2000 ℃, the carbon in the ternary catalyst is easy to reduce part of silicon dioxide in the cordierite into simple substance silicon, high silicon iron is generated by the carbon and iron added as a platinum group metal trapping agent, and the silicon iron and platinum group metal form a new alloy phase, so that the alloy has extremely strong acid and alkali resistance, and the subsequent leaching is extremely difficult.
Disclosure of Invention
The invention aims to solve the technical problems that: the method for recycling platinum, palladium and rhodium in the three-way catalyst of the automobile by the all-wet method adopts the all-wet method technology of strengthening pretreatment and strengthening leaching, combines the ion exchange and extraction separation technology, avoids the problems of high energy consumption and atmospheric pollution of the pyrogenic pretreatment technology, and improves the recovery rate of the traditional wet method recycling technology to be slightly low.
The invention provides a method for recycling platinum, palladium and rhodium in an automobile three-way catalyst by an all-wet method, which comprises the following steps:
Step one: roasting the three-way catalyst to remove carbon deposition and organic matters;
Step two: crushing, grinding and mechanically activating the decarbonized three-way catalyst, and simultaneously adding an activating agent to convert the noble metal in an oxidation state into an elemental state;
step three: two-stage countercurrent leaching of platinum, palladium and rhodium in the waste catalyst;
step four: adsorbing platinum, palladium and rhodium in the leaching liquid by using the resin, and keeping rhodium in the adsorption tail liquid; rhodium is recovered by a displacement method;
step five: adsorbing saturated resin column to wash platinum and palladium;
step six: extracting palladium and platinum from the leaching solution, and allowing the platinum to enter raffinate;
step seven: back extracting palladium, precipitating palladium in the back extraction liquid and reducing to obtain sponge palladium;
Step eight: adding platinum in the ammonium chloride precipitation raffinate, and carrying out precipitation reduction on ammonium chloroplatinate to obtain a platinum sponge product.
Preferably, in the first step, the roasting temperature is 300-900 ℃ and the roasting time is 2-8 h.
Preferably, in the second step, wet mechanical grinding is adopted, and the grinding granularity is 80-400 meshes; the activating agent is formic acid, hydrazine hydrate or sodium borohydride, and the using amount of the activating agent is 1% of the raw material amount; the activation temperature is 60 ℃, the liquid-solid ratio is 3/1, and the time is 2-4 hours.
Preferably, in the third step, the method specifically includes:
The leaching temperature of the first stage is 60-100 ℃, the liquid-solid ratio is 3/1-5/1, the sulfuric acid concentration is 10-20%, hydrochloric acid with the raw material content of 10% is added after leaching for 2 hours, sodium chlorate with the raw material content of 4% is added, stirring is continued for 2 hours after the sodium chlorate is added, and the platinum, palladium and rhodium are recovered from the leaching solution of the first stage in the next stage;
The second stage leaching temperature is 60-100 ℃, the liquid-solid ratio is 3/1-5/1, the sulfuric acid concentration is 20-40%, hydrochloric acid with the raw material content of 10-20% and sodium chlorate with the raw material content of 4-10% are added after leaching for 2 hours, stirring is continued for 2 hours after the sodium chlorate is added, and the leaching liquid returns to the first stage leaching after supplementing sulfuric acid.
Preferably, in the fourth step, the resin is chelate resin with piperidine functional groups, the adsorption contact time is 10-60 min, the acidity of the adsorption stock solution is 0.1-2 mol/L, the adsorption temperature is 10-50 ℃, and the platinum-palladium concentration of the adsorption tail solution is controlled to be less than or equal to 0.3mg/L.
Preferably, in the fifth step, the leaching agent is nitric acid, persulfuric acid or perchloric acid, the mass percentage concentration of the leaching agent is 5-30%, the leaching contact time is 30-120 min, the temperature is 20-60 ℃, the total concentration of platinum and palladium in the leaching solution is more than 8g/L, the leaching solution is removed for subsequent separation and recovery of platinum and palladium, and the leaching solution with the total concentration of platinum and palladium less than 8g/L is returned to be continuously used as the leaching agent.
Preferably, in the step flow six, the diisoamyl sulfide is used for extracting palladium in the platinum-palladium eluent, and the extraction conditions are as follows: the organic phase consists of 40% of diisoamyl sulfide, 10% of aromatic hydrocarbon and 50% of kerosene, the acidity is 0.1-6 mol/L, the contact time is 5min, the O/A=1:1, the number of stages is 3, and the extraction temperature is 15-50 ℃; more than 99% of the palladium enters the extractant and more than 99% of the platinum remains in the raffinate.
Preferably, in the step seven, the dilute ammonia water is used for back extraction of palladium, the concentration of the ammonia water is 5-15%, the contact time is 5 minutes, the O/A=1:1-3:1, the number of stages is 3, and the back extraction temperature is 15-50 ℃.
Preferably, in the fourth step, iron sheet, iron powder or copper powder is adopted to replace and adsorb rhodium in the tail liquid, the dosage is 1-50 times of the theoretical dosage, the reduction temperature is 25-90 ℃ and the time is 2-24 hours, and crude rhodium obtained by replacement is purified and recovered by adopting an ammonium nitrosorhodium precipitation method.
Compared with the prior art, the method for recycling platinum, palladium and rhodium in the automobile three-way catalyst by the full wet method has the following beneficial effects:
(1) The full wet process of strengthening pretreatment and strengthening leaching is adopted, and the ion exchange and extraction separation technology is combined, so that the high energy consumption and the air pollution of the fire pretreatment process are avoided, and the problem of low recovery rate of the traditional wet recovery process is solved;
(2) The pretreatment of roasting to remove carbon deposit and mechanical activation is adopted, so that the platinum, palladium and rhodium in the three-way catalyst have higher activity and become easy to leach.
(3) And adopting two-stage countercurrent enhanced leaching to obtain higher leaching rates of platinum, palladium and rhodium.
(4) The method adopts the ion exchange and extraction separation purification technology to separate and recycle platinum, palladium and rhodium, and has the advantages of short flow, good separation effect, high product purity and high recovery rate.
Drawings
FIG. 1 shows a flow chart of a method for recovering platinum, palladium and rhodium in an automotive three-way catalyst by an all-wet method.
Detailed Description
For a further understanding of the present invention, embodiments of the invention are described below in conjunction with the examples, but it should be understood that these descriptions are merely intended to illustrate further features and advantages of the invention, and are not limiting of the invention.
The percentages in the invention are mass percent.
The embodiment of the invention discloses a method for recycling platinum, palladium and rhodium in an automobile three-way catalyst by an all-wet method, which is shown in figure 1 and comprises the following steps:
Step one: roasting the three-way catalyst to remove carbon deposition and organic matters;
Step two: crushing, grinding and mechanically activating the decarbonized three-way catalyst, and simultaneously adding an activating agent to convert the noble metal in an oxidation state into an elemental state;
step three: two-stage countercurrent leaching of platinum, palladium and rhodium in the waste catalyst;
step four: adsorbing platinum, palladium and rhodium in the leaching liquid by using the resin, and keeping rhodium in the adsorption tail liquid; rhodium is recovered by a displacement method;
step five: adsorbing saturated resin column to wash platinum and palladium;
step six: extracting palladium and platinum from the leaching solution, and allowing the platinum to enter raffinate;
step seven: back extracting palladium, precipitating palladium in the back extraction liquid and reducing to obtain sponge palladium;
Step eight: adding platinum in the ammonium chloride precipitation raffinate, and carrying out precipitation reduction on ammonium chloroplatinate to obtain a platinum sponge product.
The invention adopts the full wet process of strengthening pretreatment and strengthening leaching, combines the ion exchange and extraction separation technology, avoids high energy consumption and air pollution of the pyrogenic pretreatment process, and solves the problem of low recovery rate of the traditional wet recovery process.
The method is realized by the following steps:
1. Roasting and decarbonizing: firstly, roasting the ternary waste catalyst to remove carbon deposit and organic matters, wherein the roasting temperature is 300-900 ℃, preferably 650-800 ℃, and the roasting time is 2-8 hours, preferably 4-6 hours.
2. Grinding and activating: crushing, grinding and mechanically activating the decarbonized three-way catalyst carrier, and simultaneously adding an activating agent to convert oxidized noble metal into an elemental state. The fine grinding particle size is 80-400 mesh, preferably 200-400 mesh. The activator is one of formic acid, hydrazine hydrate or sodium borohydride, and the dosage is 1% of the raw material. The activation temperature is 60 ℃, the mechanical activation liquid-solid ratio is 3/1, and the time is 2-4 hours.
3. Two-stage leaching: the platinum, palladium and rhodium in the waste catalyst are leached in a two-stage countercurrent mode. The leaching temperature of the first stage is 60-100 ℃, the liquid-solid ratio is 3/1-5/1, the sulfuric acid concentration is 10-20%, hydrochloric acid with the raw material content of 10% is added after leaching for 2 hours, sodium chlorate with the raw material content of 4% is added, stirring is continued for 2 hours after adding sodium chlorate, and the platinum, palladium and rhodium are recovered from the leaching solution of the first stage in the next stage.
The second stage leaching temperature is 60-100 ℃, the liquid-solid ratio is 3/1-5/1, the sulfuric acid concentration is 20-40%, hydrochloric acid with the raw material content of 10-20% and sodium chlorate with the raw material content of 4-10% are added after leaching for 2 hours, stirring is continued for 2 hours after the sodium chlorate is added, and the leaching liquid returns to the first stage leaching after supplementing sulfuric acid.
4. Adsorbing platinum and palladium: and (3) adsorbing the platinum, palladium and rhodium from the first-stage leaching solution containing the platinum, palladium and rhodium through a resin column. The resin for adsorbing platinum and palladium is chelate resin with piperidine functional groups, the adsorption contact time is 10-60 min, the acidity of the adsorption stock solution is regulated to 0.1-2 mol/L, the adsorption temperature is 10-50 ℃, the concentration of platinum and palladium in the adsorption tail solution is controlled to be less than or equal to 0.3mg/L, and rhodium is not adsorbed in the tail solution. The operating capacity of the resin for adsorbing platinum-palladium was controlled at 75g platinum-palladium metal/L resin.
Rhodium remaining in the tail liquid was recovered by the following method:
The rhodium in the tail liquid is adsorbed by adopting iron sheet, iron powder or copper powder in a replacement way, the dosage is 1-50 times of the theoretical dosage, the reduction temperature is 25-90 ℃ and the time is 2-24 hours. The crude rhodium obtained by displacement is purified and recovered by adopting an ammonium nitrosorhodium precipitation method.
5. Leaching platinum palladium: the eluent is one of nitric acid, persulfuric acid and perchloric acid, and preferably perchloric acid. The concentration of the eluent is 5-30%, the leaching contact time is 30-120 min, the temperature is 20-60 ℃, the leaching is carried out for 15 bed volumes, the total concentration of platinum and palladium in the eluent is more than 8g/L, the eluent is removed for subsequent separation and recovery of platinum and palladium, and the total concentration of platinum and palladium is less than 8g/L, and the eluent returns to be continuously used as the eluent.
6. Extracting and separating platinum and palladium: platinum and palladium in the leacheate are separated by an extraction method, and diisoamyl sulfide (code S201) is used for extracting the palladium in the leacheate, wherein the extraction conditions are as follows: the organic phase comprises 40% of S201+10% of aromatic hydrocarbon+50% of kerosene, the acidity is 0.1-6 mol/L, the contact time is 5min, the O/A=1:1, the stage number is 3, the extraction temperature is 15-50 ℃, under the condition, diisoamyl sulfide only extracts palladium and does not extract platinum, more than 99% of palladium enters an extractant, and more than 99% of platinum is remained in raffinate.
7. Back extraction of palladium: the organic phase carrying palladium is washed by 1mol/L dilute hydrochloric acid, and the main purpose is to wash the platinum carried in the organic phase. O/a=2:1, stage number 3, 100% of the entrained platinum is washed out, and the palladium elution rate is less than 0.1%. The back extraction of palladium is carried out by dilute ammonia water, the concentration of the ammonia water is 5-15%, the contact time is 5min, the O/A=2:1, the stage number is 3, the back extraction temperature is 15-50 ℃, and the back extraction rate of palladium is 99.9%.
8. And (3) preparing a platinum-palladium product: and adding ammonium chloride into platinum in the raffinate to generate ammonium chloroplatinate precipitate, filtering and washing the ammonium chloroplatinate precipitate, mixing with hot water, and adding a reducing agent for reduction to obtain a spongy platinum product. And adding hydrochloric acid into palladium in the back extraction liquid to adjust the pH value to 1, generating a palladium dichloride diammonium palladium complex precipitate, filtering and washing the palladium precipitate, performing hot water pulping, and adding a reducing agent for reduction to obtain a sponge palladium product.
The method has the advantages of short process, low recovery cost, high noble metal yield, platinum recovery rate of more than 98%, palladium recovery rate of more than 99% and rhodium recovery rate of more than 90%. The purity of the sponge platinum and the sponge palladium is more than or equal to 99.95 percent.
In order to further understand the present invention, the method for recycling platinum, palladium and rhodium in the three-way catalyst of the automobile by the total wet method provided by the present invention is described in detail below with reference to examples, and the scope of protection of the present invention is not limited by the following examples.
Example 1
The ternary waste catalyst for a certain automobile contains Pt0.056%, pd0.12% and Rh0.013%, and the X fluorescence analysis results of other components are shown in Table 1. The catalyst takes cordierite (2MgO.2Al 2O3·5SiO2) as a carrier and takes a honeycomb cylindrical shape, an alumina active coating is coated on the catalyst, the active components are oxides of transition metal elements and noble metals such as Pt, pd, rh and the like, carbon deposition is attached to the surface of the catalyst, the catalyst is partially sintered, the noble metals penetrate into an inner layer in high-temperature use, and the noble metals are partially sintered or axially wrapped by the surface of the carrier, so that oxidation, vulcanization and phosphating are performed to convert the noble metals into inertia.
TABLE 1 three-way catalyst X fluorescence analysis
1. Pretreatment of
10Kg of ternary waste catalyst is weighed, baked for 4 hours at 700 ℃, then 30 liters of water and 100g of hydrazine hydrate with concentration of 80% are added into a ball mill, ball milling mechanical activation is carried out for 3 hours at the temperature of 60 ℃, and the granularity of the ground materials is all smaller than 300 meshes.
2. Two stage leaching
Leaching in the first stage: adding 30 liters of water into a 100 liter enamel reaction kettle, adding a pretreated catalyst while stirring, heating to 60 ℃, adding 4 liters of concentrated sulfuric acid, heating to 100 ℃ for reaction for 2 hours, adding 1 liter of hydrochloric acid with 32% concentration and 300g of sodium chlorate (sodium chlorate is prepared into 3000ml of aqueous solution), controlling the uniform speed of the sodium chlorate solution to be added within 2 hours, continuing stirring for reaction for 1 hour after the addition, cooling and filtering, separating and extracting platinum, palladium and rhodium from filtrate, and leaching filter residues for the second stage.
And (3) leaching in the second stage: adding 3 liters of water into a 100 liter enamel reaction kettle, adding a section of leaching residue while stirring, heating to 60 ℃, adding 6 liters of concentrated sulfuric acid, heating to 100 ℃ for reaction for 2 hours, adding 1 liter of 32% hydrochloric acid and 600g of sodium chlorate (sodium chlorate is prepared into 6000ml of aqueous solution), controlling the sodium chlorate solution to be added at uniform speed within 2 hours, continuing stirring for 1 hour after the adding is finished, filtering, and returning the leaching solution to be used as a section of leaching agent.
The first stage leaching solution and the second stage leaching solution are combined to obtain 81.5L leaching solution, wherein the leaching solution contains Pt67.5mg/L, pd146.5 mg/L and Rh14.6 mg/L, and the leaching rates of platinum, palladium and rhodium are respectively 98.2%, 99.5% and 91.5%.
3. Adsorbing and leaching platinum and palladium and recovering rhodium
And (3) adsorbing the platinum, palladium and rhodium in the leaching solution containing the platinum, palladium and rhodium through a resin column. The resin is chelate resin with piperidine functional groups, the resin filling amount is 500ml, the adsorption contact time is 15min, the adsorption flow rate is 0.75L/h, pt0.2mg/L, pd 0.3mg/L and Rh14.5mg/L in the adsorption tail liquid are respectively 99.7% and 99.8% of the adsorption rate of platinum and palladium, and rhodium is not adsorbed.
And (3) leaching platinum and palladium by using perchloric acid with the concentration of 20% as a leaching agent, wherein the leaching contact time is 45min, the flow rate is 0.25L/h, and after leaching for 4.5 liters, the platinum and palladium in effluent is less than 10mg/L, and the leaching is finished. 1.5-liter-concentration leacheate (Pt2374.6 mg/L, pd5344.0 mg/L) and 3-liter-low-concentration leacheate (Pt606.8 mg/L, pd1248.2 mg/L) were obtained.
The rhodium in the tail liquid is adsorbed by adopting an iron sheet in a displacement way, the displacement temperature is 60 ℃ and the time is 24 hours, so that 11.6g of a displacement product is obtained, and the rhodium content is 10.1%. The tail liquid contains Rh0.14mg/L, and crude rhodium obtained by displacement is purified and recovered by adopting a nitroso-rhodium acid amine precipitation method.
4. Extraction separation of platinum and palladium
The palladium in the high concentration leacheate was extracted with diisoamyl sulfide (S201) and the organic phase consisted of 40% S201+10% aromatics+50% kerosene for 5min with O/A=1:1, stage 3, pd 0.2mg/L in the raffinate, pt2362.2mg/L. The palladium-loaded organic phase is firstly washed by 1mol/L dilute hydrochloric acid, the platinum carried in the organic phase is washed away, O/A=2:1, the number of stages is 3, the carried platinum is washed out by 100%, and the elution rate of palladium is less than 0.1%. A small amount of platinum palladium in the washing water is recovered by a displacement method. Palladium stripping was carried out using 6% strength aqueous ammonia for a contact time of 5min with O/A=3:1 to give 0.5L of a stripping solution containing Pd16.0g/L.
5. Preparation of spongy platinum and spongy palladium
And adding hydrochloric acid into the palladium back extraction liquid to adjust the pH value to 1, generating a palladium dichloride diammonium palladium complex precipitate, filtering and washing the palladium precipitate, mixing with hot water, adding a reducing agent for reduction, and obtaining a sponge palladium product. And adding ammonium chloride into platinum in the raffinate to generate ammonium chloroplatinate precipitate, filtering and washing the ammonium chloroplatinate precipitate, mixing with hot water, and adding a reducing agent for reduction to obtain a spongy platinum product. The purity of the analyzed sponge palladium and sponge platinum products is more than 99.95 percent.
The above description of the embodiments is only for aiding in the understanding of the method of the present invention and its core ideas. It should be noted that it will be apparent to those skilled in the art that various modifications and adaptations of the invention can be made without departing from the principles of the invention and these modifications and adaptations are intended to be within the scope of the invention as defined in the following claims.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (9)
1. The method for recycling platinum, palladium and rhodium in the automobile three-way catalyst by the all-wet method is characterized by comprising the following steps of:
Step one: roasting the three-way catalyst to remove carbon deposition and organic matters;
Step two: crushing, grinding and mechanically activating the decarbonized three-way catalyst, and simultaneously adding an activating agent to convert the noble metal in an oxidation state into an elemental state;
step three: two-stage countercurrent leaching of platinum, palladium and rhodium in the waste catalyst;
step four: adsorbing platinum, palladium and rhodium in the leaching liquid by using the resin, and keeping rhodium in the adsorption tail liquid; rhodium is recovered by a displacement method;
step five: adsorbing saturated resin column to wash platinum and palladium;
step six: extracting palladium and platinum from the leaching solution, and allowing the platinum to enter raffinate;
step seven: back extracting palladium, precipitating palladium in the back extraction liquid and reducing to obtain sponge palladium;
Step eight: adding platinum in the ammonium chloride precipitation raffinate, and carrying out precipitation reduction on ammonium chloroplatinate to obtain a platinum sponge product.
2. The method for recycling platinum, palladium and rhodium in an automobile three-way catalyst according to claim 1, wherein in the first step, the roasting temperature is 300-900 ℃ and the roasting time is 2-8 h.
3. The method for recycling platinum, palladium and rhodium in the three-way catalyst of the automobile according to the whole wet method of claim 1, wherein in the second step, wet mechanical grinding is adopted, and the grinding granularity is 80-400 meshes; the activating agent is formic acid, hydrazine hydrate or sodium borohydride, and the using amount of the activating agent is 1% of the raw material amount; the activation temperature is 60 ℃, the liquid-solid ratio is 3/1, and the time is 2-4 hours.
4. The method for recycling platinum, palladium and rhodium in the three-way catalyst of automobile according to claim 1, wherein in the third step, specifically comprising:
The leaching temperature of the first stage is 60-100 ℃, the liquid-solid ratio is 3/1-5/1, the sulfuric acid concentration is 10-20%, hydrochloric acid with the raw material content of 10% is added after leaching for 2 hours, sodium chlorate with the raw material content of 4% is added, stirring is continued for 2 hours after the sodium chlorate is added, and the platinum, palladium and rhodium are recovered from the leaching solution of the first stage in the next stage;
The second stage leaching temperature is 60-100 ℃, the liquid-solid ratio is 3/1-5/1, the sulfuric acid concentration is 20-40%, hydrochloric acid with the raw material content of 10-20% and sodium chlorate with the raw material content of 4-10% are added after leaching for 2 hours, stirring is continued for 2 hours after adding sodium chlorate, and the leaching liquid returns to the first stage leaching after supplementing sulfuric acid.
5. The method for recycling platinum, palladium and rhodium in the three-way catalyst of the automobile by the full wet method according to claim 1, wherein in the fourth step, the resin is chelate resin with piperidine functional groups, the adsorption contact time is 10-60 min, the acidity of the adsorption stock solution is 0.1-2 mol/L, the adsorption temperature is 10-50 ℃, and the platinum and palladium concentration of the adsorption tail solution is controlled to be less than or equal to 0.3mg/L.
6. The method for recycling platinum, palladium and rhodium in the three-way catalyst of the automobile according to the full wet method of claim 1, wherein in the fifth step, the leaching agent is nitric acid, persulfuric acid or perchloric acid, the mass percentage concentration of the leaching agent is 5-30%, the leaching contact time is 30-120 min, the temperature is 20-60 ℃, the leaching solution has the total concentration of platinum, palladium of more than 8g/L and is used as a qualified solution, the subsequent separation and recycling of platinum, palladium and the leaching solution with the total concentration of platinum, palladium and palladium of less than 8g/L are returned to be used as the leaching agent continuously.
7. The method for recycling platinum, palladium and rhodium in an automobile three-way catalyst according to claim 1, wherein in the step flow six, diisoamyl sulfide is used for extracting palladium in the platinum-palladium eluent, and the extraction conditions are as follows: the organic phase consists of 40% of diisoamyl sulfide, 10% of aromatic hydrocarbon and 50% of kerosene, the acidity is 0.1-6 mol/L, the contact time is 5min, the O/A=1:1, the number of stages is 3, and the extraction temperature is 15-50 ℃; more than 99% of the palladium enters the extractant and more than 99% of the platinum remains in the raffinate.
8. The method for recycling platinum, palladium and rhodium in the three-way catalyst of the automobile by the full wet method according to claim 1, wherein in the seventh step, dilute ammonia water is used for carrying out back extraction of palladium, the concentration of the ammonia water is 5-15%, the contact time is 5min, the ratio of O/A=1:1-3:1, the number of stages is 3, and the back extraction temperature is 15-50 ℃.
9. The method for recycling platinum, palladium and rhodium in the automobile three-way catalyst according to claim 1, wherein in the fourth step, iron sheets, iron powder or copper powder are adopted to replace rhodium in the adsorption tail liquid, the consumption is 1-50 times of the theoretical amount, the reduction temperature is 25-90 ℃ and the time is 2-24 hours, and crude rhodium obtained by replacement is purified and recycled by adopting an ammonium nitrosorhodium precipitation method.
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