CN105256145A - Method for extracting noble metal from waste vehicle exhaust catalyst - Google Patents
Method for extracting noble metal from waste vehicle exhaust catalyst Download PDFInfo
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- CN105256145A CN105256145A CN201510797480.3A CN201510797480A CN105256145A CN 105256145 A CN105256145 A CN 105256145A CN 201510797480 A CN201510797480 A CN 201510797480A CN 105256145 A CN105256145 A CN 105256145A
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Abstract
The invention relates to a method for extracting noble metal from a waste vehicle exhaust catalyst. The waste vehicle exhaust catalyst, activated carbons and alkali metal chlorides are respectively crushed, are uniformly mixed in proportion, are chlorinated with high temperature, are leached by hydrochloric acid, are condensed, are separated and are extracted to prepare the noble metal. Compared with the prior art, the method has the advantages of easy separation of the noble metal and a carrier, low investment, simple process flow and high extraction rate of the noble metal.
Description
Technical field
The present invention is a kind of method extracting precious metal from useless auto-exhaust catalyst, relates to more specifically and extract the precious metals such as platinum, palladium, rhodium from useless auto-exhaust catalyst.
Background technology
Platinum metals has unique detergent power to vehicle exhaust and is widely used in automotive industry, according to statistics, there is the platinum more than 60% every year, palladium, the platinum metals such as rhodium are for the production of cleaning catalyst for tail gases of automobiles, at present, platinum metals mineral products resource is increasingly in short supply, resource monopoly general layout is constantly aggravated, in addition platinum metals head grade is low, smelt the many factors such as long flow path, traditional mineral products platinum metals industry development prospect allows of no optimist, and the secondary resource as platinum group metals such as useless auto-exhaust catalysts has of high grade, the advantages such as extraction flow process is short, in the supply of world's precious metal, occupy critical role, China is the rare country in platinum metals, the platinum metals dependence on import of about 90%, along with developing rapidly of Domestic Automotive Industry in recent years, continuation increases by domestic platinum metals insufficiency of supply-demand.Therefore, carry out the research of extraction, purifying platinum metals from useless auto-exhaust catalyst, the development for national economy is significant.
Developed countries is to reclaiming the research starting of platinum metals comparatively early from secondary resource, tentatively achieve suitability for industrialized production, the yield of the developed regions such as the U.S., Japan, Europe has accounted for more than 20% of platinum metals production, along with the increasingly stringent of environmental requirement, the domestic research work also actively developed spent auto catalysts and recycle.
At present, the method extracting platinum metals from useless auto-exhaust catalyst mainly contains wet method and pyrogenic process two kinds.
Wet processing mainly adopts dissolution method, Chinese patent CN1385545, CN101519725 are by after catalyst breakage, with the mixed solution of sulfuric acid, hydrochloric acid as solvent, add the dissolving that oxidizer containing chlorine completes precious metal, or Chinese patent CN102732728A adopts chloroazotic acid to dissolve the catalyzer after fragmentation as solvent, but aforesaid method output wastewater flow rate is large, water pollutions serious, and platinum metals leaching yield is difficult to ensure, leached mud slag rate is higher, need carry out secondary recovery to it.
Pyrogenic process process mainly adopts the method for melting, adopt the collecting agent be applicable to, precious metal in useless auto-exhaust catalyst is captured in sulfonium, other impurity slag making such as carrier remove, bring up again from the sulfonium being enriched precious metal further again and get precious metal, Chinese patent CN101121963B adopts cupric oxide as collecting agent, it is loaded together with raw material and other material a kind of closed electric furnace that an electrode and furnace roof are at least housed and carries out melting, finally obtain the copper matte regulus being rich in precious metal; Chinese patent CN102534226A uses iron collecting agent, carries out melting, to trap the precious metal in spent auto catalysts after batching in electric furnace or electric arc furnace; But above-mentioned technique exists, and technical process is long, the rate of recovery is difficult to common problems such as calculating, precious metal easily disperses, and firing method process cost of equipment is high, and support equipment is complicated, makes industrial applications cost higher in addition.
Summary of the invention
The present invention seeks to the various shortcomings for existing in existing pyrogenic process and wet processing waste vapour tail gas catalyst technology, providing that a kind of extraction yield is high, method that precious metal and the easily separated and flow process of carrier simply extract precious metal from useless auto-exhaust catalyst.
The technical solution used in the present invention is: a kind of method extracting precious metal from useless auto-exhaust catalyst, comprises the steps:
Step a: mix after useless auto-exhaust catalyst, gac and alkali metal chloride are carried out fragmentation respectively;
Step b: be placed in cl gas flow when the mixture temperature obtained by step a is 500-800 DEG C and carry out chlorination, time of chlorinating is 3-4 hour, chlorine after chlorination in the tail gas sodium hydroxide solution of 15% absorbs, in the salt enrichment forming non-volatile, solubility and chloride slag;
Step c: by the chloride slag of step b gained in cl gas flow below Temperature fall to 30 DEG C, and repeatedly leach under hot with hydrochloric acid, leach liquor is pending after merging, and slag is not stacked;
Steps d: as the raw material being rich in precious metal after the leach liquor after being merged by step c gained concentrates, through being separated, extracting output noble metal platinum, palladium, rhodium.
Further, the useless auto-exhaust catalyst in described step a, gac and alkali metal chloride particle size after cracking are 80 ~ 100 orders.
Further, the alkali metal chloride in described step a is sodium-chlor or Repone K.
Further, the ratio of mixture in described step a is: gac: useless auto-exhaust catalyst: the mass ratio of alkali metal chloride is 1:1-3:1.
Further, the alkali lye in described step b is the sodium hydroxide solution of 15%.
Further, concentration of hydrochloric acid in described step c is 0.5-1.5mol/L, extraction temperature is 80-85 DEG C, leaching number of times is 2-3 time, during leaching, first time leaches the control of solid-liquid volume ratio is 1:4-5, when second time and afterwards leaching, hydrochloric acid add-on is successively successively decreased by 0.5 times, and leach liquor merges treats subsequent disposal, and leaching terminal is bullion content <50g/t in insoluble slag.
Further, the method for the extraction precious metal in described steps d is at least one in organic solvent extractionprocess, chloride precipitation method, exchange resin method.
The principle of the inventive method is as Al by the carrier in useless auto-exhaust catalyst
2o
3deng the method by middle temperature chlorination, make it to be converted into the muriate of metal and volatilize, and precious metals species forms nonvolatile solubility salt in chlorination process with alkali metal chloride, thus complete and being separated of carrier.In follow-up leaching process, the precious metal salt of solubility is dissolved in hydrochloric acid soln, and is separated further from leach liquor, extracts precious metal.
The present invention compared with prior art has following beneficial effect:
1. the extraction yield of the precious metal such as platinum, palladium, rhodium is all more than 93%, even reaches more than 95%;
2. reagent dosage is few, the cost of material is low, produces waste water hardly;
3. equipment is simple, floor space is little, one-time investment is few;
4. temperature of reaction is no more than 800 DEG C, compares firing method process energy consumption low;
6. flow process is short, and the used time is few, and processing speed is far above firing method process;
7. precious metal and carrier good separating effect, precious metal extraction yield is high.
Accompanying drawing explanation
Fig. 1 is present invention process schema.
Embodiment
Below in conjunction with embodiment, the present invention is described in further details.
The extraction yield of precious metal i calculates by following formula:
X
ifor the amount of precious metal in leach liquor, y
ifor the amount of precious metal in raw material.
Embodiment 1
Take respectively containing spent auto catalysts 50g(wherein platiniferous 0.32mg, palladium 5.28mg, rhodium 0.6mg), gac 50g, sodium-chlor 50g, mix after adopting jaw crusher to be crushed to 100 orders respectively, be positioned in quartz boat, 500 DEG C are warming up to pass into chlorine condition in tube furnace under, chlorination reaction 3 hours, the tail gas sodium hydroxide solution of 15% absorbs; Continue after completion of the reaction to pass into chlorine and below Temperature fall to 30 DEG C; Chloride slag is weighed as 33.26g, and successively leach 2 times at 80 DEG C with 0.5mol/L hydrochloric acid, during leaching, hydrochloric acid consumption is respectively 99.8ml, 49.9ml, and leaching bullion content in gained insoluble slag is 12.57g/t; In leach liquor, the content of platinum, palladium, rhodium is respectively 0.30mg, 5.19mg, 0.56mg, and the extraction yield calculated with this is respectively platinum 93.75%, palladium 98.29%, rhodium 93.33%.
Embodiment 2
Take respectively containing spent auto catalysts 1000g(wherein platiniferous 6.4mg, palladium 105.5mg, rhodium 12.0mg), gac 500g, Repone K 666.7g, mix after adopting jaw crusher to be crushed to 80 orders respectively, be positioned in quartz boat, 600 DEG C are warming up to pass into chlorine condition in tube furnace under, chlorination reaction 4 hours, the tail gas sodium hydroxide solution of 15% absorbs, and continues after completion of the reaction to pass into chlorine and below Temperature fall to 30 DEG C; Chloride slag is weighed as 392.37g, successively leach 3 times at 85 DEG C with 1.5mol/L hydrochloric acid, during leaching, hydrochloric acid consumption is respectively 1569.5ml, 784.8ml, 392.4ml, leaching bullion content in gained insoluble slag is 9.76g/t, in leach liquor, the content of platinum, palladium, rhodium is respectively 6.10mg, 105.09mg, 11.36mg, and the extraction yield calculated with this is respectively platinum 95.31%, palladium 99.61%, rhodium 94.67%.
Embodiment 3
According to the proportion scale in example 2, the chlorination reaction time is increased to 10 hours, leaching bullion content in gained insoluble slag is 25.91g/t, in leach liquor, the content of platinum, palladium, rhodium is respectively 6.13mg, 105.16mg, 11.38mg, and the extraction yield calculated with this is respectively platinum 95.78%, palladium 99.68%, rhodium 94.83%; Visible, even if significantly extend time of chlorinating, the extraction efficiency of precious metal promotes and not obvious.And time of chlorinating extends, by substantial chlorine, and will take measures to carry out follow-up environmental protection treatment to chloride tail gas.
Claims (7)
1. from useless auto-exhaust catalyst, extract a method for precious metal, it is characterized in that, comprise the steps:
Step a: mix after useless auto-exhaust catalyst, gac and alkali metal chloride are carried out fragmentation respectively;
Step b: be placed in cl gas flow when the mixture temperature obtained by step a is 500-800 DEG C and carry out chlorination, time of chlorinating is 3-4 hour, chlorine after chlorination in the tail gas sodium hydroxide solution of 15% absorbs, in the salt enrichment forming non-volatile, solubility and chloride slag;
Step c: by the chloride slag of step b gained in cl gas flow below Temperature fall to 30 DEG C, and repeatedly leach under hot with hydrochloric acid, leach liquor is pending after merging, and slag is not stacked;
Steps d: as the raw material being rich in precious metal after the leach liquor after being merged by step c gained concentrates, through being separated, extracting output noble metal platinum, palladium, rhodium.
2. a kind of method extracting precious metal from useless auto-exhaust catalyst according to claim 1, is characterized in that: the useless auto-exhaust catalyst in described step a, gac and alkali metal chloride particle size after cracking are 80 ~ 100 orders.
3. a kind of method extracting precious metal from useless auto-exhaust catalyst according to claim 1, is characterized in that: the alkali metal chloride in described step a is sodium-chlor or Repone K.
4. a kind of method extracting precious metal from useless auto-exhaust catalyst according to claim 1, is characterized in that: the ratio of mixture in described step a is: gac: useless auto-exhaust catalyst: the mass ratio of alkali metal chloride is 1:1-3:1.
5. a kind of method extracting precious metal from useless auto-exhaust catalyst according to claim 1, is characterized in that: the alkali lye in described step b is the sodium hydroxide solution of 15%.
6. a kind of method extracting precious metal from useless auto-exhaust catalyst according to claim 1, it is characterized in that: the concentration of hydrochloric acid in described step c is 0.5-1.5mol/L, extraction temperature is 80-85 DEG C, leaching number of times is 2-3 time, during leaching, first time leaches the control of solid-liquid volume ratio is 1:4-5, when second time and afterwards leaching, hydrochloric acid add-on is successively successively decreased by 0.5 times, and leach liquor merges treats subsequent disposal, and leaching terminal is bullion content <50g/t in insoluble slag.
7. a kind of method extracting precious metal from useless auto-exhaust catalyst according to claim 1, is characterized in that: the method for the extraction precious metal in described steps d is at least one in organic solvent extractionprocess, chloride precipitation method, exchange resin method.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105543496A (en) * | 2015-12-29 | 2016-05-04 | 武汉凯迪工程技术研究总院有限公司 | Recycling method for metallic cobalt, rhodium and aluminum in Fischer-Tropsch synthesis catalyst Co-Rh/Al2O3 |
| CN106498165A (en) * | 2016-10-21 | 2017-03-15 | 北京矿冶研究总院 | Method for recovering nickel and vanadium from waste FCC catalyst through melting, chlorination and volatilization |
| CN106756086A (en) * | 2016-12-01 | 2017-05-31 | 沈阳有色金属研究院 | A kind of method that fluidized bed process purifies platinum group metal from dead catalyst |
| CN109338107A (en) * | 2018-11-12 | 2019-02-15 | 五邑大学 | The method that useless three-way catalyst synthetical recovery environment-protective circulating utilizes |
| CN111455192A (en) * | 2020-04-29 | 2020-07-28 | 江苏北矿金属循环利用科技有限公司 | Method for recovering palladium from low-grade palladium-containing indissolvable waste catalyst |
| CN112442600A (en) * | 2020-12-02 | 2021-03-05 | 中南大学 | Method for recovering platinum group metal from waste three-way catalyst |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105543496A (en) * | 2015-12-29 | 2016-05-04 | 武汉凯迪工程技术研究总院有限公司 | Recycling method for metallic cobalt, rhodium and aluminum in Fischer-Tropsch synthesis catalyst Co-Rh/Al2O3 |
| CN105543496B (en) * | 2015-12-29 | 2017-10-20 | 武汉凯迪工程技术研究总院有限公司 | F- T synthesis dead catalyst Co Rh/Al2O3The recovery method of middle metallic cobalt, rhodium and aluminium |
| CN106498165A (en) * | 2016-10-21 | 2017-03-15 | 北京矿冶研究总院 | Method for recovering nickel and vanadium from waste FCC catalyst through melting, chlorination and volatilization |
| CN106498165B (en) * | 2016-10-21 | 2018-08-14 | 北京矿冶研究总院 | Method for recovering nickel and vanadium from waste FCC catalyst through melting, chlorination and volatilization |
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| CN106756086B (en) * | 2016-12-01 | 2019-02-05 | 沈阳有色金属研究院 | A kind of method that fluidized bed process purifies platinum group metal from dead catalyst |
| CN109338107A (en) * | 2018-11-12 | 2019-02-15 | 五邑大学 | The method that useless three-way catalyst synthetical recovery environment-protective circulating utilizes |
| CN111455192A (en) * | 2020-04-29 | 2020-07-28 | 江苏北矿金属循环利用科技有限公司 | Method for recovering palladium from low-grade palladium-containing indissolvable waste catalyst |
| CN112442600A (en) * | 2020-12-02 | 2021-03-05 | 中南大学 | Method for recovering platinum group metal from waste three-way catalyst |
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Application publication date: 20160120 |