CN103526034A - Method for activating and leaching platinum group metals from automobile spent catalysts by wet method - Google Patents
Method for activating and leaching platinum group metals from automobile spent catalysts by wet method Download PDFInfo
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- CN103526034A CN103526034A CN201310494850.7A CN201310494850A CN103526034A CN 103526034 A CN103526034 A CN 103526034A CN 201310494850 A CN201310494850 A CN 201310494850A CN 103526034 A CN103526034 A CN 103526034A
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- spent catalyst
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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
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Abstract
The invention relates to a method for recovering platinum group metals from automobile spent catalysts and in particular relates to a method for activating and leaching platinum group metals from automobile spent catalysts by a wet method. After activation and pretreatment by a wet method, oxidants are added to leach the platinum group metals in the automobile spent catalysts in an intensified manner, so that the leaching rates of the platinum group metals, especially rhodium, are substantially increased. The method is safe and reliable, is high in metal recovery rate and is lower in production cost.
Description
Technical field
The present invention relates to reclaim the method for platinum metals from automobile spent catalyst, provide especially a kind of automobile spent catalyst wet-process activation to leach the method for platinum metals.
Background technology
Platinum metals content in the earth's crust is low, reserves are few, and it is expensive, has the characteristic of high-melting-point, high boiling point and low-steam pressure.In all metallic elements, they have best oxidation-resistance and erosion resistance, are widely used in modern industry.Wherein, platinum metal catalysts is the maximum purposes of platinum metals.But in automobile catalytic reaction process, the dynamic equilibrium state of the platinum metals particulate in carrier in inside and outside movement, due to thermodiffusion, temperature raises, metal particle γ-Al around
2o
3be transformed into α-Al
2o
3, density is increased, surface-area reduces, and causes pore texture to cave in (1200 ℃ occur washcoat delamination from carrier), and tail gas is restricted into and out of the Catalytic Layer of activation, thereby reduces catalytic activity.After cooling, platinum metals is wrapped in the α-Al of indissoluble
2o
3in, if rhodium is in the well-oxygenated environment of 800 ℃, due to the Rh of oxidation state
3+be diffused into Al
2o
3in carrier, the catalysis area of rhodium will be greatly reduced.Sometimes catalyzer may adsorb organic compound and is brought other impurity into, causes catalyst surface carbon deposit, causes scrapping of catalyzer.
Traditional wet-leaching technique is that raw material is after ball milling, directly acid adding and oxygenant leach, through solid-liquid separation, the insoluble slag sampling analysis leaching platinum metals content wherein, leach liquor sampling analysis rear substitution, replacement slag washing obtains platinum metals enriched substance, and the mother liquor of displacement is neutralization discharge afterwards after testing.But the leaching yield of this technique platinum metals unstable (often having 10%～15% fluctuation), and the rate of recovery of rhodium is relatively low.Leaching front activating by automobile spent catalyst is processed and can be made platinum metals crystal change, and meanwhile, because the crystal formation of part metals in raw material changes specific surface area and the porosity increase that makes platinum metals, is more conducive to follow-up leaching process.Platinum metals wet method leaching process in automobile spent catalyst has had a lot of reports both at home and abroad, but activation treatment before leaching is strengthened and leached platinum metals and there is no detailed bibliographical information.
Summary of the invention
The object of the invention is for problems such as in existing full wet processing automobile spent catalyst technology, rate of recovery leaching yield low, rhodium in platinum metals are low, extract technology is unstable, spy provides a kind of new leaching front activating to process the technical process of automobile spent catalyst, improved platinum metals the rate of recovery, guaranteed the stability that leaches to have improved productivity effect.
Technical solution of the present invention realizes according to the following steps:
By described automobile spent catalyst fragmentation, fine grinding, mix, add according to a certain percentage activator pre-treatment, through pretreated automobile spent catalyst, add again one or more in hydrochloric acid, sulfuric acid, nitric acid, then after rising to certain temperature, slowly add oxygenant successive reaction certain hour, make the platinum metals dissolving in automobile spent catalyst enter solution.
Activator is formic acid, sodium formiate, formaldehyde, hydrazine hydrate, NaBH
4in one or more, described a kind of vapour
The solid-to-liquid ratio of automobile spent catalyst and activator is that S/L is 10 ﹕ 1～1 ﹕ 10.
Pretreatment temperature is 70～120 ℃, and pretreatment time is 2～6h.
Under acidic conditions, add oxygenant to dissolve the automobile spent catalyst after overactivation, described acid is one or more in hydrochloric acid, sulfuric acid, nitric acid, preferably hydrochloric acid.
Be that sour concentration is 1～12mo/l/L, preferably 4～10mol/L.
Acid is 1 ﹕ 10～10 ﹕ 1 with the ratio of enriched substance, preferably 6 ﹕ 1～1 ﹕ 6.
Solvent temperature is 60～120 ℃, and preferably 90～105 ℃, dissolution time is 4～12h, preferably 4～6h
Described oxygenant is to use HNO
3, H
2o
2, NaClO
3, NaClO, NaBrO
3, Cl
2in one or more.
The consumption of described oxygenant is 1%～50% of inventory, preferably 1%～30%.
The present invention compared with prior art, has the following advantages:
The leaching yield of platinum metals is significantly improved: traditional treatment process, the leaching yield of rhodium is probably in 75% left and right, the total leaching yield in platinum metals is in 90% left and right, and the present invention is by wet-process activation pre-treatment, the leaching yield of rhodium reaches more than 80%, the total leaching yield in platinum metals reaches more than 95%, has very high economic benefit.
Process stabilizing; Conventional wet extract technology, platinum metals leaching yield unstable (often having 10%～15% fluctuation), and also leaching process is due to the variation of platinum metals content in raw material, reacts and there will be extremely.The present invention can effectively guarantee platinum metals wet-leaching reacting balance and carry out.
Production cost is lower: the present invention not only leaching yield of platinum metals obviously improves, and leach liquor recycles and effectively saved production cost by mending acid.
In sum, the present invention has strengthened again the wet-leaching technique of automobile spent catalyst after by wet-process activation, improved platinum metals leaching yield, improved the stability of wet-leaching, the recovery of remarkable in economical benefits ，Dui China automobile spent catalyst has important directive significance.
Embodiment
Application technical solution of the present invention is processed automobile spent catalyst, carry out multiple batches of experiment, first carried out short run experiment, then the property produced as a trial test, the embodiment enumerating is below a part wherein, its objective is the present invention is described in further detail and verifies its effect.
Embodiment 1 automobile spent catalyst 4608g, its main component is (g/t): Pt355, Pd962, Rh156, ∑ PGMs1473, is crushed to 100～200 orders as the raw material of wet-leaching.First wet-process activation pre-treatment in glass reaction still, activator NaBH
4add-on be 2%～5%, solid-to-liquid ratio (S/L)=8 ﹕ 1～1 ﹕ 8,80～120 ℃ of activation temperatures, soak time 2～6h, reaction finishes rear filtration activation slag, activation slag returns to reactor wet-leaching, leach acidity 6～10mol/L, solid-to-liquid ratio (S/L)=10 ﹕ 1～1 ﹕ 10,80～100 ℃ of extraction temperatures, extraction time 8～12h, oxygenant HNO
3consumption is 1%～30%, detects the variation of solution potential in leaching process with potentiometer, after reaction finishes, filters leached mud.Leached mud dry weight 2744g, slag rate 59.55%, leached mud composition is (g/t): Pt35, Pd49, Rh44, ∑ PGMs128, platinum metals leaching yield is (%): Pt96.56, Pd96.82, Rh82.08, ∑ PGMs94.6.
Embodiment 2 automobile spent catalyst 600kg, its main component is (g/t): Pt519.00, Pd1032.00, Rh169.00, ∑ PGMs1720, is crushed to 150～200 orders as the raw material of wet-leaching.First wet-process activation pre-treatment in reactor, activator sodium formiate add-on is 2%～5%, solid-to-liquid ratio (S/L)=10 ﹕ 1～1 ﹕ 10, 80～100 ℃ of activation temperatures, soak time 2～6h, reaction finishes rear press filtration activation slag, activation slag returns to reactor wet-leaching, leach acidity 6～10mol/L, solid-to-liquid ratio (S/L)=9 ﹕ 1～1 ﹕ 9, 80～100 ℃ of extraction temperatures, extraction time 8～12h, oxygenant NaClO consumption is 1%～50%, in leaching process, with potentiometer, detect the variation of solution potential, when solution potential is greater than 800～1500mV, reduce the add-on of oxygenant, after reaction finishes, the press filtration of application pressure filter, leached mud dry weight 390kg, slag rate 65%, leached mud composition is (g/t): Pt18, Pd24, Rh39, ∑ PGMs81, platinum metals leaching yield is (%): Pt97.75, Pd98.49, Rh85.00, ∑ PGMs96.94.
Embodiment 3 automobile spent catalyst 600kg, its main component is (g/t): Pt519.00, Pd1032.00, Rh169.00, ∑ PGMs1720, is crushed to 100～150 orders as the raw material of wet-leaching.Elder generation's wet-process activation in reactor, activator formic acid add-on is 2%～5%, solid-to-liquid ratio (S/L)=8 ﹕ 1～1 ﹕ 8,60～100 ℃ of activation temperatures, soak time 2～6h, reaction finishes rear press filtration activation slag, and activation slag returns to reactor wet-leaching, leaches acidity 6～10mol/L, solid-to-liquid ratio (S/L)=10 ﹕ 1～1 ﹕ 10,80～100 ℃ of extraction temperatures, extraction time 8～12h, oxygenant NaClO
3consumption is 1%～20%, detects the variation of solution potential in leaching process with potentiometer, after reaction finishes, and the press filtration of application pressure filter.Leached mud dry weight 402kg, slag rate 65.72%, leached mud composition is (g/t): Pt37, Pd33, Rh54, ∑ PGMs124, leaching yield is (%): Pt95.33, Pd97.88, Rh79.12, ∑ PGMs95.25.
Embodiment 4 automobile spent catalyst 600kg, its main component is (g/t): Pt521.00, Pd1024.00, Rh170.00, ∑ PGMs1715, is crushed to 150～200 orders as the raw material of wet-leaching.Elder generation's wet-process activation in reactor, activator hydrazine hydrate add-on 2%～5%, solid-to-liquid ratio (S/L)=6 ﹕ 1～1 ﹕ 6,60～100 ℃ of activation temperatures, soak time 2～6h, reaction finishes rear press filtration activation slag, and activation slag returns to reactor wet-leaching, leaches acidity 6～10mol/L, solid-to-liquid ratio (S/L)=10 ﹕ 1～1 ﹕ 10,80～100 ℃ of extraction temperatures, extraction time 8～12h, oxygenant H
2o
2consumption is 1%～50%, detects the variation of solution potential in leaching process with potentiometer, after reaction finishes, and the press filtration of application pressure filter.Leached mud dry weight 389kg, leached mud composition is (g/t): Pt23, Pd27, Rh51, ∑ PGMs101, slag rate 64.83%, platinum metals leaching yield is (%): Pt96.96, Pd98.34, Rh82.03, ∑ PGMs96.21.
Claims (10)
1. automobile spent catalyst wet-process activation leaches a method for platinum metals, it is characterized in that realizing according to the following steps:
By described automobile spent catalyst fragmentation, fine grinding, mix, add according to a certain percentage activator pre-treatment, through pretreated automobile spent catalyst, add again one or more in hydrochloric acid, sulfuric acid, nitric acid, then after rising to certain temperature, slowly add oxygenant successive reaction certain hour, make the platinum metals dissolving in automobile spent catalyst enter solution.
2. a kind of wet-process activation pretreatment process of automobile spent catalyst according to claim 1, is characterized in that activator is formic acid, sodium formiate, formaldehyde, hydrazine hydrate, NaBH
4in one or more, the wet-process activation pretreatment process of described a kind of automobile spent catalyst, is characterized in that activator concentration is 1～50%.
3. a kind of wet-process activation pretreatment process of automobile spent catalyst according to claim 1, the solid-to-liquid ratio that it is characterized in that automobile spent catalyst and activator is that S/L is 10 ﹕ 1～1 ﹕ 10.
4. a kind of wet-process activation pretreatment process of automobile spent catalyst according to claim 1, is characterized in that pretreatment temperature is 70～120 ℃, and pretreatment time is 2～6h.
5. the wet-method for leaching of automobile spent catalyst according to claim 1, it is characterized in that the automobile spent catalyst after overactivation under acidic conditions, to add oxygenant to dissolve, described acid is one or more in hydrochloric acid, sulfuric acid, nitric acid, preferably hydrochloric acid.
6. the dissolving method of platinum metals in the automobile spent catalyst after activation according to claim 1, is characterized in that sour concentration is 1～12mo/l/L, preferably 4～10mol/L.
7. the automobile spent catalyst wet-method for leaching after activation according to claim 1, is characterized in that acid and the ratio of enriched substance are 1 ﹕ 10～10 ﹕ 1, preferably 6 ﹕ 1～1 ﹕ 6.
8. the automobile spent catalyst wet-method for leaching after activation according to claim 1, is characterized in that solvent temperature is 60～120 ℃, and preferably 90～105 ℃, dissolution time is 4～12h, preferably 4～6h.
9. the automobile spent catalyst wet-method for leaching after activation according to claim 1, is characterized in that described oxygenant is to use HNO
3, H
2o
2, NaClO
3, NaClO, NaBrO
3, Cl
2in one or more.
10. the automobile spent catalyst wet-method for leaching after activation according to claim 1, the consumption that it is characterized in that described oxygenant is inventory 1%～50%, preferably 1%～30%.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106011477A (en) * | 2016-06-28 | 2016-10-12 | 昆明贵金属研究所 | Method for recycling platinum group metal from ineffective automobile catalysts |
| CN107574303A (en) * | 2016-11-21 | 2018-01-12 | 广西大学 | A kind of method of hydrazine hydrate reduction automobile spent catalyst |
| CN107574304A (en) * | 2016-11-21 | 2018-01-12 | 广西大学 | A kind of method of microwave calcining pretreatment automobile spent catalyst |
| CN107570137A (en) * | 2016-11-21 | 2018-01-12 | 广西大学 | A kind of method that auto-exhaust catalyst is prepared using ceria base |
| CN107841635A (en) * | 2017-11-10 | 2018-03-27 | 徐州浩通新材料科技股份有限公司 | A kind of friendly process of argentiferous dead catalyst synthetical recovery |
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| CN101583729A (en) * | 2006-11-21 | 2009-11-18 | 株式会社古屋金属 | Method for recovering ruthenium |
| CN103131857A (en) * | 2011-11-29 | 2013-06-05 | 沈阳有色金属研究院 | Method for purifying platinum group metal from waste three-way catalyst |
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Patent Citations (5)
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| JPH01108323A (en) * | 1987-10-20 | 1989-04-25 | Tanaka Kikinzoku Kogyo Kk | Method for recovering platinum group metal deposited on catalyst |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106011477A (en) * | 2016-06-28 | 2016-10-12 | 昆明贵金属研究所 | Method for recycling platinum group metal from ineffective automobile catalysts |
| CN107574303A (en) * | 2016-11-21 | 2018-01-12 | 广西大学 | A kind of method of hydrazine hydrate reduction automobile spent catalyst |
| CN107574304A (en) * | 2016-11-21 | 2018-01-12 | 广西大学 | A kind of method of microwave calcining pretreatment automobile spent catalyst |
| CN107570137A (en) * | 2016-11-21 | 2018-01-12 | 广西大学 | A kind of method that auto-exhaust catalyst is prepared using ceria base |
| CN107841635A (en) * | 2017-11-10 | 2018-03-27 | 徐州浩通新材料科技股份有限公司 | A kind of friendly process of argentiferous dead catalyst synthetical recovery |
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Application publication date: 20140122 |