CN103205563A - Method for extracting rare noble metals by wet method - Google Patents
Method for extracting rare noble metals by wet method Download PDFInfo
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- CN103205563A CN103205563A CN2013101605204A CN201310160520A CN103205563A CN 103205563 A CN103205563 A CN 103205563A CN 2013101605204 A CN2013101605204 A CN 2013101605204A CN 201310160520 A CN201310160520 A CN 201310160520A CN 103205563 A CN103205563 A CN 103205563A
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Abstract
The invention relates to a method for extracting rare noble metals by a wet method. The method comprises the following steps of: pre-treating solid raw material powder containing rare noble metals by oxygen or air at 200-500 DEG C; then, treating the raw materials obtained by the step by carbon monoxide gas or hydrogen at 200-500 DEG C; then, leaching the solid raw materials treated by the two steps by sodium chlorate acidic oxidizing liquid at 30-180 DEG C; filtering and washing solid residue; and converting the rare noble metals from the solid raw materials to the filtrate so as to extract the rare noble metals. The method provided by the invention is in particular suitable for extracting platinum, palladium and rhodium in waste automobile catalysts, and the extraction rates of platinum, palladium and rhodium in optimized condition respectively reach 99%, 99% and 82%.
Description
Technical field
The present invention relates to extract the method for rare precious metal, relate more specifically to extract for example platinum metals, gold and the rare metal method of vanadium, gallium, tungsten, molybdenum, tantalum, niobium, zirconium, hafnium, gallium, indium, thallium, germanium for example of precious metal, especially extract the method for platinum metals in the junked-auto catalyzer.
Background technology
There is a serious shortage in the supply for China's platinum metals natural mineral resource reserves, and the platinum metals resource reserve of finding out in 2008 is 324.13 tons, accounts for 0.46% of world's total reserves.China's platinum metals year output is about 200 kilograms at present, can not satisfy the needs of national defence and industry far away, 90% above dependence on import of annual requirement.Therefore, how for example extract precious metal natural mineral matter, the waste material etc. from raw material efficiently very important economic and social benefit is arranged.
In recent years, along with the high speed development of Domestic Automotive Industry, formed a large amount of inefficacy cleaning catalyst for tail gases of automobiles (abbreviation automobile catalyst), wherein very big some is external manufacturer production, and raw material sources are in abroad.Platinum metals simple substance content summation is about 0.1wt.% in external most automobile catalysts of producing.Pt content is generally 300-1000ppm in the automobile catalyst, and Pd content is 200-800ppm, and Rh content is 50-100ppm.At present China produced about 500 tons inefficacy automobile catalyst in 1 year, about 600 kilograms of platiniferous, palladium, rhodium, expect 2014 after, the inefficacy automobile catalyst of generation will reach 5000 tons, platiniferous, palladium, rhodium are above 6 tons.Whole world 85%Rh, 50%Pd, 43%Pt in 2004 are used for the manufacturing of cleaning catalyst for tail gases of automobiles.The abandoned car catalyzer is primary platinum metals secondary resources in many countries at present.
In addition, in industrial production such as petrochemical complex, also can produce inefficacy rare precious metal catalyzer, also have the problem that how to reclaim rare precious metal wherein.
Overwhelming majority automobile catalyst carrier is to be made by the stupalith of good thermal shock, as trichroite or aluminium sesquioxide, wherein trichroite is the most frequently used stupalith, and the platinum metals platinum rhodium palladium and the catalyst aid Rare Earth Lanthanum cerium that play katalysis just load on such carrier.Platinum metals platinum rhodium palladium exists with metal simple-substance or metal oxide form in the abandoned car catalyzer, and the Rare Earth Lanthanum cerium exists with oxide form.The so-called extraction transferred to these elements in the catalyzer in the solution from solid exactly.
Routinely, with chloroazotic acid high temperature (95 ℃) wet processing automobile catalyst, the extraction yield of platinum and rhodium is respectively less than 60% and 45%.Although the whole world has proposed the method that many wet methods are extracted platinum, palladium, rhodium in the abandoned car catalyzer, the extraction yield that common deficiency of these methods is rhodium is low, generally is no more than 50%.
At present mainly in the thermal-flame more than 2000 ℃, automobile catalyst is carried out melting with plasma arc furnace in the world, to extract three kinds of platinum metals of platinum, palladium, rhodium wherein.The ferro-silicon that forms in the said process and platinum metals form new alloy phase Si-Fe-PGM, and this thing has extremely strong antiacid alkali ability mutually, are not easy to carry out subsequent disposal, have only a few countries to grasp this technology.Although weak points such as this process platinum metals extraction yield height exists energy consumption big, and step is many, and facility investment is big are difficult to be used by medium-sized and small enterprises.
The present invention proposes the method that a kind of wet high-effective extracts platinum, palladium, rhodium in the abandoned car catalyzer for this reason, and this method characteristics are that the extraction percentage absolute value of rhodium has improved nearly 30% than previous methods.
Summary of the invention
The present invention proposes a kind of for example platinum metals, gold and rare metal method of vanadium, gallium, tungsten, molybdenum, tantalum, niobium, zirconium, hafnium, gallium, indium, thallium, germanium for example of precious metal of from abandoned car catalyzer or other solid material, extracting.
The principle one of the inventive method is earlier part simple substance carbon in the powder stock to be transformed into gas such as CO or CO by oxygen or air roasting method
2Remove, reduce simple substance carbon to the absorption of rare precious metal in the extracting solution, and improve stock chart face road structure, be easy to follow-up wet extraction rare precious metal.The 2nd, with the above-mentioned raw material of crossing through oxygen or air roasting of carbon monoxide or hydrogen treat, make the rare precious metal oxide compound in the raw material be reduced into metal, be easy to follow-up wet extraction.The 3rd, the pressed powder raw material after above-mentioned second step processing is leached in certain temperature with the acid solution of the strong oxidizing property of chloracid sodium, make rare precious metal be oxidized to dissolve in the complexing ion of diluted acid, so just rare precious metal by solid transfer in solution, thereby extract.
Particularly, the present invention includes following steps:
A kind of method of extracting precious metal and rare metal in the solid material, it may further comprise the steps:
1) with oxygen or air more than pretreating raw material 0.2h under 200-500 ℃ the temperature;
2) under 200-500 ℃ of temperature, live through step 1) raw material 0.2-1.5h with the CO (carbon monoxide converter) gas processing again;
3) will live through step 2 again) solid material leaches under 30-180 ℃ temperature with the sodium chlorate acidic solution;
4) filter, wash solid residue.
Thus rare precious metal by solid transfer in filtrate, thereby extract.
Further, described step 2) also can use hydrogen instead lives through more than the step 1) raw material 0.5h in processing under the 200-500 ℃ of temperature.Wherein hydrogen flow rate should be more than 4cm/min.
Further, the sodium chlorate acidic solution also can be used the acidic solution that leads to chlorine instead in the described step 3).No matter be which kind of solution, the reduction potential of real solution (with respect to hydrogen electrode) should remain on about 1200mV.
Further, in the described step 3) in the sodium chlorate acidic solution acid can be that hydrochloric acid also can be the mixture of hydrochloric acid and sulfuric acid.
Further, can when the solution top temperature, add a small amount of superoxol in the sodium chlorate acidic solution in the described step 3).
Further, the flow velocity of oxygen or air is answered more than the 4mL/min in the described step 1).
Further, the CO flow velocity should be at 4-18cm/min described step 2).
Further, described solid material granularity should be less than 74 microns.
Further, described solid material is the junked-auto catalyzer.
Embodiment
Method of the present invention will at length be illustrated in this part, wherein for example platinum, rhodium, palladium junked-auto catalyzer are example to contain precious metal, yet, those skilled in the art are to be understood that, method of the present invention is not limited in and is applied to automobile catalyst, also can be applied to the raw material that other contain rare precious metal, for example the similar catalyzer that uses in the petrochemical complex industry, natural mineral etc.Precious metal can be ruthenium, rhodium, palladium, osmium, iridium, platinum, gold and silver etc.Rare metal can be vanadium, gallium, tungsten, molybdenum, tantalum, niobium, zirconium, hafnium, gallium, indium, thallium, germanium etc.
The muriatic analysis of rare precious metal can be used plasma mass (ICP-MS) or ICP-AES (ICP-AES) or other analytical procedure such as spectrophotometry in the filtrate.A certain rare precious metal concentration is designated as C in the filtrate
i(ppm).The volume of filtrate is V (mL) after measured.
Then weight is the extracted amount x of certain metal i in the raw material of W (g)
iFor:
In this article, metal fall refers to raw material powder after above-mentioned pyrogenic process pre-treatment and wet method aftertreatment, transfers in the extraction filtrate of aftertreatment the ratio percentage of actual this kind metal quality that contains in this kind of the solubility metal quality and the raw material powder that drops into reaction.The extraction yield η of metal i is expressed as:
μ is for to use other International Standards Method, and as the precious metal fire assaying analysis that the specialty analysis personnel carry out, the weight percentage of certain metal i in the raw material that draws can be regarded standard value.
Embodiment 1
The 5.0000g particle diameter is packed in the quartz boat less than 74 microns inefficacy automobile catalyst dried powders, quartz boat is placed the reaction tubes of the flat-temperature zone of openable tube furnace up and down.Then tube furnace is warming up to 300 ℃ under the argon gas condition of logical 8cm/min, again argon gas is switched to 16cm/min oxygen, 300 ℃ of reactions 2 hours.Again oxygen is switched to the 16cm/min argon gas, ventilate half an hour, residual oxygen in the pipe is removed.Again argon gas is switched to 16cm/min CO, 300 ℃ of reactions 1 hour.After the pre-treatment of low temperature pyrogenic process, furnace temperature is cooled to room temperature, quartz boat is taken out from reaction tubes.
All be transferred in the 250ml there-necked flask by quartz boat through the preprocessed catalyst powder above-mentioned, add 50ml mixed solution (mixed solution: hydrochloric acid 4mol/L and vitriol oil 6mol/L), be heated to 95 ℃ of temperature, add hydrogen peroxide 3mL again, mixing speed 230r/min slowly adds the NaClO of 2mol/L
3Solution 10ml continues insulation reaction 2h then, stops heated and stirred then, leaves standstill cooling, filters, washs filter residue.
Analyze the concentration (ppm) of platinum metals platinum, rhodium, palladium in the filtrate with plasma mass (ICP-AES).After measured, the extraction yield η of catalyst solid Pd, Pt, Rh is respectively 99%, 99%, 82%.
Embodiment 2
The 5.0000g particle diameter is packed in the quartz boat less than 74 microns inefficacy automobile catalyst dried powders, quartz boat is placed the reaction tubes of the flat-temperature zone of openable tube furnace up and down.Then tube furnace is warming up to 300 ℃ under the argon gas condition of logical 8cm/min, again argon gas is switched to 16cm/min oxygen, 300 ℃ of reactions 2 hours.Again oxygen is switched to the 16cm/min argon gas, ventilate half an hour, residual oxygen in the pipe is removed.Again argon gas is switched to 16cm/min H
2, 300 ℃ of reactions 2 hours.After the pre-treatment of low temperature pyrogenic process, furnace temperature is cooled to room temperature, quartz boat is taken out from reaction tubes.
All be transferred in the 250ml there-necked flask by quartz boat through the preprocessed catalyst powder above-mentioned, add 50ml mixed solution (mixed solution: hydrochloric acid 4mol/L and vitriol oil 6mol/L), be heated to 95 ℃ of temperature, add hydrogen peroxide 3mL again, mixing speed 230r/min slowly adds the NaClO of 2mol/L
3Solution 10ml continues insulation reaction 2h then, stops heated and stirred then, leaves standstill cooling, filters, washs filter residue.
Analyze the concentration (ppm) of platinum metals platinum, rhodium, palladium in the filtrate with plasma mass (ICP-AES).After measured, the extraction yield η of catalyst solid Pd, Pt, Rh is respectively 92%, 85%, 81%.
Embodiment 3
With the 5.0000g particle diameter less than 74 microns inefficacy automobile catalyst dried powders, without the pyrogenic process pre-treatment, all be transferred in the 250ml there-necked flask, add 50ml mixed solution (mixed solution: hydrochloric acid 4mol/L and vitriol oil 6mol/L), be heated to 95 ℃ of temperature, add hydrogen peroxide 3mL again, mixing speed 230r/min slowly adds the NaClO of 2mol/L
3Solution 10ml continues insulation reaction 2h then, stops heated and stirred then, leaves standstill cooling, filters, washs filter residue.
Analyze the concentration (ppm) of platinum metals platinum, rhodium, palladium in the filtrate with plasma mass (ICP-AES).After measured, the extraction yield η of catalyst solid Pd, Pt, Rh is respectively 82%, 67%, 55%.
Claims (10)
1. method of extracting precious metal and rare metal in the solid material, it may further comprise the steps:
1) with oxygen or air more than pretreating raw material 0.2h under 200-500 ℃ the temperature;
2) under 200-500 ℃ of temperature, live through step 1) raw material 0.2-1.5h with the CO (carbon monoxide converter) gas processing again;
3) will live through step 2 again) solid material leaches under 30-180 ℃ temperature with the sodium chlorate acidic solution;
4) filter, wash solid residue.
2. method according to claim 1, wherein step 2) also can use hydrogen instead and live through more than the step 1) raw material 0.5h handling under the 200-500 ℃ of temperature.
3. method according to claim 1, wherein the sodium chlorate acidic solution also can be used the acidic solution of logical chlorine instead in the step 3).No matter be which kind of solution, the reduction potential of real solution (with respect to hydrogen electrode) should remain on about 1200mV.
4. method according to claim 1, wherein in the step 3) in the sodium chlorate acidic solution acid can be that hydrochloric acid also can be the mixture of hydrochloric acid and sulfuric acid.
5. method according to claim 1 wherein can add a small amount of superoxol in the sodium chlorate acidic solution in the step 3) when the solution top temperature.
6. method according to claim 1, wherein the flow velocity of oxygen or air is answered more than the 4mL/min in the step 1).
7. method according to claim 1, wherein the CO flow velocity should be at 4-18cm/min.
8. method according to claim 2, wherein H
2Flow velocity should be more than 4cm/min.
9. method according to claim 1, wherein said solid material granularity should be less than 74 microns.
10. method according to claim 1, wherein said solid material is the junked-auto catalyzer.
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| CN2013101605204A CN103205563A (en) | 2013-05-06 | 2013-05-06 | Method for extracting rare noble metals by wet method |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103981363A (en) * | 2014-06-04 | 2014-08-13 | 沈少波 | Device and method for extracting rare noble metals by adopting wet process |
| CN104372179A (en) * | 2013-12-19 | 2015-02-25 | 厦门紫金矿冶技术有限公司 | Method for comprehensively recovering gold from gold-containing molybdenite |
| CN105256145A (en) * | 2015-11-18 | 2016-01-20 | 金川集团股份有限公司 | Method for extracting noble metal from waste vehicle exhaust catalyst |
| CN103695653B (en) * | 2014-01-02 | 2016-06-08 | 沈少波 | A kind of method of noble metal on wet underwater welding circuit board |
| CN112899493A (en) * | 2021-01-21 | 2021-06-04 | 有研亿金新材料有限公司 | Method for recovering and purifying platinum from platinum-tungsten alloy |
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| JPH0360742A (en) * | 1989-07-27 | 1991-03-15 | Cataler Kogyo Kk | Method for recovering platinum family metal and cerium from used catalyst |
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2013
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| JPH0360742A (en) * | 1989-07-27 | 1991-03-15 | Cataler Kogyo Kk | Method for recovering platinum family metal and cerium from used catalyst |
| CN101654740A (en) * | 2008-08-22 | 2010-02-24 | 拜尔材料科学股份公司 | Method for separating metallic ruthenium or ruthenium compounds from ruthenium-containing solids |
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Non-Patent Citations (1)
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| 李耀威等: "废汽车催化剂中铂族金属的浸出研究", 《华南师范大学学报(自然科学版)》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104372179A (en) * | 2013-12-19 | 2015-02-25 | 厦门紫金矿冶技术有限公司 | Method for comprehensively recovering gold from gold-containing molybdenite |
| CN103695653B (en) * | 2014-01-02 | 2016-06-08 | 沈少波 | A kind of method of noble metal on wet underwater welding circuit board |
| CN103981363A (en) * | 2014-06-04 | 2014-08-13 | 沈少波 | Device and method for extracting rare noble metals by adopting wet process |
| CN105256145A (en) * | 2015-11-18 | 2016-01-20 | 金川集团股份有限公司 | Method for extracting noble metal from waste vehicle exhaust catalyst |
| CN112899493A (en) * | 2021-01-21 | 2021-06-04 | 有研亿金新材料有限公司 | Method for recovering and purifying platinum from platinum-tungsten alloy |
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Application publication date: 20130717 |