CN1114362A - Process for recovering platinum from waste catalyst - Google Patents
Process for recovering platinum from waste catalyst Download PDFInfo
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- CN1114362A CN1114362A CN94106412A CN94106412A CN1114362A CN 1114362 A CN1114362 A CN 1114362A CN 94106412 A CN94106412 A CN 94106412A CN 94106412 A CN94106412 A CN 94106412A CN 1114362 A CN1114362 A CN 1114362A
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- hydrochloric acid
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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
Abstract
The process for recovering platinum from waste Pt-contained catalyst includes such technological steps as calcining platinum series catalyst using gamma-Al2Oe3 or SiO2-Al2O3 as carrier, heating reflux of the dregs after calcine in hydrochloric acid solution containing oxidant for educing out platinum, anionic exchange resin separation of solution containing platinum and purifying to obtain sponge platinum with total recovery rate of 98%.
Description
The present invention relates to a kind of method that from the platiniferous spent catalyst, platinum is reclaimed, belong to the technical field that special metal refines.
In petroleum industry and petrochemical industry, widely apply the catalysis course of processing, contain one or more catalytically-active metals components in the used catalyzer mostly, platinum is one of the most frequently used catalytically-active metals component, the platinum series multimetallic catalyst is then mostly to be to be carrier with aluminum oxide or aluminium oxide-silicon oxide, carries the catalyzer with metals such as platinum, iridium, rheniums.Platinum is that rare precious metal, price are very expensive, is very necessary so remove the platinum in the recovery and reuse spent catalyst with the higher rate of recovery as far as possible.
The key issue that reclaims platinum from the platiniferous spent catalyst has two, and the firstth, separate metal component that carries on the carrier and carrier; The secondth, from isolating metal (solution), further platinum is extract.The method of existing recovery platinum all is the scheme that proposes various solutions at these two key issues.According to the data of having published, the method that reclaims platinum from the platiniferous spent catalyst is broadly divided into three kinds: first kind is the dissolving support methods, promptly with the carrier in sulfuric acid or the alkali dissolution spent catalyst, after the filtration, platinum is present in the filter residue with solid-state, as US 3,856,912 propose to depress with the useless agent of sulfuric acid dissolution heating, platinum in the filter residue is used aqua regia dissolution again, after resin isolation, be refined into Platinic chloride, the rate of recovery of platinum is more than 98%, second kind is with carrier and platinum complete molten method of dissolved all, and as CN 85100109A, this method is with hydrochloric acid and the useless agent of a small amount of three heating for dissolving of dioxygen moisture, use diisooctyl sulfoxide solvent and centrifugal extractor extracting and separating platinum solution again, the rate of recovery of platinum is 97～98%.The third method is platinum dissolving to be kept carrier, platinum with make with extra care and the platinum that obtains reclaiming through enrichment again after carrier separates, as US 4,428,768 and the method that proposed of publication number CN 1067926A.Comprehensive relevant reported in literature, though with the rate of recovery of above method platinum mostly more than 97%, but because the operation steps of first and second kind method is many, in fact be difficult to guarantee to reach so high platinum rate of recovery, and be dissolved in the solution because of a large amount of aluminum oxide or aluminium oxide-silicon oxide carrier, cause the difficulty on the solid-liquid separation, the conditional request of relevant devices is also much higher than the third method.Though the characteristics of the third method are to make the carrier gama-alumina at high temperature transform into the Alpha-alumina of indissoluble, need with the bigger High Temperature Furnaces Heating Apparatus roasting of power consumption, this method has advantages such as technological process is simple, operation steps is few, reagent dosage is few.
Purpose of the present invention is exactly to propose a kind of novel method by recovery platinum in the useless agent of platiniferous, this method belongs to the technology category that the platinum dissolving is kept alumina supporter, except that keeping its superiority, require also that technological process is simpler, operation steps still less, the rate of recovery of platinum is further improved.
The inventive method is earlier spent catalyst to be handled at suitable roasting temperature, make the carrier gama-alumina change Alpha-alumina into, mixed solution leaching with hydrochloric acid and nitric acid, make platinum be dissolved into solution, then with solution process anionite-exchange resin, the platinum exchange is adsorbed on the resin, will just obtain the spongy platinum product after the resin roasting at last.The minute quantity platinum that remains on the carrier residue can fully utilize, as the CO burning ignition dope material in the petroleum catalytic cracking processing.The operation of the inventive method mainly can be divided into roasting, leaching, filtration washing, separation purified for four steps, and its operating process can be referring to accompanying drawing 1.
Below be the detailed description of the inventive method operation steps:
Roasting-with spent catalyst is through screening, and the porcelain ring, porcelain grain and other foreign material that are mingled with in the middle of discarding are put into High Temperature Furnaces Heating Apparatus, 800～1200 ℃ roasting temperatures 4～10 hours, is preferably 4～6 hours, then cooling.
Leach-accurately take by weighing the material after the roasting, put into the leaching still, according to the ratio adding mixing acid leaching liquid of the useless agent of per kilogram with 2～8 liters, this leaching liquid is formulated by the hydrochloric acid adding nitric acid of 2～8M concentration, and the concentration of nitric acid in leaching liquid is 40～80ml/ liter.Under 95～105 ℃ the condition of heating, reflux 1～4 hour.After leaching, platinum and other components that dissolve in the leaching liquid become solution, and Alpha-alumina and other materials that is insoluble to leaching liquid still keep with solids.It is pure that used nitric acid and hydrochloric acid are top grade.
Filtration washing-will be mixed with the leaching liquid filtration of solids, filter residue washs 4～5 times with 3% dilute hydrochloric acid, and the filtrate that dilute hydrochloric acid washings and filtration are obtained merges.According to the platinum content in the amalgamation liquid, can calculate the leaching rate of platinum in the catalyzer.
Separate, purify-above merging solution process anionite-exchange resin (as commercially available D-296 type commodity) adsorption column, platinum is by resin absorption, to adsorb the resin of platinum by drawing off in the adsorption column, toasted 2 hours down at 110～120 ℃, transfer in the stoving oven then, in 600～800 ℃ of roasting temperatures 1～2 hour, the resin organism was fully burnt, and platinum promptly reclaims becomes the spongy platinum final product.
Still leave the platinum of denier in the solid filter residue behind the comprehensive utilization of filter residue-process leaching and the filtration washing, this is difficult to reclaim, but can be 93104262.3 invention " method for preparation of catalyst cracking combustion-supporting agent " according to number of patent application, ignition dope as petroleum catalytic cracking processing reaches sufficient comprehensive utilization.
Compare with the prior art that reclaims the platinum method in the catalyst made from platonic, the feature of the inventive method is:
1. 800～1200 ℃ roasting temperature 4～10 hours, make gama-alumina change Alpha-alumina into.
2. the mixing acid leaching liquid with hydrochloric acid and nitric acid leaches reflux once after the roasting, can reach 98.5～99.5% the platinum rate of recovery.
3. the purity that reclaims back gained spongy platinum is 99.9%, and remaining platinum amount only is 0.002～0.005% on the leaching after-filtration residue, and the residue comprehensive utilization is catalyst cracking combustion-supporting agent.
Because the inventive method has feature as above, therefore the invention has the advantages that:
1. use the platinum on the mixed solution leaching carrier of hydrochloric acid and nitric acid, platinum can fully dissolve, and has been converted into the Alpha-alumina of indissoluble as the gama-alumina of carrier, is easy to filter and washing.
2. operation is few, simple to operate, need be with special equipment, and reagent dosage is few.
3. the purity that final platinum reclaims the product spongy platinum reaches 99.9%, does not need to reprocess just to be directly used in the new catalyzer of preparation.
4. the aluminum oxide filter residue that contains denier platinum also can fully utilize.
The embodiment of the inventive method is as follows:
Embodiment 1
The useless platinum tin reforming catalyst (Pt-Sn-Cl/ γ-Al that contains platinum 0.37m%
2O
3The industry code name is PS-3861) 53.7 grams, the calculating content of platinum was 199 milligrams, in 850 ℃ of following roastings 4 hours, cooling back is leaching reflux 2 hours in the nitric acid mixing solutions of the hydrochloric acid of 3M and 0.9M with 1: 5 solid-to-liquid ratio (weight/volume) in concentration, 95～105 ℃ of leaching temperatures.Cooled and filtered obtains platiniferous solution, and divides the washing filter residue 5 times with 3% dilute hydrochloric acid 20m1.Filtrate and washings are merged,, the platinum exchange is adsorbed on the post through ion exchange resin column.After exchange finishes resin is drawn off, obtain 197.3 milligrams of spongy platinums after 600 ℃ of following calcinations, the platinum rate of recovery is 99.15%.
Embodiment 2
Many reforming catalyst (Pt-Sn-Cl/ γ-the Al of useless platinum tin that contain platinum 0.59m%
2O
3The industry code name is R30-156) 10.5 grams, the calculating content of platinum is 62.0 milligrams, in 1100 ℃ of following roastings 4 hours, after being cooled to room temperature, is leaching reflux 3 hours in the nitric acid mixing solutions of the hydrochloric acid of 2.5M and 0.2M with 1: 4 solid-to-liquid ratio in concentration, 95～105 ℃ of leaching temperatures, filter according to the step identical with embodiment 1, washing, ion-exchange, and the resin operation of calcination absorption platinum obtain 61.7 milligrams of spongy platinums, the purity of spongy platinum is 99.9%, the rate of recovery of platinum is 99.52%, and by analysis, the platinum content on the aluminum oxide residue is 0.002m%.
Embodiment 3
Useless xylene isomerization catalyst (the Pt/SiO that contains platinum 0.32m%
2-Al
2O
3) 15.0 the gram, the calculating content of platinum is 48.0 milligrams, according to embodiment 2 identical operations step process, obtain 47.8 milligrams of spongy platinums, the purity of spongy platinum is 99.9%, the rate of recovery of platinum is 99.6%.
Embodiment 4
Waste reforming catalyst (Pt-Re-Cl/ γ-the Al that contains platinum 0.30m%
2O
3, industrial trade mark CB-6) and 16.2 grams, 47.1 milligrams of the calculating content of platinum, earlier according to US 3,578,395 disclosed methods reclaim rhenium, will reclaim filter residue behind the rhenium again in 1000 ℃ of following roastings 4 hours.The cooling back is to leach reflux 2 hours in 3M hydrochloric acid and the 1.5M nitric acid mixed solution with 1: 3 solid-to-liquid ratio in concentration, 95 ℃ of leaching temperatures, then according to embodiment 1 identical operations step process, obtain 46.8 milligrams of spongy platinums, its purity is 99.9%, and the platinum rate of recovery is 99.4%.
Embodiment 5
Platinum containing amount is reforming catalyst (Pt-Re-Cl/ γ-Al of 0.20m%
2O
3Industry trade mark CB-7) 20.0 grams, the calculating content of platinum is 40 milligrams, and according to obtaining 39.4 milligrams of spongy platinums with embodiment 4 identical operations steps, purity is 99.9%, and the rate of recovery of platinum is 98.5%.
Claims (5)
1. a method that reclaims platinum from the platiniferous spent catalyst comprises steps such as roasting, leaching, filtration washing, separation purification, it is characterized in that:
(1) useless agent was 800～1200 ℃ of following roastings 4～10 hours;
(2) cooled burning slag is with 1: 2～8 solid-to-liquid ratio (weight, kilogram/volume rises) add leaching liquid, the leaching reflux is 1～4 hour under 95～105 ℃ of temperature, leaching liquid is made into by the hydrochloric acid adding nitric acid of 2～8M concentration, and the concentration of nitric acid in leaching liquid is 40～80 milliliters/liter;
(3) through the material filtering after the leaching, wash filter residue 4～5 times with 3% diluted hydrochloric acid aqueous solution, filtrate and washings are merged;
(4) amalgamation liquid is passed through anionite-exchange resin, make platinum be exchanged absorption, resin draws off the back and does 600～800 ℃ of following roastings 1～2 hour after 2 hours again in baking under 110～120 ℃, and the spongy platinum that obtains is the recovery product.
2. the method for recovery platinum according to claim 1 is characterized in that useless agent was 1000～1200 ℃ of following roastings 4～6 hours.
3. the method for recovery platinum according to claim 1, it is pure to it is characterized in that the hydrochloric acid of said leaching liquid and nitric acid are top grade.
4. the method for recovery platinum according to claim 1 is characterized in that used anionite-exchange resin is commercially available D-296 type anionite-exchange resin.
5. the method for recovery platinum according to claim 1 is characterized in that through the filter residue behind leaching reflux and the filtration washing according to the method for application number 93104262.3, comprehensive utilization is as the ignition dope of hydrocarbon oil catalytic cracking.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94106412A CN1114362A (en) | 1994-06-22 | 1994-06-22 | Process for recovering platinum from waste catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94106412A CN1114362A (en) | 1994-06-22 | 1994-06-22 | Process for recovering platinum from waste catalyst |
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|---|---|
| CN1114362A true CN1114362A (en) | 1996-01-03 |
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|---|---|---|---|
| CN94106412A Pending CN1114362A (en) | 1994-06-22 | 1994-06-22 | Process for recovering platinum from waste catalyst |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100355917C (en) * | 2003-04-11 | 2007-12-19 | 隆敏有限公司 | Recovery of platinum group metals |
| CN102899498A (en) * | 2012-09-28 | 2013-01-30 | 昆明理工大学 | Method for leaching platinum metals from spent automobile exhaust catalyst |
| CN106119551A (en) * | 2016-08-01 | 2016-11-16 | 惠州Tcl环境科技有限公司 | A kind of method processing extraction metal containing metal-resin ashing |
| CN106480313A (en) * | 2015-09-02 | 2017-03-08 | 徐州北矿金属循环利用研究院 | Method for recovering platinum from indissolvable silicon-aluminum-based platinum-containing waste catalyst |
| CN107574315A (en) * | 2017-08-25 | 2018-01-12 | 金川集团股份有限公司 | A kind of method of the recovery of the short route from dead catalyst platinum group metal |
| CN107641719A (en) * | 2017-08-25 | 2018-01-30 | 金川集团股份有限公司 | A kind of method that noble metal is reclaimed from low concentration solution |
-
1994
- 1994-06-22 CN CN94106412A patent/CN1114362A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100355917C (en) * | 2003-04-11 | 2007-12-19 | 隆敏有限公司 | Recovery of platinum group metals |
| CN102899498A (en) * | 2012-09-28 | 2013-01-30 | 昆明理工大学 | Method for leaching platinum metals from spent automobile exhaust catalyst |
| CN102899498B (en) * | 2012-09-28 | 2014-04-02 | 昆明理工大学 | Method for leaching platinum metals from spent automobile exhaust catalyst |
| CN106480313A (en) * | 2015-09-02 | 2017-03-08 | 徐州北矿金属循环利用研究院 | Method for recovering platinum from indissolvable silicon-aluminum-based platinum-containing waste catalyst |
| CN106119551A (en) * | 2016-08-01 | 2016-11-16 | 惠州Tcl环境科技有限公司 | A kind of method processing extraction metal containing metal-resin ashing |
| CN107574315A (en) * | 2017-08-25 | 2018-01-12 | 金川集团股份有限公司 | A kind of method of the recovery of the short route from dead catalyst platinum group metal |
| CN107641719A (en) * | 2017-08-25 | 2018-01-30 | 金川集团股份有限公司 | A kind of method that noble metal is reclaimed from low concentration solution |
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