CN1472346A - Recovery of palladium metal from waste palladium/aluminium oxide catalyst - Google Patents

Recovery of palladium metal from waste palladium/aluminium oxide catalyst Download PDF

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Publication number
CN1472346A
CN1472346A CNA031262325A CN03126232A CN1472346A CN 1472346 A CN1472346 A CN 1472346A CN A031262325 A CNA031262325 A CN A031262325A CN 03126232 A CN03126232 A CN 03126232A CN 1472346 A CN1472346 A CN 1472346A
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palladium
aluminium oxide
oxide catalyst
recovery
useless
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CN1223688C (en
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吕淑英
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LIMING CHEMICAL INST
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LIMING CHEMICAL INST
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    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00Technologies related to metal processing
    • Y02P10/20Recycling

Abstract

A process for recovering Pd from the used Pd/alumina catalyst includes such steps as immersing in solution of ammonium chloride, burning, immersing in solution of sodium chloride, reducing and purifying. Its advantages are high safety, less corrosion to equipment, high recovery rate (95%) and high purity (99.6%).

Description

Reclaim the method for palladium metal in useless palladium/aluminium oxide catalyst
Technical field the present invention relates to a kind of method that reclaims precious metal from spent catalyst, particularly contains the method that reclaims the crude metal palladium in the palladium spent catalyst.
Background technology palladium/aluminium oxide catalyst is active the reduction behind life-time service.Spent catalyst is called spent catalyst.Contain precious metal palladium in useless palladium/aluminium oxide catalyst, should recycling.The existing multiple at present method that from useless palladium/aluminium oxide catalyst, reclaims palladium metal.Recovery method comprises from useless palladium/aluminium oxide catalyst palladium is separated with aluminum oxide and two steps of reducing metal palladium.Modal separation method is will to generate water-soluble cpds, thereby palladium is separated with aluminum oxide attached to the palladium stripping of alumina surface with hydrochloric acid and other auxiliary agents.Another kind of separation method is with sulfuric acid or sodium hydroxide alumina supporter to be dissolved, and it is separated with the solid metal palladium.These separation methods all need directly to use a large amount of strong acid, highly basic, and operational danger is big, and is serious to equipment corrosion.
Summary of the invention the purpose of this invention is to provide a kind of method that reclaims palladium metal from useless palladium/aluminium oxide catalyst, this method has overcome the problems referred to above of conventional separating step, and the danger of operating with minimizing without strong acid, highly basic in the sepn process of palladium and aluminum oxide reaches the corrodibility to equipment.
For achieving the above object, the invention provides a kind of method that from useless palladium/aluminium oxide catalyst, reclaims palladium metal.Do not use strong acid, highly basic in the process of this method separate palladium and aluminum oxide, comprise following operation steps:
(a) soak useless palladium/aluminium oxide catalyst with aqueous ammonium chloride solution, so that ammonium chloride fully is adsorbed onto in the spent catalyst.The massfraction of used aqueous ammonium chloride solution is 1%~30%, and preferable massfraction is 2%~20%.Soak time is 0.5h~5h.
(b) remove raffinate, with the useless palladium after soaking/aluminium oxide catalyst oven dry.What furnace drying method adopted is ordinary method, as drying by the fire 5h~10h in 80 ℃~120 ℃ loft drier.
(c) the useless palladium/aluminium oxide catalyst calcination after will drying.Calcination temperature is 200 ℃~600 ℃, and the calcination temperature scope is 350 ℃~450 ℃ preferably.Calcination time is 2h~10h, and 3h~8h is better.
(d) treat that useless palladium/aluminium oxide catalyst after the calcination is cooled to room temperature after, with sodium chloride aqueous solution soaking 0.5h~18h, preferred 1h~8h; The massfraction of the used sodium chloride aqueous solution is 1%~30%, and the preferable quality mark is 3%~20%.
(e) filter, discard filter residue.
(f) filtrate that obtains of step (e) makes the palladium precipitation with reductive agent.Employed method of reducing is the conventional reduction method, and is identical with the follow-up reduction step of other separation methods.Reductive agent can be used formaldehyde, hydrazine hydrate.
(g) filtration obtains thick palladium.
(h) by the above thick palladium that obtains, can adopt any conventional method further to purify.
The method that reclaims palladium metal that contains in the palladium spent catalyst provided by the invention, the raw material cheapness, the process of separate palladium and aluminum oxide is not used strong acid, highly basic, overcome operational danger greatly, to the equipment corrosion important disadvantages.Thick palladium recovery rate can reach 95.0%.Purity can reach 99.6% behind the purifying.
The recovery of palladium in useless palladium/aluminium oxide catalyst that method provided by the present invention can be used for producing in the hydrogen peroxide obtained by anthraquinone process production process.The invention will be further described below by example.Used useless palladium/aluminium oxide catalyst among the embodiment all is to produce in Liming chemical Inst's hydrogen peroxide obtained by anthraquinone process production process.
Embodiment
Embodiment 1
Being useless palladium/aluminium oxide catalyst of 0.3% with 20g palladium content soaks 1h in massfraction is 3% aqueous ammonium chloride solution, the aqueous ammonium chloride solution consumption is as the criterion with the submergence spent catalyst; Remove raffinate, solid substance is dry 8h in 100~110 ℃ of baking ovens; Then at 350 ℃~450 ℃ calcination 6h; Being cooled to after the room temperature with the 60ml massfraction is that 5% sodium chloride aqueous solution soaks 1h; Filter, discard filter residue; Add mass percent in the filtrate and be 50% hydrazine hydrate 12ml, transfer to pH 〉=10, carry out reduction reaction 1h, filter then and obtain thick palladium at 80 ℃ with ammoniacal liquor.The rate of recovery of thick palladium is 85.6%.
Embodiment 2
The massfraction of aqueous ammonium chloride solution is 5%, and the massfraction of sodium chloride aqueous solution is 20%, and the rate of recovery of thick palladium is 94.6%.Other are with embodiment 1.
Embodiment 3
The massfraction of aqueous ammonium chloride solution is 20%, and the massfraction of sodium chloride aqueous solution is 5%, and the rate of recovery of thick palladium is 95.0%.Other are with embodiment 1.
Embodiment 4
The massfraction of aqueous ammonium chloride solution is 5%, and the massfraction of sodium chloride aqueous solution is 2%, and the rate of recovery of thick palladium is 95.0%.Other are with embodiment 1.
The related data of embodiment 1~4 sees Table 1.
The data table related of table 1 embodiment 1~4
Embodiment Aqueous ammonium chloride solution massfraction/% Sodium chloride aqueous solution massfraction/% Thick palladium recovery rate/%
????1 ????3 ????5 ????85.6
????2 ????5 ????20 ????94.6
????3 ????20 ????5 ????95.0
????4 ????5 ????2 ????95.0
Embodiment 5
Make thick palladium 2.83g by embodiment 4 methods, with the aqua regia dissolution of 7 times of thick palladium quality, heating transfers to pH=10 with ammoniacal liquor, the elimination throw out after removing nitre under room temperature; Filtrate transfers to pH=1 with hydrochloric acid, generates yellow mercury oxide, and elimination solution, throw out water are heated to dissolving more than 80 ℃, is 50% hydrazine hydrate reduction with the 4ml massfraction, and the throw out of generation promptly obtains making with extra care palladium 2.82g, purity 99.6% after drying.

Claims (4)

1. method that reclaims palladium metal in useless palladium/aluminium oxide catalyst is characterized in that this method contains following steps:
(a) soak useless palladium/aluminium oxide catalyst with aqueous ammonium chloride solution;
(b) with the useless palladium after the aqueous ammonium chloride solution immersion/aluminium oxide catalyst oven dry;
(c) the useless palladium/aluminium oxide catalyst calcination after will drying;
(d) calcination, cooled useless palladium/aluminium oxide catalyst are soaked with sodium chloride aqueous solution.
2. method according to claim 1 is characterized in that used aqueous ammonium chloride solution massfraction is 2%~20%.
3. method according to claim 1 is characterized in that used sodium chloride aqueous solution massfraction is 3%~20%.
4. method according to claim 1 is characterized in that calcination temperature is 350 ℃~450 ℃.
CNB031262325A 2003-06-30 2003-06-30 Recovery of palladium metal from waste palladium/aluminium oxide catalyst Expired - Fee Related CN1223688C (en)

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CN1223688C CN1223688C (en) 2005-10-19

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100537800C (en) * 2007-06-22 2009-09-09 厦门金达威维生素股份有限公司 From the waste loading palladium hydrogenation catalyst, reclaim the method for palladium metal and Palladous chloride
CN102994771A (en) * 2011-09-13 2013-03-27 郴州市金贵银业股份有限公司 Method for extracting palladium sponge from silver electrolysis anode slime parting liquid
CN103276215A (en) * 2013-06-03 2013-09-04 贵研资源(易门)有限公司 Method for recovering noble metal from waste catalyst
CN104232900A (en) * 2014-08-27 2014-12-24 昆明贵金属研究所 Method for recovering palladium from waste palladium/alumina catalyst
CN105256146A (en) * 2015-11-26 2016-01-20 中南大学 Method for recycling metal palladium from waste palladium-aluminum oxide catalysts
CN106367595A (en) * 2016-08-26 2017-02-01 中南大学 Method for comprehensively recycling waste Pd/Al2O3 catalyst

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100537800C (en) * 2007-06-22 2009-09-09 厦门金达威维生素股份有限公司 From the waste loading palladium hydrogenation catalyst, reclaim the method for palladium metal and Palladous chloride
CN102994771A (en) * 2011-09-13 2013-03-27 郴州市金贵银业股份有限公司 Method for extracting palladium sponge from silver electrolysis anode slime parting liquid
CN102994771B (en) * 2011-09-13 2014-03-26 郴州市金贵银业股份有限公司 Method for extracting palladium sponge from silver electrolysis anode slime parting liquid
CN103276215A (en) * 2013-06-03 2013-09-04 贵研资源(易门)有限公司 Method for recovering noble metal from waste catalyst
CN103276215B (en) * 2013-06-03 2014-08-20 贵研资源(易门)有限公司 Method for recovering noble metal from waste catalyst
CN104232900A (en) * 2014-08-27 2014-12-24 昆明贵金属研究所 Method for recovering palladium from waste palladium/alumina catalyst
CN105256146A (en) * 2015-11-26 2016-01-20 中南大学 Method for recycling metal palladium from waste palladium-aluminum oxide catalysts
CN105256146B (en) * 2015-11-26 2017-08-29 中南大学 A kind of method that Metal Palladium is reclaimed from useless palladium aluminium oxide catalyst
CN106367595A (en) * 2016-08-26 2017-02-01 中南大学 Method for comprehensively recycling waste Pd/Al2O3 catalyst
CN106367595B (en) * 2016-08-26 2018-03-20 中南大学 A kind of comprehensive reutilization gives up Pd/Al2O3The method of catalyst

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