CN1472346A - Recovery of palladium metal from waste palladium/aluminium oxide catalyst - Google Patents
Recovery of palladium metal from waste palladium/aluminium oxide catalyst Download PDFInfo
- 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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- CN
- China
- Prior art keywords
- palladium
- aluminium oxide
- oxide catalyst
- useless
- recovery
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 239000003054 catalyst Substances 0.000 title claims abstract description 28
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims description 108
- 229910052763 palladium Inorganic materials 0.000 title claims description 36
- 229910003445 palladium oxide Inorganic materials 0.000 title claims description 18
- 229910052751 metal Inorganic materials 0.000 title claims description 10
- 239000002184 metal Substances 0.000 title claims description 10
- 238000011084 recovery Methods 0.000 title abstract description 10
- 239000002699 waste material Substances 0.000 title 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 26
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 20
- 235000019270 ammonium chloride Nutrition 0.000 claims abstract description 13
- 239000011780 sodium chloride Substances 0.000 claims abstract description 10
- 239000000243 solution Substances 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 238000001354 calcination Methods 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 5
- 238000007654 immersion Methods 0.000 claims 1
- 238000005260 corrosion Methods 0.000 abstract description 3
- 230000007797 corrosion Effects 0.000 abstract description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 5
- 238000006722 reduction reaction Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 2
- 150000004056 anthraquinones Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000008030 elimination Effects 0.000 description 2
- 238000003379 elimination reaction Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910000474 mercury oxide Inorganic materials 0.000 description 1
- UKWHYYKOEPRTIC-UHFFFAOYSA-N mercury(ii) oxide Chemical compound [Hg]=O UKWHYYKOEPRTIC-UHFFFAOYSA-N 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
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- Catalysts (AREA)
- Manufacture And Refinement Of Metals (AREA)
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
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 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031262325A CN1223688C (en) | 2003-06-30 | 2003-06-30 | Recovery of palladium metal from waste palladium/aluminium oxide catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031262325A CN1223688C (en) | 2003-06-30 | 2003-06-30 | Recovery of palladium metal from waste palladium/aluminium oxide catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1472346A true CN1472346A (en) | 2004-02-04 |
| CN1223688C CN1223688C (en) | 2005-10-19 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB031262325A Expired - Fee Related CN1223688C (en) | 2003-06-30 | 2003-06-30 | Recovery of palladium metal from waste palladium/aluminium oxide catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1223688C (en) |
Cited By (6)
| 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 | A method for comprehensive recovery and utilization of spent Pd/Al2O3 catalyst |
-
2003
- 2003-06-30 CN CNB031262325A patent/CN1223688C/en not_active Expired - Fee Related
Cited By (10)
| 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 | A method for comprehensive recovery and utilization of spent 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1223688C (en) | 2005-10-19 |
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| C14 | Grant of patent or utility model | ||
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Granted publication date: 20051019 |