WO2002018663A2 - Recuperation selective de metaux a partir d'une composition catalytique usee - Google Patents
Recuperation selective de metaux a partir d'une composition catalytique usee Download PDFInfo
- Publication number
- WO2002018663A2 WO2002018663A2 PCT/ZA2001/000128 ZA0100128W WO0218663A2 WO 2002018663 A2 WO2002018663 A2 WO 2002018663A2 ZA 0100128 W ZA0100128 W ZA 0100128W WO 0218663 A2 WO0218663 A2 WO 0218663A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- cobalt
- solution
- platinum
- aluminium
- catalyst composition
- Prior art date
Links
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 title claims abstract description 181
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 122
- 239000010941 cobalt Substances 0.000 title claims abstract description 122
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 121
- 239000003054 catalyst Substances 0.000 title claims abstract description 103
- 229910052697 platinum Inorganic materials 0.000 title claims abstract description 78
- 239000000203 mixture Substances 0.000 title claims abstract description 77
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 60
- 239000004411 aluminium Substances 0.000 title claims abstract description 47
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 238000011084 recovery Methods 0.000 title claims abstract description 16
- 238000002386 leaching Methods 0.000 claims abstract description 84
- 238000000034 method Methods 0.000 claims abstract description 68
- 230000008569 process Effects 0.000 claims abstract description 52
- 238000001914 filtration Methods 0.000 claims abstract description 28
- 238000005189 flocculation Methods 0.000 claims abstract description 27
- 230000016615 flocculation Effects 0.000 claims abstract description 27
- 150000002500 ions Chemical class 0.000 claims abstract description 25
- 238000001556 precipitation Methods 0.000 claims abstract description 23
- 150000001875 compounds Chemical class 0.000 claims abstract description 19
- 229910052751 metal Chemical group 0.000 claims abstract description 15
- 239000002184 metal Chemical group 0.000 claims abstract description 15
- 238000000926 separation method Methods 0.000 claims abstract description 15
- 150000003839 salts Chemical group 0.000 claims abstract description 11
- 238000005406 washing Methods 0.000 claims abstract description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 165
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 55
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 40
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 39
- 229910017604 nitric acid Inorganic materials 0.000 claims description 36
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 35
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 34
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 30
- 239000007787 solid Substances 0.000 claims description 30
- 239000000706 filtrate Substances 0.000 claims description 29
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 28
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 28
- 238000004090 dissolution Methods 0.000 claims description 24
- 239000002253 acid Substances 0.000 claims description 23
- 239000013078 crystal Substances 0.000 claims description 23
- 239000012074 organic phase Substances 0.000 claims description 23
- 239000002002 slurry Substances 0.000 claims description 23
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 claims description 22
- 229910001388 sodium aluminate Inorganic materials 0.000 claims description 22
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 21
- 238000000638 solvent extraction Methods 0.000 claims description 21
- 239000003513 alkali Substances 0.000 claims description 19
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 claims description 18
- 229910052742 iron Inorganic materials 0.000 claims description 17
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 17
- 239000011780 sodium chloride Substances 0.000 claims description 15
- 239000002585 base Substances 0.000 claims description 13
- 239000012535 impurity Substances 0.000 claims description 13
- 150000004645 aluminates Chemical class 0.000 claims description 11
- 239000011368 organic material Substances 0.000 claims description 11
- 239000000047 product Substances 0.000 claims description 10
- 229910002651 NO3 Inorganic materials 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- 230000002378 acidificating effect Effects 0.000 claims description 8
- 150000001869 cobalt compounds Chemical class 0.000 claims description 8
- 239000008394 flocculating agent Substances 0.000 claims description 8
- SEGLCEQVOFDUPX-UHFFFAOYSA-N di-(2-ethylhexyl)phosphoric acid Chemical group CCCCC(CC)COP(O)(=O)OCC(CC)CCCC SEGLCEQVOFDUPX-UHFFFAOYSA-N 0.000 claims description 7
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 claims description 7
- 229940093635 tributyl phosphate Drugs 0.000 claims description 7
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 6
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims description 6
- 239000008346 aqueous phase Substances 0.000 claims description 5
- 229910001429 cobalt ion Inorganic materials 0.000 claims description 5
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000012071 phase Substances 0.000 claims description 5
- 150000003057 platinum Chemical class 0.000 claims description 5
- 239000000292 calcium oxide Substances 0.000 claims description 4
- 235000012255 calcium oxide Nutrition 0.000 claims description 4
- 230000001143 conditioned effect Effects 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 230000014759 maintenance of location Effects 0.000 claims description 4
- 150000007522 mineralic acids Chemical class 0.000 claims description 4
- 229920002401 polyacrylamide Polymers 0.000 claims description 4
- 230000001376 precipitating effect Effects 0.000 claims description 4
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 3
- 125000000129 anionic group Chemical group 0.000 claims description 3
- 230000003311 flocculating effect Effects 0.000 claims description 3
- 239000012456 homogeneous solution Substances 0.000 claims description 3
- 238000011068 loading method Methods 0.000 claims description 3
- 239000003607 modifier Substances 0.000 claims description 3
- 239000012188 paraffin wax Substances 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 150000001399 aluminium compounds Chemical class 0.000 claims description 2
- 150000003863 ammonium salts Chemical class 0.000 claims description 2
- 229940077746 antacid containing aluminium compound Drugs 0.000 claims description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 2
- 239000000920 calcium hydroxide Substances 0.000 claims description 2
- 235000011116 calcium hydroxide Nutrition 0.000 claims description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims description 2
- 238000004064 recycling Methods 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 239000000243 solution Substances 0.000 description 107
- 238000002474 experimental method Methods 0.000 description 21
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 description 12
- 238000002425 crystallisation Methods 0.000 description 12
- 238000000605 extraction Methods 0.000 description 12
- 238000002441 X-ray diffraction Methods 0.000 description 11
- 239000002244 precipitate Substances 0.000 description 11
- 238000004458 analytical method Methods 0.000 description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 9
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 description 7
- 238000001354 calcination Methods 0.000 description 7
- 239000012065 filter cake Substances 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- 239000000908 ammonium hydroxide Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 230000000007 visual effect Effects 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000002485 combustion reaction Methods 0.000 description 5
- CRHLEZORXKQUEI-UHFFFAOYSA-N dialuminum;cobalt(2+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Al+3].[Al+3].[Co+2].[Co+2] CRHLEZORXKQUEI-UHFFFAOYSA-N 0.000 description 5
- 229910021645 metal ion Inorganic materials 0.000 description 5
- 238000000746 purification Methods 0.000 description 5
- 235000019270 ammonium chloride Nutrition 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 238000009616 inductively coupled plasma Methods 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- -1 AI2O3 Chemical class 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 150000004700 cobalt complex Chemical class 0.000 description 3
- 229910000428 cobalt oxide Inorganic materials 0.000 description 3
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000000921 elemental analysis Methods 0.000 description 3
- 238000005191 phase separation Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 230000000717 retained effect Effects 0.000 description 3
- 238000004062 sedimentation Methods 0.000 description 3
- 229910052566 spinel group Inorganic materials 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- 229910002621 H2PtCl6 Inorganic materials 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- NOWPEMKUZKNSGG-UHFFFAOYSA-N azane;platinum(2+) Chemical compound N.N.N.N.[Pt+2] NOWPEMKUZKNSGG-UHFFFAOYSA-N 0.000 description 2
- 239000010953 base metal Substances 0.000 description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 2
- 238000010908 decantation Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 230000008676 import Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 150000003058 platinum compounds Chemical class 0.000 description 2
- 229910003446 platinum oxide Inorganic materials 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- GGZZISOUXJHYOY-UHFFFAOYSA-N 8-amino-4-hydroxynaphthalene-2-sulfonic acid Chemical compound C1=C(S(O)(=O)=O)C=C2C(N)=CC=CC2=C1O GGZZISOUXJHYOY-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 1
- 229910003594 H2PtCl6.6H2O Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 239000001164 aluminium sulphate Substances 0.000 description 1
- 235000011128 aluminium sulphate Nutrition 0.000 description 1
- 229940045985 antineoplastic platinum compound Drugs 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- XZXAIFLKPKVPLO-UHFFFAOYSA-N cobalt(2+);dinitrate;hydrate Chemical compound O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XZXAIFLKPKVPLO-UHFFFAOYSA-N 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000010960 commercial process Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- BUACSMWVFUNQET-UHFFFAOYSA-H dialuminum;trisulfate;hydrate Chemical compound O.[Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O BUACSMWVFUNQET-UHFFFAOYSA-H 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 229910001679 gibbsite Inorganic materials 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 235000014413 iron hydroxide Nutrition 0.000 description 1
- 159000000014 iron salts Chemical class 0.000 description 1
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- GTTYPHLDORACJW-UHFFFAOYSA-N nitric acid;sodium Chemical compound [Na].O[N+]([O-])=O GTTYPHLDORACJW-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- MUMZUERVLWJKNR-UHFFFAOYSA-N oxoplatinum Chemical compound [Pt]=O MUMZUERVLWJKNR-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- HRGDZIGMBDGFTC-UHFFFAOYSA-N platinum(2+) Chemical class [Pt+2] HRGDZIGMBDGFTC-UHFFFAOYSA-N 0.000 description 1
- NWAHZABTSDUXMJ-UHFFFAOYSA-N platinum(2+);dinitrate Chemical compound [Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NWAHZABTSDUXMJ-UHFFFAOYSA-N 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 229910001575 sodium mineral Inorganic materials 0.000 description 1
- SPKMEXGEHZCKPG-UHFFFAOYSA-M sodium nitric acid hydroxide Chemical compound [OH-].[Na+].O[N+]([O-])=O SPKMEXGEHZCKPG-UHFFFAOYSA-M 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- VRRFSFYSLSPWQY-UHFFFAOYSA-N sulfanylidenecobalt Chemical compound [Co]=S VRRFSFYSLSPWQY-UHFFFAOYSA-N 0.000 description 1
- JOKPITBUODAHEN-UHFFFAOYSA-N sulfanylideneplatinum Chemical compound [Pt]=S JOKPITBUODAHEN-UHFFFAOYSA-N 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B11/00—Obtaining noble metals
- C22B11/04—Obtaining noble metals by wet processes
- C22B11/042—Recovery of noble metals from waste materials
- C22B11/048—Recovery of noble metals from waste materials from spent catalysts
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/02—Obtaining nickel or cobalt by dry processes
- C22B23/026—Obtaining nickel or cobalt by dry processes from spent catalysts
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0453—Treatment or purification of solutions, e.g. obtained by leaching
- C22B23/0461—Treatment or purification of solutions, e.g. obtained by leaching by chemical methods
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/009—General processes for recovering metals or metallic compounds from spent catalysts
-
- 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
Definitions
- This invention relates to the selective recovery of metal values from a spent catalyst composition.
- this invention relates to a process for the selective recovery of aluminium, Cobalt and Platinum and/or compounds thereof, from a spent catalyst composition.
- the specific spent catalyst composition of the current invention is obtained from Fischer Tropsch synthesis reactions for the production of predominantly paraffinic hydrocarbons.
- the catalyst is an impregnated Fischer Tropsch Catalyst comprising an alumina carrier and active component selected from the group consisting of cobalt and/or iron and mixtures thereof.
- the catalyst may also comprise of a group VIM noble metal as promoter.
- the Fischer-Tropsch process is used to produce hydrocarbons from carbon monoxide and hydrogen.
- a cobalt catalyst may be used to activate the catalytic reaction.
- This catalyst may be prepared with a cobalt nitrate and tetra amine platinum nitrate that are used as cobalt and platinum precursors respectively. Aluminium oxide may be used as a support.
- Continual processing causes a drop in the activity of the catalyst mainly due to sulphur, which is originally present in the mixture of gases, which may accumulate on the surface of the catalyst to form either cobalt sulphide or platinum sulphide during the process. Coke formation may also be experienced during the process and subsequently the catalyst reaches a stage of deactivation and becomes a spent catalyst.
- the spent catalyst typically contains organic material, cobalt oxide, platinum and aluminium oxide.
- organic content in the catalyst coupled with the fact that both cobalt and platinum are considered to be environmentally toxic, dumping is not a viable option.
- the chemical fixation method should be recommended. In this method, which is very expensive, the pollutants like heavy and base metals can react with cement or pozzolanic materials to form water insoluble compounds. This encapsulation of heavy and base metals on the spent catalyst is efficacious only if the heavy metals are not absolutely leached out in the soil by water. To avoid the disposal of the spent catalyst or encapsulated deactivated catalyst in the landfills, the recovery of these high value metals is important.
- the inventor is aware that the above catalyst composition contains valuable metal values which, if recovered, could lead to a substantial profit and also to eliminate the existing environmental problems. At present the catalyst composition is disposed of without substantial recovery thereof.
- either the mixture of spent catalyst and sodium carbonate or the spent catalyst containing organic material is calcined at different temperatures in the presence of air to oxidise the organic material.
- metal oxides such as cobalt oxide (CoO and C03O4), cobalt aluminate (C02AIO4) and sodium aluminate (Na2Al 2 ⁇ 4 ) are formed.
- a solution of caustic soda (sodium hydroxide) is used to selectively and efficiently dissolve aluminium oxide at a relatively high temperatures (ranging from 110 to 220 Degrees Celsius) and pressures (ranging from 5 to 20 bars) with substantially no dissolution of cobalt and platinum from the spent catalyst.
- the pH of the mixture is around 13.
- water leaching may be used to solubilise sodium aluminate formed during the calcination step.
- This sodium aluminate solution which is formed during the leaching step may be used in the precipitation step of the aluminium hydroxide.
- the cobalt and platinum which are theoretically insoluble in a solution of sodium hydroxide under afore-given conditions, remain in the leached residue after the base leaching.
- This leached residue containing mainly platinum and cobalt are dissolved in a solution of nitric acid to form cobalt nitrate while the platinum remains in the acid-residue after the acid leaching step.
- This acid residue may be dissolved in the aqua regia (a solution of nitric acid and hydrochloric acid) to form chloroplatinic acid.
- aqua regia a solution of nitric acid and hydrochloric acid
- purification methods such as solvent extraction and selective precipitation may be used to selectively remove impurities or the desired metal ions from the leach liquors of the basic residue and acidic residue.
- the purified leach liquors may be reserved for the crystallisation method. In this method, chemically pure crystalline cobalt nitrate or diammonium hexachloroplatinate are formed.
- the platinum salts are important in the purification of platinum metal and sponge while the cobalt nitrate is commercially used in the production of high purity cobalt, in the electronics and chemical industries.
- a process for the selective recovery of aluminium, cobalt and platinum, and compounds thereof, from a catalyst composition including aluminium, cobalt and platinum including the steps of: treating the catalyst composition to selectively get ions of substantially only one of the aluminium, cobalt and platinum into solution; recovering, in separate process steps, the thus treated aluminium, cobalt, or platinum in salt or metal form; and repeating the treating and recovering steps for each of the aluminium, cobalt and platinum.
- the treating steps may include process steps such as leaching, washing, dissolving, stripping, and the like.
- the recovery steps may include filtration, precipitation, separation, flocculation, and the like.
- a process for the selective recovery of aluminium, cobalt and platinum, and compounds thereof, from a catalyst composition including aluminium, cobalt and platinum including the steps of: oxidising substantially all organic material present with the catalyst composition; leaching the aluminium and/or compounds thereof from the oxidised catalyst composition with a strong or weak base to form an aluminium containing product and a filtrate; filtering of alkali insoluble residue from the filtrate; washing of the alkali insoluble residue with water to remove the residual alkali aluminate solution; - precipitating of silica from alkali aluminate with slaked lime or quicklime; filtering of insoluble silicate from alkali aluminate; crystalising aluminium trihydrate from the alkali aluminate solution; - filtering aluminium trihydrate crystals from the alkali aluminate solution recycling of the alkali solution to the leaching step; dissolving the cobalt and compounds thereof
- a flocculation step may be included to remove ultra fine solids which inhibit efficient filtration.
- a flocculation step may be included to remove ultra fine solids which may inhibit efficient separation.
- the flocculation for an alkali slurry may be carried out with the aid of flocculating agents, such as modified anionic polyacrylamides.
- the flocculation may be carried out at a pH of about 12.
- the flocculation may assist the sedimentation rate and filterability of suspended ultra fine solid particles from the slurry
- the flocculation for an acidic slurry may be carried out with the aid of flocculating agents such as cationic a flocculant.
- the flocculation may carried out at a low pH about 1.5.
- the flocculation may assist the sedimentation rate and filterability of suspended ultra fine solid particles from the slurry.
- the catalyst composition may be in the form of waxy lumps of spent catalyst composition from a hydrocarbon processing reactor.
- the oxidising step may be performed by heating the catalyst composition and contacting it with oxygen.
- the catalyst composition is heated to a temperature of between 600°C and 1400°C, generally between 700°C and 1000°C. In specific embodiments of the invention the catalyst composition was heated to 700°C, 800°C, 900°C and 1000°C.
- the oxidised spent catalyst composition typically contains about from 0.0125 g Pt per 100 g AI 2 O 3 to 0.175 g Pt per 100 g AI 2 O 3 and from 5 g Co per 100 g AI 2 O 3 to 70 g Co per 100 g AI 2 O .
- the leaching of the aluminium and/or the aluminium compounds, such as AI2O 3 , from the oxidised spent catalyst composition may be carried out with a solution of sodium hydroxide of about 20% to 50% w/w NaOH, typically 25%. This selectively and efficiently dissolves aluminium oxide at a relatively high temperature ranging from 1 10°C to 250°C, typically 200°C, and at a high pressure ranging from 5 to 20 bar, typically 15 bar, with substantially no dissolution of cobalt and platinum from the spent catalyst composition.
- the leachate may be in the form of slurry.
- the flocculation of the slurry prior to filtration may be carried out using approximately 2 % w/w of flocculant prepared using a solution of sodium hydroxide of about 2 % w/w NaOH, whereafter the flocculant solution is conditioned at ambient temperature for one hour to form homogeneous solution, whereafter it is diluted with a solution of sodium hydroxide of 2 % w/w NaOH to produce a final solution containing about 0.25 % w/w of the flocculant.
- Approximately 3000 to 6000 g/t of the final solution heated to 90 degrees Celsius may be added to the slurry and mixed thoroughly until floes form. These floes may be separated from the mixture by filtration and eventually washed with water to remove aluminium-containing filtrate absorbed during the filtration.
- water leaching could also be used to selectively solubilize sodium aluminate formed during the oxidising of the spent catalyst in the presence of either sodium carbonate or sodium chloride.
- the water leaching may be carried out at any temperature and pressure, and 50°C at atmospheric pressure has been found to be satisfactory.
- a solution of sodium aluminate from the water leaching step may be reserved for the precipitation of aluminium hydroxide while the water- washed base insoluble residue may be used in the strong or weak inorganic acid cobalt dissolving step.
- the leached residue recovered from the aluminium leaching step typically contains 51 % w/w cobalt, 0.124% w/w platinum and 4.9% w/w aluminium.
- Cobalt and platinum are currently considered to be environmentally toxic and thus dumping of this leached residue is not a viable option. Also, both cobalt and platinum are high value products.
- Cobalt recovery is initiated by dissolving the cobalt and compounds thereof present in the water- washed leached residue of the oxidised catalyst composition with a strong acid such as nitric acid.
- the water washed-leached residue may be contacted with a solution of nitric acid of about 55 % w/v HNO 3 at a temperature of between 80°C and 200°C and at a pressure of between 1 bar and 20 bar, in order to selectively dissolve cobalt.
- this cobalt dissolution step is carried out at 100° and 1 atmospheric pressure.
- the impure cobalt nitrate may be used in the chemical, ceramics Industries and the production of high purity cobalt for use in the electronics and related industries.
- the washed nitric acid insoluble residue which is mainly composed of platinum compounds and impurities, may be used in the step of producing platinum compound.
- the process includes the separating of a substantial portion of the impure cobalt nitrate, i.e. the cobalt rich solution, from the strong acid insoluble residue, i.e. the solid component present after the dissolving step.
- This separation may include a precipitation step during which impurities such as Aluminium and Iron are precipitated out of the cobalt rich solution.
- the separation may be aided by flocculating ultra fine solids using a suitable flocculant, such as ZN92V Zetafloc produced by Zetachem Company.
- a suitable flocculant such as ZN92V Zetafloc produced by Zetachem Company.
- the flocculant may be used as 0.1 % w/w solution.
- the still impure cobalt rich solution is then purified by selectivley removing substantially all only cobalt ions from the cobalt rich solution by solvent extraction.
- the impurities may remain in the aqueous phase after the solvent extraction step.
- the cobalt rich solution from the precipitation step typically contains Co, Pt, Al, Fe, NO3 " and NH 4 + ions.
- a suitable type of an acidic extractant like di- (2-ethylhexyl) phosphoric acid (DEHPA) and tributylphosphate (TBP) as a modifier in illuminating paraffin for extracting Co ions from the cobalt rich solution may be used.
- DEHPA di- (2-ethylhexyl) phosphoric acid
- TBP tributylphosphate
- this solvent extractant is used as an ammonium salt which assists in keeping the pH of the mixture relatively constant after contacting the acidic cobalt rich solution with the organic extractant phase.
- the aqueous phase recovered from the solvent extraction may be used in the precipitation of Fe and Al ions step, while the loaded organic phase (containing mainly Co ions) is reserved for a stripping step.
- the Co loaded organic phase is contacted with a solution of the stripping agent, such as a solution of nitric acid, to remove the extracted species i.e. Co ions.
- a solution of the stripping agent such as a solution of nitric acid
- the purified cobalt rich solution is finally crystallised to form a red- brown crystalline cobalt nitrate salt, Co(NO 3 )2.6H 2 O or Co(NO 3 )z4H2O depending on the retention time when heating the crystals at 55°C.
- This salt is currently used in the production of high purity cobalt and also electronics and chemical industries.
- the crystallisation liquor containing free water and nitric acid may be utilised in the crystallisation step of cobalt nitrate or in the dissolution step of cobalt from the washed insoluble basic residue.
- Platinum is recovered from the nitric acid insoluble solid component from the cobalt dissolution step by dissolving the platinum and compounds thereof, as well as non-cobalt and /or non-cobalt compound impurities from the cobalt rich solution out of the solid component to obtain a platinum rich solution.
- the dissolving of platinum may be achieved by a mixture of HCl and HNO 3 or by using H 2 O 2 and HCl or HCl and Cl 2
- the dissolved platinum may be precipitated out of the platinum rich solution by using NaOH and/or NH 4 CI to form platinum salts complex which can be recovered by a liquid: solid separation process such as filtration.
- the recovered aluminium, cobalt and platinum, and/or compounds or salts thereof may be further processed. Specific Description and Examples
- the spent catalyst composition from a Fischer-Tropsch reaction for the industrial synthesis of certain hydrocarbons from carbon monoxide and hydrogen typically contains about 60 to 75 % of the organic content.
- This spent catalyst is initially heated to a temperature ranging from 700 to 1000°C at atmospheric pressure for 2 to 6 hr in the presence of air to oxidise the organic material.
- a high temperature furnace maximum temperature of the furnace is 1400°C was used for the heating.
- the spent catalyst composition was oxidised in the presence of either sodium carbonate or sodium chloride to prevent the formation of the spinels such as cobalt aluminate (C0 2 AIO 4 ) and cobalt (II) dicobalt (III) oxide (Co 3 O 4 ) during the oxidising step.
- the aluminium oxide or cobalt oxide that is present in the spinels may possibly dissolve with difficulty in a solution of sodium hydroxide or mineral acid solution.
- sodium oxide from either sodium carbonate or sodium chloride could possibly react with water-insoluble aluminium oxide to form water-soluble compounds such as sodium aluminate or silicate.
- the oxidised spent catalyst composition sample produced in this step is digested with either water or a weak solution of sodium hydroxide (approximately 10 to 25 % w/w NaOH) at a relatively high temperature ranging from 90 to 230°C and at high pressure ranging from 1 to 20 bars.
- a weak solution of sodium hydroxide approximately 10 to 25 % w/w NaOH
- the main objective of the oxidising step is to burn out almost all of the organic material present in the spent catalyst composition prior to the leaching step as this organic material can decompose the lixiviant reagents during the leaching step.
- a second sample of free flowing powder and sodium carbonate or sodium chloride were mixed together using solid to solid ratio of 1 :1 (a sample of flowing powder: either sodium carbonate or sodium chloride) and finally, reoxidised under the above conditions. Subsequently, a sample of free flowing powder produced after a self-supporting combustion and a sample after oxidising the spent catalyst at various temperatures were submitted for the organic carbon analysis.
- the loss on ignition (L.O.I) analysis of a free flowing powder formed during self-supporting combustion was determined to be 2.7 %. This implies that the organic material was still contained in the free flowing powder after the self-supporting combustion.
- the L.O.I of the final oxidised spent catalyst was determined to be ⁇ 0.1. This implies that all of the residual carbon was effectively removed after the second oxidising step.
- the oxidised spent catalyst from the waxy lumps of the spent catalyst composition typically contains about 60 to 65 % AI 2 O3, 18.7 to 19.6 % w/w Co and 0.046 to 0.05 % w/w Pt.
- a solution of sodium hydroxide of about 20 to 50% w/w NaOH was used to selectively and efficiently dissolve aluminium oxide at relatively high temperatures ranging from 1 10 to 170°C and at high pressures ranging from 5 to 20 bars with substantially no dissolution of cobalt and platinum from the spent catalyst.
- water leaching was used to selectively solubilize sodium aluminate formed during the calcination of the spent catalyst in the presence of either sodium carbonate or sodium chloride.
- the spent catalyst sample which was oxidised in the presence of either sodium carbonate or sodium chloride was digested with water at 90°C at atmospheric pressure to remove water soluble sodium aluminate.
- the sodium hydroxide-insoluble residue was separated from the leach liquor by normal filtration and washed thoroughly with enough water to remove the residual leach liquor from the filtercake.
- two steps of leaching were used. In these two steps of leaching, the filtercake from the first leaching step was contacted with a fresh solution of sodium hydroxide and leached under above-mentioned conditions.
- the water -washed residue was dried at 90°C to remove free water.
- Cytec flocculant Approximately 2 % w/w of Cytec flocculant was prepared using a solution of sodium hydroxide (about 2 % w/w NaOH). The solution was then conditioned at ambient temperature for one hour to form homogeneous solution. It was further diluted with a solution of sodium hydroxide (2 % w/w NaOH) to produce a final solution containing about 0.25 % w/w of the flocculant.
- the turbidity value of the original slurry prior to the flocculation was measured to 3000 NTU.
- the leach liquor containing mainly sodium aluminate was produced. This solution was stored in a one-litre container for a period of one month. Visual observation indicated that white crystals were formed after keeping the solution for a month. After filtering, washing and drying of the crystals, the final solid sample was submitted for XRD analysis and sent for elemental analysis. Eventually, the filtrate containing mainly sodium hydroxide and small amounts of sodium aluminate can be recycled to the leaching step where it utilizes as a lixiviant.
- Aluminium trihydrate produced during the crystallisation step was calcined at various temperatures (ranging from 400 to 600 Degrees Celsius) in the presence of air. Following the calcination a white powdered product was formed. Subsequently, both product and alumina were submitted for XRD analysis.
- the water washed leached residue recovered from the base leaching step typically contains 51 % w/w cobalt, 0.124% w/w platinum and 4.9% w/w aluminium.
- the leached residue is contacted with a solution of nitric acid of about
- nitric acid comprising of about 400 g of 55 % w/v of nitric acid at 100°Celsius for 4 hr. The experiment was conducted at atmospheric pressure.
- the slurry formed from this leaching step was filtered at room temperature to obtain a filtercake.
- a washing step was included in the experiment using a filtercake to water ratio of 1 :4 to remove the residual leach liquor retained after the leaching step.
- the wash solution was then combined with the leach liquor to form the final parent solution. After drying the washed filtercake, the leached residue was weighed out prior to the cobalt, platinum and aluminium analysis.
- a second leaching step was conducted on the leached residue.
- the leached residue was contacted with fresh nitric acid solution and the leaching of the mixture was then carried out under above-mentioned leaching conditions
- impure acid leach liquor typically contained 68,3 g/l Co, 5,2 g/l Al, 65 mg/l Pt while the purified acid leach liquor contained 326 mg/l Fe, and 7,7 g/l Co, 18 mg/l Al, 3 mg/l Pt and 4 mg/l Fe.
- the leach liquor was heated to 90°C until its volume was reduced by 50%.
- the concentrated leach liquor was then added to a 250-ml crystalliser and on cooling off the solution, red -brown crystals were formed.
- the crystals were separated by normal filtration and dried at 55°C to further improve their crystallinity. Subsequently, the dried crystals were submitted to XRD analysis and elemental analysis. Concentrations of the substances present in the crystals were reported as percentage (% w/w) in
- Table 9 Composition of crystallised and commercially available cobalt nitrate.
- the retention time of the crystal at 55°C may be increased. This may remove free water retained in the crystals after the filtration. Eventually, an excess of nitric acid should be used during the crystallisation step. 9 Precipitation Of Fe And Al Ions From The Impure Cobalt Nitrate Containing Solution.
- the precipitation of both Fe and Al ions from the impure cobalt containing solution should be firstly conducted.
- the impure cobalt containing solution from the dissolution of the base leached residue step typically 5.2 g/l Al , 0.065 g/l Pt, 0.326 g/l Fe and 68 g/l Co.
- a solution of ammonium hydroxide (about 25 % w/v NH 4 OH) would be used to selectively precipitate both Fe and Al ions from the cobalt-containing solution.
- the filtrate produced in this way could be used in the solvent extraction step where the cobalt ions will be selectively loaded into an organic phase under certain conditions.
- the precipitate containing both Fe and Al formed after the addition of ammonium hydroxide to the impure cobalt-containing solution will be dissolved in a solution of sodium hydroxide to form sodium aluminate.
- This aluminate can be recycled in the precipitation of aluminium hydroxide step.
- a dumping option should be considered for sodium hydroxide insoluble precipitate containing mainly iron hydroxide, which is environmentally friendly by-product.
- the sodium hydroxide insoluble precipitate may be reserved for the platinum dissolution
- the precipitate containing typically Fe and Al was allowed to react with sodium hydroxide (about 25% m/v of NaOH) to form sodium aluminate which is eventually recycled to the precipitation of aluminium hydroxide step. While the sodium hydroxide insoluble precipitate, which contains Fe, may possibly be dumped or dissolved in a solution of sulphuric acid or nitric acid to form iron salts that are suitable for water purification.
- Table 11 The precipitation efficiency of metal ions at various pH when using ammonium hydroxide.
- the original aqueous filtrate from the precipitation step typically contains Co, Pt, Al, Fe, NO 3 " and NH 4 + ions.
- the organic phase salt which is suitable for the extraction of the Co ions was prepared as follows: 1000 ml of ammonium hydroxide solution (about 12.5 % w/v NH 4 OH was contacted with an equal volume of the organic phase containing 40% w/w DEHPA, 20 % w/w TriButylPhosphate (TBP) and 40 % w/w illuminating paraffin at room temperature. This mixture was stirred for 15 min. The two phases were allowed to separate at room temperature. The organic phase salt produced in this way contains ammonium ions and is suitable for the extraction of Co ions from the filtrate at pH 4.
- the loaded organic phase produced in this experiment could possibly be utilised in the stripping step where finally cobalt nitrate will be produced.
- the colour of the mixture (organic phase and aqueous phase) turned to pink at low temperature (ranging from 30 to 45°C) during the solvent extraction experiment.
- low temperature ranging from 30 to 45°C
- high temperature ranging from 50 to 90°C
- the pink colour indicates the presence of octahedral cobalt complex in the mixture whilst the blue indicates tetrahedral cobalt complex. It is therefore considered that the colour change is definitely attributed to a change in co-ordination state of the cobalt complex.
- the colour of the loaded organic phase still remained blue even if the temperature of the loaded organic phase was lowered to an ambient temperature.
- Table 12 Extraction efficiency of metal ions from the original aqueous filtrate by solvent extraction.
- solvent extraction method gave good performance in terms of both Co and Pt ions extraction efficiency and phase separation when using di-(2-ethylhexyl) phosphoric acid as an extractant and tributyl phosphate as a modifier.
- PGM Group Metals
- Pt can dissolve in 6 to 18 M aqua regia at 80 to 90 Degrees Celsius at atmospheric pressure to form a chloroplatinic acid, H 2 PtCl 6 .
- 6 M acid solution is used.
- the platinum acid obtained in this fashion could be reserved for the preparation of platinum sponge and various salts.
- the platinum dissolution in aqua regia is preferred because the yield of the Pt from the ore is around 99%.
- the residue produced during the nitric acid leaching was firstly calcined at 700 °C for 6 h to oxidise the flocculant present in the residue. Subsequently 20 g of the nitric acid insoluble residue containing 7.67% Pt was dissolved in 1000ml of aqua regia (3HCI: 1 HNO 3 ) at 80 °C to 90 °C at atmospheric pressure for 4 hr to form a chloroplatinic acid, H 2 PtCI 6 . The latter was separated from the aqua regia insoluble residue through filtration. The platinum acid obtained in this fashion could be reserved for the preparation of platinum sponge and various salts. The blue insoluble residue formed during the dissolution of platinum was dried at 90 °C prior to the submission for XRD analysis. Results
- Table 13 Composition of residue obtained after leaching nitric acid residue with aqua-regia solution.
- a solution of ammonium chloride (about 25%) is used to quantitatively precipitate the Pt(iv) from a platinic acid at 50 to 70 Degrees Celsius in the form of ammonium chloroplatinate, (NH4)2PtCl ⁇ (deep-yellow colour).
- the deep-yellow crystals are recovered with a purity of 99 to 99.5% in greater than
- Table: 14 Composition of diammoniumhexachloroplatinate produced through the sodium-nitric acid leaching process.
- Table 15 The extraction efficiency of metal ions during the Sodium hydroxide-nitric acid-aqua regia leaching process.
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Abstract
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AU2001295097A AU2001295097A1 (en) | 2000-08-29 | 2001-08-29 | Selective recovery of aluminium, cobalt and platinum values from a spent catalyst composition |
US10/363,491 US20040219082A1 (en) | 2000-08-29 | 2001-08-29 | Selective recovery of aluminium, cobalt and platinum values from a spent catalyst composition |
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RU2111791C1 (ru) * | 1997-06-17 | 1998-05-27 | Нижегородский нефтеперерабатывающий научно-исследовательский центр | Способ извлечения платины из отработанных платиносодержащих катализаторов на основе оксида алюминия |
US20010001650A1 (en) * | 1999-03-09 | 2001-05-24 | William P.C. Duyvesteyn | Recovery of nickel and cobalt from ore |
US6315812B1 (en) * | 1999-04-28 | 2001-11-13 | International Pgm Technologies Ltd | Oxidative pressure leach recovery using halide ions |
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- 2001-08-29 AU AU2001295097A patent/AU2001295097A1/en not_active Abandoned
- 2001-08-29 WO PCT/ZA2001/000128 patent/WO2002018663A2/fr active Application Filing
- 2001-08-29 US US10/363,491 patent/US20040219082A1/en not_active Abandoned
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Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2007099365A1 (fr) * | 2006-03-03 | 2007-09-07 | Johnson Matthey Plc | Régénération de catalyseur |
US7754635B2 (en) | 2006-03-03 | 2010-07-13 | Johnson Matthey Plc | Catalyst reprocessing |
AU2007220324B2 (en) * | 2006-03-03 | 2011-01-06 | Johnson Matthey Plc | Catalyst reprocessing |
EP2170479A4 (fr) * | 2007-06-18 | 2012-04-11 | Crisolteq Oy | Procédé de récupération |
US8282705B2 (en) | 2007-06-18 | 2012-10-09 | Crisolteq Oy | Method for recovering metals from a spent catalyst composition |
Also Published As
Publication number | Publication date |
---|---|
US20040219082A1 (en) | 2004-11-04 |
WO2002018663A8 (fr) | 2004-05-06 |
WO2002018663A3 (fr) | 2002-08-22 |
AU2001295097A1 (en) | 2002-03-13 |
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