WO2005042153A1 - The use of activated granulates of base metals for organic transformations - Google Patents
The use of activated granulates of base metals for organic transformations Download PDFInfo
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- WO2005042153A1 WO2005042153A1 PCT/EP2003/011702 EP0311702W WO2005042153A1 WO 2005042153 A1 WO2005042153 A1 WO 2005042153A1 EP 0311702 W EP0311702 W EP 0311702W WO 2005042153 A1 WO2005042153 A1 WO 2005042153A1
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- WIPO (PCT)
- Prior art keywords
- optionally
- caustic
- granules
- hydrogenation
- ilia
- Prior art date
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- 239000008187 granular material Substances 0.000 title claims abstract description 260
- 239000010953 base metal Substances 0.000 title claims abstract description 25
- 230000009466 transformation Effects 0.000 title claims description 3
- 238000000844 transformation Methods 0.000 title description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 116
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 106
- 239000000956 alloy Substances 0.000 claims abstract description 106
- 239000000843 powder Substances 0.000 claims abstract description 85
- 238000002156 mixing Methods 0.000 claims abstract description 83
- 239000003518 caustics Substances 0.000 claims abstract description 77
- 239000000203 mixture Substances 0.000 claims abstract description 73
- 239000011230 binding agent Substances 0.000 claims abstract description 38
- 238000002360 preparation method Methods 0.000 claims abstract description 37
- 239000002184 metal Substances 0.000 claims abstract description 32
- 230000003197 catalytic effect Effects 0.000 claims abstract description 31
- 229910052751 metal Inorganic materials 0.000 claims abstract description 31
- 230000000737 periodic effect Effects 0.000 claims abstract description 27
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 18
- 150000002739 metals Chemical class 0.000 claims abstract description 17
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 14
- 239000002243 precursor Substances 0.000 claims abstract 36
- 239000012633 leachable Substances 0.000 claims abstract 24
- 238000005507 spraying Methods 0.000 claims abstract 24
- 239000011261 inert gas Substances 0.000 claims abstract 12
- 238000010791 quenching Methods 0.000 claims abstract 12
- 230000000171 quenching effect Effects 0.000 claims abstract 12
- 230000006641 stabilisation Effects 0.000 claims abstract 12
- 238000011105 stabilization Methods 0.000 claims abstract 12
- 239000003054 catalyst Substances 0.000 claims description 218
- 238000000034 method Methods 0.000 claims description 89
- 238000005984 hydrogenation reaction Methods 0.000 claims description 53
- 230000008569 process Effects 0.000 claims description 51
- 230000004913 activation Effects 0.000 claims description 41
- 229910052759 nickel Inorganic materials 0.000 claims description 27
- 238000005469 granulation Methods 0.000 claims description 23
- 230000003179 granulation Effects 0.000 claims description 23
- BTGRAWJCKBQKAO-UHFFFAOYSA-N adiponitrile Chemical compound N#CCCCCC#N BTGRAWJCKBQKAO-UHFFFAOYSA-N 0.000 claims description 22
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- 229910052802 copper Inorganic materials 0.000 claims description 13
- 150000002894 organic compounds Chemical class 0.000 claims description 12
- DYSXLQBUUOPLBB-UHFFFAOYSA-N 2,3-dinitrotoluene Chemical compound CC1=CC=CC([N+]([O-])=O)=C1[N+]([O-])=O DYSXLQBUUOPLBB-UHFFFAOYSA-N 0.000 claims description 10
- 229910052742 iron Inorganic materials 0.000 claims description 10
- DLDJFQGPPSQZKI-UHFFFAOYSA-N but-2-yne-1,4-diol Chemical compound OCC#CCO DLDJFQGPPSQZKI-UHFFFAOYSA-N 0.000 claims description 9
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 8
- 239000008103 glucose Substances 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 7
- -1 aromatic nitrocompounds Chemical class 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 150000002825 nitriles Chemical class 0.000 claims description 3
- ZXVONLUNISGICL-UHFFFAOYSA-N 4,6-dinitro-o-cresol Chemical group CC1=CC([N+]([O-])=O)=CC([N+]([O-])=O)=C1O ZXVONLUNISGICL-UHFFFAOYSA-N 0.000 claims description 2
- 150000001336 alkenes Chemical class 0.000 claims description 2
- 150000001345 alkine derivatives Chemical class 0.000 claims description 2
- 150000002466 imines Chemical class 0.000 claims description 2
- 235000000346 sugar Nutrition 0.000 claims description 2
- 150000008163 sugars Chemical class 0.000 claims description 2
- 229920005862 polyol Polymers 0.000 claims 9
- 150000003077 polyols Chemical class 0.000 claims 9
- 208000007976 Ketosis Diseases 0.000 claims 4
- 150000001323 aldoses Chemical class 0.000 claims 4
- 150000002584 ketoses Chemical class 0.000 claims 4
- 150000003839 salts Chemical class 0.000 claims 3
- 241000478345 Afer Species 0.000 claims 1
- 150000001299 aldehydes Chemical class 0.000 claims 1
- 125000003118 aryl group Chemical group 0.000 claims 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims 1
- 150000002576 ketones Chemical class 0.000 claims 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 168
- 239000000243 solution Substances 0.000 description 152
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 103
- 239000004372 Polyvinyl alcohol Substances 0.000 description 101
- 229920002451 polyvinyl alcohol Polymers 0.000 description 101
- 239000007864 aqueous solution Substances 0.000 description 57
- 235000011121 sodium hydroxide Nutrition 0.000 description 56
- 230000015572 biosynthetic process Effects 0.000 description 54
- 229910000838 Al alloy Inorganic materials 0.000 description 31
- 238000003306 harvesting Methods 0.000 description 31
- 239000010949 copper Substances 0.000 description 27
- 238000005187 foaming Methods 0.000 description 26
- 239000000463 material Substances 0.000 description 26
- 238000003756 stirring Methods 0.000 description 26
- 238000005406 washing Methods 0.000 description 26
- 239000011651 chromium Substances 0.000 description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- 238000013019 agitation Methods 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 18
- 239000002245 particle Substances 0.000 description 17
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 15
- 229910000990 Ni alloy Inorganic materials 0.000 description 12
- 229910052804 chromium Inorganic materials 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 238000007873 sieving Methods 0.000 description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
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- 229910000599 Cr alloy Inorganic materials 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000008240 homogeneous mixture Substances 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229910052750 molybdenum Inorganic materials 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- FHKPTEOFUHYQFY-UHFFFAOYSA-N 2-aminohexanenitrile Chemical compound CCCCC(N)C#N FHKPTEOFUHYQFY-UHFFFAOYSA-N 0.000 description 3
- 229910000531 Co alloy Inorganic materials 0.000 description 3
- 239000012018 catalyst precursor Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- PFBWBEXCUGKYKO-UHFFFAOYSA-N ethene;n-octadecyloctadecan-1-amine Chemical compound C=C.CCCCCCCCCCCCCCCCCCNCCCCCCCCCCCCCCCCCC PFBWBEXCUGKYKO-UHFFFAOYSA-N 0.000 description 3
- 229910001092 metal group alloy Inorganic materials 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 229910000640 Fe alloy Inorganic materials 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 229910001182 Mo alloy Inorganic materials 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 239000002826 coolant Substances 0.000 description 2
- 238000006356 dehydrogenation reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
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- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- 238000006317 isomerization reaction Methods 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 239000006262 metallic foam Substances 0.000 description 2
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- 150000002828 nitro derivatives Chemical class 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
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- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- VOZKAJLKRJDJLL-UHFFFAOYSA-N 2,4-diaminotoluene Chemical compound CC1=CC=C(N)C=C1N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 239000007868 Raney catalyst Substances 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 229910001297 Zn alloy Inorganic materials 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- FJMNNXLGOUYVHO-UHFFFAOYSA-N aluminum zinc Chemical compound [Al].[Zn] FJMNNXLGOUYVHO-UHFFFAOYSA-N 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
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- 239000003426 co-catalyst Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
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- 238000006297 dehydration reaction Methods 0.000 description 1
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- 239000007789 gas Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
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- 239000010931 gold Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000007327 hydrogenolysis reaction Methods 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000007420 reactivation Effects 0.000 description 1
- 238000006268 reductive amination reaction Methods 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000011684 sodium molybdate Substances 0.000 description 1
- 235000015393 sodium molybdate Nutrition 0.000 description 1
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- QFJIELFEXWAVLU-UHFFFAOYSA-H tetrachloroplatinum(2+) dichloride Chemical compound Cl[Pt](Cl)(Cl)(Cl)(Cl)Cl QFJIELFEXWAVLU-UHFFFAOYSA-H 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 230000035899 viability Effects 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J25/00—Catalysts of the Raney type
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J25/00—Catalysts of the Raney type
- B01J25/02—Raney nickel
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/31—Density
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0063—Granulating
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/30—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
- C07C209/32—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups
- C07C209/36—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/44—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of carboxylic acids or esters thereof in presence of ammonia or amines, or by reduction of nitriles, carboxylic acid amides, imines or imino-ethers
- C07C209/48—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of carboxylic acids or esters thereof in presence of ammonia or amines, or by reduction of nitriles, carboxylic acid amides, imines or imino-ethers by reduction of nitriles
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/14—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group
- C07C29/141—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group with hydrogen or hydrogen-containing gases
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/143—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of ketones
- C07C29/145—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of ketones with hydrogen or hydrogen-containing gases
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/17—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/17—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds
- C07C29/172—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds with the obtention of a fully saturated alcohol
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/009—Preparation by separation, e.g. by filtration, decantation, screening
Definitions
- the present invention relates to the use of granulated forms, for the production of fixed bed activated base metal catalysts.
- These granulated forms could either be filled into the reactor as is, or they can be sintered together to form a desired structure.
- the common forms could include spheres, cylinders, ovals, and other forms as well.
- the main advantages of these catalysts are their relatively low production costs, low bulk density and high porosity.
- Activated metal catalysts are known in the field of chemical engineering as Raney-type catalysts. They are used, largely in powder form, for a large number of hydrogenation, dehydrogenation, isomerization and hydration reactions of organic compounds. These powdered catalysts are prepared from an alloy of a catalytically-active metal, also referred to herein as a catalyst metal, with a further alloying componet which is soluble in alkalis. Mainly nickel, cobalt, copper, or iron are used as catalyst metals. Aluminum is generally used as the alloying component which is soluble in alkalis, but other components may also be used, in particular zinc and silicon or mixtures of these with aluminum.
- Raney alloys are generally prepared by the ingot casting process.
- a mixture of the catalyst metal and, for example, aluminum are first melted and casted into ingots.
- Typical alloy batches on a production scale amount to about ten to one hundred kg per ingot.
- cooling times of up to two hours were obtained. This corresponds to an average rate of cooling of about 0. 2 /s.
- rates of 10 2 to 10 6 K/s are achieved in processes where rapid cooling is applied (for, example an atomizing process). The rate of cooling is affected in particular by the particle size and the cooling medium (see Materials Science and Technology edited by R. . Chan, P. Haasen, E. J. Kramer, Vol.
- the Raney alloy is first finely milled if it has not been produced in the desired powder form during preparation. Then the aluminum is partly (and if need be, totally) removed by extraction with alkalis such as, for example, caustic soda solution to activate the alloy powder. Following extraction of the aluminum the alloy power has a high specific surface area (BET) , between 20 and 100 m2/g, and is rich in active hydrogen.
- BET specific surface area
- the activated catalyst powder is pyrophoric and stored under water or organic solvents or is embedded in organic- compounds which are solid at room temperature.
- Powdered catalysts have the disadvantage that they can be ⁇ used only in a batch process and, after the catalytic reaction, have to be separated from the reaction medium by costly sedimentation and/or filtration. Therefore a variety of processes for preparing moulded items which lead to activated metal fixed-bed catalysts after extraction of the aluminum have been disclosed.
- coarse particulate Raney alloys i.e., Raney alloys which have only been coarsely milled, are obtainable and these can be activated by a treatment with caustic soda solution. Extraction and activation then occurs only in a surface layer the thickness of which can be adjusted by the conditions used during extraction.
- Patent application EP 0 648 534 Bl describes shaped, activated Raney metal fixed-bed catalysts and their preparation. To avoid the disadvantages described above, e.g., poor mechanical stability resulting from activating the outer layer of the particle, these catalysts were stabilized with the appropriate amount of binder. These catalysts were prepared by forming a homogeneous mixture of at least one catalyst alloy powder, pore builders, and a binder. The catalyst alloys each contain at least one catalytically active catalytic metal and an extractable alloying component. The pure catalyst metals or mixtures thereof which do not contain extractable components can be used as binders. The use of binder material in an amount of 0. 5 to 20 weight percent with respect to the catalyst alloy, is essential in order to achieve sufficient mechanical stability after activation.
- An object of the present invention is therefore to provide fixed bed activated base metal catalysts in the form of designed granules which largely avoids the disadvantages of the above known fixed-bed catalysts.
- the above and other objects of the invention are achieved by producing granules out of particles of the desired alloys along with organic and/or inorganic binders, calcining these granules, and activating them in caustic solution in order to make them catalytic active.
- organic and/or inorganic binders may or may not be necessary to obtain the appropriate catalyst granules.
- These granules are formed by mixing the desired alloy powder (s) with organic and/or inorganic binders and water in such a way that the particles agglomerate into granules.
- granules can be made by mixing the above mentioned mixture between two parralell plates (plate granulator) , or in any other suitable pieces of equipment such as Eirich or Lodige mixers .
- Such mixers form granules by the use of aggitators in combination with a rotating bottom plate, only a rotating bottom plate where variously oriented baffles may be put in place, or only aggitators. It would also be possible to use aggitators, rotating bottom plates, and their combination in various sequences in order to create various effects with the structure of the resulting granules .
- the granules are dried, calcined, activated in caustic, and washed.
- the organic binder can be chosen such that it expands orarrangingfoams up" during either mixing, drying or calcination thereby producing a metallic foam structure that exhibits a high porosity while maintaining its mechanical strength.
- the major advantages of this invention are its low bulk density, its high porosity, its relatively high percentage of activated metal, its relatively low production cost, and the activity these materials exhibit per kilogram of metal as well as the activity the have on a per liter of catalyst basis.
- Suitable promoters include metallic elements from the groups 1A, 2A, 3B, 4B, 5B, 6B, 7B, 8, IB, 2B, 3A, 4A, 5A, the rare earth elements and 6A of the periodic table.
- the resulting granules of the above mentioned material may be screened to remove the remaining powder and this powder may also be recycled back into granulation process so that the yield of the granules with respect to the alloy powder is very high and commercially viable.
- Another aspect of this invention is that the granulation can be started with one type of powder and the type of powder added to the granulation process may be changed as the granules reach a specific size. This change of granulation powder may be performed a number of times and this could be done continuously during the granulation, or the granules may be removed, dried and optionally calcined before they are added again to the granulation apparatus for the addition of new granulation powders.
- the approprite granulation powders for this process include Raney-type catalytic metal / Al alloys, inert powders, pore builders and binders.
- the Raney-type catalytic metal / Al alloys may be slowly cooled or rapidly cooled alloys as described above, and its average particle size may range from ⁇ 1 to 200 ⁇ m or more as required by the desired catalyst properties .
- the granules may be heated for the removal of the suspending liquid (e.g., water) during granulation so that the granules may proceed directly to calcination and/activation.
- the suspending liquid may also be left in the granules after granulation and in this case it may be removed by drying before or during calcination.
- the suspending liquid may be left in the granule so as to facilitate the formation of granule clusters that provide structures that pack looser in a reactor and lead to lower pressure drops in comparison to other fixed bed geometries.
- Fixed bed granules of catalyst precursors are formed by the addition of one or more Raney-type alloy (s) to a mixture of an organic binder (e.g., polyvinyl alcohol), water, optionally an inorganic binder (e.g., Ni, Co, Fe, Cu or other metal powders) , optionally promoters, and optionally pore builders followed by the aggitation of this mixture for the formation of granules.
- an organic binder e.g., polyvinyl alcohol
- an inorganic binder e.g., Ni, Co, Fe, Cu or other metal powders
- promoters e.g., Ni, Co, Fe, Cu or other metal powders
- pore builders optionally pore builders followed by the aggitation of this mixture for the formation of granules.
- the aggitation of this mixture into granules can be performed by placing the powder between two plates where one rotates differently than the other or by mixing this powder with aggitators, a rotating bottom plate with and without baffles and/or with both the aggitator and the forementioned rotating bottom plate together.
- Plate granulators, Eirich mixers und Lodige mixers are examples of such equipment that may be used in this granulation process.
- These resulting granules are then calcined to the desired temperature (e.g. from 100 to 1200°C), activated with an alkali leaching solution (e.g.
- an aqueous caustic solution an aqueous caustic solution
- washed with basic (e.g., caustic) and/or pH neutral aqueous solutions for the production of this fixed bed activated base metal catalyst.
- basic (e.g., caustic) and/or pH neutral aqueous solutions for the production of this fixed bed activated base metal catalyst.
- the choice of an organic binder, the types of other components, the ratio of the various components and the treatment of the resulting granules may be done so that the final fixed body foams up and create a metallic foam structure that has a high porosity and lower bulk density. This higher porosity can lead to a more complete leaching process and it leads to a catalyst with a higher activity for catalytic chemical reactions.
- the bulk density of the resulting fixed bed catalyst is very important for highly active catalysts. While the standard fixed bed activated base metal catalysts have bulk densities ranging from 2.4 to 1.8 kg/1, bulk densities similar to other fixed bed applications such as 1.0 to 1.8 kg/1 are highly desirable to keep the cost to fill a commercial reactor at a minimum.
- the ratio by weight of catalyst metal to extractable alloying component in the catalyst alloy is, as is conventional with Raney alloys, in the range from 20:80 to 80:20.
- Catalysts according to the invention may also be doped with other metals in order to have a positive effect on the catalytic properties of the invention.
- the purpose of this type of doping is, for example, to improve the activity, selectivity, and lifetime of the catalyst in a specific reaction. Doping metals are frequently also called promoters.
- the doping or promoting of Raney catalyst is described for example in U.S. patent 4,153, 578 and DE-AS 21 01 856 in DE-OS 21 00 373 and in the DE-AS 2053799.
- any known metal alloys with extractable elements such as aluminum zinc and Silicon maybe used for the present invention.
- Suitable promoters are transition elements in groups of 3B to 7B and 8 and group IB of the Periodic Table of Elements and also the rare-earth metals. The other elements mentioned previously in this document are also considered to be suitable promoters. They are also used in an amount of up to 20 wt% or more, with respect of the total weight of catalyst. Chromium, manganese, iron, cobalt, vanadium, tantalum, titanium, tungsten, rhenium, platinum, palladium, ruthenium, nickle, copper, silver, gold, and/or molybdenum and metals from platinum group are preferably used as promoters.
- the promoting elements could be added as alloying constituents in the catalyst alloy or they could be added to the catalyst after activation.
- promoters may be added as binders, they may be present as separate alloy powders with extractable elements and/or, they may be added to the catalyst after calcination and before activation. Optimum adjustment of the catalyst properties to the particular catalyst process is thus possible.
- Raney-type catalyst precursors resulting from calcination are also very important with regard the economic viability of invention. They are not pyrophoric and can be handled and transported without difficulty. Activation can be performed by the user shortly before use. Storage under water or organic solvents or embedding in organic compounds is not required for the catalyst precursors.
- Another part of this invention is the use of these activated metal granules for catalytic chemical reactions such as the hydrogenation, isomerization, hydration, reductive amination, reductive alklyation, dehydration, oxidation and dehydrogenation of organic compounds .
- These catalysts are preferred for the continuous hydrogenation of organic compounds such as nitro compounds, nitriles, imines, carbonyl compounds, alkenes, alkynes and aromatic compounds. These moeities may have already existed in the reactant(s) or they may have been incorporated into the reactant(s) just prior or during the reaction. These reactants may be sugars, nitriles, dinitriles, nitro compound, dinitro compounds and multifunctional compounds..
- These catalysts may also be used for the removal of some groups, such as, halides and sulfur containing compounds (e.g., thiols) via their hydrogenolysis.
- Example 1 Activated Ni / Al granules from a casted Ni / Al alloy (1 st Ni catalyst version)
- the remaining powder and the undersized granules could be recycled to the next batch, and the oversize particles can be ground before being recycled in the same manner.
- the 2 to 4 mm granules were treated in air while ramping the temperature from 25°C to 400°C over 60 minutes followed by a 120 minute soak at 400°C before being ramped to 800°C over 90 minutes followed by a 120 minute soak at 800°C.
- the granules were then cooled, packed into a basket that was lowered into a stirring 20-wt.% NaOH aqueous solution at 90°C and activated in this fashion for 1 hour. Another option for this activation would be to circulate the 90°C 20-wt.% NaOH aqueous solution through a fixed bed of the catalyst for 1 hour.
- the catalyst was initially washed with a caustic solution and this was followed by washing with water.
- Example 2 Activated Ni / Al granules from a casted Ni / Al alloy (2 nd Ni catalyst version)
- the bottom plate was adjusted to the rotation rate of 86 rpm for the addition of 10 grams of a 5.7-wt% aqueous polyvinyl alcohol solution and at 30 minutes 10 more grams of the 5.7-wt% aqueous polyvinyl alcohol solution were added as the .bottom plate rotation was readjusted to 43 rpm for the duration of the preparation. From the 30 to 40 minute time interval the mixer was also heated with hot air to 120°C as 20 ml of a 5.7-wt% aqueous polyvinyl alcohol solution was added.
- the remaining powder and the undersized granules could be then recycled to the next batch.
- the > 2.24 mm granules were treated in air while ramping the temperature .from 25°C to 400 °C over 60 minutes followed by a 120 minute soak at 400°C before being ramped to 775°C over 90 minutes followed by a 120 minute soak at 775°C.
- the granules were then cooled, packed into a basket that, was lowered into a stirring 20-wt.% NaOH aqueous solution at 90 °C and activated in this fashion for 1 hour. Another option for this activation would be to circulate the 90°C 20-wt.% NaOH aqueous solution through a fixed bed of the catalyst for .1 ⁇ hour.
- the catalyst was initially washed with a caustic solution and this was followed by washing with water.
- Example 3 Activated Ni / Al granules from a casted Ni / Al alloy (3 rd Ni catalyst version)
- the bottom plate was adjusted to the rotation rate of 86 rpm for the addition of 10 grams of a 5.7-wt% aqueous polyvinyl alcohol solution and at 30 minutes 10 more grams of the 5.7-wt% aqueous polyvinyl alcohol solution were added as the bottom plate rotation was readjusted to 43 rpm for the duration of the preparation. From the 30 to 40 minute time interval the mixer was also heated with hot air to 120 °C as 20 grams of a 5.7-wt% aqueous polyvinyl alcohol solution were added.
- the remaining powder and the undersized granules could be then recycled to the next batch.
- the > 2.24 mm granules were treated in air while ramping the temperature from 25 °C to 400 °C over 60 minutes followed by a 120 minute soak at 400°C before being ramped to 750 °C over 90 minutes followed by a 120 minute soak at 750°C.
- the granules were then cooled, packed into a basket that was lowered into a stirring 20-wt.% NaOH aqueous solution at 90 °C and activated in this fashion for 1 hour. Another option for this activation would be to circulate the 90°C 20-wt.% NaOH aqueous solution through a fixed bed of the catalyst for 1 hour.
- the catalyst was initially washed with a caustic solution and this was followed by washing with water.
- Example 4 Activated Ni / Al granules from a casted Ni / Al alloy (4 th Ni catalyst version)
- the granules were then cooled, packed into a basket that was lowered into a stirring 20-wt.% NaOH aqueous solution at 90 °C and activated in this fashion for 1 hour.
- Another option for this activation would be to circulate the 90°C 20-wt.% NaOH aqueous solution through a fixed bed of the catalyst for 1 hour.
- the catalyst was initially washed with a caustic solution and this was followed by washing with water.
- Example 5 Activated Ni / Al granules from a casted Ni / Al alloy (5 th Ni catalyst version)
- the granules were then cooled, packed into a basket that was lowered into a stirring 20-wt.% NaOH aqueous solution at 90 °C and activated in this fashion for 1 hour.
- Another option for this activation would be to circulate the 90 °C 20-wt.% NaOH aqueous solution through a fixed bed of the catalyst for 1 hour.
- the catalyst was initially washed with a caustic solution and this was followed by washing with water.
- Example 6 Activated Co / Al granules from a casted Co / Al alloy (1 st Co catalyst version)
- the granules were then cooled, packed into a basket that was lowered into a stirring 20-wt.% NaOH aqueous solution at 90 °C and activated in this fashion for 1 hour.
- Another option for this activation would be to circulate the 90°C 20-wt.% NaOH aqueous solution through a fixed bed of the catalyst for 1 hour.
- the catalyst was initially washed with a caustic solution and this was followed by washing with water.
- Example 7 LiOH doped activated Co / Al granules from a casted Co / Al alloy
- the granules were then cooled, packed into a basket that was lowered into a stirring 20-wt.% NaOH aqueous solution at 90°C and activated in this fashion for 1 hour.
- Another option for this activation would be to circulate the 90°C 20-wt.% NaOH aqueous solution through a fixed bed of the catalyst for 1 hour.
- the catalyst was initially washed with a caustic solution and this was followed by washing with water. Before use, the catalyst was treated for 3 hours in a 10%LiOH solution followed by being washed with water.
- Example 8 Activated Cu / Al granules from a casted Cu / Al alloy (1 st Cu catalyst version)
- the remaining powder and the undersized granules could be recycled to the next batch, and the oversize particles can be ground before being recycled in the same manner.
- the 2 to 4 mm granules were treated in air while ramping the temperature from 25°C to 400°C over 240 minutes followed by a 120 minute soak at • 400 °C before being ramped to 900°C over 240 minutes followed by a 120 minute soak at 800°C.
- the granules were then cooled, packed into a basket that was lowered into a stirring 20-wt.% NaOH aqueous solution at 90°C and activated in this fashion for 1 hour.
- Another option for this activation would be to circulate the 90°C 20-wt.% NaOH aqueous solution through a fixed bed of the catalyst for 1 hour.
- the catalyst was initially washed with a caustic solution and this was followed by washing with water.
- Example 9 Pt doped activated Cu / Al granules from a casted Cu / Al alloy
- Example 10 Fe doped activated Cu / Al granules from a casted Cu / Al alloy
- Example 11 Activated Ni / Al granules from a rapidly quenched N 2 sprayed Ni / Al alloy (6 th Ni catalyst version)
- Example 12 Activated Ni / Al granules from a rapidly quenched N 2 sprayed Ni / Al alloy (7 th Ni catalyst version)
- Example 13 Activated Cu / Al granules from a rapidly quenched water sprayed Cu / Al alloy (2 nd Cu catalyst version)
- the > 2.24 mm granules were treated in air while ramping the temperature from 25°C to 400°C over 240 minutes followed by a 120 minute soak at 400°C before being ramped to 900 °C over 240 minutes followed by a 120 minute soak at 900°C.
- the granules were then cooled, packed into a basket that was lowered into a stirring 20-wt.% NaOH aqueous solution at 90°C and activated in this fashion for 1 hour.
- Another option for this activation would be to circulate the 90°C 20-wt.% NaOH aqueous solution through a fixed bed of the catalyst for 1 hour.
- the catalyst was initially washed with a caustic solution and this was followed by washing with water.
- Example 14 Zn doped activated Cu / Al granules from a rapidly quenched water sprayed Cu / Zn / Al alloy
- the granules were then cooled, packed into a basket that was lowered into a stirring 20-wt.% NaOH aqueous solution at 90 °C and activated in this fashion for 1 hour.
- Another option for this activation would be to circulate the 90°C 20-wt.% NaOH aqueous solution through a fixed bed of the catalyst for 1 hour.
- the catalyst was initially washed with a caustic solution and this was followed by washing with water.
- Example 15 Cr doped activated Co / Al granules from a rapidly quenched water sprayed Co / Cr / Al alloy
- the granules were then cooled, packed into a basket that was lowered into a stirring 20-wt.% NaOH aqueous solution at 90°C and activated in this fashion for 1 hour.
- Another option for this activation would be to circulate the 90 °C 20-wt.% NaOH aqueous solution through a fixed bed of the catalyst for 1 hour.
- the catalyst was initially washed with a caustic solution and this was followed by washing with water.
- Example 16 Cr and Li doped activated Co / Al granules from a rapidly quenched water sprayed Co / Cr / Al alloy
- the granules were then cooled, packed into a basket that was lowered into a stirring 20-wt.% NaOH aqueous solution at 90°C and activated in this fashion for 1 hour.
- Another option for this activation would be to circulate the 90°C 20-wt.% NaOH aqueous solution through a fixed bed of the catalyst for 1 hour.
- the catalyst was initially washed with a caustic solution and this was followed by washing with water. Before use, the catalyst was treated for 4 hours in a 10%LiOH solution followed by being washed with water.
- Example 17 Mo doped activated Ni / Al granules from a rapidly quenched nitrogen sprayed Ni / Mo / Al alloy (1 st Mo doped Ni catalyst version)
- the undersized material was placed back into the mixer for 15 minutes of additional mixing followed by sieving out the granules larger than 2.24 mm for a second harvest.
- the undersized material was placed in the mixer for a third time for continued agitation as 10 grams of an aqueous 5.7-wt.% polyvinyl alcohol solution were given to it.
- This third mixing period lasted for 10 minutes and at the end all of the granules larger than 2.24 mm were sieved out for a third harvest.
- the first, second and third harvests from this process were then mixed for the further preparation of this catalyst.
- Another option for this activation would be to circulate the 90 °C 20-wt.% NaOH aqueous solution through a fixed bed of the catalyst for 1 hour.
- the catalyst was initially washed with a caustic solution and this was followed by washing with water.
- Example 18 Activated Ni / Al granules from a rapidly quenched nitrogen sprayed Ni / Al alloy (8 th Ni catalyst version)
- the > 2.24 mm granules were treated in air while ramping the temperature from 25°C to 400°C over 60 minutes followed by a 120 minute soak at 400 °C before being ramped to 900°C over 120 minutes followed by a 180 minute soak at 900°C.
- the granules were then cooled, packed into a basket that was lowered into a stirring 20-wt.% NaOH aqueous solution at 90 °C and activated in this fashion for 1 hour.
- Another option for this activation would be to circulate the 90 °C 20-wt.% NaOH aqueous solution through a fixed bed of the catalyst for 1 hour.
- the catalyst was initially washed with a caustic solution and this was followed by washing with water.
- Example 19 Cr doped activated Ni / Al granules from a rapidly quenched nitrogen sprayed Ni / Cr / Al alloy (1 st Cr doped Ni catalyst version)
- the > 2.24 mm granules were treated in air while ramping the temperature from 25°C to 400°C over 60 minutes followed by a 120 minute soak at 400°C before being ramped to 775°C over 90 minutes followed by a 120 minute soak at 775°C.
- the granules were then cooled, packed into a basket that was lowered into a stirring 20-wt.% NaOH aqueous solution at 90°C and activated in this fashion for 1 hour.
- Another option for this activation would be to circulate the 90°C 20-wt.% NaOH aqueous solution through a fixed bed of the catalyst for 1 hour.
- the catalyst was initially washed with a caustic solution and this was followed by washing with water.
- Example 20 Cr doped activated Ni / Al granules from a rapidly quenched nitrogen sprayed Ni / Cr / Al alloy (2 nd Cr doped Ni catalyst version)
- the > 2.24 mm granules were treated in air while ramping the temperature from 25°C to 400°C over 60 minutes followed by a 120 minute soak at 400°C before being ramped to 800°C over 90 minutes followed by a 120 minute soak at 800°C.
- the granules were then cooled, packed into a basket that was lowered into a stirring 20-wt.% NaOH aqueous solution at 90°C and activated in this fashion for 1 hour.
- Another option for this activation would be to circulate the 90 °C 20-wt.% NaOH aqueous solution through a fixed bed of the catalyst for 1 hour.
- the catalyst was initially washed with a caustic solution and this was followed by washing with water.
- Example 21 Cr and Fe doped activated Ni / Al granules from a rapidly cooled water sprayed Ni / Cr / Fe / Al alloy
- Example 22 Activated Ni / Al granules from a rapidly cooled water sprayed Ni / Al alloy (9 th Ni catalyst version)
- Example 23 Mo doped activated Ni / Al granules from a rapidly cooled water sprayed Ni / Al alloy (2 nd Mo doped Ni catalyst version)
- Another option for this activation would be to circulate the 90°C 20-wt.% NaOH aqueous solution through a fixed bed of the catalyst for 1 hour.
- the catalyst was initially washed with a caustic solution and this was followed by washing with water.
- This catalyst was doped with a sodium molybdate solution and after this post activation doping, the molybdenum content ' of the catalyst was 0.3%.
- the procedure can also be carried out with other Mo containing compounds such as ammonium . heptamolybdate.
- Example 24 Activated Ni / Al granules from a rapidly cooled water sprayed Ni / Al alloy (10 th Ni catalyst version)
- the granules were then cooled, packed into a basket that was lowered into a stirring 20-wt.% NaOH aqueous solution at 90 °C and activated in this fashion for 1 hour.
- Another option for this activation would be to circulate the 90°C 20-wt.% NaOH aqueous solution through a fixed bed of the catalyst for 1 hour.
- the catalyst was initially washed with a caustic solution and this was followed by washing with water.
- Example 25 Mo doped activated Ni / Al granules from a rapidly cooled nitrogen sprayed Ni / Mo / Al alloy (3 rd Mo doped Ni catalyst version)
- the > 2.24 mm granules were treated in air while ramping the temperature from 25°C to 400°C over 60 minutes followed by a 120 minute soak at 400°C before being ramped to 800°C over 120 minutes followed by a 240 minute soak at 1000°C.
- the granules were then cooled, packed into a basket that was lowered into a stirring 20-wt.% NaOH aqueous solution at 90°C and activated in this fashion for 1 hour.
- Another option for this activation would be to circulate the 90 °C 20-wt.% NaOH aqueous solution through a fixed bed of the catalyst for 1 hour.
- the catalyst was initially washed with a caustic solution and this was followed by washing with water.
- Example 26 Pd, Cr and Fe doped activated Ni / Al granules from a rapidly cooled water sprayed Ni / Cr / Fe / Al alloy
- Another option for this activation would be to circulate the 90°C 20-wt.% NaOH aqueous solution through a fixed bed of the catalyst for 1 hour.
- the catalyst was initially washed with a caustic solution and this was followed by washing with water.
- This catalyst was then doped with a palladium nitrate solution that previously had its pH to 6 with sodium carbonate adjusted.
- the end Pd content of the catalyst was 0.2%.
- Comparative Example 1 Shell activated Ni / Al tablets from a rapidly cooled water sprayed Ni / Al alloy
- the trickle phase hydrogenation of glucose was carried out over an activated base metal catalyst in a tube reactor in the presence of hydrogen with a 40% aqueous glucose solution at 140 °C and 50 bar .
- the data from this test are displayed in table 2.
- A The catalyst's bulk density.
- B The percent hexamethylendiamine selectivity.
- C The percent aminocapronitrile selectivity.
- D The percentage of adiponitrile conversion during the reaction.
- E The mmoles of adiponitrile reacted per gram of catalyst per hour.
- F The mmoles of adiponitrile reacted per ml of catalyst per hour.
- Application Example 5 The hydrogenation of adiponitrile via method 2
- A The catalyst' s bulk density.
- B The percent hexamethylendia ine selectivity.
- C The percent aminocapronitrile selectivity.
- D The percentage of adiponitrile conversion during the reaction .
- E The mmoles of adiponitrile reacted per gram of catalyst per hour .
- F The mmoles of adiponitrile reacted per ml of catalyst per hour .
- A The catalyst's bulk density.
- B The percent hexamethylendiamine selectivity.
- C The percent aminocapronitrile selectivity.
- D The percentage of adiponitrile conversion during the reaction.
- E The mmoles of adiponitrile reacted per gram of catalyst per hour.
- F The mmoles of adiponitrile reacted per ml of catalyst per hour.
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Abstract
The preparation of fixed bed activated base metal granules via the mixing of the precursor alloy powder with optionally an organic binder and optionally an inorganic binder to form granules that are dried, calcined for stabilization purposes and then activated in a caustic solution. The precursor alloy can be either slowly cooled or rapidly cooled via contact, quenching, spraying in or spraying with a variety of mediums such as, but not limited to, inert gases and water. The precursor alloy is comprised of a catalytic component, a caustic leachable component and optionally one or more promoters. The catalytic component can consist of one or more metals from groups VIII and Ib of the periodic chart of elements that are optionally promoted with one or more elements from the periodic groups Ia, IIa, IIIa, IVb, Vb, VIb, VIIb, Ib, IIb, IIIa and IVa. The caustic leachable component consists of Al, SI, Zn or mixtures therof.
Description
The Use of Activated Granulates of Base Metals for Organic Transformations
Introduction, and Background
The present invention relates to the use of granulated forms, for the production of fixed bed activated base metal catalysts. These granulated forms could either be filled into the reactor as is, or they can be sintered together to form a desired structure. The common forms could include spheres, cylinders, ovals, and other forms as well. The main advantages of these catalysts are their relatively low production costs, low bulk density and high porosity.
Activated metal catalysts are known in the field of chemical engineering as Raney-type catalysts. They are used, largely in powder form, for a large number of hydrogenation, dehydrogenation, isomerization and hydration reactions of organic compounds. These powdered catalysts are prepared from an alloy of a catalytically-active metal, also referred to herein as a catalyst metal, with a further alloying componet which is soluble in alkalis. Mainly nickel, cobalt, copper, or iron are used as catalyst metals. Aluminum is generally used as the alloying component which is soluble in alkalis, but other components may also be used, in particular zinc and silicon or mixtures of these with aluminum.
These so-called Raney alloys are generally prepared by the ingot casting process. In that' process a mixture of the catalyst metal and, for example, aluminum are first melted and casted into ingots. Typical alloy batches on a production scale amount to about ten to one hundred kg per ingot. According to DE 21 59 736 cooling times of up to two hours were obtained. This corresponds to an average rate of cooling of about 0. 2 /s. In contrast to this, rates of 102
to 106 K/s are achieved in processes where rapid cooling is applied (for, example an atomizing process). The rate of cooling is affected in particular by the particle size and the cooling medium (see Materials Science and Technology edited by R. . Chan, P. Haasen, E. J. Kramer, Vol. 15, Processing of Metals and Alloys, 1991, VCH-Verlag Weinheim, pages 57 to 110) . A process of this type is used in EP 0. 437 788 B 1 in order to prepare a Raney alloy powder. In that process the molten alloy at a temperature of 50 to 500°C above its melting point is atomized and cooled using water and/or a gas. It is also possible to produce rapidly cooled alloys where the molten alloy is added dropwise to a liquid coolant, such as water, to form rapidly cooled granules . These rapidly cooled granules may be ground for use in the production of catalysts.
To prepare a catalyst, the Raney alloy is first finely milled if it has not been produced in the desired powder form during preparation. Then the aluminum is partly (and if need be, totally) removed by extraction with alkalis such as, for example, caustic soda solution to activate the alloy powder. Following extraction of the aluminum the alloy power has a high specific surface area (BET) , between 20 and 100 m2/g, and is rich in active hydrogen. The activated catalyst powder is pyrophoric and stored under water or organic solvents or is embedded in organic- compounds which are solid at room temperature.
Powdered catalysts have the disadvantage that they can be ■ used only in a batch process and, after the catalytic reaction, have to be separated from the reaction medium by costly sedimentation and/or filtration. Therefore a variety of processes for preparing moulded items which lead to activated metal fixed-bed catalysts after extraction of the aluminum have been disclosed. Thus, for example, coarse particulate Raney alloys, i.e., Raney alloys which have only been coarsely milled, are obtainable and these can be
activated by a treatment with caustic soda solution. Extraction and activation then occurs only in a surface layer the thickness of which can be adjusted by the conditions used during extraction.
Substantial disadvantages of catalysts prepared by these prior methods are their poor mechanical stability of the activated outer layer, their low level of porosity, and their relatively very low percentage of activated metal . Since only the outer layer of these catalysts are catalytically active, abrasion leads to rapid deactivation and renewed activation of the deeper lying layers of alloy with caustic soda solution only leads, at best, to partial reactivation.
Patent application EP 0 648 534 Bl describes shaped, activated Raney metal fixed-bed catalysts and their preparation. To avoid the disadvantages described above, e.g., poor mechanical stability resulting from activating the outer layer of the particle, these catalysts were stabilized with the appropriate amount of binder. These catalysts were prepared by forming a homogeneous mixture of at least one catalyst alloy powder, pore builders, and a binder. The catalyst alloys each contain at least one catalytically active catalytic metal and an extractable alloying component. The pure catalyst metals or mixtures thereof which do not contain extractable components can be used as binders. The use of binder material in an amount of 0. 5 to 20 weight percent with respect to the catalyst alloy, is essential in order to achieve sufficient mechanical stability after activation. After shaping the catalyst alloy and the binder with conventional shaping aids and pore producers, the freshly prepared items which are obtained are calcined at temperatures below 850 °C. As a result of sintering processes in the finely divided binder, this produces solid compounds between the individual particles of the catalysts alloy. These compounds, in
contrast to catalyst alloys, are non-extractable or only extractable to a small extent so that a mechanical stable structure is obtained even after activation. As taught in european patent EP 984831 Bl, rapidly cooled alloys with very fine phase structures can be used to produce formed bodies without metallic binders and such technology may also be applicable to the current invention.
An object of the present invention is therefore to provide fixed bed activated base metal catalysts in the form of designed granules which largely avoids the disadvantages of the above known fixed-bed catalysts.
Summary of the invention
The above and other objects of the invention are achieved by producing granules out of particles of the desired alloys along with organic and/or inorganic binders, calcining these granules, and activating them in caustic solution in order to make them catalytic active. Depending on the conditions of catalyst preparation, the desired catalyst properties, and the catalyst alloys being used, the use of organic and/or inorganic binders may or may not be necessary to obtain the appropriate catalyst granules. These granules are formed by mixing the desired alloy powder (s) with organic and/or inorganic binders and water in such a way that the particles agglomerate into granules. These granules can be made by mixing the above mentioned mixture between two parralell plates (plate granulator) , or in any other suitable pieces of equipment such as Eirich or Lodige mixers . Such mixers form granules by the use of aggitators in combination with a rotating bottom plate, only a rotating bottom plate where variously oriented baffles may be put in place, or only aggitators. It would also be possible to use aggitators, rotating bottom plates, and their combination in various sequences in order to
create various effects with the structure of the resulting granules .
After mixing, the granules are dried, calcined, activated in caustic, and washed. The organic binder can be chosen such that it expands or „foams up" during either mixing, drying or calcination thereby producing a metallic foam structure that exhibits a high porosity while maintaining its mechanical strength. The major advantages of this invention are its low bulk density, its high porosity, its relatively high percentage of activated metal, its relatively low production cost, and the activity these materials exhibit per kilogram of metal as well as the activity the have on a per liter of catalyst basis.
The performance of these catalysts may be enhanced by the addition of promoters either in the alloy before activation or their adsorption of the active catalyst after it has been leached with alkalis. Suitable promoters include metallic elements from the groups 1A, 2A, 3B, 4B, 5B, 6B, 7B, 8, IB, 2B, 3A, 4A, 5A, the rare earth elements and 6A of the periodic table.
The resulting granules of the above mentioned material may be screened to remove the remaining powder and this powder may also be recycled back into granulation process so that the yield of the granules with respect to the alloy powder is very high and commercially viable. Another aspect of this invention is that the granulation can be started with one type of powder and the type of powder added to the granulation process may be changed as the granules reach a specific size. This change of granulation powder may be performed a number of times and this could be done continuously during the granulation, or the granules may be removed, dried and optionally calcined before they are added again to the granulation apparatus for the addition of new granulation powders. In these two ways, one could optain granules with layering effects that have specific
types of powders and/or various mixtures thereof at different depths of the granules . The approprite granulation powders for this process include Raney-type catalytic metal / Al alloys, inert powders, pore builders and binders. The Raney-type catalytic metal / Al alloys may be slowly cooled or rapidly cooled alloys as described above, and its average particle size may range from ~1 to 200 μm or more as required by the desired catalyst properties .
During granulation, the granules may be heated for the removal of the suspending liquid (e.g., water) during granulation so that the granules may proceed directly to calcination and/activation. The suspending liquid may also be left in the granules after granulation and in this case it may be removed by drying before or during calcination. The suspending liquid may be left in the granule so as to facilitate the formation of granule clusters that provide structures that pack looser in a reactor and lead to lower pressure drops in comparison to other fixed bed geometries.
Detailed description of invention
The present invention will now be described in further detail. Fixed bed granules of catalyst precursors are formed by the addition of one or more Raney-type alloy (s) to a mixture of an organic binder (e.g., polyvinyl alcohol), water, optionally an inorganic binder (e.g., Ni, Co, Fe, Cu or other metal powders) , optionally promoters, and optionally pore builders followed by the aggitation of this mixture for the formation of granules. The aggitation of this mixture into granules can be performed by placing the powder between two plates where one rotates differently than the other or by mixing this powder with aggitators, a rotating bottom plate with and without baffles and/or with both the aggitator and the forementioned rotating bottom plate together. Plate granulators, Eirich mixers und Lodige mixers are examples of such equipment that may be used in
this granulation process. These resulting granules are then calcined to the desired temperature (e.g. from 100 to 1200°C), activated with an alkali leaching solution (e.g. an aqueous caustic solution), and washed with basic (e.g., caustic) and/or pH neutral aqueous solutions for the production of this fixed bed activated base metal catalyst. The choice of an organic binder, the types of other components, the ratio of the various components and the treatment of the resulting granules may be done so that the final fixed body foams up and create a metallic foam structure that has a high porosity and lower bulk density. This higher porosity can lead to a more complete leaching process and it leads to a catalyst with a higher activity for catalytic chemical reactions.
The bulk density of the resulting fixed bed catalyst is very important for highly active catalysts. While the standard fixed bed activated base metal catalysts have bulk densities ranging from 2.4 to 1.8 kg/1, bulk densities similar to other fixed bed applications such as 1.0 to 1.8 kg/1 are highly desirable to keep the cost to fill a commercial reactor at a minimum.
The ratio by weight of catalyst metal to extractable alloying component in the catalyst alloy is, as is conventional with Raney alloys, in the range from 20:80 to 80:20. Catalysts according to the invention may also be doped with other metals in order to have a positive effect on the catalytic properties of the invention. The purpose of this type of doping is, for example, to improve the activity, selectivity, and lifetime of the catalyst in a specific reaction. Doping metals are frequently also called promoters. The doping or promoting of Raney catalyst is described for example in U.S. patent 4,153, 578 and DE-AS 21 01 856 in DE-OS 21 00 373 and in the DE-AS 2053799.
In principle, any known metal alloys with extractable elements such as aluminum zinc and Silicon maybe used for
the present invention. Suitable promoters are transition elements in groups of 3B to 7B and 8 and group IB of the Periodic Table of Elements and also the rare-earth metals. The other elements mentioned previously in this document are also considered to be suitable promoters. They are also used in an amount of up to 20 wt% or more, with respect of the total weight of catalyst. Chromium, manganese, iron, cobalt, vanadium, tantalum, titanium, tungsten, rhenium, platinum, palladium, ruthenium, nickle, copper, silver, gold, and/or molybdenum and metals from platinum group are preferably used as promoters. The promoting elements could be added as alloying constituents in the catalyst alloy or they could be added to the catalyst after activation. In addition, promoters may be added as binders, they may be present as separate alloy powders with extractable elements and/or, they may be added to the catalyst after calcination and before activation. Optimum adjustment of the catalyst properties to the particular catalyst process is thus possible.
The Raney-type catalyst precursors resulting from calcination are also very important with regard the economic viability of invention. They are not pyrophoric and can be handled and transported without difficulty. Activation can be performed by the user shortly before use. Storage under water or organic solvents or embedding in organic compounds is not required for the catalyst precursors.
Another part of this invention is the use of these activated metal granules for catalytic chemical reactions such as the hydrogenation, isomerization, hydration, reductive amination, reductive alklyation, dehydration, oxidation and dehydrogenation of organic compounds . These catalysts are preferred for the continuous hydrogenation of organic compounds such as nitro compounds, nitriles, imines, carbonyl compounds, alkenes, alkynes and aromatic
compounds. These moeities may have already existed in the reactant(s) or they may have been incorporated into the reactant(s) just prior or during the reaction. These reactants may be sugars, nitriles, dinitriles, nitro compound, dinitro compounds and multifunctional compounds.. These catalysts may also be used for the removal of some groups, such as, halides and sulfur containing compounds (e.g., thiols) via their hydrogenolysis.
The examples which follow are used to explain the invention in more detail. Although only a few prepared embodiments of the invention are presented in the examples, the present invention enables a person skilled in the art to prepare activated Raney-type fixed-bed catalysts with a wide range of parameters which can be adapted to the particular requirements of the application.
Example 1: Activated Ni / Al granules from a casted Ni / Al alloy (1st Ni catalyst version)
In an Eirich mixer 925 grams of a 53%Ni / 47%A1 casted alloy were mixed together with 75 grams of Ni powder and 60.2 grams of polyvinyl alcohol for 2 minutes while the bottom plate rotated at 86 rpm- and the agitator spun at 1506 rpm. This was followed by the careful addition of 85 grams of water while the mixture continued to mix. After mixing for 45 additional minutes, various amounts of 53%Ni / 47%A1 casted alloy, Ni powder, polyvinyl alcohol and water were added carefully to the agitated mixture until the process was stopped after 145 minutes from the start. From start to finish 1248.75 grams of 53%Ni / 47%A1 casted alloy, 101.25 grams of Ni powder, 82.2 grams of polyvinyl alcohol and 177 grams of water were added to the mixture and the above mentioned mixing rpm settings were kept constant throughout the whole procedure. It is important to avoid adding too much water at once because this will cause
excessive foaming and inhibit the formation of the desired granules. In the case of water addition to the granule formation procedure, it is better to add too little than it is to add too much. At the end of the process the granule sizes between 2 and 4 mm were sieved out for catalyst preparation. The remaining powder and the undersized granules could be recycled to the next batch, and the oversize particles can be ground before being recycled in the same manner. The 2 to 4 mm granules were treated in air while ramping the temperature from 25°C to 400°C over 60 minutes followed by a 120 minute soak at 400°C before being ramped to 800°C over 90 minutes followed by a 120 minute soak at 800°C. The granules were then cooled, packed into a basket that was lowered into a stirring 20-wt.% NaOH aqueous solution at 90°C and activated in this fashion for 1 hour. Another option for this activation would be to circulate the 90°C 20-wt.% NaOH aqueous solution through a fixed bed of the catalyst for 1 hour. The catalyst was initially washed with a caustic solution and this was followed by washing with water.
Example 2 : Activated Ni / Al granules from a casted Ni / Al alloy (2nd Ni catalyst version)
In an Eirich mixer heated to 120 °C with hot air about 900 grams of a 53%Ni / 47%A1 casted alloy were mixed together with 50 grams of Ni powder and 30 grams of polyvinyl alcohol for 2 minutes while the bottom plate rotated at 86 rpm and the agitator spun at 1506 rpm. This was followed by the careful addition of 80 grams of an aqueous 5.7-wt.% polyvinyl alcohol solution while the mixture continued to mix. After mixing for 5 minutes the air heater was turned off and after the total mixing time of 10 minutes, the bottom plate was adjusted to a rotation of 43 rpm as 10 more grams of the 5.7-wt% aqueous polyvinyl alcohol solution were added. At 20 minutes the bottom plate was
adjusted to the rotation rate of 86 rpm for the addition of 10 grams of a 5.7-wt% aqueous polyvinyl alcohol solution and at 30 minutes 10 more grams of the 5.7-wt% aqueous polyvinyl alcohol solution were added as the .bottom plate rotation was readjusted to 43 rpm for the duration of the preparation. From the 30 to 40 minute time interval the mixer was also heated with hot air to 120°C as 20 ml of a 5.7-wt% aqueous polyvinyl alcohol solution was added. The careful addition of the 5.7-wt% aqueous polyvinyl alcohol solution continued to the mixing time of 115 minutes at which time the process was stopped and the granules above 2.24 mm were screened out for the preparation of the catalyst. From start to finish 900 grams of 53%Ni / 47%A1 casted alloy, 50 grams of Ni powder and 185 grams of a 5.7- wt% aqueous polyvinyl alcohol solution were added to the mixture. It is important to avoid adding too much solution at once because this will cause excessive foaming and inhibit the formation of the desired granules. In the case of solution addition to the granule formation procedure, it is better to add too little than it is to add too much. The remaining powder and the undersized granules could be then recycled to the next batch. The > 2.24 mm granules were treated in air while ramping the temperature .from 25°C to 400 °C over 60 minutes followed by a 120 minute soak at 400°C before being ramped to 775°C over 90 minutes followed by a 120 minute soak at 775°C. The granules were then cooled, packed into a basket that, was lowered into a stirring 20-wt.% NaOH aqueous solution at 90 °C and activated in this fashion for 1 hour. Another option for this activation would be to circulate the 90°C 20-wt.% NaOH aqueous solution through a fixed bed of the catalyst for .1 ■ hour. The catalyst was initially washed with a caustic solution and this was followed by washing with water.
Example 3: Activated Ni / Al granules from a casted Ni / Al alloy (3rd Ni catalyst version)
In an Eirich mixer heated to 120°C with hot air about 900 grams of a 53%Ni / 47%A1 casted alloy were mixed together with 50 grams of Ni powder and 30 grams of polyvinyl alcohol for 2 minutes while the bottom plate rotated at 86 rpm and the agitator spun at 1506 rpm. This was followed by the careful addition of 80 grams of an aqueous 5.7-wt.% polyvinyl alcohol solution while the mixture continued to mix. After mixing for 5 minutes the air heater was turned off and after the total mixing time of 10 minutes, the bottom plate was adjusted to a rotation of 43 rpm as 10 more grams of the 5.7-wt% aqueous polyvinyl alcohol solution were added. At 20 minutes the bottom plate was adjusted to the rotation rate of 86 rpm for the addition of 10 grams of a 5.7-wt% aqueous polyvinyl alcohol solution and at 30 minutes 10 more grams of the 5.7-wt% aqueous polyvinyl alcohol solution were added as the bottom plate rotation was readjusted to 43 rpm for the duration of the preparation. From the 30 to 40 minute time interval the mixer was also heated with hot air to 120 °C as 20 grams of a 5.7-wt% aqueous polyvinyl alcohol solution were added. The careful addition of the 5.7-wt% aqueous polyvinyl alcohol solution continued to the mixing time of 115 minutes at which time the process was stopped and the granules above 2.24 mm were screened out for the preparation of the catalyst. From start to finish 900 grams of 53%Ni / 47%A1 casted alloy, 50 grams of Ni powder and 185 grams of a 5.7-wt% aqueous polyvinyl alcohol solution were added to the mixture. It is important to avoid adding too much solution at once because this will cause excessive foaming and inhibit the formation of the desired granules. In the case of solution addition to the granule formation procedure, it is better to add too little than it is to add too much. The remaining powder and the undersized granules could be then recycled to the next batch. The > 2.24 mm
granules were treated in air while ramping the temperature from 25 °C to 400 °C over 60 minutes followed by a 120 minute soak at 400°C before being ramped to 750 °C over 90 minutes followed by a 120 minute soak at 750°C. The granules were then cooled, packed into a basket that was lowered into a stirring 20-wt.% NaOH aqueous solution at 90 °C and activated in this fashion for 1 hour. Another option for this activation would be to circulate the 90°C 20-wt.% NaOH aqueous solution through a fixed bed of the catalyst for 1 hour. The catalyst was initially washed with a caustic solution and this was followed by washing with water.
Example 4: Activated Ni / Al granules from a casted Ni / Al alloy (4th Ni catalyst version)
In an Eirich mixer heated to 120 °C with hot air about 900 grams of a 53%Ni / 47%A1 casted alloy were mixed together with 50 grams of Ni powder and 30 grams of polyvinyl alcohol for 2 minutes while the bottom plate rotated at 86 rpm and the agitator spun at 1506 rpm. This was followed by the careful addition of 100 grams of a warm aqueous 5.7- wt.% polyvinyl alcohol solution while the mixture continued to mix. The careful addition of the 5.7-wt% aqueous polyvinyl alcohol solution continued to the mixing time of 80 minutes up to which 340 ml of the 5.7-wt% aqueous polyvinyl alcohol solution have been added to the mixture and at that time a pause in the process was taken in order to sieve out all the granules larger than 2.24 mm. After which the undersized material was placed back into the mixer for the addition of 70 more grams of a 5.7-wt% aqueous polyvinyl alcohol solution at the above mentioned conditions over 30 minutes before this mixture too was screened to the desired granule size of larger than 2.24 mm. The first and second harvests from this process were then mixed for the further preparation of this catalyst. During the granulation of the first and second harvests of
this material, it is important to avoid adding too much solution at once because this will cause excessive foaming and inhibit the formation of the desired granules. In the case of solution addition to the granule formation procedure, it is better to add too little than it is to add too much. The remaining powder and the undersized granules could be then recycled to the next batch. The > 2.24 mm granules were treated in air while ramping the temperature from 25 °C to 400 °C over 60 minutes followed by a 120 minute soak at 400°C before being ramped to 775 °C over 90 minutes followed by a 120 minute soak at 775°C. The granules were then cooled, packed into a basket that was lowered into a stirring 20-wt.% NaOH aqueous solution at 90 °C and activated in this fashion for 1 hour. Another option for this activation would be to circulate the 90°C 20-wt.% NaOH aqueous solution through a fixed bed of the catalyst for 1 hour. The catalyst was initially washed with a caustic solution and this was followed by washing with water.
Example 5 : Activated Ni / Al granules from a casted Ni / Al alloy (5th Ni catalyst version)
In an Eirich -mixer heated to 120 °C with hot air about 900 grams of a 53%Ni / 47%A1 casted alloy were mixed together with 50 grams of Ni powder and 30 grams of polyvinyl alcohol for 2 minutes while the bottom plate rotated at 86 rpm and the agitator spun at 1506 rpm. This was followed by the careful addition of 100 grams of a warm aqueous 5.7- wt.% polyvinyl alcohol solution while the mixture continued to mix. The careful addition of the 5.7-wt% aqueous polyvinyl alcohol solution continued to the mixing time of 80 minutes up to which 3.40 ml of the 5.7-wt% aqueous polyvinyl alcohol solution have been added to the mixture and at that time a pause in the process was taken in order to sieve out all the granules larger than 2.24 mm. After which the undersized material was placed back into the
mixer for the addition of 70 more grams of a 5.7-wt% aqueous polyvinyl alcohol solution at the above mentioned conditions over 30 minutes before this mixture too was screened to the desired granule size of larger than 2.24 mm. The first and second harvests from this process were then mixed for the further preparation of this catalyst. During the granulation of the first and second harvests of this material, it is important to avoid adding too much solution at once because this will cause excessive foaming and inhibit the formation of the desired granules. In the case of solution addition to the granule formation procedure, it is better to add too little than it is to add too much. The remaining powder and the undersized granules could be then recycled to the next batch. The > 2.24 mm granules were treated in air while ramping the temperature from 25°C to 400 °C over 60 minutes followed by a 120 minute soak at 400 °C before being ramped to 750 °C over 90 minutes followed by a 120 minute soak at 750°C. The granules were then cooled, packed into a basket that was lowered into a stirring 20-wt.% NaOH aqueous solution at 90 °C and activated in this fashion for 1 hour. Another option for this activation would be to circulate the 90 °C 20-wt.% NaOH aqueous solution through a fixed bed of the catalyst for 1 hour. The catalyst was initially washed with a caustic solution and this was followed by washing with water.
Example 6: Activated Co / Al granules from a casted Co / Al alloy (1st Co catalyst version)
In an Lδdige mixer heated to 40°C with hot air about 1000 grams of a 50%Co / 50%A1 casted alloy were mixed together with 50 grams of polyvinyl alcohol for 2 minutes while the agitators spun at 390 rpm. This was followed by the careful addition of 90 grams of cold water while the mixture continued to agitate. The careful addition of water continued to the mixing time of 90 minutes and this was
followed by the continued agitation of the mixture until 150 minutes after which the granule sizes between 2 to 4 mm were screened out. From start to finish 1000 grams of 50%Co / 50%A1 casted alloy, 50 grams of polyvinyl alcohol and 110 grams of water were added to the mixture and the agitators spun constantly at 390 rpm throughout the whole procedure. It is important to avoid adding too much water at once because this will cause excessive foaming and inhibit the formation of the desired granules. In the case of water addition to the granule formation procedure, it is better to add too little than it is to add too much. The remaining powder and the undersized granules could be recycled to the next batch, and the oversize particles can be ground before being recycled in the same manner. The 2 to 4 mm granules were treated in air while ramping the temperature from 25°C to 400°C over 60 minutes followed by a 120 minute soak at 400 °C before being ramped to 900°C over 120 minutes followed by a 180 minute soak at 800°C. The granules were then cooled, packed into a basket that was lowered into a stirring 20-wt.% NaOH aqueous solution at 90 °C and activated in this fashion for 1 hour. Another option for this activation would be to circulate the 90°C 20-wt.% NaOH aqueous solution through a fixed bed of the catalyst for 1 hour. The catalyst was initially washed with a caustic solution and this was followed by washing with water.
Example 7 LiOH doped activated Co / Al granules from a casted Co / Al alloy
In an Lδdige mixer heated to 40 °C with hot air about 1000 grams of a 50%Co / 50%A1 casted alloy were mixed together with 50 grams of polyvinyl alcohol for 2 minutes while the agitators spun at 390 rpm. This was followed by the careful addition of 90 grams of cold water while the mixture continued to agitate. The careful addition of water continued to the mixing time of 90 minutes and this was
followed by the continued agitation of the mixture until 150 minutes after which the granule sizes between 2 to 4 mm were screened out. From start to finish 1000 grams of 50%Co / 50%A1 casted alloy, 50 grams of polyvinyl alcohol and 110 grams of water were added to the mixture and the agitators spun constantly at 390 rpm throughout the whole procedure. It is important to avoid adding too much water at once because this will cause excessive foaming and inhibit the formation of the desired granules. In the case of water addition to the granule formation procedure, it is better to add too little than it is to add too much. The remaining powder and the undersized granules could be recycled to the next batch, and the oversize particles can be ground before being recycled in the same manner. The 2 to 4 mm granules were treated in air while ramping the temperature from 25°C to 400 °C over 60 minutes followed by a 120 minute soak at 400°C before being ramped to 900°C over 120 minutes followed by a 180 minute soak at 800°C. The granules were then cooled, packed into a basket that was lowered into a stirring 20-wt.% NaOH aqueous solution at 90°C and activated in this fashion for 1 hour. Another option for this activation would be to circulate the 90°C 20-wt.% NaOH aqueous solution through a fixed bed of the catalyst for 1 hour. The catalyst was initially washed with a caustic solution and this was followed by washing with water. Before use, the catalyst was treated for 3 hours in a 10%LiOH solution followed by being washed with water.
Example 8 : Activated Cu / Al granules from a casted Cu / Al alloy (1st Cu catalyst version)
In an Lδdige mixer heated to 40°C with hot air about 1000 grams of a 50%Cu / 50%A1 casted alloy were mixed together with 50 grams of polyvinyl alcohol for 2 minutes while the agitators spun at 390 rpm. This was followed by the careful addition of 80 grams of cold water while the mixture
continued to agitate. The careful addition of water continued to the mixing time of 90 minutes and this was followed by the continued agitation of the mixture until 130 minutes after which the granule sizes between 2 to 4 mm were screened out. From start to finish 1000 grams of 50%Cu / 50%A1 casted alloy, 50 grams of polyvinyl alcohol and 106 grams of water were added to the mixture. It is important to avoid adding too much water at once because this .will cause excessive foaming and inhibit the formation. of the desired granules. In the case of water addition to the granule formation procedure, it is better to add too little than it is to add too much. The remaining powder and the undersized granules could be recycled to the next batch, and the oversize particles can be ground before being recycled in the same manner. The 2 to 4 mm granules were treated in air while ramping the temperature from 25°C to 400°C over 240 minutes followed by a 120 minute soak at • 400 °C before being ramped to 900°C over 240 minutes followed by a 120 minute soak at 800°C. The granules were then cooled, packed into a basket that was lowered into a stirring 20-wt.% NaOH aqueous solution at 90°C and activated in this fashion for 1 hour. Another option for this activation would be to circulate the 90°C 20-wt.% NaOH aqueous solution through a fixed bed of the catalyst for 1 hour. The catalyst was initially washed with a caustic solution and this was followed by washing with water.'
Example 9: Pt doped activated Cu / Al granules from a casted Cu / Al alloy
In an Lδdige mixer heated to 40 °C with hot air about' 1000 grams of a 50%Cu / 50%A1 casted alloy were mixed together with 50 grams of polyvinyl alcohol for 2 minutes while the agitators spun at 390 rpm. This was followed by the careful addition of 80 grams of cold water while the mixture continued to agitate. The careful addition of water
continued to the mixing time of 90 minutes and this was followed by the continued agitation of the mixture until 130 minutes after which the granule sizes between 2 to 4 mm were screened out. From start to finish 1000 grams of 50%Cu / 50%A1 casted alloy, 50 grams of polyvinyl alcohol and 106 grams of water were added to the mixture. It is important to avoid adding too much water at once because this will cause excessive foaming and inhibit the formation of the desired granules. In the case of water addition to the granule formation procedure, it is better to add too little than it is to add too much. The remaining powder and the undersized granules could be recycled to the next batch, and the oversize particles can be ground before being recycled in the same manner. The 2 to 4 mm granules were treated in air while ramping the temperature from 25°C to 400°C over 240 minutes followed by a 120 minute soak at 400°C before being ramped to 900°C over 240 minutes followed by a 120 minute soak at 800°C. The granules were then cooled, packed into a basket that was lowered into a stirring 20-wt.% NaOH aqueous solution at 90 °C and activated in this fashion for 1 hour. Another option for this activation would be to circulate the 90 °C 20-wt.% NaOH aqueous solution through a fixed bed of the catalyst for 1 hour. The catalyst was initially washed with a caustic solution and this was followed by washing with water. The washed catalyst was then treated in a circulating aqueous solution containing hexachloroplatinum, whose pH value was adjusted up. The doped catalyst was then washed and the final platinum content of the catalyst was 0.3%Pt.
Example 10: Fe doped activated Cu / Al granules from a casted Cu / Al alloy
In an Lδdige mixer heated to 40°C with hot air about 1000 grams of a 50%Cu / 50%A1 casted alloy were mixed together with 50 grams of polyvinyl alcohol for 2 minutes while the . agitators spun at 390 rpm. This was followed by the careful- addition of 80 grams of cold water while the mixture continued to agitate. The careful addition of water continued to the mixing time of 90 minutes and this was followed by the continued agitation of the mixture until
130 minutes after which the granule sizes between 2 to 4 mm were screened out. From start to finish 1000 grams of 50%Cu / 50%A1 casted alloy, 50 grams of polyvinyl alcohol and 106 grams of water were added to the mixture. It is important to avoid adding too much water at once because this will cause excessive foaming and inhibit the formation of the desired granules. In the case of water addition to the granule formation procedure, it is better to add too little than it is to add too much. The remaining powder and the undersized granules, could be recycled to the next batch, and the oversize particles can be ground before being recycled in the same manner. The 2 to 4 mm granules were treated in air while ramping the . temperature from 25°C to 400°C over 240 minutes followed by a 120 minute soak at 400°C before being ramped to 900°C over 240 minutes followed by a 120 minute soak at 800°C. The granules were then cooled, packed into a basket that was lowered into a stirring 20-wt.% NaOH aqueous solution at 90°C and activated in this fashion for 1 hour. Another option for this activation would be to circulate the 90°C 20-wt.% NaOH aqueous solution through a fixed bed of the catalyst for 1 hour. The catalyst was initially washed with a caustic solution and this was followed by washing with water. The washed catalyst was then treated in a circulating aqueous solution containing Iron (III) chloride, whose pH value was
adjusted up. The doped catalyst was then washed and the final iron content of the catalyst was 1.0%Fe.
Example 11 Activated Ni / Al granules from a rapidly quenched N2 sprayed Ni / Al alloy (6th Ni catalyst version)
In an Lδdige mixer heated to 40°C with hot air about 1000 grams of a rapidly quenched N2 sprayed 50%Ni / 50%A1 alloy were mixed together with 100 grams of polyvinyl alcohol for 2 minutes while the agitators spun at 390 rpm. This was followed by the careful addition of 80 grams of cold water while the mixture continued to agitate. At 70 minutes of mixing the agitator was adjusted to 166 rpm, at 75 minutes of mixing the excess water was allowed to evaporate out and after 80 minutes of agitation the mixing process was stopped followed by sieving out the granule sizes greater than 2.24. mm. It is important to avoid adding too much water at once because this will cause excessive foaming and inhibit the formation of the desired granules. In the case of water addition to the granule formation procedure, it is better to add too little than it is to add too much. The remaining powder and the undersized granules could be recycled to the next batch. The > 2.24 4 mm granules were treated in air while ramping the temperature from 25°C to 400°C over 60 minutes followed by a 120 minute soak at 400 °C before being ramped to 700 °C over 60 minutes followed by a 120 minute soak at 700 °C. The granules were then cooled, packed into a basket that was lowered into a stirring 20-wt.% NaOH aqueous solution at 90°C and activated in this fashion for 1 hour. Another option for this activation would be to circulate the 90°C 20-wt.% NaOH aqueous solution through a fixed bed of the catalyst for 1 hour. The catalyst was initially washed with a caustic solution and this was followed by washing with water.
Example 12: Activated Ni / Al granules from a rapidly quenched N2 sprayed Ni / Al alloy (7th Ni catalyst version)
In an Lόdige mixer heated to 40 °C with hot air about 1000 grams of a rapidly quenched N2 sprayed 50%Ni / 50%A1 alloy were mixed together with 100 grams of polyvinyl alcohol for 2 minutes while the agitators spun at 390 rpm. This was followed by the careful addition of 80 grams of cold water while the mixture continued to agitate. At 70 minutes of mixing the agitator was adjusted to 166 rpm, at 75 minutes of mixing the excess water was allowed to evaporate out and after 80 minutes of agitation the mixing process was stopped followed by sieving out the granule sizes greater than 2.24 mm. It is important to avoid adding too much water at once because this will cause excessive foaming and inhibit the formation of the desired granules . In the case of water addition to the granule formation procedure, it is better to add too little than it is to add too much. The remaining powder and the undersized granules could be recycled to the next batch. The > 2.24 4 mm granules were treated in air while ramping the temperature from 25°C to 400°C over 60 minutes followed by a 120 minute soak at 400 °C before being ramped to 775 °C over 120 minutes followed by a 120 minute soak at 775°C. The granules were then cooled, packed into a basket that was lowered into a stirring 20-wt.% NaOH aqueous solution at 90 °C and activated in this fashion for 1 hour. Another option for this activation would be to circulate the 90 °C 20-wt.% NaOH aqueous solution through a fixed bed of the catalyst for 1 hour. The catalyst was initially washed with a caustic . solution and this was followed by washing with water.
Example 13: Activated Cu / Al granules from a rapidly quenched water sprayed Cu / Al alloy (2nd Cu catalyst version)
In an Eirich mixer about 700 grams of a 50%Cu / 50%A1 rapidly quenched water sprayed alloy were mixed together with 35 grams of polyvinyl alcohol for 2 minutes while the bottom plate rotated at 43 rpm and the agitator spun at 1506 rpm. This was followed by the careful addition of 80 grams of an aqueous 5.7-wt.% polyvinyl alcohol solution while the mixture continued to mix. At the mixing time of 45 minutes the agitator was adjusted to 3010 rpm, at 95 minutes the rotating bottom plate was adjusted to 86 rpm and these settings were kept for the remainder of the catalyst's preparation. The careful addition of the 5.7-wt% aqueous polyvinyl alcohol solution continued to the mixing time of 170 minutes up to which 155 ml of the 5.7-wt% aqueous polyvinyl alcohol solution had been added to the ' mixture and at that time a pause in the process was taken in order to sieve out all the granules larger than 2.24 mm. After which the undersized material was placed back into the mixer for 15 minutes of additional mixing followed by sieving out the granules larger than 2.24 mm for a second harvest. The undersized material was placed once more back into the mixer for 15 minutes of additional mixing with the addition of 5 grams of the 5.7-wt% aqueous polyvinyl alcohol solution. After mixing the granules larger than 2.24 mm were sieved out for third harvest from the starting material. The first, second and third harvests from this process were then mixed for the further preparation of this catalyst. During the granulation of the first and third harvests of this material, it is important to avoid adding too much solution at once because this will cause excessive foaming and' inhibit the formation of the desired granules. In the case of solution addition to the granule formation procedure, it is better to add too little than it is to add too much. The remaining powder and the undersized granules
could be then recycled to the next batch. The > 2.24 mm granules were treated in air while ramping the temperature from 25°C to 400°C over 240 minutes followed by a 120 minute soak at 400°C before being ramped to 900 °C over 240 minutes followed by a 120 minute soak at 900°C. The granules were then cooled, packed into a basket that was lowered into a stirring 20-wt.% NaOH aqueous solution at 90°C and activated in this fashion for 1 hour. Another option for this activation would be to circulate the 90°C 20-wt.% NaOH aqueous solution through a fixed bed of the catalyst for 1 hour. The catalyst was initially washed with a caustic solution and this was followed by washing with water.
Example 14: Zn doped activated Cu / Al granules from a rapidly quenched water sprayed Cu / Zn / Al alloy
In an Eirich mixer about 800 grams of a 50%Cu / 35%A1 / 15%Zn rapidly quenched water sprayed alloy were mixed together with 35 grams of polyvinyl alcohol for 2 minutes while the bottom plate rotated at 43 rpm and the agitator spun at 1506 rpm. This was followed by the careful addition of 85 grams of an aqueous 5.7-wt.% polyvinyl alcohol solution while the mixture continued to mix. At the mixing time of 70 minutes the rotating bottom plate was adjusted to 86 rpm, and at 110 minutes the rotating bottom plate was adjusted once more to 43 rpm for the remainder of the catalyst's preparation. The careful addition of the 5.7-wt% aqueous polyvinyl alcohol solution continued to the mixing time of 125 minutes up to which 165 ml of the 5.7-wt% aqueous polyvinyl alcohol solution had been added to the mixture and at that time a pause in the process was taken in order to sieve out all the granules larger than 2.24 mm. After that the undersized material was placed back into the mixer for 15 minutes of additional mixing followed by sieving out the granules larger than 2.24 mm for a second
harvest. The first and second harvests from this process were then mixed for the further preparation of this catalyst. During the granulation of the first harvest of this material, it is important to avoid adding too much solution at once because this will cause excessive foaming and inhibit the formation of the desired granules. In the case of solution addition to the granule formation procedure, it is better to add too little than it is to add too much. The remaining powder and the undersized granules could be then recycled to the next batch. The > 2.24 mm granules were treated in air while ramping the temperature from 25 °C to 400 °C over 60 minutes followed by a 120 minute soak at 400°C before being ramped to 900 °C over 120 minutes followed by a 180 minute soak at 900 °C. The granules were then cooled, packed into a basket that was lowered into a stirring 20-wt.% NaOH aqueous solution at 90 °C and activated in this fashion for 1 hour. Another option for this activation would be to circulate the 90°C 20-wt.% NaOH aqueous solution through a fixed bed of the catalyst for 1 hour. The catalyst was initially washed with a caustic solution and this was followed by washing with water.
Example 15 Cr doped activated Co / Al granules from a rapidly quenched water sprayed Co / Cr / Al alloy
In an Eirich mixer about 800 grams of a 30%Co / 69%A1 / l%Cr rapidly quenched water sprayed alloy were mixed together with 45 grams of polyvinyl alcohol for 2 minutes while the bottom plate rotated at 43 rpm and the agitator spun at 1506 rpm. This was followed by the careful addition of 100 grams of an aqueous 5.7-wt.% polyvinyl alcohol solution while the mixture continued to mix. At the mixing time of 65 minutes the rotating bottom plate was adjusted to 86 rpm, and at 85 minutes the rotating bottom plate was adjusted once more to' 43 rpm for the remainder of the catalyst's preparation. The careful addition of the 5.7-wt%
aqueous polyvinyl alcohol solution continued to the mixing time of 140 minutes up to which 200 ml of the 5.7-wt% aqueous polyvinyl alcohol solution had been added to the mixture and at that time a pause in the process was taken in order to sieve out all the granules larger than 2.24 mm. After that the undersized material was placed back into the mixer for 15 minutes of additional mixing followed by sieving out the granules larger than 2.24 mm for a second harvest. The first and second harvests from this process were then mixed for the further preparation of this catalyst. During the granulation of the first harvest of this material, it is important to. avoid adding too much solution at once because this will cause excessive foaming and inhibit the formation of the desired granules. In the case of solution addition to the granule formation. procedure, it is better to add too little than it is to add too much. The remaining powder and the undersized granules could be then recycled to the next batch. The > 2.24 mm granules were treated in air while ramping the temperature from 25°C to 400 °C over 60 minutes followed by a 120 minute soak at 400°C before being ramped to 900 °C over 120 minutes followed by a 180 minute soak at 900°C. The granules were then cooled, packed into a basket that was lowered into a stirring 20-wt.% NaOH aqueous solution at 90°C and activated in this fashion for 1 hour. Another option for this activation would be to circulate the 90 °C 20-wt.% NaOH aqueous solution through a fixed bed of the catalyst for 1 hour. The catalyst was initially washed with a caustic solution and this was followed by washing with water.
Example 16: Cr and Li doped activated Co / Al granules from a rapidly quenched water sprayed Co / Cr / Al alloy
In an Eirich mixer about 800 grams of a 30%Co /. 69%A1 / l%Cr rapidly quenched water sprayed alloy were mixed together with 45 grams of polyvinyl alcohol for 2. minutes
while the bottom plate rotated at 43 rpm and the agitator spun at 1506, rpm. This was followed by the careful addition of 100 grams of an aqueous 5.7-wt.% polyvinyl alcohol solution while the mixture continued to mix. At the mixing time of 65 minutes the rotating bottom plate was adjusted to 86 rpm, and at 85 minutes the rotating bottom plate was adjusted once more to 43 rpm for the remainder of the catalyst's preparation. The careful addition of the 5.7-wt% aqueous polyvinyl alcohol solution continued to the mixing time of 140 minutes up to which 200 ml of the 5.7-wt% aqueous polyvinyl alcohol solution had been added to the mixture and at that time a pause in the process was taken in' order to sieve out all the granules larger than 2.24 mm. After that the undersized material was placed back into the mixer for 15 minutes of additional mixing, followed by sieving out the granules larger than 2.24 mm for a second harvest. The first and second harvests from this process were then mixed for the further preparation of this catalyst. During the granulation of the first harvest of this material, it is important to avoid adding too much solution at once because this will cause excessive foaming and inhibit the formation of the desired granules. In the case of solution addition to the granule formation procedure, it is better to add too little than it is to add too much. The remaining powder and the undersized granules could be then recycled to the next batch. The > 2.24 mm granules were treated in air while ramping the temperature from 25°C to 400°C over 60 minutes followed by a 120 minute soak at 400 °C before being ramped to 900 °C over 120 minutes followed by a 180 minute soak at 900°C. The granules were then cooled, packed into a basket that was lowered into a stirring 20-wt.% NaOH aqueous solution at 90°C and activated in this fashion for 1 hour. Another option for this activation would be to circulate the 90°C 20-wt.% NaOH aqueous solution through a fixed bed of the catalyst for 1 hour. The catalyst was initially washed with a caustic solution and this was followed by washing with water.
Before use, the catalyst was treated for 4 hours in a 10%LiOH solution followed by being washed with water.
Example 17 : Mo doped activated Ni / Al granules from a rapidly quenched nitrogen sprayed Ni / Mo / Al alloy (1st Mo doped Ni catalyst version)
In an Eirich mixer about 900 grams of a 39%Ni / 60%A1 / l%Mo rapidly quenched nitrogen sprayed alloy were mixed together with 35 grams of polyvinyl alcohol and 100 grams of Ni powder for 2 minutes while the bottom plate rotated at 43 rpm and the agitator spun at 1506 rpm. This was followed by the careful addition of 100 grams of an aqueous 5.7-wt.% polyvinyl alcohol solution while the mixture continued to mix. At the mixing time of 35 minutes a pause in the process was taken in order to sieve out all the granules larger than 2.24 mm. After that the undersized material was placed back into the mixer for 15 minutes of additional mixing followed by sieving out the granules larger than 2.24 mm for a second harvest. The undersized material was placed in the mixer for a third time for continued agitation as 10 grams of an aqueous 5.7-wt.% polyvinyl alcohol solution were given to it. This third mixing period lasted for 10 minutes and at the end all of the granules larger than 2.24 mm were sieved out for a third harvest. The first, second and third harvests from this process were then mixed for the further preparation of this catalyst. During the initial mixing and granulation of this material, it is important to avoid adding too much solution at once because this will cause excessive foaming and inhibit the formation of the desired granules. In the case of solution addition to the granule formation procedure, it is better to add too little than it is to add too much. The remaining powder and the undersized granules could be then recycled to the next batch. The > 2.24 mm granules were treated in air while ramping the temperature
from 25°C to 400 °C over 60 minutes followed by a 120 minute soak at 400°C before being ramped to 900°C over 120 minutes followed by a 180 minute soak at 900°C. The granules were then cooled, packed into a basket that was lowered into a stirring 20-wt.% NaOH aqueous solution at 90 °C and activated in this fashion for 1 hour. Another option for this activation would be to circulate the 90 °C 20-wt.% NaOH aqueous solution through a fixed bed of the catalyst for 1 hour. The catalyst was initially washed with a caustic solution and this was followed by washing with water.
Example 18 : Activated Ni / Al granules from a rapidly quenched nitrogen sprayed Ni / Al alloy (8th Ni catalyst version)
In an Eirich mixer about 900 grams of a 40%Ni / 60%A1 rapidly quenched nitrogen sprayed alloy were mixed together with 35 grams of polyvinyl alcohol and 100 grams of Ni powder for 2 minutes while the bottom plate rotated at 43 rpm and the agitator spun at 1506 rpm. This was followed by the careful addition of 100 grams of an aqueous 5.7-wt.% polyvinyl alcohol solution while the mixture continued to mix. At the mixing time of 45 minutes a pause in the process was taken in order to sieve out all the granules larger than 2.24 mm. After that the undersized material was placed back into the mixer for 15 minutes of additional mixing as 20 grams of an aqueous 5.7-wt.% polyvinyl alcohol solution were given to it followed by sieving out the granules larger than 2.24 mm for a second harvest. The first and second harvests from this process were then mixed for the further preparation of this catalyst. During the mixing and granulation of this material, it is important to avoid adding too much solution at once because this will cause excessive foaming and inhibit the formation of the desired granules. In the case of solution addition to the granule formation procedure, it is better to add too little
than it is to add too much. The remaining powder and the undersized granules could be then recycled to the next batch. The > 2.24 mm granules were treated in air while ramping the temperature from 25°C to 400°C over 60 minutes followed by a 120 minute soak at 400 °C before being ramped to 900°C over 120 minutes followed by a 180 minute soak at 900°C. The granules were then cooled, packed into a basket that was lowered into a stirring 20-wt.% NaOH aqueous solution at 90 °C and activated in this fashion for 1 hour. Another option for this activation would be to circulate the 90 °C 20-wt.% NaOH aqueous solution through a fixed bed of the catalyst for 1 hour. The catalyst was initially washed with a caustic solution and this was followed by washing with water.
Example 19: Cr doped activated Ni / Al granules from a rapidly quenched nitrogen sprayed Ni / Cr / Al alloy (1st Cr doped Ni catalyst version)
In an Eirich mixer about 900 grams of a 38.5%Ni / 60.3%A1 / 1.2%Cr rapidly quenched nitrogen sprayed alloy were mixed together with 35 grams of polyvinyl alcohol and 100 grams of Ni powder for 2 minutes while the bottom plate rotated at 43 rpm and the agitator spun at 1506 rpm. This was followed by the careful addition of 105 grams of an aqueous 5.7-wt.% polyvinyl alcohol solution while the mixture continued to mix. At the mixing time of 45 minutes a pause in the process was taken in order to sieve out all the granules larger than 2.24 mm. After that the undersized material was placed back into the mixer for 15 minutes of additional mixing as 20 grams of an aqueous 5.7-wt.% polyvinyl alcohol solution were given to it followed by sieving out the granules larger than 2.24 mm for a second harvest. The first and second harvests from this process were then mixed for the further preparation of this catalyst. During the mixing and granulation of this
material, it is important to avoid adding too much solution at once because this will cause excessive foaming and inhibit the formation of the desired granules. In the case of solution addition to the granule formation procedure, it is better to add too little than it is to add too much. The remaining powder and the undersized granules could be then recycled to the next batch. The > 2.24 mm granules were treated in air while ramping the temperature from 25°C to 400°C over 60 minutes followed by a 120 minute soak at 400°C before being ramped to 775°C over 90 minutes followed by a 120 minute soak at 775°C. The granules were then cooled, packed into a basket that was lowered into a stirring 20-wt.% NaOH aqueous solution at 90°C and activated in this fashion for 1 hour. Another option for this activation would be to circulate the 90°C 20-wt.% NaOH aqueous solution through a fixed bed of the catalyst for 1 hour. The catalyst was initially washed with a caustic solution and this was followed by washing with water.
Example 20: Cr doped activated Ni / Al granules from a rapidly quenched nitrogen sprayed Ni / Cr / Al alloy (2nd Cr doped Ni catalyst version)
In an Eirich mixer about 900 grams of a 38.5%Ni / 60.3%A1 / 1.2%Cr rapidly quenched nitrogen sprayed alloy were mixed together with 35 grams of polyvinyl alcohol and 100 grams of Ni powder for 2 minutes while the bottom plate rotated at 43 rpm and the agitator spun at 1506 rpm. This was followed by the careful addition of 105 grams of an aqueous 5.7-wt.% polyvinyl alcohol solution while the mixture continued to mix. At the mixing time of 45 minutes a pause in the process was taken in order to sieve out all the granules larger than 2.24 mm. After that the undersized material was placed back into the mixer for 15 minutes of additional mixing as 20 grams of an aqueous 5.7-wt.% polyvinyl alcohol solution were given to it followed by
sieving out the granules larger than 2.24 mm for a second harvest. The first and second harvests from this process were then mixed for the further preparation of this catalyst. During the mixing and granulation of this material, it is important to avoid adding too much solution at once because this will cause excessive foaming and inhibit the formation of the desired granules. In the case of solution addition to the granule formation procedure, it is better to add too little than it is to add too much. The remaining powder and the undersized granules could be then recycled to the next batch. The > 2.24 mm granules were treated in air while ramping the temperature from 25°C to 400°C over 60 minutes followed by a 120 minute soak at 400°C before being ramped to 800°C over 90 minutes followed by a 120 minute soak at 800°C. The granules were then cooled, packed into a basket that was lowered into a stirring 20-wt.% NaOH aqueous solution at 90°C and activated in this fashion for 1 hour. Another option for this activation would be to circulate the 90 °C 20-wt.% NaOH aqueous solution through a fixed bed of the catalyst for 1 hour. The catalyst was initially washed with a caustic solution and this was followed by washing with water.
Example 21 : Cr and Fe doped activated Ni / Al granules from a rapidly cooled water sprayed Ni / Cr / Fe / Al alloy
In an Eirich mixer about 600 grams of a 40%Ni / l%Cr / 0.5%Fe / 58.5%A1 rapidly cooled water sprayed alloy were mixed together with 66.6 grams of Ni powder and 35 grams of polyvinyl alcohol for 2 minutes while the bottom plate rotated at 43 rpm and the agitator spun at 1506 rpm. This was followed by the careful addition of 100 grams of an aqueous 5.7-wt.% polyvinyl alcohol solution while the mixture continued to mix. After mixing for 45 minutes 20 grams of the 5.7-wt% aqueous polyvinyl alcohol solution were added. At 60 minutes of mixing 10 grams of a 5.7-wt%
aqueous polyvinyl alcohol solution were added and at 90 minutes 12 more ml of the 5.7-wt% aqueous polyvinyl alcohol solution were added. At 120 minutes of mixing the process was stopped and the granules above 2.24 mm were screened out. The undersized particles and powder were fed back into the mixer for 30 minutes of agitation where 10 grams of water were steadily added to the mixture. After the 30 minute agitation period the process was stopped and the granules above 2.24 mm were screened out and added to the first harvest of granules. It is important to avoid adding' too much solution or water at once because this will cause excessive foaming and inhibit the formation of the desired granules. In the case of solution or water addition to the granule formation procedure, it is better to add too little than it is to add too much. The remaining powder and the undersized granules could be then recycled to the next batch. The > 2.24 mm granules were treated in air while ramping the temperature from 25°C to 400°C over 60 minutes followed by a 120 minute soak at 400 °C before being ramped to 800°C over 90 minutes followed by a 120 minute soak at 800°C. The granules were then cooled, packed into a basket that was lowered into a stirring 20-wt.% NaOH aqueous solution at 90°C and activated in this fashion for 1 hour. Another option for this activation would be to circulate the 90°C 20-wt.% NaOH aqueous solution through a fixed bed of the catalyst for 1 hour. The catalyst was initially washed with a caustic solution and this was followed by washing with water.
Example 22: Activated Ni / Al granules from a rapidly cooled water sprayed Ni / Al alloy (9th Ni catalyst version)
In an Eirich mixer about 850 grams of a 49.1%Ni / 50.9%A1 rapidly cooled water sprayed alloy were mixed together with 150 grams of Ni powder and 40 grams of polyvinyl alcohol
for 2 minutes while the bottom plate rotated at 43 rpm and the agitator spun at 1506 rpm. This was followed by the careful addition of 130 grams of an aqueous 5.7-wt.% polyvinyl alcohol solution while the mixture continued to mix. After mixing for 100 minutes 20 grams of the 5.7-wt% aqueous polyvinyl alcohol solution were added. At 130 minutes of mixing 20 grams of a 5.7-wt% aqueous polyvinyl alcohol solution were added and at 150 minutes of mixing the process was stopped and the granules above 2.24 mm were screened out. The undersized particles and powder were fed back into the mixer for 15 minutes of agitation where 20 grams of the 5.7-wt% aqueous polyvinyl alcohol solution were steadily added to the mixture. After the 15 minute agitation period the process was stopped and the granules above 2.24 mm were screened out and added to the first harvest of granules. It is important to avoid adding too much solution at once because this will cause excessive foaming and inhibit the formation of the desired granules. In the case of solution addition to the granule formation procedure, it is better to add too little than it is to add too much. The remaining powder and the undersized granules could be then recycled to the next batch. The > 2.24 mm granules were treated in air while ramping the temperature from 25°C to 400°C over 60 minutes followed by a 120 minute soak at 400 °C before being ramped to 775 °C over 120 minutes followed by a 120 minute soak at 775°C. The granules were then cooled, packed into a basket that was lowered into a stirring 20-wt.% NaOH aqueous solution at 90 °C and activated in this fashion for 1 hour. Another option for this activation would be to circulate the 90°C 20-wt.% NaOH aqueous solution through a fixed bed of the catalyst for 1 hour. The catalyst was initially washed with a caustic solution and this was followed by washing with water.
Example 23: Mo doped activated Ni / Al granules from a rapidly cooled water sprayed Ni / Al alloy (2nd Mo doped Ni catalyst version)
In an Eirich mixer about 850 grams of a 49.1%Ni / 50.9%A1 rapidly cooled water sprayed alloy were mixed together with 150 grams of Ni powder and 40 grams of polyvinyl alcohol for 2 minutes while the bottom plate rotated at 43 rpm and the agitator spun at 1506 rpm. This was followed by the careful addition of 130 grams of an aqueous 5.7-wt.% polyvinyl alcohol solution while the mixture continued to mix. After mixing for 100 minutes 20 grams of the 5.7-wt% aqueous polyvinyl alcohol solution were added. At 130 minutes of mixing 20 grams of a 5.7-wt% aqueous polyvinyl alcohol solution were added and at 150 minutes of mixing the process was stopped and the granules above 2.24 mm were screened out. The undersized particles and powder were fed back into the mixer for 15 minutes of agitation where 20 grams of the 5.7-wt% aqueous polyvinyl alcohol solution were steadily added to the mixture. After the 15 minute agitation period the process was stopped and the granules above 2.24 mm were screened out and added to the first harvest of granules. It is important to avoid adding too much solution at once because this will cause excessive foaming and inhibit the formation of the desired granules. In the case of solution addition to the granule formation procedure, it is better to add too little than it is to add too much. The remaining powder and the undersized granules could be then recycled to the next batch. The > 2.24 mm granules were treated in air while ramping the temperature from 25 °C to 400°C over 60 minutes followed by a 120 minute soak at 400°C before being ramped to 775°C over 120 minutes followed by a 120 minute soak at 775°C. The granules were then cooled, packed into a basket that was lowered into a stirring 20-wt.% NaOH aqueous solution at 90°C and activated in this fashion for 1 hour. Another option for this activation would be to circulate the 90°C 20-wt.% NaOH
aqueous solution through a fixed bed of the catalyst for 1 hour. The catalyst was initially washed with a caustic solution and this was followed by washing with water. This catalyst was doped with a sodium molybdate solution and after this post activation doping, the molybdenum content ' of the catalyst was 0.3%. The procedure can also be carried out with other Mo containing compounds such as ammonium . heptamolybdate.
Example 24: Activated Ni / Al granules from a rapidly cooled water sprayed Ni / Al alloy (10th Ni catalyst version)
In an Eirich mixer about 900 grams of a 49.1%Ni / 50.9%A1 rapidly cooled water . sprayed alloy were mixed together with 100 grams of Ni powder and 40 grams of polyvinyl alcohol for 2 minutes while the bottom plate rotated at 43 rpm and the agitator spun at 1506 rpm. This was followed by the careful addition of 140 grams of an aqueous 5.7-wt.% polyvinyl alcohol solution while the mixture continued to mix. After mixing for 40 minutes 20 grams of the 5.7-wt% aqueous polyvinyl alcohol solution were added. At 70 minutes of mixing 10 grams of a 5.7-wt% aqueous polyvinyl alcohol solution were added, at 110 minutes 20 grams of a 5.7-wt% aqueous polyvinyl alcohol solution were added and at 140 minutes of mixing the process was stopped and the granules above 2.24 mm were screened out. The undersized particles and powder were fed back into the mixer for 20 minutes of agitation where 20 grams of the 5.7-wt% aqueous polyvinyl alcohol solution were steadily added to the mixture. After the 20 minute agitation period the process was stopped and the granules above 2.24 mm were screened out and added to the first harvest of granules. It is important to avoid adding too much solution at once because this will cause excessive foaming and inhibit the formation of the desired granules. In the case of solution addition
to the granule formation procedure, it is better to add too little than it is to add too much. The remaining powder and the undersized granules could be then recycled to the next batch. The > 2.24 mm granules were treated in air while ramping the temperature from 25°C to 400 °C over 60 minutes followed by a 120 minute soak at 400 °C before being ramped to 1000°C over 240 minutes followed by a 120 minute soak at 1000 °C. The granules were then cooled, packed into a basket that was lowered into a stirring 20-wt.% NaOH aqueous solution at 90 °C and activated in this fashion for 1 hour. Another option for this activation would be to circulate the 90°C 20-wt.% NaOH aqueous solution through a fixed bed of the catalyst for 1 hour. The catalyst was initially washed with a caustic solution and this was followed by washing with water.
Example 25 : Mo doped activated Ni / Al granules from a rapidly cooled nitrogen sprayed Ni / Mo / Al alloy (3rd Mo doped Ni catalyst version)
In an Eirich mixer about 850 grams of a 39%Ni / l%Mo / 60%A1 rapidly cooled nitrogen sprayed alloy were mixed together with 150 grams of Ni powder and 35 grams of polyvinyl alcohol for 2 minutes while the bottom plate rotated at 43 rpm and the agitator spun at 1506 rpm. This was followed by the careful addition of 100 grams of an aqueous 5.7-wt.% polyvinyl alcohol solution while the mixture continued to mix. After mixing for 50 minutes 20 grams of the 5.7-wt% aqueous polyvinyl alcohol solution were added. At 60 minutes of mixing 20 more grams of a 5.7- wt% aqueous polyvinyl alcohol solution were added and at 140 minutes of mixing the process was stopped and the granules above 2.24 mm were screened out. It is important to avoid adding too much solution at once because this will cause excessive foaming and inhibit the formation of the desired granules. In the case of solution addition to the
granule formation procedure, it is better to add too little than it is to add too much. The remaining powder and the undersized granules could be then recycled to the next batch. The > 2.24 mm granules were treated in air while ramping the temperature from 25°C to 400°C over 60 minutes followed by a 120 minute soak at 400°C before being ramped to 800°C over 120 minutes followed by a 240 minute soak at 1000°C. The granules were then cooled, packed into a basket that was lowered into a stirring 20-wt.% NaOH aqueous solution at 90°C and activated in this fashion for 1 hour. Another option for this activation would be to circulate the 90 °C 20-wt.% NaOH aqueous solution through a fixed bed of the catalyst for 1 hour. The catalyst was initially washed with a caustic solution and this was followed by washing with water.
Example 26: Pd, Cr and Fe doped activated Ni / Al granules from a rapidly cooled water sprayed Ni / Cr / Fe / Al alloy
In an Eirich mixer about 600 grams of a 40%Ni / l%Cr / 0.5%Fe / 58.5%A1 rapidly cooled water sprayed alloy were mixed together with 66.6 grams of Ni powder and 35 grams of polyvinyl alcohol for 2 minutes while the bottom plate rotated at 43 rpm and the agitator spun at 1506 rpm. This was followed by the careful addition of 100 grams of an aqueous 5.7-wt.% polyvinyl alcohol solution while the mixture continued to mix. After mixing for 45 minutes 20 grams of the 5.7-wt% aqueous polyvinyl alcohol solution were added. At 60 minutes of mixing 10 grams of a 5.7-wt% aqueous polyvinyl alcohol solution were added and at 90 minutes 12 more ml of the 5.7-wt% aqueous polyvinyl alcohol solution were added. At 120 minutes of mixing the process was stopped and the granules above 2.24 mm were screened out. The undersized particles and powder were fed back into the mixer for 30 minutes of agitation where 10 grams of water were steadily added to the mixture. After the 30
minute agitation period the process was stopped and the granules above 2.24 mm were screened out and added to the first harvest of granules. It is important to avoid adding too much solution or water at once because this will cause excessive foaming and inhibit the formation of the desired granules. In the case of solution or water addition to the granule formation procedure, it is better to add too little than it is to add too much. The remaining powder and the undersized granules could be then recycled to the next batch. The > 2.24 mm granules were treated in air while ramping the temperature from 25°C to 400°C over 60 minutes followed by a 120 minute soak at 400°C before being ramped to 800°C over 90 minutes followed by a 120 minute soak at 800°C. The granules were then cooled, packed into a basket that was lowered into a stirring 20-wt.% NaOH aqueous solution at 90°C and activated in this fashion for 1 hour. Another option for this activation would be to circulate the 90°C 20-wt.% NaOH aqueous solution through a fixed bed of the catalyst for 1 hour. The catalyst was initially washed with a caustic solution and this was followed by washing with water. This catalyst was then doped with a palladium nitrate solution that previously had its pH to 6 with sodium carbonate adjusted. The end Pd content of the catalyst was 0.2%.
Comparative Example 1: Shell activated Ni / Al tablets from a rapidly cooled water sprayed Ni / Al alloy
In accordance with the literature (US Patents 5536694 and 6262307) the preparation of the Ni / Al shell activated tablets started with a homogeneous mixture of 1000 grams of a 50%Ni / 50%A1 rapidly cooled water sprayed alloy, 75 grams of a pure Ni powder (99%-Ni and D5o = 21 urn) and 50 grams of ethylene bis-stearylamide that was tableted to 3 by 3 mm tablets, calcined for 2 hours at 700°C, activated in a 20 wt.% caustic solution for 2 hours at 80°C, washed
in a caustic solution, washed, in water and stored under a mildly caustic aqueous' solution (pH ~10.5) until use. The bulk densities of four different batches made in this way were 1.56, 1.58, 1.75 and 1.79 grams per mL.
Comparative Example 2 Shell activated Cu / Al tablets from a rapidly cooled water sprayed Cu / Al alloy
In accordance with the literature (US Patents 5536694 and 6262307) the preparation of the Cu / Al shell activated tablets started with a homogeneous mixture of 1000 grams of a 50%Cu / 50%A1 rapidly cooled water sprayed alloy,.75 grams of a pure Ni powder (99%Ni and D50 = 21 μm) and 50 grams of ethylene bis-stearylamide that was tableted to 3 by .3 mm tablets, calcined for 2 hours at 700°C, activated in a 20 wt.% caustic solution for 2 hours at 80°C, washed in a caustic solution, washed in water and stored under a mildly caustic aqueous solution (pH -10.5) until use.
Comparative Example 3 : Shell activated Co / Al tablets from a slowly cooled casted Co / Al alloy
In accordance with the literature (US Patents 5536694 and 6262307) the preparation of the Co / Al shell activated tablets started with a • homogeneous mixture of 1000 grams of a 50%Co / 50%A1 slowly cooled casted alloy and 50 grams of ethylene bis-stearylamide that was tableted to 3 by 3 mm tablets, calcined for 2 hours at 700°C, activated in a 20 wt.% caustic solution for 2 hours at 80°C, washed in a caustic solution, washed in water and stored under a mildly caustic aqueous solution (pH ~10.5) until use.
Application Example 1: The hydrogenation of acetone
The trickle phase hydrogenation of acetone was carried out over the activated base metal catalysts in a tube reactor in the presence of hydrogen at 75°C and 5 bar. The data from these tests are displayed in table 1.
Table 1: The acetone hydrogenation data,
A. The catalyst's bulk density. B. The percentage of acetone conversion during the reaction. C. The percent isopropanol selectivity. D. The mmoles of acetone reacted per gram of catalyst per hour. E. The mmoles of acetone reacted per ml of catalyst per hour.
Application Example 2 : The hydrogenation of glucose
The trickle phase hydrogenation of glucose was carried out over an activated base metal catalyst in a tube reactor in the presence of hydrogen with a 40% aqueous glucose solution at 140 °C and 50 bar . The data from this test are displayed in table 2.
Table 2 : The glucose hydrogenation data
A. The catalyst' s bulk density. B . The percentage of glucose conversion during the reaction. C . The mmoles of glucose reacted per gram of catalyst per hour . D. The mmoles of glucose reacted per ml of catalyst per hour .
Application Example 3 : The hydrogenation of 2-butyne-l , 4- diol
The trickle phase hydrogenation of 2-butyne-l, 4-diol was carried out over the activated base metal catalysts in a tube reactor at 135°C and 60 bar in the presence of hydrogen with a 50% aqueous 2-butyne-l, 4-diol solution that was adjusted to a pH of 7 with NaHC03. The data from these tests are displayed in table 3.
Table 3 : The 2-butyne-l, 4-diol hydrogenation data
A. The catalyst' s bulk density. B . The throughput of 2-butyne-l, 4-diol in grams per ml of catalyst per hour . C. The percentage of 2-butyne-l, 4-diol conversion during the reaction. D. The percent 1, 4-butanediol selectivity. E . The percent 2-butene-l, 4-diol selectivity. F. The 1, 4-butanediol to 2-butene-l, 4-diol ratio . G. The mmoles of 2-butyne-l, 4-diol reacted per gram of catalyst per hour. H . The mmoles of 2-butyne-l, 4-diol reacted per ml of catalyst per hour .
Application Example 4 : The hydrogenation of adiponitrile via method 1
The trickle phase hydrogenation of adiponitrile was carried out over the activated base metal catalysts in a tube reactor at 65 bar in the presence of hydrogen with a 20% adiponitrile in methanol solution . The data from these tests are displayed in table 4.
Table 4 : The adiponitrile hydrogenation data via method 1
A. The catalyst's bulk density. B. The percent hexamethylendiamine selectivity. C. The percent aminocapronitrile selectivity. D. The percentage of adiponitrile conversion during the reaction. E. The mmoles of adiponitrile reacted per gram of catalyst per hour. F. The mmoles of adiponitrile reacted per ml of catalyst per hour.
Application Example 5 The hydrogenation of adiponitrile via method 2
The trickle phase hydrogenation of adiponitrile was carried out over the activated base metal catalysts in a tube reactor at 65 bar in the presence of hydrogen with a 20% adiponitrile in methanol solution, where one liter of this methanol, originally contained 1.9 grams of NaOH . The data , from these tests are displayed in table 5.
Table 5 : The adiponitrile hydrogenation data via method 2
A. The catalyst' s bulk density. B . The percent hexamethylendia ine selectivity. C . The percent aminocapronitrile selectivity. D . The percentage of adiponitrile conversion during the reaction . E . The mmoles of adiponitrile reacted per gram of catalyst per hour . F. The mmoles of adiponitrile reacted per ml of catalyst per hour .
Application Example 6 : The hydrogenation of adiponitrile via method 3
The trickle phase hydrogenation of adiponitrile was carried out over the activated base metal catalysts in a tube reactor at 65 bar in the presence of hydrogen with a 20% adiponitrile in methanol solution, where one liter of this methanol originally contained 1.9 grams of LiOH. The data from these tests are displayed in table 6.
Table 6: The adiponitrile hydrogenation data via method 3
A. The catalyst's bulk density. B. The percent hexamethylendiamine selectivity. C. The percent aminocapronitrile selectivity. D. The percentage of adiponitrile conversion during the reaction. E. The mmoles of adiponitrile reacted per gram of catalyst per hour. F. The mmoles of adiponitrile reacted per ml of catalyst per hour.
Application Example 7 : The hydrogenation of dinitrotoluene The trickle phase hydrogenation of dinitrotoluene was carried out over the activated base metal catalysts in a tube reactor at ~80°C and 60 bar in the presence of hydrogen with a 4% dinitrotoluene in methanol solution. The data from these tests are displayed in table 7.
Table 7: The dinitrotoluene hydrogenation data
1. The catalyst's bulk density. 2. The dinitrotoluene throughput in grams of dinitrotoluene per ml of catalyst per hour. 3. The percent toluenediamine selectivity. 4. The percentage of dinitrotoluene conversion during the reaction, 5. The mmoles of dinitrotoluene reacted per gram of catalyst per hour, 6. The mmoles of dinitrotoluene reacted per ml of catalyst per hour.
Claims
1. The preparation of fixed bed activated base metal granules via the mixing of the precursor alloy powder with optionally an organic binder and optionally an inorganic binder to form granules that are dried, calcined for stabilization purposes and then activated in a caustic solution. The precursor alloy can be either slowly cooled or rapidly cooled via contact, quenching, spraying in or spraying with a variety of mediums such as, but not limited to, inert gases and water. The precursor alloy is comprised of a catalytic component, a caustic leachable component and optionally one or more promoters. The catalytic component can consist of one or more metals from groups VIII and lb of the periodic chart of elements that are optionally promoted with one or more elements from the periodic groups la, Ila, Ilia, IVb, Vb, Vlb, VIlb, lb, lib, Ilia and IVa. The caustic leachable component consists of Al, SI, Zn or mixtures therof.
2. The preparation of fixed bed activated base metal granules via the mixing of the precursor alloy powder with optionally an organic binder to form granules that are dried, calcined for stabilization purposes and then activated in a caustic solution. The precursor alloy can be either slowly cooled or rapidly cooled via contact, quenching, spraying in or spraying with a variety of mediums such as, but not limited to, inert gases and water. The precursor alloy is comprised of a catalytic component, a caustic leachable component and optionally one or more promoters. The catalytic component can consist of one or more metals from groups VIII and lb of the periodic chart of elements that are optionally promoted with one or more elements from the periodic groups la, Ila, Ilia, IVb, Vb, Vlb, Vllb, lb,
lib, Ilia and IVa. . The caustic leachable component consists of Al, SI, Zn or mixtures therof.
3. The preparation of fixed bed activated base metal granules via the mixing of the precursor alloy powder with optionally an organic binder and optionally an inorganic binder in an Eirich mixer to form granules that are dried, calcined for stabilization purposes and then activated in a caustic solution. The precursor alloy can be either slowly cooled or rapidly cooled via contact, quenching, spraying in or spraying with a variety of mediums such as, but not limited to, inert gases and water. The precursor alloy is comprised of a catalytic component, a caustic leachable component and optionally one or more promoters. The catalytic component can consist of one or more metals from groups VIII and lb of the periodic chart of elements that are optionally promoted with one or more elements from the periodic groups la, Ila, Ilia, IVb, Vb, Vlb, Vllb, lb, lib, Ilia and IVa. . The caustic leachable component consists of Al, SI, Zn or mixtures therof.
4. The preparation of fixed bed activated base metal granules via the mixing of the precursor alloy powder with optionally an organic binder in an Eirich mixer to form granules that are dried, calcined for stabilization purposes and then activated in a caustic solution. The precursor alloy can be either slowly cooled or rapidly cooled via contact, quenching, spraying in or spraying with a variety of mediums such as, but not limited to, inert gases and water. The precursor alloy is comprised of a catalytic component, a caustic leachable component and optionally one or more promoters. The catalytic component can consist of one or more metals from groups VIII and lb of the periodic chart of elements that are optionally promoted with one or more elements from the periodic groups la,
Ila, Ilia, IVb, Vb, Vlb, Vllb, lb, lib, Ilia and IVa. . The caustic leachable component consists of Al, SI, Zn or mixtures therof.
5. The preparation of fixed bed activated base metal granules via the mixing of the precursor alloy powder with optionally an organic binder and optionally an inorganic binder in a Lόdige mixer to form granules that are dried, calcined for stabilization purposes and then activated in a caustic solution. The precursor alloy can be either slowly cooled or rapidly cooled via contact, quenching, spraying in or spraying with a variety of mediums such as, but not limited to, inert gases and water. The precursor alloy is comprised of a catalytic component, a caustic leachable component and optionally one or more promoters. The catalytic component can consist of one or more metals from groups VIII and lb of the periodic chart of elements that are optionally promoted with one or more elements from the periodic groups la, Ila, Ilia, IVb, Vb, Vlb, Vllb, lb, lib, Ilia and IVa The caustic leachable component consists of Al, SI, Zn or mixtures therof.
6. The preparation of fixed bed activated base metal granules via the mixing of the precursor alloy powder with optionally an organic binder in a lδdiger mixer to form granules that are dried, calcined for stabilization purposes and then activated in a caustic solution. The precursor alloy can be either slowly cooled or rapidly cooled via contact, quenching, spraying in or spraying with a variety of mediums such as, but not limited to, inert gases and water. The precursor alloy is comprised of a catalytic component, a caustic leachable component and optionally one or more promoters. The catalytic component can consist of one or more metals from groups VIII and lb of the periodic chart of elements that are optionally promoted
with one or more elements from the periodic groups la, Ila, Ilia, IVb, Vb, Vlb, Vllb, lb, lib, Ilia and IVa. The caustic leachable component consists of Al, SI, Zn or mixtures therof.
7. The preparation of fixed bed activated base metal granules via the mixing of the precursor alloy powder with optionally an organic binder and optionally an inorganic binder to form granules that are dried, calcined for stabilization purposes and then activated in a caustic solution. The precursor alloy can be either slowly cooled or rapidly cooled via contact, quenching, spraying in or spraying with a variety of mediums such as, but not limited to, inert gases and water. The precursor alloy is comprised of a catalytic component, a caustic leachable component and optionally one or more promoters. The catalytic component can consist Ni, Co, Cu, Fe or combinations therof that are optionally promoted with one or more elements from the periodic groups la, Ila, Ilia, IVb, Vb, Vlb, Vllb, lb, lib, Ilia and IVa. The caustic leachable component consists of Al, SI, Zn or mixtures therof.
8. The preparation of fixed bed activated base metal granules via the mixing of the precursor alloy powder with optionally an organic binder and optionally an inorganic binder to form granules that are dried, calcined for stabilization purposes and then activated in a caustic solution. This granulation process, the choice of the possible binders, the drying procedure and the calcination procedure are performed in such a way that the granules form foam-type structures with high macroporosity. The precursor alloy can be either slowly cooled or rapidly cooled via contact, quenching, spraying in or spraying with a variety of mediums such as, but not limited to, inert gases and water. The precursor alloy is comprised of a catalytic component,
a caustic leachable component and optionally one or more promoters. The catalytic component can consist of one or more metals from groups VIII and lb of the periodic chart of elements that are optionally promoted with one or more elements from the periodic groups la, Ila, Ilia, IVb, Vb, Vlb, Vllb, lb, lib, Ilia and IVa. The caustic leachable component consists of Al, SI, Zn or mixtures therof.
9. The preparation of fixed bed activated base metal granules via the mixing of the precursor alloy powder with optionally an organic binder and optionally an inorganic binder to form granules that are dried, calcined for stabilization purposes and then activated in a caustic solution. After activation, the catalyst is promoted by the addition of salts of one or more elements from the periodic groups la, Ila, Ilia, IVb, Vb, Vlb, Vllb, lb, lib, Ilia and IVa to the catalyst. The precursor alloy can be either slowly cooled or rapidly cooled via contact, quenching, spraying in or spraying with a variety of mediums such as, but not limited to, inert gases and water. The precursor alloy is comprised of a catalytic component, a caustic leachable component and optionally one or more promoters. The catalytic component can consist of one or more metals from groups VIII and lb of the periodic chart of elements and the caustic leachable component consists of Al, SI, Zn or mixtures therof.
10. The preparation of fixed bed activated base metal granules via the mixing of the precursor alloy powder with optionally an organic binder and optionally an inorganic binder to form granules that are dried, calcined for stabilization purposes and then activated in a caustic solution. The precursor alloy can be either slowly cooled or rapidly cooled via contact, quenching, spraying in or spraying with a variety of
mediums such as, but not limited to, inert gases and water. The precursor alloy is comprised of a catalytic component, a caustic leachable component and one or more promoters. The catalytic component can consist of one or more metals from groups VIII and lb of the periodic chart of elements that are optionally promoted with one or more elements from the periodic groups la, Ila, Ilia, IVb, Vb, Vlb, Vllb, lb, lib, Ilia and IVa. The caustic leachable component consists of Al, SI, Zn or mixtures therof. In this case, the catalyst is promoted by the addition of one or more elements from the periodic groups la, Ila, Ilia, IVb, Vb, Vlb, Vllb, lb, lib, Ilia and IVa to the alloy before caustic activation.
11. The preparation of fixed bed activated base metal granules via the mixing of the precursor alloy powder with optionally an organic binder and optionally an inorganic binder to form granules that are dried, calcined for stabilization purposes and then activated in a caustic solution. After activation, the catalyst is promoted by the addition of salts of one or more elements from the periodic groups la, Ila, Ilia, IVb, Vb, Vlb, Vllb, lb, lib, Ilia and IVa to the catalyst. The precursor alloy can be either slowly cooled or rapidly cooled via contact, quenching, spraying in or spraying with a variety of mediums such as, but not limited to, inert gases and water. The precursor alloy is comprised of a catalytic component, a caustic leachable component and one or more promoters . The catalytic component can consist of one or more metals from groups VIII and lb of the periodic chart of elements that are optionally promoted with one or more elements from the periodic groups la, Ila, Ilia, IVb, Vb, Vlb, Vllb, lb, lib, Ilia and IVa. The caustic leachable component consists of Al, SI, Zn or mixtures therof. In this case, the catalyst is promoted via both
the addition of one or more promoters to the alloy before activation and the addition of salts of one or more promoters to the catalyst afer caustic activation,
12. The use of the catalysts described in claims 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 or 11 for the transformation of organic compounds .
13. he use of the catalysts described in claims 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 or 11 for the hydrogenation of organic compounds.
14. The use of the catalysts described in claims 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 or 11 for the partial hydrogenation of organic compounds.
15. The use of the catalysts described in claims 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 or 11 for the hydrogenation of carbonyl groups in organic compounds.
16. The use of the catalysts described in claims 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 or 11 for the hydrogenation of acetone.
17. he use of the catalysts described in claims 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 or 11 for the hydrogenation of aldehydes .
18. he use of the catalysts described in claims 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 or 11 for the hydrogenation of ketones.
19. he use of the catalysts described in claims 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 or 11 for the hydrogenation of glucose.
20. The use of the catalysts described in claims 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 or 11 for the hydrogenation of sugars to polyols.
21. he use of the catalysts described in claims 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 or 11 for the hydrogenation of aldoses to polyols.
22. The use of the catalysts described in claims 1, 2, 3, 4, 5, 6, 1 , 8, 9, 10 or 11 for the hydrogenation of ketoses to polyols.
23. he use of the catalysts described in claims 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 or 11 for the hydrogenation of monosacharide aldoses to polyols .
24. he use of the catalysts described in claims 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 or 11 for the hydrogenation of monosacharide ketoses to polyols.
25. he use of the catalysts described in claims 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 or 11 for the hydrogenation of disacharide aldoses to polyols.
26. The use of the catalysts described in claims 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 or 11 for the hydrogenation of disacharide ketoses to polyols.
27. The use of the catalysts described in claims 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 or 11 for the hydrogenation of multisacharide aldoses to polyols.
28. he use of the catalysts described in claims 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 or 11 for the hydrogenation of multisacharide ketoses to polyols.
29. he use of the catalysts described in claims 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 or 11 for the hydrogenation of nitriles.
30. The use of the catalysts described in claims 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 or 11 for the hydrogenation of imines.
31. The use of the catalysts described in claims 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 or 11 for the hydrogenation of dinitriles.
32. he use of the catalysts described in claims 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 or 11 for the hydrogenation of adiponitrile.
33. The use of the catalysts described in claims 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 or 11 ,for the hydrogenation of alkene moeities in organic compounds.
34. The use of the catalysts described in claims 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 or 11 for the hydrogenation of alkyne moeities in organic compounds.
35. The use of the catalysts described in claims 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 or 11 for the hydrogenation of aromatics.
36. The use of the catalysts described in claims 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 or 11 for the hydrogenation of 2- butyne-1, 4-diol.
37. he use of the catalysts described in claims 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 or 11 for the hydrogenation of nitro groups in organic compounds.
38. The use of the catalysts described in claims 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 or 11 for the hydrogenation of dinitro compounds.
39. The use of the catalysts described in claims 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 or 11 for the hydrogenation of aromatic nitrocompounds .
40. The use of the catalysts described in claims 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 or 11 for the hydrogenation of aromatic dinitrocompounds .
1. The use of the catalysts described in claims 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 or 11 for the hydrogenation of dinitrotoluene .
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PCT/EP2003/011702 WO2005042153A1 (en) | 2003-10-22 | 2003-10-22 | The use of activated granulates of base metals for organic transformations |
AU2003276141A AU2003276141A1 (en) | 2003-10-22 | 2003-10-22 | The use of activated granulates of base metals for organic transformations |
PCT/EP2004/011018 WO2005039764A1 (en) | 2003-10-22 | 2004-10-02 | Method for the preparation and use of activated granulates of base metals |
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PCT/EP2003/011702 WO2005042153A1 (en) | 2003-10-22 | 2003-10-22 | The use of activated granulates of base metals for organic transformations |
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PCT/EP2004/011018 WO2005039764A1 (en) | 2003-10-22 | 2004-10-02 | Method for the preparation and use of activated granulates of base metals |
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Cited By (2)
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WO2007028411A1 (en) * | 2005-09-08 | 2007-03-15 | Evonik Degussa Gmbh | The production and use of supported activated base metal catalysts for organic transformation |
EP3544728A4 (en) * | 2016-11-22 | 2020-09-30 | W.R. Grace & Co.-Conn. | Method for manufacturing catalysts with reduced attrition |
Families Citing this family (5)
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EP3050870A1 (en) | 2015-01-30 | 2016-08-03 | Evonik Degussa GmbH | Method for the preparation of 3-aminomethyl-3,5,5-trimethylcyclohexylamine |
EP3300798A1 (en) * | 2016-09-30 | 2018-04-04 | Evonik Degussa GmbH | Catalyst fixed bed containing metal foam body |
EP3300799A1 (en) | 2016-09-30 | 2018-04-04 | Evonik Degussa GmbH | Method and catalyst for producing 1,4-butanediol |
US11401224B2 (en) | 2018-02-14 | 2022-08-02 | Evonik Operations Gmbh | Method for the preparation of C3—C12-alcohols by catalytic hydrogenation of the corresponding aldehydes |
TWI793453B (en) | 2019-09-25 | 2023-02-21 | 德商贏創運營有限公司 | Catalytic reactor |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5536694A (en) * | 1993-10-16 | 1996-07-16 | Degussa Aktiengesellschaft | Catalyst precursor for an activated raney metal fixed-bed catalyst, an activated raney metal fixed-bed catalyst and a process for its preparation and use, and a method of hydrogenating organic compounds using said catalyst |
US6262307B1 (en) * | 1997-05-26 | 2001-07-17 | Degussa-Huls Aktiengesellschaft | Shaped, activated metal, fixed-bed catalyst |
EP1207149A1 (en) * | 2000-11-16 | 2002-05-22 | Basf Aktiengesellschaft | Process for the hydrogenation of nitriles on Raney catalysts |
-
2003
- 2003-10-22 AU AU2003276141A patent/AU2003276141A1/en not_active Abandoned
- 2003-10-22 WO PCT/EP2003/011702 patent/WO2005042153A1/en active Application Filing
-
2004
- 2004-10-02 WO PCT/EP2004/011018 patent/WO2005039764A1/en active Application Filing
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5536694A (en) * | 1993-10-16 | 1996-07-16 | Degussa Aktiengesellschaft | Catalyst precursor for an activated raney metal fixed-bed catalyst, an activated raney metal fixed-bed catalyst and a process for its preparation and use, and a method of hydrogenating organic compounds using said catalyst |
US6262307B1 (en) * | 1997-05-26 | 2001-07-17 | Degussa-Huls Aktiengesellschaft | Shaped, activated metal, fixed-bed catalyst |
EP1207149A1 (en) * | 2000-11-16 | 2002-05-22 | Basf Aktiengesellschaft | Process for the hydrogenation of nitriles on Raney catalysts |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2007028411A1 (en) * | 2005-09-08 | 2007-03-15 | Evonik Degussa Gmbh | The production and use of supported activated base metal catalysts for organic transformation |
EP2486976A1 (en) | 2005-09-08 | 2012-08-15 | Evonik Degussa GmbH | The production and use of supported activated base metal catalysts for organic transformation |
EP3544728A4 (en) * | 2016-11-22 | 2020-09-30 | W.R. Grace & Co.-Conn. | Method for manufacturing catalysts with reduced attrition |
US11439988B2 (en) | 2016-11-22 | 2022-09-13 | W. R. Grace & Co.-Conn. | Method for manufacturing catalysts with reduced attrition |
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