WO2006078352A2 - Reforming nanocatalysts and method of making and using such catalysts - Google Patents
Reforming nanocatalysts and method of making and using such catalystsInfo
- Publication number
- WO2006078352A2 WO2006078352A2 PCT/US2005/042841 US2005042841W WO2006078352A2 WO 2006078352 A2 WO2006078352 A2 WO 2006078352A2 US 2005042841 W US2005042841 W US 2005042841W WO 2006078352 A2 WO2006078352 A2 WO 2006078352A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- catalyst
- reforming
- dispersing agent
- multicomponent
- atoms
- Prior art date
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 425
- 238000002407 reforming Methods 0.000 title claims abstract description 170
- 239000011943 nanocatalyst Substances 0.000 title claims abstract description 89
- 238000004519 manufacturing process Methods 0.000 title claims description 23
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 166
- 239000002245 particle Substances 0.000 claims abstract description 110
- 239000002270 dispersing agent Substances 0.000 claims abstract description 101
- 239000000203 mixture Substances 0.000 claims abstract description 79
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 77
- 238000000034 method Methods 0.000 claims abstract description 71
- 229910052718 tin Inorganic materials 0.000 claims abstract description 47
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 43
- 230000003647 oxidation Effects 0.000 claims abstract description 36
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 36
- 125000000524 functional group Chemical group 0.000 claims abstract description 34
- -1 combination Substances 0.000 claims abstract description 22
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 20
- 229910052702 rhenium Inorganic materials 0.000 claims abstract description 13
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052741 iridium Inorganic materials 0.000 claims abstract description 12
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims abstract description 12
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 8
- 150000003573 thiols Chemical class 0.000 claims abstract description 8
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims abstract description 7
- 150000001266 acyl halides Chemical class 0.000 claims abstract description 7
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 7
- 239000000956 alloy Substances 0.000 claims abstract description 7
- 150000001408 amides Chemical class 0.000 claims abstract description 7
- 150000001412 amines Chemical class 0.000 claims abstract description 7
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 7
- 150000003461 sulfonyl halides Chemical class 0.000 claims abstract description 7
- 125000002524 organometallic group Chemical group 0.000 claims abstract description 6
- 230000001590 oxidative effect Effects 0.000 claims abstract description 4
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims abstract 6
- 238000005034 decoration Methods 0.000 claims abstract 4
- 229910052751 metal Inorganic materials 0.000 claims description 34
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 33
- 239000002184 metal Substances 0.000 claims description 33
- 239000000463 material Substances 0.000 claims description 31
- 239000002904 solvent Substances 0.000 claims description 30
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 22
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 21
- 230000003197 catalytic effect Effects 0.000 claims description 15
- 229930195733 hydrocarbon Natural products 0.000 claims description 15
- 150000002430 hydrocarbons Chemical class 0.000 claims description 15
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 claims description 13
- 150000002739 metals Chemical class 0.000 claims description 13
- 229920000642 polymer Polymers 0.000 claims description 12
- 239000010948 rhodium Substances 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 11
- 239000011575 calcium Substances 0.000 claims description 11
- 239000011777 magnesium Substances 0.000 claims description 11
- 229910052698 phosphorus Inorganic materials 0.000 claims description 11
- 239000010936 titanium Substances 0.000 claims description 11
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 10
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 10
- 238000004873 anchoring Methods 0.000 claims description 10
- 229910052738 indium Inorganic materials 0.000 claims description 10
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 10
- 229910052762 osmium Inorganic materials 0.000 claims description 10
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 claims description 10
- 229910052763 palladium Inorganic materials 0.000 claims description 10
- 229910052703 rhodium Inorganic materials 0.000 claims description 10
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 10
- 229910052707 ruthenium Inorganic materials 0.000 claims description 10
- 150000003839 salts Chemical class 0.000 claims description 10
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 9
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 9
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 9
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 9
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 9
- 229920002125 Sokalan® Polymers 0.000 claims description 9
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 9
- 229910052787 antimony Inorganic materials 0.000 claims description 9
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 9
- 229910052785 arsenic Inorganic materials 0.000 claims description 9
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 9
- 229910052788 barium Inorganic materials 0.000 claims description 9
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 9
- 229910052793 cadmium Inorganic materials 0.000 claims description 9
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 9
- 229910052791 calcium Inorganic materials 0.000 claims description 9
- 229910052733 gallium Inorganic materials 0.000 claims description 9
- 229910052732 germanium Inorganic materials 0.000 claims description 9
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 9
- 229910052749 magnesium Inorganic materials 0.000 claims description 9
- 239000011574 phosphorus Substances 0.000 claims description 9
- 239000004584 polyacrylic acid Substances 0.000 claims description 9
- 229910052712 strontium Inorganic materials 0.000 claims description 9
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 9
- 229910052719 titanium Inorganic materials 0.000 claims description 9
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 9
- 229910052721 tungsten Inorganic materials 0.000 claims description 9
- 239000010937 tungsten Substances 0.000 claims description 9
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 8
- 230000002829 reductive effect Effects 0.000 claims description 8
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 6
- 150000001491 aromatic compounds Chemical class 0.000 claims description 6
- 229920002554 vinyl polymer Polymers 0.000 claims description 6
- 229910052727 yttrium Inorganic materials 0.000 claims description 6
- 239000004471 Glycine Substances 0.000 claims description 5
- 239000004310 lactic acid Substances 0.000 claims description 4
- 235000014655 lactic acid Nutrition 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- ZMPRRFPMMJQXPP-UHFFFAOYSA-N 2-sulfobenzoic acid Chemical compound OC(=O)C1=CC=CC=C1S(O)(=O)=O ZMPRRFPMMJQXPP-UHFFFAOYSA-N 0.000 claims description 3
- 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 3
- QNAYBMKLOCPYGJ-REOHCLBHSA-N L-alanine Chemical compound C[C@H](N)C(O)=O QNAYBMKLOCPYGJ-REOHCLBHSA-N 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- 235000004279 alanine Nutrition 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 3
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 claims description 3
- 239000008103 glucose Substances 0.000 claims description 3
- DNZPFPGYVWVLCE-UHFFFAOYSA-N hydroxy(phenyl)methanesulfonic acid Chemical compound OS(=O)(=O)C(O)C1=CC=CC=C1 DNZPFPGYVWVLCE-UHFFFAOYSA-N 0.000 claims description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 3
- 239000011976 maleic acid Substances 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 3
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 3
- 229920001451 polypropylene glycol Polymers 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- 125000003011 styrenyl group Chemical class [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 3
- 235000000346 sugar Nutrition 0.000 claims description 3
- 150000003871 sulfonates Chemical class 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 claims description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 3
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000010457 zeolite Substances 0.000 claims description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims 2
- 239000012188 paraffin wax Substances 0.000 claims 2
- PYFPUPXEIBVIQA-UHFFFAOYSA-N phenyl(sulfanyl)methanesulfonic acid Chemical compound OS(=O)(=O)C(S)C1=CC=CC=C1 PYFPUPXEIBVIQA-UHFFFAOYSA-N 0.000 claims 2
- 239000011365 complex material Substances 0.000 claims 1
- 229910044991 metal oxide Inorganic materials 0.000 claims 1
- 150000004706 metal oxides Chemical class 0.000 claims 1
- 239000002105 nanoparticle Substances 0.000 abstract description 79
- 230000008569 process Effects 0.000 abstract description 24
- 230000000694 effects Effects 0.000 abstract description 12
- 239000000243 solution Substances 0.000 description 164
- 125000004429 atom Chemical group 0.000 description 82
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 66
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 52
- 238000001816 cooling Methods 0.000 description 31
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 27
- 229910052593 corundum Inorganic materials 0.000 description 27
- 229910001845 yogo sapphire Inorganic materials 0.000 description 27
- 238000002156 mixing Methods 0.000 description 26
- 238000006243 chemical reaction Methods 0.000 description 22
- 238000001035 drying Methods 0.000 description 22
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 21
- 238000007865 diluting Methods 0.000 description 20
- 238000010438 heat treatment Methods 0.000 description 19
- 229910052739 hydrogen Inorganic materials 0.000 description 19
- 239000001257 hydrogen Substances 0.000 description 19
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 18
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 18
- 239000000725 suspension Substances 0.000 description 16
- 239000007788 liquid Substances 0.000 description 15
- 239000000460 chlorine Substances 0.000 description 14
- 239000007787 solid Substances 0.000 description 14
- 229910052801 chlorine Inorganic materials 0.000 description 12
- 238000009826 distribution Methods 0.000 description 12
- 239000000543 intermediate Substances 0.000 description 11
- 238000003756 stirring Methods 0.000 description 11
- 239000002253 acid Substances 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000013078 crystal Substances 0.000 description 9
- 238000005054 agglomeration Methods 0.000 description 8
- 230000002776 aggregation Effects 0.000 description 8
- 238000001833 catalytic reforming Methods 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 239000002243 precursor Substances 0.000 description 7
- 239000000758 substrate Substances 0.000 description 7
- 239000004215 Carbon black (E152) Substances 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- LJSQFQKUNVCTIA-UHFFFAOYSA-N diethyl sulfide Chemical compound CCSCC LJSQFQKUNVCTIA-UHFFFAOYSA-N 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 6
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 6
- 150000007513 acids Chemical class 0.000 description 5
- 238000009835 boiling Methods 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 238000006356 dehydrogenation reaction Methods 0.000 description 5
- 238000011068 loading method Methods 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 4
- 229910002621 H2PtCl6 Inorganic materials 0.000 description 4
- 238000004517 catalytic hydrocracking Methods 0.000 description 4
- 239000003638 chemical reducing agent Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000009849 deactivation Effects 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 230000008929 regeneration Effects 0.000 description 4
- 238000011069 regeneration method Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 3
- 150000001299 aldehydes Chemical class 0.000 description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000001588 bifunctional effect Effects 0.000 description 3
- 238000004939 coking Methods 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 239000003502 gasoline Substances 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 238000006317 isomerization reaction Methods 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 229910001960 metal nitrate Inorganic materials 0.000 description 3
- 150000002823 nitrates Chemical class 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 3
- 238000006057 reforming reaction Methods 0.000 description 3
- 229910001415 sodium ion Inorganic materials 0.000 description 3
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- 150000003738 xylenes Chemical class 0.000 description 3
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 239000008241 heterogeneous mixture Substances 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 229910001510 metal chloride Inorganic materials 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 150000002902 organometallic compounds Chemical class 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000011946 reduction process Methods 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 239000003981 vehicle Substances 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- VEJOYRPGKZZTJW-FDGPNNRMSA-N (z)-4-hydroxypent-3-en-2-one;platinum Chemical compound [Pt].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O VEJOYRPGKZZTJW-FDGPNNRMSA-N 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 229910002846 Pt–Sn Inorganic materials 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 239000008186 active pharmaceutical agent Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 235000001014 amino acid Nutrition 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 150000001860 citric acid derivatives Chemical class 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 238000007327 hydrogenolysis reaction Methods 0.000 description 1
- 150000001261 hydroxy acids Chemical class 0.000 description 1
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000012280 lithium aluminium hydride Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910001463 metal phosphate Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 150000002843 nonmetals Chemical class 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 229920001456 poly(acrylic acid sodium salt) Polymers 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 230000007420 reactivation Effects 0.000 description 1
- 238000003303 reheating Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical class [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 150000008163 sugars Chemical class 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000003826 tablet Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G35/00—Reforming naphtha
- C10G35/04—Catalytic reforming
- C10G35/06—Catalytic reforming characterised by the catalyst used
- C10G35/085—Catalytic reforming characterised by the catalyst used containing platinum group metals or compounds thereof
- C10G35/09—Bimetallic catalysts in which at least one of the metals is a platinum group metal
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/42—Platinum
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/468—Iridium
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/62—Platinum group metals with gallium, indium, thallium, germanium, tin or lead
- B01J23/622—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead
- B01J23/626—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead with tin
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/656—Manganese, technetium or rhenium
- B01J23/6567—Rhenium
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8906—Iron and noble metals
-
- B01J35/23—
-
- B01J35/393—
-
- 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
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0203—Impregnation the impregnation liquid containing organic compounds
-
- 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
- B01J37/08—Heat treatment
-
- 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
- B01J37/16—Reducing
-
- 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
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G35/00—Reforming naphtha
- C10G35/04—Catalytic reforming
- C10G35/06—Catalytic reforming characterised by the catalyst used
- C10G35/085—Catalytic reforming characterised by the catalyst used containing platinum group metals or compounds thereof
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
Definitions
- the present invention relates generally to reforming nanocatalysts and methods for making and using such catalysts.
- Such reforming catalysts include supported nanocatalyst particles and are used for the reforming of naphtha and formation of BTX.
- Naphtha is a volatile, flammable liquid mixture of hydrocarbons distilled from petroleum or other fossil fuel sources. Naphtha can be used as a fuel, a solvent, or in making various chemicals. Typically naphtha is a mixture of hydrocarbons that boil between about 65°C and about 195°C and is obtained from processing crude oil and heavy oil fractions.
- Catalytic naphtha reforming is an important petroleum refining operation, hi catalytic naphtha reforming, a catalyst is used to reform the naphtha to make more valuable hydrocarbon products.
- a reforming catalyst can be used to increase the ) octane number of a naphtha mixture, thereby making it more suitable for gasoline blending.
- the reformed product, or reformate is one of the two most important contributors to the motor gasoline pool.
- Octane number gains by catalytic reforming vary depending on the feed quality and the reaction conditions, but typically range between 30 and 70.
- naphtha reforming is the production of benzene, toluene, and xylenes, also known collectively as BTX. These compounds, while useful for increasing octane, also have significant value and uses in various chemical industries.
- reforming is optimized to produce benzene, toluene, xylenes, ethyl benzene, and other aromatic compounds, the reforming procedure is called a BTX operation.
- naphtha reforming An additional benefit of naphtha reforming is the production of hydrogen. Hydrogen is used in many other refining operations, and naphtha reforming is typically the only refining process with a net production of hydrogen.
- Catalytic naphtha reforming usually includes a number of different reactions that take place in the vapor phase over a suitable catalyst.
- Important reforming reactions include: dehydrogenation of naphthenes to produce aromatics, isomerization of linear paraffins to form branched paraffins or iso-paraffins, and dehydrocyclization of paraffins to form aromatics.
- Each reaction can be favored by somewhat different reaction conditions and can take place at different catalytic active sites. Some of these reactions, such as dehydrogenation, are catalyzed by metal sites, whereas others, such as isomerization and dehydrocyclization, take place mostly via a bifunctional mechanism, meaning they require both metal and acid catalytic sites.
- Undesirable reactions can also occur. Examples of undesirable reactions include coking, which can deactivate the catalyst, and hydrogenolysis, which is a highly exothermic reaction that produces light hydrocarbon gases from larger paraffins.
- Hydrocracking is another reaction that can occur during naphtha reforming. Hydrocracking involves the cleavage of a C-C bond, resulting in the formation of lighter paraffins from heavier ones and in ring opening in naphthenes. For some hydrocarbon molecules hydrocracking is desirable, while for others it is not. Nevertheless, it usually occurs to some extent under typical reforming conditions.
- Naphtha reforming catalysts are designed to minimize undesired reactions, deactivate slowly, and show high activity and selectivity toward desired products. To achieve these properties, naphtha reforming catalysts are typically made from precious metals such as platinum.
- the present invention relates to supported reforming catalysts comprising a support and dispersed nanocatalyst particles anchored to the support.
- Such catalysts are used in the catalytic reforming of naphtha for octane number enhancement and/or for BTX formation.
- the improved dispersion and anchoring of nanoparticles and/or the improved distribution of catalyst components within the nanocatalyst particles overcome the disadvantages of prior catalysts by providing increased longevity, activity, and/or selectivity.
- supported reforming catalysts according to the invention include catalyst particles having a (111) crystal face exposure.
- Catalysts having a (111) crystal face exposure would be expected to have particular utility in forming aromatics since the catalyst atoms (e.g., Pt) are arranged in a six member ring around a central catalyst atom.
- Reforming catalysts according to the invention have been shown to have increased ability to enhance octane number and/or form aromatic compounds compared to conventional reforming catalysts, thus supporting this hypothesis. They have also resulted in an increase in net hydrogen production compared to conventional reforming catalysts.
- One exemplary embodiment for forming a supported reforming catalyst having well-dispersed nanocatalyst particles anchored to the support includes: (i) providing a plurality of catalyst atoms; (ii) providing a dispersing agent comprising a plurality of organic molecules that have at least one functional group capable of binding to the catalyst atoms; (iii) reacting the dispersing agent with the catalyst atoms to form a catalyst complex capable of forming a bond or otherwise adhering to a support; (iv) attaching the catalyst complex onto a support to form an intermediate catalyst composition in which the catalyst atoms are in a non-zero oxidation state; and (v) heat treating the intermediate catalyst composition at a temperature above about 5O 0 C while the catalyst atoms are in the non-zero oxidation state so as to form a supported catalyst having well-dispersed nanocatalyst particles having a size less than about 100 nm anchored to the support and in order to volatilize off at least one unwanted component.
- Reforming catalysts made according to the foregoing method include catalyst particles having catalyst metal atoms in a non-zero oxidation state, at least initially. Maintaining the catalyst metal atoms in a non-zero oxidation state during heat treating maintains a stronger bond between the catalyst metal atoms and the dispersing agent compared to heat treating a supported catalyst having catalyst metal atoms in the ground (or zero oxidation) state. This better inhibits agglomeration of the tiny catalyst nanoparticles, which, in turn, yields a supported catalyst having a better dispersion of nanocatalyst particles and higher catalytic activity. Such catalysts are typically reduced to a zero oxidation state prior to or during use.
- the reforming catalysts of the present invention are useful in promoting reforming reactions with naphtha, for gasoline blending and/or BTX formation. Both single- and multicomponent supported nanocatalysts according to the invention can be used for naphtha reforming.
- useful single component reforming catalysts include platinum (Pt), palladium (Pd), rhodium (Rh), and iridium (Ir).
- Multicomponent reforming catalysts may include two or more of the foregoing, or they may include one or more of the foregoing as the primary catalyst component in combination with at least one secondary catalyst component selected from the group comprising tin (Sn), rhenium (Re), germanium (Ge), lead (Pb), arsenic (As), antimony (Sb), tungsten (W), osmium (Os), cadmium (Cd), indium (In), titanium (Ti), phosphorus (P), gallium (Ga), ruthenium (Ru), calcium (Ca), magnesium (Mg), barium (Ba), and strontium (Sr).
- the secondary catalyst component(s) increase catalytic activity, promote other useful reactions, and/or help prevent catalyst deactivation by, e.g., coking.
- multicomponent ⁇ e.g., bimetallic) supported catalysts can be made in which individual catalyst nanoparticles include a mixture ⁇ e.g., an alloy) of different metals or components.
- nanoparticles comprising an alloy or combination of two or more different components is highly disfavored from a thermodynamic standpoint because of (i) the high temperatures typically necessary to cause dissimilar metals to join together in a single nanoparticle and (ii) because such high temperatures typically cause nanoparticles to agglomerate together to form larger (e.g., micron- or larger-sized particles).
- use of the dispersing agent reduces or eliminates same-component attractions that are normally present during catalyst formation and causes a more random distribution of metals within the nanocatalyst particles. Upon formation of the nanocatalyst particles, the distribution of each catalyst component in the particle is thus more random and uniform.
- multicomponent reforming catalysts can be made using other processes.
- methods for manufacturing supported multicomponent nanocatalyst particles are disclosed in copending U.S. application Serial No. 10/990,616, filed November 17, 2004, and entitled "MULTICOMPONENT NANOPARTICLES FORMED USING A DISPERSING AGENT", which was previously incorporated by reference.
- the foregoing application discloses methods of manufacturing a supported multicomponent metal catalyst in a manner than does not require a heat treatment step.
- the nanocatalyst particles are anchored to a substrate such as alumina or silica.
- the dispersing agent acts as an anchor to bind the catalyst nanoparticles to the substrate. Anchoring helps prevent particles agglomeration during use and also reduces leaching of the nanoparticles from the support material.
- the inventive reforming catalysts have improved catalytic activity and a higher resistance to deactivation.
- tin, rhenium, and iridium have the ability to improve catalyst activity and prevent undesired reactions, such as coking. These beneficial properties are typically promoted when the different catalyst atoms are intimately combined, mixed, interspersed, decorated, or alloyed together.
- the reforming catalysts according to the present invention can significantly reduce the cost of naphtha reforming operations.
- the higher activity of the catalysts means that higher octane number and/or aromatic products can be obtained with the same catalyst loadings.
- catalyst loading can be decreased while maintaining a desired catalyst activity, thereby decreasing catalyst costs.
- Increased catalyst lifetime can also reduce the cost of a reforming process since regeneration and/or replacement of the catalyst in a reforming operation may be performed less frequently.
- the present invention is directed to the manufacture of novel reforming nanocatalysts useful for reforming naphtha for octane number enhancement and for
- novel reforming nanocatalysts are manufactured in a manner so as to have well-dispersed nanocatalyst particles anchored to a support.
- a dispersing agent is used that bonds to the catalyst components and determines, at least in part, the molecular arrangement of the catalyst components.
- a dispersing agent can be used to ensure that two or more different catalyst components are distributed between nanocatalyst particles in a desired distribution. These nanocatalyst particles can be used to form supported reforming catalysts with improved catalytic activity and increased longevity
- nanoparticles or “nano-sized particles,” means particles with a diameter of less than about 100 nanometers (nm).
- minority component means the component in a multicomponent nanocatalyt particle with the lesser concentration within the particle. In the case where two or more components have essentially the same concentration within the particle, evidenced by the fact that the determination of a minority is statistically impractical, then either component is considered to be the minority component.
- N A /N B N A /N B
- NA is the number (or moles) of atoms of a more numerous component A in a given nanoparticle or set of nanoparticles
- N B is the number (or moles) of atoms of a less numerous component B in the nanoparticle or set of nanoparticles.
- NR can be expressed as the specific value (NRj).
- the average NR for all of the nanoparticles in a given set of nanoparticles is expressed as the average value (NR avg ).
- the individual NR values corresponding to the various particles within a given sample or set of nanoparticles do not equal a single discrete value but fall within a range of NR values (i.e., the "Range of NR")-
- the Range of NR for a given sample of set of nanoparticles having at least two different nanoparticle components within each particle has an upper value NR max and a lower value NR m i n .
- Supported reforming nanocatalysts according to the invention are typically manufactured using one or more different types of catalyst atoms, a dispersing agent, a support, and one or more solvents.
- one or more catalyst metals or components are initially reacted with a dispersing agent to form a catalyst complex, typically using one or more solvents to form a solution, colloid or suspension comprising the solvent, catalyst complex, and optionally excess dispersion agent and/or catalyst component(s).
- the catalyst complex is impregnated onto or otherwise attached to a support to form an intermediate catalyst composition in which the catalyst atoms have a non-zero oxidation state.
- the intermediate catalyst composition is heat treated while the catalyst atoms are maintained in a non-zero oxidation state so as to form a supported catalyst having well-dispersed nanocatalyst particles having a size less than about 100 nm anchored to the support.
- reforming catalysts (including multicomponent catalysts) according to the invention can be manufactured without a heat treatment step.
- the catalyst atoms that form the catalyst nanoparticles of the present invention can include any metal, or combination of one or more metals or other elements, that exhibit catalytic reforming activity.
- useful catalyst atoms include one or more noble metals, which include platinum, palladium, indium, gold, osmium, ruthenium, rhodium, and rhenium.
- other catalyst atoms include one or more base transition metals, rare earth metals, alkaline earth metals, alkali metals, and even non metals, which can be used alone or complexed or alloyed with other catalyst materials.
- Platinum (Pt) is particularly useful as the primary catalyst component in reforming catalysts.
- palladium (Pd), rhodium (Rh) and iridium (Ir) may also be used as the primary catalyst component, or they may be used in combination with platinum as a secondary catalyst component.
- Tin (Sn) and rhenium (Re) can be beneficially used in combination with platinum as a secondary catalyst component, as can be various other components such as germanium (Ge), lead (Pb), arsenic (As), antimony (Sb), tungsten (W), osmium (Os), cadmium (Cd), indium (In), titanium (Ti), phosphorus (P), gallium (Ga), ruthenium (Ru), calcium (Ca), magnesium (Mg), barium (Ba), and strontium (Sr).
- the catalyst atoms are added to an appropriate solvent or carrier to form a solution or suspension.
- Catalyst atoms can be added to a solution in elemental (e.g., metallic) form, or added in ionic form.
- the catalyst atoms are added in ionic form so as to more readily dissolve or disperse within the solvent or carrier.
- suitable ionic forms include metal halides, nitrates or other appropriate salts that are readily soluble in a solvent or carrier. Specific examples include metal phosphates, sulfates, tungstates, acetates, citrates, and glycolates.
- Metal components that are compounds themselves, such as oxides, can be added to a liquid medium in the appropriate compound form, or may be in a different chemical form that is converted to the appropriate chemical form during catalyst formation.
- the dispersing agent is selected to promote the formation of a catalyst complex that is able to bond or adhere to a support.
- the dispersing agent is selected to yield nanocatalyst particles that have a desired stability, size and/or uniformity.
- Dispersing agents within the scope of the invention include a variety of small organic molecules, as well as polymers and oligomers. Exemplary dispersing agents are able to interact and complex with catalyst atoms that are dissolved or dispersed within an appropriate solvent or carrier through various mechanisms, including ionic bonding, covalent bonding, Van der Waals interaction/bonding, or hydrogen bonding.
- the dispersing agent includes one or more appropriate functional groups. Suitable functional groups for complexing the dispersing agent with the catalyst atoms include one or more of a hydroxyl, a carboxyl, an amine, a thiol, an ester, an amide, a ketone, an aldehyde, a sulfonic acid, an acyl halide, a sulfonyl halide, and combinations of these.
- the dispersing agent can be monofunctional, bifunctional, or polyfunctional. In the case where the catalyst atoms are metals, the catalyst complex formed between the catalyst atoms and dispersing agent is typically an organometallic complex.
- Suitable monofunctional dispersing agents include alcohols such as ethanol and propanol and carboxylic acids such as formic acid and acetic acid.
- Useful bifunctional dispersing agents include diacids such as oxalic acid, malonic acid, maleic acid, and the like; dialcohols such as ethylene glycol, propylene glycol, 1,3-propanediol, and the like; and hydroxy acids such as glycolic acid, lactic acid, and the like.
- Useful polyfunctional dispersing agents include sugars such as glucose, polyfunctional carboxylic acids such as citric acid, hydroxy diacids, and the like.
- Other useful dispersing agents include ethanolamine, mercaptoethanol, 2- mercaptoacetate, amino acids such as glycine and alanine, sulfonic acids such as sulfobenzyl alcohol and sulfobenzoic acid, and other sulfobenzyl compounds having amino and thiol functional groups.
- Dispersing agents according to the invention also include polymers or oligomers, which can be natural or synthetic, hi the case where the dispersing agent is an oligomer or polymer, the molecular weight, measured in number average, is preferably in a range from about 300 to about 15,000 Daltons, more preferably in a range of about 600 to about 6000 Daltons.
- high molecular weight polymers i.e., greater than 15,000, can be used as the dispersing agent if they are readily soluble in solvents, carriers or vehicles and can complex with the catalyst atoms.
- the molecular weight of the polymer or oligomer molecules may be selected to yield a dispersing agent having a desired number of functional groups per molecule, hi general, the number of functional groups may range from 4 to 200 functional groups per molecule, preferably from about 8 to about 80 functional groups, and more preferably from about 10 to about 20 functional groups. In many cases, the number of functional groups within a polymer or oligomer at least approximately corresponds to the number of repeating units.
- Suitable polymers and oligomers within the scope of the invention include, but are not limited to, polyacrylic acid, polyacrylates, polyvinylbenzoates, polyvinyl sulfate, polyvinyl sulfonates, including sulfonated styrene, polybisphenol carbonates, polybenzimidizoles, polypyridine, sulfonated polyethylene terephthalate.
- Other suitable polymers include polyvinyl alcohol, polyethylene glycol, polypropylene glycol, and the like.
- dispersing agent In addition to the characteristics of the dispersing agent, it can also be advantageous to control the molar ratio of dispersing agent functional groups to catalyst atoms. For example, in the case of a divalent metal ion, two molar equivalents of a monovalent functional group would be necessary to provide the theoretical stoichiometric ratio. It may be desirable to provide an excess of dispersing agent functional groups to (1) ensure that all or substantially all of the catalyst atoms are complexed, (2) bond the nanoparticles to a support, and (3) help keep the nanoparticles segregated so that they do not clump or agglomerate together. In general, it will be preferable to include a molar ratio of dispersing agent functional groups to catalyst atoms in a range of about 1000:1 to about 1:1000 and more preferably in a range of about 50:1 to about 1:50.
- the dispersing agents of the present invention allow for the formation of very small and uniform nanoparticles.
- the catalyst nanoparticles formed in the presence of the dispersing agent are preferably less than about 100 nm, more preferably less than about 10 nm, even more preferably less than about 6 nm, more especially preferably less than about 5 nm, and most preferably less than about 4 nm.
- the nanocatalyst particles are supported on a support surface. It is believed that when a support material is added to a suspension or solution of catalyst complex, the dispersing agent acts to uniformly disperse the complexed catalyst atoms and/or suspended nanoparticles onto the support material.
- the dispersing agent can be selected such that it acts as an anchor between the naiiocatalyst particles and a support material, which is described more fully below.
- the dispersing agent can act as an anchoring agent to secure the nanoparticle to a substrate.
- the substrate has a plurality of hydroxyl or other functional groups on the surface thereof which are able to chemically bond to one or more functional groups of the dispersing agent, such as by a condensation reaction.
- One or more additional functional groups of the dispersing agent are also bonded to one or more atoms within the nanoparticle, thereby anchoring the nanoparticle to the substrate.
- the dispersing agent has the ability to inhibit agglomeration without anchoring, chemically bonding the nanoparticle to the substrate surface through the dispersing agent is an additional and particularly effective mechanism for preventing agglomeration.
- the dispersing agent is selected to yield reforming catalysts having a (111) crystal face exposure.
- small molecule dispersing agents e.g., citric acid, glycolic acid, lactic acid, and ethylene glycol
- branched oligomers or polymers e.g., branched polyacrylic acid
- catalyst complex refers to a solution, suspension, or other composition in which a bond or coordination complex is formed between a dispersing agent and one or more different types of catalyst atoms.
- the "bond" between the dispersing agent and catalyst atoms can be ionic, covalent, electrostatic, or it can involve other bonding forces such as coordination with nonbonding electrons, Van der Waals forces, and the like.
- Catalyst complexes include one or more different types of catalyst atoms complexed with one or more different types of dispersing agents, hi some cases, the catalyst complex comprises individual catalyst atoms bonded to the dispersing agent in solution or suspension within a solvent. In such cases, the catalyst particles are formed after attaching the catalyst complex to a support to form an intermediate catalyst composition and then subjecting the intermediate catalyst composition to one or more appropriate processing steps to yield the catalyst particles. In other cases, the catalyst complex includes or forms the nanocatalyst particles in suspension prior to applying the catalyst complex to the support.
- the catalyst complex may comprise an organometallic compound, either alone or in combination with another or additional dispersing agent.
- the organometallic compound may have the general formula:
- Y and Y' are electron-donating atoms, such as O, N, P, S, and others. Y and Y' may belong to a single coordinated compound or may be part of independently coordinated ligands.
- the metal center of the organometallic complex can be platinum, another noble metal, and/or other metal having desired catalytic activity.
- a solvent or carrier can be used as a vehicle for the combining of the catalyst atoms (typically in the form of an ionic salt) and/or the dispersing agent.
- the solvent used to make the inventive precursor compositions may be an organic solvent, water or a combination thereof.
- Organic solvents that can be used include alcohols, ethers, glycols, ketones, aldehydes, nitriles, and the like.
- Preferred solvents are liquids with sufficient polarity to dissolve the metal salts. These preferred solvents include water, methanol, ethanol, n-propanol, isopropyl alcohol, acetonitrile, acetone, tetrahydrofuran, ethylene glycol, dimethylformamide, dimethylsulfoxide, methylene chloride, and the like, including mixtures thereof. Other chemical modifiers may also be included in the liquid mixture. For example, acids or bases may be added to adjust the pH of the mixture. Surfactants may be added to adjust the surface tension of the mixture, or to stabilize the nanoparticles.
- the solvent for the nanoparticle components may be a neat solvent, but it is preferable to use an acidic solution, as acids aid in the dissolution of the nanoparticle components.
- the solution may be acidified with any suitable acid, including organic and inorganic acids.
- Preferred acids are mineral acids such as sulfuric, phosphoric, hydrochloric, and the like, or combinations thereof. While it is possible to use an acid in a wide range of concentrations, relatively dilute solutions generally accomplish the desired solubility enhancement. Moreover, concentrated acid solutions may present added hazard and expense. Thus, dilute acid solutions are currently preferred.
- the nanocatalyst particles are typically formed on or applied to a solid separate solid material to yield a supported reforming catalyst.
- the solid support material may be organic or inorganic and can be chemically inert in the chemical reaction environment or serve a catalytic function complementary to the function of the catalyst particles. In the case where the reforming conditions involve higher temperatures, the support will preferably comprise an inorganic material.
- any solid support material known to those skilled in the art as useful catalyst particle supports can be used as supports for the nanocatalyst particles of this invention.
- These supports may be in a variety of physical forms. They may be either porous or non-porous. They may be 3-dimensional structures such as a powder, granule, tablet, extrudates, or other 3-dimensional structure. Supports may also be in the form of 2-dimensional structures, such as films, membranes, coatings, or other mainly 2-dimensional structures. It is even conceivable for the support to be a 1- dimensional structure, such as ultra-thin fibers and filaments In a preferred embodiment, the reforming catalyst support comprises a porous inorganic material.
- porous solids such as zeolites, natural or synthetic, and related materials, which have ordered or quasi-ordered pore structures.
- the surface area of the support be at least 20 m 2 /g, and more preferably more than 50 m 2 /g.
- Another useful class of supports include carbon-based materials, such as carbon black, activated carbon, graphite, fluoridated carbon, and the like.
- Other useful classes of support materials include organic solids, such as polymers and metals and metal alloys.
- the support material may be treated with a halogen, an example of which is chlorine, in order to give the catalyst acidity.
- a halogen an example of which is chlorine
- the nanocatalyst particles can be deposited in a wide range of loadings on the support material.
- the loading can range from 0.01% to 90% by weight of the total weight of the supported catalyst.
- the preferred loading will depend on the specific reforming application involved.
- the reforming catalysts according to the invention include well-dispersed nanocatalytic particles anchored to an appropriated support material.
- Reforming catalysts suitable for the reforming of naphtha for octane number enhancement or BTX formation may include one type of catalyst metal or component, or they may be multicomponent catalysts.
- One method of manufacturing catalysts, as discussed more fully below, is particularly useful in the manufacture of reforming catalysts having multicomponent nanocatalyst particles comprising a plurality of different metals.
- Exemplary reforming catalysts comprise multicomponent nanocatalyst particles that include one or more of platinum, palladium, rhodium, or iridium as the primary catalyst component in combination with a secondary reforming catalyst component, preferably one or more of tin or rhenium.
- Other secondary reforming catalyst components include one or more of germanium, lead, arsenic, antimony, tungsten, osmium, cadmium, indium, titanium, phosphorus, gallium, ruthenium, calcium, magnesium, barium, and strontium.
- the nanocatalyst particles will preferably have a desired distribution of catalyst atoms.
- At least about 50% of the nanocatalyst particles in the reforming catalyst will preferably include two or more of the nanocatalyst components. More preferably, at least about 75% of the nanocatalyst particles within the reforming catalyst include two or more of the nanocatalyst components, even more preferably at least about 85% of the nanocatalyst particles include two or more of the nanocatalyst components, and most preferably at least about 95% of the nanocatalyst particles within the reforming catalyst include two or more of the nanocatalyst components. It is within the scope of the invention for at least about 99% of the nanocatalyst particles within a reforming catalyst according to the invention to include two or more of the nanocatalyst components.
- multicomponent nanocatalyst particles prepared according to the invention include two or more nanocatalyst components
- the benefits derived from having the catalyst components in a single multicomponent particle are more uniformly distributed throughout the nanocatalyst particles compared to heterogeneous mixtures of single component catalyst particles. Consequently, the overall catalyst has an increased display of these beneficial properties.
- the degree of distribution of the two or more components between nanoparticles prepared according to the invention can be measured by the Number Ratio (NR) or Range of NR for a given set of nanoparticles having two or more components.
- the Number Ratio NA/N B , where NA is the number (or moles) of atoms of a more numerous component A within a nanoparticle or set of nanoparticles according to the invention, and N B is the number (or moles) of atoms of a less numerous component B within the nanoparticle or set of nanoparticles.
- the value of NR can be expressed as an average value (NR avg ) for all of the nanoparticles in a given set or as the specific value (NRj) for a particular nanoparticle i.
- the value NRi for each nanoparticle i in a given set of inventive nanoparticles equals NR aV g-
- each particle i has an equal distribution of components A and B.
- the present invention also contemplates controlling the dispersion of components in bi- or multicomponent nanoparticles such that the Range of NR values for all of the nanoparticles in a particular sample is within a desired range.
- the Range of NR has an upper value NR max and a lower value NR m i n - As NR max and NR m i n deviate less from NR aT g, the Range of NR becomes narrower, which indicates that the nanoparticles are more uniform.
- the value of NR max does not exceed about 5 times the value of NR av g, more preferably does not exceed about 3 times the value of NRavg, and most preferably does not exceed about 2 times the value of NR av g.
- the value of NR m i n is preferably at least about 0.2 times the value of NR avg , more preferably at least about 0.33 times the value of NR avg , and most preferably at least about 0.5 times the value of NR aV g.
- the Range of NR is therefore preferably about 0.2 to about 5 times the value of NR aV g, more preferably about 0.33 to about 3 times the value of NR av g, and most preferably about 0.5 to about 2 times the value of NR avg .
- the foregoing ranges do not count "outliers" (i.e., particles that do not form correctly and that excessively deviate from NR aV g as to be outside the Range of NR).
- the NR of the "outliers" may in some cases count toward the NR avg , they do not fall within the "Range of NR" by definition.
- At least about 50% of the individual nanoparticles in a given reforming catalyst will have an NRj within the Range of NR. More preferably, at least about 75% of the individual nanoparticles within the catalyst will have an NRj within the Range of NR, even more preferably at least about 85% of the individual nanoparticles within the catalyst will have an NR; within the Range of NR, and most preferably at least about 95% of the individual nanoparticles within the catalyst will have an NRj within the Range of NR. It is within the scope of the invention for at least about 99% of the individual nanoparticles within a reforming catalyst according to the invention to have an NRj within the Range of NR.
- the nanoparticles in the prior art have very wide Ranges of NRj, in some cases ranging from zero to infinity, indicating that some particles have essentially none of one component, and other particles have essentially none of the other component(s).
- the following two simple numerical examples provide non-limiting examples of nanocatalyst particles of the present invention having desired Ranges of NR.
- component B comprises 1% of a bimetallic nanoparticle mixture
- component A comprises the balance in a given set of nanoparticles.
- the NR aVg for the set of nanoparticles is approximately 100.
- the preferred Range of NR for the set nanoparticles is thus 20 to 500, which translates to a range of 0.2% to 5% of component B in the individual nanoparticles that contain both components.
- the more preferred range for NR is 33 to 300, translating to a composition range of 0.33% to 3% of component B in the individual nanoparticles that contain both components.
- the most preferred range for NR is 50 to 200, or a composition range of 0.5% to 2% component B in the individual nanoparticles that contain both components.
- NRj is 0.2 to 5, corresponding to a composition range of 16% to 83% of component B in the individual nanoparticles that contain both components.
- the more preferred range of NRj is 0.33 to 3, corresponding to a composition range of 25% to 75% component B in the individual nanoparticles that contain both components.
- the most preferred range of NRj is 0.5 to 2, or a composition range of 33% to 67% component B in the individual nanoparticles that contain both components.
- the dispersing agents of the present invention are used to provide the desired dispersion and uniformity that is characteristic of the nanocatalyst particles of the present invention.
- the above-mentioned uniformity as defined by NR can be obtained.
- the dispersing agent remains as a constituent of the reforming catalyst (i.e., as an anchoring agent that anchors the nanocatalyst particles to the support).
- the inventors of the present invention have found that characteristic features attributable to the dispersing agent can be present in the final nanocatalyst product, indicating that the dispersing agent persists beyond the nanocatalyst preparation steps.
- each nanoparticle can be composed of a mixture of components regardless of how they are chemically combined.
- the components can be present as relatively isolated atoms, or as small atomic clusters. They can also be present as amorphous particles.
- the components can also be present as crystallites, including alloys.
- Component crystals can have relatively random crystal face exposures, or they can have a controlled or selective exposure of particular crystal faces.
- the uniformity made possible by using a dispersing agent yields improved reforming catalyst properties. Many properties of multicomponent reforming catalysts, such as longevity, depend on the proximity of the two components, such as platinum and tin. The substantially uniform distribution of components during catalyst preparation provides a greater possibility for these different components to come into proximity with one another to provide the desired functionality or property to the catalyst in its final form.
- the dispersing agent also makes it possible to select very precise ratios of components by controlling the average percent composition. Because the individual multicomponent catalyst particles have a percent composition that varies very little from the average composition, the percent composition of the individual nanoparticles can be more precisely controlled by adjusting the starting materials to control the average percent composition.
- Catalysts having a (111) crystal face exposure would be expected to have particular utility in forming aromatics since the catalyst atoms (e.g., Pt) are arranged in a six member ring around a central catalyst atom. Reforming catalysts according to the invention have been shown to have increased ability to enhance octane number and/or form aromatic compounds compared to conventional reforming catalysts, thus supporting this hypothesis. They have also resulted in an increase in net hydrogen production compared to conventional reforming catalysts. IV. EXEMPLARY METHODS OF MAKING REFORMING CATALYSTS Exemplary methods for manufacturing supported reforming catalysts according to the invention can be broadly summarized as follows.
- catalyst atoms e.g., metals or other components
- dispersing agent e.g., sodium bicarbonate
- the catalyst atoms and the dispersing agent are reacted or combined together to form catalyst complexes.
- the catalyst complexes are impregnated onto or otherwise attached to a support material.
- the reforming catalyst is further heat treated to activate the catalyst or prepare it for use in a reforming process.
- This method is useful in manufacturing both mono-component and multicomponent reforming catalysts.
- multicomponent reforming catalysts can be manufactured according to methods disclosed in U.S. application Serial No. 10/990,616, filed November 17, 2004, and entitled "MULTICOMPONENT NANOPARTICLES FORMED USING A DISPERSING AGENT", which was previously incorporated by reference.
- Reforming catalysts according to the invention can be manufactured with or without a heat treatment process. The heat treatment process can be performed before of after reducing the catalyst atoms from a non-zero oxidation state to a zero oxidation state.
- the catalyst complex made during the second step outlined above is generally formed by first dissolving the catalyst atoms and dispersing agent in an appropriate solvent or carrier and allowing the catalyst atoms to recombine as the catalyst complex so as to form a solution or suspension.
- dispersed nanocatalyst particles form in the suspension.
- the dispersing agent facilitates the formation of nanocatalyst particles when disposed on a support surface in one or more subsequent steps.
- the catalyst atoms can be provided in any form so as to be soluble or dispersible in the solvent or carrier that is used to form the catalyst complex.
- catalyst atoms can be provided as metal salts that are readily dissolvable in the solvent or carrier. It may be advantageous to use metal chlorides and nitrates, since metal chlorides and nitrates are typically more soluble than other metal salts.
- Catalyst atoms can be added to the solvent or carrier singly or in combination to provide final nanocatalyst particles that comprise a mixture of various types of catalyst atoms.
- a platinum/tin reforming catalyst can be formed by first forming a precursor solution of platinum and a precursor solution of tin and then combining the precursor solutions.
- the composition of the final nanocatalyst particles will be determined by the types of catalyst atoms added to the precursor solution. Therefore, control of the amounts of metal salts added to the precursor solution provides a convenient method to control the relative concentrations of different types of catalyst atoms in the final nanocatalyst particles.
- the dispersing agent is added to the solvent or carrier in a manner so as to facilitate association of the dispersing agent with the catalyst atoms in order to form the catalyst complex.
- Some dispersing agents may themselves be soluble in the solvent or carrier.
- it may be advantageous to form a metal salt of the acids e.g., an alkali or alkaline earth metal salt.
- polyacrylic acid can be provided as a sodium polyacrylate salt, which is both readily soluble in aqueous solvent systems and able to react with catalyst metal salts to form a metal-polyacrylate complex that may be soluble or which may form a suspension within the solvent or carrier.
- One aspect of the invention is that very small nanocatalyst particles can be controllably formed.
- the inventors believe that the relative amounts (or ratio) of dispersing agent to catalyst atoms may play a factor in determining the size of the resulting catalyst nanoparticles. In general, providing a stoichiometric excess of dispersing agent helps reduce particle agglomeration, thereby also generally reducing the size of the nanoparticles.
- the catalyst complex is then impregnated into or otherwise applied to a support material to yield an intermediate catalyst composition
- the catalyst complex solution or suspension is physically contacted with a solid support.
- Contacting the catalyst complex with the solid support is typically accomplished by means of an appropriate solvent or carrier within the catalyst complex solution in order to apply or impregnate the catalyst complex onto the support surface to yield the intermediate catalyst composition.
- the process of contacting or applying the catalyst complex to the support may be accomplished by a variety of methods.
- the support may be submerged or dipped into a solution or suspension comprising a solvent or carrier and the catalyst complex.
- the solution or suspension may be sprayed, poured, painted, or otherwise applied to the support, such as by incipient wetness impregnation. Thereafter, the solvent or carrier is removed, optionally in connection with a reaction step that causes the dispersing agent to become chemically bonded or adhered to the support. Either way, the process yields an intermediate catalyst composition.
- the intermediate catalyst composition is heat treated to further activate or prepare the supported catalyst atoms or particles for use in the catalytic reforming of naphtha for octane number enhancement and/or BTX formation. It has been found that, in some cases, subjecting the nanocatalyst particles to a heat treatment process before using the reforming catalyst causes the catalyst to be more active initially.
- the heat treatment is performed to volatilize unwanted molecules from the nanocatalyst particles. Heat treating can also be performed to increase the anchoring of the nanocatalyst particles to the support material. For example, in a naphtha reforming catalyst, progressively heating to
- 500° C can improve the bonding between the nanocatalyst particles and a support material such as alumina or silica.
- Heat treatment can cause initial formation of nanocatalyst particles from individual complexed atoms in the case where nanoparticles are not formed in suspension prior to applying the catalyst complex to the support material.
- the heat treatment process is carried out in an inert or oxidizing environment and with the catalyst atoms at least initially in a non- zero oxidation state. It is believed, at least in some cases, that reducing the catalyst atoms to a zero oxidation state prior to heat treating can weaken the interaction between the catalyst atoms and the dispersing agent and cause unwanted agglomeration of the nanocatalyst particles in some cases. Li the non-zero oxidation state, the catalyst atoms form a much stronger bond to the dispersing agent because of the charge on the catalyst atom.
- performing the heat treatment process in an inert or oxidizing atmosphere helps maintain the catalyst atoms in the non-zero oxidation state longer than if the treatment were carried out in a reducing environment, such as H 2 .
- heat treating in the nonzero oxidation state may improve the distribution of components between nanocatalyst particles. Maintaining a stronger bond between the dispersing agent and the different nanoparticle components reduces same-component attractions. Reducing same-component attractions allows more random distributions of the different catalyst atoms between nanoparticles and/or prevents same-component attractions from destroying distributions already present in the catalyst nanoparticles before the heat treating step is performed. Even in one-component catalyst systems, heat treating the reforming catalyst while maintaining the catalyst atoms in a non-zero oxidation state can help prevent unwanted agglomeration of the nanocatalyst particles at the higher temperatures associated with the heat treatment process.
- the heat treating process of the present invention is preferably carried out at a temperature in a range of about 5O 0 C to about 600°C, more preferably in a range of about 100°C to about 500°C, and most preferably in a range of about 150 0 C to about 400 0 C.
- the duration of the heat treatment process is preferably in a range of about 5 minutes to about 24 hours, more preferably in a range of about 30 minutes to about 12 hours, and most preferably in a range of about 1 hour to about 6 hours.
- a preferred inert environment for performing the heat treating step includes N 2 .
- One advantageous feature of heat treating the reforming catalyst while maintaining the metal catalyst particles in a non-zero oxidation state is that it does not degrade the nanoparticles or reduce catalytic activity.
- the dispersing agent provides added stability that helps prevent destroying or agglomeration of the nanoparticles due to the strong interaction between the dispersing agent and catalyst atoms in a nonzero oxidation state.
- a partial reducing step can be performed prior to heat treating to partially reduce the catalyst atoms.
- the reducing step does not reduce the catalyst atoms to the zero oxidation state; rather, the catalyst atoms are only partially reduced (i.e., from a higher to a lower non-zero oxidation state).
- the catalyst atoms are only partially reduced if the reduction step is carried out at a sufficiently low temperature.
- platinum catalyst atoms can be partially reduced by heating the nanocatalyst particles to a temperature less than about 100 0 C in the presence of H 2 .
- reduction can be performed in a reforming reactor (e.g., the naphtha itself can act as a reducing agent during catalytic dehydrogenation). Performing the reduction process after the aforementioned heat treatment process is less likely to affect the dispersion and/or distribution of the catalyst atoms. It is believed that heat treating the catalyst atoms while in a non-zero oxidation state forms better anchored catalyst particles that are better stabilized when exposed to subsequent reduction conditions.
- the catalyst nanoparticles can be reduced prior to using the reforming catalyst by using a reducing procedure (e.g., hydrogenation).
- Hydrogen is one preferred reducing agent.
- a variety of other reducing agents may be used, including but not limited to, lithium aluminum hydride, sodium hydride, sodium borohydride, sodium bisulfite, sodium thiosulfate, hydroquinone, methanol, aldehydes, carbon monoxide, ammonia, and the like.
- the reduction process may be conducted at a temperature between 2O 0 C and 600 0 C.
- the reforming catalyst can be further processed into a finished product of size and shape suitable for a specific reactor or process configuration.
- a powder may be processed by, among other methods, extrusion, pelletizing, or spray drying.
- Reforming catalysts according to the invention can be used in reforming hydrocarbons such as naphtha. Reforming catalysts can be used in dehydrogenation of naphthenes to produce aromatics, isomerization of linear paraffins to form branched paraffins or iso-paraffins, and dehydrocyclization of paraffins to form aromatics, among other reactions. Reforming catalysts can be used to enhance octane number for fuel blending and/or in BTX reactions to yield benzene, toluene, xylenes, ethyl benzene, and other aromatic compounds.
- the reforming catalysts according to the invention are superior to reforming catalysts known in the art because the nanocatalyst particles are more strongly anchored to the support, which extends the useful life of the catalyst.
- the reforming catalysts are superior because they comprise catalyst particles comprising two or more catalyst components within the nanocatalyst particle rather than a purely or mainly heterogenous mixture of different types of single component catalyst particles, as are typically found in conventional multicomponent nanocatalysts.
- the reforming process is typically carried out in a reactor.
- Three suitable reactor configurations for reactions such as naphtha catalytic reforming include: a) the semi-regenerative process, where the catalyst is regenerated every 6 to 24 months, and requires that the reactor be shut down; b) the cyclic process where a spare reactor is brought online while another is taken offline for catalyst regeneration; and c) the continuous catalyst regeneration (CCR) process, where the catalyst continuously circulates from the top to the bottom of the reforming reactor and is then fed to an external regeneration unit for reactivation and then sent to the top of the reactor.
- CCR continuous catalyst regeneration
- the reforming catalyst is first loaded into the reactor and subjected to a reductive treatment.
- This treatment usually includes heating the catalyst to a high temperature (400°C-525°C) in a pure hydrogen environment. Naphtha is then continuously fed into the reactor with continuously flowing hydrogen.
- Typical hydrogen to hydrocarbon molar ratios are between 3 and 8.
- Reaction conditions are chosen as a compromise among maximizing octane gain, minimizing losses to light gases, and extending catalyst lifetime.
- Catalytic naphtha reforming is performed in a hydrogen atmosphere to facilitate the hydrogenation of coke precursors, thus minimizing catalyst deactivation and equipment fouling.
- higher partial pressures of hydrogen tend to inhibit dehydrogenation reactions.
- Total operating pressures range between about 300 fcPa to about 3.5 MPa.
- higher values favor both higher octane numbers in the reformate and hydrocracking producing light gases.
- Typical operating temperatures are between about 460 0 C and about 525°C.
- a reforming catalyst according to the present invention was prepared using platinum and tin as catalyst components.
- the catalyst was prepared using the following steps and concentrations:
- a platinum solution was prepared by dissolving 1.0209 g of H 2 PtCl 6 -OH 2 O (Pt: 38-40%, select 39%) in water and diluting to 100.0 ml. The final concentration of the platinum solution was 0.003982 g Pt/ml.
- a tin solution was prepared by mixing 1.9390 g of SnCl 2 -2H 2 O (98%) and 5.74 g of 37% HCI solution in water to dissolve the tin Cl 2 . The Tin solution was then diluted to 200.0 ml to form a solution with a tin concentration of 0.004999 g Sn/ml.
- Solution A was prepared by diluting 23.56 g of the 0.003982 g Pt/ml solution to form 100 g solution and then adding 4.4 g of 37% HCl solution while stirring.
- Solution B was prepared by diluting 12.96 g of the 0.004999 g Sn/ml solution with water to form a 100 g solution and then adding Solution A.
- Solution C was prepared by letting Solution B stand for 1 hour and then adding 1.67 g of 37% HCl solution.
- Solution D was prepared by diluting 2.73 g of 45% polyacrylic acid sodium salt solution to 220 g using water and then adding Solution C.
- Solution D was purged with 100 ml/min N 2 for 1 hour. The N 2 was replaced by 100 ml/min H 2 for 20 min. The flask was then sealed overnight while continuously stirring.
- the resulting catalyst had a weight composition of 0.34% Pt, 0.23% Sn, and 1.08% Cl.
- a conventional reforming catalyst was used (i.e., made without the use of the dispersing agent).
- the conventional reforming catalyst was supported on the same material and had the same elemental composition as the inventive reforming catalyst of Example 1, but was prepared without the use of a dispersing agent.
- the conventional reforming catalyst and the inventive reforming catalyst of Example 1 were loaded in identical reactors and subjected to the same pretreatment and reaction conditions. For each reaction test, approximately 21 g of solid catalyst were loaded in a tubular reactor where the heated volume was divided into two equal catalyst beds separated by a reheating zone. Both catalysts were diluted with inert glass beads to improve the isothermicity of the beds.
- the oxidized catalyst Prior to reaction, was reduced in pure hydrogen for 12 h at 480 0 C.
- the reforming reaction was conducted at 48O 0 C and 100 psig, with a continuous feed of 50 g/h of naphtha and 2.11 scf/h of hydrogen.
- WHSV weight hourly space velocity
- a reforming catalyst according to the present invention was prepared using platinum and tin as catalyst components.
- the catalyst was prepared using the following steps and concentrations: (i) 30 g of an Al 2 O 3 support in form of 1/16 inch diameter spheres was impregnated with 150 ml of 2.0% sodium hydroxide solution for 2 hours. The Al 2 O 3 was collected by filter, washed with water and acetone, and then dried at 90 °C for 4 hours, (ii) 0.2335 g of cw-dichlorobis(diethyl sulfide)-platinum (II) and 0.2254g of dichlorobis(acetylacetonate)-tin (IV) was dissolved in 20 ml of toluene.
- step (iii) 30 g of the Al 2 O 3 from step (i) was added to 30 ml toluene, followed by addition of the solution prepared in step (ii). The mixture was gently agitated by a suspension stir bar for 12 hours in nitrogen atmosphere to form a solid sample. The solid sample was filtered out, washed with toluene, and then dried at 90 °C for 2 hours.
- a reforming catalyst according to the present invention was prepared using platinum and tin as catalyst components.
- the catalyst was prepared using the following steps and concentrations: (i) 209.1 mg of Pt(acac) 2 and 229.2 mg of Sn(acac) 2 Cl 2 were dissolved in
- step (ii) 30 g of Al 2 O 3 support was soaked in 100 ml acetone for 2 hours. Then the acetone was removed by decantation. (iii) The solution from step (i) was added to the pretreated Al 2 O 3 support from step (ii) and dried by rotating vacuum evaporation.
- step (iv) The resulting mixture from step (iii) was placed in an oven at 70 °C for
- the resulting catalyst had a weight composition of 0.34% Pt, 0.23% Sn, and 1.08% Cl.
- a reforming catalyst according to the present invention was prepared using platinum and tin as catalyst components.
- the catalyst was prepared using the following steps and concentrations: (i) 275.52 mg of H 2 PtCl 6 -OH 2 O (0.532 mmol) and 133.36 mg of
- a reforming catalyst according to the present invention was prepared using platinum and tin as catalyst components.
- the catalyst was prepared using the following steps and concentrations:
- a platinum solution was prepared by dissolving 0.9950 g of H 2 PtCl 6 -OH 2 O (Pt: 38-40%, select 39%) in water and diluting to 100.0 ml.
- a tin solution was prepared by mixing 7.66 g of SnCl 2 -2H 2 O (98%) and 1O g of 37% HCl solution in water to dissolve the SnCl 2 . The tin solution was then diluted to 200.0 ml to form a solution with a tin concentration of 0.01976 g Sn/ml.
- Solution A was prepared by mixing 4.0 g of 37% HCl, 24.18 g of the 0.003881 g Pt/ml solution prepared in step (i) and 3.21 g of the 0.01976 g Sn/ml solution prepared in step (ii) and then adding 6.26 g of a 0.001169 g/ml glycolic acid solution.
- Solution B was prepared by heating solution A to boiling, refluxing for
- a reforming catalyst according to the present invention was prepared using platinum and tin as catalyst components.
- the catalyst was prepared using the following steps and concentrations:
- the final concentration of platinum in solution was 0.003978 g Pt/ml.
- a tin solution was prepared by mixing 1.23 g of SnCl 2 -2H 2 O (98%) and 4.3 g of 37% HCl solution in water to dissolve the SnCl 2 . The tin solution was then diluted to 200.0 ml with water to form a solution having a tin concentration of 0.003236 g Sn/ml.
- Solution A was prepared by diluting 23.59 g of the 0.003978 g Pt/ml solution from step (i) with water to form a 100 g solution and then adding 4.4 g of 37% HCl while stirring.
- Solution B was prepared by diluting 19.62 g of the 0.003236 g Sn/ml solution from step (ii) with water to form a 100 g solution, adding this solution to Solution A, and then adding 1.67 g 37% HCl to Solution B.
- Solution C was prepared by diluting 2.73 g of a 45% polyacrylic acid (sodium salt) solution with 220 g of water and adding this to solution B.
- Solution C was purged with 100 ml/min N 2 for 1 hour. After that, the
- a reforming catalyst according to the present invention was prepared using platinum and tin as catalyst components.
- the catalyst was prepared using the following steps and concentrations:
- a platinum solution was prepared by diluting 406.35 mg of a 25.52 wt% H 2 PtCl 6 aqueous solution to 15 ml with water.
- tin solution was prepared by dissolving 133.36 mg of SnCl 2 -2H 2 O (98%) to 15 ml with de-ionized water together with 4 g 37% HCl.
- Solution A was prepared by mixing the platinum solution from step (i) with the tin solution from step (ii).
- Solution B was prepared by adding 215.75 mg citric acid to Solution A.
- Solution B was refluxed for 1 hour, then cooled down to room temperature while continuously stirring.
- the resulting catalyst had a weight composition of 0.34% Pt, 0.23% Sn, and
- Example 8 A reforming catalyst according to the present invention was prepared using platinum as the active component, an alumina support, and an ethylene glycol dispersing agent. The catalyst was prepared using the following steps and concentrations:
- a platinum solution was prepared by dissolving 5 g of H 2 PtCl 6 -OH 2 O (39 wt% Pt) in ethylene glycol and diluted to 200 ml. The final concentration of the platinum in solution was 0.00975 g Pt/ml.
- Solution A was prepared by diluting 9 ml of the 0.00975 g Pt/ml
- Solution B was prepared by adding 4.5 ml of a 1 mol/L NaOH/ethylene glycol solution to solution A while continuously stirring.
- a reforming catalyst according to the present invention was prepared using platinum as the catalyst component.
- the catalyst was prepared using the following steps and concentrations:
- a platinum solution was prepared by dissolving 1.0200 g of H 2 PtCl 6 -OH 2 O (Pt: 38-40%, select 39%) in water and diluting to 100.0 ml. The final concentration of platinum in this solution was 0.003978 g Pt/ml.
- Solution A was prepared by diluting 3.00 g of a 0.001169 g/ml glycolic acid solution to 22.6 g and then mixing this with 22.62 g of a 0.003978 g Pt/ml solution.
- Solution B was prepared by heating solution A to boiling, refluxing for 10 minutes, and then cooling to room temperature.
- a reforming catalyst according to the present invention was prepared using platinum as the catalyst component.
- the catalyst was prepared using the following steps and concentrations:
- a platinum solution was prepared by dissolving 1.0200 g of H 2 PtCl 6 -OH 2 O (Pt: 38-40%, select 39%) in water and diluting to 100.0 ml.
- the final concentration of platinum in the solution was 0.003978 g Pt/ml.
- Solution A was prepared by diluting 22.62 g of the 0.003978 g Pt/ml solution from step (i) to 204 ml with water.
- Solution B was prepared by diluting 1.23 g of a 45% polyacrylic acid
- a supported platinum reforming catalyst according to the present invention was prepared using the following steps and concentrations:
- step (iii) 30 g of the treated Al 2 O 3 from step (i) was added to 30 ml toluene, followed by addition of the solution prepared in step (ii). The whole mixture was gently agitated using a suspension stir bar for 12 hours under a nitrogen atmosphere to form a solid sample. The solid sample was removed by filteration, washed with toluene, and then dried at 90 °C for 2 hours.
- the resulting catalyst had a weight composition of 0.30% Pt and
- a reforming catalyst according to the present invention was prepared using platinum as the catalyst component.
- the catalyst was prepared using the following steps and concentrations:
- the final concentration of platinum in the solution was 0.01987 g Pt/ml.
- Solution A was prepared by mixing 4.53 g of the 0.01987 g Pt/ml solution from step (i) with 0.035 g of 98% glycine and then diluting to 25 g.
- Solution B was prepared by heating solution A to boiling, refluxing for 30 minutes, and then cooling to room temperature.
- a reforming catalyst according to the present invention was prepared using platinum as active component, an alumina support, and a citric acid dispersing agent.
- the catalyst was prepared using the following steps and concentrations:
- a platinum solution was prepared by diluting 343.73 mg of a 25.52 wt% H 2 PtCl 6 aqueous solution to 50 ml with water.
- step (ii) 86.45 mg of citric acid was dissolved to 50 ml in water and then added to the above H 2 PtCl 6 aqueous solution from step (i).
- step (iii) The mixture from step (ii) was refluxed for 1 hour, then cooled down to room temperature while continuously stirring.
- step (iv) 28.86 g of Al 2 O 3 was placed under vacuum for 30 minutes and then impregnated with about 50 ml of methanol for 30 minutes. The methanol excess was removed by pipette.
- the Al 2 O 3 support was then added to the solution from step (iii). The resulting mixture was dried on the hotplate until all the liquid evaporated.
- the resulting catalyst had a weight composition of 0.3% Pt and 1%
- a reforming catalyst according to the present invention was prepared using platinum and tin as catalyst components.
- the catalyst was prepared using the following steps and concentrations:
- the final concentration of platinum in this solution was 0.003978 g Pt/ml.
- a tin solution was prepared by mixing 1.23 g of SnCl 2 -2H 2 O (98%) and 4.3 g of 37% HCl solution in water to dissolve the SnCl 2 .
- the Tin solution was then diluted with water to 200.0 ml to form a solution with a tin concentration of 0.003236 g Sn/ml.
- Solution A was prepared by mixing 4.0 g of 37% HCl, 23.59 g of the 0.003978 g Pt/ml solution from step (i), 19.62 g of the 0.003236 g Sn/ml from step (ii), and 0.08 g of glycine.
- Solution B was prepared by heating solution A to boiling, refluxing for
Abstract
Description
Claims
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CA002594019A CA2594019A1 (en) | 2005-01-14 | 2005-11-28 | Reforming nanocatalysts and method of making and using such catalysts |
BRPI0519002-9A BRPI0519002A2 (en) | 2005-01-14 | 2005-11-28 | nanocatalyst reform and method of production and use of such catalysts |
EP05852241A EP1836278A4 (en) | 2005-01-14 | 2005-11-28 | Reforming nanocatalysts and method of making and using such catalysts |
JP2007551248A JP2008526504A (en) | 2005-01-14 | 2005-11-28 | Reforming nano-catalyst and its production and use |
AU2005325150A AU2005325150A1 (en) | 2005-01-14 | 2005-11-28 | Reforming nanocatalysts and method of making and using such catalysts |
MX2007008415A MX2007008415A (en) | 2005-01-14 | 2005-11-28 | Reforming nanocatalysts and method of making and using such catalysts. |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US64383605P | 2005-01-14 | 2005-01-14 | |
US60/643,836 | 2005-01-14 | ||
US11/101,241 US7569508B2 (en) | 2004-11-17 | 2005-04-07 | Reforming nanocatalysts and method of making and using such catalysts |
US11/101,241 | 2005-04-07 |
Publications (2)
Publication Number | Publication Date |
---|---|
WO2006078352A2 true WO2006078352A2 (en) | 2006-07-27 |
WO2006078352A3 WO2006078352A3 (en) | 2007-10-25 |
Family
ID=36692686
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US2005/042841 WO2006078352A2 (en) | 2005-01-14 | 2005-11-28 | Reforming nanocatalysts and method of making and using such catalysts |
Country Status (9)
Country | Link |
---|---|
US (1) | US7569508B2 (en) |
EP (1) | EP1836278A4 (en) |
JP (1) | JP2008526504A (en) |
KR (1) | KR20070085632A (en) |
AU (1) | AU2005325150A1 (en) |
BR (1) | BRPI0519002A2 (en) |
CA (1) | CA2594019A1 (en) |
MX (1) | MX2007008415A (en) |
WO (1) | WO2006078352A2 (en) |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1767269A2 (en) | 2005-09-27 | 2007-03-28 | Tanaka Kikinzoku Kogyo K.K. | Method for producing catalyst |
WO2007055663A1 (en) | 2005-11-14 | 2007-05-18 | Agency For Science, Technology And Research | Highly dispersed metal calatysts |
US7569508B2 (en) * | 2004-11-17 | 2009-08-04 | Headwaters Technology Innovation, Llc | Reforming nanocatalysts and method of making and using such catalysts |
WO2009139747A1 (en) * | 2008-05-16 | 2009-11-19 | Utc Power Corporation | A stabilized platinum catalyst |
WO2009139748A1 (en) * | 2008-05-16 | 2009-11-19 | Utc Power Corporation | Method of producing a stabilized platinum catalyst |
US8389175B2 (en) | 2008-05-16 | 2013-03-05 | Utc Power Corporation | Fuel cell having a stabilized cathode catalyst |
Families Citing this family (37)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7655137B2 (en) * | 2003-07-14 | 2010-02-02 | Headwaters Technology Innovation, Llc | Reforming catalysts having a controlled coordination structure and methods for preparing such compositions |
US7632775B2 (en) * | 2004-11-17 | 2009-12-15 | Headwaters Technology Innovation, Llc | Multicomponent nanoparticles formed using a dispersing agent |
US7541309B2 (en) * | 2006-05-16 | 2009-06-02 | Headwaters Technology Innovation, Llc | Reforming nanocatalysts and methods of making and using such catalysts |
US7842639B2 (en) * | 2006-05-19 | 2010-11-30 | The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration | Mechanical alloying of a hydrogenation catalyst used for the remediation of contaminated compounds |
KR100836659B1 (en) | 2006-07-06 | 2008-06-10 | 삼성전기주식회사 | Method for manufacturing metal nanoparticles |
DE102007025315A1 (en) * | 2007-05-31 | 2008-12-11 | Süd-Chemie AG | Catalyst for the selective hydrogenation of acetylenic hydrocarbons and process for its preparation |
DE102007025362A1 (en) * | 2007-05-31 | 2008-12-11 | Süd-Chemie AG | Doped Pd / Au coated catalyst, process for its preparation and its use |
DE102007025443A1 (en) * | 2007-05-31 | 2008-12-04 | Süd-Chemie AG | Pd / Au coated catalyst containing HfO 2, process for its preparation and its use |
DE102007025223A1 (en) * | 2007-05-31 | 2008-12-04 | Süd-Chemie AG | Zirconia-doped VAM shell catalyst, process for its preparation and its use |
DE102007025444A1 (en) * | 2007-05-31 | 2008-12-11 | Süd-Chemie AG | VAM shell catalyst, process for its preparation and its use |
DE102007025442B4 (en) * | 2007-05-31 | 2023-03-02 | Clariant International Ltd. | Use of a device for producing a coated catalyst and coated catalyst |
JP5531615B2 (en) * | 2007-07-19 | 2014-06-25 | 戸田工業株式会社 | Catalyst for cracking hydrocarbons |
DE102008059341A1 (en) | 2008-11-30 | 2010-06-10 | Süd-Chemie AG | Catalyst support, process for its preparation and use |
FR2939701B1 (en) * | 2008-12-16 | 2011-01-14 | St Microelectronics Tours Sas | CATALYTIC PARTICULATE SOLUTION FOR FUEL MICRO-CELL AND PROCESS RELATING THERETO |
US7799729B2 (en) * | 2009-02-23 | 2010-09-21 | Uop Llc | Reforming catalyst |
JP5322733B2 (en) * | 2009-03-31 | 2013-10-23 | Jx日鉱日石エネルギー株式会社 | Method for producing catalyst for selective oxidation reaction of carbon monoxide |
JP5140035B2 (en) * | 2009-05-25 | 2013-02-06 | 田中貴金属工業株式会社 | Colloidal solution containing metal nanoparticles |
US8450236B2 (en) * | 2010-04-13 | 2013-05-28 | Cristal Usa Inc. | Supported precious metal catalysts via hydrothermal deposition |
KR101112672B1 (en) * | 2010-05-26 | 2012-03-13 | 이화여자대학교 산학협력단 | A cadmium sulfide quantum dots-tungsten oxide nanohybrid photo-catalyst and preparation method thereof |
US9404045B2 (en) * | 2011-02-17 | 2016-08-02 | AMG Chemistry and Catalysis Consulting, LLC | Alloyed zeolite catalyst component, method for making and catalytic application thereof |
US8597383B2 (en) * | 2011-04-11 | 2013-12-03 | Saudi Arabian Oil Company | Metal supported silica based catalytic membrane reactor assembly |
US9272334B2 (en) * | 2011-04-12 | 2016-03-01 | GM Global Technology Operations LLC | Synthesis of platinum-alloy nanoparticles and supported catalysts including the same |
KR101299193B1 (en) * | 2011-07-01 | 2013-08-22 | 주식회사 지엘머티리얼즈 | Method for manufacturing supported catalyst |
US8802585B2 (en) * | 2011-09-22 | 2014-08-12 | Celanese International Corporation | Catalysts for producing acrylic acids and acrylates |
US8735314B2 (en) * | 2011-09-29 | 2014-05-27 | Celanese International Corporation | Catalysts for producing acrylic acids and acrylates |
RU2472842C1 (en) * | 2011-12-16 | 2013-01-20 | Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Башкирский государственный университет" | Use of organic salt for increase in processing depth of hydrocarbon-bearing raw material, and method for increasing processing depth of hydrocarbon-containing raw material |
KR20140015705A (en) | 2012-07-12 | 2014-02-07 | 삼성전자주식회사 | Electrode catalyst for fuel cell, method for preparing the same, membrane electrode assembly and fuel cell including the same |
KR101388924B1 (en) * | 2012-08-06 | 2014-04-24 | 인하대학교 산학협력단 | A method for preparing biodiesel |
KR101446116B1 (en) * | 2012-09-18 | 2014-10-06 | 한화케미칼 주식회사 | Metal catalyst for producing carbon nanotubes and method for preparing carbon nanotubes using thereof |
KR101467061B1 (en) * | 2012-12-11 | 2014-12-02 | 연세대학교 산학협력단 | Method to produce the cubic shape of Pt/C catalyst, Pt/C catalyst produced thereof, and fuel cell using the same |
US20140174916A1 (en) * | 2012-12-26 | 2014-06-26 | King Abdulaziz City For Science And Technology | Catalytic composition for the electrochemical reduction of carbon dioxide |
US10066299B2 (en) | 2013-02-24 | 2018-09-04 | Rohm And Haas Electronic Materials Llc | Plating catalyst and method |
CN104959140B (en) * | 2015-05-25 | 2017-08-29 | 安徽海德石油化工有限公司 | A kind of naphtha catalytic reforming prepares benzene, toluene and dimethylbenzene catalyst |
CN106391098B (en) * | 2016-08-31 | 2019-05-21 | 中科合成油技术有限公司 | A kind of catalyst for reforming naphtha and preparation method thereof |
US10753247B2 (en) * | 2018-02-22 | 2020-08-25 | GM Global Technology Operations LLC | Bi-metallic oxidation catalyst materials and appurtenant devices and systems |
KR102134386B1 (en) * | 2018-06-29 | 2020-07-16 | 효성화학 주식회사 | Preparation of dehydrogenation catalysts having excellent dispersion |
WO2022015995A1 (en) | 2020-07-17 | 2022-01-20 | Chevron Phillips Chemical Company Lp | Aromatization catalyst activity and selectivity improvement with alcohol addition during catalyst preparation |
Family Cites Families (132)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3700745A (en) | 1968-10-22 | 1972-10-24 | Ashland Oil Inc | Hydrodealkylation process with promoted group viii metals |
US3686340A (en) | 1968-10-22 | 1972-08-22 | Ashland Oil Inc | Hydrodealkylation process |
US3644200A (en) | 1968-12-23 | 1972-02-22 | Union Oil Co | Ammoniated zeolite catalysts |
US3625879A (en) | 1970-01-07 | 1971-12-07 | Gulf Research Development Co | Benzene from pyrolysis gasoline |
GB1347475A (en) * | 1970-04-10 | 1974-02-20 | Shell Int Research | Process for increasing the activity of supported catalysts |
US3674706A (en) | 1970-06-03 | 1972-07-04 | Phillips Petroleum Co | Tin impregnation regeneration of group viii reforming-dehydrogenation catalysts |
US3907852A (en) | 1972-06-23 | 1975-09-23 | Exxon Research Engineering Co | Silylhydrocarbyl phosphines and related compounds |
US4007256A (en) | 1975-04-11 | 1977-02-08 | Shell Oil Company | Catalytic production of hydrogen peroxide from its elements |
US4053531A (en) | 1975-09-29 | 1977-10-11 | Texaco Inc. | Steam reforming of polycyclic hydrocarbons |
US4064154A (en) | 1975-11-06 | 1977-12-20 | Dow Corning Corporation | Catalysts and carriers therefor |
JPS5271000A (en) | 1975-12-10 | 1977-06-13 | Tokuyama Soda Co Ltd | Production of hydrogen peroxide |
GB1516418A (en) | 1976-03-09 | 1978-07-05 | Air Prod & Chem | Synthesis of hydrogen peroxide |
US4028274A (en) | 1976-06-01 | 1977-06-07 | United Technologies Corporation | Support material for a noble metal catalyst and method for making the same |
FR2367035A1 (en) | 1976-10-11 | 1978-05-05 | Pro Catalyse | PROCESS FOR HYDRODEALKYLATION OF AROMATIC ALKYL HYDROCARBONS IN THE PRESENCE OF A CATALYST HAVING AN ALUMINATE-TYPE SUPPORT |
US4148750A (en) | 1977-01-10 | 1979-04-10 | Exxon Research & Engineering Co. | Redispersion of noble metals on supported catalysts |
FR2414034A1 (en) * | 1978-01-06 | 1979-08-03 | Inst Francais Du Petrole | DEALKYLATION PROCESS, BY WATER VAPOR, OF AROMATIC HYDROCARBONS |
FR2434131A1 (en) * | 1978-02-24 | 1980-03-21 | Inst Francais Du Petrole | PROCESS FOR WATER VAPOR DESALKYLATION OF AROMATIC HYDROCARBONS |
US4157355A (en) | 1978-03-13 | 1979-06-05 | Uop Inc. | Combination process for selected aromatic hydrocarbon production |
US4793980A (en) * | 1978-09-21 | 1988-12-27 | Torobin Leonard B | Hollow porous microspheres as substrates and containers for catalyst |
US4297205A (en) | 1978-09-28 | 1981-10-27 | Standard Oil Company (Indiana) | Reforming with a catalyst comprising iridium, zirconia, and alumina |
JPS5777019A (en) | 1980-10-30 | 1982-05-14 | Toho Rayon Co Ltd | Fibrous activated carbon and its manufacture |
US4336239A (en) | 1980-10-10 | 1982-06-22 | Air Products And Chemicals, Inc. | Synthesis of hydrogen peroxide |
US4335092A (en) | 1980-10-10 | 1982-06-15 | Air Products And Chemicals, Inc. | Synthesis of hydrogen peroxide |
US4379778A (en) | 1980-10-10 | 1983-04-12 | Air Products And Chemicals, Inc. | Hydrogen peroxide synthesis |
US4336240A (en) | 1981-04-22 | 1982-06-22 | Air Products And Chemicals, Inc. | Method of manufacturing hydrogen peroxide |
US4347231A (en) | 1981-06-17 | 1982-08-31 | Fmc Corporation | Preparation of hydrogen peroxide from its elements |
US4347232A (en) | 1981-06-17 | 1982-08-31 | Fmc Corporation | Preparation of hydrogen peroxide from its elements |
US4476242A (en) | 1981-10-29 | 1984-10-09 | Standard Oil Company (Indiana) | Process for preparing palladium on carbon catalysts for purification of crude terephthalic acid |
US4595666A (en) | 1981-11-02 | 1986-06-17 | Hri, Inc. | Catalyst rejuvenation process for removal of metal contaminants |
US4454240A (en) | 1981-11-02 | 1984-06-12 | Hri, Inc. | Catalyst regeneration process including metal contaminants removal |
US4513098A (en) | 1983-06-28 | 1985-04-23 | Mobil Oil Corporation | Multimetallic catalysts and their method of preparation from organometallic precursors |
US4503160A (en) | 1983-08-29 | 1985-03-05 | General Electric Company | Hydrosilylation method, catalyst and method for making |
US4713363A (en) | 1984-12-27 | 1987-12-15 | The Dow Chemical Company | High surface area supported noble metal catalysts and process for their preparation |
GB8509530D0 (en) | 1985-04-13 | 1985-05-15 | Bp Chem Int Ltd | Hydrogenation of carboxylic acids |
IT1187661B (en) | 1985-04-23 | 1987-12-23 | Enichem Sintesi | HIGH MECHANICAL RESISTANCE SILICON AND TITANIUM BASED CATALYST |
ES2033693T3 (en) | 1986-01-28 | 1993-04-01 | Eniricerche S.P.A. | A PROCEDURE FOR THE EXPOSURE OF OLEPHINE COMPOUNDS. |
FR2627105B3 (en) | 1988-02-16 | 1990-06-08 | Inst Francais Du Petrole | PROCESS FOR PRESULFURIZING A HYDROCARBON PROCESSING CATALYST |
US4832821A (en) * | 1988-03-07 | 1989-05-23 | Exxon Research And Engineering Company | Catalyst reforming process |
US4832938A (en) | 1988-05-13 | 1989-05-23 | E. I. Du Pont De Nemours And Company | Hydrogen peroxide production method using platinum/palladium catalysts |
US4937220A (en) | 1988-08-08 | 1990-06-26 | International Fuel Cells Corporation | Method to retard catalyst recrystallization |
JPH0697614B2 (en) | 1988-08-26 | 1994-11-30 | エヌ・イーケムキャット株式会社 | Supported platinum alloy electrocatalyst |
US5132480A (en) | 1989-02-06 | 1992-07-21 | Fuji Oil Company, Ltd. | Hydrodealkylation process |
JPH0697615B2 (en) | 1989-03-09 | 1994-11-30 | エヌ・イーケムキャット株式会社 | Platinum alloy electrode catalyst |
US5128114A (en) | 1989-04-14 | 1992-07-07 | E. I. Du Pont De Nemours And Company | Silica microspheres, method of improving attrition resistance |
US5352645A (en) | 1989-04-14 | 1994-10-04 | E. I. Du Pont De Nemours And Company | Silica microspheres, method of improving attrition resistance and use |
JP3060499B2 (en) | 1989-09-01 | 2000-07-10 | 三菱瓦斯化学株式会社 | Method for producing hydrogen peroxide |
US5166121A (en) * | 1990-05-21 | 1992-11-24 | Engelhard Corporation | Catalytic compositions |
US4999326A (en) | 1990-06-18 | 1991-03-12 | Amoco Corporation | Palladium catalyst reactivation |
EP0460300A1 (en) | 1990-06-20 | 1991-12-11 | Akzo Nobel N.V. | Process for the preparation of a presulphided catalyst; Process for the preparation of a sulphided catalyst, and use of said catalyst |
US5132099A (en) | 1990-12-27 | 1992-07-21 | Mitsubishi Gas Chemical Company, Inc. | Method for producing hydrogen peroxide |
US5234584A (en) | 1991-02-04 | 1993-08-10 | United Technologies Corporation | Catalytic oxidation of aqueous organic contaminants |
JPH0532404A (en) | 1991-02-08 | 1993-02-09 | Mitsubishi Gas Chem Co Inc | Production of hydrogen peroxide |
DE4127918A1 (en) | 1991-03-05 | 1992-09-10 | Interox Int Sa | METHOD FOR PRODUCING HYDROGEN PEROXIDE |
EP0504741B1 (en) | 1991-03-20 | 1994-12-28 | Mitsubishi Gas Chemical Company, Inc. | A method for producing hydrogen peroxide |
US5188996A (en) | 1991-05-22 | 1993-02-23 | Mobil Oil Corp. | Redispersion of noble metal on low acidity support |
US5338531A (en) | 1992-01-21 | 1994-08-16 | Chuang Karl T | Production of hydrogen peroxide |
US5166372A (en) | 1992-02-07 | 1992-11-24 | Arco Chemical Technology, L.P. | Epoxidation process |
JPH05270806A (en) | 1992-03-25 | 1993-10-19 | Mitsubishi Gas Chem Co Inc | Production of hydrogen peroxide |
US5399344A (en) | 1992-04-16 | 1995-03-21 | Sandoz Ltd. | Synergistic fly attractant composition |
US5214168A (en) | 1992-04-30 | 1993-05-25 | Arco Chemical Technology, L.P. | Integrated process for epoxide production |
US5240893A (en) | 1992-06-05 | 1993-08-31 | General Motors Corporation | Method of preparing metal-heterocarbon-nitrogen catalyst for electrochemical cells |
KR100284671B1 (en) | 1992-11-20 | 2001-10-24 | 오하시 미츠오 | Method of producing hydrogen peroxide |
JPH06305715A (en) | 1993-04-19 | 1994-11-01 | Mitsubishi Gas Chem Co Inc | Production of hydrogen peroxide |
US5500297A (en) | 1993-08-09 | 1996-03-19 | The Trustees Of Princeton University | Electron acceptor compositions technical field |
US6015485A (en) | 1994-05-13 | 2000-01-18 | Cytec Technology Corporation | High activity catalysts having a bimodal mesopore structure |
US5583085A (en) | 1994-06-13 | 1996-12-10 | W. R. Grace & Co.-Conn. | Preparation of dehydroxylated supports |
US5391531A (en) | 1994-06-13 | 1995-02-21 | W. R. Grace & Co.-Conn. | Preparation of dehydroxlated supports |
DE4425672A1 (en) | 1994-07-20 | 1996-01-25 | Basf Ag | Oxidation catalyst, process for its preparation and oxidation process using the oxidation catalyst |
JP3314897B2 (en) | 1994-08-03 | 2002-08-19 | トヨタ自動車株式会社 | Method for producing exhaust gas purifying catalyst |
DE4443701C1 (en) | 1994-12-08 | 1996-08-29 | Degussa | Shell catalyst, process for its production and its use |
US6040490A (en) | 1995-03-06 | 2000-03-21 | Toray Industries, Inc. | Process for producing aromatic compounds by dealkylation, transalkylation, or disproportionation |
DE19517598C1 (en) | 1995-05-13 | 1997-01-02 | Degussa | Platinum-aluminum alloy catalyst and its use in fuel cells |
DE69701002T2 (en) | 1996-01-30 | 2000-07-20 | Sumitomo Chemical Co | Process for the production of hydrogen peroxide |
DE19607577A1 (en) | 1996-02-29 | 1997-09-04 | Basf Ag | Mesh catalyst based on titanium or vanadium zeolites and inert mesh fabrics to accelerate oxidation reactions |
DE19608493A1 (en) | 1996-03-05 | 1997-09-11 | Basf Ag | Precious metal-free catalyst composition for the production of hydrogen peroxide |
IT1283010B1 (en) | 1996-05-15 | 1998-04-03 | Enichem Spa | SUPPORTED METALLOCENE COMPLEX AND PROCEDURE FOR ITS PREPARATION |
SE9602484D0 (en) | 1996-06-24 | 1996-06-24 | Eka Chemicals Ab | Method of producing a chemical compound |
US5851948A (en) | 1996-08-20 | 1998-12-22 | Hydrocarbon Technologies, Inc. | Supported catalyst and process for catalytic oxidation of volatile organic compounds |
US5883032A (en) | 1996-11-21 | 1999-03-16 | Uop Llc | Selective multimetallic multigradient reforming catalyst |
US6001762A (en) | 1997-02-17 | 1999-12-14 | E. I. Du Pont De Nemours And Company | Reactivation of perfluorinated ion-exchange microcomposite catalysts |
US6159267A (en) | 1997-02-24 | 2000-12-12 | Superior Micropowders Llc | Palladium-containing particles, method and apparatus of manufacture, palladium-containing devices made therefrom |
DE69819385T2 (en) | 1997-03-10 | 2004-09-09 | Japan Science And Technology Corp., Kawaguchi | Manufacturing process of a composite structure consisting of metallic nanoparticles coated with an organic polymer |
US5912367A (en) | 1997-07-01 | 1999-06-15 | Arco Chemical Technology, L.P. | High efficiency epoxidation process |
US6331500B1 (en) | 1997-08-25 | 2001-12-18 | California Institute Of Technology | Functionalized molecular sieves |
KR100341886B1 (en) | 1997-09-30 | 2002-12-06 | 한국화학연구원 | Method for manufacturing hydrogen peroxide |
US6005155A (en) | 1997-12-03 | 1999-12-21 | Exxon Chemicals Patents Inc. | Modification of molecular sieve catalyst for reduced methane production during conversion of oxygenates to olefins |
FR2774674B1 (en) | 1998-02-10 | 2000-03-24 | Atochem Elf Sa | PROCESS FOR THE PREPARATION OF AN AQUEOUS SOLUTION OF HYDROGEN PEROXIDE DIRECTLY FROM HYDROGEN AND OXYGEN AND DEVICE FOR IMPLEMENTING SAME |
FR2775622A1 (en) | 1998-03-03 | 1999-09-03 | Atochem Elf Sa | SUPPORTED BIMETALLIC CATALYZER BASED ON PLATINUM OR SILVER, ITS MANUFACTURING PROCESS AND ITS USE FOR ELECTROCHEMICAL CELLS |
US6090858A (en) | 1998-03-18 | 2000-07-18 | Georgia Tech Reseach Corporation | Shape control method for nanoparticles for making better and new catalysts |
US5976486A (en) | 1998-03-27 | 1999-11-02 | University Of Southern California | Method for catalytic production of hydrogen peroxide and catalyst therefor |
DE19824532A1 (en) | 1998-06-03 | 1999-12-09 | Basf Ag | Process for the preparation of coated catalysts for the catalytic gas phase oxidation of aromatic hydrocarbons and catalysts thus obtainable |
US6069286A (en) | 1998-07-16 | 2000-05-30 | Phillips Petroleum Company | Hydrocarbon conversion process employing promoted zeolite catalyst |
IT1301999B1 (en) | 1998-08-05 | 2000-07-20 | Enichem Spa | CATALYST, PROCESS FOR THE PRODUCTION OF OXYGEN WATER AND ITS USE IN OXIDATION PROCESSES. |
US6500968B2 (en) | 1998-08-26 | 2002-12-31 | Hydrocarbon Technologies, Inc. | Process for selective oxidation of organic feedstocks with hydrogen peroxide |
US6576214B2 (en) * | 2000-12-08 | 2003-06-10 | Hydrocarbon Technologies, Inc. | Catalytic direct production of hydrogen peroxide from hydrogen and oxygen feeds |
US6168775B1 (en) | 1998-08-26 | 2001-01-02 | Hydrocarbon Technologies, Inc. | Catalyst and process for direct catalystic production of hydrogen peroxide, (H2O2) |
DE19912733A1 (en) | 1999-03-20 | 2000-09-21 | Degussa | Process for the production of hydrogen peroxide by direct synthesis |
DE19915681A1 (en) * | 1999-04-07 | 2000-10-12 | Basf Ag | Process for the production of platinum metal catalysts |
DE10009187A1 (en) * | 2000-02-26 | 2001-08-30 | Degussa | Process for the production of hydrogen peroxide by direct synthesis and noble metal catalyst therefor |
FR2806399B1 (en) * | 2000-03-17 | 2002-09-13 | Atofina | PROCESS FOR THE DIRECT PRODUCTION OF HYDROGEN PEROXIDE |
DE10051419A1 (en) * | 2000-10-17 | 2002-04-18 | Basf Ag | Production of acrolein or acrylic acid involves absorption of propane and propene from a gas mixture followed by desorption and oxidation, with no catalytic dehydrogenation of propane and no added oxygen |
US6551960B1 (en) | 2000-06-19 | 2003-04-22 | Canon Kabushiki Kaisha | Preparation of supported nano-sized catalyst particles via a polyol process |
US6353037B1 (en) * | 2000-07-12 | 2002-03-05 | 3M Innovative Properties Company | Foams containing functionalized metal oxide nanoparticles and methods of making same |
IT1318679B1 (en) * | 2000-08-11 | 2003-08-27 | Enichem Spa | PROCESS FOR THE PRODUCTION OF OXYGEN WATER. |
IT1318682B1 (en) * | 2000-08-11 | 2003-08-27 | Enichem Spa | INTEGRATED PROCEDURE FOR THE PREPARATION OF OLEFINIC OXIDES. |
US6534440B2 (en) | 2000-11-29 | 2003-03-18 | Council Of Scientific And Industrial Research | Process for the activation of a metallic palladium based catalyst useful for the direct oxidation of hydrogen to hydrogen peroxide |
US6500969B1 (en) | 2000-12-08 | 2002-12-31 | Hydrocarbon Technologies, Inc. | Integrated hydrogen peroxide production and organic chemical oxidation |
US6740615B2 (en) * | 2000-12-22 | 2004-05-25 | Hydrocarbon Technologies, Inc. | Regeneration of used supported noble metal catalysts |
US6534661B1 (en) * | 2000-12-28 | 2003-03-18 | Hydrocarbon Technologies, Inc. | Integrated process and dual-function catalyst for olefin epoxidation |
US6730149B2 (en) * | 2001-01-22 | 2004-05-04 | Ricoh Company Limited | Ink composition and inkjet recording method and apparatus using the ink composition |
US6776606B2 (en) * | 2001-03-02 | 2004-08-17 | Emmissions Technology, Llc | Method for oxidizing mixtures |
US6713036B1 (en) * | 2001-05-07 | 2004-03-30 | Uop Llc | Process for mixing and reacting two or more fluids |
ITMI20011016A1 (en) * | 2001-05-17 | 2002-11-17 | Enichem Spa | DIRECT SYNTHESIS OF OXYGENATED WATER IN A NEW MULTI-COMPONENT SOLVENT SYSTEM |
ITMI20011015A1 (en) * | 2001-05-17 | 2002-11-17 | Enichem Spa | DIRECT SYNTHESIS OF OXYGENATED WATER IN A MULTI-COMPONENT SOLVENT SYSTEM |
CN1166019C (en) | 2001-05-25 | 2004-09-08 | 中国科学院长春应用化学研究所 | Preparation of nanometer electrical catalyst for protein exchange film fuel cell |
US6793883B2 (en) * | 2001-07-05 | 2004-09-21 | General Electric Company | Application of catalytic nanoparticles to high temperature water systems to reduce stress corrosion cracking |
ITMI20011688A1 (en) * | 2001-08-02 | 2003-02-02 | Enichem Spa | CATALYST AND ITS USE IN THE SYNTHESIS OF OXYGEN WATER |
US6686308B2 (en) * | 2001-12-03 | 2004-02-03 | 3M Innovative Properties Company | Supported nanoparticle catalyst |
US6676729B2 (en) * | 2002-01-02 | 2004-01-13 | International Business Machines Corporation | Metal salt reduction to form alloy nanoparticles |
US6746597B2 (en) * | 2002-01-31 | 2004-06-08 | Hydrocarbon Technologies, Inc. | Supported noble metal nanometer catalyst particles containing controlled (111) crystal face exposure |
US6782892B2 (en) * | 2002-08-30 | 2004-08-31 | Philip Morris Usa Inc. | Manganese oxide mixtures in nanoparticle form to lower the amount of carbon monoxide and/or nitric oxide in the mainstream smoke of a cigarette |
US6727309B1 (en) * | 2002-10-08 | 2004-04-27 | 3M Innovative Properties Company | Floor finish composition |
US7008607B2 (en) * | 2002-10-25 | 2006-03-07 | Basf Aktiengesellschaft | Process for preparing hydrogen peroxide from the elements |
US7566681B2 (en) * | 2002-10-29 | 2009-07-28 | National Research Council Of Canada | Platinum based nano-size catalysts |
US7011807B2 (en) * | 2003-07-14 | 2006-03-14 | Headwaters Nanokinetix, Inc. | Supported catalysts having a controlled coordination structure and methods for preparing such catalysts |
US7045479B2 (en) * | 2003-07-14 | 2006-05-16 | Headwaters Nanokinetix, Inc. | Intermediate precursor compositions used to make supported catalysts having a controlled coordination structure and methods for preparing such compositions |
US7569508B2 (en) * | 2004-11-17 | 2009-08-04 | Headwaters Technology Innovation, Llc | Reforming nanocatalysts and method of making and using such catalysts |
JP2005097642A (en) * | 2003-09-22 | 2005-04-14 | Tanaka Kikinzoku Kogyo Kk | Noble metal-metal oxide composite cluster |
KR20070062548A (en) * | 2004-11-17 | 2007-06-15 | 헤드워터스 테크놀로지 이노베이션 엘엘씨 | Multicomponent nanoparticles formed using a dispersing agent |
US7045481B1 (en) * | 2005-04-12 | 2006-05-16 | Headwaters Nanokinetix, Inc. | Nanocatalyst anchored onto acid functionalized solid support and methods of making and using same |
US7935652B2 (en) * | 2005-09-15 | 2011-05-03 | Headwaters Technology Innovation, Llc. | Supported nanoparticle catalysts manufactured using caged catalyst atoms |
US7541309B2 (en) * | 2006-05-16 | 2009-06-02 | Headwaters Technology Innovation, Llc | Reforming nanocatalysts and methods of making and using such catalysts |
-
2005
- 2005-04-07 US US11/101,241 patent/US7569508B2/en not_active Expired - Fee Related
- 2005-11-28 EP EP05852241A patent/EP1836278A4/en not_active Withdrawn
- 2005-11-28 KR KR1020077012416A patent/KR20070085632A/en not_active Application Discontinuation
- 2005-11-28 CA CA002594019A patent/CA2594019A1/en not_active Abandoned
- 2005-11-28 WO PCT/US2005/042841 patent/WO2006078352A2/en active Application Filing
- 2005-11-28 AU AU2005325150A patent/AU2005325150A1/en not_active Abandoned
- 2005-11-28 MX MX2007008415A patent/MX2007008415A/en active IP Right Grant
- 2005-11-28 BR BRPI0519002-9A patent/BRPI0519002A2/en not_active IP Right Cessation
- 2005-11-28 JP JP2007551248A patent/JP2008526504A/en active Pending
Non-Patent Citations (1)
Title |
---|
See references of EP1836278A4 * |
Cited By (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7569508B2 (en) * | 2004-11-17 | 2009-08-04 | Headwaters Technology Innovation, Llc | Reforming nanocatalysts and method of making and using such catalysts |
EP1767269A2 (en) | 2005-09-27 | 2007-03-28 | Tanaka Kikinzoku Kogyo K.K. | Method for producing catalyst |
EP1767269A3 (en) * | 2005-09-27 | 2007-07-25 | Tanaka Kikinzoku Kogyo K.K. | Method for producing catalyst |
WO2007055663A1 (en) | 2005-11-14 | 2007-05-18 | Agency For Science, Technology And Research | Highly dispersed metal calatysts |
EP1954393A1 (en) * | 2005-11-14 | 2008-08-13 | Agency for Science, Technology and Research | Highly dispersed metal calatysts |
EP1954393A4 (en) * | 2005-11-14 | 2012-02-01 | Agency Science Tech & Res | Highly dispersed metal calatysts |
US8926937B2 (en) | 2005-11-14 | 2015-01-06 | Agency For Science, Technology And Research | Highly dispersed metal catalysts |
WO2009139747A1 (en) * | 2008-05-16 | 2009-11-19 | Utc Power Corporation | A stabilized platinum catalyst |
WO2009139748A1 (en) * | 2008-05-16 | 2009-11-19 | Utc Power Corporation | Method of producing a stabilized platinum catalyst |
US8304365B2 (en) | 2008-05-16 | 2012-11-06 | Utc Power Corporation | Stabilized platinum catalyst |
US8389175B2 (en) | 2008-05-16 | 2013-03-05 | Utc Power Corporation | Fuel cell having a stabilized cathode catalyst |
US8920985B2 (en) | 2008-05-16 | 2014-12-30 | Ballard Power Systems Inc. | Power generation method using a fuel cell having a stabilized cathode catalyst |
Also Published As
Publication number | Publication date |
---|---|
US7569508B2 (en) | 2009-08-04 |
MX2007008415A (en) | 2007-09-06 |
BRPI0519002A2 (en) | 2008-12-23 |
EP1836278A2 (en) | 2007-09-26 |
WO2006078352A3 (en) | 2007-10-25 |
KR20070085632A (en) | 2007-08-27 |
EP1836278A4 (en) | 2011-06-01 |
US20060102521A1 (en) | 2006-05-18 |
AU2005325150A1 (en) | 2006-07-27 |
CA2594019A1 (en) | 2006-07-27 |
JP2008526504A (en) | 2008-07-24 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US7569508B2 (en) | Reforming nanocatalysts and method of making and using such catalysts | |
US7449423B2 (en) | Heat treatment of anchored nanocatalysts in a non-zero oxidation state and catalysts made by such method | |
US7541309B2 (en) | Reforming nanocatalysts and methods of making and using such catalysts | |
US7655137B2 (en) | Reforming catalysts having a controlled coordination structure and methods for preparing such compositions | |
US7045479B2 (en) | Intermediate precursor compositions used to make supported catalysts having a controlled coordination structure and methods for preparing such compositions | |
US7011807B2 (en) | Supported catalysts having a controlled coordination structure and methods for preparing such catalysts | |
US7709411B2 (en) | Method of manufacturing multicomponent nanoparticles | |
US7396795B2 (en) | Low temperature preparation of supported nanoparticle catalysts having increased dispersion | |
EP0091165B1 (en) | A silver catalyst and a method for the preparation thereof | |
KR100399304B1 (en) | Catalyst for hydrocarbon conversion reaction containing doping metal | |
US7534741B2 (en) | Supported nanocatalyst particles manufactured by heating complexed catalyst atoms | |
US7935652B2 (en) | Supported nanoparticle catalysts manufactured using caged catalyst atoms | |
WO2008042670A1 (en) | Methods for manufacturing bi-metallic catalysts having a controlled crystal face exposure | |
WO2008127742A2 (en) | Methods for manufacturing supported catalyst from a porous support and a nanocatalyst solution | |
KR19990022899A (en) | Conversion of hydrocarbons to aromatics using catalysts containing doped metals | |
EP1812158A2 (en) | Multicomponent nanoparticles formed using a dispersing agent | |
CA2532166C (en) | Supported catalysts having a controlled coordination structure and methods for preparing such catalysts | |
TW201714668A (en) | Multi-metallic catalyst doped with phosphorus and a lanthanide | |
JP2008526503A (en) | Reforming catalyst with chelation promoter | |
CA2803331A1 (en) | Platinum-free monometallic and bimetallic nanoparticles as ring-opening catalysts | |
WO1991017825A1 (en) | Catalytic compositions | |
CN117358231A (en) | Supported catalyst, preparation method and naphtha catalytic reforming method |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 200580043550.0 Country of ref document: CN |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
WWE | Wipo information: entry into national phase |
Ref document number: 2005852241 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 4121/DELNP/2007 Country of ref document: IN |
|
WWE | Wipo information: entry into national phase |
Ref document number: 1020077012416 Country of ref document: KR |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2594019 Country of ref document: CA |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2005325150 Country of ref document: AU |
|
WWE | Wipo information: entry into national phase |
Ref document number: MX/a/2007/008415 Country of ref document: MX |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2007551248 Country of ref document: JP |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
ENP | Entry into the national phase |
Ref document number: 2005325150 Country of ref document: AU Date of ref document: 20051128 Kind code of ref document: A |
|
WWP | Wipo information: published in national office |
Ref document number: 2005325150 Country of ref document: AU |
|
WWP | Wipo information: published in national office |
Ref document number: 2005852241 Country of ref document: EP |
|
ENP | Entry into the national phase |
Ref document number: PI0519002 Country of ref document: BR |