CN102413924B - 重整催化剂 - Google Patents
重整催化剂 Download PDFInfo
- Publication number
- CN102413924B CN102413924B CN201080017688.4A CN201080017688A CN102413924B CN 102413924 B CN102413924 B CN 102413924B CN 201080017688 A CN201080017688 A CN 201080017688A CN 102413924 B CN102413924 B CN 102413924B
- Authority
- CN
- China
- Prior art keywords
- reforming catalyst
- oxide
- tin
- indium
- catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 81
- 238000002407 reforming Methods 0.000 title claims abstract description 25
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 51
- 229910052738 indium Inorganic materials 0.000 claims abstract description 49
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims abstract description 48
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 18
- 239000001257 hydrogen Substances 0.000 claims abstract description 18
- 238000006057 reforming reaction Methods 0.000 claims abstract description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 72
- 239000011135 tin Substances 0.000 claims description 56
- 229910052718 tin Inorganic materials 0.000 claims description 43
- 229910052697 platinum Inorganic materials 0.000 claims description 35
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 33
- 229910052736 halogen Inorganic materials 0.000 claims description 29
- 150000002367 halogens Chemical class 0.000 claims description 28
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 12
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 11
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 11
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 10
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 10
- 229910021536 Zeolite Inorganic materials 0.000 claims description 9
- 239000010457 zeolite Substances 0.000 claims description 9
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 8
- 239000000395 magnesium oxide Substances 0.000 claims description 6
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 5
- 229910052810 boron oxide Inorganic materials 0.000 claims description 5
- 229910000423 chromium oxide Inorganic materials 0.000 claims description 5
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 5
- 239000002808 molecular sieve Substances 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 5
- ZCUFMDLYAMJYST-UHFFFAOYSA-N thorium dioxide Chemical compound O=[Th]=O ZCUFMDLYAMJYST-UHFFFAOYSA-N 0.000 claims description 5
- 229910003452 thorium oxide Inorganic materials 0.000 claims description 5
- 239000004408 titanium dioxide Substances 0.000 claims description 5
- 239000011787 zinc oxide Substances 0.000 claims description 5
- 229910000323 aluminium silicate Inorganic materials 0.000 claims description 4
- 229910001570 bauxite Inorganic materials 0.000 claims description 4
- 239000004927 clay Substances 0.000 claims description 4
- 229910052570 clay Inorganic materials 0.000 claims description 4
- 229910052573 porcelain Inorganic materials 0.000 claims description 4
- 239000000741 silica gel Substances 0.000 claims description 4
- 229910002027 silica gel Inorganic materials 0.000 claims description 4
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 4
- RJMMFJHMVBOLGY-UHFFFAOYSA-N indium(3+) Chemical compound [In+3] RJMMFJHMVBOLGY-UHFFFAOYSA-N 0.000 abstract description 7
- SYRHIZPPCHMRIT-UHFFFAOYSA-N tin(4+) Chemical compound [Sn+4] SYRHIZPPCHMRIT-UHFFFAOYSA-N 0.000 abstract description 6
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract description 3
- 229910021472 group 8 element Inorganic materials 0.000 abstract 1
- 229910052751 metal Inorganic materials 0.000 description 31
- 239000002184 metal Substances 0.000 description 31
- 238000000034 method Methods 0.000 description 29
- 230000009467 reduction Effects 0.000 description 20
- 150000001875 compounds Chemical class 0.000 description 17
- 238000001228 spectrum Methods 0.000 description 17
- 239000012876 carrier material Substances 0.000 description 14
- 238000007598 dipping method Methods 0.000 description 12
- 229930195733 hydrocarbon Natural products 0.000 description 12
- 150000002430 hydrocarbons Chemical class 0.000 description 12
- 239000004215 Carbon black (E152) Substances 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 11
- 229910052801 chlorine Inorganic materials 0.000 description 11
- 239000000460 chlorine Substances 0.000 description 11
- 230000003647 oxidation Effects 0.000 description 11
- 238000007254 oxidation reaction Methods 0.000 description 11
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 9
- 239000002253 acid Substances 0.000 description 9
- 238000003837 high-temperature calcination Methods 0.000 description 9
- 230000003197 catalytic effect Effects 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 150000002739 metals Chemical class 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000000853 adhesive Substances 0.000 description 5
- 230000001070 adhesive effect Effects 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 238000007600 charging Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- -1 halogen ion Chemical class 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- 238000001354 calcination Methods 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 230000009466 transformation Effects 0.000 description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- 229910052693 Europium Inorganic materials 0.000 description 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 239000011260 aqueous acid Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- 229910052793 cadmium Inorganic materials 0.000 description 3
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000005660 chlorination reaction Methods 0.000 description 3
- 238000000975 co-precipitation Methods 0.000 description 3
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 229910052809 inorganic oxide Inorganic materials 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 3
- 239000011133 lead Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 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
- 229910052684 Cerium Inorganic materials 0.000 description 2
- 238000006424 Flood reaction Methods 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- XURCIPRUUASYLR-UHFFFAOYSA-N Omeprazole sulfide Chemical compound N=1C2=CC(OC)=CC=C2NC=1SCC1=NC=C(C)C(OC)=C1C XURCIPRUUASYLR-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 229910002846 Pt–Sn Inorganic materials 0.000 description 2
- 229910006404 SnO 2 Inorganic materials 0.000 description 2
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 229910052732 germanium Inorganic materials 0.000 description 2
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- PIPQOOWEMLRYEJ-UHFFFAOYSA-N indium(1+) Chemical compound [In+] PIPQOOWEMLRYEJ-UHFFFAOYSA-N 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 229910052622 kaolinite Inorganic materials 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 238000001935 peptisation Methods 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- FHMDYDAXYDRBGZ-UHFFFAOYSA-N platinum tin Chemical compound [Sn].[Pt] FHMDYDAXYDRBGZ-UHFFFAOYSA-N 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910052702 rhenium Inorganic materials 0.000 description 2
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical group [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 2
- 239000011669 selenium Substances 0.000 description 2
- 238000004088 simulation Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- ZSUXOVNWDZTCFN-UHFFFAOYSA-L tin(ii) bromide Chemical compound Br[Sn]Br ZSUXOVNWDZTCFN-UHFFFAOYSA-L 0.000 description 2
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 1
- VBWYZPGRKYRKNV-UHFFFAOYSA-N 3-propanoyl-1,3-benzoxazol-2-one Chemical compound C1=CC=C2OC(=O)N(C(=O)CC)C2=C1 VBWYZPGRKYRKNV-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000370738 Chlorion Species 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RUEDMDSFOYPICP-UHFFFAOYSA-N ClC(=O)[Pt] Chemical compound ClC(=O)[Pt] RUEDMDSFOYPICP-UHFFFAOYSA-N 0.000 description 1
- 229910000846 In alloy Inorganic materials 0.000 description 1
- 229910021617 Indium monochloride Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- YVDLTVYVLJZLLS-UHFFFAOYSA-J O.Cl[Pt](Cl)(Cl)Cl Chemical compound O.Cl[Pt](Cl)(Cl)Cl YVDLTVYVLJZLLS-UHFFFAOYSA-J 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910001260 Pt alloy Inorganic materials 0.000 description 1
- 229910002847 PtSn Inorganic materials 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- 229910001128 Sn alloy Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- FDTUSPNGYPXVIO-UHFFFAOYSA-N [B+]=O.[O-2].[Al+3].[O-2] Chemical compound [B+]=O.[O-2].[Al+3].[O-2] FDTUSPNGYPXVIO-UHFFFAOYSA-N 0.000 description 1
- RPOYPGDEQYFZNE-UHFFFAOYSA-J [Cl-].[Na+].[Ir+3].[Cl-].[Cl-].[Cl-] Chemical compound [Cl-].[Na+].[Ir+3].[Cl-].[Cl-].[Cl-] RPOYPGDEQYFZNE-UHFFFAOYSA-J 0.000 description 1
- RLNMYVSYJAGLAD-UHFFFAOYSA-N [In].[Pt] Chemical compound [In].[Pt] RLNMYVSYJAGLAD-UHFFFAOYSA-N 0.000 description 1
- FHFOQXYFWKSNNF-UHFFFAOYSA-N [N+](=O)([O-])[Ir]([N+](=O)[O-])([N+](=O)[O-])([N+](=O)[O-])([N+](=O)[O-])[N+](=O)[O-] Chemical compound [N+](=O)([O-])[Ir]([N+](=O)[O-])([N+](=O)[O-])([N+](=O)[O-])([N+](=O)[O-])[N+](=O)[O-] FHFOQXYFWKSNNF-UHFFFAOYSA-N 0.000 description 1
- HIOZGGPMVODZLI-UHFFFAOYSA-N [N+](=O)([O-])[Rh]([N+](=O)[O-])([N+](=O)[O-])([N+](=O)[O-])([N+](=O)[O-])[N+](=O)[O-] Chemical compound [N+](=O)([O-])[Rh]([N+](=O)[O-])([N+](=O)[O-])([N+](=O)[O-])([N+](=O)[O-])[N+](=O)[O-] HIOZGGPMVODZLI-UHFFFAOYSA-N 0.000 description 1
- SQZFNPJUUKUJTG-UHFFFAOYSA-N [Pt].[N+](=O)([O-])N(C(N(N)[N+](=O)[O-])=O)N Chemical compound [Pt].[N+](=O)([O-])N(C(N(N)[N+](=O)[O-])=O)N SQZFNPJUUKUJTG-UHFFFAOYSA-N 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- GHTGICGKYCGOSY-UHFFFAOYSA-K aluminum silicon(4+) phosphate Chemical compound [Al+3].P(=O)([O-])([O-])[O-].[Si+4] GHTGICGKYCGOSY-UHFFFAOYSA-K 0.000 description 1
- IXWIAFSBWGYQOE-UHFFFAOYSA-M aluminum;magnesium;oxygen(2-);silicon(4+);hydroxide;tetrahydrate Chemical compound O.O.O.O.[OH-].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Mg+2].[Al+3].[Si+4].[Si+4].[Si+4].[Si+4] IXWIAFSBWGYQOE-UHFFFAOYSA-M 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 229910052789 astatine Inorganic materials 0.000 description 1
- RYXHOMYVWAEKHL-UHFFFAOYSA-N astatine atom Chemical compound [At] RYXHOMYVWAEKHL-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- XCJXQCUJXDUNDN-UHFFFAOYSA-N chlordene Chemical compound C12C=CCC2C2(Cl)C(Cl)=C(Cl)C1(Cl)C2(Cl)Cl XCJXQCUJXDUNDN-UHFFFAOYSA-N 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- BQWHLOCBVNERCO-UHFFFAOYSA-L dichloro(methyl)tin Chemical compound C[Sn](Cl)Cl BQWHLOCBVNERCO-UHFFFAOYSA-L 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium oxide Inorganic materials O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000000155 in situ X-ray diffraction Methods 0.000 description 1
- 150000002472 indium compounds Chemical class 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- APHGZSBLRQFRCA-UHFFFAOYSA-M indium(1+);chloride Chemical compound [In]Cl APHGZSBLRQFRCA-UHFFFAOYSA-M 0.000 description 1
- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical group Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- HTFVQFACYFEXPR-UHFFFAOYSA-K iridium(3+);tribromide Chemical compound Br[Ir](Br)Br HTFVQFACYFEXPR-UHFFFAOYSA-K 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 229940046892 lead acetate Drugs 0.000 description 1
- NGXWSRYOFVTCCT-UHFFFAOYSA-L lead(2+);dichlorate Chemical compound [Pb+2].[O-]Cl(=O)=O.[O-]Cl(=O)=O NGXWSRYOFVTCCT-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- VVIUOKUZBZOPQL-UHFFFAOYSA-N oxalic acid;potassium;rhodium Chemical compound [K].[Rh].OC(=O)C(O)=O VVIUOKUZBZOPQL-UHFFFAOYSA-N 0.000 description 1
- PVADDRMAFCOOPC-UHFFFAOYSA-N oxogermanium Chemical compound [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 0.000 description 1
- MUJIDPITZJWBSW-UHFFFAOYSA-N palladium(2+) Chemical compound [Pd+2] MUJIDPITZJWBSW-UHFFFAOYSA-N 0.000 description 1
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- KZTGQMIOPBMQCK-UHFFFAOYSA-N platinum sulfurous acid Chemical compound S(O)(O)=O.[Pt] KZTGQMIOPBMQCK-UHFFFAOYSA-N 0.000 description 1
- NWAHZABTSDUXMJ-UHFFFAOYSA-N platinum(2+);dinitrate Chemical compound [Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NWAHZABTSDUXMJ-UHFFFAOYSA-N 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 229910001630 radium chloride Inorganic materials 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- VXNYVYJABGOSBX-UHFFFAOYSA-N rhodium(3+);trinitrate Chemical compound [Rh+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VXNYVYJABGOSBX-UHFFFAOYSA-N 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000001119 stannous chloride Substances 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 230000002123 temporal effect Effects 0.000 description 1
- IEXRMSFAVATTJX-UHFFFAOYSA-N tetrachlorogermane Chemical compound Cl[Ge](Cl)(Cl)Cl IEXRMSFAVATTJX-UHFFFAOYSA-N 0.000 description 1
- CALMYRPSSNRCFD-UHFFFAOYSA-J tetrachloroiridium Chemical compound Cl[Ir](Cl)(Cl)Cl CALMYRPSSNRCFD-UHFFFAOYSA-J 0.000 description 1
- 229910052716 thallium Inorganic materials 0.000 description 1
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 description 1
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(ii) oxide Chemical class [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 238000010555 transalkylation reaction Methods 0.000 description 1
- HSSMNYDDDSNUKH-UHFFFAOYSA-K trichlororhodium;hydrate Chemical compound O.Cl[Rh](Cl)Cl HSSMNYDDDSNUKH-UHFFFAOYSA-K 0.000 description 1
- LYRCQNDYYRPFMF-UHFFFAOYSA-N trimethyltin Chemical compound C[Sn](C)C LYRCQNDYYRPFMF-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
-
- 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
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0207—Pretreatment of the support
-
- 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
- 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
- B01J37/22—Halogenating
- B01J37/24—Chlorinating
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
-
- 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
- B01J37/0072—Preparation of particles, e.g. dispersion of droplets in an oil bath
-
- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/70—Catalyst aspects
-
- 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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/02—Gasoline
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
在一个实施方案中，重整催化剂可包含铟、锡和催化有效量的用于一种或多种重整反应的VIII族元素。通常，在565℃的温度下暴露在包含100摩尔％氢气的气氛下30分钟以后，基于铟的总摩尔数，至少25摩尔％的铟为In(3+)类。通常，在565℃的温度下暴露在包含100摩尔％氢气的气氛下30分钟以后，基于锡的总摩尔数，不大于25摩尔％的锡为Sn(4+)类。
Description
发明领域
本发明一般地涉及可用于加氢转化方法中的重整催化剂。
相关技术描述
大量烃转化方法可用于改变烃料流的结构或性能。一般而言，这类方法包括：由直链烷烃或烯烃异构成更高度支化的烃，脱氢以生产烯烃或芳族化合物，脱氢环化以生产芳烃和发动机燃料，烷基化以生产通用化学品和发动机燃料，烷基转移等等。
通常，这类方法使用催化剂以促进烃转化反应。通常，理想的是开发具有不同性能如活性和选择性的催化剂以加工各种烃进料。因此，发现具有新性能的催化剂可能是有利的。
发明概述
在一个实施方案中，重整催化剂可包含铟、锡和催化有效量的用于一种或多种重整反应的VIII族元素。通常，在565℃的温度下暴露在包含100摩尔%氢气的气氛下30分钟以后，基于铟的总摩尔数，至少25摩尔%的铟为In(3+)类。通常，在565℃的温度下暴露在包含100摩尔%氢气的气氛下30分钟以后，基于锡的总摩尔数，不大于25摩尔%的锡为Sn(4+)类。
在另一优选实施方案中，重整催化剂可包含锡。通常在565℃的温度下暴露在包含100摩尔%氢气的气氛中30分钟以后，基于锡的总摩尔数，至少45摩尔%的锡为Sn(0)类且不大于30摩尔%的锡为Sn(4+)类。
在又一优选实施方案中，重整催化剂可包含催化有效量的用于催化一种或多种重整反应的VIII族元素、有效量的IVA族元素和有效量的还原元素。通常，如在565℃的温度下暴露在具有100摩尔%氢气的气氛下以后在室温下测定，还原元素和VIII族元素的配位数大于0。
因此，本文所公开的实施方案可提供具有促进加氢转化反应的不同性能和加工不同进料的灵活性的催化剂。
定义
如本文所用，术语“区”可指包括一个或多个设备件和/或一个或多个分区的区域。设备件可包括一个或多个反应器或反应容器、加热器、分离器、交换器、管、泵、压缩机和控制器。另外，设备件如反应器或容器可进一步包括一个或多个区或分区。
如本文所用，术语“料流”可以为包含各种烃分子如直链、支化或环状烷烃、烯烃、二烯烃和炔烃，和任选其它物质，例如气体如氢气，或杂质如重金属，及硫和氮化合物的料流。料流还可包含芳族和非芳族烃。此外，烃分子可简写为C1、C2、C3…Cn，其中“n”表示烃分子中碳原子的个数。
如本文所用，术语“金属”通常意指当它的化合物在溶液中时形成阳离子的元素。
如本文所用，术语“催化有效量”通常意指加入催化剂载体中以促进烃料流的至少一种化合物反应的量。通常，催化有效量基于催化剂的重量为至少0.005%，优选0.05%，最佳地0.10%。
如本文所用，术语“促进有效量”通常意指在催化剂载体上提高在烃料流转化中的催化性能以例如促进料流中至少一种化合物反应的量。通常，促进有效量基于催化剂的重量为至少0.005%，优选0.05%，最佳地0.10%。
如本文所用，术语“有效量”包括可改进催化性能和/或促进烃料流的至少一种化合物反应的量。
如本文所用，术语“条件”通常意指工艺条件如温度、反应时间、压力和空速。
如本文所用，术语“载体”通常意指可在加入一种或多种其它催化活性组分如贵金属以前，或在使载体经受随后方法如氧氯化或还原以前任选与粘合剂结合的多孔载体材料。
如本文所用，术语“卤素组分”通常意指卤离子或任何含卤的分子。卤素可包括氯、氟、溴或碘。作为实例，卤素组分可包括卤素、卤化氢、卤代烃，及包含卤素和金属的化合物。通常，卤素组分包含在催化剂中。
如本文所用，术语“含卤素化合物”通常意指任何含卤的分子。卤素可包括氯、氟、溴或碘。通常，含卤素化合物可以为气流的一部分，包括化合物如氯气、氯化氢或全氯乙烯，并可提供卤素组分给催化剂。
如本文所用，术语“催化剂前体”通常意指已加入一种或多种催化活性组分如贵金属，但没有经受随后方法如还原或硫化以完成催化剂生产的载体。然而，在一些情况下，催化剂前体可具有催化性能并可用作“催化剂”。
如本文所用，术语“室温”通常意指20-25℃的温度。
详述
本文所公开的催化剂可包含载体和一种或多种其它组分，该其它组分可在载体形成期间掺入载体中或之后掺入。通常，催化剂可包含载体、粘合剂和加入的组分，其可以为一种或多种金属和任选一种或多种卤素组分。在沉积金属以后，高温煅烧可产生一种或多种沉积金属的不定氧化态以赋予各种碳进料所需的选择性和活性性能。
通常，载体可通过油滴法或挤出而形成，但是也可使用其它方法。载体可包含重量比为1:99-99:1，优选10:90-90:10的多孔载体材料(如耐熔无机氧化物或分子筛)和粘合剂。载体材料可包括：
(1)耐熔无机氧化物如氧化铝、氧化镁、二氧化钛、氧化锆、氧化铬、氧化锌、氧化钍、氧化硼(boria)、二氧化硅-氧化铝、二氧化硅-氧化镁、氧化锆-氧化铝、氧化铝-氧化硼，或二氧化硅-氧化锆；
(2)陶瓷、瓷或铝土矿；
(3)合成制备或天然存在的二氧化硅或硅胶、碳化硅、粘土或硅酸盐，其可以经或未经酸处理，例如活性白土(attapulgus clay)、硅藻土、漂白土、高岭土或硅藻土；
(4)结晶沸石型硅铝酸盐，例如X-沸石、Y-沸石、丝光沸石、β-沸石、Ω-沸石或L-沸石，其为氢形式或最优选为具有占据可阳离子交换位的一种或多种碱金属的非酸性形式；
(5)非沸石型分子筛，例如铝磷酸盐或硅-铝-磷酸盐；或
(6)一种或多种来自这些组中一组或多组的材料的组合。
在一个优选实施方案中，多孔载体为氧化铝如γ-氧化铝。粘合剂可包括氧化铝、氧化镁、氧化锆、氧化铬、二氧化钛、氧化硼、氧化钍、磷酸盐、氧化锌、二氧化硅或其混合物。较高密度的载体可在高温处理以后产生较高水平的锡氧化物类。
催化剂可包含在载体形成期间加入和/或后来掺入的一种或多种其它组分。这些组分可以为一种或多种金属或非金属，包括：(1)VIII族元素，(2)促进剂如IVA族元素，(3)还原元素如一种或多种IIIA族元素或其它元素，和(4)卤素组分。任选，催化剂还可含有基于催化剂的重量为0.01-5重量%的一种或多种IA和IIA族金属(碱金属和碱土金属)。
优选VIII族元素为铂，且催化剂含有催化有效量。通常，催化剂含有基于催化剂的重量为0.01-2重量%的VIII族元素，优选铂。
促进剂可以为IVA族元素和/或其它元素。优选的IVA族元素为锡、锗或铅，更优选锡。任选可包含的又一促进剂为铼；稀土金属如铈、镧和/或铕；磷；镍；铁；钨；钼；钛；锌；或镉。也可使用这些元素的组合。通常，催化剂含有基于催化剂的重量为0.01-5重量%。IVA族元素或其它促进剂可以以氧化物或氯化物的形式存在。尽管不愿受理论束缚，但是认为这类元素如锡可首先具有金属氧键，且与本体氧化物(bulk oxide)如SnO2相反可以为一种或多种表面氧化物(surface oxide)。
催化剂还可含有促进有效量的还原元素。还原元素可以为至少一种IIIA族元素，优选铟、铁、铬、钴、镍、铅、镉、铊、硒和铕。通常，催化剂含有基于催化剂的重量为0至不大于1重量%的IIIA族元素，优选铟。如果为铟，则铟可以作为催化剂上的金属或作为一种或多种化合物如氧化铟，铂、锡和铟的合金或混合物，或氯化铟存在。优选，催化剂具有基于催化剂的重量为不大于0.6重量%的铟。尽管不愿受理论束缚，但是认为还原元素如铟可首先具有金属氧键，且与本体氧化物相反可以为一种或多种表面氧化物。
通常，还原元素充当促进剂以通过例如促进VIII族元素的催化活性而改变催化剂性能。尽管不愿受理论束缚，还原元素可实现提高的VIII族元素以及IVA族元素的还原。通常，VIII族元素为铂且IVA族元素为锡。
卤素组分可包含在催化剂中且可以为氟、氯、溴、碘、砹或其组合。优选卤素组分为氯。催化剂可通常含有基于催化剂的重量为0.1-10重量%，优选0.5-2.0重量%，最佳地0.7-1.3重量%的卤素组分，优选氯。
通过使用高温煅烧，可改变催化剂的活性和选择性。特别地，可改变一种或多种金属的氧化态和/或可产生还原元素与VIII族金属之间的相互作用。在一个优选实施方案中，如在565℃下在包含100摩尔%氢气的气氛中测量，可存在基于存在的铟的总摩尔数为至少25摩尔%的量的铟(3+)，和基于催化剂中存在的锡的总摩尔数为不大于25摩尔%的锡(4+)。尽管不愿受理论束缚，但是认为高温煅烧可提高铟(3+)的量(与铟(1+)不同)，同时降低Sn(4+)的量，与其它锡类，即Sn(2+)和Sn(0)相比。因而，这些性能可提供具有所需活性和选择性性能的催化剂。与较低温度如室温不同，所定义的铟和锡的氧化态仅可在升高的温度如565℃下存在。尽管不愿受理论束缚，但是铟(3+)/铟(1+)还原电势可足以将Sn(2+)还原成Sn(0)，如果铟在高温处理期间通过以下反应被还原：
In(1+)+Sn(2+)→In(3+)+Sn(0)
所述反应可热力学上有利地产生In(3+)和Sn(0)。
在另一理想实施方案中，如果促进剂为锡，则优选锡以基于存在于催化剂上的锡的总摩尔数(如在565℃下在包含100摩尔%氢气的气氛中测量)为至少45摩尔%，优选至少50摩尔%的锡(0)，和不大于30摩尔%，优选不大于25摩尔%的锡(4+)的量存在。尽管不愿受理论束缚，但是认为高温煅烧可提高锡(0)的量并降低锡(4+)的量，同时提高其它锡类的量。因而这些性能可提供具有所需活性和选择性性能的催化剂。此外，与较低温度如室温不同，所定义的锡的氧化态仅可在升高的温度如565℃下存在。
在又一实施方案中，还原元素和VIII族元素(分别例如为铟和铂)可证明配位数至少大于0，优选为至少0.1。尽管不愿受理论束缚，但是认为这一值指示在铟与铂原子之间的键如共价键。通常，铟可以以铟(3+)的氧化态存在。其它还原元素可以使用并以以下氧化态存在：Fe(2+)、Cr(2+)、Co(2+)、Ni(2+)、Pb(2+)、Cd(2+)、Tl(3+)、Se(2-)和Eu(2+)。另外，理想的是IVA族如锡，和VIII族元素如铂的配位数不大于1.0。配位数可在565℃下暴露在包含100摩尔%氢气的气氛下以后在室温下通过如下所述扩展X射线吸收精细结构(EXAFS)扫描测定。
载体可任选与一种或多种组分形成球或压出物。可将金属组分如一种或多种VIII族元素、促进剂和/或还原元素以任何合适方式如共沉淀、离子交换或浸渍掺入载体中。然而，通常优选在还原元素与VIII族金属的浸渍之间进行高温煅烧。优选的制备催化剂的方法可包括将多孔载体材料用可溶、可分解VIII族化合物浸渍。作为实例，铂金属可通过将载体与氯铂酸的水溶液混合而加入。其它VIII族金属的水溶性化合物或配合物可用于浸渍溶液，包括硝酸铂、亚硫酸铂、氯铂酸铵、溴铂酸、三氯化铂、四氯化铂水合物、二氯化二氯羰基铂、二硝基二氨基铂、四硝基铂酸(II)钠、氯化钯、氯钯酸、硝酸钯、硫酸钯、氢氧化二氨钯(II)、氯化四氨钯(II)、氯化六氨铑、羰基氯化铑、三氯化铑水合物、硝酸铑、六氯铑酸(III)钠、六硝基铑酸(III)钠、三溴化铱、二氯化铱、四氯化铱、六硝基铱酸(III)钠、氯铱酸、氯铱酸钾或氯铱酸钠，或草酸铑钾。这些化合物的使用也可提供至少部分卤素组分，特别是通过加入酸如盐酸。另外，浸渍可在载体的煅烧以后进行。
类似地，IIIA族金属可以以任何合适方式如共沉淀、离子交换或浸渍掺入载体中。优选的制备催化剂的方法可包括将多孔载体材料用可溶、可分解IIIA族化合物浸渍。作为实例，铟金属可通过浸渍氯化铟(InCl3)或硝酸铟(In(NO3)3)和盐酸的水溶液而加入。这些化合物的使用也可提供至少一部分卤素组分。
促进剂如IVA族金属可以以任何合适方式掺入催化剂中以实现均匀分散，例如通过在制备中的任何阶段浸渍载体材料、与多孔载体材料共沉淀或与载体材料离子交换。将IVA族金属组分掺入催化剂复合物中的一种方法包括使用IVA族金属的可溶、可分解化合物以在整个多孔载体材料上浸渍和分散金属。可在将其它组分加入载体材料中以前、同时或以后浸渍IVA族金属组分。因此，可将IVA族金属组分通过将载体材料与合适金属盐或可溶性化合物如溴化亚锡、氯化亚锡、氯化锡或氯化锡五水合物；或氧化锗、四乙醇锗或四氯化锗；或硝酸铅、乙酸铅或氯酸铅的水溶液混合而加入载体材料中。金属氯化物化合物的使用也可提供至少一部分卤素组分。在一个优选实施方案中，将至少一种有机金属化合物如氯化三甲锡和/或二氯化二甲锡在无机氧化物粘合剂胶溶期间，优选在将氧化铝用盐酸或硝酸胶溶期间掺入催化剂中。
可将其它促进剂如铼；稀土金属如铈、镧和/或铕；磷；镍；铁；钨；钼；钛；锌；镉；或其组合在载体材料制备期间或以后以任何合适方式加入载体材料中，或在掺入其它组分以前、期间或以后加入催化复合物中。
关于卤素组分，卤素组分可随一种或多种金属和/或一种或多种促进剂加入。此外，卤素组分可通过在370-600℃的温度下在空气或氧气气氛中使用含卤素化合物如氯气或氯化氢调整。在接触期间可存在水以有助于调整。
可将各组分一起浸渍，例如共浸渍，或单独地浸渍，其间具有一个或多个任选煅烧步骤。如上所述，可将催化剂前体在浸渍之间的分离步骤中煅烧。在一个优选实施方案中，将IIIA族元素，优选铟浸渍并在至少700℃，理想地700-900℃下煅烧。尽管不愿受理论束缚，但是认为高温煅烧可产生各种电荷态的还原元素。
催化剂所包含的材料的量可以通过本领域技术人员已知的方法测定。例如，在催化剂中通过电感耦合等离子体原子发射光谱法，UOP方法274-94可用于铂和其它VIII族金属，UOP方法303-87可用于锡和其它IVA族金属，UOP方法873-86可用于贵金属和改进剂，特别是铟。卤素组分，特别是氯可通过UOP方法979-02通过X射线荧光或通过UOP方法291-02通过电势滴定测定。经氧化数和配位数的物质的量可通过X射线吸收精细结构(下文可简写为“XAFS”)或EXAFS根据“Report of the InternationalXAFS Society Standards and Criteria Committee，D.E.Sayers(2000年7月25日采用)”所述程序测定。
本文所公开的催化剂实施方案可用于多种加氢转化方法中。典型催化石脑油重整或重整装置可包括连续催化剂反应和再生容器。典型装置例如公开于US5,958,216；US6,034,018和US2006/0013763A1中。另一典型装置公开于2008年4月17日提交的美国申请No.12/104,482中。
说明性实施方案
以下实施例意欲进一步说明主题颗粒。本发明这些说明性实施方案不意欲将本发明权利要求限于这些实施例的具体细节。这些实施例可基于工程计算和类似方法的实际操作经验。
实施例1
以不同的浸渍顺序和任选在基底上或在金属浸渍之间在至少750℃下在空气中煅烧(简写为“HiT”)制备9个试样。试样1和6以在铟和铂浸渍之间865℃的高温煅烧制备。
载体通过油滴法，之后进行标准热处理程序制备。将锡掺入铝溶胶中使得所形成的载体含有0.30重量%的锡。试样7的载体以类似方式制备，不同之处在于将氯化铟溶液随含锡溶液一起加入铝溶胶中并通过油滴法共胶凝。铟由含氯化铟或硝酸铟和盐酸的水溶液浸渍在载体上。铂由氯铂酸和盐酸的水溶液浸渍在载体上。对于铟和铂的共浸渍，使用铟化合物、氯铂酸和HCl的水溶液。然后将所有试样在510℃下在1000hr-1气时空速(GHSV)的气流中氧化8小时，同时注入盐酸溶液和氯气。催化剂在氮气和15摩尔%氢气的425GHSV混合物中还原。还原温度为565℃，保持2小时并在该温度下测试试样。
使试样经受原位X射线吸收精细结构(XAFS)扫描。还在原位温度编程下降研究期间通过XAFS扫描得到试样的氧化态，这通过在100摩尔%氢气中以7.5℃/min由室温倾斜至565℃，其后在565℃下保持30分钟而进行。作为选择，氧化态可当试样返回至室温时测定，如表2所述。
EXAFS数据简化和分析使用Athena软件进行，其为用于加工EXAFS数据的相互作用图解应用程序。Athena为图解前端并与IFEFFIT和FEFFIT程序连系。程序IFEFFIT提供用于EXAFS分析的交互性，将AUTOBK和FEFFIT的分析算法与图形显示结合并提供一般数据操作。程序FEFFIT还提供EXAFS数据的分析并使实验EXAFS光谱与来自软件程序FEFF的理论计算拟合。这些程序中至少一些主要由Consortium forAdvanced Radiation Sources在University of Chicago开发。
EXAFS数据对准与各个试样光谱同时采集的基准，然后平均以提高信噪比。使用Rbkg或Nyquist频率值为
和
(分别对应于铂、锡和铟光谱)的标准程序除去背景噪音。所测定光谱的傅里叶变换(FT)同时模拟为1、2和3的k-重量。χ(k)光谱为从3.5至
3.0至
和3.0至(分别对应于铂、锡和铟边缘)的傅里叶变换。傅里叶变换数以用2的k-重量处理的数据得到。理论模型基于Pt(0)、Sn(0)、In(0)、PtSn和In0.05Pt0.95的晶体结构由FEFF软件构建，如油无机晶体结构数据库序号提供。使模型对于各个试样的所有三种元素最佳化。从1.3至
1.0至和1.0至
(分别对应于铂、锡和铟边缘)模拟FT。傅里叶变换范围和模拟区域产生每光谱13、17和10个独立点，分别对应于铂、锡和铟。模型含有关于铂、锡和铟的6、10和7个变量，以及对于所有三个边缘要求相同的两个变量(Pt-Sn/In距离和σ2值)。该约束条件要求铂光谱中的Pt-Sn/In信号与相应锡和铟光谱中的Sn-Pt和In-Pt信号相同。根据稳健模型需要，模型中的变量数小于所测定的光谱中的独立点数。S0 2的值对于铂(由Pt(0)测定)、锡(由SnO2测定)和铟(由In(0)测定)光谱保持在0.93±0.03、1.00±0.04和1.06±0.08，如由模拟相应标准测定。
下表描述了方法和在各个载体上金属和卤素组分的最终重量百分数。
表1
表缩写：In,HiT,Pt：经铟浸渍，其后高温煅烧，然后经铂浸渍
co：用例如In和Pt共浸渍
Im Xx：用金属如In或Pt浸渍
重量%：基于催化剂的重量，催化剂中金属或氯离子的最终重量百分数
另外，在室温下对以上7个试样和另外两个试样8和9进行几个其它测量，如表2所述。
表2
如表1和2所示，试样1和6在铂和铟的沉积之间接受高温煅烧。通常相对于表1中如在565℃下所测定的试样1和6中铟的总摩尔数，铟(3+)的量在试样1中为28摩尔%，在试样6中为33摩尔%。另外，相对于表1中如在565℃下所测定的试样1和6中锡的总摩尔数，锡(4+)的量在试样1中为22摩尔%，在试样6中为25摩尔%。在室温下，锡(4+)的测量可相对于锡的总摩尔数超过25摩尔%，如表2中实施例6在室温下所例示的。而且，与试样1相比，试样6的较高密度还可在热处理以后产生较高的Sn(2+)浓度。
另外，使来自表1和2的试样1和2经受EXAFS扫描以测定配位数，其可以为成序和电荷转移的量度。铂-X信号的配位数(其中X可以为载体、铂或锡/铟)为对于试样中的所有铂原子，在给定距离上X原子的平均数。还测定锡和铟的配位数，其中X分别为氧、锡或铂，和氧、铟或铂。将这些试样与不具有铟的基准对比。特别地，对比例1具有0.29重量%的铂、0.28重量%的锡和1.24重量%氯。
配位数通常通过在铂、锡和铟边缘进行的EXAFS扫描测定。通常，将试样在室温下用氦气吹扫。在氦气中依次采集锡和铟K-边缘光谱。接着，使温度以5℃/min倾斜至565℃并采集交替的锡和铟光谱。然后将试样保持在565℃下30分钟。其后，将试样在氢气中冷却至室温。在氢气中在室温下依次采集锡和铟的K-边缘光谱。以类似方式采集铂的L3-边缘光谱。
数据模型化程序同时精制了各个试样类型的铂、锡和铟光谱的模型，所以将铂-锡/铟和锡/铟-铂的距离和无序项限定为相同值。因而，铂光谱中的锡信号与锡光谱中的铂信号为相同距离。
结果描述于下表3中：
表3
NDV-不可检测的值
所描述的数据误差数据与最后的有效数字相关。在试样1中，热处理试样的锡-铂配位数可以为0.7(误差±0.3)，其不大于1.0。与其明显相反，试样2和对比例1的锡-铂配位数可以大于1.0。类似地，试样1的铟-铂配位数可以为0.17±0.06，其可表示铟与铂之间存在共价键。未经热处理的试样2不显示具有该键的证据。另外，试样1和2均具有近似数量的铂-锡/铟键。尽管不愿受理论束缚，这表明高温可促进铂颗粒中锡被铟置换。
实施例2
在中试装置中在与用于转化烃进料基本相同的条件下，例如进料、温度、压力、氢气/烃摩尔比和液时空速测试试样1和3。加速稳定性试验以通过气相色谱分析计算的研究法辛烷值(RON)进行，目标为104。该目标通过连续升高温度而随时间变化保持恒定。各个催化剂的活性通过保持目标辛烷所需的温度测定。收率基于在线气体和液体流出物气相色谱分析计算。使用描述98-102%的物料平衡的数据。所有结果以0.056m3进料/l催化剂显示。结果描述于下表4中：
表4
| 性能 | 试样1 | 试样3 |
| RON | 103.9 | 104.0 |
| 转化温度℃ | 520.5 | 524.2 |
| C5+收率，重量% | 87.41 | 87.39 |
与试样3催化剂相比，试样1催化剂具有3.9℃的更高活性。
未经进一步推敲，认为使用前述说明书，本领域技术人员可最完整程度地使用本发明。因此，前述优选的具体实施方案构成仅理解为说明性，而不以任何方式限制公开内容的其余部分。
在上文中，除非另有指出，所有温度以摄氏度未经修正地陈述，所有份和百分数以重量计。
从以上说明书中，本领域技术人员可容易地确定本发明的基本特征，并可不偏离其精神和范围地作出本发明的各种改变和改进以使它适合各种用途和条件.
Claims (12)
1.一种重整催化剂，其包含：
A)铟，其中在565℃的温度下暴露在包含100摩尔%氢气的气氛下30分钟以后，基于铟的总摩尔数，至少25摩尔%的铟为In3+类；
B)锡，其中在565℃的温度下暴露在包含100摩尔%氢气的气氛下30分钟以后，基于锡的总摩尔数，不大于25摩尔%的锡为Sn4+类；和
C)催化有效量的用于一种或多种重整反应的VIII族元素。
2.根据权利要求1的重整催化剂，其中VIII族元素包括铂。
3.根据权利要求1的重整催化剂，其中重整催化剂包含基于重整催化剂的重量为0.01-2重量%的VIII族元素。
4.根据权利要求2的重整催化剂，其中重整催化剂包含基于重整催化剂的重量为0.01-2重量%的铂。
5.根据权利要求1、2或3的重整催化剂，其进一步包含基于重整催化剂的重量为0.1-10重量%的卤素组分。
6.根据权利要求1、2或3的重整催化剂，其进一步包含载体，其中所述载体包含氧化铝、氧化镁、二氧化钛、氧化锆、氧化铬、氧化锌、氧化钍、氧化硼、陶瓷、瓷、铝土矿、二氧化硅、硅胶、碳化硅、粘土、结晶沸石型硅铝酸盐和非沸石型分子筛中至少一种。
7.根据权利要求5的重整催化剂，其进一步包含载体，其中所述载体包含氧化铝、氧化镁、二氧化钛、氧化锆、氧化铬、氧化锌、氧化钍、氧化硼、陶瓷、瓷、铝土矿、二氧化硅、硅胶、碳化硅、粘土、结晶沸石型硅铝酸盐和非沸石型分子筛中至少一种。
8.根据权利要求6的重整催化剂，其中所述载体包含氧化铝。
9.根据权利要求7的重整催化剂，其中所述载体包含氧化铝。
10.根据权利要求4的重整催化剂，其进一步包含基于重整催化剂的重量为0.1-10重量%的卤素组分。
11.根据权利要求4或10的重整催化剂，其进一步包含载体，其中所述载体包含氧化铝、氧化镁、二氧化钛、氧化锆、氧化铬、氧化锌、氧化钍、氧化硼、陶瓷、瓷、铝土矿、二氧化硅、硅胶、碳化硅、粘土、结晶沸石型硅铝酸盐和非沸石型分子筛中至少一种。
12.根据权利要求11的重整催化剂，其中所述载体包含氧化铝。
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US12/391,035 US7799729B2 (en) | 2009-02-23 | 2009-02-23 | Reforming catalyst |
| US12/391,035 | 2009-02-23 | ||
| PCT/US2010/023972 WO2010096336A2 (en) | 2009-02-23 | 2010-02-12 | Reforming catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102413924A CN102413924A (zh) | 2012-04-11 |
| CN102413924B true CN102413924B (zh) | 2014-01-15 |
Family
ID=42631496
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201080017688.4A Expired - Fee Related CN102413924B (zh) | 2009-02-23 | 2010-02-12 | 重整催化剂 |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US7799729B2 (zh) |
| CN (1) | CN102413924B (zh) |
| BR (1) | BRPI1007999A2 (zh) |
| RU (1) | RU2011138946A (zh) |
| SG (1) | SG173702A1 (zh) |
| WO (1) | WO2010096336A2 (zh) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120277511A1 (en) * | 2011-04-29 | 2012-11-01 | Uop Llc | High Temperature Platformer |
| US20150045597A1 (en) | 2013-08-07 | 2015-02-12 | Uop Llc | Integrated process for gasoline or aromatics production |
| US9199893B2 (en) | 2014-02-24 | 2015-12-01 | Uop Llc | Process for xylenes production |
| CN104275194B (zh) * | 2014-10-10 | 2017-12-26 | 上海华谊（集团）公司 | 醋酸加氢制乙醇催化剂及其制备方法 |
| FR3039082B1 (fr) * | 2015-07-24 | 2017-07-21 | Ifp Energies Now | Catalyseur multi-metallique dope par du phosphore et un lanthanide |
| EP3287191A1 (en) | 2016-08-26 | 2018-02-28 | Friedrich-Alexander-Universität Erlangen-Nürnberg | Catalytically active compositions of matter |
| KR101882942B1 (ko) * | 2017-04-13 | 2018-07-30 | 한국화학연구원 | 경질 알칸 탈수소화 반응을 위한 금속 담지 제올라이트 촉매 및 이의 제조방법 |
| CN110548535B (zh) * | 2018-05-31 | 2022-01-04 | 中国石油化工股份有限公司 | 一种重整催化剂及其制备方法与应用 |
| CN111167457B (zh) * | 2020-02-19 | 2022-05-13 | 太原理工大学 | 基于硼掺杂的镍/半焦催化剂及其制备和应用 |
| RU2767681C1 (ru) * | 2021-04-29 | 2022-03-18 | Публичное акционерное общество "Нефтяная компания "Роснефть" (ПАО "НК "Роснефть") | Катализатор риформинга бензиновых фракций и способ его получения |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4487848A (en) * | 1983-06-02 | 1984-12-11 | Uop Inc. | Indium-containing catalyst for reforming hydrocarbons |
| US4522935A (en) * | 1983-06-02 | 1985-06-11 | Uop Inc. | Platinum and indium-containing catalyst for reforming hydrocarbons |
| CN1360517A (zh) * | 1999-06-30 | 2002-07-24 | 菲利浦石油公司 | 催化重整催化剂的活化 |
Family Cites Families (43)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3892657A (en) * | 1972-07-17 | 1975-07-01 | Universal Oil Prod Co | Hydrocarbon conversion with a multimetallic catalytic composite |
| FR2529101A1 (fr) | 1982-06-25 | 1983-12-30 | Prod Catalyse Ste Fse | Procede de fabrication d'un catalyseur de conversion d'hydrocarbures |
| US4529505A (en) * | 1983-06-02 | 1985-07-16 | Uop Inc. | Indium-containing catalyst for reforming hydrocarbons |
| FR2560205B1 (fr) * | 1984-02-23 | 1988-07-15 | Inst Francais Du Petrole | Procede de reformage catalytique |
| FR2593824B1 (fr) * | 1986-02-03 | 1988-11-04 | Inst Francais Du Petrole | Procede de reformage catalytique a travers au moins trois lits de catalyseur |
| US5520796A (en) * | 1986-03-27 | 1996-05-28 | Uop | Reforming/dehydrocyclization catalysts |
| US4716143A (en) * | 1986-06-06 | 1987-12-29 | Uop Inc. | Dehydrogenation catalyst composition |
| US5128300A (en) * | 1989-06-30 | 1992-07-07 | Uop | Reforming catalyst with homogeneous metals dispersion |
| FR2661905B1 (fr) | 1990-05-11 | 1992-07-24 | Inst Francais Du Petrole | Utilisation d'un catalyseur contenant une zeolithe, un metal noble de la famille du platine et un metal additionnel dans l'aromatisation des hydrocarbures contenant de 2 a 4 atomes de carbone par molecule. |
| FR2665895B1 (fr) | 1990-08-16 | 1992-10-16 | Inst Francais Du Petrole | Procede d'aromatisation des hydrocarbures contenant de 5 a 9 atomes de carbone par molecule. |
| DE69203211T2 (de) | 1991-11-15 | 1995-11-02 | Inst Francais Du Petrole | Katalysator mit MFI-Struktur und seine Verwendung zum Aromatisieren von Kohlenwasserstoffen mit 2 bis 12 Kohlenstoffatomen. |
| DE69203212T2 (de) | 1991-11-15 | 1995-11-02 | Inst Francais Du Petrole | Aluminosilikat Katalysator und seine Verwendung zum Aromatisieren von 2 bis 12 Kohlenstoffatome haltende Kohlenwasserstoffen. |
| US5211838A (en) * | 1991-12-09 | 1993-05-18 | Exxon Research & Engineering Company | Fixed-bed/moving-bed two stage catalytic reforming with interstage aromatics removal |
| EP0616632B1 (en) | 1991-12-09 | 1999-08-25 | Exxon Research And Engineering Company | Reforming with two fixed-bed units, each having a moving-bed tail reactor sharing a common regenerator |
| US5221463A (en) * | 1991-12-09 | 1993-06-22 | Exxon Research & Engineering Company | Fixed-bed/moving-bed two stage catalytic reforming with recycle of hydrogen-rich stream to both stages |
| US5565090A (en) * | 1994-11-25 | 1996-10-15 | Uop | Modified riser-reactor reforming process |
| US5677260A (en) * | 1995-06-23 | 1997-10-14 | Indian Petrochemicals Corporation Limited | Catalyst composite for dehydrogenation of paraffins to mono-olefins and method for the preparation thereof |
| US6034018A (en) * | 1995-10-20 | 2000-03-07 | Uop Llc | Method for reducing chloride emissions from a moving bed catalyst regeneration process |
| US5879537A (en) * | 1996-08-23 | 1999-03-09 | Uop Llc | Hydrocarbon conversion process using staggered bypassing of reaction zones |
| US5883032A (en) * | 1996-11-21 | 1999-03-16 | Uop Llc | Selective multimetallic multigradient reforming catalyst |
| US6495487B1 (en) * | 1996-12-09 | 2002-12-17 | Uop Llc | Selective bifunctional multimetallic reforming catalyst |
| US6013173A (en) * | 1996-12-09 | 2000-01-11 | Uop Llc | Selective bifunctional multimetallic reforming catalyst |
| US6809061B2 (en) * | 1996-12-09 | 2004-10-26 | Uop Llc | Selective bifunctional multigradient multimetallic catalyst |
| US5858908A (en) * | 1997-04-17 | 1999-01-12 | Uop Llc | Selective multimetallic-multigradient reforming catalyst |
| FR2770535B1 (fr) * | 1997-10-31 | 1999-12-10 | Inst Francais Du Petrole | Procede d'hydroreformage catalytique |
| FR2770420B1 (fr) * | 1997-10-31 | 1999-12-03 | Inst Francais Du Petrole | Lit homogene de catalyseur et procede de transformation d'hydrocarbures en composes aromatiques avec ledit lit |
| US6106696A (en) * | 1997-12-16 | 2000-08-22 | Uop Llc | Moving bed reforming process without heating between the combined feed exchanger and the lead reactor |
| US6036845A (en) * | 1998-05-04 | 2000-03-14 | Uop Llc | Modified riser-reactor reforming process with prereactor |
| US5958216A (en) * | 1998-12-18 | 1999-09-28 | Uop Llc | Catalytic reforming process with multiple zones |
| FR2789332B1 (fr) * | 1999-02-09 | 2001-04-13 | Inst Francais Du Petrole | Lit homogene de catalyseur et procede de transformation d'hydrocarbures en composes aromatiques avec ledit lit |
| DE10020049A1 (de) | 1999-04-26 | 2001-01-11 | Inst Francais Du Petrole | Herstellung eines Katalysators, der ein Metall aus der Gruppe VIII und ein zusätzliches Metall enthält, das als wasserlösliche organmetallische Verbindung eingeleitet wird, sowie seine Verwendung für die Kohlenwasserstoffumwandlung |
| FR2792550B1 (fr) * | 1999-04-26 | 2001-06-01 | Inst Francais Du Petrole | Catalyseur comprenant un element des groupes 8,9 et 10 presentant une bonne accessibilite et son utilisation dans un procede de deshydrogenation des paraffines |
| US6635598B2 (en) * | 2000-04-20 | 2003-10-21 | Indian Petrochemicals Corporation Limited | Stable and selective dehydrogenation catalyst and a process for the preparation thereof |
| US7037871B1 (en) * | 2001-11-21 | 2006-05-02 | Uop Llc | Low-temperature regeneration of zeolite L using ozone |
| US6872300B1 (en) * | 2002-03-29 | 2005-03-29 | Uop Llc | Reforming catalyst with chelated promotor |
| FR2840548B1 (fr) * | 2002-06-07 | 2005-03-18 | Inst Francais Du Petrole | Lit homogene de catalyseur et procede de transformation d'hydrocarbures en composes aromatiques avec ledit lit |
| US20040129605A1 (en) | 2002-10-29 | 2004-07-08 | Goldstein Stuart S. | Method for revamping fixed-bed catalytic reformers |
| US7569508B2 (en) * | 2004-11-17 | 2009-08-04 | Headwaters Technology Innovation, Llc | Reforming nanocatalysts and method of making and using such catalysts |
| US20060013763A1 (en) * | 2003-12-12 | 2006-01-19 | Baird Lance A | Process for the production of high purity hydrogen from a catalytic reformer |
| US20050274648A1 (en) | 2004-04-21 | 2005-12-15 | Goldstein Stuart S | Method for revamping fixed-bed catalytic reformers |
| US20060102520A1 (en) * | 2004-11-12 | 2006-05-18 | Lapinski Mark P | Reforming process using high density catalyst |
| USH2244H1 (en) * | 2005-03-22 | 2010-08-03 | Exxonmobil Research And Engineering Company | Method for operating catalytic reformers |
| US7638673B2 (en) * | 2005-05-04 | 2009-12-29 | Exxonmobil Chemical Patents Inc. | Process for hydrocarbon conversion with on-line solid particulate material removal |
-
2009
- 2009-02-23 US US12/391,035 patent/US7799729B2/en not_active Expired - Fee Related
-
2010
- 2010-02-12 CN CN201080017688.4A patent/CN102413924B/zh not_active Expired - Fee Related
- 2010-02-12 SG SG2011058740A patent/SG173702A1/en unknown
- 2010-02-12 BR BRPI1007999A patent/BRPI1007999A2/pt not_active IP Right Cessation
- 2010-02-12 RU RU2011138946/04A patent/RU2011138946A/ru not_active Application Discontinuation
- 2010-02-12 WO PCT/US2010/023972 patent/WO2010096336A2/en active Application Filing
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4487848A (en) * | 1983-06-02 | 1984-12-11 | Uop Inc. | Indium-containing catalyst for reforming hydrocarbons |
| US4522935A (en) * | 1983-06-02 | 1985-06-11 | Uop Inc. | Platinum and indium-containing catalyst for reforming hydrocarbons |
| CN1360517A (zh) * | 1999-06-30 | 2002-07-24 | 菲利浦石油公司 | 催化重整催化剂的活化 |
Also Published As
| Publication number | Publication date |
|---|---|
| SG173702A1 (en) | 2011-09-29 |
| US7799729B2 (en) | 2010-09-21 |
| US20100216630A1 (en) | 2010-08-26 |
| RU2011138946A (ru) | 2013-03-27 |
| WO2010096336A3 (en) | 2010-12-02 |
| WO2010096336A2 (en) | 2010-08-26 |
| BRPI1007999A2 (pt) | 2016-03-08 |
| CN102413924A (zh) | 2012-04-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102413924B (zh) | 重整催化剂 | |
| JP4642460B2 (ja) | ビスマスおよびリン含有触媒担体、それから作製する改質触媒、作製方法、およびナフサ改質方法 | |
| RU2388534C2 (ru) | Способ реформинга с использованием катализатора высокой плотности | |
| JP4170768B2 (ja) | 白金およびスズを含むマルチメタリック改質触媒、その調製および応用 | |
| US8912110B2 (en) | Catalyst for conversion of hydrocarbons | |
| WO2010075134A2 (en) | Methods of preparing an aromatization catalyst | |
| CN101940935B (zh) | 一种双金属重整催化剂及其制备方法 | |
| CN103596681A (zh) | 重整催化剂和方法 | |
| JPH0919639A (ja) | 少なくとも一つの貴金属を含む触媒の現場外での再生方法 | |
| CN101348405A (zh) | 利用烃类原料制备轻质芳烃和轻质烷烃的方法 | |
| CN102895995B (zh) | 一种石脑油重整催化剂及其制备方法 | |
| CN102029186B (zh) | 一种双组分石脑油重整催化剂及其制备方法 | |
| Sharma et al. | Atomically dispersed tin-modified γ-alumina for selective propane dehydrogenation under H2S co-feed | |
| CN103372454B (zh) | 一种多金属重整催化剂及其制备与应用 | |
| CN111659428B (zh) | 一种连续重整催化剂及其制备方法和应用 | |
| JP2563304B2 (ja) | 多段帯域ナフサ改質法 | |
| JP2005525933A (ja) | ビスマスおよびリン含有改質触媒、作製方法、およびナフサ改質方法 | |
| PL89067B1 (zh) | ||
| CN110064418B (zh) | 一种氧化态重整催化剂及其制备方法 | |
| CN102216426A (zh) | 在催化重整单元中原位添加助催化剂金属的方法和系统 | |
| JP2018521852A (ja) | リンとランタニドのドープ型多金属触媒 | |
| EP0017474B1 (en) | Reforming with an improved rhenium-containing catalyst | |
| CN103962135B (zh) | 一种多金属连续重整催化剂及其制备方法 | |
| CN110064419B (zh) | 一种石脑油重整催化剂及其制备方法 | |
| CN107866261B (zh) | 一种改性sba-15分子筛的烃类重整催化剂及其制备方法和应用 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20140115 Termination date: 20150212 |
|
| EXPY | Termination of patent right or utility model |