CN103596681A - 重整催化剂和方法 - Google Patents
重整催化剂和方法 Download PDFInfo
- Publication number
- CN103596681A CN103596681A CN201280029171.6A CN201280029171A CN103596681A CN 103596681 A CN103596681 A CN 103596681A CN 201280029171 A CN201280029171 A CN 201280029171A CN 103596681 A CN103596681 A CN 103596681A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- metal
- cerium
- lanthanide series
- conventionally
- 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.)
- Pending
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 150
- 238000000034 method Methods 0.000 title description 26
- 238000002407 reforming Methods 0.000 title description 10
- 230000008569 process Effects 0.000 title description 8
- 229910052751 metal Inorganic materials 0.000 claims abstract description 92
- 239000002184 metal Substances 0.000 claims abstract description 92
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 48
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 32
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 23
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 18
- 230000000737 periodic effect Effects 0.000 claims abstract description 12
- 229910052741 iridium Inorganic materials 0.000 claims abstract description 9
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 9
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 7
- 239000010948 rhodium Substances 0.000 claims abstract description 7
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims abstract description 7
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000001833 catalytic reforming Methods 0.000 claims abstract description 5
- 229910052762 osmium Inorganic materials 0.000 claims abstract description 5
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 5
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 40
- 150000002602 lanthanoids Chemical class 0.000 claims description 40
- 229910052684 Cerium Inorganic materials 0.000 claims description 34
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 34
- 150000002739 metals Chemical class 0.000 claims description 13
- 238000009826 distribution Methods 0.000 claims description 4
- 239000002344 surface layer Substances 0.000 abstract 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 43
- 229930195733 hydrocarbon Natural products 0.000 description 25
- 150000002430 hydrocarbons Chemical class 0.000 description 25
- 239000004215 Carbon black (E152) Substances 0.000 description 23
- 150000004820 halides Chemical class 0.000 description 22
- 239000002245 particle Substances 0.000 description 20
- 150000001875 compounds Chemical class 0.000 description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 16
- 239000012876 carrier material Substances 0.000 description 16
- 239000001257 hydrogen Substances 0.000 description 16
- 229910052739 hydrogen Inorganic materials 0.000 description 16
- 239000000203 mixture Substances 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 239000008187 granular material Substances 0.000 description 12
- 238000002360 preparation method Methods 0.000 description 12
- 239000002994 raw material Substances 0.000 description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- 239000002253 acid Substances 0.000 description 10
- 230000003647 oxidation Effects 0.000 description 10
- 238000007254 oxidation reaction Methods 0.000 description 10
- 230000001105 regulatory effect Effects 0.000 description 10
- 239000007789 gas Substances 0.000 description 9
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 8
- 238000006555 catalytic reaction Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 7
- 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 7
- -1 chlorocarbonyl platinous chloride Chemical compound 0.000 description 7
- 238000006356 dehydrogenation reaction Methods 0.000 description 7
- 238000007598 dipping method Methods 0.000 description 7
- 229910052809 inorganic oxide Inorganic materials 0.000 description 7
- 230000009467 reduction Effects 0.000 description 7
- 229910052708 sodium Inorganic materials 0.000 description 7
- 239000011734 sodium Substances 0.000 description 7
- 150000001335 aliphatic alkanes Chemical class 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000006187 pill Substances 0.000 description 6
- 229910052718 tin Inorganic materials 0.000 description 6
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 5
- 238000009835 boiling Methods 0.000 description 5
- 238000005336 cracking Methods 0.000 description 5
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 239000005864 Sulphur Substances 0.000 description 4
- 229910021536 Zeolite Inorganic materials 0.000 description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 150000001924 cycloalkanes Chemical class 0.000 description 4
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 4
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 4
- CYPPCCJJKNISFK-UHFFFAOYSA-J kaolinite Chemical compound [OH-].[OH-].[OH-].[OH-].[Al+3].[Al+3].[O-][Si](=O)O[Si]([O-])=O CYPPCCJJKNISFK-UHFFFAOYSA-J 0.000 description 4
- 229910052622 kaolinite Inorganic materials 0.000 description 4
- 239000002808 molecular sieve Substances 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 230000008929 regeneration Effects 0.000 description 4
- 238000011069 regeneration method Methods 0.000 description 4
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000010457 zeolite Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 3
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000000975 co-precipitation Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 229910052746 lanthanum Inorganic materials 0.000 description 3
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 3
- 239000000693 micelle Substances 0.000 description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 3
- 238000001935 peptisation Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 230000007420 reactivation Effects 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- WURBVZBTWMNKQT-UHFFFAOYSA-N 1-(4-chlorophenoxy)-3,3-dimethyl-1-(1,2,4-triazol-1-yl)butan-2-one Chemical compound C1=NC=NN1C(C(=O)C(C)(C)C)OC1=CC=C(Cl)C=C1 WURBVZBTWMNKQT-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 230000029936 alkylation Effects 0.000 description 2
- 238000005804 alkylation reaction Methods 0.000 description 2
- 150000004645 aluminates Chemical class 0.000 description 2
- 229910000323 aluminium silicate Inorganic materials 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000004517 catalytic hydrocracking Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000009849 deactivation Effects 0.000 description 2
- 238000006900 dealkylation reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000000605 extraction Methods 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
- 239000000017 hydrogel Substances 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 229910000765 intermetallic Inorganic materials 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 238000006317 isomerization reaction Methods 0.000 description 2
- NGXWSRYOFVTCCT-UHFFFAOYSA-L lead(2+);dichlorate Chemical compound [Pb+2].[O-]Cl(=O)=O.[O-]Cl(=O)=O NGXWSRYOFVTCCT-UHFFFAOYSA-L 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 150000002902 organometallic compounds Chemical class 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- IEXRMSFAVATTJX-UHFFFAOYSA-N tetrachlorogermane Chemical compound Cl[Ge](Cl)(Cl)Cl IEXRMSFAVATTJX-UHFFFAOYSA-N 0.000 description 2
- ZSUXOVNWDZTCFN-UHFFFAOYSA-L tin(ii) bromide Chemical compound Br[Sn]Br ZSUXOVNWDZTCFN-UHFFFAOYSA-L 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
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 229910052692 Dysprosium Inorganic materials 0.000 description 1
- 229910052691 Erbium Inorganic materials 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- 229910052689 Holmium Inorganic materials 0.000 description 1
- 229910052765 Lutetium Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-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
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 229910052773 Promethium Inorganic materials 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 229910052771 Terbium Inorganic materials 0.000 description 1
- 229910052775 Thulium Inorganic materials 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 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
- 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
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- YCNZFPXXIWEFCF-UHFFFAOYSA-N alumane;sodium Chemical compound [Na].[AlH3] YCNZFPXXIWEFCF-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- IHNDUGMUECOVKK-UHFFFAOYSA-N aluminum chromium(3+) oxygen(2-) Chemical compound [O-2].[Cr+3].[O-2].[Al+3] IHNDUGMUECOVKK-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 229910001570 bauxite Inorganic materials 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- 229910052810 boron oxide Inorganic materials 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 150000001768 cations Chemical group 0.000 description 1
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 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
- 238000005660 chlorination reaction Methods 0.000 description 1
- CZRDZAGTSCUWNG-UHFFFAOYSA-M chloro(dimethyl)tin Chemical compound C[Sn](C)Cl CZRDZAGTSCUWNG-UHFFFAOYSA-M 0.000 description 1
- KWTSZCJMWHGPOS-UHFFFAOYSA-M chloro(trimethyl)stannane Chemical compound C[Sn](C)(C)Cl KWTSZCJMWHGPOS-UHFFFAOYSA-M 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay 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
- 230000000052 comparative effect Effects 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000020335 dealkylation Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 description 1
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 description 1
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 1
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000003349 gelling agent Substances 0.000 description 1
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium oxide Inorganic materials O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- 239000004312 hexamethylene tetramine Substances 0.000 description 1
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 1
- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium atom Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 0.000 description 1
- DKAGJZJALZXOOV-UHFFFAOYSA-N hydrate;hydrochloride Chemical compound O.Cl DKAGJZJALZXOOV-UHFFFAOYSA-N 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 238000007327 hydrogenolysis reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- HTFVQFACYFEXPR-UHFFFAOYSA-K iridium(3+);tribromide Chemical compound Br[Ir](Br)Br HTFVQFACYFEXPR-UHFFFAOYSA-K 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 description 1
- 229940046892 lead acetate Drugs 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 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
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 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
- 230000001590 oxidative effect Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- PVADDRMAFCOOPC-UHFFFAOYSA-N oxogermanium Chemical compound [Ge]=O PVADDRMAFCOOPC-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
- 239000012071 phase Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 125000002743 phosphorus functional group Chemical group 0.000 description 1
- 239000011505 plaster Substances 0.000 description 1
- HRGDZIGMBDGFTC-UHFFFAOYSA-N platinum(2+) Chemical compound [Pt+2] HRGDZIGMBDGFTC-UHFFFAOYSA-N 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- VQMWBBYLQSCNPO-UHFFFAOYSA-N promethium atom Chemical compound [Pm] VQMWBBYLQSCNPO-UHFFFAOYSA-N 0.000 description 1
- 229910001630 radium chloride Inorganic materials 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000006057 reforming reaction Methods 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 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
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- 238000009938 salting Methods 0.000 description 1
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000001568 sexual effect Effects 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000019795 sodium metasilicate Nutrition 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000001119 stannous chloride Substances 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 description 1
- CALMYRPSSNRCFD-UHFFFAOYSA-J tetrachloroiridium Chemical compound Cl[Ir](Cl)(Cl)Cl CALMYRPSSNRCFD-UHFFFAOYSA-J 0.000 description 1
- AGGKEGLBGGJEBZ-UHFFFAOYSA-N tetramethylenedisulfotetramine Chemical compound C1N(S2(=O)=O)CN3S(=O)(=O)N1CN2C3 AGGKEGLBGGJEBZ-UHFFFAOYSA-N 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- ZCUFMDLYAMJYST-UHFFFAOYSA-N thorium dioxide Chemical compound O=[Th]=O ZCUFMDLYAMJYST-UHFFFAOYSA-N 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- HSSMNYDDDSNUKH-UHFFFAOYSA-K trichlororhodium;hydrate Chemical compound O.Cl[Rh](Cl)Cl HSSMNYDDDSNUKH-UHFFFAOYSA-K 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000003403 water pollutant Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Images
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
- 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
- B01J23/63—Platinum group metals with rare earths or actinides
-
- 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
-
- 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
- B01J23/8933—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 also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8966—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 also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with 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
- B01J23/90—Regeneration or reactivation
- B01J23/96—Regeneration or reactivation of catalysts comprising metals, oxides or hydroxides of the noble 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/128—Halogens; Compounds thereof with iron group metals or platinum group metals
- B01J27/13—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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/28—Regeneration or reactivation
- B01J27/32—Regeneration or reactivation of catalysts comprising compounds of halogens
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/31—Density
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/396—Distribution of the active metal ingredient
- B01J35/397—Egg shell like
-
- 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
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
-
- 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
-
- 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
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
一个典型实施方案可以为用于石脑油的催化重整的催化剂。该催化剂可具有包含铂、钯、铑、钌、锇和铱中的一种或多种的贵金属、包含周期表原子序数57-71的一种或多种元素的镧系金属和载体。通常,催化剂的平均堆积密度为0.300-0.620g/cm3,且镧系金属:贵金属的原子比为小于1.3:1。此外,镧系金属可以以催化剂100μm表面层中的镧系金属浓度小于催化剂中心核心处的镧系金属浓度的2倍分布。
Description
优先权陈述
本申请要求2011年7月15日提交的美国申请No.13/184,248的优先权,通过引用将其全部内容并入本文中。
发明领域
本发明一般性地涉及重整催化剂和方法。
相关技术描述
一些催化剂可具有氢化-脱氢功能和裂化功能并用于促进宽范围的烃转化反应。不同的组分如载体可对裂化功能做出贡献,同时其它部分如沉积金属可对氢化-脱氢功能做出贡献。一些组分贡献裂化和氢化-脱氢功能。通常,双功能催化剂用于促进多种烃转化反应,例如脱氢、氢化、加氢裂化、氢解、异构化、脱硫、环化、烷基化、聚合、裂化和加氢异构化。
通常,理想的是具有用于各种方法如重整中的催化剂功能灵活性。在一个典型的重整方法中,希望提高一种或多种C5 +烃、氢气的产率和芳烃产率。任选地,催化剂的酸度可通过将金属和/或其它元素加入催化剂中而改变。通常,酸功能的改变导致降低的链烷烃裂化成C3和C4轻馏分,从而容许提高的芳烃形成的选择性。还可发生金属功能的改变,导致降低的链烷烃裂化成甲烷和乙烷。还可存在芳烃的脱烷基化反应减少,留下较重和更有价值的C8 +芳烃。
除产率外,可赋予催化剂活性,从而获得商业上有用的转化率水平而不使用额外量的催化剂或使用过高的温度,这可导致不希望的较高成本。较高的催化剂活性也可用于加工更大量的进料或提高转化率,因此提高有价值产物的产量。
发明概述
一个典型实施方案可以为用于石脑油的催化重整的催化剂。该催化剂可具有包含铂、钯、铑、钌、锇和铱中的一种或多种的贵金属,包含周期表原子序数57-71的一种或多种元素的镧系金属,和载体。通常,催化剂的平均堆积密度为0.300-0.620g/cm3,且镧系金属:贵金属的原子比为小于1.3:1。此外,镧系金属可以以催化剂100μm表面层中的镧系金属浓度小于催化剂中心核心处的镧系金属浓度的2倍分布。
另一典型实施方案可以为用于石脑油的催化重整的催化剂。该催化剂可包含铂、铈、氯化物和载体。另外,催化剂的平均堆积密度为0.300-0.620g/cm3,铈:铂的原子比为小于1.3:1,且氯化物:铈的原子比为14:1-20:1。
另一典型实施方案可以为重整方法。该重整方法可包括将烃原料和富氢气体装入重整区中,和使烃原料和富氢气体在反应器中在重整区中接触。通常,催化剂包含:包含铂、钯、铑、钌、锇和铱中的一种或多种的贵金属,包含周期表原子序数57-71的一种或多种元素的镧系金属,和载体。通常,催化剂的平均堆积密度为0.300-0.620g/cm3,且镧系金属:贵金属的原子比为小于1.3:1。此外,镧系金属可以以催化剂100μm表面层中的镧系金属浓度小于催化剂中心核心处的镧系金属浓度2倍分布。
在一个典型实施方案中,将周期表的镧系金属加入低密度球形氧化铝载体中,这得到高的一种或多种C5+烃产率而不具有大的活性缺陷(debit)。具体而言,限定提供产率和活性优点的镧系金属:贵金属的原子比以及金属浓度分布。
定义
如本文所用,术语“料流”可包含各种烃分子,例如直链、支化或环状链烷烃、链烯烃、二烯烃和炔烃,和任选其它物质,例如气体如氢气,或杂质如金属,和硫和氮化合物。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”表示一个或多个烃分子中的碳原子数。此外,上标“+”或“-”可以与缩写的一种或多种烃符号一起使用,例如C3 +或C3 -,其包含在简写的一种或多种烃内。例如,缩写“C3 +”意指一种或多种具有3个和/或更多碳原子的烃分子。
如本文所用,术语“区”可指包括一个或多个设备项和/或一个或多个分区的区域。设备项可包括一个或多个反应器或反应容器、加热器、交换器、管、泵、压缩机和控制器。另外,设备项如反应器、干燥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“富含”可意指料流中至少通常50%,优选70摩尔%的量的一种化合物或一类化合物。
如本文所用,术语“基本”可意指料流中至少通常80%,优选90%,最佳地99摩尔%的量的一种化合物或一类化合物。
如本文所用,术语“组成均匀”可意指未分层载体不具有对其组成而言固有的物质的浓度梯度,且在组成方面是基本均匀的。如果载体为两种或更多种耐熔材料的混合物,这些材料的相对量在整个载体中可以为恒定且均匀的。
如本文所用,术语“表面层”意指与颗粒表面相邻的催化剂颗粒层。通常,表面层金属的浓度从催化剂颗粒的表面至中心逐渐减少。
如本文所用,术语“层”为自催化剂颗粒表面起基本均匀的距离处具有基本均匀厚度的催化剂颗粒层。
如本文所用,术语“中心核心”为代表催化剂颗粒直径的50%的催化剂颗粒核心。
如本文所用,术语“直径”定义为通过催化剂颗粒的中心的最小规则尺寸,例如该尺寸会为挤出物圆柱的直径。
如本文所用,术语“卤化物”可意指离子,例如氯,其获得一个电子以形成阴离子,例如氯化物。
如本文所用,术语“烧失量”可缩写为“LOI”。
如本文所用,术语“平均堆积密度”可缩写为“ABD”。
如本文所用,术语“研究法辛烷值”可缩写为“RON”。
如本文所用,术语“重量百分比”可缩写为“重量%”。
如本文所用,术语“平方米/克”可缩写为“m2/g”。
如本文所用,术语“毫米”可缩写为“mm”。
如本文所用,术语“克/立方厘米”可缩写为“g/cc”或“g/cm3”。
如本文所用,术语“原子比”可与“摩尔比”互换使用。
如本文所用,术语“烷烃”和“链烷烃”可互换使用。
如本文所用,术语“链烯烃”和“烯烃”可互换使用。
如本文所用,术语“环烷烃”和“环烷”可互换使用。
附图简述
图1为几个试样的图示,其对比在恒定RON下相对于以℃表示的温度以重量%表示的C5+产率。
图2为几个试样的图示,其对比在恒定RON下相对于以℃表示的温度以重量%表示的C5+产率。
详述
本文公开的实施方案可提供适于重整的催化剂,所述催化剂包含具有并入或沉积其上的一种或多种金属的载体。该催化剂可通过组分的具体比表征。通常,金属包括贵金属、周期表14族金属和周期表原子序数57-71的镧系金属。通常,催化剂通过将镧系金属与周期表8-10族金属,通常铂一起加入盐酸溶液中并在单一或多个步骤中浸渍氧化铝载体而制备。接着,可将催化剂以氧氯化和还原最后处理。一些材料和制备催化剂的方法公开于例如US6,809,061中。
通常,载体为具有25-500m2/g的表面积的多孔、吸附性、高表面积载体。多孔载体材料还应是组成均匀且对烃转化方法中所用条件而言是相对耐熔的。因此,载体材料可包含如下一种或多种:(1)耐熔无机氧化物,例如氧化铝、氧化镁、二氧化钛、氧化锆、氧化铬、氧化锌、二氧化钍、氧化硼、二氧化硅-氧化铝、二氧化硅-氧化镁、氧化铬-氧化铝、氧化铝-氧化硼和二氧化硅-氧化锆;(2)陶瓷、瓷和铝土矿;(3)二氧化硅、硅胶、碳化硅、粘土和合成制备或天然存在的任选酸处理的硅酸盐;(4)具有占据阳离子可交换部位的一种或多种碱金属的结晶型沸石铝硅酸盐,例如X型沸石、Y型沸石、丝光沸石和L型沸石,其为氢形式或优选非酸性形式;和(5)非沸石型分子筛,例如铝磷酸盐或硅铝磷酸盐。
优选载体包含一种或多种无机氧化物,优选的无机氧化物为氧化铝。合适的氧化铝材料可包括称为γ-、η-和θ-氧化铝的结晶氧化铝,γ-或η-氧化铝是最优选的。优选的耐熔无机氧化物可具有通常0.300-0.620g/cm3,优选0.550-0.580g/cm3,最佳地0.555-0.580g/cm3的表观堆积密度。表面积特征可包括20-300埃的平均孔直径、0.1-1cm3/g的孔体积和100-500m2/g的表面积。
一种典型的氧化铝作为如例如US2,892,858所述的来自齐格勒高级醇合成反应的副产物公开于例如US3,852,190和US4,012,313中,其在下文中称为“齐格勒氧化铝”。高纯度拟勃姆石在高温下煅烧以后可提供具有高纯度的γ-氧化铝。
氧化铝粉末可形成具有任何所需形状的颗粒,例如球、条、丸粒、团粒、片、颗粒和挤出物。通常,这类颗粒具有0.7-3.5mm的至少一个规则尺寸,通常圆形横截面,在本文中称为“直径”。
通常,催化剂载体为具有0.7-3.5mm的优选直径的球形颗粒。通常,氧化铝球通过油滴方法连续生产。通常,油滴法包括形成氧化铝水溶胶并使铝金属与盐酸反应,将所得水溶胶与合适的胶凝剂结合并将所得混合物滴入保持在升高的温度下的油浴中。混合物的液滴可保持在油浴中直至它们凝结并形成水凝胶球。然后可将球连续地从油浴中取出并通常经受在油和氨溶液中的特殊老化处理以进一步改善它们的物理特征。然后可将所得胶凝且老化的颗粒洗涤,在205-1,500℃的温度下干燥并经受在450-700℃的温度下煅烧1-20小时。该处理实现将氧化铝水凝胶转化成相应的结晶γ-氧化铝,并公开于例如US2,620,314中。
替代性地,载体可以为圆柱形挤出物,其优选通过将氧化铝粉末与水和合适的胶溶剂如盐酸或硝酸混合直至形成可挤出胶团。加入的形成胶团的水的量通常足以得到45-65重量%的500℃LOI,其中优选55重量%的值。通常,酸加入速率足以提供混合物中2-7重量%的无挥发物氧化铝粉末,其中优选3-4重量%的值。所得胶团可通过适当尺寸的模挤出以形成挤出物颗粒。然后可将这些颗粒在260-427℃的温度下干燥0.1-5小时以形成挤出物颗粒。通常,圆柱形挤出物颗粒的直径可以为0.7-3.5mm,优选具有1:1-5:1的长度:直径比。
通常将贵金属并入催化剂中。贵金属可包括铂、钯、钌、铑、铱和锇中的一种或多种,优选铂。贵金属可作为化合物如氧化物、硫化物、卤化物或氧卤化物以与复合物的一种或多种其它成分的化学组合或作为元素金属存在于最终催化剂内。在一个典型实施方案中,贵金属以元素状态存在并均匀分散于载体材料内。替代性地,贵金属与镧系金属共沉淀以在催化剂中形成梯度。该组分可以以催化有效量,例如基于催化剂的重量基于元素计算最终催化剂的0.01-2重量%存在于最终催化剂复合物中。优异的结果可用基于催化剂的重量0.05-1重量%的铂得到。
贵金属可以以任何合适的方式如共沉淀、离子交换或浸渍并入多孔载体材料中。制备催化剂的一种优选方法可以为以相对均匀的方式用贵金属的可溶、可分解化合物浸渍载体材料。例如,可通过将后者与氯铂酸、氯铱酸或氯钯酸的水溶液混合而将组分加入载体中。贵金属的其它水溶性化合物或配合物可用于浸渍溶液中,并包括如下一种或多种:氯铂酸铵、溴铂酸、三氯化铂、四氯化铂水合物、二氯羰基二氯化铂、二硝基二氨基铂、四硝基铂(II)酸钠、氯化钯、硝酸钯、硫酸钯、二胺钯(II)氢氧化物、四胺钯(II)氯化物、六胺铑氯化物、羰基氯化铑、三氯化铑水合物、硝酸铑、六氯铑(III)酸钠、六硝基铑(III)酸钠、三溴化铱、二氯化铱、四氯化铱、六硝基铱(III)酸钠、氯铱酸钾或钠和草酸铑钾。通常优选使用铂、铱、铑或钯氯化物如氯铂酸、氯铱酸或氯钯酸或三氯化铱水合物。通常,也可将氯化氢或其它类似的酸加入浸渍溶液中以进一步促进卤化物组分的并入和金属组分在整个载体材料中的均匀分布。此外,通常优选将载体材料在将它煅烧以后浸渍以使洗去贵金属的风险最小化。
通常,贵金属均匀分散于催化剂中。优选贵金属的分散通过扫描透射电子显微镜(本文中可缩写为“STEM”)通过对比金属浓度与总催化剂金属含量而测定。替代性地,一种或多种贵金属可作为表面层组分存在,如例如US4,677,094所述。
还可包括周期表14族金属。理想地,14族金属为锗或锡,特别优选锡。14族金属可作为元素金属如氧化物、硫化物、卤化物或氧氯化物或者作为与多孔载体材料和/或催化剂的其它组分的物理或化学组合存在。优选实质部分的14族金属以元素金属以上的氧化态存在于最终催化剂中。14族金属,优选锡最佳地以足以产生含有基于催化剂的重量基于元素计算不多于5重量%,理想地0.01-5重量%的最终催化剂的量使用。理想地,包含基于催化剂的重量基于元素计算0.1-2重量%的14族金属。
14族金属可以以任何合适的方式并入催化剂中以实现均匀的分散,例如通过与多孔载体材料共沉淀、与载体材料离子交换或在制备的任何阶段浸渍载体材料。将14族金属并入催化剂复合物中的一种方法可涉及使用14族金属的可溶性可分解化合物以浸渍和分散金属于整个多孔载体材料中。14族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。因此,可将14族金属通过将后者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、氯化锡五水合物、氧化锗、四乙醇锗、四氯化锗、硝酸铅、乙酸铅和氯酸铅的水溶液混合而加入载体材料中。特别优选使用14族金属氯化物,例如氯化锡、四氯化锗或氯酸铅。当在上文所述尤其优选的氧化铝胶溶步骤期间与氯化氢结合时,可得到14族金属的均匀分散。替代性地,将一种或多种有机金属化合物如三甲基氯化锡和二甲基二氯化锡在无机氧化物粘合剂胶溶期间,最优选将氧化铝用硫化氢或硝酸胶溶期间并入催化剂中。
还可包含周期表原子序数57-71的镧系金属。镧系金属可包括镧、铈、镨、钕、钷、钐、铕、钆、铽、镝、钬、铒、铥、镱和镥,其中优选铈。镧系金属可以以任何催化有效形式,例如元素金属、化合物如氧化物、氢氧化物、卤化物、氧卤化物、铝酸盐,或者以与催化剂的一种或多种其它组分的化学组合存在。镧系金属可以以元素金属以上的氧化态存在,例如氧化物、氧卤化物、卤化物或其混合物。优选氧化和还原阶段用于如下文所述的制备中。
镧系金属可富集在各催化剂颗粒的表面层中。表面层浓度为在自外表面起100μm深的表面层内测量的平均值。表面层镧系金属的浓度自催化剂颗粒的表面至中心逐渐减少,其可以为逐步或更急剧的方式。对于本文公开的实施方案的优选球形颗粒,中心核心可以为直径为球形颗粒的50%的颗粒中心的球形部分。表面层组分测量为自颗粒表面起延伸100μm的层中的浓度且中心核心代表颗粒直径的50%。
例如,半径为0.08cm的球形催化剂可具有100μm或0.01cm深的表面层、0.92g/cm3的丸粒密度和1重量%的铈。整个催化剂的体积可计算为:
整个催化剂丸粒的体积=4/3*π*(r)3
其中r为催化剂的半径。
催化剂的体积[4/3*π*(0.08)3]可计算为0.002145cm3,不存在于表面层中的催化剂(或中心核心)的体积[4/3*π*(0.07)3]可计算为0.001437cm3。这两个体积的差可得到表面层的体积,即0.000708cm3。
整个催化剂、中心核心和表面层的重量可通过体积乘以密度可计算,并描述如下:
表1
体积(cm3) | 丸粒密度(g/cm3) | 催化剂重量(g) | |
整个催化剂 | 0.002145 | 0.92 | 0.001973 |
中心核心 | 0.001437 | 0.92 | 0.001322 |
表面层 | 0.000708 | 0.92 | 0.000651 |
具有1重量%铈的催化剂可通过铈的重量分数乘以催化剂重量而具有0.01973mg铈。如果催化剂具有包含在表面层中的50重量%铈,则0.009865mg铈可包含在表面层中且0.009865mg可包含在中心核心中。以重量%表示的浓度可通过给定体积中的铈重量(以g表示)除以该体积中的相应催化剂重量(以g表示)以得到0.75重量%的中心核心浓度和1.52重量%的表面层浓度而计算。因此,该实例中的表面层证明两倍于中心核心的铈浓度。
优选金属梯度通过扫描电子显微镜(本文中可缩写成“SEM”)测定。局部金属浓度的SEM测定在来自催化剂颗粒床的至少三个试样颗粒上进行。试样通过本领域技术人员已知的技术从床中随机地选择。通常,SEM基于金属分布状况相对于载体的量测定催化剂颗粒内一系列深度的近似金属含量。金属浓度可在特定点或者通过自催化剂丸粒表面起指定深度的同心片中浓度的平均值测定。100μm表面层的浓度通过在至少三个催化剂丸粒,优选至少6个丸粒,更优选至少12个丸粒的表面层中至多100μm的增加的深度取得的一系列金属浓度的平均值而计算。
优选,表面层镧系金属具有在催化剂颗粒表面层中基于元素如通过SEM测量的浓度,其小于颗粒中心核心中镧系金属浓度的两倍。更优选表面层与中心核心中的金属浓度比为1:1-小于2:1。在可选定义中,小于50%的表面层金属包含在催化剂的表面层中。
表面层镧系元素可以以任何合适的方式并入催化剂颗粒中以影响自颗粒的表面至中心降低的金属梯度。其一个实例是通过喷雾浸渍。喷雾喷嘴可位于保持催化剂载体的滚筒中,并使用空气将表面层金属的盐溶液从喷嘴喷射以形成喷雾的细液滴,所述细液滴接触滚筒中的载体以有效混合。合适的盐可包括硝酸盐、硫酸盐、乙酸盐、氯化物、溴化物、碘化物、胺配合物,和有机金属化合物如烷基和醇盐化合物。溶液与载体的体积比足以得到催化剂中所需的表面层金属浓度并可以为0.1-1.0重量%。
替代性地,金属作为化合物,尤其是盐浸渍,其在5或更大的pH下分解。例如,优选的金属作为当接触时分解的氯盐浸渍。替代性地,可使用与其它组分配合或不渗入颗粒内部的金属化合物。实例为多齿配体,例如羧酸,或者含有氨基、硫醇基团、磷基团或其它极性基团的金属化合物,其可强力结合在氧化物载体上。
镧系金属以任何催化有效量并入催化剂中,得到基于催化剂的重量基于元素在催化剂中0.05-5重量%的镧系元素。优选可使用基于催化剂的重量基于元素计算0.2-2重量%镧系元素。镧系元素,优选铈,与贵金属,优选铂的优选的原子比为0.45:1.00-1.29:1.00、0.50:1.00-1.29:1.00、0.94:1.00-1.29:1.00、0.94:1.00-1.26:1.00和1.00:1.00-1.26:1.00。
任选地,催化剂还可包含作为催化剂改进剂单独或协同改善活性、选择性或稳定性的其它组分或其混合物。一些已知的催化剂改进剂包括铼、钴、镍、铁、钨、钼、铬、铋、锑、锌、镉和铜。可将催化有效量的这些组分在其制备期间或以后以任何合适方式加入载体材料中,或者在并入其它组分以前、期间或以后加入催化剂中。
然而,优选催化剂的金属组分基本由贵金属、14族金属和镧系金属,更优选由铂、锡和铈组成。镧系金属,优选铈,与贵金属,优选铂,的原子比为0.50:1.00-1.29:1.00、0.94:1.00-1.29:1.00或0.94:1.00-1.26:1.00。
用于烃转化实施方案,包括脱氢、脱氢环化或氢化反应中的催化剂的任选组分为碱或碱土金属。更确切地讲,该任选成分选自碱金属—铯、铷、钾、钠和锂—和碱土金属—钙、锶、钡和镁的化合物。通常,当该组分构成基于催化剂的重量基于元素计算0.01-5重量%的复合物时,在这些实施方案中得到良好结果。该任选碱或碱土金属可以以任何已知方法并入复合物中,其中优选浸渍合适水溶性可分解化合物的水溶液。催化剂可具有0.300-0.620g/cm3,优选0.550-0.580g/cm3或最佳地0.555-0.580g/cm3的平均堆积密度。
通常至少一个氧化步骤用于催化剂的制备中。氧化步骤通常在370-650℃的温度下进行。通常使用氧气气氛,包括空气。通常氧化步骤进行0.5-10小时或更久的期间。通常,确切的时间期间是将基本所有金属组分转化成它们相应的氧化物形式需要的任何时间。当然,该时间随着所用的氧化温度和所用气氛的氧气含量而变化。
除氧化步骤外,卤化物调节步骤也可用于制备催化剂中。卤化物调节步骤可具有双重功能。首先,卤化物调节步骤可帮助贵金属和其它金属的均匀分散。另外,卤化物调节步骤可用作将所需水平的卤化物并入最终催化剂中的方式。通常卤化物调节步骤使用在空气或氧气气氛中的卤素或含卤化物化合物。由于用于并入催化剂中的优选卤化物可包括氯化物,卤化物调节步骤期间使用的优选卤素或含卤化物化合物为氯气、氯化氢或这些化合物的前体。
在进行卤化物调节步骤期间,催化剂与空气或氧气气氛中的卤素或含卤化物化合物化合物在370-650℃的升高温度下接触。进一步希望在接触步骤期间存在水以帮助调节。特别地,当催化剂的卤化物组分可包括氯化物时,优选使用5:1-100:1的水:氯化氢摩尔比。卤化步骤的持续时间通常为0.5-5小时或更久。由于调件的相似性,卤化物调节步骤可在氧化步骤期间进行。替代性地,卤化物调节步骤可根据需要在氧化步骤以前或以后通过用于制备催化剂的特定方法进行。不管所用的确切卤化物调节步骤,最终催化剂的卤化物含量应使得存在足够的卤化物以包含基于催化剂的重量基于元素0.1-10重量%。通常,卤化物:镧系金属、优选氯化物:铈的原子比为14:1-20:1。
还原步骤对制备催化剂而言是希望的。还原步骤可将基本所有贵金属还原成相应的元素金属态并确保该组分相对均匀且细碎分散在整个耐熔无机氧化物中。优选还原步骤在基本无水环境中进行。通常,还原气体为基本纯的干氢气,即小于20体积ppm水。然而,可使用其它还原气体如含有轻质烃的一氧化碳、氮气或氢气。通常使还原气体与氧化催化复合物在包括315-650℃的还原温度的条件下接触0.5-10或更多小时的时间以有效地将基本所有贵金属还原成元素金属态。还原步骤可在将催化复合物装入烃转化区中以前进行,或者它可作为烃转化方法启动程序的一部分原位进行。然而,如果使用该后一种技术,则可采取合适的预防措施以将转化装置预干燥至基本无水状态,并应使用基本无水还原气体。任选可使催化复合物经受预硫化步骤。可通过任何已知的技术将任选硫组分并入催化剂中。
在一个典型实施方案中,催化剂可具有作为烃转化催化剂的特定效用。通常,使待转化的烃与催化剂在包括40-600℃的温度、100-21,000kPa的压力和0.1-100hr-1的液时空速在内的烃转化条件下接触。催化剂特别适于汽油范围原料的催化重整,以及可尤其用于脱氢环化、脂族烃和芳烃的异构化、脱氢、加氢裂化、歧化、脱烷基化、烷基化、烷基交换和低聚。
通常,重整方法在包括选自100-7,000kPa,优选350-2,500kPa的压力的条件下进行。重整温度为315-600℃,优选425-565℃。通常,该宽范围内温度的初始选择主要作为产品重整油的所需辛烷值的函数进行,其中考虑进料和催化剂的特征。通常,然后将温度在运行期间缓慢提高以补偿不可避免地发生的减活,以提供恒定辛烷值产物。提供足够的氢气以提供1-20,优选2-10摩尔氢气/摩尔进入重整区中的烃进料的量。同样,液时空速为0.1-20hr-1,优选1-5hr-1。
优选烃原料为石脑油原料,包括在汽油范围内沸腾的环烷烃和链烷烃。优选的原料为主要由环烷烃和链烷烃组成的石脑油,但在许多情况下还存在芳烃。这一优选类别包括直馏汽油、天然汽油和合成汽油。替代性地,通常有利的是装入热或催化裂化汽油、部分重整石脑油或脱氢石脑油。也可使用直馏和裂化汽油范围石脑油的混合物。汽油范围石脑油进料可以为具有40-80℃的初始ASTM D-86沸点和160-220℃的终沸点的全沸汽油,或者可以为其通常具有较高沸点馏分的选择部分,通常称为重石脑油。例如,沸点为100-200℃的石脑油可认为是重石脑油。如果重整涉及苯、甲苯和二甲苯中一种或多种的制备,则沸程可以为60-150℃。在一些情况下,还有利的是加工从萃取装置中回收的纯烃或烃混合物。例如,将来自芳烃萃取的萃余液或直链链烷烃转化成芳烃。
理想地,催化剂用于基本无水环境中。通常,控制存在于装入重整区中的原料和氢气流中的水含量。当从任何来源进入转化区中的水的总量保持在作为原料中的当量水的重量表示小于50ppm,优选小于20ppm的水平时,得到最好的结果。通常,这可通过谨慎地控制原料和氢气流中的水而实现。可将原料通过使用任何合适的干燥方法干燥。例如,可通过合适的汽提操作在分馏塔中调整原料的水含量。替代性地或者额外地,可使用具有高水选择性的常规固体吸附剂,所述吸附剂例如结晶铝硅酸钠或钙、硅胶、活性氧化铝、分子筛、无水硫酸钙和高表面积钠。在一些情况下,吸附剂干燥和蒸馏干燥的组合可有利地用于进行从原料中几乎完全除去水。通常,进入烃转化区中的氢气流的水含量保持在基于氢气流体积10-20体积ppm或更少。
通常催化剂在基本无硫环境中操作。可使用任何合适的控制方法以处理待装入重整反应区中的石脑油原料。例如,可使原料经受吸附方法、催化方法或其组合。吸附方法可使用分子筛、高表面积二氧化硅-氧化铝、碳分子筛、结晶铝硅酸盐、活性炭和高表面积含金属如镍或铜组合物。通常,将这些原料通过常规催化预处理方法如加氢精制、加氢处理和加氢脱硫处理以从其中除去基本所有含硫、含氮和出水污染物,并使可能包含在其中的任何烯烃饱和。催化方法可使用本领域中已知的传统硫还原催化剂,包括含有周期表6、8-10和12族金属的耐熔无机氧化物载体。
通常,将烃原料和富氢气体预加热并装入通常含有2-5个串联反应器的重整区中。在反应器之间提供合适的加热装置以补偿各反应器中反应的净吸热。可使反应物在各反应器中以向上流、向下流或径向流动方式接触催化剂,其中优选径向流动模式。催化剂可包含在固定床系统中或者优选具有相关连续催化剂再生的移动床系统中。使减活的催化剂再活化的可选路线包括半再生操作,其包括关闭用于催化剂再生和再活化的整个装置,或者摆动反应器操作(swing-reactor operation),其包括将单一反应器与系统分离,再生和再活化,同时其它反应器保持运行。通常,与移动床系统有关的连续催化剂再生尤其公开于例如US3,647,680;US3,652,231;US3,692,496;和US4,832,921中。
通常,来自重整区的流出物通过冷却装置进入通常保持在0-65℃下的分离区中,在那里将富氢气体与通常称为“不稳定重整油”的液流分离。然后可使所得氢气流再循环通过合适的压缩装置返回重整区中。通常,将来自分离区的液相取出并在分馏系统中加工以调整丁烷浓度,由此控制所得重整油的前端挥发度。
说明性实施方案
以下实施例意欲进一步阐述主题催化剂。对本发明实施方案的这些阐述不意欲将本发明的权利要求书限于这些实施例的具体细节。这些实施例基于工程计算和类似方法的实际操作经验。
实施例1
制备包含氧化铝上的铂、锡和铈(或镧)的球形催化剂。将锡并入氧化铝溶胶中并将含锡氧化铝溶胶以油滴方法以形成1.6mm球,将其以10%LOI汽蒸至干燥并在650℃下煅烧。接着,将球形载体与氯化铈(或氯化镧)和氯铂酸的溶液共浸渍并在350℃下煅烧2小时,干燥并在510℃下氧氯化,其后在565℃下用纯氢气还原。试样的组成和性能描述于下面:
表2
表3
将这些催化剂试样在重整中试装置中通过提高温度以保持103.2或104.7的恒定RON以加速稳定性模式进行中试装置测试,如通过在620kPa下、2的氢气:烃摩尔比、1.7hour-1的液时空速和42小时的运行时间通过气相色谱法测定。所有运行的石脑油进料基本相同。一些催化剂试样,即催化剂C、D、F和G在中试装置中测试两次,如图中所述。
参考图1,相对于铂,提高铈含量以恒定103.2RON操作提高C5+产率。特别地,至多0.94的原子比提供C5+产率从85.8重量%至86.2重量%的提高。具有1.39的Ce/Pt的原子比的催化剂D证明较高的比不进一步改善C5+产率,但与催化剂C相比降低催化剂活性1-3℃。参考图2,相对于铂,提高铈含量的量以恒定的104.7RON操作保持85%的稳定C5+产率。因此,明显且出乎意料的是当提高铈和镧的量时,产率不提高,而是观察到催化剂活性的明显损失。因此,0.45:1.00-1.29:1.00、0.50:1.00-1.29:1.00、0.94:1.00-1.29:1.00、0.94:1.00-1.26:1.00或1.00:1.00-1.26:1.00的铈:铂的原子比可得到明显且出乎意料的结果。
实施例2
如通过实施例1所制备的,制备其它催化剂试样。这些试样的组成和性能描述于下面:
表4
对于含有铈的催化剂M、N和O,提供其它性能,包括通过SEM得到的金属浓度数据:
表5:
中试装置试验类似于实施例1,用催化剂L-N进行。然而,使用不同的中试装置,因此,实现103.3RON的目标的温度轻微不同。在装入反应器中用于中试装置试验以前将催化剂M和N结合并良好地混合。石脑油进料对所有运行而言基本相同。结果描述如下:
表6
通过相对于具有0.0重量%铈的参比催化剂L计算相对温度和C5+产率,结果描述了对催化剂M加N而言C5+产率大0.6-0.9重量%,其中对恒定的RON操作而言仅提高1-3℃。这显示了对于1.2:1的Ce/Pt比显著更高的产率,其中仅具有1-3℃的催化剂活性降低。该温差与实施例1的催化剂C一致。特别地,图1描述了对催化剂而言2-3℃的温差C(关于其中的典型实施方案),相对于就对比催化剂A而言0.0重量%铈。
没有进一步描述,相信本领域技术人员可使用先前的描述,最完整程度地使用本发明。因此,前述优选的具体实施方案应理解为仅是说明性的,且不以任何方式限制公开内容的其余部分。
在前文中,除非另有指出,所有温度以℃描述,所有份和百分数为重量计。
由先前描述中,本领域技术人员可容易地确定本发明的必要特征,且可不偏离其精神和范围地作出本发明的各种变化和改进以使它适于各种用途和条件。
Claims (10)
1.用于石脑油的催化重整的催化剂,其包含:
A)包含铂、钯、铑、钌、锇和铱中的一种或多种的贵金属;
B)包含周期表原子序数57-71的一种或多种元素的镧系金属;和
C)载体;
其中催化剂的平均堆积密度为0.300-0.620g/cm3,镧系金属:贵金属的原子比为小于1.3:1,且镧系金属的分布使得催化剂100μm表面层中的镧系金属的浓度小于催化剂中心核心处的镧系金属的浓度的2倍。
2.权利要求1的催化剂,其中镧系金属包含铈且铈:贵金属的原子比为0.50:1.00-1.29:1.00。
3.权利要求1的催化剂,其中镧系金属包含铈且铈:贵金属的原子比为0.94:1.00-1.26:1.00。
4.权利要求1的催化剂,其中镧系金属包含铈且铈:贵金属的原子比为1.00:1.00-1.26:1.00。
5.权利要求1的催化剂,其中镧系金属包含铈且贵金属包含铂。
6.权利要求5的催化剂,其中铈:铂的原子比为0.94:1.00-1.29:1.00。
7.权利要求5的催化剂,其中铈:铂的原子比为0.94:1.00-1.26:1.00。
8.权利要求5的催化剂,其中铈:铂的原子比为1.00:1.00-1.26:1.00。
9.权利要求1、2、3、4或5的催化剂,其中催化剂的平均堆积密度为0.555-0.580g/cm3。
10.权利要求1、2、3、4或5的催化剂,其中催化剂进一步包含周期表14族金属。
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US13/184,248 | 2011-07-15 | ||
US13/184,248 US8758599B2 (en) | 2011-07-15 | 2011-07-15 | Reforming catalyst and process |
PCT/US2012/041819 WO2013012489A2 (en) | 2011-07-15 | 2012-06-11 | Reforming catalyst and process |
Publications (1)
Publication Number | Publication Date |
---|---|
CN103596681A true CN103596681A (zh) | 2014-02-19 |
Family
ID=47518314
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201280029171.6A Pending CN103596681A (zh) | 2011-07-15 | 2012-06-11 | 重整催化剂和方法 |
Country Status (12)
Country | Link |
---|---|
US (1) | US8758599B2 (zh) |
EP (1) | EP2731712A4 (zh) |
JP (1) | JP2014518151A (zh) |
KR (1) | KR101539170B1 (zh) |
CN (1) | CN103596681A (zh) |
AU (1) | AU2012284529B2 (zh) |
BR (1) | BR112013026346A2 (zh) |
CA (1) | CA2831581C (zh) |
MY (1) | MY161685A (zh) |
RU (1) | RU2547466C1 (zh) |
SG (1) | SG194211A1 (zh) |
WO (1) | WO2013012489A2 (zh) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110064422A (zh) * | 2018-01-23 | 2019-07-30 | 中国石油天然气股份有限公司 | 一种多金属连续重整催化剂及其制备方法 |
CN111432925A (zh) * | 2017-11-02 | 2020-07-17 | 环球油品有限责任公司 | 用于选择性转化烃的催化剂和方法 |
Families Citing this family (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8912110B2 (en) * | 2012-03-29 | 2014-12-16 | Uop Llc | Catalyst for conversion of hydrocarbons |
CN105246590A (zh) * | 2013-07-11 | 2016-01-13 | 沙特基础工业全球技术公司 | 镧系氧化物减少催化剂烧结的用途 |
FR3039082B1 (fr) | 2015-07-24 | 2017-07-21 | Ifp Energies Now | Catalyseur multi-metallique dope par du phosphore et un lanthanide |
RU2593376C1 (ru) * | 2015-07-28 | 2016-08-10 | Общество с ограниченной ответственностью "Уникат" | Катализатор переработки тяжелых нефтей и способ его приготовления |
CN111432929A (zh) * | 2017-11-02 | 2020-07-17 | 环球油品有限责任公司 | 再生用于选择性转化烃的催化剂的方法 |
FR3074062B1 (fr) | 2017-11-30 | 2020-06-26 | IFP Energies Nouvelles | Catalyseur multi-metallique dope par du phosphore et de l'yttrium |
FR3074063B1 (fr) * | 2017-11-30 | 2019-11-01 | IFP Energies Nouvelles | Catalyseur multi-metallique dope par du phosphore et de l'ytterbium |
US11001767B2 (en) * | 2019-04-26 | 2021-05-11 | Exxonmobil Research And Engineering Company | Naphtha reformer yield using modified zeolitic catalysts |
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 (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3915845A (en) * | 1973-12-06 | 1975-10-28 | Universal Oil Prod Co | Hydrocarbon conversion with a multimetallic catalytic composite |
CN1044488A (zh) * | 1986-09-22 | 1990-08-08 | 环球油品公司 | 以石脑油为原料的催化重整的方法 |
US5102850A (en) * | 1990-10-17 | 1992-04-07 | W. R. Grace & Co. - Conn. | Catalyst supports having promoter oxide gradient, resulting catalyst and method of making the supports |
US5665223A (en) * | 1995-06-05 | 1997-09-09 | Uop | Selective bifunctional multimetallic reforming catalyst |
US20020155946A1 (en) * | 1996-12-09 | 2002-10-24 | Bogdan Paula L. | Selective bifunctional multigradient multimetallic catalyst |
Family Cites Families (27)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2892858A (en) | 1959-06-30 | Certificate of correction | ||
NL76445C (zh) | 1950-03-08 | |||
US3647680A (en) | 1969-09-25 | 1972-03-07 | Universal Oil Prod Co | Continuous reforming-regeneration process |
US3652231A (en) | 1969-09-25 | 1972-03-28 | Universal Oil Prod Co | Reconditioning system for moving column of reforming catalyst |
US3692496A (en) | 1971-04-19 | 1972-09-19 | Universal Oil Prod Co | Apparatus for continuous reforming-regeneration process |
US4012313A (en) | 1972-04-30 | 1977-03-15 | Chevron Research Company | Catalytic reforming process and catalyst |
US3852190A (en) | 1972-10-27 | 1974-12-03 | Chevron Res | Reforming with platinum on alumina derived from a byproduct of a ziegler process |
JPS58177153A (ja) | 1982-04-12 | 1983-10-17 | Nissan Motor Co Ltd | メタノ−ル改質用触媒 |
JPS59199042A (ja) | 1983-04-28 | 1984-11-12 | Nissan Motor Co Ltd | メタノ−ル改質用触媒 |
US4832921A (en) | 1985-12-27 | 1989-05-23 | Uop Inc. | Apparatus for regeneration of hydrocarbon conversion catalyst |
US4714694A (en) | 1986-06-30 | 1987-12-22 | Engelhard Corporation | Aluminum-stabilized ceria catalyst compositions, and methods of making the same |
US6059960A (en) | 1995-06-05 | 2000-05-09 | Uop Llc | Catalytic reforming utilizing a selective bifunctional multimetallic reforming catalyst |
FR2735488B1 (fr) | 1995-06-16 | 1997-08-22 | Inst Francais Du Petrole | Procede de transformation catalytique d'hydrocarbures en composes aromatiques avec un catalyseur contenant des lanthanides |
US5883032A (en) | 1996-11-21 | 1999-03-16 | Uop Llc | Selective multimetallic multigradient reforming catalyst |
US6013173A (en) | 1996-12-09 | 2000-01-11 | Uop Llc | Selective bifunctional multimetallic reforming catalyst |
US6419820B1 (en) | 1996-12-09 | 2002-07-16 | Uop Llc | Catalytic reforming process employing a selective bifunctional multigradient multimetallic catalyst |
RU2186622C2 (ru) * | 1997-09-08 | 2002-08-10 | Юоп | Катализатор конверсии углеводородов, способ каталитического реформинга исходной нафты с использованием катализатора |
CA2428180A1 (en) | 2000-11-08 | 2002-05-16 | Idemitsu Kosan Co., Ltd. | Catalyst for hydrocarbon reforming and method of reforming hydrocarbon with the same |
CN1384175A (zh) | 2001-04-28 | 2002-12-11 | 中国石油化工股份有限公司 | 含铂、锡的多金属重整催化剂及其制备与应用 |
US6790432B2 (en) | 2002-06-12 | 2004-09-14 | Engelhard Corporation | Suppression of methanation activity of platinum group metal water-gas shift catalysts |
JP4245464B2 (ja) | 2003-11-28 | 2009-03-25 | 株式会社東芝 | 燃料電池 |
US20060102520A1 (en) * | 2004-11-12 | 2006-05-18 | Lapinski Mark P | Reforming process using high density catalyst |
RU2357799C2 (ru) * | 2005-01-18 | 2009-06-10 | Юоп Ллк | Катализатор для риформинга нафты и способ каталитического риформинга нафты |
US20070060470A1 (en) | 2005-09-14 | 2007-03-15 | Bogdan Paula L | Process for the isomerization of xylenes and catalyst therefor |
US7381677B1 (en) | 2005-09-14 | 2008-06-03 | Uop Llc | Ethylbenzene conversion and xylene isomerization processes and catalysts therefor |
US8291695B2 (en) | 2008-12-05 | 2012-10-23 | GM Global Technology Operations LLC | Method and apparatus for controlling exhaust emissions in a spark-ignition direct-injection engine |
US8912110B2 (en) * | 2012-03-29 | 2014-12-16 | Uop Llc | Catalyst for conversion of hydrocarbons |
-
2011
- 2011-07-15 US US13/184,248 patent/US8758599B2/en active Active
-
2012
- 2012-06-11 KR KR1020137035137A patent/KR101539170B1/ko active IP Right Grant
- 2012-06-11 SG SG2013077458A patent/SG194211A1/en unknown
- 2012-06-11 MY MYPI2013003503A patent/MY161685A/en unknown
- 2012-06-11 EP EP12814501.8A patent/EP2731712A4/en not_active Withdrawn
- 2012-06-11 CA CA2831581A patent/CA2831581C/en active Active
- 2012-06-11 RU RU2013156568/04A patent/RU2547466C1/ru active
- 2012-06-11 BR BR112013026346A patent/BR112013026346A2/pt not_active IP Right Cessation
- 2012-06-11 WO PCT/US2012/041819 patent/WO2013012489A2/en active Application Filing
- 2012-06-11 JP JP2014515896A patent/JP2014518151A/ja active Pending
- 2012-06-11 CN CN201280029171.6A patent/CN103596681A/zh active Pending
- 2012-06-11 AU AU2012284529A patent/AU2012284529B2/en not_active Ceased
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3915845A (en) * | 1973-12-06 | 1975-10-28 | Universal Oil Prod Co | Hydrocarbon conversion with a multimetallic catalytic composite |
CN1044488A (zh) * | 1986-09-22 | 1990-08-08 | 环球油品公司 | 以石脑油为原料的催化重整的方法 |
US5102850A (en) * | 1990-10-17 | 1992-04-07 | W. R. Grace & Co. - Conn. | Catalyst supports having promoter oxide gradient, resulting catalyst and method of making the supports |
US5665223A (en) * | 1995-06-05 | 1997-09-09 | Uop | Selective bifunctional multimetallic reforming catalyst |
US20020155946A1 (en) * | 1996-12-09 | 2002-10-24 | Bogdan Paula L. | Selective bifunctional multigradient multimetallic catalyst |
Non-Patent Citations (1)
Title |
---|
练涛等: "PS-VI型连续重整催化剂的工业应用", 《石油炼制与化工》 * |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111432925A (zh) * | 2017-11-02 | 2020-07-17 | 环球油品有限责任公司 | 用于选择性转化烃的催化剂和方法 |
CN110064422A (zh) * | 2018-01-23 | 2019-07-30 | 中国石油天然气股份有限公司 | 一种多金属连续重整催化剂及其制备方法 |
CN110064422B (zh) * | 2018-01-23 | 2022-01-04 | 中国石油天然气股份有限公司 | 一种多金属连续重整催化剂及其制备方法 |
Also Published As
Publication number | Publication date |
---|---|
EP2731712A2 (en) | 2014-05-21 |
RU2547466C1 (ru) | 2015-04-10 |
KR20140022927A (ko) | 2014-02-25 |
BR112013026346A2 (pt) | 2019-02-26 |
US20130015103A1 (en) | 2013-01-17 |
CA2831581A1 (en) | 2013-01-24 |
US8758599B2 (en) | 2014-06-24 |
WO2013012489A3 (en) | 2013-05-10 |
AU2012284529B2 (en) | 2016-02-04 |
SG194211A1 (en) | 2013-11-29 |
WO2013012489A2 (en) | 2013-01-24 |
CA2831581C (en) | 2016-05-31 |
MY161685A (en) | 2017-05-15 |
AU2012284529A1 (en) | 2013-10-17 |
KR101539170B1 (ko) | 2015-07-23 |
EP2731712A4 (en) | 2015-08-12 |
JP2014518151A (ja) | 2014-07-28 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN103596681A (zh) | 重整催化剂和方法 | |
RU2605406C2 (ru) | Катализатор конверсии углеводородов | |
RU2388534C2 (ru) | Способ реформинга с использованием катализатора высокой плотности | |
RU2582343C1 (ru) | Катализаторы риформинга с отрегулированной кислотностью для достижения максимального выхода ароматических соединений | |
US4487848A (en) | Indium-containing catalyst for reforming hydrocarbons | |
CA2486572C (en) | Bismuth-and phosphorus-containing catalysts support, reforming catalysts made from same, method of making and naphtha reforming process | |
RU2259233C2 (ru) | Полиметаллический катализатор риформинга, содержащий платину и олово, его получение и применение | |
US6048449A (en) | Process for reforming NAPHTHA feedstock using selective multimetallic-multigradient reforming catalyst | |
US6872300B1 (en) | Reforming catalyst with chelated promotor | |
CA2214550C (en) | Selective bifunctional multimetallic hydrocarbon conversion catalytic composite and process for the use thereof | |
CN1030329C (zh) | 烷烃脱氢芳构化催化剂及制备方法 | |
US4529505A (en) | Indium-containing catalyst for reforming hydrocarbons | |
JP2563304B2 (ja) | 多段帯域ナフサ改質法 | |
JP2018521852A (ja) | リンとランタニドのドープ型多金属触媒 | |
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 | |
RU2186622C2 (ru) | Катализатор конверсии углеводородов, способ каталитического реформинга исходной нафты с использованием катализатора | |
CN110064415B (zh) | 一种半再生重整催化剂及其制备方法 | |
JPH0433991A (ja) | 多種類の触媒を用いた多層触媒改質法 | |
JP4043556B2 (ja) | 多金属を含む炭化水素転化触媒複合物及びその使用方法 | |
RU2768643C2 (ru) | Полиметаллический катализатор, легированный фосфором и иттербием | |
ES2210435T3 (es) | Material compuesto catalitico multimetalico, bifuncional y selectivo para la converion de hidrocarburos y procedimiento para su uso. | |
AU742568B2 (en) | Selective bifunctional multimetallic hydrocarbon conversion catalytic composite and process for the use thereof | |
KR800000881B1 (ko) | 탄화수소 전화방법 | |
KR100444486B1 (ko) | 선택적이기능다금속탄화수소전환반응에촉매복합체및그사용방법 | |
MXPA97006838A (en) | Composite catalytic conversion of multimetal bifunctional selective hydrocarbon and process for the use of the |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20140219 |