CN107020084A - 具有强烈金属相互作用的多金属催化剂 - Google Patents
具有强烈金属相互作用的多金属催化剂 Download PDFInfo
- Publication number
- CN107020084A CN107020084A CN201710095799.0A CN201710095799A CN107020084A CN 107020084 A CN107020084 A CN 107020084A CN 201710095799 A CN201710095799 A CN 201710095799A CN 107020084 A CN107020084 A CN 107020084A
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- CN
- China
- Prior art keywords
- catalyst
- tin
- carrier
- metal
- platinum
- 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
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- 239000003054 catalyst Substances 0.000 title claims abstract description 87
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 25
- 239000002184 metal Substances 0.000 title claims abstract description 25
- 230000003993 interaction Effects 0.000 title abstract description 6
- 238000002407 reforming Methods 0.000 title abstract description 5
- 229910052718 tin Inorganic materials 0.000 claims abstract description 52
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 49
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 34
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000011574 phosphorus Substances 0.000 claims abstract description 30
- 229910052738 indium Inorganic materials 0.000 claims abstract description 26
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims abstract description 26
- 150000001875 compounds Chemical class 0.000 claims abstract description 15
- 230000009467 reduction Effects 0.000 claims abstract description 8
- 238000004611 spectroscopical analysis Methods 0.000 claims abstract description 7
- 229910004774 CaSnO3 Inorganic materials 0.000 claims abstract description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 78
- 229910052697 platinum Inorganic materials 0.000 claims description 36
- 239000000460 chlorine Substances 0.000 claims description 28
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 27
- 229910052801 chlorine Inorganic materials 0.000 claims description 27
- 238000001354 calcination Methods 0.000 claims description 22
- 239000002243 precursor Substances 0.000 claims description 19
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 230000015572 biosynthetic process Effects 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical group [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 5
- FGUUSXIOTUKUDN-IBGZPJMESA-N C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 Chemical compound C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 FGUUSXIOTUKUDN-IBGZPJMESA-N 0.000 claims description 4
- 239000004411 aluminium Substances 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 238000007493 shaping process Methods 0.000 claims description 4
- 238000003786 synthesis reaction Methods 0.000 claims description 4
- 230000007935 neutral effect Effects 0.000 claims description 3
- 229910052763 palladium Chemical group 0.000 claims description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 239000011630 iodine Substances 0.000 claims description 2
- 229910052740 iodine Inorganic materials 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims 1
- 229910001928 zirconium oxide Inorganic materials 0.000 claims 1
- 229910052797 bismuth Inorganic materials 0.000 abstract description 9
- 229910052733 gallium Inorganic materials 0.000 abstract description 9
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 abstract description 8
- 229910052716 thallium Inorganic materials 0.000 abstract description 8
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 abstract description 8
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 abstract description 7
- 229910052787 antimony Inorganic materials 0.000 abstract description 5
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052785 arsenic Inorganic materials 0.000 abstract description 4
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 abstract description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 17
- 238000002360 preparation method Methods 0.000 description 17
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 9
- 239000011324 bead Substances 0.000 description 9
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 8
- 239000002253 acid Substances 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 8
- -1 halo Compound Chemical class 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000000571 coke Substances 0.000 description 6
- 150000002430 hydrocarbons Chemical class 0.000 description 6
- 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 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 5
- 229930195733 hydrocarbon Natural products 0.000 description 5
- 239000001119 stannous chloride Substances 0.000 description 5
- 235000011150 stannous chloride Nutrition 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- 229910002651 NO3 Inorganic materials 0.000 description 4
- 238000000151 deposition Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 206010013786 Dry skin Diseases 0.000 description 3
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 3
- 229910002846 Pt–Sn Inorganic materials 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 3
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 description 3
- GNFTZDOKVXKIBK-UHFFFAOYSA-N 3-(2-methoxyethoxy)benzohydrazide Chemical compound COCCOC1=CC=CC(C(=O)NN)=C1 GNFTZDOKVXKIBK-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-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
- 229910009038 Sn—P Inorganic materials 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- PQLAYKMGZDUDLQ-UHFFFAOYSA-K aluminium bromide Chemical compound Br[Al](Br)Br PQLAYKMGZDUDLQ-UHFFFAOYSA-K 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 238000001833 catalytic reforming Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- LKRFCKCBYVZXTC-UHFFFAOYSA-N dinitrooxyindiganyl nitrate Chemical compound [In+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O LKRFCKCBYVZXTC-UHFFFAOYSA-N 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- CHPZKNULDCNCBW-UHFFFAOYSA-N gallium nitrate Chemical compound [Ga+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CHPZKNULDCNCBW-UHFFFAOYSA-N 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
- 125000005843 halogen group Chemical group 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910052702 rhenium Inorganic materials 0.000 description 2
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical class CC(Cl)Cl SCYULBFZEHDVBN-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
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 1
- 241000580063 Ipomopsis rubra Species 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229910003978 SiClx Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910018956 Sn—In Inorganic materials 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- APQHKWPGGHMYKJ-UHFFFAOYSA-N Tributyltin oxide Chemical compound CCCC[Sn](CCCC)(CCCC)O[Sn](CCCC)(CCCC)CCCC APQHKWPGGHMYKJ-UHFFFAOYSA-N 0.000 description 1
- QYSYEILYXGRUOM-UHFFFAOYSA-N [Cl].[Pt] Chemical compound [Cl].[Pt] QYSYEILYXGRUOM-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 229910052767 actinium Inorganic materials 0.000 description 1
- QQINRWTZWGJFDB-UHFFFAOYSA-N actinium atom Chemical compound [Ac] QQINRWTZWGJFDB-UHFFFAOYSA-N 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- JZQOJFLIJNRDHK-CMDGGOBGSA-N alpha-irone Chemical compound CC1CC=C(C)C(\C=C\C(C)=O)C1(C)C JZQOJFLIJNRDHK-CMDGGOBGSA-N 0.000 description 1
- JRLDUDBQNVFTCA-UHFFFAOYSA-N antimony(3+);trinitrate Chemical compound [Sb+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JRLDUDBQNVFTCA-UHFFFAOYSA-N 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229950005499 carbon tetrachloride Drugs 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005660 chlorination reaction Methods 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
- 238000000975 co-precipitation Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- 125000003963 dichloro group Chemical group Cl* 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229940044658 gallium nitrate Drugs 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- RHZWSUVWRRXEJF-UHFFFAOYSA-N indium tin Chemical compound [In].[Sn] RHZWSUVWRRXEJF-UHFFFAOYSA-N 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000032696 parturition Effects 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 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
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000006057 reforming reaction Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229940095064 tartrate Drugs 0.000 description 1
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 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
- 229910021509 tin(II) hydroxide Inorganic materials 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- OJZNYUDKNVNEMV-UHFFFAOYSA-M trimethylstannanylium;hydroxide Chemical compound C[Sn](C)(C)O OJZNYUDKNVNEMV-UHFFFAOYSA-M 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- 229910000859 α-Fe Inorganic materials 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/22—Halogenating
- B01J37/24—Chlorinating
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- B—PERFORMING OPERATIONS; TRANSPORTING
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Abstract
本发明涉及具有强烈金属相互作用的多金属催化剂。本发明涉及一种催化剂,其包括至少一种来自VIII族的金属M,锡,磷促进剂,卤代化合物,多孔载体和至少一种选自镓、铟、铊、砷、锑和铋的促进剂X1。在119Sn Mössbauer光谱学中,还原形式的催化剂具有0至0.45 mm/s的四极分岐值信号,和相对于CaSnO3的1.5至2.4 mm/s的异构体位移IS,所述信号相当于信号总面积的1%至30%。
Description
技术领域
本申请是申请日为2010年6月15日、申请号为" 201080030119.3"、名称为"具有强烈金属相互作用的多金属催化剂"的发明专利申请的分案申请。本发明涉及烃类转化领域,更具体地涉及在催化剂存在下重整烃类进料产生汽油馏分。本发明还涉及用于所述转化的基于至少一种来自铂族的金属的改进催化配制料,以及涉及其制备方法。
背景技术
许多专利描述向铂族催化剂中添加促进剂,以改善其关于烃类进料重整的性能。因此,专利US 2 814 599描述向基于铂或钯的催化剂中添加例如镓、铟、钪、钇、镧、铊或锕的促进剂。
专利US 4 522 935描述包括沉积在载体上铂、锡铟和卤代化合物的重整催化剂,其中铟/铂原子比超过1.14。
专利FR 2 840 548描述均匀颗粒床形式的催化剂,包括无定形基体、至少一种贵金属、至少一种卤素和至少一种另外的金属。所述另外的金属优选选自锡、锗、铅、镓、铟、铊、铼、锰、铬、钼和钨。
磷也已知提高精确包含多于4个碳原子的烃类化合物(C5+),特别是芳族产物的产率。专利US 2 890 167、3 706 815、US 4 367 137、US 4 416 804、US 4 426 279和US 4463 104中请求保护该性能。近年来,专利US 2007/0215523描述添加小于1 wt%的稀释量的磷,使载体稳定化,在用于催化重整法期间允许更好地维持比表面积和氯。
专利US 6 864 212和US 6 667 270描述一种包含以均匀方式分布的铋和磷并用于制备催化重整加氢处理石脑油的催化剂的载体。根据那些专利,向载体中单独添加铋可以减缓形成焦炭并降低活性,但是同时降低了C5+产率,而单独添加磷提高产率,但不改善催化剂稳定性。这两种元素的组合可以进一步减缓焦炭形成,同时对0.10 wt%至0.06 wt%的Bi含量,和0.3 wt%的P含量具有更好的选择性。这两个专利没有请求保护其它元素。
此外,在专利EP 1 656 991中,一种催化剂包括铂、锡、由至少一种包括氧化铝和磷酸盐的无机氧化物组成的高密度载体,和任选另一种选自锗、镓、铼、磷、铟或其混合物的元素,特征在于至少33 wt%的锡与铂以使用Mössbauer光谱学观察到的特殊Pt-Sn晶簇的形式结合。该催化剂的重要性在于相对于本领域中已知的催化剂,其稳定性增加,焦炭产生降到最小。
发明内容
本发明涉及一种催化剂,其包括至少一种来自VIII族的金属M,锡,磷促进剂,卤代化合物,多孔载体和至少一种选自镓、铟、铊、砷、锑和铋的促进剂X1。在119Sn Mössbauer光谱学中,还原形式的催化剂具有0至0.45 mm/s的四极分岐值信号,和相对于CaSnO3的1.5至2.4 mm/s的异构体位移IS,所述信号相当于信号总面积的1%至30%。
具体实施方式
本发明涉及一种催化剂,包括至少一种选自铂族的金属M、锡、磷促进剂、卤代化合物、多孔载体和至少一种选自镓、铟、铊、砷、锑和铋,优选镓、铊、铟和铋,高度优选镓和铟,和更优选铟的促进剂X1,还原形式下的所述催化剂在119Sn Mössbauer光谱学中具有0至0.45 mm/s的四极分岐值信号和相对于CaSnO3的1.5至2.4 mm/s的异构体位移IS,所述信号相当于信号总面积的1%至30%,优选4%至20%。
本发明的催化剂产生改善的催化性能。特别地,所述催化剂对C5+化合物(即包括至少5个碳原子的化合物)的选择性提高,同时焦炭形成显著降低。
催化剂制备方法包括在载体制备步骤期间引入磷和一种或多种促进剂X1的步骤。
Sn/M原子比通常为0.5至4.0,更优选为1.0至3.5,和高度优选为1.3至3.2。X1/M比通常为0.1至5.0,更优选为0.2至3.0,和高度优选为0.4至2.2。P/M比通常为0.2至30.0,更优选为0.5至20.0,和高度优选为1.0至15.0。金属M的量通常为0.01 wt%至5 wt%,更优选为0.01 wt%至2 wt%,和更优选为0.1 wt%至1 wt%。
金属M通常为铂或钯,高度优选为铂。卤代化合物通常选自氟、氯、溴和碘。卤代化合物的量通常为0.1 wt%至15.0 wt%,更优选为0.1 wt%至8.0 wt%,和更优选为0.2 wt%至5wt%。如果卤代化合物为氯,则氯的量通常为0.0至5.0 wt%,优选为0.5 wt%至2.0 wt%。
可用于确定锡的局部电子结构的分析使用常规Mössbauer光谱学来进行,借助于γ辐射的Ba119mSnO3源,和10 mCi的标称活性。分光光度计以传输模式操作,利用以三角形模式工作的等加速度运动发生器,和由微处理器控制的512通道分析仪。测试仪为NaI晶体(T1) 0.1 mm厚。使用由57Co (Rh)源得到的α铁的标准6-线光谱校准比例尺。相对于CaSnO3给出全部异构体位移。ISO软件用来将实验光谱去卷积(deconvolute)成为Lorentzian曲线,并测定各个参数(W.Künding,Nucl Instrum Method,75,336 (1969))。
在119Sn Mössbauer光谱学中,本发明的还原形式的催化剂通常具有0至0.45 mm/s的四极分岐值信号,和相对于CaSnO3的1.5至2.4 mm/s的异构体位移IS,所述信号相当于信号总面积的1%至30%,优选4%至20%。
根据由J Olivier Fourcade等人,在ChemPhysChem,2004,5,1734公布的归属,制备方法因此涉及在还原的催化剂上形成与一部分来自铂族的金属原子形成合金的锡Sn0物质。因此观察到合金MxSny在来自铂族的金属和锡原子之间表现出非常强的相互作用。
载体通常包括选自镁、钛、锆、铝和硅的氧化物的至少一种氧化物。优选,其为二氧化硅、氧化铝或二氧化硅-氧化铝,和高度优选为氧化铝。根据本发明,所述多孔载体有利地为珠粒、挤出物、颗粒或粉末形式。高度有利地,所述载体为珠粒或挤出物形式。载体的孔容优选为0.1至1.5 cm3/g,更优选为0.4至0.8 cm3/g。此外,所述多孔载体具有有利地为50至600 m2/g,优选为100至400 m2/g,或甚至为150至300 m2/g的比表面积。
制备本发明催化剂的方法通常包括以下步骤:
a) 在子步骤a1)或a2)之一期间,引入一种或多种促进剂X1和磷,所述子步骤a1)对应于合成主氧化物的前体,所述子步骤a2)对应于成型载体;
b) 在子步骤a1)和a2)的至少一个期间引入锡,步骤a)和b)可是连续或同时的;
c) 干燥步骤b)末尾获得的产物;
d) 在350℃至650℃下锻烧步骤c)中获得的产物;
e) 沉积至少一种来自铂族的金属M;
f) 在中性气体流或含氧气体流中,在不超过150℃下干燥;
g) 在350℃至650℃下锻烧步骤f)中获得的产物。
锡可以仅在成型载体时部分引入,该方法因此包括在载体上沉积互补百分率的锡的步骤,该步骤在步骤d)和e)之间,之后为干燥和锻烧或者相反,或在步骤e)和f)之间,或在步骤g)之后,之后为干燥和锻烧。
步骤g)的锻烧通常在任选富氧或富氮的空气存在下进行。
可以使用本领域技术人员已知的任何技术引入促进剂X1、P和Sn。引入载体期间,促进剂X1、P和Sn可以通过混合、共沉淀或溶解来添加;这些方法没有限制。
因此,锡可以与前体X1和P同时引入,或者可以在前体X1和P之前或之后单独引入。
在引入一种或多种促进剂X1和磷,即在合成氧化物前体期间的情况下,根据本发明的优选制备方法,锡、磷和一种或多种前体X1在使用溶胶-凝胶型技术合成主氧化物的前体期间引入。
根据另一个优选的方法,前体加入到制得的主氧化物前体的溶胶中。使用现有技术的载体成型技术,例如包括挤出或油滴凝聚的成型步骤,来成型载体。
X1前体具有多个类型,取决于X1的性质,并且可以单独使用或以混合物的形式使用。在铟的情况下,铟卤化物、硝酸盐、硫酸盐、过氯酸盐、氰化物或氢氧化物是合适的。可以使用镓卤化物、硝酸盐、硫酸盐、氰化物、氢氧化物和卤氧化物类型的前体。铊可以以铊硝酸盐、硫酸盐和氢氧化物的形式引入。在锑的情况下,锑硝酸盐、硫酸盐和氢氧化物是合适的。可以使用砷卤化物和卤氧化物的前体。铋可以以铋卤化物、硝酸盐、氢氧化物、卤氧化物或碳酸盐,或铋酸的形式引入。
在类型方面,锡前体可以是矿物的或者可以是有机金属,可以属于水溶性有机金属类型。可以单独或以混合物形式使用各种前体。特别地,可以选择锡;以非限制方式,锡可以选自卤代、氢氧化物、碳酸盐、羧酸盐、硫酸盐、酒石酸盐和硝酸盐化合物。当它们原位产生或可被原位产生(例如通过引入锡和羧酸)时,锡的这些形式可以引入催化剂制备介质中。有机金属锡基类型前体的实例为SnR4,其中R表示烷基,例如丁基,Me3SnCl,Me2SnCl2,Et3SnCl,Et2SnCl2,EtSnCl3,iPrSnCl2族,和氢氧化物Me3SnOH,Me2Sn(OH)2,Et3SnOH,Et2Sn(OH)2,氧化物(Bu3Sn)2O,乙酸盐Bu3SnOC(O)Me。优选使用锡的卤代形式,特别是氯化形式。特别有利地使用SnCl2或SnCl4。
在锡的情况下已经将促进剂Sn、X1和P引入已经成型的载体之中或之上,制备本发明催化剂的规程要求在沉积来自铂族的金属M之前进行锻烧(步骤d)。所述锻烧优选在350℃至650℃,优选400℃至600℃,和更优选400℃至550℃下进行。升温可以是规则的,或可以包括中间恒温阶段,利用固定或可变的温度分布曲线达到所述阶段。温度的升高因此可以速率相同或不同(以每分钟或每小时的度数计)。锻烧期间使用的气氛包含优选2体积%至50体积%和更优选5体积%至25体积%的氧气。该锻烧步骤期间因此也可以使用空气。
获得载体之后,沉积至少一种来自铂族的金属M (步骤e)。在该步骤中,可以通过干燥浸渍或过量溶液浸渍,使用包含来自铂族的金属M的前体或前体混合物引入金属M。浸渍可以在基于金属M前体和载体之间的相互作用有效的物质存在下进行。在非限制方式中,所述物质可以为矿物酸(HCl、HNO3)或有机酸(羧酸或多羧酸类型),和有机络合型化合物。优选,使用本领域技术人员已知的任何技术进行浸渍,用于在催化剂内达到金属M的均匀分布。
金属M的前体形成以下组的一部分,但是该列表没有限制:六氯铂酸、溴铂酸、氯铂酸铵、氯化铂、二氯碳酰二氯化铂和四胺氯化铂。
在该阶段,在优选不超过250℃的适度温度下,在中性气氛或包含氧气(可以使用空气)的气氛中,干燥包含X1、Sn、P和铂的催化剂(步骤f)。优选,干燥在200℃或更低的温度下进行几分钟至几小时。
该步骤之后为锻烧步骤f)中获得的产物。所述锻烧优选在空气存在下进行。空气也可以富含氧气或氮气。优选,所述气体中的氧气含量达到0.5体积%至30.0体积%,更优选为2体积%至25体积%。
所述锻烧在350℃至650℃,优选400℃至650℃,和更优选450℃至550℃下进行。温度分布曲线可以任选包含恒温阶段。
当本发明催化剂的制备中使用的各种前体不包含卤素或包含不足量的卤素时,可能必要的是在制备期间添加卤代化合物。可以使用本领域技术人员已知的任何化合物,并将其引入本发明催化剂的制备的任一个步骤中。特别地,可以使用Friedel-Crafts型化合物,例如氯化铝或溴化铝。也可使用有机化合物,例如甲基或乙基卤化物,例如二氯甲烷、氯仿、二氯乙烷、甲基氯仿或四氯甲烷。
也可以使用氧氯化处理将氯加入到本发明的催化剂中。所述处理可以例如在空气流中在500℃进行4小时,所述空气流包含沉积所需氯量所需的气态氯量和H2O/Cl摩尔比接近例如20的水量。
也可以借助于用水性盐酸溶液浸渍来添加氯。典型的规程由浸渍固体组成,以引入所需氯量。催化剂与水溶液保持接触足够长的时间,以沉积氯量,然后排出催化剂并在80℃至150℃下干燥,然后最后在450℃至650℃下在空气中锻烧。
典型地,催化剂经历还原处理。还原步骤通常在稀释的或纯的氢气气氛中,有利地在400℃至600℃,优选450℃至550℃下进行。
实施例
以下实施例说明本发明。
实施例1 (对比)
催化剂A的制备:Pt/(Al
2
O
3
-Sn)-Cl
通过使二氯化锡与由氯化铝水解获得的氧化铝水溶胶接触,制备氧化铝珠粒形式的载体,其包含0.3 wt%的锡并具有1.2 mm的平均直径。由此获得的氧化铝水溶胶然后进入充满添加剂油的垂直柱。在至多600℃下热处理由此获得的球体,以获得具有优良机械强度的珠粒。由此获得的载体具有205 m2/g的BET表面。
通过在最终的催化剂上沉积0.3 wt%的铂和1 wt%的氯,在该载体上制备催化剂A。向100 g包含锡的氧化铝载体中添加400 cm3的六氯铂酸和盐酸的水溶液。使其保持接触4小时,然后排出。在120℃使其干燥,然后在每小时100升的空气流中在500℃锻烧2小时,温度陡升为每分钟7℃。锻烧之后获得的催化剂A包含0.29 wt%的铂,0.30 wt%的锡和1.02wt%的氯。
实施例2 (对比)
催化剂B的制备:Pt/(Al
2
O
3
-Sn-In)-Cl
通过使二氯化锡和硝酸铟与由氯化铝水解获得的氧化铝水溶胶接触,制备氧化铝珠粒形式的载体,其包含0.3 wt%的锡和0.3 wt%的铟,具有1.2 mm的平均直径。由此获得的氧化铝水溶胶然后进入充满添加剂油的垂直柱。在至多600℃下热处理由此获得的球体,以获得具有优良机械强度的珠粒。由此获得的载体具有201 m2/g的BET表面。
在该载体上制备催化剂B,目标为与实施例1中的铂和氯含量相同。锻烧之后获得的催化剂B包含0.29 wt%的铂,0.29 wt%的锡,0.30 wt%的铟和1.05 wt%的氯。
实施例3 (对比)
催化剂C的制备:Pt/(Al
2
O
3
-Sn-P)-Cl
通过使二氯化锡和磷酸与氧化铝水溶胶接触,以类似于实施例1中所述的方式获得氧化铝珠粒形式的载体,其包含0.3 wt%的锡和0.4 wt%的磷,具有1.2 mm的平均直径。由此获得的载体具有198 m2/g的BET表面。
在该载体上制备催化剂C,目标为与实施例1中的铂和氯含量相同。锻烧之后获得的催化剂C包含0.30 wt%的铂,0.31 wt%的锡,0.39 wt%的磷和1.00 wt%的氯。
实施例4 (本发明)
催化剂D的制备:Pt/(Al
2
O
3
-Sn-In-P)-Cl
通过使二氯化锡、硝酸铟和磷酸与氧化铝水溶胶接触,以类似于实施例1中所述的方式获得氧化铝珠粒形式的载体,其包含0.3 wt%的锡,0.3 wt%的铟和0.4 wt%的磷,具有1.2mm的平均直径。由此获得的载体具有196 m2/g的BET表面。
在该载体上制备催化剂D,目标为与实施例1中的铂和氯含量相同。锻烧之后获得的催化剂D包含0.30 wt%的铂,0.31 wt%的锡,0.32 wt%的铟,0.38 wt%的磷和1.00 wt%的氯。
实施例5 (本发明)
催化剂E的制备:Pt/(Al
2
O
3
-Sn-In-P)-Cl
用和实施例4一样的方法制备氧化铝珠粒形式的载体,具有相同的锡和磷量,但是仅引入0.2 wt%的铟。由此获得的载体具有210 m2/g的BET表面。
在该载体上制备催化剂E,目标为与实施例1中的铂和氯含量相同。锻烧之后获得的催化剂E包含0.31 wt%的铂,0.31 wt%的锡,0.22 wt%的铟,0.40 wt%的磷和1.02 wt%的氯。
实施例6 (对比)
催化剂F的制备:Pt-In/(Al
2
O
3
-Sn-P)-Cl
制备载体,目标为与实施例3中的锡和磷量相同。由此获得的载体具有180 m2/g的BET表面。
在该载体上制备催化剂F,目标为最终催化剂上的0.3 wt%的铂,0.3 wt%的铟和1wt%的氯。
向100 g包含锡和磷的氧化铝载体中添加400 cm3的六氯铂酸和盐酸的水溶液。使其保持接触4小时,然后排出。在90℃将其干燥,然后在盐酸存在下使其与200 cm3的硝酸铟水溶液接触。使其保持接触4小时,排出,在120℃干燥,然后在每小时100升的空气流中在500℃锻烧2小时,温度陡升为每分钟7℃。锻烧之后获得的催化剂F包含0.30 wt%的铂,0.32wt%的锡,0.29 wt%的铟,0.41 wt%的磷和1.04 wt%的氯。
实施例7 (对比)
催化剂G的制备:Pt-In-P/(Al
2
O
3
-Sn)-Cl
制备载体,目标为与实施例1中的锡量相同。
在该载体上制备催化剂G,目标为最终催化剂上的0.3 wt%的铂,0.3 wt%的铟,0.4wt%的磷和1 wt%的氯。由此获得的载体具有209 m2/g的BET表面。
向100 g包含锡和磷的氧化铝载体中添加400 cm3的六氯铂酸和盐酸的水溶液。使其保持接触4小时,然后排出。在90℃将其干燥,然后在盐酸存在下使其与200 cm3的硝酸铟和磷酸水溶液接触。使其保持接触4小时,排出,在120℃干燥,然后在每小时100升的空气流中在500℃锻烧2小时,温度陡升为每分钟7℃。锻烧之后获得的催化剂G包含0.30 wt%的铂,0.31 wt%的锡,0.33 wt%的铟,0.38 wt%的磷和1.05 wt%的氯。
实施例8 (本发明)
催化剂H的制备:Pt-Sn/(Al
2
O
3
-Sn-In-P)-Cl
制备载体,目标为与实施例4中的铟和磷量相同,但具有0.2 wt%的锡。由此获得的载体具有182 m2/g的BET表面。
通过沉积0.35 wt%的铂,补足的0.2 wt%的锡,以在最终催化剂上获得0.4 wt%的锡和1 wt%的氯,在该载体上制备催化剂H。
向100 g包含锡和铟的氧化铝载体中添加400 cm3的六氯铂酸和盐酸的水溶液。使其保持接触4小时,然后排出。在90℃将其干燥,然后在盐酸存在下使其与200 cm3的四氯化锡水溶液接触。使其保持接触4小时,排出,在120℃干燥,然后在每小时100升的空气流中在500℃锻烧2小时,温度陡升为每分钟7℃。锻烧之后获得的催化剂H包含0.36 wt%的铂,0.41wt%的锡,0.29 wt%的铟,0.41 wt%的磷和0.99 wt%的氯。
实施例9 (本发明)
催化剂I的制备:Pt-Sn/(Al
2
O
3
-Sn-Sb-P)-Cl
以类似于实施例4中所述的方式,使用二氯化锡、硝酸镓和磷酸,制备包含0.1 wt%的锡,0.4 wt%的锑和0.4 wt%的磷并具有1.2 mm平均直径的氧化铝珠粒载体。由此获得的载体具有191 m2/g的BET表面。
由所述载体制备催化剂I,具有与实施例7相同的铂、锡和氯量。锻烧之后获得的催化剂G包含0.29 wt%的铂,0.30 wt%的锡,0.32 wt%的铟,0.42 wt%的磷和1.10 wt%的氯。
实施例10催化剂A至I的Mössbauer特征
在450℃下在氢气流中将催化剂A至I还原两小时,并在没有空气进入的前提下转移进入适合于Mössbauer装置的密封玻璃槽中。实施例1至9的催化剂A至I的异构体位移值和四极分岐值使用说明书中描述的方法测定,并在表1中示出。
表1:催化剂A至I的异构体位移和四极分岐值。
实施例11:催化剂A至I在催化重整中的表现评价
将如实施例1至9所述制备的催化剂试样放入反应床中,该反应床适合于转化衍生自油蒸馏的石脑油型烃类进料。该石脑油具有以下组成(按重量计):
● 52.6%的链烷烃化合物;
● 31.6%的环烷烃;
● 15.8%的芳族分子;
总密度为0.759 g/cm3。
进料的研究辛烷值接近55。
加入到反应器中之后,通过在490℃下在纯氢气气氛中热处理2小时活化该催化剂。
在上述氢气和石脑油存在下,在重整反应条件下评价催化表现。特别地,使用的条件和催化剂对比如下:
● 反应器压力保持在8 bar g (0.8 MPa g);
● 每千克催化剂,进料流速为2.0 kg/h;
● 进料的氢气/烃类摩尔比:4。
对比由进料的催化转化产生的液体排放物(也称作重整产品)的研究辛烷值的异构-性能(iso-quality)。对比104的研究辛烷值。
催化剂 | 148h下的C5+产率(wt%) | 148h下的C4-产率(wt %) | 钝化(℃/h) | 焦炭(wt%/h) |
A | 88.38 | 8.37 | +0.088 | +0.034 |
B | 88.79 | 8.05 | +0.140 | +0.038 |
C | 88.29 | 8.39 | +0.099 | +0.033 |
D | 89.36 | 7.34 | +0.084 | +0.026 |
E | 89.12 | 7.58 | +0.099 | +0.030 |
F | 88.64 | 8.11 | +0.102 | +0.034 |
G | 88.51 | 8.23 | +0.092 | +0.038 |
H | 89.22 | 7.45 | +0.085 | +0.029 |
I | 89.25 | 7.48 | +0.089 | +0.029 |
表2:催化剂性能。
本发明的催化剂(催化剂D、E、H和I)具有改善的选择性(更高的C5+产率)和改善的稳定性(更少的焦炭量)。
Claims (10)
1.一种催化剂,由至少一种选自铂族的金属M、锡、磷促进剂、卤代化合物、多孔载体和选自铟的促进剂X1组成,还原形式下的所述催化剂在119Sn Mössbauer光谱学中具有四极分岐值为0至0.45 mm/s的信号和相对于CaSnO3的1.5至2.4 mm/s的异构体位移IS,所述信号相当于信号总面积的1%至30%,其中所述催化剂通过包括以下步骤的方法制备:
a) 在子步骤a1)或a2)之一期间,引入一种或多种促进剂X1和磷,所述子步骤a1)对应于合成主氧化物的前体,所述子步骤a2)对应于成型载体;
b) 在子步骤a1)和a2)的至少一个期间引入锡,步骤a)和b)可是连续或同时的;
c) 干燥步骤b)末尾获得的产物;
d) 在350℃至650℃温度下锻烧步骤c)中获得的产物;
e) 沉积至少一种来自铂族的金属M;
f) 在中性气体流或含氧气体流中,在不超过150℃的适度温度干燥;
g) 在350℃至650℃温度下锻烧步骤f)中获得的产物。
2.根据权利要求1的催化剂,其中Sn/M原子比为0.5至4.0。
3.根据权利要求1或权利要求2的催化剂,其中X1/M比为0.1至5.0。
4.根据权利要求1至3任一项的催化剂,其中P/M比为0.2至30.0。
5.根据权利要求1至4任一项的催化剂,其中金属M的量为0.01 wt%至5 wt%。
6.根据权利要求1至5任一项的催化剂,其中金属M为铂或钯。
7.根据权利要求1至6任一项的催化剂,其中卤代化合物选自氟、氯、溴和碘。
8.根据权利要求1至7任一项的催化剂,其中卤代化合物的量为0.1 wt%至15.0 wt%。
9.根据权利要求1至8任一项的催化剂,其中卤代化合物为氯,氯含量为0.1 wt%至5.0wt%。
10.根据权利要求1至9任一项的催化剂,其中载体包括至少一种选自镁、钛、锆、铝和硅的氧化物的氧化物。
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- 2010-06-15 EP EP10734171.1A patent/EP2448671B1/fr active Active
- 2010-06-15 RU RU2012103327/04A patent/RU2533586C2/ru active
- 2010-06-15 JP JP2012518104A patent/JP5599881B2/ja active Active
- 2010-06-15 DK DK10734171.1T patent/DK2448671T3/en active
- 2010-06-15 CN CN201710095799.0A patent/CN107020084A/zh active Pending
- 2010-06-15 US US13/381,394 patent/US20120122665A1/en not_active Abandoned
- 2010-06-15 WO PCT/FR2010/000444 patent/WO2011001042A2/fr active Application Filing
- 2010-06-15 CN CN2010800301193A patent/CN102470347A/zh active Pending
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2011
- 2011-12-15 ZA ZA2011/09267A patent/ZA201109267B/en unknown
Patent Citations (5)
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US4522935A (en) * | 1983-06-02 | 1985-06-11 | Uop Inc. | Platinum and indium-containing catalyst for reforming hydrocarbons |
CN87103444A (zh) * | 1987-04-29 | 1988-11-30 | 环球油品公司 | 链烷烃异构化用的复合催化剂 |
CN1655868A (zh) * | 2002-05-22 | 2005-08-17 | 国际壳牌研究有限公司 | 含铋和磷的催化剂载体、由其制备的重整催化剂、其制备方法和石脑油重整方法 |
CN101160376A (zh) * | 2005-01-14 | 2008-04-09 | 上游技术革新有限公司 | 重整纳米催化剂以及制备和使用这类催化剂的方法 |
WO2008087273A2 (fr) * | 2006-12-22 | 2008-07-24 | Ifp | Catalyseur bimetallique ou multi-metallique presentant un indice de bimetallicite et une capacite d'adsorption d'hydrogene optimises |
Also Published As
Publication number | Publication date |
---|---|
WO2011001042A3 (fr) | 2011-10-06 |
JP5599881B2 (ja) | 2014-10-01 |
ZA201109267B (en) | 2012-08-29 |
WO2011001042A2 (fr) | 2011-01-06 |
EP2448671B1 (fr) | 2015-09-23 |
EP2448671A2 (fr) | 2012-05-09 |
JP2012531307A (ja) | 2012-12-10 |
RU2012103327A (ru) | 2013-08-10 |
FR2947464B1 (fr) | 2011-07-22 |
CN102470347A (zh) | 2012-05-23 |
US20120122665A1 (en) | 2012-05-17 |
RU2533586C2 (ru) | 2014-11-20 |
DK2448671T3 (en) | 2016-01-11 |
FR2947464A1 (fr) | 2011-01-07 |
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