WO2005113141A1 - Catalyst for selective opening of cyclic paraffins and process for using the catalyst - Google Patents
Catalyst for selective opening of cyclic paraffins and process for using the catalyst Download PDFInfo
- Publication number
- WO2005113141A1 WO2005113141A1 PCT/US2004/012039 US2004012039W WO2005113141A1 WO 2005113141 A1 WO2005113141 A1 WO 2005113141A1 US 2004012039 W US2004012039 W US 2004012039W WO 2005113141 A1 WO2005113141 A1 WO 2005113141A1
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- WO
- WIPO (PCT)
- Prior art keywords
- catalyst
- uzm
- group
- mixtures
- molecular sieve
- Prior art date
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- 239000003054 catalyst Substances 0.000 title claims abstract description 102
- 238000000034 method Methods 0.000 title claims abstract description 29
- 125000004122 cyclic group Chemical group 0.000 title claims abstract description 14
- 229910052751 metal Inorganic materials 0.000 claims abstract description 39
- 239000002184 metal Substances 0.000 claims abstract description 39
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 32
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000002808 molecular sieve Substances 0.000 claims abstract description 31
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 19
- 239000003607 modifier Substances 0.000 claims abstract description 16
- 229910052809 inorganic oxide Inorganic materials 0.000 claims abstract description 15
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 8
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 8
- 239000010948 rhodium Substances 0.000 claims abstract description 8
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052769 Ytterbium Inorganic materials 0.000 claims abstract description 6
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 6
- 241000269350 Anura Species 0.000 claims abstract description 5
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 5
- 239000010936 titanium Substances 0.000 claims abstract description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 4
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims description 36
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 34
- 238000007142 ring opening reaction Methods 0.000 claims description 20
- 230000003197 catalytic effect Effects 0.000 claims description 17
- 239000000377 silicon dioxide Substances 0.000 claims description 16
- -1 clays Chemical compound 0.000 claims description 10
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 7
- 229910052707 ruthenium Inorganic materials 0.000 claims description 7
- 229910052741 iridium Inorganic materials 0.000 claims description 6
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052758 niobium Inorganic materials 0.000 claims description 6
- 239000010955 niobium Substances 0.000 claims description 6
- 239000011148 porous material Substances 0.000 claims description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 4
- 125000002015 acyclic group Chemical group 0.000 claims description 4
- 229910052746 lanthanum Inorganic materials 0.000 claims description 4
- 229910052702 rhenium Inorganic materials 0.000 claims description 4
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims description 4
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052732 germanium Inorganic materials 0.000 claims description 3
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 3
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 3
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 2
- 239000000292 calcium oxide Substances 0.000 claims description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 2
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 239000000395 magnesium oxide Substances 0.000 claims description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims 1
- 150000002739 metals Chemical class 0.000 abstract description 7
- 239000010457 zeolite Substances 0.000 description 46
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 42
- 229910021536 Zeolite Inorganic materials 0.000 description 33
- 239000000243 solution Substances 0.000 description 26
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 25
- 150000001768 cations Chemical class 0.000 description 25
- 239000002253 acid Substances 0.000 description 23
- 238000005342 ion exchange Methods 0.000 description 21
- 238000011282 treatment Methods 0.000 description 20
- 238000001354 calcination Methods 0.000 description 18
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 15
- 229910052782 aluminium Inorganic materials 0.000 description 14
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 238000004458 analytical method Methods 0.000 description 12
- 230000000694 effects Effects 0.000 description 12
- 229910001868 water Inorganic materials 0.000 description 12
- 229910021529 ammonia Inorganic materials 0.000 description 11
- 239000011541 reaction mixture Substances 0.000 description 11
- 238000010025 steaming Methods 0.000 description 11
- 238000000605 extraction Methods 0.000 description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 9
- 229910052739 hydrogen Inorganic materials 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical group CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 8
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 7
- 229910000323 aluminium silicate Inorganic materials 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 150000002892 organic cations Chemical class 0.000 description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 150000001412 amines Chemical class 0.000 description 6
- YOUGRGFIHBUKRS-UHFFFAOYSA-N benzyl(trimethyl)azanium Chemical group C[N+](C)(C)CC1=CC=CC=C1 YOUGRGFIHBUKRS-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 229910052710 silicon Inorganic materials 0.000 description 6
- 230000002378 acidificating effect Effects 0.000 description 5
- 150000001342 alkaline earth metals Chemical class 0.000 description 5
- 150000001336 alkenes Chemical class 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- 229910052681 coesite Inorganic materials 0.000 description 5
- 229910052593 corundum Inorganic materials 0.000 description 5
- 229910052906 cristobalite Inorganic materials 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 238000005470 impregnation Methods 0.000 description 5
- 238000006317 isomerization reaction Methods 0.000 description 5
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methylcyclopentane Chemical compound CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 229910052682 stishovite Inorganic materials 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 229910052905 tridymite Inorganic materials 0.000 description 5
- 229910001845 yogo sapphire Inorganic materials 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 150000004985 diamines Chemical class 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 229940104869 fluorosilicate Drugs 0.000 description 4
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 4
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- 239000012265 solid product Substances 0.000 description 4
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical group C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 3
- 229910052796 boron Inorganic materials 0.000 description 3
- 239000012159 carrier gas Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 238000000634 powder X-ray diffraction Methods 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
- 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 2
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- 229910019804 NbCl5 Inorganic materials 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- IJRVQAXSAHHCNH-UHFFFAOYSA-M butyl(trimethyl)azanium;hydroxide Chemical compound [OH-].CCCC[N+](C)(C)C IJRVQAXSAHHCNH-UHFFFAOYSA-M 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 2
- 239000008119 colloidal silica Substances 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 229910052733 gallium Inorganic materials 0.000 description 2
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- YHBDIEWMOMLKOO-UHFFFAOYSA-I pentachloroniobium Chemical compound Cl[Nb](Cl)(Cl)(Cl)Cl YHBDIEWMOMLKOO-UHFFFAOYSA-I 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 125000006850 spacer group Chemical group 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000004230 steam cracking Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- KIDHWZJUCRJVML-UHFFFAOYSA-P 1,4-butanediammonium Chemical compound [NH3+]CCCC[NH3+] KIDHWZJUCRJVML-UHFFFAOYSA-P 0.000 description 1
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- 239000001763 2-hydroxyethyl(trimethyl)azanium Substances 0.000 description 1
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 1
- 239000005695 Ammonium acetate Substances 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 235000019743 Choline chloride Nutrition 0.000 description 1
- 241000640882 Condea Species 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 229910002339 La(NO3)3 Inorganic materials 0.000 description 1
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 1
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 description 1
- 239000007832 Na2SO4 Substances 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 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
- 229910021604 Rhodium(III) chloride Inorganic materials 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 159000000021 acetate salts Chemical class 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 1
- 229940043376 ammonium acetate Drugs 0.000 description 1
- 235000019257 ammonium acetate Nutrition 0.000 description 1
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- NOWPEMKUZKNSGG-UHFFFAOYSA-N azane;platinum(2+) Chemical compound N.N.N.N.[Pt+2] NOWPEMKUZKNSGG-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- WRMFBHHNOHZECA-UHFFFAOYSA-N butan-2-olate Chemical compound CCC(C)[O-] WRMFBHHNOHZECA-UHFFFAOYSA-N 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- SGMZJAMFUVOLNK-UHFFFAOYSA-M choline chloride Chemical compound [Cl-].C[N+](C)(C)CCO SGMZJAMFUVOLNK-UHFFFAOYSA-M 0.000 description 1
- 229960003178 choline chloride Drugs 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 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
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 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
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- JQDCIBMGKCMHQV-UHFFFAOYSA-M diethyl(dimethyl)azanium;hydroxide Chemical compound [OH-].CC[N+](C)(C)CC JQDCIBMGKCMHQV-UHFFFAOYSA-M 0.000 description 1
- CXKWBOPHHLLCKC-UHFFFAOYSA-M ethyl-dimethyl-propylazanium;hydroxide Chemical compound [OH-].CCC[N+](C)(C)CC CXKWBOPHHLLCKC-UHFFFAOYSA-M 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000012013 faujasite Substances 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910000373 gallium sulfate Inorganic materials 0.000 description 1
- SBDRYJMIQMDXRH-UHFFFAOYSA-N gallium;sulfuric acid Chemical compound [Ga].OS(O)(=O)=O SBDRYJMIQMDXRH-UHFFFAOYSA-N 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000008241 heterogeneous mixture Substances 0.000 description 1
- 229950006187 hexamethonium bromide Drugs 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000005216 hydrothermal crystallization Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical compound Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 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
- 239000008188 pellet Substances 0.000 description 1
- 239000006069 physical mixture Substances 0.000 description 1
- 239000006187 pill Substances 0.000 description 1
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 description 1
- OGHBATFHNDZKSO-UHFFFAOYSA-N propan-2-olate Chemical compound CC(C)[O-] OGHBATFHNDZKSO-UHFFFAOYSA-N 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 239000011369 resultant mixture Substances 0.000 description 1
- 230000000717 retained effect Effects 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
- IREVRWRNACELSM-UHFFFAOYSA-J ruthenium(4+);tetrachloride Chemical compound Cl[Ru](Cl)(Cl)Cl IREVRWRNACELSM-UHFFFAOYSA-J 0.000 description 1
- 229920006395 saturated elastomer Polymers 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
- 150000004760 silicates Chemical class 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 1
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 1
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 1
- WOZZOSDBXABUFO-UHFFFAOYSA-N tri(butan-2-yloxy)alumane Chemical compound [Al+3].CCC(C)[O-].CCC(C)[O-].CCC(C)[O-] WOZZOSDBXABUFO-UHFFFAOYSA-N 0.000 description 1
- QENJZWZWAWWESF-UHFFFAOYSA-N tri-methylbenzoic acid Natural products CC1=CC(C)=C(C(O)=O)C=C1C QENJZWZWAWWESF-UHFFFAOYSA-N 0.000 description 1
- UAIHPMFLFVHDIN-UHFFFAOYSA-K trichloroosmium Chemical compound Cl[Os](Cl)Cl UAIHPMFLFVHDIN-UHFFFAOYSA-K 0.000 description 1
- JAJRRCSBKZOLPA-UHFFFAOYSA-M triethyl(methyl)azanium;hydroxide Chemical compound [OH-].CC[N+](C)(CC)CC JAJRRCSBKZOLPA-UHFFFAOYSA-M 0.000 description 1
- OLNCQUXQEJCISO-UHFFFAOYSA-M trimethyl(propyl)azanium;hydroxide Chemical compound [OH-].CCC[N+](C)(C)C OLNCQUXQEJCISO-UHFFFAOYSA-M 0.000 description 1
- FAPSXSAPXXJTOU-UHFFFAOYSA-L trimethyl-[6-(trimethylazaniumyl)hexyl]azanium;dibromide Chemical compound [Br-].[Br-].C[N+](C)(C)CCCCCC[N+](C)(C)C FAPSXSAPXXJTOU-UHFFFAOYSA-L 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/58—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins
- C10G45/60—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used
- C10G45/64—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
-
- 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
- B01J23/54—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
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/648—Vanadium, niobium or tantalum or polonium
- B01J23/6484—Niobium
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/50—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the erionite or offretite type, e.g. zeolite T, as exemplified by patent document US2950952
- B01J29/52—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the erionite or offretite type, e.g. zeolite T, as exemplified by patent document US2950952 containing iron group metals, noble metals or copper
- B01J29/54—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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/74—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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/82—Phosphates
- B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
- B01J29/85—Silicoaluminophosphates [SAPO compounds]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/19—Catalysts containing parts with different compositions
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/22—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
- C07C5/27—Rearrangement of carbon atoms in the hydrocarbon skeleton
- C07C5/31—Rearrangement of carbon atoms in the hydrocarbon skeleton changing the number of rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/82—Phosphates
- C07C2529/84—Aluminophosphates containing other elements, e.g. metals, boron
- C07C2529/85—Silicoaluminophosphates (SAPO compounds)
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1081—Alkanes
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/40—Characteristics of the process deviating from typical ways of processing
- C10G2300/4018—Spatial velocity, e.g. LHSV, WHSV
-
- 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
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Definitions
- This invention relates to a catalyst for the selective opening of cyclic 5 paraffins which comprises a Group VTJI metal component, a molecular sieve, a refractory oxide and optionally a modifier.
- This invention also relates to a process for selective ring opening using the catalyst.
- Olefins are used in various reactions to produce important chemical compounds. Accordingly, demand for olefins is ever increasing and therefore new 10 processes or increased efficiencies in existing processes are required.
- One of the main processes used in preparing light olefins is naphtha steam cracking. It is known that the efficiency of steam cracking depends on the specific composition of the naphtha feed.
- Reformulated gasoline differs from the traditional product in having a lower vapor pressure, lower final boiling point, increased content of oxygenates, and lower content of olefins, benzene and aromatics.
- Reduction in gasoline benzene content often has been addressed by changing the cut point between light and heavy naphtha, directing more of the potential benzene formers to isomerization instead of to reforming.
- No benzene is formed in isomerization, wherein benzene is converted to C 6 naphthenes and C 6 naphthenes are isomerized toward an equilibrium mixture of cyclohexane and methylcyclopentane or converted to paraffins through ring opening.
- Catalysts which are useful for ring opening are known and include a high chloride platinum component dispersed on a refractory inorganic oxide which is described in US-A-5,463,155.
- US-A-5,811,624 describes a catalyst for the selective opening of 5 and 6 membered rings which consists of a transition metal catalyst selected from the group consisting of carbides, nitrides, oxycarbides, oxynitrides, and oxycarbonitrides.
- the transition metal is selected from the group consisting of metals from Group IVA, VA, VIA of the Periodic Table of the Elements.
- US-A-6, 235,962 Bl discloses a catalyst for ring opening which comprises a carrier consisting of alumina, a metal modifier selected from the group consisting of scandium, yttrium and lanthanum, and at least one catalytically active metal selected from the group consisting of platinum, palladium, rhodium, rhenium, iridium, ruthenium, and cobalt.
- US-A-5, 382,730 discloses a process for ring opening and isomerization of hydrocarbons where the catalyst comprises an aluminosilicate zeolite such as Zeolite Y or Zeolite Beta and a hydrogenation component.
- US-A-5,345,026 discloses a process for conversion of cyclic hydrocarbons to non-cyclic paraffin hydrocarbons where the catalyst comprises a hydrogenation-dehydrogenation component and an acidic solid component comprising a group IVB metal oxide modified with an oxyanion of a group VIB metal.
- US-A-3,617,511 discloses a catalyst for conversion of cyclic hydrocarbons to paraffins where the catalyst comprises rhodium or ruthenium on a halogen promoted refractory oxide.
- US-A-6,241,876 discloses a ring opening catalyst which comprises a large pore crystalline molecular sieve component with a faujasite structure and an alpha acidity of less than one and a Group VUI noble metal.
- U.S. Publication No. 2002/43481 Al discloses a catalyst for naphthalene ring opening which comprises at least one Group VUI metal selected from iridium, platinum, rhodium and ruthenium on a refractory inorganic oxide substrate containing at least one of an alkali metal and alkaline earth metal.
- U.S. Publication No. 2002/40175 Al discloses a naphthene ring opening catalyst comprising a Group VUI metal selected from iridium, platinum, palladium, rhodium, ruthenium and combinations thereof. With the metal being supported on the substrate comprising at least one of a Group IB, UB, and IVA metal.
- One aspect of the present invention is a catalyst which is useful for opening or cleaving naphthenic rings.
- the catalyst of the present invention comprises a Group VUI metal component an optional modifier component, a molecular sieve and a refractory inorganic oxide.
- the molecular sieves which can be used in the present invention are any of those which have 8, 10 or 12 ring pores and which have weak to medium acidity. Acidity of the molecular sieves can be determined by one of several techniques. One method involves measuring the ability of the molecular sieves to crack heptane, i.e. heptane cracking test.
- the cracking test involves placing a sample (250 mg) of the molecular sieve to be tested into a microreactor and drying the catalyst for 30 minutes at 200°C using flowing hydrogen. The sample is then reduced by heating for one hour at 500°C in flowing hydrogen. After cooling to 450°C a feedstream comprising hydrogen gas saturated with heptane at 0°C is flowed over the sample. Online analysis of the effluent gas is carried out using gas chromatography after holding for 20 minutes at a temperature from 450-550°C.
- a weakly acidic molecular sieve will have a heptane conversation of no more that 20% and preferably no more than 10%, while a moderately acidic molecular sieve will have a cracking conversion of no more than 40% and preferably no more than 30%.
- Another test method is ammonia temperature programmed desorption or NH 3 -TPD. This test basically involves contacting a molecular sieve sample with ammonia and then measuring the amount of ammonia desorbed over a temperature range of 200°C to 500°C. Details of this test procedure are provided in US-A-4,894,142 which is incorporated herein by reference.
- Molecular sieves with moderate acidity will desorb less than 0.4mmol of NH 3 /g total over the 200°C to 500°C range, while a weakly acidic molecular sieve will desorb a total of less than 0.2mmol of NH 3 /g over the 200°C to 500°C temperature range.
- acidity can be measured by pyridine infrared (IR).
- molecular sieves with weak to moderate acidity include but are not limited to MAPSOs, SAPOs, UZM-4, UZM-4M, UZM-5, UZM- 5P, UZM-5HS, UZM-6, UZM-8, UZM-8HS, UZM-15, UZM-15HS, UZM- 16, UZM- 16HS and mixtures thereof.
- MAPSO molecular sieves are disclosed in US-A- 4,758,419.
- a preferred MAPSO is MAPSO-31.
- SAPO molecular sieves are disclosed in US-A-4,440,871.
- Preferred SAPOs are SAPO-11, SAPO-34 and SM-3 (US-A-4,943,424).
- UZM-4 is described in US-A-6,419,895 Bl while UZM-5, UZM- 5P and UZM-6 are described in US-A-6,388,157 Bl.
- the other UZM molecular sieves are described in the following U.S. Patent Applications.
- UZM zeolites all the molecular sieves identified by a UZM designation will collectively be referred to as UZM zeolites.
- UZM zeolites For completeness, the following brief description of the UZM zeolites described in the patent applications above will be provided below.
- UZM zeolites have a microporous crystalline structure of at least AlO 2 and SiO 2 tetrahedral units.
- UZM-8, UZM-15 and UZM-16 have a composition on an as-synthesized and anhydrous basis expressed by an empirical formula of: M is at least one exchangeable cation selected from the group consisting of alkali and alkaline earth metals, "m" is the mole ratio of M to (Al + E) and, "n” is the weighted average valence of M.
- R is defined as follows: 1) UZM-8: R is at least one organoammonium cation selected from the group consisting of quaternary ammonium cations, diquaternary ammonium cations, protonated amines, protonated diamines, protonated alkanolamines and quaternized alkanolammonium cations, "r" is the mole ratio of R to (Al + E).
- UZM-15 R is at least one first quaternary organoammonium cation comprising at least one organic group having at least two carbon atoms, and optionally a second organoammonium cation selected from the group consisting of quaternary ammonium cations, protonated amines, protonated diamines, protonated alkanolamines, diquaternaryammonium cations, quaternized alkanolamines and mixtures thereof, "r” is the mole ratio of R to (Al + E); and 3) UZM-16: R is benzyltrimethylammonium (BzTMA) cation or a combination of BzTMA and at least one organoammonium cation selected from the group consisting of quaternary ammonium cations, protonated amines, protonated diamines, protonated alkanolamines, diquaternaryammonium cations, quaternized alkanolamines and mixtures thereof
- E is an element selected from the group consisting of Ga, Fe, In, Cr, B, and mixtures thereof.
- the other variables are defined as "p” is the weighted average valence of R; "x” is the mole fraction of E, “y' is the mole ratio of Si to (Al + E) and “z” is the mole ratio of O to (Al + E).
- p is the weighted average valence of R
- x is the mole fraction of E
- y' is the mole ratio of Si to (Al + E)
- z is the mole ratio of O to (Al + E).
- Table A Table A
- These zeolites are also characterized by x-ray diffraction patterns having at least the rf-spacings and relative intensities set forth in Table B (UZM-8), Table C (UZM-15) and Table D (UZM-16).
- the UZM-8, UZM-15 and UZM-16 zeolites are prepared by a hydrothermal crystallization of a reaction mixture prepared by combining reactive sources of R, aluminum, silicon and optionally M and E.
- the sources of aluminum include but are not limited to aluminum alkoxides, precipitated aluminas, aluminum metal, sodium aluminate, organoammonium aluminates, aluminum salts and alumina sols.
- Specific examples of aluminum alkoxides include, but are not limited to aluminum ortho sec- butoxide and aluminum ortho isopropoxide.
- Sources of silica include but are not limited to tetraethylorthosilicate, colloidal silica, precipitated silica, alkali silicates and organoammonium silicates.
- a special reagent consisting of an organoammonium aluminosilicate solution can also serve as the simultaneous source of Al, Si, and R.
- Sources of the E elements include but are not limited to alkali borates, boric acid, precipitated gallium oxyhydroxide, gallium sulfate, ferric sulfate, ferric chloride, chromium nitrate and indium chloride.
- Sources of the M metals include the halide salts, nitrate salts, acetate salts, and hydroxides of the respective alkali or alkaline earth metals.
- R can be introduced as an organoammonium cation or an amine.
- the sources include but are not limited to the hydroxide, chloride, bromide, iodide and fluoride compounds.
- DEDMA hydroxide examples include without limitation DEDMA hydroxide, ETMA hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, hexamethonium bromide, tetrapropylammonium hydroxide, methyltriethylammonium hydroxide, tetramethylammonium chloride, propylethyldimethylammonium hydroxide (PEDMAOH), trimethylpropylammonium hydroxide, trimethylbutylammonium hydroxide (TMBAOH), N,N,N,N',N',N'-hexamethyl 1,4 butanedi ammonium hydroxide (DQ4), and choline chloride.
- DEDMA hydroxide examples include without limitation DEDMA hydroxide, ETMA hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, hexamethonium
- the source of R may also be neutral amines, diamines, and alkanolamines that subsequently hydrolyzes to form an organoammonium cation.
- Specific examples are triethanolamine, triethylamine, and N,N,N',N'tetramethyl-l,6- hexanediamine.
- Preferred sources of R without limitation are ETMAOH, DEDMAOH, and HM(OH) 2 .
- a reagent in the form of an aluminosilicate stock solution may be used.
- These solutions consist of one or more organoammonium hydroxides and sources of silicon and aluminum that are processed to form a clear homogenous solution that is generally stored and used as a reagent.
- the reagent contains aluminosilicate species that typically don't show up in zeolite reaction mixtures derived directly from separate sources of silicon and aluminum.
- the reagent is generally alkali-free or contains alkali at impurity levels from the silicon, aluminum, and organoammonium hydroxide sources.
- One or more of these solutions may be used in a zeolite synthesis.
- the corresponding metallosilicate solution may also be employed in a synthesis.
- UZM-15 requires at least one first organoammonium cation having at least one organic group with at least two carbon atoms, e.g. DEDMA, ETMA, TMBA, DQ4 and PEDMA and optionally (in addition to the first organoammonium cation) a second organoammonium compound.
- the preparation of UZM-16 requires benzyltrimethylammonium (BzTMA) or a combination of BzTMA and at least one organoammonium cation as described above.
- the reaction mixture containing reactive sources of the desired components can be described in terms of molar ratios of the oxides by the formula: aM 2/n O:bR 2 p O:(l-c)Al 2 O 3 :cE 2 O 3 :dSiO 2 :eH 2 O .
- the values of the variables for the UZM-8, 15 and 16 are presented in Table E along with general and preferred reaction conditions.
- the reaction mixtures are reacted at the stated conditions in a sealed reaction vessel under autogenous pressure.
- the solid product is isolated from the heterogeneous mixture by means such as filtration or centrifugation, and then washed with de-ionized water and dried in air at ambient temperature up to 100°C.
- the zeolites will contain some of the exchangeable or charge balancing cations in its pores. These exchangeable cations can be exchanged for other cations, or in the case of organic cations, they can be removed by heating under controlled conditions. Ion exchange involves contacting the zeolites with a solution containing the desired cation (at molar excess) at exchange conditions. Exchange conditions include a temperature of 15°C to 100°C and a time of 20 minutes to 50 hours.
- Calcination conditions include a temperature of 300°C to 600°C for a time of 2 to 24 hours.
- a special treatment for removing organic cations which provides the ammonium form of the zeolite is ammonia calcination. Calcination in an ammonia atmosphere can decompose organic cations, presumably to a proton form that can be neutralized by ammonia to form the ammonium cation. The resulting ammonium form of the zeolite can be further ion-exchanged to any other desired form.
- Ammonia calcination conditions include treatment in the ammonia atmosphere at temperatures between 250°C and 600°C and more preferably between 250°C and 450°C for times of 10 minutes to 5 hours.
- the treatments can be carried out in multiple steps within this temperature range such that the total time in the ammonia atmosphere does not exceed 5 hours.
- the treatments should be brief, less than a half hour and more preferably on the order of 5-10 minutes. Extended calcination times above 500°C can lead to unintended dealumination along with the desired ammonium ion- exchange and are unnecessarily harsh as most organoammonium templates easily decompose at lower temperatures.
- UZM-4M, UZM-5HS, UZM-8HS, UZM-15HS and UZM-16HS zeolites are prepared from their respective parent zeolite by a number of various techniques and are represented by the empirical formula:
- E and "x" are as defined above except for UZM-4M and UZM-5HS where "x" varies from 0 to 0.5.
- Ml is at least one exchangeable cation selected from the group consisting of alkali metals, alkaline earth metals, rare earth metals, ammonium ion, hydrogen ion and mixtures thereof, a is the mole ratio of Ml to (Al + E), n is the weighted average valence of Ml, y' is the mole ratio of Si to (Al + E) and z" is the mole ratio of O to (Al + E).
- Table F Table F
- y' is greater than the specific value set forth in Table F to virtually pure silica.
- virtually pure silica is meant that virtually all the aluminum and/or the E metals have been removed from the framework. It is well know that it is virtually impossible to remove all the aluminum and/or E metal.
- a zeolite is virtually pure silica when y' has a value of at least 3,000, preferably 10,000 and most preferably 20,000.
- ranges for y' are from 3, 5, 6.5 or 7 to 3,000 preferably greater than 10 to 3,000; 3, 5, 6.5 or 7 to 10,000 preferably greater than 10 to 10,000 and 3, 5, 6.5 or 7 to 20,000 preferably greater than 10 to 20,000.
- the zeolites UZM-4M, UZM-5HS, UZM-8HS, UZM-15HS and UZM- 16HS are further characterized by an x-ray diffraction pattern having at least the d- spacings and relative intensities set forth in Tables G, H, I, J and K respectively.
- the UZM-4M, UZM-5HS, UZM-8HS, 15HS and 16HS are prepared by removing aluminum and optionally inserting silicon into the structure thereby increasing the Si/Al ratio and thus modifying the acidity and ion exchange properties of the zeolites.
- These treatments include: a) contacting with a fluorosilicate solution or slurry; b) calcining or steaming followed by acid extraction or ion-exchange; c) acid extraction or d) any combination of these treatments in any order.
- Fluorosilicate treatment is known in the art and is described in US-A- 6,200,463 Bl, which cites US- A-4,711,770 as describing a process for treating a zeolite with a fluorosilicate salt. Both patents are incorporated by reference in their entirety. General conditions for this treatment are contacting the zeolite with a solution containing a fluorosilicate salt such as ammonium fluorosilicate (AFS) at a temperature of 20°C to 90°C.
- a fluorosilicate salt such as ammonium fluorosilicate (AFS)
- the acids which can be used in carrying out acid extraction include without limitation mineral acids, carboxylic acids and mixtures thereof. Examples of these include sulfuric acid, nitric acid, ethylenediaminetetraacetic acid (EDTA), citric acid, oxalic acid, etc.
- the concentration of acid which can be used is not critical but is conveniently between 1 wt-% to 80 wt-% acid and preferably between 5 wt-% and 40 wt-% acid.
- Acid extraction conditions include a temperature of 10°C to 100°C for a time of 10 minutes to 24 hours. Once treated with the acid, the treated UZM zeolite is isolated by means such as filtration, washed with deionized water and dried at ambient temperature up to 100°C.
- the extent of dealumination obtained from acid extraction depends on the cation form of the starting UZM as well as the acid concentration and the time and temperature over which the extraction is conducted. For example, if organic cations are present in the starting UZM zeolite, the extent of dealumination will be slight compared to a UZM zeolite in which the organic cations have been removed. This may be preferred if it is desired to have dealumination just at the surface of the UZM zeolite. As stated above, convenient ways of removing the organic cations include calcination, ammonia calcination, steaming and ion exchange. Calcination, ammonia calcination and ion exchange conditions are as set forth above.
- Steaming conditions include a temperature of 400°C to 850°C with from 1% to 100% steam for a time of 10 minutes to 48 hours and preferably a temperature of 500°C to 600°C, steam concentration of 5 to 50% and a time of 1 to 2 hours.
- both calcination and steaming treatments not only remove organic cations, but can also dealuminate the zeolite.
- alternate embodiments for dealumination include: a calcination treatment followed by acid extraction and steaming followed by acid extraction.
- a further embodiment for dealumination comprises calcining or steaming the starting UZM zeolite followed by an ion-exchange treatment.
- an acid extraction can be carried out concurrently with, before or after the ion exchange.
- the ion exchange conditions are the same as set forth above, namely a temperature of 15°C to 100°C and a time of 20 minutes to 50 hours.
- Ion exchange can be carried out with a solution comprising a cation (Ml') selected from the group consisting of alkali metals, alkaline earth metals, rare earth metals, hydrogen ion, ammonium ion, and mixtures thereof.
- Ml' a cation
- the Ml cation is exchanged for a secondary or different Ml' cation.
- the UZM composition after the steaming or calcining steps is contacted with an ion exchange solution comprising an ammonium salt.
- ammonium salts include but are not limited to ammonium nitrate, ammonium chloride, ammonium bromide, and ammonium acetate.
- the ammonium ion containing solution can optionally contain a mineral acid such as but not limited to nitric, hydrochloric, sulfuric and mixtures thereof.
- concentration of the mineral acid is that amount necessary to give a ratio of H + to NFL* of 0 to 1.
- This ammonium ion exchange aids in removing any debris present in the pores after the steaming and/or calcination treatments.
- a convenient technique for assessing the crystallinity of the products relative to the crystallinity of the starting material is the comparison of the relative intensities of the -spacing of their respective X-ray powder diffraction patterns.
- the sum of the peak intensities, in arbitrary units above the background, of the starting material is used as the standard and is compared with the corresponding peak intensities of the products.
- the numerical sum of the peak heights of the molecular sieve product is 85 percent of the value of the sum of the peak intensities of the starting zeolite, then 85 percent of the crystallinity has been retained.
- the UZM zeolite After having undergone any of the dealumination treatments as described above, the UZM zeolite is usually dried and can be used as discussed below.
- the properties of the modified UZM zeolite can be further modified by one or more additional treatment.
- These treatments include steaming, calcining or ion exchanging and can be carried out individually or in any combination. Some of these combinations include but are not limited to: steam calcine ion exchange; calcine ⁇ steam ion exchange; ion exchange calcine steam ion exchange steam calcine; steam calcine;
- anhydrous state of the zeolite will be intended unless otherwise stated.
- the term “anhydrous state” is employed herein to refer to a zeolite substantially devoid of both physically adsorbed and chemically adsorbed water.
- a second component of the catalyst of the invention is a catalytic metal component which is selected from the metals of Group VUI (Groups 8, 9 and 10 of the IUPAC designation) of the Periodic Table of the Elements and preferably from the noble metals.
- the group of noble metals are ruthenium, rhodium, palladium, platinum, iridium and osmium.
- Preferred catalytic metals are platinum, palladium, rhodium, ruthenium, iridium and mixtures thereof.
- the catalytic metal component can be deposited either on the molecular sieve or on a refractory inorganic oxide component.
- Inorganic oxides which can be used are any of those well known in the art and include but are not limited to aluminas, silica/alumina, silica, titania, calcium oxide, magnesium oxide, clays and zirconia.
- silica/alumina does not mean a physical mixture of silica and alumina but means an acidic and amorphous material that has been cogelled or coprecipitated.
- the term is well known in the art, see e.g. US-A-3,909,450; US-A-3,274,124 and US-A-4,988,659.
- the aluminas which can be used include gamma alumina, theta alumina, delta and alpha alumina.
- the catalytic metal component is deposited onto either the zeolite or inorganic oxide by means well known in the art such as spray impregnation or evaporative impregnation. Both spray or evaporative impregnation use a solution containing a decomposable compound of the desired metal.
- decomposable is meant that upon heating the compound decomposes to provide the catalytic metal or catalytic metal oxide.
- Non-limiting examples of decomposable compounds which can be used include chloroplatinic acid, palladic acid, chloroiridic acid, rhodium trichloride, ruthenium tetrachloride, osmium trichloride, iron chloride, cobalt chloride, nickel chloride, iron nitrate, cobalt nitrate, nickel nitrate, rhodium nitrate, ammonium chloroplatinate, platinum tetrachloride hydrate, palladium chloride, palladium nitrate, tetraamine platinum chloride and tetraamminepalladium (U) chloride.
- the solvent which is used to prepare the solution is usually water although organic solvents such as alcohols, dimethyl formamide (DMF), dimethylsulfoxide (DMSO), tetrahydrofuran (THF) and amines, e.g., pyridine can be used.
- organic solvents such as alcohols, dimethyl formamide (DMF), dimethylsulfoxide (DMSO), tetrahydrofuran (THF) and amines, e.g., pyridine can be used.
- Spray impregnation involves taking a small volume of the solution and spraying it over the support (zeolite or oxide) while the support is moving. When the spraying is over, the wetted support can be transferred to other apparatus for drying or finishing steps.
- One particular method of evaporative impregnation involves the use of a steam-jacketed rotary dryer.
- the support is immersed in the impregnating solution which has been placed in the dryer and the support is tumbled by the rotating motion of the dryer. Evaporation of the solution in contact with the tumbling support is expedited by applying steam to the dryer jacket.
- the impregnated support is then dried at a temperature of 60°C to 300°C and then calcined at a temperature of 300°C to 850°C for a time of 30 minutes to 8 hours to give the calcined catalyst.
- the catalytic metal component can also be deposited thereon by ion-exchange.
- Ion-exchange is carried out by contacting the molecular sieve with a solution containing a compound of the desired metal at ion-exchange conditions which include a temperature of 20°C to 100°C for a time from 5 minutes to 6 hours.
- the catalyst comprises separate particles.
- One configuration is a loose mixture of the two particles (refractory oxide and zeolite particles) or the particles are mixed and then formed into shaped articles such as cylinders, pellets, pills, spheres, irregularly shaped particles, etc. Methods of preparing such shaped articles are well known in the art.
- the inorganic oxide acts as a binder so that the resultant mixture can be formed into any of the shapes described above.
- the molecular sieve and inorganic oxide are first mixed and formed into a shaped article and then the catalytic metal is deposited onto the composite article by any of the means described above.
- the catalytic metal is believed to be deposited on both the inorganic oxide and zeolite supports. Regardless of how and where the catalytic metal is deposited, it is present in the final catalyst in an amount from 0.01 to 10 weight percent of the catalyst expressed as the metal. It should also be pointed out that the metal component can be present on the catalyst in its elemental (zero valent) state or as the oxide.
- the catalyst can also contains a modifier which modifies the activity of the catalytic metal.
- the modifier is selected from the group consisting of titanium, niobium, rare earth elements, tin, rhenium, zinc, germanium and mixtures thereof. Preferred rare earth elements are cerium, ytterbium, lanthanum, dysprosium and mixtures thereof.
- the modifier component is deposited by the same techniques as described above for the catalytic metals. Further, the modifier can be deposited on the support before, after or simultaneously with the catalytic metal, although not necessarily with equivalent results. It is preferred to deposit the modifier with the catalytic metal.
- the amount of modifier can vary substantially but is usually in the range of 0.1 to 50 wt.-%, preferably 1 to 10 wt.-% of the catalyst as the element.
- the catalyst described above is used in a process where cyclic paraffins are opened or cleaved to acyclic paraffins.
- the feeds which can be used in the ring opening process are any of those which comprises C 5 - C 6 aliphatic rings, i.e. naphthenic rings.
- Naphtha feeds can vary considerably in the amount of aromatic, naphthene and paraffin components which they complain. Depending on the source, feeds can contain from 15% to 55% naphthenes.
- One example of naphtha feed was found to contain 17 wt.-% aromatics, 44 wt.-% naphthenes and 39 wt.-% aromatics.
- the feedstream is contacted with the catalyst at ring opening conditions which include a temperature of 200°C to 600°C, a pressure of atmospheric to 20,684 kPag, and preferably from 1379 kPag to 13790 kPag, a liquid hourly space velocity of 0.1 to 30 hr "1 and preferably 2 to 10 hr "1 and H 2 /HC (hydrocarbon) ratio from 0.1 to 30 and preferably from 1 to 10.
- ring opening conditions which include a temperature of 200°C to 600°C, a pressure of atmospheric to 20,684 kPag, and preferably from 1379 kPag to 13790 kPag, a liquid hourly space velocity of 0.1 to 30 hr "1 and preferably 2 to 10 hr "1 and H 2 /HC (hydrocarbon) ratio from 0.1 to 30 and preferably from 1 to 10.
- An aluminum sol was prepared by dissolving aluminum metal in HC1.
- a container 822.4g of the Al-sol containing 105.32g Al (as Al 2 O 3 ) and 94g CI were blended with 2.91g of NbCl 5 at 60°C for 12 hours.
- HMT hexamethylene tetraamine
- the spheres were then aged at 140°C for 1.5 hours, washed with 20 liters of 0.25% NH 3 solution for 2 hours at 95 °C, dried at 100°C for 16 hours and then calcined at 550°C for 2 hours in air with 3% steam.
- Catalysts B to I were tested for methylcyclopentane ring opening activity and selectivity as follows.
- the catalysts were tested by placing 35mg of 250-450 um meshed particles into a microreactor and pretreated at 450°C for 4 hours using dry hydrogen floured at 45 cm 3 /min.
- the samples were then tested using a feed of 2.7% methylcyclopentane in hydrogen as a carrier gas at temperatures of 200°C to 350°C at weight hourly space velocities (w 2/sv) of 0.5 to 6hr " '.
- the results of the testing at 350°C and WHSV of 0.5hr " ' are presented in Table 1.
- Example 10 show that modifiers such as Nb, Ti, and Yb improve both the activity and selectivity of platinum for ring opening.
- the feed consisted of methylcyclohexane (>98% purity) which was mixed with hydrogen carrier gas (>99% pure) in a heated mixing chamber and then downflowed through the catalyst bed at a weight hourly space velocity of 1.5 hr "1 . Measurements were taken at temperatures of 260-400 C and a pressure of 5516 kPag (800 psig). The reactor effluent was analyzed by an on-line gas chromatograph and the results are presented in Table 2. Table 2 Effect of Molecular Sieves on Ring Opening Activity
- the 0.6L autoclave was heated to and held at 150°C for 120 hr. after which the solids were collected by centrifugation, washed with de-ionized water and dried at 95°C.
- the products isolated from the 0.6L reaction exhibited an x-ray diffraction pattern consistent with the characteristic lines for the zeolite designated UZM-15.
- a sample of the UZM-15 (60 g) was then mixed with 120 ml of 1.57 M HCl solution and heated to 95°C for 1 hour to remove a good portion of organic templates The slurry was then filtered while still hot and washed with 500 ml of de-ionized H 2 O.
- Extrudates of 70 wt-% zeolite (UZM-15) and 30% alumina were prepared by first mulling 19.1 grams of Condea SBTM alumina with 29.0 grams of 20% HNO 3 .
- the HCl extracted UZM-15 (37.0 grams), Solka Floe (1.5 grams) extrusion aid and additional de-ionized H 2 O were then added to the peptized alumina and mulled for additional time until a consistent dough texture was obtained.
- the dough was then pushed through a die plate with 0.16 cm die holes to form green extrudate, which was then activated first in N 2 and then air at 500°C for 2 hours. This catalyst was identified as sample J.
- An aluminosilicate reaction mixture was prepared by adding 35.2 grams of Al (Osec-Bu) 3 (95+%) to 927.5 grams BzTMAOH (40%), and then stirring for 20 minutes, followed by the slow addition of 416.5 grams of colloidal silica (LUDOXTM AS-40, 40% SiO 2 ). The resulting mixture was then reacted in an autoclave at 125°C for 120 hours. The solid product was recovered and washed, and showed an x-ray pattern consistent with that of UZM-16. The powder was then calcined at 500°C and then NF t NO: ⁇ exchanged, filtered, washed with de-ionized H 2 O and dried at 90°C. The catalyst comprising 70 wt-% UZM-16 and 30 wt-% Al 2 O 3 was prepared using a procedure similar to that described in Example 12. This catalyst was identified as sample K. EXAMPLE 14
- An aluminosilicate reaction mixture was prepared in the following manner. Al(Osec-Bu) 3 (97%), 804.4g, was added to 7330g of DEDMAOH, (20% aq) with vigorous stirring. To this mixture, 2530g precipitated silica, (UltrasilTM VN SP3, 89% SiO 2 ) was added with continuous mixing. A solution of 127g NaOH in 3115g deionized H 2 O was prepared and added to the previous mixture and homogenized for 30 min. The resulting mixture was reacted in an autoclave at 150°C for 185 hours. The solid product was collected by filtration, washed with de-ionized water, and dried at 95°C.
- the product was identified as UZM-8 by powder x-ray diffraction analysis.
- the zeolite was first NFLiNOs exchanged to remove sodium, then prepared into a catalyst of 70 wt-% UZM-8 and 30 wt-% Al 2 O 3 using a procedure similar to that described in Example 12. This catalyst was identified as sample L.
- EXAMPLE 15 [0065] An aluminosilicate reaction mixture was prepared in the following manner. Al(Osec-Bu) 3 (97%), 66.51g, was added to 918.29g of DEDMAOH, (20% aq) with vigorous stirring. To this mixture, 208.95g precipitated silica, (UltrasilTM VN SP3, 89% SiO 2 ) was added with continuous mixing.
- the zeolite was first NH 4 NO 3 exchanged to remove sodium, then prepared into a catalyst of 70 wt-% UZM-8 and 30 wt-% Al 2 O 3 using a procedure similar to that described in Example 12. This catalyst was identified as sample M.
- EXAMPLE 16 [0066] In a container 219.3g of alumina were mixed with 12.9g of HNO 3 (70%) and to this peptized mixture there were added 109.6g of alumina, 84.3g of SM-3 molecular sieve (prepared according to US-A-4,943,424) , 1.5g of methacel A4M and 197.4g water. The resulting dough was mixed for 35 minutes and then extruded through a 0.16 cm die. The extrudates were dried at 300°C for 1 hour and then 550°C for 2 hours in flowing air. This catalyst was identified as sample N.
- EXAMPLE 17 [0066] In a container 219.3g of alumina were mixed with 12.9g
- a catalyst containing SAPO-11 and alumina was prepared per Example 5.
- the SAPO-11 was prepared according to US-A-4,440,871. This catalyst was identified as sample O.
- Catalysts J to O were tested for methylcyclohexane ring opening activity and selectivity as follows.
- IncolloyTM tube reactor there were placed 3g of 40-60 mesh crushed extrudates of each sample.
- the reactor was heated using an infrared furnace.
- Inert spacers were placed before the catalyst bed to minimize dead volume and pre-heat the feed.
- the feed consisted of methylcyclohexane (>98% purity) which was mixed with hydrogen carrier gas (>99% pure) in a heated mixing chamber and then flowed through the catalyst bed at a weight hourly space velocity of 5 hr "1 .
- Measurements were taken at various temperatures and a pressure of 5516 kPa (800 psi).
- the reactor effluent was analyzed by an on-line gas chromatograph and the results are presented in Table 3 below.
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CN103785462B (en) * | 2012-11-01 | 2017-03-01 | 中国石油化工股份有限公司 | A kind of cycloalkane hydrogenation catalyst and its preparation method and application |
CN103864558B (en) * | 2012-12-14 | 2016-01-13 | 中国石油化工股份有限公司 | A kind of opening cyclic paraffins cleavage method |
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US20210370276A1 (en) * | 2018-10-30 | 2021-12-02 | Exxonmobil Chemical Patents Inc. | Group 1 Metal Ion Content of Microporous Molecular Sieve Catalysts |
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Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4894142A (en) | 1987-03-24 | 1990-01-16 | Uop | Hydrocracking process employing low acidity Y zeolite |
US5885438A (en) * | 1993-02-12 | 1999-03-23 | Mobil Oil Corporation | Wax hydroisomerization process |
US6204426B1 (en) | 1999-12-29 | 2001-03-20 | Chevron U.S.A. Inc. | Process for producing a highly paraffinic diesel fuel having a high iso-paraffin to normal paraffin mole ratio |
US20020040175A1 (en) | 2000-07-21 | 2002-04-04 | Baird William C. | Naphthene ring opening over group VIII metal catalysts containing cracking moderators |
US6458265B1 (en) | 1999-12-29 | 2002-10-01 | Chevrontexaco Corporation | Diesel fuel having a very high iso-paraffin to normal paraffin mole ratio |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2004504135A (en) * | 2000-07-21 | 2004-02-12 | エクソンモービル リサーチ アンド エンジニアリング カンパニー | Ring opening of naphthenes over iridium ring opening catalysts |
FI119588B (en) * | 2003-11-27 | 2009-01-15 | Neste Oil Oyj | Precious metal catalyst for hydrocarbon conversion, process of production thereof and process for production of diesel fuel |
-
2004
- 2004-04-20 EP EP04750322A patent/EP1742737A1/en not_active Withdrawn
- 2004-04-20 CN CNA2004800433820A patent/CN1972748A/en active Pending
- 2004-04-20 CA CA2562702A patent/CA2562702C/en not_active Expired - Fee Related
- 2004-04-20 JP JP2007509430A patent/JP4637172B2/en not_active Expired - Fee Related
- 2004-04-20 WO PCT/US2004/012039 patent/WO2005113141A1/en active Application Filing
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4894142A (en) | 1987-03-24 | 1990-01-16 | Uop | Hydrocracking process employing low acidity Y zeolite |
US5885438A (en) * | 1993-02-12 | 1999-03-23 | Mobil Oil Corporation | Wax hydroisomerization process |
US6204426B1 (en) | 1999-12-29 | 2001-03-20 | Chevron U.S.A. Inc. | Process for producing a highly paraffinic diesel fuel having a high iso-paraffin to normal paraffin mole ratio |
US20010006155A1 (en) | 1999-12-29 | 2001-07-05 | Miller Stephen J. | Process for producing a highly paraffinic diesel fuel having a high iso-paraffin to normal paraffin mole ratio |
US6458265B1 (en) | 1999-12-29 | 2002-10-01 | Chevrontexaco Corporation | Diesel fuel having a very high iso-paraffin to normal paraffin mole ratio |
US20020040175A1 (en) | 2000-07-21 | 2002-04-04 | Baird William C. | Naphthene ring opening over group VIII metal catalysts containing cracking moderators |
Also Published As
Publication number | Publication date |
---|---|
CA2562702C (en) | 2012-01-03 |
EP1742737A1 (en) | 2007-01-17 |
CN1972748A (en) | 2007-05-30 |
CA2562702A1 (en) | 2005-12-01 |
JP2007533446A (en) | 2007-11-22 |
JP4637172B2 (en) | 2011-02-23 |
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