WO2009148772A2 - Multi-stage reforming process to produce high octane gasoline - Google Patents
Multi-stage reforming process to produce high octane gasoline Download PDFInfo
- Publication number
- WO2009148772A2 WO2009148772A2 PCT/US2009/043580 US2009043580W WO2009148772A2 WO 2009148772 A2 WO2009148772 A2 WO 2009148772A2 US 2009043580 W US2009043580 W US 2009043580W WO 2009148772 A2 WO2009148772 A2 WO 2009148772A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- reformate
- reforming
- stage
- final
- penultimate
- Prior art date
Links
- 238000002407 reforming Methods 0.000 title claims abstract description 138
- 238000000034 method Methods 0.000 title claims abstract description 86
- 230000008569 process Effects 0.000 title claims abstract description 75
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 title abstract description 18
- 238000009835 boiling Methods 0.000 claims abstract description 33
- 239000003054 catalyst Substances 0.000 claims description 124
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 67
- 239000010457 zeolite Substances 0.000 claims description 61
- 229930195733 hydrocarbon Natural products 0.000 claims description 57
- 150000002430 hydrocarbons Chemical class 0.000 claims description 53
- 229910021536 Zeolite Inorganic materials 0.000 claims description 48
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 46
- 229910052751 metal Inorganic materials 0.000 claims description 35
- 239000002184 metal Substances 0.000 claims description 35
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 26
- 239000000203 mixture Substances 0.000 claims description 23
- 229910052697 platinum Inorganic materials 0.000 claims description 22
- 239000000446 fuel Substances 0.000 claims description 21
- 229910052702 rhenium Inorganic materials 0.000 claims description 12
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims description 12
- 229910052809 inorganic oxide Inorganic materials 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 5
- 229910052792 caesium Inorganic materials 0.000 claims description 4
- 238000000926 separation method Methods 0.000 abstract description 26
- 239000002808 molecular sieve Substances 0.000 description 42
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 42
- 229910052739 hydrogen Inorganic materials 0.000 description 39
- 239000001257 hydrogen Substances 0.000 description 39
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 36
- 239000000047 product Substances 0.000 description 34
- 238000006243 chemical reaction Methods 0.000 description 28
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 25
- 239000011148 porous material Substances 0.000 description 20
- 238000004519 manufacturing process Methods 0.000 description 15
- 229910052736 halogen Inorganic materials 0.000 description 14
- 150000002367 halogens Chemical class 0.000 description 14
- 239000007788 liquid Substances 0.000 description 14
- -1 but not limited to Chemical class 0.000 description 12
- 239000000463 material Substances 0.000 description 12
- 150000002739 metals Chemical class 0.000 description 12
- 238000004821 distillation Methods 0.000 description 11
- 239000000377 silicon dioxide Substances 0.000 description 11
- 239000004215 Carbon black (E152) Substances 0.000 description 10
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 10
- 125000004429 atom Chemical group 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 8
- 239000011230 binding agent Substances 0.000 description 7
- 238000001833 catalytic reforming Methods 0.000 description 7
- 239000002609 medium Substances 0.000 description 7
- 229910052710 silicon Inorganic materials 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 6
- 230000008901 benefit Effects 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- 150000001768 cations Chemical class 0.000 description 6
- 229910052732 germanium Inorganic materials 0.000 description 6
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 6
- 239000012263 liquid product Substances 0.000 description 6
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 5
- 239000003513 alkali Substances 0.000 description 5
- 229910000323 aluminium silicate Inorganic materials 0.000 description 5
- 238000004517 catalytic hydrocracking Methods 0.000 description 5
- 238000006356 dehydrogenation reaction Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229910052763 palladium Inorganic materials 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 229910052718 tin Inorganic materials 0.000 description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 4
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- 239000008186 active pharmaceutical agent Substances 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 229910052733 gallium Inorganic materials 0.000 description 4
- 238000006057 reforming reaction Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000003377 acid catalyst Substances 0.000 description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 3
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 229910052796 boron Inorganic materials 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 239000004927 clay Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 229910052738 indium Inorganic materials 0.000 description 3
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- 229910052741 iridium Inorganic materials 0.000 description 3
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 3
- 238000006317 isomerization reaction Methods 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 125000004430 oxygen atom Chemical group O* 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 230000008929 regeneration Effects 0.000 description 3
- 238000011069 regeneration method Methods 0.000 description 3
- 229910052703 rhodium Inorganic materials 0.000 description 3
- 239000010948 rhodium Substances 0.000 description 3
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 3
- 229910052707 ruthenium Inorganic materials 0.000 description 3
- 239000011973 solid acid Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 238000011144 upstream manufacturing Methods 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000000440 bentonite Substances 0.000 description 2
- 229910000278 bentonite Inorganic materials 0.000 description 2
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000005341 cation exchange Methods 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 238000006900 dealkylation reaction Methods 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000011777 magnesium Chemical class 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229910052615 phyllosilicate Inorganic materials 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 241000269350 Anura Species 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 229910014780 CaAl2 Inorganic materials 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical class [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 description 1
- 239000004113 Sepiolite Substances 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 229910052770 Uranium Inorganic materials 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 238000005899 aromatization reaction Methods 0.000 description 1
- 238000010420 art technique Methods 0.000 description 1
- 229960000892 attapulgite Drugs 0.000 description 1
- 235000012216 bentonite Nutrition 0.000 description 1
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical class [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 150000001649 bromium compounds Chemical class 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 230000020335 dealkylation Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229910001657 ferrierite group Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000007792 gaseous phase Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910000271 hectorite Inorganic materials 0.000 description 1
- KWLMIXQRALPRBC-UHFFFAOYSA-L hectorite Chemical compound [Li+].[OH-].[OH-].[Na+].[Mg+2].O1[Si]2([O-])O[Si]1([O-])O[Si]([O-])(O1)O[Si]1([O-])O2 KWLMIXQRALPRBC-UHFFFAOYSA-L 0.000 description 1
- 229910052677 heulandite Inorganic materials 0.000 description 1
- 239000000017 hydrogel Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000039 hydrogen halide Inorganic materials 0.000 description 1
- 239000012433 hydrogen halide Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910052909 inorganic silicate Inorganic materials 0.000 description 1
- 150000004694 iodide salts Chemical class 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 150000002500 ions Chemical group 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 229910052625 palygorskite Inorganic materials 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 239000006187 pill Substances 0.000 description 1
- DBJYYRBULROVQT-UHFFFAOYSA-N platinum rhenium Chemical group [Re].[Pt] DBJYYRBULROVQT-UHFFFAOYSA-N 0.000 description 1
- HWBBAGKLDSBYRI-UHFFFAOYSA-J platinum tetrachlororhenium Chemical compound [Re](Cl)(Cl)(Cl)Cl.[Pt] HWBBAGKLDSBYRI-UHFFFAOYSA-J 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000006152 selective media Substances 0.000 description 1
- 229910052624 sepiolite Inorganic materials 0.000 description 1
- 235000019355 sepiolite Nutrition 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 150000003376 silicon Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 238000007655 standard test method Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- ZCUFMDLYAMJYST-UHFFFAOYSA-N thorium dioxide Chemical compound O=[Th]=O ZCUFMDLYAMJYST-UHFFFAOYSA-N 0.000 description 1
- 229910001428 transition metal ion Chemical class 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 229910052902 vermiculite Inorganic materials 0.000 description 1
- 239000010455 vermiculite Substances 0.000 description 1
- 235000019354 vermiculite Nutrition 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 150000003738 xylenes Chemical class 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
- C10G59/00—Treatment of naphtha by two or more reforming processes only or by at least one reforming process and at least one process which does not substantially change the boiling range of the naphtha
- C10G59/02—Treatment of naphtha by two or more reforming processes only or by at least one reforming process and at least one process which does not substantially change the boiling range of the naphtha plural serial stages only
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G35/00—Reforming naphtha
- C10G35/04—Catalytic reforming
- C10G35/06—Catalytic reforming characterised by the catalyst used
- C10G35/085—Catalytic reforming characterised by the catalyst used containing platinum group metals or compounds thereof
- C10G35/09—Bimetallic catalysts in which at least one of the metals is a platinum group metal
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G35/00—Reforming naphtha
- C10G35/04—Catalytic reforming
- C10G35/06—Catalytic reforming characterised by the catalyst used
- C10G35/095—Catalytic reforming characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
Definitions
- the present invention relates to a multistage naphtha reforming process using an interstage separation step to produce a high octane product at high liquid yield and hydrogen production.
- Catalytic reforming is one of the basic petroleum refining processes for upgrading light hydrocarbon feedstocks, frequently referred to as naphtha feedstocks.
- Products from catalytic reforming can include high octane gasoline useful as automobile fuel, aromatics (for example benzene, toluene, xylenes and ethylbenzene), and/or hydrogen.
- Reactions typically involved in catalytic reforming include dehydrocylization, isomerization and dehydrogenation of naphtha range hydrocarbons, with dehydrocyclization and dehydrogenation of linear and slightly branched alkanes and dehydrogenation of cycloparaffins leading to the production of aromatics.
- Dealkylation and hydrocracking are generally undesirable due to the low value of the resulting light hydrocarbon products.
- Catalysts commonly used in commercial reforming reactions often include a Group VIII metal, such as platinum or palladium, or a Group VIII metal plus a second catalytic metal, which acts as a promoter.
- metals useful as promoters include rhenium, tin, tungsten, germanium, cobalt, nickel, rhodium, ruthenium, iridium or combinations thereof.
- the catalytic metal or metals may be dispersed on a support such as alumina, silica, or silica-alumina. Typically, a halogen such as chlorine is incorporated on the support to add acid functionality.
- other reforming catalysts include aluminosilicate zeolite catalysts.
- U.S. Pat. Nos. 3,761,389, 3,756,942 and 3,760,024 teach aromatization of a hydrocarbon fraction with a ZSM-5 type zeolite catalyst.
- U.S. Pat. No. 4,927,525 discloses catalytic reforming processes with beta zeolite catalysts containing a noble metal and an alkali metal.
- Other reforming catalysts include other molecular sieves such as borosilicates and silicoaluminophosphates, layered crystalline clay-type phyllosilicates, and amorphous clays.
- 3,950,241 discloses a process for upgrading naphtha by separating it into low- and high-boiling fractions, reforming the low-boiling fraction, combining the high-boiling naphtha with the reformate, and contacting the combined fractions with a ZSM-5-type catalyst.
- U.S. Pat. No. 4, 181 ,599 discloses a process for reforming naphtha comprising separating the naphtha into heavy and light fractions and reforming and isomerizing the naphtha fractions.
- 4,190,519 teaches a process for upgrading a naphtha-boiling-range hydrocarbon which comprises separating the naphtha feedstock into a light naphtha fraction containing C6 paraffins and lower- boiling hydrocarbons and a heavy naphtha fraction containing higher-boiling hydrocarbons, reforming the heavy naphtha fraction and passing at least a portion of the reformate together with the light naphtha fraction over a zeolite catalyst to produce an aromatics-enriched effluent.
- Different catalysts may be employed in different process steps during the reforming of naphtha feedstocks as described in U.S. Pat. Nos. 4,627,909, U.S. 4,443,326, U.S.
- the present invention is based on the discovery that in a multi-stage reforming process, selective reforming of Cs-Cg hydrocarbons in a separate or additional reforming stage provides improved performance of the overall reforming process of naphtha feedstocks.
- the present invention relates to processes for catalytically reforming a naphtha feed to produce a product reformate in a multistage reforming operation.
- the process comprises (1) contacting a naphtha boiling range feedstock in a penultimate stage of a multi-stage reforming process at a first reforming pressure with a first reforming catalyst to produce a penultimate effluent; (2) separating at least a portion of the penultimate effluent into at least an intermediate reformate comprising at least 70 vol% C 5 -C 8 hydrocarbons and a heavy reformate comprising at least 70 vol% C 9+ hydrocarbons; and (3) contacting the intermediate reformate in a final stage of the multi-stage reforming process at a second reforming pressure with a second reforming catalyst to produce a final effluent comprising a final reformate, wherein the final reformate has a higher RON than the intermediate reformate.
- the pressure in the final stage is lower than the pressure in the penultimate stage.
- the reforming catalyst within the penultimate and final stages is the same. In another embodiment, the reforming catalyst within the penultimate stage and final stage are different. In one embodiment the reforming catalyst of the penultimate stage and final stage comprises a Group VIII metal and a promoter supported on a porous refractory inorganic oxide support. In a preferred embodiment, the penultimate stage catalyst is platinum and rhenium on an alumina support. In another embodiment, the final stage catalyst is selected from the group consisting of a Group VIII metal, a molecular sieve, acid catalyst, clays and combinations thereof. In a preferred embodiment the reforming catalyst of the penultimate stage comprises a Group VIII metal and a promoter supported on a porous refractory inorganic oxide support and the reforming catalyst within the final stage comprises zeolite Beta.
- the process of the present invention comprises
- -3- produce a penultimate effluent; (2) separating at least a portion of the penultimate effluent into at least a light reformate, an intermediate reformate and a heavy reformate, wherein the light reformate has a mid-boiling point that is lower than that of the intermediate reformate and wherein the light reformate comprises at least 70 vol% Cs hydrocarbons, and wherein the intermediate reformate has a mid-boiling point that is lower than that of the heavy reformate and wherein the intermediate reformate comprises at least 70 vol% Ce-Ce hydrocarbons; and (3) contacting the intermediate reformate in a final stage of the multi-stage reforming process at a second reforming pressure with a second reforming catalyst to produce a final effluent comprising a final reformate, wherein the final reformate has a higher RON than the intermediate reformate.
- Fig. 1 is a schematic diagram of one embodiment of the invention.
- Fig. 2 is a schematic diagram of a second embodiment of the invention.
- a naphtha boiling range feedstock is processed in a multi-stage reforming process, in which said process involves at least a penultimate stage for reforming the naphtha feedstock to produce a penultimate effluent and a final stage for further reforming a portion of the penultimate effluent.
- the reforming process is operated at conditions and with catalysts selected for conducting dehydrocyclization, isomerization and dehydrogenation reactions of paraffins thus converting low octane normal paraffins and cycloparaffins into high octane materials. In this way, a product having increased octane and/or containing an increased amount of aromatics is produced.
- the multistage reforming process is operated at conditions and with one or more catalysts for producing a net positive quantity of hydrogen.
- the multi-stage reforming process of the invention comprises passing a refinery stream through at least two reforming stages in series.
- each reforming stage is characterized by one or more reforming reactor vessels, each containing a catalyst and maintained at reforming reaction conditions.
- the product from each stage before the final stage is passed, at least in part, to the succeeding stage in the multi-stage process.
- the temperature of the product from each stage which is passed to a succeeding stage may be increased or decreased to meet the particular needs of the process.
- the pressure of the product which is passed to a succeeding stage before the final stage may be increased or decreased.
- the final stage is run at a lower pressure than the penultimate stage.
- the present invention is based in part on the discovery that selective reforming of Cj-Cs paraffins in a separate or additional reforming stage provides improved performance of the overall reforming process.
- a penultimate reforming stage using a conventional reforming catalyst is operated at relatively low severity, since it is not required to reach the high octane levels normally desired for a naphtha fuel or fuel blend stock. While not being bound to any theory, we believe that under these conditions the reforming catalyst of the penultimate stage catalyzes the more facile reactions, such as cyclohexane and alkycyclohexane dehydrogenation, while keeping hydrocracking to a minimum.
- a conventional catalyst used to dehydrocyclize paraffins under more severe conditions produces higher quantities of light C 1 -C 4 gases, on account of the catalyst being somewhat unselective for dehydrocyclization.
- an intermediate reformate comprising at least 70 vol.% Cj-Ce hydrocarbons from a penultimate reforming stage is passed to a final reforming stage containing the same or a different reforming catalyst as the penultimate stage.
- the C 9 + fraction from the penultimate stage has higher octane than the Cs-Cg fraction, and is not further reformed in the final stage, thus preventing any unwanted dealkyation or cracking of the C 9 + hydrocarbons.
- the final stage is run at a lower pressure than the penultimate stage.
- runs the final stage at a lower pressure than the penultimate stage leads to improvements including one or more of the following characteristics - 1) increased yield of C 5 + liquid products, 2) minimized unwanted hydrocracking/dealkylation reactions, and 3) increased hydrogen production.
- Lower pressure of the final stage can, in some cases, lead to higher catalyst fouling rates
- boiling point temperatures are based on ASTM D-
- the mid-boiling point is defined as the 50% by volume boiling temperature, based on an ASTM D-2887 simulated distillation.
- carbon number values i.e. Cs, Cg, Ce, C 9 and the like
- Cs, Cg, Ce, C 9 and the like may be determined by standard gas chromatography methods.
- feed rate to a catalytic reaction zone is reported as the volume of feed per volume of catalyst per hour.
- the feed rate as disclosed herein is reported in reciprocal hours (i.e. hr '1 ) which is also referred to as liquid hourly space velocity (LHSV).
- a C 4 - stream comprises a high proportion of hydrocarbons with 4 or fewer carbon atoms per molecule.
- a Cs+ stream comprises a high proportion of hydrocarbons with S or more carbon atoms per molecule.
- hydrocarbon streams in refinery processes are generally separated by boiling range using a distillation process.
- the C4- stream would be expected to contain a small quantity of C 5 , Q and even C7 molecules.
- a typical distillation would be designed and operated such that at least about 70% by volume of a C 4 - stream would contain molecules having 4 carbon atoms or fewer per molecule.
- at least about 70 vol% of a C4- stream boils in the C 4 - boiling range.
- Cs+, Ce-Cg, C 9 + and other hydrocarbon fractions identified by carbon number ranges would be interpreted likewise.
- silicon to alumina ratio refers to the molar ratio of silicon oxide (S1O2) to aluminum oxide (AI 2 O 3 ).
- molecular sieve refers to a crystalline material containing pores, cavities, or interstitial spaces of a uniform size in which molecules small enough to pass through the pores, cavities, or interstitial spaces are adsorbed while larger molecules are not.
- molecular sieves include zeolites and non-zeolitic molecular sieves such as zeolite analogs including, but not limited to, SAPOs (silicoaluminophosphates), MeAPOs (metalloaluminophosphates), AIPO4, and ELAPOs (nonmetal substituted aluminophosphate families).
- the naphtha boiling range feed entering the penultimate stage of the multi-stage process is a naphtha fraction boiling within the range of 50° to 550 0 F, preferably from 70° to 45O 0 F, more preferably from 80° to 400 0 F, and most preferably from 90° to 360 0 F.
- the naphtha feed is a C 5 + feed.
- at least 85 vol% of the naphtha feedstock boils from about 70° to 450 0 F.
- the naphtha feed can include, for example, straight run naphthas, paraffinic raffinates from aromatic extraction or adsorption, Ce-C 10 paraffin-rich feeds,
- the reformer feed may comprise at least a portion of the product generated in a preceding stage.
- the reforming catalyst used in the penultimate reforming stage may be any catalyst known to have catalytic reforming activity
- the penultimate stage catalyst comprises a Group VIII metal disposed on an oxide support.
- Group VIII metals include platinum and palladium.
- the catalyst may further comprise a promoter, such as rhenium, tin, tungsten, germanium, cobalt, nickel, iridium, rhodium, ruthenium, or combinations thereof.
- the promoter metal is rhenium or tin.
- the above mentioned metals can be disposed on a support comprising one or more of (1) a refractory inorganic oxide such as alumina, silica, titania, magnesia, zirconia, chromia, thoria, boria or mixtures thereof; (2) a synthetically prepared or naturally occurring clay or silicate, which may be acid-treated; (3) a crystalline zeolitic aluminosilicate, either naturally occurring or synthetically prepared such as FAU, MEL, MFI, MOR, MTW (IUPAC Commission on Zeolite Nomenclature), in hydrogen form or in a form which has been exchanged with metal cations; (4) a spinel such as MgAl ⁇ O- t , FeAbOo, ZnAhO ⁇ CaAl 2 C ⁇ ; (5) a silicoaluminophosphate; and (6) combinations of materials from one or more of these groups.
- the refractory support of the reforming catalyst preferably comprises an inorganic
- Halogen may be incorporated into the catalyst by combining it with a source of halogen such as alkali or alkaline earth chlorides, fluorides, iodides or bromides.
- a source of halogen such as alkali or alkaline earth chlorides, fluorides, iodides or bromides.
- Other halogen sources include compounds such as hydrogen halide, e.g., hydrogen chloride, and ammonium halides, e.g., ammonium chloride.
- the preferred halogen source is a source of chlorine.
- the amount of halogen source combined with the catalyst should be such that the catalyst contains from about 0.1 to 3 wt % halogen, more preferably from about 0.2 to about 1.5 wt % halogen, and most preferably between 0.5 to 1.5 wt % halogen.
- the catalyst if it includes a promoter metal, suitably includes sufficient promoter metal to provide a promoter to platinum ratio between 0.5:1 and 10:1, more preferably between 1 : 1 and 6: 1 » most preferably between 2:1 and 5:1.
- the precise conditions, compounds, and procedures for catalyst manufacture are known to those persons skilled in the art. Some examples of conventional catalysts are shown in U.S. Pat Nos. 3,631,216; 3,415,737; and 4,511,746, which are hereby incorporated by reference in their entireties.
- the reforming catalyst in the penultimate stage and final stage may be employed in the form of pills, pellets, granules, broken fragments, or various special shapes, disposed as a fixed bed within a reaction zone, and the charging stock may be passed through in the liquid, vapor, or mixed phase, and in either upward, downward or radial flow.
- the reforming catalysts can be used in moving beds or in fluidized-solid processes, in which the charging stock is passed upward through a turbulent bed of finely divided catalyst.
- a fixed bed system or a dense-phase moving bed system are preferred due to less catalyst attrition and other operational advantages.
- the feed is preheated (by any suitable heating means) to the desired reaction temperature and then passed into a reaction zone containing a fixed bed of the catalyst.
- This reaction zone may be one or more separate reactors with suitable means to maintain the desired temperature at the reactor entrance. The temperature must be maintained because reforming reactions are typically endothermic in nature.
- the penultimate stage is maintained at relatively mild reaction conditions, so as to inhibit the cracking of the stream being upgraded, and to increase the useful lifetime of the catalyst in the penultimate stage.
- the naphtha boiling range feedstock to be upgraded in the penultimate stage contacts the penultimate stage catalyst at reaction conditions, which conditions include a temperature in the range from about 800 0 F to about 1100 6 F, a pressure in the range from about 70 psig to about 400 psig, and a feed rate in the range of from about 0.5 LHSV to about 5
- the pressure in the penultimate stage is in the range from about 200 psig to about 400 psig.
- the effluent from the penultimate stage is an upgraded product, in that the RON has been increased during reaction in the penultimate stage as compared to the RON of the naphtha feedstock.
- the penultimate stage effluent comprises hydrocarbons and hydrogen generated during reaction in the penultimate stage and at least some of the hydrogen, if any, which is added to the feed upstream of the penultimate stage.
- the effluent hydrocarbons may be characterized as a mixture of C4- hydrocarbons and Cs+ hydrocarbons, the distinction relating to the molecular weight of the hydrocarbons in each group.
- the C 5 + hydrocarbons in the effluent have a combined RON of at least 85.
- penultimate effluent comprises C 5 + hydrocarbons which are separated into at least an intermediate reformate and a heavy reformate.
- the effluent further comprises hydrogen and C 4 - hydrocarbons.
- a hydrogen-rich stream is separated from the effluent in a preliminary separation step, using, for example, a high pressure separator or other flash zone.
- C 4 - hydrocarbons in the effluent may also be separated in a preliminary separation, either along with the hydrogen or in a subsequent flash zone.
- the intermediate reformate is characterized as having a lower mid-boiling point than that of the heavy reformate. In some embodiments, the intermediate reformate boils in the range from about 7O 0 F to about 28O 0 F.
- the intermediate reformate comprises at least 70 vol% Cs-Cg hydrocarbons. In some embodiments, the intermediate reformate boils in the range from about 100 0 F to about 28O 0 F. In some such embodiments, the intermediate reformate comprises at least 70 vol% Q-Cs hydrocarbons. In some embodiments, the intermediate reformate boils in the range from about 100 0 F to about 230 0 F. In some such embodiments, the intermediate reformate comprises at least 70 vol% C 6 -C 7 hydrocarbons. Recovery of an intermediate reformate fraction may be accompanied by the further recovery of a largely Cs light reformate fraction. The light reformate is characterized as having a lower mid-boiling point than that of the intermediate reformate.
- the light reformate fraction boils in the range from about 7O 0 F to about 140 0 F. In some such embodiments, the light reformate fraction comprises at least 70 vol% Cs hydrocarbons.
- the heavy reformate that is produced during separation of the upgraded product boils in the range of about 220 0 F and higher. In some such embodiments, the heavy reformate comprises at least 70 vol% C 9 + hydrocarbons.
- the RON of the intermediate reformate is indicative of the mild reforming conditions in the penultimate stage.
- the intermediate reformate typically has an RON within the range of about 65 to 90.
- the intermediate reformate has a RON of about 70 to about 90.
- the intermediate reformate has an RON within the range of about 70 to about 85.
- the reforming catalyst used in the final stage may be any catalyst known to have catalytic reforming activity. Catalysts described above for the penultimate stage can be used in the final stage. Examples of catalysts useful in the final stage include: (1) molecular sieves such as zeolites, borosilicates, and silicoaluminophosphates; (2) amorphous Group VIII metal catalysts with an optional promoter metal selected from the group consisting of a non-platinum Group VIII metal, e.g. rhenium, germanium, tin, lead, gallium, indium, and mixtures thereof; and (3) additional catalysts comprising acid catalysts and clays.
- molecular sieves such as zeolites, borosilicates, and silicoaluminophosphates
- the final stage catalyst may include a single catalyst or a mixture of more than one of the above catalysts.
- the final stage catalyst comprises a zeolite and a group VIII metal.
- the final stage catalyst is a platinum rhenium catalyst supported on alumina.
- Molecular sieves particularly useful in the practice of the present invention include zeolites, zeolite analogs, and nonzeolitic molecular sieves.
- zeolite analog it is meant that a portion of the silicon and/or aluminum atoms in the zeolite are replaced with other tetrahedraUy coordinated atoms such as germanium, boron, titanium, phosphorus, gallium, zinc, iron, or mixtures thereof.
- nonzeolitic molecular sieve refers to molecular sieves whose frameworks are not formed of substantially only silicon and aluminum atoms in tetrahedral coordination with oxygen atoms.
- T tetrahedral units
- zeolite analog, or nonzeolitic molecular sieve the properties of the material are affected.
- the presence of aluminum in a zeolite introduces a negative charge in the zeolite framework and affects the acidity and activity of the zeolite as a reforming catalyst.
- the Si/Al ratio in zeolites can vary from about 1 to infinity.
- the lower limit arises from the avoidance of neighboring tetrahedral units with negative charges (AT-O-AT). It is generally accepted that the linking of two AIO 4 tetrahedra is energetically unfavorable enough to preclude such occurrences.
- Negative charges in a zeolite, zeolite analog, or nonzeolitic molecular sieve framework are compensated by extraframework cations such as protons and alkali cations.
- the properties of zeolites, zeolite analog, or nonzeolitic molecular sieve can be altered through exchange of these extraframework cations with other positively charged species.
- the type of cations present in the zeolite, zeolite analog, or nonzeolitic molecular sieve framework help determine the acidity of the molecular sieve.
- the molecular sieve preferably contains an alkali metal and/or an alkaline earth metal.
- the alkali or alkaline earth metals are preferably incorporated into the catalyst during or after synthesis of the molecular sieve.
- at least 90% of the acid sites are neutralized by introduction of the metals, more preferably at least 95%, most preferably at least 99%.
- the intermediate pore molecular sieve has less than 5,000 ppm alkali.
- Such intermediate pore silicate molecular sieves are disclosed, for example, in U.S. Patent No.
- zeolite Z U.S. Pat. No. 2,882,243
- zeolite X U.S. Pat. No. 2,882,244
- zeolite Y U.S. Pat. No. 3,130,007
- zeolite ZK-5 U.S. Pat. No. 3,247,195
- zeolite ZK-4 U.S. Pat. No. 3,314,752
- zeolite ZSM-5 U.S. Pat. No. 3,702,886
- zeolite ZSM-11 U.S. Pat. No.
- Zeolite Beta is described in U.S. Pat. No. 3,308,069 and RE 28,341 both to Wadlinger, and reference is made to these patents for a general description of zeolite Beta.
- the zeolite Beta of Wadlinger is described as having a silica-to-alumina ratio going from 10 to 100 and possibly as high as 150.
- Highly silicious zeolite Beta described as having silica-to-alumina ratios within the range of 20-1000 is disclosed in Valyocsik et al, U.S. Pat. No. 4,923,690.
- the catalytic properties of the zeolitic molecular sieve can be altered by isomorphous substitution of at least some of the tetrahedral atoms to make zeolite analogs or nonzeolitic molecular sieves wherein a portion or all of the silicon or aluminum atoms of the zeolite framework are replaced with, for example, germanium, titanium, boron, phosphorus, gallium, iron, or zinc.
- zeolite synthesis has often led to materials with novel topologies or to materials with properties that are very different from their aluminosilicate (zeolite) counterparts which have equivalent framework topologies.
- the aluminosilicate zeolite RHO cannot currently be synthesized with a Si/Al ratio much below 3.
- the aluminogermanate and gallosilicate analogues of zeolite RHO can be made with a Ge/Al ratio and a Si/Ga ratio of 1.0 and 1.3 respectively.
- the cation-exchange capacities of these RHO materials are therefore very different
- Aluminophosphate and gallophosphate analogues of zeolites are other example of molecular sieves based on replacement of silicon with other atoms. These materials are usually composed of strictly alternating AIO 4 (or GaO 4 ) and PO4 tetrahedral units, but they can be altered by isomorphous substitution of silicon, magnesium, beryllium, or transition metal ions.
- Molecular sieves have uniformly sized pores (3 to 10 A) which are determined by their unique crystal structures.
- the pores in zeolites and zeolite analogs are often classified as small (8 T atoms), medium (10 T atoms), large (12 T atoms), or extra-large ( > 14 T atoms) according to the number of tetrahedral atoms that surround the pore apertures.
- Zeolite A (LTA) and zeolite Rho are examples of molecular sieves with small pores delimited by 8-membered rings, wherein the pore aperture measures about 4.1 A, while zeolite X (FAU) and zeolite Beta are examples of zeolites with large pores delimited by 12-membered rings wherein the pore aperture measures about 7.4 A.
- the final stage catalyst can comprise large pore molecular sieves such as zeolite X, in a preferred embodiment the final stage catalyst comprises a medium pore molecular sieve.
- medium pore means having a crystallographic tree diameter in the range of from about 3.9 to about 7.1 Angstrom when the molecular sieve is in the calcined form.
- Shape selective medium pore molecular sieves used in some embodiments of the practice of the present invention have generally 1-, 2-, or 3-dimensional channel structures, with the pores characterized as being 9 or 10-ring structures.
- the crystallographic free diameters of the channels of molecular sieves are published in the "Atlas of Zeolite Framework Types", Fifth Revised Edition, 2001, by Ch. Baerlocher, W. M. Meier, and D. H. Olson, Elsevier, pp lG[ndash]15, which is incorporated herein by reference.
- Non-limiting examples of medium pore molecular sieves include ZSM-5, ZSM- 11, ZSM-22, ZSM-23, ZSM-35, ZSM-38, ZSM-48, ZSM-57, MCM-22, SSZ- 20, SSZ-25, SSZ-32, SSZ-35, SSZ-37, SSZ-44, SSZ-45, SSZ-47, SSZ-57, SSZ-58, SSZ-74, SUZ-4, EU-I, NU-85. NU-87, NU-88, IM-5, TNU-9, ESR-10, TNU-10 and combinations thereof.
- the crystallite size of the molecular sieve can vary depending on preparation conditions and may be tuned depending on the desired product and reactor conditions in the final stage of the reforming process.
- manipulating crystal size in order to change the selectivity of the catalyst has been described in U.S. Pat. No. 4,517,402 which is incorporated herein by reference. Additional references disclosing ZSM-5 are provided in U.S. Pat. No. 4,401,555 to Miller, hereby incorporated by reference in its entirety and in U.S. Pat. No. 5407558.
- the final stage catalyst is a high silica to alumina ZSM-5 having a silica to alumina molar ratio of at least 40:1, preferably at least 200:1 and more preferably at least 500:1.
- the final stage catalyst is high silica to alumina ZSM-5 with a small crystallite size wherein the crystallite size less than 10 microns, more preferably less than 5 microns, and most preferably less than 1 micron.
- ZSM-5 is more particularly described in U.S. Pat. No. 3,702,886 and
- ZSM-11 is more particularly described in U.S. Pat. No. 3 ,709,979 the entire contents of which are incorporated herein by reference.
- ZSM-12 is more particularly described in U.S. Pat. No. 3,832,449, the entire contents of which are incorporated herein by reference,
- ZSM-22 is more particularly described in U.S. Pat. Nos. 4,481 , 177,
- ZSM-23 is more particularly described in U.S. Pat. No. 4,076,842, the entire contents of which are incorporated herein by reference.
- ZSM-35 is more particularly described in U.S. Pat. No. 4,016,245, the entire contents of which are incorporated herein by reference.
- ZSM-38 is more particularly described in U.S. Pat. No. 4,046,859, the entire contents of which are incorporated herein by reference.
- ZSM-48 is more particularly described in U.S. Pat No. 4,397,827 the entire contents of which are incorporated herein by reference.
- zeolites useful in the practice of the present invention include, but are not limited to: Y zeolite, morderu ' te, ofifretite, omega, ferrierite, heulandite, SSZ-24, SSZ-25, SSZ-26, SSZ-31, SSZ-32, SSZ-33, SSZ-35, SSZ-37, SSZ-42, SSZ- 44, EU-I, NU-86, NU-87, UTD-I, MCM-22, MCM-36, MCM-56, and mixtures thereof.
- Examples of zeolite analogs useful in the process of the invention include borosilicates, where boron replaces at least a portion of the aluminum of the zeolitic form of the material.
- Examples of borosilicates are described in U.S. Pat. Nos. 4,268,420; 4,269,813; 4,327,236 to Klotz, the disclosures of which patents are incorporated herein.
- SAPOs Silicoaluminophosphates
- SAPOs are an example of nonzeolitic molecular sieves useful in the practice of the present invention.
- SAPOs comprise a molecular framework of corner-sharing [SiO4 ] tetrahedra, [A104 ] tetrahedra and [P04 ] tetrahedra linked by oxygen atoms.
- P/Al and Si/Al By varying the ratio of P/Al and Si/Al the acidity of the SAPO can be modified to minimize unwanted hydrocracking and maximize advantageous isomerization reactions.
- Preferred molar ratios of P/Al are from about 0.75 to 1.3 and preferred molar ratios of Si/Al are from about 0.08 to 0.5.
- Examples of a silcoaluminophosphate useful to the present invention include SAPO- 11, SAPO-31, and SAPO-41, which are also disclosed in detail in U.S. Pat. No. 5,135,638.
- the molecular sieves optionally include an amorphous support or binder such as amorphous alumina or amorphous silica.
- amorphous supports are selected from the group consisting of alumina, silica, titania, vanadia, chromia, zirconia, and mixtures thereof.
- Other supports such as naturally occurring or synthetic clays including, but not limited to, bentonite, kaolin, sepiolite, attapulgite, and hallyosite can be used in the process of this invention.
- the support may make up to 80% by weight of the catalyst.
- the molecular sieve catalysts according to the present invention may also contain one or more Group VIII metals, e.g., nickel, ruthenium, rhodium, palladium, indium or platinum.
- the preferred Group VIII metals are iridium, palladium, and platinum. Most preferred is platinum due to its high selectivity with regard to dehydrocyclization and stability under the dehydrocyclization reaction conditions.
- the preferred percentage of the Group VIII metals, such as platinum, in the catalyst is between O.lwt.% and 5 wt.%, more preferably from 0.3 wt.% to 2.5 wt.%.
- amorphous Group VIII metal catalysts include those detailed in "penultimate zone catalyst" above.
- Suitable catalysts for the final stage include platinum-containing amorphous reforming catalysts which optionally contain a promoter metal selected from the group consisting of a non-platinum Group VlII metal, e.g. rhenium, germanium, tin, lead, gallium, indium, and mixtures thereof.
- the platinum may exist within the catalyst as a compound such as the oxide, sulfide, halide, oxyhalide, in chemical combination with one or more other ingredients of the catalytic composite, or as an elemental metal.
- substantially all of the platinum exists in the catalytic composite in a reduced state.
- the preferred platinum component generally comprises from about 0.01 wt.% to 2 wt. % of the catalytic composite, preferably 0.05 to 1 wt. %, calculated on an elemental basis.
- the catalyst can also include a binder material.
- Binders include inorganic oxide supports such as alumina, silica, silica-alumina, titania, vanadia, chromia, zirconia, clays, zeolites, non-zeolitic molecular sieves, and mixtures thereof.
- the binder may make up to 80% by weight of the catalyst.
- any conventional impregnation, mulling, ion exchange or other known methods for adding the metals to the binder may be used.
- the Group VIII noble metals may be introduced into the amorphous binder by, for example, ion exchange, impregnation, carbonyl decomposition, adsorption from the gaseous phase, introduction during synthesis, and adsorption of metal vapor.
- the preferred technique is ion exchange or impregnation by the so-called incipient witness method. Preparations of such catalysts are taught, e.g., in U.S. Pat. Nos. 3,415,737; 4,636,298; and 4,645,586, the disclosures of which are incorporated herein by references.
- the catalyst optionally contains a halogen component.
- the halogen component may be either fluorine, chlorine, bromine, iodine or mixtures thereof. Chlorine is the preferred halogen component.
- the halogen component is generally present in a combined state with the inorganic-oxide support.
- the halogen component is preferably well dispersed throughout the catalyst and may comprise from more than 0.2 wt. % to about 15 wt. %, calculated on an elemental basis, of the final catalyst.
- Conventional acid catalysts such as solid acid catalyst including, but not limited to, acidic clays and acidic zeolites may also be used in the practice of the present invention as a final stage catalyst or as a component of the final stage catalyst.
- the zeolite molecular sieves discussed above with protons as counterions in the anionic zeolite framework are examples of solid acid catalysts.
- MCM-22 is an example of a layered aluminosilicate clay which can act as a solid acid.
- the final stage catalyst may comprise acidic or non acidic phyllosilicate clay compositions derived from the smectites such as those described in U.S. Pat. Nos. 4,248,739 and 5,414,185.
- Final stage catalysts may comprise any natural or synthetic clays having a lamellar structure, examples of which include, but are not limited to, bentonite, montmorillonite, berdellite, hectorite, vermiculite and the like. Layered clays can be delaminated or pillared to produce high surface area materials with a majority of their active sites or cations exposed at the crystal surface.
- the clays may further comprise active metals such as Group VIII metals, preferably platinum or palladium.
- active metals such as Group VIII metals, preferably platinum or palladium.
- the clays mentioned above may be used alone or admixed with inorganic oxide matrix components such as silica, alumina, silica-alumina, hydrogels and other clays.
- the clays may be any suitable size or shape as to ensure good contact with the reactants. Examples include powder, pellets, granules, extrudates, and spheres.
- reaction conditions in the final reforming stage are specified to effectively utilize the particular performance advantages of the catalyst used in the stage.
- the reaction pressure of the final reforming stage is less than the pressure in the penultimate stage. Low pressure in the final stage may lead to increased catalyst fouling.
- the process of the invention requires at least two stages- a penultimate and a final stage- catalyst regeneration in the final stage reactor can occur as needed to maintain high catalyst activity in the final stage. For example, as naphtha reforming is taking place in the penultimate reactor, catalyst regeneration can take place in the final reactor.
- the severity of the penultimate stage can be temporarily increased to meet RON targets for the total blended reformate which would otherwise be achieved with both the penultimate and final stages in operation.
- Operating the final reforming stage at a lower relative pressure than the penultimate stage minimizes the formation of light (C- J .) products while increasing the yield of high octane naphtha and overall liquid yield in the two stage process of the invention. Because the penultimate stage is operated at relatively mild conditions, catalyst life in that stage is lengthened while giving good yields of desired high octane products.
- the naphtha feed to the final stage is the intermediate reformate which is separated from the effluent of the penultimate stage.
- the intermediate reformate contacts the catalyst in the final stage at reforming reaction conditions, which reaction conditions include a temperature in the range from about 800 0 F to about 1100 0 F, a pressure in the range from about 40 psig to about 400 psig and a feed rate in the range of from about 0.5 LHSV to about 5 LHSV.
- the pressure in the final reforming stage is less than 100 psig.
- the pressure in the final reforming stage is from about 40 psig to about 200 psig, and more preferably from about 40 psig to about 100 psig.
- Hydrogen is preferably added as an additional feed to the final reforming stage, but it is not required. In embodiments, hydrogen added with the feed is recovered from the process and is recycled to the final stage.
- the effluent from the final reforming stage may contain light (i.e. C 4 - products and/or hydrogen) products which may be removed from the reformate prior to further processing or blending to make a fuel product.
- the Cs+ reformate herein referred to as the final reformate, which is produced in the final reforming stage has an increased RON relative to that of the intermediate reformate which is the feed to the final reforming stage.
- the final reformate may be used as a fuel or a fuel component by blending with other hydrocarbons.
- the RON of the final reformate is 80 or higher, preferably 90 or higher, and most preferably 95 or higher.
- the reformate is useful as a fuel or as a blend stock for a fuel.
- at least a portion of the reforraate from the final reforming stage is blended with at least a portion of the heavy reformate, which is recovered from the penultimate reforming stage; the blend may be used as a fuel or as a blend stock for a fuel.
- final effluent from the final reforming stage may contain light (i.e. C 4 - products and/or hydrogen) products which may be removed from the reformate in a final separation step prior to further processing for blending or use as a fuel.
- a hydrogen- rich stream may be separated from the effluent prior to the separation step, using, for example, a high pressure separator or other flash zone.
- Q- hydrocarbons in the effluent may also be separated in a preliminary flash zone, either along with the hydrogen or in a subsequent flash zone.
- the reformate which is produced in the final reforming stage has an increased RON relative to that of the intermediate reformate which is the feed to the final reforming stage.
- the RON of the final reformate is at least 90 or at least 95, or at least 98.
- the final reformate boils in the range from about 70 0 F to about 280 0 F.
- the final reformate comprises at least 70 vol% Cs-Ce hydrocarbons.
- the final reformate boils in the range from about 100 0 F to about 28O 0 F,
- the final reformate comprises at least 70 vol°/o C 6 - Ce hydrocarbons.
- the final reformate boils in the range from about 100 0 F to about 230 0 F. Ln some such embodiments, the final reformate comprises at least 70 vol% Cg-C 7 hydrocarbons.
- a final light stream may also be recovered from the final effluent.
- the final light stream boils in the range of about 70° to about 14O 0 F.
- the final light stream comprises at least 70 vol% Cs hydrocarbons.
- the reformate is useful as a fuel or as a blend stock for a fuel.
- at least a portion of the reformate from the final reforming stage is blended with at least a portion of the heavy reformate, which is recovered from the penultimate reforming stage; the blend may be used as a fuel or as a blend stock for a fuel.
- a naphtha boiling range fraction 5 which boils within the range of 5O 0 F to 55O 0 F passes into the reaction stage 10 at a feed rate in the range of about 0.5 hr" 1 to about 5 hr '1 LHSV.
- Reaction conditions in the reforming stage 10 include a temperature in the range from about 800 0 F to about 1100 0 F and a total pressure in the range of greater than 70 psig to about 400 psig.
- the effluent 11 from the penultimate stage is an upgraded product, in that the RON has been increased during reaction in the penultimate stage 10.
- the penultimate stage effluent 11 comprises hydrocarbons and hydrogen generated during reaction in the penultimate stage and at least some of the hydrogen (if any) added to the feed upstream of the penultimate stage.
- the effluent is separated in separation zone 20 into a hydrogen-rich stream 21, a C 4 - stream 22, an intermediate reformate 25 and a heavy reformate 26.
- this separation occurs in a single separation zone.
- this separation is done in sequential zones, with the hydrogen, and optionally the C 4 - stream, separated in one or more preliminary separation zones prior to the separation of the intermediate reformate 25 and the heavy reformate 26.
- the intermediate reformate 25 comprises a substantial amount of the Cs-Cg hydrocarbons contained in the effluent, with smaller quantities of C4 and C ? hydrocarbons. At least a portion of intermediate reformate 25 is passed to final reforming stage 30. Heavy reformate 26 contains a substantial amount of the C 9 + hydrocarbons contained in the effluent 11, and has an RON of greater than 98, preferably greater than 100.
- Intermediate reformate 25 is passed to final reforming stage 30 for contact with a catalyst comprising platinum and at least one medium pore molecular sieve, at reaction conditions which include a temperature in the range from about 800 0 F to about 1100 ⁇ F and a pressure in the range from about 50 psig to about 250 psig.
- Effluent 31 from the final reforming stage is separated in separation zone 40, yielding at least a hydrogen-rich stream 41, a C4- stream 42, and a final reformate stream 45.
- the final reformate stream boils in the Cs+ boiling range. As described above, this separation may take place in one, or multiple, separation zones, depending on the specific requirements of a particular process.
- the final reformate stream 45 may be further combined with the heavy reformate 26 before further processing or use as a fuel or fuel blend stock.
- Hydrogen-rich stream 41 is combined with hydrogen-rich stream 21 before using in other refinery processes, and C 4 - stream 42 is combined with C 4 - stream 22.
- a naphtha boiling range fraction 5 which boils within the range of 50F° to 550 0 F passes into the reaction stage 10 at a feed rate in the range of about 0.5 hr -1 to about 5 hr -1 LHSV.
- Reaction conditions in the reforming stage 10 include a temperature in the range from about 800 0 F to about 1100 0 F and a total pressure in the range of greater than 70 psig to about 400 psig.
- the effluent 11 from the penultimate stage is an upgraded product, in that the RON has been increased during reaction in the penultimate stage 10.
- the penultimate stage effluent 11 comprises hydrocarbons and hydrogen generated during reaction in the penultimate stage and at least some of the hydrogen (if any) added to the feed upstream of the penultimate stage,
- the effluent is separated in separation zone 20 into a hydrogen-rich stream 21, a C 4 - stream 22, a light reformate 23, an intermediate reformate 24 and a heavy reformate 26.
- this separation occurs in a single separation zone.
- this separation is done in sequential zones, with the hydrogen, and optionally the C4- stream, separated in one or more preliminary separation zones prior to the separation of the light reformate 23, the intermediate reformate 24 and the heavy reformate 26.
- the light reformate 23 comprises a substantial amount of the C 5 hydrocarbons contained in the effluent, with smaller quantities of C4 and Ce hydrocarbons.
- the intermediate stream comprises a substantial portion of the Ce - C 8 hydrocarbons contained in the effluent; the heavy reformate 26 contains a substantial amount of the C9+ hydrocarbons contained in the effluent 11.
- Intermediate reformate 24 is passed to final reforming stage 30 at a feed rate in the range of from about 0.5 hr -1 to about 5 hr -1 LHSV, for contact with a catalyst comprising platinum and at least one medium pore molecular sieve, at reaction conditions which include a temperature in the range from about 800 0 F to about 1100 0 F and a pressure in the range from about 50 psig to about 250 psig.
- Effluent 31 from the final reforming stage is separated in separation zone 40, yielding at least a hydrogen-rich stream 41, a C 4 - stream 42, a final Cs stream 43 and a final reformate stream 44.
- the final reformate stream boils in the Ce+ boiling range. As described above, this separation may take place in one, or multiple, separation zones, depending on the specific requirements of a particular process. As shown in the embodiment illustrated in Fig.
- the final reformate stream 44 is further combined with the heavy reformate 26 before further processing or use as a fuel or fuel blend stock
- hydrogen-rich stream 41 is combined with hydrogen-rich stream 21 before using in other refinery processes
- C 4 - stream 42 is combined with C4- stream 22
- final C 5 stream 43 is combined with C 5 stream 23.
- the RON values are calculated values, based on RON blending correlations applied to a composition analysis using gas chromatography. The method was calibrated to achieve a difference between measured RON values, determined by ASTM D2699, and calculated RON values of within ⁇ 0.8.
- This C5+ liquid product (penultimate effluent) collected from the penultimate stage had an API of 46.6, an RON of 89 and an ASTM D-2887 simulated distillation as given in Table 2.
- the Cs+ liquid product from Example 1 was distilled into an intermediate reformate and a heavy reformate.
- the intermediate reformate was found to represent 80 vol% of the C 5 + liquid product from Example 1.
- the intermediate reformate had an API of 55.7, an RON of 85 and an ASTM D-2887 simulated distillation as shown in Table 3, and was used as feed in a final reforming stage in Examples 3-6.
- the heavy reformate was found to represent 20 vol.% of the C 5 + liquid
- Example 1 -24- product from Example 1.
- the heavy reformate had an API of 28.9 and an RON of 105, and is further described in Table 4.
- Example 2 The intermediate reformate produced in Example 2 was used as feed to the final reforming stage which used a ZSM-5 zeolite based catalyst composited with 35% alumina binder material.
- the ZSM-5 had a SiO 2 ZAl 2 O 3 molar ratio of -2000 and was ion exchanged to the ammonium form before incorporating in a 65% zeolite/35% alumina extrudate.
- the extrudate was impregnated with 0.8% Pt, 0.3% Na, and 0.3% Mg by an incipient wetness procedure to make the final catalyst.
- the reaction conditions and experimental results are listed in Tables 4 and 5.
- Example 2 A product which was produced in the final stage reforming of the intermediate reformate in Example 3 was blended with the heavy reformate (Example 2) which was not subjected to the final stage reforming.
- the total RON of Cs+, total Cs+ yield and total H 2 production of the blended final product are given in Table 4 based on using the total C 5 + penultimate effluent as feed (which is distilled into intermediate reformate and heavy reformate in Example 2).
- the results are compared to those obtained from Comparative Example 1 where the total C 5 + product was produced from the total C 5 + penultimate effluent as feed, without distillation into an intermediate and heavy reformate.
- Example 2 The intermediate reformate produced in Example 2 was contacted with the platinum/rhenium on alumina based catalyst described in Example 1 in a final reforming stage.
- the reaction conditions and experimental results are listed in Table 5 and compared with Example 3.
- Example 2 The intermediate reformate produced in Example 2 is contacted with the platinum/rhenium on alumina based catalyst described in Example 1 in a final reforming stage wherein the final reforming stage pressure is less than 200 psig.
- the final reforming stage is run at the same temperatures, LHSV, and hydrogen to hydrocarbon ratio as in Example 5.
- the C 5 + liquid yield for Example 6 is higher than the C 5 +liquid yield for Example 5 at the same or similar RON.
- the higher Cs+ liquid yield of Example 6 as compared to Example 5 illustrates the benefits of running the final stage at a lower pressure than the penultimate stage with a platinum/rhenium on alumina catalyst.
- Example 1 The total Cs+ product produced in Example 1, without distillation into an intermediate and heavy reformate, was contacted with the ZSM-5 based catalyst of Example 3 in a final reforming stage at 930 0 F, 80 psig, 2:1 molar ratio of hydrogen to hydrocarbon and 1.5 hr -1 LHSV feed rate.
- the C 5 + liquid yield was 89.9 wt,% and RON of the C 5 + liquid product from the final reforming stage was 97.4.
- the hydrogen production was 190 standard cubic feet per barrel feed.
- Example 3 RON of Cs+, Cs+ yield and H2 production of the product are given based on the intermediate reformate as feed.
- Example 4 Total RON of C 5 +, total C 5 + yield and total H 2 production are given based on the total C5+ penultimate effluent as feed (which is distilled into intermediate reformate and heavy reformate in Example 2).
- the final product of Example 4 consists of a blend of (i) the product from the final stage reforming of the intermediate reformate and (ii) the heavy reformate which is not subjected to the final stage reforming.
- Table 4 demonstrates the benefits of the present invention when using the intermediate reformate as the feedstock at lower reaction temperature (900 0 F vs. 930 0 F) by showing improved hydrogen yield, higher C s + liquid yield and higher RON versus the full boiling range Cs+ feedstock.
- Table 5 demonstrates a preferred embodiment of the present invention, wherein the pressure of the final stage reactor is lower than the pressure in the penultimate stage. Improvements at the lower pressure with the ZSM-5 based catalyst in terms of Cs+ yield and hydrogen production at similar C 5 + RON are seen versus the Pt/Re catalyst at higher pressure.
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Abstract
Description
Claims
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
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EP09758935A EP2297281A2 (en) | 2008-06-05 | 2009-05-12 | Multi-stage reforming process to produce high octane gasoline |
AU2009255497A AU2009255497A1 (en) | 2008-06-05 | 2009-05-12 | Multi-stage reforming process to produce high octane gasoline |
CN2009801263618A CN102083945A (en) | 2008-06-05 | 2009-05-12 | Multi-stage reforming process to produce high octane gasoline |
JP2011512504A JP2011522926A (en) | 2008-06-05 | 2009-05-12 | Catalytic reforming process for high-octane gasoline production |
CA2726906A CA2726906A1 (en) | 2008-06-05 | 2009-05-12 | Multi-stage reforming process to produce high octane gasoline |
Applications Claiming Priority (2)
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US12/134,153 | 2008-06-05 | ||
US12/134,153 US20090301934A1 (en) | 2008-06-05 | 2008-06-05 | Multi-stage reforming process to produce high octane gasoline |
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WO2009148772A2 true WO2009148772A2 (en) | 2009-12-10 |
WO2009148772A3 WO2009148772A3 (en) | 2010-01-21 |
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PCT/US2009/043580 WO2009148772A2 (en) | 2008-06-05 | 2009-05-12 | Multi-stage reforming process to produce high octane gasoline |
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US (1) | US20090301934A1 (en) |
EP (1) | EP2297281A2 (en) |
JP (1) | JP2011522926A (en) |
CN (1) | CN102083945A (en) |
AU (1) | AU2009255497A1 (en) |
CA (1) | CA2726906A1 (en) |
WO (1) | WO2009148772A2 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105778986A (en) * | 2016-02-23 | 2016-07-20 | 新疆恒晟能源科技有限公司 | Method for producing mixed arene from naphtha |
Families Citing this family (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8658021B2 (en) | 2008-06-05 | 2014-02-25 | Chevron U.S.A. Inc. | Multi-stage reforming process to produce high octane gasoline |
US8366909B2 (en) * | 2009-02-26 | 2013-02-05 | Chevron U.S.A. Inc. | Reforming process at low pressure |
US20120024752A1 (en) * | 2010-07-28 | 2012-02-02 | Chevron U.S.A. Inc. | Multi-Stage Hydroprocessing for the Production of High Octane Naphtha |
US8763364B2 (en) * | 2011-04-18 | 2014-07-01 | Chevron U.S.A. Inc. | Treatment of cold start engine exhaust |
CN102994146A (en) * | 2011-09-19 | 2013-03-27 | 中国石油化工集团公司 | System and method for improving liquid yield of reforming device |
US20130158320A1 (en) * | 2011-12-15 | 2013-06-20 | Uop Llc | Initial hydrotreating of naphthenes with subsequent high temperature reforming |
CN107868674B (en) * | 2016-09-26 | 2019-11-15 | 中国石油化工股份有限公司 | A kind of Benzin naphtha catalytic reforming method |
US10611705B2 (en) * | 2017-05-03 | 2020-04-07 | Exxonmobil Chemical Patents Inc. | Process for conversion of acyclic C5 compounds to cyclic C5 compounds and formulated catalyst compositions used therein |
US11066345B2 (en) * | 2019-06-27 | 2021-07-20 | Uop Llc | Processes for increasing an octane value of a gasoline component |
CN113980702B (en) * | 2021-12-27 | 2022-04-15 | 中化弘润石油化工有限公司 | Environment-friendly process method for producing gasoline for vehicles from naphtha |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3640818A (en) * | 1969-10-31 | 1972-02-08 | Exxon Research Engineering Co | Hydroforming naphthas |
US3729409A (en) * | 1970-12-24 | 1973-04-24 | Mobil Oil Corp | Hydrocarbon conversion |
US3770614A (en) * | 1971-01-15 | 1973-11-06 | Mobil Oil Corp | Split feed reforming and n-paraffin elimination from low boiling reformate |
US4443326A (en) * | 1981-10-16 | 1984-04-17 | Chevron Research Company | Two-step reforming process |
US5347061A (en) * | 1993-03-08 | 1994-09-13 | Mobil Oil Corporation | Process for producing gasoline having lower benzene content and distillation end point |
Family Cites Families (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4190519A (en) * | 1978-10-23 | 1980-02-26 | Chevron Research Company | Combination process for upgrading naphtha |
US4181599A (en) * | 1978-10-23 | 1980-01-01 | Chevron Research Company | Naphtha processing including reforming, isomerization and cracking over a ZSM-5-type catalyst |
US4401555A (en) * | 1980-04-28 | 1983-08-30 | Chevron Research Company | Hydrocarbon conversion with low-sodium crystalline silicates |
US4457832A (en) * | 1983-01-19 | 1984-07-03 | Chevron Research Company | Combination catalytic reforming-isomerization process for upgrading naphtha |
US4627909A (en) * | 1985-05-02 | 1986-12-09 | Chevron Research Company | Dual recycle pressure-step reformer with cyclic regeneration |
US5182012A (en) * | 1987-09-16 | 1993-01-26 | Chevron Research And Technology Company | Crystalline silicate catalyst and processes using the catalyst |
US4764267A (en) * | 1987-10-29 | 1988-08-16 | Chevron Research Company | Multi-stage catalytic reforming with high rhenium content catalyst |
US6063723A (en) * | 1990-03-02 | 2000-05-16 | Chevron U.S.A. Inc. | Sulfur tolerant zeolite catalyst |
US5171691A (en) * | 1990-03-02 | 1992-12-15 | Chevron Research And Technology Company | Method for controlling multistage reforming process to give high octane barrel per calendar day throughput |
US5407558A (en) * | 1990-03-02 | 1995-04-18 | Chevron Research And Technology Company | Method for controlling multistage aromatization process to give high aromatic barrel per calendar day throughput |
US5169813A (en) * | 1990-03-02 | 1992-12-08 | Chevron Research And Technology Company | Dehydrocyclization or catalytic reforming sulfur tolerant zeolite catalyst |
US5073250A (en) * | 1990-03-02 | 1991-12-17 | Chevron Research & Technology Company | Staged catalyst reforming to produce optimum octane barrel per calendar day reformate production |
JPH05507096A (en) * | 1990-03-02 | 1993-10-14 | シェブロン リサーチ アンド テクノロジー カンパニー | Multi-step modification method |
US5376259A (en) * | 1990-03-02 | 1994-12-27 | Chevron Research And Technology Company | Staged catalyst processing to produce optimum aromatic barrel per calendar day aromatic production |
US5294328A (en) * | 1990-05-24 | 1994-03-15 | Uop | Production of reformulated gasoline |
US5430218A (en) * | 1993-08-27 | 1995-07-04 | Chevron U.S.A. Inc. | Dehydrogenation using dehydrogenation catalyst and polymer-porous solid composite membrane |
-
2008
- 2008-06-05 US US12/134,153 patent/US20090301934A1/en not_active Abandoned
-
2009
- 2009-05-12 EP EP09758935A patent/EP2297281A2/en not_active Withdrawn
- 2009-05-12 JP JP2011512504A patent/JP2011522926A/en active Pending
- 2009-05-12 CN CN2009801263618A patent/CN102083945A/en active Pending
- 2009-05-12 AU AU2009255497A patent/AU2009255497A1/en not_active Abandoned
- 2009-05-12 CA CA2726906A patent/CA2726906A1/en not_active Abandoned
- 2009-05-12 WO PCT/US2009/043580 patent/WO2009148772A2/en active Application Filing
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3640818A (en) * | 1969-10-31 | 1972-02-08 | Exxon Research Engineering Co | Hydroforming naphthas |
US3729409A (en) * | 1970-12-24 | 1973-04-24 | Mobil Oil Corp | Hydrocarbon conversion |
US3770614A (en) * | 1971-01-15 | 1973-11-06 | Mobil Oil Corp | Split feed reforming and n-paraffin elimination from low boiling reformate |
US4443326A (en) * | 1981-10-16 | 1984-04-17 | Chevron Research Company | Two-step reforming process |
US5347061A (en) * | 1993-03-08 | 1994-09-13 | Mobil Oil Corporation | Process for producing gasoline having lower benzene content and distillation end point |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105778986A (en) * | 2016-02-23 | 2016-07-20 | 新疆恒晟能源科技有限公司 | Method for producing mixed arene from naphtha |
Also Published As
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EP2297281A2 (en) | 2011-03-23 |
CA2726906A1 (en) | 2009-12-10 |
WO2009148772A3 (en) | 2010-01-21 |
JP2011522926A (en) | 2011-08-04 |
US20090301934A1 (en) | 2009-12-10 |
CN102083945A (en) | 2011-06-01 |
AU2009255497A1 (en) | 2009-12-10 |
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