JP2018500151A - 高い酸点分布を有する安定化yゼオライトを高含有する中間留分水素化分解触媒 - Google Patents
高い酸点分布を有する安定化yゼオライトを高含有する中間留分水素化分解触媒 Download PDFInfo
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- JP2018500151A JP2018500151A JP2017523454A JP2017523454A JP2018500151A JP 2018500151 A JP2018500151 A JP 2018500151A JP 2017523454 A JP2017523454 A JP 2017523454A JP 2017523454 A JP2017523454 A JP 2017523454A JP 2018500151 A JP2018500151 A JP 2018500151A
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- Prior art keywords
- zeolite
- hydrocracking
- stabilized
- hydrocracking catalyst
- catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- 238000004517 catalytic hydrocracking Methods 0.000 title claims abstract description 104
- 239000003054 catalyst Substances 0.000 title claims abstract description 88
- 239000010457 zeolite Substances 0.000 title claims abstract description 49
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 44
- 238000009826 distribution Methods 0.000 title claims abstract description 25
- 239000002253 acid Substances 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 claims description 32
- 229910052751 metal Inorganic materials 0.000 claims description 18
- 239000002184 metal Substances 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 14
- 229930195733 hydrocarbon Natural products 0.000 claims description 11
- 150000002430 hydrocarbons Chemical class 0.000 claims description 9
- 238000005984 hydrogenation reaction Methods 0.000 claims description 8
- 230000000737 periodic effect Effects 0.000 claims description 8
- 239000004215 Carbon black (E152) Substances 0.000 claims description 7
- 239000011959 amorphous silica alumina Substances 0.000 claims description 6
- 238000005336 cracking Methods 0.000 claims description 4
- 239000000047 product Substances 0.000 description 31
- 238000009835 boiling Methods 0.000 description 20
- 239000007789 gas Substances 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 15
- 238000004519 manufacturing process Methods 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 239000003921 oil Substances 0.000 description 12
- 239000011148 porous material Substances 0.000 description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 10
- 229910052739 hydrogen Inorganic materials 0.000 description 10
- 239000001257 hydrogen Substances 0.000 description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical compound CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 229910052717 sulfur Inorganic materials 0.000 description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 7
- 238000005470 impregnation Methods 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 239000011593 sulfur Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- QMMFVYPAHWMCMS-UHFFFAOYSA-N Dimethyl sulfide Chemical compound CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 description 6
- 229910052759 nickel Inorganic materials 0.000 description 6
- 229910052721 tungsten Inorganic materials 0.000 description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 5
- 238000004821 distillation Methods 0.000 description 5
- 229910052750 molybdenum Inorganic materials 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- 239000002585 base Substances 0.000 description 4
- UHOVQNZJYSORNB-MZWXYZOWSA-N benzene-d6 Chemical compound [2H]C1=C([2H])C([2H])=C([2H])C([2H])=C1[2H] UHOVQNZJYSORNB-MZWXYZOWSA-N 0.000 description 4
- 239000002283 diesel fuel Substances 0.000 description 4
- 239000003502 gasoline Substances 0.000 description 4
- 239000000395 magnesium oxide Substances 0.000 description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 239000002808 molecular sieve Substances 0.000 description 4
- 229920001021 polysulfide Polymers 0.000 description 4
- 239000005077 polysulfide Substances 0.000 description 4
- 150000008117 polysulfides Polymers 0.000 description 4
- 238000004064 recycling Methods 0.000 description 4
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000003039 volatile agent Substances 0.000 description 4
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 230000033228 biological regulation Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000010779 crude oil Substances 0.000 description 3
- 238000006356 dehydrogenation reaction Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000003607 modifier Substances 0.000 description 3
- -1 naphtha Substances 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 229910003452 thorium oxide Inorganic materials 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- 208000036574 Behavioural and psychiatric symptoms of dementia Diseases 0.000 description 2
- 239000007848 Bronsted acid Substances 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- LTPBRCUWZOMYOC-UHFFFAOYSA-N beryllium oxide Inorganic materials O=[Be] LTPBRCUWZOMYOC-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 239000003245 coal Substances 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
- 238000010276 construction Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 238000007327 hydrogenolysis reaction Methods 0.000 description 2
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000010454 slate Substances 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 238000005486 sulfidation Methods 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- FRWYFWZENXDZMU-UHFFFAOYSA-N 2-iodoquinoline Chemical compound C1=CC=CC2=NC(I)=CC=C21 FRWYFWZENXDZMU-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 241001364569 Cofana spectra Species 0.000 description 1
- 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 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000008186 active pharmaceutical agent Substances 0.000 description 1
- 125000002015 acyclic group Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 1
- HIVLDXAAFGCOFU-UHFFFAOYSA-N ammonium hydrosulfide Chemical compound [NH4+].[SH-] HIVLDXAAFGCOFU-UHFFFAOYSA-N 0.000 description 1
- UYJXRRSPUVSSMN-UHFFFAOYSA-P ammonium sulfide Chemical compound [NH4+].[NH4+].[S-2] UYJXRRSPUVSSMN-UHFFFAOYSA-P 0.000 description 1
- XYXNTHIYBIDHGM-UHFFFAOYSA-N ammonium thiosulfate Chemical compound [NH4+].[NH4+].[O-]S([O-])(=O)=S XYXNTHIYBIDHGM-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 150000001934 cyclohexanes Chemical class 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 238000004508 fractional distillation Methods 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000028161 membrane depolarization Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 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
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001741 organic sulfur group Chemical group 0.000 description 1
- 239000010815 organic waste Substances 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- ZCUFMDLYAMJYST-UHFFFAOYSA-N thorium dioxide Chemical compound O=[Th]=O ZCUFMDLYAMJYST-UHFFFAOYSA-N 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
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- 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
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
-
- 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
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/16—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J29/166—Y-type faujasite
-
- 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
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/10—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing iron group metals, noble metals or copper
- B01J29/106—Y-type faujasite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
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- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
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- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/66—Pore distribution
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
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Abstract
Description
<導入>
「周期表」は、IUPAC元素周期表の2007年6月22日付けの版を指し、そして周期表の族の番号付け体系は、Chemical and Engineering News、63(5)巻、27頁(1985年)に記載されている通りである。
(a)ブレンステッド酸性度:T.J.Gricus Kofke、R.K.Gorte、W.E.FarnethによるJ.Catal.114巻、34−45頁、1988年;T.J.Gricus Kifke、R.J.Gorte、G.T.KokotailoによるJ.Catal.115巻、265−272頁、1989年;J.G.Tittensor、R.J.Gorte及びD.M.ChapmanによるJ.Catal.138巻、714−720頁、1992年、の公開された記載から適応されたイソプロピルアミン−温度−プログラム脱着(IPam TPD)によって決定される。
(b)SiO2/Al2O3比(SAR):ICP元素分析によって決定される。無限大(∞)のSARは、ゼオライト中にアルミニウムが存在しない場合、即ち、シリカ対アルミナのモル比が、無限大となる場合を表す。その場合、モレキュラーシーブ(molecular sieve)は、本質的に全てがシリカから構成される。
(c)表面積:沸騰温度でのN2吸着によって決定される。BET表面積は、P/P0=0.050、0.088、0.125、0.163、及び0.200にて、5ポイント法により計算される。サンプルは、最初に、水又は有機物のような吸着した揮発性物質を除去するために、乾燥N2の流れの存在下で、400℃にて6時間、前処理される。
(d)ナノ細孔及びミクロ細孔の容積:沸騰温度でのN2吸着によって決定される。ミクロ細孔容積は、P/P0=0.050、0.088、0.125、0.163、及び0.200にて、t-プロット法により計算される。サンプルは、最初に、水又は有機物のような吸着した揮発性物質を除去するように、乾燥N2の流れの存在下で、400℃にて6時間、前処理される。
(e)ナノ細孔径:沸騰温度でのN2吸着によって決定される。メソ細孔細孔径は、E.P.Barrett、L.G.Joyner、及びP.P.Halendaによる「多孔質物質の細孔容積と面積分布の決定.I.窒素等温線からコンピュータを使用した計算」J.Am.Chem.Soc.73巻、373から380頁、1951年、に記載のBJH法によりN2等温線から計算される。サンプルは、最初に、水又は有機物のような吸着した揮発性物質を除去するように、乾燥N2流れの存在下で、400℃にて6時間、前処理される。
(f)全ナノ細孔容積:P/P0=0.990にて沸騰温度でのN2吸着によって決定される。サンプルは、最初に、水又は有機物のような吸着した揮発性物質を除去するように、乾燥N2流れの存在下で、400℃にて6時間、前処理される。
(g)ユニットセルサイズ:X線粉末回折により決定される。
(h)API比重:ASTM D4052-11により決定される、水と比較した石油供給原料/生成物の比重(gravity)。
(i)酸点密度:材料のブレンステッド酸点分布を定量化するためのイソプロピルアミン(IPAm)の昇温脱離(temperature−programmed desorption:TPD)については、MaesenとHertzenbergによるJournal of Catalysis 182巻,270から273頁(1999年)に記載されている。
(j)酸点分布及びインデックスファクター:E.J.M.Hensen、D.G.Poduval、D.A.J.Michel Ligthart、J.A.Rob van Veen、M.S.RiguttoによるJ.Phys.Chem.C.I.114巻、8363から8374頁、2010年により公開された記載から適応されるH−D交換FTIRにより決定される酸点分布。FTIR測定に先立って、サンプルを1時間、400から450℃にて1×10−5Torr未満の減圧下で加熱した。次に、サンプルにC6D6を添加して80℃で平衡にした。C6D6の(添加)前後で、OH及びOD伸縮領域についてスペクトルを収集した。ブレンステッド酸点密度は、第1の高周波OD(HF)として2676cm−1、第2の高周波OD(HF’)として2653cm−1、第1の低周波OD(LF)として2632cm−1及び2620cm−1、並びに第2の低周波OD(LF’)として2600cm−1のピークの積分面積を使用することによって決定した。酸点分布インデックス(ASDI)ファクターは以下の式により決定した:ASDI=(HF’+LF’)/(HF+LF);これは、ゼオライトサンプル中の過活性部位の含有量を表す。
供給原料の水素化分解を行うために使用するHNPV SY系水素化分解触媒には、HNPV SYゼオライト、担体成分、非晶質シリカアルミナ(ASA)材料、1種以上の金属、及び任意選択的に1種以上の促進剤が含まれる。最終的なHNPV SY触媒のバルク乾燥重量に基づく最終的なHNPV SY触媒の組成物を、以下の表1に記載する。
一般に、本明細書に記載される水素化分解触媒は、以下の段階により調製される:
(a)HNPV SY、ASA及び担体を混合し且つ解膠して、押出物ベースを作成する段階;
(b)前記ベースを、少なくとも1種の金属を含有する金属含浸溶液に含浸する段階;及び
(c)前記金属担持押出物を乾燥及びか焼に供することを含む、前記押出物を後処理する段階。
本明細書に記載される水素化分解触媒は、例えば、ビスブロークン軽油、重質コーカー軽油、残油水素化分解又は残油脱硫から誘導される軽油、他の熱分解油、脱アスファルト油、フィッシャー・トロプシュ誘導供給原料、FCCユニットからのサイクル油、重質石炭由来留分、石炭ガス化副生成物タール、及び重質シェール由来油、有機系廃油、例えばパルプ/製紙工場又は廃バイオマスの熱分解ユニットからのもの等の、従来の1つ又は2つのステージの水素化分解プロセスを使用することによっては、通常は、中間留分の生成には至らない不利な供給原料を含む種々の炭化水素系供給原料を水素化処理するのに適している。
(a)炭化水素系供給原料を水素化分解して第1ステージの水素化分解流出物を生成する段階;
(b)前記水素化分解供給原料を常圧蒸留により蒸留して、少なくとも1種の中間留分画分と常圧塔底画分を形成する段階;
(c)前記常圧塔底画分を減圧蒸留により更に蒸留して、サイドカット減圧軽油画分と重質減圧軽油FCC供給原料を形成する段階;
(d)前記サイドカット減圧軽油画分を水素化分解して、第2ステージ水素化分解流出物を形成する段階;及び
(e)前記第2ステージ水素化分解流出物を前記第1ステージ水素化分解流出物に組合せる段階。
本発明のプロセスは、約380から700°F(193から371℃)の範囲で沸騰する中間留分画分の生成に特に有用である。中間留分の成分の少なくとも75体積%、好ましくは、少なくとも85体積%は、380°F(193℃)より高い標準沸点を有する。中間留分の成分の少なくとも約75体積%、好ましくは、少なくとも85体積%は、700°F(371℃)よりも低い標準沸点を有する。
<水素化分解触媒の調製>
従来のUSY系水素化分解触媒は、以下の手順で調製された。本明細書に記載される56.4重量%のUSY、21重量%の非晶質シリコアルミナート粉末(SasolのSiral−30)、及び22.6重量%の擬ベーマイトアルミナ粉末(SasolのCATAPAL C1)を十分に混合した。この混合物に、希釈したHNO3の酸水溶液(3重量%)を添加して、押出可能なペーストを形成した。このペーストを1/16”(インチ)の非対称四辺形に押し出し、そして248°F(120℃)で1時間乾燥させた。乾燥押出物を、過剰の乾燥空気をパージしながら1100°F(593℃)で1時間か焼し、そして室温まで冷却した。
<水素化分解性能>
従来のUSY系及びHNPV USY系の触媒を使用して、典型的な中東のVGOを処理した。フィード特性を表11に示す。実験は、パイロットプラントユニットにて、2300psigの全圧及び1.0から2.2LHSVの下で操作した。フィードは、水素化分解ゾーンに流入する前に、水素化処理触媒を充填した触媒床を通過した。フィードの導入前に、触媒を、DMDS(気相硫化)か、或いはDMDS(液相硫化)を入れたディーゼルフィードのいずれかで活性化した。
Claims (15)
- 担体と、
非晶質シリカアルミナ材料と、
0.02から0.12の間の酸点分布インデックスファクターを有する安定化Yゼオライトと、
周期表6族及び8から10族の元素からなる群から選択される少なくとも1種の金属と
を含む、水素化分解触媒。 - 前記安定化Yゼオライトが、20nmから50nmの範囲に0.15から0.6cc/gのナノ細孔容積を有する高ナノ細孔容積の安定化Yゼオライトである、請求項1に記載の水素化分解触媒。
- 20から30%の前記ナノ細孔容積が8nmから20nmの範囲にある、請求項2に記載の水素化分解触媒。
- 40から60%の前記ナノ細孔容積が20nmから50nmの範囲にある、請求項2に記載の水素化分解触媒。
- 15から25%の前記ナノ細孔容積が50nmより大きい、請求項2に記載の水素化分解触媒。
- 高ナノ細孔容積の安定化Yゼオライトが、0.06から0.12の間の酸点分布インデックスファクターを有する、請求項1に記載の水素化分解触媒。
- 高ナノ細孔容積の安定化Yゼオライトが、0.08から0.11の間の酸点分布インデックスファクターを有する、請求項1に記載の水素化分解触媒。
- 炭化水素系供給原料を水素化分解触媒と水素化分解条件下で接触させて、水素化分解された流出物を生成することを含む炭化水素系供給原料を水素化分解する方法であって;
前記水素化分解触媒が、
担体と、
非晶質シリカアルミナ材料と、
0.02から0.12の間の酸点分布インデックスファクターを有する安定化Yゼオライトと、
周期表6族及び8から10族の元素からなる群から選択される少なくとも1種の金属と
を含む、方法。 - 前記安定化Yゼオライトが、20nmから50nmの範囲に0.15から0.6cc/gのナノ細孔容積を有する高ナノ細孔容積の安定化Yゼオライトである、請求項8に記載の方法。
- 20から30%の前記ナノ細孔容積が8nmから20nmの範囲にある、請求項9に記載の方法。
- 40から60%の前記ナノ細孔容積が20nmから50nmの範囲にある、請求項9に記載の方法。
- 15から25%の前記ナノ細孔容積が50nmより大きい、請求項9に記載の方法。
- 高ナノ細孔容積の安定化Yゼオライトが、0.06と0.12の間の酸点分布インデックスファクターを有する、請求項8に記載の方法。
- 高ナノ細孔容積の安定化Yゼオライトが、0.08と0.11の間の酸点分布インデックスファクターを有する、請求項8に記載の方法。
- 前記水素化分解された流出物が、380から700°F(193から371℃)の範囲の重質中間留分生成物である、請求項8に記載の方法。
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EP (1) | EP3212329A2 (ja) |
JP (3) | JP2018500151A (ja) |
KR (2) | KR20170078715A (ja) |
CN (2) | CN117960231A (ja) |
AU (1) | AU2015339950A1 (ja) |
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RU (1) | RU2017118406A (ja) |
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KR101895497B1 (ko) * | 2016-10-26 | 2018-10-04 | 에쓰대시오일 주식회사 | 경방향족 탄화수소 제조용 수소화 분해 반응 촉매, 이의 제조방법 및 이를 이용한 경방향족 탄화수소의 제조방법 |
CN113171802A (zh) * | 2020-11-30 | 2021-07-27 | 谷育英 | 一种丙烷脱氢制丙烯催化剂的活化还原方法 |
US11590485B2 (en) | 2021-01-13 | 2023-02-28 | Saudi Arabian Oil Company | Process for modifying a hydroprocessing catalyst |
FR3130640A1 (fr) | 2021-12-21 | 2023-06-23 | IFP Energies Nouvelles | Catalyseur comprenant un support à base de matrice silico-aluminique et de zéolithe, sa préparation et procédé d’hydrocraquage de charges hydrocarbonées |
CN116351391A (zh) * | 2022-11-23 | 2023-06-30 | 中国矿业大学 | 一种煤气化细渣合成沸石/多孔炭复合吸附剂材料的制备方法及其应用 |
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Also Published As
Publication number | Publication date |
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US20160121313A1 (en) | 2016-05-05 |
CN117960231A (zh) | 2024-05-03 |
CA2966402A1 (en) | 2016-05-06 |
AU2015339950A8 (en) | 2017-05-25 |
RU2017118406A (ru) | 2018-12-04 |
CA2966402C (en) | 2023-09-19 |
JP2020182947A (ja) | 2020-11-12 |
EP3212329A2 (en) | 2017-09-06 |
SG11201703503UA (en) | 2017-05-30 |
AU2015339950A1 (en) | 2017-05-18 |
CN106999919A (zh) | 2017-08-01 |
SG10202004621UA (en) | 2020-06-29 |
JP2023093493A (ja) | 2023-07-04 |
KR20220165834A (ko) | 2022-12-15 |
WO2016069071A2 (en) | 2016-05-06 |
KR20170078715A (ko) | 2017-07-07 |
RU2017118406A3 (ja) | 2018-12-04 |
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