JP2009530090A - シリコアルミノホスフェート異性化触媒 - Google Patents
シリコアルミノホスフェート異性化触媒 Download PDFInfo
- Publication number
- JP2009530090A JP2009530090A JP2009500764A JP2009500764A JP2009530090A JP 2009530090 A JP2009530090 A JP 2009530090A JP 2009500764 A JP2009500764 A JP 2009500764A JP 2009500764 A JP2009500764 A JP 2009500764A JP 2009530090 A JP2009530090 A JP 2009530090A
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- JP
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- Prior art keywords
- catalyst system
- sapo
- alumina
- matrix
- 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.)
- Granted
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- 239000003054 catalyst Substances 0.000 title claims abstract description 80
- 238000006317 isomerization reaction Methods 0.000 title description 9
- 239000002808 molecular sieve Substances 0.000 claims abstract description 33
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910052751 metal Inorganic materials 0.000 claims abstract description 31
- 239000002184 metal Substances 0.000 claims abstract description 31
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000011159 matrix material Substances 0.000 claims abstract description 28
- 239000000203 mixture Substances 0.000 claims abstract description 28
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 24
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 20
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 20
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 20
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 12
- 239000011734 sodium Substances 0.000 claims abstract description 11
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 10
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 9
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 8
- 239000011574 phosphorus Substances 0.000 claims abstract description 8
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000010936 titanium Substances 0.000 claims abstract description 5
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 5
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 4
- 239000010948 rhodium Substances 0.000 claims abstract description 4
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 45
- 239000011148 porous material Substances 0.000 claims description 17
- 238000005342 ion exchange Methods 0.000 claims description 11
- 239000001257 hydrogen Substances 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- 241001465754 Metazoa Species 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 239000011733 molybdenum Substances 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 238000012545 processing Methods 0.000 claims description 3
- 239000010937 tungsten Substances 0.000 claims description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 239000010775 animal oil Substances 0.000 claims description 2
- 235000015112 vegetable and seed oil Nutrition 0.000 claims description 2
- 239000008158 vegetable oil Substances 0.000 claims description 2
- 235000019737 Animal fat Nutrition 0.000 claims 1
- 235000019484 Rapeseed oil Nutrition 0.000 claims 1
- 235000019864 coconut oil Nutrition 0.000 claims 1
- 239000003240 coconut oil Substances 0.000 claims 1
- 230000001351 cycling effect Effects 0.000 claims 1
- 235000012424 soybean oil Nutrition 0.000 claims 1
- 239000003549 soybean oil Substances 0.000 claims 1
- 239000003760 tallow Substances 0.000 claims 1
- 239000003921 oil Substances 0.000 description 20
- 235000019198 oils Nutrition 0.000 description 20
- 239000000047 product Substances 0.000 description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 10
- 238000009835 boiling Methods 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 229910052782 aluminium Inorganic materials 0.000 description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 239000010703 silicon Substances 0.000 description 8
- 229910052710 silicon Inorganic materials 0.000 description 8
- 150000001768 cations Chemical class 0.000 description 7
- 238000005336 cracking Methods 0.000 description 7
- 239000013078 crystal Substances 0.000 description 7
- 150000002739 metals Chemical class 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000002425 crystallisation Methods 0.000 description 6
- 230000008025 crystallization Effects 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 239000000314 lubricant Substances 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000001993 wax Substances 0.000 description 6
- 239000002841 Lewis acid Substances 0.000 description 5
- 239000002585 base Substances 0.000 description 5
- 238000001354 calcination Methods 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 150000007517 lewis acids Chemical class 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- -1 SAPO-11 Chemical compound 0.000 description 4
- 229910004298 SiO 2 Inorganic materials 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
- 238000007710 freezing Methods 0.000 description 4
- 230000008014 freezing Effects 0.000 description 4
- 238000005984 hydrogenation reaction Methods 0.000 description 4
- 239000012188 paraffin wax Substances 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 238000004517 catalytic hydrocracking Methods 0.000 description 3
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 239000003502 gasoline Substances 0.000 description 3
- 238000005216 hydrothermal crystallization Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 239000002879 Lewis base Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003925 fat Substances 0.000 description 2
- 235000019197 fats Nutrition 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000005194 fractionation Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 150000007527 lewis bases Chemical class 0.000 description 2
- 230000001050 lubricating effect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 229910017090 AlO 2 Inorganic materials 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 241000269350 Anura Species 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910004283 SiO 4 Inorganic materials 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- YCOASTWZYJGKEK-UHFFFAOYSA-N [Co].[Ni].[W] Chemical compound [Co].[Ni].[W] YCOASTWZYJGKEK-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000002015 acyclic group Chemical group 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 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
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 229910001422 barium ion Inorganic materials 0.000 description 1
- 239000002199 base oil Substances 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000010724 circulating oil Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- WHDPTDWLEKQKKX-UHFFFAOYSA-N cobalt molybdenum Chemical compound [Co].[Co].[Mo] WHDPTDWLEKQKKX-UHFFFAOYSA-N 0.000 description 1
- NVIVJPRCKQTWLY-UHFFFAOYSA-N cobalt nickel Chemical compound [Co][Ni][Co] NVIVJPRCKQTWLY-UHFFFAOYSA-N 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 150000001923 cyclic compounds Chemical class 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000007857 degradation product Substances 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 229940043279 diisopropylamine Drugs 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
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- 239000003344 environmental pollutant Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
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- 239000000499 gel Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 238000004442 gravimetric analysis Methods 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 239000000017 hydrogel Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000007327 hydrogenolysis reaction Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 150000004681 metal hydrides Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000004200 microcrystalline wax Substances 0.000 description 1
- 235000019808 microcrystalline wax Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- MOWMLACGTDMJRV-UHFFFAOYSA-N nickel tungsten Chemical compound [Ni].[W] MOWMLACGTDMJRV-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 125000001477 organic nitrogen group Chemical group 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920013639 polyalphaolefin Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 150000003385 sodium Chemical class 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 229910001427 strontium ion Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 235000019871 vegetable fat Nutrition 0.000 description 1
- 238000007704 wet chemistry method Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/82—Phosphates
- B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
- B01J29/85—Silicoaluminophosphates [SAPO compounds]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J29/064—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof containing iron group metals, noble metals or copper
- B01J29/068—Noble metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/22—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
- C07C5/27—Rearrangement of carbon atoms in the hydrocarbon skeleton
- C07C5/2767—Changing the number of side-chains
- C07C5/277—Catalytic processes
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Abstract
Description
められた異性化選択性をもたらす。SAPOモレキュラーシーブの特定の結晶ネットワークはイソメレート(isomerate)形状選択性を決定し:モレキュラーシーブの細孔系が十分に「広い」場合、全ての可能な異性体が形成されることができ;逆に、シーブ内に空間制約がある場合、「より大きい」異性体は生成物においてあまり見られない。一般に、触媒の細孔幅を減少するとともにメチル分枝は増加し、一方、エチルおよびプロピル分枝異性体は、広い細孔開口および大きな空洞から得られる。
Company)は、<0.5μの結晶子サイズおよび4.8〜7.1オングストロームの間の直径の細孔を有するSAPO−11、SAPO−31、SAPO−41のような中間細孔サイズモレキュラーシーブと供給原料を非常に特定の異性化条件下で接触させる、>10の炭素原子を有する直鎖状パラフィンを含有する炭化水素系供給原料の脱ろうの方法を記述する。
位のバランスを最適化する水素化異性化のための触媒系の当該技術分野における必要性が存在する。
oil)および溶媒脱ろう油が包含され、該供給原料は約177℃〜700℃の範囲で沸騰する。水素化処理により、例えばヘテロ原子化合物および芳香族化合物を除くために水素化処理により前処理されている供給原料の水素化異性化もまた、当該技術分野において既知である。
に分枝したパラフィンを含んでなる任意の供給原料を定義するために本明細書において用いられる。
原料を活性水素化脱酸素(HDO)触媒、活性水素化脱窒素(HDN)触媒および活性水素化脱硫(HDS)触媒の少なくとも1つと接触させる反応ゾーンの下流に該触媒系を配置することができる。空間的に効率のよい商業的処理のために、これらのさらなる触媒は該触媒系と単一反応器内に配置することができる。
本明細書に言及されるモレキュラーシーブのシリカ対アルミナの比率は、通常の分析により決定することができる。この比率は、シリコアルミノホスフェート結晶の堅固な陰イオン性フレームワークにおける比率をできる限り厳密に表し、そしてマトリックス材料におけるまたはチャンネル内の陽イオン性もしくは他の形態におけるアルミニウムを除くものとする。
D=(K.λ)/(β.cosθ)
ここで、D=結晶子サイズ(オングストローム);K=定数(〜1);λは波長(オングストローム)であり、β=ラジアン単位の修正半値幅;θ=回折角。
I.E.C=k[Na2O/SiO2]
に代入し、ここで、「k」はNaClイオン交換溶液との接触直前のシリコアルミノホスフェートのSiO2/Al2O3モル比である。
本発明の触媒系における使用のためのSAPO−11シリコアルミノホスフェートモレキュラーシーブは、3次元のミクロ多孔性結晶フレームワークとして隅を共有する(corner sharing)[SiO2]四面体、[AlO2]四面体および[PO2]四面体単位を含んでなり、その無水ベースでの実験式は:
mR:(SixAlyPz)O2
であり、ここで、「R」は結晶内細孔系に存在する1つの有機鋳型剤を表し;「m」は(mR:(SixAlyPz)O2)のモル当たり存在する「R」のモルを表しそして0〜約0.3の値を有し;「x」、「y」および「z」はそれぞれケイ素、アルミニウムおよびリンのモル分率を表し、該モル分率は上記に定義した関係内である。
a)アルミニウム源、ケイ素源、リン源および有機鋳型を混合して
aR:Al2O3:bP2O5:cSiO2:dH2O
のモル組成を有するゼラチン状反応混合物を生成せしめる段階、
ここで、
aは0.2〜2.0、好ましくは0.3〜1.5、より好ましくは0.5〜1.0の値を有し;
bは0.6〜1.2、好ましくは0.8〜1.1の値を有し;
cは0.1〜1.5、好ましくは0.3〜1.2の値を有し;そして
dは15〜50、好ましくは20〜40、より好ましくは25〜35の値を有し、
そしてここで、ゲル化温度を用いる該混合段階は約25〜約60℃、好ましくは約28〜約42℃、そしてより好ましくは約30〜約40℃の範囲である;
b)約140〜約190℃、好ましくは約150〜約180℃、そしてより好ましくは約160〜約175℃の範囲内の温度で、自生圧力(autogenous pressure)で、そして約4〜約60時間、好ましくは約10〜約40時間の間の期間にわたって密封圧力容器において蒸気処理により混合物を結晶化させる段階;および
c)結晶生成物を回収する段階
を含んでなる。
の少なくとも一部を合わせそしてその後でアルミニウムおよびリン源を含んでなる得られる反応混合物をケイ素源と合わせることにより行われる。SAPO−11がこの好ましい技術を用いて合成される場合、式(1)における「m」の値は一般に約0.02を上回る。
〜約0.7wt.%の範囲内でSAPO−11に含まれる。記載した主要な触媒活性金属の中で、白金およびパラジウムは好ましく、その中で白金は最も好ましい。
そうでなければ密接に混合することができるような形態でなければならない。マトリックス自体が例えばより長鎖のn−パラフィンのクラッキングを促進するために触媒活性であることは可能であるが、マトリックスは水素化分解の意味において触媒活性でないことが好ましい。
給原料を(指向的に)通過させる同じ反応器内であってもよい。
4つの異なるSAPO−11材料を上記のように製造しそして特性化した。これらの特性化方法の結果を表1に示す。これらの中で、SAPO−11−AおよびSAPO−11−Dは、本発明の触媒系における使用に必要とされる特徴的な特性を有する。
点より有意に低いとは言えないが、供給原料を触媒系Eと接触させることにより得られる水素化イソメレートにおける分解生成物(<C10)の割合は、同じ供給原料を比較触媒系Fと接触させることにより得られる水素化イソメレートにおける分解生成物(<C10)の割合より有意に低い。 本発明の実施における様々な他の態様および改変は、上記の本発明の範囲および精神からそれることなしに当業者に明らかであり、そして容易に行われ得ることが理解される。
Claims (17)
- アルミナ、シリカアルミナ、チタンアルミナおよびその混合物よりなる群から選択されるマトリックス;SAPO−11モレキュラーシーブを含んでなる該マトリックス中に実質的に均一に分布している担持媒体(support medium);ならびに該媒体上に担持され且つ白金、パラジウム、ルテニウム、ロジウムもしくはその混合物よりなる群から選択される金属を含んでなる0.1〜1.0wt%(触媒系の総重量に基づく)の触媒活性金属相を含んでなる炭化水素系供給原料(feed)を処理するための触媒系であって、該SAPO−11モレキュラーシーブが:
a)約0.08〜約0.24のシリカ対アルミナのモル比率;
b)約0.75〜約0.83のリン対アルミナの比率;
c)少なくとも約150m2/gのミクロ表面積(MiSA);
d)約250〜約600オングストロームの範囲内の結晶子サイズ;および
e)約2000重量ppm未満のナトリウム含有量(酸化物として測定される)
を有することを特徴とする該触媒系。 - 該マトリックスが触媒活性でない請求項1に記載の触媒系。
- 該マトリックスがアルミナを含んでなる請求項1に記載の触媒系。
- 該SAPO−11モレキュラーシーブが少なくとも600マイクロモルSi/gのイオン交換容量(I.E.C.)によりさらに特徴付けられる請求項1に記載の触媒系。
- 該SAPO−11モレキュラーシーブが少なくとも0.220ml/gの平均細孔容積によりさらに特徴付けられる請求項1に記載の触媒系。
- 該触媒活性金属が白金である請求項1に記載の触媒系。
- 該触媒活性金属相として約0.3〜約2.0wt%の白金を含んでなる請求項6に記載の触媒系。
- 該マトリックス上に担持され且つニッケル、コバルト、鉄およびその混合物よりなる群から選択される金属を含んでなる約0.01〜約6.0wt.%の追加の活性金属相をさらに含んでなる請求項1に記載の触媒系。
- 該マトリックス上に担持され且つタングステン、モリブデンおよびその混合物よりなる群から選択される金属を含んでなる約10〜約30wt.%の追加の活性金属相をさらに含んでなる請求項1に記載の触媒系。
- 該担持媒体および該マトリックスが約0.1〜約1.0の間の担持媒体対マトリックスの重量比で存在する請求項1に記載の触媒系。
- 水素化処理条件下で該炭化水素系供給原料を請求項1に記載の触媒系と接触させることを含んでなる炭化水素系供給原料のイソパラフィン含有量を選択的に高める方法。
- 該水素化処理条件が約280℃〜約450℃の間の温度、約5〜約60barの間の圧力、約0.1hr−1〜約20hr−1の液体毎時空間速度および約150〜約2000SCF/bblの水素循環率を含んでなる請求項11に記載の方法。
- 該炭化水素系供給原料がC15〜C40直鎖状パラフィンを実質的に含んでなる請求項
11に記載の方法。 - 水素化処理条件下で炭化水素系供給原料を活性水素化脱酸素(HDO)触媒、活性水素化脱窒素(HDN)触媒および活性水素化脱硫(HDS)触媒の少なくとも1つと接触させる反応ゾーンの下流に該触媒系が配置される請求項13に記載の方法。
- 該少なくとも1つのさらなる触媒が該触媒系と共に単一反応器内に配置される請求項14に記載の方法。
- 該炭化水素系供給原料が、好ましくは動物油もしくは植物油またはその混合物を含んでなる、生物学的起源のものである請求項15に記載の方法。
- 該炭化水素系供給原料がナタネ油、ヤシ油、ダイズ油、獣脂、動物脂肪もしくはその混合物を含んでなる請求項16に記載の方法。
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JP2012529414A (ja) * | 2009-06-12 | 2012-11-22 | アルベマール・ユーロプ・エスピーアールエル | Sapo分子篩触媒と、その調製および使用 |
JP2013506323A (ja) * | 2009-09-27 | 2013-02-21 | ゼットティーイー コーポレーション | 状態遷移方法及び装置 |
US8743752B2 (en) | 2009-09-27 | 2014-06-03 | Zte Corporation | Method and apparatus for status transition |
Also Published As
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CA2646590C (en) | 2015-12-29 |
JP5523093B2 (ja) | 2014-06-18 |
BRPI0710250A2 (pt) | 2011-08-02 |
WO2007107336A3 (en) | 2007-11-01 |
CA2646590A1 (en) | 2007-09-27 |
CN101421040A (zh) | 2009-04-29 |
US20070287871A1 (en) | 2007-12-13 |
CN101421040B (zh) | 2012-08-29 |
BRPI0710250B1 (pt) | 2016-06-21 |
WO2007107336A2 (en) | 2007-09-27 |
EP1996324A2 (en) | 2008-12-03 |
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