JP5189740B2 - Hydrorefining method - Google Patents
Hydrorefining method Download PDFInfo
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- JP5189740B2 JP5189740B2 JP2006138297A JP2006138297A JP5189740B2 JP 5189740 B2 JP5189740 B2 JP 5189740B2 JP 2006138297 A JP2006138297 A JP 2006138297A JP 2006138297 A JP2006138297 A JP 2006138297A JP 5189740 B2 JP5189740 B2 JP 5189740B2
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- oil
- hydrogen
- catalyst
- mass
- treated
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- 238000000034 method Methods 0.000 title claims description 49
- 239000003921 oil Substances 0.000 claims description 133
- 235000019198 oils Nutrition 0.000 claims description 132
- 239000003054 catalyst Substances 0.000 claims description 86
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 58
- 229910052739 hydrogen Inorganic materials 0.000 claims description 52
- 239000001257 hydrogen Substances 0.000 claims description 52
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 50
- 229910052760 oxygen Inorganic materials 0.000 claims description 50
- 239000001301 oxygen Substances 0.000 claims description 50
- 229910052751 metal Inorganic materials 0.000 claims description 39
- 239000002184 metal Substances 0.000 claims description 39
- 238000006243 chemical reaction Methods 0.000 claims description 32
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 30
- 229910052710 silicon Inorganic materials 0.000 claims description 28
- 239000010703 silicon Substances 0.000 claims description 28
- 150000002430 hydrocarbons Chemical class 0.000 claims description 26
- 238000005984 hydrogenation reaction Methods 0.000 claims description 26
- 239000002808 molecular sieve Substances 0.000 claims description 25
- 239000012188 paraffin wax Substances 0.000 claims description 25
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 25
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 21
- 229910052717 sulfur Inorganic materials 0.000 claims description 21
- 239000011593 sulfur Substances 0.000 claims description 21
- 235000015112 vegetable and seed oil Nutrition 0.000 claims description 19
- 239000008158 vegetable oil Substances 0.000 claims description 18
- 241001465754 Metazoa Species 0.000 claims description 17
- 150000002739 metals Chemical class 0.000 claims description 17
- 229910052782 aluminium Inorganic materials 0.000 claims description 16
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 16
- 239000010775 animal oil Substances 0.000 claims description 15
- 239000007788 liquid Substances 0.000 claims description 14
- 229910052697 platinum Inorganic materials 0.000 claims description 14
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 12
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 12
- 229910052763 palladium Inorganic materials 0.000 claims description 11
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 10
- 229910021472 group 8 element Inorganic materials 0.000 claims description 10
- 230000000737 periodic effect Effects 0.000 claims description 10
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 9
- 229910021536 Zeolite Inorganic materials 0.000 claims description 9
- 239000000470 constituent Substances 0.000 claims description 9
- 229910052741 iridium Inorganic materials 0.000 claims description 9
- 229910052759 nickel Inorganic materials 0.000 claims description 9
- 229910052719 titanium Inorganic materials 0.000 claims description 9
- 239000010936 titanium Substances 0.000 claims description 9
- 239000010457 zeolite Substances 0.000 claims description 9
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 8
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 8
- 229910052796 boron Inorganic materials 0.000 claims description 8
- 229910052809 inorganic oxide Inorganic materials 0.000 claims description 8
- 238000010791 quenching Methods 0.000 claims description 8
- 238000001179 sorption measurement Methods 0.000 claims description 8
- 229910052726 zirconium Inorganic materials 0.000 claims description 8
- 229910052737 gold Inorganic materials 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 229910052749 magnesium Inorganic materials 0.000 claims description 6
- 239000011777 magnesium Substances 0.000 claims description 6
- 125000005457 triglyceride group Chemical group 0.000 claims description 6
- 125000004429 atom Chemical group 0.000 claims description 5
- 150000002431 hydrogen Chemical class 0.000 claims description 5
- 229910052703 rhodium Inorganic materials 0.000 claims description 5
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 238000000746 purification Methods 0.000 claims description 4
- 230000000694 effects Effects 0.000 description 24
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 20
- 239000003925 fat Substances 0.000 description 18
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 17
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 14
- 235000019197 fats Nutrition 0.000 description 14
- 239000007789 gas Substances 0.000 description 13
- 239000002994 raw material Substances 0.000 description 11
- 230000007423 decrease Effects 0.000 description 10
- -1 fatty acid esters Chemical class 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- 238000009835 boiling Methods 0.000 description 9
- 239000000446 fuel Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 7
- 239000002585 base Substances 0.000 description 7
- 229910002092 carbon dioxide Inorganic materials 0.000 description 7
- 239000001569 carbon dioxide Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 239000002028 Biomass Substances 0.000 description 6
- 229910002835 Pt–Ir Inorganic materials 0.000 description 6
- 235000014113 dietary fatty acids Nutrition 0.000 description 6
- 239000000194 fatty acid Substances 0.000 description 6
- 229930195729 fatty acid Natural products 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 229910001868 water Inorganic materials 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 239000006227 byproduct Substances 0.000 description 5
- 238000000354 decomposition reaction Methods 0.000 description 5
- 230000006872 improvement Effects 0.000 description 5
- 239000003350 kerosene Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 235000019871 vegetable fat Nutrition 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 229910002845 Pt–Ni Inorganic materials 0.000 description 4
- 229910018967 Pt—Rh Inorganic materials 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 235000019387 fatty acid methyl ester Nutrition 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 4
- 239000003209 petroleum derivative Substances 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- 241000196324 Embryophyta Species 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 235000019482 Palm oil Nutrition 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 229940024546 aluminum hydroxide gel Drugs 0.000 description 3
- SMYKVLBUSSNXMV-UHFFFAOYSA-K aluminum;trihydroxide;hydrate Chemical compound O.[OH-].[OH-].[OH-].[Al+3] SMYKVLBUSSNXMV-UHFFFAOYSA-K 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910001593 boehmite Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000006392 deoxygenation reaction Methods 0.000 description 3
- 238000006477 desulfuration reaction Methods 0.000 description 3
- 230000023556 desulfurization Effects 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 239000010696 ester oil Substances 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 150000004665 fatty acids Chemical class 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 239000002540 palm oil Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000010948 rhodium Substances 0.000 description 3
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 235000019484 Rapeseed oil Nutrition 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 2
- AQBOUNVXZQRXNP-UHFFFAOYSA-L azane;dichloropalladium Chemical compound N.N.N.N.Cl[Pd]Cl AQBOUNVXZQRXNP-UHFFFAOYSA-L 0.000 description 2
- KHCPSOMSJYAQSY-UHFFFAOYSA-L azane;dichloroplatinum Chemical compound N.N.N.N.Cl[Pt]Cl KHCPSOMSJYAQSY-UHFFFAOYSA-L 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000007872 degassing Methods 0.000 description 2
- 239000002283 diesel fuel Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 239000000295 fuel oil Substances 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 235000014593 oils and fats Nutrition 0.000 description 2
- 238000005504 petroleum refining Methods 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 235000019353 potassium silicate Nutrition 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000011946 reduction process Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 229910001388 sodium aluminate Inorganic materials 0.000 description 2
- 235000012424 soybean oil Nutrition 0.000 description 2
- 239000003549 soybean oil Substances 0.000 description 2
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical class C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 1
- 229910017398 Au—Ni Inorganic materials 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- 229910018885 Pt—Au Inorganic materials 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 229940024545 aluminum hydroxide Drugs 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 235000015278 beef Nutrition 0.000 description 1
- 239000007767 bonding agent Substances 0.000 description 1
- HGHPQUIZVKPZEU-UHFFFAOYSA-N boranylidynezirconium Chemical compound [B].[Zr] HGHPQUIZVKPZEU-UHFFFAOYSA-N 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000008264 cloud Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- IYYZUPMFVPLQIF-UHFFFAOYSA-N dibenzothiophene Chemical class C1=CC=C2C3=CC=CC=C3SC2=C1 IYYZUPMFVPLQIF-UHFFFAOYSA-N 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 150000002019 disulfides Chemical class 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000004231 fluid catalytic cracking Methods 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 230000029553 photosynthesis Effects 0.000 description 1
- 238000010672 photosynthesis Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000000629 steam reforming Methods 0.000 description 1
- RCYJPSGNXVLIBO-UHFFFAOYSA-N sulfanylidenetitanium Chemical compound [S].[Ti] RCYJPSGNXVLIBO-UHFFFAOYSA-N 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000003760 tallow Substances 0.000 description 1
- OSBSFAARYOCBHB-UHFFFAOYSA-N tetrapropylammonium Chemical class CCC[N+](CCC)(CCC)CCC OSBSFAARYOCBHB-UHFFFAOYSA-N 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 150000003577 thiophenes Chemical class 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical compound [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
Description
本発明は、水素化精製方法に関し、より詳しくは、動植物油由来の油脂成分を含む被処理油の水素化精製方法に関する。 The present invention relates to a hydrorefining method, and more particularly, to a hydrotreating method for oil to be treated containing fat and oil components derived from animal and vegetable oils.
地球温暖化の防止対策として、バイオマスエネルギーの有効利用に注目が集まっている。バイオマスエネルギーの中でも植物由来のバイオマスエネルギーは、植物の成長過程で光合成により二酸化炭素から変換された炭化水素を有効利用できるため、ライフサイクルの観点からすると大気中の二酸化炭素の増加につながらない、いわゆる、カーボンニュートラルという性質を持つ。 Attention has been focused on the effective use of biomass energy as a measure to prevent global warming. Among biomass energy, biomass energy derived from plants can effectively use hydrocarbons converted from carbon dioxide by photosynthesis in the growth process of plants, so it does not lead to an increase in carbon dioxide in the atmosphere from the viewpoint of life cycle, so-called, It has the property of being carbon neutral.
このようなバイオマスエネルギーの利用は、輸送用燃料の分野においても種々検討がなされている。例えば、ディーゼル燃料として動植物油由来の燃料を使用できれば、ディーゼルエンジンの高いエネルギー効率との相乗効果により二酸化炭素の排出量削減において有効な役割を果たすと期待されている。動植物油を利用したディーゼル燃料としては、脂肪酸メチルエステル油（Ｆａｔｔｙ Ａｃｉｄ Ｍｅｔｈｙｌ Ｅｓｔｅｒ）が知られている。脂肪酸メチルエステル油は、動植物油の一般的な構造であるトリグリセリド構造に対し、アルカリ等によってメタノールとのエステル交換を行うことで製造されている。しかしながら、脂肪酸メチルエステル油を製造するプロセスにおいては、以下の特許文献１に記載されている通り、副生するグリセリンの処理が必要であったり、生成油の洗浄などにコストやエネルギーがかかったりすることが指摘されている。
動植物油由来の油脂成分やこれを原料として製造される燃料を使用するには、上記のような問題に加え、以下のような問題がある。すなわち、動植物油由来の油脂成分は、一般に分子中に酸素原子を有しているため、酸素分がエンジン材質に与える悪影響が懸念されること、並びに、当該酸素分を極低濃度まで除去することが困難であることなどである。 In addition to the above problems, there are the following problems in order to use oil and fat components derived from animal and vegetable oils and fuels produced from these components. That is, since the oil and fat component derived from animal and vegetable oils generally has an oxygen atom in the molecule, there is a concern that the oxygen content may adversely affect the engine material, and that the oxygen content is removed to an extremely low concentration. Is difficult.
更に、動植物油脂を構成する脂肪酸は、直鎖パラフィン又は直鎖オレフィンを炭化水素骨格として有しているが、水素化精製によって得られるパラフィン分は曇り点等の低温性能が十分実用的なものとは言えない恐れがある。 Furthermore, the fatty acids that make up animal and vegetable fats and oils have straight-chain paraffins or straight-chain olefins as hydrocarbon skeletons, but the paraffin content obtained by hydrorefining is sufficiently practical for low-temperature performance such as cloud point. There is a fear that can not be said.
そこで、本発明は、含酸素炭化水素化合物を含有する被処理油を用いた場合に、酸素分が十分に低減され、且つ、十分な低温性能を有する水素化精製油を得ることが可能な水素化精製方法を提供することを目的とする。 Therefore, the present invention provides a hydrogen that can be obtained as a hydrorefined oil that has a sufficiently reduced oxygen content and sufficient low-temperature performance when the oil to be treated containing an oxygen-containing hydrocarbon compound is used. An object of the present invention is to provide a chemical purification method.
上記課題を解決するために、本発明は、水素の存在下、含酸素炭化水素化合物を含有する被処理油と、結晶性モレキュラシーブを含む担体、並びに、該担体に担持された周期律表第６Ａ族及び第８族の元素から選ばれる１種以上の金属を含有する触媒と、を接触させる水素化精製工程を経て精製油を得る水素化精製方法であり、上記含酸素炭化水素化合物は、動植物油に由来する油脂成分であり、上記水素は、上記被処理油に随伴して導入される水素ガスと、クエンチ水素として導入される水素ガスとを含み、上記被処理油に随伴して導入される水素ガスに対する上記クエンチ水素の割合が１０〜６０容量％であり、上記水素化精製工程は、上記被処理油と、結晶性モレキュラシーブを含む担体、又は、アルミニウム、ケイ素、ジルコニウム、ホウ素、チタン及びマグネシウムから選ばれる２種以上の元素を含んで構成される多孔性無機酸化物、並びに、上記担体又は上記多孔性無機酸化物に担持された周期律表第６Ａ族及び第８族の元素から選ばれる１種以上の金属を含有する触媒とを、水素圧力２〜１３ＭＰａ、液空間速度０．１〜３．０ｈ−１、水素油比２５０〜１５００ＮＬ／Ｌ、反応温度１５０〜３８０℃の条件下で接触させて第一精製油を得る第一水素化工程と、上記第一精製油と、結晶性モレキュラシーブを含む担体、並びに、該担体に担持された周期律表第６Ａ族及び第８族の元素から選ばれる１種以上の金属を含有する触媒とを、水素圧力２〜１３ＭＰａ、液空間速度０．１〜３．０ｈ−１、水素油比２５０〜１５００ＮＬ／Ｌ、反応温度１５０〜３８０℃の条件下で接触させて第二精製油を得る第二水素化工程と、を含み、上記第一水素化工程は、上記被処理油に含まれる初期酸素分の７０質量％以上を除去して上記第一精製油を得る工程であり、上記第二水素化工程は、上記初期酸素分の９５質量％以上が除去されるように、上記第一精製油に残存する酸素分を除去して上記第二精製油を得る工程であり、上記第二水素化工程は、上記第二精製油の１５０〜３５０℃の留分に含まれるパラフィン分において、ノルマルパラフィンに対するイソパラフィンの比（イソパラフィンの質量／ノルマルパラフィンの質量）が０．２以上となるように行うことを特徴とする水素化精製方法を提供する。 In order to solve the above problems, the present invention provides an oil to be treated containing an oxygen-containing hydrocarbon compound in the presence of hydrogen, a carrier containing a crystalline molecular sieve, and a periodic table 6A supported on the carrier. A hydrorefining method for obtaining a refined oil through a hydrorefining step in which a catalyst containing one or more metals selected from elements of Group 8 and Group 8 is contacted, wherein the oxygenated hydrocarbon compound comprises animals and plants It is an oil and fat component derived from oil, and the hydrogen includes a hydrogen gas introduced along with the oil to be treated and a hydrogen gas introduced as quench hydrogen, and is introduced along with the oil to be treated. that the ratio of the quench hydrogen to the hydrogen gas is 10 to 60 volume%, the hydrotreating step, and the treated oil, the carrier comprising a crystalline molecular sieve, or aluminum, silicon, zirconium Boron, porous inorganic oxide includes a 2 or more elements selected from titanium and magnesium, as well as the carrier or the porous Group 6A of the periodic table is supported on an inorganic oxide and a Group 8 A catalyst containing one or more metals selected from these elements is hydrogen pressure 2-13 MPa, liquid space velocity 0.1-3.0 h −1 , hydrogen oil ratio 250-1500 NL / L, reaction temperature 150-380. A first hydrogenation step in which a first refined oil is obtained by contact under the condition of ° C., a carrier containing the first refined oil and the crystalline molecular sieve, and a periodic table group 6A supported on the carrier, and A catalyst containing one or more metals selected from Group 8 elements, hydrogen pressure 2-13 MPa, liquid space velocity 0.1-3.0 h −1 , hydrogen oil ratio 250-1500 NL / L, reaction temperature 150-380 ° C A second hydrogenation step to obtain a second refined oil is contacted in matters under only contains, the first hydrogenation step removes more than 70 wt% of the initial oxygen component contained in the treated oil A step of obtaining the first refined oil, wherein the second hydrogenation step is performed by removing the oxygen content remaining in the first refined oil so that 95% by mass or more of the initial oxygen content is removed. The second hydrogenation step is a step of obtaining a second refined oil, wherein the ratio of isoparaffin to normal paraffin (mass of isoparaffin / normal) in the paraffin content contained in the fraction of 150 to 350 ° C of the second refined oil. Provided is a hydrorefining method, characterized in that the paraffin mass) is 0.2 or more .
本発明の水素化精製方法によれば、含酸素炭化水素化合物を含有する被処理油と上記特定の触媒とを上記特定の条件下で接触させることによって、酸素分が十分に低減され、且つ、十分に実用的な低温性能を有する水素化精製油を経済的に極めて有効に得ることができる。 According to the hydrorefining method of the present invention, the oxygen content is sufficiently reduced by contacting the oil to be treated containing the oxygen-containing hydrocarbon compound with the specific catalyst under the specific conditions, and A hydrorefined oil having sufficiently practical low-temperature performance can be obtained extremely effectively economically.
本発明の水素化精製方法においては、被処理油の全量を基準として、酸素分の含有量が０．１〜１５質量％であることが好ましい。また、被処理油には、硫黄分が含まれていないか又は含まれていてもその含有量が十分に低いことが好ましく、被処理油の全量を基準として、硫黄分の含有量が５０質量ｐｐｍ以下であることが好ましい。被処理油の酸素分及び硫黄分がそれぞれ上記の範囲内であると、安定した脱酸素活性を長期にわたって維持することができる。 In the hydrorefining method of this invention, it is preferable that content of oxygen content is 0.1-15 mass% on the basis of the whole quantity of to-be-processed oil. Further, even if the oil to be treated does not contain or contain a sulfur content, the content thereof is preferably sufficiently low, and the content of sulfur is 50 masses based on the total amount of the oil to be treated. It is preferably at most ppm. When the oxygen content and sulfur content of the oil to be treated are within the above ranges, stable deoxygenation activity can be maintained over a long period of time.
本発明の水素化精製方法においては、バイオマスエネルギーの有効利用の点から、含酸素炭化水素化合物は動植物油に由来する油脂成分である。 In hydrorefining process of the present invention, from the viewpoint of effective utilization of biomass energy, oxygenated hydrocarbon compounds Ru fat component der derived from an animal or vegetable oil.
また、原材料の加工に必要なエネルギーを低減できることから、含酸素炭化水素化合物に占めるトリグリセリド構造を有する化合物の割合は９０モル％以上であることが好ましい。 Moreover, since the energy required for processing raw materials can be reduced, the proportion of the compound having a triglyceride structure in the oxygen-containing hydrocarbon compound is preferably 90 mol% or more.
また、本発明の水素化精製方法においては、上記被処理油から得られる上記精製油の１５０〜３５０℃の留分に含まれるパラフィン分において、ノルマルパラフィンに対するイソパラフィンの比（イソパラフィンの質量／ノルマルパラフィンの質量）が０．２以上となるように上記水素化精製工程を行うことが好ましい。これにより、精製油の曇り点などに代表される燃料としての低温性能の向上をより十分に達成することができる。 In the hydrorefining method of the present invention, the ratio of isoparaffin to normal paraffin (mass of isoparaffin / normal paraffin) in the paraffin contained in the fraction of 150 to 350 ° C. of the refined oil obtained from the oil to be treated The hydrorefining step is preferably carried out so that the mass of Thereby, the improvement of the low temperature performance as a fuel represented by the cloud point etc. of refined oil can be achieved more fully.
また、本発明の水素化精製方法において、上記触媒を構成する上記結晶性モレキュラシーブがケイ素を含むゼオライトを含有し、該ゼオライトは、酸素及びケイ素を除く構成元素に対するケイ素の比（ケイ素の原子数／酸素及びケイ素以外の元素の原子数）が３以上のものであることが好ましい。これにより、過度の分解反応を抑制し、効率のよい燃料製造と低温性能の向上をより十分に達成することができる。 In the hydrorefining method of the present invention, the crystalline molecular sieve constituting the catalyst contains a zeolite containing silicon, and the zeolite has a ratio of silicon to constituent elements excluding oxygen and silicon (number of silicon atoms / The number of atoms of elements other than oxygen and silicon is preferably 3 or more. Thereby, excessive decomposition reaction can be suppressed and efficient fuel production and improvement in low-temperature performance can be more sufficiently achieved.
また、本発明の水素化精製方法において、上記触媒を構成する上記金属が、Ｐｄ、Ｐｔ、Ｒｈ、Ｉｒ、Ａｕ、Ｎｉ及びＭｏから選ばれる１種以上の元素を含むものであることが好ましい。これにより、水素化脱酸素反応が促進されるとともに、水素化異性化反応、パラフィンの分解除去反応といった低温性能の向上をより十分に達成することができる。 In the hydrorefining method of the present invention, it is preferable that the metal constituting the catalyst contains one or more elements selected from Pd, Pt, Rh, Ir, Au, Ni and Mo. As a result, the hydrodeoxygenation reaction is promoted, and the improvement in low-temperature performance such as hydroisomerization reaction and paraffin decomposition / removal reaction can be more sufficiently achieved.
また、上記金属が還元状態にある上記触媒１ｇ当たりの一酸化炭素吸着量が０．００３〜０．０５ｍｍｏｌの範囲であることが好ましい。これにより、十分な活性を長期間安定して発揮することができる。 Moreover, it is preferable that the carbon monoxide adsorption amount per 1 g of the catalyst in which the metal is in a reduced state is in the range of 0.003 to 0.05 mmol. Thereby, sufficient activity can be exhibited stably for a long period of time.
また、上記水素化精製工程において、上記被処理油と上記触媒とは、水素圧力２〜１３ＭＰａ、液空間速度０．１〜３．０ｈ−１、水素油比２５０〜１５００ＮＬ／Ｌ、反応温度１５０〜３８０℃の条件下で接触させる。これにより、設備投資や運転経費などの運転コストが経済的に見合う範囲において、十分な活性を長期間安定して発揮することができる。 In the hydrorefining step, the oil to be treated and the catalyst have a hydrogen pressure of 2 to 13 MPa, a liquid space velocity of 0.1 to 3.0 h −1 , a hydrogen oil ratio of 250 to 1500 NL / L, and a reaction temperature of 150. Ru is brought into contact under conditions of ~380 ℃. As a result, sufficient activity can be stably exhibited for a long period of time within a range where operating costs such as capital investment and operating costs can be economically met.
更に、本発明の水素化精製方法において、上記第一水素化工程は、上記被処理油に含まれる初期酸素分の７０質量％以上を除去して上記第一精製油を得る工程であり、上記第二水素化工程は、上記初期酸素分の９５質量％以上が除去されるように、上記第一精製油に残存する酸素分を除去して上記第二精製油を得る工程であり、上記第二水素化工程は、上記第二精製油の１５０〜３５０℃の留分に含まれるパラフィン分において、ノルマルパラフィンに対するイソパラフィンの比（イソパラフィンの質量／ノルマルパラフィンの質量）が０．２以上となるように行う。これにより、精製油の曇り点などに代表される燃料としての低温性能の向上をより十分に達成することができる。 Furthermore, in the hydrorefining method of the present invention, the first hydrogenation step is a step of obtaining the first refined oil by removing 70% by mass or more of the initial oxygen content contained in the oil to be treated. The second hydrogenation step is a step of obtaining the second refined oil by removing the oxygen content remaining in the first refined oil so that 95% by mass or more of the initial oxygen content is removed. In the dihydrogenation step, the ratio of isoparaffin to normal paraffin (mass of isoparaffin / mass of normal paraffin) is 0.2 or more in the paraffin content contained in the 150-350 ° C. fraction of the second refined oil. line intends to. Thereby, the improvement of the low temperature performance as a fuel represented by the cloud point etc. of refined oil can be achieved more fully.
本発明によれば、含酸素炭化水素化合物を含有する被処理油を用いた場合に、酸素分が十分に低減され、且つ、十分に実用的な低温性能を有する水素化精製油を経済的に極めて有効に得ることが可能な水素化精製方法が提供される。 According to the present invention, when an oil to be treated containing an oxygen-containing hydrocarbon compound is used, a hydrorefined oil having an oxygen content sufficiently reduced and sufficiently practical low-temperature performance is economically obtained. A hydrorefining method that can be obtained very effectively is provided.
以下、本発明の好適な実施形態について詳細に説明する。 Hereinafter, preferred embodiments of the present invention will be described in detail.
本発明においては、含酸素炭化水素化合物を含有する被処理油が用いられる。含酸素炭化水素化合物としては、動植物油由来の油脂成分が好適である。ここで、本発明における油脂成分には、天然もしくは人工的に生産、製造される動植物油脂及び動植物油成分及び／又はこれらの油脂を由来して生産、製造される成分及びこれらの油脂製品の性能を維持、向上させる目的で添加される成分が包含される。 In the present invention, an oil to be treated containing an oxygen-containing hydrocarbon compound is used. As the oxygen-containing hydrocarbon compound, oil and fat components derived from animal and vegetable oils are suitable. Here, the fats and oils component in the present invention includes natural and artificially produced and manufactured animal and vegetable oils and fats and / or animal and vegetable oil components and / or components produced and produced from these fats and oils and the performance of these fat and oil products. Components added for the purpose of maintaining and improving the above are included.
動植物油に由来する油脂成分としては、例えば、牛脂、菜種油、大豆油、パーム油などが挙げられる。本発明においては動植物油に由来する油脂成分として、いかなる油脂を用いてもよく、これら油脂を使用した後の廃油でもよい。ただし、カーボンニュートラルの観点からは植物油脂が好ましく、脂肪酸アルキル鎖炭素数及びその反応性の観点から、菜種油、大豆油及びパーム油がより好ましい。なお、上記の油脂は１種を単独で又は２種以上を混合して用いてもよい。 Examples of the oil and fat component derived from animal and vegetable oils include beef tallow, rapeseed oil, soybean oil, and palm oil. In the present invention, any fats and oils derived from animal and vegetable oils may be used, and waste oil after using these fats and oils may be used. However, vegetable oils and fats are preferable from the viewpoint of carbon neutral, and rapeseed oil, soybean oil, and palm oil are more preferable from the viewpoint of the number of fatty acid alkyl chain carbons and their reactivity. In addition, you may use said fats and oils individually by 1 type or in mixture of 2 or more types.
動植物油に由来する油脂成分は、一般に脂肪酸トリグリセリド構造を有しているが、その他の脂肪酸や脂肪酸メチルエステルなどのエステル体に加工されている油脂成分を含んでいてもよい。ただし、植物油脂から脂肪酸や脂肪酸エステルを製造する際には二酸化炭素が発生するため、二酸化炭素の排出量を低減化する観点から、植物油脂としてトリグリセリド構造を有した成分が主体であることが好ましい。本発明においては、被処理油に含まれる含酸素炭化水素化合物に占めるトリグリセリド構造を有する化合物の割合が９０モル％以上であることが好ましく、９２モル％以上であることがより好ましく、９５モル％以上であることが更に好ましい。 Oils and fats derived from animal and vegetable oils generally have a fatty acid triglyceride structure, but may contain other oils and fats processed into esters such as fatty acids and fatty acid methyl esters. However, since carbon dioxide is generated when producing fatty acids and fatty acid esters from vegetable oils and fats, it is preferable that the components having a triglyceride structure are mainly used as vegetable oils and fats from the viewpoint of reducing carbon dioxide emissions. . In the present invention, the proportion of the compound having a triglyceride structure in the oxygenated hydrocarbon compound contained in the oil to be treated is preferably 90 mol% or more, more preferably 92 mol% or more, and 95 mol%. It is still more preferable that it is above.
なお、被処理油は、含酸素炭化水素化合物として、上記の動植物油由来の油脂成分の他、プラスチックや溶剤等の化学品由来の化合物を含んでいてもよく、一酸化炭素と水素とからなる合成ガスを原料としたフィッシャートロプシュ反応を経由して得られる合成油を含んでいてもよい。 The oil to be treated may contain, as an oxygen-containing hydrocarbon compound, a compound derived from a chemical such as a plastic or a solvent, in addition to the oil and fat component derived from the above-mentioned animal and vegetable oils, and consists of carbon monoxide and hydrogen. A synthetic oil obtained via a Fischer-Tropsch reaction using synthesis gas as a raw material may be contained.
被処理油に含まれる酸素分は、被処理油全量を基準として、好ましくは０．１〜１５質量％であり、より好ましくは１〜１５質量％、更に好ましくは３〜１４質量％、特に好ましくは５〜１３質量％である。酸素分の含有量が０．１質量％未満であると、脱酸素活性及び脱硫活性を安定的に維持することが困難となる傾向にある。他方、酸素分の含有量が１５質量％を超えると、副生する水の処理に要する設備が必要となることや、水と触媒担体との相互作用が過度となり活性低下したり触媒強度が低下したりする。なお、酸素分の含有量は、一般的な元素分析装置で測定することができ、例えば、試料を白金炭素上で一酸化炭素に変換し、もしくは更に二酸化炭素に変換した後に熱伝導度検出器を用いて測定することができる。 The oxygen content contained in the oil to be treated is preferably 0.1 to 15% by mass, more preferably 1 to 15% by mass, still more preferably 3 to 14% by mass, particularly preferably based on the total amount of the oil to be treated. Is 5 to 13% by mass. If the oxygen content is less than 0.1% by mass, it tends to be difficult to stably maintain the deoxygenation activity and desulfurization activity. On the other hand, if the oxygen content exceeds 15% by mass, equipment required for the treatment of by-product water is required, the interaction between water and the catalyst carrier becomes excessive, and the activity decreases or the catalyst strength decreases. To do. The oxygen content can be measured with a general elemental analyzer. For example, the sample is converted to carbon monoxide on platinum carbon, or further converted to carbon dioxide, and then a thermal conductivity detector. Can be measured.
また、被処理油は、場合により含硫黄炭化水素化合物を含有していてもよい。含硫黄炭化水素化合物は特に制限されないが、具体的には、スルフィド、ジスルフィド、ポリスルフィド、チオール、チオフェン、ベンゾチオフェン、ジベンゾチオフェン及びこれらの誘導体などが挙げられる。被処理油に含まれる含硫黄炭化水素化合物は単一の化合物であってもよく、あるいは２種以上の混合物であってもよい。さらに、硫黄分を含有する石油系炭化水素留分を被処理油に混合してもよい。 Moreover, the to-be-processed oil may contain the sulfur-containing hydrocarbon compound depending on the case. The sulfur-containing hydrocarbon compound is not particularly limited, and specific examples include sulfides, disulfides, polysulfides, thiols, thiophenes, benzothiophenes, dibenzothiophenes, and derivatives thereof. The sulfur-containing hydrocarbon compound contained in the oil to be treated may be a single compound or a mixture of two or more. Furthermore, a petroleum hydrocarbon fraction containing a sulfur content may be mixed with the oil to be treated.
石油系炭化水素留分としては、一般的な石油精製工程で得られる留分を用いることができる。例えば、常圧蒸留装置や減圧蒸留装置から得られる所定の沸点範囲に相当する留分、あるいは、水素化脱硫装置、水素化分解装置、残油直接脱硫装置、流動接触分解装置などから得られる、所定の沸点範囲に相当する留分を使用してもよい。なお、上記の各装置から得られる留分は１種を単独で又は２種以上を混合して用いてもよい。 As the petroleum hydrocarbon fraction, a fraction obtained in a general petroleum refining process can be used. For example, a fraction corresponding to a predetermined boiling range obtained from an atmospheric distillation apparatus or a vacuum distillation apparatus, or obtained from a hydrodesulfurization apparatus, a hydrocracking apparatus, a residual oil direct desulfurization apparatus, a fluid catalytic cracking apparatus, etc. A fraction corresponding to a predetermined boiling range may be used. In addition, you may use the fraction obtained from each said apparatus individually by 1 type or in mixture of 2 or more types.
被処理油における硫黄分の含有量は、被処理油全量を基準として、好ましくは５０質量ｐｐｍ以下であり、より好ましくは２０質量ｐｐｍ以下であり、更に好ましくは１０質量ｐｐｍ以下である。硫黄分の含有量が５０質量ｐｐｍを超えると、脱酸素活性を安定的に維持することが困難となる傾向にあるとともに、水素化精製油に含まれる硫黄分含有量が増加する傾向にあり、ディーゼルエンジン等の燃料として用いる場合にエンジン排ガス浄化装置への悪影響が懸念される。なお、本発明における硫黄分は、ＪＩＳ Ｋ ２５４１「硫黄分試験方法」又はＡＳＴＭ−５４５３に記載の方法に準拠して測定される硫黄分の質量含有量を意味する。 The content of sulfur in the oil to be treated is preferably 50 mass ppm or less, more preferably 20 mass ppm or less, still more preferably 10 mass ppm or less, based on the total amount of the oil to be treated. When the sulfur content exceeds 50 mass ppm, it tends to be difficult to stably maintain the deoxygenation activity, and the sulfur content contained in the hydrorefined oil tends to increase. When used as a fuel for a diesel engine or the like, there is a concern about an adverse effect on the engine exhaust gas purification device. In addition, the sulfur content in this invention means the mass content of the sulfur content measured based on the method of JISK2541 "Sulfur content test method" or ASTM-5453.
被処理油に含硫黄炭化水素化合物を含有させる場合、含硫黄炭化水素化合物は、被処理油と予め混合してその混合物を水素化精製装置の反応器に導入してもよく、あるいは被処理油を反応器に導入する際に、反応器の前段において供給してもよい。 When the sulfur-containing hydrocarbon compound is included in the oil to be treated, the sulfur-containing hydrocarbon compound may be mixed with the oil to be treated in advance and the mixture may be introduced into the reactor of the hydrotreating apparatus, or the oil to be treated May be supplied at the front stage of the reactor.
本発明で用いられる被処理油は、沸点３００℃以上の留分を含有することが好ましく、また、沸点７００℃を超える重質な留分を含んでいないことが好ましい。沸点３００℃以上の留分を含有しない被処理油を用いると、過度の分解によって十分な収率を得ることが困難となる傾向にある。他方、被処理油が沸点７００℃を超える重質な留分を含む場合は、重質成分によって触媒における炭素の析出が促進され、活性が低下する傾向にある。なお、本発明における沸点は、ＪＩＳ Ｋ ２２５４「蒸留試験方法」又はＡＳＴＭ−Ｄ８６に記載の方法に準拠して測定される値である。 The oil to be treated used in the present invention preferably contains a fraction having a boiling point of 300 ° C. or higher, and preferably does not contain a heavy fraction having a boiling point exceeding 700 ° C. When the oil to be treated that does not contain a fraction having a boiling point of 300 ° C. or higher is used, it tends to be difficult to obtain a sufficient yield due to excessive decomposition. On the other hand, when the oil to be treated contains a heavy fraction having a boiling point higher than 700 ° C., carbon deposition in the catalyst is promoted by the heavy components, and the activity tends to decrease. In addition, the boiling point in this invention is a value measured based on the method as described in JISK2254 "distillation test method" or ASTM-D86.
本発明の水素化精製方法においては、結晶性モレキュラシーブを含む担体、並びに、該担体に担持された周期律表第６Ａ族及び第８族の元素から選ばれる１種以上の金属を含有する触媒が用いられる。 In the hydrorefining method of the present invention, a support containing crystalline molecular sieve, and a catalyst containing one or more metals selected from Group 6A and Group 8 elements of the periodic table supported on the support are provided. Used.
本発明で用いられる触媒に含まれる結晶性モレキュラシーブは、十分な水素化脱酸素活性と水素化異性化活性を付与するために、少なくともケイ素を含有していることが好ましい。また、結晶性モレキュラシーブは、ケイ素以外の構成元素として、アルミニウム、ジルコニウム、ホウ素、チタン、ガリウム、亜鉛、リンのうちの１種以上を含有していることが好ましく、アルミニウム、ジルコニウム、ホウ素、チタン、リンのうちの１種以上を含有していることがより好ましい。結晶性モレキュラシーブがこれらの元素を含有していることにより、水素化脱酸素反応と炭化水素の骨格異性化反応とを同時に促進し、精製油の低温性能向上をより十分に達成することができる。こうした結晶性モレキュラシーブとしては、ゼオライトが好ましく、ケイ素及びアルミニウムを含有するゼオライト、すなわちアルミノシリケートがより好ましい。 The crystalline molecular sieve contained in the catalyst used in the present invention preferably contains at least silicon in order to impart sufficient hydrodeoxygenation activity and hydroisomerization activity. The crystalline molecular sieve preferably contains at least one of aluminum, zirconium, boron, titanium, gallium, zinc, and phosphorus as a constituent element other than silicon. Aluminum, zirconium, boron, titanium, More preferably, it contains one or more of phosphorus. When the crystalline molecular sieve contains these elements, the hydrodeoxygenation reaction and the skeletal isomerization reaction of the hydrocarbon can be promoted simultaneously, and the low-temperature performance improvement of the refined oil can be achieved more sufficiently. As such crystalline molecular sieve, zeolite is preferable, and zeolite containing silicon and aluminum, that is, aluminosilicate is more preferable.
結晶性モレキュラシーブを構成する元素のうち酸素を除く元素について、酸素及びケイ素を除く構成元素に対するケイ素の比（ケイ素の原子数／酸素及びケイ素以外の元素の原子数）が３以上であることが好ましく、１０以上であることがより好ましく、３０以上であることが更に好ましい。この比が３未満である場合、パラフィンの分解反応が促進され、コーキングによる活性低下を招く恐れがある。 The ratio of silicon to the constituent elements excluding oxygen and silicon (number of atoms of silicon / number of atoms of elements other than silicon and silicon) of the elements constituting the crystalline molecular sieve excluding oxygen is preferably 3 or more. 10 or more is more preferable, and 30 or more is still more preferable. When this ratio is less than 3, the decomposition reaction of paraffin is promoted, and there is a possibility that the activity is reduced due to coking.
また、結晶性モレキュラシーブの細孔直径は、０．８ｎｍ以下であることが好ましく、０．６５ｎｍ以下であることがより好ましい。細孔直径が０．８ｎｍよりも大きい場合、パラフィンの分解反応が起こる懸念がある。結晶性モレキュラシーブの結晶構造としては、特に限定されるものではないが、国際ゼオライト学会が定める構造でいう、ＦＡＵ、ＡＥＬ、ＭＦＩ、ＭＭＷ、ＴＯＮ、ＭＴＷ、＊ＢＥＡ、ＭＯＲなどが挙げられる。 Further, the pore diameter of the crystalline molecular sieve is preferably 0.8 nm or less, and more preferably 0.65 nm or less. When the pore diameter is larger than 0.8 nm, there is a concern that a decomposition reaction of paraffin occurs. The crystal structure of the crystalline molecular sieve is not particularly limited, and examples thereof include FAU, AEL, MFI, MMW, TON, MTW, * BEA, MOR and the like, which are structures defined by the International Zeolite Society.
本発明で用いられる触媒を構成する結晶性モレキュラシーブの合成方法は、特に限定されるものではなく、一般的に知られているように、構成成分原料とアミン化合物を構造指示剤とした水熱合成法などを用いることができる。構成成分原料としては、例えば、ケイ素含有化合物の場合にはケイ酸ナトリウム、コロイダルシリカ、ケイ酸アルコキサイドなどが、アルミニウムの場合には水酸化アルミニウム、アルミン酸ナトリウムなどが挙げられる。構造指示剤としては、テトラプロピルアンモニウム塩などが挙げられる。 The method for synthesizing the crystalline molecular sieve constituting the catalyst used in the present invention is not particularly limited, and as is generally known, hydrothermal synthesis using a component raw material and an amine compound as a structure indicator. The method etc. can be used. Examples of the constituent raw materials include sodium silicate, colloidal silica, alkoxide silicate and the like in the case of a silicon-containing compound, and aluminum hydroxide and sodium aluminate in the case of aluminum. Examples of the structure directing agent include tetrapropylammonium salt.
また、結晶性モレキュラシーブは、必要に応じてスチーム等による水熱処理、アルカリ性又は酸性の水溶液による浸漬処理、イオン交換、塩素ガスやアンモニア等の塩基性又は酸性ガスによる表面処理などを、単独又は複数の工程を組み合わせて施すことによって、物性を調整することができる。 Further, the crystalline molecular sieve may be subjected to hydrothermal treatment with steam or the like, immersion treatment with an alkaline or acidic aqueous solution, ion exchange, surface treatment with a basic or acidic gas such as chlorine gas or ammonia, etc. The physical properties can be adjusted by combining the steps.
本発明で用いられる触媒において、結晶性モレキュラシーブ以外の構成物としては、アルミニウム、ケイ素、ジルコニウム、ホウ素、チタン及びマグネシウムから選ばれる元素を含む無機酸化物等が挙げられる。これらの無機酸化物は、結晶性モレキュラシーブを成型する際の接合剤として用いられるとともに、水素化脱酸素と水素異性化を促進する活性成分としても機能する点から、アルミニウム、ケイ素、ジルコニウム、ホウ素、チタン及びマグネシウムから選ばれる２種以上の元素を含むものであることが好ましい。 In the catalyst used in the present invention, examples of the constituent other than the crystalline molecular sieve include inorganic oxides containing an element selected from aluminum, silicon, zirconium, boron, titanium and magnesium. These inorganic oxides are used as a bonding agent when forming a crystalline molecular sieve, and also function as an active component that promotes hydrodeoxygenation and hydroisomerization, so that aluminum, silicon, zirconium, boron, It is preferable that it contains two or more elements selected from titanium and magnesium.
触媒全体に占める結晶性モレキュラシーブの含有量は、触媒全量を基準として２〜９０質量％であることが好ましく、５〜８５質量％であることがより好ましく、１０〜８０質量％であることが更に好ましい。この含有量が２質量％未満である場合、触媒としての水素化脱酸素活性及び水素化異性化活性が低下する傾向にあり、９０質量％を超える場合、触媒成形性が低下し、触媒の工業的な製造に支障が生じる恐れがある。 The content of the crystalline molecular sieve in the entire catalyst is preferably 2 to 90% by mass, more preferably 5 to 85% by mass, and further preferably 10 to 80% by mass based on the total amount of the catalyst. preferable. When this content is less than 2% by mass, the hydrodeoxygenation activity and hydroisomerization activity as a catalyst tend to decrease, and when it exceeds 90% by mass, the catalyst moldability decreases, and the catalyst industry Production may be hindered.
本発明で用いられる触媒における結晶性モレキュラシーブ以外の構成物について、アルミニウム以外の構成元素である、ケイ素、ジルコニウム、ホウ素、チタン及びマグネシウムを担体に導入する方法は特に制限されず、これらの元素を含有する溶液などを原料として用いればよい。例えば、ケイ素については、ケイ酸、水ガラス、シリカゾルなど、ホウ素についてはホウ酸など、リンについては、リン酸やリン酸のアルカリ金属塩など、チタンについては硫化チタン、四塩化チタンや各種アルコキサイド塩など、ジルコニウムについては硫酸ジルコニウムや各種アルコキサイド塩などを用いることができる。 Regarding the constituents other than the crystalline molecular sieve in the catalyst used in the present invention, the method of introducing silicon, zirconium, boron, titanium and magnesium, which are constituent elements other than aluminum, into the support is not particularly limited, and contains these elements. A solution to be used may be used as a raw material. For example, for silicon, silicic acid, water glass, silica sol, etc., for boron, boric acid, etc., for phosphorous, phosphoric acid and alkali metal salts of phosphoric acid, for titanium, titanium sulfide, titanium tetrachloride and various alkoxide salts For zirconium, zirconium sulfate and various alkoxide salts can be used.
酸化アルミニウム以外の担体構成成分の原料は、担体の焼成より前の工程において添加することが好ましい。例えば、アルミニウム水溶液に予め上記原料を添加した後、これらの構成成分を含む水酸化アルミニウムゲルを調製してもよく、調合した水酸化アルミニウムゲルに対して上記原料を添加してもよい。あるいは、市販の酸化アルミニウム中間体やベーマイトパウダーに水もしくは酸性水溶液を添加して混練する工程において上記原料を添加してもよいが、水酸化アルミニウムゲルを調合する段階で共存させることがより好ましい。酸化アルミニウム以外の担体構成成分の効果発現機構は必ずしも解明されたわけではないが、アルミニウムと複合的な酸化物状態を形成していると推察され、このことが担体表面積の増加や活性金属との相互作用を生じることにより、活性に影響を及ぼしていると考えられる。 It is preferable to add the raw materials of the carrier component other than aluminum oxide in the step prior to the baking of the carrier. For example, after adding the said raw material previously to aluminum aqueous solution, the aluminum hydroxide gel containing these structural components may be prepared, and the said raw material may be added with respect to the prepared aluminum hydroxide gel. Alternatively, the above raw materials may be added in a step of adding water or an acidic aqueous solution to a commercially available aluminum oxide intermediate or boehmite powder and kneading them, but it is more preferable to coexist at the stage of preparing aluminum hydroxide gel. Although the mechanism of the effect of the carrier constituents other than aluminum oxide has not necessarily been elucidated, it is presumed that it forms a complex oxide state with aluminum, which increases the surface area of the carrier and the interaction with the active metal. It is considered that the activity is affected by producing the action.
結晶性モレキュラシーブを含有する担体には、周期律表第６Ａ族及び第８族の元素から選ばれる１種以上の金属が担持される。これらの金属の中でも、Ｐｄ、Ｐｔ、Ｒｈ、Ｉｒ、Ａｕ、Ｎｉ及びＭｏから選ばれる１種以上の金属を用いることが好ましく、これらから選ばれる２種以上の金属を組み合わせて用いることがより好ましい。好適な組み合せとしては、例えば、Ｐｄ−Ｐｔ、Ｐｄ−Ｉｒ、Ｐｄ−Ｒｈ、Ｐｄ−Ａｕ、Ｐｄ−Ｎｉ、Ｐｔ−Ｒｈ、Ｐｔ−Ｉｒ、Ｐｔ−Ａｕ、Ｐｔ−Ｎｉ、Ｒｈ−Ｉｒ、Ｒｈ−Ａｕ、Ｒｈ−Ｎｉ、Ｉｒ−Ａｕ、Ｉｒ−Ｎｉ、Ａｕ−Ｎｉ、Ｐｄ−Ｐｔ−Ｒｈ、Ｐｄ−Ｐｔ−Ｉｒ、Ｐｄ−Ｐｔ−Ｎｉなどが挙げられる。このうち、Ｐｄ−Ｐｔ、Ｐｄ−Ｎｉ、Ｐｔ−Ｎｉ、Ｐｄ−Ｉｒ、Ｐｔ−Ｒｈ、Ｐｔ−Ｉｒ、Ｒｈ−Ｉｒ、Ｐｄ−Ｐｔ−Ｒｈ、Ｐｄ−Ｐｔ−Ｉｒ、Ｐｔ−Ｐｄ−Ｎｉの組み合わせがより好ましく、Ｐｄ−Ｐｔ、Ｐｄ−Ｎｉ、Ｐｔ−Ｎｉ、Ｐｄ−Ｉｒ、Ｐｔ−Ｉｒ、Ｐｄ−Ｐｔ−Ｉｒ、Ｐｔ−Ｐｄ−Ｎｉの組み合わせが更に好ましい。 The carrier containing the crystalline molecular sieve carries one or more metals selected from Group 6A and Group 8 elements of the periodic table. Among these metals, it is preferable to use one or more metals selected from Pd, Pt, Rh, Ir, Au, Ni and Mo, and it is more preferable to use a combination of two or more metals selected from these metals. . Suitable combinations include, for example, Pd—Pt, Pd—Ir, Pd—Rh, Pd—Au, Pd—Ni, Pt—Rh, Pt—Ir, Pt—Au, Pt—Ni, Rh—Ir, Rh— Au, Rh—Ni, Ir—Au, Ir—Ni, Au—Ni, Pd—Pt—Rh, Pd—Pt—Ir, Pd—Pt—Ni, and the like can be given. Of these, combinations of Pd—Pt, Pd—Ni, Pt—Ni, Pd—Ir, Pt—Rh, Pt—Ir, Rh—Ir, Pd—Pt—Rh, Pd—Pt—Ir, and Pt—Pd—Ni Is more preferable, and a combination of Pd—Pt, Pd—Ni, Pt—Ni, Pd—Ir, Pt—Ir, Pd—Pt—Ir, and Pt—Pd—Ni is more preferable.
本発明で用いられる上記触媒は、反応に供する前に触媒に含まれる活性金属を還元処理しておくことが好ましい。還元処理は特に限定されないが、水素気流下、２００〜４００℃の温度で処理することによって還元される。また、この還元処理は、２４０〜３８０℃の範囲で行うことが好ましい。還元温度が２００℃未満である場合、活性金属の還元が十分進行せず、水素化脱酸素及び水素化異性化活性が十分に発揮できない恐れがある。また、還元温度が４００℃を超える場合、活性金属の凝集が進行し、同様に活性が十分に発揮できなくなる恐れがある。 The catalyst used in the present invention is preferably subjected to a reduction treatment of the active metal contained in the catalyst before being subjected to the reaction. Although a reduction process is not specifically limited, it reduces by processing at the temperature of 200-400 degreeC under hydrogen stream. Moreover, it is preferable to perform this reduction process in the range of 240-380 degreeC. When the reduction temperature is less than 200 ° C., the reduction of the active metal does not proceed sufficiently, and the hydrodeoxygenation and hydroisomerization activity may not be sufficiently exhibited. Further, when the reduction temperature exceeds 400 ° C., the aggregation of the active metal proceeds, and there is a risk that the activity cannot be sufficiently exhibited.
触媒質量を基準とする活性金属の合計含有量としては、金属として０．１〜２質量％が好ましく、０．２〜１．５質量％がより好ましく、０．５〜１．３質量％が更に好ましい。金属の合計担持量が０．１質量％未満であると、活性点が少なくなり、十分な活性が得られなくなる傾向がある。他方、２質量％を越えると、金属が効果的に分散せず、十分な活性が得られなくなる傾向がある。 The total content of active metals based on the catalyst mass is preferably 0.1 to 2% by mass, more preferably 0.2 to 1.5% by mass, and 0.5 to 1.3% by mass as the metal. Further preferred. If the total supported amount of the metal is less than 0.1% by mass, the active sites tend to decrease and sufficient activity cannot be obtained. On the other hand, if it exceeds 2% by mass, the metal is not effectively dispersed and sufficient activity tends not to be obtained.
これらの活性金属を触媒に含有させる方法は特に限定されず、通常の脱硫触媒を製造する際に適用される公知の方法を用いることができる。通常、活性金属の塩を含む溶液を触媒担体に含浸する方法が好ましく採用される。また、平衡吸着法、Ｐｏｒｅ−ｆｉｌｌｉｎｇ法、Ｉｎｃｉｐｉｅｎｔ−ｗｅｔｎｅｓｓ法なども好ましく採用される。例えば、Ｐｏｒｅ−ｆｉｌｌｉｎｇ法は、担体の細孔容積を予め測定しておき、これと同じ容積の金属塩溶液を含浸する方法である。なお、含浸方法は特に限定されるものではなく、金属担持量や触媒担体の物性に応じて適当な方法で含浸することができる。 The method for incorporating these active metals into the catalyst is not particularly limited, and a known method applied when producing an ordinary desulfurization catalyst can be used. Usually, a method of impregnating a catalyst carrier with a solution containing a salt of an active metal is preferably employed. In addition, an equilibrium adsorption method, a pore-filling method, an incident-wetness method, and the like are also preferably employed. For example, the pore-filling method is a method in which the pore volume of the carrier is measured in advance and impregnated with a metal salt solution having the same volume. The impregnation method is not particularly limited, and it can be impregnated by an appropriate method according to the amount of metal supported and the physical properties of the catalyst carrier.
本発明で用いられる上記触媒の活性金属が還元状態にあるとき、触媒１ｇ当たりの一酸化炭素吸着量が０．００３〜０．０５ｍｍｏｌであることが好ましく、０．００５〜０．０４ｍｍｏｌであることがより好ましく、０．００９〜０．０３ｍｍｏｌであることが更に好ましい。この吸着量が０．００３ｍｍｏｌ未満であると、金属が凝集した状態となって活性点が減少する傾向にある。他方、吸着量が０．０５ｍｍｏｌを超えると、反応時間の経過とともに活性低下が促進される傾向にある。一酸化炭素吸着量の測定は、還元金属を担持した触媒に用いる一般的な測定方法を適用することができる。具体的には、一定量の触媒を水素気流下３５０℃で還元した後に、５０℃まで冷却して、パルス法や定容法によって求めることができる。 When the active metal of the catalyst used in the present invention is in a reduced state, the carbon monoxide adsorption amount per 1 g of the catalyst is preferably 0.003 to 0.05 mmol, and 0.005 to 0.04 mmol. Is more preferable, and 0.009 to 0.03 mmol is even more preferable. If the amount of adsorption is less than 0.003 mmol, the metal is in an aggregated state and the active sites tend to decrease. On the other hand, when the adsorption amount exceeds 0.05 mmol, the activity decrease tends to be promoted with the lapse of the reaction time. For the measurement of the carbon monoxide adsorption amount, a general measurement method used for a catalyst supporting a reduced metal can be applied. Specifically, after a certain amount of the catalyst is reduced at 350 ° C. under a hydrogen stream, it is cooled to 50 ° C. and can be obtained by a pulse method or a constant volume method.
また、本発明においては、上記の触媒（水素化精製触媒）以外に、必要に応じて被処理油に随伴して流入するスケール分をトラップしたり触媒床の区切り部分で水素化精製触媒を支持したりする目的でガード触媒、脱金属触媒、不活性充填物を用いてもよい。なお、これらは単独又は組み合せて用いることができる。 In addition, in the present invention, in addition to the above catalyst (hydrorefining catalyst), if necessary, the scale component flowing in accompanying the oil to be treated is trapped, or the hydrorefining catalyst is supported at the separation part of the catalyst bed. For this purpose, a guard catalyst, a metal removal catalyst, or an inert filler may be used. In addition, these can be used individually or in combination.
水素の存在下で上記の被処理油と触媒とを接触させる際の条件は、水素圧力２〜１３ＭＰａ、液空間速度（ＬＨＳＶ）０．１〜３．０ｈ−１、水素油比（水素／油比）２５０〜１５００ＮＬ／Ｌであり、好ましくは、水素圧力２．５〜１０ＭＰａ、液空間速度０．５〜２．０ｈ−１、水素油比３００〜１２００ＮＬ／Ｌであり、より好ましくは、水素圧力３〜８ＭＰａ、空間速度０．８〜１．８ｈ−１、水素油比３５０〜１０００ＮＬ／Ｌである。これらの条件はいずれも反応活性を左右する因子であり、例えば水素圧力及び水素油比が上記の下限値に満たない場合には、反応性が低下したり活性が急速に低下したりする傾向がある。他方、水素圧力及び水素油比が上記の上限値を超える場合には、圧縮機等の過大な設備投資が必要となる傾向がある。また、液空間速度は低いほど反応に有利な傾向にあるが、上記の下限値未満の場合は、極めて大きな内容積の反応器が必要となり過大な設備投資が必要となる傾向があり、他方、液空間速度が上記の上限値を超える場合は、反応が十分に進行しなくなる傾向がある。 The conditions for contacting the oil to be treated and the catalyst in the presence of hydrogen are as follows: hydrogen pressure 2-13 MPa, liquid space velocity (LHSV) 0.1-3.0 h −1 , hydrogen oil ratio (hydrogen / oil Ratio) 250-1500 NL / L, preferably hydrogen pressure 2.5-10 MPa, liquid space velocity 0.5-2.0 h −1 , hydrogen oil ratio 300-1200 NL / L, more preferably hydrogen The pressure is 3 to 8 MPa, the space velocity is 0.8 to 1.8 h −1 , and the hydrogen oil ratio is 350 to 1000 NL / L. These conditions are factors that influence the reaction activity. For example, when the hydrogen pressure and the hydrogen oil ratio are less than the above lower limit values, the reactivity tends to decrease or the activity rapidly decreases. is there. On the other hand, when the hydrogen pressure and the hydrogen oil ratio exceed the above upper limit values, there is a tendency that excessive equipment investment such as a compressor is required. Further, the lower the liquid space velocity tends to be advantageous for the reaction, but if the liquid space velocity is less than the above lower limit value, there is a tendency that an extremely large internal volume reactor is required and excessive equipment investment is required, When the liquid space velocity exceeds the above upper limit, the reaction tends not to proceed sufficiently.
反応器の形式としては、固定床方式を採用することができる。すなわち、水素は被処理油に対して向流又は並流のいずれの形式を採用することができる。また、複数の反応器を用いて、向流、並流を組み合せた形式としてもよい。一般的な形式としては、ダウンフローであり、気液双並流形式を採用することができる。また、反応器は単独又は複数を組み合せてもよく、一つの反応器内部を複数の触媒床に区分した構造を採用してもよい。 As the type of the reactor, a fixed bed system can be adopted. That is, hydrogen can adopt either a countercurrent or a parallel flow type with respect to the oil to be treated. Moreover, it is good also as a form which combined the countercurrent and the parallel flow using several reactors. As a general format, it is a down flow, and a gas-liquid twin parallel flow format can be adopted. Moreover, the reactor may be used alone or in combination, and a structure in which one reactor is divided into a plurality of catalyst beds may be adopted.
反応器内で水素化精製された水素化精製油は気液分離工程や精留工程等を経て所定の留分を含有する水素化精製油に分画される。例えば、軽油留分や残さ留分に分画される。さらに必要に応じてガス、ナフサ留分、灯油留分を分画することもある。生成するこのような軽質炭化水素留分の一部を水蒸気改質装置において改質することにより水素を製造することができる。このようにして製造された水素は、水蒸気改質に用いた原料がバイオマス由来炭化水素であることから、カーボンニュートラルという特徴を有しており、環境への負荷を低減することができる。なお、被処理油に含まれている酸素分や硫黄分の反応に伴って水、一酸化炭素、二酸化炭素、硫化水素などが発生する可能性があるが、複数の反応器の間や生成物回収工程に気液分離設備やその他の副生ガス除去装置を設置してもよい。副生ガス除去装置によって副生ガスが除去されたガス分は、被処理油と混合してリサイクルして使用してもよい。被処理油に混合する前段に膜分離装置や圧力スイング吸着装置によってガス中に含まれる水素純度を増加せしめた後に用いることもできる。なお、リサイクルするガスに含まれる一酸化炭素濃度は、触媒活性を維持する観点から、０．５容量％以下であることが好ましく、０．１容量％以下であることがより好ましい。 The hydrorefined oil hydrorefined in the reactor is fractionated into a hydrorefined oil containing a predetermined fraction through a gas-liquid separation process, a rectification process, and the like. For example, it is fractionated into a light oil fraction and a residual fraction. Furthermore, the gas, naphtha fraction, and kerosene fraction may be fractionated as necessary. Hydrogen can be produced by reforming a part of the light hydrocarbon fraction produced in a steam reformer. The hydrogen produced in this way has a characteristic of carbon neutral because the raw material used for steam reforming is a biomass-derived hydrocarbon, and can reduce the burden on the environment. In addition, water, carbon monoxide, carbon dioxide, hydrogen sulfide, etc. may be generated due to the reaction of oxygen and sulfur contained in the oil to be treated. A gas-liquid separation facility or other by-product gas removal device may be installed in the recovery process. The gas component from which the by-product gas has been removed by the by-product gas removing device may be mixed with the oil to be treated and recycled for use. It can also be used after the purity of hydrogen contained in the gas is increased by a membrane separation device or a pressure swing adsorption device before mixing with the oil to be treated. Note that the concentration of carbon monoxide contained in the gas to be recycled is preferably 0.5% by volume or less, and more preferably 0.1% by volume or less, from the viewpoint of maintaining catalytic activity.
水素ガスは加熱炉を通過前もしくは通過後の被処理油に随伴させて最初の反応器の入口から導入することが一般的であるが、これとは別に、反応器内の温度を制御するとともに、反応器内全体にわたって水素圧力を維持する目的で触媒床の間や複数の反応器の間から水素ガスを導入してもよい。このようにして導入される水素を一般にクエンチ水素と呼ぶ。被処理油に随伴して導入する水素ガスに対するクエンチ水素の割合は、１０〜６０容量％であることが好ましく、１５〜５０容量％であることがより好ましい。クエンチ水素の割合が１０容量未満であると後段の反応部位での反応が十分に進行しない傾向があり、クエンチ水素の割合が６０容積％を超えると反応器入口付近での反応が十分に進行しない傾向がある。 In general, hydrogen gas is introduced from the inlet of the first reactor along with the oil to be treated before or after passing through the heating furnace, but separately from this, the temperature in the reactor is controlled. In order to maintain the hydrogen pressure throughout the reactor, hydrogen gas may be introduced between the catalyst beds or between a plurality of reactors. The hydrogen thus introduced is generally called quench hydrogen. The ratio of quench hydrogen to hydrogen gas introduced along with the oil to be treated is preferably 10 to 60% by volume, and more preferably 15 to 50% by volume. If the rate of quench hydrogen is less than 10 volumes, the reaction at the subsequent reaction site tends not to proceed sufficiently. If the rate of quench hydrogen exceeds 60% by volume, the reaction near the reactor inlet does not proceed sufficiently. Tend.
本発明によって製造される水素化精製油を軽油留分基材として用いる場合は、少なくとも２６０〜３００℃の沸点を有する留分を含有し、硫黄分の含有量が１０質量ｐｐｍ以下であり且つ酸素分の含有量が０．３質量％以下であることが好ましく、硫黄分の含有量が７質量ｐｐｍ以下であり且つ酸素分の含有量が０．３質量％以下であることがより好ましく、硫黄分の含有量が３質量ｐｐｍ以下であり且つ酸素分の含有量が０．２質量％以下であることが更に好ましい。硫黄分及び酸素分が上記の上限値を超える場合、ディーゼルエンジンの排出ガス処理装置で使用されるフィルターや触媒、さらにエンジンその他の材質に影響を及ぼす恐れがある。 When the hydrorefined oil produced according to the present invention is used as a light oil fraction base, it contains a fraction having a boiling point of at least 260 to 300 ° C., a sulfur content of 10 mass ppm or less, and oxygen The content of min is preferably 0.3% by mass or less, the content of sulfur is 7% by mass or less, and the content of oxygen is more preferably 0.3% by mass or less. It is more preferable that the content of the component is 3 mass ppm or less and the content of the oxygen component is 0.2 mass% or less. When the sulfur content and the oxygen content exceed the above upper limit values, there is a risk of affecting the filter and catalyst used in the exhaust gas treatment device of the diesel engine, and further the engine and other materials.
また、本発明によって製造される水素化精製油を軽油留分基材として用いる場合には、当該留分に含有されるパラフィン分のうち、ノルマルパラフィンに対するイソパラフィンの比（イソパラフィンの質量／ノルマルパラフィンの質量）が０．２以上であることが好ましく、０．５以上であることがより好ましく、１．０以上であることが更に好ましい。この比が０．２未満である場合には、低温環境下で留分が十分な流動性を維持できず、あるいは低温環境下で析出する結晶によってディーゼルエンジンの燃料ろ過装置での目詰まりなどが発生し、トラブルを招く恐れがある。 Further, when the hydrorefined oil produced by the present invention is used as a light oil fraction base material, the ratio of isoparaffin to normal paraffin in the paraffin content contained in the fraction (mass of isoparaffin / normal paraffin Mass) is preferably 0.2 or more, more preferably 0.5 or more, and even more preferably 1.0 or more. When this ratio is less than 0.2, the distillate cannot maintain sufficient fluidity in a low-temperature environment, or crystals precipitated in the low-temperature environment may cause clogging in a fuel filter device of a diesel engine. May occur and cause trouble.
本発明によって製造される水素化精製油は、特にディーゼル軽油や重油基材として好適に用いることができる。水素化精製油は単独でディーゼル軽油や重油基材として用いてもよいが、他の基材などの成分を混合したディーゼル軽油又は重質基材として用いることができる。他の基材としては、一般的な石油精製工程で得られる軽油留分及び／又は灯油留分、本発明の水素化精製方法で得られる残さ留分を混合することもできる。さらに、水素と一酸化炭素から構成される、いわゆる合成ガスを原料とし、フィッシャートロプシュ反応などを経由して得られる合成軽油もしくは合成灯油を混合することができる。これらの合成軽油や合成灯油は芳香族分をほとんど含有せず、飽和炭化水素を主成分とし、セタン価が高いことが特徴である。なお、合成ガスの製造方法としては公知の方法を用いることができ、特に限定されるものではない。 The hydrorefined oil produced by the present invention can be suitably used particularly as a diesel light oil or heavy oil base material. The hydrorefined oil may be used alone as a diesel light oil or heavy oil base material, but can be used as a diesel light oil or a heavy base material mixed with components such as other base materials. As other base materials, a light oil fraction and / or kerosene fraction obtained in a general petroleum refining process and a residual fraction obtained by the hydrorefining method of the present invention can be mixed. Furthermore, a synthetic light oil or a kerosene obtained through a Fischer-Tropsch reaction or the like using so-called synthesis gas composed of hydrogen and carbon monoxide as a raw material can be mixed. These synthetic light oils and kerosene are characterized by containing almost no aromatic content, having a saturated hydrocarbon as a main component, and a high cetane number. In addition, a well-known method can be used as a manufacturing method of synthesis gas, and it is not specifically limited.
本発明において被処理油を水素化精製する水素化精製工程は、被処理油に含まれる初期酸素分の７０質量％以上を除去して第一精製油を得る第一水素化工程と、上記初期酸素分の９５質量％以上が除去されるように、上記第一精製油に残存する酸素分を除去して第二精製油を得る第二水素化工程と、を含み、上記第二水素化工程は、上記第二精製油の１５０〜３５０℃の留分に含まれるパラフィン分において、ノルマルパラフィンに対するイソパラフィンの比（イソパラフィンの質量／ノルマルパラフィンの質量）が０．２以上となるように行うことが好ましい。第一水素化工程における酸素分除去率が７０質量％に満たない場合、第二水素化工程における水素化脱酸素及び水素化異性化反応が十分に進行しない恐れがある。 The hydrorefining step for hydrotreating the oil to be treated in the present invention includes a first hydrogenation step for obtaining a first refined oil by removing 70% by mass or more of an initial oxygen content contained in the oil to be treated; A second hydrogenation step, wherein a second refined oil is obtained by removing oxygen remaining in the first refined oil so that 95% by mass or more of the oxygen content is removed. Is carried out so that the ratio of isoparaffin to normal paraffin (mass of isoparaffin / mass of normal paraffin) is 0.2 or more in the paraffin contained in the fraction of 150 to 350 ° C. of the second refined oil. preferable. When the oxygen content removal rate in the first hydrogenation step is less than 70% by mass, the hydrodeoxygenation and hydroisomerization reaction in the second hydrogenation step may not proceed sufficiently.
本発明の水素化精製方法においては、第一水素化工程及び第二水素化工程のうちの少なくとも一方の工程を、水素の存在下で、上述した含酸素炭化水素化合物を含有する被処理油と、結晶性モレキュラシーブを含む担体、並びに、該担体に担持された周期律表第６Ａ族及び第８族の元素から選ばれる１種以上の金属を含有する触媒と、を接触させることにより行えばよい。すなわち、第一水素化工程及び第二水素化工程のいずれか一方の工程は、上記触媒以外の触媒を用いて行ってもよい。 In the hydrorefining method of the present invention, at least one of the first hydrogenation step and the second hydrogenation step is performed in the presence of hydrogen with the oil to be treated containing the oxygen-containing hydrocarbon compound described above. And a carrier containing crystalline molecular sieve, and a catalyst containing one or more metals selected from Group 6A and Group 8 elements of the periodic table supported on the carrier. . That is, any one of the first hydrogenation step and the second hydrogenation step may be performed using a catalyst other than the above catalyst.
第一水素化工程においては、アルミニウム、ケイ素、ジルコニウム、ホウ素、チタン及びマグネシウムから選ばれる２種以上の元素を含んで構成される多孔性無機酸化物、並びに、該多孔性無機酸化物に担持された周期律表第６Ａ族及び第８族の元素から選ばれる１種以上の金属（活性金属）を含有する触媒を用いることが好ましい。ここで、活性金属としては、Ｐｄ、Ｐｔ、Ｒｈ、Ｉｒ、Ａｕ、Ｎｉ及びＭｏから選ばれる１種以上の元素であることがより好ましい。 In the first hydrogenation step, a porous inorganic oxide comprising two or more elements selected from aluminum, silicon, zirconium, boron, titanium and magnesium, and the porous inorganic oxide are supported. It is preferable to use a catalyst containing one or more metals (active metals) selected from Group 6A and Group 8 elements of the periodic table. Here, the active metal is more preferably one or more elements selected from Pd, Pt, Rh, Ir, Au, Ni, and Mo.
そして、第二水素化工程においては、結晶性モレキュラシーブを含む担体、並びに、該担体に担持された周期律表第６Ａ族及び第８族の元素（好ましくは第８族の元素）から選ばれる１種以上の金属を含有する触媒を用いることが好ましい。なお、第二水素化工程において使用する触媒は、１種類でも複数種用いてもよく、精製油の安定性を向上させる目的で、第二水素化工程後段に水素化活性を有する触媒を充填してもよい。 In the second hydrogenation step, 1 selected from the carrier containing the crystalline molecular sieve and the Group 6A and Group 8 elements (preferably the Group 8 element) supported on the carrier. It is preferable to use a catalyst containing more than one metal. In addition, the catalyst used in the second hydrogenation step may be used alone or in combination, and for the purpose of improving the stability of the refined oil, a catalyst having hydrogenation activity is charged after the second hydrogenation step. May be.
以下、実施例及び比較例に基づき本発明を更に具体的に説明するが、本発明は以下の実施例に何ら限定されるものではない。 EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example and a comparative example, this invention is not limited to a following example at all.
（触媒の調製）
＜触媒Ａ＞
ポリテトラフルオロエチレンビーカーに、市販のベーマイトパウダー（触媒化成工業社製）とシリカアルミナパウダー（触媒化成工業社製）とを、ケイ素／アルミニウムの原子数の比が１５となるように混合し、蒸留水を加えて、加熱しながら濃縮、混練して粘土状の混練物を得た。この混練物に、ゼオライトとしての合成したプロトン型ＺＳＭ−５（ケイ素／アルミニウムの原子数の比：４０）を酸化物換算で触媒全量の６５質量％となるように加え、さらに混練した。得られた混練物を押出し成形機によって直径１．５ｍｍのシリンダーの形状に押し出し、１１０℃で１時間乾燥した後、５００℃で焼成し、成形担体を得た。
(Preparation of catalyst)
<Catalyst A>
A polytetrafluoroethylene beaker was mixed with commercially available boehmite powder (catalyst chemical industry) and silica alumina powder (catalyst chemical industry) so that the silicon / aluminum atomic ratio was 15, and distilled. Water was added, and the mixture was concentrated and kneaded while heating to obtain a clay-like kneaded product. To this kneaded product, synthesized proton type ZSM-5 (ratio of silicon / aluminum atoms: 40) as zeolite was added so as to be 65% by mass of the total amount of the catalyst in terms of oxide, and further kneaded. The obtained kneaded product was extruded into the shape of a cylinder having a diameter of 1.5 mm by an extrusion molding machine, dried at 110 ° C. for 1 hour, and then fired at 500 ° C. to obtain a molded carrier.
得られた成形担体１０ｇをナス型フラスコに入れ、ロータリーエバポレーターで脱気しながら、テトラアンミン白金（ＩＩ）クロライドとテトラアンミンパラジウム（ＩＩ）クロライドの混合水溶液をフラスコ内に注入して成形担体に金属を含浸せしめ、１１０℃で乾燥した後、３５０℃で焼成を行い、触媒Ａを得た。触媒Ａにおける白金、パラジウムの担持量は、触媒全量を基準として、白金が０．５質量％、パラジウムが０．７質量％であった。 10 g of the obtained shaped carrier was put into an eggplant-shaped flask, and a mixed aqueous solution of tetraammineplatinum (II) chloride and tetraamminepalladium (II) chloride was poured into the flask while degassing with a rotary evaporator, and the shaped carrier was impregnated with metal. After drying at 110 ° C., firing was performed at 350 ° C. to obtain Catalyst A. The supported amounts of platinum and palladium in the catalyst A were 0.5% by mass of platinum and 0.7% by mass of palladium based on the total amount of the catalyst.
＜触媒Ｂ＞
ポリテトラフルオロエチレンビーカーに、市販のベーマイトパウダー（触媒化成工業社製）とシリカアルミナパウダー（触媒化成工業社製）とを、ケイ素／アルミニウムの原子数の比が１５となるように混合し、蒸留水を加えて、加熱しながら濃縮、混練して粘土状の混練物を得た。この混練物に、ゼオライトとしての合成したプロトン型ＺＳＭ−２２（ケイ素／アルミニウムの原子数の比：４５）を酸化物換算で触媒全量の６５質量％となるように加え、さらに混練した。得られた混練物を押出し成形機によって直径１．５ｍｍのシリンダーの形状に押し出し、１１０℃で１時間乾燥した後、５００℃で焼成し、成形担体を得た。得られた成形担体１０ｇに、触媒Ａと同様に白金、パラジウムを担持して触媒Ｂを得た。触媒Ｂにおける白金、パラジウムの担持量は、触媒全量を基準として、白金が０．５質量％、パラジウムが０．７質量％であった。
<Catalyst B>
A polytetrafluoroethylene beaker was mixed with commercially available boehmite powder (catalyst chemical industry) and silica alumina powder (catalyst chemical industry) so that the silicon / aluminum atomic ratio was 15, and distilled. Water was added, and the mixture was concentrated and kneaded while heating to obtain a clay-like kneaded product. To this kneaded product, a synthesized proton type ZSM-22 (a ratio of the number of atoms of silicon / aluminum: 45) as zeolite was added so as to be 65% by mass of the total amount of the catalyst in terms of oxide, and further kneaded. The obtained kneaded product was extruded into the shape of a cylinder having a diameter of 1.5 mm by an extrusion molding machine, dried at 110 ° C. for 1 hour, and then fired at 500 ° C. to obtain a molded carrier. In the same manner as Catalyst A, platinum and palladium were supported on 10 g of the obtained molded carrier to obtain Catalyst B. The supported amount of platinum and palladium in the catalyst B was 0.5% by mass of platinum and 0.7% by mass of palladium based on the total amount of the catalyst.
＜触媒Ｃ＞
濃度５質量％のアルミン酸ナトリウム水溶液３０００ｇに水ガラス３号１８．０ｇを加えた混合液を、６５℃に保温した濃度２．５質量％の硫酸アルミニウム水溶液に、ｐＨが７．０になるまで滴下した。得られたスラリー状の生成物をフィルターに通して濾取し、ケーキ状のスラリーを得た。
<Catalyst C>
A solution obtained by adding 18.0 g of water glass No. 3 to 3000 g of a sodium aluminate aqueous solution having a concentration of 5% by mass is added to an aluminum sulfate aqueous solution having a concentration of 2.5% by mass kept at 65 ° C. until the pH becomes 7.0. It was dripped. The resulting slurry product was filtered through a filter to obtain a cake slurry.
ケーキ状のスラリーを還流冷却器を取り付けた容器に移し、蒸留水１５０ｍｌと２７％アンモニア水溶液１０ｇを加え、７５℃で２０時間加熱攪拌した。該スラリーを混練装置に入れ、８０℃以上に加熱し水分を除去しながら混練し、粘土状の混練物を得た。得られた混練物を押出し成形機によって直径１．５ｍｍのシリンダーの形状に押し出し、１１０℃で１時間乾燥した後、５５０℃で焼成し、成形担体を得た。成形担体のアルミニウム含有量は、酸化アルミニウム換算で９０．１質量％、ケイ素含有量はケイ酸換算で９．９質量％であった。 The cake-like slurry was transferred to a container equipped with a reflux condenser, 150 ml of distilled water and 10 g of 27% aqueous ammonia solution were added, and the mixture was heated and stirred at 75 ° C. for 20 hours. The slurry was put in a kneading apparatus and heated to 80 ° C. or higher and kneaded while removing moisture to obtain a clay-like kneaded product. The obtained kneaded product was extruded into the shape of a cylinder having a diameter of 1.5 mm by an extrusion molding machine, dried at 110 ° C. for 1 hour, and then fired at 550 ° C. to obtain a molded carrier. The aluminum content of the molded carrier was 90.1% by mass in terms of aluminum oxide, and the silicon content was 9.9% by mass in terms of silicic acid.
得られた成形担体５０ｇをナス型フラスコに入れ、ロータリーエバポレータ−で脱気しながらテトラアンミン白金（ＩＩ）クロライドとテトラアンミンパラジウム（ＩＩ）クロライドの混合水溶液をフラスコ内に注入して成形担体に金属を含浸せしめ、１１０℃で乾燥した後、３５０℃で焼成を行い、触媒Ｃを得た。触媒Ｃにおける白金、パラジウムの担持量は、触媒全量を基準として、白金が０．５質量％、パラジウムが０．７質量％であった。 50 g of the obtained shaped carrier was placed in an eggplant-shaped flask, and a mixed aqueous solution of tetraammineplatinum (II) chloride and tetraamminepalladium (II) chloride was poured into the flask while degassing with a rotary evaporator, and the shaped carrier was impregnated with metal. After drying at 110 ° C., firing was performed at 350 ° C. to obtain Catalyst C. The supported amount of platinum and palladium in the catalyst C was 0.5% by mass of platinum and 0.7% by mass of palladium based on the total amount of the catalyst.
（実施例１）
触媒Ａ（５０ｍｌ）を充填した第一反応管（内径２０ｍｍ）と、同じく触媒Ａ（５０ｍｌ）を充填した第二反応管（内径２０ｍｍ）を直列に固定床流通式反応装置に取り付けた。その後、触媒層平均温度３２０℃、水素分圧５ＭＰａ、水素ガス量８３ｍｌ／ｍｉｎの条件下で、６時間触媒の還元処理を行った。なお、還元状態にある触媒Ａ１ｇ当たりの一酸化炭素吸着量は０．０３７ｍｍｏｌであった。
Example 1
A first reaction tube (inner diameter 20 mm) filled with catalyst A (50 ml) and a second reaction tube (inner diameter 20 mm) also filled with catalyst A (50 ml) were attached in series to a fixed bed flow reactor. Thereafter, the catalyst was reduced for 6 hours under the conditions of an average catalyst layer temperature of 320 ° C., a hydrogen partial pressure of 5 MPa, and a hydrogen gas amount of 83 ml / min. The amount of carbon monoxide adsorbed per 1 g of the catalyst A in the reduced state was 0.037 mmol.
触媒還元操作後、被処理油としてパーム油（含酸素炭化水素化合物に占めるトリグリセリド構造を有する化合物の割合：９８モル％）を用いて水素化精製を行った。被処理油の１５℃密度は０．９１６ｇ／ｍｌ、酸素分含有量は１１．４質量％、硫黄分含有量は０．２質量ｐｐｍ以下であった。また、水素化精製の条件は、第一及び第二反応管の反応温度を３１０℃、圧力を５ＭＰａ、液空間速度を０．７ｈ−１とした。なお、第一反応管と第二反応管の間で導入する水素ガスの容量比率（クエンチ水素比率）は全導入水素の２０容量％とし、導入した全水素によって求めた水素／油比を６００ＮＬ／Ｌとした。得られた結果を表１に示す。 After the catalytic reduction operation, hydrorefining was performed using palm oil (ratio of the compound having a triglyceride structure in the oxygen-containing hydrocarbon compound: 98 mol%) as the oil to be treated. The 15 ° C. density of the oil to be treated was 0.916 g / ml, the oxygen content was 11.4 mass%, and the sulfur content was 0.2 mass ppm or less. The hydrorefining conditions were such that the reaction temperature of the first and second reaction tubes was 310 ° C., the pressure was 5 MPa, and the liquid space velocity was 0.7 h −1 . The volume ratio of hydrogen gas introduced between the first reaction pipe and the second reaction pipe (quenched hydrogen ratio) is 20% by volume of the total introduced hydrogen, and the hydrogen / oil ratio obtained from the total hydrogen introduced is 600 NL / L. The obtained results are shown in Table 1.
（実施例２）
触媒Ａの代わりに触媒Ｂを用いたこと以外は実施例１と同様にして水素化精製を行った。得られた結果を表１に示す。なお、還元状態にある触媒Ｂ１ｇ当たりの一酸化炭素吸着量は０．０３５ｍｍｏｌであった。
(Example 2)
The hydrorefining was performed in the same manner as in Example 1 except that the catalyst B was used instead of the catalyst A. The obtained results are shown in Table 1. The amount of carbon monoxide adsorbed per 1 g of the catalyst B in the reduced state was 0.035 mmol.
（実施例３）
第一反応管に触媒Ｃ（５０ｍｌ）を充填し、第二反応管に触媒Ａ（５０ｍｌ）を充填して、実施例１と同様にして水素化精製を行った。得られた結果を表１に示す。なお、還元状態にある触媒Ｃ１ｇ当たりの一酸化炭素吸着量は０．０３８ｍｍｏｌであった。
(Example 3)
The first reaction tube was filled with catalyst C (50 ml), the second reaction tube was filled with catalyst A (50 ml), and hydrogenation purification was performed in the same manner as in Example 1. The obtained results are shown in Table 1. The amount of carbon monoxide adsorbed per 1 g of the catalyst C in the reduced state was 0.038 mmol.
（比較例１）
触媒Ａの代わりに触媒Ｃを用い、第一反応管の反応温度を２００℃、第二反応管の反応温度を３１０℃とし、実施例１と同様にして水素化精製を行った。得られた結果を表１に示す。
(Comparative Example 1)
The catalyst C was used in place of the catalyst A, the reaction temperature of the first reaction tube was 200 ° C., the reaction temperature of the second reaction tube was 310 ° C., and hydrorefining was performed in the same manner as in Example 1. The obtained results are shown in Table 1.
（低温性能の評価）
実施例１〜３及び比較例１の水素化精製により得られた精製油は、蒸留によって沸点１５０℃より軽質な留分を除いた後、残さ（灯軽油留分）について、曇り点をＪＩＳ Ｋ２２６９「原油及び石油製品の流動点並びに石油製品曇り点試験方法」に準拠して測定した。また、上記残さ中のパラフィン分について、ノルマルパラフィンに対するイソパラフィンの質量比（イソパラフィンの質量／ノルマルパラフィンの質量）を測定した。結果を表１に示す。
(Evaluation of low temperature performance)
The refined oils obtained by hydrorefining in Examples 1 to 3 and Comparative Example 1 were subjected to distillation to remove fractions having a boiling point lower than 150 ° C., and then the cloud point of the residue (kerosene oil fraction) was determined according to JIS K2269. It was measured according to “Pour point of crude oil and petroleum product and cloud point test method of petroleum product”. Moreover, about the paraffin content in the said residue, the mass ratio (mass of isoparaffin / mass of normal paraffin) with respect to normal paraffin was measured. The results are shown in Table 1.
Claims (6)
含酸素炭化水素化合物を含有する被処理油と、
結晶性モレキュラシーブを含む担体、並びに、該担体に担持された周期律表第６Ａ族及び第８族の元素から選ばれる１種以上の金属を含有する触媒と、を接触させる水素化精製工程を経て精製油を得る水素化精製方法であり、
前記含酸素炭化水素化合物は、動植物油に由来する油脂成分であり、
前記水素は、前記被処理油に随伴して導入される水素ガスと、クエンチ水素として導入される水素ガスとを含み、前記被処理油に随伴して導入される水素ガスに対する前記クエンチ水素の割合が１０〜６０容量％であり、
前記水素化精製工程は、
前記被処理油と、結晶性モレキュラシーブを含む担体、又は、アルミニウム、ケイ素、ジルコニウム、ホウ素、チタン及びマグネシウムから選ばれる２種以上の元素を含んで構成される多孔性無機酸化物、並びに、前記担体又は前記多孔性無機酸化物に担持された周期律表第６Ａ族及び第８族の元素から選ばれる１種以上の金属を含有する触媒とを、水素圧力２〜１３ＭＰａ、液空間速度０．１〜３．０ｈ−１、水素油比２５０〜１５００ＮＬ／Ｌ、反応温度１５０〜３８０℃の条件下で接触させて第一精製油を得る第一水素化工程と、
前記第一精製油と、結晶性モレキュラシーブを含む担体、並びに、該担体に担持された周期律表第６Ａ族及び第８族の元素から選ばれる１種以上の金属を含有する触媒とを、水素圧力２〜１３ＭＰａ、液空間速度０．１〜３．０ｈ−１、水素油比２５０〜１５００ＮＬ／Ｌ、反応温度１５０〜３８０℃の条件下で接触させて第二精製油を得る第二水素化工程と、を含み、
前記第一水素化工程は、前記被処理油に含まれる初期酸素分の７０質量％以上を除去して前記第一精製油を得る工程であり、
前記第二水素化工程は、前記初期酸素分の９５質量％以上が除去されるように、前記第一精製油に残存する酸素分を除去して前記第二精製油を得る工程であり、
前記第二水素化工程は、前記第二精製油の１５０〜３５０℃の留分に含まれるパラフィン分において、ノルマルパラフィンに対するイソパラフィンの比（イソパラフィンの質量／ノルマルパラフィンの質量）が０．２以上となるように行うことを特徴とする水素化精製方法。 In the presence of hydrogen,
An oil to be treated containing an oxygen-containing hydrocarbon compound;
Through a hydrorefining step of contacting a carrier containing crystalline molecular sieve and a catalyst containing one or more metals selected from Group 6A and Group 8 elements of the periodic table supported on the carrier. A hydrorefining method to obtain refined oil,
The oxygen-containing hydrocarbon compound is an oil and fat component derived from animal and vegetable oils,
The hydrogen includes a hydrogen gas introduced along with the oil to be treated and a hydrogen gas introduced as quench hydrogen, and the ratio of the quench hydrogen to the hydrogen gas introduced along with the oil to be treated Is 10-60% by volume,
The hydrorefining step includes
Wherein the treated oil, the carrier comprising a crystalline molecular sieve, or aluminum, silicon, zirconium, boron, porous inorganic oxide includes a 2 or more elements selected from titanium and magnesium, as well as the carrier Or a catalyst containing one or more metals selected from Group 6A and Group 8 elements of the periodic table supported on the porous inorganic oxide , with a hydrogen pressure of 2 to 13 MPa and a liquid space velocity of 0.1. A first hydrogenation step of obtaining a first refined oil by contacting under a condition of ˜3.0 h −1 , a hydrogen oil ratio of 250 to 1500 NL / L, and a reaction temperature of 150 to 380 ° C .;
Hydrogen containing the first refined oil, a carrier containing crystalline molecular sieve, and a catalyst containing one or more metals selected from Group 6A and Group 8 elements of the periodic table supported on the carrier. Second hydrogenation to obtain a second refined oil by contact under conditions of pressure 2-13 MPa, liquid space velocity 0.1-3.0 h −1 , hydrogen oil ratio 250-1500 NL / L, reaction temperature 150-380 ° C. and the process, only including,
The first hydrogenation step is a step of obtaining the first refined oil by removing 70% by mass or more of the initial oxygen content contained in the oil to be treated.
The second hydrogenation step is a step of obtaining the second refined oil by removing the oxygen content remaining in the first refined oil so that 95% by mass or more of the initial oxygen content is removed.
In the second hydrogenation step, the ratio of isoparaffin to normal paraffin (mass of isoparaffin / mass of normal paraffin) is 0.2 or more in the paraffin content contained in the fraction of 150 to 350 ° C. of the second refined oil. The hydrorefining method characterized by performing so that it may become .
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