JP3978064B2 - Two-stage hydroprocessing method for heavy hydrocarbon oil - Google Patents
Two-stage hydroprocessing method for heavy hydrocarbon oil Download PDFInfo
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- JP3978064B2 JP3978064B2 JP2002088655A JP2002088655A JP3978064B2 JP 3978064 B2 JP3978064 B2 JP 3978064B2 JP 2002088655 A JP2002088655 A JP 2002088655A JP 2002088655 A JP2002088655 A JP 2002088655A JP 3978064 B2 JP3978064 B2 JP 3978064B2
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- 238000000034 method Methods 0.000 title claims description 44
- 239000004215 Carbon black (E152) Substances 0.000 title claims description 25
- 229930195733 hydrocarbon Natural products 0.000 title claims description 25
- 150000002430 hydrocarbons Chemical class 0.000 title claims description 25
- 239000003054 catalyst Substances 0.000 claims description 231
- 239000011148 porous material Substances 0.000 claims description 112
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 53
- 239000003921 oil Substances 0.000 claims description 52
- 229910052751 metal Inorganic materials 0.000 claims description 46
- 239000002184 metal Substances 0.000 claims description 46
- 238000005984 hydrogenation reaction Methods 0.000 claims description 34
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 28
- 238000009826 distribution Methods 0.000 claims description 26
- 229910044991 metal oxide Inorganic materials 0.000 claims description 26
- 150000004706 metal oxides Chemical class 0.000 claims description 26
- 230000000737 periodic effect Effects 0.000 claims description 25
- 238000002156 mixing Methods 0.000 claims description 16
- 239000000377 silicon dioxide Substances 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 13
- 239000001257 hydrogen Substances 0.000 claims description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 12
- 238000009835 boiling Methods 0.000 claims description 9
- 239000000295 fuel oil Substances 0.000 claims description 5
- 239000013049 sediment Substances 0.000 description 33
- 238000006477 desulfuration reaction Methods 0.000 description 22
- 230000023556 desulfurization Effects 0.000 description 22
- 239000000243 solution Substances 0.000 description 21
- 238000006243 chemical reaction Methods 0.000 description 20
- 238000004519 manufacturing process Methods 0.000 description 17
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 16
- 238000000354 decomposition reaction Methods 0.000 description 15
- 239000012535 impurity Substances 0.000 description 15
- 239000000203 mixture Substances 0.000 description 14
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 13
- 230000000694 effects Effects 0.000 description 13
- 239000011593 sulfur Substances 0.000 description 13
- 229910052717 sulfur Inorganic materials 0.000 description 13
- 230000015572 biosynthetic process Effects 0.000 description 12
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 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 8
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 8
- 229910052759 nickel Inorganic materials 0.000 description 8
- 229910001388 sodium aluminate Inorganic materials 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 150000002739 metals Chemical class 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
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- 235000020679 tap water Nutrition 0.000 description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 5
- 229910017052 cobalt Inorganic materials 0.000 description 5
- 239000010941 cobalt Substances 0.000 description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 5
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- 239000011733 molybdenum Substances 0.000 description 5
- 229910052750 molybdenum Inorganic materials 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 4
- 239000012378 ammonium molybdate tetrahydrate Substances 0.000 description 4
- FIXLYHHVMHXSCP-UHFFFAOYSA-H azane;dihydroxy(dioxo)molybdenum;trioxomolybdenum;tetrahydrate Chemical compound N.N.N.N.N.N.O.O.O.O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O FIXLYHHVMHXSCP-UHFFFAOYSA-H 0.000 description 4
- 229910052804 chromium Inorganic materials 0.000 description 4
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- 238000004898 kneading Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- 235000019353 potassium silicate Nutrition 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 4
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- 230000001629 suppression Effects 0.000 description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 4
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- 239000010937 tungsten Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 239000004115 Sodium Silicate Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
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- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000000571 coke Substances 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 3
- 238000005504 petroleum refining Methods 0.000 description 3
- 235000011007 phosphoric acid Nutrition 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 229910052911 sodium silicate Inorganic materials 0.000 description 3
- 238000005979 thermal decomposition reaction Methods 0.000 description 3
- 239000011135 tin Substances 0.000 description 3
- 229910052718 tin Inorganic materials 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052787 antimony Inorganic materials 0.000 description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 2
- 229910052785 arsenic Inorganic materials 0.000 description 2
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
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- 239000002904 solvent Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
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- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 241000257465 Echinoidea Species 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-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
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
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- 238000005054 agglomeration Methods 0.000 description 1
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- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate 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
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
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- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
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- 239000011575 calcium Substances 0.000 description 1
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
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- 150000002431 hydrogen Chemical class 0.000 description 1
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- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
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- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 1
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は、重質炭化水素油の水素化処理方法、特に炭化水素油の中でも重質な留分である減圧残渣油の水素化処理において高性能を発揮する触媒組み合わせ方法に関する。
より詳しくは、硫黄、金属、アスファルテン等の夾雑物（不純物）を多量に含有する重質炭化水素油の水素化処理において、機能の異なる触媒同士を組み合わせて用いることにより、目的とする水素化脱硫（ＨＤＳ）、水素化脱金属（ＨＤＭ）及び水素化脱アスファルテン（asphaltene removal）を進めながら、且つ装置運転時に熱交換器に堆積して運転の障害となるセディメント生成を抑制できる水素化処理方法に関する。
【０００２】
【従来の技術】
石油精製時に生じる、例えば５３８℃以上の沸点を有する成分を５０重量％以上含むような常圧残油（Atmospheric residue；ＡＲ）や９０重量％以上含む減圧残油（Vacuum Residue；ＶＲ）は重質炭化水素油と呼ばれている。このような重質炭化水素油を水素化処理して、硫黄等の夾雑物の除去並びに付加価値の高い軽質油への転換を行って利用に供することが強く求められている。
こうした重質留分の分解により生成される軽質油は、相当する直留留分に比べて高硫黄濃度であるため、再度脱硫、水素化処理を必要とする。
【０００３】
水素化・分解処理によって除去される対象である夾雑物としては、硫黄、残留炭素（Conradson Carbon Residue；ＣＣＲ）、各種金属、窒素、アスファルテンが挙げられるが、今日、触媒などの改良によってこうした夾雑物を高度に除去できるようになった。
しかし、アスファルテンは縮合芳香族化合物の集合体であり、周囲の溶剤成分とバランス良く解け合っているので、過度にアスファルテンを分解した場合、凝集して粒子状物質（スラッジ；sludge）や堆積物（セディメント；sediment）が生成してしまう。
【０００４】
かかるセディメントとは、詳しくはShell Hot Filteration Solid Test（SHFST）により試料を試験することで測定される沈殿物であり（Van Kerknoortらの文献、J. Inst. pet. 37 p.596-604(1951)参照）、通常の含有量は、精製工程中のフラッシュドラム缶出液から回収される沸点が３４０℃以上の生成物中において約０.１９〜１重量％程度であると言われている。
【０００５】
セディメントは、石油精製時に熱交換器や反応器等の装置内に沈殿し堆積するので、流路を閉塞させ装置の運転に大きな支障をきたす恐れがある。特に減圧残渣油を多く含む、より重質な炭化水素油の水素化処理においては、アスファルテン量が多いことによりセディメントの生成が顕著となる。
このため、高度な水素化処理を達成しつつ、同時にセディメントの生成をできるだけ少なくすることが水素化処理用触媒の改良において新たな課題となっている。
【０００６】
一方、重質留分の分解により生成される軽質油は、相当する直留留分に比べ硫黄濃度が高いので、再度脱硫、水素化処理を必要とする。そこで低硫黄の軽質油を製造するには、重質留分の水素化・分解においてセディメント生成を抑制し、安定運転を行いつつ、分解軽質留分に対する脱硫性能の高い触媒または触媒の組み合わせが必要とされる。
【０００７】
本発明者らは、２段階水素化処理における第１段階と第２段階で異なる機能を持つ触媒を組み合わせて使用し、さらに第２段階で特定の触媒組成と細孔径分布を有する２種類の触媒を混在させて使用することにより、それぞれの触媒を単独で使用した場合よりもセディメント生成の抑制に優れ、なおかつ軽質留分に対する高度な脱硫性能を発揮することを見出した。
すなわち、特定の細孔径を有する異なる触媒を３種類（第１段階で１種及び第２段階で２種）組み合わせて用いることにより、重質な留分を含む減圧残渣油に対し、運転時支障となるセディメントの生成を極力抑制しつつ、高度に脱硫された経済的付加価値の高い白油製品を高収率で生産できる方法を見出した。
【０００８】
本発明は、より具体的には、水素化処理の第１段階でアスファルテン分解、高脱金属用の触媒により、セディメントの生成原因となるアスファルテンを極力低減し、続いて第２段階（最終段階）に高脱硫性能を示す触媒を配することで、所望の脱硫生成油を得ながら、セディメント生成の少ない運転を行うことができる。特に第２段階では、セディメントの生成を抑制しながら高度の脱硫を行う必要があるため、特定の触媒組成、細孔径分布を持つ異なる２種類の触媒を混在させて使用することにより、これまで困難とされていたセディメントの抑制維持と高脱硫・水素化が達成される。
【０００９】
一方、従来技術においては、以下のとおりセディメントの抑制維持と水素化高脱硫の両立が十分に図られていない。
特公平７−６５０５５号公報には、硫黄不純物と金属性不純物を含む炭化水素油の重質分を少なくとも２段階で変換させる水素化処理方法が開示されている。当該公報では、第１段階で水素化脱金属を目的として０.１〜５重量％の金属酸化物触媒を使用し、続く第２段階で水素化脱硫を目的として同じく金属酸化物として７〜３０重量％の金属酸化物触媒で水素化処理する方法が提案されている。この方法によると第１段階で脱金属と水素化クラッキングを行い、第２段階で入念な脱硫を行うことにより残渣分を処理することがよいとされている。特に『ウニ状』の構造を持ったアルミナ凝集状態の触媒の組み合わせが顕著な結果を示している。
【００１０】
しかし当該技術によると、第１段階で必要とされる脱金属機能は向上するものの、第１段階で使用される触媒の触媒担持量が低いため、脱硫、水素化機能が低下し、このため第２段階で高脱硫機能が必要となり、どうしても触媒担持量の多い触媒を必要とする。また第２段階で高度な脱硫を行う場合は触媒は高度に発熱するが、この時、分解率が進むことに伴いアスファルテン分の凝集を起こす。当該発明の実施例を見る限りアスファルテン凝集の防止策が十分でなく、その結果、装置の運転上支障がでる恐れがある。
【００１１】
特開平８−３２５５８０号公報には、重質石油原料の完全な接触水素化転化法が開示されている。当該方法では、第１段階にアルミナ・シリカ及びこれらの組み合わせから選ばれる担体物質に、カドミウム、クロム、コバルト、鉄、モリブデン、ニッケル、スズ、タングステン及びこれらの組み合わせからなる選ばれる活性金属酸化物を合計２〜２５重量％担持した触媒を供給し、反応温度４３８〜４６８℃、水素分圧１０５〜２４５kg／cm2、空間速度０.３〜１.０ (Vf／hr／Vr)の反応条件で反応させ、次いで第２段階で同様の触媒を供給し、反応温度３７１〜４２７℃、水素分圧１０５〜２４５kg／cm2、空間速度０.１〜０.８(Vf／hr／Vr)の反応条件で水素化転換する方法が記載されている。
当該方法は、重質石油原料である「Ｈ−Ｏｉｌ(登録商標)」の接触水素化転化法であり、未反応残留分の処理に対しそれらの再循環によって解決を提案するものである。
【００１２】
また、原料のより完全な水素化転換及び触媒の効果的な使用を達成するため、第１段階の反応器に、より高い反応温度及びより低い触媒活性を与え、第２段階の反応器に、より低い反応温度及びより高い触媒活性を与えることによって、反応条件の改良された調和及び各段階の反応器に必要な触媒活性を備えるとしている。
【００１３】
しかし、当該公報に開示されている第１段階の高温反応は、アスファルテンの熱縮合を促進させ、一方で油の熱分解を伴って生成するレジン質などのフラグメントを安定化できなくなり、第２段階で触媒の急激なコーク劣化を引き起こしかねない。
【００１４】
また、当該方法では、第２段階で引き起こされるアスファルテンの凝集、セディメント析出を防止するのに適した触媒を使うことにはなっていないので、この点で装置の運転時に障害となる恐れがある。
【００１５】
特公平６−５３８７５号公報には、重質炭化水素液体供給原料の高転化用多段階接触方法が記載されている。第１段階では固定床または沸騰床反応器で、反応温度が４１５〜４５５℃で水素分圧が７０〜２１１kg／cm2、空間速度が０.２〜２.０、第２段階が沸騰床反応器で、反応温度が４１５〜４５５℃、同じく水素分圧が７０〜２１１kg／cm2、空間速度が０.２〜２.０である多段接触水素化処理方法が記載されている。使用できる触媒は、アルミナ、シリカ及びこれらの組み合わせ群から選ばれた担体物質に、カドミウム、クロム、コバルト、鉄、モリブデン、ニッケル、スズ、タングステン及びこれらの混合物から選ばれた活性金属酸化物を含有する触媒である。当該方法では、高分解率とするため真空ボトムズを再循環させて高分解率の達成を図っているものの、高分解率運転時に支障となるアスファルテン凝集に対する防止策は示されておらず、装置の運転時に問題となる。
【００１６】
また使用触媒についても触媒に対する記載は、水素転化反応の促進に対して、あるいは金属含有量の高い原料油の場合には、脱金属型触媒を第１段階反応で使用することとの内容があるだけで、実際の触媒の開示がない。また、触媒の開示に関し、当該公報は不十分であるので、運転時支障となるセディメントの析出に対して効果的な結果が期待できるとは判断できない。
よって、上記の先行技術による触媒組み合わせでは、重質炭化水素油の水素化分解で、高度な脱硫、分解を達成しながら、且つ装置の運転制約となるセディメント生成を抑制する効果が十分に図られていない。
【００１７】
【発明が解決しようとする課題】
本発明は、硫黄、残留炭素、金属、窒素、アスファルテン等の夾雑物を多量に含有する重質の炭化水素油、特に減圧残油留分を８０％以上含む重質油を高度に水素化処理して適度に除去できるよう機能を考慮した触媒を組み合わせ、また第２段階で特定の細孔径分布、触媒組成を有する２種類の異なる触媒を混在させることにより効果的な水素化処理方法を提供することを目的とする。
特に、前記従来技術では十分な解決がなされていない、アスファルテンの高度な分解除去、転化率の増加に随伴して生成するセディメントの低減に対し優れた性能を示し、なおかつ脱硫性能を高くできる触媒組み合わせの提供を目的としている。
【００１８】
【課題を解決するための手段】
本発明者らは、上記問題点に鑑みて鋭意研究を重ねた結果、接触２段水素化転化法において、第１段階で特定の細孔径分布を有する触媒を用いて重質炭化水素油中の夾雑物の低減、特に脱金属とアスファルテン凝集防止に効果的な脱アスファルテンを効率的に達成し、次いで第２段階で第１段階とは異なる特定の細孔径分布、触媒組成を有する触媒を２種類混在させて用いることにより、これまでに問題とされてきた水添とセディメントとの関係を改善できることを見出し、特に高度な脱硫、水添反応を達成しつつ、アスファルテン凝集によるセディメント生成を抑制し、安定した運転ができる重質油の接触水素化処理方法を見出し、本発明を完成するに至った。
【００１９】
すなわち、第１段階で特定の細孔径分布を有する触媒を用い、続く第２段階で、第１段階とは異なる特有の細孔径分布、触媒組成を有する２種類の異なる機能の触媒を混在させて用い、これによる相乗効果によって、高度に脱硫、水添は進むが、セディメントの生成が抑制された安定運転を可能とすることを見出した。本発明によれば、特に重質な炭化水素油の水素化処理に対して効果が大きい。
【００２０】
より具体的には、２段階からなる水素化処理方法において、第１段階の反応装置にある特定の細孔径分布を有する触媒を供給し、セディメントの生成を促進させるアスファルテンの分解を高度に行ないつつ、適度な水添反応を行ない、続く第２段階の反応装置では、脱硫性能を向上させる細孔径分布、触媒組成の触媒と、適度なアスファルテン分解を行わせる細孔径分布、触媒組成の触媒を供給することで、高度な脱硫を達成しながら、セディメントを極力生成させない方法を提供するものである。
また、第１段階で高度にアスファルテンを除去することにより、第２段階の熱分解で触媒上に堆積する好ましくないコーク生成を抑えて触媒性能の低下を防ぐ効果をもたらす。
【００２１】
要するに、本発明の水素化処理方法は、重質炭化水素油を、下記触媒（１）が充填された第１の反応装置において水素存在下、触媒（１）と接触させて第１段階の水素化処理を行い、次いで第１段階で得られた水素化処理油を、下記触媒（２ａ）及び触媒（２ｂ）が混在して充填された第２の反応装置において水素存在下、触媒（２ａ）及び触媒（２ｂ）と接触させて第２段階の水素化処理を行うことを特徴とする重質炭化水素油の水素化処理方法である。
【００２２】
触媒（１）は多孔質のアルミナ担体に、触媒重量を基準として周期表の第６Ａ族金属の酸化物が７〜２０重量％、周期表の第８族金属の酸化物が０.５〜６重量％で担持され、触媒の
(a)比表面積が１００〜１８０m2／ｇ、
(b)全細孔容積が０.５５ml／ｇ以上であり、
触媒の細孔分布径が全細孔容積を基準として
(c1)直径が２００Å以上の細孔容積の割合が全細孔容 積の５０％以上、
(c2)直径が２,０００Å以上の細孔容積の割合が全細孔容積の１０〜３０％、
(c3)直径が１０,０００Å以上の細孔容積の割合が全細孔容積の０〜１％
である水素化処理用触媒である。
【００２３】
触媒（２ａ）は多孔質アルミナ担体に触媒重量を基準として周期表の第６Ａ族金属の酸化物が７〜２０重量％、周期表の第８族金属の酸化物が０.５〜６重量％の量で担持され、触媒の
(a)比表面積が１００〜１８０m2／ｇ、
(b)全細孔容積が０.５５ml／ｇ以上であり、
触媒の細孔分布径が全細孔容積を基準として
(d1)直径が１００〜１,２００Åの容積の割合が８５％以上、
(d2)細孔の直径が４,０００Å以上の容積の割合が０〜２％、
(d3)細孔の直径が１０,０００Å以上の容積の割合が０〜１％、
(d4)直径が２００Å以上の細孔容積の割合が全細孔容積の５０％以上
である水素化処理触媒である。
【００２４】
触媒（２ｂ）は耐熱性無機多孔質担体に少なくとも１種の水素化活性成分が担持され、触媒の
(a)比表面積が１５０m2／ｇ以上、
(b)全細孔容積が０.５５ml／ｇ以上であり、
触媒の細孔分布径が全細孔容積を基準として
(d1)直径が１００〜１,２００Åの細孔容積の割合が全細孔容積の７５％以上、
(d2)直径が４,０００Å以上の容積の割合が０〜２％、
(d3)直径が１０,０００Å以上の細孔容積の割合が全細孔容積の０〜１％、
(d4)直径が２００Å以上の細孔容積の割合が全細孔容積の５０％未満
である水素化処理用触媒である。
【００２５】
また、本発明は、触媒（２ｂ）の耐熱性無機多孔質担体が、シリカ量として３.５重量％以上含むシリカ−アルミナ担体であることを特徴とする。
また、本発明は、触媒（２ｂ）が、シリカ量として３.５重量％以上含むシリカ−アルミナ担体に、触媒重量を基準として周期表の第６Ａ族金属の酸化物が７〜２０重量％、周期表の第８族金属の酸化物が０.５〜６重量％、周期表の第１Ａ族金属の酸化物が０.１〜１重量％の量で担持されている水素化処理用触媒であることを特徴とする。
【００２６】
また、本発明は、触媒（２ｂ）が、シリカ量として３.５重量％以上含むシリカ−アルミナ担体に、触媒重量を基準として周期表の第６Ａ族金属の酸化物が７〜２０重量％、周期表の第８族金属の酸化物が０.５〜６重量％、周期表の第１Ａ族金属の酸化物が０.１〜１重量％、周期表の第５Ｂ族元素の酸化物が０.１〜２重量％の量で担持されている水素化処理用触媒であることを特徴とする。
【００２７】
また、本発明は、重質炭化水素油が減圧残油留分を８０重量％以上含む重質油であることを特徴とし、第１段階及び第２段階において、温度３５０〜４５０℃、圧力５〜２５ＭＰａの条件下で水素化処理を行うことを特徴とする。
【００２８】
また、第２段階の反応装置に充填された触媒における触媒（２ｂ）の混在割合が１重量％以上であることを特徴とし、さらに重質炭化水素油を沸騰床の様態で水素化処理触媒と接触させることを特徴とする。
【００２９】
【発明の実施の形態】
〔Ｉ〕触 媒
本発明における水素化処理方法の第１段階で使用される水素化処理用触媒（触媒（１））、及び第２段階で使用される水素化処理用触媒（触媒（２ａ）及び触媒（２ｂ））は、それぞれ水素化活性を有する金属酸化物である触媒物質と当該触媒物質を担持する担体とから構成される。
【００３０】
本発明において触媒物質に使用される成分は、触媒（１）及び触媒（２ａ）に関しては、周期表（例えば、「岩波理化学辞典 第４版」、岩波書店（１９８７年発行）の見返し掲載の「II 元素の周期表 (a)長周期型」を参照）の第６Ａ族金属及び第８族金属の酸化物の２成分からなる組成物である。
【００３１】
触媒（２ｂ）には、少なくとも１種の水素化活性成分が担持されるが、かかる成分としては、周期表の第１Ａ族金属（リチウム、ナトリウム等）、第２Ａ族金属（マグネシウム、カルシウム等）、第６Ａ族金属（クロム、モリブデン、タングステン等）、第８族金属（鉄、コバルト、ニッケル、白金、パラジウム等）、第４Ｂ族元素（スズ、鉛等）や第５Ｂ族元素（リン、砒素、アンチモン等）が挙げられる。
【００３２】
触媒（２ｂ）に担持される水素化活性成分は、上記周期表の第６Ａ族金属、第８族金属及び第１Ａ族金属の３成分からなる組成物が好ましく、特に上記周期表の第６Ａ族金属、第８族金属、第１Ａ族金属及び第５Ｂ族元素の酸化物の４成分からなる組成物が好ましい。
なお、上記第１Ａ族、第２Ａ族、第４Ｂ族、第５Ｂ族、第６Ａ族、第８族は、Ａ、Ｂ亜族に分けない１８族長周期型周期表（ＩＵＰＡＣ方式）の第１族、第２族、第１４族、第１５族、第６族、第８〜１０族にそれぞれ対応する。
【００３３】
本発明の触媒に使用される第８族金属は、鉄、コバルト、ニッケルから選ばれる少なくとも１種であるが、性能及び経済性の観点からコバルト、ニッケルが好ましく、中でもニッケルが好ましい。
また第６Ａ族金属は、クロム、モリブデン、タングステンから選ばれる少なくとも１種であるが、性能及び経済性の観点からモリブデンが好ましい。
【００３４】
また、触媒（２ｂ）の好適な態様として、担体がシリカを含有するシリカ−アルミナ担体である場合に、第６Ａ族金属及び第８族金属に加えて使用される第１Ａ族金属としては、リチウム、ナトリウムやカリウム等が挙げられるが、性能の点からナトリウムが好ましい。
【００３５】
また、触媒（２ｂ）の特に好適な態様として第６Ａ族金属、第８族金属及び第１Ａ族金属に加えてさらに担持される第５Ｂ族元素は、リン、ヒ素、アンチモン、ビスマスから選ばれる少なくとも１種であるが、性能の点からリンが好ましい。
【００３６】
前述のとおり重質炭化水素油の水素化処理においては水素化を高めるに伴ってセディメント生成も上昇する傾向にあるが、本発明においては、第２段階に特定の細孔構造と活性成分を有する触媒を一部混在させることによって、より高度な水素化とセディメント生成抑制とをバランス良く達成することができるのである。
【００３７】
完成後の触媒重量を基準（１００重量％）とした場合における上記の各金属酸化物の担持量は次の通りである。
すなわち、触媒（１）、触媒（２ａ）及び触媒（２ｂ）に共通して担持される第６Ａ族金属の酸化物は、７〜２０重量％であり、８〜１６重量％が好ましい。かかる金属酸化物が７重量％未満では触媒性能の発現が不十分となり、一方、２０重量％を超えても触媒性能の増分はない。
【００３８】
また、触媒（１）、触媒（２ａ）及び触媒（２ｂ）に共通して担持される第８族金属酸化物は０.５〜６重量％であり、１〜５重量％が好ましい。０.５重量％未満では触媒性能の発現が不十分で、一方、６重量％を超えても触媒性能の増分はない。
【００３９】
さらに、第１Ａ族金属酸化物が触媒（２ｂ）に担持される場合の量は、０.１〜１重量％であり、好ましくは０.１〜０.５重量％である。０.１重量％未満では表面活性を制御するのに十分でなく、セディメント生成が増加し好ましくない。１重量％を超えると、触媒性能の発現が不十分となる。
【００４０】
また、第５Ｂ族元素酸化物が触媒（２ｂ）に担持される場合の量は、０.１〜２重量％であり、好ましくは０.１〜１.０重量％である。２重量％超過では、アスファルテン以外への水素化が進みすぎ、その結果セディメントの急激な増加を招く。一方、０.１重量％未満では効率的な水素化が図られない。
【００４１】
次に触媒を構成する担体について説明する。
触媒（１）及び触媒（２ａ）の担体は、工業的に生成される方法で得ることができる多孔質アルミナで、その代表としてアルミン酸ソーダ（アルミン酸ナトリウム）と硫酸アルミニウムを共沈させることにより得られるものを用いることができる。この際得られるゲル（擬ベーマイト）を、乾燥、成形、焼成してアルミナ担体として得る。
【００４２】
一方、触媒（２ｂ）の担体として用いる耐熱性無機多孔質担体は、アルミナ、シリカ、シリカ−アルミナ、マグネシア、酸化亜鉛、チタニア、ジルコニア、ゼオライト、粘土鉱物やこれらの複合酸化物が例示されるが、中でも経済性及び性能上の観点からシリカ−アルミナが好ましい。
触媒（２ｂ）の担体がシリカ−アルミナ担体である場合は、シリカ源として水ガラス（ケイ酸ソーダ）を使用してアルミナ沈殿時に同時に共沈する方法で得ることもできるし、次工程の浸漬時に水溶性シリカ源の溶液を浸漬することでも良い。
【００４３】
担体の具体的な製造方法は以下のとおりである。
まず、水道水または温水を蓄えたタンクに、アルミン酸ソーダ、水酸化アンモニウムや水酸化ナトリウム等のアルカリ溶液を入れ、次いで硫酸アルミニウムや硝酸アルミニウム等の酸性アルミニウム溶液を用いて加混合を行う。触媒（２ｂ）がシリカ−アルミナ担体である場合の製造法としては、シリカ源として、予め水ガラスを蓄えたタンクとしてもよい。
【００４４】
混合溶液中の 水素イオン濃度（ｐＨ）は反応が進むにつれて変化するが、酸性アルミニウム溶液の添加が終了する時のｐＨが７〜９、混合時の温度は第１段階の触媒（１）には７０〜８５℃、第２段階の触媒（２ａ）、触媒（２ｂ）には６０〜７５℃であることが好ましい。また適当な大きさの細孔を得るため、保持時間は約０.５〜１.５時間が好ましく、特に４０分〜８０分が好ましい。かかる加混合の諸条件を適宜調整することで所望のアルミナ水和物、またはシリカ−アルミナのゲルが得られる。
【００４５】
次に、得られたアルミナ水和物またはシリカ−アルミナゲルを溶液から分離した後、工業的に広く用いられている洗浄方法、例えば水道水や温水を用いて洗浄処理を行い、ゲル中の不純物を除去する。
次に混練機を用いてゲルの成形性を向上させた後、成型器にて所望の形状に成形する。触媒活性成分を担持する前に、所望の形状に成形しておくことが好ましく、直径が０.９〜１mm、例えば０.９５mm、長さが２.５〜１０mm、例えば３.５mmの円柱形状の粒子が好適である。
【００４６】
最後に、成形されたアルミナゲル、またはシリカ−アルミナゲルに乾燥及び焼成処理を施す。
乾燥条件は、空気存在下で常温から２００℃の温度で、また焼成条件は、空気存在下で３００〜９５０℃、好ましくは６００〜９００℃の温度条件で、３０分間から２時間程度行う。また焼成処理時には水蒸気を導入して、アルミナ粒子、シリカ−アルミナ結晶の成長をコントロールすることもできる。
【００４７】
以上の製造方法によって、後述する完成触媒の比表面積や細孔分布とほぼ一致する性状を備えたアルミナ担体、またはシリカ−アルミナ担体を得ることができる。
なお、前述の混練し成形する工程において、成形助剤として酸、例えば硝酸、酢酸、蟻酸を添加し、あるいは水を添加してアルミナゲル、シリカ−アルミナゲル中の水分量を調整することにより、細孔分布の調整を適宜行うこともできる。
【００４８】
触媒物質の金属成分を担持する前の担体の比表面積は、完成後の触媒において特定範囲の比表面積や細孔分布をもたらすために、触媒（１）のアルミナ担体は１００〜２００m2／ｇ、特に１３０〜１７０m2／ｇが好ましく、また全細孔容積が０.５〜１.２ml／ｇ、特に０.７〜１.１ml／ｇが好ましい。
一方、触媒（２ａ）のアルミナ担体、及び触媒（２ｂ）のシリカ−アルミナ担体の比表面積は、完成後の触媒において特定範囲の比表面積や細孔分布をもたらすために１８０〜３００m2／ｇ、特に１８５〜２５０m2／ｇが好ましく、また全細孔容積が０.５〜１.０ml／ｇ、特に０.６〜０.９ml／ｇが好ましい。
【００４９】
触媒（２ｂ）の耐熱性無機多孔質単体がシリカ−アルミナ担体である場合のシリカ含有量は、触媒物質を含めた完成された触媒を基準として（１００重量％）として、３.５重量％以上、好ましくは４.５〜１０重量％である。３.５重量％未満では触媒性能の発現が不十分である。
【００５０】
本発明の触媒は以下に述べる方法で製造され完成する。
前記の触媒物質用の各種金属成分をアルカリ性または酸性の金属塩とし、この金属塩を水に溶解した浸漬液に、触媒（１）、触媒（２ａ）、触媒（２ｂ）の担体を浸漬し担持させる。この場合、複数の金属塩からなる混合水溶液に浸漬して同時に担持させても良いし、あるいは個別に金属塩水溶液を調製して浸漬担持させても良い。
また、浸漬液の安定化のために少量のアンモニア水、過酸化水素水、グルコン酸、洒石酸、クエン酸、リンゴ酸、ＥＤＴＡ（エチレンジアミン四酢酸）等を添加することが好ましい。
【００５１】
第８族金属の金属水溶液は、通常水溶性の炭酸塩または硝酸塩を使用し、例えば硝酸ニッケルの１０〜４０重量％水溶液であり、好ましくは ２５重量％水溶液が使用される。また、第６Ａ族金属は水溶性のアンモニウム塩を使用でき、例えばモリブデン酸アンモニウムの１０〜２５重量％水溶液であり、好ましくは１５重量％水溶液が使用される。
【００５２】
触媒（２ｂ）に特有な水素化活性成分である第１Ａ族金属は、水溶性の炭酸塩または硝酸塩を使用でき、例えば硝酸ナトリウムが使用される。
同様に触媒（２ｂ）に特有な水素化活性成分である第５Ｂ族元素は、リン化合物が使用でき、例えば正リン酸（オルトリン酸）が使用される。
【００５３】
３０〜６０分間程度の時間、担体を金属塩水溶液に浸漬した後、空気気流下で常温〜２００℃の温度で、０.５〜１６時間程度乾燥を行い、次いで空気気流下で２００〜８００℃、好ましくは４５０〜６５０℃の加熱条件で１〜３時間程度焼成（か焼）を行って各金属酸化物が担持された触媒が完成する。
【００５４】
上述の製法により完成した細孔を多数有する多孔質触媒が、それらを組み合わせることによって所望の目的を達成するためには、以下の比表面積や細孔径分布を有することが重要である。
【００５５】
触媒（１）の比表面積は１００〜１８０m2／ｇ、好ましくは１５０〜１７０m2／ｇである。比表面積が１００m2／ｇ未満では触媒性能が不十分となる。一方１８０m2／ｇを超えると、所望の細孔径分布が得られないことが多く、仮に添加物などにより得られたとしても高い比表面積による水添活性の増加により、セディメントの増加を引き起こすことになる。
【００５６】
触媒（２ａ）の比表面積は１００〜１８０m2／ｇ、好ましくは１５０〜１７０m2／ｇである。比表面積が１００m2／ｇ未満では触媒性能が不十分となる。また１８０m2／ｇを超えても触媒性能の増分はない。
触媒（２ｂ）の比表面積は１５０m2／ｇ以上、好ましくは１８５〜２５０m2／ｇである。比表面積が１５０m2／ｇ未満では触媒性能が不十分となる。
ここで比表面積は窒素（Ｎ2）吸着によるＢＥＴ式で求められる比表面積である。
【００５７】
さらに、水銀圧入法で測定される全細孔容積は触媒（１）、触媒（２ａ）、触媒（２ｂ）に共通して０.５５ml／ｇ以上、好ましくは０.６〜０.９ml／ｇである。０.５５ml／ｇ未満では触媒性能が不十分となる。
ここで水銀圧入法による測定とは、例えばマイクロメリティクス（Micromeritics）社製の水銀多孔度測定機器「オートポア（Autopore）II」（商品名）を使用し接触角１４０°、表面張力４８０dyne／cmの条件下で測定して得られる値である。
【００５８】
また、触媒（１）では直径が２００Å以上の容積の割合が全細孔容積の５０％以上、好ましくは６０〜８０％の範囲である。(ここで本明細書において記号「Å」は長さの単位であるオングストロームを表し１Å＝１０-10ｍである)。直径が２００Å以上の細孔の容積割合が全細孔容積の５０％未満では、触媒性能、特にアスファルテン分解性能の低下を招き、セディメントの生成の抑制が十分でない。なお、金属酸化物が担持される前の担体においては、該細孔の総容積割合は全細孔容積の４３％以上、好ましくは４５〜７０％の範囲である。
【００５９】
また、触媒（１）では、直径が２,０００Å以上の細孔の容積割合が、全細孔容積の１０〜３０％である。かかる割合が１０％未満では、反応装置の最終出口で脱アスファルテン性能の低下を招き、セディメントの生成が多くなり、３０％を超えると触媒の機械強度が極端に低くなってもろくなり、商業使用において十分耐えることができない。
【００６０】
また、特に減圧残油の多い原料油を処理する場合、触媒(１)では、直径が１００〜１,２００Åの細孔の総容積割合は、前記全細孔容積を基準とした場合に８２％以下、特に８０％以下とすることが好ましい。かかる割合が８２％を超えると２,０００Å以上の細孔の総容積の割合が相対的に減少し、第１段階に必要とされる超重質留分の触媒細孔内拡散が不十分となることで減圧残油留分の分解率の低下を招きやすくなるからである。
【００６１】
触媒（１）では、その細孔の直径が５００〜１,５００Åの細孔容積は０.２ml／ｇ未満が好ましい、０.２ml／ｇを超えた場合、脱硫、脱金属反応に有効な直径３００Å以下の細孔が相対的に減少することで、触媒性能が低下しやすくなるからである。さらに、直径３００Å以下の細孔が超重質成分で閉塞されやすくなることから触媒寿命の短命化も懸念されるからである。
また、触媒（１）の細孔径分布として、直径が１００Å以下の細孔容積の割合が全細孔容積の２５％以下が好ましい。２５％を超える場合には、アスファルテン以外の成分への水添が高度に進み、セディメントの生成が増える傾向がある。
【００６２】
触媒（２ａ）は、細孔径分布が全細孔容積を基準として直径が１００〜１,２００Åの細孔容積の割合が８５％以上、より望ましくは８７％以上である。１００〜１,２００Åの容積割合が８５％未満であると、脱硫、分解等の水素化反応が十分発揮されない。
【００６３】
触媒（２ｂ）は、細孔径分布が全細孔容積を基準として直径が１００〜１,２００Åの細孔容積の割合が７５％以上、より望ましくは７８％以上であることが好ましい。１００〜１,２００Åの細孔容積の割合が７５％未満であると、脱硫、分解等の水素化反応が十分発揮されない。
【００６４】
触媒（２ａ）及び触媒（２ｂ）共に、直径４,０００Å以上の細孔容積の割合が０〜２％、直径が１０,０００Å以上の細孔容積の割合が０〜１％とすることにより脱硫や水素化活性、特に減圧残渣油留分の分解率の極端な低下を防ぐことが可能となる。
【００６５】
さらに触媒（２ａ）及び触媒（２ｂ）共に、細孔分布として、直径が１００Å以下の細孔容積の割合が全細孔容積の２５％以下が好ましい。２５％を越える場合には、アスファルテン以外の成分への水添が高度に進み、セディメントの生成が増える傾向がある。
【００６６】
また、触媒（２ａ）は直径が２００Å以上の細孔容積の割合が全細孔容積の５０％以上、好ましくは６０〜８０％である。直径が２００Å以上の細孔容積の割合が全細孔容積の５０％未満であると、アスファルテン分解性能が不十分となり、セディメント生成の抑制が不十分となる。
【００６７】
一方、触媒（２ｂ）は、直径が２００Å以上の細孔容積の割合が全細孔容積の５０％未満、好ましくは４０％以下である。直径が２００Å以上の細孔容積の割合が全細孔容積の５０％以上であると水素化活性の低下を招くため触媒（２ａ）によって分解されたアスファルテンの適度な水素化ができずセディメントの生成を抑制できない。また、脱硫性能も低下するため触媒（２ａ）に対する添加効果もなくなる。
【００６８】
水素化処理の第２段階において、触媒（２ａ）と混在させる触媒（２ｂ）の割合、すなわち(２ｂ)／〔(２ａ)+(２ｂ)〕は、１重量％以上であるが、好ましい割合は１〜５０重量％、より好ましくは１０〜３０重量％である。混在割合が５０重量％を超えた場合は、第２段階での水添が過度に進行するため、セディメント生成が顕著となる傾向を示す。一方、１重量％未満では脱硫性能が不十分となる。
【００６９】
〔II〕水素化処理方法
本発明の水素化処理の対象である重質炭化水素油は、石油系残渣油、溶剤脱瀝油、石炭液化油、頁岩油、タールサンド油、典型的には常圧残油（ＡＲ）や減圧残油（ＶＲ）やそれらの混合物、特に減圧残（渣）油である。
【００７０】
特に、５３８℃以上で沸騰する成分（減圧残油留分）を８０重量％以上、硫黄を３重量％以上、残留炭素を１０重量％以上、その他高濃度の金属が存在する夾雑物を含む重質油が、本発明の水素化処理の対象として好適であり、上記触媒の組み合わせることにより、夾雑物の除去や軽質油への転換を行うことができる。
【００７１】
水素化処理における第１及び第２の反応装置は、固定床、移動床あるいは沸騰床を備えた一般的なものを使用できるが、反応温度を均一に保持できる点から沸騰床の様態で水素化処理を行うことが好ましい。
【００７２】
具体的には、直径０.９〜１.０mmで長さ３.５mmの円柱形状の触媒を反応装置に充填し、炭化水素油を液相中、全液空間速度（ＬＨＳＶ）０.１〜３hr-1、好ましくは０.３〜２.０hr-1で導入し、一方、水素は炭化水素油との流量比（Ｈ2／Ｏｉｌ）３００〜１,５００Nl／L、好ましくは６００〜１,０００Nl／Lで導入し、圧力５〜２５MPa、好ましくは１４〜１９MPa、温度３５０〜４５０℃、好ましくは４００〜４４０℃の条件下にて反応させる。
【００７３】
第２の反応装置での触媒（２ａ）及び触媒（２ｂ）の混在の様態としては、固定床においては均一に混在するように充填するが、移動床や沸騰床の場合は触媒（２ａ）を装入後、触媒（２ｂ）を徐々に装入する方法を用いてもよい。
また、第１の反応装置と第２の反応装置は、直列に連結してもよいが双方の装置の途中に硫化水素を除くストリッピング工程や水素を供給するクエンチラインを設けてもよい。
【００７４】
【実施例】
以下に示す実施例によって、本発明を更に具体的に説明する。
ただし、下記実施例は本発明を限定するものではない。
〔Ｉ〕触媒の製造
▲１▼ 触媒Ａ（上記の触媒（１）に相当）の製造
(ｉ) 担体の製造
水道水を貯えたタンクに、アルミン酸ソーダ溶液、硫酸アルミニウム溶液を同時滴下し加混合を行った。混合時のｐＨを８.５、温度を７７℃、保持時間は７０分とした。かかる加混合によってアルミナ水和物のゲルが生じた。
前記工程で得られたアルミナ水和物のゲルを溶液から分離した後、温水を用いて洗浄処理を行い、ゲル中の不純物を除去した。
次いで、混練機を用いて２０分ほど混練してゲルの成形性を向上させた後、成型機にて直径０.９〜１mm、長さが３.５mmの円柱形状の粒子に押し出し成形した。
最後に、成形したアルミナゲルを空気存在下１２０℃で１６時間かけて乾燥した後、８００℃で２時間焼成してアルミナ担体を得た。
【００７５】
(ii) 触媒の製造
モリブデン酸アンモニウム四水和物１７.５ｇ、硝酸ニッケル六水和物９.８ｇを添加したクエン酸溶液１００mlに上記のアルミナ担体１００ｇを２５℃、４５分間浸漬し、金属成分担持担体を得た。
次いで担持担体を、乾燥機を使用して１２０℃で３０分間乾燥した後、６２０℃で１.５時間、キルンでか焼して触媒を完成させた。
製造した触媒Ａ中の各成分の量及び性状は下記の表１に示す通りである。
【００７６】
▲２▼ 触媒Ｂ(上記の触媒（２ａ）に相当)の製造
(ｉ) 担体の製造
水道水を貯えたタンクに、アルミン酸ソーダ溶液、硫酸アルミニウム溶液を同時滴下し加混合を行った。混合時のｐＨを８.５、温度を６５℃、保持時間は７０分とした。かかる加混合によってアルミナ水和物のゲルが生じた。
前記工程で得られたアルミナ水和物のゲルを溶液から分離した後、温水を用いて洗浄処理を行い、ゲル中の不純物を除去した。
次いで、混練機を用いて２０分ほど混練してゲルの成形性を向上させた後、成型機にて直径０.９〜１mm、長さが３.５mmの円柱形状の粒子に押し出し成形した。
最後に、成形したアルミナゲルを空気存在下１２０℃で１６時間かけて乾燥した後、９００℃で２時間焼成してアルミナ担体を得た。
【００７７】
(ii) 触媒の製造
モリブデン酸アンモニウム四水和物１６.４ｇ、硝酸ニッケル六水和物９.８ｇを添加したクエン酸溶液１００mlに上記のアルミナ担体１００ｇを２５℃、４５分間浸漬し、金属成分担持担体を得た。
次いで担持担体を、乾燥機を使用して１２０℃で３０分間乾燥した後、６００℃で１.５時間、キルンでか焼して触媒を完成させた。
製造した触媒Ｂ中の各成分の量及び性状は下記の表１に示す通りである。
【００７８】
▲３▼ 触媒Ｃ（上記の触媒（２ｂ）に相当）の製造方法
(ｉ) 担体の製造
水道水を貯えたタンクに、アルミン酸ソーダ溶液を入れ、硫酸アルミニウム溶液を用いて加混合を行った。硫酸アルミニウム溶液の添加終了時にｐＨが８.５となるように添加し、混合時の温度を６４℃、保持時間は１.５時間とした。次にシリカ源の水ガラス（ケイ酸ソーダ）を混合した。水ガラスは、硫酸アルミニウム溶液と共に前記タンクに入れておいた。このときのアルミナゲル中のケイ酸ソーダの濃度を１.６重量％に設定した。
前記工程により得られたシリカ−アルミナ水和物のゲルを溶液から分離した後、温水を用いて洗浄処理を行い、ゲル中の不純物を除去した。
次いで、混練機を用いて１時間混練してゲルの成型性を向上させた後、成型機にて直径が０.９〜１mm、長さが３.５mmの円柱形状の粒子に押出成型した。
最後に成型したシリカ−アルミナ粒子を空気存在下１２０℃で１６時間かけて乾燥させた後、８００℃の温度で２時間焼成し、シリカ−アルミナ担体を得た。得られた担体中のシリカ含有量は７重量％であった。
【００７９】
(ii) 触媒の製造
モリブデン酸アンモニウム四水和物１６.２ｇ、炭酸ニッケル４.７ｇ、硝酸ナトリウム ０.６６ｇ、正リン酸２.１ｇに上記のシリカ−アルミナ担体１００ｇを２５℃、４５分間浸漬し、金属成分担持担体を得た。
次いで担持担体を、乾燥機を使用して１２０℃で３０分間乾燥した後、５４０℃で１.５時間、キルンでか焼して触媒を完成させた。
製造した触媒Ｃ中の各成分の量及び性状は下記の表１に示す通りである。
【００８０】
▲４▼ 触媒Ｄの製造
(ｉ) 担体の製造
水道水を張ったタンクに、硫酸アルミニウム、アルミン酸ソーダ溶液を同時滴下し加混合を行った。混合時の温度は７０℃とし、滴下時ｐＨを７.５とした後、最終ｐＨを９.５とするまで更にアルミン酸ソーダを加えた。保持時間は７０分間である。
得られたアルミナゲルを実施例１と同様の成形、焼成を行い、アルミナ粒子を得た。
【００８１】
(ii)触媒の製造
モリブデン酸アンモニウム四水和物１７.２ｇ、硝酸ニッケル六水和物９.８ｇを添加したクエン酸水溶液１００mlにアルミナ担体１００ｇを２５℃、４５分間浸漬し、実施例１と同様の条件で乾燥並びに焼成を行い、金属成分担持担体を得た。
製造した触媒Ｄ中の各成分の量及び性状は下記の表１に示す通りである。
【００８２】
【表１】
（II）水素化処理
表２に通油した原料油の性状を示した。この原料油は５３８℃を越える沸点を有する成分を約９３重量％含有し、硫黄含有量が約４.９重量％、全窒素含有量が約３３００重量ppm、バナジウム含有量が１０９重量ppm及びニッケル含有量が４６重量ppm、ノルマルヘプタン不溶解分で示されるアスファルテン分を約８重量％含有するものである。
【００８４】
【表２】
上記触媒Ａ、触媒Ｂ、触媒Ｃ及び触媒Ｄを、表３及び表４に示した組み合わせで反応装置の固定床に充填し、それぞれについて水素化処理を行った。
表２に記載した性状の原料油を圧力１６.０MPa、全液空間速度（Liquid Hourly Space Velocity :ＬＨＳＶ）１.５hr-1、平均温度４２７℃、供給する水素と原料油の比（Ｈ2／Ｏｉｌ）を８００Nl／Lとして固定床に導入し、生成油を得た。
生成油を捕集し分析して水素化によって脱離された硫黄（Sulfur）、金属(バナジウム＋ニッケル)及びアスファルテン(Asp.)量を算出し、下記計算式に基づいて比活性（Relative Volume Activity；ＲＶＡ）を求め、表３、表４に示した。比活性は、比較例1の触媒の水素化脱硫（ＨＤＳ）、水素化脱金属（ＨＤＭ）、及び水素化脱アスファルテン(HDAsp.)の各指数である
【００８６】
【数１】
【表３】
【表４】
上記の表３及び表４の結果から、実施例１及び実施例２は、重質留分を含む減圧残油の処理において、種々の組み合わせの比較例と比べて、石油精製工程で問題となるセディメント生成を抑制しつつ、高度な脱硫、脱金属、アスファルテン分解を達成していることが理解される。
【００９０】
【発明の効果】
本発明によれば、硫黄、残留炭素、金属、窒素、アスファルテン等の夾雑物を大量に含有する重質の炭化水素油、特に減圧残油留分を８０重量％以上含む重質油の水素化処理において、装置運転上の支障となるセディメントの生成を抑制しながら、高度な夾雑物の除去および付加価値の高い留出油の製造を可能とする。
また、水素化処理の第１段階で高度にアスファルテンを除去することにより、第２段階の熱分解で触媒上に堆積する好ましくないコーク生成を抑えて触媒性能の低下を防ぐ効果をもたらす。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for hydrotreating heavy hydrocarbon oils, and more particularly to a catalyst combination method that exhibits high performance in hydrotreating reduced-pressure residue oil that is a heavy fraction among hydrocarbon oils.
More specifically, in the hydrotreatment of heavy hydrocarbon oils containing a large amount of impurities (impurities) such as sulfur, metals, and asphaltenes, the target hydrodesulfurization is achieved by using a combination of catalysts having different functions. (HDS), hydrodemetallation (HDM), and hydrodeasphalene (asphaltene removal), and a hydrotreating method capable of suppressing sediment formation that accumulates in a heat exchanger during operation of the apparatus and hinders operation .
[0002]
[Prior art]
For example, an atmospheric residue (AR) that contains 50% by weight or more of a component having a boiling point of 538 ° C. or higher, or a vacuum residue (VR) that contains 90% by weight or more that is generated during petroleum refining is heavy. It is called hydrocarbon oil. There is a strong demand to use such heavy hydrocarbon oils by hydrotreating them, removing impurities such as sulfur, and converting them to light oils with high added value.
The light oil produced by the cracking of such heavy fraction has a higher sulfur concentration than the corresponding straight fraction, and therefore requires desulfurization and hydrogenation again.
[0003]
Contaminants to be removed by hydrogenation / cracking treatment include sulfur, carbon residue (CCR), various metals, nitrogen, and asphaltenes. Today, these impurities are improved by improving the catalyst. Can be removed to a high degree.
However, asphaltenes are aggregates of condensed aromatic compounds that are well-balanced with the surrounding solvent components, so when asphaltenes are decomposed excessively, they aggregate to form particulate matter (sludge) and sediment ( Sediment) is generated.
[0004]
Such a sediment is, in detail, a precipitate measured by testing a sample by Shell Hot Filteration Solid Test (SHFST) (Van Kerknoort et al., J. Inst. Pet. 37 p. 596-604 (1951)). ))), The normal content is said to be about 0.19 to 1% by weight in the product having a boiling point of 340 ° C. or higher recovered from the liquid discharged from the flash drum during the purification process.
[0005]
Sediment precipitates and accumulates in equipment such as heat exchangers and reactors during petroleum refining, which may clog the flow path and cause a major hindrance to the operation of the equipment. In particular, in the hydrotreating of heavier hydrocarbon oils containing a large amount of residual oil under reduced pressure, the generation of sediments becomes significant due to the large amount of asphaltenes.
For this reason, it is a new problem in improving the hydrotreating catalyst to achieve advanced hydrotreating and at the same time reduce generation of sediment as much as possible.
[0006]
On the other hand, light oil produced by cracking the heavy fraction has a higher sulfur concentration than the corresponding straight fraction, and therefore requires desulfurization and hydrogenation again. Therefore, to produce light oil with low sulfur, it is necessary to use a catalyst or combination of catalysts with high desulfurization performance for cracked light fractions while suppressing the formation of sediment in the hydrogenation and cracking of heavy fractions and performing stable operation. It is said.
[0007]
The present inventors use a combination of catalysts having different functions in the first stage and the second stage in the two-stage hydrotreatment, and further two kinds of catalysts having a specific catalyst composition and pore size distribution in the second stage. It has been found that the use of a mixture of these compounds is superior in suppression of sediment formation compared to the case where each catalyst is used alone, and exhibits high desulfurization performance for light fractions.
That is, by using a combination of three different catalysts having specific pore diameters (one in the first stage and two in the second stage), it is difficult to reduce the operating pressure against the vacuum residue oil containing heavy fractions. The present inventors have found a method capable of producing a highly desulfurized and economically-added white oil product with a high yield while suppressing the generation of cediments as much as possible.
[0008]
More specifically, according to the present invention, asphaltene decomposition and high demetallation catalyst are reduced as much as possible in the first stage of hydrotreating, and asphaltenes that cause generation of sediment are reduced as much as possible, followed by the second stage (final stage). By disposing a catalyst exhibiting high desulfurization performance, it is possible to perform operation with less generation of sediment while obtaining a desired desulfurization product oil. In particular, in the second stage, it is necessary to carry out a high degree of desulfurization while suppressing the formation of sediment, so it has been difficult until now by using a mixture of two different types of catalysts having a specific catalyst composition and pore size distribution. Suppressed maintenance and high desulfurization and hydrogenation were achieved.
[0009]
On the other hand, in the prior art, coexistence between suppression and maintenance of sediment and high hydrodesulfurization is not sufficiently achieved as described below.
Japanese Examined Patent Publication No. 7-65055 discloses a hydroprocessing method in which a heavy component of a hydrocarbon oil containing sulfur impurities and metallic impurities is converted in at least two stages. In this publication, 0.1 to 5% by weight of a metal oxide catalyst is used for the purpose of hydrodemetallation in the first stage, and 7 to 30 as a metal oxide for the purpose of hydrodesulfurization in the subsequent second stage. A method of hydrotreating with a weight percent metal oxide catalyst has been proposed. According to this method, it is recommended that the residue is treated by performing demetallization and hydrogenation cracking in the first stage and careful desulfurization in the second stage. In particular, a combination of alumina-agglomerated catalysts having a “sea urchin” structure shows remarkable results.
[0010]
However, according to this technique, although the demetalization function required in the first stage is improved, the catalyst loading amount of the catalyst used in the first stage is low, so that the desulfurization and hydrogenation functions are reduced, and therefore the first A high desulfurization function is required in two stages, and a catalyst having a large amount of catalyst is inevitably required. Further, when highly desulfurizing is performed in the second stage, the catalyst generates a high degree of heat. At this time, as the decomposition rate proceeds, the asphaltenes are aggregated. As far as the examples of the present invention are concerned, there are insufficient measures for preventing asphaltene aggregation, and as a result, there is a risk that the operation of the apparatus may be hindered.
[0011]
JP-A-8-325580 discloses a complete catalytic hydroconversion process for heavy petroleum feedstocks. In this method, the active metal oxide selected from cadmium, chromium, cobalt, iron, molybdenum, nickel, tin, tungsten and combinations thereof is added to the support material selected from alumina / silica and combinations thereof in the first stage. A total of 2 to 25% by weight of supported catalyst was supplied, reaction temperature was 438 to 468 ° C., and hydrogen partial pressure was 105 to 245 kg / cm. 2 The reaction is carried out under the reaction conditions of a space velocity of 0.3 to 1.0 (Vf / hr / Vr), and then the same catalyst is supplied in the second stage, the reaction temperature is 371 to 427 ° C., the hydrogen partial pressure is 105 to 245 kg / cm 2 Describes a method of hydroconversion under reaction conditions of space velocity of 0.1 to 0.8 (Vf / hr / Vr).
This method is a catalytic hydroconversion method of “H-Oil (registered trademark)”, which is a heavy petroleum feedstock, and proposes a solution for the treatment of unreacted residues by recycling them.
[0012]
Also, in order to achieve more complete hydroconversion of the feed and effective use of the catalyst, the first stage reactor is given a higher reaction temperature and lower catalyst activity, and the second stage reactor is By providing lower reaction temperatures and higher catalytic activity, it is said to provide improved coordination of reaction conditions and the catalytic activity required for each stage reactor.
[0013]
However, the high temperature reaction in the first stage disclosed in the publication promotes the thermal condensation of asphaltenes, while it becomes impossible to stabilize the resinous and other fragments produced with the thermal decomposition of the oil. This can cause rapid coke degradation of the catalyst.
[0014]
Further, in this method, a catalyst suitable for preventing the asphaltene aggregation and sediment precipitation caused in the second stage is not used, so that there is a risk that the operation may be hindered in this respect.
[0015]
Japanese Examined Patent Publication No. 6-53875 describes a multi-stage contact method for high conversion of a heavy hydrocarbon liquid feedstock. In the first stage, the reaction temperature is 415 to 455 ° C. and the hydrogen partial pressure is 70 to 211 kg / cm in a fixed bed or boiling bed reactor. 2 The space velocity is 0.2 to 2.0, the second stage is an ebullated bed reactor, the reaction temperature is 415 to 455 ° C., and the hydrogen partial pressure is 70 to 211 kg / cm. 2 Describes a multi-stage catalytic hydrotreating process with a space velocity of 0.2 to 2.0. Catalysts that can be used include active metal oxides selected from cadmium, chromium, cobalt, iron, molybdenum, nickel, tin, tungsten and mixtures thereof in a support material selected from the group of alumina, silica and combinations thereof. Catalyst. In this method, vacuum bottoms are recirculated to achieve a high decomposition rate in order to achieve a high decomposition rate, but no preventive measures against asphaltene agglomeration that hinders operation at a high decomposition rate are shown. It becomes a problem when driving.
[0016]
As for the catalyst used, the description of the catalyst includes that the hydrogen conversion reaction is promoted, or that in the case of a feedstock having a high metal content, a demetalized catalyst is used in the first stage reaction. There is no actual catalyst disclosure. In addition, regarding the disclosure of the catalyst, since this publication is insufficient, it cannot be determined that an effective result can be expected for precipitation of sediments that hinders operation.
Therefore, the catalyst combination according to the above-mentioned prior art sufficiently achieves the effect of suppressing the generation of sediment, which is an operation restriction of the apparatus, while achieving high desulfurization and decomposition by hydrocracking heavy hydrocarbon oil. Not.
[0017]
[Problems to be solved by the invention]
The present invention highly hydrotreats heavy hydrocarbon oils containing a large amount of impurities such as sulfur, residual carbon, metal, nitrogen and asphaltenes, particularly heavy oils containing 80% or more of the vacuum residue fraction. Thus, an effective hydrotreating method is provided by combining catalysts considering functions so that they can be removed moderately, and mixing two different types of catalysts having specific pore size distribution and catalyst composition in the second stage. For the purpose.
In particular, a catalyst combination that has not been sufficiently solved by the above-mentioned prior art, has excellent performance with respect to the advanced decomposition and removal of asphaltenes and the reduction of the sediments that accompany the increase in the conversion rate, and can also improve the desulfurization performance. The purpose is to provide.
[0018]
[Means for Solving the Problems]
As a result of intensive studies in view of the above problems, the present inventors have found that in a catalytic two-stage hydroconversion process, a catalyst having a specific pore size distribution in the first stage is used in a heavy hydrocarbon oil. Two types of catalysts with specific pore size distribution and catalyst composition that are different from the first stage in the second stage, which efficiently achieves deasphaltenation, which is effective in reducing impurities, especially demetalization and asphaltene aggregation prevention By using it in combination, it has been found that the relationship between hydrogenation and sediment, which has been considered a problem so far, can be improved. The inventors have found a catalytic hydrotreating method for heavy oil that can be stably operated, and have completed the present invention.
[0019]
That is, a catalyst having a specific pore size distribution is used in the first stage, and in the subsequent second stage, two kinds of catalysts having different pore sizes distribution and catalyst compositions different from those in the first stage are mixed. It was found that, due to the synergistic effect by this, desulfurization and hydrogenation proceeded to a high degree, but stable operation with suppressed generation of sediment was made possible. According to the present invention, the effect is particularly great for the hydroprocessing of heavy hydrocarbon oils.
[0020]
More specifically, in a two-stage hydrotreating method, a catalyst having a specific pore size distribution in the first stage reactor is supplied, and asphaltene is highly decomposed to promote formation of sediment. In the second stage reactor, which performs an appropriate hydrogenation reaction, supplies a catalyst with a pore size distribution and catalyst composition that improves desulfurization performance, and a catalyst with a pore size distribution and catalyst composition that allows moderate asphaltene decomposition. Thus, the present invention provides a method that does not generate sediment as much as possible while achieving a high degree of desulfurization.
Further, by removing asphaltenes at a high level in the first stage, it is possible to suppress the formation of undesirable coke deposited on the catalyst by the thermal decomposition in the second stage, thereby preventing the deterioration of the catalyst performance.
[0021]
In short, in the hydrotreating method of the present invention, the heavy hydrocarbon oil is brought into contact with the catalyst (1) in the presence of hydrogen in the first reactor charged with the following catalyst (1) to form the first stage hydrogen. In the second reactor in which the hydrotreating oil obtained in the first stage and the catalyst (2a) and the catalyst (2b) below are mixed and charged in the presence of hydrogen, the catalyst (2a) And a second hydrotreating process in contact with the catalyst (2b), and a heavy hydrocarbon oil hydrotreating method.
[0022]
Catalyst (1) is a porous alumina support, the oxide of Group 6A metal of the periodic table is 7 to 20% by weight, and the oxide of Group 8 metal of the periodic table is 0.5 to 6 based on the weight of the catalyst. Supported by weight percent of the catalyst
(a) Specific surface area of 100 to 180 m 2 / G,
(b) the total pore volume is 0.55 ml / g or more,
The pore distribution diameter of the catalyst is based on the total pore volume.
(c1) The ratio of the pore volume having a diameter of 200 mm or more is 50% or more of the total pore volume,
(c2) The proportion of the pore volume having a diameter of 2,000 mm or more is 10 to 30% of the total pore volume,
(c3) The proportion of pore volume with a diameter of 10,000 mm or more is 0 to 1% of the total pore volume
This is a hydrotreating catalyst.
[0023]
The catalyst (2a) is 7 to 20% by weight of the Group 6A metal oxide of the periodic table and 0.5 to 6% by weight of the Group 8 metal oxide of the periodic table based on the weight of the catalyst on the porous alumina support. Supported by the amount of catalyst
(a) Specific surface area of 100 to 180 m 2 / G,
(b) the total pore volume is 0.55 ml / g or more,
The pore distribution diameter of the catalyst is based on the total pore volume.
(d1) The proportion of the volume with a diameter of 100 to 1,200 mm is 85% or more,
(d2) The ratio of the volume of the pore diameter of 4,000 mm or more is 0 to 2%,
(d3) The volume ratio of the pore diameter of 10,000 mm or more is 0 to 1%,
(d4) The proportion of the pore volume with a diameter of 200 mm or more is 50% or more of the total pore volume
Is a hydrotreating catalyst.
[0024]
The catalyst (2b) has at least one hydrogenation active component supported on a heat-resistant inorganic porous carrier,
(a) Specific surface area is 150 m 2 / G or more,
(b) the total pore volume is 0.55 ml / g or more,
The pore distribution diameter of the catalyst is based on the total pore volume.
(d1) The ratio of the pore volume having a diameter of 100 to 1,200 mm is 75% or more of the total pore volume,
(d2) The proportion of the volume with a diameter of 4,000 mm or more is 0 to 2%,
(d3) The proportion of the pore volume having a diameter of 10,000 mm or more is 0 to 1% of the total pore volume,
(d4) The proportion of pore volume with a diameter of 200 mm or more is less than 50% of the total pore volume
This is a hydrotreating catalyst.
[0025]
Further, the present invention is characterized in that the heat-resistant inorganic porous carrier of the catalyst (2b) is a silica-alumina carrier containing 3.5% by weight or more of silica.
Further, the present invention provides a silica-alumina support in which the catalyst (2b) contains at least 3.5% by weight of silica, 7 to 20% by weight of a Group 6A metal oxide in the periodic table based on the weight of the catalyst, A hydrotreating catalyst in which the Group 8 metal oxide of the periodic table is supported in an amount of 0.5 to 6% by weight, and the Group 1A metal oxide of the periodic table is supported in an amount of 0.1 to 1% by weight. It is characterized by being.
[0026]
Further, the present invention provides a silica-alumina support in which the catalyst (2b) contains at least 3.5% by weight of silica, 7 to 20% by weight of a Group 6A metal oxide in the periodic table based on the weight of the catalyst, 0.5 to 6% by weight of Group 8 metal oxide of the periodic table, 0.1 to 1% by weight of Group 1A metal oxide of the periodic table, 0% of Group B element oxide of the periodic table The catalyst is a hydrotreating catalyst supported in an amount of 0.1 to 2% by weight.
[0027]
Further, the present invention is characterized in that the heavy hydrocarbon oil is a heavy oil containing 80% by weight or more of a vacuum residue fraction, and in the first stage and the second stage, the temperature is 350 to 450 ° C., the pressure is 5 The hydrogenation treatment is performed under a condition of ˜25 MPa.
[0028]
Further, the mixing ratio of the catalyst (2b) in the catalyst charged in the second stage reactor is 1% by weight or more, and further, the heavy hydrocarbon oil is converted into a hydrotreating catalyst in the form of a boiling bed. It is made to contact.
[0029]
DETAILED DESCRIPTION OF THE INVENTION
[I] Catalyst
The hydrotreating catalyst (catalyst (1)) used in the first stage of the hydrotreating method in the present invention, and the hydrotreating catalyst used in the second stage (catalyst (2a) and catalyst (2b)) ) Is composed of a catalyst material which is a metal oxide having hydrogenation activity and a carrier supporting the catalyst material.
[0030]
The components used for the catalyst material in the present invention are the periodic table (for example, “Iwanami Rikagaku Dictionary 4th edition”, Iwanami Shoten (published in 1987)) II element periodic table (see (a) long-period type)), a composition comprising two components of Group 6A metal and Group 8 metal oxide.
[0031]
The catalyst (2b) carries at least one hydrogenation active component. Examples of such components include Group 1A metals (lithium, sodium, etc.) and Group 2A metals (magnesium, calcium, etc.) of the periodic table. , Group 6A metals (chromium, molybdenum, tungsten, etc.), Group 8 metals (iron, cobalt, nickel, platinum, palladium, etc.), Group 4B elements (tin, lead, etc.) and Group 5B elements (phosphorus, arsenic) And antimony).
[0032]
The hydrogenation active component supported on the catalyst (2b) is preferably a composition comprising three components of Group 6A metal, Group 8 metal and Group 1A metal of the periodic table, and particularly Group 6A of the periodic table. A composition comprising four components of metal, Group 8 metal, Group 1A metal and Group 5B element oxide is preferred.
Group 1A, Group 2A, Group 4B, Group 5B, Group 6A, Group 8 are Group 1 of the Group 18 long-period periodic table (IUPAC system) that is not divided into Groups A and B. , Group 2, Group 14, Group 15, Group 6, and Groups 8-10.
[0033]
The Group 8 metal used in the catalyst of the present invention is at least one selected from iron, cobalt, and nickel. From the viewpoint of performance and economy, cobalt and nickel are preferable, and nickel is particularly preferable.
The Group 6A metal is at least one selected from chromium, molybdenum, and tungsten, but molybdenum is preferable from the viewpoint of performance and economy.
[0034]
Further, as a preferred embodiment of the catalyst (2b), when the carrier is a silica-alumina carrier containing silica, the Group 1A metal used in addition to the Group 6A metal and the Group 8 metal is lithium. Sodium and potassium, and sodium is preferable from the viewpoint of performance.
[0035]
As a particularly preferred embodiment of the catalyst (2b), the Group 5B element further supported in addition to the Group 6A metal, Group 8 metal and Group 1A metal is at least selected from phosphorus, arsenic, antimony and bismuth. Although it is 1 type, phosphorus is preferable from the point of performance.
[0036]
As described above, in the hydrotreatment of heavy hydrocarbon oil, the generation of sediment tends to increase as the hydrogenation is increased. In the present invention, the second stage has a specific pore structure and active component. By mixing a part of the catalyst, more advanced hydrogenation and suppression of sediment formation can be achieved in a balanced manner.
[0037]
The amount of each metal oxide supported on the basis of the weight of the catalyst after completion (100% by weight) is as follows.
That is, the Group 6A metal oxide supported in common on the catalyst (1), the catalyst (2a) and the catalyst (2b) is 7 to 20% by weight, and preferably 8 to 16% by weight. If the metal oxide is less than 7% by weight, the catalyst performance is not sufficiently developed, while if it exceeds 20% by weight, there is no increase in the catalyst performance.
[0038]
The Group 8 metal oxide supported in common in the catalyst (1), the catalyst (2a) and the catalyst (2b) is 0.5 to 6% by weight, preferably 1 to 5% by weight. If it is less than 0.5% by weight, the catalyst performance is not sufficiently developed. On the other hand, if it exceeds 6% by weight, there is no increase in the catalyst performance.
[0039]
Further, the amount of the Group 1A metal oxide supported on the catalyst (2b) is 0.1 to 1% by weight, preferably 0.1 to 0.5% by weight. If it is less than 0.1% by weight, it is not sufficient for controlling the surface activity, and the formation of sediment is unfavorable. When it exceeds 1% by weight, the expression of the catalyst performance becomes insufficient.
[0040]
The amount of the Group 5B element oxide supported on the catalyst (2b) is 0.1 to 2% by weight, preferably 0.1 to 1.0% by weight. If it exceeds 2% by weight, hydrogenation to other than asphaltenes proceeds too much, resulting in a rapid increase in the sediment. On the other hand, if it is less than 0.1% by weight, efficient hydrogenation cannot be achieved.
[0041]
Next, the carrier constituting the catalyst will be described.
The carrier of the catalyst (1) and the catalyst (2a) is porous alumina that can be obtained by an industrially produced method, and representatively, by coprecipitation of sodium aluminate (sodium aluminate) and aluminum sulfate. What is obtained can be used. The gel (pseudo boehmite) obtained at this time is dried, shaped and fired to obtain an alumina carrier.
[0042]
On the other hand, examples of the heat-resistant inorganic porous carrier used as the carrier for the catalyst (2b) include alumina, silica, silica-alumina, magnesia, zinc oxide, titania, zirconia, zeolite, clay minerals, and complex oxides thereof. Of these, silica-alumina is preferred from the viewpoints of economy and performance.
When the support of the catalyst (2b) is a silica-alumina support, it can be obtained by a method of co-precipitation at the time of alumina precipitation using water glass (sodium silicate) as a silica source. A solution of a water-soluble silica source may be immersed.
[0043]
A specific method for producing the carrier is as follows.
First, an alkaline solution such as sodium aluminate, ammonium hydroxide, or sodium hydroxide is placed in a tank that stores tap water or warm water, and then mixed using an acidic aluminum solution such as aluminum sulfate or aluminum nitrate. As a manufacturing method in case a catalyst (2b) is a silica-alumina support | carrier, it is good also as a tank which stored water glass beforehand as a silica source.
[0044]
Although the hydrogen ion concentration (pH) in the mixed solution changes as the reaction proceeds, the pH at the end of the addition of the acidic aluminum solution is 7 to 9, and the temperature at the time of mixing is the temperature of the first stage catalyst (1). It is preferable that it is 60-75 degreeC for 70-85 degreeC and the 2nd stage catalyst (2a) and catalyst (2b). In order to obtain pores having an appropriate size, the holding time is preferably about 0.5 to 1.5 hours, particularly preferably 40 to 80 minutes. A desired alumina hydrate or silica-alumina gel can be obtained by appropriately adjusting the various conditions of the mixing.
[0045]
Next, after separating the obtained alumina hydrate or silica-alumina gel from the solution, a washing method widely used in industry, for example, washing treatment using tap water or warm water is performed, and impurities in the gel Remove.
Next, after improving the moldability of the gel using a kneader, it is formed into a desired shape using a molding machine. Before loading the catalytically active component, it is preferably molded into a desired shape, and has a cylindrical shape with a diameter of 0.9 to 1 mm, for example 0.95 mm, and a length of 2.5 to 10 mm, for example 3.5 mm. The particles are preferred.
[0046]
Finally, the formed alumina gel or silica-alumina gel is dried and fired.
Drying conditions are from room temperature to 200 ° C. in the presence of air, and firing conditions are from 300 to 950 ° C., preferably from 600 to 900 ° C. in the presence of air, for 30 minutes to 2 hours. Also, water vapor can be introduced during the firing treatment to control the growth of alumina particles and silica-alumina crystals.
[0047]
By the above production method, it is possible to obtain an alumina carrier or a silica-alumina carrier having properties substantially matching the specific surface area and pore distribution of the finished catalyst described later.
In the above-mentioned kneading and forming step, an acid such as nitric acid, acetic acid, formic acid is added as a forming aid, or water is added to adjust the water content in alumina gel and silica-alumina gel, The pore distribution can be adjusted as appropriate.
[0048]
The specific surface area of the support before supporting the metal component of the catalyst substance provides a specific surface area and pore distribution within a specific range in the completed catalyst. Therefore, the alumina support of the catalyst (1) is 100 to 200 m. 2 / G, especially 130-170m 2 The total pore volume is preferably 0.5 to 1.2 ml / g, particularly preferably 0.7 to 1.1 ml / g.
On the other hand, the specific surface area of the alumina support of the catalyst (2a) and the silica-alumina support of the catalyst (2b) is 180 to 300 m in order to provide a specific surface area and pore distribution in a specific range in the completed catalyst. 2 / G, especially 185-250m 2 The total pore volume is preferably 0.5 to 1.0 ml / g, particularly preferably 0.6 to 0.9 ml / g.
[0049]
When the heat-resistant inorganic porous simple substance of the catalyst (2b) is a silica-alumina support, the silica content is not less than 3.5% by weight based on the completed catalyst including the catalyst substance (100% by weight). It is preferably 4.5 to 10% by weight. If it is less than 3.5% by weight, the performance of the catalyst is insufficient.
[0050]
The catalyst of the present invention is produced and completed by the method described below.
Various metal components for the above-mentioned catalyst substance are made into alkaline or acidic metal salts, and the carrier of catalyst (1), catalyst (2a), catalyst (2b) is immersed and supported in an immersion liquid in which this metal salt is dissolved in water. Let In this case, it may be immersed in a mixed aqueous solution composed of a plurality of metal salts and supported simultaneously, or a metal salt aqueous solution may be prepared separately and immersed and supported.
Moreover, it is preferable to add a small amount of aqueous ammonia, hydrogen peroxide, gluconic acid, aragonic acid, citric acid, malic acid, EDTA (ethylenediaminetetraacetic acid), etc. for stabilization of the immersion liquid.
[0051]
The metal aqueous solution of the Group 8 metal usually uses a water-soluble carbonate or nitrate, for example, a 10 to 40% by weight aqueous solution of nickel nitrate, preferably a 25% by weight aqueous solution. The Group 6A metal may be a water-soluble ammonium salt, for example, a 10 to 25% by weight aqueous solution of ammonium molybdate, and preferably a 15% by weight aqueous solution.
[0052]
As the Group 1A metal, which is a hydrogenation active component specific to the catalyst (2b), a water-soluble carbonate or nitrate can be used. For example, sodium nitrate is used.
Similarly, as the Group 5B element, which is a hydrogenation active component unique to the catalyst (2b), a phosphorus compound can be used, for example, orthophosphoric acid (orthophosphoric acid) is used.
[0053]
After immersing the carrier in the metal salt aqueous solution for about 30 to 60 minutes, drying is performed for about 0.5 to 16 hours at a temperature of normal temperature to 200 ° C. under an air stream, and then 200 to 800 ° C. under an air stream. Preferably, the catalyst on which each metal oxide is supported is completed by firing (calcination) for about 1 to 3 hours under heating conditions of 450 to 650 ° C.
[0054]
In order for the porous catalyst having a large number of pores completed by the above-described production method to achieve a desired purpose by combining them, it is important to have the following specific surface area and pore size distribution.
[0055]
The specific surface area of the catalyst (1) is 100 to 180 m. 2 / G, preferably 150-170 m 2 / G. Specific surface area is 100m 2 If it is less than / g, the catalyst performance becomes insufficient. 180m 2 If it exceeds / g, the desired pore size distribution is often not obtained, and even if it is obtained by an additive or the like, an increase in hydrogenation activity due to a high specific surface area will cause an increase in sediment.
[0056]
The specific surface area of the catalyst (2a) is 100 to 180 m. 2 / G, preferably 150-170 m 2 / G. Specific surface area is 100m 2 If it is less than / g, the catalyst performance becomes insufficient. 180m 2 There is no increase in catalyst performance beyond / g.
The specific surface area of the catalyst (2b) is 150 m 2 / G or more, preferably 185 to 250 m 2 / G. Specific surface area is 150m 2 If it is less than / g, the catalyst performance becomes insufficient.
Here, the specific surface area is nitrogen (N 2 ) Specific surface area determined by BET formula by adsorption.
[0057]
Further, the total pore volume measured by the mercury intrusion method is 0.55 ml / g or more, preferably 0.6 to 0.9 ml / g in common with the catalyst (1), the catalyst (2a) and the catalyst (2b). It is. If it is less than 0.55 ml / g, the catalyst performance becomes insufficient.
Here, the measurement by the mercury intrusion method is, for example, using a mercury porosity measuring instrument “Autopore II” (trade name) manufactured by Micromeritics and having a contact angle of 140 ° and a surface tension of 480 dyne / cm. It is a value obtained by measuring under conditions.
[0058]
In the catalyst (1), the ratio of the volume having a diameter of 200 mm or more is 50% or more, preferably 60 to 80% of the total pore volume. (Here, in this specification, the symbol “Å” represents angstrom, which is a unit of length, and 1Å = 10. -Ten m). If the volume ratio of the pores having a diameter of 200 mm or more is less than 50% of the total pore volume, the catalyst performance, particularly the asphaltene decomposition performance is deteriorated, and the formation of sediment is not sufficiently suppressed. In the carrier before the metal oxide is supported, the total volume ratio of the pores is 43% or more of the total pore volume, preferably 45 to 70%.
[0059]
In the catalyst (1), the volume ratio of pores having a diameter of 2,000 mm or more is 10 to 30% of the total pore volume. If this ratio is less than 10%, deasphalten performance will be reduced at the final outlet of the reactor, and the formation of sediment will increase. If it exceeds 30%, the mechanical strength of the catalyst will become extremely low and it will become brittle. I can't endure it.
[0060]
In particular, when processing a raw material oil with a large amount of vacuum residual oil, in the catalyst (1), the total volume ratio of pores having a diameter of 100 to 1,200 mm is 82% based on the total pore volume. Hereinafter, it is particularly preferably 80% or less. When this ratio exceeds 82%, the ratio of the total volume of pores of 2,000 mm or more is relatively reduced, and the diffusion of the superheavy fraction required in the first stage into the catalyst pores becomes insufficient. This is because it tends to cause a reduction in the decomposition rate of the vacuum residue fraction.
[0061]
In the catalyst (1), the pore volume of the pore diameter of 500 to 1,500 mm is preferably less than 0.2 ml / g. When the pore volume exceeds 0.2 ml / g, the diameter effective for desulfurization and demetallization reactions. This is because the catalyst performance tends to be lowered by relatively reducing the pores of 300 mm or less. Furthermore, since pores having a diameter of 300 mm or less are easily clogged with superheavy components, there is a concern that the catalyst life may be shortened.
Further, as the pore size distribution of the catalyst (1), the proportion of the pore volume having a diameter of 100 mm or less is preferably 25% or less of the total pore volume. When it exceeds 25%, hydrogenation to components other than asphaltenes proceeds to a high degree, and there is a tendency that generation of cediments increases.
[0062]
In the catalyst (2a), the proportion of the pore volume having a pore size distribution of 100 to 1,200 mm on the basis of the total pore volume is 85% or more, more desirably 87% or more. When the volume ratio of 100 to 1,200% is less than 85%, hydrogenation reactions such as desulfurization and decomposition are not sufficiently exhibited.
[0063]
In the catalyst (2b), the proportion of the pore volume having a pore size distribution of 100 to 1,200 mm on the basis of the total pore volume is preferably 75% or more, more preferably 78% or more. When the ratio of the pore volume of 100 to 1,200 kg is less than 75%, hydrogenation reactions such as desulfurization and decomposition are not sufficiently exhibited.
[0064]
Both the catalyst (2a) and the catalyst (2b) are desulfurized by setting the ratio of the pore volume with a diameter of 4,000 mm or more to 0 to 2% and the ratio of the pore volume with a diameter of 10,000 or more to 0 to 1%. In addition, it is possible to prevent an extreme decrease in the decomposition rate of the hydrogenation activity, particularly the reduced-pressure residue oil fraction.
[0065]
Further, in both the catalyst (2a) and the catalyst (2b), the pore distribution ratio of the pore volume having a diameter of 100 mm or less is preferably 25% or less of the total pore volume. When it exceeds 25%, hydrogenation to components other than asphaltenes proceeds to a high degree, and there is a tendency that generation of cediments increases.
[0066]
Further, the proportion of the pore volume having a diameter of 200 mm or more in the catalyst (2a) is 50% or more, preferably 60 to 80% of the total pore volume. When the ratio of the pore volume having a diameter of 200 mm or more is less than 50% of the total pore volume, the asphaltene decomposition performance becomes insufficient, and the suppression of sediment formation becomes insufficient.
[0067]
On the other hand, in the catalyst (2b), the proportion of the pore volume having a diameter of 200 mm or more is less than 50%, preferably 40% or less of the total pore volume. When the ratio of the pore volume with a diameter of 200 mm or more is 50% or more of the total pore volume, the hydrogenation activity is reduced, so that asphaltene decomposed by the catalyst (2a) cannot be appropriately hydrogenated and a sediment is generated. Can not be suppressed. Moreover, since the desulfurization performance is also reduced, the effect of addition to the catalyst (2a) is lost.
[0068]
In the second stage of the hydrotreatment, the ratio of the catalyst (2b) mixed with the catalyst (2a), that is, (2b) / [(2a) + (2b)] is 1% by weight or more, but a preferable ratio is 1 to 50% by weight, more preferably 10 to 30% by weight. When the mixing ratio exceeds 50% by weight, hydrogenation in the second stage proceeds excessively, so that the generation of sediment tends to be remarkable. On the other hand, if it is less than 1% by weight, the desulfurization performance is insufficient.
[0069]
[II] Hydrotreatment method
Heavy hydrocarbon oils subject to hydrotreating of the present invention include petroleum residue oil, solvent defoaming oil, coal liquefied oil, shale oil, tar sand oil, typically atmospheric residue (AR) and A vacuum residue (VR) or a mixture thereof, in particular a vacuum residue oil.
[0070]
In particular, components that boil at 538 ° C or higher (vacuum residue fraction) are 80% by weight or more, sulfur is 3% by weight or more, residual carbon is 10% by weight or more, and other heavy impurities including high-concentration metals are present. A refined oil is suitable as an object of the hydrotreating of the present invention, and by combining the above catalyst, impurities can be removed or converted to a light oil.
[0071]
As the first and second reactors in the hydrotreating, a general apparatus having a fixed bed, a moving bed or a boiling bed can be used. However, hydrogenation is carried out in the form of a boiling bed because the reaction temperature can be kept uniform. It is preferable to carry out the treatment.
[0072]
Specifically, a cylindrical catalyst having a diameter of 0.9 to 1.0 mm and a length of 3.5 mm is filled in a reaction apparatus, and hydrocarbon liquid is in a liquid phase and a total liquid space velocity (LHSV) of 0.1 to 0.1 mm. 3hr -1 , Preferably 0.3 to 2.0 hr -1 On the other hand, hydrogen is flow rate ratio (H 2 / Oil) 300-1500 Nl / L, preferably 600-1,000 Nl / L, pressure 5-25 MPa, preferably 14-19 MPa, temperature 350-450 ° C., preferably 400-440 ° C. React with.
[0073]
In the second reactor, the catalyst (2a) and the catalyst (2b) are mixed so that they are mixed uniformly in the fixed bed, but the catalyst (2a) is installed in the case of a moving bed or a boiling bed. After charging, a method of gradually charging the catalyst (2b) may be used.
In addition, the first reaction apparatus and the second reaction apparatus may be connected in series, but a stripping process for removing hydrogen sulfide and a quench line for supplying hydrogen may be provided in the middle of both apparatuses.
[0074]
【Example】
The following examples further illustrate the present invention.
However, the following examples do not limit the present invention.
[I] Production of catalyst
(1) Production of catalyst A (corresponding to catalyst (1) above)
(i) Production of carrier
A sodium aluminate solution and an aluminum sulfate solution were simultaneously added dropwise to a tank in which tap water was stored for mixing. The pH during mixing was 8.5, the temperature was 77 ° C., and the holding time was 70 minutes. This addition and mixing resulted in an alumina hydrate gel.
The alumina hydrate gel obtained in the above step was separated from the solution, and then washed with warm water to remove impurities in the gel.
Then, after kneading for about 20 minutes using a kneader to improve the moldability of the gel, it was extruded and molded into cylindrical particles having a diameter of 0.9 to 1 mm and a length of 3.5 mm.
Finally, the formed alumina gel was dried at 120 ° C. for 16 hours in the presence of air, and then calcined at 800 ° C. for 2 hours to obtain an alumina carrier.
[0075]
(ii) Catalyst production
100 g of the above alumina carrier was immersed in 100 ml of a citric acid solution to which 17.5 g of ammonium molybdate tetrahydrate and 9.8 g of nickel nitrate hexahydrate had been added to obtain a metal component-supported carrier.
The supported carrier was then dried at 120 ° C. for 30 minutes using a dryer and calcined in a kiln at 620 ° C. for 1.5 hours to complete the catalyst.
The amounts and properties of each component in the produced catalyst A are as shown in Table 1 below.
[0076]
(2) Production of catalyst B (corresponding to catalyst (2a) above)
(i) Production of carrier
A sodium aluminate solution and an aluminum sulfate solution were simultaneously added dropwise to a tank in which tap water was stored for mixing. The pH during mixing was 8.5, the temperature was 65 ° C., and the holding time was 70 minutes. This addition and mixing resulted in an alumina hydrate gel.
The alumina hydrate gel obtained in the above step was separated from the solution, and then washed with warm water to remove impurities in the gel.
Then, after kneading for about 20 minutes using a kneader to improve the moldability of the gel, it was extruded and molded into cylindrical particles having a diameter of 0.9 to 1 mm and a length of 3.5 mm.
Finally, the formed alumina gel was dried at 120 ° C. for 16 hours in the presence of air, and then calcined at 900 ° C. for 2 hours to obtain an alumina carrier.
[0077]
(ii) Catalyst production
100 g of the alumina carrier was immersed in 100 ml of a citric acid solution to which 16.4 g of ammonium molybdate tetrahydrate and 9.8 g of nickel nitrate hexahydrate had been added to obtain a metal component-supported carrier.
The supported carrier was then dried at 120 ° C. for 30 minutes using a dryer and calcined at 600 ° C. for 1.5 hours in a kiln to complete the catalyst.
The amounts and properties of each component in the produced catalyst B are as shown in Table 1 below.
[0078]
(3) Method for producing catalyst C (corresponding to catalyst (2b) above)
(i) Production of carrier
A sodium aluminate solution was placed in a tank in which tap water was stored, and mixing was performed using an aluminum sulfate solution. At the end of the addition of the aluminum sulfate solution, the solution was added so that the pH was 8.5, the temperature during mixing was 64 ° C., and the holding time was 1.5 hours. Next, water glass (sodium silicate) as a silica source was mixed. Water glass was placed in the tank along with the aluminum sulfate solution. The concentration of sodium silicate in the alumina gel at this time was set to 1.6% by weight.
The silica-alumina hydrate gel obtained in the above step was separated from the solution, and then washed with warm water to remove impurities in the gel.
Subsequently, after kneading for 1 hour using a kneader to improve the moldability of the gel, it was extruded into cylindrical particles having a diameter of 0.9 to 1 mm and a length of 3.5 mm.
Finally, the molded silica-alumina particles were dried at 120 ° C. in the presence of air for 16 hours and then calcined at a temperature of 800 ° C. for 2 hours to obtain a silica-alumina carrier. The silica content in the obtained carrier was 7% by weight.
[0079]
(ii) Catalyst production
100 g of the above silica-alumina carrier is immersed in 25 g at 45 ° C. for 45 minutes in 16.2 g of ammonium molybdate tetrahydrate, 4.7 g of nickel carbonate, 0.66 g of sodium nitrate, and 2.1 g of normal phosphoric acid. Got.
The supported carrier was then dried using a dryer at 120 ° C. for 30 minutes and then calcined at 540 ° C. for 1.5 hours in a kiln to complete the catalyst.
The amounts and properties of each component in the produced catalyst C are as shown in Table 1 below.
[0080]
(4) Manufacture of catalyst D
(i) Production of carrier
Aluminum sulfate and sodium aluminate solution were simultaneously added dropwise to a tank filled with tap water and mixed. The temperature at the time of mixing was set to 70 ° C., the pH at the time of dropping was adjusted to 7.5, and sodium aluminate was further added until the final pH was set to 9.5. The holding time is 70 minutes.
The obtained alumina gel was molded and fired in the same manner as in Example 1 to obtain alumina particles.
[0081]
(ii) Catalyst production
100 g of an alumina carrier was immersed in 100 ml of an aqueous citric acid solution to which 17.2 g of ammonium molybdate tetrahydrate and 9.8 g of nickel nitrate hexahydrate had been added, dried at 25 ° C. for 45 minutes, dried under the same conditions as in Example 1. Firing was performed to obtain a metal component-supporting carrier.
The amounts and properties of each component in the produced catalyst D are as shown in Table 1 below.
[0082]
[Table 1]
(II) Hydrotreatment
Table 2 shows the properties of the feed oil. This feedstock contains about 93% by weight of a component having a boiling point exceeding 538 ° C., a sulfur content of about 4.9% by weight, a total nitrogen content of about 3300 ppm by weight, a vanadium content of 109% by weight and nickel The content is 46 ppm by weight, and about 8% by weight of the asphaltene content represented by normal heptane insoluble matter.
[0084]
[Table 2]
The catalyst A, catalyst B, catalyst C and catalyst D were filled in the fixed bed of the reactor in the combinations shown in Tables 3 and 4 and subjected to hydrogenation treatment.
The raw material oil having the properties shown in Table 2 was pressure 16.0 MPa, and the total liquid space velocity (LHSV) 1.5 hr. -1 , Average temperature 427 ° C., ratio of supplied hydrogen and feedstock (H 2 / Oil) was introduced into the fixed bed at 800 Nl / L to obtain a product oil.
The amount of sulfur (Sulfur), metal (vanadium + nickel) and asphaltene (Asp.) Desorbed by hydrogenation is calculated by collecting and analyzing the generated oil, and the specific activity (Relative Volume Activity) based on the following formula RVA) was determined and shown in Tables 3 and 4. Specific activity is an index of hydrodesulfurization (HDS), hydrodemetallation (HDM), and hydrodesulfurization (HDAsp.) Of the catalyst of Comparative Example 1.
[0086]
[Expression 1]
[Table 3]
[Table 4]
From the results of Tables 3 and 4 above, Example 1 and Example 2 are problematic in the petroleum refining process in the treatment of vacuum residue containing heavy fractions compared to various combinations of comparative examples. It is understood that advanced desulfurization, metal removal, and asphaltene decomposition are achieved while suppressing the formation of sediment.
[0090]
【The invention's effect】
According to the present invention, hydrogenation of heavy hydrocarbon oil containing a large amount of impurities such as sulfur, residual carbon, metal, nitrogen, asphaltene, particularly heavy oil containing 80% by weight or more of the vacuum residue fraction In the treatment, it is possible to remove advanced contaminants and produce a high-value-added distillate oil while suppressing the generation of sediments that hinder the operation of the apparatus.
Further, asphaltene is removed at a high level in the first stage of the hydrotreating process, thereby suppressing the generation of undesirable coke that accumulates on the catalyst by the thermal decomposition in the second stage, thereby preventing the deterioration of the catalyst performance.
Claims (6)
触媒(１)：多孔質のアルミナ担体に、触媒重量を基準として周期表の第６Ａ族金属の酸化物が７〜２０重量％、周期表の第８族金属の酸化物が０.５〜６重量％で担持され、触媒の
(a)比表面積が１００〜１８０m2／ｇ、
(b)全細孔容積が０.５５ml／ｇ以上であり、
触媒の細孔分布径が全細孔容積を基準として
(c1)直径が２００Å以上の細孔容積の割合が全細孔容積の５０％以上、
(c2)直径が２,０００Å以上の細孔容積の割合が全細孔容積の１０〜３０％、
(c3)直径が１０,０００Å以上の細孔容積の割合が全細孔容積の０〜１％
である水素化処理用触媒；
触媒(２ａ)：多孔質アルミナ担体に触媒重量を基準として周期表の第６Ａ族金属の酸化物が７〜２０重量％、周期表の第８族金属の酸化物が０.５〜６重量％の量で担持され、触媒の
(a)比表面積が１００〜１８０m2／ｇ、
(b)全細孔容積が０.５５ml／ｇ以上であり、
触媒の細孔分布径が全細孔容積を基準として
(d1)直径が１００〜１,２００Åの容積の割合が８５％以上、
(d2)細孔の直径が４,０００Å以上の容積の割合が０〜２％、
(d3)細孔の直径が１０,０００Å以上の容積の割合が０〜１％、
(d4)直径が２００Å以上の細孔容積の割合が全細孔容積の５０％以上
である水素化処理触媒；
触媒(２ｂ)：耐熱性無機多孔質担体に触媒重量を基準として周期表の第６Ａ族金属の酸化物が７〜２０重量％、周期表の第８族金属の酸化物が０.５〜６重量％、周期表の第１Ａ族金属の酸化物が０.１〜１重量％、周期表の第５Ｂ族元素の酸化物が０.１〜２重量％の量で担持され、触媒の
(a)比表面積が１５０m2／ｇ以上、
(b)全細孔容積が０.５５ml／ｇ以上であり、
触媒の細孔分布径が全細孔容積を基準として
(d1)直径が１００〜１,２００Åの細孔容積の割合が全細孔容積の７５％以上、
(d2)直径が４,０００Å以上の容積の割合が０〜２％、
(d3)直径が１０,０００Å以上の細孔容積の割合が全細孔容積の０〜１％、
(d4)直径が２００Å以上の細孔容積の割合が全細孔容積の５０％未満
である水素化処理用触媒。Heavy hydrocarbon oil is obtained in the first stage by contacting it with the catalyst (1) in the presence of hydrogen in the first reactor filled with the following catalyst (1), and then in the first stage. The hydrotreated oil thus obtained is brought into contact with the catalyst (2a) and the catalyst (2b) in the presence of hydrogen in the second reactor filled with the following catalyst (2a) and catalyst (2b), and second A method for hydrotreating heavy hydrocarbon oil, characterized by performing hydrotreating in stages.
Catalyst (1): On a porous alumina support, the oxide of the Group 6A metal in the periodic table is 7 to 20% by weight based on the catalyst weight, and the oxide of the Group 8 metal in the periodic table is 0.5 to 6 Supported by weight percent of the catalyst
(a) a specific surface area of 100 to 180 m 2 / g,
(b) the total pore volume is 0.55 ml / g or more,
The pore distribution diameter of the catalyst is based on the total pore volume.
(c1) The proportion of the pore volume having a diameter of 200 mm or more is 50% or more of the total pore volume,
(c2) The proportion of the pore volume having a diameter of 2,000 mm or more is 10 to 30% of the total pore volume,
(c3) The proportion of pore volume with a diameter of 10,000 mm or more is 0 to 1% of the total pore volume
A hydrotreating catalyst;
Catalyst (2a): 7 to 20% by weight of Group 6A metal oxide of periodic table and 0.5 to 6% by weight of Group 8 metal oxide of periodic table based on catalyst weight on porous alumina support Supported by the amount of catalyst
(a) a specific surface area of 100 to 180 m 2 / g,
(b) the total pore volume is 0.55 ml / g or more,
The pore distribution diameter of the catalyst is based on the total pore volume.
(d1) The proportion of the volume with a diameter of 100 to 1,200 mm is 85% or more,
(d2) The ratio of the volume of the pore diameter of 4,000 mm or more is 0 to 2%,
(d3) The volume ratio of the pore diameter of 10,000 mm or more is 0 to 1%,
(d4) A hydrotreating catalyst in which the proportion of the pore volume having a diameter of 200 mm or more is 50% or more of the total pore volume;
Catalyst (2b): 7 to 20% by weight of Group 6A metal oxide of periodic table and 0.5 to 6 of Group 8 metal oxide of periodic table based on catalyst weight on heat resistant inorganic porous support The oxide of the Group 1A metal in the periodic table is supported in an amount of 0.1 to 1% by weight, and the oxide of the Group 5B element of the periodic table is supported in an amount of 0.1 to 2% by weight.
(a) a specific surface area of 150 m 2 / g or more,
(b) the total pore volume is 0.55 ml / g or more,
The pore distribution diameter of the catalyst is based on the total pore volume.
(d1) The ratio of the pore volume having a diameter of 100 to 1,200 mm is 75% or more of the total pore volume,
(d2) The proportion of the volume with a diameter of 4,000 mm or more is 0 to 2%,
(d3) The proportion of the pore volume having a diameter of 10,000 mm or more is 0 to 1% of the total pore volume,
(d4) A hydrotreating catalyst in which the proportion of the pore volume having a diameter of 200 mm or more is less than 50% of the total pore volume.
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| JP4822705B2 (en) * | 2004-12-24 | 2011-11-24 | 日揮触媒化成株式会社 | Heavy hydrocarbon oil hydrotreating catalyst composition and method for producing the same |
| JP2008093493A (en) * | 2006-10-05 | 2008-04-24 | Idemitsu Kosan Co Ltd | Demetallization catalyst and method for hydrotreating heavy oil by using the same |
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| CN103789004B (en) * | 2012-11-01 | 2015-07-22 | 中国石油化工股份有限公司 | Hydrodemetalization process |
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