JP4477266B2 - Hydrotreating catalyst - Google Patents
Hydrotreating catalyst Download PDFInfo
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- JP4477266B2 JP4477266B2 JP2001292972A JP2001292972A JP4477266B2 JP 4477266 B2 JP4477266 B2 JP 4477266B2 JP 2001292972 A JP2001292972 A JP 2001292972A JP 2001292972 A JP2001292972 A JP 2001292972A JP 4477266 B2 JP4477266 B2 JP 4477266B2
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- type zeolite
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- 239000003054 catalyst Substances 0.000 title claims description 41
- 239000010457 zeolite Substances 0.000 claims description 97
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 96
- 229910021536 Zeolite Inorganic materials 0.000 claims description 95
- 239000011148 porous material Substances 0.000 claims description 85
- 229910052751 metal Inorganic materials 0.000 claims description 26
- 239000002184 metal Substances 0.000 claims description 26
- 239000007858 starting material Substances 0.000 claims description 14
- 230000000737 periodic effect Effects 0.000 claims description 6
- 230000000694 effects Effects 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- 239000003921 oil Substances 0.000 description 16
- 238000000034 method Methods 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 7
- 239000004215 Carbon black (E152) Substances 0.000 description 7
- 238000006477 desulfuration reaction Methods 0.000 description 7
- 230000023556 desulfurization Effects 0.000 description 7
- 229930195733 hydrocarbon Natural products 0.000 description 7
- 239000002002 slurry Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 239000000725 suspension Substances 0.000 description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- 150000002430 hydrocarbons Chemical class 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000004517 catalytic hydrocracking Methods 0.000 description 5
- 238000005342 ion exchange Methods 0.000 description 5
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 4
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 4
- 235000011130 ammonium sulphate Nutrition 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 4
- 238000005336 cracking Methods 0.000 description 4
- 229910052809 inorganic oxide Inorganic materials 0.000 description 4
- 229910052750 molybdenum Inorganic materials 0.000 description 4
- 239000011733 molybdenum Substances 0.000 description 4
- 229910052759 nickel Inorganic materials 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
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 4
- 229910052721 tungsten Inorganic materials 0.000 description 4
- 239000010937 tungsten Substances 0.000 description 4
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 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
- 238000002459 porosimetry Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 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 2
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 2
- -1 ammonium ions Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229910001388 sodium aluminate Inorganic materials 0.000 description 2
- 238000010025 steaming Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- AEQDJSLRWYMAQI-UHFFFAOYSA-N 2,3,9,10-tetramethoxy-6,8,13,13a-tetrahydro-5H-isoquinolino[2,1-b]isoquinoline Chemical compound C1CN2CC(C(=C(OC)C=C3)OC)=C3CC2C2=C1C=C(OC)C(OC)=C2 AEQDJSLRWYMAQI-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 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
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 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
- 239000008188 pellet Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000000176 sodium gluconate Substances 0.000 description 1
- 229940005574 sodium gluconate Drugs 0.000 description 1
- 235000012207 sodium gluconate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は水素化処理触媒に関する。更に詳しくは、細孔直径３．５〜５ｎｍの範囲の細孔容積が制御された超安定Ｙ型ゼオライトを用いることにより、炭化水素油、特に軽油の水素処理に使用したときに、分解活性および脱硫活性が高い水素化処理触媒に関する。
【０００２】
【従来の技術】
従来、炭化水素油の水素化分解を主目的とする水素化処理触媒には、超安定Ｙ型ゼオライト（以下、ＵＳＹということがある。）に水素化活性金属成分を担持した触媒が使用されてきた。例えば、特開平２−２１４５４４号公報には、アルミナとＵＳＹからなる担体に、周期律表第５族金属、第６族金属および第８族金属から選ばれる少なくとも１種の水素化活性金属とホウ素および／またはリンを担持してなることを特徴とする重質石油類の水素化分解触媒が開示されている。
【０００３】
超安定Ｙ型ゼオライトは、特有の固体酸、細孔分布などの特性を有するため、接触分解、水素化分解、異性化、アルキル化、リホーミングなどの石油精製用触媒として広く使用されているほか、吸着剤などにも利用されている。特に、水素化分解触媒に使用される超安定Ｙ型ゼオライトは、ゼオライト特有の均一細孔以外に大孔径細孔を有することが望ましい。
【０００４】
出発原料ＮａＹ型ゼオライトのＮａ+をＮＨ4 +にイオン交換して、水熱法によってＳｉＯ2／Ａｌ2Ｏ3比を向上させた超安定Ｙ型ゼオライトは、Ｙ型ゼオライト特有の細孔以外に大孔径細孔を有することが知られている〔例えば、堀越ら、日本化学会誌、（３）、３９８（１９８９）〕。しかし、従来のこのような方法で得られる超安定Ｙ型ゼオライトは、大孔径細孔の容積が小さいため、該容積を大きくすることが望まれていた。
【０００５】
特開平９−２５５３２６号公報において、（ａ）結晶度１００〜１３０％、（ｂ）比表面積 ５００〜８００ｍ2／ｇ、（ｃ）ＳｉＯ2／Ａｌ2Ｏ3のモル比が８〜１８、（ｄ）細孔径が６００Å以下である細孔の全細孔容積が０．３５〜０．５０ｍｌ／ｇ、（ｅ）細孔径が２０Å未満である細孔の細孔容積が０．１５〜０．３５ｍｌ／ｇ、（ｆ）細孔径２０Å〜６００Åの範囲にある細孔の細孔容積（ＰＶｍ）が０．１５〜０．３０ｍｌ／ｇ、（ｇ）細孔径２０Å〜６００Åの範囲にある細孔の細孔容積（ＰＶｍ）のうち、細孔径３５Å〜５０Åの細孔の細孔容積（ＰＶｓ）が０．１０〜０．２５ｍｌ／ｇ、（ｈ）ＰＶｍとＰＶｓの差（ＰＶｍ−ＰＶｓ）が０．０５ｍｌ／ｇ以下、であることを特徴とする均一なミクロポアと均一なメソポアの２種類の細孔を有するフォージャサイト型ゼオライトおよびその製造方法が提案されている。
【０００６】
また、特表平９−５０２４１６号公報には、ゼオライトＹ物質の２〜６０ｎｍ範囲の直径のメソポア容量を、処理溶液の大気圧沸点以上の温度において、そのゼオライトを熱水処理することによって増加させる方法が記載されている。
【０００７】
通常、超安定Ｙ型ゼオライトの大孔径細孔の大部分は、細孔直径が３．５〜５ｎｍの範囲の均一な細孔であることが知られている。しかし、従来の処理方法では、細孔直径３．５〜５ｎｍの細孔の細孔容積を制御することができなかったし、また、制御された超安定Ｙ型ゼオライトも知られていなかった。
【０００８】
【発明が解決しようとする課題】
本発明の目的は、細孔直径３．５〜５ｎｍの範囲の細孔容積が制御された超安定Ｙ型ゼオライトを用いることにより、炭化水素油、特に軽油の水素分解に使用したときに、分解活性および脱硫活性が高い水素化処理触媒を提供することにある。
【０００９】
【課題を解決するための手段】
本発明者らは、超安定Ｙ型ゼオライトの大孔径細孔の大部分を占める細孔直径３．５〜５ｎｍの範囲の均一な細孔の細孔容積を制御する方法について鋭意研究をした結果、出発原料ＮａＹ型ゼオライトの結晶子径と超安定Ｙ型ゼオライトの細孔直径３．５〜５ｎｍの範囲の細孔容積とが密接な関係にあること、そして、細孔直径３．５〜５ｎｍの範囲の細孔容積が制御された超安定Ｙ型ゼオライトを使用した水素化処理触媒は、炭化水素油、特に、軽油の水素処理に使用した場合に、高い分解活性と脱硫活性を示すことを見出し、本発明を完成するに至った。
【００１０】
すなわち、本発明は、超安定Ｙ型ゼオライトと周期律表第６族金属および／または第８族金属から選ばれた活性金属成分を含有する水素化処理触媒であって、該超安定Ｙ型ゼオライトの細孔直径３．５〜５ｎｍの範囲の細孔容積ｙが、下記式の関係を満たすものであることを特徴とする水素化処理触媒に関する。
２．１１×１０-3ｘ−０．１４０≦ｙ≦２．１１×１０-3ｘ−０．１１０
〔式中、ｙは、超安定Ｙ型ゼオライトの細孔直径３．５〜５ｎｍの範囲の細孔容積（ｍｌ／ｇ）を表し、ｘは、超安定Ｙ型ゼオライトの出発原料ＮａＹ型ゼオライトの結晶子径（ｎｍ）を表す。但し、ｘは、６６．５ｎｍ以上である。〕
【００１１】
【発明の実施の形態】
以下、本発明について詳細に説明する。
本発明の水素化処理触媒は、後述する特定の超安定Ｙ型ゼオライトと周期律表第６族金属および／または第８族金属から選ばれた活性金属成分を含有する。
【００１２】
本発明においては、超安定Ｙ型ゼオライトの出発原料であるＮａＹ型ゼオライトの結晶子径（ｘ）は６６．５ｎｍ以上であることが必要である。該結晶子径（ｘ）が６６．５ｎｍより小さい場合には、得られる超安定Ｙ型ゼオライトの細孔直径３．５〜５ｎｍの範囲の細孔容積（ｙ）はほとんど生成しないため好ましくない。出発原料ＮａＹ型ゼオライトの該結晶子径（ｘ）は、好ましくは７５ｎｍ以上であり、更に好ましくは８０ｎｍ以上、５００ｎｍ以下の範囲にあることが望ましい。特に、水素化処理触媒に利用される超安定Ｙ型ゼオライトは、細孔容積（ｙ）の大きいものが好ましく、該結晶子径（ｘ）は、９０〜３００ｎｍの範囲にあるものが望ましい。
【００１３】
なお、本発明において、出発原料ＮａＹ型ゼオライトの結晶子径（ｘ）とは、Ｘ線回折の（５３３）面の回折線プロファイルをＧａｕｓｓ関数型で近似してＳｃｈｅｒｒｅｒの式により求めた値である。
【００１４】
本発明での超安定Ｙ型ゼオライトは、該ゼオライトの細孔直径３．５〜５ｎｍの範囲の細孔容積（ｙ）が出発原料ＮａＹ型ゼオライトの結晶子径（ｘ）と下記の式（Ｉ）で表される関係にあることが大切である。
２．１１×１０-3ｘ−０．１４０≦ｙ≦２．１１×１０-3ｘ−０．１１０ （Ｉ）
〔式中、ｙは、超安定Ｙ型ゼオライトの細孔直径３．５〜５ｎｍの範囲の細孔容積（ｍｌ／ｇ）を表し、ｘは、超安定Ｙ型ゼオライトの出発原料ＮａＹ型ゼオライトの結晶子径（ｎｍ）を表す。但し、ｘは、６６．５ｎｍ以上である。〕
【００１５】
本発明によれば、出発原料ＮａＹ型ゼオライトの結晶子径（ｘ）の大きさを適宜選択することにより、超安定Ｙ型ゼオライトにおける細孔直径３．５〜５ｎｍの範囲の細孔容積（ｙ）を目的とする細孔容積（ｙ）に制御することが可能となる。
なお、結晶子径（ｘ）の大きさが異なる出発原料ＮａＹ型ゼオライトは、ＮａＹ型ゼオライトの種子を使用する合成方法において、合成時における種子量を変化させることにより製造することができる。
【００１６】
本発明において、超安定Ｙ型ゼオライトの細孔直径３．５〜５ｎｍの範囲の細孔容積（ｙ）とは、窒素吸脱着等温線の脱着等温線からＢ．Ｊ．Ｈ法で計算した細孔分布より求めた値である。
【００１７】
本発明での超安定Ｙ型ゼオライトは、前述の制御された細孔容積（ｙ）を有する外、単位格子定数（ＵＤ）が２．４５５ｎｍ以下、好ましくは２．４５０〜２．４１９ｎｍの範囲であることが望ましい。また、該超安定Ｙ型ゼオライトは、ＳｉＯ2／Ａｌ2Ｏ3モル比が８以上であることが望ましく、比表面積が４００〜９００ｍ2／ｇの範囲にあることが望ましく、また結晶度（リンデ社ＳＫ−４０を１００％とした相対結晶度）は９５％以上であることが望ましい。
【００１８】
前述の超安定Ｙ型ゼオライトは、例えば、結晶子径が６６．５ｎｍ以上である出発原料ＮａＹ型ゼオライトをアンモニウムイオンでイオン交換してイオン交換率８０％以上にしたＮＨ4Ｙ型ゼオライトを水蒸気雰囲気中で加熱処理して単位格子定数を２．４５５ｎｍ以下にした後、鉱酸などの脱アルミニウム剤で処理し、骨格外アルミニウムを除去して製造することができる。
【００１９】
本発明の水素化処理触媒は、前述の超安定Ｙ型ゼオライトを含有する耐火性無機酸化物からなる担体に、周期律表第６族金属および／または第８族金属から選ばれた少なくとも一種の活性金属成分を担持した触媒が好適である。耐火性無機酸化物としては、通常、水素化処理触媒に使用される耐火性無機酸化物が使用可能で、具体的には、アルミナ、シリカ、チタニア、ジルコニア、アルミナ−シリカ、アルミナ−チタニア、アルミナ−ボリア、アルミナ−リン、アルミナ−ボリア−リン、アルミナ−チタニア−ボリア、アルミナ−チタニア−リンなどが例示される。担体中に含有される該超安定Ｙ型ゼオライトの量は、１〜５０質量％、好ましくは５〜２０質量％の範囲が望ましい。
【００２０】
本発明での周期律表第６族金属および／または第８族金属から選ばれた活性金属成分としては、モリブデン、タングステン、ニッケル、コバルト、ロジウム、パラジウム、白金などが例示される。特に、モリブデン、タングステン、ニッケル、コバルトが好ましく、ニッケルおよび／またはコバルトとモリブデンおよび／またはタングステンの組み合わせが望ましい。該活性金属成分の含有量は、通常の水素化処理触媒で使用される量が用いられる。好ましい該活性金属成分の含有量は、酸化物として、モリブデン、タングステンでは５〜２５質量％、ニッケル、コバルトでは０．５〜１０質量％、ロジウム、パラジウム、白金では０．０１〜２質量％の範囲が望ましい。
【００２１】
本発明の水素化処理触媒は、例えば、前述の超安定Ｙ型ゼオライトと耐火性無機酸化物の前駆体とを混合した後、所望の形状に成型し、乾燥、焼成して得た担体に、前述の活性金属成分の前駆物質を周知の方法により担持し、乾燥、焼成して製造される。
【００２２】
本発明の水素化処理触媒は、炭化水素油の通常の水素化処理条件で使用可能である。特に本発明の水素化処理触媒は減圧軽油の水素化処理に好適に使用することができる。このときの水素化処理条件としては、例えば、反応温度３００〜４５０℃、水素分圧２．０〜２０ＭＰａ、液空間速度０．１〜４ｈｒ-1などの条件が好ましく採用される。
【００２３】
本発明の水素化処理触媒に使用される超安定Ｙ型ゼオライトは、ゼオライト特有の均一細孔以外に、制御された細孔直径３．５〜５ｎｍの範囲の細孔容積を有するため、炭化水素油、特に、減圧軽油の水素処理に使用して、高い分解活性、高い脱硫活性を示す。
【００２４】
【実施例】
以下に実施例を挙げて本発明を説明するが、本発明はこれにより限定されるものでない。
【００２５】
（参考例１）
結晶子径が６６．５ｎｍ以上であるＮａＹ型ゼオライト（Ａ、Ｂ、Ｃ、Ｄ、Ｅの５種）を調製した。各ゼオライトの性状を表１に示す。
表１示すＡ、Ｂ、Ｃ、ＤおよびＥのＮａＹ型ゼオライト４１１３ｇを、それぞれ６０℃の温水３３リットルに懸濁した。次いで、ゼオライトに対して１モル倍の硫安９２４ｇを加え、９０℃で１時間攪拌してイオン交換した。その後、濾過し、再度、硫安９２４ｇを６０℃の温水１０リットルに溶解した溶液で同様にイオン交換した後、濾過し、６０℃の純水３０リットルで洗浄し、乾燥、粉砕を行ない、各々６５％イオン交換されたＹ型ゼオライト（ＮＨ4 65Ｙ）を得た。
【００２６】
次いで、各々のＹ型ゼオライト（ＮＨ4 65Ｙ）３４８７ｇを回転スチミング装置で６００℃で１時間飽和水蒸気雰囲気中で焼成して焼成Ｙ型ゼオライト（Ｈ65Ｙ）を得た。
【００２７】
各々の焼成Ｙ型ゼオライト（Ｈ65Ｙ）２７１８ｇを６０℃の温水３０リットルに懸濁し、硫安をゼオライトに対して２モル倍量の１８４８ｇを加え、９０℃で１時間攪拌してイオン交換した後、濾過し、６０℃の純水３０リットルで洗浄した。洗浄したゼオライトを、再度、６０℃の温水３０リットルに懸濁し、この懸濁に硫安１８１２ｇを加え、９０℃で１時間攪拌してイオン交換した。その後、濾過し、６０℃の純水３０リットルで洗浄し、乾燥、粉砕を行ない、各々８５％イオン交換されたＹ型ゼオライト（ＮＨ4 85Ｙ）を得た。
【００２８】
それぞれのイオン交換されたＹ型ゼオライト（ＮＨ4 85Ｙ）２９５２ｇを回転スチミング装置で７８０℃で１時間飽和水蒸気雰囲気中で焼成して格子定数２．４３１〜２．４３２ｎｍの焼成Ｙ型ゼオライト（Ｈ85Ｙ）を得た。
【００２９】
各焼成Ｙ型ゼオライト（Ｈ85Ｙ）２８５６ｇを６０℃温水３０リットルに懸濁し、この懸濁液に２５％硫酸５５３０ｇを徐々に添加した後、９５℃で１時間攪拌して脱アルミニウム処理をした。その後、濾過、洗浄、乾燥を行い超安定Ｙ型ゼオライトＡ、Ｂ、Ｃ、ＤおよびＥを得た。各超安定Ｙ型ゼオライトＡ〜Ｅの性状を表２に示す。また、出発原料ＮａＹ型ゼオライトの結晶子径（ｘ）と超安定Ｙ型ゼオライトの細孔直径３．５〜５ｎｍの範囲の細孔容積（ｙ）の関係を図１に示す。
【００３０】
【表１】
【表２】
図１に示した、出発原料ＮａＹ型ゼオライトの結晶子径（ｘ）と超安定Ｙ型ゼオライトの細孔直径３．５〜５ｎｍの範囲の細孔容積（ｙ）の関係は、次の実験式（II）で表される。
ｙ＝２．１１×１０-3ｘ−０．１２５ （II）
〔式中、ｙは、超安定Ｙ型ゼオライトの細孔直径３．５〜５ｎｍの範囲の細孔容積（ｍｌ／ｇ）を表し、ｘは、超安定Ｙ型ゼオライトの出発原料ＮａＹ型ゼオライトの結晶子径（ｎｍ）を表す。但し、ｘは、６６．５ｎｍ以上である。〕
【００３３】
そして、式（II）で表される細孔容積の各測定値との標準誤差（σ）は、±０．００５（ｍｌ／ｇ）であり、誤差範囲を３σ＝±０．０１５（ｍｌ／ｇ）とすると、超安定Ｙ型ゼオライトの細孔直径３．５〜５ｎｍの範囲の細孔容積（ｙ）は、下記式（Ｉ）で表される。
２．１１×１０-3ｘ−０．１４０≦ｙ≦２．１１×１０-3ｘ−０．１１０ （Ｉ）
〔式中、ｙは、超安定Ｙ型ゼオライトの細孔直径３．５〜５ｎｍの範囲の細孔容積（ｍｌ／ｇ）を表し、ｘは、超安定Ｙ型ゼオライトの出発原料ＮａＹ型ゼオライトの結晶子径（ｎｍ）を表す。但し、ｘは、６６．５ｎｍ以上である。〕
【００３４】
（実施例１）
参考例１の超安定Ｙ型ゼオライトＥ（出発原料ＮａＹ型ゼオライトＥから得られたＵＳＹ）を使用して水素化処理触媒を調製した。
すなわち、スチームジャケット付１００リットルタンクにＡｌ2Ｏ3濃度換算で２２％のアルミン酸ナトリウム水溶液８８．８２ｋｇを入れ、イオン交換水で希釈し４０ｋｇとした後、２６質量％グルコン酸ナトリウム０．２２ｋｇを加え攪拌しながら６０℃に加温した。一方、５０リットル容器にＡｌ2Ｏ3濃度換算で７％の硫酸アルミニウム水溶液１３．８６ｋｇを入れ６０℃の温水で希釈し４０ｋｇとした。ロータリーポンプを用いてアルミン酸ナトリウム溶液中に硫酸アルミニウム溶液を一定速度で添加して、ｐＨ＝７．２とし、アルミナ水和物の懸濁スラリーを得た。該懸濁スラリーを攪拌しながら６０℃で１時間熟成した後、懸濁スラリーを脱水、洗浄した。洗浄後のケーキ状スラリーをイオン交換水で希釈し、Ａｌ2Ｏ3濃度で１０質量％になるようにした後、１５％アンモニア水を用いてスラリーのｐＨを１０．５に調製した。これを還流器付熟成タンクに移し、攪拌しながら９５℃で１０時間熟成してアルミナ水和物熟成スラリーを得た。
【００３５】
次に、参考例１の超安定Ｙ型ゼオライトＥ０．２７ｋｇ（固形分重量）をイオン交換水０．６３リットルに懸濁させ、ゼオライトの懸濁溶液を調製した。この懸濁溶液をＡｌ2Ｏ3換算で２．３５ｋｇの前述のアルミナ水和物熟成スラリーと混合した後、スチームジャケットを備えた双腕式ニーダーで練りながら加温し、所定の水分量まで濃縮した。これにホウ酸（Ｂ2Ｏ3換算）０．７４ｋｇ及びイオン交換水０．８４ｋｇを加えた後、所定の水分量まで更に捏和した。得られた捏和物を押出成形機で直径１．８ｍｍの円柱状に成形し１１０℃で乾燥させた。乾燥したペレットは電気炉中で５５０℃の温度で焼成して、超安定Ｙ型ゼオライトＥを１０質量％含有する担体を得た。
【００３６】
次いで、三酸化モリブデン１７０．２ｇ、及び炭酸ニッケル７５．４ｇをイオン交換水６００ｍｌに加え、さらに含カルボン酸化合物を加えて攪拌、加熱して溶解した。この溶液を前述の担体１．００ｋｇに含浸した後、乾燥させ、５５０℃で１時間焼成して水素化処理触媒Ｅを調製した。該水素化処理触媒Ｅの活性金属組成はＭｏＯ3が１４．０質量％、ＮｉＯが３．８質量％で、触媒の窒素吸着法による細孔容積は０．４０ｍｌ／ｇ、比表面積は２３０ｍ2／ｇ、水銀圧入法による細孔径は７．８ｎｍであった。
【００３７】
（実施例２）
実施例１と同様にして、参考例１の超安定Ｙ型ゼオライトＣ（出発原料ＮａＹ型ゼオライトＣから得られたＵＳＹ）を使用して水素化処理触媒Ｃを調製した。該水素化処理触媒Ｃの活性金属組成はＭｏＯ3が１４．０質量％、ＮｉＯが３．８質量％で、触媒の窒素吸着法による細孔容積は０．３９ｍｌ／ｇ、比表面積は２４２ｍ2／ｇ、水銀圧入法による細孔径は７．６ｎｍであった。
【００３８】
（比較例１）
実施例１と同様にして、市販の超安定Ｙ型ゼオライトを使用して水素化処理触媒Ｚを調製した。このゼオライトのＮａＹ型ゼオライトの結晶子径は３５ｎｍであり、超安定Ｙ型ゼオライトの細孔直径３．５〜５ｎｍの範囲の細孔容積は０．００５ｍｌ／ｇである。該水素化処理触媒Ｚの活性金属組成はＭｏＯ3が１４．０質量％、ＮｉＯが３．８質量％で、触媒の窒素吸着法による細孔容積は０．４０ｍｌ／ｇ、比表面積は２３８ｍ2／ｇ、水銀圧入法による細孔径は７．７ｎｍであった。
【００３９】
（実施例３）
実施例１、２及び比較例１の水素化処理触媒Ｅ、Ｃ及びＺを用いて、減圧留出油（ＶＧＯ）の水素化処理を行い、脱硫活性、分解活性を測定した。反応装置には固定床流通式反応装置を用いた。
反応条件および用いた原料油ＶＧＯの性状をそれぞれ表３および表４に示す。
【００４０】
【表３】
【表４】
反応により得られた生成油中の硫黄分を測定し、硫黄の除去率を求め比較例１の水素化処理触媒Ｚの活性と比較した。また、生成油を蒸留装置にかけ、３６０℃より高沸点分（３６０℃+）の含有量を測定し、原料油中の量に対する減少率を分解活性として評価した。反応温度３８０℃における触媒Ｚに対する相対活性を表５に示した。
【００４３】
【表５】
以上の結果から明らかなように、水素化処理触媒ＥおよびＣは、水素化処理触媒Ｚに比較して、脱硫、分解共に高活性を示した。
【００４５】
【発明の効果】
以上のように、細孔直径３．５〜５ｎｍの範囲の細孔容積を制御した超安定Ｙ型ゼオライトを用い、これを炭化水素油の水素化処理触媒として使用したとき、すぐれた脱硫活性および分解活性を発揮する。
【図面の簡単な説明】
【図１】出発原料ＮａＹ型ゼオライトの結晶子径（ｘ）と超安定Ｙ型ゼオライトの細孔直径３．５〜５ｎｍの範囲の細孔容積（ｙ）との関係を示すグラフである。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a hydroprocessing catalyst. More specifically, by using an ultrastable Y-type zeolite with a controlled pore volume in the pore diameter range of 3.5 to 5 nm, when used for hydroprocessing hydrocarbon oils, particularly light oils, cracking activity and The present invention relates to a hydroprocessing catalyst having high desulfurization activity.
[0002]
[Prior art]
Conventionally, as a hydrotreating catalyst whose main purpose is hydrocracking of hydrocarbon oils, a catalyst in which a hydrogenation active metal component is supported on an ultrastable Y-type zeolite (hereinafter sometimes referred to as USY) has been used. It was. For example, JP-A-2-214544 discloses that a support made of alumina and USY has at least one hydrogenation active metal selected from Group 5 metal, Group 6 metal and Group 8 metal in the periodic table and boron. And / or a hydrocracking catalyst for heavy petroleum, characterized by carrying phosphorus.
[0003]
Ultrastable Y-type zeolite has characteristics such as unique solid acid and pore distribution, so it is widely used as a catalyst for petroleum refining for catalytic cracking, hydrocracking, isomerization, alkylation, reforming, etc. It is also used for adsorbents. In particular, it is desirable that the ultrastable Y-type zeolite used for the hydrocracking catalyst has large pores in addition to the uniform pores unique to zeolite.
[0004]
The ultra-stable Y-type zeolite, in which Na + in the starting material NaY-type zeolite is ion-exchanged to NH 4 + and the SiO 2 / Al 2 O 3 ratio is improved by the hydrothermal method, has pores other than those unique to Y-type zeolite. It is known to have large pores [for example, Horikoshi et al., The Chemical Society of Japan, (3), 398 (1989)]. However, since the conventional ultrastable Y-type zeolite obtained by such a method has a small volume of large pores, it has been desired to increase the volume.
[0005]
In JP-A-9-255326, (a)
[0006]
Also, Japanese Patent Publication No. 9-502416 discloses that the mesopore capacity of the zeolite Y substance having a diameter in the range of 2 to 60 nm is increased by hydrothermal treatment of the zeolite at a temperature not lower than the atmospheric pressure boiling point of the treatment solution. A method is described.
[0007]
Usually, it is known that most of the large pores of the ultrastable Y-type zeolite are uniform pores having a pore diameter in the range of 3.5 to 5 nm. However, the conventional treatment method could not control the pore volume of pores having a pore diameter of 3.5 to 5 nm, and a controlled ultrastable Y-type zeolite was not known.
[0008]
[Problems to be solved by the invention]
The object of the present invention is to use an ultrastable Y-type zeolite with a controlled pore volume in a pore diameter range of 3.5 to 5 nm, so that when used for hydrocracking hydrocarbon oils, particularly light oil, An object of the present invention is to provide a hydroprocessing catalyst having high activity and high desulfurization activity.
[0009]
[Means for Solving the Problems]
As a result of intensive studies on a method for controlling the pore volume of uniform pores in the pore diameter range of 3.5 to 5 nm, which occupies most of the large pores of ultrastable Y-type zeolite, the present inventors The crystallite size of the starting material NaY zeolite and the pore volume of the ultrastable Y zeolite in the pore diameter range of 3.5 to 5 nm are closely related, and the pore diameter is 3.5 to 5 nm. The hydrotreating catalyst using ultra-stable Y-type zeolite with controlled pore volume in the range of 1 shows that it has high cracking activity and desulfurization activity when used for hydrotreating hydrocarbon oils, especially light oil. The headline and the present invention were completed.
[0010]
That is, the present invention is a hydrotreating catalyst containing an ultrastable Y-type zeolite and an active metal component selected from Group 6 metal and / or Group 8 metal of the periodic table, the ultrastable Y-type zeolite The hydrotreating catalyst is characterized in that the pore volume y having a pore diameter of 3.5 to 5 nm satisfies the relationship of the following formula.
2.11 × 10 −3 x−0.140 ≦ y ≦ 2.11 × 10 −3 x−0.110
[Wherein y represents the pore volume (ml / g) of the ultrastable Y-type zeolite with a pore diameter of 3.5 to 5 nm, and x represents the starting material NaY-type zeolite of the ultrastable Y-type zeolite. Represents the crystallite size (nm). However, x is 66.5 nm or more. ]
[0011]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in detail.
The hydrotreating catalyst of the present invention contains a specific ultrastable Y-type zeolite described later and an active metal component selected from Group 6 metal and / or Group 8 metal of the Periodic Table.
[0012]
In the present invention, the crystallite size (x) of NaY-type zeolite, which is a starting material for ultra-stable Y-type zeolite, needs to be 66.5 nm or more. When the crystallite diameter (x) is smaller than 66.5 nm, the obtained ultrastable Y-type zeolite is not preferable because the pore volume (y) in the pore diameter range of 3.5 to 5 nm is hardly generated. The crystallite diameter (x) of the starting material NaY-type zeolite is preferably 75 nm or more, more preferably 80 nm or more and 500 nm or less. In particular, the ultrastable Y-type zeolite used for the hydrotreating catalyst preferably has a large pore volume (y), and the crystallite diameter (x) is preferably in the range of 90 to 300 nm.
[0013]
In the present invention, the crystallite diameter (x) of the starting raw material NaY-type zeolite is a value obtained by approximating the diffraction line profile of the (533) plane of X-ray diffraction with a Gaussian function type by the Scherrer equation. .
[0014]
The ultrastable Y-type zeolite in the present invention has a pore volume (y) in the range of 3.5 to 5 nm in pore diameter of the zeolite, the crystallite diameter (x) of the starting material NaY-type zeolite and the following formula (I ) Is important.
2.11 × 10 −3 x−0.140 ≦ y ≦ 2.11 × 10 −3 x−0.110 (I)
[Wherein y represents the pore volume (ml / g) of the ultrastable Y-type zeolite with a pore diameter of 3.5 to 5 nm, and x represents the starting material NaY-type zeolite of the ultrastable Y-type zeolite. Represents the crystallite size (nm). However, x is 66.5 nm or more. ]
[0015]
According to the present invention, by appropriately selecting the crystallite size (x) of the starting raw material NaY-type zeolite, the pore volume (y ) Can be controlled to the desired pore volume (y).
The starting material NaY-type zeolite having a different crystallite diameter (x) can be produced by changing the seed amount during synthesis in a synthesis method using NaY-type zeolite seeds.
[0016]
In the present invention, the pore volume (y) in the range of the pore diameter of 3.5 to 5 nm of the ultrastable Y-type zeolite refers to the desorption isotherm of the nitrogen adsorption / desorption isotherm. J. et al. It is a value obtained from the pore distribution calculated by the H method.
[0017]
The ultrastable Y-type zeolite in the present invention has the above controlled pore volume (y), and the unit cell constant (UD) is 2.455 nm or less, preferably 2.450 to 2.419 nm. It is desirable to be. The ultrastable Y-type zeolite preferably has a SiO 2 / Al 2 O 3 molar ratio of 8 or more, a specific surface area of 400 to 900 m 2 / g, and a crystallinity (linde The relative crystallinity (with SK-40 of 100%) is desirably 95% or more.
[0018]
The ultra-stable Y-type zeolite described above is, for example, a NH 4 Y-type zeolite obtained by ion-exchange of a starting material NaY-type zeolite having a crystallite diameter of 66.5 nm or more with ammonium ions to an ion exchange rate of 80% or more in a steam atmosphere. It is possible to manufacture by removing the extra-framework aluminum by treating with a dealumination agent such as a mineral acid after the unit cell constant is reduced to 2.455 nm or less by heat treatment.
[0019]
The hydrotreating catalyst of the present invention has at least one selected from Group 6 metal and / or Group 8 metal on the periodic table on a support made of a refractory inorganic oxide containing the ultrastable Y-type zeolite. A catalyst carrying an active metal component is preferred. As the refractory inorganic oxide, refractory inorganic oxides usually used for hydrotreating catalysts can be used. Specifically, alumina, silica, titania, zirconia, alumina-silica, alumina-titania, alumina -Boria, alumina-phosphorus, alumina-boria-phosphorus, alumina-titania-boria, alumina-titania-phosphorus, etc. The amount of the ultrastable Y-type zeolite contained in the carrier is 1 to 50% by mass, preferably 5 to 20% by mass.
[0020]
Examples of the active metal component selected from Group 6 metal and / or Group 8 metal of the periodic table in the present invention include molybdenum, tungsten, nickel, cobalt, rhodium, palladium, platinum and the like. In particular, molybdenum, tungsten, nickel, and cobalt are preferable, and a combination of nickel and / or cobalt and molybdenum and / or tungsten is desirable. As the content of the active metal component, an amount used in a normal hydroprocessing catalyst is used. The content of the active metal component is preferably 5 to 25% by mass for molybdenum and tungsten, 0.5 to 10% by mass for nickel and cobalt, and 0.01 to 2% by mass for rhodium, palladium and platinum as oxides. A range is desirable.
[0021]
The hydrotreating catalyst of the present invention, for example, after mixing the above-mentioned ultrastable Y-type zeolite and a precursor of a refractory inorganic oxide, formed into a desired shape, dried and calcined, The active metal component precursor is supported by a known method, dried and fired.
[0022]
The hydrotreating catalyst of the present invention can be used under normal hydrotreating conditions for hydrocarbon oils. In particular, the hydrotreating catalyst of the present invention can be suitably used for hydrotreating vacuum gas oil. As hydrotreating conditions at this time, for example, conditions such as a reaction temperature of 300 to 450 ° C., a hydrogen partial pressure of 2.0 to 20 MPa, and a liquid space velocity of 0.1 to 4 hr −1 are preferably employed.
[0023]
The ultrastable Y-type zeolite used in the hydrotreating catalyst of the present invention has a controlled pore volume in the range of 3.5 to 5 nm in addition to the uniform pores unique to the zeolite, so that it is a hydrocarbon. Used for hydrotreating oils, especially vacuum gas oils, exhibits high cracking activity and high desulfurization activity.
[0024]
【Example】
Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited thereto.
[0025]
(Reference Example 1)
NaY-type zeolite (5 types of A, B, C, D, and E) having a crystallite diameter of 66.5 nm or more was prepared. Table 1 shows the properties of each zeolite.
4113 g of NaY-type zeolites A, B, C, D and E shown in Table 1 were suspended in 33 liters of hot water at 60 ° C., respectively. Next, 924 g of 1 molar ammonium sulfate was added to the zeolite, and the mixture was stirred at 90 ° C. for 1 hour for ion exchange. Thereafter, the mixture was filtered, and again ion-exchanged with a solution obtained by dissolving 924 g of ammonium sulfate in 10 liters of hot water at 60 ° C., filtered, washed with 30 liters of pure water at 60 ° C., dried and crushed, % Ion-exchanged Y-type zeolite (NH 4 65 Y) was obtained.
[0026]
Next, 3487 g of each Y-type zeolite (NH 4 65 Y) was calcined in a saturated steam atmosphere at 600 ° C. for 1 hour by a rotary steaming apparatus to obtain calcined Y-type zeolite (H 65 Y).
[0027]
After suspending 2718 g of each calcined Y-type zeolite (H 65 Y) in 30 liters of warm water at 60 ° C., adding 1848 g of ammonium sulfate 2 mol times the amount of zeolite and stirring for 1 hour at 90 ° C. for ion exchange. , Filtered, and washed with 30 liters of pure water at 60 ° C. The washed zeolite was suspended again in 30 liters of hot water at 60 ° C., 1812 g of ammonium sulfate was added to this suspension, and ion exchange was performed by stirring at 90 ° C. for 1 hour. Thereafter, the mixture was filtered, washed with 30 liters of pure water at 60 ° C., dried and pulverized to obtain Y-type zeolite (NH 4 85 Y) each ion-exchanged by 85%.
[0028]
Each ion-exchanged Y-type zeolite (NH 4 85 Y) (2952 g) was calcined in a rotary steaming apparatus at 780 ° C. for 1 hour in a saturated water vapor atmosphere, and calcined Y-type zeolite having a lattice constant of 2.431 to 2.432 nm (H 85 Y) was obtained.
[0029]
2856 g of each calcined Y-type zeolite (H 85 Y) was suspended in 30 liters of hot water at 60 ° C., and 5530 g of 25% sulfuric acid was gradually added to the suspension, followed by stirring at 95 ° C. for 1 hour for dealumination. . Thereafter, filtration, washing and drying were performed to obtain ultrastable Y-type zeolites A, B, C, D and E. Table 2 shows the properties of each ultrastable Y-type zeolite A to E. FIG. 1 shows the relationship between the crystallite size (x) of the starting raw material NaY zeolite and the pore volume (y) in the pore diameter range of 3.5 to 5 nm of the ultrastable Y zeolite.
[0030]
[Table 1]
[Table 2]
The relationship between the crystallite diameter (x) of the starting raw material NaY zeolite shown in FIG. 1 and the pore volume (y) in the pore diameter range of 3.5 to 5 nm of the ultrastable Y zeolite is expressed by the following empirical formula: It is represented by (II).
y = 2.11 × 10 −3 x−0.125 (II)
[Wherein y represents the pore volume (ml / g) of the ultrastable Y-type zeolite with a pore diameter of 3.5 to 5 nm, and x represents the starting material NaY-type zeolite of the ultrastable Y-type zeolite. Represents the crystallite size (nm). However, x is 66.5 nm or more. ]
[0033]
The standard error (σ) with respect to each measured value of the pore volume represented by the formula (II) is ± 0.005 (ml / g), and the error range is 3σ = ± 0.015 (ml / g). When g), the pore volume (y) in the range of the pore diameter of 3.5 to 5 nm of the ultrastable Y-type zeolite is represented by the following formula (I).
2.11 × 10 −3 x−0.140 ≦ y ≦ 2.11 × 10 −3 x−0.110 (I)
[Wherein y represents the pore volume (ml / g) of the ultrastable Y-type zeolite with a pore diameter of 3.5 to 5 nm, and x represents the starting material NaY-type zeolite of the ultrastable Y-type zeolite. Represents the crystallite size (nm). However, x is 66.5 nm or more. ]
[0034]
Example 1
A hydrotreating catalyst was prepared using the ultrastable Y-type zeolite E of Reference Example 1 (USY obtained from the starting material NaY-type zeolite E).
In other words, 88.82 kg of 22% sodium aluminate aqueous solution in terms of Al 2 O 3 concentration was placed in a 100 liter tank with a steam jacket, diluted to 40 kg with ion-exchanged water, and then 0.22 kg of 26 mass% sodium gluconate was added. The mixture was heated to 60 ° C. with stirring. On the other hand, 13.86 kg of 7% aluminum sulfate aqueous solution in terms of Al 2 O 3 concentration was placed in a 50 liter container and diluted with hot water at 60 ° C. to make 40 kg. Using a rotary pump, the aluminum sulfate solution was added to the sodium aluminate solution at a constant rate to obtain pH = 7.2, and a suspension slurry of alumina hydrate was obtained. The suspension slurry was aged at 60 ° C. for 1 hour with stirring, and then the suspension slurry was dehydrated and washed. The cake slurry after washing was diluted with ion-exchanged water so that the Al 2 O 3 concentration was 10% by mass, and then the pH of the slurry was adjusted to 10.5 using 15% ammonia water. This was transferred to an aging tank equipped with a refluxer and aged at 95 ° C. for 10 hours with stirring to obtain an alumina hydrate aging slurry.
[0035]
Next, 0.27 kg (solid weight) of the ultrastable Y-type zeolite E of Reference Example 1 was suspended in 0.63 liter of ion-exchanged water to prepare a suspension solution of zeolite. This suspension solution is mixed with 2.35 kg of the above-mentioned alumina hydrate maturation slurry in terms of Al 2 O 3 , then heated while kneading with a double-arm kneader equipped with a steam jacket, and concentrated to a predetermined water content. did. After adding boric acid (converted to B 2 O 3 ) 0.74 kg and ion-exchanged water 0.84 kg to this, the mixture was further kneaded to a predetermined water content. The obtained kneaded product was formed into a columnar shape having a diameter of 1.8 mm with an extruder and dried at 110 ° C. The dried pellets were fired in an electric furnace at a temperature of 550 ° C. to obtain a carrier containing 10% by mass of ultrastable Y-type zeolite E.
[0036]
Next, 170.2 g of molybdenum trioxide and 75.4 g of nickel carbonate were added to 600 ml of ion-exchanged water, and a carboxylic acid compound was further added, stirred and heated to dissolve. The solution was impregnated with 1.00 kg of the carrier, dried, and calcined at 550 ° C. for 1 hour to prepare a hydrotreating catalyst E. The active metal composition of the hydrotreating catalyst E is 14.0% by mass of MoO 3 and 3.8% by mass of NiO, the pore volume of the catalyst by the nitrogen adsorption method is 0.40 ml / g, and the specific surface area is 230 m 2. / G, the pore diameter by mercury porosimetry was 7.8 nm.
[0037]
(Example 2)
In the same manner as in Example 1, hydrotreating catalyst C was prepared using ultrastable Y-type zeolite C of Reference Example 1 (USY obtained from starting raw material NaY-type zeolite C). The active metal composition of the hydrotreating catalyst C is 14.0% by mass of MoO 3 and 3.8% by mass of NiO, the pore volume by the nitrogen adsorption method of the catalyst is 0.39 ml / g, and the specific surface area is 242 m 2. / G, the pore diameter by mercury porosimetry was 7.6 nm.
[0038]
(Comparative Example 1)
In the same manner as in Example 1, a hydrotreating catalyst Z was prepared using a commercially available ultrastable Y-type zeolite. The crystallite size of the NaY zeolite of this zeolite is 35 nm, and the pore volume of the ultrastable Y zeolite in the pore diameter range of 3.5 to 5 nm is 0.005 ml / g. The active metal composition of the hydrotreating catalyst Z is 14.0% by mass of MoO 3 and 3.8% by mass of NiO, the pore volume by the nitrogen adsorption method of the catalyst is 0.40 ml / g, and the specific surface area is 238 m 2. / G, the pore diameter by mercury porosimetry was 7.7 nm.
[0039]
(Example 3)
Using the hydrotreating catalysts E, C, and Z of Examples 1 and 2 and Comparative Example 1, hydrotreating of vacuum distillate oil (VGO) was performed, and desulfurization activity and cracking activity were measured. A fixed bed flow reactor was used as the reactor.
Tables 3 and 4 show the reaction conditions and the properties of the feedstock VGO used, respectively.
[0040]
[Table 3]
[Table 4]
The sulfur content in the product oil obtained by the reaction was measured and the sulfur removal rate was determined and compared with the activity of the hydrotreating catalyst Z of Comparative Example 1. Further, the produced oil was subjected to a distillation apparatus, the content of a boiling point higher than 360 ° C. (360 ° C. + ) was measured, and the reduction rate relative to the amount in the raw material oil was evaluated as the decomposition activity. Table 5 shows the relative activity with respect to catalyst Z at a reaction temperature of 380 ° C.
[0043]
[Table 5]
As is clear from the above results, the hydrotreating catalysts E and C showed higher activity in both desulfurization and decomposition than the hydrotreating catalyst Z.
[0045]
【The invention's effect】
As described above, when an ultrastable Y-type zeolite having a controlled pore volume in a pore diameter range of 3.5 to 5 nm is used and used as a hydrotreating catalyst for hydrocarbon oil, excellent desulfurization activity and Degrading activity is demonstrated.
[Brief description of the drawings]
FIG. 1 is a graph showing the relationship between the crystallite diameter (x) of a starting material NaY-type zeolite and the pore volume (y) in the pore diameter range of 3.5 to 5 nm of an ultrastable Y-type zeolite.
Claims (2)
２．１１×１０-3ｘ−０．１４０≦ｙ≦２．１１×１０-3ｘ−０．１１０
〔式中、ｙは、超安定Ｙ型ゼオライトの細孔直径３．５〜５ｎｍの範囲の細孔容積（ｍｌ／ｇ）を表し、ｘは、超安定Ｙ型ゼオライトの出発原料ＮａＹ型ゼオライトの結晶子径（ｎｍ）を表す。但し、ｘは、６６．５ｎｍ以上である。〕2. A hydrotreating catalyst containing an ultrastable Y-type zeolite and an active metal component selected from Group 6 metal and / or Group 8 metal of the periodic table, wherein the pore diameter of the ultrastable Y-type zeolite is 3. A hydrotreating catalyst, wherein the pore volume y in the range of 5 to 5 nm satisfies the relationship of the following formula.
2.11 × 10 −3 x−0.140 ≦ y ≦ 2.11 × 10 −3 x−0.110
[Wherein y represents the pore volume (ml / g) of the ultrastable Y-type zeolite with a pore diameter of 3.5 to 5 nm, and x represents the starting material NaY-type zeolite of the ultrastable Y-type zeolite. Represents the crystallite size (nm). However, x is 66.5 nm or more. ]
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