JP2002255537A - Solid acid catalyst - Google Patents
Solid acid catalystInfo
- Publication number
- JP2002255537A JP2002255537A JP2001047290A JP2001047290A JP2002255537A JP 2002255537 A JP2002255537 A JP 2002255537A JP 2001047290 A JP2001047290 A JP 2001047290A JP 2001047290 A JP2001047290 A JP 2001047290A JP 2002255537 A JP2002255537 A JP 2002255537A
- Authority
- JP
- Japan
- Prior art keywords
- zeolite
- catalyst
- ratio
- aluminum
- metal oxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 100
- 239000011973 solid acid Substances 0.000 title claims abstract description 34
- 239000010457 zeolite Substances 0.000 claims abstract description 163
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 159
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 157
- 239000011148 porous material Substances 0.000 claims abstract description 50
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 22
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 12
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 6
- 239000010703 silicon Substances 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 35
- 229910052751 metal Inorganic materials 0.000 claims description 33
- 239000002184 metal Substances 0.000 claims description 33
- 229910044991 metal oxide Inorganic materials 0.000 claims description 33
- 150000004706 metal oxides Chemical class 0.000 claims description 33
- 239000000295 fuel oil Substances 0.000 claims description 17
- 238000004517 catalytic hydrocracking Methods 0.000 claims description 14
- 238000005984 hydrogenation reaction Methods 0.000 claims description 14
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical group O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000003870 refractory metal Substances 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 description 35
- 230000000704 physical effect Effects 0.000 description 24
- 239000002994 raw material Substances 0.000 description 22
- 239000007864 aqueous solution Substances 0.000 description 19
- 238000002474 experimental method Methods 0.000 description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 150000004703 alkoxides Chemical class 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 235000019441 ethanol Nutrition 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 239000011882 ultra-fine particle Substances 0.000 description 7
- 239000002131 composite material Substances 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 6
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 150000002894 organic compounds Chemical class 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 229910001388 sodium aluminate Inorganic materials 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 238000001354 calcination Methods 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 238000010304 firing Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 229910010413 TiO 2 Inorganic materials 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 238000003780 insertion Methods 0.000 description 3
- 230000037431 insertion Effects 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- HDUMBHAAKGUHAR-UHFFFAOYSA-J titanium(4+);disulfate Chemical compound [Ti+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O HDUMBHAAKGUHAR-UHFFFAOYSA-J 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 2
- 235000011130 ammonium sulphate Nutrition 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000006477 desulfuration reaction Methods 0.000 description 2
- 230000023556 desulfurization Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 239000003350 kerosene Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000012702 metal oxide precursor Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000011164 primary particle Substances 0.000 description 2
- 102200118166 rs16951438 Human genes 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate group Chemical group S(=O)(=O)([O-])[O-] QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 229910003296 Ni-Mo Inorganic materials 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical compound N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910001422 barium ion Inorganic materials 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000007327 hydrogenolysis reaction Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- -1 platinum group metals Chemical class 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000000371 solid-state nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical compound [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 description 1
- 229910000350 zirconium(IV) sulfate Inorganic materials 0.000 description 1
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、メソポア含量の大
きい新規ゼオライト、ゼオライト系の触媒担体、ゼオラ
イト系の固体酸触媒、その触媒担体を用いる水素化処理
用触媒及びその触媒を用いる重質油の水素化分解方法に
関する。The present invention relates to a novel zeolite having a large mesopore content, a zeolite-based catalyst carrier, a zeolite-based solid acid catalyst, a hydrotreating catalyst using the catalyst carrier, and a heavy oil using the catalyst. It relates to a hydrocracking method.
【０００２】[0002]
【従来の技術】固体酸触媒は、石油精製はじめ化学産業
に大量にかつ極めて重要な機能性材料として利用されて
いる。例えば、世界的に高品質な輸送用燃料の需要は今
後も増大し、重質油の効率的な分解技術として、高度の
水素化分解技術の開発が必要とされている。この水素化
分解技術開発の中心課題として、高機能固体酸触媒、特
にゼオライト系固体酸触媒の開発が必須であるとされて
いる。触媒反応において、ゼオライト系固体酸のすぐれ
た分解機能を高度に利用するためには、反応場における
炭化水素の重縮合などの副反応を抑制する目的で高度な
水素化機能を複合化した水素化分解触媒が必要である。
例えば、重質油を水素化分解することによって、灯油、
軽油などの中間留分を製造する目的で水素化機能を複合
化した金属担持固体酸触媒が用いられている。シリカ・
アルミナ、アルミナ・ボリアなどの複合酸化物系の固体
酸の場合は４２０℃以上の高い反応温度および高い水素
分圧が必要である。また、反応速度が遅いために触媒充
てん量が多い。ゼオライト系触媒、特にＵＳＹゼオライ
ト系の触媒の場合は高活性であるが、アスファルテンを
含有する重質油への適用では活性劣化が激しいため工業
的な使用は困難である。特に、効率的な反応を行う為の
反応場であるメソポアを十分なサイズ・容量のものに修
飾すると固体酸点密度が極端に減少してしまい、分解性
の大幅な低下が避けられず、従来の技術ではゼオライト
の固体酸の特徴を有効に利用することは困難であった。2. Description of the Related Art Solid acid catalysts are used in the chemical industry such as petroleum refining in large quantities and as very important functional materials. For example, the demand for high quality transportation fuels worldwide is increasing in the future, and the development of advanced hydrocracking technology as an efficient cracking technology for heavy oil is required. It is said that development of a high-performance solid acid catalyst, particularly a zeolite-based solid acid catalyst, is indispensable as a central issue in the development of this hydrocracking technology. In the catalytic reaction, in order to utilize the excellent decomposition function of zeolite-based solid acids to a high degree, hydrogenation that combines advanced hydrogenation functions to suppress side reactions such as polycondensation of hydrocarbons in the reaction field A decomposition catalyst is required.
For example, by hydrocracking heavy oil, kerosene,
BACKGROUND ART For the purpose of producing middle distillates such as light oil, a metal-supported solid acid catalyst having a complexed hydrogenation function is used. silica·
In the case of solid oxide-based solid acids such as alumina and alumina-boria, a high reaction temperature of 420 ° C. or higher and a high hydrogen partial pressure are required. In addition, since the reaction rate is low, the amount of catalyst charged is large. Zeolite-based catalysts, particularly USY zeolite-based catalysts, have high activity, but when applied to heavy oils containing asphaltenes, their activity is severely degraded and industrial use is difficult. In particular, if the mesopore, which is the reaction field for efficient reaction, is modified to have a sufficient size and volume, the density of solid acid sites will be extremely reduced, and a drastic decrease in degradability cannot be avoided. It has been difficult to effectively utilize the characteristics of the solid acid of zeolite by the technique described above.
【０００３】[0003]
【発明が解決しようとする課題】本発明は、すぐれた固
体酸触媒を与えるメソポア含量の大きい新規ゼオライ
ト、該ゼオライトを用いた触媒担体、該ゼオライトを用
いた固体酸触媒、該触媒担体を用いた水素化処理用触
媒、該水素化処理用触媒を用いた重質油の水素化分解方
法を提供することをその課題とする。DISCLOSURE OF THE INVENTION The present invention provides a novel zeolite having a large mesopore content that provides an excellent solid acid catalyst, a catalyst carrier using the zeolite, a solid acid catalyst using the zeolite, and a catalyst using the catalyst carrier. It is an object of the present invention to provide a hydrotreating catalyst and a method for hydrocracking heavy oil using the hydrotreating catalyst.
【０００４】[0004]
【課題を解決するための手段】本発明者らは、前記課題
を解決すべく鋭意研究を重ねた結果、本発明を完成する
に至った。即ち、本発明によれば、以下に示すゼオライ
ト、触媒担体、固体酸触媒、水素化処理用触媒及び重質
油の水素化分解方法が提供される。 （１）アルミニウムとケイ素との原子比［Ａｌ］／［Ｓ
ｉ］が０．０１〜０．２の範囲にあり、細孔直径が５０
〜１０００Åのメソポアの容積割合が３０〜５０％の範
囲にあり、かつ該メソポアの容積が０．１４ｃｃ／ｇ以
上であり、さらに、全アルミニウム原子に対する４配位
アルミニウム原子の割合が２５原子％以上であることを
特徴とするメソポア含量の大きいゼオライト。 （２）細孔直径１００〜５００Åのメソポアの容積割合
が２０〜４０％である前記（１）のゼオライト。 （３）該メソポア内表面に超微粒子状難還元性金属酸化
物が複合化されている前記（１）又は（２）のゼオライ
ト。 （４）該難還元性金属酸化物の含有量が１〜１０重量％
である前記（１）〜（３）のいずれかのゼオライト。 （５）該難還元性金属酸化物がチタニア及び／又はジル
コニアからなる前記（１）〜（４）のいずれかのゼオラ
イト。 （６）前記（１）〜（５）のいずれかのゼオライトから
なる触媒担体。 （７）前記（１）〜（５）のいずれかのゼオライトから
なる固体酸触媒。 （８）前記（６）の触媒担体に水素化活性金属を担持さ
せてなる水素化処理用触媒。 （９）水素化処理用触媒の存在下で重質油と水素化分解
する方法において、該触媒として前記（８）の水素化処
理用触媒を用いることを特徴とする重質油の水素化分解
方法。 （１０）該水素処理用触媒を構成するゼオライトとの原
子比［Ａｌ］／［Ｓｉ］が０．０１〜０．１の範囲にあ
り、かつ該ゼオライト中の全アルミニウム原子に対する
４配位アルミニウム原子の割合が２５原子％以上である
前記（９）の方法。Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have completed the present invention. That is, according to the present invention, there are provided the following zeolite, catalyst carrier, solid acid catalyst, hydrotreating catalyst, and method for hydrocracking heavy oil. (1) Atomic ratio of aluminum to silicon [Al] / [S
i] is in the range of 0.01 to 0.2 and the pore diameter is 50
The volume ratio of the mesopore of ~ 1000 ° is in the range of 30 to 50%, the volume of the mesopore is 0.14 cc / g or more, and the ratio of tetracoordinate aluminum atoms to all aluminum atoms is 25 atom% or more. A zeolite having a large mesopore content, characterized in that: (2) The zeolite according to (1), wherein the volume ratio of mesopores having a pore diameter of 100 to 500 ° is 20 to 40%. (3) The zeolite according to the above (1) or (2), wherein the ultrafine particulate inreducible metal oxide is complexed on the inner surface of the mesopore. (4) The content of the hardly reducible metal oxide is 1 to 10% by weight.
The zeolite according to any one of the above (1) to (3). (5) The zeolite according to any one of (1) to (4), wherein the hardly-reducible metal oxide comprises titania and / or zirconia. (6) A catalyst carrier comprising the zeolite according to any of (1) to (5). (7) A solid acid catalyst comprising the zeolite according to any of (1) to (5). (8) A hydrotreating catalyst obtained by supporting a hydrogenation active metal on the catalyst support of (6). (9) A method for hydrocracking with heavy oil in the presence of a hydrotreating catalyst, wherein the hydrotreating catalyst of (8) is used as the catalyst. Method. (10) The atomic ratio [Al] / [Si] with the zeolite constituting the hydrotreating catalyst is in the range of 0.01 to 0.1, and the tetracoordinate aluminum atom is based on all aluminum atoms in the zeolite. (9) wherein the proportion of is at least 25 atomic%.
【０００５】[0005]
【発明の実施の形態】本発明のゼオライトにおいて、そ
のアルミニウム／ケイ素原子比［Ａｌ］／［Ｓｉ］は、
０．０１〜０．２、好ましくは０．０２〜０．１の範囲
にある。その細孔直径が５０〜１０００Åのメソポア
（メソ細孔）の容積割合は、３０〜５０％、好ましくは
３５〜５０％、より好ましくは４０〜５０％の範囲にあ
る。また、その細孔直径が１００〜５００Åのメソポア
の容積割合は、２０〜４０％、好ましくは３５〜４０
％、この場合、該メソポアの容積割合は、細孔直径２０
〜２０００Åの全細孔容積に対する割合である。また、
その細孔直径が５０〜１０００Åのメソポアの容積は
０．１４ｃｃ／ｇ以上、好ましくは０．２０ｃｃ／ｇ以
上である。その上限値は、通常、０．４ｃｃ／ｇ程度で
ある。さらに、その全アルミニウム原子に対する４配位
アルミニウム原子の割合は、２５原子％以上、好ましく
は４０原子％以上、より好ましくは５０原子％以上であ
る。その上限値は、通常、９０原子％程度である。BEST MODE FOR CARRYING OUT THE INVENTION In the zeolite of the present invention, the aluminum / silicon atomic ratio [Al] / [Si] is as follows:
It is in the range of 0.01 to 0.2, preferably 0.02 to 0.1. The volume ratio of mesopores (mesopores) having a pore diameter of 50 to 1000 ° is in the range of 30 to 50%, preferably 35 to 50%, more preferably 40 to 50%. The volume ratio of mesopores having a pore diameter of 100 to 500 ° is 20 to 40%, preferably 35 to 40%.
%, In which case the volume fraction of the mesopores is
割 合 2000 ° relative to the total pore volume. Also,
The volume of a mesopore having a pore diameter of 50 to 1000 ° is 0.14 cc / g or more, preferably 0.20 cc / g or more. The upper limit is usually about 0.4 cc / g. Further, the ratio of the four-coordinate aluminum atoms to the total aluminum atoms is 25 atomic% or more, preferably 40 atomic% or more, and more preferably 50 atomic% or more. The upper limit is usually about 90 atomic%.
【０００６】本発明のゼオライトは、一般的には、０．
２〜１ｍｍｏｌ／ｇ、好ましくは０．３〜０．６ｍｍｏ
ｌ／ｇの固体酸強度（ＮＨ3−ＴＰＤ、高温側ピーク）
及び２０〜１００％、好ましくは３０〜９５％の結晶化
度を有する。また、本発明のゼオライトに含まれるメソ
ポアにおいて、その平均細孔直径は１００〜５００Å、
好ましくは１５０〜４００Åである。ミクロポア（直径
５０Å未満の細孔）の容積割合は、７０％以下、好まし
くは５５％以下であり、そのマクロポア（直径１０００
Å超の細孔）の容積割合は、２０％以下、好ましくは１
０％以下である。本発明のゼオライトにおいて、そのＢ
ＥＴ表面積は、４００ｍ2／ｇ以上、好ましくは６００
〜７００ｍ2／ｇである。その細孔直径５０〜１０００
Åのメソポアの比表面積は、２０〜５０ｍ2／ｇ、好ま
しくは２５〜４５ｍ2／ｇである。また、その細孔直径
１００〜５００Åのメソポアの比表面積は、１５〜４５
ｍ2／ｇ、好ましくは２０〜４０ｍ2／ｇである。その細
孔直径１００〜５００Åのメソポアの容積は、０．１ｃ
ｃ／ｇ以上、好ましくは０．１３〜０．１８ｃｃ／ｇで
ある。[0006] The zeolites of the present invention generally have a pH of 0.1.
2-1 mmol / g, preferably 0.3-0.6 mmol
1 / g solid acid strength (NH 3 -TPD, high temperature peak)
And a crystallinity of 20-100%, preferably 30-95%. In the mesopore contained in the zeolite of the present invention, the average pore diameter is 100 to 500 °,
Preferably it is 150 to 400 °. The volume ratio of the micropores (pores having a diameter of less than 50 °) is 70% or less, preferably 55% or less,
The volume ratio of (extra pores) is 20% or less, preferably 1%.
0% or less. In the zeolite of the present invention, the B
The ET surface area is 400 m 2 / g or more, preferably 600 m 2 / g.
７００700 m 2 / g. Its pore diameter 50-1000
The specific surface area of mesopores Å is, 20~50m 2 / g, preferably from 25~45m 2 / g. The specific surface area of the mesopore having a pore diameter of 100 to 500 ° is 15 to 45.
m 2 / g, preferably from 20 to 40 m 2 / g. The volume of the mesopore having a pore diameter of 100 to 500 ° is 0.1 c
c / g or more, preferably 0.13 to 0.18 cc / g.
【０００７】本発明のゼオライトは、前記のように、
［Ａｌ］／［Ｓｉ］比が０．０１〜０．２の範囲にあ
り、かつ全アルミニウム原子に対する４配位アルミニウ
ムの割合が２５原子％以上と高い、即ち、良好な固体酸
としての特性を有しながら、そのメソポアの割合が非常
に大きいという特徴を有する。この固体酸的性質を有す
る大容量のメソポアは、触媒の複合化に適したものであ
る。即ち、本発明のゼオライトは、固体酸触媒として有
用である他、触媒担体としてすぐれたものである。[0007] The zeolite of the present invention, as described above,
The ratio of [Al] / [Si] is in the range of 0.01 to 0.2, and the ratio of four-coordinate aluminum to all aluminum atoms is as high as 25 atomic% or more. It has the characteristic that the ratio of the mesopores is very large. This large-capacity mesopore having solid acid properties is suitable for complexing a catalyst. That is, the zeolite of the present invention is useful not only as a solid acid catalyst but also as an excellent catalyst carrier.
【０００８】本発明のゼオライトは、その製造原料とし
て、［Ａｌ］／［Ｓｉ］原子比が小さいメソポア含有量
の大きいゼオライト、特にＵＳＹゼオライト（疎水性高
耐熱性ゼオライト）を用いることにより製造される。こ
のようなゼオライトは、従来公知のものであり、例え
ば、（東ソー（株））社から商品名「ＵＨＳ−ＵＳＹ」
として入手可能である。この原料ゼオライトにおいて、
その［Ａｌ］／［Ｓｉ］原子比は、通常、０．０１５以
下、好ましくは０．０１以下、より好ましくは０．００
８以下である。その下限値は特に制約されないが、通
常、０．０１程度である。そのメソポア（細孔直径５０
〜１０００Å）の容積割合は、全細孔容積（細孔直径２
０〜２０００Å）に対して、３０〜５０％、好ましくは
３５〜５０％の割合である。その細孔直径１００〜５０
０Åのメソポアの容積割合は、３０〜４０％、好ましく
は３５〜４０％である。そのメソポア（細孔直径５０〜
１０００Å）の容積は、０．１５ｃｃ／ｇ以上、好まし
くは０．２０ｃｃ／ｇ以上である。その上限値は、通
常、０．４ｃｃ／ｇ程度である。また、そのメソポア
（細孔直径５０〜１０００Å）における平均細孔直径
は、１００〜５００Å、好ましくは１５０〜４００Åで
ある。そのメソポア（細孔直径５０〜１０００Å）の比
表面積は、３０ｍ2／ｇ以上、好ましくは４０ｍ2／ｇ以
上である。その上限値は、通常、６０ｍ2／ｇ程度であ
る。原料ゼオライトの結晶化度は９０％以上、好ましく
は９５％以上である。The zeolite of the present invention is produced by using a zeolite having a small [Al] / [Si] atomic ratio and a large mesopore content, particularly a USY zeolite (a hydrophobic high heat-resistant zeolite) as a raw material for producing the zeolite. . Such a zeolite is conventionally known, and for example, a product name “UHS-USY” from Tosoh Corporation.
It is available as In this raw material zeolite,
The [Al] / [Si] atomic ratio is usually 0.015 or less, preferably 0.01 or less, more preferably 0.00 or less.
8 or less. The lower limit is not particularly limited, but is usually about 0.01. Its mesopore (pore diameter 50
Å1000 °) is the total pore volume (pore diameter 2
0 to 2000%), preferably 30 to 50%, preferably 35 to 50%. Its pore diameter is 100-50
The volume fraction of 0 ° mesopores is 30-40%, preferably 35-40%. The mesopore (pore diameter 50 ~
The volume of 1000 °) is 0.15 cc / g or more, preferably 0.20 cc / g or more. The upper limit is usually about 0.4 cc / g. The average pore diameter of the mesopores (pore diameter: 50 to 1000) is 100 to 500, preferably 150 to 400. The specific surface area of the mesopores (pore diameter: 50 to 1000 °) is 30 m 2 / g or more, preferably 40 m 2 / g or more. The upper limit is usually about 60 m 2 / g. The crystallinity of the raw material zeolite is 90% or more, preferably 95% or more.
【０００９】本発明で原料として用いるゼオライト中の
Ｎａ等のアルカリ金属の含有量は、通常、０．０１重量
％以下であり、本発明で用いる原料ゼオライトは、実質
上、Ｈ型のものである。その粒径は、平均一次粒径で、
通常、０．１〜１μｍ、好ましくは０．２〜０．５μｍ
である。The content of alkali metals such as Na in the zeolite used as a raw material in the present invention is usually 0.01% by weight or less, and the raw material zeolite used in the present invention is substantially H-type. . The particle size is the average primary particle size,
Usually, 0.1 to 1 μm, preferably 0.2 to 0.5 μm
It is.
【００１０】本発明の新規ゼオライトを製造するには、
前記原料ゼオライトの骨格中に、アルミニウム原子を挿
入する。このためには、原料ゼオライトをアルミン酸ナ
トリウム水溶液中に浸漬して反応させる。この場合、そ
の水溶液中のアルミニウム濃度は、０．０３〜０．１モ
ル／Ｌ、好ましくは０．０４〜０．０９モル／Ｌであ
り、その水溶液のｐＨは１１〜１２である。その反応温
度は１０〜５０℃、好ましくは２０〜４０℃であり、そ
の反応時間は１〜２００時間である。In order to produce the novel zeolite of the present invention,
An aluminum atom is inserted into the framework of the raw material zeolite. For this purpose, the raw material zeolite is immersed in an aqueous solution of sodium aluminate and reacted. In this case, the aluminum concentration in the aqueous solution is 0.03 to 0.1 mol / L, preferably 0.04 to 0.09 mol / L, and the pH of the aqueous solution is 11 to 12. The reaction temperature is 10 to 50 ° C, preferably 20 to 40 ° C, and the reaction time is 1 to 200 hours.
【００１１】前記のようにして、ゼオライトの骨格中に
アルミニウム原子が挿入された本発明の新規ゼオライト
が得られる。そのアルミニウム原子のゼオライト骨格中
への挿入割合は、得られるゼオライトにおける［Ａｌ］
／［Ｓｉ］原子比が、少なくとも０．０１、好ましくは
０．０５以上となる割合である。このアルミニウム原子
の挿入割合は、水溶液中のアルミニウム濃度や、ゼオラ
イトとアルミン酸ナトリウムとの反応時間等によって調
整することができる。ゼオライト骨格中の４配位アルミ
ニウム原子は、固体酸点を与えるが、本発明の場合、前
記アルミニウム原子挿入後のゼオライト中の４配位アル
ミニウム原子の割合は、前記のように、ゼオライト骨格
中に含まれる全アルミニウム原子に対して２５〜９０原
子％、好ましくは５０〜８０原子％の範囲に調整するの
がよい。As described above, the novel zeolite of the present invention in which an aluminum atom is inserted in the framework of the zeolite is obtained. The rate of insertion of the aluminum atoms into the zeolite skeleton depends on the [Al] in the resulting zeolite.
/ [Si] atomic ratio is at least 0.01, preferably 0.05 or more. The aluminum atom insertion ratio can be adjusted by the aluminum concentration in the aqueous solution, the reaction time between zeolite and sodium aluminate, and the like. The four-coordinate aluminum atom in the zeolite skeleton gives a solid acid point. In the case of the present invention, the ratio of the four-coordinate aluminum atom in the zeolite after the insertion of the aluminum atom is, as described above, in the zeolite skeleton. It is preferable to adjust the content to 25 to 90 atomic%, preferably 50 to 80 atomic%, based on all aluminum atoms contained.
【００１２】前記のようにして、ゼオライトの骨格中に
アルミニウム原子を挿入する場合、その原料ゼオライト
には、あらかじめ低分子量の有機化合物を吸着させてお
くのが有利である。この有機化合物を吸着させた原料ゼ
オライトに対してアルミニウム原子の挿入処理を行うと
きには、ゼオライト結晶構造崩解の抑制、メソポアサイ
ズの増大等の効果を得ることができる。有機化合物は、
原料ゼオライト中のミクロポアに選択的に吸着し得るも
のであればよい。このような有機化合物には、アルコー
ル、アミン、ケトン、エーテル等が包含される。その分
子量は、３０〜２００、好ましくは３０〜１００であ
る。その具体例を示すと、エタノール、ｎ−プロパノー
ル、イソプロパノール、ｎ−ブタノール、ｔ−ブタノー
ルの他、テトラヒドロフラン等が挙げられる。ゼオライ
トに対する有機化合物の吸着量は、原料ゼオライトに対
して、１０〜１００重量％、好ましくは２０〜９０重量
％程度である。When an aluminum atom is inserted into the framework of zeolite as described above, it is advantageous to previously adsorb a low molecular weight organic compound to the raw material zeolite. When an aluminum atom is inserted into the raw material zeolite on which the organic compound is adsorbed, effects such as suppression of the collapse of the zeolite crystal structure and an increase in mesopore size can be obtained. Organic compounds
Any material can be used as long as it can be selectively adsorbed on the micropores in the raw material zeolite. Such organic compounds include alcohols, amines, ketones, ethers and the like. Its molecular weight is between 30 and 200, preferably between 30 and 100. Specific examples thereof include ethanol, n-propanol, isopropanol, n-butanol, t-butanol, and tetrahydrofuran. The amount of the organic compound adsorbed on the zeolite is about 10 to 100% by weight, preferably about 20 to 90% by weight, based on the raw material zeolite.
【００１３】本発明による前記アルミニウム原子挿入ゼ
オライトは、原料ゼオライトが保有する大きな容積割合
のメソポアを含有し、かつ原料ゼオライトが保持してい
なかった固体酸触媒として有用な固体酸点を有する。従
って、このゼオライトは、固体酸触媒として有用である
と同時に、触媒担体として有用であり、このゼオライト
上に各種の触媒金属を担持させることにより、各種の触
媒を得ることができる。例えば、該ゼオライトに水素化
活性金属を担持させることにより、水素化処理用触媒
（超深度脱硫触媒、脱窒素触媒、芳香族水素化用触媒、
重質油の水素化分解触媒等）を得ることができる。The aluminum-inserted zeolite according to the present invention contains a large volume fraction of mesopores contained in the raw material zeolite, and has a solid acid point useful as a solid acid catalyst not held by the raw material zeolite. Therefore, this zeolite is useful not only as a solid acid catalyst but also as a catalyst carrier, and various catalysts can be obtained by supporting various catalyst metals on the zeolite. For example, by supporting a hydrogenation active metal on the zeolite, a hydrotreating catalyst (ultra-deep desulfurization catalyst, denitrification catalyst, aromatic hydrogenation catalyst,
Heavy oil hydrocracking catalyst).
【００１４】本発明のアルミニウム原子挿入ゼオライト
（以下、単にＡｌ−ゼオライトとも言う）には、担持さ
せる触媒金属の高度分散性にすぐれた触媒担体とするた
めに、超微粒子状の難還元性金属酸化物を複合化（担
持）させるのが好ましい。この場合の難還元性金属酸化
物は、水素圧５０〜２００ｋｇ／ｃｍ2及び温度１００
〜４００℃の条件で金属形態に実質的に還元されない金
属酸化物を意味する。このような金属酸化物には、好ま
しいものとして、チタン属金属酸化物（チタニア、ジル
コニア等）等が包含される。なお、本明細書で言う超微
粒状の金属酸化物とは、その直径が１０ｎｍ（１００
Å）以下の金属酸化物を意味する。The aluminum atom-inserted zeolite of the present invention (hereinafter, also simply referred to as Al-zeolite) is used in the form of ultrafine particles of a non-reducible metal oxide in order to provide a catalyst carrier having excellent dispersibility of the supported catalyst metal. It is preferable to compound (support) the substance. In this case, the hardly reducible metal oxide has a hydrogen pressure of 50 to 200 kg / cm 2 and a temperature of 100 kg / cm 2.
It means a metal oxide that is not substantially reduced to a metal form under the condition of ４００400 ° C. Such metal oxides preferably include metal oxides of the titanium group (titania, zirconia, etc.). Note that the ultrafine metal oxide referred to in this specification has a diameter of 10 nm (100 nm).
Ii) Means the following metal oxides.
【００１５】超微粒子状の難還元性金属酸化物を複合化
さたＡｌ−ゼオライトを得るには、プロトン型（Ｈ型）
のＡｌ−ゼオライトを用い、これに難還元性金属（以
下、単に金属とも言う）塩を反応させる（以下、Ａ法と
も言う）か又は金属のアルコキシドを反応させる（以
下、Ｂ法とも言う）。以下これらの方法について詳述す
る。In order to obtain an Al-zeolite in which ultra-fine particles of a non-reducible metal oxide are complexed, a proton type (H type)
And a non-reducible metal (hereinafter, also simply referred to as metal) salt is reacted with the Al-zeolite (hereinafter, also referred to as Method A) or a metal alkoxide is reacted (hereinafter, also referred to as Method B). Hereinafter, these methods will be described in detail.
【００１６】（１）Ａ法 この方法は、被処理原料としてのＡｌ−ゼオライトに対
して、難還元性金属塩の強酸性水溶液を接触させた後、
乾燥し、焼成することによって実施される。この場合、
金属塩には、硫酸塩や、ハロゲン化物等が包含される。
水溶液中の金属塩の濃度は、金属濃度で、０．０２〜
０．１モル／Ｌ、好ましくは０．０５〜０．１モル／Ｌ
である。該水溶液のｐＨは、０．８〜２、好ましくは
１．０〜１．９である。その接触温度（反応温度）は、
２５〜８０℃、好ましくは３０〜５０℃である。前記Ａ
ｌ−ゼオライトと金属塩との反応においては、Ａｌ−ゼ
オライト（ケイ酸アルミニウム）表面のアルミニウムと
強酸との間で脱アルミニウム反応が起り、この反応を伴
いながら、超微粒子状の金属酸化物前駆体がゼオライト
の細孔（ポア）内表面に析出する。前記反応後、得られ
たゼオライトは、乾燥し、焼成する。この場合、乾燥温
度は、５０〜２００℃、好ましくは１００〜１５０℃で
ある。焼成温度は、３５０〜６００℃、好ましくは４５
０〜５００℃である。前記焼成は、窒素等の不活性ガス
中で実施するのが好ましいが、空気中で実施することも
できる。このＡ法の場合、前記のように、ゼオライト中
のアルミニウムの一部が脱離されることから、所望の
［Ａｌ］／［Ｓｉ］比が得られるように、［Ａｌ］／
［Ｓｉ］比が所望比よりも大きなＡｌ−ゼオライトに対
して適用される。なお、脱アルミニウム量は、水溶液と
の接触時間や温度、水溶液のｐＨ等の接触条件により調
節することができる。前記Ａ法においては、焼成により
金属酸化物前駆体は金属酸化物に変換され、これによ
り、細孔（ポア）内表面に超微粒子状金属酸化物が複合
化（担持）されたゼオライトが得られる。(1) Method A In this method, a strongly acidic aqueous solution of a non-reducible metal salt is brought into contact with Al-zeolite as a raw material to be treated.
It is carried out by drying and baking. in this case,
The metal salts include sulfates, halides and the like.
The concentration of the metal salt in the aqueous solution is 0.02-
0.1 mol / L, preferably 0.05 to 0.1 mol / L
It is. The pH of the aqueous solution is 0.8 to 2, preferably 1.0 to 1.9. The contact temperature (reaction temperature)
The temperature is 25 to 80C, preferably 30 to 50C. Said A
In the reaction between l-zeolite and a metal salt, a dealumination reaction occurs between aluminum on the surface of Al-zeolite (aluminum silicate) and a strong acid, and this reaction is accompanied by an ultrafine metal oxide precursor. Precipitates on the inner surface of the pores of the zeolite. After the reaction, the obtained zeolite is dried and calcined. In this case, the drying temperature is 50 to 200C, preferably 100 to 150C. The firing temperature is 350-600 ° C., preferably 45
0-500 ° C. The calcination is preferably performed in an inert gas such as nitrogen, but can also be performed in air. In the case of the method A, as described above, a part of the aluminum in the zeolite is desorbed, so that [Al] / [Si] is obtained so that a desired [Al] / [Si] ratio is obtained.
Applies to Al-zeolites whose [Si] ratio is greater than the desired ratio. The amount of dealumination can be adjusted by the contact conditions such as the time and temperature of contact with the aqueous solution and the pH of the aqueous solution. In the method A, the metal oxide precursor is converted into a metal oxide by calcination, whereby a zeolite in which the ultrafine metal oxide is composited (supported) on the inner surface of the pores is obtained. .
【００１７】（２）Ｂ法 この方法は、被処理原料としてのＡｌ−ゼオライトに対
して、難還元性金属アルコキシド溶液を接触させた後、
乾燥し、焼成することにより実施される。この場合、金
属アルコキシドには、炭素数１〜４、好ましくは２〜３
の脂肪族基（アルキル基、アルケニル基等）を有するも
の等が包含される。金属アルコキシドの溶液は、金属ア
ルコキシドを有機溶媒に溶解させることによって調製さ
れる。この場合、有機溶媒には、アルコール（エタノー
ル、イソプロパノール、ブタノール、ヘキサノール等）
や、炭化水素（ヘキサン、シクロヘキサン、オクタン
等）等が包含される。溶液中の金属アルコキシドの濃度
は、金属濃度で０．１〜１モル／Ｌ、好ましくは０．３
〜０．７モル／Ｌである。前記接触温度は、２０〜５０
℃、好ましくは２５〜４０℃である。前記接触処理後、
得られたゼオライトは、乾燥し、焼成する。この場合、
乾燥温度は、５０〜２００℃、好ましくは１００〜１５
０℃である。焼成温度は、４００〜６００℃、好ましく
は４５０〜５００℃である。前記焼成は、空気等の含酸
素ガス中で実施するのが好ましい。このＢ法において
は、ゼオライト中に含浸された金属アルコキシドは、焼
成に際して分解し、これにより、ゼオライトの細孔（ポ
ア）内表面には超微粒子状金属酸化物が複合化（担持）
される。(2) Method B In this method, after contacting a non-reducible metal alkoxide solution with Al-zeolite as a raw material to be treated,
It is carried out by drying and firing. In this case, the metal alkoxide has 1-4 carbon atoms, preferably 2-3 carbon atoms.
And the like having an aliphatic group (such as an alkyl group or an alkenyl group). The metal alkoxide solution is prepared by dissolving the metal alkoxide in an organic solvent. In this case, the organic solvent includes alcohol (ethanol, isopropanol, butanol, hexanol, etc.)
And hydrocarbons (hexane, cyclohexane, octane, etc.). The concentration of the metal alkoxide in the solution is 0.1 to 1 mol / L, preferably 0.3 to 1 mol / L in terms of metal concentration.
0.7 mol / L. The contact temperature is 20-50
° C, preferably 25 to 40 ° C. After the contact treatment,
The obtained zeolite is dried and calcined. in this case,
The drying temperature is 50 to 200 ° C, preferably 100 to 15 ° C.
0 ° C. The firing temperature is 400 to 600 ° C, preferably 450 to 500 ° C. The calcination is preferably performed in an oxygen-containing gas such as air. In the method B, the metal alkoxide impregnated in the zeolite is decomposed during calcination, whereby the ultrafine metal oxide is complexed (supported) on the inner surfaces of the pores (pores) of the zeolite.
Is done.
【００１８】このＢ法の場合、前記Ａ法の場合とは異な
り、難還元性金属酸化物の複合化前後においては、［Ａ
ｌ］／［Ｓｉ］比は変化しない。従って、所望の［Ａ
ｌ］／［Ｓｉ］比の製品を得るには、Ａｌ−ゼオライト
の［Ａｌ］／［Ｓｉ］比をあらかじめ調節することが必
要である。例えば、Ａｌ−ゼオライトの［Ａｌ］／［Ｓ
ｉ］比が所望比より大きい場合には、そのゼオライトか
らアルミニウム原子を脱離させる。このためには、Ａｌ
−ゼオライトを硫酸水溶液と接触させればよい。この場
合の水溶中の硫酸濃度は０．０５〜１．０モル／Ｌ、好
ましくは０．１〜０．５モル／Ｌである。In the case of the method B, unlike the case of the method A, before and after the compounding of the non-reducible metal oxide, [A
The l] / [Si] ratio does not change. Therefore, the desired [A
In order to obtain a product having an [l] / [Si] ratio, it is necessary to adjust the [Al] / [Si] ratio of Al-zeolite in advance. For example, [Al] / [S
i] If the ratio is greater than the desired ratio, desorb aluminum atoms from the zeolite. For this, Al
The zeolite may be brought into contact with an aqueous sulfuric acid solution; In this case, the concentration of sulfuric acid in the aqueous solution is 0.05 to 1.0 mol / L, preferably 0.1 to 0.5 mol / L.
【００１９】前記のようにしてゼオライトの細孔内表面
に複合化される超微粒子状難還元性金属酸化物におい
て、その金属酸化物の平均粒子径は、１５〜１００Å、
好ましくは２０〜５０Åである。その金属酸化物の含有
量は、ゼオライト中、１〜１０重量％、好ましくは２〜
８重量％である。金属酸化物の粒径は、ゼオライト中に
複合化させる金属酸化物量等によって調節することがで
き、その複合化量が多くなるにつれて金属酸化物の粒径
は大きくなる傾向を示す。In the ultrafine particulate inreducible metal oxide compounded on the inner surface of the pores of zeolite as described above, the metal oxide has an average particle size of 15 to 100 °,
Preferably it is 20 to 50 °. The content of the metal oxide in the zeolite is 1 to 10% by weight, preferably 2 to 10% by weight.
8% by weight. The particle size of the metal oxide can be adjusted by the amount of the metal oxide to be complexed in the zeolite, and the particle size of the metal oxide tends to increase as the amount of the complex increases.
【００２０】前記超微粒子状難還元性金属酸化物の複合
化されたゼオライトにおいて、その［Ａｌ］／［Ｓｉ］
比は０．０１〜０．２、好ましくは０．０２〜０．１で
ある。そのメソポアの容積割合は３０〜５０％、好まし
くは３５〜５０％である。そのメソポアの容積は、０．
１ｃｃ／ｇ以上、好ましくは０．１３ｃｃ／ｇ以上であ
り、その上限値は、通常、０．４ｃｃ／ｇ程度である。
直径１００〜５００Åのメソポアの容積割合は、３０〜
４０％、好ましくは３５〜４０％である。その全アルミ
ニウム原子に対する４配位アルミニウム原子の割合は、
２５原子％以上、好ましくは５０〜８０原子％である。
この超微粒子状難還元性金属酸化物を複合化させたゼオ
ライトの結晶化度は、２５％以上、好ましくは５０〜９
０％である。また、その固体酸強度（ＮＨ3−ＴＰＤ、
高温側ピーク）は、０．２〜１ｍｍｏｌ／ｇ、好ましく
は０．３〜０．６ｍｍｏｌ／ｇである。そのメソポアの
比表面積は、３０ｍ2／ｇ以上、好ましくは３５ｍ2／ｇ
以上、であり、その上限値は、通常、５０ｍ2／ｇ程度
である。In the zeolite in which the ultrafine particulate insoluble metal oxide is compounded, the [Al] / [Si]
The ratio is between 0.01 and 0.2, preferably between 0.02 and 0.1. The volume ratio of the mesopore is 30 to 50%, preferably 35 to 50%. The volume of the mesopore is 0.
It is at least 1 cc / g, preferably at least 0.13 cc / g, and its upper limit is usually about 0.4 cc / g.
The volume ratio of mesopores with a diameter of 100 to 500 mm is 30 to
It is 40%, preferably 35-40%. The ratio of four-coordinate aluminum atoms to the total aluminum atoms is
It is at least 25 atomic%, preferably 50 to 80 atomic%.
The crystallinity of the zeolite in which the ultrafine particle-like hardly reducible metal oxide is complexed is 25% or more, preferably 50 to 9%.
0%. Also, its solid acid strength (NH 3 -TPD,
High-temperature side peak) is 0.2 to 1 mmol / g, preferably 0.3 to 0.6 mmol / g. The specific surface area of the mesopore is 30 m 2 / g or more, preferably 35 m 2 / g.
The upper limit is usually about 50 m 2 / g.
【００２１】前記ゼオライトは、そのメソポアの内表面
に超微粒子状の難還元性金属酸化物が複合化されている
ことから、触媒金属をその凝集を生じさせることなく、
高度に均一分散させる機能にすぐれたもので、各種触媒
金属担持用の触媒担体として好適のものである。このゼ
オライトは、その複合化された超微粒子状金属酸化物が
難還元性のものであり、水素加圧下でも安定性のよいも
のであることから、特に、水素が反応に関与する反応に
おける触媒担体、例えば、水素化処理（超深度脱硫、脱
窒素、芳香族水素化、重質油の水素化分解等）用触媒担
体として好適である。その他、骨格異性化二元機能型触
媒用担体として好適である。In the zeolite, since ultrafine particulate insoluble metal oxide is compounded on the inner surface of the mesopore, the catalyst metal is not aggregated without causing aggregation.
It has excellent function of highly uniform dispersion and is suitable as a catalyst carrier for supporting various catalyst metals. This zeolite is a catalyst carrier in a reaction in which hydrogen participates in the reaction, because the composite ultrafine metal oxide is difficult to reduce and has good stability even under hydrogen pressure. For example, it is suitable as a catalyst carrier for hydrotreating (ultra deep desulfurization, denitrification, aromatic hydrogenation, hydrocracking of heavy oil, etc.). In addition, it is suitable as a carrier for a skeletal isomerization bifunctional catalyst.
【００２２】本発明による超微粒子状の難還元性金属酸
化物が複合化されたゼオライトは、水素化処理用触媒担
体として好適のものであり、これに水素化活性金属を担
持させることにより、良好な水素化処理用触媒を得るこ
とができる。以下、この水素化処理用触媒について詳述
する。The zeolite composited with the ultrafine hard-to-reduce metal oxide according to the present invention is suitable as a catalyst support for hydrotreating. A hydrotreating catalyst can be obtained. Hereinafter, the hydrotreating catalyst will be described in detail.
【００２３】担体ゼオライトに担持させる水素化活性金
属としては、従来公知の各種のものが用いられる。この
ようなものとしては、例えば、モリブデン、タングステ
ン、ニッケル、コバルトの他、白金、パラジウム等の白
金族金属等の周期律表８族金属が挙げられる。水素化活
性の高められた触媒を得るには、Ｎｉ−Ｍｏ、Ｃｏ−Ｍ
ｏ、Ｎｉ−Ｗ等の複合金属種を用いるのが好ましい。担
体ゼオライトに対する水素化活性金属の担持方法として
は、平衡吸着法、含浸法等の従来公知の方法を採用する
ことができる。本発明の水素化処理用触媒において、そ
の水素化活性金属の含有量は、金属換算量で、０．１〜
１０重量％、好ましくは１〜８重量％であるが、難還元
性金属酸化物に対して２０重量％以上、好ましくは２５
〜５０重量％になるように担持させるのがよい。触媒担
体に担持された水素活性化金属の形態は、酸化物、硫化
物及び／または金属の形態であるが、白金、パラジウム
等は、金属状態で高い水素化能を有する。As the hydrogenation active metal to be supported on the carrier zeolite, various conventionally known ones can be used. Examples of such a material include molybdenum, tungsten, nickel, cobalt, and metals of the Periodic Table 8 such as platinum group metals such as platinum and palladium. In order to obtain a catalyst having enhanced hydrogenation activity, Ni-Mo, Co-M
It is preferable to use composite metal species such as o and Ni-W. As a method for supporting the hydrogenation active metal on the carrier zeolite, a conventionally known method such as an equilibrium adsorption method or an impregnation method can be employed. In the hydrotreating catalyst of the present invention, the content of the hydrogenation active metal is 0.1 to
The content is 10% by weight, preferably 1 to 8% by weight, but 20% by weight or more, preferably 25% by weight, based on the non-reducible metal oxide.
It is preferable that the carrier is supported so as to be 50% by weight. The form of the hydrogen-activated metal supported on the catalyst carrier is an oxide, a sulfide, and / or a metal, and platinum, palladium, and the like have a high hydrogenation ability in a metal state.
【００２４】本発明の水素化処理用触媒を構成するゼオ
ライトの性状は、前記した超微粒子状難還元性金属酸化
物を複合化させたゼオライトの性状と実質的に同じであ
る。この触媒を残油等の重質油の水素化分解に適用する
場合、その［Ａｌ］／［Ｓｉ］比は、０．０１〜０．
１、好ましくは０．０２〜０．０６の範囲に規定するの
がよい。前記比が０．１より大きくなると、アスファル
テン分解率が低く、触媒の活性低下が激しい上に、ガス
成分の生成が多くなる。一方、前記比が０．０１より小
さくなると、減圧残油成分（５２０℃以上の留分）の分
解速度が急激に低下する傾向を示す。The properties of the zeolite constituting the hydrotreating catalyst of the present invention are substantially the same as those of the zeolite obtained by compounding the above-mentioned ultrafine-particle hardly reducible metal oxide. When this catalyst is applied to hydrocracking of heavy oil such as residual oil, the [Al] / [Si] ratio is 0.01 to 0.5.
1, preferably in the range of 0.02 to 0.06. When the ratio is greater than 0.1, the asphaltene decomposition rate is low, the activity of the catalyst is significantly reduced, and the generation of gas components is increased. On the other hand, when the ratio is less than 0.01, the decomposition rate of the vacuum residual oil component (a fraction at 520 ° C. or higher) tends to rapidly decrease.
【００２５】本発明の水素化処理用触媒は、従来の水素
化用触媒と同様に各種の水素化処理目的に適用すること
ができるが、特に、重質油の水素化分解用触媒として有
利に用いることができる。本発明の水素化処理用触媒を
用いて重質油の水素化分解を行うには、本発明の触媒の
存在下、重質油を、３５０〜４４０℃、好ましくは３９
０〜４２０℃の温度及び８０〜２５０気圧、好ましくは
１００〜２００気圧の水素圧力下において、水素化処理
する。重質油としては、原油の他、常圧蒸留残渣、減圧
蒸留残渣、減圧軽油等を挙げることができる。本発明の
触媒を用いて重質油を水素化処理するときには、重質油
中の高沸点成分を効率よく水素化分解（軽質化）するこ
とができる上、高いアスファルテン分解率を得ることが
できる。The hydrotreating catalyst of the present invention can be applied to various hydrotreating purposes similarly to the conventional hydrotreating catalyst, and is particularly advantageous as a catalyst for hydrocracking heavy oil. Can be used. In order to carry out hydrocracking of heavy oil using the catalyst for hydrotreating of the present invention, heavy oil is heated at 350 to 440 ° C., preferably 39 ° C. in the presence of the catalyst of the present invention.
Hydrotreating is performed at a temperature of 0 to 420 ° C. and a hydrogen pressure of 80 to 250 atm, preferably 100 to 200 atm. Examples of heavy oil include crude oil, atmospheric distillation residue, vacuum distillation residue, vacuum gas oil, and the like. When hydrotreating heavy oil using the catalyst of the present invention, high-boiling components in heavy oil can be efficiently hydrocracked (lightened) and a high asphaltene cracking rate can be obtained. .
【００２６】本明細書中で示したゼオライトに関するメ
ソポア等の細孔容積や原子比［Ａｌ］／［Ｓｉ］等の物
性（いずれもゼオライトの一次粒子に関する物性）は、
以下のようにして測定されたものである。 （１）細孔容積（ｃｃ／ｇ） Ｎ2吸着法により細孔分布を求め、その細孔分布に基づ
いて算出した。測定装置としては、micromeritics（マ
イクロメリテックス）社製、製品名ＡＳＡＰ２０１０を
用いた。測定温度としては、−１９６℃を用いた。 （２）メソポアの比表面積（ｍ2／ｇ） Ｎ2吸着法により測定した。測定装置としては、前記
（１）で示した装置を用いた。 （３）アルミニウムとケイ素との原子比［Ａｌ］／［Ｓ
ｉ］の測定 この原子比は、組成分析（溶解／ＩＣＰ法）結果に基づ
いて算出した。 （４）４配位アルミニウム原子の割合（原子％） この割合は、固体ＮＭＲ（27Ａｌ・ＭＡＳＮＭＲ）法の
詳細解析で算出した。通常の解析では４配位Ａｌと６配
位Ａｌに分離するがここでは、４配位Ａｌをさらに無定
形Ａｌと結晶形Ａｌに分離した。 （５）固体酸強度（ｍｍｏｌ／ｇ） 酸強度は、ＮＨ3−ＴＰＤ法により測定した。この場
合、高温側ピーク（ゼオライト骨格Ａｌに対応）から算
出した。その測定装置としては、日本ベル（株）社製、
製品名ＴＰＤ−１−ＡＴ装置温度制御脱離装置を用い
た。The physical properties such as the pore volume of mesopores and the like and the atomic ratio [Al] / [Si] and the like (both of the physical properties related to the primary particles of the zeolite) shown in the present specification are as follows.
It was measured as follows. (1) Pore volume (cc / g) The pore distribution was determined by the N 2 adsorption method and calculated based on the pore distribution. As a measuring device, ASAP2010 manufactured by micromeritics (product name) was used. As the measurement temperature, -196 ° C was used. (2) Specific surface area of mesopore (m 2 / g) Measured by N 2 adsorption method. As the measuring device, the device shown in the above (1) was used. (3) Atomic ratio of aluminum to silicon [Al] / [S
Measurement of i] This atomic ratio was calculated based on the result of composition analysis (dissolution / ICP method). (4) four-coordinate proportion of aluminum atoms (atom%) This percentage was calculated by the detailed analysis of the solid NMR (27 Al · MASNMR) method. In the usual analysis, it is separated into four-coordinate Al and six-coordinate Al. Here, the four-coordinate Al is further separated into amorphous Al and crystalline Al. (5) Solid acid strength (mmol / g) The acid strength was measured by the NH 3 -TPD method. In this case, it was calculated from the high temperature side peak (corresponding to zeolite framework Al). As the measuring device, manufactured by Nippon Bell Co., Ltd.,
Product name TPD-1-AT device A temperature controlled desorption device was used.
【００２７】[0027]
【実施例】次に、本発明を実施例によりさらに詳細に説
明する。Next, the present invention will be described in more detail with reference to examples.
【００２８】実施例１［アルミニウム挿入ゼオライト
（Ａｌ−ＵＳＹ）の製造］ 原料ゼオライトとしては、下記物性を有する市販の高メ
ソポアＵＳＹゼオライト（Ｉ）を用いた。 （細孔構造、結晶構造） （ｉ）メソポア（細孔直径：５０〜１０００Å）の容
積：０．１９７ｃｃ／ｇ （ii）メソポアの容積割合（細孔直径２０〜２０００Å
の全細孔容積に対する割合）：４２％ （iii）細孔直径１００〜５００Åのメソポアの容積：
０．１７３ｃｃ／ｇ及びその容積割合：３７％ （iv）メソポア（細孔直径５０〜１０００Å）の比表面
積：４０ｍ2／ｇ （ｖ）ＢＥＴ比表面積：６７７ｍ2／ｇ （vi）結晶化度（ナトリウムＹ型ゼオライト（ＮａＹ）
の結晶化度を１００％とした相対値〕：９５％ （vii）単位格子サイズ：２４．２６Å （組成等） （ｉ）Ｓｉ：４５．６ｗｔ％ （ii）Ａｌ：０．３４ｗｔ％ （iii）Ｎａ：０．０１ｗｔ％以下 （iv）原子比［Ａｌ］／［Ｓｉ］：０．００８ （ｖ）固体酸強度（ＮＨ3−ＴＰＤ、高温ピーク側）：
６×１０-3ｍｍｏｌ／ｇExample 1 [Production of aluminum-inserted zeolite (Al-USY)] As a raw material zeolite, a commercially available high mesopore USY zeolite (I) having the following physical properties was used. (Pore structure, crystal structure) (i) Volume of mesopore (pore diameter: 50 to 1000 mm): 0.197 cc / g (ii) Volume ratio of mesopore (pore diameter: 20 to 2000 mm)
Of the mesopore with a pore diameter of 100 to 500 °:
0.173 cc / g and its volume ratio: 37% (iv) Specific surface area of mesopores (pore diameter 50 to 1000 °): 40 m 2 / g (v) BET specific surface area: 677 m 2 / g (vi) Crystallinity ( Sodium Y-type zeolite (NaY)
(Vii) Unit cell size: 24.26 ° (composition etc.) (i) Si: 45.6 wt% (ii) Al: 0.34 wt% (iii) Na: 0.01 wt% or less (iv) Atomic ratio [Al] / [Si]: 0.008 (v) Solid acid strength (NH 3 -TPD, high temperature peak side):
6 × 10 −3 mmol / g
【００２９】原料ゼオライトとして前記ＵＳＹゼオライ
ト（Ｉ）６０ｇとアルミン酸ナトリウム水溶液（Ｎａ濃
度：０．０７５ｍｏｌ／Ｌ）の１．８Ｌを反応容器（３
Ｌ）に投入し、温度１５℃で９０時間強制攪拌した。次
いで、処理ゼオライトを濾過分離した。２Ｌの温水で洗
浄し、ゼオライトケーキを回収し、７５℃の送風乾燥機
で乾燥した。次に、Ｈ型ゼオライトを得るために、前記
乾燥ゼオライトを硫酸アンモニウム（ＮＨ4)2ＳＯ4濃
度：０．４ｍｏｌ／Ｌ）の１Ｌ中で攪拌処理（１ｈ、５
０℃）した。更に、硫酸アンモニウム水溶液２Ｌで濾過
洗浄した。加温水約３Ｌで水洗し、濾液がＢａイオンに
より白濁しないことを確認した。ついで、ケーキを乾燥
（１２０℃、８時間）し、窒素ガス気流中で、焼成（３
５０℃、３ｈ）した。カチオン（Ｎａ）交換を完全にす
るため、更に硫酸洗浄を行った。得られたＨ型Ａｌ−Ｕ
ＳＹゼオライト（ＴＺ−１１３）について、組成分析、
細孔分布、結晶化度、固体酸点密度、固体ＮＭＲによる
４配位Ａｌ比率、等によって、その物性評価を行った。
その結果を表１に示す。As a raw material zeolite, 60 g of the above USY zeolite (I) and 1.8 L of an aqueous solution of sodium aluminate (Na concentration: 0.075 mol / L) were placed in a reaction vessel (3).
L) and forcedly stirred at a temperature of 15 ° C. for 90 hours. Subsequently, the treated zeolite was separated by filtration. After washing with 2 L of warm water, the zeolite cake was collected and dried with a blast dryer at 75 ° C. Next, in order to obtain an H-type zeolite, the dried zeolite was stirred in 1 L of ammonium sulfate (NH 4 ) 2 SO 4 concentration: 0.4 mol / L (1 h, 5 h).
0 ° C). Further, the mixture was filtered and washed with 2 L of an ammonium sulfate aqueous solution. After washing with about 3 L of warm water, it was confirmed that the filtrate was not turbid due to Ba ions. Then, the cake was dried (120 ° C., 8 hours), and calcined (3
50 ° C., 3 h). To complete the cation (Na) exchange, washing with sulfuric acid was further performed. The obtained H-type Al-U
About SY zeolite (TZ-113), composition analysis,
The physical properties were evaluated based on pore distribution, crystallinity, solid acid point density, tetracoordinate Al ratio by solid state NMR, and the like.
Table 1 shows the results.
【００３０】実施例２ 実施例１において、原料ゼオライトとアルミン酸ナトリ
ウム水溶液との反応温度を８℃とした以外は同様にして
実験を行った。得られたＨ型Ａｌ−ＵＳＹゼオライト
（ＴＺ−１２７）の物性を表１に示す。Example 2 An experiment was conducted in the same manner as in Example 1 except that the reaction temperature between the raw material zeolite and the aqueous solution of sodium aluminate was changed to 8 ° C. Table 1 shows the physical properties of the obtained H-type Al-USY zeolite (TZ-127).
【００３１】実施例３ 実施例１において、原料ゼオライトとアルミン酸ナトリ
ウム水溶液との反応温度を５０℃とし、反応時間を３時
間とした以外は同様にして実験を行った。得られたＨ型
Ａｌ−ＵＳＹゼオライト（ＴＺ−１５０）の物性を表１
に示す。Example 3 An experiment was conducted in the same manner as in Example 1 except that the reaction temperature between the raw material zeolite and the aqueous solution of sodium aluminate was changed to 50 ° C., and the reaction time was changed to 3 hours. Table 1 shows the physical properties of the obtained H-type Al-USY zeolite (TZ-150).
Shown in
【００３２】実施例４ 実施例１において、原料ゼオライトとして、ＵＳＹゼオ
ライト（Ｉ）６０ｇにｎ−プロピルアルコール（ｎ−Ｃ
3Ｈ7ＯＨ）５０ｇを吸着混合させたものを用いるととも
に、反応条件として、温度：５０℃、時間：３時間を用
いた以外は同様にして実験を行った。得られたＨ型Ａｌ
−ＵＳＹゼオライト（ＴＺ−１４７）の物性を表１に示
す。Example 4 In Example 1, as raw material zeolite, n-propyl alcohol (nC) was added to 60 g of USY zeolite (I).
With use of 3 H 7 OH) that the 50g adsorbed mixture, reaction conditions, temperature: 50 ° C., time: the experiments were carried out in the same manner except for using 3 hours. H-type Al obtained
Table 1 shows the physical properties of -USY zeolite (TZ-147).
【００３３】実施例５ 実施例１において、原料ゼオライトとして、ＵＳＹゼオ
ライト（Ｉ）６０ｇにエチルアルコール５０ｇを吸着混
合させたものを用いるとともに、反応条件として、温
度：５０℃、時間：３時間を用いた以外は同様にして実
験を行った。得られたＨ型Ａｌ−ＵＳＹゼオライト（Ｔ
Ｚ−１４８）の物性を表１に示す。Example 5 In Example 1, 60 g of USY zeolite (I) adsorbed and mixed with 50 g of ethyl alcohol was used as the raw material zeolite, and the reaction conditions were a temperature of 50 ° C. and a time of 3 hours. The experiment was conducted in the same manner except for the presence of The obtained H-type Al-USY zeolite (T
Table 1 shows the physical properties of Z-148).
【００３４】実施例６ 実施例１において、原料ゼオライトとして、ＵＳＹゼオ
ライト（Ｉ）６０ｇとエチルアルコール８０〜１００ｇ
を吸着させたものを用いるとともに、反応条件として、
温度５０℃、時間：３時間を用いた以外は同様にして実
験を行った。得られたＨ型Ａｌ−ＵＳＹゼオライト（Ｔ
Ｚ−１５４（混合品））の物性を表１に示す。Example 6 In Example 1, 60 g of USY zeolite (I) and 80 to 100 g of ethyl alcohol were used as raw material zeolites.
Is used, and the reaction conditions are as follows:
The experiment was performed in the same manner except that a temperature of 50 ° C. and a time of 3 hours were used. The obtained H-type Al-USY zeolite (T
Table 1 shows the physical properties of Z-154 (mixed product).
【００３５】[0035]
【表１】 [Table 1]
【００３６】表１に示したＢＪＨ（１）、ＢＪＨ（２）
及びＢＪＨ（２）細孔容積の具体的内容は以下のとおり
である。 （１）ＢＪＨ（１） 細孔直径１７〜３０００Åの細孔の比表面積（ｍ2／
ｇ） （２）ＢＪＨ（２） 細孔直径５０〜１０００Åの細孔の比表面積（ｍ2／
ｇ） （３）ＢＪＨ（２）細孔容積 細孔直径２０〜２０００Åの細孔の細孔容積（ｃｃ／
ｇ）BJH (1) and BJH (2) shown in Table 1
And the specific contents of the BJH (2) pore volume are as follows. (1) BJH (1) Specific surface area of pores having a pore diameter of 17 to 3000 ° (m 2 /
g) (2) BJH (2) Specific surface area (m 2 /
g) (3) BJH (2) Pore volume The pore volume of pores having a pore diameter of 20 to 2000 mm (cc /
g)
【００３７】実施例７（難還元性金属酸化物の複合化） 硫酸チタン（IV）水溶液（Ｔｉ濃度：０．０３５ｍｏｌ
／Ｌ）８３３ｍｌを調合し、２Ｌのガラス製フラスコに
入れた。４５℃に加温し、実施例６で得たゼオライトＴ
Ｚ−１５４の２０ｇを攪拌しながら投入した。２時間の
反応処理を継続した。反応前の酸性度はｐＨ＝１．１７
であったが、反応処理後の酸性度はｐＨ＝１．２０に上
昇した。反応終了後はスラリーを減圧濾過し、５０℃の
加温水１Ｌを用いて洗浄した。更にＢａ水溶液による硫
酸根の確認を行い、硫酸根が認められなくなるまでイオ
ン交換水で洗浄した。洗浄を十分に行った後、処理ゼオ
ライトケーキを室温で風乾し、ついで、１１０℃で３時
間乾燥処理を行った。乾燥処理後の粉末は窒素気流中
（１００ｍｌ／ｍｉｎ）で５００℃、３時間焼成した。
焼成後の重量は１９ｇであった。得られた修飾ゼオライ
トＴＺ−１５４tについては、ＩＣＰ法による組成分
析、Ｘ線回析法による相対結晶化度測定、ＮＨ3−ＴＰ
Ｄ法による固体酸強度測定、Ｎ2吸着法による細孔分
布、比表面積測定を行った。その結果を表２に示す。ま
た、電子顕微鏡（ＴＥＭ）観察によるメソ細孔内部の超
微粒子（ＴｉＯ2）サイズの測定を行った。その結果、
そのＴｉＯ2の平均粒径は６０Åであり、その含有量は
１．２ｗｔ％であった。Example 7 (Composite of non-reducible metal oxide) Titanium (IV) sulfate aqueous solution (Ti concentration: 0.035 mol)
/ L) 833 ml was prepared and placed in a 2 L glass flask. Heated to 45 ° C., the zeolite T obtained in Example 6
20 g of Z-154 were charged with stirring. The reaction treatment for 2 hours was continued. The acidity before the reaction was pH = 1.17
However, the acidity after the reaction treatment increased to pH = 1.20. After the completion of the reaction, the slurry was filtered under reduced pressure and washed with 1 L of warm water at 50 ° C. Further, the sulfate group was confirmed with a Ba aqueous solution, and washed with ion-exchanged water until no sulfate group was observed. After sufficient washing, the treated zeolite cake was air-dried at room temperature and then dried at 110 ° C. for 3 hours. The powder after the drying treatment was fired in a nitrogen stream (100 ml / min) at 500 ° C. for 3 hours.
The weight after firing was 19 g. About the obtained modified zeolites TZ-154t, composition analysis by ICP method, relative crystallinity measurement by X-ray diffraction method, NH 3 -TP
The solid acid strength was measured by the method D, the pore distribution and the specific surface area were measured by the N 2 adsorption method. Table 2 shows the results. The size of ultrafine particles (TiO 2 ) inside the mesopores was measured by electron microscope (TEM) observation. as a result,
The average particle size of the TiO 2 was 60 °, and the content was 1.2% by weight.
【００３８】実施例８ 実施例７において、反応条件として、温度４５℃、時
間：１時間を用いた以外は同様にして実験を行った。得
られたゼオライトＴＺ−１５４ｔ２の物性を表２に示
す。Example 8 An experiment was carried out in the same manner as in Example 7, except that the reaction conditions were a temperature of 45 ° C. and a time of 1 hour. Table 2 shows the physical properties of the obtained zeolite TZ-154t2.
【００３９】実施例９ 実施例７において、硫酸チタン（IV）水溶液の代りに、
硫酸チタン（IV）と硫酸ジルコニウム（IV）を含む水溶
液（Ｔｉ濃度：０．０２ｍｏｌ／Ｌ、Ｚｒ濃度：０．０
１ｍｏｌ／Ｌを用いた以外は同様にして実験を行った。
得られたゼオライトＴＺ−１５４tzの物性を表２に示
す。複合化された超微粒子の平均粒径は５０Åであり、
その含有量は１．１ｗｔ％であった。Example 9 In Example 7, instead of the aqueous titanium (IV) sulfate solution,
An aqueous solution containing titanium (IV) sulfate and zirconium (IV) sulfate (Ti concentration: 0.02 mol / L, Zr concentration: 0.0
The experiment was performed in the same manner except that 1 mol / L was used.
Table 2 shows the physical properties of the obtained zeolite TZ-154tz. The average diameter of the composite ultrafine particles is 50 °,
Its content was 1.1 wt%.
【００４０】実施例１０ 実施例６で得たゼオライトＴＺ−１５４（［Ａｌ］／
［Ｓｉ］＝０．１０３）の２０ｇを、硫酸水溶液（濃
度：０．０５ｍｏｌ／Ｌ）に投入し、５０℃で１時間処
理した。次いで、実施例７と同様にして後処理を実施し
た。スラリーのｐＨは、処理前がｐＨ＝１．０、処理後
はｐＨ＝１．２であった。得られたゼオライト（ＴＺ１
５４ｄ）のＡｌ／Ｓｉｍｏｌ比は０．０６２であった。
その他の物性を表２に示す。次に、上記の脱アルミ処理
ゼオライト（ＴＺ−１５４ｄ）にＴｉＯ2超微粒子を担
持するために、ＴＺ−１５４ｄ １０ｇをチタンテトラ
プロキシドのエタノール溶液（濃度１５％）に１時間浸
せきし、濾過、乾燥、焼成（５００℃、３時間）した。
このようにして得られたゼオライトｔＴＺ−１５４ｄの
物性を表２に示す。複合化された超微粒子の平均粒径は
４０Åであり、その含有量は６．７ｗｔ％であった。Example 10 The zeolite TZ-154 obtained in Example 6 ([Al] /
20 g of [Si] = 0.103) was put into an aqueous sulfuric acid solution (concentration: 0.05 mol / L) and treated at 50 ° C. for 1 hour. Next, post-processing was performed in the same manner as in Example 7. The pH of the slurry was pH = 1.0 before the treatment and pH = 1.2 after the treatment. The obtained zeolite (TZ1
The Al / Simol ratio of 54d) was 0.062.
Table 2 shows other physical properties. Next, in order to carry the TiO 2 ultrafine particles on the dealuminated zeolite (TZ-154d), 10 g of TZ-154d was immersed in an ethanol solution of titanium tetraproxide (concentration: 15%) for 1 hour, followed by filtration. It was dried and fired (500 ° C., 3 hours).
Table 2 shows the physical properties of the thus obtained zeolite tTZ-154d. The average particle size of the composite ultrafine particles was 40 °, and the content thereof was 6.7 wt%.
【００４１】[0041]
【表２】 [Table 2]
【００４２】実施例１１（水素化処理用触媒の調製） アンモニウムヘプタモリブテン酸塩（ＡＨＭ：（ＮＨ4)
6Ｍｏ7Ｏ24４Ｈ2Ｏ）の濃度０．００７ｍｏｌ／Ｌの水
溶液（ｐＨ＝２．０に調整）を用意した。このＭｏ水溶
液の１４０ｍｌに修飾ゼオライトＴＺ−１５４の３．５
ｇを秤量し混合した。密閉容器に入れて、振盪攪拌しな
がら５０℃で２４時間保持して平衡吸着操作を行った。
平衡吸着操作を終了後に内容物を取り出し、減圧濾過し
た。得られたゼオライトケーキを室温で１２時間風乾し
た。次いで、１１０℃、３時間乾燥した。更に空気雰囲
気中で５００℃、３時間の焼成処理を行った。得られた
Ｍｏ種複合化修飾ゼオライトの性状を表３に示す。Example 11 (Preparation of catalyst for hydrotreating) Ammonium heptamolybdate (AHM: (NH 4 ))
An aqueous solution (adjusted to pH = 2.0) having a concentration of 0.007 mol / L of 6 Mo 7 O 24 4H 2 O) was prepared. 3.5 ml of the modified zeolite TZ-154 was added to 140 ml of this Mo aqueous solution.
g were weighed and mixed. An equilibrium adsorption operation was performed by placing the mixture in a closed container and holding it at 50 ° C. for 24 hours while shaking and stirring.
After completion of the equilibrium adsorption operation, the contents were taken out and filtered under reduced pressure. The obtained zeolite cake was air-dried at room temperature for 12 hours. Next, it was dried at 110 ° C. for 3 hours. Further, a baking treatment was performed at 500 ° C. for 3 hours in an air atmosphere. Table 3 shows the properties of the obtained Mo-type composite modified zeolite.
【００４３】実施例１２ 実施例１１において、被処理ゼオライトとして、ｔＴＺ
−１５４を用いた以外は同様にして実験を行った。この
ようにして得られたＭｏ担持ゼオライトＭｔＴＺ−１５
４の物性を表３に示す。Example 12 In Example 11, tTZ was used as the zeolite to be treated.
The experiment was performed in the same manner except that -154 was used. The Mo-supported zeolite MtTZ-15 thus obtained
Table 3 shows the physical properties of the sample No. 4.
【００４４】実施例１３ 実施例１１において、被処理ゼオライトとして、ｔＴＺ
−１５４ｄを用いた以外は同様にして実験を行った。こ
のようにして得られたＭｏ担持ゼオライトＭｔＴＺ−１
５４ｄの物性を表３に示す。Example 13 In Example 11, tTZ was used as the zeolite to be treated.
The experiment was performed in the same manner except that -154d was used. Mo-supported zeolite MtTZ-1 thus obtained
Table 3 shows the physical properties of 54d.
【００４５】実施例１４ 実施例１１において、被処理ゼオライトとして、ｔＴＺ
−１５４ｄ２を用いた以外は同様にして実験を行った。
このようにして得られたＭｏ担持ゼオライトＭｔＴＺ−
１５４ｄ２の物性を表３に示す。Example 14 In Example 11, tTZ was used as the zeolite to be treated.
The experiment was performed in the same manner except that -154d2 was used.
The thus obtained Mo-supported zeolite MtTZ-
Table 3 shows the physical properties of 154d2.
【００４６】実施例１５ 実施例１１において、被処理ゼオライトとして、ＴＺ−
１５４ｔｚを用いた以外は同様にして実験を行った。こ
のようにして得られたＭｏ担持ゼオライトＭＴＺ−１５
４ｔｚの物性を表３に示す。Example 15 In Example 11, TZ- was used as the zeolite to be treated.
The experiment was performed in the same manner except that 154tz was used. Mo-supported zeolite MTZ-15 thus obtained
Table 3 shows the physical properties of 4tz.
【００４７】実施例１６ 実施例１１において、被処理ゼオライトとして、ＴＺ−
１５４ｔ２を用いた以外は同様にして実験を行った。こ
のようにして得られたＭｏ担持ゼオライトＭＴＺ−１５
４ｔ２の物性を表３に示す。Example 16 In Example 11, TZ- was used as the zeolite to be treated.
The experiment was performed in the same manner except that 154t2 was used. Mo-supported zeolite MTZ-15 thus obtained
Table 3 shows the physical properties of 4t2.
【００４８】実施例１７ 実施例１１において、被処理ゼオライトとして、ｔＴＺ
−１５０を用いた以外は同様にして実験を行った。この
ようにして得られたＭｏ担持ゼオライトＭｔＴＺ−１５
０の物性を表３に示す。Example 17 In Example 11, tTZ was used as the zeolite to be treated.
The experiment was performed in the same manner except that -150 was used. The Mo-supported zeolite MtTZ-15 thus obtained
Table 3 shows the physical properties of No. 0.
【００４９】比較例１ 実施例１１において、被処理ゼオライトとして、ＴＺ−
４４、４５を用いた以外は同様にして実験を行った。こ
のようにして得られたＭｏ担持ゼオライトＭＴＺ−４
４、４５の物性を表３に示す。Comparative Example 1 In Example 11, TZ- was used as the zeolite to be treated.
The experiment was performed in the same manner except that 44 and 45 were used. Mo-supported zeolite MTZ-4 thus obtained
Table 3 shows the physical properties of Nos. 4 and 45.
【００５０】比較例２ 実施例１１において、被処理ゼオライトとして、ＴＺ−
２８−１を用いた以外は同様にして実験を行った。この
ようにして得られたＭｏ担持ゼオライトＭＴＺ−２８−
１の物性を表３に示す。Comparative Example 2 In Example 11, TZ- was used as the zeolite to be treated.
An experiment was performed in the same manner except that 28-1 was used. Mo-supported zeolite MTZ-28- thus obtained
Table 3 shows the physical properties of No. 1.
【００５１】比較例３ 実施例１１において、被処理ゼオライトとして、ＴＺ−
５２を用いた以外は同様にして実験を行った。このよう
にして得られたＭｏ担持ゼオライトＭＴＺ−５２の物性
を表３に示す。Comparative Example 3 In Example 11, TZ- was used as the zeolite to be treated.
The experiment was performed in the same manner except that 52 was used. Table 3 shows the physical properties of the Mo-supported zeolite MTZ-52 thus obtained.
【００５２】比較例４ 実施例１１において、被処理ゼオライトとして、ＴＺ−
３９を用いた以外は同様にして実験を行った。このよう
にして得られたＭｏ担持ゼオライトＭＴＺ−３９の物性
を表３に示す。Comparative Example 4 In Example 11, TZ- was used as the zeolite to be treated.
The experiment was performed in the same manner except that 39 was used. Table 3 shows the physical properties of the Mo-supported zeolite MTZ-39 thus obtained.
【００５３】比較例１ 実施例１１において、被処理ゼオライトとして、ＴＺ−
３８を用いた以外は同様にして実験を行った。このよう
にして得られたＭｏ担持ゼオライトＭＴＺ−３８の物性
を表３に示す。Comparative Example 1 In Example 11, TZ- was used as the zeolite to be treated.
The experiment was performed in the same manner except that 38 was used. Table 3 shows the physical properties of the Mo-supported zeolite MTZ-38 thus obtained.
【００５４】[0054]
【表３】 [Table 3]
【００５５】実施例１８〜３５、比較例６〜１５（重質
物の水素化分解） アラビアンヘビー常圧残油（ＡＲ）１０ｇと触媒として
前記Ｍｏ複合化修飾ゼオライト１ｇを内容積１４０ｍｌ
のオートクレーブに仕込み、水素を初期充填圧力＝９．
８ＭＰａ、反応温度４１０℃、６時間の条件で反応を実
施した。反応終了後、内容物を取りだしＴＣＤガスクロ
マトグラフ（Hewlett Packard/AC社製）により、Ｈ2、
ガス状炭化水素、Ｈ2Ｓを同時に分析した。反応処理油
は二硫化炭素で希釈し触媒と分離し、高温蒸留ガスクロ
（Hewlett Packard/AC社製）を用いて高沸点留分（常圧
換算７５０℃）までの蒸留性状および留分得率を測定、
算出した。残存するアスファルテン分はヘプタン不溶解
分として求めた。常圧残油（ＡＲ）（３４３℃＋）の転
化率、ガス（Ｃ1〜Ｃ4）収率、アスファルテン転化率、
各留分（ナフサ、灯油、軽由）得率などを算出して各触
媒の性能を評価した。その結果を表４に示す。Examples 18 to 35, Comparative Examples 6 to 15 (Hydrolysis of Heavy Substances) 10 g of Arabian Heavy Atmospheric Residue (AR) and 1 g of the above Mo-modified modified zeolite as a catalyst were used as a catalyst in an internal volume of 140 ml.
And charged with hydrogen at an initial filling pressure of 9.
The reaction was performed under the conditions of 8 MPa, a reaction temperature of 410 ° C., and 6 hours. After the completion of the reaction, the contents were taken out and analyzed by TCD gas chromatography (manufactured by Hewlett Packard / AC) for H 2 ,
Gaseous hydrocarbons and H 2 S were analyzed simultaneously. The reaction oil is diluted with carbon disulfide and separated from the catalyst. The distillation properties and fraction yield up to a high-boiling fraction (normal pressure reduced to 750 ° C) are determined using a high-temperature distillation gas chromatograph (manufactured by Hewlett Packard / AC). Measurement,
Calculated. The remaining asphaltenes were determined as heptane insolubles. Atmospheric pressure residue (AR) (343 ° C. +) conversion, gas (C 1 -C 4 ) yield, asphaltene conversion,
The yield of each fraction (naphtha, kerosene, light) was calculated to evaluate the performance of each catalyst. Table 4 shows the results.
【００５６】[0056]
【表４】 [Table 4]
【００５７】実施例３６ 各種触媒を用いて常圧残油（ＡＲ）を水素化分解した。
この場合、その条件としては、実施例１８の場合と同じ
条件、即ち、触媒／油比＝０．１、温度＝４１０℃、水
素初期充填圧力＝９．８ＭＰａを用いた。前記ＡＲの水
素化分解反応において、そのガス（Ｃ1〜Ｃ4）とナフサ
の合計収率（％）と、触媒の固体酸強度（ｍｍｏｌ／
ｇ）との関係を調べた。その結果を表５に示す。また、
ＡＲ転化率＝５０％に達するまでの反応時間（ｈｒ）
と、触媒の固体酸強度（ｍｍｏｌ／ｇ）との関係を調べ
た。その結果を表６に示す。Example 36 Atmospheric residue (AR) was hydrocracked using various catalysts.
In this case, the same conditions as in Example 18 were used, that is, the catalyst / oil ratio = 0.1, the temperature = 410 ° C., and the hydrogen initial charging pressure = 9.8 MPa. In the hydrogenolysis reaction of the AR, the total yield (%) of the gas (C 1 to C 4 ) and naphtha and the solid acid strength of the catalyst (mmol /
g) was examined. Table 5 shows the results. Also,
AR conversion time = reaction time until reaching 50% (hr)
And the solid acid strength (mmol / g) of the catalyst were examined. Table 6 shows the results.
【００５８】[0058]
【表５】 [Table 5]
【００５９】[0059]
【表６】 [Table 6]
【００６０】前記表中に示した触媒の具体的内容は以下
のとおりである。 （１）触媒Ａ 実施例３０で示したＭＴＺ−１５４ｔ２ （２）触媒Ｂ 比較例１１で示したＭＴＺ−５２ （３）触媒Ｃ 比較例２で示したＭＴＺ−２８−１The specific contents of the catalysts shown in the above table are as follows. (1) Catalyst A MTZ-154t2 shown in Example 30 (2) Catalyst B MTZ-52 shown in Comparative Example 11 (3) Catalyst C MTZ-28-1 shown in Comparative Example 2
【００６１】表５及び表６の結果からわかるように、本
発明の触媒の場合、その活性は高く、高められた水素化
分解速度を与えると共に、反応選択性に優れ、その（ガ
ス＋ナフサ）収率は低いという特徴を有する。As can be seen from the results in Tables 5 and 6, in the case of the catalyst of the present invention, its activity is high, it gives an increased hydrocracking rate, it has excellent reaction selectivity, and its (gas + naphtha) It is characterized by low yield.
【００６２】[0062]
【発明の効果】本発明のゼオライトは、反応場として有
利に作用するメソポアを非常に多く含有するとともに、
固体酸触媒として作用する適切な固体酸強度を有する。
従って、本発明のゼオライトは、固体酸触媒として有用
であると同時に、触媒担体としてすぐれたもので、これ
に所望の触媒金属を担持させることにより、固体酸触媒
としての機能を有する種々の触媒を得ることができる。
本発明のゼオライトは、特に水素化処理用触媒担体とし
て有用であり、これに難還元性金属酸化物を複合化さ
せ、それに水素化活性金属種を担持させることにより、
反応活性及び反応選択性において高められた水素化処理
用触媒を得ることができる。The zeolite of the present invention contains a very large amount of mesopores which advantageously act as a reaction field,
It has the appropriate solid acid strength to act as a solid acid catalyst.
Therefore, the zeolite of the present invention is useful as a solid acid catalyst and at the same time, is excellent as a catalyst carrier.By supporting a desired catalyst metal on the zeolite, various types of catalysts having a function as a solid acid catalyst can be obtained. Obtainable.
The zeolite of the present invention is particularly useful as a catalyst support for hydrotreating, by complexing a non-reducible metal oxide with it and supporting a hydrogenation active metal species on it.
It is possible to obtain a hydrotreating catalyst having enhanced reaction activity and reaction selectivity.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｃ１０Ｇ 47/16 Ｃ１０Ｇ 47/16 (72)発明者 荒木 泰博 東京都港区虎ノ門４丁目３番９号 財団法 人石油産業活性化センター内 (72)発明者 島田 広道 茨城県つくば市東１−１ 経済産業省産業 技術総合研究所物質工学工業技術研究所内 Ｆターム(参考） 4G069 AA01 AA03 AA12 BA04A BA05A BA07A BA07B BA45A BB04A BB04B BC16A BC16B BC59A BC59B CC05 EC03Y EC04Y EC06X EC06Y EC14X EC14Y EC15X EC15Y EC18X EC18Y EC27 FC08 ZA01A ZA05A ZA05B ZC04 ZD06 ZE03 ZE04 ZF05A ZF05B 4G073 BA20 BA21 BA29 BA30 BA40 BA44 BA45 BA46 BA57 BA87 BB24 BD15 CZ06 DZ02 FA14 FA15 FA30 FB07 FB26 FC13 FC18 UA01 UA02 4H029 CA00 DA00 ──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. 7 Identification symbol FI Theme court ゛ (Reference) C10G 47/16 C10G 47/16 (72) Inventor Yasuhiro Araki 4-3-9 Toranomon, Minato-ku, Tokyo Foundation (72) Inventor Hiromichi Shimada 1-1, Higashi, Tsukuba, Ibaraki Prefecture F-term (Reference) 4M069 AA01 AA03 AA12 BA04A BA05A BA07A BA07B BA45A BB04A BB04B BC16A BC16B BC59A BC59B CC05 EC03Y EC04Y EC06X EC06Y EC14X EC14Y EC15X EC15Y EC18X EC18Y EC27 FC08 ZA01A ZA05A ZA05B ZC04 ZD06 ZE03 ZE04 ZF05A ZF05B 4BA07BA18 BA18BA30BA18 BA18BA30BA18 UA01 UA02 4H029 CA00 DA00
Claims (10)
ｌ］／［Ｓｉ］が０．０１〜０．２の範囲にあり、細孔
直径が５０〜１０００Åのメソポアの容積割合が３０〜
５０％の範囲にあり、かつ該メソポアの容積が０．１４
ｃｃ／ｇ以上であり、さらに、全アルミニウム原子に対
する４配位アルミニウム原子の割合が２５原子％以上で
あることを特徴とするメソポア含量の大きいゼオライ
ト。An atomic ratio of aluminum to silicon [A
l] / [Si] is in the range of 0.01 to 0.2, and the volume ratio of mesopores having a pore diameter of 50 to 1000 ° is 30 to
50% and the mesopore volume is 0.14
A zeolite having a large mesopore content, wherein the zeolite has a cc / g or more and a ratio of tetracoordinate aluminum atoms to all aluminum atoms is 25 at% or more.
容積割合が２０〜４０％である請求項１のゼオライト。2. The zeolite according to claim 1, wherein the volume fraction of mesopores having a pore diameter of 100 to 500 ° is 20 to 40%.
金属酸化物が複合化されている請求項１又は２のゼオラ
イト。3. The zeolite according to claim 1, wherein said mesopore has an inner surface in which an ultrafine refractory metal oxide is complexed.
０重量％である請求項１〜３のいずれかのゼオライト。4. The content of said hardly reducible metal oxide is from 1 to 1.
The zeolite according to any one of claims 1 to 3, which is 0% by weight.
又はジルコニアからなる請求項１〜４のいずれかのゼオ
ライト。5. The method according to claim 1, wherein the hardly reducible metal oxide is titania and / or
5. The zeolite according to claim 1, which is made of zirconia.
らなる触媒担体。6. A catalyst carrier comprising the zeolite according to claim 1.
らなる固体酸触媒。7. A solid acid catalyst comprising the zeolite according to claim 1.
担持させてなる水素化処理用触媒。8. A hydrotreating catalyst obtained by supporting a hydrogenation active metal on the catalyst carrier according to claim 6.
素化分解する方法において、該触媒として請求項８の水
素化処理用触媒を用いることを特徴とする重質油の水素
化分解方法。9. A method for hydrocracking heavy oil with a hydrotreating catalyst in the presence of a hydrotreating catalyst, wherein the hydrotreating catalyst according to claim 8 is used as the catalyst. Disassembly method.
イト中のアルミニウムとケイ素との原子比［Ａｌ］／
［Ｓｉ］が０．０１〜０．１の範囲にあり、かつ該ゼオ
ライト中の全アルミニウム原子に対する４配位アルミニ
ウム原子の割合が２５原子％以上である請求項９の方
法。10. The atomic ratio [Al] / aluminum / silicon in the zeolite constituting the hydrotreating catalyst.
10. The method according to claim 9, wherein [Si] is in the range of 0.01 to 0.1, and the ratio of tetracoordinate aluminum atoms to all aluminum atoms in the zeolite is 25 atomic% or more.
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