JP2920238B2 - Catalyst for hydrocracking of hydrocarbon oils - Google Patents
Catalyst for hydrocracking of hydrocarbon oilsInfo
- Publication number
- JP2920238B2 JP2920238B2 JP4357866A JP35786692A JP2920238B2 JP 2920238 B2 JP2920238 B2 JP 2920238B2 JP 4357866 A JP4357866 A JP 4357866A JP 35786692 A JP35786692 A JP 35786692A JP 2920238 B2 JP2920238 B2 JP 2920238B2
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- weight
- pore diameter
- hydrocracking
- alumina
- 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.)
- Expired - Lifetime
Links
- 239000003054 catalyst Substances 0.000 title claims description 60
- 239000003921 oil Substances 0.000 title claims description 27
- 238000004517 catalytic hydrocracking Methods 0.000 title claims description 21
- 239000004215 Carbon black (E152) Substances 0.000 title claims description 7
- 229930195733 hydrocarbon Natural products 0.000 title claims description 7
- 150000002430 hydrocarbons Chemical class 0.000 title claims description 7
- 239000011148 porous material Substances 0.000 claims description 83
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 19
- 229910052751 metal Inorganic materials 0.000 claims description 18
- 239000002184 metal Substances 0.000 claims description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- 238000009826 distribution Methods 0.000 claims description 12
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 9
- 229910052753 mercury Inorganic materials 0.000 claims description 9
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 description 31
- 229910004298 SiO 2 Inorganic materials 0.000 description 14
- 230000000694 effects Effects 0.000 description 13
- 239000007789 gas Substances 0.000 description 11
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 10
- 239000002002 slurry Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 6
- 238000005984 hydrogenation reaction Methods 0.000 description 5
- 239000004115 Sodium Silicate Substances 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 4
- 229910052911 sodium silicate Inorganic materials 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 3
- 239000004327 boric acid Substances 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 description 2
- RGHNJXZEOKUKBD-SQOUGZDYSA-N Gluconic acid Natural products OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 239000002253 acid Substances 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
- 238000009835 boiling Methods 0.000 description 2
- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical compound CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000000174 gluconic acid Substances 0.000 description 2
- 235000012208 gluconic acid Nutrition 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 238000004898 kneading 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
- 230000000737 periodic effect Effects 0.000 description 2
- 229910001388 sodium aluminate Inorganic materials 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 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
- 239000010779 crude oil Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000004231 fluid catalytic cracking Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007327 hydrogenolysis reaction Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052976 metal sulfide Chemical class 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 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
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000002459 porosimetry Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Landscapes
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は炭化水素油の水素化分解
用触媒に関するもので詳しくは特定の担体に水素化活性
金属を担持させた触媒であって、減圧炭化水素油を効率
よく水素化分解して軽質油に転化せしめることのできる
触媒に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a catalyst for the hydrocracking of hydrocarbon oils, and more particularly to a catalyst having a hydrogenation active metal supported on a specific carrier. The present invention relates to a catalyst which can be decomposed and converted into light oil.
【０００２】[0002]
【従来の技術】最近の石油類の需要は軽質化傾向にあ
り、ガソリン、ナフサに関しては流動的接触分解によっ
て増産を図ることは可能であるが、中間留分と呼ばれる
灯油、軽油留分は流動接触分解では好ましいものが得ら
れず、減圧軽油を水素化分解する方法が用いられてい
る。ところで、減圧軽油の水素化分解は高温、高圧下
で、原料油を触媒と接触させ、目的の留分を得るが、そ
のため反応条件と触媒の選定は重要である。例えば、転
化率を上げるには、反応条件をより厳しくするか、固体
酸性の強いゼオライト系担体に水素化活性金属種を担持
した触媒を用いればよいが、該触媒を用いて反応せしめ
ると転化率は高くなるがガスやナフサが生成し、中間留
分の選択率が悪くなるという欠点がある。また、アルミ
ナ、シリカ−アルミナ、ボリア−アルミナ等の担体に水
素化活性金属種を担持した触媒では中間留分の選択率は
高いといわれているが、転化率が低いという欠点があ
る。2. Description of the Related Art The demand for petroleum has recently become lighter, and it is possible to increase the production of gasoline and naphtha by fluid catalytic cracking. However, kerosene and gas oil fractions called middle distillates are The catalytic cracking does not provide a preferable product, and a method of hydrocracking the vacuum gas oil is used. By the way, in the hydrocracking of reduced pressure gas oil, a raw oil is brought into contact with a catalyst at a high temperature and a high pressure to obtain a target fraction. Therefore, the reaction conditions and the selection of the catalyst are important. For example, in order to increase the conversion, the reaction conditions may be stricter or a catalyst in which a hydrogenation active metal species is supported on a zeolite-based carrier having a strong solid acidity may be used. However, gas and naphtha are generated, and the selectivity of the middle distillate is deteriorated. Further, catalysts in which a hydrogenation-active metal species is supported on a carrier such as alumina, silica-alumina, and boria-alumina are said to have a high selectivity for the middle distillate, but have a drawback of low conversion.
【０００３】本発明者は先願（特願平３−３３４，４５
７号公報）で水素化処理用触媒の固体酸性に着目し、ゼ
オライトより固体酸性の酸点は弱いが、酸量を多く有す
るＢ2 Ｏ3 として３〜１０重量％とＳｉＯ2 として４〜
１９重量％と残量がＡｌ2 Ｏ3 から成るボリア−シリカ
−アルミナ組成物担体を見出だしたが、さらに本発明で
は水素化分解用触媒として好適な担体組成と触媒の細孔
特性を検討することにより、転化率を高め且つ中間留分
の選択性を向上させるのに適したボリア−シリカ−アル
ミナ担体組成と触媒の細孔特性を見出だし、本発明に到
達したものである。The present inventor has filed a prior application (Japanese Patent Application No. 3-334,45).
No. 7), paying attention to the solid acidity of the hydrotreating catalyst, the solid acidic acid point is weaker than that of zeolite, but 3 to 10% by weight as B 2 O 3 having a larger amount of acid and 4 to 4 as SiO 2 .
A boria-silica-alumina composition carrier having a residual amount of 19% by weight of Al 2 O 3 has been found. In the present invention, a carrier composition suitable as a hydrocracking catalyst and pore characteristics of the catalyst are examined. As a result, a boria-silica-alumina carrier composition and a pore characteristic of a catalyst suitable for increasing the conversion and improving the selectivity of the middle distillate have been found, and have reached the present invention.
【０００４】[0004]
【発明が解決しようとする課題】本発明は炭化水素油
類、特に減圧軽油に対して転化率が高く、しかも中間留
分の選択性を向上させた水素化分解用触媒を提供するこ
とを目的とする。SUMMARY OF THE INVENTION It is an object of the present invention to provide a hydrocracking catalyst which has a high conversion rate with respect to hydrocarbon oils, particularly vacuum gas oil, and has improved selectivity for middle distillates. And
【０００５】[0005]
【課題を解決するための手段】本発明者は前記の目的を
達成するため鋭意検討を行った結果、本発明は、Ｂ2Ｏ
3 として５〜１０重量％とＳｉＯ2 として１０〜１５重
量％と残量がＡｌ2 Ｏ3 から成るボリアとシリカとアル
ミナ担体に周期律表第６族金属および第８族金属に属す
る水素化活性金属を担持し、細孔特性が水銀圧入法で測
定分布で平均細孔直径が９０〜１２０Åであり、平均細
孔直径±１０Åの細孔が占める容積が細孔直径２０〜９
７，０００Åの細孔容積に対する割合が６０％以上であ
る炭化水素油の水素化分解用触媒であることを特徴とす
る。The present inventors have conducted intensive studies to achieve the above object, and as a result, the present invention has found that B 2 O
5 to 10% by weight as 3 and 10 to 15% by weight as SiO 2 , and a hydrogenation activity belonging to Group 6 and Group 8 metals of the periodic table on a boria, silica, and alumina carrier having a balance of Al 2 O 3. A metal is supported, and the pore characteristics have a mean pore diameter of 90 to 120 ° in a distribution measured by a mercury intrusion method, and the volume occupied by pores having a mean pore diameter of ± 10 ° is a pore diameter of 20 to 9 °.
The catalyst is characterized in that it is a catalyst for hydrocracking hydrocarbon oil having a ratio of not less than 60% to a pore volume of 7,000 °.
【０００６】[0006]
【作用】本発明のボリアとシリカとアルミナから成る担
体を製造する方法としては、特願平３−３３４，４５７
号公報記載の製造方法により得ることができるが、例え
ば硫酸アルミニウム水溶液とアルミン酸ナトリウム水溶
液を混合し、加水分解して生成したアルミナ水和物スラ
リーに所定量の珪酸ナトリウム水溶液を添加して、濾過
・洗浄しシリカ−アルミナ水和物ケーキを得、該水和物
に所定量のホウ酸を添加し、成型可能な水分まで捏和し
て所望の形状に成型した後、乾燥し、次いで焼成するこ
とによりボリアとシリカとアルミナから成る担体を製造
することができる。尚、触媒の細孔特性を満足させるた
め前記捏和工程で硝酸・酢酸等を添加してもよい。本発
明の水素化分解触媒担体においてＢ２Ｏ３としての含量
を５〜１０重量％とし、ＳｉＯ２としての含量を１０〜
１５重量％とするのは、Ｂ２Ｏ３として５〜１０重量
％、ＳｉＯ２として１０〜１５重量％の範囲をはずれて
含有させると触媒の細孔特性が本発明の範囲に入らず、
水素化活性金属種を担持した触媒の水素化分解活性にお
いて、中間留分の選択性が劣るからである。The method for producing a carrier comprising boria, silica and alumina according to the present invention is disclosed in Japanese Patent Application No. 3-334457.
For example, an aqueous solution of aluminum sulfate and an aqueous solution of sodium aluminate are mixed, and a predetermined amount of an aqueous solution of sodium silicate is added to an alumina hydrate slurry produced by hydrolysis, followed by filtration. Washing to obtain a silica-alumina hydrate cake, adding a predetermined amount of boric acid to the hydrate, kneading to a formable water content to form a desired shape, drying, and then firing This makes it possible to produce a carrier composed of boria, silica and alumina. Incidentally, in order to satisfy the pore characteristics of the catalyst, nitric acid, acetic acid and the like may be added in the kneading step. In the hydrocracking catalyst carrier of the present invention, the content as B 2 O 3 is 5 to 10% by weight, and the content as SiO 2 is 10 to 10% by weight.
When the content is set to 15% by weight, if the content is out of the range of 5 to 10% by weight as B 2 O 3 and 10 to 15% by weight as SiO 2 , the pore characteristics of the catalyst do not fall within the range of the present invention.
This is because, in the hydrocracking activity of the catalyst supporting the hydrogenation active metal species, the selectivity of the middle distillate is inferior.
【０００７】本発明でいう水素化活性金属としては周期
律表第６族金属と第８族金属から選ばれる金属が用いら
れる。この第６族と第８族の金属は、併用することが必
要であり、どちらか一方のみの使用では本発明の目的を
達成することはできない。第６族に属する金属として
は、タングステンまたはモリブデンが好ましく、第８族
に属する金属としてはニッケルまたはコバルトを用いる
ことが好ましい。また金属の担持量は、特に制限はな
く、適宜定めればよいが、通常触媒中に酸化物換算で第
６族金属は１５〜２０重量％で第８族金属は３〜５重量
％程度担持することが望ましい。上記の活性金属の担持
方法は特に限定しないが、金属酸化物、金属硫化物の形
の溶液を担体に含浸法等の公知の方法で担持することが
できる。As the hydrogenation active metal in the present invention, a metal selected from Group 6 metals and Group 8 metals of the periodic table is used. The Group 6 and Group 8 metals must be used in combination, and the use of either one alone cannot achieve the object of the present invention. As the metal belonging to Group 6, tungsten or molybdenum is preferable, and as the metal belonging to Group 8, it is preferable to use nickel or cobalt. The amount of the metal carried is not particularly limited and may be appropriately determined. Usually, the amount of the Group 6 metal is about 15 to 20% by weight and the amount of the Group 8 metal is about 3 to 5% by weight in terms of oxide. It is desirable to do. The method for supporting the active metal is not particularly limited, but a solution in the form of a metal oxide or metal sulfide can be supported on a carrier by a known method such as impregnation.
【０００８】本発明の水素化分解用触媒は上述の如く調
製されるが、同時に水銀圧入法で測定した細孔分布で平
均細孔直径が９０〜１２０Åであり、平均細孔直径±１
０Åの細孔が占める容積が細孔直径２０〜９７，０００
Åの細孔容積に対する割合が６０％以上である細孔特性
を持つものであることが好ましい。平均細孔直径を９０
〜１２０Åの範囲にするのは減圧軽油の水素化分解反応
において高い転化率で、中間留分を多く得るために適し
た細孔径であり、平均細孔直径±１０Åの細孔が占める
容積が細孔直径２０〜９７，０００Åの細孔容積に対す
る割合が６０％以上にするのは、いわゆる触媒作用をす
るのに有効な細孔直径の細孔をできるだけ多く持つこと
で、水素化分解反応を長期間にわたって高活性が維持す
ることができるからである。また、触媒の平均細孔直径
±１０Åの細孔が占める容積が細孔直径２０〜９７，０
００Åの細孔容積に対する割合が６０％未満のとき、即
ち細孔が特定の範囲に集中していないときは、たとえ平
均細孔直径が９０〜１２０Åに入っていたとしても、触
媒作用する有用な細孔が減少するので水素化分解活性は
低下する。The hydrocracking catalyst of the present invention is prepared as described above, but has a mean pore diameter of 90 to 120 ° in the pore distribution measured by a mercury intrusion method, and a mean pore diameter of ± 1.
The volume occupied by 0 ° pores is pore diameter of 20 to 97,000.
It is preferable that Å has pore characteristics in which the ratio to the pore volume is 60% or more. Average pore diameter of 90
The range of about 120 ° is a pore diameter suitable for obtaining a large amount of middle distillate at a high conversion rate in the hydrocracking reaction of vacuum gas oil, and the volume occupied by pores having an average pore diameter of ± 10 ° is small. The reason why the ratio of the pore diameter of 20 to 97,000% to the pore volume is 60% or more is that the hydrocracking reaction is prolonged by having as many pores as possible having a pore diameter effective for so-called catalysis. This is because high activity can be maintained over a period. The volume occupied by pores having an average pore diameter of ± 10 ° of the catalyst is 20 to 97,0.
When the ratio of 00 ° to the pore volume is less than 60%, that is, when the pores are not concentrated in a specific range, even if the average pore diameter is in the range of 90 to 120 °, it is useful to catalyze. Hydrocracking activity is reduced due to reduced pores.
【０００９】本発明の炭化水素油とは、原油の常圧残
油、減圧残油、あるいはアスファルテン分を実質含まな
い常圧流出油、減圧流出油等が挙げられるが、本発明に
おいては減圧流出油のうち減圧軽油であり、沸点範囲３
６０〜５６０℃の留分が９０重量％以上含まれているも
のである。この減圧軽油中に含まれている硫黄分は約
２．０重量％程度であり、窒素分は約０．１重量％以下
である。触媒の評価は固定床流通装置を用い、水素化分
解の反応条件としては圧力５０〜１５０ｋｇ／ｃｍ2 Ｇ
で、温度３５０〜４５０℃で、水素／油供給比５００〜
２，０００Ｎｌ／ｌでＬＨＳＶ＝０．２〜１．５ｈｒ-1
である。次に、実施例等によって本発明を更に詳しく述
べる。The hydrocarbon oil of the present invention includes a normal pressure residual oil, a vacuum residual oil of a crude oil, a normal pressure spilled oil substantially free of asphaltenes, and a reduced pressure spilled oil. It is a vacuum gas oil among oils and has a boiling point range of 3
It contains 90% by weight or more of a fraction at 60 to 560 ° C. The sulfur content in the vacuum gas oil is about 2.0% by weight, and the nitrogen content is about 0.1% by weight or less. The catalyst was evaluated using a fixed bed flow system, and the reaction conditions for hydrocracking were pressures of 50 to 150 kg / cm 2 G
At a temperature of 350 to 450 ° C. and a hydrogen / oil supply ratio of 500 to
LHSV at 2,000 Nl / l = 0.2-1.5 hr -1
It is. Next, the present invention will be described in more detail with reference to examples and the like.
【００１０】[0010]
【実施例】実施例１ 内容積１００リットルの攪拌機付きステンレス製反応槽
に、水４９．５リットルと濃度５０％のグルコン酸溶液
２０４ｇ（加水分解で生成するＡｌ2 Ｏ3 に対して０．
０５重量％）を反応槽内に入れ、７０℃まで加温し保持
し、攪拌しながらＡｌ2 Ｏ3 として７７４ｇを含む硫酸
アルミニウム水溶液９５４０ｇとＡｌ2Ｏ3 として１２
７５ｇを含むアルミン酸ナトリウム水溶液６２３０ｇを
同時またはほぼ同時に全量滴下してｐＨ９．０のアルミ
ナ水和物スラリーを得た。次ぎに該スラリーを３０分間
熟成した後、濃度３１％の硝酸５０ｇを加えてｐＨ６．
３とし、次いでＳｉＯ2 として２５５を含むケイ酸ナト
リウム水溶液１８２０ｇを全量滴下してｐＨが８．８の
シリカ−アルミナ水和物を得た。該水和物を３０分間熟
成した後、Ｎａ2 Ｏとして０．１重量％以下、ＳＯ4 と
して０．５重量％以下になるまで濾過・洗浄して得られ
たシリカ−アルミナ−水和物ケーキ２５００ｇ（ＳｉＯ
2 −Ａｌ2 Ｏ3 として５００ｇ）にホウ酸４７ｇ（Ｂ2
Ｏ3 として２６．６ｇ）と濃度３１％の硝酸２５ｇを加
え、加温ジャケット付きニーダ中で加熱捏和し、Ｂ2 Ｏ
3 −ＳｉＯ2 −Ａｌ2 Ｏ3 濃度として６２重量％の可塑
性のある捏和物を得、次いでこの捏和物を直径１．５ｍ
ｍφのダイスを有する押出し成型機で成型し、乾燥後、
電気炉で８００℃で２時間焼成してＢ2 Ｏ3 として５重
量％、ＳｉＯ2 として１０．５重量％を含むボリア−シ
リカ−アルミナ担体を得た。 EXAMPLE 1 In a stainless steel reaction tank with a stirrer having an internal volume of 100 liters, 49.5 liters of water and 204 g of a 50% gluconic acid solution (0.2 g of Al 2 O 3 produced by hydrolysis) were added.
05% by weight) were placed in a reaction vessel, heated and held to 70 ° C., as with stirring Al 2 O 3 aqueous solution of aluminum sulfate 9540g and Al 2 O 3 containing 774g as 12
A total of 6230 g of an aqueous sodium aluminate solution containing 75 g was simultaneously or almost simultaneously added dropwise to obtain an alumina hydrate slurry having a pH of 9.0. Next, the slurry was aged for 30 minutes, and then 50 g of nitric acid having a concentration of 31% was added thereto to adjust the pH to 6.0.
Then, a total of 1820 g of an aqueous sodium silicate solution containing 255 as SiO 2 was added dropwise to obtain a silica-alumina hydrate having a pH of 8.8. After aging the hydrate for 30 minutes, the silica-alumina-hydrate cake obtained by filtering and washing until 0.1% by weight or less as Na 2 O and 0.5% by weight or less as SO 4 is obtained. 2500g (SiO
2 -Al 2 O 3 as 500 g) borate 47 g (B 2
O 3 as 26.6 g) and a 31% strength nitric acid 25g was added, and kneaded heated warming a jacketed kneader, B 2 O
3 -SiO 2 -Al 2 O 3 to obtain a 62% by weight of a thermoplastic having certain kneaded product as concentration, then the diameter 1.5m The kneaded product
Molded with an extrusion molding machine having a mφ die, dried,
It was calcined at 800 ° C. for 2 hours in an electric furnace to obtain a boria-silica-alumina support containing 5% by weight as B 2 O 3 and 10.5% by weight as SiO 2 .
【００１１】次いで、該担体１００ｇに三酸化モリブデ
ン２３．１ｇ、炭酸ニッケル６．７ｇを水５０ｍｌに懸
濁し、酒石酸２．０ｇを添加して加熱下で溶解し、担体
の吸水量に見合う液量に水で液量調節した含浸溶液に
て、含浸し１１０℃で１６時間乾燥して、５００℃で２
時間焼成してＭｏＯ3 として１８重量％、ＮｉＯとして
４重量％含む触媒Ａを得た。得られた触媒Ａについて水
銀圧入法で細孔分布を測定した結果平均細孔直径は９８
Åであり、平均細孔直径±１０Åの細孔が占める容積が
細孔直径２０〜９７，０００Åの細孔容積に対する割合
は６４％であった。Next, 23.1 g of molybdenum trioxide and 6.7 g of nickel carbonate are suspended in 50 ml of water, and 2.0 g of tartaric acid is added to 100 g of the carrier, dissolved under heating, and dissolved in an amount corresponding to the water absorption of the carrier. And then dried at 110 ° C. for 16 hours, and then dried at 500 ° C. for 2 hours.
Calcination was performed for 18 hours to obtain a catalyst A containing 18% by weight of MoO 3 and 4% by weight of NiO. As a result of measuring the pore distribution of the obtained catalyst A by a mercury intrusion method, the average pore diameter was 98.
And the ratio of the volume occupied by pores having an average pore diameter of ± 10 ° to the volume of pores having a pore diameter of 20 to 97,000 ° was 64%.
【００１２】次ぎに、触媒充填量１０ｍｌの固定床流通
型反応装置に触媒Ａを充填し、ジメチルジサルファイド
を２．５重量％添加したライトガスオイルで水素／油供
給３００Ｎｌ／ｌ、ＬＨＳＶ＝２．０ｈｒ-1、圧力３０
ｋｇ／ｃｍ2 Ｇの条件下１００℃から３１５℃まで７時
間かけて昇温し、保持して１６時間予備硫化した後沸点
範囲３６０〜５６０℃の留分が９０重量％以上ある減圧
軽油を用い圧力１００ｋｇ／ｃｍ2 Ｇ、水素／油供給比
１，５００Ｎｌ／ｌ、ＬＨＳＶ＝０．５ｈｒ-1、反応温
度３９５℃の反応条件で水素化分解反応を行い転化率、
中間留分収率について求めた結果それぞれ８４．５重量
％、４０．２重量％であった。Next, catalyst A was charged into a fixed bed flow type reactor having a catalyst loading amount of 10 ml, and hydrogen / oil supply was 300 Nl / l, LHSV = 2 with light gas oil containing 2.5% by weight of dimethyl disulfide. 0.0 hr -1 , pressure 30
The temperature was raised from 100 ° C. to 315 ° C. over 7 hours under the condition of kg / cm 2 G, held and presulfurized for 16 hours, and then a vacuum gas oil having a fraction in the boiling range of 360 to 560 ° C. of 90% by weight or more was used. The hydrocracking reaction was carried out under the reaction conditions of a pressure of 100 kg / cm 2 G, a hydrogen / oil supply ratio of 1,500 Nl / l, an LHSV of 0.5 hr −1 and a reaction temperature of 395 ° C.
The results obtained for the middle distillate yield were 84.5% by weight and 40.2% by weight, respectively.
【００１３】実施例２ 実施例１で得たシリカ−アルミナ水和物ケーキに添加す
るホウ酸の添加量をＳｉＯ2 −Ａｌ2 Ｏ3 に対して、Ｂ
2 Ｏ3 として１０重量％になるように加えたこと以外実
施例１に示す触媒Ａを得る方法とほぼ同様の方法で触媒
Ｂを得、次いで実施例１に示す水素化分解反応方法とほ
ぼ同様の方法で活性評価した。得られた触媒Ｂについて
水銀圧入法で細孔分布を測定した結果は平均細孔直径は
９４Åであり、平均細孔直径±１０Åの細孔が占める容
積が細孔直径２０〜９７，０００Åの細孔容積に対する
割合は６２％であり、活性評価した結果は転化率は８
６．２重量％中間留分収率は３７．４重量％であった。[0013] Silica was obtained in Example 1 - the amount of boric acid added to the alumina hydrate cake with respect to SiO 2 -Al 2 O 3, B
A catalyst B was obtained in substantially the same manner as that for obtaining the catalyst A shown in Example 1, except that it was added so as to become 10% by weight as 2 O 3 , and then substantially the same as the hydrocracking reaction method shown in Example 1. The activity was evaluated by the following method. As a result of measuring the pore distribution of the obtained catalyst B by a mercury intrusion method, the average pore diameter was 94 °, and the volume occupied by pores having an average pore diameter of ± 10 ° was 20 to 97,000 °. The ratio to the pore volume was 62%, and the result of activity evaluation was that the conversion was 8%.
The 6.2% by weight middle distillate yield was 37.4% by weight.
【００１４】実施例３ 実施例１とほぼ同様にして得たアルミナ水和物スラリー
に添加するケイ酸ナトリウム水溶液の添加量をアルミナ
水和物スラリー中のＡｌ2 Ｏ3 に対して、ＳｉＯ2 とし
て１５重量％になるように添加したこと以外実施例１に
示す触媒Ａを得る方法とほぼ同様の方法で触媒Ｃを得、
次いで、実施例１に示す水素化分解反応方法とほぼ同様
の方法で活性評価した。得られた触媒Ｃについて水銀圧
入法で細孔分布を測定した結果は、平均細孔直径は１０
８Åであり、平均細孔直径±１０Åの細孔が占める容積
が細孔直径２０〜９７，０００Åの細孔容積に対する割
合は６０％であり、活性評価した結果は転化率は８８．
６重量％、中間留分収率は３８．５重量％であった。 Example 3 The amount of the aqueous sodium silicate solution added to the alumina hydrate slurry obtained in substantially the same manner as in Example 1 was calculated as SiO 2 with respect to Al 2 O 3 in the alumina hydrate slurry. A catalyst C was obtained in substantially the same manner as the method for obtaining the catalyst A shown in Example 1, except that the catalyst C was added so as to be 15% by weight.
Next, the activity was evaluated by a method substantially similar to the hydrocracking reaction method shown in Example 1. As a result of measuring the pore distribution of the obtained catalyst C by a mercury intrusion method, the average pore diameter was 10%.
The volume occupied by pores having an average pore diameter of ± 10 ° is 60% of the volume of pores having a pore diameter of 20 to 97,000 °.
6% by weight, and the middle distillate yield was 38.5% by weight.
【００１５】比較例１ 反応槽内にグルコン酸を添加しなかったこと以外実施例
１に示す触媒Ａを得る方法とほぼ同様の方法で触媒Ｄを
得、次いで実施例１に示す水素化分解反応方法とほぼ同
様の方法で活性評価した。得られた触媒Ｄについて水銀
圧入法で細孔分布を測定した結果は、平均細孔直径は１
０６Åであり、平均細孔直径±１０Åの細孔が占める容
積が細孔直径２０〜９７，０００Åの細孔容積に対する
割合は５２％であり、活性評価した結果は転化率は７
４．８重量％、中間留分収率は２８．７重量％であっ
た。触媒Ｄはボリア−シリカ−アルミナから成る担体の
組成は本発明の範囲内ではあるが、触媒の平均細孔直径
±１０Åの細孔が占める容積が細孔直径２０〜９７，０
００Åの細孔容積に対する割合が低い、つまり細孔分布
が広い触媒であり、実施例１に示す触媒Ａと比べ転化率
および中間留分収率が共に劣っていることが明らかであ
る。 Comparative Example 1 A catalyst D was obtained in substantially the same manner as that for obtaining the catalyst A shown in Example 1 except that gluconic acid was not added to the reactor, and then a hydrocracking reaction shown in Example 1 was carried out. The activity was evaluated in almost the same manner as described above. As a result of measuring the pore distribution of the obtained catalyst D by a mercury intrusion method, the average pore diameter was 1
06%, the ratio of the volume occupied by pores having an average pore diameter of ± 10 ° to the volume of pores having a pore diameter of 20 to 97,000 ° is 52%, and the result of activity evaluation shows that the conversion rate is 7%.
4.8% by weight and the middle distillate yield was 28.7% by weight. Catalyst D has a composition of a support composed of boria-silica-alumina within the scope of the present invention, but the volume occupied by pores having an average pore diameter of ± 10 ° of the catalyst has a pore diameter of 20 to 97,0.
It is clear that the catalyst has a low ratio to the pore volume of 00 °, that is, a catalyst having a wide pore distribution, and is inferior in both the conversion and the middle distillate yield as compared with the catalyst A shown in Example 1.
【００１６】比較例２ 実施例１とほぼ同様にして得たシリカ−アルミナ水和物
ケーキに添加するホウ酸の添加量をＳｉＯ2 −Ａｌ2 Ｏ
3 に対してＢ2 Ｏ3 として２重量％になるように加えた
こと以外実施例１に示す触媒Ａを得る方法とほぼ同様の
方法で触媒Ｅを得、次いで実施例１に示す水素化分解反
応方法とほぼ同様の方法で活性評価した。得られた触媒
Ｅについて水銀圧入法で細孔分布を測定した結果は、平
均細孔直径は１００Åであり、平均細孔直径±１０Åの
細孔が占める容積が細孔直径２０〜９７，０００Åの細
孔容積に対する割合は６５％であり、活性評価した結果
は転化率は７６．７重量％、中間留分収率は３１．１重
量％であった。触媒Ｅは細孔特性が本発明の範囲内であ
ってもボリア−シリカ−アルミナから成る担体のＢ2 Ｏ
3 含有量が少ない触媒であり、実施例１の触媒Ａと比
べ、転化率および中間留分収率共に低いことが判る。 Comparative Example 2 The amount of boric acid added to the silica-alumina hydrate cake obtained in substantially the same manner as in Example 1 was changed to SiO 2 —Al 2 O
Obtain catalyst E in substantially the same manner as obtaining the catalyst A in Example 1 except for the addition to be a B 2 O 3 to 2 wt% relative to 3, then hydrogenolysis in Example 1 The activity was evaluated by a method substantially similar to the reaction method. As a result of measuring the pore distribution of the obtained catalyst E by a mercury intrusion method, the average pore diameter was 100 °, and the volume occupied by pores having an average pore diameter of ± 10 ° was 20 to 97,000 °. The ratio to the pore volume was 65%, and as a result of activity evaluation, the conversion was 76.7% by weight, and the middle distillate yield was 31.1% by weight. Catalyst E has a B 2 O support of boria-silica-alumina even though the pore properties are within the scope of the present invention.
3 It is a catalyst having a small content, and it is found that both the conversion and the middle distillate yield are lower than that of the catalyst A of Example 1.
【００１７】比較例３ 実施例１とほぼ同様にして得たアルミナ水和物スラリー
に添加するケイ酸ナトリウム水溶液の添加量をアルミナ
水和物スラリー中のＡｌ2 Ｏ3 に対してＳｉＯ2 として
５重量％、２０重量％となるように添加したこと以外実
施例１に示す触媒Ａを得る方法とほぼ同様の方法で触媒
Ｆ，Ｇを得、次いで実施例１に示す水素化分解反応方法
とほぼ同様の方法で活性評価した。得られた触媒Ｆ，Ｇ
について水銀圧入法で細孔分布を測定した結果は、平均
細孔直径はそれぞれ１０２Å，１１４Åであり、平均細
孔直径±１０Åの細孔が占める容積が細孔直径２０〜９
７，０００Åの細孔容積に対する割合はそれぞれ６７
％，４５％であり、活性評価した結果は触媒Ｆの転化率
は６９．４重量％、中間留分収率は２６．６重量％であ
り、触媒Ｇの転化率は９０．０重量％，中間留分収率は
２４．３重量％であった。 Comparative Example 3 The amount of the aqueous sodium silicate solution to be added to the alumina hydrate slurry obtained in substantially the same manner as in Example 1 was 5 as SiO 2 with respect to Al 2 O 3 in the alumina hydrate slurry. Catalysts F and G were obtained in substantially the same manner as in the method for obtaining Catalyst A shown in Example 1, except that they were added so as to be 20% by weight and 20% by weight, respectively. Activity was evaluated in the same manner. Catalysts F and G obtained
As a result of measuring the pore distribution by mercury porosimetry, the average pore diameter was 102 ° and 114 °, respectively, and the volume occupied by pores having an average pore diameter of ± 10 ° was 20 to 9
The ratio to the pore volume of 7,000 ° is 67
%, 45%, and the activity was evaluated. The conversion of Catalyst F was 69.4% by weight, the yield of middle distillate was 26.6% by weight, the conversion of Catalyst G was 90.0% by weight, The middle distillate yield was 24.3% by weight.
【００１８】触媒Ｆは細孔特性が本発明の範囲内ではあ
るが、ボリア−シリカ−アルミナから成る担体のＳｉＯ
2 含有量が少ない触媒であり、実施例１の触媒Ａと比べ
転化率および中間留分収率共に劣っていることが明らか
で、触媒Ｇは平均細孔直径±１０Åの細孔が占める容積
が細孔直径２０〜９７，０００Åの細孔容積に対する割
合が低い、つまり触媒の細孔分布が広く、またボリア−
シリカ−アルミナから成る担体のＳｉＯ2 含有量が多い
本発明の範囲外の触媒であり、実施例３の触媒Ｃと比べ
転化率は同等ではあるが、中間留分収率が著しく低いこ
とが判る。このように、本発明に係る実施例１〜３の触
媒は比較例１〜３と比較して高い転化率が得られるのと
同時に、中間留分の選択率も優れていることが明らかで
ある。The catalyst F has a pore characteristic within the scope of the present invention, but has a support composed of a boria-silica-alumina SiO 2 support.
2 It is clear that the catalyst has a low content and is inferior in both conversion rate and middle distillate yield as compared with catalyst A of Example 1, and catalyst G has a volume occupied by pores having an average pore diameter of ± 10 °. The ratio of the pore diameter to the pore volume of 20 to 97,000 ° is low, that is, the pore distribution of the catalyst is wide, and
It is a catalyst outside the range of the present invention in which the support composed of silica-alumina has a large SiO 2 content, and the conversion is the same as that of the catalyst C of Example 3, but the middle distillate yield is remarkably low. . As described above, it is clear that the catalysts of Examples 1 to 3 according to the present invention can obtain a high conversion as compared with Comparative Examples 1 to 3, and at the same time, have excellent selectivity of the middle distillate. .
【００１９】[0019]
【発明の効果】以上に示した本発明の水素化分解用触媒
によれば、炭化水素油類、特に減圧軽油の水素化分解反
応において高い転化率で、しかも中間留分を多く得るこ
とができる。According to the above-described hydrocracking catalyst of the present invention, a high conversion rate and a large amount of middle distillate can be obtained in the hydrocracking reaction of hydrocarbon oils, particularly vacuum gas oil. .
Claims (1)
して１０〜１５重量％、残量がアルミナからなるボリア
とシリカとアルミナから成る担体に、周期律表第６族金
属及び第８族金属に属する水素化活性金属を担持し、細
孔特性が水銀圧入法で測定した細孔分布で平均細孔直径
が９０〜１２０Åであり、平均細孔直径±１０Åの細孔
が占める容積が細孔直径２０〜９７，０００Åの細孔容
積に対する割合が６０％以上であることを特徴とする炭
化水素油の水素化分解用触媒。1 to 10% by weight of boria, 10 to 15% by weight of silica, and a balance of boria comprising alumina and a carrier comprising silica and alumina; The hydrogenation-active metal belongs to, and the average pore diameter in the pore distribution is 90 to 120 ° in the pore distribution measured by the mercury intrusion method, and the volume occupied by pores having an average pore diameter of ± 10 ° is the pore diameter. A catalyst for hydrocracking hydrocarbon oils, wherein a ratio to a pore volume of 20 to 97,000 ° is 60% or more.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4357866A JP2920238B2 (en) | 1992-12-25 | 1992-12-25 | Catalyst for hydrocracking of hydrocarbon oils |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4357866A JP2920238B2 (en) | 1992-12-25 | 1992-12-25 | Catalyst for hydrocracking of hydrocarbon oils |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06190278A JPH06190278A (en) | 1994-07-12 |
| JP2920238B2 true JP2920238B2 (en) | 1999-07-19 |
Family
ID=18456340
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4357866A Expired - Lifetime JP2920238B2 (en) | 1992-12-25 | 1992-12-25 | Catalyst for hydrocracking of hydrocarbon oils |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2920238B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GC0000065A (en) | 1998-09-01 | 2004-06-30 | Japan Energy Corp | Hydrocracking catalyst, producing method threof, and hydrocracking method. |
-
1992
- 1992-12-25 JP JP4357866A patent/JP2920238B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH06190278A (en) | 1994-07-12 |
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