JP6251107B2 - Hydrocarbon oil hydrodesulfurization catalyst - Google Patents
Hydrocarbon oil hydrodesulfurization catalyst Download PDFInfo
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- JP6251107B2 JP6251107B2 JP2014075345A JP2014075345A JP6251107B2 JP 6251107 B2 JP6251107 B2 JP 6251107B2 JP 2014075345 A JP2014075345 A JP 2014075345A JP 2014075345 A JP2014075345 A JP 2014075345A JP 6251107 B2 JP6251107 B2 JP 6251107B2
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- 239000003054 catalyst Substances 0.000 title claims description 128
- 239000004215 Carbon black (E152) Substances 0.000 title claims description 11
- 229930195733 hydrocarbon Natural products 0.000 title claims description 11
- 150000002430 hydrocarbons Chemical class 0.000 title claims description 11
- 239000007788 liquid Substances 0.000 claims description 71
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 20
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 18
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 14
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 10
- 229910052750 molybdenum Inorganic materials 0.000 claims description 10
- 239000011733 molybdenum Substances 0.000 claims description 10
- 239000010941 cobalt Substances 0.000 claims description 9
- 229910017052 cobalt Inorganic materials 0.000 claims description 9
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 9
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims description 9
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims description 9
- 229910052759 nickel Inorganic materials 0.000 claims description 9
- 239000000377 silicon dioxide Substances 0.000 claims description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 7
- 229910052698 phosphorus Inorganic materials 0.000 claims description 7
- 239000011574 phosphorus Substances 0.000 claims description 7
- 230000005540 biological transmission Effects 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 238000001237 Raman spectrum Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 2
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- 230000000694 effects Effects 0.000 description 31
- 230000000052 comparative effect Effects 0.000 description 25
- 238000006477 desulfuration reaction Methods 0.000 description 24
- 230000023556 desulfurization Effects 0.000 description 24
- 238000006243 chemical reaction Methods 0.000 description 20
- 238000002360 preparation method Methods 0.000 description 20
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 18
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 15
- 239000001257 hydrogen Substances 0.000 description 15
- 229910052739 hydrogen Inorganic materials 0.000 description 15
- 238000000034 method Methods 0.000 description 11
- 239000002283 diesel fuel Substances 0.000 description 10
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- 229910000147 aluminium phosphate Inorganic materials 0.000 description 9
- 230000007423 decrease Effects 0.000 description 9
- 150000002500 ions Chemical class 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 238000010992 reflux Methods 0.000 description 9
- 239000007921 spray Substances 0.000 description 9
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 8
- 238000005984 hydrogenation reaction Methods 0.000 description 8
- 229910052717 sulfur Inorganic materials 0.000 description 8
- 239000011593 sulfur Substances 0.000 description 8
- 239000000725 suspension Substances 0.000 description 8
- 229910021446 cobalt carbonate Inorganic materials 0.000 description 7
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 description 7
- 239000013078 crystal Substances 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 7
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 7
- 238000005486 sulfidation Methods 0.000 description 7
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- 239000000203 mixture Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000001069 Raman spectroscopy Methods 0.000 description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 4
- 229910004298 SiO 2 Inorganic materials 0.000 description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 description 4
- 239000000446 fuel Substances 0.000 description 4
- 239000000295 fuel oil Substances 0.000 description 4
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 3
- 229910010413 TiO 2 Inorganic materials 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 3
- 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 3
- 230000008859 change Effects 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 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
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000004523 catalytic cracking Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000010779 crude oil Substances 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical compound CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
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- 238000004898 kneading Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002923 metal particle Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 229910001388 sodium aluminate Inorganic materials 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- 238000005987 sulfurization reaction Methods 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 101000878457 Macrocallista nimbosa FMRFamide Proteins 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 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
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000012018 catalyst precursor Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- OBWXQDHWLMJOOD-UHFFFAOYSA-H cobalt(2+);dicarbonate;dihydroxide;hydrate Chemical compound O.[OH-].[OH-].[Co+2].[Co+2].[Co+2].[O-]C([O-])=O.[O-]C([O-])=O OBWXQDHWLMJOOD-UHFFFAOYSA-H 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
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- 239000003350 kerosene Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 239000003027 oil sand Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
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- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
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- 229910001773 titanium mineral Inorganic materials 0.000 description 1
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- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
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Description
本発明は、石油などの炭化水素油の脱硫、脱窒素などに用いられる水素化脱硫触媒に関し、特には軽油中の硫黄分を低減させる水素化処理に使用して、高い脱硫活性を示す水素化脱硫触媒に関する。 The present invention relates to a hydrodesulfurization catalyst used for desulfurization, denitrogenation, etc. of hydrocarbon oils such as petroleum, and in particular, it is used for hydrotreating to reduce sulfur content in light oil and to exhibit high desulfurization activity. The present invention relates to a desulfurization catalyst.
近年、硫黄含有量が低いクリーンな液体燃料への要求が急速に高まっている。これに応じて、燃料油製造業界においても既に種々のクリーン燃料製造法が検討されている。特に、ディーゼル燃料油においては日本であれば硫黄分10質量ppm以下という規制があり、石油会社は触媒の改良や設備の増設により、クリーンな液体燃料を製造する体制をとってきた。
一般にディーゼル燃料油の主基材は、常圧蒸留装置や分解装置から留出する軽油留分であり、水素化精製装置によりこれら基材に含有される硫黄分を除去する必要がある。
通常、軽油の水素化精製は固定床反応装置に脱硫触媒を充填し、水素存在下、高温高圧の反応条件で行われる。脱硫触媒には、担体としてアルミナ、活性金属としてモリブデンやタングステン、助触媒としてコバルトやニッケルがよく用いられる。脱硫活性は、担体の組成、活性金属の組成、細孔構造などに大きく影響され、例えば非特許文献1に担体(アルミナまたはシリカ)および活性金属(モリブデンまたはモリブデンとコバルトの混合)の影響が開示されている。さらに、非特許文献2には担体としてジルコニアやチタニアを用い、活性金属としてニッケルやタングステンを用いた時の脱硫活性について開示されている。
このように、クリーンな液体燃料を効率よく製造するために、高活性な脱硫触媒の開発について種々の検討が行われてきた。しかし、比較的有効な担体や金属種は限られており、その組み合わせや組成の調整だけでは、今以上に脱硫活性を向上させることは難しくなっている。
In recent years, the demand for clean liquid fuels with low sulfur content has increased rapidly. In response to this, various clean fuel production methods have already been studied in the fuel oil production industry. In particular, diesel fuel oil has a regulation of sulfur content of 10 mass ppm or less in Japan, and oil companies have taken a system to produce clean liquid fuel by improving the catalyst and adding equipment.
Generally, the main base material of diesel fuel oil is a light oil fraction distilled from an atmospheric distillation apparatus or a cracking apparatus, and it is necessary to remove sulfur contained in these base materials by a hydrorefining apparatus.
Usually, hydrorefining of light oil is carried out under high-temperature and high-pressure reaction conditions in the presence of hydrogen by filling a fixed-bed reactor with a desulfurization catalyst. In the desulfurization catalyst, alumina as a support, molybdenum or tungsten as an active metal, and cobalt or nickel as a cocatalyst are often used. Desulfurization activity is greatly influenced by the composition of the support, the composition of the active metal, the pore structure, etc. For example, Non-Patent Document 1 discloses the influence of the support (alumina or silica) and the active metal (molybdenum or a mixture of molybdenum and cobalt). Has been. Further, Non-Patent Document 2 discloses desulfurization activity when zirconia or titania is used as a carrier and nickel or tungsten is used as an active metal.
As described above, in order to efficiently produce clean liquid fuel, various studies have been conducted on the development of a highly active desulfurization catalyst. However, relatively effective carriers and metal species are limited, and it is difficult to improve the desulfurization activity more than just by adjusting the combination and composition.
本発明の目的は、優れた脱硫活性を示す炭化水素油の水素化脱硫触媒を提供することにあるが、新規な触媒の製造工程を用いることで、特別な担体や特殊な金属の担持方法によることなく活性を高めた脱硫触媒を製造可能にしたものである。 An object of the present invention is to provide a hydrodesulfurization catalyst for hydrocarbon oils that exhibits excellent desulfurization activity. By using a novel catalyst production process, a special carrier or a special metal loading method is used. This makes it possible to produce a desulfurization catalyst with increased activity without any problems.
本発明者らは、上記課題を解決するために鋭意研究を進めた結果、シリカ−チタニア−アルミナ担体に、特定のラマン分光スペクトルをもつモリブデン、コバルト、ニッケルおよびリンを含有する担持液を担持した場合に、二硫化モリブデンが担体上に高分散し、優れた脱硫性能を有する触媒が調製できることを見出した。 As a result of diligent research to solve the above-mentioned problems, the present inventors supported a silica-titania-alumina support with a support liquid containing molybdenum, cobalt, nickel and phosphorus having a specific Raman spectrum. In some cases, it has been found that molybdenum disulfide is highly dispersed on the support and a catalyst having excellent desulfurization performance can be prepared.
すなわち、本発明は、担体基準で、シリカを1質量%以上5質量%以下、チタニアを10質量%以上30質量%以下、アルミナを65質量%以上含有する担体に、モリブデン、コバルト、ニッケルおよびリンを含む担持液を担持した水素化脱硫触媒であって、予備硫化処理を行った後の該触媒中の二硫化モリブデンを透過型電子顕微鏡で観察した時、(002)面の面長が3.0nm以下となる二硫化モリブデンの割合が63%以上である水素化脱硫触媒に関する。 That is, according to the present invention, a carrier containing 1% by mass to 5% by mass of silica, 10% by mass to 30% by mass of titania, and 65% by mass or more of alumina on a carrier basis, molybdenum, cobalt, nickel and phosphorus When the molybdenum disulfide in the catalyst after the presulfidation treatment is observed with a transmission electron microscope, the surface length of the (002) plane is 3. The present invention relates to a hydrodesulfurization catalyst in which the proportion of molybdenum disulfide that is 0 nm or less is 63% or more.
また本発明は、担体基準で、シリカを1質量%以上5質量%以下、チタニアを10質量%以上30質量%以下、アルミナを65質量%以上含有する担体に、ラマン分光スペクトルにおいて、1020〜960cm−1の範囲にあるピークAと、960〜910cm−1の範囲にあるピークBとの強度比B/Aが1.3以上であるモリブデン、コバルト、ニッケルおよびリンを含有する担持液を担持することにより、予備硫化処理を行った後の該触媒中の二硫化モリブデンを透過型電子顕微鏡で観察した時、(002)面の面長が3.0nm以下となる二硫化モリブデンの割合が63%以上である水素化脱硫触媒を得ることを特徴とする炭化水素油の水素化脱硫触媒の製造方法に関する。 Further, the present invention relates to a carrier containing 1% by mass to 5% by mass of silica, 10% by mass to 30% by mass of titania, and 65% by mass or more of alumina on the basis of a carrier. carrying a peak a in the range of -1, molybdenum intensity ratio B / a and the peak B in the range of 960~910Cm -1 is 1.3 or more, cobalt, supported solution containing nickel and phosphorus Thus, when the molybdenum disulfide in the catalyst after the preliminary sulfidation treatment was observed with a transmission electron microscope, the proportion of molybdenum disulfide having a (002) plane length of 3.0 nm or less was 63%. The present invention relates to a method for producing a hydrodesulfurization catalyst for hydrocarbon oil, characterized in that the hydrodesulfurization catalyst as described above is obtained.
本発明の水素化脱硫触媒を用いることで、炭化水素油から硫黄分を高度に除去することができる。 By using the hydrodesulfurization catalyst of the present invention, it is possible to highly remove sulfur from hydrocarbon oil.
以下、本発明について説明する。
本発明に係るシリカ−チタニア−アルミナ担体は、担体基準で、シリカ(SiO2)を1質量%以上、5質量%以下含有することが好ましい。シリカの含有量が1質量%未満では比表面積が低くなるため、活性金属の粒子が凝集しやすくなり、脱硫活性が低下する。また、シリカの含有量が5質量%を超えると、得られる担体の細孔分布がブロードになり、脱硫活性が低下する場合がある。
The present invention will be described below.
The silica-titania-alumina carrier according to the present invention preferably contains 1% by mass or more and 5% by mass or less of silica (SiO 2 ) based on the carrier. When the content of silica is less than 1% by mass, the specific surface area becomes low, so that the active metal particles tend to aggregate and the desulfurization activity decreases. On the other hand, when the content of silica exceeds 5% by mass, the pore distribution of the obtained carrier becomes broad, and the desulfurization activity may decrease.
また、シリカ−チタニア−アルミナ担体は、担体基準で、チタニア(TiO2)を10質量%以上、30質量%以下含有することが好ましく、より好ましくは12質量%以上、28質量%以下含有するのが望ましい。チタニアの含有量が10質量%未満ではチタニアによる水素化脱硫効果が少なく、脱硫活性が向上しない。また、チタニアの含有量が30質量%を超えると、触媒の機械的強度が低くなりがちな上、比表面積が低くなることで活性金属の粒子が凝集しやすくなり、脱硫活性が低下する。 The silica-titania-alumina carrier preferably contains 10% by mass to 30% by mass of titania (TiO 2 ), more preferably 12% by mass to 28% by mass, based on the carrier. Is desirable. When the content of titania is less than 10% by mass, the hydrodesulfurization effect by titania is small and the desulfurization activity is not improved. If the titania content exceeds 30% by mass, the mechanical strength of the catalyst tends to be low, and the specific surface area is low, so that the active metal particles tend to aggregate and the desulfurization activity decreases.
さらに、シリカ−チタニア−アルミナ担体は、担体基準で、アルミナ(Al2O3)を65質量%以上含有することが好ましく、より好ましくは70質量%以上含有するのが望ましい。アルミナの含有量が65質量%未満では二硫化モリブデンが凝集しやすいため、触媒が劣化しやすくなる傾向にあるため好ましくない。 Further, the silica-titania-alumina carrier preferably contains 65% by mass or more, more preferably 70% by mass or more of alumina (Al 2 O 3 ) based on the carrier. If the content of alumina is less than 65% by mass, molybdenum disulfide tends to aggregate, and the catalyst tends to deteriorate.
本発明に係る水素化脱硫触媒は、前記のシリカ−チタニア−アルミナ担体に、モリブデン、コバルト、ニッケルおよびリンを含有する担持液を担持することにより得られる。 The hydrodesulfurization catalyst according to the present invention can be obtained by supporting a supporting liquid containing molybdenum, cobalt, nickel and phosphorus on the silica-titania-alumina support.
モリブデンは、酸化物、アンモニウム塩、塩化物などの化合物として担持液に加えることができる。コバルトおよびニッケルは、それぞれ炭酸塩、硝酸塩、塩化物などの化合物として担持液に加えることができる。また、リンは、リン酸、亜リン酸、リン酸アンモニウム、リンモリブデン酸などの化合物として担持液に加えることができる。また、本発明の範囲内であれば、担持液中の金属の溶解性を高め、沈殿が生成しないように、硝酸、過酸化水素、過マンガン酸塩などの酸化剤を担持液に添加してもよい。 Molybdenum can be added to the support liquid as a compound such as an oxide, ammonium salt or chloride. Cobalt and nickel can be added to the support liquid as compounds such as carbonates, nitrates and chlorides, respectively. Phosphorus can be added to the support liquid as a compound such as phosphoric acid, phosphorous acid, ammonium phosphate, or phosphomolybdic acid. Also, within the scope of the present invention, an oxidizing agent such as nitric acid, hydrogen peroxide, permanganate or the like may be added to the supporting liquid so as to increase the solubility of the metal in the supporting liquid and prevent precipitation. Also good.
本発明に用いる担持液は、モリブデン、コバルト、ニッケルおよびリンを含有し、ラマン分光スペクトルにおいて、1020〜960cm−1の範囲にあるピークAと、960〜910cm−1の範囲にあるピークBとの強度比B/Aが1.3以上であることが好ましく、1.35以上であることがより好ましい(図1参照)。なお、下記で述べるようにB/A比が大きいことはMoが高分散していることを意味し、触媒の活性を向上させることができるため、その上限については特に限定されない。 The supporting liquid used in the present invention contains molybdenum, cobalt, nickel, and phosphorus, and has a peak A in the range of 1020 to 960 cm −1 and a peak B in the range of 960 to 910 cm −1 in the Raman spectrum. The intensity ratio B / A is preferably 1.3 or more, and more preferably 1.35 or more (see FIG. 1). In addition, as described below, a large B / A ratio means that Mo is highly dispersed, and the activity of the catalyst can be improved, so the upper limit is not particularly limited.
図1において、ピークAとピークCは[P2Mo18O62]6−錯イオン、ピークBは[P2Mo5O23]6−錯イオンによるものと考えられる。[P2Mo5O23]6−錯イオンは[P2Mo18O62]6−錯イオンよりも1個の錯イオンあたりのMo数が少ないため、[P2Mo5O23]6−錯イオンを担体に担持すると、[P2Mo18O62]6−錯イオンを用いた場合よりも担持されたMo粒子が小さくなると考えられる。そのため、[P2Mo5O23]6−錯イオンを多く含む担持液、すなわちB/Aの値が高い担持液を用いるとMoが高分散し、活性点が増えるため、触媒の活性向上につながる。
しかし、Moが高分散するということは、Moと担体との相互作用(結合)が強くなることを意味し、Moが硫化されにくくなる(脱硫活性を発揮する二硫化モリブデン(MoS2)になりにくくなる)という欠点がある。MoS2に変化しないMoが増えれば、活性点は減少する。そのため、Moの分散性を保ち、かつ硫化されやすいMoとなるように、担体の性質を制御して相互作用の強さを調整する必要がある。本発明に用いるシリカ−チタニア−アルミナ担体と該担持液を組み合わせて使用することにより、Moの分散性を維持し、硫化しやすさを維持することができ、触媒の活性を向上させることができる。
In FIG. 1, it is considered that peak A and peak C are due to [P 2 Mo 18 O 62 ] 6- complex ion, and peak B is due to [P 2 Mo 5 O 23 ] 6- complex ion. Since [P 2 Mo 5 O 23 ] 6- complex ions have a smaller number of Mo per complex ion than [P 2 Mo 18 O 62 ] 6- complex ions, [P 2 Mo 5 O 23 ] 6- When the complex ions are supported on the carrier, the supported Mo particles are considered to be smaller than when the [P 2 Mo 18 O 62 ] 6- complex ions are used. Therefore, if a supporting liquid containing a large amount of [P 2 Mo 5 O 23 ] 6- complex ions, that is, a supporting liquid having a high B / A value is used, Mo is highly dispersed and the number of active points increases, thereby improving the activity of the catalyst. Connected.
However, high dispersion of Mo means that the interaction (bonding) between Mo and the carrier becomes stronger, and Mo is less likely to be sulfided (molybdenum disulfide (MoS 2 ) exhibiting desulfurization activity). Has the disadvantage of becoming difficult). If Mo that does not change to MoS 2 increases, the active point decreases. Therefore, it is necessary to adjust the strength of the interaction by controlling the properties of the carrier so that Mo dispersibility is maintained and Mo is easily sulfided. By using a combination of the silica-titania-alumina support used in the present invention and the supporting liquid, it is possible to maintain the dispersibility of Mo, maintain the easiness of sulfiding, and improve the activity of the catalyst. .
前記[P2Mo18O62]6−、[P2Mo5O23]6−錯イオンは、担持液組成の他、pHによっても構造が変化するため、担持液には最適なpH範囲が存在する。
前記担持液のpHは2.4以上、3.0以下であることが好ましい。担持液のpHが2.4未満では[P2Mo18O62]6−が担持液中に主に存在するため好ましくない。また、pHが3.0を超えると担持液の安定性が低くなり、時間の経過とともに沈殿が生成しやすくなるため好ましくない。
The structure of the [P 2 Mo 18 O 62 ] 6− and [P 2 Mo 5 O 23 ] 6- complex ions change depending on the pH of the supported liquid as well as the composition of the supported liquid. Exists.
The pH of the support liquid is preferably 2.4 or more and 3.0 or less. If the pH of the support liquid is less than 2.4, [P 2 Mo 18 O 62 ] 6- is mainly present in the support liquid, which is not preferable. On the other hand, if the pH exceeds 3.0, the stability of the supported liquid is lowered, and precipitation is likely to occur with the passage of time, which is not preferable.
担体に活性金属を担持させて触媒前駆体を調製する方法としては、例えば、含浸法が挙げられる。ここで含浸法とは担体に活性金属の溶液(担持液)を含浸させた後、乾燥、焼成する方法のことである。 Examples of a method for preparing a catalyst precursor by supporting an active metal on a support include an impregnation method. Here, the impregnation method is a method of impregnating a support with an active metal solution (supporting solution), followed by drying and firing.
本発明の水素化脱硫触媒は、炭化水素油と硫化剤の混合油、あるいは硫化水素と、温度が200℃以上、400℃以下で接触させて予備硫化処理を行う。これにより、水素化脱硫触媒のMoは、MoS2結晶となって担体上に層状に配設される。
本発明においては、予備硫化処理を行った後の該触媒中のMoS2結晶を透過型電子顕微鏡(TEM)で観察した時、(002)面の面長が3.0nm以下となるMoS2の割合が63%以上であることが好ましい。該割合が63%未満になるとMoS2の分散性が低くなるため、触媒活性が低下する。
ここで、MoS2の(002)面の面長が3.0nm以下のMoS2の割合は、以下の方法により求められる。すなわち、予備硫化処理した水素化脱硫触媒の透過型電子顕微鏡写真を撮影し、画像に見られる各MoS2の(002)面の面長を調べる。そして、以下の式により、割合を求める。
3.0nm以下のMoS2の割合(%)=3.0nm以下のMoS2の個数/測定対象のMoS2の合計数×100
The hydrodesulfurization catalyst of the present invention performs a preliminary sulfidation treatment by contacting a mixed oil of hydrocarbon oil and sulfiding agent or hydrogen sulfide at a temperature of 200 ° C. or higher and 400 ° C. or lower. Thereby, Mo of the hydrodesulfurization catalyst becomes MoS 2 crystals and is arranged in layers on the support.
In the present invention, when observed MoS 2 crystals of the catalyst after the pre-sulfurization treatment with a transmission electron microscope (TEM), of MoS 2 to be less 3.0nm is face length of (002) plane The ratio is preferably 63% or more. When the ratio is less than 63%, the dispersibility of MoS 2 is lowered, and the catalytic activity is lowered.
Here, the ratio of MoS 2 having a (002) plane length of MoS 2 of 3.0 nm or less is obtained by the following method. That is, a transmission electron micrograph of the pre-sulfurized hydrodesulfurization catalyst is taken, and the surface length of the (002) plane of each MoS 2 seen in the image is examined. And a ratio is calculated | required with the following formula | equation.
Ratio of MoS 2 of 3.0 nm or less (%) = number of MoS 2 of 3.0 nm or less / total number of MoS 2 to be measured × 100
予備硫化処理は、具体的には、水素化脱硫触媒に硫黄化合物(例えば硫化水素、ジメチルジスルフィド等)および水素を反応させる処理である。この処理により、MoS2の積層構造を形成させて、活性を発現させることができる。 Specifically, the preliminary sulfidation treatment is a treatment in which a sulfur compound (for example, hydrogen sulfide, dimethyl disulfide, etc.) and hydrogen are reacted with a hydrodesulfurization catalyst. By this treatment, a laminated structure of MoS 2 can be formed and the activity can be expressed.
予備硫化処理の条件によって、Moの硫化の度合い、およびMoS2の長さが変わるため、(002)面の面長が3.0nm以下のMoS2の割合が本発明の範囲になるように、圧力(水素分圧)や温度等の条件を適宜調整する。
具体的に、予備硫化条件では、圧力を2.0MPa以上にすることが好ましく、3.0MPa以上にすることがより好ましい。圧力が2.0MPa以上であれば、十分にMoを硫化でき、活性を高くできる。また、予備硫化装置の耐圧の観点から、15.0MPa以下であることが好ましい。
そして温度は240以上380℃以下にすることが好ましく、250℃以上350℃以下にすることがより好ましい。予備硫化処理の温度が240℃以上であれば、十分にMoを硫化でき、380℃以下であれば、Moの凝集を抑制でき、分散性を保つことができる。
Since the degree of sulfurization of Mo and the length of MoS 2 vary depending on the conditions of the preliminary sulfidation treatment, the ratio of MoS 2 having a (002) plane length of 3.0 nm or less falls within the scope of the present invention. Conditions such as pressure (hydrogen partial pressure) and temperature are appropriately adjusted.
Specifically, under presulfiding conditions, the pressure is preferably 2.0 MPa or more, and more preferably 3.0 MPa or more. If the pressure is 2.0 MPa or more, Mo can be sufficiently sulfided and the activity can be increased. Moreover, it is preferable that it is 15.0 Mpa or less from a viewpoint of the pressure | voltage resistance of a presulfurization apparatus.
The temperature is preferably 240 to 380 ° C., more preferably 250 to 350 ° C. If the temperature of the preliminary sulfiding treatment is 240 ° C. or higher, Mo can be sufficiently sulfided, and if it is 380 ° C. or lower, aggregation of Mo can be suppressed and dispersibility can be maintained.
炭化水素油の水素化脱硫は、上述の水素化脱硫触媒を用いて、固定床反応装置に当該触媒を充填して水素雰囲気下、高温高圧条件に行われる。 Hydrodesulfurization of hydrocarbon oil is performed using the above-mentioned hydrodesulfurization catalyst in a fixed bed reactor filled with the catalyst under high-temperature and high-pressure conditions in a hydrogen atmosphere.
本発明に用いられる炭化水素油としては、原油の常圧蒸留装置から得られる直留軽油、常圧蒸留装置から得られる直留重質油や残渣油を減圧蒸留装置で処理して得られる減圧軽油、減圧重質軽油あるいは脱硫重油を接触分解して得られる接触分解軽油、減圧重質軽油あるいは脱硫重油を水素化分解して得られる水素化分解油、コーカー等の熱分解装置から得られる熱分解軽油等が挙げられ、沸点が260〜360℃の留分を70容量%以上含んだ留分である。常圧蒸留装置で処理される油は特に限定されないが、石油系の原油、オイルサンド由来の合成油、石炭液化油、ビチュメン改質等を挙げることができる。
なお、ここでいう蒸留性状(沸点)の値は、JIS K2254「石油製品−蒸留試験方法」に記載の方法に準拠して測定される値である。
The hydrocarbon oil used in the present invention is a straight-run gas oil obtained from a crude oil atmospheric distillation apparatus, a straight-run heavy oil or residual oil obtained from an atmospheric distillation apparatus, which is obtained by treating with a vacuum distillation apparatus. Heat obtained from thermal cracking equipment such as catalytic cracking gas oil obtained by catalytic cracking of light oil, vacuum heavy gas oil or desulfurized heavy oil, hydrocracked oil obtained by hydrocracking vacuum heavy gas oil or desulfurized heavy oil, coker, etc. A cracked light oil etc. are mentioned, It is a fraction which contained 70 volume% or more of the fraction whose boiling point is 260-360 degreeC. The oil to be treated in the atmospheric distillation apparatus is not particularly limited, and examples thereof include petroleum-based crude oil, synthetic oil derived from oil sand, coal liquefied oil, and bitumen reforming.
In addition, the value of distillation property (boiling point) here is a value measured based on the method described in JIS K2254 “Petroleum product-distillation test method”.
本発明に係る炭化水素油の水素化脱硫方法は、以下の反応条件で行なわれることが好ましい。 The hydrodesulfurization method for hydrocarbon oil according to the present invention is preferably carried out under the following reaction conditions.
反応温度は特に制限されないが、300〜420℃であることが好ましく、より好ましくは320〜380℃である。反応温度が300℃未満では脱硫活性が著しく低下する傾向にあり実用的でない。また、反応温度が420℃を超えると触媒劣化が顕著になると共に、反応装置の耐熱温度(通常約425℃)に近づくため好ましくない。 Although reaction temperature in particular is not restrict | limited, It is preferable that it is 300-420 degreeC, More preferably, it is 320-380 degreeC. If the reaction temperature is less than 300 ° C., the desulfurization activity tends to be remarkably lowered, which is not practical. Further, when the reaction temperature exceeds 420 ° C., catalyst deterioration becomes remarkable, and it approaches the heat resistant temperature of the reaction apparatus (usually about 425 ° C.), which is not preferable.
水素分圧(反応圧力)は特に制限されないが、3.0〜15.0MPaであることが好ましい。反応圧力が3.0MPa未満では脱硫活性が著しく低下する傾向にあるため、3.0MPa以上が好ましく、3.5MPa以上がより好ましい。一方、反応圧力が15.0MPaを超えると水素消費が大きくなり運転コストが増加するので好ましくないため、15.0MPa以下が好ましく、11.0MPa以下がより好ましい。 The hydrogen partial pressure (reaction pressure) is not particularly limited, but is preferably 3.0 to 15.0 MPa. When the reaction pressure is less than 3.0 MPa, the desulfurization activity tends to be remarkably lowered, so 3.0 MPa or more is preferable, and 3.5 MPa or more is more preferable. On the other hand, when the reaction pressure exceeds 15.0 MPa, the hydrogen consumption increases and the operating cost increases, which is not preferable. Therefore, the pressure is preferably 15.0 MPa or less, and more preferably 11.0 MPa or less.
液空間速度は特に制限されないが、0.5〜4.0h−1であることが好ましく、より好ましくは0.5〜3.0h−1である。液空間速度が0.5h−1未満では処理量が低いので生産性が低くなり実用的ではない。また、液空間速度が4.0h−1を超えると反応温度が高くなり、触媒劣化が速くなるので好ましくない。 But not liquid hourly space velocity particularly limited, is preferably a 0.5~4.0H -1, more preferably 0.5~3.0h -1. If the liquid space velocity is less than 0.5 h −1 , the throughput is low and the productivity is low, which is not practical. Further, if the liquid space velocity exceeds 4.0 h −1 , the reaction temperature is increased, and the catalyst deterioration is accelerated.
水素/油比は特に制限されないが、120〜420NL/Lであることが好ましく、より好ましくは170〜340NL/Lである。水素/油比が120NL/L未満では脱硫率が低下するので好ましくない。また、420NL/Lを超えても脱硫活性に大きな変化がなく、運転コストが増加するだけなので好ましくない。 The hydrogen / oil ratio is not particularly limited, but is preferably 120 to 420 NL / L, and more preferably 170 to 340 NL / L. A hydrogen / oil ratio of less than 120 NL / L is not preferable because the desulfurization rate decreases. Moreover, even if it exceeds 420 NL / L, since there is no big change in desulfurization activity and only an operating cost increases, it is not preferable.
以下に実施例及び比較例を挙げ、本発明を具体的に説明するが、本発明はこれらに限定
されるものではない。
EXAMPLES The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to these.
(比較例1)
(1)担体の調製
容量が100Lのスチームジャケット付タンクに、Al2O3濃度換算で22質量%のアルミン酸ナトリウム水溶液8.16kgを入れ、イオン交換水41kgで希釈後、SiO2濃度換算で5質量%の珪酸ナトリウム溶液1.80kgを攪拌しながら添加し、60℃に加温して、塩基性アルミニウム塩水溶液を作成した。
また、Al2O3濃度換算で7質量%の硫酸アルミニウム水溶液7.38kgを13kgのイオン交換水で希釈した酸性アルミニウム塩水溶液と、TiO2濃度換算で33質量%の硫酸チタン1.82kgを10kgのイオン交換水に溶解したチタニウム鉱酸塩水溶液とを混合し、60℃に加温して、混合水溶液を作成した。塩基性アルミニウム塩水溶液が入ったタンクに、ローラーポンプを用いて混合水溶液をpHが7.2となるまで一定速度で添加(添加時間:10分)し、シリカ、チタニア、及びアルミナを含有する水和物スラリーaを調製した。
得られた水和物スラリーaを攪拌しながら60℃で1時間熟成した後、平板フィルターを用いて脱水し、更に、0.3質量%アンモニア水溶液150Lで洗浄した。洗浄後のケーキ状のスラリーをAl2O3濃度換算で10質量%となるようにイオン交換水で希釈した後、15質量%アンモニア水でpHを10.5に調整した。
pHを調整したスラリーを還流機付熟成タンクに移し、攪拌しながら95℃で10時間熟成した。熟成終了後のスラリーを脱水し、スチームジャケットを備えた双腕式ニーダーにて練りながら所定の水分量まで濃縮捏和した。得られた捏和物を押出成型機にて直径が1.8mmの円柱形状に成型し、110℃で乾燥した。乾燥した成型品は電気炉で550℃の温度で3時間焼成し、担体aを得た。担体aは、シリカがSiO2濃度換算で3質量%(担体基準)、チタニアがTiO2濃度換算で20質量%(担体基準)、アルミニウムがAl2O3濃度換算で77質量%(担体基準)含有されていた。
(2)担持液の調製
三酸化モリブデン267gと炭酸コバルト57gとを、イオン交換水500mlに懸濁させ、この懸濁液を95℃で5時間、液容量が減少しないように適当な還流措置を施して加熱した後、リン酸54gを加えて溶解させ、担持液aを作製した。
(3)担持
担持液aを、担体a1000gに噴霧含浸させた後、250℃で乾燥し、更に電気炉にて550℃で1時間焼成して水素化脱硫触媒A(以下、単に「触媒A」ともいう。以下の実施例についても同様である。)を得た。触媒Aに担持されていたのは、MoO3が20質量%(触媒基準)で、CoOが2.5質量%(触媒基準)で、P2O5が2.5質量%(触媒基準)であった。触媒Aの性状を表1に示す。
(4)水素化脱硫
触媒Aを充填した反応管を固定床流通式水素化脱硫装置に取り付けた。その後、硫黄分濃度が1重量%の炭化水素油を用いて触媒層平均温度340℃、水素分圧6.5MPa、液空間速度1.0h−1、水素/油比100NL/Lの条件下で、5時間以上触媒の予備硫化を行なった。
予備硫化後、水素雰囲気下、直留軽油(表2に性状を示す)を反応温度330℃、水素分圧6.5MPa、液空間速度1.2h−1、水素/油比300NL/Lの条件で通油して水素化処理を行なった。水素化脱硫活性を表1に示す。
水素化脱硫活性は、反応温度330℃で採取した生成油中の硫黄分を分析し、脱硫に関する反応次数を1.35次として、脱硫反応速度定数を求め、触媒Aを基準(100%)として比較した結果として表1に示した。
(Comparative Example 1)
(1) Preparation of carrier In a tank with a steam jacket having a capacity of 100 L, 8.16 kg of a 22 mass% sodium aluminate aqueous solution in terms of Al 2 O 3 concentration was added, diluted with 41 kg of ion-exchanged water, and then converted into SiO 2 concentration. 1.80 kg of 5 mass% sodium silicate solution was added with stirring and heated to 60 ° C. to prepare a basic aluminum salt aqueous solution.
Further, 10 kg of an acidic aluminum salt aqueous solution obtained by diluting 7.38 kg of an aluminum sulfate aqueous solution of 7% by mass in terms of Al 2 O 3 concentration with 13 kg of ion-exchanged water, and 1.82 kg of 33% by mass of titanium sulfate in terms of TiO 2 concentration The aqueous solution of titanium mineral salt dissolved in the ion-exchanged water was mixed and heated to 60 ° C. to prepare a mixed aqueous solution. Water containing silica, titania, and alumina is added to the tank containing the basic aqueous aluminum salt solution at a constant rate using a roller pump until the pH is 7.2 (addition time: 10 minutes). A Japanese slurry a was prepared.
The obtained hydrate slurry a was aged at 60 ° C. for 1 hour with stirring, dehydrated using a flat plate filter, and further washed with 150 L of a 0.3 mass% aqueous ammonia solution. The cake-like slurry after washing was diluted with ion-exchanged water so as to be 10% by mass in terms of Al 2 O 3 concentration, and then the pH was adjusted to 10.5 with 15% by mass ammonia water.
The slurry whose pH was adjusted was transferred to an aging tank equipped with a reflux machine and aged at 95 ° C. for 10 hours with stirring. The slurry after completion of aging was dehydrated and concentrated and kneaded to a predetermined moisture content while kneading with a double-arm kneader equipped with a steam jacket. The obtained kneaded product was molded into a cylindrical shape having a diameter of 1.8 mm by an extrusion molding machine and dried at 110 ° C. The dried molded product was baked in an electric furnace at a temperature of 550 ° C. for 3 hours to obtain a carrier a. As for the carrier a, silica is 3% by mass in terms of SiO 2 (support standard), titania is 20% by mass in terms of TiO 2 (support standard), and aluminum is 77% by mass in terms of Al 2 O 3 concentration (support standard). Contained.
(2) Preparation of supported liquid 267 g of molybdenum trioxide and 57 g of cobalt carbonate are suspended in 500 ml of ion-exchanged water, and appropriate suspension measures are taken so that the liquid volume does not decrease at 95 ° C. for 5 hours. After applying and heating, 54 g of phosphoric acid was added and dissolved to prepare a support liquid a.
(3) Support After 1000 g of support a is spray impregnated with support liquid a, it is dried at 250 ° C., and further calcined at 550 ° C. for 1 hour in an electric furnace to be hydrodesulfurized catalyst A (hereinafter simply referred to as “catalyst A”). The same applies to the following examples. The catalyst A was loaded with 20% by mass of MoO 3 (based on catalyst), 2.5% by mass of CoO (based on catalyst), and 2.5% by mass (based on catalyst) of P 2 O 5. there were. Properties of catalyst A are shown in Table 1.
(4) Hydrodesulfurization The reaction tube filled with the catalyst A was attached to a fixed bed flow type hydrodesulfurization apparatus. Thereafter, using hydrocarbon oil having a sulfur concentration of 1% by weight, under conditions of an average catalyst layer temperature of 340 ° C., a hydrogen partial pressure of 6.5 MPa, a liquid space velocity of 1.0 h −1 , and a hydrogen / oil ratio of 100 NL / L. The catalyst was presulfided for 5 hours or more.
After preliminary sulfidation, straight-run gas oil (characterized in Table 2) is subjected to a reaction temperature of 330 ° C., a hydrogen partial pressure of 6.5 MPa, a liquid space velocity of 1.2 h −1 , and a hydrogen / oil ratio of 300 NL / L in a hydrogen atmosphere. The oil was passed through and hydrogenated. The hydrodesulfurization activity is shown in Table 1.
The hydrodesulfurization activity is determined by analyzing the sulfur content in the product oil collected at a reaction temperature of 330 ° C., determining the reaction order for desulfurization as 1.35 and determining the desulfurization reaction rate constant, with Catalyst A as the standard (100%). The comparison results are shown in Table 1.
(比較例2)
(1)担体の調製
比較例1と同様にして担体aを調製した。
(2)担持液の調製
三酸化モリブデン268g、炭酸コバルト55gと炭酸ニッケル12gを、イオン交換水500mlに懸濁させ、この懸濁液を95℃で5時間、液容量が減少しないように適当な還流措置を施して加熱した後、リン酸54gを加えて溶解させ、担持液bを作製した。
(3)担持
担持液bを、担体a1000gに噴霧含浸させた後、250℃で乾燥し、更に電気炉にて550℃で1時間焼成して水素化脱硫触媒Bを得た。触媒Bに担持されていたのは、MoO3が20質量%(触媒基準)で、CoOが2.5質量%(触媒基準)で、NiOが0.5質量%(触媒基準)で、P2O5が2.5質量%(触媒基準)であった。触媒Bの性状を表1に示す。
(4)水素化脱硫
触媒Aの代わりに触媒Bを使用したこと以外は、比較例1と同様の予備硫化処理と水素化処理を行った。直留軽油の水素化脱硫活性を表1に示す。
(Comparative Example 2)
(1) Preparation of carrier A carrier a was prepared in the same manner as in Comparative Example 1.
(2) Preparation of supported liquid 268 g of molybdenum trioxide, 55 g of cobalt carbonate and 12 g of nickel carbonate were suspended in 500 ml of ion-exchanged water, and this suspension was suitable at 95 ° C. for 5 hours so as not to reduce the liquid volume. After heating with refluxing, 54 g of phosphoric acid was added and dissolved to prepare a support liquid b.
(3) Support The support liquid b was spray impregnated into the support a1000 g, dried at 250 ° C., and further calcined at 550 ° C. for 1 hour in an electric furnace to obtain a hydrodesulfurization catalyst B. The catalyst B supported was 20% by mass of MoO 3 (catalyst reference), 2.5% by mass of CoO (catalyst reference), 0.5% by mass of NiO (catalyst reference), P 2 O 5 was 2.5% by mass (based on catalyst). Properties of catalyst B are shown in Table 1.
(4) Hydrodesulfurization Presulfurization treatment and hydrogenation treatment were performed in the same manner as in Comparative Example 1 except that catalyst B was used instead of catalyst A. The hydrodesulfurization activity of straight run diesel oil is shown in Table 1.
(比較例3)
(1)担体の調製
比較例1と同様にして担体aを調製した。
(2)担持液の調製
三酸化モリブデン270g、炭酸コバルト55gと炭酸ニッケル25gを、イオン交換水500mlに懸濁させ、この懸濁液を95℃で5時間、液容量が減少しないように適当な還流措置を施して加熱した後、リン酸55gを加えて溶解させ、担持液cを作製した。
(3)担持
担持液cを、担体a1000gに噴霧含浸させた後、250℃で乾燥し、更に電気炉にて550℃で1時間焼成して水素化脱硫触媒Cを得た。触媒Cに担持されていたのは、MoO3が20質量%(触媒基準)で、CoOが2.5質量%(触媒基準)で、NiOが1.0質量%(触媒基準)で、P2O5が2.5質量%(触媒基準)であった。触媒Cの性状を表1に示す。
(4)水素化脱硫
触媒Aの代わりに触媒Cを使用したこと以外は、比較例1と同様の予備硫化処理と水素化処理を行った。直留軽油の水素化脱硫活性を表1に示す。
(Comparative Example 3)
(1) Preparation of carrier A carrier a was prepared in the same manner as in Comparative Example 1.
(2) Preparation of supported liquid 270 g of molybdenum trioxide, 55 g of cobalt carbonate and 25 g of nickel carbonate are suspended in 500 ml of ion-exchanged water, and this suspension is suitable at 95 ° C. for 5 hours so that the liquid volume does not decrease. After heating under reflux, 55 g of phosphoric acid was added and dissolved to prepare a support liquid c.
(3) Support The support liquid c was spray impregnated into 1000 g of support a, dried at 250 ° C., and further calcined at 550 ° C. for 1 hour in an electric furnace to obtain a hydrodesulfurization catalyst C. The catalyst C supported was 20% by mass of MoO 3 (based on catalyst), 2.5% by mass of CoO (based on catalyst), 1.0% by mass of NiO (based on catalyst), P 2 O 5 was 2.5% by mass (based on catalyst). The properties of catalyst C are shown in Table 1.
(4) Hydrodesulfurization Presulfurization treatment and hydrogenation treatment were performed in the same manner as in Comparative Example 1 except that catalyst C was used instead of catalyst A. The hydrodesulfurization activity of straight run diesel oil is shown in Table 1.
(実施例1)
(1)担体の調製
比較例1と同様にして担体aを調製した。
(2)担持液の調製
三酸化モリブデン271g、炭酸コバルト56gと炭酸ニッケル30gを、イオン交換水500mlに懸濁させ、この懸濁液を95℃で5時間、液容量が減少しないように適当な還流措置を施して加熱した後、リン酸55gを加えて溶解させ、担持液dを作製した。
(3)担持
担持液dを、担体a1000gに噴霧含浸させた後、250℃で乾燥し、更に電気炉にて550℃で1時間焼成して水素化脱硫触媒Dを得た。触媒Dに担持されていたのは、MoO3が20質量%(触媒基準)で、CoOが2.5質量%(触媒基準)で、NiOが1.2質量%(触媒基準)で、P2O5が2.5質量%(触媒基準)であった。触媒Dの性状を表1に示す。
(4)水素化脱硫
触媒Aの代わりに触媒Dを使用したこと以外は、比較例1と同様の予備硫化処理と水素化処理を行った。直留軽油の水素化脱硫活性を表1に示す。
Example 1
(1) Preparation of carrier A carrier a was prepared in the same manner as in Comparative Example 1.
(2) Preparation of supported liquid 271 g of molybdenum trioxide, 56 g of cobalt carbonate and 30 g of nickel carbonate are suspended in 500 ml of ion-exchanged water, and this suspension is suitable at 95 ° C. for 5 hours so that the liquid volume does not decrease. After heating under reflux, 55 g of phosphoric acid was added and dissolved to prepare a support liquid d.
(3) Support After the support liquid d was spray impregnated into 1000 g of support a, it was dried at 250 ° C. and further calcined at 550 ° C. for 1 hour in an electric furnace to obtain a hydrodesulfurization catalyst D. The catalyst D was supported by 20% by mass of MoO 3 (catalyst reference), 2.5% by mass of CoO (catalyst reference), 1.2% by mass of NiO (catalyst reference), P 2 O 5 was 2.5% by mass (based on catalyst). Properties of catalyst D are shown in Table 1.
(4) Hydrodesulfurization Presulfurization treatment and hydrogenation treatment were performed in the same manner as in Comparative Example 1 except that catalyst D was used instead of catalyst A. The hydrodesulfurization activity of straight run diesel oil is shown in Table 1.
(実施例2)
(1)担体の調製
比較例1と同様にして担体aを調製した。
(2)担持液の調製
三酸化モリブデン272g、炭酸コバルト56gと炭酸ニッケル37gを、イオン交換水500mlに懸濁させ、この懸濁液を95℃で5時間、液容量が減少しないように適当な還流措置を施して加熱した後、リン酸55gを加えて溶解させ、担持液eを作製した。
(3)担持
担持液eを、担体a1000gに噴霧含浸させた後、250℃で乾燥し、更に電気炉にて550℃で1時間焼成して水素化脱硫触媒Eを得た。触媒Eに担持されていたのは、MoO3が20質量%(触媒基準)で、CoOが2.5質量%(触媒基準)で、NiOが1.5質量%(触媒基準)で、P2O5が2.5質量%(触媒基準)であった。触媒Eの性状を表1に示す。
(4)水素化脱硫
触媒Aの代わりに触媒Eを使用したこと以外は、比較例1と同様の予備硫化処理と水素化処理を行った。直留軽油の水素化脱硫活性を表1に示す。
(Example 2)
(1) Preparation of carrier A carrier a was prepared in the same manner as in Comparative Example 1.
(2) Preparation of supported liquid 272 g of molybdenum trioxide, 56 g of cobalt carbonate and 37 g of nickel carbonate were suspended in 500 ml of ion-exchanged water, and this suspension was suitable at 95 ° C. for 5 hours so as not to reduce the liquid volume. After heating under reflux, 55 g of phosphoric acid was added and dissolved to prepare a support liquid e.
(3) Support After the support liquid e was spray impregnated into 1000 g of support a, it was dried at 250 ° C. and further calcined at 550 ° C. for 1 hour in an electric furnace to obtain a hydrodesulfurization catalyst E. The catalyst E was loaded with 20% by mass of MoO 3 (catalyst standard), 2.5% by mass of CoO (catalyst standard), 1.5% by mass of NiO (catalyst standard), P 2 O 5 was 2.5% by mass (based on catalyst). Properties of catalyst E are shown in Table 1.
(4) Hydrodesulfurization Presulfurization treatment and hydrogenation treatment were performed in the same manner as in Comparative Example 1 except that catalyst E was used instead of catalyst A. The hydrodesulfurization activity of straight run diesel oil is shown in Table 1.
(実施例3)
(1)担体の調製
比較例1と同様にして担体aを調製した。
(2)担持液の調製
三酸化モリブデン273g、炭酸コバルト56gと炭酸ニッケル45gを、イオン交換水500mlに懸濁させ、この懸濁液を95℃で5時間、液容量が減少しないように適当な還流措置を施して加熱した後、リン酸55gを加えて溶解させ、担持液fを作製した。
(3)担持
担持液fを、担体a1000gに噴霧含浸させた後、250℃で乾燥し、更に電気炉にて550℃で1時間焼成して水素化脱硫触媒Fを得た。触媒Fに担持されていたのは、MoO3が20質量%(触媒基準)で、CoOが2.5質量%(触媒基準)で、NiOが1.8質量%(触媒基準)で、P2O5が2.5質量%(触媒基準)であった。触媒Fの性状を表1に示す。
(4)水素化脱硫
触媒Aの代わりに触媒Fを使用したこと以外は、比較例1と同様の予備硫化処理と水素化処理を行った。直留軽油の水素化脱硫活性を表1に示す。
(Example 3)
(1) Preparation of carrier A carrier a was prepared in the same manner as in Comparative Example 1.
(2) Preparation of supported liquid 273 g of molybdenum trioxide, 56 g of cobalt carbonate and 45 g of nickel carbonate were suspended in 500 ml of ion-exchanged water, and this suspension was suitable at 95 ° C. for 5 hours so as not to reduce the liquid volume. After heating with refluxing, 55 g of phosphoric acid was added and dissolved to prepare a support liquid f.
(3) Support The support liquid f was spray impregnated into 1000 g of the support a, dried at 250 ° C., and further calcined in an electric furnace at 550 ° C. for 1 hour to obtain a hydrodesulfurization catalyst F. The catalyst F was loaded with 20% by mass of MoO 3 (based on catalyst), 2.5% by mass of CoO (based on catalyst), 1.8% by mass of NiO (based on catalyst), P 2 O 5 was 2.5% by mass (based on catalyst). Properties of catalyst F are shown in Table 1.
(4) Hydrodesulfurization Presulfurization treatment and hydrogenation treatment were performed in the same manner as in Comparative Example 1 except that catalyst F was used instead of catalyst A. The hydrodesulfurization activity of straight run diesel oil is shown in Table 1.
(比較例4)
(1)担体の調製
比較例1と同様にして担体aを調製した。
(2)担持液の調製
三酸化モリブデン274g、炭酸コバルト56gと炭酸ニッケル50gを、イオン交換水500mlに懸濁させ、この懸濁液を95℃で5時間、液容量が減少しないように適当な還流措置を施して加熱した後、リン酸56gを加えて溶解させ、担持液gを作製した。
(3)担持
担持液gを、担体a1000gに噴霧含浸させた後、250℃で乾燥し、更に電気炉にて550℃で1時間焼成して水素化脱硫触媒Gを得た。触媒Gに担持されていたのは、MoO3が20質量%(触媒基準)で、CoOが2.5質量%(触媒基準)で、NiOが2.0質量%(触媒基準)で、P2O5が2.5質量%(触媒基準)であった。触媒Gの性状を表1に示す。
(4)水素化脱硫
触媒Aの代わりに触媒Gを使用したこと以外は、比較例1と同様の予備硫化処理と水素化処理を行った。直留軽油の水素化脱硫活性を表1に示す。
(Comparative Example 4)
(1) Preparation of carrier A carrier a was prepared in the same manner as in Comparative Example 1.
(2) Preparation of supported liquid 274 g of molybdenum trioxide, 56 g of cobalt carbonate and 50 g of nickel carbonate were suspended in 500 ml of ion-exchanged water, and this suspension was suitable at 95 ° C. for 5 hours so as not to reduce the liquid volume. After heating under reflux, 56 g of phosphoric acid was added and dissolved to prepare a carrier liquid g.
(3) Support The support liquid g was spray impregnated into the support a1000 g, dried at 250 ° C., and further calcined in an electric furnace at 550 ° C. for 1 hour to obtain a hydrodesulfurization catalyst G. The catalyst G was loaded with 20% by mass of MoO 3 (catalyst standard), 2.5% by mass of CoO (catalyst standard), 2.0% by mass of NiO (catalyst standard), P 2 O 5 was 2.5% by mass (based on catalyst). Properties of catalyst G are shown in Table 1.
(4) Hydrodesulfurization Presulfurization treatment and hydrogenation treatment were performed in the same manner as in Comparative Example 1 except that catalyst G was used instead of catalyst A. The hydrodesulfurization activity of straight run diesel oil is shown in Table 1.
(比較例5)
(1)担体の調製
比較例1と同様にして担体aを調製した。
(2)担持液の調製
実施例2と同様にして担持液eを調製した。担持液eに硝酸を加えてpHを1.0に調整し、担持液hを作製した。
(3)担持
担持液hを、担体a1000gに噴霧含浸させた後、250℃で乾燥し、更に電気炉にて550℃で1時間焼成して水素化脱硫触媒Hを得た。触媒Hに担持されていたのは、MoO3が20質量%(触媒基準)で、CoOが2.5質量%(触媒基準)で、NiOが1.5質量%(触媒基準)で、P2O5が2.5質量%(触媒基準)であった。触媒Hの性状を表1に示す。
(4)水素化脱硫
触媒Aの代わりに触媒Hを使用したこと以外は、比較例1と同様の予備硫化処理と水素化処理を行った。直留軽油の水素化脱硫活性を表1に示す。
(Comparative Example 5)
(1) Preparation of carrier A carrier a was prepared in the same manner as in Comparative Example 1.
(2) Preparation of support liquid Support liquid e was prepared in the same manner as in Example 2. Nitric acid was added to the support liquid e to adjust the pH to 1.0, thereby preparing a support liquid h.
(3) Support The support liquid h was spray impregnated into 1000 g of support a, dried at 250 ° C., and further calcined in an electric furnace at 550 ° C. for 1 hour to obtain a hydrodesulfurization catalyst H. The catalyst H was loaded with 20% by mass of MoO 3 (catalyst reference), 2.5% by mass of CoO (catalyst reference), 1.5% by mass of NiO (catalyst reference), P 2 O 5 was 2.5% by mass (based on catalyst). Properties of catalyst H are shown in Table 1.
(4) Hydrodesulfurization Presulfurization treatment and hydrogenation treatment were performed in the same manner as in Comparative Example 1 except that catalyst H was used instead of catalyst A. The hydrodesulfurization activity of straight run diesel oil is shown in Table 1.
(比較例6)
(1)担体の調製
容量が100Lのスチームジャケット付タンクに、Al2O3濃度換算で22質量%のアルミン酸ナトリウム水溶液8.55kgを入れ、イオン交換水31kgで希釈した。その後、P2O5濃度換算で2.5質量%のリン酸三ナトリウム溶液3.6kgとSiO2濃度換算で5.0質量%の珪酸ナトリウム溶液1.8kgを攪拌しながら添加し、60℃に加熱して、担体調製用溶液を得た。
また、50L容器に、Al2O3濃度換算で7質量%の硫酸アルミニウム水溶液13kgを入れ、イオン交換水24kgで希釈した。次いで、ローラーポンプを用いて、前記希釈した硫酸アルミニウム溶液を、前記担体調製用溶液に一定速度でpHが7.2となるまで添加して、水和物スラリーbを調製した。
得られた水和物スラリーbを攪拌しながら60℃で1時間熟成した後、平板フィルターを用いて脱水し、0.3質量%アンモニア水溶液150Lで洗浄した。洗浄後のケーキ状スラリーをイオン交換水で希釈してAl2O3濃度で10質量%となるようにした後、15質量%アンモニア水でpHを10.5に調整した。
pHを調整したスラリーを還流機付熟成タンクに移し、攪拌しながら95℃で10時間熟成した。熟成終了後のスラリーを脱水し、スチームジャケットを備えた双腕式ニーダーにて練りながら所定の水分量まで濃縮捏和した後、ホウ酸280gを添加し、再度所定の水分量まで濃縮捏和した。得られた捏和物を押し出し成型機にて直径1.8mm、長さ2〜3mmの円柱状に成型し、110℃で乾燥した。次いで、乾燥した成型品を、電気炉で550℃の温度で3時間焼成して担体bを得た。この担体中のSiO2濃度は2.8質量%、P2O5濃度は2.8質量%、B2O3濃度は5.0質量%であった。
(2)担持液の調製
三酸化モリブデン235g、塩基性炭酸ニッケル24gおよび塩基性炭酸コバルト75gをイオン交換水500mlに懸濁させ、この懸濁液を95℃で5時間、液容量が減少しないように還流させながら加熱した。その後、加熱後の液にクエン酸88gおよびリン酸21gを加えて溶解させて担持液iを作製した。
(3)担持
担持液iを担体b1000gに噴霧含浸させた。この含浸品を、乾燥した後、電気炉にて550℃で1時間焼成して、水素化脱硫触媒Iを得た。触媒Iに担持されていたのは、MoO3が18.0質量%(触媒基準)で、CoOが3.5質量%(触媒基準)で、NiOが1.0質量%(触媒基準)で、P2O5が1.0質量%(触媒基準)であった。触媒Iの性状を表1に示す。
(4)水素化脱硫
触媒Aの代わりに触媒Iを使用したこと以外は、比較例1と同様の予備硫化処理と水素化処理を行った。直留軽油の水素化脱硫活性を表1に示す。
(Comparative Example 6)
(1) Preparation of carrier In a tank with a steam jacket having a capacity of 100 L, 8.55 kg of a 22% by mass sodium aluminate aqueous solution in terms of Al 2 O 3 concentration was added and diluted with 31 kg of ion-exchanged water. Thereafter, 3.6 kg of a 2.5% by mass trisodium phosphate solution in terms of P 2 O 5 concentration and 1.8 kg of a 5.0% by mass sodium silicate solution in terms of SiO 2 concentration were added with stirring, and 60 ° C. To obtain a carrier preparation solution.
Further, the 50L vessel, Al 2 O 3 at a concentration in terms of putting 7 wt% aqueous solution of aluminum sulfate 13 kg, and diluted with ion-exchanged water 24 kg. Then, using a roller pump, the diluted aluminum sulfate solution was added to the carrier preparation solution at a constant rate until the pH reached 7.2, to prepare a hydrate slurry b.
The obtained hydrate slurry b was aged at 60 ° C. for 1 hour with stirring, dehydrated using a flat plate filter, and washed with 150 L of a 0.3 mass% aqueous ammonia solution. The cake slurry after washing was diluted with ion-exchanged water so that the Al 2 O 3 concentration was 10% by mass, and then the pH was adjusted to 10.5 with 15% by mass ammonia water.
The slurry whose pH was adjusted was transferred to an aging tank equipped with a reflux machine and aged at 95 ° C. for 10 hours with stirring. The slurry after ripening was dehydrated and concentrated and kneaded to a predetermined moisture amount while kneading with a double-arm kneader equipped with a steam jacket, then 280 g of boric acid was added, and again concentrated and kneaded to a predetermined moisture amount. . The obtained kneaded product was molded into a cylindrical shape having a diameter of 1.8 mm and a length of 2 to 3 mm by an extrusion molding machine, and dried at 110 ° C. Next, the dried molded product was baked in an electric furnace at a temperature of 550 ° C. for 3 hours to obtain a carrier b. The SiO 2 concentration in the carrier was 2.8% by mass, the P 2 O 5 concentration was 2.8% by mass, and the B 2 O 3 concentration was 5.0% by mass.
(2) Preparation of supported liquid 235 g of molybdenum trioxide, 24 g of basic nickel carbonate and 75 g of basic cobalt carbonate are suspended in 500 ml of ion-exchanged water, and this suspension is kept at 95 ° C. for 5 hours so that the liquid volume does not decrease. Heated to reflux. Thereafter, 88 g of citric acid and 21 g of phosphoric acid were added to the heated solution and dissolved to prepare a support liquid i.
(3) Support The support liquid i was spray impregnated on 1000 g of the support b. The impregnated product was dried and then calcined in an electric furnace at 550 ° C. for 1 hour to obtain a hydrodesulfurization catalyst I. The catalyst I was loaded with MoO 3 at 18.0% by mass (catalyst reference), CoO at 3.5% by mass (catalyst reference), and NiO at 1.0% by mass (catalyst reference). P 2 O 5 was 1.0 wt% (catalyst basis). Properties of catalyst I are shown in Table 1.
(4) Hydrodesulfurization Presulfurization treatment and hydrogenation treatment were performed in the same manner as in Comparative Example 1 except that catalyst I was used instead of catalyst A. The hydrodesulfurization activity of straight run diesel oil is shown in Table 1.
なお、担持液の評価方法、予備硫化方法、MoS2結晶の(002)面の観察方法については以下の方法によった。 In addition, the evaluation method of the supporting liquid, the preliminary sulfidation method, and the observation method of the (002) plane of the MoS 2 crystal were as follows.
<担持液の評価方法>
担持液をラマン分光により評価した。日本分光社製NRS−1000顕微ラマン分光分析装置によって、Arレーザーを使用し、分解能2cm−1、露出時間10秒、積算回数16回にて測定した。比較例1(触媒A)と実施例2(触媒E)の測定結果を図1に示した。各担持液のラマン強度比B/Aは表1に示した。
<Method for evaluating the supported liquid>
The supported liquid was evaluated by Raman spectroscopy. Using an NRS-1000 micro Raman spectroscopic analyzer manufactured by JASCO Corporation, an Ar laser was used, and the measurement was performed at a resolution of 2 cm −1 , an exposure time of 10 seconds, and an integration count of 16 times. The measurement results of Comparative Example 1 (Catalyst A) and Example 2 (Catalyst E) are shown in FIG. The Raman intensity ratio B / A of each supported liquid is shown in Table 1.
各担持液のラマン強度比B/Aは、実施例1〜3(触媒D〜F)の担持液組成ならびにpH範囲でのみ、1.3以上の値となることが分かる。 It can be seen that the Raman intensity ratio B / A of each supported liquid has a value of 1.3 or more only in the supported liquid compositions and pH ranges of Examples 1 to 3 (catalysts D to F).
<MoS2結晶の(002)面の観察方法>
触媒を充填した反応管を固定床流通式水素化脱硫装置に取り付けた後、硫黄分濃度が1.0重量%となるように二硫化炭素を加えた灯油留分を用いて、触媒層平均温度340℃、水素分圧6.5MPa、液空間速度1.0h−1、水素/油比100NL/Lの条件下で、11時間、触媒の予備硫化を行なった。
予備硫化終了後、反応管を室温まで冷却し、流通ガスを窒素に切り替えた。圧力を常圧まで下げた後、反応管入口と出口を、開閉弁を閉じることにより封じ、反応管を取り外した。窒素で満たされたグローブボックス内で反応管から抜き出した予備硫化処理済みの触媒をメノウ乳鉢で粉砕した。
粉砕した硫化触媒中のMoS2結晶を、日本電子社製JEM−2010透過型電子顕微鏡(TEM)にて観察し、画像を撮影して触媒A〜IのMoS2結晶の(002)面の長さを測定した。測定結果を表1に示した。
<Observation method of (002) plane of MoS 2 crystal>
After attaching the reaction tube filled with the catalyst to the fixed bed flow-type hydrodesulfurization unit, the kerosene fraction added with carbon disulfide so that the sulfur concentration is 1.0% by weight, the catalyst layer average temperature The catalyst was presulfided for 11 hours under conditions of 340 ° C., hydrogen partial pressure 6.5 MPa, liquid space velocity 1.0 h −1 , and hydrogen / oil ratio 100 NL / L.
After the preliminary sulfidation, the reaction tube was cooled to room temperature, and the flow gas was switched to nitrogen. After the pressure was reduced to normal pressure, the reaction tube inlet and outlet were sealed by closing the on-off valve, and the reaction tube was removed. The presulfided catalyst extracted from the reaction tube in a glove box filled with nitrogen was pulverized in an agate mortar.
The MoS 2 crystals in the pulverized sulfide catalyst were observed with a JEM-2010 transmission electron microscope (TEM) manufactured by JEOL Ltd., and images were taken to obtain the length of the (002) plane of the MoS 2 crystals of catalysts A to I. Was measured. The measurement results are shown in Table 1.
各触媒のMoS2結晶の(002)面の面長が3.0nm以下の割合が63%以上である触媒は、触媒D、E、Fのみであった。 Catalysts D, E, and F were the only catalysts having a ratio of the surface length of the (002) plane of MoS 2 crystals of each catalyst of 3.0 nm or less of 63% or more.
表1に示すように、本発明の実施例1〜3である触媒D〜Fは、比較例(触媒A〜C、G〜I)に比較して高い脱硫性能を示しており、高活性であることが分かる。 As shown in Table 1, Catalysts D to F, which are Examples 1 to 3 of the present invention, exhibit high desulfurization performance as compared with Comparative Examples (Catalysts A to C, G to I), and have high activity. I know that there is.
Claims (1)
In a carrier containing silica in an amount of 1% by mass to 5% by mass, titania in an amount of 10% by mass to 30% by mass and alumina in an amount of 65% by mass or more, in the Raman spectrum, in the range of 1020 to 960 cm −1 . It contains molybdenum, cobalt, nickel, and phosphorus having an intensity ratio B / A of 1.3 or more and a peak A in the range of 960 to 910 cm −1 and a pH of 2.4 or more and 3. After supporting a supporting liquid that is 0 or less , drying and firing are performed, and further, presulfiding treatment is performed under conditions of a pressure of 2.0 MPa to 15.0 MPa and a temperature of 240 ° C to 380 ° C. when observed with a transmission electron microscope molybdenum disulfide catalyst in medium after, the percentage of molybdenum disulfide as a less 3.0nm is face length of (002) plane Method for producing a hydrodesulfurization catalyst for hydrocarbon oil, characterized in that to obtain a 3% or more in a hydrodesulfurization catalyst.
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