JP3990675B2 - Hydrodesulfurization method of light oil - Google Patents
Hydrodesulfurization method of light oil Download PDFInfo
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- JP3990675B2 JP3990675B2 JP2004038895A JP2004038895A JP3990675B2 JP 3990675 B2 JP3990675 B2 JP 3990675B2 JP 2004038895 A JP2004038895 A JP 2004038895A JP 2004038895 A JP2004038895 A JP 2004038895A JP 3990675 B2 JP3990675 B2 JP 3990675B2
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- 238000000034 method Methods 0.000 title claims description 53
- 239000003054 catalyst Substances 0.000 claims description 132
- 238000006477 desulfuration reaction Methods 0.000 claims description 52
- 230000023556 desulfurization Effects 0.000 claims description 52
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 52
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 50
- 239000010457 zeolite Substances 0.000 claims description 32
- 229910021536 Zeolite Inorganic materials 0.000 claims description 31
- 229910052751 metal Inorganic materials 0.000 claims description 29
- 239000002184 metal Substances 0.000 claims description 29
- 229910052717 sulfur Inorganic materials 0.000 claims description 28
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 27
- 239000011593 sulfur Substances 0.000 claims description 27
- 229910021529 ammonia Inorganic materials 0.000 claims description 25
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 23
- 229910000323 aluminium silicate Inorganic materials 0.000 claims description 20
- 238000001179 sorption measurement Methods 0.000 claims description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 14
- 238000003795 desorption Methods 0.000 claims description 13
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 11
- 229910052809 inorganic oxide Inorganic materials 0.000 claims description 11
- 230000000737 periodic effect Effects 0.000 claims description 11
- 229910052698 phosphorus Inorganic materials 0.000 claims description 11
- 239000011574 phosphorus Substances 0.000 claims description 11
- 239000012013 faujasite Substances 0.000 claims description 4
- 239000003921 oil Substances 0.000 description 70
- 239000007789 gas Substances 0.000 description 35
- 239000011148 porous material Substances 0.000 description 27
- 150000003464 sulfur compounds Chemical class 0.000 description 25
- 230000000694 effects Effects 0.000 description 20
- 238000006243 chemical reaction Methods 0.000 description 17
- 238000004519 manufacturing process Methods 0.000 description 13
- 239000000243 solution Substances 0.000 description 13
- 239000011973 solid acid Substances 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 230000007423 decrease Effects 0.000 description 10
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 9
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 9
- 229910052753 mercury Inorganic materials 0.000 description 9
- 239000002002 slurry Substances 0.000 description 9
- 239000000725 suspension Substances 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- NICUQYHIOMMFGV-UHFFFAOYSA-N 4-Methyldibenzothiophene Chemical compound S1C2=CC=CC=C2C2=C1C(C)=CC=C2 NICUQYHIOMMFGV-UHFFFAOYSA-N 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 238000000354 decomposition reaction Methods 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000009826 distribution Methods 0.000 description 5
- 238000005470 impregnation Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 238000002459 porosimetry Methods 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 5
- 238000004438 BET method Methods 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 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 4
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- IYYZUPMFVPLQIF-UHFFFAOYSA-N dibenzothiophene Chemical compound C1=CC=C2C3=CC=CC=C3SC2=C1 IYYZUPMFVPLQIF-UHFFFAOYSA-N 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 229910001388 sodium aluminate Inorganic materials 0.000 description 4
- 230000032683 aging Effects 0.000 description 3
- 230000003009 desulfurizing effect Effects 0.000 description 3
- 239000002283 diesel fuel Substances 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- AEQDJSLRWYMAQI-UHFFFAOYSA-N 2,3,9,10-tetramethoxy-6,8,13,13a-tetrahydro-5H-isoquinolino[2,1-b]isoquinoline Chemical compound C1CN2CC(C(=C(OC)C=C3)OC)=C3CC2C2=C1C=C(OC)C(OC)=C2 AEQDJSLRWYMAQI-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 238000007872 degassing Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910017464 nitrogen compound Inorganic materials 0.000 description 2
- 150000002830 nitrogen compounds Chemical class 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 239000002574 poison Substances 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- 239000000176 sodium gluconate Substances 0.000 description 2
- 229940005574 sodium gluconate Drugs 0.000 description 2
- 235000012207 sodium gluconate Nutrition 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000004434 sulfur atom Chemical group 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
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000004523 catalytic cracking Methods 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
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229910052675 erionite Inorganic materials 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 125000001905 inorganic group Chemical group 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 1
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005486 sulfidation Methods 0.000 description 1
- 238000009849 vacuum degassing Methods 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
Description
本発明は、硫黄分を含有する炭化水素の軽油留分の水素化脱硫方法に関し、さらに詳しくは軽油留分を水素化脱硫して硫黄分を超深度脱硫する軽油の水素化脱硫方法に関する。 The present invention relates to a hydrodesulfurization method for hydrocarbon gas oil fractions containing sulfur, and more particularly to a hydrodesulfurization method for gas oil in which a diesel oil fraction is hydrodesulfurized and sulfur content is ultra-deep desulfurized.
軽油を燃料とするディーゼルエンジンは高熱効率及び低燃費であり、ヨーロッパなどでは小型乗用車の約半数はディーゼルエンジンを搭載しているが、ディーゼルエンジンからの排出ガス中に存在する有害物質による大気汚染問題が深刻化してきており、大気環境改善のために軽油の品質規制値が世界的に厳しくなる傾向にある。
軽油中の硫黄化合物の低減に関して、我が国では２００５年度より（一部都内では２００４年度より）軽油中の硫黄濃度を５０ｐｐｍ以下に規制することが決定しており、既に多くの石油精製会社が該規制に対する対応を行っている。
しかしながらこの分野に関してはヨーロッパが最も進んでおり、ドイツ、オーストリア、北欧などでは軽油中の硫黄濃度を１０ｐｐｍ以下に低減する事を既に決定し、その対応を進めている。また、アメリカでも軽油中の硫黄濃度を１５ｐｐｍ以下にする事を検討中であり２００６年から実施することが計画されている。この様な世界的な動向から見て、我が国においても今後さらに規制値が厳しくなることが予測される。
Diesel engines powered by light oil have high thermal efficiency and low fuel consumption. In Europe and other countries, about half of small passenger cars are equipped with diesel engines, but there are problems with air pollution caused by harmful substances present in exhaust gas from diesel engines. As the air quality improves, the quality standards for diesel oil tend to be stricter worldwide.
Regarding the reduction of sulfur compounds in light oil, it has been decided in Japan that the sulfur concentration in light oil will be regulated to 50 ppm or less from fiscal 2005 (in some cities from fiscal 2004). Is responding to.
However, Europe is the most advanced in this field, and Germany, Austria, Northern Europe, etc. have already decided to reduce the sulfur concentration in light oil to 10 ppm or less and are responding to it. In the United States, the sulfur concentration in light oil is under consideration to be 15 ppm or less, and it is planned to be implemented from 2006. In view of such global trends, it is predicted that regulatory values will become even stricter in Japan.
前述のような事情から軽油の超深度脱硫について種々の方法が提案されており、例えば、特許文献１〜３などが例示される。
しかしながら、これらの文献における脱硫の程度は、それぞれ５０ｐｐｍ、３０ｐｐｍ、４０ｐｐｍまでであって、軽油中の硫黄濃度を１０ｐｐｍ以下に低減する軽油の超深度脱硫方法については全く記載されていない。
また、特許文献１〜３においても脱硫を２段又は多段で行っているが、硫黄化合物を易脱硫性硫黄化合物と難脱硫性硫黄化合物に分け、両者の水素化脱硫を分けて行う目的で２段階脱硫を行うという本発明の技術思想については記載も示唆もされていない。
Various methods have been proposed for ultra-deep desulfurization of light oil due to the circumstances as described above, and examples thereof include Patent Documents 1 to 3.
However, the degree of desulfurization in these documents is up to 50 ppm, 30 ppm, and 40 ppm, respectively, and there is no description of the ultra-deep desulfurization method for light oil that reduces the sulfur concentration in light oil to 10 ppm or less.
In Patent Documents 1 to 3, desulfurization is performed in two stages or in multiple stages. However, the sulfur compound is divided into an easily desulfurizable sulfur compound and a hardly desulfurizable sulfur compound, and the hydrodesulfurization of both is performed separately for the purpose of 2 There is no description or suggestion of the technical idea of the present invention to perform staged desulfurization.
従来の方法で軽油中の硫黄濃度を１０ｐｐｍ以下に低減するためには、製油所では軽油の水素化脱硫処理量を低下させて低液空間速度〔ＬＨＳＶ（ｈｒ―１）〕で運転するか、または、現状の処理量を維持するためには反応塔の容量を大きくすることが必要であった。 In order to reduce the sulfur concentration in light oil to 10 ppm or less by a conventional method, the refinery is operated at a low liquid space velocity [LHSV (hr- 1 )] by reducing the hydrodesulfurization amount of light oil, Alternatively, it was necessary to increase the capacity of the reaction tower in order to maintain the current throughput.
前述の問題点を解決するために本発明者は、特願２００２−２９３６１２号えお出願して「硫黄分を含有する軽油の水素化脱硫に於いて、第一段目で軽油中に含有される硫黄化合物のうちガスクロマトグラフ分析での保持時間が４―メチルジベンゾチオフェンよりも短い硫黄化合物を脱硫触媒の存在下に水素化脱硫して除去し、第二段目で前記第一段目の脱硫触媒よりも固体酸量を多く有する脱硫触媒の存在下に水素化脱硫して前記保持時間が４―メチルジベンゾチオフェン以上の硫黄化合物を除去し、軽油中の硫黄分を１０ｐｐｍ以下にすることを特徴とする軽油の水素化脱硫方法」にかかる発明を提案した。 In order to solve the above-mentioned problems, the present inventor filed Japanese Patent Application No. 2002-293612 "In the hydrodesulfurization of light oil containing sulfur, it is contained in light oil in the first stage. Sulfur compounds having a retention time in gas chromatographic analysis shorter than 4-methyldibenzothiophene are removed by hydrodesulfurization in the presence of a desulfurization catalyst, and the first stage desulfurization is performed in the second stage. Hydrodesulfurization is performed in the presence of a desulfurization catalyst having a larger amount of solid acid than the catalyst to remove sulfur compounds having a retention time of 4-methyldibenzothiophene or higher, and the sulfur content in light oil is reduced to 10 ppm or lower. Proposed an invention relating to a hydrodesulfurization method for diesel oil.
本発明の目的は、前述の問題点を解決して、軽油の水素化脱硫処理量を低下させることなく、また、反応塔の増設をも必要とすることなく軽油中の硫黄濃度を１０ｐｐｍ以下に低減する軽油の超深度脱硫方法を提供することにある。 The object of the present invention is to solve the above-mentioned problems and to reduce the sulfur concentration in light oil to 10 ppm or less without reducing the hydrodesulfurization amount of light oil and without requiring additional reaction towers. An object of the present invention is to provide an ultra-deep desulfurization method for gas oil.
本発明者は、先に提案した発明の知見に基づき、更に鋭意研究した結果、軽油を先の提案発明に記載されていない新しい特定の水素化脱硫触媒の組み合わせにより水素化脱硫すると、軽油中の硫黄濃度を１０ｐｐｍ以下に低減できることを見出し、本発明を完成するに至った。 As a result of further diligent research based on the knowledge of the previously proposed invention, the present inventor found that when hydrodesulfurization was performed using a combination of new specific hydrodesulfurization catalysts not described in the previous proposed invention, It has been found that the sulfur concentration can be reduced to 10 ppm or less, and the present invention has been completed.
即ち、本発明の第１は、硫黄分を含有する軽油を、第一段目で下記触媒（１）と接触させて水素化脱硫し、次いで第二段目で下記触媒（２）と接触させて水素化脱硫して軽油中の硫黄分を１０ｐｐｍ以下にすることを特徴とする軽油の水素化脱硫方法に関する。
触媒（１）：アルミナを主成分とする担体に周期律表第VIＢ族金属成分と第VIII族金属成分およびリン成分を担持した触媒であって、触媒の（１ａ）アンモニア昇温脱離法によるアンモニア吸着量が０．５５ｍｍｏｌ／ｇ以下である脱硫触媒。
触媒（２）：結晶性アルミノシリケートゼオライトを含有する多孔性無機酸化物担体に周期律表第VIＢ族金属成分と第VIII族金属成分およびリン成分を担持した触媒であって、触媒の（２ａ）アンモニア昇温脱離法によるアンモニア吸着量が０．６０ｍｍｏｌ／ｇ以上である脱硫触媒。
本発明の第２は、前記触媒（１）のアルミナを主成分とする担体が、シリカ（ＳｉＯ２）を２〜２０重量％（担体基準）の範囲で含有するものである請求項１記載の軽油の水素化脱硫方法に関する。
本発明の第３は、前記触媒（２）の結晶性アルミノシリケートゼオライトを含有する多孔性無機酸化物担体が、結晶性アルミノシリケートゼオライトを３〜７０重量％（担体基準）の範囲で含有するものである請求項１または２記載の軽油の水素化脱硫方法に関する。
本発明の第４は、前記触媒（２）の結晶性アルミノシリケートゼオライトが、フォージャサイト型ゼオライトである請求項１〜３いずれか記載の軽油の水素化脱硫方法に関する。
本発明の第５は、前記第一段目の触媒（１）と前記第二段目の触媒（２）の触媒使用量の割合〔触媒（１）／触媒（２）〕が１０／９０〜９０／１０容量比である請求項１〜４いずれか記載の軽油の水素化脱硫方法に関する。
That is, according to the first aspect of the present invention, gas oil containing sulfur is contacted with the following catalyst (1) in the first stage and hydrodesulfurized, and then is contacted with the following catalyst (2) in the second stage. The present invention relates to a hydrodesulfurization method for gas oil, characterized in that the sulfur content in gas oil is reduced to 10 ppm or less by hydrodesulfurization.
Catalyst (1): A catalyst in which a group VIB metal component, a group VIII metal component, and a phosphorus component of the periodic table are supported on a carrier mainly composed of alumina, and (1a) of the catalyst according to the ammonia temperature-programmed desorption method A desulfurization catalyst having an ammonia adsorption amount of 0.55 mmol / g or less.
Catalyst (2): A catalyst comprising a porous inorganic oxide support containing a crystalline aluminosilicate zeolite carrying a Group VIB metal component, a Group VIII metal component and a phosphorus component of the periodic table, the catalyst (2a) A desulfurization catalyst having an ammonia adsorption amount of 0.60 mmol / g or more by an ammonia temperature-programmed desorption method.
The second aspect of the present invention is the catalyst according to claim 1, wherein the support mainly composed of alumina of the catalyst (1) contains silica (SiO 2 ) in the range of 2 to 20% by weight (support basis). The present invention relates to a hydrodesulfurization method for light oil.
A third aspect of the present invention is that the porous inorganic oxide support containing the crystalline aluminosilicate zeolite of the catalyst (2) contains the crystalline aluminosilicate zeolite in the range of 3 to 70% by weight (support basis). The method for hydrodesulfurization of gas oil according to claim 1 or 2.
The fourth aspect of the present invention relates to the hydrodesulfurization method of gas oil according to any one of claims 1 to 3, wherein the crystalline aluminosilicate zeolite of the catalyst (2) is a faujasite type zeolite.
According to a fifth aspect of the present invention, the ratio of the amount of catalyst used between the first stage catalyst (1) and the second stage catalyst (2) [catalyst (1) / catalyst (2)] is 10/90 to The hydrodesulfurization method for gas oil according to any one of claims 1 to 4, wherein the volume ratio is 90/10.
本発明での水素化脱硫処理に共される原料油は、硫黄分（Ｓ）を数百ｐｐｍ〜３ｗｔ％程度含有する軽油で、例えば、原油の常圧あるいは減圧蒸留により得られる直留軽油、接触分解軽油、熱分解軽油、水素化処理軽油、減圧蒸留軽油（ＶＧＯ）などの軽油留分、あるいはこれらを混合したものが例示される。 The raw material oil used in the hydrodesulfurization treatment in the present invention is a light oil containing a sulfur content (S) of about several hundred ppm to 3 wt%, for example, straight-run gas oil obtained by atmospheric or vacuum distillation of crude oil, Examples of the gas oil fraction include catalytic cracking gas oil, pyrolysis gas oil, hydrotreated gas oil, vacuum distilled gas oil (VGO), and mixtures thereof.
本発明の軽油の水素化脱硫方法では、第一段目で前述の軽油を触媒（１）の存在下に水素化脱硫して軽油中に含有される易脱硫性硫黄化合物を主として除去し、次いで、第二段目で触媒（２）と接触させて水素化脱硫し軽油中の難脱硫性硫黄化合物をさらに除去して軽油中の硫黄分を１０ｐｐｍ以下にすることを特徴とする。
本発明での触媒（１）は、アルミナを主成分とする担体に周期律表第VIＢ族金属成分と第VIII族金属成分およびリン成分を担持した触媒であって、触媒の（１ａ）アンモニア昇温脱離法によるアンモニア吸着量が０．５５ｍｍｏｌ／ｇ以下である脱硫触媒である。
アルミナを主成分とする担体とは、アルミナ（Ａｌ２Ｏ３）の含有量が５０重量％（担体基準）を超える（多孔性）担体である。担体中のアルミナ（Ａｌ２Ｏ３）の含有量が５０重量％（担体基準）以下の場合には、触媒の脱硫活性が低下することがあるので好ましくない。このような担体としては、アルミナ担体の他に、シリカ−アルミナ、アルミナ−ボリア、アルミナ−チタニア、アルミナ−ジルコニア、シリカ−アルミナーボリア、アルミナ−チタニア−シリカ、アルミナ−チタニア−ボリアなどの担体が例示される。
In the hydrodesulfurization method of gas oil according to the present invention, the gas oil described above is hydrodesulfurized in the first stage in the presence of the catalyst (1) to mainly remove the easily desulfurizing sulfur compound contained in the gas oil, In the second stage, the catalyst is brought into contact with the catalyst (2) and hydrodesulfurized to further remove the hard-to-desulfurize sulfur compound in the gas oil, thereby reducing the sulfur content in the gas oil to 10 ppm or less.
The catalyst (1) in the present invention is a catalyst in which a group VIB metal component, a group VIII metal component and a phosphorus component of the periodic table are supported on a support mainly composed of alumina, and the catalyst (1a) This is a desulfurization catalyst having an ammonia adsorption amount of 0.55 mmol / g or less by the thermal desorption method.
The carrier mainly composed of alumina is a (porous) carrier in which the content of alumina (Al 2 O 3 ) exceeds 50% by weight (carrier basis). When the content of alumina (Al 2 O 3 ) in the support is 50% by weight (based on the support) or less, the desulfurization activity of the catalyst may decrease, which is not preferable. As such a carrier, in addition to an alumina carrier, a carrier such as silica-alumina, alumina-boria, alumina-titania, alumina-zirconia, silica-alumina-boria, alumina-titania-silica, alumina-titania-boria, etc. Illustrated.
前記触媒（１）としては、前述の担体に活性金属成分としてモリブデン、タングステンなどの周期律表第VIＢ族金属成分を酸化物として１０〜３０重量％、コバルト、ニッケルなどの第VIII族金属成分を酸化物として１〜１０重量％およびリン成分をＰ２Ｏ５として１〜６重量％の範囲で担持した脱硫触媒が好適に採用される。 As the catalyst (1), 10% to 30% by weight of a Group VIB metal component of the periodic table such as molybdenum and tungsten as an active metal component as an oxide and a Group VIII metal component such as cobalt and nickel as the active metal component. A desulfurization catalyst carrying 1 to 10% by weight as an oxide and 1 to 6% by weight of a phosphorus component as P 2 O 5 is preferably employed.
また、前述の第一段目の触媒（１）は、触媒の（１ａ）アンモニア昇温脱離法によるアンモニア吸着量が０．５５ｍｍｏｌ／ｇ以下であることが必要である。第一段目の触媒（１）では、例えば、４―メチルジベンゾチオフェン（４−ＭＤＢＴ）より軽質な反応性の高い易脱硫性硫黄化合物を主として除去するが、難脱硫性硫黄化合物の一部をも除去することも可である。触媒（１）の（１ａ）アンモニア昇温脱離法（ＮＨ３−ＴＰＤ法）によるアンモニア吸着量が０．５５ｍｍｏｌ／ｇより多い場合には、固体酸量が多くなるため、軽油中に含まれる塩基性を示す窒素化合物が触媒の固体酸点に吸着して分解活性と共に脱硫活性点をも被毒するため脱硫活性の低下が促進されるので好ましくない。触媒（１）の（１ａ）アンモニア昇温脱離法によるアンモニア吸着量は、好ましくは０．５０〜０．０５ｍｍｏｌ／ｇの範囲であることが望ましい。 Further, the first stage catalyst (1) needs to have an ammonia adsorption amount of 0.55 mmol / g or less by (1a) ammonia temperature-programmed desorption method of the catalyst. In the first stage catalyst (1), for example, a light and highly reactive easily desulfurizing sulfur compound which is lighter than 4-methyldibenzothiophene (4-MDBT) is mainly removed, but a part of the hardly desulfurizing sulfur compound is removed. Can also be removed. When the ammonia adsorption amount of the catalyst (1) by (1a) ammonia temperature-programmed desorption method (NH 3 -TPD method) is more than 0.55 mmol / g, the amount of solid acid increases, so it is contained in light oil. The basic nitrogen compound is adsorbed on the solid acid point of the catalyst and poisons the desulfurization active site as well as the decomposition activity. The ammonia adsorption amount of the catalyst (1) by the (1a) ammonia temperature-programmed desorption method is preferably in the range of 0.50 to 0.05 mmol / g.
前述の触媒（１）は、特に、シリカ（ＳｉＯ２）を２〜２０重量％（担体基準）の範囲で含有するアルミナ担体を使用した触媒が好ましい。シリカ（ＳｉＯ２）を２〜２０重量％（担体基準）の範囲で含有するアルミナ担体は、ある程度の固体酸を有しているため分解活性も適度に有している。シリカ（ＳｉＯ２）の含有量が２重量％（担体基準）より少ない場合には固体酸量が少なくなるため分解活性が不足することがあり、また、反対にシリカ（ＳｉＯ２）の含有量が２０重量％（担体基準）より多い場合には、固体酸量が多くなるため窒素化合物が固体酸点に吸着して脱硫活性点をも被毒するため脱硫活性が低下することがある。更に好ましいシリカ（ＳｉＯ２）の含有量は、７〜１５重量％（担体基準）の範囲にあることが望ましい。 The catalyst (1) is particularly preferably a catalyst using an alumina support containing silica (SiO 2 ) in the range of 2 to 20% by weight (based on the support). An alumina support containing silica (SiO 2 ) in the range of 2 to 20% by weight (based on the support) has a certain amount of solid acid, and therefore has moderate decomposition activity. When the content of silica (SiO 2 ) is less than 2% by weight (support basis), the amount of solid acid decreases, so that the decomposition activity may be insufficient, and conversely, the content of silica (SiO 2 ) When the amount is more than 20% by weight (based on the carrier), the amount of solid acid increases, so that the nitrogen compound is adsorbed on the solid acid point and poisons the desulfurization active site, so that the desulfurization activity may decrease. The more preferable content of silica (SiO 2 ) is desirably in the range of 7 to 15% by weight (based on the carrier).
さらに、前述の第一段目の触媒（１）は、工業触媒として使用する上で、（１ｂ）ＢＥＴ法による表面積（ＳＡ）が２００〜４００ｍ２／ｇ、（１ｃ）窒素吸着法による細孔容積（ＰＶ）が０．３５〜０．８０ｍｌ／ｇ、（１ｄ）水銀圧入法で測定した細孔分布での平均細孔直径（ＰＤ）が５５〜８０Åの範囲にあることが望ましい。（１ｂ）ＢＥＴ法による表面積（ＳＡ）が２００ｍ２／ｇより小さい場合には触媒の活性点の数が減少して脱硫活性が低下することがあり、該表面積（ＳＡ）が４００ｍ２／ｇより大きい触媒は平均細孔直径（ＰＤ）が５５Åより小さくなる傾向にある。（１ｄ）水銀圧入法で測定した細孔分布での平均細孔直径（ＰＤ）が５５Åより小さい場合には、触媒細孔内への原料油の拡散速度が減少し、細孔内に存在する活性点への接触頻度が減少するため、脱硫活性が低下することがある。また、該平均細孔直径（ＰＤ）が８０Åより大きくなると、前記表面積（ＳＡ）が２００ｍ２／ｇより小さくなる傾向にあり、脱硫活性が低下することがある。なお、水銀圧入法で測定した細孔分布での平均細孔直径（ＰＤ）は、接触角１５０度、表面張力４８０ｄｙｎ／ｃｍの値を使用して測定した細孔直径３１．８Å（水銀圧入圧力４００ＭＰａに相当）以上の細孔容積の１／２に相当する細孔直径である。また、（１ｃ）窒素吸着法による細孔容積（ＰＶ）が０．３５ｍｌ／ｇより小さい場合には脱硫活性が低下することがあり、該細孔容積（ＰＶ）が０．８０ｍｌ／ｇより大きい場合には工業触媒としての機械的強度が弱くなることがある。 Further, when the above-mentioned first stage catalyst (1) is used as an industrial catalyst, (1b) surface area (SA) by BET method is 200 to 400 m 2 / g, (1c) pores by nitrogen adsorption method It is desirable that the volume (PV) is 0.35 to 0.80 ml / g and (1d) the average pore diameter (PD) in the pore distribution measured by mercury porosimetry is in the range of 55 to 80 mm. (1b) When the surface area (SA) by the BET method is smaller than 200 m 2 / g, the number of active sites of the catalyst may be reduced and the desulfurization activity may be reduced, and the surface area (SA) may be less than 400 m 2 / g. Larger catalysts tend to have an average pore diameter (PD) of less than 55 mm. (1d) When the average pore diameter (PD) in the pore distribution measured by the mercury intrusion method is smaller than 55 mm, the diffusion rate of the raw material oil into the catalyst pores decreases and exists in the pores. Since the frequency of contact with active sites is reduced, desulfurization activity may be reduced. Further, when the average pore diameter (PD) is larger than 80 mm, the surface area (SA) tends to be smaller than 200 m 2 / g, and the desulfurization activity may be lowered. The average pore diameter (PD) in the pore distribution measured by the mercury intrusion method is 31.8 mm (mercury intrusion pressure) measured using a contact angle of 150 degrees and a surface tension of 480 dyn / cm. This is a pore diameter corresponding to 1/2 of the above pore volume. Further, (1c) when the pore volume (PV) by the nitrogen adsorption method is smaller than 0.35 ml / g, the desulfurization activity may be reduced, and the pore volume (PV) is larger than 0.80 ml / g. In some cases, the mechanical strength as an industrial catalyst may be weakened.
前述の触媒（１）は、例えば、本出願人に係わる特公平０４−０４６６１９号公報に記載の方法、即ち、擬ベーマイトを主成分とするアルミナ水和物に平均粒径４〜６ｎｍのシリカゾルを、酸化物基準で２〜２０重量％の範囲となるように加えて混練し、この混練物を任意の形状と寸法を有する粒子に成型して乾燥した後、４００〜９００℃で０．５〜５時間焼成してシリカ含有アルミナ担体を調製し、得られた担体に周知の方法で周期律表第VIＢ族金属成分と第VIII族金属成分およびリン成分を含浸させ、しかる後乾燥、焼成して製造することができる。 The above catalyst (1) is prepared by, for example, the method described in Japanese Patent Publication No. 04-046619 related to the present applicant, that is, silica sol having an average particle size of 4 to 6 nm in alumina hydrate mainly composed of pseudoboehmite. In addition, the mixture is kneaded so as to be in the range of 2 to 20% by weight based on the oxide, and the kneaded product is molded into particles having an arbitrary shape and size and dried, and then at 400 to 900 ° C., 0.5 to A silica-containing alumina support is prepared by firing for 5 hours, and the obtained support is impregnated with a Group VIB metal component, a Group VIII metal component and a phosphorus component in the periodic table by a well-known method, and then dried and fired. Can be manufactured.
第一段目での水素化脱硫の処理条件は、通常の軽油の水素化脱硫処理条件が採用可能で、具体的には、反応温度は３２０〜３５０℃、水素圧力は３〜７ＭＰａ、液空間速度（ＬＨＳＶ）は０．５〜２．５ｈｒ―１、水素／油比は１００〜３００Ｎｍ３／ｍ３の範囲が例示される。 As the hydrodesulfurization treatment conditions in the first stage, the usual hydrodesulfurization treatment conditions of light oil can be adopted. Specifically, the reaction temperature is 320 to 350 ° C., the hydrogen pressure is 3 to 7 MPa, the liquid space Examples of the speed (LHSV) are 0.5 to 2.5 hr −1 , and the hydrogen / oil ratio is 100 to 300 Nm 3 / m 3 .
本発明での触媒（２）は、結晶性アルミノシリケートゼオライトを含有する多孔性無機酸化物担体に周期律表第VIＢ族金属成分と第VIII族金属成分およびリン成分を担持した触媒であって、触媒の（２ａ）アンモニア昇温脱離法（ＮＨ３−ＴＰＤ法）によるアンモニア吸着量が０．６０ｍｍｏｌ／ｇ以上の脱硫触媒である。
なお、本出願の先願にかかる本発明者の提出した特願２００２−２９３６１２号における実施例１および２で用いた第２段目の触媒である触媒ＡおよびＢの担体は、「シリカ−アルミナ担体」で、これはアモルファス系のものであり、本発明の担体とは異なるものである。
本発明での結晶性アルミノシリケートゼオライトとしては、フォージャサイト型ゼオライト、ベータゼオライト、ＺＳＭ型ゼオライト、モルデナイト、エリオナイトなど固体酸を有する合成または天然ゼオライトが例示される。特に、フォージャサイト型ゼオライトは適度な固体酸量と酸強度を有するので好ましい。フォージャサイト型ゼオライトの中でも、結晶構造（ＦＡＵ構造）からアルミニウム（Ａｌ）を除去してケイバンを高めた超安定性Ｙ型ゼオライト（ＵＳＹ）は耐酸性、耐熱性に優れているのでさらに好ましい。
前記多孔性無機酸化物としては、例えば、アルミナ、シリカ、チタニア、ジルコニア、シリカ−アルミナ、アルミナ−ボリア、アルミナ−チタニア、アルミナ−ジルコニア、シリカ−アルミナ−ボリア、アルミナ−チタニア−シリカ、アルミナ−チタニア−ボリアなどが例示される。特に、アルミナは好適である。
前述の結晶性アルミノシリケートゼオライトを含有する多孔性無機酸化物担体に周期律表第VIＢ族金属成分と第VIII族金属成分およびリン成分を担持した触媒は、周知の製造方法で得られる。即ち、該触媒（２）は、前記結晶性アルミノシリケートゼオライトを多孔性無機酸化物前駆物質と混練して得られる混練物を任意の形状と寸法を有する粒子に成型し、乾燥、焼成して得られた担体に活性金属成分を含浸させ、しかる後乾燥、焼成して製造することができる。
また、前記活性金属成分としては、モリブデン、タングステンなどの周期律表第VIＢ族金属成分を酸化物として１０〜３０重量％、コバルト、ニッケルなどの第VIII族金属成分を酸化物として１〜１０重量％およびリン成分をＰ２Ｏ５として１〜６重量％の範囲が好適に採用される。
前記結晶性アルミノシリケートゼオライトを含有する多孔性無機酸化物担体に周期律表第VIＢ族金属成分と第VIII族金属成分およびリン成分を担持した触媒は、結晶性アルミノシリケートゼオライトの含有量が多いので高い分解活性と脱硫活性を示す。
The catalyst (2) in the present invention is a catalyst in which a periodic inorganic group VIB metal component, a Group VIII metal component and a phosphorus component are supported on a porous inorganic oxide support containing a crystalline aluminosilicate zeolite, The catalyst (2a) is a desulfurization catalyst having an ammonia adsorption amount of 0.60 mmol / g or more by ammonia temperature-programmed desorption method (NH 3 -TPD method).
The carriers of the catalysts A and B, which are the second stage catalysts used in Examples 1 and 2 in Japanese Patent Application No. 2002-293612 filed by the present inventor for the prior application of the present application, are “silica-alumina”. "Support", which is amorphous and is different from the support of the present invention.
Examples of the crystalline aluminosilicate zeolite in the present invention include synthetic or natural zeolite having a solid acid such as faujasite type zeolite, beta zeolite, ZSM type zeolite, mordenite, and erionite. In particular, the faujasite type zeolite is preferable because it has an appropriate amount of solid acid and acid strength. Among the faujasite-type zeolites, ultrastable Y-type zeolite (USY) obtained by removing aluminum (Al) from the crystal structure (FAU structure) to enhance the quartz is more preferable because it is excellent in acid resistance and heat resistance.
Examples of the porous inorganic oxide include alumina, silica, titania, zirconia, silica-alumina, alumina-boria, alumina-titania, alumina-zirconia, silica-alumina-boria, alumina-titania-silica, and alumina-titania. -Boria and the like are exemplified. Alumina is particularly preferred.
A catalyst in which a Group VIB metal component, a Group VIII metal component, and a phosphorus component of the periodic table are supported on a porous inorganic oxide support containing the crystalline aluminosilicate zeolite described above can be obtained by a well-known production method. That is, the catalyst (2) is obtained by molding a kneaded product obtained by kneading the crystalline aluminosilicate zeolite with a porous inorganic oxide precursor into particles having an arbitrary shape and size, drying and firing. The obtained carrier can be impregnated with an active metal component, and then dried and fired.
The active metal component includes 10 to 30% by weight of a Group VIB metal component of the periodic table such as molybdenum and tungsten as an oxide, and 1 to 10% of a Group VIII metal component such as cobalt and nickel as an oxide. % And a phosphorus component of P 2 O 5 are preferably used in the range of 1 to 6% by weight.
The catalyst in which the group VIB metal component, the group VIII metal component and the phosphorus component of the periodic table are supported on the porous inorganic oxide support containing the crystalline aluminosilicate zeolite has a high content of the crystalline aluminosilicate zeolite. High decomposition and desulfurization activity.
本発明では、前述の第二段目の触媒（２）は、触媒の（２ａ）アンモニア昇温脱離法（ＮＨ３−ＴＰＤ法）によるアンモニア吸着量が０．６０ｍｍｏｌ／ｇ以上であることが必要である。軽油中の難脱硫性硫黄化合物は、その化合物の構造に起因する立体障害のため脱硫触媒の活性点と硫黄原子との接触が阻害される。この脱硫触媒の活性点と硫黄原子との接触を阻害する難脱硫性硫黄化合物の構造を変える上で、第二段目の脱硫触媒はバランスのとれた分解能と水素化能を有することが重要である。該触媒の分解能が強すぎると過分解が生じて軽油収率が低下することがあり、また、分解能が弱すぎると難脱硫性硫黄化合物の水素化脱硫が十分に行なわれないことがある。該触媒の（２ａ）アンモニア昇温脱離法（ＮＨ３−ＴＰＤ法）によるアンモニア吸着量が０．６０ｍｍｏｌ／ｇより少ない場合には、難脱硫性硫黄化合物の分解能が十分でないため所望の脱硫効果が得られない。さらに、軽油の超深度脱硫では、反応塔の前段での脱硫反応により生成した硫化水素が後段の脱硫触媒の水素化活性点に優先吸着して活性低下をもたらすが、前記アンモニア吸着量が０．６０ｍｍｏｌ／ｇより少ない場合には、これを防止することが困難でありし、充分活性低下を抑制することができない。触媒の（２ａ）アンモニア昇温脱離法（ＮＨ３−ＴＰＤ法）によるアンモニア吸着量は、好ましくは０．６５〜０．９０ｍｍｏｌ／ｇの範囲であることが望ましい。 In the present invention, the second stage catalyst (2) has an ammonia adsorption amount of 0.60 mmol / g or more by (2a) ammonia temperature programmed desorption method (NH 3 -TPD method) of the catalyst. is necessary. The hardly desulfurizable sulfur compound in light oil is impeded from contacting the active site of the desulfurization catalyst with the sulfur atom due to steric hindrance caused by the structure of the compound. In order to change the structure of the hard-to-desulfurize sulfur compound that inhibits contact between the active sites of this desulfurization catalyst and sulfur atoms, it is important that the desulfurization catalyst in the second stage has a balanced resolution and hydrogenation ability. is there. If the resolution of the catalyst is too strong, overdecomposition may occur and the yield of light oil may decrease, and if the resolution is too weak, hydrodesulfurization of the hardly-desulfurizable sulfur compound may not be performed sufficiently. When the ammonia adsorption amount of the catalyst by (2a) ammonia temperature-programmed desorption method (NH 3 -TPD method) is less than 0.60 mmol / g, the desired desulfurization effect is obtained because the resolution of the hardly desulfurizable sulfur compound is not sufficient. Cannot be obtained. Further, in ultra-deep desulfurization of light oil, hydrogen sulfide produced by the desulfurization reaction in the former stage of the reaction tower is preferentially adsorbed on the hydrogenation active point of the desulfurization catalyst in the latter stage, resulting in a decrease in activity. When the amount is less than 60 mmol / g, it is difficult to prevent this, and the decrease in activity cannot be sufficiently suppressed. The ammonia adsorption amount of the catalyst by the (2a) ammonia temperature-programmed desorption method (NH 3 -TPD method) is preferably in the range of 0.65 to 0.90 mmol / g.
前述の触媒（２）は、特に、結晶性アルミノシリケートゼオライトを含有する多孔性無機酸化物担体が、結晶性アルミノシリケートゼオライトを３〜７０重量％（担体基準）の範囲で含有する担体を使用した触媒が好ましい。結晶性アルミノシリケートゼオライトの含有量が３重量％（担体基準）より少ない場合には固体酸量が少なくなるため分解活性が不足することがあり、また、反対に結晶性アルミノシリケートゼオライトの含有量が７０重量％（担体基準）より多い場合には、分解活性は高くなるが脱硫活性が低下することがある。更に好ましい結晶性アルミノシリケートゼオライトの含有量は、５〜６０重量％（担体基準）の範囲にあることが望ましい。 In the catalyst (2), a porous inorganic oxide carrier containing a crystalline aluminosilicate zeolite was used, in particular, a carrier containing a crystalline aluminosilicate zeolite in the range of 3 to 70% by weight (based on the carrier). A catalyst is preferred. When the content of the crystalline aluminosilicate zeolite is less than 3% by weight (based on the carrier), the solid acid amount decreases, so that the decomposition activity may be insufficient, and conversely, the content of the crystalline aluminosilicate zeolite is When the amount is more than 70% by weight (based on the carrier), the desulfurization activity may be reduced although the decomposition activity is increased. The more preferable content of the crystalline aluminosilicate zeolite is desirably in the range of 5 to 60% by weight (based on the carrier).
さらに、前述の第二段目の触媒（２）は、工業触媒として使用する上で、（２ｂ）ＢＥＴ法による表面積（ＳＡ）が１００〜４００ｍ２／ｇ、（２ｃ）窒素吸着法による細孔容積（ＰＶ）が０．４０〜０．７０ｍｌ／ｇ、（２ｄ）水銀圧入法で測定した細孔分布での平均細孔直径（ＰＤ）が８０〜１２０Åの範囲にあることが望ましい。（２ｂ）ＢＥＴ法による表面積（ＳＡ）が１００ｍ２／ｇより小さい場合には触媒の活性点の数が減少して触媒の水素化能が減少し、軽油留分の収率低下と共に脱硫活性も低下することがある。該表面積（ＳＡ）が４００ｍ２／ｇより大きい触媒は、前記結晶性アルミノシリケートゼオライトの含有量が７０重量％（担体基準）より多く、多孔性無機酸化物の量が３０重量％より少なくない触媒となるので、分解能が高くなり脱硫活性が低下することがある。また、（２ｃ）窒素吸着法による細孔容積（ＰＶ）が０．４０ｍｌ／ｇより小さい場合には、脱硫活性が低下することがあり、該細孔容積（ＰＶ）が０．７０ｍｌ／ｇより大きい場合には工業触媒としての機械的強度が弱くなることがある。（２ｄ）水銀圧入法で測定した細孔分布での平均細孔直径（ＰＤ）が８０Åより小さい場合には、難脱硫性硫黄化合物の触媒細孔内への拡散が制限されて脱硫活性が低下することがあり、該平均細孔直径（ＰＤ）が１２０Åより大きくなると前記表面積（ＳＡ）が１００ｍ２／ｇより小さくなる傾向にあり、脱硫活性が低下することがある。 Further, when the above-mentioned second stage catalyst (2) is used as an industrial catalyst, (2b) the surface area (SA) by BET method is 100 to 400 m 2 / g, (2c) pores by nitrogen adsorption method It is desirable that the volume (PV) is 0.40 to 0.70 ml / g, and (2d) the average pore diameter (PD) in the pore distribution measured by mercury porosimetry is in the range of 80 to 120 mm. (2b) When the surface area (SA) according to the BET method is smaller than 100 m 2 / g, the number of active sites of the catalyst is reduced and the hydrogenation ability of the catalyst is reduced. May decrease. The catalyst having a surface area (SA) greater than 400 m 2 / g is a catalyst in which the content of the crystalline aluminosilicate zeolite is more than 70% by weight (support basis) and the amount of the porous inorganic oxide is not less than 30% by weight. Therefore, the resolution is increased and the desulfurization activity may be reduced. In addition, (2c) when the pore volume (PV) by the nitrogen adsorption method is smaller than 0.40 ml / g, the desulfurization activity may be reduced, and the pore volume (PV) is less than 0.70 ml / g. If it is large, the mechanical strength as an industrial catalyst may be weakened. (2d) When the average pore diameter (PD) in the pore distribution measured by the mercury intrusion method is less than 80 mm, the diffusion of the hardly-desulfurizable sulfur compound into the catalyst pores is limited and the desulfurization activity is reduced. When the average pore diameter (PD) is larger than 120 mm, the surface area (SA) tends to be smaller than 100 m 2 / g, and the desulfurization activity may be lowered.
前述の第二段目での水素化脱硫の処理条件は、通常の軽油の水素化脱硫処理条件が採用可能で、具体的には、反応温度は３２０〜３５０℃、水素圧力は３〜７ＭＰａ、液空間速度（ＬＨＳＶ）は０．５〜２．５ｈｒ―１、水素／油比は１００〜３００Ｎｍ３／ｍ３の範囲が例示される。 As the hydrodesulfurization treatment conditions in the second stage described above, normal gas oil hydrodesulfurization treatment conditions can be adopted. Specifically, the reaction temperature is 320 to 350 ° C., the hydrogen pressure is 3 to 7 MPa, The liquid space velocity (LHSV) is 0.5 to 2.5 hr −1 , and the hydrogen / oil ratio is 100 to 300 Nm 3 / m 3 .
本発明の軽油の水素化脱硫方法では、第一段目の触媒（１）と第二段目の触媒（１）をそれぞれ異なる反応塔に充填して行うこともできるし、また、一つの反応塔の前段側に第一段目の触媒（１）を充填し、後段側に第二段目の触媒（２）を充填して行うこともできる。
反応塔への触媒の充填量は、前記第一段目の触媒（１）と前記第二段目の触媒（２）の触媒使用量（充填量）の割合〔触媒（１）／触媒（２）〕が１０／９０〜９０／１０容量比の範囲であることが好ましい。触媒使用量の割合〔触媒（１）／触媒（２）〕が前記範囲から外れる場合には、１０ｐｐｍ以下の硫黄分（以下、硫黄濃度ということがある）の軽油が得られる運転期間が短くなることがある。第一段目の触媒（１）充填量は、通常、前述の軽油中に含有される硫黄化合物のうちガスクロマトグラフ分析での保持時間が４―メチルジベンゾチオフェンよりも短い硫黄化合物だけを全て除去することができる量あれば良い。本発明での第一段目の触媒（１）と第二段目の触媒（２）との充填割合（第一段目／第二段目）は、好ましくは１０／９０〜８０／２０容量比、さらに好ましくは２０／８０〜７０／３０容量比の範囲であることが望ましい。
In the hydrodesulfurization method of gas oil of the present invention, the first stage catalyst (1) and the second stage catalyst (1) can be charged in different reaction towers, respectively, or one reaction can be performed. The first stage catalyst (1) can be packed on the front side of the tower, and the second stage catalyst (2) can be packed on the rear side.
The amount of catalyst packed in the reaction tower is the ratio of the amount of catalyst used (packing amount) between the first stage catalyst (1) and the second stage catalyst (2) [catalyst (1) / catalyst (2 )] Is preferably in the range of 10/90 to 90/10 capacity ratio. When the ratio of the amount of catalyst used [catalyst (1) / catalyst (2)] is out of the above range, the operation period for obtaining light oil having a sulfur content of 10 ppm or less (hereinafter sometimes referred to as sulfur concentration) is shortened. Sometimes. The first stage catalyst (1) packing amount normally removes only the sulfur compounds whose retention time in gas chromatographic analysis is shorter than 4-methyldibenzothiophene among the sulfur compounds contained in the aforementioned light oil. Any amount that can be used. The filling ratio (first stage / second stage) of the first stage catalyst (1) and the second stage catalyst (2) in the present invention is preferably 10/90 to 80/20 volume. Ratio, more preferably in the range of 20/80 to 70/30 capacity ratio.
軽油中の硫黄化合物には容易に脱硫される易脱硫性硫黄化合物と脱硫が困難な難脱硫性硫黄化合物があり、例えば、ジベンゾチオフェン（ＤＢＴ）などの易脱硫性硫黄化合物は温和な水素化脱硫処理条件で容易に除去することができるが、例えば、４―メチルジベンゾチオフェン（４−ＭＤＢＴ）などの難脱硫性硫黄化合物は過酷な水素化脱硫処理条件でないと除去することができないため、軽油の水素化脱硫処理量を減らして低液空間速度で運転するなどの方法がとられていた。
本発明の軽油の水素化脱硫方法では、第一段目で固体酸量の少ない脱硫触媒の存在下に温和な条件で水素化脱硫して軽油中の易脱硫性硫黄化合物を主として除去し、次いで第二段目で固体酸量が多い特定の性状を有する脱硫触媒の存在下に水素化脱硫することにより難脱硫性硫黄化合物を過酷な水素化脱硫処理条件で処理することなく除去することができる。
即ち、本発明の軽油の水素化脱硫方法は、軽油の水素化脱硫処理量を低下させることなく、また、反応塔の増設を必要とすることもなく、通常の水素化脱硫処理条件で軽油中の硫黄濃度を１０ｐｐｍ以下に低減することが可能な軽油の超深度脱硫方法を提供する。
There are two types of sulfur compounds in light oil: easy desulfurization sulfur compounds that are easily desulfurized and difficult desulfurization sulfur compounds that are difficult to desulfurize. For example, easy desulfurization sulfur compounds such as dibenzothiophene (DBT) Although it can be easily removed under the treatment conditions, for example, difficult desulfurization sulfur compounds such as 4-methyldibenzothiophene (4-MDBT) cannot be removed unless the conditions are severe hydrodesulfurization treatment. Methods such as reducing the hydrodesulfurization throughput and operating at a low liquid space velocity have been adopted.
In the hydrodesulfurization method of gas oil of the present invention, hydrodesulfurization is performed mainly in the presence of a desulfurization catalyst with a small amount of solid acid in the first stage to remove easily desulfurizable sulfur compounds in the gas oil, and then By performing hydrodesulfurization in the second stage in the presence of a desulfurization catalyst having a specific property with a large amount of solid acid, it is possible to remove difficult-to-desulfurize sulfur compounds without treatment under severe hydrodesulfurization treatment conditions. .
That is, the hydrodesulfurization method of gas oil according to the present invention does not reduce the hydrodesulfurization treatment amount of gas oil, and does not require an additional reaction tower. An ultra-deep desulfurization method for gas oil that can reduce the sulfur concentration of the oil to 10 ppm or less is provided.
以下に実施例を示して本発明をさらに具体的に説明するが、本発明はこれにより何ら限定されるものではない。 The present invention will be described more specifically with reference to the following examples, but the present invention is not limited thereto.
製造例１
スチームジャケット付１００ＬタンクにＡｌ２Ｏ３濃度換算で２２ｗｔ％のアルミン酸ナトリウム水溶液９．０９ｋｇを入れ、イオン交換水で希釈し４０ｋｇとした。この溶液の中に２６ｗｔ％グルコン酸ナトリウム０．２２ｋｇを加え攪拌しながら６０℃に加温した。別途、５０Ｌ容器にＡｌ２Ｏ３濃度換算で７ｗｔ％の硫酸アルミニウム水溶液１３．８６ｋｇを入れ６０℃の温水で希釈し４０ｋｇとした。次に、ロータリーポンプを用いて前記アルミン酸ナトリウム水溶液中に前記硫酸アルミニウム水溶液を一定速度で添加し、１０分でｐＨが７．１となるようにした。得られた懸濁スラリーを攪拌しながら６０℃で１時間熟成した。熟成後の懸濁スラリーを平板フィルターを用いて脱水し、６０℃の温水１５０Ｌで洗浄した。洗浄終了後のケーキ状スラリーにＳｉＯ２濃度として２０％のシリカゾル〔触媒化成工業（株）製：ｃａｔａｌｏｉｄ ＳＩ−５５０〕を１．８５ｋｇ加えた後イオン交換水で希釈し、Ａｌ２Ｏ３濃度で１０ｗｔ％になるようにした。次いで、これを環流機付タンクに移し、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加温し所定の水分量まで濃縮した後、降温し３０分捏和した。得られた捏和物を押し出し成形機にて１．８ｍｍの円柱状に成形し１１０℃で乾燥させた。乾燥したペレットを電気炉中で５５０℃の温度で３時間焼成し、１１ｗｔ％ＳｉＯ２−８９ｗｔ％Ａｌ２Ｏ３担体を得た。該担体の水銀圧入法による平均細孔径は７０Åであった。
別途、１Ｌ容器に三酸化モリブデン２７７．８ｇ、塩基性炭酸コバルト１１５．７ｇを入れイオン交換水６００ｍｌを加え攪拌して懸濁し、この懸濁液を９５℃で５時間溶液量が減少しないよう適当な環流手段を施し加熱した。その後、この懸濁溶液に８５％リン酸６７．７ｇを加え懸濁物を溶解し含浸溶液を調製した。
次いで、真空脱気可能な回転式ブレンダーに前記担体１０００ｇを入れ、真空ポンプにて脱気しながら５分放置した後、先に調製した含浸溶液を担体の吸水率に合うよう液量を調節し、ブレンダーを回転させながら添加した。含浸溶液添加後、真空ポンプを停止し常圧下とし２０分間回転させ、担体中に含浸液が十分浸透するようにした。含浸された物を取り出し昇温プログラム付回転乾燥機にいれ、４０℃から２５０℃まで１時間昇温して乾燥させた。該乾燥品を電気炉に入れ５５０℃で１時間焼成して触媒（Ａ）を得た。触媒（Ａ）の活性金属組成はＭｏＯ３：２０．０ｗｔ％、ＣｏＯ：５．０ｗｔ％、Ｐ２Ｏ５：３．０ｗｔ％であった。
該触媒（Ａ）のアンモニア吸着量をアンモニア昇温脱離法（ＮＨ３−ＴＰＤ法）により測定した。測定法は、測定セル中にサンプル０．０５ｍｇを入れ４００℃で６０分間前処理を行った後室温まで冷却し、ＮＨ３ガスを導入して１分間保持しＮＨ３を吸着させる。次いで、Ｈｅパージにより系内の余剰ＮＨ３を除去した後昇温を開始し、温度上昇にともなって脱離するＮＨ３の量を計測する。昇温は８００℃まで行い、その間脱離したＮＨ３の総量をＮＨ３吸着量とした。触媒（Ａ）のＮＨ３吸着量および性状を表１に示す。
Production Example 1
In a 100 L tank with a steam jacket, 9.09 kg of a 22 wt% sodium aluminate aqueous solution in terms of Al 2 O 3 concentration was added and diluted with ion-exchanged water to 40 kg. To this solution, 0.22 kg of 26 wt% sodium gluconate was added and heated to 60 ° C. with stirring. Separately, 13.86 kg of a 7 wt% aluminum sulfate aqueous solution in terms of Al 2 O 3 concentration was placed in a 50 L container and diluted with hot water at 60 ° C. to make 40 kg. Next, the aluminum sulfate aqueous solution was added to the sodium aluminate aqueous solution at a constant rate using a rotary pump, so that the pH became 7.1 in 10 minutes. The obtained suspension slurry was aged at 60 ° C. for 1 hour with stirring. The suspension slurry after aging was dehydrated using a flat plate filter and washed with 150 L of hot water at 60 ° C. After adding 1.85 kg of 20% silica sol [catalyst chemical industry Co., Ltd .: catalyst SI-550] as SiO 2 concentration to the cake-like slurry after completion of washing, it was diluted with ion-exchanged water, and Al 2 O 3 concentration was used. It was made to become 10 wt%. Next, this was transferred to a tank with a reflux machine and aged at 95 ° C. for 10 hours with stirring. The slurry after completion of aging was heated while being kneaded with a double-arm kneader equipped with a steam jacket, concentrated to a predetermined moisture content, then cooled and kneaded for 30 minutes. The obtained kneaded product was molded into a 1.8 mm cylindrical shape by an extrusion molding machine and dried at 110 ° C. The dried pellet was fired in an electric furnace at a temperature of 550 ° C. for 3 hours to obtain an 11 wt% SiO 2 -89 wt% Al 2 O 3 support. The average pore diameter of the carrier determined by mercury porosimetry was 70 mm.
Separately, 277.8 g of molybdenum trioxide and 115.7 g of basic cobalt carbonate are placed in a 1 L container, and 600 ml of ion-exchanged water is added and stirred to suspend the suspension. The mixture was heated with appropriate refluxing means. Thereafter, 67.7 g of 85% phosphoric acid was added to this suspension solution to dissolve the suspension to prepare an impregnation solution.
Next, 1000 g of the carrier is put into a rotary blender that can be degassed and left for 5 minutes while degassing with a vacuum pump. Then, the amount of the impregnated solution prepared above is adjusted to match the water absorption rate of the carrier. , Added while rotating the blender. After the impregnation solution was added, the vacuum pump was stopped and the system was rotated at normal pressure for 20 minutes so that the impregnation solution sufficiently permeated into the carrier. The impregnated product was taken out and placed in a rotary dryer with a temperature raising program, and dried by heating from 40 ° C. to 250 ° C. for 1 hour. The dried product was put in an electric furnace and calcined at 550 ° C. for 1 hour to obtain a catalyst (A). The active metal composition of the catalyst (A) was MoO 3 : 20.0 wt%, CoO: 5.0 wt%, and P 2 O 5 : 3.0 wt%.
The ammonia adsorption amount of the catalyst (A) was measured by an ammonia temperature programmed desorption method (NH 3 -TPD method). In the measurement method, 0.05 mg of a sample is put in a measurement cell, pretreated at 400 ° C. for 60 minutes, cooled to room temperature, introduced with NH 3 gas and held for 1 minute to adsorb NH 3 . Next, after removing excess NH 3 in the system by He purge, the temperature rise is started, and the amount of NH 3 desorbed as the temperature rises is measured. Heated is conducted to 800 ° C., and the adsorbed NH 3 amount to the total amount of NH 3 desorbed therebetween. Table 1 shows the NH 3 adsorption amount and properties of the catalyst (A).
製造例２
スチームジャケット付１００ＬタンクにＡｌ２Ｏ３濃度換算で２２ｗｔ％のアルミン酸ナトリウム水溶液９．０９ｋｇを入れ、イオン交換水で希釈し４０ｋｇとした。この溶液の中に２６ｗｔ％グルコン酸ナトリウム０．２２ｋｇを加え攪拌しながら６０℃に加温した。
また、５０Ｌ容器にＡｌ２Ｏ３濃度換算で７ｗｔ％の硫酸アルミニウム水溶液１３．８６ｋｇを入れ６０℃の温水で希釈し４０ｋｇとした。
次いで、ロータリーポンプを用いて前記アルミン酸ナトリウム水溶液中に前記硫酸アルミニウム水溶液を一定速度で、ｐＨが７．１となるように１０分間で添加してアルミナ水和物スラリーを調製した。得られたアルミナ水和物スラリーを攪拌しながら６０℃で１時間熟成し、熟成後の該スラリーを平板フィルターを用いて脱水し、６０℃の温水１５０Ｌで洗浄した。洗浄終了後のケーキ状アルミナ水和物スラリーをイオン交換水で希釈し、Ａｌ２Ｏ３濃度で１０ｗｔ％になるようにし、これを環流器付タンクに入れて攪拌しながら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加温し所定の水分量まで濃縮した後、降温し３０分捏和した。該捏和物に、格子定数２４．００Åの超安定Ｙ型ゼオライト（ＵＳＹ）１．６６ｋｇをニーダーで練り込みながら添加し混練した。得られた捏和物を押し出し成形機にて１．８ｍｍの円柱状に成形した後、１１０℃で乾燥し、次いで、電気炉中で５５０℃の温度で３時間焼成して、５０ｗｔ％超安定Ｙ型ゼオライト（ＵＳＹ）含有アルミナ担体を得た。該担体の水銀圧入法による平均細孔直径は１１５Åであった。
別途、１Ｌ容器に三酸化モリブデン２７７．８ｇ、塩基性炭酸ニッケル１７０．６ｇを入れイオン交換水６００ｍｌを加え攪拌し懸濁させた。この懸濁液を９５℃で５時間溶液量が減少しないよう適当な環流手段を施し加熱した。その後この懸濁溶液に８５ｗｔ％リン酸６７．７ｇを加え懸濁物を溶解し含浸溶液を調製した。
次いで、真空脱気可能な回転式ブレンダーに前記担体１０００ｇを入れ真空ポンプにて脱気しながら５分間放置した後、先に調製した含浸溶液を担体の吸水率に合うよう液量を調節し、ブレンダーを回転させながら添加した。溶液添加後、真空ポンプを停止し常圧下として２０分間回転させ、担体中に含浸溶液が十分浸透するようにした。含浸された物を取り出し昇温プログラム付回転乾燥機にいれ、４０℃から２５０℃まで１時間昇温して乾燥させた。乾燥品を電気炉に入れ５５０℃で１時間焼成して触媒（Ｂ）を調製した。得られた触媒Ｂの活性金属組成は、ＭｏＯ３：２０．０ｗｔ％、ＮｉＯ：５．０ｗｔ％、Ｐ２Ｏ５：３．０ｗｔ％であった。触媒（Ｂ）のＮＨ３吸着量および性状を表１に示す。
Production Example 2
In a 100 L tank with a steam jacket, 9.09 kg of a 22 wt% sodium aluminate aqueous solution in terms of Al 2 O 3 concentration was added and diluted with ion-exchanged water to 40 kg. To this solution, 0.22 kg of 26 wt% sodium gluconate was added and heated to 60 ° C. with stirring.
Moreover, was 40kg diluted with the concentration of Al 2 O 3 in terms of at 7 wt% of the hot water 60 ° C. Put the aluminum sulfate aqueous solution 13.86kg in 50L vessel.
Subsequently, the aluminum sulfate aqueous solution was added to the sodium aluminate aqueous solution at a constant rate using a rotary pump for 10 minutes so that the pH was 7.1 to prepare an alumina hydrate slurry. The obtained alumina hydrate slurry was aged at 60 ° C. for 1 hour with stirring. The aged slurry was dehydrated using a flat plate filter and washed with 150 L of 60 ° C. warm water. The cake-like alumina hydrate slurry after washing is diluted with ion-exchanged water so that the concentration of Al 2 O 3 is 10 wt%, and this is aged at 95 ° C. for 10 hours with stirring in a tank equipped with a circulator. did. The slurry after completion of aging was heated while being kneaded with a double-arm kneader equipped with a steam jacket, concentrated to a predetermined moisture content, then cooled and kneaded for 30 minutes. To this kneaded product, 1.66 kg of ultrastable Y-type zeolite (USY) having a lattice constant of 24.00Å was added while kneading with a kneader, and kneaded. The resulting kneaded product was molded into a 1.8 mm cylindrical shape with an extrusion molding machine, dried at 110 ° C., and then fired in an electric furnace at a temperature of 550 ° C. for 3 hours to be ultra-stable at 50 wt%. A Y-type zeolite (USY) -containing alumina support was obtained. The average pore diameter of the carrier determined by mercury porosimetry was 115 mm.
Separately, 277.8 g of molybdenum trioxide and 170.6 g of basic nickel carbonate were placed in a 1 L container, and 600 ml of ion-exchanged water was added and stirred for suspension. This suspension was heated at 95 ° C. for 5 hours so that the amount of the solution did not decrease and was appropriately refluxed. Thereafter, 67.7 g of 85 wt% phosphoric acid was added to this suspension solution to dissolve the suspension to prepare an impregnation solution.
Next, 1000 g of the carrier is placed in a rotary blender capable of vacuum degassing and left for 5 minutes while degassing with a vacuum pump, and then the amount of the impregnated solution prepared above is adjusted to match the water absorption rate of the carrier, The blender was added while rotating. After the addition of the solution, the vacuum pump was stopped and rotated under normal pressure for 20 minutes so that the impregnation solution sufficiently permeated into the carrier. The impregnated product was taken out and placed in a rotary dryer with a temperature raising program, and dried from 40 ° C. to 250 ° C. for 1 hour. The dried product was put in an electric furnace and calcined at 550 ° C. for 1 hour to prepare a catalyst (B). The active metal composition of the obtained catalyst B was MoO 3 : 20.0 wt%, NiO: 5.0 wt%, and P 2 O 5 : 3.0 wt%. Table 1 shows the NH 3 adsorption amount and properties of the catalyst (B).
製造例３
製造例２において、超安定Ｙ型ゼオライト（ＵＳＹ）の使用量を０．３３ｋｇとした以外は製造例２と全く同様にして、１０ｗｔ％超安定Ｙ型ゼオライト（ＵＳＹ）含有アルミナ担体を得た。該担体の水銀圧入法による平均細孔直径は１１０Åであった。該担体を使用して製造例２と同様にして触媒（Ｃ）を調製した。触媒（Ｃ）の活性金属組成は、ＭｏＯ３：２０．０ｗｔ％、ＮｉＯ：５．０ｗｔ％、Ｐ２Ｏ５：３．０ｗｔ％であった。触媒（Ｃ）のＮＨ３吸着量および性状を表１に示す。
Production Example 3
A 10 wt% ultra-stable Y-type zeolite (USY) -containing alumina support was obtained in exactly the same manner as in Production Example 2, except that the amount of ultra-stable Y-type zeolite (USY) used was 0.33 kg. The average pore diameter of the carrier determined by mercury porosimetry was 110 mm. Using the carrier, a catalyst (C) was prepared in the same manner as in Production Example 2. The active metal composition of the catalyst (C) was MoO 3 : 20.0 wt%, NiO: 5.0 wt%, and P 2 O 5 : 3.0 wt%. Table 1 shows the NH 3 adsorption amount and properties of the catalyst (C).
実施例１
第一段目として、容量５０ｍｌの高圧流通式反応装置に製造例１の脱硫触媒（Ａ）３０ｍｌを充填し、第二段目として、第一段目と同じ容量５０ｍｌの高圧流通式反応装置に製造例２の脱硫触媒（Ｂ）を３０ｍｌを充填して軽油の脱硫反応試験を行った。
脱硫反応の前処理として３％Ｈ２Ｓ／Ｈ２ガス流通下で３３０℃３時間硫化処理した。原料油として硫黄（Ｓ）分１．２％、窒素（Ｎ）濃度１５０ｐｐｍ、比重０．８５００の直留軽油を用いた。第一段目、第二段目の反応条件は、それぞれ反応圧力５．５ＭＰａ、水素純度９０％、水素／油比２５０Ｎｍ３／ｍ３、液空間速度２．０ｈｒ−１、反応温度３４０℃の条件で行い、生成油中の硫黄分をＨＯＲＩＢＡ製硫黄・重金属分析機ＭＤＸ１０６０にて分析した。第一段目の高圧流通式反応装置出口の生成油の硫黄濃度を測定したところ３５０ｐｐｍであり、ＨＰ製ＧＣ−ＡＥＤ ＨＰ６８９０／Ｇ２３５０Ａにて分析したところ４−ＭＤＢＴより保持時間の短い硫黄化合物は確認されなかった。第二段目の高圧流通式反応装置出口の生成油の硫黄濃度を表１に示す。
Example 1
As a first stage, a high-pressure flow reactor having a capacity of 50 ml is filled with 30 ml of the desulfurization catalyst (A) of Production Example 1, and as a second stage, a high-pressure flow reactor having the same capacity as that of the first stage is 50 ml. The desulfurization catalyst (B) of Production Example 2 was filled with 30 ml, and a desulfurization reaction test of light oil was performed.
As a pretreatment for the desulfurization reaction, sulfidation was performed at 330 ° C. for 3 hours under a 3% H 2 S / H 2 gas flow. A straight-run gas oil having a sulfur (S) content of 1.2%, a nitrogen (N) concentration of 150 ppm, and a specific gravity of 0.8500 was used as a raw material oil. The reaction conditions for the first stage and the second stage are as follows: reaction pressure 5.5 MPa, hydrogen purity 90%, hydrogen / oil ratio 250 Nm 3 / m 3 , liquid space velocity 2.0 hr −1 , reaction temperature 340 ° C. Under the conditions, the sulfur content in the product oil was analyzed with a sulfur / heavy metal analyzer MDX1060 manufactured by HORIBA. The sulfur concentration of the product oil at the outlet of the first-stage high-pressure flow reactor was measured and found to be 350 ppm. When analyzed by HP GC-AED HP6890 / G2350A, a sulfur compound having a shorter retention time than 4-MDBT was confirmed. Was not. Table 1 shows the sulfur concentration of the product oil at the outlet of the second-stage high-pressure flow reactor.
実施例２
第二段目の触媒を製造例３で調製した触媒（Ｃ）を用いたこと以外は実施例１と全く同様にして軽油の脱硫反応試験を行った。試験結果を表１に示す。
Example 2
A desulfurization reaction test of light oil was performed in the same manner as in Example 1 except that the catalyst (C) prepared in Production Example 3 was used as the second stage catalyst. The test results are shown in Table 1.
比較例１
第一段目、第二段目共に製造例１の触媒（Ａ）を用いたこと以外は実施例１と全く同様にして軽油の脱硫反応試験を行った。試験結果を表１に示す。
Comparative Example 1
A gas oil desulfurization reaction test was conducted in the same manner as in Example 1 except that the catalyst (A) of Production Example 1 was used in both the first and second stages. The test results are shown in Table 1.
比較例２
第一段目、第二段目共に製造例２で調製した触媒（Ｂ）を用いたこと以外は実施例１と全く同様にして軽油の脱硫反応試験を行った。試験結果を表１に示す。
Comparative Example 2
A gas oil desulfurization test was conducted in the same manner as in Example 1 except that the catalyst (B) prepared in Production Example 2 was used in both the first and second stages. The test results are shown in Table 1.
比較例３
第一段目に製造例２で調製した触媒（Ｂ）、第二段目に製造例１で調製した触媒（Ａ）を用いたこと以外は実施例１と全く同様にして軽油の脱硫反応試験を行った。試験結果を表１に示す。
Comparative Example 3
Test for desulfurization of light oil in exactly the same manner as in Example 1 except that the catalyst (B) prepared in Production Example 2 was used in the first stage and the catalyst (A) prepared in Production Example 1 was used in the second stage. Went. The test results are shown in Table 1.
実施例１及び２の水素化脱硫方法では、生成油硫黄分を１０ｐｐｍ以下まで低減させることができたが、比較例１〜３の水素化脱硫方法では生成油硫黄分を１０ｐｐｍ以下まで低減させることができなかった。
In the hydrodesulfurization methods of Examples 1 and 2, the product oil sulfur content could be reduced to 10 ppm or less, but in the hydrodesulfurization methods of Comparative Examples 1 to 3, the product oil sulfur content should be reduced to 10 ppm or less. I could not.
Claims (5)
触媒（１）：アルミナを主成分とする担体に周期律表第VIＢ族金属成分と第VIII族金属成分およびリン成分を担持した触媒であって、触媒の（１ａ）アンモニア昇温脱離法によるアンモニア吸着量が０．５５ｍｍｏｌ／ｇ以下である脱硫触媒。
触媒（２）：結晶性アルミノシリケートゼオライトを含有する多孔性無機酸化物担体に周期律表第VIＢ族金属成分と第VIII族金属成分およびリン成分を担持した触媒であって、触媒の（２ａ）アンモニア昇温脱離法によるアンモニア吸着量が０．６０ｍｍｏｌ／ｇ以上である脱硫触媒。 Gas oil containing sulfur is brought into contact with the following catalyst (1) in the first stage and then hydrodesulfurized, and then in the second stage, it is brought into contact with the following catalyst (2) and hydrodesulfurized to undergo hydrodesulfurization. A hydrodesulfurization method for light oil, characterized in that the sulfur content is 10 ppm or less.
Catalyst (1): A catalyst in which a group VIB metal component, a group VIII metal component, and a phosphorus component of the periodic table are supported on a carrier mainly composed of alumina, and (1a) of the catalyst according to the ammonia temperature-programmed desorption method A desulfurization catalyst having an ammonia adsorption amount of 0.55 mmol / g or less.
Catalyst (2): A catalyst comprising a porous inorganic oxide support containing a crystalline aluminosilicate zeolite carrying a Group VIB metal component, a Group VIII metal component and a phosphorus component of the periodic table, the catalyst (2a) A desulfurization catalyst having an ammonia adsorption amount of 0.60 mmol / g or more by an ammonia temperature-programmed desorption method.
The ratio of the amount of catalyst used between the first stage catalyst (1) and the second stage catalyst (2) [catalyst (1) / catalyst (2)] is 10/90 to 90/10 volume ratio. The hydrodesulfurization method of the light oil in any one of Claims 1-4.
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