JP5508744B2 - Method for producing beta zeolite and method for producing hydrocracking catalyst - Google Patents
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- 229910021536 Zeolite Inorganic materials 0.000 title claims description 103
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims description 103
- 239000010457 zeolite Substances 0.000 title claims description 103
- 239000003054 catalyst Substances 0.000 title claims description 60
- 238000004517 catalytic hydrocracking Methods 0.000 title claims description 49
- 238000004519 manufacturing process Methods 0.000 title claims description 21
- 229910052751 metal Inorganic materials 0.000 claims description 34
- 239000002184 metal Substances 0.000 claims description 34
- 238000000034 method Methods 0.000 claims description 34
- 238000005984 hydrogenation reaction Methods 0.000 claims description 30
- 239000002253 acid Substances 0.000 claims description 26
- 239000011148 porous material Substances 0.000 claims description 18
- 238000010306 acid treatment Methods 0.000 claims description 15
- 230000000694 effects Effects 0.000 claims description 13
- 229910052782 aluminium Inorganic materials 0.000 claims description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 9
- -1 ammonium ions Chemical class 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 7
- 239000011230 binding agent Substances 0.000 claims description 6
- 238000004898 kneading Methods 0.000 claims description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 3
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 3
- 239000003921 oil Substances 0.000 description 31
- 238000006243 chemical reaction Methods 0.000 description 16
- 229910052809 inorganic oxide Inorganic materials 0.000 description 15
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 13
- 238000010438 heat treatment Methods 0.000 description 13
- 238000005470 impregnation Methods 0.000 description 12
- 239000002994 raw material Substances 0.000 description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 229930195733 hydrocarbon Natural products 0.000 description 5
- 150000002739 metals Chemical class 0.000 description 5
- 239000011574 phosphorus Substances 0.000 description 5
- 229910052698 phosphorus Inorganic materials 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 5
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 229910052810 boron oxide Inorganic materials 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 229910052750 molybdenum Inorganic materials 0.000 description 4
- 239000011733 molybdenum Substances 0.000 description 4
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 150000007524 organic acids Chemical class 0.000 description 4
- 230000000737 periodic effect Effects 0.000 description 4
- 229910052721 tungsten Inorganic materials 0.000 description 4
- 239000010937 tungsten Substances 0.000 description 4
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical compound CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 239000001630 malic acid Substances 0.000 description 3
- 235000011090 malic acid Nutrition 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 125000002950 monocyclic group Chemical group 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 150000003018 phosphorus compounds Chemical class 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- 238000004438 BET method Methods 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 239000002734 clay mineral Substances 0.000 description 2
- 229910021446 cobalt carbonate Inorganic materials 0.000 description 2
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 2
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 2
- 239000002358 oil sand bitumen Substances 0.000 description 2
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 2
- 235000011007 phosphoric acid Nutrition 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 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 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- 125000002619 bicyclic group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 150000001869 cobalt compounds Chemical class 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 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
- 238000005536 corrosion prevention Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- VLXBWPOEOIIREY-UHFFFAOYSA-N dimethyl diselenide Natural products C[Se][Se]C VLXBWPOEOIIREY-UHFFFAOYSA-N 0.000 description 1
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000012013 faujasite Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000004231 fluid catalytic cracking Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229910052500 inorganic mineral Chemical class 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 239000011707 mineral Chemical class 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000005078 molybdenum compound Substances 0.000 description 1
- 150000002752 molybdenum compounds Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 150000002816 nickel compounds Chemical class 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 239000003027 oil sand Substances 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- 150000003658 tungsten compounds Chemical class 0.000 description 1
Description
本発明は、ベータゼオライトの製造方法及び水素化分解触媒の製造方法に関する。 The present invention relates to a method for producing beta zeolite and a method for producing a hydrocracking catalyst.
ベータゼオライトは、１９６７年に提示されたゼオライトである。ベータゼオライトは、現在、石油精製触媒として主に使用されているフォージャサイト型に比べて、ゼオライトのミクロ細孔が小さいという特徴がある。また、ベータゼオライトは、吸着剤としての使用例がある。 Beta zeolite is a zeolite presented in 1967. Beta zeolite is characterized in that the micropores of the zeolite are small compared to the faujasite type, which is currently mainly used as a petroleum refining catalyst. Beta zeolite is also used as an adsorbent.
ところで、ゼオライトを水蒸気処理する手法は以前から知られており、主に骨格内のアルミを骨格外に除去し、ケイバン比（ＳｉＯ2／Ａｌ2Ｏ3）を上げる目的で行われてきた。
ベータゼオライトについても同様であり、例えば、ベータゼオライトを水蒸気処理し、その後、酸水溶液で処理することでケイバン比を上げる検討が行われている（例えば、特許文献１参照）。特許文献１に開示される技術は、水蒸気処理後の酸処理工程において、酸を含むアンモニウム溶液で処理することが特徴であり、アンモニウムイオンを含むことで、ゼオライトが安定すると記載されている。
また、特許文献１では、ケイバン比、赤外線吸収スペクトル（ＩＲ）、全表面積についての記述はあるが、メソ細孔についての記載はない。
By the way, the technique of steam-treating zeolite has been known for a long time, and has been mainly performed for the purpose of removing aluminum in the framework outside the framework and increasing the quartz ratio (SiO 2 / Al 2 O 3 ).
The same applies to beta zeolite. For example, studies have been made to increase the Keiban ratio by treating beta zeolite with steam and then treating with an aqueous acid solution (see, for example, Patent Document 1). The technique disclosed in Patent Document 1 is characterized in that it is treated with an ammonium solution containing an acid in the acid treatment step after the steam treatment, and it is described that the zeolite is stabilized by containing ammonium ions.
Moreover, in patent document 1, although there exists description about a Keiban ratio, an infrared absorption spectrum (IR), and a total surface area, there is no description about a mesopore.
本発明は、細孔径２〜１０ｎｍのいわゆるメソ細孔を有し、２８０ｍ2／ｇ以上の外表面積を付与したベータゼオライトの製造方法、及び該ベータゼオライトを用いた水素化分解触媒の製造方法を提供することを目的とする。 The present invention relates to a method for producing beta zeolite having so-called mesopores having a pore diameter of 2 to 10 nm and having an outer surface area of 280 m 2 / g or more, and a method for producing a hydrocracking catalyst using the beta zeolite. The purpose is to provide.
本発明者らは、鋭意検討を重ねた結果、従来から知られているベータゼオライトを、特定の条件で処理することで、細孔径２〜１０ｎｍの細孔、いわゆるメソ細孔を発現させることができることを見出した。本発明はかかる知見に基づいて完成したものである。
すなわち、本発明は、
（１）原料ベータゼオライトを、水蒸気雰囲気下、５５０〜７００℃で処理し、次いで、酸処理する工程を含むベータゼオライトの製造方法であって、前記酸処理に使用する酸量が、原料ベータゼオライトの骨格外アルミニウムを、化学量論的に全量溶解するのに必要な酸量の、１〜１．５倍であることを特徴とする、ＢＪＨ法で求めた細孔径２〜１０ｎｍの細孔の細孔容量が０．２２〜０．５ｍＬ／ｇであるベータゼオライトの製造方法、
（２）前記酸が、アンモニウムイオンを含有しない上記（１）に記載のベータゼオライトの製造方法、
（３）前記原料ベータゼオライトのＳｉＯ2／Ａｌ2Ｏ3比（モル比）が、２０〜３９である上記（１）又は（２）に記載のベータゼオライトの製造方法、
（４）（ｉ）上記（１）〜（３）のいずれかに記載の製造方法により得られるベータゼオライトをバインダーとともに混練し、押し出し、次いで焼成して、ベータゼオライト成形体を得る工程、及び
（ii）ベータゼオライト成形体を少なくとも含有する担体に、少なくとも１つの水素化活性を有する金属成分を担持する工程を有する、水素化分解触媒の製造方法、
（５）上記（１）〜（３）のいずれかに記載の方法により得られるベータゼオライト、及び
（６）上記（４）に記載の方法により得られる水素化分解触媒、
を提供するものである。
As a result of intensive studies, the inventors of the present invention can develop a so-called mesopore having a pore diameter of 2 to 10 nm by treating a conventionally known beta zeolite under specific conditions. I found out that I can do it. The present invention has been completed based on such findings.
That is, the present invention
(1) A process for producing beta zeolite comprising a step of treating a raw beta zeolite in a steam atmosphere at 550 to 700 ° C. and then an acid treatment, wherein the amount of acid used for the acid treatment is the raw beta zeolite 1 to 1.5 times the amount of acid required to dissolve all the stoichiometrically-extra-aluminum aluminum in a pore having a pore diameter of 2 to 10 nm determined by the BJH method. A method for producing beta zeolite having a pore volume of 0.22 to 0.5 mL / g ,
(2) The method for producing beta zeolite according to the above (1), wherein the acid does not contain ammonium ions,
(3) The method for producing beta zeolite according to the above (1) or (2), wherein the raw beta zeolite has a SiO 2 / Al 2 O 3 ratio (molar ratio) of 20 to 39,
(4) (i) a step of kneading the beta zeolite obtained by the production method according to any one of the above (1) to (3) together with a binder, extruding and then calcining to obtain a beta zeolite compact, and ( ii) a method for producing a hydrocracking catalyst, comprising a step of supporting at least one metal component having hydrogenation activity on a support containing at least a beta zeolite molded article,
(5) above (1) to (3) beta zeolite obtainable by the method according to any one of, and (6) above (4) to the hydrocracking catalyst obtained by the method described in
Is to provide.
本発明によれば、メソ細孔を十分に有し、高い外表面積を有するベータゼオライトが得られる。該ベータゼオライトを水素化触媒の担体として用いることで、水素化性能の高い水素化分解触媒を得ることができる。特に、高芳香族炭化水素油を水素化処理して得られる留分を、本発明の方法により製造した水素化分解触媒で水素化分解することにより、石油化学原料として有用な１環芳香族化合物を効率良く得ることができる。 According to the present invention, a beta zeolite having sufficient mesopores and a high outer surface area can be obtained. By using the beta zeolite as a carrier for the hydrogenation catalyst, a hydrocracking catalyst having high hydrogenation performance can be obtained. In particular, a monocyclic aromatic compound useful as a petrochemical raw material by hydrocracking a fraction obtained by hydrotreating a highly aromatic hydrocarbon oil with a hydrocracking catalyst produced by the method of the present invention Can be obtained efficiently.
本発明のベータゼオライトの製造方法は、原料ベータゼオライトを、水蒸気雰囲気下、５５０〜７００℃で処理し、次いで、酸処理する工程を含む。
（原料ベータゼオライト）
原料のベータゼオライト（以下「原料ベータゼオライト」と記載する。）は、ケイバン比が２０〜３９の範囲であることが好ましい。ケイバン比が２０以上であると、十分な水素化分解能力を有するベータゼオライトが得られ、３９以下であると、十分な量のメソ細孔が得られる。以上の観点から、原料ベータゼオライトのケイバン比は、２０〜３０の範囲がさらに好ましい。
また、原料ベータゼオライトは、水蒸気処理する前に、空気雰囲気中、５００〜７００℃の温度で、１〜１２時間程度焼成することが好ましい。該焼成によって、ゼオライト合成時に用いる有機物などを揮散させるためである。
なお、焼成に用いる装置については、特に制限はなく、例えば、ロータリーキルンなどを用いることができる。
The manufacturing method of the beta zeolite of this invention includes the process of processing raw material beta zeolite at 550-700 degreeC in water vapor | steam atmosphere, and then acid-treating.
(Raw material beta zeolite)
The raw beta zeolite (hereinafter referred to as “raw beta beta zeolite”) preferably has a caivan ratio in the range of 20-39. A beta zeolite having a sufficient hydrocracking ability is obtained when the caivan ratio is 20 or more, and a sufficient amount of mesopores is obtained when the ratio is 39 or less. From the above viewpoint, the cayban ratio of the raw material beta zeolite is more preferably in the range of 20-30.
The raw beta zeolite is preferably calcined in an air atmosphere at a temperature of 500 to 700 ° C. for about 1 to 12 hours before steaming. This is to volatilize organic substances used during zeolite synthesis by the calcination.
In addition, there is no restriction | limiting in particular about the apparatus used for baking, For example, a rotary kiln etc. can be used.
（水蒸気処理）
前述の焼成した原料ベータゼオライトを、５５０〜７００℃の水蒸気雰囲気下に曝すことで処理する（以下、「水蒸気処理」と記載する）。水蒸気雰囲気温度が５５０℃未満であると、十分に脱アルミが進行せず、７００℃を超えると、ベータゼオライトの結晶性が低下し、メソ細孔が少なくなる。
水蒸気処理の具体的方法としては、特に制限はなく、例えばロータリーキルンを用い、水蒸気分圧を、通常１０〜１００ｋＰａ、好ましくは、２０〜８０ｋＰａとし、空気により水蒸気分圧を３０〜１００％にして行うことが好適である。
(Steam treatment)
The above-mentioned calcined raw material beta zeolite is treated by exposing it to a steam atmosphere at 550 to 700 ° C. (hereinafter referred to as “steam treatment”). When the steam atmosphere temperature is less than 550 ° C., dealumination does not proceed sufficiently, and when it exceeds 700 ° C., the crystallinity of beta zeolite is lowered and mesopores are reduced.
A specific method of the water vapor treatment is not particularly limited. For example, a rotary kiln is used, the water vapor partial pressure is usually 10 to 100 kPa, preferably 20 to 80 kPa, and the water vapor partial pressure is set to 30 to 100% with air. Is preferred.
（酸処理）
水蒸気処理した後のベータゼオライトをスラリー化し、該スラリーと酸溶液を混合する等の方法で、ベータゼオライトを酸に曝して、ゼオライト中のアルミニウムを除去する。
ここで用いる酸は、アルミニウムを溶解可能であれば特に制限はなく、硝酸、塩酸、硫酸等の鉱酸が使用できるが、入手し易さ、酸強度、装置の腐食防止の面から硫酸あるいは硝酸が好ましい。
(Acid treatment)
The beta zeolite after the steam treatment is slurried, and the beta zeolite is exposed to an acid by a method such as mixing the slurry and an acid solution to remove aluminum in the zeolite.
The acid used here is not particularly limited as long as it can dissolve aluminum, and mineral acids such as nitric acid, hydrochloric acid, and sulfuric acid can be used. However, sulfuric acid or nitric acid is used in terms of availability, acid strength, and corrosion prevention of the apparatus. Is preferred.
酸処理に用いる酸量は、原料ベータゼオライトの骨格外アルミニウムを、化学量論的に全量溶解するのに必要な酸量の、１〜１．５倍であることが必要である。該酸量が１倍未満であると、脱アルミがあまり進行せず、得られるゼオライトの炭化水素分解能力が十分でない。一方、１．５倍を超えると、必要以上にアルミが抜けたり、メソ細孔が少なくなる等の悪影響が生じる。以上の観点から、酸量は、必要酸量の１〜１．４倍であることが好ましい。
酸溶液の濃度は、所望の脱アルミに必要な酸量を含んでいれば特に制限はないが、酸濃度で１〜５０質量％が好ましい。酸濃度が１質量％未満の場合は、必要以上に反応装置の大型化につながり、加熱加圧するためのエネルギーも余分に必要となる。一方、５０質量％を超えると、酸溶液が少なすぎてゼオライトと酸が十分に反応しない部分が生じる。以上の観点から、酸濃度は、５〜３０質量％の範囲が好ましい。
又、本発明で用いる酸溶液は、アンモニウムイオンを含まない事が好ましい。アンモニウムイオンを含む酸溶液を用いると、アルミニウムがゼオライトから抜け難くなる。
The amount of acid used for the acid treatment needs to be 1 to 1.5 times the amount of acid necessary to dissolve all of the extra-framework aluminum of the raw material beta zeolite stoichiometrically. When the acid amount is less than 1 time, dealumination does not proceed so much, and the resulting zeolite has insufficient hydrocarbon decomposition ability. On the other hand, when it exceeds 1.5 times, there are adverse effects such as aluminum coming out more than necessary or mesopores being reduced. From the above viewpoint, the acid amount is preferably 1 to 1.4 times the required acid amount.
The concentration of the acid solution is not particularly limited as long as it contains the amount of acid necessary for desired dealumination, but the acid concentration is preferably 1 to 50% by mass. When the acid concentration is less than 1% by mass, the reaction apparatus becomes larger than necessary, and extra energy for heating and pressurization is required. On the other hand, if it exceeds 50% by mass, there will be a portion where the acid solution is too small and the zeolite and the acid do not sufficiently react. From the above viewpoint, the acid concentration is preferably in the range of 5 to 30% by mass.
Moreover, it is preferable that the acid solution used by this invention does not contain an ammonium ion. When an acid solution containing ammonium ions is used, it becomes difficult for aluminum to escape from the zeolite.
（ベータゼオライトの物性）
上述の水蒸気処理及び酸処理を行ったベータゼオライトは、ＢＪＨ法で求めた細孔径２〜１０ｎｍの細孔（以下「メソ細孔」と記載する場合がある。）の細孔容量が０．２０ｍＬ／ｇ以上であることが好ましい。該細孔容量が０．２０ｍＬ／ｇ以上であると、高い水素化分解能力を有する。水蒸気処理及び酸処理の条件を最適化することで、メソ細孔の細孔容量は、０．２２ｍＬ／ｇ以上とすることができ、さらに高い水素化分解能力を有するベータゼオライトが得られる。
なお、水蒸気処理及び酸処理の条件が過酷な場合には、該細孔容量が過度に大きくなり、ベータゼオライトの結晶化度が低下し、水素化分解能力が十分でない場合がある。以上の観点から、ベータゼオライトのメソ細孔の細孔容量は、０．２２〜０．５ｍＬ／ｇの範囲となるように、水蒸気処理及び酸処理の条件は決定されることがさらに好ましい。
(Physical properties of beta zeolite)
The beta zeolite subjected to the above steam treatment and acid treatment has a pore volume of 0.20 mL of pores having a pore diameter of 2 to 10 nm (hereinafter sometimes referred to as “mesopores”) determined by the BJH method. / G or more is preferable. When the pore volume is 0.20 mL / g or more, the hydrocracking ability is high. By optimizing the steam treatment and acid treatment conditions, the pore volume of the mesopores can be 0.22 mL / g or more, and a beta zeolite having a higher hydrocracking ability can be obtained.
When the conditions of the steam treatment and the acid treatment are severe, the pore volume becomes excessively large, the crystallinity of the beta zeolite is lowered, and the hydrocracking ability may not be sufficient. From the above viewpoint, it is more preferable that the conditions of the steam treatment and the acid treatment are determined so that the pore volume of the mesopores of the beta zeolite is in the range of 0.22 to 0.5 mL / g.
また、上述の水蒸気処理及び酸処理を行ったベータゼオライトは、ｔ−ｐｌｏｔ法で求めた外表面積が２８０ｍ2／ｇ以上であることが好ましい。外表面積が２８０ｍ2／ｇ以上である場合、十分な水素化分解能力が得られる。また、水蒸気処理及び酸処理の条件を最適化することで、外表面積は３００ｍ2／ｇ以上とすることができ、さらに高い水素化分解能力を有するベータゼオライトが得られる。
なお、水蒸気処理及び酸処理の条件が過酷な場合には、該外表面積が過度に大きくなり、ベータゼオライトの結晶化度が低下し、水素化分解能力が十分でない場合がある。以上の観点から、ベータゼオライトの外表面積は、３００〜４００ｍ2／ｇの範囲となるように、水蒸気処理及び酸処理の条件は決定されることがさらに好ましい。
Moreover, it is preferable that the external surface area calculated | required by the t-plot method is 280 m < 2 > / g or more as for the beta zeolite which performed the above-mentioned steam treatment and acid treatment. When the outer surface area is 280 m 2 / g or more, sufficient hydrocracking ability is obtained. Further, by optimizing the conditions of the steam treatment and the acid treatment, the outer surface area can be set to 300 m 2 / g or more, and a beta zeolite having a higher hydrocracking ability can be obtained.
In addition, when the conditions of steam treatment and acid treatment are severe, the outer surface area becomes excessively large, the crystallinity of beta zeolite is lowered, and the hydrocracking ability may not be sufficient. From the above viewpoint, it is more preferable that the conditions of the steam treatment and the acid treatment are determined so that the outer surface area of the beta zeolite is in the range of 300 to 400 m 2 / g.
（水素化分解触媒）
本発明の製造方法により得られるベータゼオライトは、水素化分解触媒の担体として有用である。すなわち、該ベータゼオライトを含む担体に、水素化活性を有する金属成分を担持してなる水素化分解触媒は、非常に有用であり、本発明に包含されるものである。
また、上記水素化分解触媒の担体としては、本発明のベータゼオライトのみからなってもよいが、触媒の物理的強度を増大させ、必要とする分解能力が得られ、かつ過分解が起きないように、さらに耐火性無機酸化物を含むことが好ましい。なお、該耐火性無機酸化物は、後に説明する、触媒担体を製造する際に用いられるバインダーの役割を兼ねることもできる。
耐火性無機酸化物を用いる場合のベータゼオライトの含有量は、担体の質量を基準として、１０〜８０質量％が好適である。１０質量％以上であれば、一定の分解能力が確保でき、８０質量％以下であれば、分解能力が高すぎて、水素化分解が進みすぎることがなく、生成油に含まれる必要な成分、例えば１環芳香族や灯軽油留分が確保される。以上の観点から、担体中のベータゼオライトの含有量は、２０〜８０質量％の範囲がさらに好ましく、３０〜８０質量％の範囲が特に好ましい。
なお、担体の形状としては、特に限定されないが、円柱、三葉、四葉等の成型体が均一な充填がしやすい点で好適である。
(Hydrocracking catalyst)
The beta zeolite obtained by the production method of the present invention is useful as a support for a hydrocracking catalyst. That is, a hydrocracking catalyst obtained by supporting a metal component having hydrogenation activity on a support containing the beta zeolite is very useful and is included in the present invention.
Further, the carrier of the above hydrocracking catalyst may be composed only of the beta zeolite of the present invention, but the physical strength of the catalyst is increased, the required cracking ability is obtained, and no excessive cracking occurs. In addition, it is preferable to further contain a refractory inorganic oxide. The refractory inorganic oxide can also serve as a binder used when producing a catalyst carrier, which will be described later.
When the refractory inorganic oxide is used, the content of beta zeolite is preferably 10 to 80% by mass based on the mass of the support. If it is 10% by mass or more, a certain decomposition ability can be secured, and if it is 80% by mass or less, the decomposition ability is too high and hydrocracking does not proceed excessively, and necessary components contained in the product oil, For example, a single ring aromatic or kerosene oil fraction is secured. From the above viewpoint, the content of beta zeolite in the carrier is more preferably in the range of 20 to 80% by mass, and particularly preferably in the range of 30 to 80% by mass.
The shape of the carrier is not particularly limited, but it is preferable in that a molded body such as a cylinder, a trilobe, or a four-leaf is easily filled uniformly.
＜耐火性無機酸化物＞
耐火性無機酸化物としては特に制限はなく、アルミナ、シリカ−アルミナ、シリカ−ボリア（酸化ホウ素）、アルミナ−ボリア（酸化ホウ素）、粘土鉱物などが挙げられる。本発明においては、触媒の表面積を広くでき、水素化活性金属を含む水溶液で、該金属を担持させやすい点から、アルミナが好ましい。なお、本発明における耐火性無機酸化物には、ベータゼオライトは含まない。
このような耐火性無機酸化物は、１種を単独で用いることもできるし、また２種以上を併用することもできる。
<Fireproof inorganic oxide>
The refractory inorganic oxide is not particularly limited, and examples thereof include alumina, silica-alumina, silica-boria (boron oxide), alumina-boria (boron oxide), and clay mineral. In the present invention, alumina is preferred because the surface area of the catalyst can be increased and the metal can be easily supported in an aqueous solution containing a hydrogenation active metal. The refractory inorganic oxide in the present invention does not contain beta zeolite.
Such refractory inorganic oxides can be used alone or in combination of two or more.
＜水素化活性を有する金属成分＞
水素化活性を有する金属成分（以下「水素化活性金属成分」と記載する。）とは、炭化水素を水素化処理可能な性能を持つ金属又は金属化合物を意味する。通常は、水素化脱硫、水素化脱窒素、水素化脱メタル、水素化分解の少なくとも一つの効果を有する。水素化活性金属成分としては、周期律第６、８、９、及び１０族金属が挙げられ、特に、モリブデン、タングステン、コバルト、ニッケル等が水素化処理能力に優れる点で好適である。
モリブデン化合物としては三酸化モリブデン、モリブデン酸アンモニウム等が好ましく、タングステン化合物としては、三酸化タングステン、タングステン酸アンモニウム等が好ましい。コバルト化合物としては、炭酸コバルト、塩基性炭酸コバルト、硝酸コバルト等が好ましく、ニッケル化合物としては、炭酸ニッケル、塩基性炭酸ニッケル、硝酸ニッケル等が好ましい。
さらに、リン化合物も担持成分として好適に用いることができ、リン化合物としては、五酸化リン、正リン酸等の各種リン酸が使用される。
<Metal component having hydrogenation activity>
The metal component having hydrogenation activity (hereinafter referred to as “hydrogenation active metal component”) means a metal or metal compound having a performance capable of hydrotreating hydrocarbons. Usually, it has at least one effect of hydrodesulfurization, hydrodenitrogenation, hydrodemetallation, and hydrocracking. Examples of the hydrogenation active metal component include metals of Group 6, 8, 9, and 10 in the periodic table, and molybdenum, tungsten, cobalt, nickel, and the like are particularly preferable in terms of excellent hydrogenation treatment ability.
As the molybdenum compound, molybdenum trioxide, ammonium molybdate and the like are preferable, and as the tungsten compound, tungsten trioxide, ammonium tungstate and the like are preferable. As the cobalt compound, cobalt carbonate, basic cobalt carbonate, cobalt nitrate and the like are preferable, and as the nickel compound, nickel carbonate, basic nickel carbonate, nickel nitrate and the like are preferable.
Furthermore, phosphorus compounds can also be suitably used as the supporting component, and various phosphoric acids such as phosphorus pentoxide and orthophosphoric acid are used as the phosphorus compound.
本発明の水素化分解触媒中の水素化活性金属の担持量は、触媒体として、酸化物基準で１〜４０質量％の範囲が好ましい。水素化活性金属の担持量が１質量％以上であると、触媒活性が十分に発現し、４０質量％以下であると、金属の分散不良による活性低下がなく、触媒の強度不足等の悪影響を触媒体に与えることがない。また、担持した金属量に見合う触媒活性も得られない。以上の観点から、水素化活性金属の担持量は、酸化物基準で５〜３０質量％の範囲がより好ましい。
さらに、好ましい担持量は、水素化活性金属の種類に応じて異なり、触媒体として、酸化物基準で、モリブデン（ＭｏＯ3）、タングステン（ＷＯ3）の場合は、１０〜３０質量％の範囲が好ましく、コバルト（ＣｏＯ）、ニッケル（ＮｉＯ）の場合は１〜６質量％の範囲が好ましく、リン（Ｐ2Ｏ5）は５質量％以下が好適である。
The supported amount of the hydrogenation active metal in the hydrocracking catalyst of the present invention is preferably in the range of 1 to 40% by mass on the oxide basis as the catalyst body. When the supported amount of the hydrogenation active metal is 1% by mass or more, the catalytic activity is sufficiently developed, and when it is 40% by mass or less, there is no decrease in activity due to poor metal dispersion and there is an adverse effect such as insufficient catalyst strength. It is not given to the catalyst body. In addition, catalytic activity commensurate with the amount of supported metal cannot be obtained. From the above viewpoint, the supported amount of the hydrogenation active metal is more preferably in the range of 5 to 30% by mass on the oxide basis.
Further, the preferred loading varies depending on the type of hydrogenation active metal, and in the case of molybdenum (MoO 3 ) and tungsten (WO 3 ) as the catalyst body on the oxide basis, the range is from 10 to 30% by mass. Preferably, in the case of cobalt (CoO) and nickel (NiO), the range of 1 to 6% by mass is preferable, and phosphorus (P 2 O 5 ) is preferably 5% by mass or less.
（水素化分解触媒の製造方法）
本発明の水素化分解触媒の製造方法は、下記（ｉ）及び（ii）の工程を含むものである。
（ｉ）本発明の方法により得られるベータゼオライトをバインダーとともに混練し、押し出し、次いで焼成して、ベータゼオライト成形体を得る工程、及び
（ii）ベータゼオライト成形体を少なくとも含有する担体に、少なくとも1つの水素化活性を有する金属成分を担持する工程
(Method for producing hydrocracking catalyst)
The method for producing a hydrocracking catalyst of the present invention includes the following steps (i) and (ii).
(I) a step of kneading the beta zeolite obtained by the method of the present invention together with a binder, extruding and then calcining to obtain a beta zeolite molded body, and (ii) a carrier containing at least the beta zeolite molded body at least 1 For supporting a metal component having two hydrogenation activities
上記（ｉ）の工程において用いられる、バインダーとしては前述の耐火性無機酸化物にて例示したものを用いることができ、これらのうち、特にアルミナ、シリカ、シリカアルミナ、ボリア、ボリアアルミナなどが好適に挙げられる。
上述の工程で得られたベータゼオライトをバインダーとともに、通常の方法で混練し、押し出し成形し、焼成して、ベータゼオライト成形体を得る。押し出しの際の担体の形状は、特に限定されないが、前述のように、均一な充填がしやすい点から、円柱、三葉、四葉等となるように押し出される。また、焼成温度は３００〜７５０℃であることが好ましく、通常０．１〜２４時間程度行われる。なお、焼成の前に３０〜２００℃程度の温度で乾燥工程を有していてもよい。
As the binder used in the step (i), those exemplified in the above-mentioned refractory inorganic oxide can be used, and among these, alumina, silica, silica alumina, boria, boria alumina and the like are particularly preferable. It is mentioned in.
The beta zeolite obtained in the above process is kneaded together with a binder by an ordinary method, extruded, and fired to obtain a beta zeolite molded body. Although the shape of the carrier at the time of extrusion is not particularly limited, as described above, it is extruded so as to be a cylinder, a trilobal, a four-lobed, etc. from the viewpoint of easy uniform filling. Moreover, it is preferable that a calcination temperature is 300-750 degreeC, and is normally performed for about 0.1 to 24 hours. In addition, you may have a drying process at the temperature of about 30-200 degreeC before baking.
上記（ii）の工程における水素化活性を有する金属成分は、前記水素化活性金属成分と同様である。
水素化活性金属成分は、通常、含浸法により、担体に担持されるが、本発明においては、本発明の新規ベータゼオライトを担体として、これに水素化活性金属成分を担持することができる。また、担体として、耐火性無機酸化物を併用する場合には、水素化活性金属成分を、本発明の方法により得られたベータゼオライト、又は耐火性無機酸化物の一方に担持させた後、両者を混合してもよいし、新規ベータゼオライトと耐火性無機酸化物をあらかじめ混合して担体を調製しておき、これに水素化活性金属成分を担持してもよい。
The metal component having hydrogenation activity in the step (ii) is the same as the hydrogenation active metal component.
The hydrogenation active metal component is usually supported on a support by an impregnation method. In the present invention, the hydrogenation active metal component can be supported on the novel beta zeolite of the present invention as a support. Further, when a refractory inorganic oxide is used in combination as a carrier, the hydrogenation active metal component is supported on one of the beta zeolite obtained by the method of the present invention or the refractory inorganic oxide, The carrier may be prepared by previously mixing a novel beta zeolite and a refractory inorganic oxide, and a hydrogenation active metal component may be supported on the support.
上記の周期律第６、８、９、及び１０族金属ならびにリン化合物は別々に含浸してもよいが、同時に行なうのが効率的である。通常は、含浸液中の水素化活性金属及びリンの含有量は、目標とする担持量から計算で求める。これらの金属を脱イオン水に溶解させた後、その含浸液の液量を用いる担体の吸水量に等しくなるように調整した後、含浸させる。
なお、水素化活性金属の溶解性や触媒体内部における分布を改善するために、含浸液に有機酸を添加することも行なわれる。有機酸としては、クエン酸やリンゴ酸が好適である。
さらには、上述した活性金属を高分散化するために界面活性剤等の水溶性有機物を添加することができ、その中でも分子量が９０〜１００００のポリエチレングリコールが好適である。該ポリエチレングリコールを添加する場合、添加量は担体に対して好ましくは２〜２０質量％、より好ましくは３〜１５質量％の範囲が好適である。添加量が小さすぎると効果がなく、多すぎても効果がないためである。
Although the above-mentioned periodic groups 6, 8, 9, and 10 metals and phosphorus compounds may be impregnated separately, it is efficient to carry out them simultaneously. Usually, the content of the hydrogenation active metal and phosphorus in the impregnating solution is obtained by calculation from the target loading amount. After these metals are dissolved in deionized water, the amount of the impregnating liquid is adjusted to be equal to the amount of water absorbed by the carrier, and then impregnated.
In order to improve the solubility of the hydrogenation active metal and the distribution inside the catalyst body, an organic acid is also added to the impregnation liquid. As the organic acid, citric acid and malic acid are suitable.
Furthermore, in order to highly disperse the active metal described above, a water-soluble organic substance such as a surfactant can be added, and among these, polyethylene glycol having a molecular weight of 90 to 10,000 is preferable. When the polyethylene glycol is added, the addition amount is preferably 2 to 20% by mass, more preferably 3 to 15% by mass with respect to the carrier. This is because if the amount added is too small, there is no effect, and if it is too much, there is no effect.
上記含浸処理の後に、通常熱処理を行なう。逐次的に含浸を実施する場合には、含浸の度に熱処理を行なうことも可能であるし、複数の含浸を行なった後、最後に熱処理を行なうこともできる。熱処理は空気中で、３００〜７５０℃、好ましくは４５０〜７００℃で行なう。熱処理時間としては、１〜１０時間程度、さらには２〜７時間程度行なうことが好適である。 After the impregnation treatment, a normal heat treatment is performed. When the impregnation is performed sequentially, the heat treatment can be performed every time the impregnation is performed, or after a plurality of impregnations, the heat treatment can be finally performed. The heat treatment is performed in air at 300 to 750 ° C, preferably 450 to 700 ° C. The heat treatment time is preferably about 1 to 10 hours, more preferably about 2 to 7 hours.
（水素化分解方法）
本発明の製造方法により得られる水素化分解触媒を用いて、炭化水素類を水素化分解する方法としては、例えば、固定床（充填層）、移動床、懸濁床（スラリー床）、沸騰床などの反応形式を用いて、炭化水素類と共に、該水素化分解触媒を装入し、水素ガス含有雰囲気下で、３００〜５００℃程度に加熱することにより行うことができる。
本発明により製造される水素化分解触媒は、種々の原料油に対して用いることができるが、特に、多環芳香族を１０容量％以上含む高芳香族炭化水素油、例えば、流動接触分解装置由来のもの（Light Cyclic Oil；以下「ＬＣＯ」と記載する。）、コーカー等の熱分解装置由来のもの（以下「コーカー油」と記載する。）、あるいはオイルサンド等の劣質な油を起源としたもの（以下「オイルサンドビチューメン」と記載する。）、ならびにこれらの高芳香族含有炭化水素油を混合したもの（以下、単に「混合油」と記載する。）を原料油として用いることが好ましい。これらの留分は、一般に２環、３環芳香族が多く、本発明の新規水素化分解触媒で処理することで、付加価値の高い１環芳香族に変換することが可能である。
(Hydrolysis method)
Examples of the method for hydrocracking hydrocarbons using the hydrocracking catalyst obtained by the production method of the present invention include a fixed bed (packed bed), a moving bed, a suspended bed (slurry bed), and a boiling bed. The reaction can be carried out by charging the hydrocracking catalyst together with hydrocarbons and heating to about 300 to 500 ° C. in a hydrogen gas-containing atmosphere.
The hydrocracking catalyst produced according to the present invention can be used for various feedstock oils, and in particular, a highly aromatic hydrocarbon oil containing 10% by volume or more of a polycyclic aromatic, such as a fluid catalytic cracker. Originated from light-derived oil (Light Cyclic Oil; hereinafter referred to as “LCO”), derived from a pyrolysis device such as coker (hereinafter referred to as “coker oil”), or inferior oil such as oil sand. (Hereinafter referred to as “oil sand bitumen”) and a mixture of these highly aromatic hydrocarbon oils (hereinafter simply referred to as “mixed oil”) are preferably used as the raw material oil. . These fractions generally have many bicyclic and tricyclic aromatics, and can be converted to monocyclic aromatics with high added value by treating with the novel hydrocracking catalyst of the present invention.
本発明の水素化分解触媒を用い、ＬＣＯ、コーカー油、オイルサンドビチューメン、混合油などを処理して、１環芳香族の多い油を得る方法として、これらの原料油を、例えば市販の水素化処理触媒で水素化処理し、その上で本発明の水素化分解触媒を用いて、水素化分解することが好ましい。
水素化処理の条件としては、反応温度：２５０〜４２０℃、水素分圧：５〜１５ＭＰａ、液空間速度：０．２〜３．０ｈ-1であることが好ましく、水素化分解の条件としては、反応温度：３００〜４４０℃、水素分圧：５〜１５ＭＰａ、好ましくは６〜１２ＭＰａ、ＬＨＳＶ(液空間速度)：０．３〜３．０ｈ-1である。
なお、ここで水素化処理とは、通常、水素化脱硫、水素化脱金属、水素化脱窒素、芳香族への核水添のいずれか一以上の処理を行うことをいう。
As a method of treating LCO, coker oil, oil sand bitumen, mixed oil and the like using the hydrocracking catalyst of the present invention to obtain an oil having a large amount of monocyclic aromatics, these feedstock oils are obtained by, for example, commercially available hydrogenation. It is preferable to hydrotreat with the treating catalyst and then hydrocrack using the hydrocracking catalyst of the present invention.
The hydrotreating conditions are preferably a reaction temperature: 250 to 420 ° C., a hydrogen partial pressure: 5 to 15 MPa, and a liquid space velocity: 0.2 to 3.0 h −1. Reaction temperature: 300 to 440 ° C., hydrogen partial pressure: 5 to 15 MPa, preferably 6 to 12 MPa, LHSV (liquid space velocity): 0.3 to 3.0 h −1 .
Here, the hydrotreating usually means performing at least one of hydrodesulfurization, hydrodemetallation, hydrodenitrogenation, and nuclear hydrogenation to aromatics.
上記水素化処理触媒としては，周期律第６、８、９、及び１０族金属のうちの少なくとも一種を耐火性無機酸化物担体に担持した触媒を好適に用いることができる。
水素化活性金属成分としては、例えば、モリブデン、タングステン、コバルト、ニッケル等が好適である。さらに、リン化合物を担持させることができる。担持量は触媒体として、酸化物基準で、モリブデン、タングステンが１０〜４０質量％、コバルト、ニッケルが２〜１０質量％、リンが１〜１０質量％が好適である。
As the above-mentioned hydrotreating catalyst, a catalyst in which at least one of Periodic Group 6, 8, 9, and 10 metals is supported on a refractory inorganic oxide carrier can be suitably used.
As the hydrogenation active metal component, for example, molybdenum, tungsten, cobalt, nickel and the like are suitable. Furthermore, a phosphorus compound can be supported. The supported amount of the catalyst body is preferably 10 to 40% by mass of molybdenum and tungsten, 2 to 10% by mass of cobalt and nickel, and 1 to 10% by mass of phosphorus on the oxide basis.
これらの水素化活性金属化合物は、通常含浸法により各種耐火性無機酸化物担体に担持される。上記の周期律第６、８、９、及び１０族金属ならびにリン化合物は別々に含浸しても良いが、同時に行なうのが効率的である。なお、水素化活性金属の触媒体内部における分布を改善するために、含浸液に有機酸を添加することも行なわれる。有機酸としては、クエン酸やリンゴ酸が好適である。さらには、上述した活性金属を高分散化するために界面活性剤等の水溶性有機物を添加することができる。添加量は担体に対して２〜２０質量％の範囲が好ましく、３〜１５質量％の範囲がより好ましい。上記含浸処理の後に、通常熱処理を行なう。逐次的に含浸を実施する場合には、含浸の度に熱処理を行なうことも可能であるし、複数の含浸を行なった後、最後に熱処理を行なうこともできる。熱処理は空気中で、通常５５０℃以下の条件で行なう。触媒の種類に応じて、３００℃以下の比較的低温で熱処理を行なうこともある。熱処理時間としては、０．５〜４８時間程度、さらに好ましくは１〜２４時間程度行である。 These hydrogenated active metal compounds are usually supported on various refractory inorganic oxide supports by an impregnation method. The above-mentioned periodic rules Group 6, 8, 9, and 10 metals and phosphorus compounds may be impregnated separately, but it is efficient to carry out them simultaneously. In order to improve the distribution of the hydrogenation active metal inside the catalyst body, an organic acid is also added to the impregnation liquid. As the organic acid, citric acid and malic acid are suitable. Furthermore, a water-soluble organic substance such as a surfactant can be added in order to highly disperse the active metal described above. The addition amount is preferably in the range of 2 to 20% by mass, more preferably in the range of 3 to 15% by mass with respect to the support. After the impregnation treatment, a normal heat treatment is performed. When the impregnation is performed sequentially, the heat treatment can be performed every time the impregnation is performed, or after a plurality of impregnations, the heat treatment can be finally performed. The heat treatment is usually performed in air at a temperature of 550 ° C. or lower. Depending on the type of catalyst, heat treatment may be performed at a relatively low temperature of 300 ° C. or lower. The heat treatment time is about 0.5 to 48 hours, more preferably about 1 to 24 hours.
担体として用いられる耐火性無機酸化物としては、特に制限はないが、アルミナ、シリカ−アルミナ、シリカ−ボリア（酸化ホウ素）、アルミナ−ボリア（酸化ホウ素）、粘土鉱物及びそれらの混合物等が好適に使用される。これらの中でも、アルミナ、シリカ−アルミナが好適である。
さらには、アルミナに水溶性チタン化合物を含浸・担持したものも好適に使用される。チタンを担持する場合、１〜１０質量％、好ましくは２〜５質量％の担持量が好適である。これらの耐火性無機酸化物の表面積は、通常１００〜４００ｍ2／ｇであることが好ましく、１５０〜３００ｍ2／ｇがより好ましい。
また、担体の平均細孔径は、通常５〜３０ｎｍの範囲、さらには６〜１５ｎｍの範囲が好適である。担体の形状としては特に限定されないが、円柱、三葉、四葉等の成型体が好適に使用される。
The refractory inorganic oxide used as the carrier is not particularly limited, but alumina, silica-alumina, silica-boria (boron oxide), alumina-boria (boron oxide), clay minerals and mixtures thereof are preferable. used. Among these, alumina and silica-alumina are preferable.
Furthermore, what impregnated and carry | supported the water-soluble titanium compound in the alumina is used suitably. When titanium is supported, a supported amount of 1 to 10% by mass, preferably 2 to 5% by mass is suitable. The surface area of these refractory inorganic oxide is preferably from normal 100~400m 2 / g, 150~300m 2 / g is more preferable.
Moreover, the average pore diameter of the carrier is usually preferably in the range of 5 to 30 nm, and more preferably in the range of 6 to 15 nm. Although it does not specifically limit as a shape of a support | carrier, Moldings, such as a cylinder, a trilobe, and a four-leaf, are used suitably.
以下に、本発明を実施例によりさらに具体的に説明するが、本発明は、これらの実施例によってなんら限定されるものではない。
（ベータゼオライトの物性評価方法）
１．表面積
前処理として試料を４００℃、３時間、真空排気を行った。表面積は、ＢＥＴ多点法により測定した（Ｐ／Ｐ０＝０．１以下、Ｐ０は液体窒素温度での窒素の飽和蒸気圧、Ｐは導入した窒素分圧）。
２．細孔径２〜１０ｎｍの細孔容量（ｍＬ／ｇ）及び平均メソ細孔径
ＢＥＴ法により測定した値からＢＪＨ法にて計算して求めた。
３．外表面積（ｍ2／ｇ）
ＢＥＴ法により測定した値からｔ−ｐｌｏｔ法にて計算して求めた。
EXAMPLES The present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples.
(Method for evaluating physical properties of beta zeolite)
1. Surface area As a pretreatment, the sample was evacuated at 400 ° C. for 3 hours. The surface area was measured by the BET multipoint method (P / P0 = 0.1 or less, P0 is the saturated vapor pressure of nitrogen at the liquid nitrogen temperature, and P is the introduced nitrogen partial pressure).
2. The pore volume (mL / g) and the average mesopore diameter with a pore diameter of 2 to 10 nm were calculated by the BJH method from the values measured by the BET method.
3. External surface area (m 2 / g)
It calculated | required by calculating with the t-plot method from the value measured by BET method.
（触媒活性の評価）
１．原料油
第１表に記載の重油流動接触分解装置から留出する高芳香族炭化水素油（分解軽油、以下「ＬＣＯ１」と記載する。）を、後述する水素化処理触媒Ａを充填した反応器に通油して、水素化処理し、第１表に記載する性状を有する高芳香族炭化水素油（以下「ＬＣＯ２」と記載する。）を得た。反応条件は、反応温度３４５℃、反応圧力６．８６ＭＰａ、ＬＨＳＶ（液空間速度）１．６ｈ-1で行った。なお、水素化処理触媒Ａに通油した後の油については、窒素バブリング等による硫化水素の除去を行わずに回収した。
(Evaluation of catalytic activity)
1. Reactor filled with hydrotreating catalyst A, which will be described later, as a highly aromatic hydrocarbon oil (cracked light oil, hereinafter referred to as “LCO1”) distilled from the heavy oil fluid catalytic cracking apparatus shown in Table 1 And high-hydrocarbon hydrocarbon oil (hereinafter referred to as “LCO 2”) having the properties described in Table 1. The reaction conditions were a reaction temperature of 345 ° C., a reaction pressure of 6.86 MPa, and an LHSV (liquid space velocity) of 1.6 h −1 . The oil after passing through the hydrotreating catalyst A was recovered without removing hydrogen sulfide by nitrogen bubbling or the like.
２．水素化処理触媒Ａ
ＣｏＭｏ系の市販軽油水素化脱硫触媒（日本ケッチェン社製「ＫＦ７５７Ｈ」）を、軽油水素化脱硫装置にて、硫黄分の目標を１０質量ｐｐｍ以下で、反応温度３３０〜３７０℃、ＬＨＳＶ＝１．０〜１．５ｈ-1、水素分圧４．９ＭＰａ、水素／油比２５０Ｎｍ3／ｋＬで２年間運転したものを水素化処理触媒Ａとした。
2. Hydrotreating catalyst A
A CoMo commercial light oil hydrodesulfurization catalyst (“KF757H” manufactured by Nippon Ketjen Co., Ltd.) was used in a light oil hydrodesulfurization device, with a sulfur content target of 10 mass ppm or less, a reaction temperature of 330 to 370 ° C., LHSV = 1. A catalyst that was operated for 2 years at 0 to 1.5 h −1 , a hydrogen partial pressure of 4.9 MPa, and a hydrogen / oil ratio of 250 Nm 3 / kL was designated as a hydrotreating catalyst A.
３．評価方法
高圧固定床流通式のベンチ反応器を直列に連結し、実施例及び比較例にて調製した水素化分解触媒を用いて水素化分解反応を実施した。原料油は水素ガス（ボンベの純水素を昇圧して使用）とともに反応管の上段から導入するダウンフロー形式で反応器内に流通させた
水素化分解触媒を５ｍＬ、反応器に充填した。前処理として、ＤＭＤＳ（ジメチルジスルフィド）を添加し、硫黄濃度を２質量％に調整した軽油留分（Light Gas Oil；ＬＧＯ）をベースとする予備硫化油を水素ガスとともに反応器に流通させて、温度２５０℃で１０時間予備硫化を行なった。
次に、第１表に記載したＬＣＯ２に切り替えて、水素化分解反応を行なった。反応温度は３６０〜３７５℃の範囲で、転化率が７５質量％になるように制御した。反応圧力は水素化分解反応器出口で６．９ＭＰａ、水素／原料油比は、反応器入口で２，０００Ｎｍ3／ｋＬ、ＬＨＳＶ（液空間速度）は１．５ｈ-1の条件に調整し、ベンチ試験を行なった。水素化分解触媒に通油後のガスについては流量を測定するとともに、ガスクロにて分析し、生成油については秤量した。生成油は、蒸留ガスクロおよびＦＩＤのガスクロにて、バックフラッシュを行い、定性を行った。
触媒活性は、原料油中の、常圧での沸点が３４０℃以上の留分の転化率及び１環芳香族の収率で評価した。なお、３環芳香族であるフェナントレンの沸点が３４０℃であるので、３４０℃以上の留分の転化率が高いほど、３環芳香族の分解率が高いことを意味する。
3. Evaluation Method A high pressure fixed bed flow type bench reactor was connected in series, and a hydrocracking reaction was carried out using the hydrocracking catalysts prepared in Examples and Comparative Examples. The raw material oil was charged with 5 mL of hydrocracking catalyst circulated in the reactor in a down flow manner introduced from the upper stage of the reaction tube together with hydrogen gas (using pure hydrogen in a cylinder under pressure). As a pretreatment, DMDS (dimethyl disulfide) was added and a presulfurized oil based on a light oil fraction (LGO) with a sulfur concentration adjusted to 2% by mass was passed through the reactor together with hydrogen gas, Presulfiding was performed at a temperature of 250 ° C. for 10 hours.
Next, the hydrocracking reaction was carried out by switching to LCO2 described in Table 1. The reaction temperature was controlled in the range of 360 to 375 ° C. so that the conversion rate was 75% by mass. The reaction pressure was adjusted to 6.9 MPa at the hydrocracking reactor outlet, the hydrogen / feed oil ratio was adjusted to 2,000 Nm 3 / kL at the reactor inlet, and the LHSV (liquid space velocity) was 1.5 h −1 . A bench test was performed. The flow rate of the gas after passing through the hydrocracking catalyst was measured and analyzed by gas chromatography, and the product oil was weighed. The produced oil was qualitatively subjected to backflushing by distillation gas chromatography and FID gas chromatography.
The catalytic activity was evaluated by the conversion rate of the fraction having a boiling point of 340 ° C. or higher in the raw material oil and the yield of monocyclic aromatics. In addition, since the boiling point of phenanthrene which is tricyclic aromatic is 340 degreeC, it means that the decomposition rate of tricyclic aromatic is so high that the conversion of the fraction of 340 degreeC or more is high.
実施例１（本発明のベータゼオライトの調製）
市販のベータゼオライト(東ソー（株）製「９２０ＮＨＡ」、ケイバン比２０)を原料ベータゼオライトとして用い、該ベータゼオライトを、空気雰囲気中で５８０℃にて、１．５時間、ロータリーキルンを用いて焼成した。焼成により得られたゼオライトをベータゼオライト１とする。
該ベータゼオライト１を、水蒸気に空気を混合したもの（水蒸気の混合率８０容量％、水蒸気分圧２０ｋＰａ（０．２Ｂａｒ））を用いて、６３０℃で３０分間、水蒸気処理を行った。その後、該ゼオライトを７０℃の温水に１０質量％スラリーとし、１０質量％硫酸水溶液３２８．４４ｍＬを３０分で添加した後、３０分熟成した。その後、吸引ろ過で回収し、６０℃の温水で洗浄し、本発明のベータゼオライト２を得た。
なお、ここで用いた硫酸水溶液は、ゼオライトの骨格外アルミニウムを全量、硫酸アルミニウムとして溶解した場合の１．４倍量に相当する。
ベータゼオライト２について、上記方法にて物性を評価した。評価結果を第２表に示す。また、参考例として、ベータゼオライト１についても、同様に評価結果を示す。
Example 1 (Preparation of beta zeolite of the present invention)
A commercially available beta zeolite (“920NHA” manufactured by Tosoh Corporation, Kayban ratio 20) was used as a raw material beta zeolite, and the beta zeolite was calcined in an air atmosphere at 580 ° C. for 1.5 hours using a rotary kiln. . The zeolite obtained by calcination is designated as beta zeolite 1.
The beta zeolite 1 was steam-treated at 630 ° C. for 30 minutes using a mixture of steam and air (mixing ratio of steam 80% by volume, steam partial pressure 20 kPa (0.2 Bar)). Thereafter, the zeolite was made into a 10% by mass slurry in warm water at 70 ° C., 328.44 mL of 10% by mass sulfuric acid aqueous solution was added in 30 minutes, and then aged for 30 minutes. Then, it collect | recovered by suction filtration and wash | cleaned with 60 degreeC warm water, and obtained the beta zeolite 2 of this invention.
In addition, the sulfuric acid aqueous solution used here corresponds to 1.4 times the total amount of zeolite extra-framework aluminum dissolved as aluminum sulfate.
About the beta zeolite 2, the physical property was evaluated by the said method. The evaluation results are shown in Table 2. As a reference example, the evaluation results of beta zeolite 1 are also shown.
比較例１（比較水素化分解触媒の調製）
アルミナ粉に硝酸水溶液を添加し、２０分程度捏和した後、実施例１において、原料ゼオライトを焼成処理して得たベータゼオライト１（上記、第２表参考例）を添加し、１時間捏和した。アルミナと該ゼオライトは乾燥物基準の重量比で５０対５０になる割合とした。この捏和物を１／１６の四葉型の成型物とし、１２０℃で３時間乾燥し、さらに５５０℃で３時間焼成し、ゼオライト含有組成物を得た。
次いで、三酸化モリブデンと炭酸コバルトを純水に懸濁したものを９０℃に加熱し、次いでリンゴ酸を加え溶解させた。この溶解液を該ゼオライト含有組成物にそれぞれ触媒全体に対して、仕込みのＭｏＯ3として６質量％、ＣｏＯとして２質量％になるように含浸し、次いで乾燥させ、５５０℃で３時間焼成し、比較水素化分解触媒１を得た。該比較水素化分解触媒１について、上記方法にて評価した結果を第３表に示す。
Comparative Example 1 (Preparation of comparative hydrocracking catalyst)
After adding nitric acid aqueous solution to the alumina powder and kneading for about 20 minutes, in Example 1, beta zeolite 1 (above, reference example in Table 2) obtained by calcining the raw material zeolite was added, and the mixture was stirred for 1 hour. It was summed up. Alumina and the zeolite were in a ratio of 50 to 50 on a dry matter basis weight ratio. This kneaded product was formed into a 1/16 four-leaf molded product, dried at 120 ° C. for 3 hours, and further calcined at 550 ° C. for 3 hours to obtain a zeolite-containing composition.
Next, a suspension of molybdenum trioxide and cobalt carbonate in pure water was heated to 90 ° C., and then malic acid was added and dissolved. The solution was impregnated in the zeolite-containing composition so that the total amount of the catalyst was 6% by mass as the charged MoO 3 and 2% by mass as CoO, then dried and calcined at 550 ° C. for 3 hours. A comparative hydrocracking catalyst 1 was obtained. Table 3 shows the results of the comparative hydrocracking catalyst 1 evaluated by the above method.
実施例２（本発明の水素化分解触媒の調製）
比較例１において、ベータゼオライト１に代えて、実施例１で調製したベータゼオライト２を用いたこと以外は、比較例１と同様にして、水素化分解触媒２（本発明の水素化分解触媒）を得た。該水素化分解触媒２について、上記方法にて評価した結果を第３表に示す。
Example 2 (Preparation of hydrocracking catalyst of the present invention)
In Comparative Example 1, hydrocracking catalyst 2 (hydrocracking catalyst of the present invention) was used in the same manner as in Comparative Example 1, except that beta zeolite 2 prepared in Example 1 was used instead of beta zeolite 1. Got. The results of evaluating the hydrocracking catalyst 2 by the above method are shown in Table 3.
実施例２より調製された触媒は、担体のベータゼオライトにメソ細孔が付与されているため、重質分が触媒内に拡散しやすくなり、重質分がより分解されていることがわかる。 In the catalyst prepared from Example 2, since the mesopores are imparted to the support beta zeolite, it is understood that the heavy component is easily diffused into the catalyst, and the heavy component is further decomposed.
本発明の製造方法により得られるベータゼオライトは、メソ細孔を十分に有し、高い外表面積を有するベータゼオライトである。該ベータゼオライトを水素化触媒の担体として用いることで、水素化性能の高い水素化分解触媒を得ることができる。特に、高芳香族炭化水素油を水素化処理して得られる留分を、本発明の方法により製造した水素化分解触媒で水素化分解することにより、石油化学原料として有用な１環芳香族化合物を効率良く得ることができる。 The beta zeolite obtained by the production method of the present invention is a beta zeolite having sufficient mesopores and a high outer surface area. By using the beta zeolite as a carrier for the hydrogenation catalyst, a hydrocracking catalyst having high hydrogenation performance can be obtained. In particular, a monocyclic aromatic compound useful as a petrochemical raw material by hydrocracking a fraction obtained by hydrotreating a highly aromatic hydrocarbon oil with a hydrocracking catalyst produced by the method of the present invention Can be obtained efficiently.
Claims (6)
（ii）ベータゼオライト成形体を少なくとも含有する担体に、少なくとも1つの水素化活性を有する金属成分を担持する工程を有する、水素化分解触媒の製造方法。 (I) a step of kneading the beta zeolite obtained by the production method according to any one of claims 1 to 3 together with a binder, extruding and then calcining to obtain a beta zeolite molded product; and (ii) a beta zeolite molded product. A process for producing a hydrocracking catalyst, comprising a step of supporting a metal component having at least one hydrogenation activity on a support containing at least one of the above.
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| KR101743293B1 (en) * | 2010-10-22 | 2017-06-05 | 에스케이이노베이션 주식회사 | Hydrocracking catalyst for preparing valuable light aromatic hydrocarbons from polycyclic aromatic hydrocarbons |
| JP5470592B2 (en) * | 2011-11-25 | 2014-04-16 | ユニゼオ株式会社 | Zeolite, method for producing the same, and catalytic cracking catalyst for paraffin |
| KR102026498B1 (en) | 2011-11-25 | 2019-09-27 | 미쓰이금속광업주식회사 | Zeolite and method for producing same, and cracking catalyst for paraffin |
| SG11201503017XA (en) * | 2012-10-18 | 2015-05-28 | Basf Se | Post-treatment of a zeolitic material |
| CN103964458B (en) * | 2013-01-29 | 2015-09-16 | 中国石油大学(北京) | Beta zeolite of a kind of high silica alumina ratio multistage pore canal and preparation method thereof |
| KR101767658B1 (en) | 2014-10-20 | 2017-08-14 | 주식회사 엘지화학 | Core material for vacuum insulation panel comprising porous aluminosilicate and vacuum insulation panel with the core material |
| KR101736197B1 (en) | 2015-10-07 | 2017-05-17 | 한국화학연구원 | Beta zeolite catalyst for preparation of mixture of BTEX(Benzene, Toluene, Ethylbenzene, Xylene) from poly aromatic hydrocarbons and preparation method thereof |
| CN109311684B (en) * | 2016-06-07 | 2022-05-06 | 日挥触媒化成株式会社 | Chabazite-type zeolite having high resistance to hydrothermal and process for producing the same |
| JP6817022B2 (en) | 2016-06-07 | 2021-01-20 | 日揮触媒化成株式会社 | Highly water-resistant chabazite type zeolite and its manufacturing method |
| US10773248B2 (en) * | 2017-05-17 | 2020-09-15 | Saudi Arabian Oil Company | Zeolites, the production thereof, and their uses for upgrading heavy oils |
| CN113891762A (en) * | 2019-07-03 | 2022-01-04 | 三井金属矿业株式会社 | Beta-zeolite and catalyst containing same |
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