JP6744099B2 - Method for producing hydrocarbon fraction - Google Patents
Method for producing hydrocarbon fraction Download PDFInfo
- Publication number
- JP6744099B2 JP6744099B2 JP2016004664A JP2016004664A JP6744099B2 JP 6744099 B2 JP6744099 B2 JP 6744099B2 JP 2016004664 A JP2016004664 A JP 2016004664A JP 2016004664 A JP2016004664 A JP 2016004664A JP 6744099 B2 JP6744099 B2 JP 6744099B2
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- JP
- Japan
- Prior art keywords
- catalyst
- group
- metal
- oil
- mass
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000004215 Carbon black (E152) Substances 0.000 title claims description 23
- 229930195733 hydrocarbon Natural products 0.000 title claims description 23
- 150000002430 hydrocarbons Chemical class 0.000 title claims description 23
- 238000004519 manufacturing process Methods 0.000 title claims description 20
- 239000003054 catalyst Substances 0.000 claims description 96
- 229910052751 metal Inorganic materials 0.000 claims description 91
- 239000002184 metal Substances 0.000 claims description 91
- 229910052809 inorganic oxide Inorganic materials 0.000 claims description 52
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 39
- 239000011148 porous material Substances 0.000 claims description 36
- 238000000034 method Methods 0.000 claims description 31
- 150000007524 organic acids Chemical class 0.000 claims description 25
- 229910052739 hydrogen Inorganic materials 0.000 claims description 24
- 239000001257 hydrogen Substances 0.000 claims description 24
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 23
- 150000001875 compounds Chemical class 0.000 claims description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 239000011574 phosphorus Substances 0.000 claims description 11
- 229910052698 phosphorus Inorganic materials 0.000 claims description 11
- 150000005846 sugar alcohols Polymers 0.000 claims description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- 150000002739 metals Chemical class 0.000 claims description 10
- 230000000737 periodic effect Effects 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 8
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 8
- 229910052753 mercury Inorganic materials 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 238000001179 sorption measurement Methods 0.000 claims description 5
- 238000005987 sulfurization reaction Methods 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 1
- 239000003921 oil Substances 0.000 description 40
- 235000019198 oils Nutrition 0.000 description 39
- 229910001392 phosphorus oxide Inorganic materials 0.000 description 21
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 20
- 239000003925 fat Substances 0.000 description 20
- VSAISIQCTGDGPU-UHFFFAOYSA-N tetraphosphorus hexaoxide Chemical compound O1P(O2)OP3OP1OP2O3 VSAISIQCTGDGPU-UHFFFAOYSA-N 0.000 description 20
- 235000019197 fats Nutrition 0.000 description 18
- 238000005470 impregnation Methods 0.000 description 15
- 239000000243 solution Substances 0.000 description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 11
- 230000000694 effects Effects 0.000 description 10
- 239000002994 raw material Substances 0.000 description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 9
- 229910021536 Zeolite Inorganic materials 0.000 description 8
- 239000002253 acid Substances 0.000 description 8
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- 229910052750 molybdenum Inorganic materials 0.000 description 8
- -1 phosphoric acid compound Chemical class 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 239000010457 zeolite Substances 0.000 description 8
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 239000011733 molybdenum Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 6
- 229910017052 cobalt Inorganic materials 0.000 description 6
- 239000010941 cobalt Substances 0.000 description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- 235000011007 phosphoric acid Nutrition 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 239000000377 silicon dioxide Substances 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- 241001465754 Metazoa Species 0.000 description 5
- SCNCIXKLOBXDQB-UHFFFAOYSA-K cobalt(3+);2-hydroxypropane-1,2,3-tricarboxylate Chemical compound [Co+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O SCNCIXKLOBXDQB-UHFFFAOYSA-K 0.000 description 5
- 239000012188 paraffin wax Substances 0.000 description 5
- 230000000704 physical effect Effects 0.000 description 5
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- 150000001732 carboxylic acid derivatives Chemical group 0.000 description 4
- 238000004898 kneading Methods 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
- 235000015112 vegetable and seed oil Nutrition 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- UPPLJLAHMKABPR-UHFFFAOYSA-H 2-hydroxypropane-1,2,3-tricarboxylate;nickel(2+) Chemical compound [Ni+2].[Ni+2].[Ni+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O UPPLJLAHMKABPR-UHFFFAOYSA-H 0.000 description 3
- QTZURURAKNSDHT-UHFFFAOYSA-K 2-hydroxypropane-1,2,3-tricarboxylate;nickel(3+) Chemical class [Ni+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O QTZURURAKNSDHT-UHFFFAOYSA-K 0.000 description 3
- 239000002028 Biomass Substances 0.000 description 3
- 241000196324 Embryophyta Species 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 229910021446 cobalt carbonate Inorganic materials 0.000 description 3
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000002283 diesel fuel Substances 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 150000002736 metal compounds Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 238000002459 porosimetry Methods 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 235000019871 vegetable fat Nutrition 0.000 description 3
- 239000008158 vegetable oil Substances 0.000 description 3
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 235000019482 Palm oil Nutrition 0.000 description 2
- YDHWWBZFRZWVHO-UHFFFAOYSA-N [hydroxy(phosphonooxy)phosphoryl] phosphono hydrogen phosphate Chemical compound OP(O)(=O)OP(O)(=O)OP(O)(=O)OP(O)(O)=O YDHWWBZFRZWVHO-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical compound CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 description 2
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 235000019387 fatty acid methyl ester Nutrition 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 239000012013 faujasite Substances 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 239000003350 kerosene Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000000463 material Substances 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
- 235000005985 organic acids Nutrition 0.000 description 2
- 239000002540 palm oil Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- 229940005657 pyrophosphoric acid Drugs 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- UNXRWKVEANCORM-UHFFFAOYSA-N triphosphoric acid Chemical compound OP(O)(=O)OP(O)(=O)OP(O)(O)=O UNXRWKVEANCORM-UHFFFAOYSA-N 0.000 description 2
- 229940048102 triphosphoric acid Drugs 0.000 description 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- 239000007848 Bronsted acid Substances 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
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- ODBLHEXUDAPZAU-ZAFYKAAXSA-N D-threo-isocitric acid Chemical compound OC(=O)[C@H](O)[C@@H](C(O)=O)CC(O)=O ODBLHEXUDAPZAU-ZAFYKAAXSA-N 0.000 description 1
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- 229910003294 NiMo Inorganic materials 0.000 description 1
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- 241001125046 Sardina pilchardus Species 0.000 description 1
- 241000269821 Scombridae Species 0.000 description 1
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- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
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- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- IEXXNGVQCLMTKU-UHFFFAOYSA-H cobalt(2+);2-hydroxypropane-1,2,3-tricarboxylate Chemical compound [Co+2].[Co+2].[Co+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O IEXXNGVQCLMTKU-UHFFFAOYSA-H 0.000 description 1
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- 239000010970 precious metal Substances 0.000 description 1
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- 150000003626 triacylglycerols Chemical class 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 238000007039 two-step reaction Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
Description
本発明は、生物由来の油脂成分からなる被処理油を特定の触媒を用いて水素化処理する炭化水素留分の製造方法に関する。 TECHNICAL FIELD The present invention relates to a process for producing a hydrocarbon fraction, which comprises subjecting an oil to be treated composed of a fat component derived from a living body to a hydrotreatment using a specific catalyst.
地球温暖化の防止対策として、バイオマスエネルギーの有効活用が注目されている。バイオマスエネルギーの有効活用は、輸送用燃料の分野においても種々検討がなされている。例えば、第一世代水素化バイオディーゼルとして知られている脂肪酸メチルエステルは、動植物油中のトリグリセリドや脂肪酸に対し、塩基性触媒によってメタノールとのエステル交換を行うことで製造されている。 As a measure to prevent global warming, the effective use of biomass energy is drawing attention. Various studies have been made on the effective use of biomass energy also in the field of transportation fuels. For example, fatty acid methyl esters known as first generation hydrogenated biodiesel are produced by transesterifying triglycerides and fatty acids in animal and vegetable oils with methanol using a basic catalyst.
しかし、脂肪酸メチルエステルは酸素原子を含有しているため、ディーゼル油として利用した場合には、酸素分がエンジン材質に与える悪影響が懸念される。また、塩基性触媒を用いてトリグリセリド等とメタノールとをエステル交換する方法では、副生成物のグリセリンやアルカリ排水の処理が必要であるという問題がある。そこで、動植物由来の油脂成分について水素化処理を行い、炭化水素油からなる燃料油を製造する方法が検討されている。 However, since the fatty acid methyl ester contains oxygen atoms, when used as diesel oil, there is a concern that the oxygen content may adversely affect the engine material. In addition, the method of transesterifying triglyceride or the like with methanol using a basic catalyst has a problem that it is necessary to treat glycerin as a by-product and alkaline waste water. Therefore, a method of producing a fuel oil composed of a hydrocarbon oil by subjecting an oil and fat component derived from animals and plants to a hydrogenation treatment has been studied.
例えば、特許文献１には、バイオマス原料から水素化処理条件下、ＣｏＭｏ触媒又はＮｉＭｏ触媒の存在下で生成物の混合物を得るディーゼル燃料用の添加剤を製造する方法が開示されている。しかし、当該方法による生成物は本質的にｎ−パラフィンであり、そのままの状態では、炭化水素留分としての基材として扱いづらく、その使用が限定されることが考えられる。 For example, Patent Document 1 discloses a method for producing an additive for diesel fuel, which obtains a mixture of products from a biomass raw material under hydrotreating conditions in the presence of a CoMo catalyst or a NiMo catalyst. However, the product obtained by the method is essentially n-paraffin, and in the state as it is, it is difficult to handle as a base material as a hydrocarbon fraction, and it is considered that its use is limited.
また、特許文献２には、原料油を単一の工程で水素化脱酸素化処理及び水素化異性化処理することを含む、動植物油脂からのディーゼル燃料の製造方法が開示されており、生成物として、イソ−パラフィンが得られている。しかし、その水素化処理で用いている触媒は、担持金属として貴金属の白金、パラジウムを用いており、触媒耐久性の点で、事前の不純物の除去を行う必要があるなど、その取扱いに関して難点がある。 Further, Patent Document 2 discloses a method for producing a diesel fuel from animal and vegetable fats and oils, which comprises subjecting a feedstock oil to a hydrodeoxygenation treatment and a hydroisomerization treatment in a single step. Is obtained as iso-paraffin. However, the catalyst used in the hydrotreatment uses precious metals platinum and palladium as supporting metals, and in terms of catalyst durability, it is necessary to remove impurities in advance. is there.
さらに、特許文献３には、生成物由来の油脂を水素化脱酸素化工程、続く水素化異性化工程の２段階反応により、イソ−パラフィンを得る方法が開示されている。しかし、このプロセスは複数の工程からなり、両工程では、異なる触媒及び別々のユニットを必要とし、それぞれの反応条件も異なり、プロセス全体的が複雑となる。 Further, Patent Document 3 discloses a method for obtaining iso-paraffin by a two-step reaction of a fat and oil derived from a product, which is a hydrodeoxygenation step and a subsequent hydroisomerization step. However, this process consists of multiple steps, both of which require different catalysts and separate units, and different reaction conditions, complicating the overall process.
そこで、本発明は、生物由来の油脂成分からなる被処理油を水素化精製するに際し、特定の触媒を用いることにより、単一の工程で、イソ−パラフィンを含む炭化水素留分を製造する方法を提供することを目的とする。 Therefore, the present invention is a method for producing a hydrocarbon fraction containing iso-paraffin in a single step by using a specific catalyst when hydrotreating an oil to be treated consisting of a fat component derived from a living organism. The purpose is to provide.
本発明者は、上記目的を達成するために検討を行ったところ、無機酸化物担体上に、周期律表第６族金属から選ばれた少なくとも１種を含む化合物と、周期律表第８族金属から選ばれた少なくとも１種を含む化合物と、有機酸又は多価アルコールとを含み、比表面積、細孔容積、及び平均細孔直径が特定の範囲内である水素化処理触媒の存在下、水素と生物由来の油脂成分からなる原料油を特定の条件下で接触させることによって、単一の工程で、当該油脂成分の水素化脱酸素及び水素化異性化が進行し、イソ−パラフィンを含む炭化水素油を得ることができることを見出し、本発明を完成した。 The inventors of the present invention conducted a study to achieve the above object, and found that a compound containing at least one metal selected from Group 6 metals of the Periodic Table on the inorganic oxide carrier and Group 8 Group of the Periodic Table. In the presence of a hydrotreating catalyst containing a compound containing at least one selected from metals, an organic acid or a polyhydric alcohol, and having a specific surface area, a pore volume, and an average pore diameter within a specific range, By contacting a feedstock consisting of hydrogen and a biological fat component under specific conditions, hydrodeoxygenation and hydroisomerization of the fat component proceed in a single step, and iso-paraffin is contained. They have found that a hydrocarbon oil can be obtained, and completed the present invention.
すなわち、本発明は、下記の炭化水素留分の製造方法に関するものである。
［１］ 無機酸化物担体上に、周期律表第６族金属から選ばれた少なくとも１種を含む化合物と、周期律表第８族金属から選ばれた少なくとも１種を含む化合物と、有機酸又は多価アルコールとを含み、窒素吸着法で測定した比表面積が１００〜４００ｍ２／ｇであり、水銀圧入法で測定した細孔容積が０．２〜０．６ｍＬ／ｇであり、水銀圧入法で測定した平均細孔直径が５０〜２００Åである水素化処理触媒を用いて、
水素の存在下、生物由来の油脂成分からなる原料油を、水素分圧２〜１０ＭＰａ、反応温度１５０〜４００℃、水素油比１００〜２０００ＮＬ／Ｌ、及び液空間速度約０．１〜５．０ｈ−１の条件で水素化処理することを特徴とする炭化水素留分の製造方法。
［２］ ６族金属の含有量が、触媒基準、酸化物換算で、１０〜４０質量％であり、８族金属の含有量が、触媒基準、酸化物換算で、１〜１５質量％であり、有機酸又は多価アルコール由来の炭素の担持量が、触媒基準で、２〜１０質量％である、前記［１］の炭化水素留分の製造方法。
［３］ 前記触媒が、さらにリンを含む、前記［１］又は［２］の炭化水素留分の製造方法。
［４］ 前記無機酸化物担体が、さらにリンを含有する、前記［３］の炭化水素留分の製造方法。
［５］ 前記有機酸がクエン酸である、前記［１］〜［４］のいずれかの炭化水素留分の製造方法。
That is, the present invention relates to the following method for producing a hydrocarbon fraction.
[1] A compound containing at least one metal selected from Group 6 metals of the periodic table, a compound containing at least one metal selected from Group 8 metals of the periodic table, and an organic acid on an inorganic oxide carrier. Or a polyhydric alcohol, a specific surface area measured by a nitrogen adsorption method of 100 to 400 m 2 /g, a pore volume measured by a mercury injection method of 0.2 to 0.6 mL/g, and a mercury injection method. Using a hydrotreating catalyst having an average pore diameter of 50 to 200Å measured by the
In the presence of hydrogen, a feedstock oil composed of a fat component derived from a living organism was used to obtain a hydrogen partial pressure of 2 to 10 MPa, a reaction temperature of 150 to 400° C., a hydrogen oil ratio of 100 to 2000 NL/L, and a liquid space velocity of about 0.1 to 5. A process for producing a hydrocarbon fraction, which comprises hydrotreating under the condition of 0 h -1 .
[2] The content of Group 6 metal is 10 to 40% by mass based on the catalyst, based on oxide, and the content of Group 8 metal is 1 to 15% by mass based on the catalyst, based on oxide. The method for producing a hydrocarbon fraction according to the above [1], wherein the supported amount of carbon derived from an organic acid or a polyhydric alcohol is 2 to 10% by mass based on the catalyst.
[3] The method for producing a hydrocarbon fraction according to [1] or [2], wherein the catalyst further contains phosphorus.
[4] The method for producing a hydrocarbon fraction according to [3], wherein the inorganic oxide carrier further contains phosphorus.
[5] The method for producing a hydrocarbon fraction according to any one of [1] to [4], wherein the organic acid is citric acid.
本発明に係る炭化水素留分の製造方法は、特定の水素化処理触媒を用い、特定の条件下で水素と接触させることにより、単一の工程で、生物由来の油脂成分からなる原料油からイソ−パラフィンを含む炭化水素油を得ることができる。 The method for producing a hydrocarbon fraction according to the present invention, using a specific hydrotreating catalyst, by bringing it into contact with hydrogen under specific conditions, in a single step, from a feedstock oil consisting of a fat component derived from a living organism, Hydrocarbon oils containing iso-paraffins can be obtained.
本発明に係る炭化水素留分の製造方法は、無機酸化物担体上に、周期律表第６族金属から選ばれた少なくとも１種を含む化合物と、周期律表第８族金属から選ばれた少なくとも１種を含む化合物と、有機酸又は多価アルコールとを含み、窒素吸着法で測定した比表面積が１００〜４００ｍ２／ｇであり、水銀圧入法で測定した細孔容積が０．２〜０．６ｍＬ／ｇであり、水銀圧入法で測定した平均細孔直径が５０〜２００Åである水素化処理触媒を用いて、水素の存在下、生物由来の油脂成分からなる原料油を、水素分圧２〜１０ＭＰａ、反応温度１５０〜４００℃、水素油比１００〜２０００ＮＬ／Ｌ、及び液空間速度約０．１〜５．０ｈ−１の条件で水素化処理することを特徴とする。
以下、詳述する。
The method for producing a hydrocarbon fraction according to the present invention is selected from a compound containing at least one metal selected from Group 6 metals of the periodic table on an inorganic oxide support, and a metal selected from Group 8 metals of the periodic table. It contains a compound containing at least one kind and an organic acid or a polyhydric alcohol, has a specific surface area of 100 to 400 m 2 /g as measured by a nitrogen adsorption method, and has a pore volume of 0.2 to as measured by a mercury intrusion method. 0.6 mL/g, and using a hydrotreating catalyst having an average pore diameter of 50 to 200 Å measured by mercury porosimetry, a feed oil composed of a fat component derived from a living organism was converted into a hydrogen content in the presence of hydrogen. The hydrotreatment is characterized in that the pressure is 2 to 10 MPa, the reaction temperature is 150 to 400° C., the hydrogen oil ratio is 100 to 2000 NL/L, and the liquid hourly space velocity is about 0.1 to 5.0 h −1 .
The details will be described below.
＜原料油＞
本発明において原料油として用いられる生物由来の油脂成分は、生物から抽出された油脂成分であれば特に限定されるものではなく、動物や植物、藻類等から抽出された油脂成分自体であってもよく、当該油脂成分を他の目的に使用した後の廃油であってもよい。植物由来の油脂成分としては、菜種油、大豆油、パーム油、パーム核油、コーン油、ココナッツ油、オリーブ油、及びアマニ油等が挙げられる。動物由来の油脂成分としては、ニシン油、イワシ油、サバ油等の魚油、ラード、ヘット等の獣脂等が挙げられる。原料油として用いる生物由来の油脂成分は、１種類のみであってもよく、２種類以上の混合物であってもよい。
<Feed oil>
The biological fat component used as the feedstock in the present invention is not particularly limited as long as it is a fat component extracted from a living organism, and may be a fat component itself extracted from animals, plants, algae or the like. Of course, it may be a waste oil after using the oil component for other purposes. Examples of plant-derived oils and fats include rapeseed oil, soybean oil, palm oil, palm kernel oil, corn oil, coconut oil, olive oil, and linseed oil. Examples of the oil and fat component derived from animals include fish oil such as herring oil, sardine oil and mackerel oil, and tallow such as lard and het. The biological fat component used as the raw material oil may be only one kind, or may be a mixture of two or more kinds.
原料油としては、生物由来の油脂成分１００質量％のものであってもよく、生物由来の油脂成分に加えて、原油を精製して得られる灯油や軽油などの石油系留分を含有してもよい。さらに、フィシャー・トロプシュ反応で得られる生成油や、一般的な有機溶剤を含有してもよい。原料油に占める生物由来の油脂成分の量としては、特に限定されるものではなく、例えば、極少量から５０質量％程度までにすることができる。通常は、灯油や軽油等の石油留分に対して、生物由来の油脂成分を２〜１５質量％、好適には５〜１０質量％程度含有させる。 The feedstock oil may be 100% by mass of a biological fat component, and in addition to the biological fat component, it contains a petroleum fraction such as kerosene or light oil obtained by refining crude oil. Good. Further, the product oil obtained by the Fischer-Tropsch reaction and a general organic solvent may be contained. The amount of the biologically derived oil and fat component in the raw material oil is not particularly limited, and can be, for example, an extremely small amount to about 50% by mass. Usually, a petroleum fraction such as kerosene or light oil is allowed to contain a biologically-derived oil and fat component in an amount of 2 to 15% by mass, preferably 5 to 10% by mass.
＜水素化処理触媒＞
本発明において用いられる水素化処理触媒は、無機酸化物担体上に活性金属を担持したものである。当該無機酸化物担体としては、各種無機酸化物担体を用いることができるが、主成分がアルミナである無機酸化物が好ましい。担体に用いるアルミナは、α−アルミナ、γ−アルミナ、δ−アルミナ、アルミナ水和物等の種々のアルミナを使用することができるが、多孔質で高比表面積であるアルミナが好ましく、中でもγ−アルミナが適している。アルミナの純度は、約９８質量％以上、好ましくは約９９質量％以上のものが適している。
<Hydrotreatment catalyst>
The hydrotreating catalyst used in the present invention is one in which an active metal is supported on an inorganic oxide carrier. As the inorganic oxide carrier, various inorganic oxide carriers can be used, but an inorganic oxide whose main component is alumina is preferable. As the alumina used as the carrier, various aluminas such as α-alumina, γ-alumina, δ-alumina, and alumina hydrate can be used, but porous alumina having a high specific surface area is preferable, and among them, γ- Alumina is suitable. Alumina having a purity of about 98% by mass or more, preferably about 99% by mass or more is suitable.
本発明において用いられる水素化処理触媒を製造するための無機酸化物担体としては、後述する６族金属、８族金属の分散性を向上させ活性を向上させることができるため、無機酸化物担体としては、リン酸化合物を含有するものが好ましい。無機酸化物担体中のリン酸化物の含有量は、担体を基準として１５質量％以下であることが好ましく、通常０．１〜１５質量％の範囲であり、より好ましくは０．５〜１５質量％、更に好ましくは１〜１３質量％、より更に好ましくは１〜１０質量％である。リン酸化物の含有量が前記範囲であることにより、より活性の高い水素化処理触媒が得られる。 As the inorganic oxide carrier for producing the hydrotreating catalyst used in the present invention, since it is possible to improve the dispersibility of the Group 6 metal and Group 8 metal described later to improve the activity, the inorganic oxide carrier is used as an inorganic oxide carrier. Are preferably those containing a phosphoric acid compound. The content of phosphorus oxide in the inorganic oxide carrier is preferably 15% by mass or less based on the carrier, usually in the range of 0.1 to 15% by mass, and more preferably 0.5 to 15% by mass. %, more preferably 1 to 13% by mass, still more preferably 1 to 10% by mass. When the phosphorus oxide content is within the above range, a hydrotreating catalyst having higher activity can be obtained.
担体とするアルミナを主成分とする無機酸化物にリン酸化物を含有させる方法としては、特に調製法を限定するものではなく、平衡吸着法、共沈法、混練法等により行うことができる。本発明において用いられる水素化処理触媒を製造するための無機酸化物担体としては、活性の高い水素化処理触媒が得られる点で、担体の原料であるアルミナゲルとリン酸化物の原料とを混練する混練法によることが好ましく、その際、リン酸化物の原料は水溶液として用いることが好ましい。リン酸化物の原料としては、種々の化合物を用いることができる。例えば、オルトリン酸、メタリン酸、ピロリン酸、三リン酸、四リン酸が挙げられるがオルトリン酸が好ましい。 The method for incorporating phosphorus oxide into the inorganic oxide containing alumina as a main component as a carrier is not particularly limited to a preparation method, and may be an equilibrium adsorption method, a coprecipitation method, a kneading method, or the like. As the inorganic oxide carrier for producing the hydrotreating catalyst used in the present invention, an alumina gel which is a raw material of the carrier and a raw material of a phosphorus oxide are kneaded in that a highly active hydrotreating catalyst can be obtained. It is preferable that the kneading method is used, and the raw material of the phosphorus oxide is preferably used as an aqueous solution. Various compounds can be used as the raw material of the phosphorus oxide. Examples thereof include orthophosphoric acid, metaphosphoric acid, pyrophosphoric acid, triphosphoric acid and tetraphosphoric acid, with orthophosphoric acid being preferred.
本発明で用いる無機酸化物担体としては、主成分であるアルミナに、リン酸化物の他、他の酸化物成分を添加することができる。当該他の酸化物成分としては、ゼオライト、ボリア、シリカ及びジルコニアから選ばれる一種以上をあげることができる。このうちゼオライトとしては、フォージャサイトＸ型ゼオライト、フォージャサイトＹ型ゼオライト、βゼオライト、モルデナイト型ゼオライト、ＺＳＭ系ゼオライトが好ましい。前記のボリア、シリカ、ジルコニアは、一般に、この種の触媒担体成分として使用されるものを使用することができる。前記のゼオライト、ボリア、シリカ、及びジルコニアは、それぞれ単独で、あるいは２種以上を組合せて使用できる。 As the inorganic oxide carrier used in the present invention, in addition to phosphorus oxide, other oxide components can be added to alumina as the main component. Examples of the other oxide component include one or more selected from zeolite, boria, silica and zirconia. Of these, as the zeolite, faujasite X-type zeolite, faujasite Y-type zeolite, β zeolite, mordenite-type zeolite, and ZSM-based zeolite are preferable. As the above-mentioned boria, silica and zirconia, those generally used as a catalyst carrier component of this kind can be used. The above zeolite, boria, silica, and zirconia can be used alone or in combination of two or more.
本発明で用いる無機酸化物担体のうち、アルミナ以外の成分の配合量は、通常、アルミナが６５質量％より多く９９．５質量％以下に対し、０．５質量％以上３５質量％未満であり、好ましくはアルミナが約７０〜９９．５質量％に対し、約０．５〜３０質量％であり、より好ましくはアルミナが約８５〜９９．５質量％に対し、約０．５〜１５質量％である。これらの成分が前記の範囲であれば、ブレンステッド酸点やルイス酸点を十分に付与でき、６族金属、特にモリブデンを高分散できる。 In the inorganic oxide carrier used in the present invention, the content of components other than alumina is usually 0.5% by mass or more and less than 35% by mass with respect to alumina in an amount of more than 65% by mass and 99.5% by mass or less. , Preferably about 0.5 to 30% by mass with respect to about 70 to 99.5% by mass of alumina, and more preferably about 0.5 to 15% by mass with respect to about 85 to 99.5% by mass of alumina. %. When these components are within the above ranges, Bronsted acid points and Lewis acid points can be sufficiently provided, and Group 6 metal, especially molybdenum, can be highly dispersed.
本発明で用いる無機酸化物担体は、例えば、４００℃〜７００℃で０．５〜１０時間焼成して調製される。本発明において用いられる水素化処理触媒は、後述するように、無機酸化物担体に活性成分を担持させた後は、２００℃以下で乾燥だけで調製するため、触媒の機械特性（側面破壊強度や最密充填かさ密度等）を得るために、無機酸化物担体を焼成する。このとき、４００℃未満で０．５時間未満の焼成では十分な機械強度を得ることができず、７００℃を超えると高温度下で１０時間を超える長時間の焼成を行っても、この効果が飽和するばかりでなく、焼き締めにより、無機酸化物担体の比表面積、細孔容積、平均細孔直径と言った特性を却って低下してしまうおそれがある。 The inorganic oxide carrier used in the present invention is prepared, for example, by firing at 400°C to 700°C for 0.5 to 10 hours. As will be described later, the hydrotreating catalyst used in the present invention is prepared only by drying at 200° C. or lower after supporting the active component on the inorganic oxide carrier, and therefore the mechanical properties of the catalyst (side fracture strength and The inorganic oxide support is calcined to obtain the closest packed bulk density, etc.). At this time, sufficient mechanical strength cannot be obtained by firing at less than 400° C. for less than 0.5 hours, and even if firing is performed at a high temperature for more than 10 hours at a high temperature of more than 700° C., this effect In addition to being saturated, there is a possibility that the characteristics such as the specific surface area, the pore volume, and the average pore diameter of the inorganic oxide carrier may be deteriorated due to baking.
本発明で用いる無機酸化物担体の比表面積、細孔容積、及び平均細孔直径は、特に制限されないが、活性の高い水素化処理触媒にするためには、比表面積が２３０〜５００ｍ２／ｇ、好ましくは２７０〜５００ｍ２／ｇ、細孔容積０．５〜１ｍＬ／ｇ、好ましくは０．５５〜０．９ｍＬ／ｇ、平均細孔直径４０〜１８０Åであるものが適している。この理由については次の通りである。 The specific surface area, pore volume, and average pore diameter of the inorganic oxide carrier used in the present invention are not particularly limited, but in order to obtain a highly active hydrotreating catalyst, the specific surface area is 230 to 500 m 2 /g. , 270 to 500 m 2 /g, pore volume of 0.5 to 1 mL/g, preferably 0.55 to 0.9 mL/g, and average pore diameter of 40 to 180Å are suitable. The reason for this is as follows.
含浸溶液中で６族金属と８族金属は錯体を形成していると考えられるため、無機酸化物担体の比表面積を２３０ｍ２／ｇ以上とすることにより、含浸の際、錯体の嵩高さのために金属の高分散化を担保することができる。また、比表面積が５００ｍ２／ｇ以下であれば、細孔直径が極端に小さくならないため、触媒の細孔直径も小さくならず、好ましい。 Since it is considered that the Group 6 metal and the Group 8 metal form a complex in the impregnation solution, by setting the specific surface area of the inorganic oxide support to 230 m 2 /g or more, the bulkiness of the complex during impregnation can be improved. Therefore, high dispersion of metal can be secured. Further, if the specific surface area is 500 m 2 /g or less, the pore diameter does not become extremely small, so that the catalyst pore diameter does not become small either, which is preferable.
無機酸化物担体の細孔容積が０．５ｍＬ／ｇ以上では、通常の含浸法で触媒を調製する場合、細孔容積内に入り込む溶媒が少量とならないため、好ましい。溶媒が少量であると、活性金属化合物の溶解性が悪くなり、金属の分散性が低下し低活性な触媒となるおそれがある。活性金属化合物の溶解性を上げるためには、硝酸等の酸を多量に加える方法があるが、余り加えすぎると担体の低表面積化が起こり、活性低下の主原因となる。細孔容積が１ｍＬ／ｇ以下であれば、比表面積が小さくならず、活性金属の分散性が良くなり、活性の高い触媒となるため、好ましい。 When the pore volume of the inorganic oxide carrier is 0.5 mL/g or more, when preparing a catalyst by a normal impregnation method, a small amount of solvent enters the pore volume, which is preferable. When the amount of the solvent is small, the solubility of the active metal compound is deteriorated, the dispersibility of the metal is lowered, and the catalyst may have low activity. In order to increase the solubility of the active metal compound, there is a method of adding a large amount of acid such as nitric acid, but if it is added too much, the surface area of the carrier becomes low, which is the main cause of the activity decrease. When the pore volume is 1 mL/g or less, the specific surface area is not reduced, the dispersibility of the active metal is improved, and the catalyst becomes highly active, which is preferable.
無機酸化物担体の平均細孔直径が４０Å以上では、活性金属を担持した触媒の細孔直径も小さくならず、好ましい。触媒の細孔直径が小さいと、反応物の触媒細孔内への拡散が不十分となり、活性が低下するおそれがある。無機酸化物担体の平均細孔直径が１８０Å以下であれば、触媒の比表面積が小さくならず、好ましい。触媒の比表面積が小さいと、活性金属の分散性が悪くなり、活性の低い触媒となるおそれがある。 When the average pore diameter of the inorganic oxide carrier is 40Å or more, the pore diameter of the catalyst supporting the active metal is not small, which is preferable. When the pore diameter of the catalyst is small, the diffusion of the reactant into the catalyst pores may be insufficient and the activity may be reduced. When the average pore diameter of the inorganic oxide carrier is 180 Å or less, the specific surface area of the catalyst does not decrease, which is preferable. When the specific surface area of the catalyst is small, the dispersibility of the active metal deteriorates, and the catalyst may have low activity.
本発明において用いられる水素化処理触媒は、前記無機酸化物担体に、活性金属として、周期律表第６族金属から選ばれた少なくとも１種を含む化合物及び周期律表第８族金属から選ばれた少なくとも１種を含む化合物を担持させたものである。 The hydrotreating catalyst used in the present invention is selected from a compound containing at least one metal selected from Group 6 metals of the Periodic Table as an active metal in the inorganic oxide support and a Group 8 metal of the Periodic Table. In addition, a compound containing at least one kind is supported.
水素化処理触媒に含有させる６族金属としては、モリブデン、タングステンが好ましく、モリブデンが特に好ましい。水素化処理触媒における６族金属の含有量は、触媒基準、酸化物換算で、１０〜４０質量％が好ましく、１０〜３０質量％がより好ましい。６族金属の含有量が１０質量％以上では、６族金属に起因する効果を発現させるのに十分であり、好ましい。また、６族金属の含有量が４０質量％以下では、６族金属の含浸（担持）工程で６族金属化合物の凝集が生じず、６族金属の分散性が良くなり、また、効率的に分散する６族金属担持量の限度を超えず、触媒表面積が大幅に低下しない等により、触媒活性の向上がみられ、好ましい。 As the Group 6 metal contained in the hydrotreating catalyst, molybdenum and tungsten are preferable, and molybdenum is particularly preferable. The content of the Group 6 metal in the hydrotreating catalyst is preferably 10 to 40% by mass, more preferably 10 to 30% by mass, based on the catalyst, in terms of oxide. When the content of the Group 6 metal is 10% by mass or more, it is sufficient and sufficient to exert the effect caused by the Group 6 metal, which is preferable. Further, when the content of the Group 6 metal is 40% by mass or less, the Group 6 metal compound does not aggregate in the impregnation (supporting) step of the Group 6 metal, the dispersibility of the Group 6 metal is improved, and the efficiency is improved. It is preferable because the catalyst activity is improved by not exceeding the limit of the amount of the Group 6 metal to be dispersed and by not significantly reducing the catalyst surface area.
水素化処理触媒に含有させる８族金属としては、コバルト、ニッケルが好ましい。水素化処理触媒における８族金属の含有量は、触媒基準、酸化物換算で、１〜１５質量％が好ましく、３〜８質量％がより好ましく、３．５〜６質量％がさらに好ましい。８族金属の含有量が１質量％以上では、８族金属に帰属する活性点を十分に得ることができ好ましい。また、８族金属の含有量を１５質量％以下とすることにより、金属の凝集を抑制することができ好ましい。 Cobalt and nickel are preferable as the Group 8 metal contained in the hydrotreating catalyst. The content of the Group 8 metal in the hydrotreating catalyst is preferably 1 to 15% by mass, more preferably 3 to 8% by mass, and even more preferably 3.5 to 6% by mass in terms of catalyst, based on oxide. When the content of the Group 8 metal is 1% by mass or more, it is preferable because the active sites belonging to the Group 8 metal can be sufficiently obtained. Further, when the content of the Group 8 metal is 15% by mass or less, aggregation of the metal can be suppressed, which is preferable.
水素化処理触媒において、８族金属と６族金属の前記した含有量において、８族金属と６族金属の最適質量比は、好ましくは、酸化物換算で、［８族金属］／［８族金属＋６族金属］の値で、０．１〜０．２５である。この値が０．１以上、０．２５以下とすることにより触媒活性が向上されるので好ましい。 In the hydrotreating catalyst, the optimum mass ratio of the Group 8 metal and the Group 6 metal in the above-mentioned contents of the Group 8 metal and the Group 6 metal is preferably [group 8 metal]/[group 8] in terms of oxide. The value of [metal+group 6 metal] is 0.1 to 0.25. When this value is 0.1 or more and 0.25 or less, the catalytic activity is improved, which is preferable.
本発明において用いられる水素化処理触媒は、前記無機酸化物担体に、さらに有機酸又は多価アルコールが担持されている。前記無機酸化物担体に担持させる有機酸は、１種類のみであってもよく、２種類以上であってもよい。同様に、前記無機酸化物担体に担持させる多価アルコールは、１種類のみであってもよく、２種類以上であってもよい。さらに、１種類又は２種類以上の有機酸と１種類又は２種類以上の多価アルコールを前記無機酸化物担体に担持させてもよい。水素化処理触媒における有機酸又は多価アルコール（以下、「有機酸等」）由来の炭素の含有量は、触媒基準で、２〜１０質量％が好ましく、２〜７質量％がより好ましく、３〜６質量％がさらに好ましい。有機酸等由来の炭素の含有量を２質量％以上、１０質量％とすることにより、触媒表面上で８族金属が有機酸と錯化合物を十分に形成することができる。 In the hydrotreating catalyst used in the present invention, an organic acid or a polyhydric alcohol is further supported on the inorganic oxide carrier. The organic acid supported on the inorganic oxide carrier may be only one kind or two or more kinds. Similarly, the polyhydric alcohol supported on the inorganic oxide carrier may be only one type or two or more types. Furthermore, one or more organic acids and one or more polyhydric alcohols may be supported on the inorganic oxide carrier. The content of carbon derived from an organic acid or a polyhydric alcohol (hereinafter, “organic acid”) in the hydrotreating catalyst is preferably 2 to 10% by mass, more preferably 2 to 7% by mass, based on the catalyst. -6% by mass is more preferable. By setting the content of carbon derived from an organic acid or the like to 2% by mass or more and 10% by mass, the Group 8 metal can sufficiently form a complex compound with the organic acid on the catalyst surface.
有機酸等の添加量は、得られる触媒中に前記の炭素含有量で炭素が残る量とすることが重要であり、また８族金属に対して有機酸等の添加量をモル比で、［有機酸等］／［８族金属］＝０．２〜１．２、好ましくは０．６〜１．０、より好ましくは０．６〜０．８とすることが適している。このモル比を０．２以上、１．２以下とすることにより、８族金属が有機酸等と錯体化合物を十分に形成して活性点が得られるため好ましい。 It is important that the amount of the organic acid or the like added is such that carbon remains at the above-mentioned carbon content in the obtained catalyst, and the amount of the organic acid or the like added to the Group 8 metal is a molar ratio [[ It is suitable that [organic acid, etc.]/[Group 8 metal]=0.2 to 1.2, preferably 0.6 to 1.0, and more preferably 0.6 to 0.8. By setting this molar ratio to 0.2 or more and 1.2 or less, the Group 8 metal sufficiently forms a complex compound with an organic acid or the like and an active site can be obtained, which is preferable.
無機酸化物担体に担持させる６族金属を含む化合物としては、三酸化モリブデン、モリブドリン酸、モリブデン酸アンモニウム、モリブデン酸等が挙げられ、好ましくは三酸化モリブデン、モリブドリン酸である。 Examples of the compound containing a Group 6 metal supported on the inorganic oxide carrier include molybdenum trioxide, molybdophosphoric acid, ammonium molybdate, molybdic acid and the like, and molybdenum trioxide and molybdophosphoric acid are preferable.
無機酸化物担体に担持させる８族金属を含む化合物としては、炭酸コバルト、炭酸ニッケル、クエン酸コバルト、クエン酸ニッケル、硝酸コバルト６水和物、硝酸ニッケル６水和物等が挙げられ、好ましくは、炭酸コバルト、炭酸ニッケル、クエン酸コバルト、クエン酸ニッケル化合物であり、特に好ましくは、クエン酸コバルト、クエン酸ニッケル化合物である。クエン酸コバルトとしては、クエン酸第一コバルト（Ｃｏ３（Ｃ６Ｈ５Ｏ７）２）、クエン酸水素コバルト（ＣｏＨＣ６Ｈ５Ｏ７）、クエン酸コバルトオキシ塩（Ｃｏ３（Ｃ６Ｈ５Ｏ７・ＣｏＯ）等が挙げられ、クエン酸ニッケルとしては、クエン酸第一ニッケル（Ｎｉ３（Ｃ６Ｈ５Ｏ７）２）、クエン酸水素ニッケル（ＮｉＨＣ６Ｈ５Ｏ７）、クエン酸ニッケルオキシ塩（Ｎｉ３（Ｃ６Ｈ５Ｏ７）・ＮｉＯ）等が挙げられる。これらのコバルトとニッケルのクエン酸化合物の製造は、例えば、コバルトの場合、クエン酸の水溶液に炭酸コバルトを溶かすことにより得られる。 Examples of the compound containing a Group 8 metal supported on the inorganic oxide carrier include cobalt carbonate, nickel carbonate, cobalt citrate, nickel citrate, cobalt nitrate hexahydrate, nickel nitrate hexahydrate, and the like, and preferably , Cobalt carbonate, nickel carbonate, cobalt citrate and nickel citrate compounds, and particularly preferably cobalt citrate and nickel citrate compounds. Examples of cobalt citrate include cobalt citrate (Co 3 (C 6 H 5 O 7 ) 2 ), cobalt hydrogen citrate (CoHC 6 H 5 O 7 ), and cobalt citrate oxy salt (Co 3 (C 6 H 5 O 7 .CoO) and the like. Examples of nickel citrate include primary nickel citrate (Ni 3 (C 6 H 5 O 7 ) 2 ), nickel hydrogen citrate (NiHC 6 H 5 O 7 ), and citrate. Acid nickel oxy salt (Ni 3 (C 6 H 5 O 7 ).NiO), etc. These cobalt and nickel citrate compounds can be produced, for example, in the case of cobalt by adding cobalt carbonate to an aqueous solution of citric acid. Obtained by melting.
無機酸化物担体に担持させる有機酸としては、カルボン酸が好ましく、より好ましくは多価カルボン酸、さらに好ましくは、脂肪族多価カルボン酸を挙げることができる。無機酸化物担体に担持させる有機酸は、硫黄を実質的に含まない化合物を使用することが好ましい。無機酸化物担体に担持させるカルボン酸としては、例えば、クエン酸、イソクエン酸、リンゴ酸、酒石酸、シュウ酸、コハク酸、グルタン酸、グルコン酸、アジピン酸、安息香酸、フタル酸、イソフタル酸、サリチル酸、マロン酸等が挙げられ、中でもクエン酸が好ましい。クエン酸を使用する場合は、クエン酸単独であってもよいし、コバルトやニッケル等の８族金属とのクエン酸化合物であってもよい。 The organic acid supported on the inorganic oxide carrier is preferably a carboxylic acid, more preferably a polyvalent carboxylic acid, and further preferably an aliphatic polyvalent carboxylic acid. As the organic acid supported on the inorganic oxide carrier, it is preferable to use a compound that does not substantially contain sulfur. Examples of the carboxylic acid supported on the inorganic oxide carrier include citric acid, isocitric acid, malic acid, tartaric acid, oxalic acid, succinic acid, glutanoic acid, gluconic acid, adipic acid, benzoic acid, phthalic acid, isophthalic acid, salicylic acid. , Malonic acid and the like, and citric acid is preferable among them. When citric acid is used, it may be citric acid alone or a citric acid compound with a Group 8 metal such as cobalt or nickel.
無機酸化物担体に担持させる多価アルコールとしては、エチレングリコール、プロピレングリコール、グリセリン、トリメチロールエタン、トリメチロールプロパン、ジエチレングリコール、ジプロピレングリコール、トリメチレングリコール、トリエチレングリコール、トリブチレングリコール、テトラエチレングリコール類が挙げられ、中でも、ジエチレングリコールが好ましく用いられる。 Examples of the polyhydric alcohol supported on the inorganic oxide carrier include ethylene glycol, propylene glycol, glycerin, trimethylolethane, trimethylolpropane, diethylene glycol, dipropylene glycol, trimethylene glycol, triethylene glycol, tributylene glycol, tetraethylene glycol. Among them, diethylene glycol is preferably used.
本発明において用いられる水素化処理触媒は、さらに、リン酸化物を担持していてもよい。前記無機酸化物担体にリン酸化物が担持されていることにより、６族金属及び８族金属の分散性を向上させることができる。担持させるリン酸化物の原料としては、オルトリン酸、ピロリン酸、三リン酸、四リン酸等が挙げられ、オルトリン酸が好ましい。また、リン化合物を担持させる方法としては、担体にこれらのリン化合物原料を含浸させる方法がある。 The hydrotreating catalyst used in the present invention may further carry a phosphorus oxide. By supporting the phosphorus oxide on the inorganic oxide carrier, the dispersibility of the Group 6 metal and the Group 8 metal can be improved. Examples of the raw material of the phosphorus oxide to be supported include orthophosphoric acid, pyrophosphoric acid, triphosphoric acid, tetraphosphoric acid and the like, and orthophosphoric acid is preferable. As a method for supporting the phosphorus compound, there is a method of impregnating a carrier with these phosphorus compound raw materials.
無機酸化物担体に担持させるリン酸化物の量は、無機酸化物担体にリン酸化物を含有させた場合は、担体調製時に使用したリン酸化物を含めた合計量が、上記で規定した担体中のリン酸化物の最大含有量値（触媒基準、酸化物換算で１５質量％）を越えないようにすることが好ましい。例えば、担体を、無機酸化物とリン酸化物とを混練法で調製した場合は、混練時に使用するリン酸化物の一部を担持用のリン酸化物として使用する。 The amount of phosphorus oxide supported on the inorganic oxide carrier is such that, when the inorganic oxide carrier contains phosphorus oxide, the total amount including the phosphorus oxide used at the time of carrier preparation is in the carrier specified above. It is preferable not to exceed the maximum content value of phosphorus oxide (15% by mass in terms of oxide, based on the catalyst). For example, when the carrier is prepared by a kneading method of an inorganic oxide and a phosphorus oxide, a part of the phosphorus oxide used during the kneading is used as a supporting phosphorus oxide.
また、活性金属に対するリンの含有量としては、例えば活性金属としてモリブデンを用いる場合は、リン酸化物とモリブデンとの質量比[Ｐ２Ｏ５]／[ＭｏＯ３]の値で、好ましくは０．０５〜０．２５、より好ましくは１〜０．１５である。モリブデンとリンの質量比（[Ｐ２Ｏ５]／[ＭｏＯ３]）を約０．０５以上、０．２５以下とすることにより、触媒の表面積や細孔容積を好適な範囲を保ち、触媒上での炭素析出などを抑制することができる。 The content of phosphorus with respect to the active metal is, for example, when molybdenum is used as the active metal, the mass ratio [P 2 O 5 ]/[MoO 3 ] of phosphorus oxide and molybdenum, and preferably 0. 05-0.25, more preferably 1-0.15. By setting the mass ratio of molybdenum to phosphorus ([P 2 O 5 ]/[MoO 3 ]) to be about 0.05 or more and 0.25 or less, the surface area and the pore volume of the catalyst can be maintained within a suitable range, and the catalyst It is possible to suppress carbon deposition and the like above.
本発明において用いられる水素化処理触媒は、前記無機酸化物担体に、６族金属、８族金属、リンの各成分を含む化合物を、水、酸等の溶媒に溶解させて調製した溶液を含浸させることによって調製することができる。 The hydrotreating catalyst used in the present invention is impregnated with a solution prepared by dissolving a compound containing each component of Group 6 metal, Group 8 metal and phosphorus in the inorganic oxide carrier in a solvent such as water or acid. Can be prepared.
前記無機酸化物担体に、６族金属、８族金属、有機酸等の各成分、及び必要に応じてリン成分を担持させる方法は、特に制限はないが、これら各成分を同時に含浸させる一段含浸法が好ましい。一段含浸法は、脱硫活性点数、酸性質、細孔等の触媒の特性の面、又は操作性の面から有利と考えられるためである。すなわち、一段含浸法によれば、６族金属及び８族金属が渾然一体化して無機酸化物担体に取り込まれることとなるため、例えば、６族金属にモリブデン、８族金属にコバルトを用いる場合、最終的に活性点を増加させることができる。このとき、リン成分が含浸溶液に存在していると、ＣｏとＭｏの渾然一体化が促進される。 There is no particular limitation on the method for supporting each component such as Group 6 metal, Group 8 metal, and organic acid, and optionally the phosphorus component on the inorganic oxide carrier, but one-step impregnation in which these components are simultaneously impregnated Method is preferred. This is because the one-stage impregnation method is considered to be advantageous in terms of the desulfurization active point, acid properties, catalyst characteristics such as pores, or operability. That is, according to the one-step impregnation method, the group 6 metal and the group 8 metal are naturally integrated and taken into the inorganic oxide carrier. For example, when molybdenum is used as the group 6 metal and cobalt is used as the group 8 metal, Finally, the number of active sites can be increased. At this time, if the phosphorus component is present in the impregnation solution, the spontaneous integration of Co and Mo is promoted.
一段含浸法は、具体的には、例えば、前記した６族金属を少なくとも１種を含む化合物、前記した８族金属を少なくとも１種を含む化合物、必要に応じてリン酸化物、有機酸、又は多価アルコールを含有する含浸用溶液に、前記無機酸化物担体を含浸させて６族金属、８族金属、炭素を前記した担持量となるように担時させた後、乾燥する方法により行う。含浸用溶液中の６族金属を含む化合物及び８族金属を含む化合物の添加量は、得られる触媒中に６族金属及び８族金属がそれぞれ前記した範囲内で含有される量とする。また、８族金属を含む化合物として、クエン酸の水溶液にコバルトやニッケル等の８族金属を溶かすことにより得られたクエン酸化合物を用いる場合、当該製法で得られたクエン酸化合物の水分を除去しないで、そのまま、含浸用溶液に添加して触媒調製に用いてもかまわない。 Specifically, the one-step impregnation method includes, for example, a compound containing at least one kind of the group 6 metal described above, a compound containing at least one kind of the group 8 metal described above, a phosphorus oxide, an organic acid, or A method of impregnating the inorganic oxide carrier with a solution for impregnation containing a polyhydric alcohol to support the Group 6 metal, Group 8 metal, and carbon so as to have the above-described supported amounts, and then drying. The addition amount of the compound containing the Group 6 metal and the compound containing the Group 8 metal in the impregnating solution is such that the Group 6 metal and the Group 8 metal are contained in the above-mentioned catalyst within the ranges described above. When a citric acid compound obtained by dissolving a Group 8 metal such as cobalt or nickel in an aqueous solution of citric acid is used as the compound containing the Group 8 metal, the water content of the citric acid compound obtained by the manufacturing method is removed. Alternatively, the catalyst may be directly added to the impregnating solution and used for catalyst preparation.
前記含浸用溶液において、前記の各成分を溶解させるために用いる溶媒は、水である。溶媒の使用量は、少なすぎれば、担体を十分に浸漬することができず、多すぎれば、溶解した活性金属の一部が担体上に担持しきれず、含浸用溶液をいれた容器のへりなどに付着してしまい、所望の担持量が得られないおそれがある。このため、無機酸化物担体１００ｇに対して、溶媒量は５０〜９０ｇが好ましい。前記溶媒に前記成分を溶解させて含浸用溶液を調製するが、このとき温度は、０℃を超え１００℃以下でよく、この範囲であれば、前記溶媒に各成分を良好に溶解させることができる。 In the impregnating solution, the solvent used for dissolving each of the above components is water. If the amount of the solvent used is too small, the carrier cannot be sufficiently immersed, and if it is too large, a part of the dissolved active metal cannot be fully supported on the carrier, and the edge of the container containing the impregnating solution, etc. There is a risk that the desired amount of supported particles will not be obtained due to the adherence to the surface. Therefore, the amount of solvent is preferably 50 to 90 g with respect to 100 g of the inorganic oxide carrier. The above components are dissolved in the solvent to prepare an impregnating solution. At this time, the temperature may be higher than 0° C. and 100° C. or lower, and within this range, the respective components can be well dissolved in the solvent. it can.
このようにして調製した含浸用溶液を、前記無機酸化物担体に含浸させて、含浸用溶液中の前記の各成分を無機酸化物担体に担持させる。含浸条件は、種々の条件を採ることができるが、通常、含浸温度は、好ましくは０℃を超え１００℃未満が適している。含浸時間は、好ましくは１５分間〜３時間、より好ましくは２０分間〜２時間、さらに好ましくは３０分間〜１時間である。なお、温度が高すぎると、含浸中に乾燥が起こり、分散度が偏ってしまうおそれがある。また、含浸中は攪拌することが好ましい。 The impregnating solution thus prepared is impregnated into the inorganic oxide carrier to support the above-mentioned components in the impregnating solution on the inorganic oxide carrier. Although various conditions can be adopted as the impregnation condition, usually, the impregnation temperature is preferably higher than 0°C and lower than 100°C. The impregnation time is preferably 15 minutes to 3 hours, more preferably 20 minutes to 2 hours, and further preferably 30 minutes to 1 hour. If the temperature is too high, drying may occur during impregnation and the degree of dispersion may be biased. Moreover, it is preferable to stir during impregnation.
含浸用溶液を含浸させた無機酸化物担体は、常温〜約８０℃、窒素気流中、空気気流中、又は真空中で、水分をある程度［ＬＯＩ（Ｌｏｓｓ ｏｎ ｉｇｎｉｔｉｏｎ）が５０％以下となるように］除去し、その後、空気気流中、窒素気流中、又は真空中で、２００℃以下で、５時間〜２０時間の乾燥を行う。乾燥を２００℃以下の温度で行うと、金属と錯体化していると思われる有機酸等が触媒表面上から脱離せず、その結果、得られる触媒を硫化処理したときに水素化脱酸素と水素化異性化の活性点が得られると考えられる。真空中で乾燥を行う場合は、圧力７６０ｍｍＨｇ換算で、前記の温度範囲になるようにして乾燥を行うことが好ましい。 The inorganic oxide carrier impregnated with the impregnating solution has a certain amount of moisture [LOI (Loss on ignition) of 50% or less at room temperature to about 80° C., in a nitrogen stream, an air stream, or a vacuum). ] After that, it is dried in an air stream, a nitrogen stream, or a vacuum at 200° C. or less for 5 hours to 20 hours. When the drying is carried out at a temperature of 200° C. or lower, organic acids which are considered to be complexed with a metal are not desorbed from the surface of the catalyst, and as a result, hydrodeoxygenation and hydrogen are eliminated when the obtained catalyst is subjected to sulfurization treatment. It is considered that the active site of chemical isomerization is obtained. When the drying is performed in vacuum, it is preferable to perform the drying within the above temperature range in terms of pressure of 760 mmHg.
前記のようにして、前記無機酸化物担体に、所定量の６族金属、８族金属、有機酸等に由来する炭素、必要に応じリン酸化物を担持させ、所定温度で乾燥させて得られた本発明において用いられる水素化処理触媒は、その窒素吸着法（ＢＥＴ法）で測定した比表面積が１００〜４００ｍ２／ｇ、好ましくは１５０〜３５０ｍ２／ｇであり、水銀圧入法で測定した細孔容積が０．２〜０．６ｍＬ／ｇ、好ましくは０．３〜０．６ｍＬ／ｇ、より好ましくは０．３〜０．５ｍＬ／ｇであり、水銀圧入法で測定した平均細孔直径が５０〜２００Å、好ましくは５０〜１８０Å、より好ましくは５０〜１５０Åである。水素化処理触媒の比表面積、細孔容積、及び平均細孔直径の各物性が前記範囲であるときに、所望の触媒活性が得られ、所期の目的を達成できる。 As described above, a predetermined amount of carbon derived from a Group 6 metal, a Group 8 metal, an organic acid or the like, and optionally a phosphorus oxide, is supported on the inorganic oxide carrier, and dried at a predetermined temperature. hydrotreating catalyst used in the present invention, the nitrogen adsorption method specific surface area measured by (BET method) 100 to 400 m 2 / g, preferably 150~350m 2 / g, measured by mercury porosimetry Mean pores having a pore volume of 0.2 to 0.6 mL/g, preferably 0.3 to 0.6 mL/g, more preferably 0.3 to 0.5 mL/g, and measured by mercury porosimetry. The diameter is 50 to 200Å, preferably 50 to 180Å, more preferably 50 to 150Å. When the physical properties of the hydrotreating catalyst such as the specific surface area, the pore volume and the average pore diameter are within the above ranges, desired catalytic activity can be obtained and the intended purpose can be achieved.
水素化処理触媒の前記各物性を前記範囲にすることは、触媒調製に当って、無機酸化物担体の前記各物性を前記した担体に関する前記各物性の範囲内で選択し、６族金属、８族金属などの必要担持成分の担持量を前記範囲内で制御し、必要担持成分を担持した後の乾燥条件を前記範囲内で制御することによって容易に達成できる。 Setting each of the above-mentioned physical properties of the hydrotreating catalyst to the above-mentioned range means that, in catalyst preparation, each of the above-mentioned physical properties of the inorganic oxide carrier is selected within the range of each of the above-mentioned physical properties of the carrier, and a Group 6 metal, 8 This can be easily achieved by controlling the loading amount of the necessary supporting component such as a group metal within the above range and controlling the drying condition after supporting the necessary supporting component within the above range.
また、本発明において用いられる水素化処理触媒の形状は、特に限定されず、通常、この種の触媒に用いられている種々の形状、例えば、円柱状、三葉状、四葉状等を採用することができる。水素化処理触媒の大きさは、直径が約１〜２ｍｍ、長さ約２〜５ｍｍが好ましい。水素化処理触媒の機械的強度は、側面破壊強度（ＳＣＳ《Ｓｉｄｅ ｃｒｕｓｈ ｓｔｒｅｎｇｔｈ》）で約２ｌｂｓ／ｍｍ以上が好ましい。ＳＣＳが約２ｌｂｓ／ｍｍ以上であれば、反応装置に充填した触媒が破壊され、反応装置内で差圧が発生し、水素化処理運転の続行が不可能となることはない。また、本発明において用いられる水素化処理触媒の最密充填かさ密度（ＣＢＤ：Ｃｏｍｐａｃｔｅｄ Ｂｕｌｋ Ｄｅｎｓｉｔｙ）は、約０．６〜１．２ｇ／ｍＬが好ましい。また、水素化処理触媒中の活性金属の分散状態は、触媒中で活性金属が均一に分布しているユニフォーム型が好ましい。 Further, the shape of the hydrotreating catalyst used in the present invention is not particularly limited, and various shapes usually used for this type of catalyst, for example, a columnar shape, a trilobal shape, a tetralobal shape, etc. may be adopted. You can The hydrotreating catalyst preferably has a diameter of about 1 to 2 mm and a length of about 2 to 5 mm. The mechanical strength of the hydrotreating catalyst is preferably about 2 lbs/mm or more in terms of side surface fracture strength (SCS <<Side crash strength>>). When the SCS is about 2 lbs/mm or more, the catalyst packed in the reactor is destroyed, a differential pressure is generated in the reactor, and continuation of the hydrotreating operation is not impossible. In addition, the closest packed bulk density (CBD) of the hydrotreating catalyst used in the present invention is preferably about 0.6 to 1.2 g/mL. Further, the dispersion state of the active metal in the hydrotreatment catalyst is preferably a uniform type in which the active metal is uniformly distributed in the catalyst.
本発明において用いられる水素化処理触媒は、使用前に（即ち、本発明に係る炭化水素留分の製造方法を行うのに先立って）、硫化処理して活性化することが好ましい。この硫化処理方法は、液相又は気相で実施できる。液相の場合、約２００〜４００℃、好ましくは約２５０〜３５０℃、常圧又はそれ以上の水素分圧の水素雰囲気下で、硫黄化合物を含む石油蒸留物、それにジメチルジスルファイドや二硫化炭素等の硫化剤を加えたもの、又は硫化水素を用いて行う。気相の場合、Ｈ２Ｓ混合ガス（硫黄分５質量％）を用いて約４００℃、圧力０．３ＭＰａ、Ｈ２Ｓガス流量１．２Ｌ／ｈの条件下で、６時間行う。 The hydrotreating catalyst used in the present invention is preferably activated by a sulfurating treatment before use (that is, prior to carrying out the method for producing a hydrocarbon fraction according to the present invention). This sulfurization treatment method can be carried out in a liquid phase or a gas phase. In the case of a liquid phase, a petroleum distillate containing a sulfur compound, and dimethyldisulfide or disulfide under a hydrogen atmosphere at a hydrogen partial pressure of about 200 to 400° C., preferably about 250 to 350° C. at atmospheric pressure or higher. It is performed by adding a sulfurizing agent such as carbon or hydrogen sulfide. In the case of the gas phase, H 2 S mixed gas (sulfur content 5% by mass) is used for about 6 hours under the conditions of about 400° C., pressure 0.3 MPa, and H 2 S gas flow rate 1.2 L/h.
＜炭化水素留分の製造方法＞
本発明に係る炭化水素留分の製造方法は、前記水素化処理触媒を用いて、水素の存在下、前記原料油を水素化処理する。原料油の水素化処理条件は、水素分圧約２〜１０ＭＰａ、約１５０〜４００℃、水素油比１００〜２０００ＮＬ／Ｌ、及び液空間速度約０．１〜５．０ｈ−１の条件が好ましく、水素分圧約２．５〜８ＭＰａ、約２００〜３９０℃、水素油比１２５〜１９００ＮＬ／Ｌ、及び液空間速度約０．２〜４ｈ−１の条件がより好ましく、水素分圧約３〜６ＭＰａ、約２５０〜３８０℃、水素油比１５０〜１８００ＮＬ／Ｌ、及び液空間速度約０．３〜３ｈ−１の条件がさらに好ましい。この理由については次の通りである。
<Method for producing hydrocarbon fraction>
In the method for producing a hydrocarbon fraction according to the present invention, the feed oil is hydrotreated in the presence of hydrogen using the hydrotreatment catalyst. The hydrotreating conditions of the feed oil are preferably hydrogen partial pressure of about 2 to 10 MPa, about 150 to 400° C., hydrogen oil ratio of 100 to 2000 NL/L, and liquid space velocity of about 0.1 to 5.0 h −1 . The conditions of hydrogen partial pressure of about 2.5 to 8 MPa, about 200 to 390° C., hydrogen oil ratio of 125 to 1900 NL/L, and liquid space velocity of about 0.2 to 4 h −1 are more preferable, and hydrogen partial pressure of about 3 to 6 MPa, about. The conditions of 250 to 380° C., hydrogen oil ratio of 150 to 1800 NL/L, and liquid hourly space velocity of about 0.3 to 3 h −1 are more preferable. The reason for this is as follows.
水素圧力が２ＭＰａ未満では、反応性の低下や活性低下が推測される。水素圧力が１０ＭＰａを超える場合では、過分解によりガス発生の増加が推測される。水素油比も同様である。液空間速度が５．０ｈ−１を超える場合では、反応性の低下が推測される。反応温度が１５０℃未満の場合では、十分な反応性が得られないと推測される。反応温度が４００℃を超える場合では、分解が進行し、生成物の液収率の低下が推測される。 When the hydrogen pressure is less than 2 MPa, it is presumed that the reactivity and the activity are lowered. When the hydrogen pressure exceeds 10 MPa, an increase in gas generation is estimated due to overdecomposition. The hydrogen oil ratio is similar. When the liquid hourly space velocity exceeds 5.0 h- 1 , it is estimated that the reactivity is lowered. When the reaction temperature is lower than 150°C, it is presumed that sufficient reactivity cannot be obtained. When the reaction temperature exceeds 400° C., the decomposition proceeds, and it is presumed that the liquid yield of the product decreases.
以下に本発明の内容を実施例及び比較例により更に詳しく説明するが、本発明はこれらによって制限されるものではない。 Hereinafter, the contents of the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto.
［実施例１］触媒Ａの調製
シリカとアルミナ水和物とオルトリン酸を混練し、押出成形後、６００℃で２時間焼成して、直径１／１６インチの柱状成形物のリン酸化物−シリカ−アルミナ複合担体（リン酸化物−シリカ／アルミナ質量比＝４．４／５／９０．５、細孔容積０．７８ｍ２／ｇ、比表面積３２４ｍ２／ｇ、平均細孔直径９８Å）を得た。
一方、イオン交換水２６．４０ｇに、クエン酸第一コバルト９．８１ｇ及びモリブドリン酸２６．４０ｇを投入し、８０℃に加温して１０分間攪拌して含浸用溶液を調製した。
ナス型フラスコ中に、前記リン酸化物−シリカ−アルミナ複合担体３０．０ｇを投入し、そこへ前記含浸用溶液の全量をピペットで添加し、約２５℃で３時間浸漬した。この後、窒素気流中で風乾し、マッフル炉中１２０℃で約１６時間乾燥させ、触媒Ａを得た。
[Example 1] Preparation of catalyst A Silica, alumina hydrate, and orthophosphoric acid were kneaded, extruded, and then calcined at 600°C for 2 hours to form a phosphorous oxide-silica of a columnar molded product having a diameter of 1/16 inch. - alumina composite support - resulting (phosphorus oxides silica / alumina mass ratio = 4.4 / 5 / 90.5, pore volume 0.78 m 2 / g, a specific surface area of 324m 2 / g, average pore diameter 98A) of It was
On the other hand, to 26.40 g of ion-exchanged water, 9.81 g of cobaltous citrate and 26.40 g of molybdophosphoric acid were added, heated to 80° C. and stirred for 10 minutes to prepare an impregnating solution.
30.0 g of the phosphorous oxide-silica-alumina composite carrier was placed in an eggplant-shaped flask, the whole amount of the impregnating solution was added thereto with a pipette, and the mixture was immersed at about 25° C. for 3 hours. Then, it was air-dried in a nitrogen stream and dried in a muffle furnace at 120° C. for about 16 hours to obtain a catalyst A.
［比較例１］触媒Ｂの調製
実施例１で調製した触媒Ａを、マッフル炉中５００℃で約３時間乾させ、クエン酸を除去した触媒Ｂを得た。
Comparative Example 1 Preparation of Catalyst B Catalyst A prepared in Example 1 was dried in a muffle furnace at 500° C. for about 3 hours to obtain a catalyst B from which citric acid was removed.
以上の実施例及び比較例で得た触媒の元素分析値を表１に示し、物性値を表２に示す。表１中の数値の単位は質量％（触媒基準）であり、「Ｐ２Ｏ５／ＭｏＯ３」は担体中のＰ２Ｏ５を含む値である。また、表２中、「ＳＡ」は比表面積、「ＰＶ」は細孔容積、「ＭＰＤ」は平均細孔直径の略であり、「ＭＰＤ±１５Å」は、平均細孔直径±１５Åの細孔割合である。 The elemental analysis values of the catalysts obtained in the above Examples and Comparative Examples are shown in Table 1, and the physical property values are shown in Table 2. The unit of the numerical values in Table 1 is% by mass (based on the catalyst), and “P 2 O 5 /MoO 3 ”is a value including P 2 O 5 in the carrier. In Table 2, “SA” is a specific surface area, “PV” is a pore volume, “MPD” is an abbreviation for average pore diameter, and “MPD±15Å” is a pore with an average pore diameter ±15Å. It is a ratio.
［試験例１］
触媒Ａ及びＢをそれぞれ用いて、水素化処理反応を行った。
具体的には、触媒（３０ｃｃ）を充填した反応管を固定床流通式反応装置に取り付け、Ｈ２Ｓ混合ガス（硫黄分５質量％）を用いて触媒層平均温度４００℃、圧力０．３ＭＰａ、Ｈ２Ｓガス流量１．２Ｌ／ｈの条件下で、６時間、気相での触媒予備硫化を行った。
[Test Example 1]
The hydrotreating reaction was performed using the catalysts A and B, respectively.
Specifically, a reaction tube filled with a catalyst (30 cc) was attached to a fixed bed flow reactor, and a H 2 S mixed gas (sulfur content 5% by mass) was used to obtain a catalyst layer average temperature of 400° C. and a pressure of 0.3 MPa. , H 2 S gas flow rate of 1.2 L/h, catalyst presulfidation in the gas phase was performed for 6 hours.
予備硫化後、原料油として、表３に示す性状を有する植物油脂（パーム油脂肪酸留出物:ＰＦＡＤ）と、当該植物油脂に対して質量比９．０のデカヒドロナフタレンとを混合した混合油を原料油として用いて、水素化処理を行った。反応には、 内部攪拌式反応装置を用い、水素化条件は、表４に示す反応条件で実施し、生成油を得た。得られた生成油の性状を表５にまとめた。この結果、クエン酸を担持させた触媒Ａを用いた場合のほうが、クエン酸を除去した触媒Ｂを用いた場合よりも、イソーパラフィンの割合が明らかに多く、ノルマル−パラフィンの割合が少ない生成物が得られた。 After pre-sulfurization, a mixed oil obtained by mixing, as a raw material oil, a vegetable oil/fat (palm oil fatty acid distillate: PFAD) having the properties shown in Table 3 and decahydronaphthalene in a mass ratio of 9.0 to the vegetable oil/fat. Was used as a feedstock oil for hydrotreating. For the reaction, an internal stirring type reaction device was used, and the hydrogenation was carried out under the reaction conditions shown in Table 4 to obtain a product oil. The properties of the produced oil thus obtained are summarized in Table 5. As a result, a product with a higher proportion of iso-paraffins and a lower proportion of normal-paraffins was obtained when the catalyst A supporting citric acid was used, as compared with the case where the catalyst B from which citric acid was removed was used. was gotten.
Claims (5)
水素の存在下、水素分圧２〜１０ＭＰａ、反応温度１５０〜４００℃、水素油比１００〜２０００ＮＬ／Ｌ、及び液空間速度約０．１〜５．０ｈ−１の条件で接触処理することにより反応を開始し、前記原料油を水素化処理することを特徴とする炭化水素留分の製造方法。 On an inorganic oxide carrier, a compound containing at least one member selected from Group 6 metals of the Periodic Table, a compound containing at least one member selected from Group 8 metals of the Periodic Table, an organic acid or a polyvalent compound. It contains alcohol and has a specific surface area of 100 to 400 m 2 /g measured by a nitrogen adsorption method and a pore volume of 0.2 to 0.6 mL/g measured by a mercury intrusion method, and a mercury intrusion method. The activated hydrotreating catalyst obtained by subjecting the hydrotreated catalyst having an average pore diameter of 50 to 200 Å to sulfurization treatment at 200 to 400° C., and a feed oil comprising a biological fat component .
By contact treatment in the presence of hydrogen under the conditions of a hydrogen partial pressure of 2 to 10 MPa, a reaction temperature of 150 to 400° C., a hydrogen oil ratio of 100 to 2000 NL/L, and a liquid space velocity of about 0.1 to 5.0 h −1. A method for producing a hydrocarbon fraction , which comprises starting a reaction and hydrotreating the feedstock oil .
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