JP4925653B2 - Method for producing liquefied fuel gas composition - Google Patents
Method for producing liquefied fuel gas composition Download PDFInfo
- Publication number
- JP4925653B2 JP4925653B2 JP2005347278A JP2005347278A JP4925653B2 JP 4925653 B2 JP4925653 B2 JP 4925653B2 JP 2005347278 A JP2005347278 A JP 2005347278A JP 2005347278 A JP2005347278 A JP 2005347278A JP 4925653 B2 JP4925653 B2 JP 4925653B2
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- JP
- Japan
- Prior art keywords
- alumina
- mol
- silica
- fuel gas
- less
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
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- 239000000203 mixture Substances 0.000 title claims description 48
- 239000002737 fuel gas Substances 0.000 title claims description 38
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 64
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 41
- 239000001257 hydrogen Substances 0.000 claims description 41
- 229910052739 hydrogen Inorganic materials 0.000 claims description 41
- 150000002430 hydrocarbons Chemical class 0.000 claims description 40
- 229930195733 hydrocarbon Natural products 0.000 claims description 39
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 36
- 239000004215 Carbon black (E152) Substances 0.000 claims description 34
- 239000003921 oil Substances 0.000 claims description 34
- 241001465754 Metazoa Species 0.000 claims description 29
- 229910052751 metal Inorganic materials 0.000 claims description 27
- 239000002184 metal Substances 0.000 claims description 27
- 239000003054 catalyst Substances 0.000 claims description 25
- 229910052750 molybdenum Inorganic materials 0.000 claims description 24
- 238000004517 catalytic hydrocracking Methods 0.000 claims description 20
- 239000000377 silicon dioxide Substances 0.000 claims description 18
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 17
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 16
- 239000000446 fuel Substances 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 13
- 235000019871 vegetable fat Nutrition 0.000 claims description 13
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 12
- 229910052809 inorganic oxide Inorganic materials 0.000 claims description 12
- 229910003296 Ni-Mo Inorganic materials 0.000 claims description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 10
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 9
- 229910052717 sulfur Inorganic materials 0.000 claims description 9
- 239000011593 sulfur Substances 0.000 claims description 9
- 238000005984 hydrogenation reaction Methods 0.000 claims description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 7
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 6
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 6
- 239000002131 composite material Substances 0.000 claims description 5
- 239000003209 petroleum derivative Substances 0.000 claims description 5
- 239000010773 plant oil Substances 0.000 claims description 5
- 239000010779 crude oil Substances 0.000 claims description 4
- 239000003350 kerosene Substances 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 238000005336 cracking Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 2
- 239000005977 Ethylene Substances 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 235000019198 oils Nutrition 0.000 description 29
- 239000003925 fat Substances 0.000 description 20
- 239000007789 gas Substances 0.000 description 20
- 239000003915 liquefied petroleum gas Substances 0.000 description 20
- 230000000694 effects Effects 0.000 description 15
- 239000010775 animal oil Substances 0.000 description 14
- 235000019197 fats Nutrition 0.000 description 14
- 239000002994 raw material Substances 0.000 description 14
- 235000015112 vegetable and seed oil Nutrition 0.000 description 14
- 239000008158 vegetable oil Substances 0.000 description 14
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 12
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 11
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 10
- 239000010457 zeolite Substances 0.000 description 10
- 229910021536 Zeolite Inorganic materials 0.000 description 9
- 150000002739 metals Chemical class 0.000 description 9
- 238000010998 test method Methods 0.000 description 9
- 238000005260 corrosion Methods 0.000 description 8
- 230000007797 corrosion Effects 0.000 description 8
- 230000000737 periodic effect Effects 0.000 description 8
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- 239000001273 butane Substances 0.000 description 6
- 239000000470 constituent Substances 0.000 description 6
- -1 glyceride compound Chemical class 0.000 description 6
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 6
- 239000001294 propane Substances 0.000 description 6
- 238000009835 boiling Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 235000014113 dietary fatty acids Nutrition 0.000 description 5
- 239000000194 fatty acid Substances 0.000 description 5
- 229930195729 fatty acid Natural products 0.000 description 5
- 150000004665 fatty acids Chemical group 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 4
- 238000005755 formation reaction Methods 0.000 description 4
- 239000002028 Biomass Substances 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 229940024546 aluminum hydroxide gel Drugs 0.000 description 3
- SMYKVLBUSSNXMV-UHFFFAOYSA-K aluminum;trihydroxide;hydrate Chemical compound O.[OH-].[OH-].[OH-].[Al+3] SMYKVLBUSSNXMV-UHFFFAOYSA-K 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 239000000571 coke Substances 0.000 description 3
- 239000000306 component Substances 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000012013 faujasite Substances 0.000 description 3
- 238000010335 hydrothermal treatment Methods 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 229910052721 tungsten Inorganic materials 0.000 description 3
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 3
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 3
- 239000003981 vehicle Substances 0.000 description 3
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 2
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 2
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- 240000002791 Brassica napus Species 0.000 description 2
- 235000004977 Brassica sinapistrum Nutrition 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- 239000005639 Lauric acid Substances 0.000 description 2
- OYHQOLUKZRVURQ-HZJYTTRNSA-N Linoleic acid Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(O)=O OYHQOLUKZRVURQ-HZJYTTRNSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 239000005642 Oleic acid Substances 0.000 description 2
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 238000010306 acid treatment Methods 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- 230000008676 import Effects 0.000 description 2
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 2
- 235000020778 linoleic acid Nutrition 0.000 description 2
- OYHQOLUKZRVURQ-IXWMQOLASA-N linoleic acid Natural products CCCCC\C=C/C\C=C\CCCCCCCC(O)=O OYHQOLUKZRVURQ-IXWMQOLASA-N 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 2
- 150000004671 saturated fatty acids Chemical class 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000003760 tallow Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000006200 vaporizer Substances 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- TWJNQYPJQDRXPH-UHFFFAOYSA-N 2-cyanobenzohydrazide Chemical compound NNC(=O)C1=CC=CC=C1C#N TWJNQYPJQDRXPH-UHFFFAOYSA-N 0.000 description 1
- 244000266618 Atriplex confertifolia Species 0.000 description 1
- 235000012137 Atriplex confertifolia Nutrition 0.000 description 1
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 description 1
- 239000005635 Caprylic acid (CAS 124-07-2) Substances 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- 244000068988 Glycine max Species 0.000 description 1
- 235000010469 Glycine max Nutrition 0.000 description 1
- 244000020551 Helianthus annuus Species 0.000 description 1
- 235000003222 Helianthus annuus Nutrition 0.000 description 1
- 240000006240 Linum usitatissimum Species 0.000 description 1
- 235000004431 Linum usitatissimum Nutrition 0.000 description 1
- 235000021360 Myristic acid Nutrition 0.000 description 1
- TUNFSRHWOTWDNC-UHFFFAOYSA-N Myristic acid Natural products CCCCCCCCCCCCCC(O)=O TUNFSRHWOTWDNC-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- 244000000231 Sesamum indicum Species 0.000 description 1
- 235000003434 Sesamum indicum Nutrition 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- DTOSIQBPPRVQHS-PDBXOOCHSA-N alpha-linolenic acid Chemical compound CC\C=C/C\C=C/C\C=C/CCCCCCCC(O)=O DTOSIQBPPRVQHS-PDBXOOCHSA-N 0.000 description 1
- 235000020661 alpha-linolenic acid Nutrition 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 235000015278 beef Nutrition 0.000 description 1
- 239000003225 biodiesel Substances 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 235000014121 butter Nutrition 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 235000019864 coconut oil Nutrition 0.000 description 1
- 239000003240 coconut oil Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 235000012343 cottonseed oil Nutrition 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 235000021323 fish oil Nutrition 0.000 description 1
- 235000004426 flaxseed Nutrition 0.000 description 1
- 238000004231 fluid catalytic cracking Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 229960004488 linolenic acid Drugs 0.000 description 1
- KQQKGWQCNNTQJW-UHFFFAOYSA-N linolenic acid Natural products CC=CCCC=CCC=CCCCCCCCC(O)=O KQQKGWQCNNTQJW-UHFFFAOYSA-N 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 210000004185 liver Anatomy 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 229910052680 mordenite Inorganic materials 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- 239000005445 natural material Substances 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 229960002446 octanoic acid Drugs 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 235000015277 pork Nutrition 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- WBHHMMIMDMUBKC-XLNAKTSKSA-N ricinelaidic acid Chemical compound CCCCCC[C@@H](O)C\C=C\CCCCCCCC(O)=O WBHHMMIMDMUBKC-XLNAKTSKSA-N 0.000 description 1
- 229960003656 ricinoleic acid Drugs 0.000 description 1
- FEUQNCSVHBHROZ-UHFFFAOYSA-N ricinoleic acid Natural products CCCCCCC(O[Si](C)(C)C)CC=CCCCCCCCC(=O)OC FEUQNCSVHBHROZ-UHFFFAOYSA-N 0.000 description 1
- 235000003441 saturated fatty acids Nutrition 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000029305 taxis Effects 0.000 description 1
- NUMQCACRALPSHD-UHFFFAOYSA-N tert-butyl ethyl ether Chemical compound CCOC(C)(C)C NUMQCACRALPSHD-UHFFFAOYSA-N 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 229910000348 titanium sulfate Inorganic materials 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000010698 whale oil Substances 0.000 description 1
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical compound [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
- C10L3/12—Liquefied petroleum gas
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
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- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
- C10G1/06—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by destructive hydrogenation
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
- C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
- C10G47/10—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used with catalysts deposited on a carrier
- C10G47/12—Inorganic carriers
- C10G47/16—Crystalline alumino-silicate carriers
- C10G47/18—Crystalline alumino-silicate carriers the catalyst containing platinum group metals or compounds thereof
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
- C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
- C10G47/10—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used with catalysts deposited on a carrier
- C10G47/12—Inorganic carriers
- C10G47/16—Crystalline alumino-silicate carriers
- C10G47/20—Crystalline alumino-silicate carriers the catalyst containing other metals or compounds thereof
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
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- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
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Description
本発明は液化燃料ガス組成物に関し、特に動植物油脂および動物油脂由来成分を含有した炭化水素留分を原料油として、周期律表第６Ａ族および第８族から選ばれる少なくとも一種類以上の金属と酸性質を有する無機酸化物を含有する水素化分解触媒と水素加圧下で接触させることにより得られる炭化水素を含む液化燃料ガス組成物に関するものである。 The present invention relates to a liquefied fuel gas composition, and in particular, a hydrocarbon fraction containing components derived from animal and vegetable oils and animal fats and oils as a raw material oil, and at least one metal selected from Groups 6A and 8 of the periodic table; The present invention relates to a liquefied fuel gas composition containing a hydrocarbon obtained by contacting a hydrocracking catalyst containing an inorganic oxide having acid properties with hydrogen under pressure.
近年、大気汚染状況の悪化に伴い自動車の排気ガスに対する規制が強化されており、軽油を燃料とするディーゼル車、ことにディーゼルトラック車の使用が制限される状況が起きてきている。これに対応するためディーゼル車の排気ガス浄化システムの開発が行なわれているが、より排出ガスがクリーンな低公害車への代替も検討されており、液化石油ガス（ＬＰＧ）を燃料とするトラックなどがディーゼルトラック車の代替として期待されている。さらに、タクシーではＬＰＧがその主たる燃料として過去４０年近くにわたり使用されている実績がある。（例えば、非特許文献１参照。）。また、自動車用液化石油ガス（オートガス）の品質に関しても、排気ガスの更なる低減を目指して検討された例はあるが（例えば、特許文献１参照。）、二酸化炭素低減について検討された例はない。
わが国で使用されるＬＰＧは、その約１／４を国内生産により、約３／４を輸入によりまかなわれている。昨今、輸入ＬＰＧ供給源の多様化を図るため輸入先を広げる試みなども行なわれており、また国内生産分も製油所にて原油蒸留時に分離されるもの以外に各種石油精製プラントや石油化学工場のプラントなどからの副生物などより得られるものもあり、ＬＰＧの品質に関し必ずしも従来と同一とはいえない状況になりつつある。
しかしながらそれらはいずれも化石燃料由来のものに限定されていた。
About one-quarter of the LPG used in Japan is domestically produced, and about three-quarters is imported. In recent years, attempts have been made to expand import destinations in order to diversify import LPG supply sources, and various oil refineries and petrochemical plants in addition to those that are separated at the refinery during crude oil distillation. Some of these can be obtained from by-products from other plants, and the quality of LPG is not necessarily the same as before.
However, they were all limited to those derived from fossil fuels.
排出ガスの低減と同時に地球温暖化問題にも対応するため、二酸化炭素削減に効果的な燃料性状が求められており、その解決手段の１つとして再生可能エネルギーであるバイオマス由来燃料を代替燃料として用いることが検討されている。現在は、バイオエタノールやＥＴＢＥ、バイオディーゼルなど、従来の化石燃料であるガソリンや軽油に直接混合し、代替できる燃料が検討されている。しかしながら従来の液化石油ガスに直接混合して用いる事のできるバイオマス由来液化燃料ガス組成物に関する検討例、知見は存在していない。 In order to cope with global warming issues as well as reducing emissions, there is a need for fuel properties that are effective in reducing carbon dioxide. As one of the solutions, biomass-derived fuel, which is renewable energy, can be used as an alternative fuel. Use is under consideration. Currently, fuels such as bioethanol, ETBE, and biodiesel that can be mixed directly with gasoline and light oil, which are conventional fossil fuels, are being investigated. However, there are no study examples and knowledge regarding biomass-derived liquefied fuel gas compositions that can be directly mixed with conventional liquefied petroleum gas.
本発明者らは、前記課題について鋭意研究を重ねた結果、動植物油脂および動物油脂由来成分を含有した炭化水素留分を原料油として、周期律表第６Ａ族および第８族から選ばれる少なくとも一種類以上の金属と酸性質を有する無機酸化物を含有する水素化分解触媒と水素加圧下で接触させることにより得られる炭化水素を用いた液化燃料ガス組成物を見出し、本発明を完成するに至ったものである。 As a result of intensive studies on the above problems, the present inventors have used hydrocarbon fractions containing components derived from animal and vegetable oils and animal fats as feedstocks, and at least one selected from Groups 6A and 8 of the periodic table. The inventors have found a liquefied fuel gas composition using hydrocarbons obtained by contacting under pressure of hydrogen with a hydrocracking catalyst containing an inorganic oxide having at least two kinds of metals and acid properties, and have completed the present invention. It is a thing.
すなわち、本発明は、動植物油脂および／または動植物油脂由来成分を含有した炭化水素留分からなる原料油を、Ｃｏ−Ｍｏ、Ｎｉ−Ｍｏ、Ｎｉ−Ｃｏ−ＭｏおよびＮｉ−Ｗから選ばれる金属およびアルミナと、シリカ、チタニア、ジルコニアおよびボリアから選ばれる少なくとも１種類以上を含む複合酸化物を含有する水素化前処理触媒と水素加圧下で水素圧力５〜２０ＭＰａ、液空間速度（ＬＨＳＶ）０．１〜２．２ｈ −１ 、水素／油比３００〜１５００ＮＬ／Ｌで接触させた後に、Ｃｏ−Ｍｏ、Ｎｉ−Ｍｏ、Ｎｉ−Ｃｏ−ＭｏおよびＮｉ−Ｗから選ばれる金属およびシリカ−アルミナ、ボリア−アルミナ、ジルコニア−アルミナ、チタニア−ジルコニア−アルミナ、シリカ−ボリア−アルミナ、シリカ−ジルコニア−アルミナおよびシリカ−チタニア−アルミナから選ばれる無機酸化物を含有する水素化分解触媒と水素加圧下で水素圧力５〜２０ＭＰａ、液空間速度（ＬＨＳＶ）０．１〜２．２ｈ −１ 、水素／油比３００〜１５００ＮＬ／Ｌで接触させ水素化分解処理することにより、硫黄分含有量１０質量ｐｐｍ以下、炭素数３の炭化水素が１．０モル％以上９９．０モル％以下、炭素数４の炭化水素が１．０モル％以上９９．０モル％以下である炭化水素を得、この炭化水素を１容量％以上含有する液化燃料ガス組成物を得ることを特徴とする液化燃料ガス組成物の製造方法に関する。 That is, the metal present invention, a feedstock comprising a hydrocarbon fraction containing animal or vegetable fats and / or dynamic plant oils derived components are selected from Co-Mo, Ni-Mo, Ni-Co-Mo and Ni-W And a hydrogenation pretreatment catalyst containing a composite oxide containing at least one selected from silica, titania, zirconia and boria, a hydrogen pressure of 5 to 20 MPa, a liquid space velocity (LHSV) of 0. Metals selected from Co-Mo, Ni-Mo, Ni-Co-Mo and Ni-W, and silica-alumina, boria after contacting at 1-2 to 2 h -1 , hydrogen / oil ratio of 300-1500 NL / L -Alumina, zirconia-alumina, titania-zirconia-alumina, silica-boria-alumina, silica-zirconia-alumina and Rica - titania - hydride containing an inorganic oxide selected from alumina cracking catalyst and hydrogen under pressure in the hydrogen pressure 5 to 20 mPa, liquid hourly space velocity (LHSV) 0.1~2.2h -1, a hydrogen / oil ratio of 300 By hydrocracking by contacting at 1500 NL / L , the sulfur content is 10 mass ppm or less, the hydrocarbon having 3 carbon atoms is 1.0 mol% or more and 99.0 mol% or less, and the hydrocarbon having 4 carbon atoms. method of manufacturing but give the hydrocarbon is less than 99.0 mol% 1.0 mol%, the liquefied fuel gas composition, characterized in that to obtain a liquefied fuel gas composition containing the hydrocarbon 1 vol% About.
また本発明は、動植物油脂および／または動植物油脂由来成分を含有した炭化水素留分と原油等から精製された灯油留分を有する石油系炭化水素留分を任意の比率で混合した混合油からなる原料油を、Ｃｏ−Ｍｏ、Ｎｉ−Ｍｏ、Ｎｉ−Ｃｏ−ＭｏおよびＮｉ−Ｗから選ばれる金属およびアルミナと、シリカ、チタニア、ジルコニアおよびボリアから選ばれる少なくとも１種類以上を含む複合酸化物を含有する水素化前処理触媒と水素加圧下で水素圧力５〜２０ＭＰａ、液空間速度（ＬＨＳＶ）０．１〜２．２ｈ −１ 、水素／油比３００〜１５００ＮＬ／Ｌで接触させた後に、Ｃｏ−Ｍｏ、Ｎｉ−Ｍｏ、Ｎｉ−Ｃｏ−ＭｏおよびＮｉ−Ｗから選ばれる金属およびシリカ−アルミナ、ボリア−アルミナ、ジルコニア−アルミナ、チタニア−ジルコニア−アルミナ、シリカ−ボリア−アルミナ、シリカ−ジルコニア−アルミナおよびシリカ−チタニア−アルミナから選ばれる酸性質を有する無機酸化物を含有する水素化分解触媒と水素加圧下で水素圧力５〜２０ＭＰａ、液空間速度（ＬＨＳＶ）０．１〜２．２ｈ −１ 、水素／油比３００〜１５００ＮＬ／Ｌで接触させ水素化分解処理することにより、硫黄分含有量１０質量ｐｐｍ以下、炭素数３の炭化水素が１．０モル％以上９９．０モル％以下、炭素数４の炭化水素が１．０モル％以上９９．０モル％以下である炭化水素を得、この炭化水素を１容量％以上含有する液化燃料ガス組成物を得ることを特徴とする液化燃料ガス組成物の製造方法に関する。 The present invention is a mixed oil obtained by mixing petroleum hydrocarbon fractions having a kerosene fraction purified from a hydrocarbon fraction and crude oil containing animal or vegetable fats and / or dynamic plant oils derived components in any ratio A composite oxide containing a metal oil selected from Co-Mo, Ni-Mo, Ni-Co-Mo and Ni-W, and at least one selected from silica, titania, zirconia and boria After contact with a hydrogenation pretreatment catalyst containing hydrogen under hydrogen pressure at a hydrogen pressure of 5 to 20 MPa, a liquid space velocity (LHSV) of 0.1 to 2.2 h −1 , and a hydrogen / oil ratio of 300 to 1500 NL / L, Metals selected from Co-Mo, Ni-Mo, Ni-Co-Mo and Ni-W and silica-alumina, boria-alumina, zirconia-alumina, titania-zil Near - alumina, silica - boria - alumina, silica - zirconia - alumina and silica - titania - hydrocracking catalyst containing an inorganic oxide having acid properties selected from alumina and under hydrogen pressure in the hydrogen pressure 5 to 20 mPa, liquid Hydrocarbon cracking by contacting with a space velocity (LHSV) of 0.1 to 2.2 h −1 and a hydrogen / oil ratio of 300 to 1500 NL / L, and a hydrocarbon having a sulfur content of 10 mass ppm or less and a carbon number of 3 Of 1.0 mol% or more and 99.0 mol% or less, and a hydrocarbon having 4 carbon atoms of 1.0 mol% or more and 99.0 mol% or less, and containing 1% by volume or more of this hydrocarbon The present invention relates to a method for producing a liquefied fuel gas composition characterized by obtaining a liquefied fuel gas composition.
以下、本発明について詳述する。
本発明は、動植物油脂および／または動物油脂由来成分を含有した炭化水素留分を原料油として用いるものである。
また本発明は、動植物油脂および／または動物油脂由来成分を含有した炭化水素留分とを任意の比率で混合した混合油を原料油として用いるものである。
Hereinafter, the present invention will be described in detail.
The present invention uses a hydrocarbon fraction containing a component derived from animal and vegetable oils and / or animal fats as a raw material oil.
Moreover, this invention uses the mixed oil which mixed the hydrocarbon fraction containing the component derived from animal and vegetable fats and / or animal fats and fats in arbitrary ratios as raw material oil.
本発明における動植物油脂および動植物油脂由来成分とは、天然もしくは人工的に生産、製造される動植物油脂および動植物油脂由来成分を示している。動物油脂および動物油の原料としては、牛脂、牛乳脂質（バター）、豚脂、羊脂、鯨油、魚油、肝油等が挙げられ、植物油脂および植物油原料としては、ココヤシ、パームヤシ、オリーブ、べにばな、菜種（菜の花）、米ぬか、ひまわり、綿実、とうもろこし、大豆、ごま、アマニ等の種子部及びその他の部分が挙げられるが、これ以外の油脂、油であっても使用に問題はない。これらの原料油に関してはその状態が固体、液体であることは問わないが、取り扱いの容易さおよび二酸化炭素吸収能や生産性の高さから植物油脂、植物油を原料とする方が好ましい。また、本発明においては、これらの動物油、植物油を民生用、産業用、食用等で使用した廃油も雑物等の除去工程を加えた後に原料とすることができる。 The animal and vegetable oils and fats and components derived from animal and vegetable oils and fats in the present invention refer to animal and vegetable oils and fats and components derived from animal and vegetable oils and fats that are produced or manufactured naturally or artificially. Examples of animal fats and animal oil materials include beef tallow, milk lipid (butter), pork tallow, sheep fat, whale oil, fish oil, liver oil, and the like. Examples include rapeseed (rapeseed), rice bran, sunflower, cottonseed, corn, soybeans, sesame seeds, and other parts of the linseed, but other fats and oils can be used without problems. These raw oils may be solid or liquid, but it is preferable to use vegetable oils and vegetable oils as raw materials because of ease of handling, high carbon dioxide absorption capacity and high productivity. Moreover, in this invention, the waste oil which used these animal oils and vegetable oils for consumer use, industrial use, food use etc. can also be used as a raw material after adding the removal process of miscellaneous matters.
これらの原料中に含有されるグリセライド化合物の脂肪酸部分の代表的な組成としては、飽和脂肪酸と称する分子構造中に不飽和結合を有しない脂肪酸である酪酸（Ｃ３Ｈ７ＣＯＯＨ）、カプロン酸（Ｃ５Ｈ１１ＣＯＯＨ）、カプリル酸（Ｃ７Ｈ１５ＣＯＯＨ）、カプリン酸（Ｃ９Ｈ１９ＣＯＯＨ）、ラウリン酸（Ｃ１１Ｈ２３ＣＯＯＨ）、ミリスチン酸（Ｃ１３Ｈ２７ＣＯＯＨ）、パルミチン酸（Ｃ１５Ｈ３１ＣＯＯＨ）、ステアリン酸（Ｃ１７Ｈ３５ＣＯＯＨ）、及び不飽和結合を１つもしくは複数有する不飽和脂肪酸であるオレイン酸（Ｃ１７Ｈ３３ＣＯＯＨ）、リノール酸（Ｃ１７Ｈ３１ＣＯＯＨ）、リノレン酸（Ｃ１７Ｈ２９ＣＯＯＨ）、リシノレン酸（Ｃ１７Ｈ３２（ＯＨ）ＣＯＯＨ）等が挙げられる。自然界の物質におけるこれら脂肪酸の炭化水素部は一般に直鎖であることが多いが、本発明において本発明で規定する性状を満たす限りで、側鎖を有する構造、すなわち異性体であっても使用することができる。また、不飽和脂肪酸における分子中の不飽和結合の位置も、本発明において本発明で規定する性状を満たす限りで、自然界で一般に存在確認されているものだけでなく、化学合成によって任意の位置に設定されたものも使用することができる。
上述の原料油（動植物油脂および動植物油脂由来成分）はこれらの脂肪酸を１種または複数種有しており、原料によってその有する脂肪酸類は異なっている。例えば、ココヤシ油はラウリン酸、ミリスチン酸等の飽和脂肪酸を比較的多く有しているが、大豆油はオレイン酸、リノール酸等の不飽和脂肪酸を多く有している。
As a typical composition of the fatty acid portion of the glyceride compound contained in these raw materials, butyric acid (C 3 H 7 COOH), which is a fatty acid having no unsaturated bond in the molecular structure called saturated fatty acid, caproic acid ( C 5 H 11 COOH), caprylic acid (C 7 H 15 COOH), capric acid (C 9 H 19 COOH), lauric acid (C 11 H 23 COOH), myristic acid (C 13 H 27 COOH), palmitic acid ( C 15 H 31 COOH), stearic acid (C 17 H 35 COOH), and oleic acid (C 17 H 33 COOH), which is an unsaturated fatty acid having one or more unsaturated bonds, linoleic acid (C 17 H 31 COOH) ), linolenic acid (C 17 H 29 COOH), ricinoleic acid (C 17 H 32 (OH) COOH) Hitoshigakyo It is. The hydrocarbon part of these fatty acids in natural substances is generally linear, but it is used in the present invention even if it has a structure having a side chain, that is, an isomer, as long as the properties defined in the present invention are satisfied. be able to. Further, the position of the unsaturated bond in the molecule of the unsaturated fatty acid is not limited to those generally found in nature as long as the properties defined in the present invention are satisfied in the present invention. The set one can also be used.
The above-mentioned raw material oils (animal and vegetable oils and fats and components derived from animal and vegetable oils and fats) have one or more of these fatty acids, and the fatty acids they have differ depending on the raw materials. For example, coconut oil has a relatively large amount of saturated fatty acids such as lauric acid and myristic acid, while soybean oil has a large amount of unsaturated fatty acids such as oleic acid and linoleic acid.
動植物油脂および／または動物油脂由来成分を含有した炭化水素留分に、任意の比率で混合して用いる原油等から精製された灯油留分を有する石油系炭化水素留分とは、一般的な石油精製工程で得られる留分を用いることができ、例えば、常圧蒸留装置や減圧蒸留装置から得られる所定の沸点範囲に相当する留分や水素化脱硫装置、水素化分解装置、残油直接脱硫装置、流動接触分解装置などから得られる、相当する沸点範囲の留分を単独で混合していてもよく、複数の装置からの相当する留分を混合していてもよい。該石油系炭化水素留分は少なくとも沸点３００℃以上の留分を含んでいることが望ましく、沸点７００℃より重質な留分を含んでいないことがより望ましい。該石油系炭化水素留分が３００℃以上の留分を含んでいない場合、過度の分解によって十分な液収率が得られない恐れがあり、７００℃より重質な留分を含む場合、重質成分によって触媒上での炭素質形成が促進されることによって活性点を被覆し、活性低下に繋がる恐れがある。なお、本明細書における沸点範囲とは、ＪＩＳ Ｋ ２２５４「蒸留試験方法」またはＡＳＴＭ−Ｄ８６に記載の方法に準拠して測定される値である。 Petroleum hydrocarbon fractions having kerosene fractions refined from crude oil or the like used by mixing them in any proportion with hydrocarbon fractions containing components derived from animal and vegetable fats and / or animal fats The fraction obtained in the refining process can be used. For example, the fraction corresponding to a predetermined boiling range obtained from an atmospheric distillation apparatus or a vacuum distillation apparatus, hydrodesulfurization apparatus, hydrocracking apparatus, residual oil direct desulfurization A fraction having a corresponding boiling range obtained from an apparatus, a fluid catalytic cracking apparatus, or the like may be mixed alone, or corresponding fractions from a plurality of apparatuses may be mixed. The petroleum hydrocarbon fraction desirably contains at least a fraction having a boiling point of 300 ° C or higher, and more desirably does not contain a fraction heavier than a boiling point of 700 ° C. If the petroleum hydrocarbon fraction does not contain a fraction at 300 ° C. or higher, there is a risk that sufficient liquid yield may not be obtained due to excessive decomposition. If a fraction heavier than 700 ° C. is contained, The formation of carbonaceous matter on the catalyst is promoted by the quality component, which may cover the active sites and lead to a decrease in activity. In addition, the boiling point range in this specification is a value measured based on the method described in JIS K 2254 “Distillation test method” or ASTM-D86.
動植物油脂および／または動物油脂由来成分を含有した炭化水素留分からなる原料油、または動植物油脂および／または動物油脂由来成分を含有した炭化水素留分と原油等から精製された灯油留分を有する石油系炭化水素留分を任意の比率で混合した混合油を原料油は、次に周期律表第６Ａ族および第８族から選ばれる少なくとも一種類以上の金属と酸性質を有する無機酸化物を含有する水素化分解触媒と水素加圧下で接触させる。 Petroleum having a kerosene fraction refined from a raw material oil comprising a hydrocarbon fraction containing a component derived from animal or vegetable oils and / or animal fats or a hydrocarbon fraction containing a component derived from animal or vegetable oils and / or animal fats and oils The mixed oil in which the system hydrocarbon fraction is mixed at an arbitrary ratio, then the feedstock oil contains at least one metal selected from Groups 6A and 8 of the periodic table and an inorganic oxide having acid properties Contacting with a hydrocracking catalyst under hydrogen pressure.
水素化分解触媒としては、周期律表第６Ａ族および第８族金属から選ばれる少なくとも一種類の金属を含有し、望ましくは第６Ａ族および第８族から二種類以上の金属を含有している。例えばＣｏ−Ｍｏ，Ｎｉ−Ｍｏ，Ｎｉ−Ｃｏ−Ｍｏ，Ｎｉ−Ｗが挙げられ、望ましくはＮｉ−Ｍｏ、Ｎｉ−Ｃｏ−Ｍｏ，Ｎｉ−Ｗが選ばれる。水素化分解に際しては水素化前処理触媒と同様にこれらの金属を硫化物の状態に転換して使用する。 The hydrocracking catalyst contains at least one kind of metal selected from Group 6A and Group 8 metals of the periodic table, and preferably contains two or more kinds of metals from Groups 6A and 8 . For example, Co-Mo, Ni-Mo, Ni-Co-Mo, and Ni-W are mentioned, and Ni-Mo, Ni-Co-Mo, and Ni-W are desirably selected. In hydrocracking, these metals are used after being converted to a sulfide state in the same manner as the pretreatment catalyst for hydrogenation.
水素化分解触媒の担体としては、酸性質を有する無機酸化物が採用されるが、シリカ、アルミナ、ボリア、ジルコニア、マグネシア、ゼオライトのうち少なくとも二種類を含有していることが望ましい。例えば、シリカ−アルミナ、チタニア−アルミナ、ボリア−アルミナ、ジルコニア−アルミナ、チタニア−ジルコニア−アルミナ、シリカ−ボリア−アルミナ、シリカ−ジルコニア−アルミナ、シリカ−チタニア−アルミナ、シリカ−チタニア−ジルコニア−アルミナが望ましく、シリカ−アルミナ、ボリア−アルミナ、ジルコニア−アルミナ、チタニア−ジルコニア−アルミナ、シリカ−ボリア−アルミナ、シリカ−ジルコニア−アルミナ、シリカ−チタニア−アルミナがより望ましく、シリカ−アルミナ、シリカ−ジルコニア−アルミナがさらにより望ましい。これらの複合酸化物にゼオライトを含有されていることがもっとも望ましい。アルミナが含まれる場合、アルミナと他の成分との比率は担体に対して任意の割合を取りうるが、アルミナの含有量が担体重量の９６重量％以下であることが望ましく、９０重量％以下であることがより望ましい。アルミナ含有量が９６重量％を越える場合には、十分な酸性質が得られず所定の水素化分解活性を発揮することが難しい傾向にある。 As the carrier of the hydrocracking catalyst, an inorganic oxide having an acid property is adopted, but it is desirable to contain at least two of silica, alumina, boria, zirconia, magnesia and zeolite. For example, silica-alumina, titania-alumina, boria-alumina, zirconia-alumina, titania-zirconia-alumina, silica-boria-alumina, silica-zirconia-alumina, silica-titania-alumina, silica-titania-zirconia-alumina Desirably, silica-alumina, boria-alumina, zirconia-alumina, titania-zirconia-alumina, silica-boria-alumina, silica-zirconia-alumina, silica-titania-alumina are more desirable, silica-alumina, silica-zirconia-alumina Is even more desirable. Most preferably, these composite oxides contain zeolite. When alumina is contained, the ratio of alumina to other components can be any ratio with respect to the support, but the content of alumina is preferably 96% by weight or less of the support weight, and 90% by weight or less. More desirable. When the alumina content exceeds 96% by weight, sufficient acid properties cannot be obtained and it tends to be difficult to exhibit a predetermined hydrocracking activity.
水素化分解触媒に用いられるゼオライトの結晶骨格を構成する成分としては、シリカのほかアルミナ、チタニア、ボリア、ガリウムなどがあるが、シリカとアルミナを含むゼオライト、すなわちアルミノシリケートが望ましい。ゼオライトの結晶構造には多くの種類が報告されているが、たとえばフォージャサイト型、ベータ型、モルデナイト型、ペンタシル型などがある。本発明においては、十分な水素化分解活性を発揮するという点でフォージャサイト型、ベータ型、ペンタシル型がより望ましく、特にフォージャサイト型、ベータ型がさらにより望ましい。これらのゼオライトは、合成開始時の原材料の量論比に応じてアルミナ含有量を調整したもの、あるいは所定の水熱処理および／または酸処理を施したものを用いることができる。このうち、水熱処理および／または酸処理により超安定化した超安定化Ｙ型がもっとも望ましい。この超安定化Ｙ型はゼオライト本来の２０Å以下のミクロ細孔と呼ばれる微細細孔構造に加え、２０〜１００Åの範囲に新たな細孔が形成されており油脂成分の酸素分を転換するために良好な反応場を提供しているものと推察され、該細孔直径を有する細孔の容積は０．０３ｍｌ／ｇ以上が望ましく、０．０４ｍｌ／ｇがより望ましい。なお、ここでいう細孔容積は、一般的には水銀圧入法によって求めることができる。水熱処理条件としては公知の条件を用いることができる。超安定化Ｙ型の物性としては、シリカ／アルミナのモル比率として１０〜１２０が好ましく、１５〜７０がより好ましく、２０〜５０がさらにより好ましい。シリカ／アルミナのモル比率が１２０よりも高い場合酸性質が低く、十分な水素化分解活性を発揮できない恐れがある。また、シリカ／アルミナのモル比率が１０より低い場合には酸性質が強すぎ、コーク生成反応を促進することにより急激な活性低下を招く恐れがある。ゼオライトの含有量は担体重量に対して２〜８０重量％が望ましく、４〜７５重量％がより望ましい。ゼオライト含有量が前記下限値に満たない場合には水素化分解活性を発揮できない恐れがあり、ゼオライト含有量が前記上限値を超える場合には酸性質が強すぎ、コーク生成反応を促進する恐れがある。 In addition to silica, there are alumina, titania, boria, gallium, and the like as components constituting the zeolite crystal skeleton used in the hydrocracking catalyst. Zeolite containing silica and alumina, that is, aluminosilicate is preferable. Many types of crystal structures of zeolite have been reported, and examples thereof include faujasite type, beta type, mordenite type, and pentasil type. In the present invention, the faujasite type, the beta type, and the pentasil type are more preferable, and the faujasite type and the beta type are even more preferable in that sufficient hydrocracking activity is exhibited. As these zeolites, those having an alumina content adjusted according to the stoichiometric ratio of raw materials at the start of synthesis, or those subjected to a predetermined hydrothermal treatment and / or acid treatment can be used. Of these, the super-stabilized Y type that is super-stabilized by hydrothermal treatment and / or acid treatment is most desirable. This ultra-stabilized Y type has a fine pore structure called micropores of 20 cm or less, which is the original size of zeolite, and new pores are formed in the range of 20 to 100 cm to convert the oxygen content of the fat and oil component. It is presumed to provide a good reaction field, and the volume of the pores having the pore diameter is preferably 0.03 ml / g or more, more preferably 0.04 ml / g. The pore volume here can be generally determined by a mercury intrusion method. Known conditions can be used as the hydrothermal treatment conditions. As the physical property of the ultra-stabilized Y-type, the silica / alumina molar ratio is preferably 10 to 120, more preferably 15 to 70, and still more preferably 20 to 50. When the silica / alumina molar ratio is higher than 120, the acidity is low, and sufficient hydrocracking activity may not be exhibited. On the other hand, when the silica / alumina molar ratio is lower than 10, the acidity is too strong, and the coke generation reaction may be promoted to cause a rapid decrease in activity. The content of zeolite is preferably 2 to 80% by weight, more preferably 4 to 75% by weight, based on the weight of the carrier. If the zeolite content is less than the lower limit, the hydrocracking activity may not be exhibited, and if the zeolite content exceeds the upper limit, the acidity is too strong and the coke formation reaction may be accelerated. is there.
本発明では、原料油を水素加圧下で接触処理するに際しては、周期律表第６Ａ族および第８族から選ばれる少なくとも一種類以上の金属を含有する水素化前処理触媒と水素加圧下で接触させた後に、前記水素化分解触媒と水素加圧下で接触させることが好ましい。 In the present invention, when the feedstock is subjected to contact treatment under hydrogen pressure, it is contacted with hydrogenation pretreatment catalyst containing at least one metal selected from Groups 6A and 8 of the periodic table under hydrogen pressure. Then, it is preferable to contact the hydrocracking catalyst under hydrogen pressure.
水素化前処理触媒の活性金属としては、周期律表第６Ａ族および第８族金属から選ばれる少なくとも一種類の金属を含有し、望ましくは第６Ａ族および第８族から選択される二種類以上の金属を含有している。例えばＣｏ−Ｍｏ，Ｎｉ−Ｍｏ，Ｎｉ−Ｃｏ−Ｍｏ，Ｎｉ−Ｗが挙げられ、水素化前処理に際しては、これらの金属を硫化物の状態に転換して使用する。 The active metal of the pretreatment catalyst for hydrogenation contains at least one metal selected from Group 6A and Group 8 metals of the periodic table, preferably two or more selected from Group 6A and Group 8 Contains metals. For example, Co-Mo, Ni-Mo, Ni-Co-Mo, and Ni-W can be mentioned. In the pretreatment for hydrogenation, these metals are converted into sulfides and used.
水素化前処理触媒の担体としては多孔性の無機酸化物が用いられる。一般的にはアルミナを含む多孔性無機酸化物であり、その他の担体構成成分としてはシリカ、チタニア、ジルコニア、ボリアなどが挙げられる。望ましくはアルミナとその他構成成分から選ばれる少なくとも１種類以上を含む複合酸化物である。また、このほかの成分として、リンを含んでいてもよい。アルミナ以外の成分の合計含有量は１〜２０重量％であることが好ましく、２〜１５重量％含有していることがより望ましい。含有量が１重量％に満たない場合、十分な触媒表面積を得ることが出来ず、活性が低くなる恐れがあり、含有量が２０重量％を超える場合、担体の酸性質が上昇し、コーク生成による活性低下を招く恐れがある。リンを担体構成成分として含む場合には、その含有量は、酸化物換算で１〜５重量％であることが望ましく、２〜３．５重量％がさらに望ましい。 A porous inorganic oxide is used as the support for the hydrogenation pretreatment catalyst. Generally, it is a porous inorganic oxide containing alumina, and examples of other carrier constituents include silica, titania, zirconia, and boria. Desirably, it is a complex oxide containing at least one selected from alumina and other constituent components. Moreover, phosphorus may be included as another component. The total content of components other than alumina is preferably 1 to 20% by weight, and more preferably 2 to 15% by weight. If the content is less than 1% by weight, a sufficient catalyst surface area cannot be obtained and the activity may be lowered. If the content exceeds 20% by weight, the acidity of the support will increase and coke formation will occur. May cause a decrease in activity. When phosphorus is included as a carrier constituent, the content is preferably 1 to 5% by weight, more preferably 2 to 3.5% by weight in terms of oxide.
アルミナ以外の担体構成成分である、シリカ、チタニア、ジルコニア、ボリアの前駆体となる原料は特に限定されず、一般的なケイ素、チタン、ジルコニウム、ボロンを含む溶液を用いることができる。例えば、ケイ素についてはケイ酸、水ガラス、シリカゾルなど、チタンについては硫酸チタン、四塩化チタンや各種アルコキサイド塩など、ジルコニウムについては硫酸ジルコニウム、各種アルコキサイド塩など、ボロンについてはホウ酸などを用いることができる。リンとしては、リン酸あるいはリン酸のアルカリ金属塩などを用いることができる。 There are no particular limitations on the raw materials that are precursors of silica, titania, zirconia, and boria, which are carrier constituents other than alumina, and general solutions containing silicon, titanium, zirconium, and boron can be used. For example, silicic acid, water glass and silica sol for silicon, titanium sulfate, titanium tetrachloride and various alkoxide salts for titanium, zirconium sulfate and various alkoxide salts for zirconium, and boric acid for boron, etc. it can. As phosphorus, phosphoric acid or an alkali metal salt of phosphoric acid can be used.
これらのアルミナ以外の担体構成成分の原料は、担体の焼成より前のいずれかの工程において添加する方法が望ましい。例えば予めアルミニウム水溶液に添加した後にこれらの構成成分を含む水酸化アルミニウムゲルとしてもよく、調合した水酸化アルミニウムゲルに添加してもよく、あるいは市販のアルミナ中間体やベーマイトパウダーに水あるいは酸性水溶液を添加して混練する工程に添加してもよいが、水酸化アルミニウムゲルを調合する段階で共存させる方法がより望ましい。これらのアルミナ以外の担体構成成分の効果発現機構は解明できていないが、アルミニウムと複合的な酸化物状態を形成していると思われ、このことが担体表面積の増加や、活性金属となんらかの相互作用を生じることにより、活性に影響を及ぼしていることが考えられる。 It is desirable that the raw materials for the carrier constituents other than alumina be added in any step prior to the firing of the carrier. For example, it may be added to an aluminum aqueous solution in advance and then an aluminum hydroxide gel containing these components, may be added to a prepared aluminum hydroxide gel, or water or an acidic aqueous solution may be added to a commercially available alumina intermediate or boehmite powder. Although it may be added to the step of adding and kneading, a method of coexisting at the stage of preparing aluminum hydroxide gel is more desirable. Although the mechanism of the effect of these carrier constituents other than alumina has not been elucidated, it is thought that they form a complex oxide state with aluminum, which increases the surface area of the carrier and some interaction with the active metal. It is considered that the activity is affected by producing the action.
活性金属の含有量は、例えば、ＷとＭｏの合計担持量は、望ましくは酸化物換算で触媒重量に対して１２〜３５重量％、より望ましくは１５〜３０重量％である。ＷとＭｏの合計担持量が前記下限値に満たない場合、活性点数の減少により活性が低下する可能性があり、前記上限値を超える場合には、金属が効果的に分散せず、同様に活性の低下を招く可能性がある。また、ＣｏとＮｉの合計担持量は、望ましくは酸化物換算で触媒重量に対して１．５〜１０重量％、より望ましくは２〜８重量％である。コバルトとニッケルの合計担持量が１．５重量％未満の場合には充分な助触媒効果が得られず活性が低下してしまう恐れがあり、１０重量％より多い場合には、金属が効果的に分散せず、同様に活性を招く可能性がある。 As for the content of the active metal, for example, the total supported amount of W and Mo is preferably 12 to 35% by weight, more preferably 15 to 30% by weight based on the catalyst weight in terms of oxide. If the total supported amount of W and Mo is less than the lower limit, the activity may decrease due to the decrease in the number of active points. If the upper limit is exceeded, the metal is not effectively dispersed, and similarly It may cause a decrease in activity. The total supported amount of Co and Ni is preferably 1.5 to 10% by weight, more preferably 2 to 8% by weight based on the catalyst weight in terms of oxide. If the total supported amount of cobalt and nickel is less than 1.5% by weight, a sufficient cocatalyst effect may not be obtained and the activity may be reduced. If more than 10% by weight, the metal is effective. In the same manner, there is a possibility of causing activity.
水素加圧下における接触反応条件としては、水素圧力５〜２０ＭＰａ、液空間速度（ＬＨＳＶ）０．１〜２．２ｈ−１、水素／油比３００〜１５００ＮＬ／Ｌといった条件で行われることが望ましく、水素圧力６．５〜１８ＭＰａ、液空間速度０．２〜２．０ｈ−１、水素／油比３００〜１５００ＮＬ／Ｌといった条件がより望ましく、水素圧力８〜１５ＭＰａ、液空間速度０．３〜１．５ｈ−１、水素／油比３５０〜１０００ＮＬ／Ｌといった条件がさらにより望ましい。 The catalytic reaction conditions under hydrogen pressure are preferably carried out under conditions such as a hydrogen pressure of 5 to 20 MPa, a liquid space velocity (LHSV) of 0.1 to 2.2 h −1 , and a hydrogen / oil ratio of 300 to 1500 NL / L. The conditions such as hydrogen pressure 6.5-18 MPa, liquid space velocity 0.2-2.0 h −1 , hydrogen / oil ratio 300-1500 NL / L are more desirable, hydrogen pressure 8-15 MPa, liquid space velocity 0.3-1 Even more desirable are conditions such as 0.5 h −1 , hydrogen / oil ratio 350-1000 NL / L.
水素加圧下での接触処理により、硫黄分含有量１０質量ｐｐｍ以下、炭素数３の炭化水素が１．０モル％以上９９．０モル％以下、炭素数４の炭化水素が１．０モル％以上９９．０モル％以下である炭化水素が得られる。
本発明の液化燃料ガス組成物はかかる炭化水素を含有するものであり、その含有割合は少なくとも１．０容量％以上であり、好ましくは２０．０容量％以上、さらに好ましくは９８．０容量％以上である。
By contact treatment under hydrogen pressure, the sulfur content is 10 mass ppm or less, the hydrocarbon having 3 carbon atoms is 1.0 mol% or more and 99.0 mol% or less, and the hydrocarbon having 4 carbon atoms is 1.0 mol%. A hydrocarbon having a content of 99.0 mol% or less is obtained.
The liquefied fuel gas composition of the present invention contains such hydrocarbon, and its content is at least 1.0% by volume, preferably 20.0% by volume, more preferably 98.0% by volume. That's it.
本発明の液化燃料ガス組成物は、主成分として炭素数３の炭化水素であるプロパン混合物と炭素数４の炭化水素であるブタン混合物とからなる。両者の割合は使用地域、季節により任意に規定できる。プロパン混合物は主にプロパンおよびプロピレンよりなり、ブタン混合物は主にブタンおよびブチレンよりなる。本発明の液化燃料ガス組成物の組成はこれら以外に少量のエタン混合物、ブタジエン、ペンタンなどを含有することができる。エタン混合物はエタンおよびエチレンよりなり、液化燃料ガス組成物中におけるエタン混合物の含有量は５モル％以下であることが好ましい。また液化燃料ガス組成物中におけるブタジエンの含有量は０．５モル％以下であることが好ましく、ペンタンの含有量は２モル％以下であることが好ましい。 The liquefied fuel gas composition of the present invention comprises a propane mixture, which is a hydrocarbon having 3 carbon atoms, and a butane mixture, which is a hydrocarbon having 4 carbon atoms, as main components. The ratio of both can be defined arbitrarily according to the region of use and the season. The propane mixture mainly consists of propane and propylene, and the butane mixture mainly consists of butane and butylene. In addition to these, the liquefied fuel gas composition of the present invention can contain a small amount of ethane mixture, butadiene, pentane and the like. The ethane mixture is composed of ethane and ethylene, and the content of the ethane mixture in the liquefied fuel gas composition is preferably 5 mol% or less. Further, the butadiene content in the liquefied fuel gas composition is preferably 0.5 mol% or less, and the pentane content is preferably 2 mol% or less.
本発明の液化燃料ガス組成物は、１０５℃残渣分が１０質量ｐｐｍ以下であることが好ましい。１０５℃残渣分は、デポジット生成速度およびドレン抜き出し頻度を減少させることができる観点から５質量ｐｐｍ以下であることがより好ましく、２質量ｐｐｍ以下であることが特に好ましい。
なお、ここでいう１０５℃残渣分とは、ＡＳＴＭ Ｄ２１５８に定める方法に準拠して測定される値であるが、初期サンプル量をＡＳＴＭ法記載の１００ｍＬから４Ｌに変更し、設定温度を３８℃からさらに７５℃、１０５℃と順に変えてゆき、最終的には１０５℃にて残った残渣の重量を秤量することにより測定される値のことをいう。この際、各温度での保持時間はＡＳＴＭ法記載の５分ではなくその温度での蒸発がほぼ認められなくなるまでの十分な時間をとるものとする。
In the liquefied fuel gas composition of the present invention, the residue at 105 ° C. is preferably 10 mass ppm or less. The residue at 105 ° C. is more preferably 5 mass ppm or less, and particularly preferably 2 mass ppm or less from the viewpoint of reducing the deposit generation rate and the drain drawing frequency.
In addition, although 105 degreeC residue here is a value measured based on the method prescribed | regulated to ASTMD2158, the initial sample amount is changed from 100 mL of ASTM method description to 4L, and setting temperature is from 38 degreeC. Further, it is a value measured by measuring the weight of the residue remaining at 105 ° C. in the order of 75 ° C. and 105 ° C. At this time, the holding time at each temperature is not 5 minutes as described in the ASTM method, but a sufficient time is taken until almost no evaporation at that temperature is recognized.
本発明の液化燃料ガス組成物は、１０５℃残渣分のｐＨが６以上であることが好ましい。１０５℃残渣分のｐＨが６未満であると、ベーパライザー内部のデポジット生成が増加する恐れがある。一方、燃料ラインとベーパライザーの腐食防止の点でｐＨは８以下であることが好ましい。より好ましくはｐＨが６〜７であり、さらに好ましくはｐＨが７である。
なお、ここでいう１０５℃残渣分のｐＨとは、上述の１０５℃残渣分の測定方法で得られた１０５℃残渣分に残渣分の１０００倍量の蒸留水（残渣分が１ｍｇ以下の場合は１ｍＬの蒸留水）を加え攪拌した後、水相部分のｐＨをｐＨ試験紙により測定することによって得られる値のことをいう。
In the liquefied fuel gas composition of the present invention, the pH of the residue at 105 ° C. is preferably 6 or more. If the pH of the residue at 105 ° C. is less than 6, deposit formation inside the vaporizer may increase. On the other hand, the pH is preferably 8 or less from the viewpoint of preventing corrosion of the fuel line and the vaporizer. More preferably, pH is 6-7, More preferably, pH is 7.
Here, the pH of the 105 ° C. residue is the same as that of the 105 ° C. residue obtained by the method for measuring a 105 ° C. residue described above, but 1000 times the amount of distilled water (if the residue is 1 mg or less). 1 mL of distilled water) is added and stirred, and then the value obtained by measuring the pH of the aqueous phase with a pH test paper.
本発明の液化燃料ガス組成物の硫黄分は、燃料ラインの腐食防止と排気ガス中への硫黄酸化物排出防止の点から液化燃料ガス全量基準で０．０２質量％以下であることが好ましく、０．０１５質量％以下であることがより好ましく、０．００５質量％以下であることがさらに好ましく、０．００１質量％以下であることが最も好ましい。
なお、ここでいう硫黄分とは、ＪＩＳ Ｋ ２２４０「液化石油ガス（ＬＰガス）−硫黄分試験方法」により測定される値を意味する。
The sulfur content of the liquefied fuel gas composition of the present invention is preferably 0.02% by mass or less based on the total amount of the liquefied fuel gas from the viewpoint of preventing corrosion of the fuel line and preventing sulfur oxide emission into the exhaust gas, More preferably, it is 0.015 mass% or less, More preferably, it is 0.005 mass% or less, Most preferably, it is 0.001 mass% or less.
In addition, the sulfur content here means a value measured by JIS K 2240 “Liquefied petroleum gas (LP gas) -sulfur content test method”.
本発明の液化燃料ガス組成物の４０℃における蒸気圧は、低温時始動性確保の点から０．２８ＭＰａ以上であることが好ましく、０．３８ＭＰａ以上がより好ましい。一方、取り扱い上の安全性の点から１．５５ＭＰａ以下であることが好ましく、１．２５ＭＰａ以下がより好ましく、０．５２ＭＰａ以下が最も好ましい。
なお、ここでいう４０℃における蒸気圧とは、ＪＩＳ Ｋ ２２４０「液化石油ガス（ＬＰガス）−蒸気圧試験方法」により測定される値を意味する。
The vapor pressure at 40 ° C. of the liquefied fuel gas composition of the present invention is preferably 0.28 MPa or more, and more preferably 0.38 MPa or more from the viewpoint of securing startability at low temperatures. On the other hand, from the viewpoint of safety in handling, it is preferably 1.55 MPa or less, more preferably 1.25 MPa or less, and most preferably 0.52 MPa or less.
Here, the vapor pressure at 40 ° C. means a value measured according to JIS K 2240 “Liquefied petroleum gas (LP gas) —vapor pressure test method”.
本発明の液化燃料ガス組成物の１５℃における密度は、燃費向上の点から０．５００ｇ／ｃｍ３以上であることが好ましく、一方、重質分の混入を防止する点から０．６２０ｇ／ｃｍ３以下であることが好ましく、０．６００ｇ／ｃｍ３以下がより好ましい。
なお、ここでいう１５℃における密度とは、ＪＩＳ Ｋ ２２４０「液化石油ガス（ＬＰＧ）−密度試験方法」により測定される値を意味する。
The density at 15 ° C. of the liquefied fuel gas composition of the present invention is preferably 0.500 g / cm 3 or more from the viewpoint of improving fuel efficiency, and 0.620 g / cm from the viewpoint of preventing heavy components from being mixed. 3 or less is preferable, and 0.600 g / cm 3 or less is more preferable.
Here, the density at 15 ° C. means a value measured by JIS K 2240 “Liquefied petroleum gas (LPG) —density test method”.
本発明の液化燃料ガス組成物の銅板腐食は、燃料配管の腐食防止の点から１以下であることが好ましく、１ａがより好ましい。
なお、ここでいう銅板腐食とは、ＪＩＳ Ｋ ２２４０「液化石油ガス（ＬＰガス）−銅板腐食試験方法」により測定される値を意味する。
The copper plate corrosion of the liquefied fuel gas composition of the present invention is preferably 1 or less, more preferably 1a, from the viewpoint of preventing corrosion of fuel piping.
In addition, copper plate corrosion here means the value measured by JISK2240 "liquefied petroleum gas (LP gas)-copper plate corrosion test method".
本発明の液化燃料ガス組成物は自動車用燃料として好適に使用することができる。 The liquefied fuel gas composition of the present invention can be suitably used as an automobile fuel.
本発明の液化燃料ガス組成物は、動植物油脂および動物油脂由来成分を含有した炭化水素留分を原料油として、周期律表第６Ａ族および第８族から選ばれる少なくとも一種類以上の金属と酸性質を有する無機酸化物を含有する水素化分解触媒と水素加圧下で接触させることにより得られる炭化水素を用いることにより、排出ガスを低減し、かつＣＯ２排出量を低減することができる。 The liquefied fuel gas composition of the present invention comprises at least one metal and acid selected from Groups 6A and 8 of the periodic table using a hydrocarbon fraction containing components derived from animal and plant oils and animal fats as raw material oil. By using a hydrocarbon obtained by contacting a hydrocracking catalyst containing an inorganic oxide having properties under hydrogen pressure, exhaust gas can be reduced and CO 2 emission can be reduced.
以下に実施例により本発明を具体的に説明するが、本発明はこれらによって何ら限定されるものではない。 EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.
［実施例１〜２および比較例１］
動植物油脂および／または動物油脂由来成分を含有した炭化水素留分からなる原料油を周期律表第６Ａ族および第８族から選ばれる少なくとも一種類以上の金属と酸性質を有する無機酸化物を含有する水素化分解触媒と水素加圧下で接触させることにより得られる炭化水素を用いて、実施例１および２の液化燃料ガス組成物を調製した。一方、製油所より生産されるブタン、プロパンおよび輸入ブタン、輸入プロパンを用いて、比較例１の液化燃料ガス組成物を調製した。実施例、比較例に用いた各液化燃料ガス組成物の性状を表１に示す。これらの液化燃料ガス組成物について、排出ガス試験を行い、排出ガス評価を下記の方法により実施し、その結果を表２に記した。またこれら実施例および比較例の排出ＣＯ２のライフサイクルアセスメント（ＬＣＡ）を実施し、排出されるＣＯ２を計算して表２に併記した。
（ａ）性状測定
[Examples 1 and 2 and Comparative Example 1]
A raw material oil comprising a hydrocarbon fraction containing a component derived from animal and vegetable fats and / or animal fats and fats contains at least one metal selected from Groups 6A and 8 of the periodic table and an inorganic oxide having acid properties. The liquefied fuel gas compositions of Examples 1 and 2 were prepared using hydrocarbons obtained by contacting a hydrocracking catalyst with hydrogen under pressure. On the other hand, a liquefied fuel gas composition of Comparative Example 1 was prepared using butane, propane, imported butane, and imported propane produced from a refinery. Table 1 shows the properties of each liquefied fuel gas composition used in Examples and Comparative Examples. These liquefied fuel gas compositions were subjected to an exhaust gas test, and an exhaust gas evaluation was performed by the following method. The results are shown in Table 2. In addition, the life cycle assessment (LCA) of the exhausted CO 2 of these examples and comparative examples was performed, and the exhausted CO 2 was calculated and shown in Table 2.
(A) Property measurement
各液化燃料ガス組成物の性状は以下の方法により測定した。
プロパン、ブタン等の組成分析は、ＪＩＳ Ｋ ２２４０「液化石油ガス（ＬＰガス）−組成分析方法（ガスクロマトグラフ法）」により測定される値である。
１０５℃残渣分は、ＡＳＴＭ Ｄ２１５８に定める方法に準拠し、初期サンプル量をＡＳＴＭ法記載の１００ｍＬから４Ｌに変更し、設定温度をＡＳＴＭ法記載の３８℃からさらに７５℃、１０５℃と順に変えてゆき、最終的には１０５℃にて残った残渣の重量を秤量することにより測定される値である。
１０５℃残渣分のｐＨは、上記１０５℃残渣分の測定方法にて得られた１０５℃残渣分に残渣分の１０００倍量の蒸留水（残渣分が１ｍｇ以下の場合は１ｍＬの蒸留水）を加え攪拌した後、水相部分のｐＨをｐＨ試験紙（東洋濾紙社製ｐＨ試験紙）により測定することによって得られる値である。
硫黄分含有量は、ＪＩＳ Ｋ ２２４０「液化石油ガス（ＬＰガス）−硫黄分試験方法」により測定される値である。
４０℃における蒸気圧は、ＪＩＳ Ｋ ２２４０「液化石油ガス（ＬＰガス）−蒸気圧試験方法」により測定される値である。
１５℃における密度は、ＪＩＳ Ｋ ２２４０「液化石油ガス（ＬＰＧ）−密度試験方法」により測定される値である。
銅板腐食は、ＪＩＳ Ｋ ２２４０「液化石油ガス（ＬＰガス）−銅板腐食試験方法」により測定される値である。
The properties of each liquefied fuel gas composition were measured by the following method.
The composition analysis of propane, butane, etc. is a value measured by JIS K 2240 “Liquefied petroleum gas (LP gas) -composition analysis method (gas chromatographic method)”.
For the 105 ° C residue, the initial sample amount was changed from 100 mL described in the ASTM method to 4 L in accordance with the method specified in ASTM D2158, and the set temperature was changed in order from 38 ° C described in the ASTM method to 75 ° C and 105 ° C in this order. Finally, it is a value measured by weighing the residue remaining at 105 ° C.
The pH of the 105 ° C. residue is obtained by adding 1000 times the amount of distilled water (if the residue is 1 mg or less, 1 mL of distilled water) to the 105 ° C. residue obtained by the above 105 ° C. residue measurement method. After the addition and stirring, the pH is obtained by measuring the pH of the aqueous phase with a pH test paper (pH test paper manufactured by Toyo Roshi Kaisha, Ltd.).
The sulfur content is a value measured by JIS K 2240 “Liquefied petroleum gas (LP gas) -sulfur content test method”.
The vapor pressure at 40 ° C. is a value measured according to JIS K 2240 “Liquefied petroleum gas (LP gas) —vapor pressure test method”.
The density at 15 ° C. is a value measured by JIS K 2240 “Liquefied Petroleum Gas (LPG) —Density Test Method”.
The copper plate corrosion is a value measured by JIS K 2240 “Liquefied petroleum gas (LP gas) -copper plate corrosion test method”.
（ｂ）排出ガス評価
下記試験車両を用いて、１０・１５モードによる排出ガス測定を行った。排ガス試験およびＣＯ２排出量ＬＣＡの評価結果を表２に記した。
（試験車両）
エンジン：直列４気筒
排気量：１９９８ｃｃ
燃料供給方式：電子制御式キャブレター
ミッション：オートマチックトランスミッション
(B) Exhaust gas evaluation Exhaust gas was measured in the 10.15 mode using the following test vehicle. The evaluation results of the exhaust gas test and the CO 2 emission amount LCA are shown in Table 2.
(Test vehicle)
Engine: Inline 4-cylinder Displacement: 1998cc
Fuel supply system: Electronically controlled carburetor Mission: Automatic transmission
表２に示すとおり、本発明の液化燃料ガス組成物は、従来のＬＰＧ燃料に比べ排出ガス成分（ＴＨＣ，ＣＯ，ＮＯｘ）を低減できることがわかる。
さらにこれら実施例および比較例の排出ＣＯ２のライフサイクルアセスメント（ＬＣＡ）を実施し、排出されるＣＯ２を計算した。本実施例では燃焼時に生じるＣＯ２についてバイオマス由来分はゼロカウントとなるため大幅なＣＯ２削減を達成することができた。
As shown in Table 2, it can be seen that the liquefied fuel gas composition of the present invention can reduce exhaust gas components (THC, CO, NOx) compared to conventional LPG fuel.
Further, a life cycle assessment (LCA) of the exhausted CO 2 of these examples and comparative examples was performed, and the emitted CO 2 was calculated. In this example, the biomass-derived component of CO 2 generated during combustion becomes zero count, so that a significant CO 2 reduction can be achieved.
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| Application Number | Priority Date | Filing Date | Title |
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| JP2005347278A JP4925653B2 (en) | 2005-11-30 | 2005-11-30 | Method for producing liquefied fuel gas composition |
| CNA2006800449993A CN101341232A (en) | 2005-11-30 | 2006-11-29 | Liquefied fuel gas composition |
| KR1020087013041A KR20080071580A (en) | 2005-11-30 | 2006-11-29 | Liquefied fuel gas composition |
| PCT/JP2006/324306 WO2007064019A1 (en) | 2005-11-30 | 2006-11-29 | Liquefied fuel gas composition |
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| JP2005347278A JP4925653B2 (en) | 2005-11-30 | 2005-11-30 | Method for producing liquefied fuel gas composition |
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| JP2007153940A JP2007153940A (en) | 2007-06-21 |
| JP4925653B2 true JP4925653B2 (en) | 2012-05-09 |
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| KR (1) | KR20080071580A (en) |
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| US8003834B2 (en) | 2007-09-20 | 2011-08-23 | Uop Llc | Integrated process for oil extraction and production of diesel fuel from biorenewable feedstocks |
| US7982075B2 (en) | 2007-09-20 | 2011-07-19 | Uop Llc | Production of diesel fuel from biorenewable feedstocks with lower hydrogen consumption |
| US7982076B2 (en) | 2007-09-20 | 2011-07-19 | Uop Llc | Production of diesel fuel from biorenewable feedstocks |
| US7982078B2 (en) | 2007-09-20 | 2011-07-19 | Uop Llc | Production of diesel fuel from biorenewable feedstocks with selective separation of converted oxygen |
| US7999143B2 (en) | 2007-09-20 | 2011-08-16 | Uop Llc | Production of diesel fuel from renewable feedstocks with reduced hydrogen consumption |
| US7982077B2 (en) | 2007-09-20 | 2011-07-19 | Uop Llc | Production of diesel fuel from biorenewable feedstocks with selective separation of converted oxygen |
| US7999142B2 (en) | 2007-09-20 | 2011-08-16 | Uop Llc | Production of diesel fuel from biorenewable feedstocks |
| US7915460B2 (en) | 2007-09-20 | 2011-03-29 | Uop Llc | Production of diesel fuel from biorenewable feedstocks with heat integration |
| US8742183B2 (en) | 2007-12-21 | 2014-06-03 | Uop Llc | Production of aviation fuel from biorenewable feedstocks |
| US8193400B2 (en) | 2008-03-17 | 2012-06-05 | Uop Llc | Production of diesel fuel from renewable feedstocks |
| US8058492B2 (en) | 2008-03-17 | 2011-11-15 | Uop Llc | Controlling production of transportation fuels from renewable feedstocks |
| US8193399B2 (en) | 2008-03-17 | 2012-06-05 | Uop Llc | Production of diesel fuel and aviation fuel from renewable feedstocks |
| US8198492B2 (en) | 2008-03-17 | 2012-06-12 | Uop Llc | Production of transportation fuel from renewable feedstocks |
| US8039682B2 (en) | 2008-03-17 | 2011-10-18 | Uop Llc | Production of aviation fuel from renewable feedstocks |
| US8329967B2 (en) | 2008-04-06 | 2012-12-11 | Uop Llc | Production of blended fuel from renewable feedstocks |
| US8324438B2 (en) | 2008-04-06 | 2012-12-04 | Uop Llc | Production of blended gasoline and blended aviation fuel from renewable feedstocks |
| US8329968B2 (en) | 2008-04-06 | 2012-12-11 | Uop Llc | Production of blended gasoline aviation and diesel fuels from renewable feedstocks |
| CN102057019B (en) | 2008-04-06 | 2014-07-02 | 环球油品公司 | Fuel and fuel blending components from biomass derived pyrolysis oil |
| US8766025B2 (en) | 2008-06-24 | 2014-07-01 | Uop Llc | Production of paraffinic fuel from renewable feedstocks |
| US8304592B2 (en) | 2008-06-24 | 2012-11-06 | Uop Llc | Production of paraffinic fuel from renewable feedstocks |
| US7982079B2 (en) | 2008-09-11 | 2011-07-19 | Uop Llc | Integrated process for production of diesel fuel from renewable feedstocks and ethanol denaturizing |
| US8921627B2 (en) | 2008-12-12 | 2014-12-30 | Uop Llc | Production of diesel fuel from biorenewable feedstocks using non-flashing quench liquid |
| US8471079B2 (en) | 2008-12-16 | 2013-06-25 | Uop Llc | Production of fuel from co-processing multiple renewable feedstocks |
| US8314274B2 (en) | 2008-12-17 | 2012-11-20 | Uop Llc | Controlling cold flow properties of transportation fuels from renewable feedstocks |
| US8283506B2 (en) | 2008-12-17 | 2012-10-09 | Uop Llc | Production of fuel from renewable feedstocks using a finishing reactor |
| WO2011037901A2 (en) * | 2009-09-25 | 2011-03-31 | Exxonmobil Research And Engineering Company | Fuel production from feedstock containing triglyceride and/or fatty acid alkyl ester |
| US8471081B2 (en) | 2009-12-28 | 2013-06-25 | Uop Llc | Production of diesel fuel from crude tall oil |
| US8900443B2 (en) | 2011-04-07 | 2014-12-02 | Uop Llc | Method for multi-staged hydroprocessing using quench liquid |
| US8816144B2 (en) * | 2012-10-04 | 2014-08-26 | Gas Technology Institute | Direct production of fractionated and upgraded hydrocarbon fuels from biomass |
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| JP2007153940A (en) | 2007-06-21 |
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