CN106929094A - 生产可再生中间馏出物组合物的方法，该组合物的用途和含有该组合物的燃料 - Google Patents
生产可再生中间馏出物组合物的方法，该组合物的用途和含有该组合物的燃料 Download PDFInfo
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- CN106929094A CN106929094A CN201611248585.4A CN201611248585A CN106929094A CN 106929094 A CN106929094 A CN 106929094A CN 201611248585 A CN201611248585 A CN 201611248585A CN 106929094 A CN106929094 A CN 106929094A
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- fuel
- middle distillate
- levulic acid
- oligomer
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- 239000000446 fuel Substances 0.000 title claims abstract description 83
- 239000000203 mixture Substances 0.000 title claims abstract description 71
- 238000004519 manufacturing process Methods 0.000 title claims description 17
- JOOXCMJARBKPKM-UHFFFAOYSA-N 4-oxopentanoic acid Chemical class CC(=O)CCC(O)=O JOOXCMJARBKPKM-UHFFFAOYSA-N 0.000 claims abstract description 78
- 239000000539 dimer Substances 0.000 claims abstract description 53
- 239000002994 raw material Substances 0.000 claims abstract description 30
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 22
- 150000001491 aromatic compounds Chemical class 0.000 claims abstract description 11
- 238000004508 fractional distillation Methods 0.000 claims abstract description 5
- 238000005859 coupling reaction Methods 0.000 claims description 37
- 238000000034 method Methods 0.000 claims description 28
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 239000003054 catalyst Substances 0.000 claims description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 17
- 239000002253 acid Substances 0.000 claims description 10
- 235000019602 lubricity Nutrition 0.000 claims description 10
- 238000007710 freezing Methods 0.000 claims description 9
- 150000001924 cycloalkanes Chemical class 0.000 claims description 8
- 230000008014 freezing Effects 0.000 claims description 8
- 150000002148 esters Chemical class 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 239000002803 fossil fuel Substances 0.000 claims description 6
- 238000005194 fractionation Methods 0.000 claims description 5
- 125000001931 aliphatic group Chemical group 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 3
- 239000011347 resin Substances 0.000 claims description 3
- 229920005989 resin Polymers 0.000 claims description 3
- 235000015112 vegetable and seed oil Nutrition 0.000 claims description 2
- 239000008158 vegetable oil Substances 0.000 claims description 2
- 239000000047 product Substances 0.000 description 21
- 239000001257 hydrogen Substances 0.000 description 17
- 229910052739 hydrogen Inorganic materials 0.000 description 17
- 239000002283 diesel fuel Substances 0.000 description 16
- 229910052799 carbon Inorganic materials 0.000 description 14
- 230000008878 coupling Effects 0.000 description 13
- 238000010168 coupling process Methods 0.000 description 13
- 239000007789 gas Substances 0.000 description 11
- 229930195733 hydrocarbon Natural products 0.000 description 10
- 150000002430 hydrocarbons Chemical group 0.000 description 10
- 238000006317 isomerization reaction Methods 0.000 description 10
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 7
- 239000003456 ion exchange resin Substances 0.000 description 7
- 229920003303 ion-exchange polymer Polymers 0.000 description 7
- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 description 6
- 150000002596 lactones Chemical class 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- 239000004215 Carbon black (E152) Substances 0.000 description 5
- 230000002349 favourable effect Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 150000001721 carbon Chemical group 0.000 description 4
- 239000000470 constituent Substances 0.000 description 4
- 238000006471 dimerization reaction Methods 0.000 description 4
- 238000006384 oligomerization reaction Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 description 3
- 239000003225 biodiesel Substances 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 239000003502 gasoline Substances 0.000 description 3
- 239000012978 lignocellulosic material Substances 0.000 description 3
- 229910052987 metal hydride Inorganic materials 0.000 description 3
- 150000004681 metal hydrides Chemical class 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910003294 NiMo Inorganic materials 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 238000006114 decarboxylation reaction Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052809 inorganic oxide Inorganic materials 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
- JOOXCMJARBKPKM-UHFFFAOYSA-M 4-oxopentanoate Chemical compound CC(=O)CCC([O-])=O JOOXCMJARBKPKM-UHFFFAOYSA-M 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- 229910003978 SiClx Inorganic materials 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229920001429 chelating resin Polymers 0.000 description 1
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- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 150000001923 cyclic compounds Chemical class 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002085 enols Chemical class 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 125000000468 ketone group Chemical group 0.000 description 1
- -1 levulic acid lactone Chemical class 0.000 description 1
- 229940058352 levulinate Drugs 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 230000032696 parturition Effects 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 230000007306 turnover Effects 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
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- C10G50/00—Production of liquid hydrocarbon mixtures from lower carbon number hydrocarbons, e.g. by oligomerisation
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- C10L10/00—Use of additives to fuels or fires for particular purposes
- C10L10/14—Use of additives to fuels or fires for particular purposes for improving low temperature properties
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
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- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
- C07C51/353—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by isomerisation; by change of size of the carbon skeleton
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- C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
- C10G3/50—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids in the presence of hydrogen, hydrogen donors or hydrogen generating compounds
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- C07C13/00—Cyclic hydrocarbons containing rings other than, or in addition to, six-membered aromatic rings
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- C07C13/08—Monocyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with a five-membered ring
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- C07C13/32—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings
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- C10L2200/00—Components of fuel compositions
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- C10L2200/0407—Specifically defined hydrocarbon fractions as obtained from, e.g. a distillation column
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Abstract
本发明提供了一种燃料，其包含可通过包含乙酰丙酸二聚体/低聚物的原料的加氢脱氧和分级蒸馏获得的可再生中间馏出物组合物。可再生中间馏出物组合物包含小于10.0重量％的芳族化合物。
Description
技术领域
本发明涉及一种生产可再生中间馏出物(middle-distillate)烃组合物的方法，该组合物的用途和含有该组合物的燃料。特别地，本发明涉及通过加氢处理衍生自用于生产燃料或燃料组分的可再生来源的乙酰丙酸二聚体/低聚物获得的烃组合物，包含这些烃组合物的燃料以及这些烃组合物作为航空燃料的用途。
背景技术
US2012/0283493A1公开了用于处理脂肪酸和木质纤维素材料的各种方法，包括加氢脱氧处理。
WO2006/067171A1公开了将选自内酯、具有γ-酮基的羧酸或其酯的反应物转化为非环状饱和羧酸或酯，其中非环状饱和酯可用于柴油燃料中。
EP2 924 097 A2公开了乙酰丙酸的C-C-偶合反应，其产生高达35重量％的二聚体以及(更高级的)低聚物。产物可以进行HDO处理，然后分馏用于例如柴油、航空或汽油燃料。汽油馏分可以包含小于10重量％的芳族化合物。柴油馏分(其是中间馏出物馏分)含有至少30重量％的芳族化合物。
WO2015/144994A1公开了乙酰丙酸的热C-C-偶合，其导致例如二聚体，随后进行HDO和任选的异构化。汽油、航空和柴油范围馏分可以通过分馏获得。WO2015/144994A1陈述了异构化导致环状化合物的减少，但是仍然没有提及中间馏出物馏分中芳族化合物的含量。
发明内容
本发明涉及一种生产可再生中间馏出物烃组合物的方法，该组合物的用途和含有该组合物的燃料。该组合物特别适合作为航空燃料/喷气燃料中的组分，但也可用于柴油范围燃料中。特别地，本发明涉及通过加氢处理衍生自用于生产燃料或燃料组分的可再生来源的乙酰丙酸二聚体/低聚物获得的组合物，包含这些组合物的燃料以及这些组合物作为航空燃料的用途。
迄今为止，有三条ASTM认证的可再生航空燃料生产路径：费-托合成、酯和脂肪酸的加氢处理(HEFA)和直接糖至烃(DSHC)转化。根据芬兰交通和运输部的设想，到2050年，目前使用的航空燃料中有40％将被生物煤油代替。这么大的量需要替代的来源用于生产可再生航空燃料，特别是满足最高需求的高质量燃料。
因此，从可大量获得的可再生来源生产高质量航空燃料仍然是一个需要解决的问题。此外，生物柴油越来越多的使用提出了找到合适的来源用于生产具有期望的燃料特性的生物柴油或生物柴油添加剂的问题。
这些问题通过所附权利要求中限定的方法、产品和用途来解决。
具体地，本发明提供了中间馏出物组合物，其可以用作燃料组分而无需进一步纯化，因为它们具有低含量的不期望的组分。
附图说明
图1显示了作为本发明的可再生中间馏出物组合物在与化石燃料的共混物中的含量函数的BOCLE润滑性(mm)(实施例3)。
具体实施方式
本发明涉及可用作航空燃料或柴油燃料的组分的可再生中间馏出物组合物，其通过对获自可再生来源的乙酰丙酸二聚体/低聚物进行加氢处理而获得。
具体地，本发明涉及包含可再生中间馏出物组合物的燃料，其中可再生中间馏出物组合物可通过包含乙酰丙酸二聚体/低聚物的原料进行加氢脱氧(或加氢处理)，然后分馏而获得。进行分馏以从加氢脱氧后获得的产物获得中间馏出物馏分。根据ASTM D2425测定，可再生中间馏出物组合物含有小于10.0重量％的芳族化合物。
根据ASTM D2425测定，可再生中间馏出物组合物优选含有至多9.5重量％，至多9.3重量％，至多9.0重量％，至多8.0重量％，至多7.0重量％，至多6.0重量％，至多5.0重量％，至多4.0重量％，或至多3.0重量％的芳族化合物。本发明人惊奇地发现，可以从乙酰丙酸二聚体/低聚物生产具有非常低的芳族化合物含量的中间馏出物馏分。考虑到排放和燃烧特性，低芳族化合物含量是有利的。
由于使用含有乙酰丙酸二聚体/低聚物的原料，产物分布窄，并且产物性质可以控制在良好特定的范围内。此外，当单独使用或与常规燃料组合使用时，所得产物(即中间馏出物馏分)提供非常低的凝固点。此外，当以混合物使用中间馏出物时，柴油燃料的浊点也非常低。因此，可以使用木质纤维素材料作为可大量获得的可再生来源来生产高质量燃料。
在本发明中，乙酰丙酸可以以酸形式或作为选自乙酰丙酸的酯和/或乙酰丙酸的内酯的组的衍生物使用。因此，乙酰丙酸二聚体/低聚物包括从单独的乙酰丙酸(游离酸形式)、单独的乙酰丙酸酯、单独的乙酰丙酸内酯和这些的混合二聚体/低聚物获得的所有种类的二聚体/低聚物。在本发明中，表述“含有乙酰丙酸二聚体/低聚物”是指含有至少一种乙酰丙酸二聚体/低聚物。
乙酰丙酸二聚体/低聚物进一步包括在C-C-偶合反应或蒸馏的条件下通过其它反应(例如(内部的)内酯化和脱水和进一步缩合反应产生例如LA-三聚体)可由乙酰丙酸二聚体/低聚物直接获得的所有化合物。根据本发明的乙酰丙酸二聚体/低聚物的实例由下式显示，使用游离酸二聚体作为实例：
在本发明中，可再生中间馏出物组合物的凝固点优选为-70℃或更低。此外，可再生中间馏出物组合物的凝固点可以为-80℃或更低，-90℃或更低，或-95℃或更低。凝固点可以例如按照IP529确定。本发明的发明人惊奇地发现，由乙酰丙酸二聚体/低聚物获得的中间馏出物组合物提供极低的凝固点，这使得其特别适合作为航空燃料组分或冬季柴油组分。
在本发明中，“中间馏出物组合物”通常涉及本发明的燃料中所含的中间馏出物馏分、通过本发明的方法生产的中间馏出物馏分和根据本发明使用的中间馏出物馏分。此外，中间馏出物馏分可以是柴油范围馏分或航空燃料范围馏分，并且优选是航空燃料范围馏分。
优选地，可再生中间馏出物组合物包含至少50重量％，优选至少55重量％，更优选至少60重量％，或至少65重量％的环烷烃，如根据ASTM D2425测定的。
令人惊讶地，高含量的环烷烃提供良好的燃料性质(例如低凝固点和低浊点)，并且当使用乙酰丙酸二聚体/低聚物作为原料时通过适当调整HDO条件可以实现。
可再生中间馏出物组合物适当地包含至多80重量％，优选至多75重量％，更优选至多72重量％，或至多70重量％的环烷烃，如根据ASTM D2425测定的。通常，链烷烃(paraffin)为喷气燃料和柴油燃料提供最理想的燃烧清洁特性。环烷烃是用于该用途的下一个最理想的烃。
尽管本发明的燃料中中间馏出物馏分的含量没有特别限制，并且可以在0.01重量％至100重量％的范围内(净中间馏出物馏分)，考虑到调节燃料性质(例如密度、润滑性、粘度、凝固点等)到所需值(和/或以满足法规要求)，可能需要将中间馏出物馏分与化石燃料和/或与其它可再生燃料(除了源自含有乙酰丙酸二聚体/低聚物的原料的HDO的可再生燃料)共混。
特别地，燃料还可以包含化石燃料、HEFA(加氢处理的酯和脂肪酸)燃料和/或HVO(加氢处理的植物油)燃料。
可再生中间馏出物组合物的BOCLE润滑性可以为0.75mm或更小，优选0.72mm或更小，更优选0.70mm或更小，0.69mm或更小，0.68mm或更小，或0.67mm或更小，如根据ASTMD5001-10(2014)测定的。本发明人的令人惊讶的发现之一是中间馏出物馏分，特别是航空燃料馏分(LBAF；乙酰丙酸基航空燃料馏分)的BOCLE润滑性是非常有利的，即中间馏出物馏分获得非常低的磨损值。
此外，LBAF和化石航空燃料的共混物可以实现甚至更低的BOCLE值，特别是对于含有1.5重量％LBAF或更高，优选2.5重量％LBAF或更高，3.0重量％LBAF或更高，或4.0重量％LBAF或更高的共混物。即使共混物中的LBAF含量为40.0重量％或更少，优选30.0重量％或更少，20.0重量％或更少，15.0重量％或更少，12.0重量％或更少，或10.0重量％或更少，所述效果是非常突出的。优选地，本发明的燃料的BOCLE润滑性为0.70mm或更小，优选0.67mm或更小，更优选0.66mm或更小，0.65mm或更小，或0.64mm或更小，如根据ASTM D5001-10(2014)测定的。润滑性是柴油燃料中非常重要的性质，在军用喷气燃料用途中也非常重要。
因此，本发明适当地提供了具有非常有利的BOCLE润滑性同时允许密封/垫片弹性体的所需膨胀和由于低芳族化合物含量允许更清洁燃烧的航空燃料组分。
接着，对中间馏出物馏分的生产方法进行描述。本发明的燃料中所含的中间馏出物馏分优选通过本发明的方法生产。此外，通过所述方法生产的中间馏出物馏分优选具有如上用于本发明的燃料中所含的中间馏出物馏分所定义的中间馏出物馏分的性质。
生产可再生中间馏出物组合物的方法包括以下步骤：使包含乙酰丙酸二聚体/低聚物的原料经受至少一次加氢脱氧(HDO)反应(HDO步骤)，和分馏(例如分级蒸馏)所得HDO产物以获得中间馏出物组合物(分馏步骤)。
通过使用乙酰丙酸二聚体/低聚物，本发明的中间馏出物组合物特别适合作为航空和/或柴油燃料组分。也就是说，该组合物含有高数量的具有8至15个碳原子的烷属烃(paraffinic hydrocarbons)(具有高含量的环烷烃和异链烷烃)，其中大部分(50重量％或更多)的产物具有9或10个碳原子。
具体地，本发明的方法提供了具有高含量(通常大于50％)源自乙酰丙酸二聚体/低聚物，即具有8至10个碳原子的链烷烃的产物。这里，10是两个乙酰丙酸碳链的总数，并且减少1至2个碳原子考虑了在C-C-偶合步骤或HDO步骤中发生的碳损失(例如脱羧基)反应。在此方面，一定量的较高分子量化合物(即衍生自乙酰丙酸三聚体的烃)可能是有利的，特别对于燃料应用，因为这样的碳数分布模拟化石油馏分(化石燃料)的碳数分布。
优选地，本发明的中间馏出物的沸点范围为150℃至370℃，更优选150℃至285℃，155℃至260℃或180℃至285℃。低于285℃的范围通常适合作为航空燃料，其在本发明中是优选的，其中特别优选在155℃至260℃范围内沸腾的馏分。
乙酰丙酸二聚体/低聚物可以通过乙酰丙酸的二聚/低聚获得。因此，本发明的方法可以包括对至少包含乙酰丙酸的原料进行C-C偶合反应以产生乙酰丙酸二聚体/低聚物的步骤(C-C-偶合步骤)。如上所述，乙酰丙酸可以是任何形式，例如游离酸形式、酯形式或内酯形式。
C-C-偶合反应可以在100-200℃，优选120-180℃，更优选120-160℃，最优选120-140℃的温度下进行，特别是当C-C-偶合反应在氢的存在下并使用酸性离子交换树脂(IER)进行时。发现该温度范围特别适合于获得适合用于原料中的高产率的乙酰丙酸二聚体/低聚物。
应当注意，本说明书或权利要求中提到的每个范围的上限和下限可以组合以给出旨在包括在本发明的公开内容中的新范围。
在一个实施方案中，本发明提供了从乙酰丙酸开始制备中间馏出物馏分的方法。该方法包括以下步骤：提供至少包含乙酰丙酸的原料(制备步骤)；使原料经受C-C偶合反应以生产含有乙酰丙酸二聚体/低聚物的C-C-偶合产物(上述C-C-偶合步骤)，其中所述C-C偶合反应在氢气存在下并使用携带氢化金属作为催化剂的酸性离子交换树脂(IER)进行；使至少包含所述乙酰丙酸二聚体/低聚物的原料进行加氢脱氧反应以生产HDO产物(上述HDO步骤)；和分馏HDO产物以获得中间馏出物组合物(上述分馏步骤)。
该方法是特别优选的，因为其确保除了有利量的三聚体和更高级低聚物之外，在C-C-偶合步骤中产生高数量的乙酰丙酸二聚体，使得HDO步骤可以在没有进一步纯化/分离的情况下进行或仅仅较小的纯化/分离(例如除去乙酰丙酸单体、气态反应产物和/或水)。然而，本发明不限于该方法，可以应用任何用于生产乙酰丙酸二聚体/低聚物的方法，或者可以购买乙酰丙酸二聚体/低聚物。视情况而定，乙酰丙酸二聚体/低聚物的纯化/分离(例如分馏)可能是期望的，以实现原料中乙酰丙酸二聚体/低聚物的有利含量。
将原料进行C-C-偶合反应的步骤中，乙酰丙酸与原料中存在的另一个乙酰丙酸进行C-C-偶合反应，以产生乙酰丙酸二聚体/低聚物。
根据实际反应条件，乙酰丙酸可能经历不同的C-C-偶合反应。特别地，所述C-C-偶合反应可为酮基化反应或通过烯醇或烯醇化物中间体进行的反应。因此，所述C-C-偶合反应可为含醛醇型反应和缩合反应、酮基化作用、其中C-C-偶合涉及烯烃的反应和其他二聚/低聚反应。此外，脱羧、脱水和/或氢化可以在C-C-偶合反应期间或之后发生，因此提供具有比仅从C-C-偶合反应所预期的更少的氧和/或碳原子的二聚体/低聚物衍生物。
不希望受理论束缚，认为IER(离子交换树脂)催化剂主要催化乙酰丙酸的醛醇缩合反应。在C-C-偶合反应的反应条件下，所得二聚体/低聚物容易进行内酯化。
加氢脱氧(HDO)反应可以在任何温度下进行，优选在至少200℃，至少250℃，至少270℃，至少290℃，至少300℃，至少305℃，或至少310℃的温度下。在HDO步骤中280℃或更高的温度导致HDO步骤中的进一步(热)C-C-偶合反应(进一步的低聚反应)。
除非明确说明，本发明中的压力值涉及绝对压力。此外，当通常讲到氢气压力或特定气体的压力时，意味着氢气(或指定气体)的分压。
此外，原料中的乙酰丙酸二聚体/低聚物可以含有酮基、醛基、酸基(游离酸形式、酯形式或内酯形式)和/或羟基。
在本发明中，应注意的是，术语“原料”包括供应至反应器的所有非气态物料，除了构成催化剂体系的物料外。因此，原料中所述乙酰丙酸二聚体/低聚物含量的计算不考虑催化剂的量。这同样适用于在HDO步骤或本发明方法的任何其它步骤中进料的反应物的量。
本发明的方法还可以包括在进行HDO反应之前除去未反应的乙酰丙酸和其它单体的步骤(分离步骤)。
在实际反应条件下，使用酸性IER催化剂体系的二聚/低聚反应达到约50重量％的乙酰丙酸周转(turnover)。因此，约50重量％的C-C-偶合反应产物由未反应的乙酰丙酸(单体)组成。该单体优选在HDO步骤之前除去。最合适地，在C-C-偶合反应之后立即除去所述单体。蒸馏是除去单体的合适方法，但是也可以使用其它方法。具体地，C-C-偶合反应产物可被分馏以移除潜在的未反应的乙酰丙酸单体和其他轻组分例如在C-C-偶合反应中形成的水和CO2。未反应的乙酰丙酸(单体)可以再循环并与原料合并。
在乙酰丙酸缩合步骤期间的氢化/加氢脱氧反应可以使用氢化金属作为催化剂进行，其中氢化金属选自元素周期表第VIII族的金属，优选Co、Ni、Ru、Rh、Pd和Pt，更优选Pd，或其组合。
已发现这些金属，特别是Pd，提供良好的氢化性能，并且与使用IER的C-C-偶合反应的要求良好相容。
本发明还涉及可通过乙酰丙酸二聚体/低聚物的加氢脱氧、然后分级蒸馏得到的可再生中间馏出物组合物作为航空燃料或航空燃料组分的用途。当用作航空燃料时，中间馏出物馏分被制备为航空燃料馏分，即具有在航空燃料范围内的沸点范围。可再生中间馏出物组合物也可以用作柴油燃料或柴油燃料组分，特别是作为冬季柴油燃料组分。
优选地，根据上述用途的可再生中间馏出物组合物可通过本发明的方法获得和/或具有如对于本发明的燃料中所含的中间馏出物馏分所述的性质。换句话说，优选燃料的中间馏出物组合物、本发明的方法和用途是相同的。
下面描述本发明的其它方面，而所有这些方面可以与上述方面结合而没有限制。
在使用氢气的方法步骤中，氢气可以与一种或多种其它气体(稀释气体)，优选惰性气体如氮气、氩气、氦气或另一种稀有气体，或者对本发明的反应条件表现为惰性行为的气体混合。表现惰性意思是该气体不应该在很大程度上作为反应成员参与，并且优选地惰性气体应当尽可能少参与，例如根本不参与。
尽管C-C-偶合步骤中的高氢气压力需要更精密的设备，但是仍然可能省略温和的氢化步骤，无需使用长反应时间或高反应性催化剂。此外，意外地发现C-C-偶合步骤中的高氢气压力使C-C-偶合反应产物(二聚体/低聚物)从内酯形式转变为二酸形式。由于内酯形式的二聚体/低聚物倾向于在HDO之后产生环烷烃或芳族产物，所以该实施方案特别适用于生产汽油、喷气燃料组分和化学组分。
在C-C-偶合步骤的该实施方案中，氢气压力优选为至少35巴，更优选至少40巴，进一步优选在45至55巴的范围。然而，上氢气压力不一定受限，并且可以为200巴或更小，100巴或更小，80巴或更小，70巴或更小，或60巴或更小。
可通过调节数个参数来控制C-C-偶合反应，包括通过选择反应条件例如重量时空速度(WHSV)(kg原料/kg催化剂每小时)
所述原料可通过处理木质纤维素材料获得，且在本发明的方法中可直接使用这样处理的材料，或在用作原料之前将其纯化到不同的程度。所述乙酰丙酸可例如使用US5608105中公开的Biofine方法制备。
优选地，在加氢脱氧步骤中，使用包含在载体上的具有氢化催化剂作用的金属的HDO催化剂，诸如例如选自由Pd、Pt、Ni、Co、Mo、Ru、Rh、W或它们任何组合组成的组的HDO催化剂金属。具有氢化催化剂作用的金属可以负载在载体上，优选无机氧化物载体，更优选二氧化硅、氧化铝、二氧化钛、氧化锆、碳或其组合。高度优选的HDO催化剂包含硫化的(sulfided)NiMo，其优选负载在无机氧化物如氧化铝上。
加氢脱氧步骤可以在高达500℃的温度和10-150巴的压力下进行。
本发明的方法可以在反应器例如搅拌的釜式反应器，优选连续搅拌的釜式反应器，或管式流动反应器，优选连续流动反应器中进行。此外，本发明的各个步骤可以在相同的反应器中或在不同的反应器中进行。优选地，C-C-偶合步骤和HDO步骤在不同的反应器中进行。
HDO步骤的产物可任选地在氢气和异构化催化剂存在下经受异构化步骤。HDO步骤和异构化步骤二者可在同一反应器中实施。在一些实施方案中，所述异构化催化剂可为贵金属双官能催化剂，例如Pt-SAPO或Pt-ZSM-催化剂。所述异构化步骤可例如在200-400℃的温度和20-150bar的压力下实施。分馏可以在异构化之前或之后进行，但优选在异构化之后进行。优选地，不进行异构化处理。
实施例
实施例1(生产乙酰丙酸二聚体)
提供了含有98重量份商业级乙酰丙酸(97重量％纯度)和2重量份水的原料。将原料和氢气进料到负载Amberlyst CH-34催化剂(商品名；Pd掺杂的离子交换树脂)的管式反应器中。将反应器中的温度调节至130℃，氢气压力为20巴，WHSV为0.2h-1，氢气与原料(液体原料)流量比为1170Nl/l。
在管式反应器之后获得的C-C-偶合反应产物含有44重量％的未反应的乙酰丙酸(LA)和γ-戊内酯(GVL)、53重量％的二聚体和约2重量％的低聚物。通过蒸馏分离未反应的LA(+GVL)以及轻质反应产物(例如CO2)和水。
蒸馏的产物(C-C-偶合)具有95重量％的LA二聚体含量。
实施例2(LA二聚体/低聚物的HDO)
将实施例1的产物在管式反应器中在80巴的氢气压力，306℃的温度，0.3h-1的WHSV，使用负载在氧化铝上的硫化的NiMo氢化催化剂和2100Nl/l的氢与C-C偶合的流率下进行HDO。
将HDO产物分馏并评价由此获得的LBAF馏分(乙酰丙酸基航空燃料馏分)(155-260℃)的组成。结果显示在表1中，其进一步显示了化石Jet A-1燃料(Neste生产)和HEFA组分喷气燃料要求(ASTM D7566规格)和常规Jet A1要求的典型性能。后者还涵盖含有合成烃(即HEFA组分)的Jet A1燃料。
燃料的粘度与在温度范围内的泵送能力和喷嘴喷射模式的一致性密切相关。主喷气燃料规格允许最大粘度(在-20℃)为8mm2/s。在-40℃下12mm2/s的最大粘度值是由一些航空原始设备制造商(OEM′s)提供的操作极限。
可以看出，试验结果符合JET A-1要求，而润滑性甚至优于常规化石燃料。然而，任何新的生产路线和组分无论如何都需要ASTM认证。
实施例3(LBAF和化石燃料的共混物)
以与实施例2中相同的方式制备LBAF。测试化石Jet A-1燃料(Neste生产)和LBAF的共混物的凝固点和BOCLE润滑性。结果显示在表2和图1中。
实施例4(LBAF和NEXBTL燃料的共混物)
除了使用沸点范围为180-285℃的航空燃料馏分之外，以与实施例2相同的方式制备LBAF。测试NEXBTL喷气燃料1(由Neste生产的HEFA-SPK Jet A-1燃料；根据EP 2141217B1的实施例1生产)和LBAF的共混物，结果示于表3中。
参考例5(乙酰丙酸基柴油)
除了使用沸点范围为180-360℃的柴油燃料馏分之外，以与实施例2相同的方式制备LA基柴油。测试结果示于表4。
表1
*)直到-100℃未检测到晶体
表2
表3
表4
Claims (14)
1.包含可再生中间馏出物组合物的燃料，其特征在于所述可再生中间馏出物组合物可通过包含乙酰丙酸的和/或乙酰丙酸衍生物的二聚体和/或低聚物(乙酰丙酸二聚体/低聚物)的原料的加氢脱氧、然后分级蒸馏获得，其中如根据ASTMD2425测定的，所述可再生中间馏出物组合物包含小于10.0重量％的芳族化合物。
2.根据权利要求1所述的燃料，其中可再生中间馏出物组合物含有至多9.5重量％，至多9.3重量％，至多9.0重量％，至多8.0重量％，至多7.0重量％，至多6.0重量％，至多5.0重量％，至多4.0重量％，或至多3.0重量％的芳族化合物，如根据ASTM D2425测定的。
3.根据权利要求1或2所述的燃料，其中可再生中间馏出物组合物的凝固点为-70℃或更低，-80℃或更低，-90℃或更低，或-95℃或更低。
4.根据权利要求1-3任一项所述的燃料，其中可再生中间馏出物组合物包含至少50重量％，优选至少55重量％，更优选至少60重量％，或至少65重量％的环烷烃，如根据ASTMD2425测定的。
5.根据权利要求1-4任一项所述的燃料，其中可再生中间馏出物组合物包含至多80重量％，优选至多75重量％，更优选至多72重量％，或至多70重量％的环烷烃，如根据ASTMD2425测定的。
6.根据权利要求1-5中任一项所述的燃料，其中所述燃料还包含化石燃料、HEFA(加氢处理的酯和脂肪酸)燃料和/或HVO(加氢处理的植物油)燃料。
7.根据权利要求1-6任一项所述的燃料，其中可再生中间馏出物组合物的BOCLE润滑性为0.75mm或更小，优选0.72mm或更小，更优选0.70mm或更小，0.69mm或更小，0.68mm或更小，或0.67mm或更小，如根据ASTM D5001-10(2014)测定的。
8.一种用于生产可再生中间馏出物组合物的方法，所述方法包含下面的步骤：
使包含乙酰丙酸的和/或乙酰丙酸衍生物的二聚体和/或低聚物(乙酰丙酸二聚体/低聚物)的原料进行至少一次加氢脱氧(HDO)反应，以及
分馏所得的HDO产物，以获得中间馏出物组合物，
其中可再生中间馏出物组合物含有小于10.0重量％的芳族化合物，如根据ASTM D2425测定的。
9.根据权利要求8所述的方法，其中可再生中间馏出物组合物含有至多9.5重量％，至多9.3重量％，至多9.0重量％，至多8.0重量％，至多7.0重量％，至多6.0重量％，至多5.0重量％，至多4.0重量％，或至多3.0重量％的芳族化合物，如根据ASTM D2425测定的。
10.根据权利要求8或9所述的方法，进一步包括如下步骤：
将至少包含乙酰丙酸的原料进行C-C偶合反应，以产生乙酰丙酸的和/或乙酰丙酸衍生物的二聚体和/或低聚物(乙酰丙酸二聚体/低聚物)。
11.根据权利要求10所述的方法，其中所述C-C-偶合反应在100-200℃，优选120-180℃，更优选120-160℃，最优选120-140℃的温度下实施。
12.根据权利要求8-11任一项所述的方法，包括如下步骤：
提供至少包含乙酰丙酸和/或其衍生物的原料，
使所述原料经受C-C偶合反应，其中所述C-C偶合反应在氢气的存在下并使用带有氢化金属作为催化剂的酸性离子交换树脂进行，以产生含有乙酰丙酸的和/或乙酰丙酸衍生物的二聚体和/或低聚物(乙酰丙酸二聚体/低聚物)，
使至少包含所述乙酰丙酸二聚体/低聚物的原料进行加氢脱氧(HDO)反应以产生HDO产物，和
分馏所述HDO产物，以获得中间馏出物组合物。
13.根据权利要求1-7中任一项所述的燃料，其中所述中间馏出物组合物可通过权利要求8-12中任一项所述的方法获得。
14.可通过乙酰丙酸的和/或乙酰丙酸衍生物的二聚体和/或低聚物(乙酰丙酸二聚体/低聚物)的加氢脱氧、然后分级蒸馏获得的可再生中间馏出物组合物作为航空燃料或航空燃料组分的用途，其中所述可再生中间馏出物组合物包含小于10.0重量％的芳族化合物，如根据ASTM D2425测定的。
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| CN102027097A (zh) * | 2008-03-17 | 2011-04-20 | 环球油品公司 | 由可再生原料生产航空燃料 |
| US20130144098A1 (en) * | 2011-12-06 | 2013-06-06 | Phillips 66 Company | Direct conversion of biomass oxygenates to hydrocarbons |
| WO2015144994A1 (en) * | 2014-03-26 | 2015-10-01 | Neste Oil Oyj | Method for thermal conversion of ketoacids and hydrotreatment to hydrocarbons |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111527185A (zh) * | 2017-12-28 | 2020-08-11 | 耐思特公司 | 航空燃料组合物的制备 |
| CN111527185B (zh) * | 2017-12-28 | 2022-12-30 | 耐思特公司 | 航空燃料组合物的制备 |
| CN113166662A (zh) * | 2018-12-13 | 2021-07-23 | 耐思特公司 | 可再生燃料的共混 |
| CN113166662B (zh) * | 2018-12-13 | 2024-02-09 | 耐思特公司 | 可再生燃料的共混 |
Also Published As
| Publication number | Publication date |
|---|---|
| ES2866043T3 (es) | 2021-10-19 |
| US20170183593A1 (en) | 2017-06-29 |
| US10640721B2 (en) | 2020-05-05 |
| CA2952512A1 (en) | 2017-06-29 |
| EP3187567B1 (en) | 2021-03-31 |
| EP3187567A1 (en) | 2017-07-05 |
| BR102016030777A2 (pt) | 2017-07-11 |
| BR102016030777B1 (pt) | 2021-07-13 |
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