CN107880957B - 改质5-壬酮 - Google Patents
改质5-壬酮 Download PDFInfo
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- CN107880957B CN107880957B CN201710875620.3A CN201710875620A CN107880957B CN 107880957 B CN107880957 B CN 107880957B CN 201710875620 A CN201710875620 A CN 201710875620A CN 107880957 B CN107880957 B CN 107880957B
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- Prior art keywords
- catalyst
- nonone
- condensation
- reaction
- metal oxide
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- 239000000446 fuel Substances 0.000 claims abstract description 83
- 238000000034 method Methods 0.000 claims abstract description 61
- 239000003054 catalyst Substances 0.000 claims description 96
- 238000006243 chemical reaction Methods 0.000 claims description 85
- 239000000203 mixture Substances 0.000 claims description 56
- 238000005984 hydrogenation reaction Methods 0.000 claims description 52
- 239000007859 condensation product Substances 0.000 claims description 42
- 239000000047 product Substances 0.000 claims description 41
- JOOXCMJARBKPKM-UHFFFAOYSA-N 4-oxopentanoic acid Chemical compound CC(=O)CCC(O)=O JOOXCMJARBKPKM-UHFFFAOYSA-N 0.000 claims description 32
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 32
- 239000001257 hydrogen Substances 0.000 claims description 32
- 229910052739 hydrogen Inorganic materials 0.000 claims description 32
- 229910044991 metal oxide Inorganic materials 0.000 claims description 30
- 150000004706 metal oxides Chemical class 0.000 claims description 30
- WSGCRAOTEDLMFQ-UHFFFAOYSA-N nonan-5-one Chemical compound CCCCC(=O)CCCC WSGCRAOTEDLMFQ-UHFFFAOYSA-N 0.000 claims description 26
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 23
- 229930195733 hydrocarbon Natural products 0.000 claims description 23
- 150000002430 hydrocarbons Chemical group 0.000 claims description 23
- 150000002576 ketones Chemical class 0.000 claims description 22
- 238000004519 manufacturing process Methods 0.000 claims description 21
- KPADFPAILITQBG-UHFFFAOYSA-N non-4-ene Chemical compound CCCCC=CCCC KPADFPAILITQBG-UHFFFAOYSA-N 0.000 claims description 18
- 238000009833 condensation Methods 0.000 claims description 16
- 230000005494 condensation Effects 0.000 claims description 16
- 229940040102 levulinic acid Drugs 0.000 claims description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 239000004215 Carbon black (E152) Substances 0.000 claims description 13
- 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 claims description 12
- 239000012159 carrier gas Substances 0.000 claims description 12
- 239000003456 ion exchange resin Substances 0.000 claims description 12
- 229920003303 ion-exchange polymer Polymers 0.000 claims description 12
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 10
- 230000002378 acidificating effect Effects 0.000 claims description 9
- 150000002431 hydrogen Chemical class 0.000 claims description 9
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 8
- 150000001335 aliphatic alkanes Chemical group 0.000 claims description 7
- 239000002585 base Substances 0.000 claims description 6
- 238000006471 dimerization reaction Methods 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 239000001569 carbon dioxide Substances 0.000 claims description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 5
- 229910000000 metal hydroxide Inorganic materials 0.000 claims description 5
- 150000004692 metal hydroxides Chemical class 0.000 claims description 5
- 238000006384 oligomerization reaction Methods 0.000 claims description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 4
- 150000004703 alkoxides Chemical class 0.000 claims description 4
- 238000009826 distribution Methods 0.000 claims description 4
- 229910003455 mixed metal oxide Inorganic materials 0.000 claims description 4
- 229910001463 metal phosphate Inorganic materials 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 2
- 239000007858 starting material Substances 0.000 claims 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 53
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 27
- 229940005605 valeric acid Drugs 0.000 description 17
- 150000001875 compounds Chemical class 0.000 description 16
- 238000006482 condensation reaction Methods 0.000 description 15
- 238000006317 isomerization reaction Methods 0.000 description 15
- 229910052760 oxygen Inorganic materials 0.000 description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 14
- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 description 14
- 239000001301 oxygen Substances 0.000 description 14
- 125000004432 carbon atom Chemical group C* 0.000 description 13
- 239000000539 dimer Substances 0.000 description 11
- 150000001336 alkenes Chemical class 0.000 description 10
- 239000007795 chemical reaction product Substances 0.000 description 10
- 239000002283 diesel fuel Substances 0.000 description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 8
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 8
- 239000003502 gasoline Substances 0.000 description 8
- ZUBZATZOEPUUQF-UHFFFAOYSA-N isononane Chemical compound CCCCCCC(C)C ZUBZATZOEPUUQF-UHFFFAOYSA-N 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 239000003921 oil Substances 0.000 description 7
- 235000019198 oils Nutrition 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000005882 aldol condensation reaction Methods 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 6
- 239000011541 reaction mixture Substances 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 5
- 150000001735 carboxylic acids Chemical class 0.000 description 5
- 239000002803 fossil fuel Substances 0.000 description 5
- 239000005431 greenhouse gas Substances 0.000 description 5
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 4
- 229910003294 NiMo Inorganic materials 0.000 description 4
- 235000014113 dietary fatty acids Nutrition 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000194 fatty acid Substances 0.000 description 4
- 229930195729 fatty acid Natural products 0.000 description 4
- 238000007210 heterogeneous catalysis Methods 0.000 description 4
- -1 i.e. Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- ZWRUINPWMLAQRD-UHFFFAOYSA-N nonan-1-ol Chemical compound CCCCCCCCCO ZWRUINPWMLAQRD-UHFFFAOYSA-N 0.000 description 4
- 238000007086 side reaction Methods 0.000 description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 150000004665 fatty acids Chemical class 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000007172 homogeneous catalysis Methods 0.000 description 3
- 239000008172 hydrogenated vegetable oil Substances 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 239000006104 solid solution Substances 0.000 description 3
- 241000894007 species Species 0.000 description 3
- 238000011282 treatment Methods 0.000 description 3
- WBRFDUJXCLCKPX-UHFFFAOYSA-N 2,3-dimethylheptane Chemical compound CCCCC(C)C(C)C WBRFDUJXCLCKPX-UHFFFAOYSA-N 0.000 description 2
- KBPCCVWUMVGXGF-UHFFFAOYSA-N 2,6-dimethylheptane Chemical compound CC(C)CCCC(C)C KBPCCVWUMVGXGF-UHFFFAOYSA-N 0.000 description 2
- DZJTZGHZAWTWGA-UHFFFAOYSA-N 3,5-dimethylheptane Chemical compound CCC(C)CC(C)CC DZJTZGHZAWTWGA-UHFFFAOYSA-N 0.000 description 2
- SEEOMASXHIJCDV-UHFFFAOYSA-N 3-methyloctane Chemical compound CCCCCC(C)CC SEEOMASXHIJCDV-UHFFFAOYSA-N 0.000 description 2
- DOGIHOCMZJUJNR-UHFFFAOYSA-N 4-methyloctane Chemical compound CCCCC(C)CCC DOGIHOCMZJUJNR-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- YIYBQIKDCADOSF-UHFFFAOYSA-N alpha-Butylen-alpha-carbonsaeure Natural products CCC=CC(O)=O YIYBQIKDCADOSF-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 125000000468 ketone group Chemical group 0.000 description 2
- 238000004811 liquid chromatography Methods 0.000 description 2
- FCBBRODPXVPZAH-UHFFFAOYSA-N nonan-5-ol Chemical compound CCCCC(O)CCCC FCBBRODPXVPZAH-UHFFFAOYSA-N 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- YIYBQIKDCADOSF-ONEGZZNKSA-N trans-pent-2-enoic acid Chemical compound CC\C=C\C(O)=O YIYBQIKDCADOSF-ONEGZZNKSA-N 0.000 description 2
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 description 2
- 239000013638 trimer Substances 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- YZUPZGFPHUVJKC-UHFFFAOYSA-N 1-bromo-2-methoxyethane Chemical compound COCCBr YZUPZGFPHUVJKC-UHFFFAOYSA-N 0.000 description 1
- 241000269350 Anura Species 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 229910003134 ZrOx Inorganic materials 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- 238000010420 art technique Methods 0.000 description 1
- 150000003819 basic metal compounds Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 238000006664 bond formation reaction Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 229920001429 chelating resin Polymers 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 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
- 238000005191 phase separation Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 238000001577 simple distillation Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 150000003626 triacylglycerols Chemical class 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 229940070710 valerate Drugs 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Images
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
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/18—Organic compounds containing oxygen
- C10L1/185—Ethers; Acetals; Ketals; Aldehydes; Ketones
- C10L1/1857—Aldehydes; Ketones
-
- 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
- C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
- C10G3/42—Catalytic treatment
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/10—Magnesium; Oxides or hydroxides thereof
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- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/12—Silica and alumina
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- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
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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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/892—Nickel and noble metals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/82—Phosphates
- B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
- B01J29/85—Silicoaluminophosphates [SAPO compounds]
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- C—CHEMISTRY; METALLURGY
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
- C07C1/207—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms from carbonyl compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
- C07C1/207—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms from carbonyl compounds
- C07C1/2072—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms from carbonyl compounds by condensation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
- C07C1/207—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms from carbonyl compounds
- C07C1/2072—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms from carbonyl compounds by condensation
- C07C1/2074—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms from carbonyl compounds by condensation of only one compound
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
- C07C1/207—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms from carbonyl compounds
- C07C1/2076—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms from carbonyl compounds by a transformation in which at least one -C(=O)- moiety is eliminated
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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Abstract
提供燃料组分,用于生产燃料组分的方法,燃料组分的用途和含有基于5‑壬酮的燃料组分的燃料。
Description
技术领域
本发明涉及改质5-壬酮。具体地,本发明涉及化石和/或可再生燃料组分,用于生产化石和/或可再生燃料组分的方法,燃料组分的用途和含有燃料组分的燃料。特别地,本发明涉及基于5-壬酮(二丁基酮)并衍生自可再生来源的燃料组分。
背景技术
鉴于使用常规燃料即化石燃料或化石燃料组分和除酮以外的可再生燃料组分的混合物时产生温室气体,来自可再生来源的燃料组分的生产越来越受到关注。因此,现有技术中已经研究了用于改质可再生材料以便适用于燃料的各种方法。这些方法中的许多方法使用大量氢气,以将含氧可再生材料转化成适用于燃料应用的烃组合物。然而,由于氢气主要由化石源生产,所以仍然需要改进使用较少氢气的方法,同时还提供高质量的燃料组分。
可以由各种可再生来源生产5-壬酮。例如,从乙酰丙酸(LA)生产5-壬酮的最常见方法是将LA转化为γ-戊内酯(GVL),随后将GVL转化为戊酸(PA),然后将其转化为5-壬酮。
作为燃料组分生产的中间体,5-壬酮显示出几个优点。5-壬酮与水自发分离,因此不需要采用昂贵的分离方法。此外,可以通过酮化反应从戊酸生产5-壬酮,该方法不需要加入氢气,但是显著降低生物衍生物质的氧含量。在酮化反应中,以二氧化碳和水的形式除去氧。然而,现有技术仍然面临5-壬酮生产中的选择性和转化率问题。因此,非常需要由可再生能源以工业规模和高选择性和转化率生产5-壬酮的方法。
涉及5-壬酮生产并通过5-壬酮生产燃料组分和其它化学品的现有技术是本领域已知的。
已知可以通过GVL和戊酸由LA生产5-壬酮。然后将戊酸在Pd/Nb2O5转化为5-壬酮。未反应的戊酸是产物5-壬酮即二丁基酮(DBK)中的主要杂质。5-壬酮和戊酸的沸点非常相似,使得使用简单蒸馏方法分离这两种化合物比较困难。可以使用一系列闪蒸分离和蒸馏以及使用甲醇的任选萃取来获得90%或更高的纯度。然而,这种技术需要大规模的蒸馏并消耗大量的能量。因此,仍然需要使用简化且较低能耗的方法生产5-壬酮的方法。
将戊酸酮化为5-壬酮,然后氢化以提供壬醇以及任选的烯烃(例如衍生自壬醇的壬-4-烯)低聚反应以制备烃组合物也是已知的。
WO 2010/151343A1公开了戊酸到5-壬酮的酮化反应,并且使用5-壬酮作为燃料应用的前体。
发明内容
本发明在独立权利要求中限定。在从属权利要求中阐述了进一步的有益实施方案。具体地说,本发明涉及一个或多个下面的项目:
1.一种用于生产燃料组分的方法,该方法包括:
提供包含至少5重量%(5wt-%)5-壬酮的原料的准备步骤,和
在缩合催化剂的存在下,至少将原料中的5-壬酮缩合以得到缩合产物的缩合步骤。
本发明的反应提供了具有大量碳原子(通常在13-18范围内)和低氧含量的化合物(或各种化合物的混合物),使其适合作为燃料组分和/或燃料组分前体。此外,由于该反应不消耗氢气,所以仅仅使用通常仅由化石源生产的最少的氢气就能获得产物。因此,本发明有助于温室气体的节约。
在本发明中,术语“改质”是指通过化学反应来改性和/或精制组分,使其可以用作燃料组分。
2.根据项目1所述的方法,其中所述原料包含至少7重量%的5-壬酮,优选至少10重量%的5-壬酮,更优选至少15重量%的5-壬酮,至少20重量%的5-壬酮,至少30重量%的5-壬酮,至少40重量%的5-壬酮,至少50重量%的5-壬酮,至少60重量%的5-壬酮,至少70重量%的5-壬酮,至少80重量%的5-壬酮,至少90重量%的5-壬酮或至少95重量%的5-壬酮。
本发明的方法可以使用高含量的5-壬酮实施,甚至可以仅使用5-壬酮作为原料实施,使得可以使由于与原料的附加组分的副反应产生的杂质的量最小化。
3.根据项目1或2所述的方法,其中在所述缩合步骤中不进行氢化反应。例如,在该实施方案中,在缩合步骤中不添加氢气。
在下面更详细描述的本发明的方法中,使5-壬酮进行缩合反应,导致反应中涉及的分子的氧含量进一步降低。因此,可以获得高缺氧产物,而不需要额外的或同时的氢化反应。
4.根据项目1-3任一项所述的方法,其中所述缩合催化剂是:
i)离子交换树脂催化剂,优选酸性离子交换树脂催化剂,
ii)酸或碱催化剂,其选自金属氧化物催化剂、金属氢氧化物催化剂、金属醇盐催化剂、金属碳酸盐催化剂或金属磷酸盐催化剂,或
iii)混合金属氧化物催化剂或负载型金属氧化物催化剂。
这些催化剂显示出对本发明的方法具有良好的活性和高适应性。
5.根据项目1-4任一项所述的方法,其中
所述缩合步骤在载气流下进行,所述载气例如氮气、氢气、二氧化碳、甲烷或水。
在项目5的该实施方案中,载气是不与原料或与所述缩合步骤的产物反应的气体。具体地说,该实施方案中的氢气仅用作载体而不是反应物。换句话说,尽管在反应混合物中存在氢气,但缩合步骤中的反应条件使得不发生氢化反应。
6.根据项目1-5中任一项所述的方法,还包括氢化所述缩合产物以获得氢化缩合产物的氢化步骤。
虽然缩合产物已经具有低氧含量,但是可能需要生产例如烃组合物,即基本上由烃组成且不含氧化物(杂质除外)的组合物。因此,可以通过氢化反应进一步处理缩合产物。由于缩合产物已经具有非常低的氧含量,所以氢化反应仅需要少量的氢气,使得可以仅使用少量的氢气来获得适合作为燃料的烃组合物。
7.根据项目6所述的方法,其中所述氢化缩合产物是烃组合物,优选烷烃或烷烃混合物。
烃组合物非常适合作为燃料组分。具体地说,由于常规燃料主要包括烃类,所以可通过本发明的方法获得的烃组合物可以与传统的燃料组分以宽范围混合,并且甚至可直接用作燃料,例如作为柴油燃料、汽油燃料或喷气燃料。
具体地,本发明的燃料可以是化合物的混合物,其中主要组分优选为50体积%或更多,为含有4至25个碳原子的烃类。柴油燃料可以是化合物的混合物,其中主要组分优选为50体积%或更多,为含有11至25个碳原子的烃类。喷气燃料可以是化合物的混合物,其中主要组分优选为50体积%或更多,为含有9至16个碳原子的烃类。汽油燃料可以是化合物的混合物,其中主要组分优选为50体积%或更多,为含有4至9个碳原子的烃类。
8.可通过根据项目1至5中任一项所述的方法获得的缩合产物或可通过根据项目6或7的方法获得的氢化缩合产物作为燃料组分的用途。
9.柴油、喷气或汽油燃料共混物,其包含可通过根据项目1至5中任一项所述的方法获得的缩合产物或可通过根据项目6或7的方法获得的氢化缩合产物作为燃料组分。
所述燃料共混物可以由上述项目8或9的燃料组分组成,或者可以是包含至少上述项目8或9的燃料组分以及化石燃料组分和可再生燃料组分中的至少一种的共混物。
附图说明
图1是显示用于由5-壬酮合成烃燃料组分的路线的方案。
图2是显示在本发明的5-壬酮的改质方法中氮气流量对5-壬酮转化率和二聚体产物形成的影响的图。
具体实施方式
通常,本发明涉及改质5-壬酮,优选来自可再生来源的5-壬酮的方法,用于生产燃料组分的方法和含有改质的燃料组分的燃料。
在下文中,将逐步提供本发明的详细描述。
5-壬酮的生产方法
本发明的一个部分方面涉及例如从可再生来源以高选择性(优选大于95体积%)和高转化率(优选大于95体积%)生产5-壬酮。优选根据本发明改质的5-壬酮使用下面公开的方法生产。
乙酰丙酸(LA)是一种合适的原料,可从可再生能源以工业规模大量获得。
可用于本发明方法的由LA生产5-壬酮的示意性反应路线如下:
其他酮也可以衍生自LA,例如通过具有2至6个碳原子的羧酸中间体。当使用单一类型的羧酸,例如戊酸时,将产生对称的酮。当使用两种类型的羧酸例如R1COOH和R2COOH时将形成两种对称酮(R1C(O)R1和R2C(O)R2)和一种不对称酮(R1C(O)R2)的混合物。如果存在三种或更多种不同的羧酸,则将获得甚至更多不同酮的混合物。
以合理的产率由LA生产戊酸(PA)的方法是本领域已知的,并且任何已知的生产戊酸的方法可以用于本发明。在一个实施方案中,将来自可再生来源的LA进行氢化反应以产生GVL。随后或同时通过氢化反应将GVL转化为戊酸。在氢化反应中可以使用任何合适的催化剂,但优选是含有酸官能团(具有例如沸石、SAPO或IER作为催化剂组分)和金属官能团(具有例如Pt或Pd作为催化剂组分)的双官能催化剂,使得GVL开环成戊烯酸和戊烯酸氢化成PA可以同时进行。
可以使用任何其它反应方案来生产戊酸,优选从可再生来源。此外,反应方案不限于使用LA作为原料的路线,尽管优选该路线。
现有技术公开了由戊酸生产5-壬酮的几种方法。然而,现有技术中没有一种技术实现高选择性和高转化率两者。具体地,已知的方法实现至多90重量%的选择性,其中主要的残基是戊酸(PA)。这将导致在进一步程序中出现问题。要么PA必须用复杂的方法分离,或者PA会导致后续处理中的副反应。
然而,本发明优选的5-壬酮生产方法使用由碱金属氧化物和至少一种与碱金属氧化物不同的另外的金属氧化物构成的特定氧化物催化剂,并且实现羧酸几乎完全转化为5-壬酮,优选相对于所有液体有机反应产物大于95体积%。因此,不需要复杂的分离技术,其提高了该方法的整体能量效率。
氧化物催化剂可以是混合氧化物、固溶体氧化物或其中一种金属氧化物负载在另一种金属氧化物上的催化剂。碱金属氧化物可以负载在至少一种其它金属氧化物上。氧化物催化剂还可以负载在金属氧化物以外的载体上。
在一个实施方案中,碱金属氧化物是K2O,其显示出提供优异的转化效率。所述至少一种其它金属氧化物可以选自二氧化钛、二氧化硅、二氧化铈、氧化锆和γ-氧化铝,或它们的混合物、混合氧化物或固溶体。所述至少一种其它金属氧化物可以是二氧化铈-氧化锆混合氧化物、二氧化钛、或氧化铝和二氧化钛的混合物。在一个实施方案中,所述至少一种其它金属氧化物至少包含二氧化钛。特别优选的是氧化物催化剂是K2O/TiO2,利用该催化剂已经实现了良好的转化率。
该反应可以在间歇式反应器中或在连续流动式反应器中进行。反应温度可以在300℃至450℃的范围内,优选在360℃至390℃的范围内。
取决于工艺参数的大小,重时空速WHSV可以在0.2h-1至5.0h-1的范围内。压力(绝对)可以在1.0巴至25.0巴的范围内,例如10±2巴或20±2巴。
所述反应可以在载气诸如氮气、氢气、二氧化碳、H2O(水蒸气)或甲烷,优选H2、CO2或H2O的存在下进行。这些气体可以混合到反应混合物中和/或可以在反应过程中形成。载气可用于从产物混合物如H2O或CO2中排出气态或挥发性反应产物。
此外,可以在反应中使用溶剂。该反应不需要溶剂的存在。如果反应在溶剂存在下进行,其含量为50体积%或更少。此外,优选不使用溶剂。
虽然不希望受理论的束缚,但是5-壬酮生产方法通常被称为酮化反应。该方法具有以下益处:氧含量为约11重量%的高度缺氧的产物例如5-壬酮可以由氧含量为约31重量%的PA生产,而不需要加氢气。因此,优选在酮化反应中不加入氢气,同时由戊酸形成5-壬酮。
在根据本发明的改质方法中,通常使用5-壬酮作为原料的组分。在替代实施方案中,除了或代替5-壬酮外可以使用其他酮如R1C(O)R2,其中R1和R2可以相同或不同并且可以是具有1至5个碳原子的烷基,优选直链烷基;条件是其他酮不是5-壬酮。当除了5-壬酮之外使用其他酮时,原料中其他酮的含量小于95重量%,并且可以为90重量%或更少,80重量%或更少,70重量%或更少,60重量%或更少,50重量%或更少,40重量%或更少,30重量%或更少,20重量%或更少,或10重量%或更少。所述其他酮优选衍生自乙酰丙酸,进一步优选使用上述公开的方法。此外,所述其他酮可以是单酮,例如对称或不对称的,或者可以是如上所公开的酮的混合物。
根据5-壬酮生产方法,以通常高于95体积%的高选择性和通常高于95体积%的高转化率生产5-壬酮,这不需要回收未转化的酸或分离步骤。因此,特别优选不进行除去水和气体组分以外的分离。5-壬酮与水自发分离。因此,在该实施方案中,能够高效率地使用简单的相分离技术。作为蒸气分离水是进一步选择。
将5-壬酮转化成汽油、柴油和/或喷气燃料组分
在本发明中,术语燃料涉及化合物的共混物。具体地,本发明的燃料是内燃机燃料,例如柴油燃料、汽油燃料或喷气燃料。
更具体地,本发明的燃料可以是化合物的混合物,其中主要组分优选为50体积%或更多,为含有4至25个碳原子的烃类。柴油燃料可以是化合物的混合物,其中主要组分优选为50体积%或更多,为含有11至25个碳原子的烃类。喷气燃料可以是化合物的混合物,其中主要组分优选为50体积%或更多,为含有9至16个碳原子的烃类。汽油燃料可以是化合物的混合物,其中主要组分优选为50体积%或更多,为含有4至9个碳原子的烃类。
在本发明中,5-壬酮可以通过氢化反应进一步转化,最终产生适合作为燃料或作为燃料组分的烃组合物。
具体地,可以使用任何常规的催化剂,例如硫化NiMo/氧化铝加氢处理催化剂将5-壬酮转化为正壬烷。例如在240℃和40巴,以WHSV=1和H2/油比为300-500NL/L,或在265℃以WHSV=2或在290℃下以WHSV=3,可以实现全部5-壬酮HDO成正壬烷。如果使用太严格的反应条件,可能发生酮分解成甲基酮。
5-壬酮可以与甘油三酯/脂肪酸油组合,然后经受氢化植物油(HVO)型加工例如由Neste Corporation发明的可再生NEXBTL技术,该技术包括HDO和异构化程序。使用5-壬酮作为原料的这种程序的产物是异链烷烃,类似于HVO产物,但具有比脂肪酸基异链烷烃(C15-C18)低的沸点(C4-C9异链烷烃)。因此,从5-壬酮衍生的该馏分可以容易地从源自甘油三酯/脂肪酸油的可再生柴油组分分离并且适用于汽油和/或喷气燃料组分。另一个有益的现象是用于由5-壬酮生产5-壬烷的HDO需要比甘油三酯的HDO少得多的氢,因此产生少得多的反应热。因此,5-壬酮可用作植物油的稀释剂,其产生大量的反应热。这也意味着可以减少目前引入的原料的产物循环稀释。这种现象提高了HDO过程的效率和通过量。
因此,在HDO工艺步骤中组合使用油基例如脂肪酸油脂原料和5-壬酮提供了协同效应,因为促进了加工控制,并且避免或减少了反应产物作为稀释剂的使用,同时分离产物是容易的。因此,这样的组合是优选的。
也可以实施5-壬酮的部分氢化,5-壬酮转化为5-壬醇,其也可以用作燃料组分,并且与5-壬酮完全HDO为壬烷相比具有更好的产物收率。
随后在氢气存在下,在异构化催化剂上的正壬烷异构化,得到适合作为燃料组分的支链C4至C9烷烃的混合物。
正壬烷甚至可以不经异构化使用,因为它本身具有良好的冷性能。此外,它提供优异的冷性能,使得正壬烷也适用于喷气燃料共混物。
正壬烷的十六烷值约为60。通常,当烃的链长度增加时,辛烷值减少,对于C9分子,辛烷值可能甚至低于0。然而,在实验中,在异构化后已达到48.4的辛烷值。此外,异构化改善了冷性能并提高了辛烷值。
异构化反应可以使用任何常规的异构化催化剂进行,优选在加氢异构化反应中在氢气存在下进行。取决于工艺参数的大小,反应温度优选在220℃至350℃的范围内。其中油是指用作进料的液体有机材料的氢气/油的比例优选在100-500NL/L的范围内,这取决于工艺参数的大小。反应可以在10-80巴,优选15巴或更多,或20巴或更多,优选60巴或更少,或50巴或更少的压力(绝对)下进行。该反应可以在间歇式反应器或流动式反应器中进行,优选在流动式反应器中进行。
所得到的异构化的烃组合物可以直接用作汽油、柴油和/或喷气燃料,或者可以与可再生燃料或常规燃料,即化石燃料或化石燃料组分和可再生燃料组分例如生物乙醇的混合物共混。共混物中异构化烃组合物的含量优选为10重量%或更多,20重量%或更多,30重量%或更多,或40重量%或更多,并且可以为至多100重量%,或者可以为60重量%或更少。
5-壬酮缩合反应
本发明还涉及用于生产燃料组分的5-壬酮的缩合反应。5-壬酮优选通过上述的5-壬酮生产方法制备。缩合反应优选是不是必然要求加入氢气的反应,并且被称为醛醇缩合,尽管不希望受理论束缚。
可以进行缩合反应以缩合两个或更多个5-壬酮分子,得到C18或C27单元。在缩合反应过程中的其它反应可能引起裂解或低聚反应而产生副反应产物,例如含有1个氧原子和约18至35个碳原子,优选18至27个碳原子的酮。进一步的裂化可产生烯烃,例如C13烯烃。
下面提供用于5-壬酮二聚反应的反应方案,表示使用离子交换树脂催化剂时的主要反应产物:
上述反应方案的详细描述在图1中提供,尽管不希望受限于特定反应方案。从图1可以看出,5-壬酮的二聚反应可以产生具有醇基和酮基的C18物质。该C18物质可以通过除去水和戊酸转化为C13烯烃,例如作为柴油燃料组分。该反应在不加氢气的情况下进行。可以将戊酸再循环用于生产5-壬酮,优选使用上述方法。如果C13烯烃不直接用作燃料组分,则可以进行氢化反应,得到C13链烷烃。在一替代途径中,C18物质可以进行水裂去,产生C18酮-烯。该酮-烯可以进行氢化反应(HDO)以产生C18链烷烃。应当注意,上述方案显示了具体的化合物,但本领域技术人员将承认这些方案也包括这些化合物的异构形式。
反应类似地可以使用5-壬酮和任何其它酮或另外的酮如丙酮或任何其它含羰基化合物如LA进行。然而,优选的是,反应主要导致5-壬酮的二聚和/或低聚反应。5-壬酮的含量越高,两个或更多个5-壬酮分子之间的反应的概率越高。因此,优选的是,相对于原料中的所有有机组分,用包含至少5重量%的5-壬酮的原料进行反应。含量可以为10重量%或更多,15重量%或更多,20重量%或更多,25重量%或更多,35重量%或更多,或者45重量%或更多。
此外,由于反应不一定需要溶剂,原料中5-壬酮的含量可以高达100重量%。如果反应在溶剂存在下进行,其含量优选小于50重量%,小于30重量%,小于20重量%,小于10重量%,或小于5重量%,相对于所有液体化合物计,即相对于整个原料。可以不使用溶剂。
从上述反应方案可以看出,缩合反应导致氧含量进一步降低,并产生作为主要副产物的水。由于该反应不要求添加氢,因此进一步有助于节省温室气体。
可以使用任何合适的缩合催化剂来促进5-壬酮的缩合反应。酸性或碱性缩合催化剂的具体实例是离子交换树脂催化剂,例如酸性离子交换树脂催化剂,由碱性金属化合物组成的催化剂如金属氢氧化物催化剂或金属氧化物催化剂,由酸性金属化合物组成的催化剂如金属磷酸盐催化剂或金属氧化物催化剂,由至少两种金属氧化物组成的催化剂如混合金属氧化物催化剂或负载型金属氧化物催化剂。
催化剂可以是用于均相催化或非均相催化的催化剂。
作为酸性离子交换树脂催化剂,可以使用市售产品,如Amberlyst-15、16、35、36、39或70。离子交换树脂催化剂通常是用于非均相催化的催化剂。
当使用离子交换树脂催化剂时,反应温度优选为80℃或更高,更优选为90℃或更高,100℃或更高或者110℃或更高,进一步优选为170℃或更低,160℃或更低,140℃或更低,或者130℃或更低。使用适度的反应温度允许生产高分子量反应产物,例如5-壬酮的“二聚体”,同时降低了不希望的副反应的风险。反应可以在0.2-100.0巴,优选0.5-50.0巴,更优选1.0-20.0巴的压力下进行。重时空速(kg原料/kg催化剂*h)可以在0.05h-1-2.00h-1,优选0.10h-1-1.50h-1,更优选0.15h-1-1.00h-1,最优选0.20h-1-0.75h-1的范围内。
碱催化剂可以是任何常规的碱催化剂,例如用于均相催化或非均相催化的催化剂,并且可以包括金属氢氧化物,例如NaOH、KOH或Ca(OH)2,金属氧化物如CaO,金属醇盐如NaOCH3或金属盐,如K2CO3。金属氢氧化物催化剂和金属醇盐催化剂主要用于均相催化,但不限于此。当使用碱催化剂时,反应温度优选为70℃或更高,更优选为80℃或更高,90℃或更高或者100℃或更高,进一步优选为195℃或更低,160℃或更低,140℃或更低,或者120℃或更低。在这种情况下,优选在反应开始前在反应混合物中含有水,优选用量相对于反应混合物的所有液体成分为2-30重量%,但是可以不存在水。相对于反应混合物的所有液体组分,替代或除水以外,可以存在2至30重量%的醇,例如甲醇、乙醇或丙醇。所述碱可以是碱金属或碱土金属的氢氧化物、碳酸盐或磷酸盐,优选为Na、Li、Be、Mg、K、Ca、Sr或Ba中的一种的氢氧化物、碳酸盐或磷酸盐,或它们的组合,更优选为氢氧化钠、氢氧化钾或氢氧化锂或它们的组合。
氧化物催化剂如金属氧化物催化剂可以是任何常规的催化剂,并且可以是酸性氧化物催化剂,例如氧化钨基催化剂,例如WO3,并优选为包含至少两种不同的金属氧化物作为混合物的金属氧化物催化剂,包括将一种金属氧化物负载在另一种金属氧化物上、作为混合氧化物或作为固溶体的情况。金属氧化物催化剂优选为用于非均相催化的固体金属氧化物催化剂。混合金属氧化物催化剂的实例包括MgO·Al2O3(碱性)、SiO2·Al2O3(酸性),和负载型金属氧化物催化剂的实例包括K/Al2O3(碱性)和WO3/ZrO2(酸性)。
当使用金属氧化物催化剂时,反应温度可以为70℃或更高,优选80℃或更高,90℃或更高,110℃或更高,130℃或更高,150℃或更高,180℃或更高或者200℃或更高,进一步优选为300℃或更低,280℃或更低,250℃或更低,或者240℃或更低。在使用包含两种金属氧化物(即两种彼此不同的金属氧化物)的金属氧化物催化剂的情况下,两种或更多种氧化物的任何组合可以选自如下物质的氧化物:Be、B、Mg、Al、Si、P、Ca、Sc、Ti、V、Cr、Mn、Fe、Co、Ni、Cu、Zn、Ga、Ge、Sr、Y、Zr、Nb、Mo、Cd、Sn、Sb、Ba、W、Re、Bi、La或Ce。反应可以在0.5-100巴,优选1.0-50巴,更优选1.0-20巴的压力下进行。重时空速(kg原料/kg催化剂*h)可以在0.05h-1-2.0h-1,优选0.1h-1-1.8h-1,更优选0.2h-1-1.5h-1,最优选0.25h-1-1.25h-1的范围内。
该反应可以在间歇式反应器中或在连续流动式反应器中进行。
所述反应在载气流下进行,所述载气例如氮气、氢气、二氧化碳、甲烷或水。载气流可增加5-壬酮的总体转化率。特别是当制备柴油燃料时,缩合反应最为理想的产物是C18二聚产物,因此载气流应保持较低,优选低于10.0NL/L原料,更优选低于5.0NL/L,低于2.0NL/L,低于1.0NL/L,低于0.5NL/L,或低于0.3NL/L,但可高于0NL/L,优选高于0.05NL/L。也可以不使用载气。
此外,应当注意,本发明的缩合反应不消耗氢气,而是进一步降低有机材料的氧含量。也就是说,在如上述方案所示的生产二聚产物如C18产物的情况下,产物的氧含量约为7重量%,而原料(5-壬酮)的氧含量约为11重量%。
鉴于温室气体节约,因此优选在缩合反应步骤中不向反应混合物中加入氢气。另一方面,少量的氢气可能增加催化剂的稳定性,特别是在使用酸性离子交换树脂催化剂的情况下,因此为了提高催化剂稳定性,加入少量的氢可能是有益的。
在任何情况下,本发明的缩合反应是其中直接缩合5-壬酮的缩合反应。换句话说,5-壬酮不转化成5-壬醇或烯烃,例如通过在C-C键形成反应如烯烃低聚之前进行氢化。
可以纯化缩合反应的原始产物以除去未反应的组分以及水和气态和/或挥发性组分,以获得具有更高选择性和转化率的缩合产物。
缩合产物和包含缩合产物的燃料的用途
本发明方法的5-壬酮缩合产物是高度缺氧的,而在生产过程中仅消耗最少量的氢。
为了保持这种极好的温室气体节约效果,5-壬酮缩合产物,通常为C18酮、任选的C13烯烃和少量其它组分的混合物,可直接用作燃料组分而不被氢化。
因此,本发明还提供了缩合产物作为燃料组分的用途,优选作为柴油燃料共混物和/或喷气燃料共混物中的燃料组分,以及提供了包含缩合产物的燃料共混物,优选柴油共混物和/或喷气燃料共混物。
燃料共混物中的缩合产物的含量可以为2重量%或更多,优选为5重量%或更多,10重量%或更多,15重量%或更多,20重量%或更多,优选50重量%或更少,40重量%或更少,30重量%或更少或者25重量%或更少。
缩合产物的氢化,氢化缩合产物的用途和包含氢化缩合产物的燃料
为了进一步提高缩合产物作为燃料组分的性质或相容性,缩合产物可以进行氢化反应。例如,当烯烃如C13烯烃转化为相应的链烷烃时,十六烷值会增加。当结合本申请的其它方法时,从LA作为可再生来源开始的整体过程可概括如下:
氢化反应可以是用于选择性除去存在于缩合产物(例如C18或C13缩合产物)中的双键的反应,用于选择性除去存在于缩合产物中的酮基的反应,或完全氢化,从而产生烷烃/链烷烃组合物。任何这些氢化处理可以是单步骤氢化或多步骤,优选2步氢化。特别是在完全氢化的情况下,使用多步(2步)方法可能是有益的。
使用任何已知催化剂的任何已知方法可用于氢化或加氢脱氧缩合产物。优选地,氢化催化剂包含在载体上的氢化金属,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氢化或HDO催化剂金属。例如,可以在氢化反应中使用硫化的NiMo催化剂。
氢化可以在100-500℃,优选250-380℃范围的温度和10-150巴,优选30-80巴范围的压力下进行。
本发明还提供了氢化缩合产物作为燃料组分的用途,优选作为柴油燃料共混物中的燃料组分,以及提供了包含氢化缩合产物的燃料共混物,优选柴油共混物。
燃料共混物中的氢化缩合产物的含量没有特别限制,可以为5重量%或更多,优选为10重量%或更多,20重量%或更多,25重量%或更多,30质量%或更多,40重量%或更多,50重量%或更多,60重量%或更多,70重量%或更多,80重量%或更多,90重量%或更多,95重量%或更多,或者99重量%或更多。
实施例
通过实施例进一步说明本发明。然而,应当注意,本发明不旨在限于在实施例中呈现的示例性实施方案。
实施例1
在正壬烷异构化实验中,测试了正壬烷的异构化处理是否可以改善燃料性能。在流动式反应器中正壬烷异构化为异壬烷的试验期间的条件是:作为催化剂的常规异构化催化剂,初始反应器温度分别为310℃和330℃,压力40巴,进料WHSV为0.4h-1和氢/油比300NL/L。
表1.正壬烷的异构化结果
在本发明中,液体混合物/液体共混物中的材料的相对含量(重量%)可以从GC-MS分析中的GC面积确定。
正壬烷转化为异壬烷随着温度的升高而增加。温度从310℃升高到330℃,转化率从84%提高到了90%。
通过GC进料色谱分析异构化产物(330℃)的详细组成。该产物具有16.7重量%的正链烷烃和82.8重量%的异链烷烃。产物组合物具有26%的4-甲基-辛烷,25%的3-甲基-辛烷,16%的2-甲基-辛烷,16%的正壬烷,7%的3,5-二甲基-庚烷,4%的2,6-二甲基-庚烷,3%的2,3-二甲基-庚烷,2%的二甲基-庚烷和3%的其它组分。
正壬烷的十六烷值约为60,异构化(310℃)后试验组分的十六烷值在异构化期间降至51.2。异构化后组分的辛烷值(330℃)测量为48.4。通常,当链长度增加时,辛烷值减少,对于C9分子,辛烷值可能甚至低于0。然而,在实验中,已达到48.4的辛烷值。
实施例2
5-壬酮在各种条件下进行醛醇缩合,因此主要形成来自C-9酮的二聚体和三聚体。来自5-壬酮的二聚体和三聚体具有作为柴油燃料组分的潜力。
使用以下条件在流动式反应器中进行5-壬酮缩合试验:Amberlyst 36作为催化剂,温度为120℃,WHSV为0.22h-1,环境压力。
使用氮气作为载气,并测试0L/h、1L/h、2L/h和11L/h的流量。在没有氮气流量(0L/h)的情况下,观察到5-壬酮的转化率低。氮气流速升高到2L/h显著提高了转化率。但是,产物分布没有改善。最需要的产物是C18二聚体产物。通常,发现增加氮气流速降低了产物中二聚体部分的量。总体产物分布示于表2中。氮气流速与5-壬酮转化率和二聚体产物形成的关系如图2所示。
表2:5-壬酮醛醇缩合反应的结果
当引入少量氮气时,5-壬酮转化率增加。在高氮气流下,转化率再次下降。除了C18二聚体外,还形成了裂解的C13馏分和C5(戊酸)。
实施例3
在具有和不具有N2作为载气的情况下在不同催化剂上,在间歇式反应器中进行5-壬酮的醛醇缩合反应。具体的反应条件如下表3所示。评价了反应条件对5-壬酮二聚体形成的影响。
表3:在间歇式反应器中的醛醇缩合反应-反应条件
液相色谱(LC)-分析结果源自如下的实验:使用5-壬酮作为进料,在Amberlyst-36催化剂上,反应温度为120℃,氮气10L/h流经反应器(入口1)或无氮气(入口2),分别如下表4和5所示。24小时后,氮气流下的转化率为46.3%,主要反应产物为小于二聚体的产物(<C18)。
表4:5-壬酮的转化率和反应产物(入口1)。检测到戊酸、C13-烯烃和5-壬酮二聚体/更高级的低聚物。
表5:5-壬酮的转化率和反应产物(入口2)。
根据该结果,可以通过使氮气通过反应器系统从而将平衡移向产物来增加5-壬酮的转化率。
在使用乙酰丙酸和5-壬酮的实验中(入口6),转化率保持在低水平。反应时间为23h后,5-壬酮转化率约为20%。
此外,即使在24h的反应时间之后,在其中5-壬酮在La/ZrOx(入口4)上反应的实验中,5-壬酮的转化率也低。当用GC-MS分析产物时,5-壬酮的面积%(重量%)约为96%。当丙酮在Amberlyst-36催化剂上与5-壬酮反应(入口5)时,用GC-MS检测到少量产物。
实施例4
在间歇式反应器(实施例3的表4)中生产的5-壬酮醛醇缩合产物在NiMo催化剂上在温度为310℃,压力为60巴和反应时间为20小时进行HDO,以除去来自产物混合物的氧。最终产物用GC-MS分析。样品性能可在表6中看到。HDO产物的结构用GC-MS表征;比照下表7。
表6.产物性能:
表7:使用GC-MS检测的产物
实施例5
在流动式反应器中生产的5-壬酮醛醇缩合产物(实施例2)在NiMo催化剂上在320℃,50巴氢气压力下进行HDO条件48小时。最终产物性能可见下表8。
表8:HDO条件下5-壬酮醛醇缩合产物的产物性质。
HDO产物的结构用GC-MS表征(表9)。
表9:使用GC-MS确定的产物
根据沸点的产物分布通过SimDist(ASTM D2887)分析测定(表10)。
表10:HDO最终产物的SimDist分析。
Claims (8)
1. 一种用于生产燃料组分的方法,该方法包括:
提供包含至少5重量% 5-壬酮的原料的准备步骤,其中使用了源自可再生来源的乙酰丙酸作为原材料;其中使用了由碱金属氧化物和至少一种与碱金属氧化物不同的另外的金属氧化物构成的特定氧化物催化剂;其中5-壬酮以高于95体积%的高选择性和高于95体积%的高转化率生产;并且其中在所述准备步骤中不需要加入氢气;和
在缩合催化剂的存在下,至少将原料中的5-壬酮缩合以得到缩合产物的缩合步骤;
其中缩合步骤导致5-壬酮的二聚和/或5-壬酮的低聚和/或5-壬酮与其他酮的缩合,
条件是其他酮不是5-壬酮并且除了5-壬酮之外使用,并且原料中其他酮的含量小于95重量%,
并且其中所述缩合步骤在载气流下进行,所述载气选自氮气、氢气、二氧化碳、甲烷或水,其中载气流速根据所需的产品分布和所需的5-壬酮转化率在0-10NL/L的范围内调整,
任选地还包括氢化缩合产物以获得氢化缩合产物的氢化步骤,并且
采用所述缩合产物或者氢化缩合产物作为燃料组分。
2.根据权利要求1所述的方法,其中在所述缩合步骤中不进行氢化反应。
3.根据权利要求1或2所述的方法,其中所述缩合催化剂是:
i)离子交换树脂催化剂,
ii)酸或碱催化剂,其选自金属氧化物催化剂、金属氢氧化物催化剂、金属醇盐催化剂、金属碳酸盐催化剂或金属磷酸盐催化剂,或
iii)混合金属氧化物催化剂或负载型金属氧化物催化剂。
4.根据权利要求3所述的方法,其中所述离子交换树脂催化剂是酸性离子交换树脂催化剂。
5.根据权利要求1或2所述的方法,还包括氢化所述缩合产物以获得氢化缩合产物的氢化步骤。
6.根据权利要求5所述的方法,其中所述氢化缩合产物是烃组合物。
7.根据权利要求6所述的方法,其中所述氢化缩合产物是烷烃或烷烃混合物。
8.根据权利要求1所述的方法,其中所述碱金属氧化物是K2O。
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Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
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DE3825873A1 (de) * | 1988-07-29 | 1990-02-01 | Basf Ag | Verfahren zur herstellung von ketonen |
WO2015148412A2 (en) * | 2014-03-24 | 2015-10-01 | The Regents Of The University Of California | Methods for producing cyclic and acyclic ketones |
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Publication number | Publication date |
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EP3301142B1 (en) | 2020-11-18 |
CN107880957A (zh) | 2018-04-06 |
BR102017020819A2 (pt) | 2018-05-02 |
EP3301142A1 (en) | 2018-04-04 |
US20180086677A1 (en) | 2018-03-29 |
CA2979256A1 (en) | 2018-03-29 |
ES2842199T3 (es) | 2021-07-13 |
US10315966B2 (en) | 2019-06-11 |
BR102017020819B1 (pt) | 2022-04-12 |
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