CN101679883A - Fischer-tropsch derived diesel fuel and process for making same - Google Patents
Fischer-tropsch derived diesel fuel and process for making same Download PDFInfo
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- CN101679883A CN101679883A CN200780044879A CN200780044879A CN101679883A CN 101679883 A CN101679883 A CN 101679883A CN 200780044879 A CN200780044879 A CN 200780044879A CN 200780044879 A CN200780044879 A CN 200780044879A CN 101679883 A CN101679883 A CN 101679883A
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- Prior art keywords
- alcohol
- cut
- fischer
- oxygen
- distillment
- Prior art date
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- Pending
Links
- 239000002283 diesel fuel Substances 0.000 title claims description 50
- 238000000034 method Methods 0.000 title claims description 43
- 239000000446 fuel Substances 0.000 claims abstract description 72
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 52
- 239000001301 oxygen Substances 0.000 claims abstract description 51
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 51
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 claims abstract description 32
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 claims abstract description 30
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims abstract description 28
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000005968 1-Decanol Substances 0.000 claims abstract description 16
- ZWRUINPWMLAQRD-UHFFFAOYSA-N nonan-1-ol Chemical compound CCCCCCCCCO ZWRUINPWMLAQRD-UHFFFAOYSA-N 0.000 claims abstract description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 85
- 150000002430 hydrocarbons Chemical class 0.000 claims description 36
- 229930195733 hydrocarbon Natural products 0.000 claims description 35
- 239000000203 mixture Substances 0.000 claims description 35
- -1 1-enanthol Chemical compound 0.000 claims description 16
- 238000004517 catalytic hydrocracking Methods 0.000 claims description 14
- 239000007859 condensation product Substances 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 8
- 238000012545 processing Methods 0.000 claims description 8
- 238000006297 dehydration reaction Methods 0.000 claims description 6
- 238000005516 engineering process Methods 0.000 claims description 5
- 238000011084 recovery Methods 0.000 claims description 5
- 238000010521 absorption reaction Methods 0.000 claims description 4
- 230000018044 dehydration Effects 0.000 claims description 4
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 abstract 2
- 150000001298 alcohols Chemical class 0.000 abstract 1
- 229910052799 carbon Inorganic materials 0.000 description 24
- 238000009835 boiling Methods 0.000 description 21
- 239000004215 Carbon black (E152) Substances 0.000 description 20
- 239000002808 molecular sieve Substances 0.000 description 20
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 20
- 229910021536 Zeolite Inorganic materials 0.000 description 16
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 16
- 239000000047 product Substances 0.000 description 16
- 239000010457 zeolite Substances 0.000 description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 14
- 239000003054 catalyst Substances 0.000 description 13
- 239000007789 gas Substances 0.000 description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 12
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 12
- 229910052751 metal Inorganic materials 0.000 description 12
- 239000002184 metal Substances 0.000 description 12
- 239000012188 paraffin wax Substances 0.000 description 12
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 10
- BTFJIXJJCSYFAL-UHFFFAOYSA-N icosan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCCCO BTFJIXJJCSYFAL-UHFFFAOYSA-N 0.000 description 10
- 239000000126 substance Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 8
- 238000004821 distillation Methods 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 8
- 150000001336 alkenes Chemical class 0.000 description 7
- 125000003118 aryl group Chemical group 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 150000001335 aliphatic alkanes Chemical class 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- 229960000541 cetyl alcohol Drugs 0.000 description 6
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 6
- 238000005984 hydrogenation reaction Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 229910052697 platinum Inorganic materials 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- 239000000377 silicon dioxide Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000005864 Sulphur Substances 0.000 description 5
- 238000006317 isomerization reaction Methods 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 239000003208 petroleum Substances 0.000 description 5
- 150000003138 primary alcohols Chemical class 0.000 description 5
- 230000009466 transformation Effects 0.000 description 5
- 239000001993 wax Substances 0.000 description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 239000010779 crude oil Substances 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 229910052763 palladium Inorganic materials 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000003245 coal Substances 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 238000007598 dipping method Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 239000011733 molybdenum Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000010970 precious metal Substances 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 229960001866 silicon dioxide Drugs 0.000 description 3
- 239000002594 sorbent Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 239000011275 tar sand Substances 0.000 description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 3
- 229910052721 tungsten Inorganic materials 0.000 description 3
- 239000010937 tungsten Substances 0.000 description 3
- XFRVVPUIAFSTFO-UHFFFAOYSA-N 1-Tridecanol Chemical compound CCCCCCCCCCCCCO XFRVVPUIAFSTFO-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000002154 agricultural waste Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 235000009508 confectionery Nutrition 0.000 description 2
- 238000007710 freezing Methods 0.000 description 2
- 230000008014 freezing Effects 0.000 description 2
- 239000002737 fuel gas Substances 0.000 description 2
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 238000001465 metallisation Methods 0.000 description 2
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- REIUXOLGHVXAEO-UHFFFAOYSA-N pentadecan-1-ol Chemical compound CCCCCCCCCCCCCCCO REIUXOLGHVXAEO-UHFFFAOYSA-N 0.000 description 2
- 239000011295 pitch Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000003079 shale oil Substances 0.000 description 2
- 238000004808 supercritical fluid chromatography Methods 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 238000001159 Fisher's combined probability test Methods 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- 102220500397 Neutral and basic amino acid transport protein rBAT_M41T_mutation Human genes 0.000 description 1
- 229910003294 NiMo Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 239000008186 active pharmaceutical agent Substances 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 1
- 229940001007 aluminium phosphate Drugs 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- LTPBRCUWZOMYOC-UHFFFAOYSA-N beryllium oxide Inorganic materials O=[Be] LTPBRCUWZOMYOC-UHFFFAOYSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- UNYSKUBLZGJSLV-UHFFFAOYSA-L calcium;1,3,5,2,4,6$l^{2}-trioxadisilaluminane 2,4-dioxide;dihydroxide;hexahydrate Chemical compound O.O.O.O.O.O.[OH-].[OH-].[Ca+2].O=[Si]1O[Al]O[Si](=O)O1.O=[Si]1O[Al]O[Si](=O)O1 UNYSKUBLZGJSLV-UHFFFAOYSA-L 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 229910052676 chabazite Inorganic materials 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 238000009795 derivation Methods 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical class O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- AZRCNKIZGKJWOA-UHFFFAOYSA-N dioxosilane oxygen(2-) zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4].O=[Si]=O AZRCNKIZGKJWOA-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 229910052675 erionite Inorganic materials 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 230000009931 harmful effect Effects 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical class O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052680 mordenite Inorganic materials 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000000629 steam reforming Methods 0.000 description 1
- HLZKNKRTKFSKGZ-UHFFFAOYSA-N tetradecan-1-ol Chemical compound CCCCCCCCCCCCCCO HLZKNKRTKFSKGZ-UHFFFAOYSA-N 0.000 description 1
- 229910003452 thorium oxide Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- KJIOQYGWTQBHNH-UHFFFAOYSA-N undecanol Chemical compound CCCCCCCCCCCO KJIOQYGWTQBHNH-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 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
- C10L1/00—Liquid carbonaceous fuels
- C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
- C10L1/026—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only for compression ignition
-
- 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
- C10G51/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more cracking processes only
- C10G51/06—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more cracking processes only plural parallel stages only
-
- 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
- C10L1/04—Liquid carbonaceous fuels essentially based on blends of hydrocarbons
- C10L1/08—Liquid carbonaceous fuels essentially based on blends of hydrocarbons for compression ignition
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/30—Fuel from waste, e.g. synthetic alcohol or diesel
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Liquid Carbonaceous Fuels (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention is directed to a Fischer-Trospch derived distillate suitable for use as a distillate fuel having a flash point 38 DEG C minimum measured by ASTM D 93 and a cloud point of +14 DEG C or less and further containing not less than 0.01 wt.% oxygen in each of 1-pentanol, 1-hexanol, 1-heptanol, 1-octanol, 1-nonanol, 1-decanol and not more than 0.01 wt.% oxygen in C11+ linear alcohols. Preferably, the Fischer-Trospch derived distillate will have a cloud point at or below 0 DEG C, and more preferably the cloud point of the Fischer-Tropsch derived distillate will be at or below-15 DEG C.
Description
Invention field
The present invention relates to Fischer-Tropsch diesel oil fuel, distillment fuel or also satisfy the specification of diesel oil fuel but the density blend component lighter than conventional diesel fuel, and the method for preparing described fuel.
Background of invention
Distillment fuel is meant such fuel, and it contains the component that boiling point is higher than general gasoline final boiling point (about 400 or 204 ℃), but does not comprise the component that can not be obtained by distillation (boiling point is higher than the material of 1100 or 593 ℃).Distillment fuel can for example be used for generating electricity at stationary engine those in burn.Diesel oil fuel is meant to burn in diesel motor and comes to provide for various mankind's activities the distillment of energy.The specification of diesel oil fuel is stricter than distillment fuel.For example in the U.S., the final boiling point specification of diesel oil fuel is 640 °F (338 ℃) and be 550 °F (288 ℃) for No.1-D for No.2-D.
The diesel oil fuel of different grades has the specification that restriction is set on cloud point.These are often owing to the geographic area with change throughout the year.For example, in the U.S., ASTM D975-00 has stipulated the specification of No.1-D and No.2-D diesel oil fuel.It comprises the statement of the footnote j of table 1, and " the minimum air themperature that provides ten percentage points for U.S. area in appendix X4 is as the mean estimates of the regional temperature of expectation.This guidance is general.Some equipment designs or operation can allow fuel higher or the lower cloud point of requirement ".Temperature among the appendix X4 from northern territory, Alaska the low value-49 in January ℃ to the south, Florida October+14 ℃.WorldWide Fuel Charter (2002) comprises the statement " maximum must be equal to or less than the envrionment temperature of minimum expectation " to cloud point equally.Therefore, receivable diesel oil fuel should have for+14 ℃ or be lower than+14 ℃ cloud point, and for example be 0 ℃ or be lower than 0 ℃, or for-15 ℃ or be lower than-15 ℃, or for-25 ℃ or be lower than-25 ℃, or for-49 ℃ or be lower than-49 ℃.
Alkane belongs to because their composition will be height, and their density can be lower than specification.When needs were kept the specification density of conventional diesel fuel, these compositions of the present invention were preferably as blend fuel.
Fischer-tropsch process provides the method for various hydrocarbon resource conversion for the product that usually provided by oil.These comprise diesel oil fuel.Preparing via Fischer-tropsch process in the process of hydrocarbon, at first with the hydrocarbon resource, for example Sweet natural gas, coal, refinery fuel gas, tar sand, resinous shale, municipal waste, agricultural waste, forestry waste, timber, shale oil, pitch, crude oil and crude oil fractions, be converted into synthetic gas, synthetic gas is the mixture that comprises carbon monoxide and hydrogen.
It is to be the technology of synthetic gas with the hydrocarbon resource conversion by the using gas oxygenant that synthetic gas generates technology.Gaseous oxidant can be pure O
2, oxygen-rich air, air, water vapour, carbonic acid gas and composition.This technology can be carried out on the ground or original position is carried out.Using carbon number is autothermal reformer (ATR), partial oxidation (POX), gas heater convertor (GHR) and steam reforming less than 20 carburet hydrogen (for example methane) as the example that the ground synthetic gas of reactor feedstocks generates technology.When these raw materials contain C more than 2mol%
2During heavier hydrocarbon, use pre-converter (pre-converter) usually with C
2+ hydrocarbon is converted into methane.This pre-converter uses the catalyzer that contains group VIII metal catalyst (for example Ni) to carry out under super-atmospheric pressure with hydrogen.The case description that synthetic gas is produced is in Kirk Othmer On-Line Edition " Fuels, Synthetic, Liquid Fuels " especially the 1st chapter 2-14 page or leaf, and online version is incorporated this paper by reference into.
" Methanol 4.Manufacture and Processing " with same online reference 299-311 page or leaf incorporates this paper by reference into.
Can generate synthetic gas by making the reaction of subterranean hydrocarbon resource and gaseous oxidant.The case description of this in-situ process is authorized people's such as Karanikas United States Patent (USP) 6,698,515 on March 2nd, 2004.The example of subterranean hydrocarbon resource is coal, resinous shale, heavy oil, tar sand, petroleum deposits and pitch.The example that is suitable for the petroleum deposits of converted in-situ be by ordinary method for example pump take out, inject water vapour and inject the petroleum deposits that water has therefrom extracted the oil of easy extraction.
And then synthetic gas is converted into the synthetic hydrocarbon compound, it mainly has linear chain structure, mainly is other species of normal paraffin, 1-alcohol, 1-alkene and trace.These hydrocarbon species can be refined into the various products that comprise distillment fuel.
European patent 0861311,0885275, United States Patent (USP) 5689031,6274029,6296757,6607568,6822131 have been described and have been contained C
5-C
24Straight chain primary alcohol and preferred C
12-C
24Straight chain primary alcohol or C
12+The preparation of the Fischer-tropsch derived product of straight chain primary alcohol.Which kind of definite straight chain primary alcohol that imagination comprises is unclear.But the density of these medium distillments is lower than the specification of diesel oil fuel.The existence of alcohol it is said the oilness of having improved these medium distillment fuel.The employing stated limit alcohol of regrettably, instructing in these documents particularly adopts C
11+The composition of alcohol can not satisfy the cloud point specification of diesel oil fuel, and therefore they are not suitable as commercial diesel fuel.The present invention comes from and recognizes that alcohol must be C
10Or lower, and be particularly related to the Fischer-tropsch derived diesel fuel composition that can satisfy cloud point, preferably can improve the productive rate of process.
Cloud point represents to be lower than the temperature that this temperature then may form hydrocarbon solid in the diesel oil fuel.Cloud point adopts ASTM D2500 to determine, the fuel temperature when generating the hydrocarbon solid crystal when this ASTM D2500 measures cooling.
Used word " Fischer-tropsch derived " is meant except that the hydrogen that adds major portion derived from the hydrocarbon flow of Fischer-tropsch process in the present disclosure, no matter whether passes through subsequent process steps and regardless of the method for preparing synthetic gas.The charging that is used for the generation of " Fischer-tropsch derived " is meant the product derived from any carbon source such as Sweet natural gas, coal, refinery fuel gas, tar sand, resinous shale, Municipal waste, agricultural waste, forestry waste, timber, shale oil, pitch, crude oil and crude oil fractions.
Used speech " comprises " or is intended as " comprising " the conversion saying of opening in the present disclosure, is meant to comprise the composition of being nominated, but is not other composition of not nominating of certain eliminating.Word " substantially by ... form " or " constituting by .. basically " plan expression and do not comprise other composition that composition is had any essential meaning.Word " by ... form " or " by ... constitute " the meaning change a saying and be meant that other all compositions all foreclose except that described composition, but minute quantity impurity can be arranged.
Summary of the invention
The present invention relates to be suitable as the Fischer-tropsch derived distillment of diesel oil fuel, its have by ASTM D93 measured minimum be 38 ℃ flash-point and+14 ℃ or lower cloud point, and contain the oxygen at least two kinds of 1-alcohol of 1-amylalcohol, 1-hexanol, 1-enanthol, 1-octanol, 1 nonyl alcohol and 1-decanol that is no less than 0.01wt% and no more than 0.01wt% at C
11+Oxygen in the straight chain alcohol.All C
5-C
10The mixture of alcohol within the scope of the invention.The upper limit wt% oxygen of described alcohol is lower than makes fuel can not reach the amount that is fit to cloud point and/or other fuel specification.Randomly, can use among three kinds of alcohol two kinds, i.e. C by the concentration that for two kinds of species, is no less than 0.03wt% oxygen
5And C
7Or C
5And C
6Or C
6And C
7Described Fischer-tropsch derived distillment fuel will have for+14 ℃ or be lower than+14 ℃ cloud point, and for example, be 0 ℃ or be lower than 0 ℃, or for-15 ℃ or be lower than-15 ℃, or for-25 ℃ or be lower than-25 ℃, or for-49 ℃ or be lower than-49 ℃.All wt% oxygen all are the benchmark metering with anhydrous.When density constitutes diesel fuel specifications a part of, Fischer-Tropsch diesel oil will contain fill-in to reach appropriate density specification.
The boiling point of summarizing various paraffinic hydrocarbonss and alcohol is useful.
| Carbon number | The boiling point of n-paraffin (°F, ℃) | The boiling point of 1-alcohol (°F, ℃) | The fusing point of n-paraffin (°F, ℃) | The fusing point of 1-alcohol (°F, ℃) |
| ??5 | ??97，36 | ??281，138 | ??-201，-130 | ??-110，-79 |
| ??8 | ??258，125 | ??381，193 | ??-71，-56 | ??+2，-17 |
| ??10 | ??346，174 | ??441，227 | ??-23，-30 | ??+45，+7 |
| ??11 | ??384，195 | ??469，242 | ??-14，-25 | ??+61，+16 |
| ??12 | ??422，216 | ??495，257 | ??+14，-10 | ??+79，+26 |
| ??14 | ??489，254 | ??545，285 | ??+42，+6 | ??+103，39 |
To need boiling point be 250 °F (121 ℃) or higher in order to reach 38 ℃ the flash-point of being surveyed by ASTM D93.Because paraffinic hydrocarbons is different with the boiling point of alcohol, this is corresponding to n-C
8With the 1-amylalcohol.Equally, if by using distillation with C
11+Alcohol forecloses, and they are at 495 °F (257 ℃) or be higher than 495 (257 ℃) down boiling, and then this is corresponding to being higher than n-C
14Following ebullient paraffinic hydrocarbons, for example C
15+Product.When paraffinic hydrocarbons is less than or equal to C
20The time, satisfied the final boiling point of 640 (338 ℃) of No.2-D diesel oil fuel.Can comprise until C
24The paraffinic hydrocarbons of some branching.When paraffinic hydrocarbons is less than or equal to C
16The time, satisfied the final boiling point of 550 (288 ℃) of No.1-D diesel oil fuel, but can comprise until C
18The paraffinic hydrocarbons of some branching.When the source beyond fischer-tropsch reaction materials flow product added alcohol, cut point can be higher, because there is not deleterious higher alcohol.
The present invention also relates to prepare the method for Fischer-tropsch derived distillment fuel, preferably by making C
15+Product is promoted to a higher rank and kept C in lighter cut
14-Product and alcohol make the productive rate maximization.Described method comprises that (a) is divided into first cut and second cut with the Fischer-Tropsch condensation product, wherein (i) described first cut comprise be no less than 0.01wt% from oxygen in 1-amylalcohol, 1-hexanol, 1-enanthol, 1-octanol, 1 nonyl alcohol and 1-decanol at least two kinds and no more than 0.01wt% at C
11+Oxygen in the straight chain alcohol and (ii) described second cut comprise C
11+Straight chain alcohol; (b) from least a portion of described heavy the 3rd cut, remove described C
11+Straight chain alcohol, and recovery does not contain C substantially
11+Last running after the processing of straight chain alcohol; (c) part with the last running after the processing of at least a portion of first cut of step a (i) and step (b) is in harmonious proportion in the proper ratio to prepare Fischer-tropsch derived distillment fuel, wherein the C of Cun Zaiing
5-C
10To the scope of 1wt% oxygen, described cloud point is not higher than the oxygenates level summation of alcohol at 0.01wt% oxygen+and 14 ℃ and the flash-point measured by ASTM D93 are minimum to be 38 ℃.At minimum 5% when being 121 ℃ (250 °F) that measures by ASTM D2887, this flash-point can reach usually.In implementing method of the present invention, can in step (a), from the Fischer-Tropsch condensation product, isolate and contain C
4-The 3rd cut of straight chain alcohol.
The invention reside in following discovery: at C
11+There is the cloud point that will significantly improve composition more than the oxygen of 0.01wt% in the straight chain alcohol, makes it be not suitable for use in diesel oil fuel.Because C
14-Paraffinic hydrocarbons is adapted at using in the diesel oil fuel, so to C
15+Component is further handled also can improve productive rate.Used term " the C of present disclosure
4-Straight chain alcohol " be meant and contain 4 or the still less straight chain alcohol of carbon atom, for example methyl alcohol, ethanol, 1-butanols and 1-propyl alcohol in the molecule.Term " C
11+Straight chain alcohol " be meant the straight chain alcohol that contains 11 or more a plurality of carbon atoms in the molecule, for example 1-undecyl alcohol, 1-lauryl alcohol, 1-tridecanol, 1-tetradecyl alcohol, 1-pentadecanol, 1-hexadecanol etc.The straight chain C of mentioning in the present disclosure
5-C
10Alcohol is 1-amylalcohol, 1-hexanol, 1-enanthol, 1-octanol, 1 nonyl alcohol and 1-decanol and these mixture.
Detailed Description Of The Invention
The present invention is based on following discovery: exist in the Fischer-tropsch derived distillment fuel few to 0.01wt% at C
11+Oxygen in the straight chain alcohol will make cloud point rise to unacceptable temperature.Surprisingly, in same fuel, there is C
5-C
10Straight chain 1-alcohol, more specifically say so 1-amylalcohol, 1-hexanol, 1-enanthol, 1-octanol, 1 nonyl alcohol and 1-decanol then can be ignored the influence of cloud point.As long as satisfy the cloud point specification of diesel oil fuel, can comprise the alcohol of a small amount of other pure species and Geng Gao carbon number.This often means that other pure species will only exist as impurity.The problem that will solve is to satisfy the cloud point requirement of diesel oil fuel simultaneously by the preparation cost that the severity that reduces hydrotreatment operation (this hydrotreatment operation improves productive rate) reduces diesel oil fuel in addition.
In the method for the invention, described Fischer-Tropsch product (condensation product, wax or temper) is separated at least two cuts, comprises C
10With first cut of even lower level alcohol with than last running.Described lighter fraction preferably has oxygen in the 1-amylalcohol, 1-hexanol, 1-enanthol, 1-octanol, 1 nonyl alcohol and the 1-decanol that are no less than 0.01wt% at least two kinds and no more than 0.01wt% at C
11+Oxygen in the straight chain alcohol and second comprises C than last running
11+Straight chain alcohol.Desire is in harmonious proportion back the part of heavier second cut of described first cut to be handled substantially all to remove existing C
11+Straight chain alcohol.At last, at least a portion of heavier second cut after handling and described first cut is in harmonious proportion in the calculating ratio is not less than to obtain cloud point+14 ℃ Fischer-tropsch derived distillment fuel.In general, be present in C in the described Fischer-tropsch derived distillment fuel
5-C
10Alcohol the oxygenates level summation will for 0.01wt% oxygen to 1wt% oxygen.The combination of any two kinds of alcohol, i.e. C
5And C
6Or C
5And C
7Or C
6And C
7, can be to exist from 0.01wt% oxygen, preferred 0.03wt% oxygen to the amount of 1.0wt% oxygen.This fuel preferably also should have the minimum 38 ℃ flash-point of being measured by ASTM D93.Unless be in harmonious proportion with traditional petroleum, its density will be lower than standard but still can effectively be used as distillment and diesel oil fuel.
The oxygenatedchemicals that will contain various amounts by the product (condensation product, wax and temper) of Fischer-Tropsch operation recovery.Existing most oxygenatedchemicals is in the form of alcohol; Yet, also can have more a spot of ketone, aldehyde, carboxylic acid and acid anhydrides.For preparing the described C that do not contain substantially
11+The last running of straight chain alcohol is necessary to remove described C
11+Straight chain alcohol or they are converted into other hydrocarbon.There are many methods known to those skilled in the art to can be used to implement this step.These methods are including but not limited to the various combinations of hydrotreatment, hydrocracking, hydroisomerization, dehydration, absorption, absorption or these methods.What present disclosure was used " does not contain C substantially
11+Straight chain alcohol " the meaning be the contained C of distillment cut
11+The amount of alcohol is less than the concentration that cloud point is risen to be higher than the value of diesel fuel specifications.
Hydrocracking and hydrotreatment are similar methods, and they are mainly different on severe degree.In this disclosure they are called synoptically " hydroprocessing ".In the method for the invention, hydrocracking and the hydrotreatment purpose that at first will reach is to remove the alcohol that exists in the described Fischer-Tropsch distillment." hydrotreatment " relates to catalytic process, usually carry out in the presence of free hydrogen, wherein main purpose is to remove various metallic impurity for example arsenic, heteroatoms such as sulphur and nitrogen and remove aromatic substance from raw material when being used for handling the raw material of traditional petroleum derivation.In the method, main purpose is to remove described alcohol, secondly is that the alkene that will exist is saturated.In general, in hydrotreatment operation, it is minimized to make the promptly bigger hydrocarbon molecule of cracking reaction of hydrocarbon molecule fragment into the reaction of less hydrocarbon molecule.With regard to the purpose of this paper discussion, the term hydrotreatment is meant that transformation efficiency is 20% or littler hydroprocessing process.Transformation efficiency can be lower than the increasing amount of 5% material of charging and the ratio of charging defines based on the product mid-boiling point, and its mid-boiling point is measured by ASTM D 2887." hydrocracking " relates to catalytic process, carries out in the presence of free hydrogen usually, and wherein the cracking with big hydrocarbon molecule is main operation purpose.For the purpose of present disclosure, different with hydrotreatment is that the transformation efficiency of hydrocracking will be higher than 20%.In the present invention, hydrocracking is used for removing described alcohol and makes hydrogenation of olefins.
The catalyzer that is used for implementing hydrotreatment and hydrocracking operation is well known in the art.For example, incorporate their full content into this paper by reference, be used for that the used typical catalyst of hydrotreatment, hydrocracking and each method is carried out generality and describe referring to United States Patent (USP) 4347121 and 4810357.Suitable catalyzer comprises the precious metal from VIIIA family (according to pure and applied chemistry international federation rule in 1975), aluminum oxide or contain platinum or palladium on the silicon substrate for example, with unvulcanized VIIIA family and group vib metal, aluminum oxide or contain nickel-molybdenum or nickel-Xi on the silicon substrate for example.United States Patent (USP) 3852207 has been described suitable noble metal catalyst and gentle condition.Other suitable catalyzer for example is described in United States Patent (USP) 4157294 and 3904513.Non-your hydrogenation metal for example nickel-molybdenum usually with oxide compound or more preferably or more may be present in the final catalyst composition with sulphided form (when related special metal easily forms this compounds).Preferred non-noble metal catalyst compositions contains above the molybdenum of 5wt% oxygen, the preferred about 40wt% oxygen of 5-and/or tungsten and 0.5wt%, the nickel and/or the cobalt of 1-15wt% oxygen usually at least, by corresponding oxide compound mensuration.Contain precious metal for example the catalyzer of platinum contain and surpass 0.01% metal, the preferred metal between 0.1 and 1.0%.Also can use the combination of precious metal, for example the mixture of platinum and palladium.
Can be by in any catalyst composition that described hydrogenation component introducing is whole in many methods.Can described hydrogenation component be joined in the matrix component and can make VI family component by dipping, common grinding or co-precipitation by common grinding, dipping or ion-exchange be that molybdenum and tungsten mix with refractory oxide.Although these components can be mixed with catalyst matrix with sulphided form, not preferred usually, because sulphur compound can have interference to fischer-tropsch catalysts.
Described matrix component can be a lot of types, comprises that to have acidic catalyst more active.Have that active matrix component comprises soft silica-aluminum oxide or can be crystalline molecular sieve zeolitization or nonzeoliteization.The example of the substrate molecule sieve that is fit to comprises the Y zeolite of Y zeolite, X zeolite and so-called overstable gamma zeolite and high structural silica dioxide/alumina ration, and for example United States Patent (USP) 4401556,4820402 and 5059567 is described.Also can use for example United States Patent (USP) 5073530 described small crystalline size Y zeolite.The molecular sieve of spendable nonzeoliteization comprise United States Patent (USP) 4913799 for example and the reference quoted described in aluminosilicophosphate (SAPO), iron aluminium phosphate, titanium aluminate or phosphate and various ELAPO molecular sieve.The visible United States Patent (USP) 5114563 of the details relevant (SAPO) with the preparation of various non-zeolite molecular sieves and 4913799 and United States Patent (USP) 4913799 in each reference of being quoted.Also can use mesoporous molecular sieve, J.Am.Chem.Soc. for example, 114:10834-10843 (1992), M41S series material of describing in MCM-41, the United States Patent (USP) 5246689,5198203 and 5334368 and MCM-48 people such as (, Nature 359:710 (1992)) Kresge.Suitable body material also can comprise synthetic or crude substance and inorganic materials clay for example, silicon-dioxide and/or metal oxide be silica-alumina for example, silica-magnesia, silicon-dioxide-zirconium dioxide, silica-thorium oxide, silica-beryllia, silica-titania and ternary composition be silica-alumina-Thorotrast for example, silica-alumina-zirconium dioxide, silica-alumina-magnesium oxide and silica-magnesia-zirconium dioxide.The latter can be naturally occurring or comprise the form of the gelatinous precipitate or the gel of silicon-dioxide and metal oxide mixture.Can comprise those of montmorillonite series and kaolin series with the naturally occurring clay of described catalyzer compound.These clays can use with the unprocessed state of initial recovery, or at first use through after calcining, acid treatment or the chemical modification.
In the implementation process of hydrocracking and/or hydrotreatment operation, can in reactor, use more than a kind of catalyst type.But different catalyst type layering or mixing.
Hydrocracking condition is to be documented in the literature.In general, total LHSV is 0.1-15.0hr
-1(v/v), preferred 0.25-2.5hr
-1Reaction pressure is generally 500-3500psig (10.4-24.2MPa), preferred 1500-5000psig (3.5-34.5MPa).Hydrogen gas consumption is generally 500-2500SCF/ bucket charging (89.1-445m
3H
2/ m
3Charging).Temperature in the reactor is 400-950 °F (205-510 a ℃), is preferably 650-850 °F (340-455 ℃).
Typical hydroprocessing condition mobility scale is very wide.In general, total LHSV is 0.5-5.0.Total pressure is 200-2000psig.The hydrogen recycle ratio is generally greater than 50SCF/Bbl, and preferably 1000 and 5000SCF/Bbl between.Temperature in the reactor is 400-800 °F (205-425 a ℃).
" hydroisomerization " also is called for short " isomerization ", and intention adds the cold flow properties that branch improves Fischer-tropsch derived product by selectivity in molecular structure.In the present invention, it also can be used to remove described alcohol.Isomerization will realize the high level of conversion of normal paraffin to isomerization alkanes ideally, and the conversion that is produced by cracking is minimized.Be fit to the common catalyzer that comprises acidic components and can randomly contain active metal component that uses of isomerization operation that the present invention adopts with hydrogenation activity.The acidic components of described catalyzer preferably include mesopore SAPO, for example SAPO-11, SAPO-31 and SAPO-41, especially preferably SAPO-11.Mesopore zeolite is ZSM-22, ZSM-23, SSZ-32, ZSM-35 and ZSM-48 for example, also can be used to implement this isomerization.Typical reactive metal comprises molybdenum, nickel, vanadium, cobalt, tungsten, zinc, platinum and palladium.Especially preferable alloy platinum and palladium are as reactive metal, and the most normal use is platinum.
Word used herein " intermediate pore size " is meant when porous inorganic oxide is in burnt form, the effective pore radius in the about 7.1 dust scopes of about 4.0-.The molecular sieve of aperture in this scope often has unique molecule screening characteristics.For example erionite is different with chabazite with pore zeolite, and they will allow some ramose hydrocarbon and enter the molecular sieve pores space.With more large pore molecular sieve such as faujusite and mordenite are different, they can with normal paraffin and slightly branching alkene with for example have that the bigger alkane of quaternary carbon atom makes a distinction.Referring to United States Patent (USP) 5413695.Term " SAPO " is meant silicoaluminophosphamolecular molecular sieve, for example states in United States Patent (USP) 4440871 and 5208005.
When preparation contains the molecular sieve of nonzeoliteization and have those catalyzer of hydrogenation component, usually preferably use method that non-water becomes with described metal deposition on described catalyzer.The molecular sieve of nonzeoliteization comprises tetrahedral coordination [AlO2 and PO2] oxide unit, and described oxide unit can be chosen wantonly and comprise silicon-dioxide.Referring to United States Patent (USP) 5514362.Use method that non-water becomes with the catalyzer of the metal deposition molecular sieve that contains nonzeoliteization thereon, particularly contain the catalyzer of SAPO series, those catalyzer that deposit reactive metal with the method that adopts water to become are compared, and present bigger selectivity and activity.United States Patent (USP) 5939349 has been instructed the non-water of reactive metal has been deposited on method on the molecular sieve of nonzeoliteization with becoming.In general, this method comprises that the compound dissolution with reactive metal is deposited on the molecular sieve it in non-water, non-reacted solvent and by ion-exchange or dipping.
Can be by for example handling the dehydration that described raw material is realized alcohol on the gama-alumina at catalyzer.In dehydration, alcohol is converted into alkene.The dehydration reaction of alcohol to alkene has been discussed in " Catalytic Processes and ProvenCatalysts " the 5th chapter " dehydration reaction " that the Charles L.Thoma s that Academic press published in 1970 is shown.Another kind method is disclosed in United States Patent (USP) 6933323, and it is incorporated herein by reference in full.
Also described the another kind of method that is used for removing alcohol among the embodiment of United States Patent (USP) 6933323, comprised making condensation product by containing the adsorption bed that can adsorb the sorbent material of described alcohol.Gratifying sorbent material can comprise the molecular sieve with low silica/alumina ration.Large pore molecular sieve with low silica/alumina ration particularly to have those molecular sieves that the FAU framework types is a feature, is suitable as the sorbent material of pure and mild other oxygenatedchemicals usually.Preferred FAU molecular sieve is the X zeolite, preferred especially 13X molecular sieve.Term used herein " FAU molecular sieve " is with reference to IZA structure council standard, and it not only comprises the X zeolite but also comprises Y zeolite.
United States Patent (USP) 2882244,3685963,5370879,3789107 and 4007253 has been described the synthetic of X type zeolite, and their full text is incorporated herein by reference.The 13X zeolite is faujusite (FAU) type X zeolite.It has low silica/alumina ratio and is made up of silicon, aluminium and oxygen.The oxygen ring provides the hole opening of 7.4 dusts, but adsorbable molecule up to 10 dusts.The chemical abstracts of 13X zeolite (CAS) is numbered [63231-69-6].The 13X zeolite can be commercially available from several sources, comprises the Davision department of Ardrich Chemical Company and W.R.Grace.Can adopt the method described in the above-mentioned United States Patent (USP) 6933323 in addition.
Flash-point is a temperature, and fuel must be heated to this temperature and produce enough fuel vapourss with the liquid fuel within surface, in order to be lighted when contacting with naked light.Flash-point is measured by ASTM D93 and is preferably minimum 38 ℃.
The following example has been given prominence to by recognizing in the distillment fuel and has been comprised C
11+Alcohol influence and can not satisfy diesel cloud point specification problem to be solved.
Embodiment 1
In this embodiment, prepare and tested have high isomery/final boiling point of positive structure ratio is the Fischer-Tropsch diesel oil fuel of 600 (315 ℃) (being surveyed by ASTM D2887).
Obtain Fischer-Tropsch C from Moore and Munger company
80The commercial sample of wax.It is that boiling point under 790 and the 5wt% is 856 °F that its initial boiling point is surveyed by ASTM D 2887.It is being carried out hydrocracking under single-pass operation (not having circulation) transformation efficiency about 90% under 669,1.0LHSV, 1000psig, 10000SCF/Bbl hydrogen condition in single-stage demo plant.Use commercially available sulfurized hydrocracking catalyst.Reclaim 260-600 product with following character by distillation.This product contains the n-C above 2wt%
14+Normal paraffin, but still have-51 ℃ cloud point.
| Density under 15 ℃, g/ml | ??0.7626 |
| Sulphur, ppm | ??0 |
| Viscosity under-20 ℃, cSt | ??6.382 |
| Freezing point, ℃ | ??-47.7 |
| Cloud point, ℃ | ??-51 |
| Flash-point, ℃ | ??54 |
| Smoke point, mm | ??＞45 |
| Hydrocarbon types | Wt% (ASTM D 2789) by mass spectroscopy |
| Paraffinic hydrocarbons | ??93.1 |
| The monocycle paraffinic hydrocarbons | ??5.2 |
| The dicyclo paraffinic hydrocarbons | ??1.5 |
| Alkylbenzene | ??0.1 |
| The benzo naphthalene | ??0.0 |
| Naphthalene | ??0.1 |
Carry out the normal paraffin analysis by GC
| Carbon number | Distribute (Wt%) | Normal paraffin | Non-normal paraffin |
| ??6 ??7 ??8 ??9 ??10 ??11 ??12 ??13 ??14 ??15 ??16 ??17 ??18 ??19 ??20 ??21 ??22-52 | ??0.00 ??0.00 ??0.12 ??8.75 ??10.92 ??11.25 ??11.24 ??11.26 ??10.66 ??10.21 ??9.70 ??9.37 ??6.36 ??0.12 ??0.02 ??0.00 ??0.00 | ??0.00 ??0.00 ??0.10 ??1.83 ??1.56 ??1.22 ??1.19 ??0.68 ??0.77 ??0.58 ??0.41 ??0.30 ??0.03 ??0.00 ??0.00 ??0.00 ??0.00 | ??0.00 ??0.00 ??0.02 ??6.92 ??9.39 ??10.03 ??10.05 ??10.58 ??9.90 ??9.62 ??9.29 ??9.07 ??6.33 ??0.12 ??0.02 ??0.00 ??0.00 |
| Amount to | ??100.00 | ??8.67 | ??91.33 |
| Average carbon number | ??13.28 | ||
| Molecular-weight average | ??187.93 |
| Simulation distil | °F represent ASTM D 2887 with wt% |
| ??0.5％ ??5％ ??10％ ??20％ ??30％ ??40％ ??50％ ??60％ ??70％ ??80％ ??90％ ??95％ ??99％ ??99.5％ | ??267 ??287 ??310 ??342 ??378 ??405 ??439 ??472 ??504 ??535 ??564 ??579 ??595 ??598 |
This sample mixed with the n-dodecanol of variable quantity and measure cloud point.The cloud point of primary sample is-51 ℃, and this has reached the strictest cloud point specification among the ASTM D975, but add few oxygen as lauryl alcohol to 0.1wt% cloud point is significantly raise.
Embodiment 2
Having prepared final boiling point is the other diesel fuel sample and as follows test of 675 (357 ℃) and 450 (232 ℃) and medium isomery/positive structure ratio.This sample satisfies final boiling point and the flash-point requirement of ASTM D975 for No.2-D fuel.
Make the sample of Fischer-Tropsch condensation product and wax by cobalt catalyst.Under 3.36LHSV, 1000psig stagnation pressure, 5000SCFB circulation gas ratio at the nonacid NiMo/Al of the commercially available whole extrudate of sulfurized
2O
3On the catalyzer this condensation product is carried out hydrotreatment.Under 1.2LHSV, the transformation efficiency, 1000psig stagnation pressure, 5000SCFB circulation gas ratio of 66% every journey below 675 (357 ℃) at the acid NiW/Al of the commercially available whole extrudate of sulfurized
2O
3-SiO
2On the catalyzer this wax is carried out hydrocracking.To mix continuously and distillation from the product of two equipment.Boiling point is higher than the material recirculation of diesel oil cut point (about 675-357 ℃) to consume light in hydrocracker.
The character of 250-675 (121-357 ℃) diesel oil fuel is as follows:
| Proportion, ° API | ??52.7 |
| Nitrogen, ppm | ??0.24 |
| Sulphur, ppm | ??＜1 |
| Water, ppm is surveyed ppm by Karl Fisher method | ??21.5 |
| Pour point/cloud point/CFPP, ℃/freezing point, ℃ | ??-23/-18/-21/-14 |
| Flash-point, ℃ | ??58 |
| Viscosity under 25 ℃/40 ℃, cSt | ??2.564/1.981 |
| Cetane value | ??74 |
| By the aromatic substance that supercritical fluid chromatography is surveyed, wt% | ??＜1 |
| The neutralization number | ??0 |
| The ash oxide compound, wt% | ??＜0.001 |
| Ramsbottom coke, wt% | ??0.02 |
| The corrosion of Cu bar | ??1A |
| Colourity, ASTM D1500 | ??0 |
| GC-MS analyzes | |
| Paraffinic hydrocarbons, wt% | ??100 |
| Paraffinic hydrocarbons isomery/positive structure ratio | ??2.1 |
| As the oxygen of oxygenatedchemicals, ppm | ??＜6 |
| Alkene, wt% | ??0 |
| Average carbon number | ??15.15 |
| By D-2887 distillation, by the wt% decision °F and by D-86 distillations, by volume % decision °F | ??D-2887 | ??D-86 |
| ??0.5/5 | ??255/300 | ??329/356 |
| ??10/20 | ??326/368 | ??366/393 |
| ??30/40 | ??406/449 | ??419/449 |
| ??50 | ??487 | ??480 |
| ??60/70 | ??523/562 | ??510/539 |
| ??80/90 | ??600/637 | ??567/597 |
| ??95/99.5 | ??659/705 | ??615/630 |
Detailed GC-MS analyzes
| Molecular formula | Normal paraffin area % | Branched alkane area % | Total alkane | Isomery/positive structure according to carbon number |
| ??C9H20 | ??2.96 | ??0.00 | ??2.96 | ??- |
| ??C10H22 | ??3.59 | ??4.24 | ??7.83 | ??1.18 |
| ??C11H24 | ??3.80 | ??4.65 | ??8.45 | ??1.22 |
| ??C12H26 | ??3.65 | ??4.77 | ??8.42 | ??1.31 |
| ??C13H28 | ??3.41 | ??5.34 | ??8.75 | ??1.57 |
| ??C14H30 | ??3.00 | ??5.34 | ??8.34 | ??1.78 |
| ??C15H32 | ??2.61 | ??5.56 | ??8.17 | ??2.13 |
| ??C16H34 | ??2.33 | ??8.65 | ??10.98 | ??3.71 |
| ??C17H36 | ??1.99 | ??5.74 | ??7.72 | ??2.89 |
| ??C18H38 | ??1.51 | ??6.11 | ??7.62 | ??4.04 |
| ??C19H40 | ??1.60 | ??5.98 | ??7.58 | ??3.73 |
| ??C20H42 | ??1.18 | ??5.35 | ??6.53 | ??4.52 |
| ??C21H44 | ??0.58 | ??3.82 | ??4.41 | ??6.54 |
| ??C22H46 | ??0.22 | ??2.00 | ??2.23 | ??8.94 |
This diesel oil fuel mixed with various straight chain primary alcohols and measure cloud point.Add the 1-enanthol and do not make cloud point generation noticeable change, but add C
11+Alcohol has improved cloud point really.These results show, as the C as oxygenatedchemicals
16+When alcohol content surpasses 0.3wt% oxygen, can not realize+14 ℃ cloud point.Add the 1-hexanol and do not significantly improve cloud point, accomplished but add the 1-lauryl alcohol.Work as C
11+When alcohol is present in the temper with the 1-hexanol, in most of the cases still observed significantly improving of cloud point.High level 1-hexadecanol and 1-eicosanol envrionment temperature (with in addition at 50 ℃) under be insoluble.Therefore energy measurement cloud point not.They are much higher than+and 14 ℃.
| Experiment numbers | Alcohol | Actual measurement oxygen wt% | Cloud point | Note |
| ??1 | Do not have | ??0 | ??-18，-19；-20；-20 | |
| ??2 | The 1-hexanol | ??0.0010 | ??-19 | |
| ??3 | The 1-hexanol | ??0.0101 | ??-19 | |
| ??4 | The 1-hexanol | ??0.3000 | ??-20 | Solvable under envrionment conditions |
| ??5 | The 1-lauryl alcohol | ??0.0010 | ??-17 | |
| ??6 | The 1-lauryl alcohol | ??0.0101 | ??-14 | |
| ??7 | The 1-lauryl alcohol | ??0.2996 | ??-3 | Solvable under envrionment conditions |
| ??8 | The 1-hexadecanol | ??0.0010 | ??-19 | |
| ??9 | The 1-hexadecanol | ??0.0101 | ??-10 | |
| ??10 | The 1-hexadecanol | ??0.3000 | Can not detect | Soluble under envrionment conditions |
| ??11 | The 1-eicosanol | ??0.0010 | ??-12 | |
| ??12 | The 1-eicosanol | ??0.0100 | ??13 | Solvable under envrionment conditions |
| ??13 | The 1-eicosanol | ??0.2999 | Solid | Under envrionment conditions, can not hold and change solid into, can not measure cloud point |
| ??14 | Alcohol mixture | ??0.0010 | ??-18 | |
| ??15 | Alcohol mixture | ??0.0101 | ??-10 | |
| ??16 | Alcohol mixture | ??0.3000 | ??17 | Soluble under envrionment conditions |
Alcohol mixture is the mixture that waits 1-hexanol, 1-lauryl alcohol, 1-hexadecanol and the 1-eicosanol of wt%.
Embodiment 3
Further to obtain 250-400 (121-204 ℃) diesel fuel fractions, this cut has been simulated the No.1-D fuel with these character from the diesel product of embodiment 2 in distillation.
| Character | Value | Unit |
| Density under 20 ℃ | ??0.7269 | ??g?cm -1 |
| Refractive index under 20 ℃ | ??1.4096 | |
| Molecular weight | ??142 | Dalton |
| N-d-M analyzes | ||
| The % alkane belongs to carbon | ??98.42 | ??Wt％ |
| % cycloalkanes belongs to carbon | ??1.52 | ??Wt％ |
| % aromatics carbon | ??0.00 | ??Wt％ |
| The naphthenic ring of per molecule | ??0.03 | |
| The aromatic ring of per molecule | ??0.00 | |
| Cloud point | ??-60 | ??℃ |
| Sulphur | ??2.3 | Ppm weight |
| Nitrogen | ??0.178 | Ppm weight |
| Bromine index | ??228 | |
| By the aromatic substance that SFC surveyed | ||
| Single aromatic substance | ??＜0.5 | ??Wt％ |
| Polyaromatic compound | ??＜0.5 | ??Wt％ |
| Total aromatic substance | ??＜0.5 | ??Wt％ |
| ??FIAM(D1319) | ||
| Aromatic substance | ??1 | ??Vol％ |
| Alkene | ??0 | ??Vol％ |
| Paraffinic hydrocarbons/naphthenic hydrocarbon | ??99 | ??Vol％ |
| The n-paraffin analysis of being undertaken by carbon number | ||
| ??n-C 5 | ??0.01 | ??Wt％ |
| ??n-C 6 | ??0.01 | ??Wt％ |
| ??n-C 7 | ??0.50 | ??Wt％ |
| ??n-C 8 | ??11.13 | ??Wt％ |
| ??n-C 9 | ??16.42 | ??Wt％ |
| ??n-C 10 | ??16.97 | ??Wt％ |
| ??n-C 11 | ??13.59 | ??Wt％ |
| ??n-C 12 | ??0.46 | ??Wt％ |
| ??n-C 13Heavier | ??0.00 | ??Wt％ |
| Total normal paraffin | ??59.09 | ??Wt％ |
| By the distillation that D-2887 surveyed, by wt% decision °F | ??Wt％ | |
| ??St/5wt％ | ??196/256 | |
| ??10/30wt％ | ??260/304 | |
| ??50wt％ | ??330 | |
| ??70/90wt％ | ??350/388 | |
| ??95/99wt％ | ??389/406 |
These studies show that adding a spot of lauryl alcohol has significant harmful effect to cloud point.Add few oxygen, cause cloud point (survey, ℃) to substantially exceed the minimum cloud point limit-49 ℃ as ASTM D2500 as the 1-lauryl alcohol to 0.01wt%.Add C
5-C
10Alcohol does not cause the remarkable increase of cloud point.Above-mentioned all wt% oxygen concns are the benchmark metering with the anhydrous state.
Preferably has 1-C
5To 1-C
10FT Diesel alcohol examples of compositions as follows.
FT diesel oil with 1-enanthol
| Test number | 1-enanthol weight g | The weight g of diesel oil fuel | Gross weight g | 1-enanthol actual measurement wt% | 1-enanthol target wt% | Wt% oxygen | Cloud point ℃ |
| ??6 | ??0 | Do not add alcohol | Do not add alcohol | Do not add alcohol | Do not add alcohol | ??0 | ??--63 |
| ??7 | ??0.00597 | ??8.49875 | ??8.50472 | ??0.07 | ??0.0725 | ??0.01 | ??-61.6 |
| ??8 | ??0.03208 | ??4.38771 | ??4.41979 | ??0.73 | ??0.725 | ??0.10 | ??-58.8 |
FT diesel oil with 1-amylalcohol
| Test number | 1-amylalcohol weight g | The weight g of diesel oil | Gross weight g | 1-amylalcohol actual measurement wt% | 1-amylalcohol target wt% | Wt% oxygen | Cloud point ℃ |
| ??9 | ??0.00315 | ??6.00633 | ??6.00948 | ??0.05 | ??0.055 | ??0.01 | ??-61.6 |
| ??10 | ??0.03231 | ??6.02061 | ??6.05292 | ??0.53 | ??0.55 | ??0.10 | ??-55.8 |
FT diesel oil with 1-lauryl alcohol
| Test number | 1-lauryl alcohol weight g | The weight g of diesel oil fuel | Gross weight g | 1-lauryl alcohol actual measurement wt% | 1-lauryl alcohol target wt% | Wt% oxygen | Cloud point ℃ |
| ??11 | ??0.01050 | ??9.00597 | ??9.01647 | ??0.116 | ??0.11625 | ??0.01 | ??-37 |
| ??12 | ??0.06792 | ??6.00194 | ??6.06986 | ??1.119 | ??1.1625 | ??0.10 | ??-11 |
FT diesel oil with 1-decanol
| Test number | 1-decanol weight g | The weight g of diesel oil fuel | Gross weight g | 1-decanol actual measurement wt% | 1-decanol target wt% | Wt% oxygen | Cloud point ℃ |
| ??13 | ??0.0233 | ??23.9778 | ??24.0011 | ??0.10 | ??0.09875 | ??0.01 | ??-52 |
FT diesel oil with 1-octanol
| Test number | 1-decanol weight g | The weight g of diesel oil fuel | Gross weight g | 1-decanol actual measurement wt% | 1-decanol target wt% | Wt% oxygen | Cloud point ℃ |
| ??14 | ??0.00331 | ??4.00237 | ??4.00568 | ??0.083 | ??0.08125 | ??0.01 | ??-60.7 |
| ??15 | ??0.08838 | ??10.93777 | ??11.02615 | ??0.802 | ??0.8125 | ??0.10 | ??-61 |
These embodiment explanations, use n-alkanol for example 1-dodecanol can not obtain low cloud point, and can use C
5-C
10N-alkanol also obtains low cloud point, especially when the final boiling point of distillatory cut is lower than the embodiment of front and have medium isomery/positive structure ratio.
Claims (23)
1. be suitable as the Fischer-tropsch derived distillment of diesel oil fuel, its have by ASTM D93 measured minimum be 38 ℃ flash-point and+14 ℃ or lower cloud point, and contain be no less than 0.01wt% be selected from 1-amylalcohol, 1-hexanol, 1-enanthol, 1-octanol, 1 nonyl alcohol, 1-decanol and more than the oxygen at least two kinds of alcohol in the mixture of two kinds of alcohol, and contain the C of no more than 0.01wt%
11+Oxygen in the straight chain alcohol.
2. the Fischer-tropsch derived distillment of claim 1, wherein said cloud point is 0 ℃.
3. the Fischer-tropsch derived distillment of claim 2, wherein said cloud point is-15 ℃ or lower.
4. the Fischer-tropsch derived distillment of claim 3, wherein said cloud point is-25 ℃ or lower.
5. the Fischer-tropsch derived distillment of claim 4, wherein said cloud point is-49 ℃ or lower.
6. the Fischer-tropsch derived distillment of claim 1, wherein existing C
5-C
10Oxygenates level summation in the straight chain alcohol at 0.01wt% oxygen to the scope of 1wt% oxygen.
7. Fischer-tropsch derived distillment fuel preparation method, described method comprises:
(a) the Fischer-Tropsch condensation product is divided into first cut and second cut, wherein
(i) described first cut comprise the oxygen that is selected from the multiple alcohol in 1-amylalcohol, 1-hexanol, 1-enanthol, 1-octanol, 1 nonyl alcohol, 1-decanol and their mixture that is no less than 0.01wt% and no more than 0.01wt% at C
11+Oxygen in the straight chain alcohol and
(ii) described second cut comprises C
11+Straight chain alcohol;
(b) from least a portion of described second cut, remove described C
11+Straight chain alcohol, and recovery does not conform to C substantially
11+Last running after the processing of straight chain alcohol; With
(c) part with the last running after the processing of at least a portion of first cut of step a (i) and step (b) is in harmonious proportion in the proper ratio to prepare Fischer-tropsch derived distillment fuel, the wherein C of Cun Zaiing
5-C
10To the scope of 1wt% oxygen, cloud point is not higher than the oxygenates level summation of alcohol at 0.01wt% oxygen+and 14 ℃ and the flash-point measured by ASTM D93 are minimum to be 38 ℃.
8. the method for claim 7 wherein is in harmonious proportion described first cut and described second cut in the proper ratio and is not higher than 0 ℃ Fischer-tropsch derived distillment fuel with the preparation cloud point in step (c).
9. the method for claim 8 wherein is in harmonious proportion described first cut and described second cut in the proper ratio and is not higher than-15 ℃ Fischer-tropsch derived distillment fuel with the preparation cloud point in step (c).
10. the method for claim 7 wherein is divided into first cut, second cut and the 3rd cut with described Fischer-Tropsch condensation product, and wherein said first cut and second cut comprise C with described the 3rd cut as mentioned above
4-Straight chain alcohol.
11. the method for claim 7 is wherein handled described second cut to obtain the described C that do not contain substantially by the technology that is selected from hydrotreatment, hydrocracking, hydroisomerization, dehydration, absorption, absorption or their combination
11+Last running after the processing of straight chain alcohol.
12. cloud point is+14 ℃ or lower distillment fuel, improvements be to comprise be no less than 0.01wt% be selected from 1-amylalcohol, 1-hexanol, 1-enanthol, 1-octanol, 1 nonyl alcohol, 1-decanol and more than oxygen at least two kinds of alcohol in the mixture of two kinds of alcohol and no more than 0.01wt% at C
11+Oxygen in the straight chain alcohol.
13. the distillment fuel of claim 12, wherein said cloud point are 0 ℃ or lower.
14. the distillment fuel of claim 13, wherein said cloud point are-15 ℃ or lower.
15. the distillment fuel of claim 12, wherein existing C
5-C
10The oxygenates level summation of straight chain alcohol at 0.01wt% oxygen to the scope of 1wt% oxygen.
16. the diesel oil fuel of claim 12, wherein said alcohol are the C that total concn is less than 1wt% oxygen
5-C
10Any two kinds of straight chain alcohol.
17. the Fischer-tropsch derived distillment of claim 1, wherein said alcohol are the C that total concn is less than 1wt% oxygen
5-C
10Any two kinds of straight chain alcohol.
18. the Fischer-tropsch derived distillment of claim 7, wherein said alcohol are the C that total concn is less than 1wt% oxygen
5-C
10Any two kinds of straight chain alcohol.
19.
20. the Fischer-tropsch derived distillment of claim 19, it has the C of being selected from
5And C
6, C
5And C
7Or C
6And C
71-alcohol.
21. the method for claim 7, wherein said first cut also comprises C
8, C
9And C
101-alcohol and step b remove C from least a portion of described second cut
11+Straight chain alcohol and recovery do not contain C substantially
11+Last running after the processing of straight chain alcohol, and the part of the last running of step (c) after with the processing of at least a portion of first cut of step a (i) and step (b) is in harmonious proportion.
22. the diesel oil fuel of claim 12 also comprises and is selected from C
8, C
9And C
10And the multiple 1-alcohol of these pure mixtures and wherein paraffinic hydrocarbons at least 90% be isoparaffin.
23. the diesel oil fuel of claim 1 also comprises and is selected from C
8, C
9And C
10And the multiple 1-alcohol of these pure mixtures and wherein paraffinic hydrocarbons at least 90% be isoparaffin.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US86835806P | 2006-12-04 | 2006-12-04 | |
| US60/868,358 | 2006-12-04 | ||
| PCT/US2007/086401 WO2008070677A1 (en) | 2006-12-04 | 2007-12-04 | Fischer-tropsch derived diesel fuel and process for making same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101679883A true CN101679883A (en) | 2010-03-24 |
Family
ID=39492612
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200780044879A Pending CN101679883A (en) | 2006-12-04 | 2007-12-04 | Fischer-tropsch derived diesel fuel and process for making same |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US20080155889A1 (en) |
| JP (1) | JP2010522249A (en) |
| CN (1) | CN101679883A (en) |
| AU (1) | AU2007329380A1 (en) |
| GB (1) | GB2457190A (en) |
| WO (1) | WO2008070677A1 (en) |
| ZA (1) | ZA200903686B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110628473A (en) * | 2018-06-22 | 2019-12-31 | 内蒙古伊泰煤基新材料研究院有限公司 | Oil performance modifier and preparation method and application thereof |
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|---|---|---|---|---|
| GB2462044B (en) * | 2007-05-31 | 2011-12-14 | Sasol Tech Pty Ltd | Cold flow response of diesel fuels |
| JP5417329B2 (en) * | 2009-03-13 | 2014-02-12 | Ｊｘ日鉱日石エネルギー株式会社 | Method for producing low sulfur gas oil base and low sulfur gas oil |
| WO2013188917A1 (en) * | 2012-06-19 | 2013-12-27 | Linc Energy Ltd | Solution for coal condensate |
| US20150014222A1 (en) * | 2013-07-09 | 2015-01-15 | David Tessel | Systems and methods for using gas to liquids (gtl) technology |
| FI20176132A1 (en) * | 2017-12-18 | 2019-06-19 | Neste Oyj | Fuel compositions |
| CN115698230A (en) * | 2020-06-17 | 2023-02-03 | 国际壳牌研究有限公司 | Process for the preparation of fischer-tropsch derived middle distillates and base oils |
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| DE1812339B2 (en) * | 1968-12-03 | 1977-03-10 | Bayer Ag, 5090 Leverkusen | PROCESS FOR THE PRODUCTION OF SYNTHETIC ZEOLITHES WITH THE CRYSTAL STRUCTURE OF FAUJASITE |
| US3789107A (en) * | 1971-05-04 | 1974-01-29 | Grace W R & Co | Process for producing a crystalline zeolite |
| US3852207A (en) * | 1973-03-26 | 1974-12-03 | Chevron Res | Production of stable lubricating oils by sequential hydrocracking and hydrogenation |
| US3904513A (en) * | 1974-03-19 | 1975-09-09 | Mobil Oil Corp | Hydrofinishing of petroleum |
| DE2437914A1 (en) * | 1974-08-07 | 1976-02-19 | Bayer Ag | PROCESS FOR PRODUCING SYNTHETIC ZEOLITE WITH FAUJASITE STRUCTURE |
| US4157294A (en) * | 1976-11-02 | 1979-06-05 | Idemitsu Kosan Company Limited | Method of preparing base stocks for lubricating oil |
| US4401556A (en) * | 1979-11-13 | 1983-08-30 | Union Carbide Corporation | Midbarrel hydrocracking |
| US4347121A (en) * | 1980-10-09 | 1982-08-31 | Chevron Research Company | Production of lubricating oils |
| US4820402A (en) * | 1982-05-18 | 1989-04-11 | Mobil Oil Corporation | Hydrocracking process with improved distillate selectivity with high silica large pore zeolites |
| US4440871A (en) * | 1982-07-26 | 1984-04-03 | Union Carbide Corporation | Crystalline silicoaluminophosphates |
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| US4913799A (en) * | 1984-12-18 | 1990-04-03 | Uop | Hydrocracking catalysts and processes employing non-zeolitic molecular sieves |
| SE8602341D0 (en) * | 1986-05-22 | 1986-05-22 | Eka Nobel Ab | SET TO MAKE A MODIFIED ZEOLIT Y |
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-
2007
- 2007-12-04 AU AU2007329380A patent/AU2007329380A1/en not_active Abandoned
- 2007-12-04 ZA ZA200903686A patent/ZA200903686B/en unknown
- 2007-12-04 CN CN200780044879A patent/CN101679883A/en active Pending
- 2007-12-04 US US11/950,175 patent/US20080155889A1/en not_active Abandoned
- 2007-12-04 WO PCT/US2007/086401 patent/WO2008070677A1/en active Search and Examination
- 2007-12-04 JP JP2009540426A patent/JP2010522249A/en not_active Abandoned
-
2009
- 2009-05-29 GB GB0909228A patent/GB2457190A/en not_active Withdrawn
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110628473A (en) * | 2018-06-22 | 2019-12-31 | 内蒙古伊泰煤基新材料研究院有限公司 | Oil performance modifier and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| GB2457190A (en) | 2009-08-12 |
| AU2007329380A1 (en) | 2008-06-12 |
| ZA200903686B (en) | 2010-08-25 |
| GB0909228D0 (en) | 2009-07-15 |
| US20080155889A1 (en) | 2008-07-03 |
| JP2010522249A (en) | 2010-07-01 |
| WO2008070677A1 (en) | 2008-06-12 |
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