CN102066527A - An integrated process for producing diesel fuel from biological material and products and uses relating to said process - Google Patents
An integrated process for producing diesel fuel from biological material and products and uses relating to said process Download PDFInfo
- Publication number
- CN102066527A CN102066527A CN2008801299579A CN200880129957A CN102066527A CN 102066527 A CN102066527 A CN 102066527A CN 2008801299579 A CN2008801299579 A CN 2008801299579A CN 200880129957 A CN200880129957 A CN 200880129957A CN 102066527 A CN102066527 A CN 102066527A
- Authority
- CN
- China
- Prior art keywords
- hydrocarbon
- paraffinic hydrocarbons
- fuel
- fischer
- hydrocarbon stream
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000000034 method Methods 0.000 title claims abstract description 152
- 230000008569 process Effects 0.000 title claims abstract description 79
- 239000002283 diesel fuel Substances 0.000 title claims abstract description 50
- 239000012620 biological material Substances 0.000 title claims abstract description 6
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 291
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 287
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 284
- 238000006243 chemical reaction Methods 0.000 claims abstract description 45
- 238000012545 processing Methods 0.000 claims abstract description 31
- 239000006227 byproduct Substances 0.000 claims abstract description 29
- 238000009826 distribution Methods 0.000 claims abstract description 13
- 230000003197 catalytic effect Effects 0.000 claims abstract description 11
- 239000000446 fuel Substances 0.000 claims description 100
- 229910052739 hydrogen Inorganic materials 0.000 claims description 91
- 239000001257 hydrogen Substances 0.000 claims description 90
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 80
- 238000005336 cracking Methods 0.000 claims description 71
- 238000006317 isomerization reaction Methods 0.000 claims description 64
- 239000007789 gas Substances 0.000 claims description 57
- 238000005984 hydrogenation reaction Methods 0.000 claims description 48
- 239000003921 oil Substances 0.000 claims description 34
- 230000009183 running Effects 0.000 claims description 33
- 230000010354 integration Effects 0.000 claims description 32
- 238000007600 charging Methods 0.000 claims description 28
- 239000002699 waste material Substances 0.000 claims description 28
- 239000002994 raw material Substances 0.000 claims description 27
- 239000002028 Biomass Substances 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 22
- 239000002253 acid Substances 0.000 claims description 20
- 238000005194 fractionation Methods 0.000 claims description 18
- 229920001131 Pulp (paper) Polymers 0.000 claims description 16
- 238000000926 separation method Methods 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 241000196324 Embryophyta Species 0.000 claims description 14
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 13
- 239000005864 Sulphur Substances 0.000 claims description 13
- 238000009795 derivation Methods 0.000 claims description 12
- 229910052799 carbon Inorganic materials 0.000 claims description 11
- 241000202567 Fatsia japonica Species 0.000 claims description 10
- 241001465754 Metazoa Species 0.000 claims description 10
- -1 alkane hydrocarbon Chemical class 0.000 claims description 9
- 239000012978 lignocellulosic material Substances 0.000 claims description 9
- 239000003784 tall oil Substances 0.000 claims description 8
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 7
- 241000251468 Actinopterygii Species 0.000 claims description 6
- 238000013459 approach Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 238000004523 catalytic cracking Methods 0.000 claims description 5
- 238000010977 unit operation Methods 0.000 claims description 5
- 239000000654 additive Substances 0.000 claims description 4
- 238000011084 recovery Methods 0.000 claims description 4
- 229920006395 saturated elastomer Polymers 0.000 claims description 4
- 239000002440 industrial waste Substances 0.000 claims description 3
- 239000002154 agricultural waste Substances 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims description 2
- 239000007858 starting material Substances 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims 1
- 125000004432 carbon atom Chemical group C* 0.000 claims 1
- 239000012075 bio-oil Substances 0.000 abstract description 3
- 239000006280 diesel fuel additive Substances 0.000 abstract description 3
- 235000014593 oils and fats Nutrition 0.000 abstract 1
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 32
- 235000019198 oils Nutrition 0.000 description 31
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 27
- 238000009835 boiling Methods 0.000 description 21
- 239000003054 catalyst Substances 0.000 description 18
- 239000000047 product Substances 0.000 description 18
- 150000002431 hydrogen Chemical class 0.000 description 16
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerol Natural products OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 13
- 238000002309 gasification Methods 0.000 description 13
- 239000012188 paraffin wax Substances 0.000 description 13
- 229910002091 carbon monoxide Inorganic materials 0.000 description 12
- 238000004821 distillation Methods 0.000 description 12
- 238000004519 manufacturing process Methods 0.000 description 11
- 239000001993 wax Substances 0.000 description 11
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 10
- 230000008676 import Effects 0.000 description 10
- 239000002023 wood Substances 0.000 description 10
- 230000008901 benefit Effects 0.000 description 8
- 150000002632 lipids Chemical class 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- CZRCFAOMWRAFIC-UHFFFAOYSA-N 5-(tetradecyloxy)-2-furoic acid Chemical compound CCCCCCCCCCCCCCOC1=CC=C(C(O)=O)O1 CZRCFAOMWRAFIC-UHFFFAOYSA-N 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 230000007246 mechanism Effects 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- 238000007670 refining Methods 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 150000001721 carbon Chemical group 0.000 description 5
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 5
- 239000003925 fat Substances 0.000 description 5
- 235000011187 glycerol Nutrition 0.000 description 5
- 239000012528 membrane Substances 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000010457 zeolite Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000002551 biofuel Substances 0.000 description 4
- 150000001720 carbohydrates Chemical class 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 239000003350 kerosene Substances 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- 239000002808 molecular sieve Substances 0.000 description 4
- 239000000123 paper Substances 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 4
- 239000003760 tallow Substances 0.000 description 4
- 235000013311 vegetables Nutrition 0.000 description 4
- 239000002351 wastewater Substances 0.000 description 4
- 239000002916 wood waste Substances 0.000 description 4
- 208000016444 Benign adult familial myoclonic epilepsy Diseases 0.000 description 3
- 229910003294 NiMo Inorganic materials 0.000 description 3
- 229910021536 Zeolite Inorganic materials 0.000 description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 description 3
- 239000003225 biodiesel Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229920002678 cellulose Polymers 0.000 description 3
- 239000001913 cellulose Substances 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000009977 dual effect Effects 0.000 description 3
- 208000016427 familial adult myoclonic epilepsy Diseases 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 235000019387 fatty acid methyl ester Nutrition 0.000 description 3
- ZGNITFSDLCMLGI-UHFFFAOYSA-N flubendiamide Chemical compound CC1=CC(C(F)(C(F)(F)F)C(F)(F)F)=CC=C1NC(=O)C1=CC=CC(I)=C1C(=O)NC(C)(C)CS(C)(=O)=O ZGNITFSDLCMLGI-UHFFFAOYSA-N 0.000 description 3
- 239000000314 lubricant Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000005809 transesterification reaction Methods 0.000 description 3
- 238000005292 vacuum distillation Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 244000025254 Cannabis sativa Species 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 229910000323 aluminium silicate Inorganic materials 0.000 description 2
- 235000011089 carbon dioxide Nutrition 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 238000006477 desulfuration reaction Methods 0.000 description 2
- 230000023556 desulfurization Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 235000021323 fish oil Nutrition 0.000 description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 239000002655 kraft paper Substances 0.000 description 2
- 239000010687 lubricating oil Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000010902 straw Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000010512 thermal transition Effects 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 description 2
- 238000004148 unit process Methods 0.000 description 2
- ZEMPKEQAKRGZGQ-AAKVHIHISA-N 2,3-bis[[(z)-12-hydroxyoctadec-9-enoyl]oxy]propyl (z)-12-hydroxyoctadec-9-enoate Chemical compound CCCCCCC(O)C\C=C/CCCCCCCC(=O)OCC(OC(=O)CCCCCCC\C=C/CC(O)CCCCCC)COC(=O)CCCCCCC\C=C/CC(O)CCCCCC ZEMPKEQAKRGZGQ-AAKVHIHISA-N 0.000 description 1
- 241000609240 Ambelania acida Species 0.000 description 1
- 241000370685 Arge Species 0.000 description 1
- 241000195493 Cryptophyta Species 0.000 description 1
- 229920002488 Hemicellulose Polymers 0.000 description 1
- 206010021143 Hypoxia Diseases 0.000 description 1
- 235000019484 Rapeseed oil Nutrition 0.000 description 1
- 235000019486 Sunflower oil Nutrition 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000010905 bagasse Substances 0.000 description 1
- 239000002199 base oil Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000828 canola oil Substances 0.000 description 1
- 235000019519 canola oil Nutrition 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 238000005314 correlation function Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006392 deoxygenation reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 238000005243 fluidization Methods 0.000 description 1
- 235000021588 free fatty acids Nutrition 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 208000018875 hypoxemia Diseases 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000010893 paper waste Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002600 sunflower oil Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000001131 transforming effect Effects 0.000 description 1
- 125000005457 triglyceride group Chemical group 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000005418 vegetable material Substances 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- ABDKAPXRBAPSQN-UHFFFAOYSA-N veratrole Chemical compound COC1=CC=CC=C1OC ABDKAPXRBAPSQN-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Images
Classifications
-
- 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
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
-
- 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
- C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
- C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
- C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
-
- 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
- C10G3/44—Catalytic treatment characterised by the catalyst used
- C10G3/45—Catalytic treatment characterised by the catalyst used containing iron group metals or compounds thereof
- C10G3/46—Catalytic treatment characterised by the catalyst used containing iron group metals or compounds thereof in combination with chromium, molybdenum, tungsten metals or compounds thereof
-
- 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
- C10G3/50—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids in the presence of hydrogen, hydrogen donors or hydrogen generating compounds
-
- 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
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/58—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
-
- 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
- C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
- C10G65/14—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural parallel stages only
- C10G65/16—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural parallel stages only including only refining steps
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
-
- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1011—Biomass
- C10G2300/1014—Biomass of vegetal origin
-
- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1011—Biomass
- C10G2300/1018—Biomass of animal origin
-
- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1022—Fischer-Tropsch products
-
- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/30—Physical properties of feedstocks or products
- C10G2300/304—Pour point, cloud point, cold flow properties
-
- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/30—Physical properties of feedstocks or products
- C10G2300/307—Cetane number, cetane index
-
- 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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/04—Diesel oil
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
- C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
- C10J2300/0913—Carbonaceous raw material
- C10J2300/0916—Biomass
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
- C10J2300/16—Integration of gasification processes with another plant or parts within the plant
- C10J2300/164—Integration of gasification processes with another plant or parts within the plant with conversion of synthesis gas
- C10J2300/1656—Conversion of synthesis gas to chemicals
- C10J2300/1659—Conversion of synthesis gas to chemicals to liquid hydrocarbons
-
- 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
- Y02E50/10—Biofuels, e.g. bio-diesel
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/141—Feedstock
- Y02P20/145—Feedstock the feedstock being materials of biological origin
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Combustion & Propulsion (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Liquid Carbonaceous Fuels (AREA)
Abstract
The present invention relates to an integrated process for producing diesel fuel or fuel additive from biological material by producing paraffins by a Fischer-Tropsch reaction on one hand and by a catalytic hydrodeoxygenation of bio oils and fats on the other hand. Two hydrocarbon streams, which both comprises predominately hydrocarbons of a certain chain length are treated separately and finally combined and distilled together. The invention also relates to the use of by-products of the wood- processing industry for producing diesel fuel and to a method for narrowing the chain length distribution of Fischer-Tropsch derived diesel fuel. The invention provides a high-quality middle distillate fraction from various biological sources and most preferably from by-products of the wood-processing industry.
Description
Technical field
The present invention relates to from biological raw material, produce the integration method of diesel oil fuel by producing paraffinic hydrocarbons, described method has been utilized fischer-tropsch (FT) reaction on the one hand, has utilized the catalytic hydrodeoxygenation reaction (HDO) of biological hydrocarbon on the other hand.The FT paraffinic hydrocarbons is separated into the long different cut of hydrocarbon chain, is handled respectively then.The byproduct that the invention still further relates to lignocellulosic material such as wood-processing industry is in the application of producing aspect the diesel oil fuel, and to the chain length distribution method that narrows of Fisher-Tropsch derived diesel oil fuel.The invention provides and derive from various biogenetic derivations, most preferably derive from the high-quality middle runnings of the byproduct of wood-processing industry.The present invention also provides the application of described cut as cetane number improver.
Background technology
The obnoxious flavour that is discharged in reserves that fossil oil is exhausted day by day and the use thereof makes people pay close attention to biological raw material all the more, especially is the utilization of non-edible-type renewable biological source, is used to prepare the liquid fuel of alternative fossil oil.At present known have Several Methods to can be used for producing liquid fuel from biological raw material.Wherein, be by the transesterification reaction production biofuel (FAME) of biomass-derived oil in commercial a kind of method of having succeeded with alcohol.But, because of FAME pour point height, instability, and incompatible with the automobile that uses particulate filter, so the application of method is restricted.
The gasifying biomass method has been used for many years, and these class methods can be the energy with Wood Adhesives from Biomass.One of application time method at most is the gas mixture (CO+H that the gasification back is produced
2) directly as the fuel of oil engine.As long as water content is 5%-35%, almost the biomass of any kind of are all gasifiable.The example in suitable biomass source comprises trees branches and leaves, city waste wood, papermaking byproduct and waste material, Wood waste, wood chip, sawdust, straw, firewood, agricultural residue, muck etc.
Be under the controlled condition of feature with hypoxemia and high temperature, most biological materials can be converted into the geseous fuel that is called synthetic gas.United States Patent (USP) has been described the gasification of cellulose biomass in single still No. 4592762, and it is a single back mixed fluidized bed of cellulose biomass directly being sent into the high heat capacity inert solid.US 4968325 has disclosed a kind of equipment for gasification, and it has autoclave, comprises the husky bed of fluidisation of heat in the still.With biomass predrying be 10 weight %-35 weight % to water content.Under 400 kPas-1750 kPas operating pressure,, the working temperature of fluidized-bed is remained on 750-860 ℃ by the input rate of controlling flow gasification and the feeding rate of biomass.
The synthetic gas that derives from renewable source and fossil sources all has been used for by the synthetic liquid fuel of producing of fischer-tropsch.US 2007/0225383 has disclosed a kind of method, and being used for Wood Adhesives from Biomass is synthetic gas, and the Fischer-Tropsch reaction that makes this synthesis gas reaction generate fuel and chemical is provided.The gasification reaction that the heat that this invention produces the Fischer-Tropsch reaction of heat release is used to absorb heat, thus the reaction energy balance improved.
Standard three-phase slurry Fischer-Tropsch process adopts heterogeneous cobalt catalyst usually, and the main n-paraffin with wide molecular weight distribution that produces specifically depends on one group of working conditions.The mixture of gained hydrocarbon need be processed in the following process device, to obtain useful fuel.The typical processing comprises isomerization/cracking step, adopts the known catalysts that comprises the VII family metal on molecular sieve or zeolite and the carrier.
The catalyzer that is used for the fischer-tropsch paraffinic hydrocarbons should have cracking and isomerization function simultaneously.Cracking is blocked long chain hydrocarbon and is the short chain in the diesel range (middle runnings), and isomerization increases methyl side groups along carbochain, reduces the pour point and the cloud point of middle distillate product.Recommended the catalyzer of aluminosilicate zeolites of intermediate pore size (ZSM) and aluminosilicophosphate (SAPO) molecular sieve as dewaxing technique.
This area is well-known, but the silicoaluminophosphamolecular molecular sieve SAPO isomerization long chain alkane of intermediate pore size and can not make it cracking, but the aluminosilicate zeolites ZSM-5 of intermediate pore size and ZMS 23 can carry out cracking and isomerization simultaneously.Therefore, United States Patent (USP) has disclosed a kind of method No. 5833837, and this method is distilled the waxy oil raw material, obtains two independently wax slops, i.e. heavy and light lubricating oil base oil.Lighting end is with the isomerization of non-cracking SAPO type catalyzer, and last running is with having the ZSM-5 zeolite treatment of cracking.
It also is known producing liquid fuel by the biological raw material that comprises glycerin fatty acid ester or free fatty acids.These raw materials comprise high-load oxygen and a spot of sulphur, phosphorus, nitrogen, and they are known catalyst posions.US4992605 has disclosed by hydrotreatment vegetables oil such as Canadian Canola oil, sunflower oil, soybean oil or rapeseed oil and has produced C
15-C
18Paraffinic hydrocarbons.US 5705722 has disclosed the method for producing the hydrocarbon component in the diesel range, and it is vegetables oil, Yatall MA, fractionation Yatall MA, animal tallow and composition thereof to be carried out hydrogenation deoxidation (HDO) handle.Raw material is at hydroprocessing condition contact hydrogen and Hydrobon catalyst such as NiMo/Al
2O
3Or CoMo/Al
2O
3This patent is described as products obtained therefrom to have the diesel fuel additive of high n-Hexadecane number.
FI 100248 has disclosed the two-step approach by the vegetable oil production middle distillate, earlier oil is carried out hydrogenation, obtains n-paraffin, to the alkane hydrocarbon isomerisation, obtains branched paraffin then.7232935 couples of FI 100248 of US have done improvement, and pre-hydrogenation step was adopted in suggestion before hydrogenation deoxidation, and carry out isomerization with reflux type.US 7279018 has disclosed a kind of fuel composition, and it comprises: a) component that is obtained by hydrogenation and isomerization by animal tallow; B) oxygen-containing component, described component a) and b) mix or be dissolved in c) in the diesel component based on crude oil or fischer-tropsch distillate.A kind of method of utilizing triglyceride level to provide high n-Hexadecane to count diesel oil has been provided US 2007/0068848, and it combines thermally splitting and catalytic hydroprocessing, and reclaiming cetane value by distillation then is the diesel fuel fractions of 70-80.
Although relevantly utilize research and development that renewable resources produces fuel also to carry out continuing, people still need to improve one's methods, and utilize or do not utilize under the prerequisite of edible-type plant resources few, provide high-quality diesel oil fuel with rudimentary raw material.People also need to utilize industrial waste production nearby, to exempt high transportation and to store cost.
FI 20075794 has disclosed a kind of by producing the integration method that paraffinic hydrocarbons is produced diesel oil fuel with biological raw material, this method is utilized fischer-tropsch (FT) reaction on the one hand, utilize catalytic hydrodeoxygenation reaction (HDO) on the other hand, wherein except that the lighting end from FT, cracking/isomerization all takes place in whole hydrocarbon stream.
The invention provides the high-quality diesel oil fuel from full Biological resources, it is that two independent solutions of industrial production biofuel are joined together, and avoids overcracking by separating the essentially identical hydrocarbon of chain length.
Summary of the invention
The present invention relates to produce the integration method of diesel oil fuel by biological raw material.Described method is characterised in that following a few step: the hydrocarbon that a) separates different chain length in the fischer-tropsch paraffinic hydrocarbons with biogenetic derivation; B) provide first hydrocarbon stream, it comprises the C in the described fischer-tropsch paraffinic hydrocarbons that catalytic cracking/isomerization is handled
21-C
100+Hydrocarbon; C) provide second hydrocarbon stream, it comprises by what biological hydrocarbon is carried out catalytic hydrodeoxygenation obtains and mainly contains C
15-C
18First cut of hydrocarbon, and contain C in the described fischer-tropsch paraffinic hydrocarbons
5-C
20Second cut of hydrocarbon; D) mix described first and second hydrocarbon streams; E) fractionation gained mixing hydrocarbon stream; And f) reclaims middle runnings, preferably be rich in C
15-C
18Hydrocarbon.
The objective of the invention is hydrogenation deoxidation (HDO) and fischer-tropsch (FT) method are combined, produce the high-quality alkane biodiesel fuel of aromatic free, oxygen and sulphur.A purpose is the fuel that the production quality is better than alligatoring ground mass diesel oil fuel and FAME biofuel.
Another object of the present invention is at utmost to bring into play the operation usefulness of common treatment unit in FT and the HDO fuel production technology.In the present invention, all, merge at last, reclaim middle distillate again based on two bursts of hydrocarbon stream separate treatment of the hydrocarbon of certain chain lengths.Yet, owing to the hydrocarbon of certain chain lengths is handled together, so also avoided hydrocarbon stream is carried out unnecessary processing.
According to an embodiment of integration method of the present invention, hydrogen is round-robin in whole process.In integration method, hydrogen not only produces but also consume in each reaction.In the method, by recovery, conversion and round-robin associated plant are provided for hydrogen, can obtain technical benefit.
An advantage of integration method is to produce hydrogen automatically.This has increased and has been the degree of freedom of fuel production addressing, because there is no need near the petrochemical plant of producing hydrogen.When using Wood waste and byproduct,, can obtain great benefit near paper pulp papermaking factory with regard to energy integration, material transportation, storage and waste disposal.
The invention still further relates to the waste material of lignocellulosic material such as wood-processing industry and/or byproduct and be used for the application of producing diesel oil fuel by pure biological renewable resources.Application according to the present invention may further comprise the steps: a) gasification lignocellulosic material, as comprise the biomass of Wood waste and/or byproduct, and be used to provide the fischer-tropsch paraffinic hydrocarbons, described paraffinic hydrocarbons is separated into the different cut of hydrocarbon chain length; B) then, under isomerisation conditions, to comprising the C in the described fischer-tropsch paraffinic hydrocarbons
21-C
100+The cut of hydrocarbon carries out cracking, obtains first hydrocarbon stream; C) under non-cracking conditions, optional to comprising biological hydrocarbon C in the fischer-tropsch paraffinic hydrocarbons and as described in comprising as first cut of Yatall MA or ready denier oil acid
5-C
20Second cut of hydrocarbon carries out isomerization, obtains second hydrocarbon stream, and wherein said biological hydrocarbon produces through hydrogenation deoxidation and mainly contains C
15-C
18The alkane hydrocarbon stream, preferred normal paraffin hydrocarbon stream, described C
5-C
20Hydrocarbon is optional through hydrogenation deoxidation; D) two strands of hydrocarbon streams are merged, carry out fractionation; And e) reclaims middle runnings, preferably be rich in C
15-C
18Hydrocarbon.
The invention still further relates to the chain length distribution method that narrows that makes the diesel oil fuel that is derived from Fischer-Tropsch reaction.Said method comprising the steps of: the C that a) will be derived from Fischer-Tropsch reaction
5-C
20Hydrocarbon with obtain by biological hydrocarbon hydrogenation deoxidation mainly contain C
15-C
18Hydrocarbon merge, obtain hydrocarbon stream; B) with this hydrocarbon stream and the C that is derived from Fischer-Tropsch reaction
21-C
100+Hydrocarbon hydrocarbon stream after the cracking under isomerisation conditions merges, and is combined hydrocarbon stream and carries out fractionation; And c) reclaims C
11-C
20Hydrocarbon-fraction preferably is rich in C
15-C
18Hydrocarbon.Preferably, the C of 5%-95%
1-C
100+First hydrocarbon stream of hydrocarbon and second hydrocarbon stream of 5%-95% merge.
The invention still further relates to the biological middle runnings that can obtain by method of the present invention, it comprises second hydrocarbon stream of the hydrocarbon that mainly comprises 15-18 carbon atom of first hydrocarbon stream of 5%-95% and 5%-95%.Described cut comprises at least 25% usually, preferably the C of about 40%-80%
15-C
18Hydrocarbon.Described cut even can comprise and surpass 80% C
15-C
18Hydrocarbon.
Middle runnings can directly be used as diesel oil fuel.But, the invention still further relates to biological middle runnings, be used to improve cetane value and/or the cloud point or the pour point of the fuel of producing by additive method as Application of Additives.
The present invention also provides the equipment of being produced fuel by biological raw material.Described equipment comprises the hydrogenation deoxidation reactor, is used for hydrogenation deoxidation is carried out in biological hydrocarbon charging, and optional to the C in the FT paraffinic feedstock with biogenetic derivation
5-C
20Hydrocarbon-fraction carries out hydrogenation deoxidation; Cracking/isomerization reactor is used for the C to the fischer-tropsch paraffinic feedstock with biogenetic derivation
21-C
100+Hydrocarbon-fraction carries out catalytic cracking and isomerization; Tripping device is used to distill merging hydrocarbon charging from described reactor, is recovered in 150-400 ℃ of ebullient middle distillate, is separated in lesser temps ebullient overhead fraction; Hydrogen separation device, for example permeable hydrogen membrane is used for hydrogen is separated from described overhead fraction, and described hydrogen is sent into the mechanism of described reactor, also has the mechanism that more hydrogen are provided to described reactor from the impermeable part of described overhead fraction.
One of advantage of the present invention is in shared processor different hydrocarbon streams to be carried out integration processing.Therefore, avoided the eclipsed processing unit (plant).
In an embodiment of the invention, described integration fuel production equipment has further been integrated the equipment of paper pulp papermaking factory, thereby the waste material and the byproduct that produce in the paper pulp papermaking technology can be sent into fuel engineering, and energy that produces in the fuel engineering and waste material can be supplied with paper pulp papermaking factory.
Description of drawings
Fig. 1 is the indicative flowchart of expression an embodiment of the invention.
Fig. 2 is the indicative flowchart of expression another embodiment of the invention.
Fig. 3 is a schema shown in Figure 2, has wherein set the mass balance measurement point.
Fig. 4 is the indicative flowchart of expression another embodiment of the invention.
Fig. 5 is the indicative flowchart of expression another embodiment of the invention.
Fig. 6 is the indicative flowchart of expression another embodiment of the invention.
Embodiment
The invention provides a kind of integration method, be used for producing senior diesel oil fuel by two kinds of different biological raw material sources.By merging the hydrocarbon stream of two kinds of different sourcess, what be improved in the fractionation that merges stream is chain length distribution.This method has obtained having the fuel of improved cetane value and cloud point.Generations by combination water distilling apparatus, hydrogenation deoxidation, non-cracking isomerization, hydrogen recycle and conversion, waste disposal, energy etc., the integration of described method has also obtained technical advantages.
In specification sheets of the present invention and claims, following term has hereinafter defined implication." integration method " is meant the method that two or more correlation functions that can independently carry out are combined, thereby to have an important method step at least be that these two kinds of methods are total.
In this manual, term " biofuel " only refers to be produced and oxygen containing traditional biological fuel product by transesterification reaction by biomass-derived oil and alcohol.
" biodiesel fuel " produced according to the invention or " diesel oil fuel of biogenetic derivation " are based on the diesel oil fuel of the technology beyond the transesterification reaction.Diesel oil fuel of the present invention is substantially free of oxygen.
Term " middle distillate " is to be generally the hydrocarbon of 11-20 by carbon chain lengths basically (note is made C
11-C
20) hydrocarbon-fraction formed.The boiling point of middle runnings is usually in 150-400 ℃, preferred 175-350 ℃ scope.The centre distillates hydrocarbon usually as diesel oil fuel.Should be pointed out that because distillation can not be well-separated with hydrocarbon by concrete chain length, so various cut may comprise the low slightly or high slightly hydrocarbon of very small amount of carbon chain lengths.Cut-out point in the distillation is looked the target purposes of middle distillate and required character and is changed slightly.Therefore, comprise the carbohydrate (carbohydrate) of relative broad range as C
9-C
22Or than the carbohydrate (carbohydrate) of close limit as C
14-C
18Cut also be interpreted as middle runnings.
Term " last running " is meant the hydrocarbon-fraction of being made up of above 20 hydrocarbon carbon chain lengths basically.In this manual, this cut note is made C
21-C
100+" 100+ " is meant that carbon atom nearly 100 reaches above uncertain value, specifically depends on FT process and the cracking/isomerized condition of carrying out.It is less usually that carbon chain lengths surpasses 100 hydrocarbon, but described cut even may to comprise chain length be 200 or higher molecule.
What term " naphtha fraction " was meant that distillation obtains is that (note is made C for the hydrocarbon of 5-10 by carbon chain lengths basically
5-C
10) hydrocarbon-fraction formed.The naphtha fraction hydrocarbon as light fuel, solvent or raw material, for example is used for based on steam cracked treating processes usually.
Term " kerosene(oil)fraction " is meant that being included in the middle distillate defined above is that (note is made C for the hydrocarbon of 11-15 by carbon chain lengths basically
11-C
15) hydrocarbon-fraction formed.The kerosene(oil)fraction hydrocarbon is usually as jet fuel.
Term " lighting end " is meant that (note is made C by chain length 1-4
1-C
4) the hydrocarbon-fraction formed of hydrocarbon.Lighting end also comprises other gaseous components, as hydrogen and carbon monoxide, specifically depends on the process that produces lighting end.
Term " mainly contains C
15-C
18Hydrocarbon " be wherein to surpass 60%, preferably surpass 80%, most preferably surpass the hydrocarbon stream that 90% hydrocarbon comprises 15-18 carbon atom.Hydrocarbon from factory almost only comprises C usually
14-C
18Hydrocarbon, wherein C
15-C
18Be the abundantest.
Term " synthesis gas " or " synthetic gas " are meant and comprise the carbon monoxide that is produced through gasification by carbonaceous material of various content and the gas mixture of hydrogen.The gasification of biological raw material can provide certain hydrogen/carbon monoxide ratio, and this ratio is about 2.Described gas is fit to obtain hydrocarbon by fischer-tropsch is synthetic, particularly after having added some extra hydrogen.
" fischer-tropsch " is synthetic to be a kind of catalyzed chemical reaction, and hydrogen and carbon monoxide are converted into the hydrocarbon chain of the different lengths that has Gaussian distribution basically, and (note is made C
1-C
100x+).Used typical catalyst is based on the catalyzer of iron and cobalt.Term " fischer-tropsch condition " is meant the reaction conditions that is fit to carry out Fischer-Tropsch reaction.For producing diesel oil fuel, so-called α value (the α value is the numerical value between the 0-1, and the α value of methane is minimum, and the α value of solid wax is the highest) should be higher, preferably approaches 0.89, and it is the maximum α value of middle distillate.This condition is well known in the art, and bibliographical information is arranged.
Term " separation " is meant that the hydrocarbon with different chain length in the FT paraffinic hydrocarbons of biogenetic derivation is separated into different fractions, perhaps separates in the FT process, perhaps separates by one or more independent processing devices.Described separation is undertaken by distillation, flash separation [under reduced pressure gas (steam) being separated from liquid ingredient], condensation or other any suitable separation methods.
Term " narrow chain length distribution " is meant at this branch and plants that hydrocarbon stream or cut have significantly more certain chain lengths than the hydrocarbon stream or the cut of Gaussian distribution.The synthetic hydrocarbon that provides of fischer-tropsch has wide (Gauss) chain length distribution (C
1-C
100+), and the hydrogenation deoxidation of bio oil, fat, wax or lipid acid can provide very narrow chain length distribution (mainly be C
15-C
18).
The used term of this specification sheets and claims " catalytic hydrodeoxygenation " (HDO) is meant under catalytic condition, with hydrogen catalytic treatment is carried out in biological hydrocarbon charging, following reaction takes place in this treating processes: disconnect triglyceride structure, deoxidation or deoxygenation also generate water, and hydrogenation makes two keys saturated.The preferred HDO of the present invention also removes unwanted impurity, generates hydrogen sulfide as sulphur removal, denitrogenates generation ammonia.Useful HDO catalyzer is the catalyzer that is fit to its described HDO step mentioned of US 7232935 for example.
The used term of this specification sheets and claims " biological hydrocarbon " is meant the charging that comprises vegetables oil, animal tallow, fish oil, natural wax, lipid acid and composition thereof.The example that is used for the charging of HDO process of the present invention has biological glycerol three esters and/or the raw material of fatty acid based on plant, animal and/or fish, and its form is oil, fat, wax and/or acid.Preferred charging has crude tall oil, ready denier oil acid and diasphaltene Yatall MA.
Term " isomerization " and " hydroisomerization " are meant in katalysis and hydrogen down auxiliary, introduce short-chain branch (normally methyl) in paraffinic hydrocarbons, preferred n-paraffin.
The term " non-cracking and hydrogenation isomerization " that is used for second hydrocarbon stream of the present invention is meant that use is very little or do not have an isomerization that the catalyzer of influence carries out to the cracking influence of the hydrocarbon studied.Typical non-cracking catalyst comprises silicoaluminophosphamolecular molecular sieve (SAPO) catalyzer of intermediate pore size.Useful non-cracking isomerization catalyst is the catalyzer that is used for its described isomerization steps mentioned of US 7232935 for example.
The term " catalytic cracking/isomerization " that is used for first paraffinic hydrocarbons produced according to the invention is meant in the presence of hydrogen, cracking and the hydroisomerisation step of utilizing the known catalyzer that has cracking and isomerization character simultaneously to carry out simultaneously.Typical cracking/isomerization catalyst comprises the ZSM zeolite catalyzer, as US4222855,4229282 and 4247388 described selective cracking and isomerized ZSM-5 and the ZSM-23 catalyzer that are used for paraffinic feedstock such as fischer-tropsch wax.
Term " from thermal transition " is meant partial oxidation and steam conversion is combined, under katalysis, by charging such as hydrocarbon and methyl alcohol generation hydrogen.
Term " water-gas shift " is meant that water and reaction of carbon monoxide form the inorganic chemistry reaction (water decomposition) of carbonic acid gas and hydrogen.
Term " biological raw material " and " biogenetic derivation " be meant extensively from plant, animal and/or fish, promptly from the biomass of biological renewable resources rather than fossil resource.
Term " lignocellulosic material " is meant the plant biomass of being made up of Mierocrystalline cellulose and hemicellulose, and xylogen.Biomass have many dissimilar, can be classified as four primary categories: the timber resistates comprises sawdust and paper plant's waste; City waste paper; Agricultural residue comprises corn stalk (handle and grass) and bagasse; And the dedicated energy crop, mainly form by tall and big woody grass.
Term " wood-processing industry " is meant with any industry of timber as raw material.Typical wood-processing industry comprises paper pulp papermaking factory, sawmill, panel company, firewood manufactory, timber granulation factory etc.
Term " n-Hexadecane number " or " cetane value " relate to the ignition quality of diesel oil fuel.It is to carry out the numerical value that stdn relatively obtains by fuel or blend to analysis fuel and known n-Hexadecane number.Reference fuel n-hexadecane (C
16) the n-Hexadecane number be 100.
Term " cloud point " is measuring of the work capacity of diesel oil fuel under cold weather conditions.It is defined as, when diesel oil fuel cools off under standard test condition, and the wax visible temperature that becomes first.
Term " pour point " is meant that when diesel oil fuel cooled off, diesel oil fuel can the mobile minimum temperature under standard conditions.
Method of the present invention is implemented in integrating industrial equipments, this method relates to two the main processes (FT and HDO) that mutually combine by at least one shared fractionation process, reclaim diesel fuel fractions as the product cut, and the optional recycle lighting end is in order to reclaim and/or to transform hydrogen.
The raw material of these two main processes all is a biogenetic derivation.For the FT process, almost the biomass of any kind all are fit to gasification.If need, first dried biomass makes its water content reduce to 35% or lower.Biomass are selected from the starting materials and the waste material in plant, animal and/or fish source usually, as Municipal waste, industrial waste or byproduct, agricultural waste or byproduct (also comprising muck), wood-processing industry waste material or byproduct, foodstuffs industry refuse or byproduct, marine plant (as algae) and combination thereof.Biological material preferentially is selected from non-edible-type resource, as unedible waste material and non-edible-type vegetable material, comprises oil, fat and wax.The preferred biological material of the present invention comprises wood-processing industry waste material and byproduct, as branches and leaves, city waste wood, Wood waste, wood chip, sawdust, straw, firewood, timber, paper, papermaking or wood working byproduct etc.The biomass material that is used for the FT process also can comprise vegetables oil, animal tallow, fish oil, natural wax and lipid acid.This oil, fat, wax and acid are the examples of the plant, animal and/or the fish based raw material that are used for HDO process of the present invention.The raw material that is used for the HDO process is preferably non-edible-type oil, as curcas oil, Viscotrol C, ready denier oil acid (TOFA) or Yatall MA, particularly crude tall oil or diasphaltene Yatall MA etc.
The raw material that can be used for the inventive method can have various multi-form, can carry out any appropriate pretreatment to them, to improve their utilization ratios in integration fuel process of the present invention.Therefore, can carry out sorting, cleaning, washing, drying, grinding, compression, mixing, pre-hydrogenation etc.,, provide to be fit to the incoming flow that the synthetic gas in FT reaction and/or the HDO reaction is produced to remove impurity to raw material.
First or the FT hydrocarbon stream generally the initial gasification by the biomass charging obtain synthetic gas and provide.Then, can form C
1-C
100+Under the condition of paraffinic hydrocarbons, make synthetic gas generation fischer-tropsch (FT) reaction.With C
1-C
100+Paraffinic hydrocarbons is divided into different fractions, and wherein lighting end mainly comprises vent gas (off-gas) C
1-C
4Hydrocarbon, it can merge with other vent gas in this process waits until further processing; Naphtha fraction mainly comprises C
5-C
10Hydrocarbon, it with mainly comprise C
11-C
20The middle runnings of hydrocarbon together or separately; And be divided into and mainly comprise C
21-C
100+The last running of hydrocarbon.Comprise C
5-C
20The cut of hydrocarbon and biological hydrocarbon one reinstate hydrogenation deoxidation and/or non-cracking and hydrogenation isomerization is handled.The C of remainder in the alkane hydrocarbon stream
21-C
100+Paraffinic hydrocarbons constitutes first hydrocarbon stream, and it is carried out cracking/isomerization, to shorten chain length.This has increased C in first hydrocarbon stream
11-C
20The ratio that paraffinic hydrocarbons is shared.Simultaneously, isomerization has obtained branched hydrocarbon, has improved the cloud point of final fuel product.
Second or the HDO hydrocarbon stream generally by biological hydrocarbon charging, for example the hydrogenation deoxidation (HDO) of fat, oil, wax and/or lipid acid charging provides, obtain with the FT paraffinic hydrocarbons in C
5-C
20The paraffinic hydrocarbons stream that hydrocarbon merges.Because of the lipid acid of triglyceride level of natural fat and oil has the chain length that the hydrocarbon with 12-20 carbon atom enriches the most, so the gained paraffinic hydrocarbons also comprises with C
12-C
20Be main carbochain, preferably with C
15-C
18It is main carbochain.HDO handles and makes any unsaturated chain saturated, thereby hydrocarbon will be basically by C
15-C
18N-paraffin is formed.In an embodiment of the invention, n-paraffin has improved the ratio of isoparaffin in second hydrocarbon stream through hydroisomerization.But, n-paraffin can directly use, to improve the n-Hexadecane number of FT hydrocarbon stream.The optional isomerization that second hydrocarbon stream is carried out is carried out with non-cracking catalyst, in order to avoid shorten C
5-C
20And C
15-C
18Carbochain.Hydroisomerization can independently carry out in the isomerization reactor, also can carry out in carrying out the same reactor of hydrogenation deoxidation.C in the FT paraffinic hydrocarbons
5-C
20Hydrocarbon also can both be handled by the hydrogenation deoxidation process, also handled by non-cracking isomerization process; Handle by one of preceding method; Perhaps handle by integration processing method with united catalyst.
Then, two strands of hydrocarbon streams are merged into the mixing hydrocarbon stream.In principle, any ratio of mixture all is possible.But, for real purpose, and for the finished product are carried out required improvement, what mixed flow should comprise 3%-95% does not contain C
5-C
20The FT hydrocarbon of hydrocarbon-fraction, i.e. first hydrocarbon stream; And 5%-97% with the FT hydrocarbon in C
5-C
20The HDO hydrocarbon that hydrocarbon-fraction merges, i.e. second hydrocarbon stream.Preferably, mixed flow comprises 20%-80% first hydrocarbon stream and 20%-80% second hydrocarbon stream.Best is, the content of first hydrocarbon stream is 40%-60%, and the content of second hydrocarbon stream is 40%-60%.Discover that it is ideal that ratio is essentially 50/50 mixed flow because the diesel oil fuel that it provides have very narrow chain length distribution and aspect n-Hexadecane number and cloud point improved character.One preferred embodiment in, maximum n-Hexadecane number is 100.Cloud point can be low to moderate-20 ℃.
By merging the mixing hydrocarbon stream fractionation in separator that obtains through cracking/isomerized first hydrocarbon stream and second hydrocarbon stream.Described separator comprises water distilling apparatus, and parallel feeding is separated into different cuts according to selected boiling range in this water distilling apparatus.Preferred fractionation process provides and comprises C
11-C
20The middle distillate of hydrocarbon and comprise hydrogen and C
1-C
4The lighting end of hydrocarbon.Reclaim middle distillate, as improved biodiesel fuel.It also can be used as additive, with the fuel mix that obtains by other approach.Should be appreciated that the cutting in the fractionation process is not absolute, may comprise some lighter or heavier hydrocarbon in each cut.For intended application, this lighter/content of heavier hydrocarbon is inappreciable.
The hydrocarbon that the merging of two class hydrocarbon streams and the distillation of mixed flow have improved gained middle distillate fuel distributes, because by contained middle distillate (C in the hydrocarbon stream of HDO generation
11-C
20) hydrocarbon is very abundant, so avoided the overcracking of naphtha fraction and middle runnings in the FT paraffinic hydrocarbons.The HDO hydrocarbon stream that is derived from bio oil or lipid acid is almost entirely by C
15-C
18Hydrocarbon is formed, and these hydrocarbon are most preferred hydrocarbon in the middle distillate, because they have improved the cetane value of diesel oil fuel.
Gained middle distillate fuel or fuel dope have especially good hydrocarbon and distribute, and wherein surpass 25% hydrocarbon and have 15-18 carbon atom.In one embodiment, C
15-C
18The ratio of hydrocarbon is higher than 40%, and this ratio may be up to 80% even higher.This provides excellent ignition quality and homogeneous combustion.
In an embodiment of the invention, also from separator, reclaimed by C
5-C
10The naphtha fraction that hydrocarbon is formed and/or by C
21-C
100+The last running of forming.Naphtha fraction can directly be used as solvent.Last running is recyclable as for example lubricating oil.In an embodiment of the invention, FT cracking/isomerization steps is delivered at least a portion last running circulation, carries out cracking and hydroisomerization, to increase C in first hydrocarbon stream
11-C
20The amount of hydrocarbon.
Obviously, if need, other cuts beyond the also recyclable above-mentioned cut, and can distill mixing hydrocarbon stream or above-mentioned any cut, so that other wideer slightly and/or narrower slightly carbon chain lengths scopes to be provided.If set distillation range, provide mainly by C
15-C
18The cut that n-paraffin and isoparaffin are formed, then products therefrom is ideal high hexadecane value/low cloud point fuel or fuel dope.In an embodiment of the invention, also from the middle runnings of remainder, separate and obtain kerosene(oil)fraction.
By making hydrocarbon charging one or both of isomerization, the cloud point and the pour point of gained diesel oil fuel significantly improve.In addition, biological HDO and FT process all can provide the very hydrocarbon product of cleaning, are substantially free of sulphur, phosphorus and nitrogen compound.The gained diesel oil fuel also is substantially free of aromatic hydrocarbons.Aromaticity content preferably is lower than 1 weight %.
According to an embodiment of the invention, the overhead fraction that is lower than required middle distillate from the boiling point of tripping device is used in to be integrated in the fuel process, for the catalyzed reaction that produces first and/or second hydrocarbon stream provides hydrogen.In one embodiment, described overhead fraction comprises and contains hydrogen and C
1-C
4The lighting end of hydrocarbon imports hydrogen separation device with it, isolates hydrogen, and cracking/isomerization steps, hydrogenation deoxidation step and/or hydroisomerisation step are sent in circulation.
Hydrogen separation device comprises permeable hydrogen membrane usually, by this film recover hydrogen.In an embodiment of the invention, the C that will reclaim from other positions of this film and/or described method
1-C
4Hydrocarbon and carbon monoxide import a device, and this device can be converted into light incoming flow the gas that comprises hydrogen, carbon monoxide, carbonic acid gas, nitrogen G﹠W.In an embodiment of the invention, to be that those skilled in the art is known install from thermal transition (ATR) described conversion system.
The gas that the ATR device produces can be used to provide more hydrogen, for example, it is imported water-gas shift (WGS) device, by carbon monoxide and the more hydrogen of water generates.Hydrogen is fit to utilize transformation absorption (PSA) device to wait and separates out.Hydrogen also can separate in hydrogen separation membrane, and described film is preferably identical with the used film of separator overhead fraction.Then, in described method, hydrogen recycle is delivered to hydrogenation deoxidation step, hydroisomerisation step and/or cracking/isomerization steps.
In an embodiment of the invention, also with the hydrogen in the fischer-tropsch paraffinic hydrocarbons, carbon monoxide and C
1-C
4The lighting end of hydrocarbon imports hydrogen separation device.In addition, also will import above-mentioned film, recover hydrogen and the gas that can produce hydrogen from the hydrogen of HDO stage and/or isomerization stage and the gas of lighting end.
The hydrogen that is used for integration method can be provided as methyl alcohol by any standard source.But, by circulating in the integration mode and transforming hydrogen, need the hydrogen in the adding integration process considerably less.When described mistake range request added hydrogen, it can be provided by any standard source.But, in one embodiment, hydrogen make-up produces by methyl alcohol is sent into from heat conversion device.Methyl alcohol is preferably the methyl alcohol that renewable resources produces, promptly so-called biological methanol.Conversion system promptly for example from heat conversion device, changes with used outside hydrogen source.
In one embodiment, whole integration fuel process of the present invention is implemented in conjunction with wood-processing industry, and the biological feed source that is used for this method is from described wood-processing industry or its byproduct.In this case, the biogenetic derivation of FT hydrocarbon stream comprises the waste material or the byproduct of wood-processing industry, and the biological hydrocarbon that is used for the HDO hydrocarbon stream comprises Yatall MA or ready denier oil acid.Wood-processing industry generally includes the ox-hide paper plant that produces Yatall MA, ready denier oil acid or tall oil fatty acid mixture.
When the integration fuel process is implemented in conjunction with wood-processing industry, will integrate the described wood-processing industry of the water supply that produces in the fuel process usually, be used for purification process.In addition, will integrate the sulphur that discharges in the fuel process,, send into the sulphur cycle process of wood-processing industry as the sulphur that in hydrogenation deoxidation step and/or synthetic gas production, discharges.
The maximum benefit of integration fuel process of the present invention obtains by it further being incorporated into paper pulp papermaking factory.In this case, lignocellulosic material can be very effectively as the raw material of producing fuel as the refuse and/or the byproduct of paper pulp papermaking factory.Simultaneously, the refuse of fuel process such as water and hydrogen sulfide can be respectively be effectively addressed in the conventional waste water disposal system in paper pulp and/or paper mill and sulphur cycle system.It is also important that the energy that the fischer-tropsch thermopositive reaction in the fuel process discharges is very useful for the unit operation of paper pulp papermaking factory.Therefore, can carry out with fischer-tropsch reaction heat by highly beneficial land productivity the drying of paper in the paper mill.
Except the fuel/benefit of wood-working factory's embodiment aspect raw material, waste treatment and energy of above-mentioned dual integration, for the different material stream that transmits between fuel production process and wood-working factory, also there is benefit in it aspect conveying and the storage.
According to the present invention, might utilize lignocellulosic material, as the waste material and/or the byproduct of wood-processing industry, produce high-quality diesel oil fuel by pure biological renewable resources.In this case, will comprise the waste material that for example is derived from timber and/or the gasifying biomass of byproduct, be used to provide fischer-tropsch alkane hydrocarbon stream, disengaging latch alkane stream then, and in the cracking of isomerisation conditions lower section.Biological hydrocarbon such as Yatall MA or ready denier oil acid are mainly comprised C through hydrogenation deoxidation
15-C
18The alkane hydrocarbon stream, preferred n-paraffin is chosen wantonly under non-cracking conditions the C in described paraffinic hydrocarbons and the FT paraffinic hydrocarbons
5-C
20Hydrocarbon isomerization.C in the FT paraffinic hydrocarbons
5-C
20Optional hydrogenation deoxidation of hydrocarbon and/or isomerization.Merge two strands of hydrocarbon streams, middle runnings (C is reclaimed in fractionation then
11-C
20Hydrocarbon).Preferably, provide hydrogen, be recycled in the production and/or isomerization process of two strands of hydrocarbon streams with overhead fraction.Bottom fraction is preferably recycled in cracking and the isomerization process.
The present invention also provides the chain length distribution method that narrows that makes Fisher-Tropsch derived diesel oil fuel.In this method, Fisher-Tropsch derived by C
5-C
20The hydrocarbon-fraction that hydrocarbon is formed earlier with obtain by biological hydrocarbon hydrogenation deoxidation mainly by C
15-C
18The hydrocarbon-fraction that hydrocarbon is formed is handled together.Then, with this hydrocarbon stream and Fisher-Tropsch derived by C
21-C
100+The hydrocarbon stream that hydrocarbon is formed merges, and the hydrocarbon stream of fractionation merging reclaims by C then
11-C
20Hydrocarbon is formed middle runnings, and it preferably is rich in C
15-C
18Hydrocarbon.The cut that reclaims comprises at least 25% usually, the preferred C of about 40%-80%
15-C
18Hydrocarbon.For specific purposes, described fuel process can suitably be implemented, and produces to comprise to surpass 80% C
15And C
18Fuel fraction.This can realize by following approach: for HDO selects biological hydrocarbon charging, optimize the fischer-tropsch process condition, select suitable hydrocarbon stream ratio and/or fractionation conditions and the boiling range in the adjusting separator.
The equipment that uses in the design of the fuel/wood working of the structure of integrating fuel process and dual integration comprises ready-made parts usually, also can be improved the parts of acquisition by ready-made parts.
The required infrastructure device of integration fuel process of the present invention comprise to biological hydrocarbon charging carry out hydrogenation deoxidation the hydrogenation deoxidation reactor, the fischer-tropsch paraffinic feedstock of biogenetic derivation is carried out catalytic cracking and isomerized cracking/isomerization reactor, and the merging hydrocarbon charging that described reactor produces is distilled and is reclaimed the tripping device of boiling point at 150-400 ℃ middle distillate.
By hydrogen gas recovering device, hydrogen recycle pipeline and device are provided,, be self-centered aspect the required hydrogen of each reactor thereby make described integration fuel factory so that lighting end and/or vent gas that self-separation device and/or each reactor produce provide hydrogen.At first, and under the situation of the hydrogen that the hydrogen of needs can provide more than the hydrogen conversion/working cycle of this method itself, adopt the additional hydrogen of this process outside.
Integrate hydrogen treat and handling equipment and comprise and to send into the pipeline of hydrogen separation device from the vent gas of arbitrary reactor in hydrogenation deoxidation reactor, cracking/isomerization reactor, Fischer-Tropsch reaction device and the hydroisomerization reactor, and the hydrogen that will reclaim and/or transform is sent into the pipeline of described arbitrary reactor.
In the fuel/wood-working factory of dual integration, described equipment also comprises the mechanism that the water of the reactor used generation of fuel process is sent into the wastewater treatment equipment of paper pulp papermaking factory.Described equipment also comprises the mechanism that the energy that produces in the Fischer-Tropsch reaction device is sent into the drying process of described paper pulp papermaking factory.Also provide the wooden basic waste material of biomass such as paper pulp papermaking factory has been sent into the mechanism that the Fischer-Tropsch reaction device is used to produce synthetic gas.Similarly, also has the mechanism that the Yatall MA/ready denier oil acid of paper pulp papermaking factory is sent into the hydrogenation deoxidation reactor.
Set forth the present invention below in conjunction with embodiment and accompanying drawing.
Fig. 1 has shown the integrated process schematic flow sheet of the operation according to the present invention.Described integrated process facility is positioned near the kraft pulp factory.Two main processes of the present invention comprise by unit operation 1,3,10 produces the HDO hydrocarbon and produces the FT hydrocarbon by unit operation 2,4,11.Carry out partially disposed with 10 pairs of FT hydrocarbon of unit operation.Described hydrocarbon merges in tripping device 12, and required product cut reclaims at 20 places.
Choose wantonly at 1 place and to carry out heat refining, deliver to then CoMo/Al is housed comprising from the biological glycerol three ester chargings of the crude tall oil of ox-hide paper plant
2O
3The catalysis HDO reactor 3 of the accurate hydrogenation deoxidation/desulfurization catalyst of disjunction mark.In another embodiment, adopt NiMo/Al
2O
3Catalyzer.From the chain length of the saturated n-paraffin of HDO reactor 3 in required diesel range, promptly at C
11-C
20In the middle distillate scope; For Yatall MA, lipid acid mainly is C
15-C
18, in fact, chain length almost is C entirely
18, this provides the diesel oil fuel with very high n-Hexadecane number.Yet, to use for cold-resistant, the cloud point of HDO n-paraffin is partial to too high.In order to reduce cloud point, with the C in normal paraffin hydrocarbon stream and the FT paraffinic hydrocarbons
5-C
20Hydrocarbon imports the reactor 10 that further carries out hydroisomerization together.
Because the product that HDO step 3 obtains has the ideal chain length, and the C in the FT hydrocarbon
5-C
20Hydrocarbon need not cracking, so use non-cracking catalyst in hydroisomerization 10.Catalyzer is known Pt/SAPO-11 with low cracking activity.The overcracking characteristic that should be pointed out that isomerization catalyst is harmful to the finished product, because it can reduce diesel yield.
By gasification bark and trees branches and leaves, abreast produce purified (do not contain tar and sulphur) synthetic gas with the HDO process at 2 places, wherein bark and trees branches and leaves are waste products of ox-hide paper plant.The H of gained synthetic gas
2/ CO volume ratio is about 2, and it is sent into FT reactor 4.Pressurization FT reactor 4 is ARGE type fixed-bed reactor, but also can adopt other any FT reactors, and moves according to the three-phase slurry technology (referring to for example US 4906671) of for example SASOL Synthol method.The commercially available Fischer-Tropsch catalyst with alumina load Co is housed in the reactor.
The hydrocarbon that produces in the FT reactor comprises C
1To very long (C
100+) hydrocarbon.In this embodiment, these hydrocarbon separate in tripping device 23, also can take place in the FT reactor but separate.Vent gas is by unconverted synthetic gas, methane and reach C most
4Light hydrocarbon form, it is collected, send into permeable hydrogen membrane device 9 by suitable pipeline, with recover hydrogen.With C
5-C
20Hydrocarbon is introduced non-cracking and hydrogenation isomerization unit 10, to avoid overcracking, separates by C then
21-C
100+The last running that hydrocarbon is formed.C
21-C
100+Hydrocarbon stream itself is not the suitable ingredients of liquid fuel, needs cracking to the chain length that is more suitable for liquid fuel.This carries out in cracking/isomerization reactor 11, the known active Pt/ZSM-23 catalyzer of considerable cracking-hydroisomerization that has of packing in this reactor 11.
Except that hydrocarbon stream, HDO and FT reaction all produce disadvantageous water byproduct 22.Merge current, nearby purifying in the existing waste water disposal facility (not shown) of ox-hide paper plant.
From the overhead fraction of tripping device 12, collect light vent gas (CO, H
2, CO
2, C
1-C
4), collect lighting end from treatment unit 3 and 4, through suitable pipeline it is sent into permeable hydrogen membrane device 9 then, with recover hydrogen.In another operational mode (Fig. 1 is not shown), also will deliver to film 9 from the vent gas of isomerization stage 10 and 11 by pipeline.To import autothermal reformer 13 from the hydrocarbon of film device 9 and the impermeable mixture of other gases, be processed into H
2, CO, CO
2, N
2And H
2The mixture of O.The effect of the gas products mixture of convertor 13 is to supply raw materials for follow-up water-gas shift (WGS) reactor 15, so that produce more hydrogen by the reaction between carbon monoxide and the water.Hydrogen adsorbs in (PSA) device 8 in following transformation and separates, and then it is sent into the hydrogen recycle pipeline, supplies with each process.When supplying extra hydrogen is arranged, it can be sent into synthetic gas pond 16, with H
2/ CO ratio is to required ratio adjustment.Remaining all gas mainly is CO
2And N
2, by pipeline 17 emptyings.
If the hydrogen that original position produces can not satisfy the wastage in bulk or weight to hydrogen, then can introduce extra hydrogen from external source, perhaps produce extra hydrogen to convertor 13 supply methyl alcohol 14 from outside.
In the whole gas phases and liquid phase effluent of hydroisomerization 10 and cracking/hydroisomerization 11, the ratio of first hydrocarbon stream is 40%-60%, the ratio of second hydrocarbon stream is 40%-60%, with its lead-in separation device 12, and any hydrocarbon gas (C that unreacted gas and cracking form
1-C
4) then separated as overhead fraction, the oriented film sepn process 9 then, transform subsequently.Tripping device 12 distillations mix hydrocarbon stream, reclaim cut according to selected boiling range.Mainly be lower than 150 ℃ C by boiling point
5-C
10The naphtha fraction that hydrocarbon is formed is collected at 19 places, and is main by the C of boiling point between 150 ℃-350 ℃
11-C
20The middle runnings that hydrocarbon is formed is then reclaimed at 20 places, as diesel oil fuel.Diesel oil distillate is rich in C
15-C
18Hydrocarbon, particularly C
18Hydrocarbon has excellent n-Hexadecane and counts 60-70 and low cloud point.
By the heaviest that part of hydrocarbon (＞C
21) bottom fraction 18 formed, major part is circulated to cracking/hydroisomerization process 11, obtains having the C of target cloud point in diesel range through cracking and hydroisomerization
11-C
20Hydrocarbon.If also remaining any bottom fraction then imports vacuum distillation process 21 with it, isolate the cut of boiling point between 350-490 ℃, be lubricant base with its refining.
Fig. 2 has shown another integrated process schematic flow sheet of the operation according to the present invention.Described integrated process facility is positioned near the kraft pulp factory.Integrated process as the HDO charging, uses synthetic gas from trees branches and leaves, waste wood and bark as the FT charging with ready denier oil acid (TOFA), moves in embodiment 1 described process facility.
The difference of embodiments of the present invention shown in Figure 2 and embodiment 1 described technology is, before entering embodiment 1 described catalysis HDO reactor 3, will comprise C
5-C
20The streams of hydrocarbon and TOFA charging merge, described C
5-C
20Hydrocarbon separates with other hydrocarbon of forming in the FT reactor in optional tripping device 23.In yet another embodiment of the present invention, hydrogenation deoxidation 3 and isomerization 10 adopt united catalyst to carry out in same device.
The current 22 of HDO and FT merge, purifying in the close existing waste water disposal facility (not shown) of ox-hide paper plant.
In the whole gas phases and liquid phase effluent of hydroisomerization 10 and cracking/hydroisomerization 11, the ratio that the ratio of first hydrocarbon stream is about 50%, the second hydrocarbon stream is about 50%, with its lead-in separation device 12, and any hydrocarbon gas (C that unreacted gas and cracking form
1-C
4) then separated as overhead fraction, hydrogen gas recovering device 24 then leads.When supplying extra hydrogen is arranged, it can be sent into synthetic gas pond 16, with H
2/ CO ratio is to required ratio adjustment.Remaining all gas mainly is CO
2And N
2, by pipeline 17 emptyings.
If the hydrogen that original position produces can not satisfy the wastage in bulk or weight to hydrogen, then can introduce extra hydrogen from external source 14.
Tripping device 12 distillations mix hydrocarbon stream, reclaim cut according to selected boiling range.Mainly be lower than 150 ℃ C by boiling point
5-C
10The naphtha fraction that hydrocarbon is formed is collected at 19 places, and is main by the C of boiling point between 150 ℃-350 ℃
11-C
20The middle runnings that hydrocarbon is formed is then reclaimed at 20 places, as diesel oil fuel.Diesel oil distillate is rich in C
15-C
18Hydrocarbon, particularly C
18Hydrocarbon has excellent n-Hexadecane and counts 60-70 and low cloud point.
By the heaviest that part of hydrocarbon (＞C
21) bottom fraction 18 formed, major part is circulated to cracking/hydroisomerization process 11, obtains having the C of target cloud point in diesel range through cracking and hydroisomerization
11-C
20Hydrocarbon.If also remaining any bottom fraction then imports vacuum distillation process 21 with it, isolate the cut of boiling point between 350-490 ℃, be lubricant base with its refining.
Integrated process as the HDO charging, uses synthetic gas from trees branches and leaves, waste wood and bark as the FT charging with ready denier oil acid (TOFA), moves in embodiment 2 described process facility.Mix two strands of hydrocarbon streams (I.) and (E.), distillation obtains middle distillate (M.), naphtha fraction (N.), overhead fraction (O.) and bottom fraction (S.).Overhead fraction is imported the hydrogen recovery process, bottom fraction is circulated to cracking/isomerization process 11.
Fig. 3 has shown the measurement point of mass balance in the schema shown in Figure 2.Following table 1 has been listed along the amount of the charging of measurement point A. to S. and product and mass balance.The kt/a of unit represents kiloton (1000 tonnes) every year.
Mass balance shows that required diesel oil fuel product cut (M.) is maximum product cut.Because C in the TOFA charging of HDO reactor
18The content height of hydrocarbon is so this diesel fuel fractions has very a high proportion of C
18, thereby have high hexadecane value.
Fig. 4 has shown according to another integrated process schematic flow sheet of the invention process.
Choose wantonly at 1 place and to carry out heat refining, deliver to then NiMo/Al is housed comprising from the biological glycerol three ester chargings of the crude tall oil of ox-hide paper plant
2O
3The catalysis HDO reactor 3 of the accurate hydrogenation deoxidation/desulfurization catalyst of disjunction mark.The hydrocarbon stream and the C that form
5-C
20Hydrocarbon merges, described C
5-C
20Hydrocarbon separates with other hydrocarbon of forming in the FT reactor in optional tripping device 23.In isomerization 10, adopt non-cracking catalyst Pt/SAPO-11.
FT is sent in the synthetic gas charging of purified (not the containing tar and sulphur) that will produce by gasification bark and trees branches and leaves at 2 places.Hydrogen gas recovering device 24 is sent in light ends fractionation, and the extra hydrogen of the optional use of described retrieving arrangement is as commercial methanol 14.Heavy hydrocarbon fraction is separated, send into cracking/isomerization process 11.
As described in embodiment 1, hydrogenation deoxidation reactor 3 and two isomerization reactors 10 and 11 move under hydrogen pressure, and why this just shown the hydrogen that adds in the schematic flow sheet of Fig. 4.
The current 22 of HDO and FT merge, purifying in the close existing waste water disposal facility (not shown) of ox-hide paper plant.
In the whole gas phases and liquid phase effluent of hydroisomerization 10 and cracking/hydroisomerization 11, the ratio of first hydrocarbon stream is 40%-60%, the ratio of second hydrocarbon stream is 60%-40%, with its lead-in separation device 12, and any hydrocarbon gas (C that unreacted gas and cracking form
1-C
4) then separated as overhead fraction, hydrogen gas recovering device 24 then leads.
Tripping device 12 distillations mix hydrocarbon stream, reclaim cut according to selected boiling range.Mainly be lower than 150 ℃ C by boiling point
5-C
10The naphtha fraction that hydrocarbon is formed is collected at 19 places, and is main by the C of boiling point between 150-350 ℃
11-C
20The middle runnings that hydrocarbon is formed is then reclaimed at 20 places, as diesel oil fuel.Diesel oil distillate is rich in C
15-C
18Hydrocarbon, particularly C
18Hydrocarbon has excellent n-Hexadecane and counts 60-70 and low cloud point.
By the heaviest that part of hydrocarbon (＞C
21) bottom fraction 18 major parts formed are circulated to cracking/hydroisomerization process 11, obtain having the C of target cloud point in diesel range through cracking and hydroisomerization
11-C
20Hydrocarbon.If also remaining any bottom fraction then imports vacuum distillation process 21 with it, isolate the cut of boiling point between 350-490 ℃, be lubricant base with its refining.
Embodiment 5
Fig. 5 has shown the schematic flow sheet according to another integration method of the invention process.
Choose wantonly at 1 place and to carry out heat refining, with itself and C comprising from the biological glycerol three ester chargings of the crude tall oil of ox-hide paper plant
5-C
20Hydrocarbon feeds catalytic hydrodeoxygenation and the isomerization machinery 26 that united catalyst is housed together, separates with other hydrocarbon of 4 li formation of FT reactor in optional tripping device 23 then.Perhaps, described sepn process takes place in FT process 4 shown in Figure 6.In process shown in Figure 6, there are not catalytic hydrodeoxygenation and isomerization machinery, so not with C
5-C
20Hydrocarbon feeds hydrogenation deoxidation device 3, but directly feeds non-cracking isomerization unit 10, and this device is that two strands of hydrocarbon streams are shared.
To produce the also synthetic gas charging of purified (not containing tar and sulphur) by gasification bark and trees branches and leaves at 2 places and send into the FT device.Hydrogen gas recovering device 24 is sent in light ends fractionation, and this device is optional to use extra hydrogen to originate, as commercial methanol 14.In another embodiment, the required hydrogen of said process produces by electrolysis and/or by Sweet natural gas.Heavy hydrocarbon fraction directly separates from FT, and sends into optional hydrogenation deoxidation device 25, sends into cracking/isomerization unit 11 then.In yet another embodiment of the present invention, cracking/isomerization unit 11 is directly sent in last running, and do not sent into optional hydrogenation deoxidation device 25.
In the whole gas phases and liquid phase effluent of hydroisomerization 10 and cracking/hydroisomerization 11, the ratio of first hydrocarbon stream is 40%-60%, the ratio of second hydrocarbon stream is 60%-40%, with its lead-in separation device 12, and any hydrocarbon gas (C that unreacted gas and cracking form
1-C
4) then separated as overhead fraction, import hydrogen gas recovering device 24 then.
Tripping device 12 distillations mix hydrocarbon stream, reclaim cut by selected boiling range.Mainly be lower than 150 ℃ C by boiling point
5-C
10The naphtha fraction that hydrocarbon is formed is collected at 19 places, and is main by the C of boiling point between 150-350 ℃
11-C
20The middle runnings that hydrocarbon is formed is then collected at 20 places, as diesel oil fuel.Diesel oil distillate is rich in C
15-C
18Hydrocarbon, particularly C
18Hydrocarbon has excellent n-Hexadecane and counts 60-70 and low cloud point.Choose wantonly and separately and exclusively collect independently kerosene(oil)fraction 27 from the middle runnings of remainder, it is mainly by the C of boiling point between 150 ℃-275 ℃
11-C
15Hydrocarbon is formed.
Before entering hydrogenation deoxidation device 25 and/or before cracking/hydroisomerization device 11, by the heaviest that part of hydrocarbon (＞C
21) bottom fraction 18 formed is circulated in the streams, so that obtain having the C of target cloud point in diesel range through cracking and hydroisomerization
11-C
20Hydrocarbon.Because the heaviest part recycle in the hydrocarbon, so the incoming flow of HDO, promptly TOFA or crude tall oil may comprise last running and can not disturb related process, reaction or product.
The present invention has been described above in conjunction with embodiment.But, it will be apparent to those skilled in the art that these processes can change in claims restricted portion.
Claims (22)
1. produce the integration method of diesel oil fuel by biomaterial for one kind, it is characterized in that may further comprise the steps:
A. the hydrocarbon of different chain length in the fischer-tropsch paraffinic hydrocarbons in separating bio source;
B., first hydrocarbon stream is provided, and it comprises the C in the described fischer-tropsch paraffinic hydrocarbons of handling with catalytic cracking/isomerization
21-C
100+Hydrocarbon;
C., second hydrocarbon stream is provided, and it comprises by what biological hydrocarbon is carried out catalytic hydrodeoxygenation obtains and mainly contains C
15-C
18First cut of hydrocarbon, and contain C in the described fischer-tropsch paraffinic hydrocarbons
5-C
20Second cut of hydrocarbon;
D. mix described first and second hydrocarbon streams;
E. fractionation gained mixing hydrocarbon stream; And
F. reclaim middle runnings.
2. the method for claim 1 is characterized in that, described first hydrocarbon stream provides like this: the gasified bio-matter charging obtains synthetic gas; Make described synthetic gas generation Fischer-Tropsch reaction, obtain C
1-C
100+Paraffinic hydrocarbons; Separation of C
1-C
4Paraffinic hydrocarbons, C
5-C
20Paraffinic hydrocarbons and C
21-C
100+Paraffinic hydrocarbons; Remove described C
1-C
4Paraffinic hydrocarbons and C
5-C
20Paraffinic hydrocarbons; And make gained C
21-C
100+Paraffinic hydrocarbons generation cracking/isomerization is to improve diesel hydrocarbon C
11-C
20The ratio of paraffinic hydrocarbons in winning hydrocarbon stream.
3. the method for claim 1 is characterized in that, described second hydrocarbon stream provides like this: hydrogenation deoxidation is carried out in described biological hydrocarbon charging, obtain mainly by saturated C
15-C
18The streams that paraffinic hydrocarbons is formed, and optional to described C
5-C
20Paraffinic hydrocarbons carries out hydrogenation deoxidation; And described paraffinic hydrocarbons carried out non-cracking and hydrogenation deoxidation, to improve the ratio of isoparaffin in gained second hydrocarbon stream.
4. the method for claim 1 is characterized in that, described first hydrocarbon stream of 3%-95% and described second hydrocarbon stream of 5%-97% merge in separator, gained hydrocarbon mixture stream is fractionated into comprise C
11-C
20The middle distillate of hydrocarbon and comprise hydrogen and C
1-C
4Described middle distillate is reclaimed in the lighting end of hydrocarbon, as diesel oil fuel.
5. method as claimed in claim 4 is characterized in that, returns packet receiving and contains C
21-C
100+The weight part of hydrocarbon and comprise C
5-C
10The naphtha fraction of hydrocarbon.
6. method as claimed in claim 5 is characterized in that, at least a portion in the described weight part is circulated to carries out cracking and hydroisomerization in described cracking/isomerization process, to increase C in described first hydrocarbon stream
11-C
20The content of hydrocarbon.
7. the method for claim 1 is characterized in that, sets described fractionation, so that provide mainly by C
15-C
18The cut that hydrocarbon is formed.
8. the method for claim 1, it is characterized in that, the biogenetic derivation of described fischer-tropsch paraffinic hydrocarbons comprises the biomass that are selected from down group: the starting materials and the waste material in plant, animal and/or fish source, wherein said biological alkyl is in oil, fat and/or the wax in plant, animal and/or fish source.
9. method as claimed in claim 8 is characterized in that, described biomass are selected from Municipal waste, industrial waste or byproduct, agricultural waste or byproduct, wood-processing industry waste material or byproduct, foodstuffs industry refuse or byproduct, marine plant and combination thereof.
10. the method for claim 1 is characterized in that, described method is implemented in conjunction with wood-processing industry, the biological feed source of described integration method from or the by product or the waste material of described wood-processing industry.
11. method as claimed in claim 10 is characterized in that, the biogenetic derivation of described fischer-tropsch paraffinic hydrocarbons comprises the waste material or the byproduct of wood-processing industry, and the described biological hydrocarbon of described second hydrocarbon stream comprises Yatall MA or ready denier oil acid.
12. method as claimed in claim 10 is characterized in that, described wood-processing industry comprises the ox-hide paper plant that produces crude tall oil and/or ready denier oil acid.
13. method as claimed in claim 10 is characterized in that, the described wood-processing industry of water supply with producing in the described integration fuel process is used for purification process; The sulphur of removing in the described fuel process is sent into the sulphur cycle of described wood-processing industry.
14. each described method in the claim as described above, it is characterized in that, described integration fuel process is further integrated with paper pulp papermaking factory, the refuse of wherein said paper pulp papermaking factory and/or byproduct be as the raw material of described fuel process, and the refuse of described fuel process and energy are handled in the unit operation of described paper pulp papermaking factory and/or utilized.
15. ligno-cellulosic materials is characterized in that may further comprise the steps in the application of being produced by pure biological renewable resources in the diesel oil fuel:
A. the ligno-cellulosic materials that gasifies is used to provide the fischer-tropsch paraffinic hydrocarbons, described paraffinic hydrocarbons is separated into the cut of the different hydrocarbon of chain length;
B. then under isomerisation conditions, to comprising the C in the described fischer-tropsch paraffinic hydrocarbons
21-C
100+The cut of hydrocarbon carries out cracking, obtains first hydrocarbon stream;
C. under non-cracking conditions, optional to first cut that comprises biological hydrocarbon and the C that comprises in the described fischer-tropsch paraffinic hydrocarbons
5-C
20Second cut of hydrocarbon carries out isomerization, obtains second hydrocarbon stream, and wherein said biological hydrocarbon produces through hydrogenation deoxidation and mainly contains C
15-C
18The alkane hydrocarbon stream, described C
5-C
20Hydrocarbon is optional through hydrogenation deoxidation;
D. two strands of hydrocarbon streams are merged, carry out fractionation; And
E. reclaim middle runnings.
16. application as claimed in claim 15 is characterized in that, described ligno-cellulosic materials is the waste material and/or the byproduct of wood-processing industry.
17. a chain length distribution method that narrows that makes the diesel oil fuel that is derived from Fischer-Tropsch reaction is characterized in that said method comprising the steps of:
A. will be derived from the C of Fischer-Tropsch reaction
5-C
20Hydrocarbon with obtain by biological hydrocarbon hydrogenation deoxidation mainly contain C
15-C
18Hydrocarbon merge, obtain hydrocarbon stream;
B. with this hydrocarbon stream and the C that is derived from Fischer-Tropsch reaction
21-C
100+Hydrocarbon hydrocarbon stream after the cracking under isomerisation conditions merges;
C. be combined hydrocarbon stream and carry out fractionation; And
D. reclaim C
11-C
20Hydrocarbon-fraction.
18. method as claimed in claim 17 is characterized in that, described recovery cut comprises at least 25%, preferably about 40%-80% or more C
15-C
18Hydrocarbon.
19. the biological middle runnings that can obtain by each described method among the claim 1-14, it comprises second hydrocarbon stream of the hydrocarbon that mainly contains 15-18 carbon atom of first hydrocarbon stream of 5%-95% and 5%-95%.
20. middle runnings as claimed in claim 19 is characterized in that, described cut comprises at least 25%, preferably about 40%-80% or more C
15-C
18Hydrocarbon.
21. the biological middle runnings that obtains according to each described method among the claim 1-14 is as the Application of Additives of the cetane value that is used to improve the fuel of producing by other approach.
22. application as claimed in claim 21 is characterized in that, described cut also is used for improving the cloud point and/or the pour point of the described fuel of producing by described other approach.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US7313808P | 2008-06-17 | 2008-06-17 | |
| US61/073,138 | 2008-06-17 | ||
| PCT/EP2008/064782 WO2009152873A1 (en) | 2008-06-17 | 2008-10-31 | An integrated process for producing diesel fuel from biological material and products and uses relating to said process |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102066527A true CN102066527A (en) | 2011-05-18 |
Family
ID=40887169
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008801299579A Pending CN102066527A (en) | 2008-06-17 | 2008-10-31 | An integrated process for producing diesel fuel from biological material and products and uses relating to said process |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US20110155631A1 (en) |
| EP (1) | EP2307524A1 (en) |
| CN (1) | CN102066527A (en) |
| BR (1) | BRPI0822791A2 (en) |
| CA (1) | CA2725768A1 (en) |
| WO (1) | WO2009152873A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104220567A (en) * | 2012-03-30 | 2014-12-17 | 吉坤日矿日石能源株式会社 | Gas oil composition |
Families Citing this family (26)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2275514A1 (en) * | 2009-07-17 | 2011-01-19 | Neste Oil Oyj | Process for the preparation of light fuels |
| US9382489B2 (en) | 2010-10-29 | 2016-07-05 | Inaeris Technologies, Llc | Renewable heating fuel oil |
| US9447350B2 (en) | 2010-10-29 | 2016-09-20 | Inaeris Technologies, Llc | Production of renewable bio-distillate |
| FI20106204L (en) * | 2010-11-16 | 2012-05-17 | Vapo Oy | Procedure for utilizing distillate fractions obtained during the distillation of pine oil in a BtL or cellulose factory |
| US8764855B2 (en) | 2010-12-15 | 2014-07-01 | Uop Llc | Process for producing a biofuel while minimizing fossil fuel derived carbon dioxide emissions |
| US8853475B2 (en) | 2010-12-15 | 2014-10-07 | Uop Llc | Process for producing a renewable hydrocarbon fuel |
| US9315739B2 (en) | 2011-08-18 | 2016-04-19 | Kior, Llc | Process for upgrading biomass derived products |
| RU2608522C2 (en) | 2011-04-18 | 2017-01-19 | ЮПМ-Кюммене Корпорейшн | Catalytic process and apparatus for producing hydrocarbons from biooil |
| WO2012143550A1 (en) * | 2011-04-21 | 2012-10-26 | Shell Internationale Research Maatschappij B.V. | Process for converting a solid biomass material |
| US9676678B1 (en) | 2011-06-21 | 2017-06-13 | Emerging Fuels Technology, Inc. | Renewable fuels co-processing |
| US9677005B1 (en) | 2011-06-21 | 2017-06-13 | Emerging Fuels Technology, Inc. | Integrated fuel processing with biomass oil |
| US10427069B2 (en) | 2011-08-18 | 2019-10-01 | Inaeris Technologies, Llc | Process for upgrading biomass derived products using liquid-liquid extraction |
| FR2981360B1 (en) * | 2011-10-14 | 2015-08-07 | IFP Energies Nouvelles | PROCESS FOR THE PRODUCTION OF MEDIUM DISTILLATES FROM A MIXTURE OF A CHARGE FROM RENEWABLE SOURCES AND A PARAFFINIC EFFLUENT |
| US9534181B2 (en) | 2012-06-19 | 2017-01-03 | Inaeris Technologies, Llc | Method of using renewable fuel composition |
| US9624446B2 (en) | 2012-06-19 | 2017-04-18 | Inaeris Technologies, Llc | Low temperature property value reducing compositions |
| ITTO20120760A1 (en) * | 2012-09-03 | 2014-03-04 | Welt Company S R L | PROCEDURE AND PLANT FOR THE DISPOSAL OF WASTE OF ALGAL ORIGIN |
| US20140073827A1 (en) * | 2012-09-07 | 2014-03-13 | Mississippi State University | Upgrading of bio-oil using synthesis gas |
| US9024096B2 (en) | 2012-12-11 | 2015-05-05 | Lummus Technology Inc. | Conversion of triacylglycerides-containing oils |
| US9162938B2 (en) | 2012-12-11 | 2015-10-20 | Chevron Lummus Global, Llc | Conversion of triacylglycerides-containing oils to hydrocarbons |
| US9587180B2 (en) | 2012-12-18 | 2017-03-07 | Exxonmobil Research And Engineering Company | Process for making lube base stocks from renewable feeds |
| EP2749627A1 (en) * | 2012-12-31 | 2014-07-02 | Shell Internationale Research Maatschappij B.V. | Process to distill Fischer-Tropsch product |
| US9453169B2 (en) * | 2013-09-13 | 2016-09-27 | Uop Llc | Process for converting fischer-tropsch liquids and waxes into lubricant base stock and/or transportation fuels |
| FI126812B (en) | 2013-11-21 | 2017-05-31 | Upm Kymmene Corp | INTEGRATED HYDROCARBON PROCESSING |
| ES2958518T3 (en) * | 2014-05-29 | 2024-02-09 | Eni Spa | Production process of a diesel hydrocarbon fraction from a renewable raw material |
| TW201602336A (en) | 2014-06-09 | 2016-01-16 | Ｗ Ｒ 康格雷氏公司 | Method for catalytic deoxygenation of natural oils and greases |
| SG11202105999UA (en) * | 2018-12-31 | 2021-07-29 | Neste Oyj | Process for integrated production of renewable fuels and chemicals |
Family Cites Families (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4222855A (en) * | 1979-03-26 | 1980-09-16 | Mobil Oil Corporation | Production of high viscosity index lubricating oil stock |
| US4229282A (en) * | 1979-04-27 | 1980-10-21 | Mobil Oil Corporation | Catalytic dewaxing of hydrocarbon oils |
| US4247388A (en) * | 1979-06-27 | 1981-01-27 | Mobil Oil Corporation | Hydrodewaxing catalyst performance |
| US4592762A (en) * | 1981-10-22 | 1986-06-03 | Institute Of Gas Technology | Process for gasification of cellulosic biomass |
| US4968325A (en) * | 1987-08-24 | 1990-11-06 | Centre Quebecois De Valorisation De La Biomasse | Fluidized bed gasifier |
| US4992605A (en) * | 1988-02-16 | 1991-02-12 | Craig Wayne K | Production of hydrocarbons with a relatively high cetane rating |
| CA2149685C (en) * | 1994-06-30 | 1999-09-14 | Jacques Monnier | Conversion of depitched tall oil to diesel fuel additive |
| US5833837A (en) * | 1995-09-29 | 1998-11-10 | Chevron U.S.A. Inc. | Process for dewaxing heavy and light fractions of lube base oil with zeolite and sapo containing catalysts |
| AU2001266868A1 (en) * | 2000-06-30 | 2002-01-14 | Chevron U.S.A. Inc. | Synthesis of high quality normal alpha olefins |
| US6583186B2 (en) * | 2001-04-04 | 2003-06-24 | Chevron U.S.A. Inc. | Method for upgrading Fischer-Tropsch wax using split-feed hydrocracking/hydrotreating |
| US7232935B2 (en) * | 2002-09-06 | 2007-06-19 | Fortum Oyj | Process for producing a hydrocarbon component of biological origin |
| US7279018B2 (en) * | 2002-09-06 | 2007-10-09 | Fortum Oyj | Fuel composition for a diesel engine |
| US8022108B2 (en) * | 2003-07-02 | 2011-09-20 | Chevron U.S.A. Inc. | Acid treatment of a fischer-tropsch derived hydrocarbon stream |
| US7354507B2 (en) * | 2004-03-17 | 2008-04-08 | Conocophillips Company | Hydroprocessing methods and apparatus for use in the preparation of liquid hydrocarbons |
| US7973086B1 (en) * | 2010-10-28 | 2011-07-05 | Chevron U.S.A. Inc. | Process of synthesis gas conversion to liquid hydrocarbon mixtures using alternating layers of synthesis gas conversion catalyst and hydrocracking catalyst |
| US7754931B2 (en) * | 2005-09-26 | 2010-07-13 | Her Majesty The Queen In Right Of Canada As Represented By The Minister Of Natural Resources | Production of high-cetane diesel fuel from low-quality biomass-derived feedstocks |
| US7998339B2 (en) * | 2005-12-12 | 2011-08-16 | Neste Oil Oyj | Process for producing a hydrocarbon component |
| MY150300A (en) * | 2006-03-24 | 2013-12-31 | Wisconsin Alumni Res Found | Method for producing bio-fuel that integrates heat from carbon-carbon bond-forming reactions to drive biomass gasification reactions |
| US7999142B2 (en) * | 2007-09-20 | 2011-08-16 | Uop Llc | Production of diesel fuel from biorenewable feedstocks |
-
2008
- 2008-10-31 CA CA2725768A patent/CA2725768A1/en not_active Abandoned
- 2008-10-31 WO PCT/EP2008/064782 patent/WO2009152873A1/en active Application Filing
- 2008-10-31 US US12/999,558 patent/US20110155631A1/en not_active Abandoned
- 2008-10-31 CN CN2008801299579A patent/CN102066527A/en active Pending
- 2008-10-31 BR BRPI0822791A patent/BRPI0822791A2/en not_active IP Right Cessation
- 2008-10-31 EP EP08874685A patent/EP2307524A1/en not_active Withdrawn
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104220567A (en) * | 2012-03-30 | 2014-12-17 | 吉坤日矿日石能源株式会社 | Gas oil composition |
| CN104220567B (en) * | 2012-03-30 | 2017-06-27 | 吉坤日矿日石能源株式会社 | Gas oil composition |
Also Published As
| Publication number | Publication date |
|---|---|
| EP2307524A1 (en) | 2011-04-13 |
| BRPI0822791A2 (en) | 2017-05-09 |
| CA2725768A1 (en) | 2009-12-23 |
| WO2009152873A1 (en) | 2009-12-23 |
| US20110155631A1 (en) | 2011-06-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102066527A (en) | An integrated process for producing diesel fuel from biological material and products and uses relating to said process | |
| RU2491319C2 (en) | Integrated method of obtaining diesel fuel from biological material, products, application and installation related to this method | |
| Chew et al. | Catalytic processes towards the production of biofuels in a palm oil and oil palm biomass-based biorefinery | |
| US10731085B2 (en) | Renewable hydrocarbon composition | |
| US10450521B2 (en) | Renewable hydrocarbon composition | |
| US9039790B2 (en) | Hydroprocessing of fats, oils, and waxes to produce low carbon footprint distillate fuels | |
| Serrano-Ruiz et al. | From biodiesel and bioethanol to liquid hydrocarbon fuels: new hydrotreating and advanced microbial technologies | |
| RU2489348C2 (en) | Application of biomethanol for production of hydrogen and biofuel, method of biohydrogen production and plant to this end | |
| EP1741767B1 (en) | Process for the manufacture of diesel range hydrocarbons | |
| Perego et al. | Diesel fuel from biomass | |
| FI124508B (en) | Method and apparatus for making fuel components from crude tall oil | |
| US8648226B2 (en) | Process for producing renewable gasoline, and fuel compositions produced therefrom | |
| US20090253947A1 (en) | Production of Blended Fuel from Renewable Feedstocks | |
| JP2022540531A (en) | Method for producing synthetic jet fuel | |
| Aghamiri et al. | Catalytic conversion of biomass and plastic waste to alternative aviation fuels: A review | |
| US11959034B2 (en) | Flexible integrated production plant system and method | |
| Bandi et al. | 6 New liquid hydrocarbon fuels |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20110518 |
|
| WD01 | Invention patent application deemed withdrawn after publication |