WO2009126379A1 - Process for conversion of biogas to liquid fuel - Google Patents
Process for conversion of biogas to liquid fuel Download PDFInfo
- Publication number
- WO2009126379A1 WO2009126379A1 PCT/US2009/036054 US2009036054W WO2009126379A1 WO 2009126379 A1 WO2009126379 A1 WO 2009126379A1 US 2009036054 W US2009036054 W US 2009036054W WO 2009126379 A1 WO2009126379 A1 WO 2009126379A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- liquid
- biogas
- gas
- product
- vessel
- Prior art date
Links
- 239000007788 liquid Substances 0.000 title claims abstract description 80
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 49
- 238000000034 method Methods 0.000 title claims abstract description 32
- 239000000446 fuel Substances 0.000 title claims abstract description 19
- 239000007789 gas Substances 0.000 claims abstract description 59
- 239000000047 product Substances 0.000 claims abstract description 52
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 21
- 150000003624 transition metals Chemical class 0.000 claims abstract description 21
- 239000003208 petroleum Substances 0.000 claims abstract description 20
- 239000003345 natural gas Substances 0.000 claims abstract description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 18
- 239000003921 oil Substances 0.000 claims description 17
- 229910052751 metal Inorganic materials 0.000 claims description 14
- 239000002184 metal Substances 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 13
- 239000002480 mineral oil Substances 0.000 claims description 12
- 235000010446 mineral oil Nutrition 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 11
- 239000001257 hydrogen Substances 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 10
- 239000002283 diesel fuel Substances 0.000 claims description 9
- 229910017052 cobalt Inorganic materials 0.000 claims description 8
- 239000010941 cobalt Substances 0.000 claims description 8
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 8
- 239000003502 gasoline Substances 0.000 claims description 8
- 150000002739 metals Chemical class 0.000 claims description 8
- 229910052759 nickel Inorganic materials 0.000 claims description 8
- 229910052721 tungsten Inorganic materials 0.000 claims description 8
- 239000010937 tungsten Substances 0.000 claims description 8
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 6
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 239000003350 kerosene Substances 0.000 claims description 5
- 238000012856 packing Methods 0.000 claims description 4
- 238000009835 boiling Methods 0.000 claims description 3
- 230000003197 catalytic effect Effects 0.000 claims description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 2
- -1 naphtha Substances 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims 2
- 238000004064 recycling Methods 0.000 claims 2
- 239000003054 catalyst Substances 0.000 abstract description 28
- 239000004215 Carbon black (E152) Substances 0.000 abstract description 6
- 229930195733 hydrocarbon Natural products 0.000 abstract description 6
- 150000002430 hydrocarbons Chemical class 0.000 abstract description 6
- 239000012263 liquid product Substances 0.000 abstract description 5
- 239000005416 organic matter Substances 0.000 abstract description 3
- 230000029087 digestion Effects 0.000 abstract description 2
- 239000012429 reaction media Substances 0.000 description 21
- 238000012360 testing method Methods 0.000 description 15
- 229910052782 aluminium Inorganic materials 0.000 description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 239000010779 crude oil Substances 0.000 description 6
- 239000008187 granular material Substances 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- 241000196324 Embryophyta Species 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- 238000002485 combustion reaction Methods 0.000 description 5
- 238000000354 decomposition reaction Methods 0.000 description 5
- 229910001018 Cast iron Inorganic materials 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 4
- 239000003245 coal Substances 0.000 description 4
- 238000013461 design Methods 0.000 description 4
- 239000003863 metallic catalyst Substances 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- 239000002826 coolant Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 238000010574 gas phase reaction Methods 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- 210000002268 wool Anatomy 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 238000004517 catalytic hydrocracking Methods 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
- 229910001092 metal group alloy Inorganic materials 0.000 description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 2
- 239000012925 reference material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000004227 thermal cracking Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 108010053481 Antifreeze Proteins Proteins 0.000 description 1
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 241000209504 Poaceae Species 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000008186 active pharmaceutical agent Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000002154 agricultural waste Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000002528 anti-freeze Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 238000005524 ceramic coating Methods 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000010227 cup method (microbiological evaluation) Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 210000003608 fece Anatomy 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 238000004231 fluid catalytic cracking Methods 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000013529 heat transfer fluid Substances 0.000 description 1
- 239000010763 heavy fuel oil Substances 0.000 description 1
- 229940097789 heavy mineral oil Drugs 0.000 description 1
- 230000002706 hydrostatic effect Effects 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000010871 livestock manure Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000013520 petroleum-based product Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- JTJMJGYZQZDUJJ-UHFFFAOYSA-N phencyclidine Chemical compound C1CCCCN1C1(C=2C=CC=CC=2)CCCCC1 JTJMJGYZQZDUJJ-UHFFFAOYSA-N 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000002760 rocket fuel Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/58—Fabrics or filaments
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/888—Tungsten
-
- 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
- C10G2/33—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used
- C10G2/331—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals
- C10G2/332—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals of the iron-group
-
- 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
- C10G2/34—Apparatus, reactors
- C10G2/341—Apparatus, reactors with stationary catalyst bed
-
- 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
- C10G29/00—Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
- C10G29/02—Non-metals
-
- 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
- C10G29/00—Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
- C10G29/20—Organic compounds not containing metal atoms
- C10G29/205—Organic compounds not containing metal atoms by reaction with hydrocarbons added to the hydrocarbon oil
-
- 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
- C10G49/00—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00
- C10G49/007—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 in the presence of hydrogen from a special source or of a special composition or having been purified by a special treatment
-
- 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
- C10G49/00—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00
- C10G49/02—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 characterised by the catalyst used
- C10G49/04—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 characterised by the catalyst used containing nickel, cobalt, chromium, molybdenum, or 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
- C10G50/00—Production of liquid hydrocarbon mixtures from lower carbon number hydrocarbons, e.g. by oligomerisation
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/04—Liquid carbonaceous fuels essentially based on blends of hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/04—Liquid carbonaceous fuels essentially based on blends of hydrocarbons
- C10L1/06—Liquid carbonaceous fuels essentially based on blends of hydrocarbons for spark ignition
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/04—Liquid carbonaceous fuels essentially based on blends of hydrocarbons
- C10L1/08—Liquid carbonaceous fuels essentially based on blends of hydrocarbons for compression ignition
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
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- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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- C10G2300/1044—Heavy gasoline or naphtha having a boiling range of about 100 - 180 °C
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
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- C10G2300/1048—Middle distillates
- C10G2300/1055—Diesel having a boiling range of about 230 - 330 °C
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
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- C10G2300/1048—Middle distillates
- C10G2300/1059—Gasoil having a boiling range of about 330 - 427 °C
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/40—Characteristics of the process deviating from typical ways of processing
- C10G2300/4006—Temperature
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/70—Catalyst aspects
Definitions
- This invention lies in the field of biogas and its use as a source of energy and its conversion to liquid fuel.
- biogas refers generally to gases resulting from the decomposition of organic matter in the absence of oxygen.
- the decomposition can occur in disposal facilities for treating municipal waste and waste products in general, and the decomposition processes generally include anaerobic digestion and fermentation of biodegradable materials such as biomass, manure, sewage, municipal waste, and energy crops.
- the decomposition can also occur naturally in geological formations.
- biogas can include hydrogen, methane, and carbon monoxide, as well as relatively benign gases such as nitrogen and carbon dioxide. Natural gas is one form of biogas.
- biogas can be converted to a clean-burning liquid fuel that can drive an engine or any other machinery or appliance that is typically run by a petroleum- based fuel.
- clean-burning when used to describe a liquid fuel means a liquid fuel that upon combustion produces a gaseous combustion product that is at least substantially free of particulate emissions and odor.
- the conversion of biogas to such a fuel in accordance with this invention is achieved by passing the biogas through a liquid reaction medium that contains a petroleum fraction, and doing so at an elevated but non-boiling temperature, while contacting the reaction medium with a transition metal catalyst.
- the gaseous product that results from the contact contains a vapor that can be condensed to achieve the liquid fuel.
- a preferred design for a chemical plant in which the process of this invention is performed is one that includes a gas-liquid reaction vessel and a product vessel, with a gas feed to the reaction vessel for inlet biogas and a port on the product vessel from which to draw liquid product.
- Fluid transfer conduits connect the two vessels, including one such conduit transferring vaporized product from the reaction vessel through a condenser and then to the product vessel, and another such conduit transferring uncondensed gas from the product vessel back to the reaction vessel.
- Mounted inside the reaction vessel are a grid of transition metal catalyst and gas distributors for both the feed gas and the recycle gas, both under the liquid level.
- Optional features include a supplementary gas-phase reaction vessel downstream of the gas-liquid reaction vessel and upstream of the condenser, the supplementary vessel itself containing a grid of transition metal catalyst to react unreacted materials in the stream of vaporized product emerging from the reaction vessel. Further features of the plant design are described below.
- the reaction medium in the gas-liquid reaction vessel is a liquid petroleum fraction
- the liquid product emerging from the product vessel is a hydrocarbon fuel of a composition that is distinct from the liquid petroleum fraction.
- the plant is operated on a continuous basis, and the reaction can be performed for a prolonged period of time, continuously producing product without adding further quantities of liquid petroleum fraction to the reaction vessel, although such further quantities can be added as needed to supplement the liquid level or compensate for liquid that has been entrained with the vaporized product. In either case, the product is readily produced in a volume that far exceeds the starting volume of the liquid petroleum fraction.
- FIG. 1 The Figure is a process flow diagram embodying an example of an implementation of the invention.
- biogas is used herein to include any non-inert gas that can be produced by the biological degradation of organic matter.
- prime examples of biogas are hydrogen, methane, and carbon monoxide, although other gaseous petroleum-based products such as ethane and ethylene, and decomposition products of agricultural waste such as wood chips, grains, grasses, leaves, and the like, are likewise included within the scope of the term.
- the term is also used herein to include the same gases that are obtained from other sources.
- methane associated with coal commonly known as “coal bed methane,” “coal mine methane,” and “abandoned mine methane.”
- Such methane can be derived by bacterial activity or by heating. Gases containing 90% to 100% methane on a mole percent basis are of particular interest, and this includes natural gas, of which methane typically constitutes approximately 95 mole percent.
- the petroleum fraction in the liquid reaction medium in the process of this invention includes fossil fuels, crude oil fractions, and many of the components derived from these sources.
- the fossil fuels include any carbonaceous liquids that are derived from petroleum, coal, or any other naturally occurring material, as well as processed fuels such as gas oils and products of fluid catalytic cracking units, hydrocracking units, thermal cracking units, and cokers. Included among these fuels are automotive fuels such as gasoline, diesel fuel, jet fuel, and rocket fuel, as well as petroleum residuum-based fuel oils including bunker fuels and residual fuels.
- Fractions or products in the diesel range can also be used, such as straight-run diesel fuel, feed- rack diesel fuel (diesel fuel that is commercially available to consumers at gasoline stations), light cycle oil, and blends of straight-run diesel and light cycle oil.
- Crude oil fractions include any of the various refinery products produced from crude oil, either by atmospheric distillation or by vacuum distillation, as well as fractions that have been treated by hydrocracking, catalytic cracking, thermal cracking, or coking, and those that have been desulfurized.
- fractions are light straight-run naphtha, heavy straight-run naphtha, light steam-cracked naphtha, light thermally cracked naphtha, light catalytically cracked naphtha, heavy thermally cracked naphtha, reformed naphtha, alkylate naphtha, kerosene, hydrotreated kerosene, gasoline and light straight-run gasoline, straight-run diesel, atmospheric gas oil, light vacuum gas oil, heavy vacuum gas oil, residuum, vacuum residuum, light coker gasoline, coker distillate, FCC (fluid catalytic cracker) cycle oil, and FCC slurry oil.
- Preferred reaction media are mineral oil, diesel oil, naphtha, kerosene, gas oil, and gasoline.
- the transition metal catalyst can be any single transition metal or combination of transition metals, either as metal salts, pure metals, or metal alloys, and can also be used in combination with metals other than transition metals.
- Preferred catalysts for use in this invention are metals and metal alloys. Transition metals having atomic numbers ranging from 23 to 79 are preferred, and those with atomic numbers ranging from 24 to 74 are more preferred. Cobalt, nickel, tungsten, and iron, particularly in combination, are the most preferred. An example of an additional metal that can be included is aluminum.
- the metallic catalyst is used in solid form and is preferably maintained below the liquid level in the reaction vessel as the biogas is bubbled through the liquid and through or past the catalyst.
- the catalyst can assume any form that allows intimate contact with both the liquid petroleum fraction and the biogas and allows free flow of gas over and past the catalyst. Examples of suitable forms of the catalyst are pellets, granules, wires, mesh screens, perforated plates, rods, and strips. Granules and wires suspended across plates or between mesh matrices such as steel or iron wool are preferred for their relatively accessible high surface area. When granules are used, the granules can be maintained in a fluidized state in the reaction medium or held stationary in the form of a fixed bed.
- a reactor can contain a single frame strung with wires in this manner or two or more such frames, depending on the size of the reactor.
- a still further variation of the catalyst configuration that can be used is a coil or other wrapping of the metallic wire around or over piping that serves as a gas distributor for incoming gas.
- the reaction vessel will typically contain one or more gas distributors for incoming gas, and in certain embodiments of the invention as explained below, the distributor(s) may have a wheel-and-spokes configuration or any other shape that includes a network of hollow pipes with an array of apertures to form the gas into small bubbles for release into the reaction vessel.
- These pipes, or at least the apertures can be covered for example with a steel mesh or steel wool in combination with wires of the various metals listed above, to intercept the gas bubbles before they enter the reaction medium.
- metallic grid is used herein to denote any fixed form of metallic catalyst that is submerged in the reaction medium and allows gas to bubble through the grid.
- the term thus encompasses fixed (as opposed to fluidized) beds, screens, open-weave wire networks, and any other forms described above.
- the metal can be in bare form or supported on inert supports as ceramic coatings or laminae.
- the reaction is performed under non-boiling conditions to maintain the liquid petroleum fraction used as the reaction medium in a liquid state and to avoid or at least minimize the amount of the liquid that is vaporized and leaves the reaction vessel with the product.
- An elevated temperature i.e., one above ambient temperature, is used, preferably one that is about 80°C or above, more preferably one within the range of about 100°C to about 25O 0 C.
- the most preferred temperature range is about 100°C to about 150°C, and in certain other embodiments, the most preferred temperature range is about 150°C to about 200°C.
- the operating pressure can vary as well, and can be either atmospheric, below atmospheric, or above atmospheric. The process is readily and most conveniently performed at either atmospheric pressure or a pressure moderately above atmospheric. Preferred operating pressures are those within the range of 1 atmosphere to 2 atmospheres.
- the supplementary gas-phase reaction vessel referenced above as an optional feature of the invention is a flow-through vessel with a grid of metallic catalyst, in which the term "grid" has the same scope of meaning as stated above in connection with the gas-liquid reaction vessel.
- the grid is not submerged in a liquid but instead supported within the vessel in the path of the vaporized product emerging from the gas-liquid reaction vessel.
- the metals in the grid can be the same as those in the grid of the gas-liquid reaction vessel, or different combinations of transition metals.
- a process flow diagram representing one example of a plant design for implementation of the present invention is presented in the attached Figure.
- the reaction vessel 11 and the product vessel 12 are both shown. Each of these vessels is a closed cylindrical tank with a volumetric capacity of 2,000 gallons (U.S.) (7,570 cubic meters).
- the reaction vessel 11 is charged with a petroleum fraction used as a liquid reaction medium 13 with a gaseous head space 14 above the liquid.
- the liquid level is maintained by a level control 15 which is actuated by a pair of float valves inside the vessel.
- the level control 15 governs a motor valve 16 on a drain line 17 at the base of the vessel.
- Biogas is fed to the reaction vessel 11 underneath the liquid level at an inlet gas pressure of from about 5 psig to about 20 psig, through a gas inlet line 18 which is divided among two gas distributors 21, 22 inside the reactor vessel, each distributor being large enough to deliver 1,000 scfm of gas to the vessel.
- Each distributor spans substantially the full cross section of the vessel in either a grid configuration, a wheel-and-spokes configuration, or any other configuration that will support an array of outlet ports distributed across the cross section of the vessel. While two distributors are shown, the optimal number of distributors and outlet ports and the optimal configuration for any individual distributor will be readily determinable by routine experimentation, with greater or lesser numbers of distributors being optimal for reactor vessels of different capacities.
- a resistance heater 23 is positioned in the reactor above the gas distributors, and a third gas distributor 24 is positioned above the resistance heater.
- the third gas distributor 24 receives return gas from the product receiving vessel 12 as explained below.
- the resistance heater 23 maintains the liquid at a temperature of approximately 240-250°F (116- 121°C).
- a series of catalyst grids 25 Positioned above the three gas distributors 21, 22, 24 and the resistance heater 23 but still beneath the liquid level are a series of catalyst grids 25 arranged in a stack. Each grid is a circular ring or apertured plate with metallic catalyst wires strung across the ring and supported by pegs affixed to the ring along the ring periphery.
- one example is a cast iron ring and chromium pegs.
- the sizes of the wires and the total length of each wire will be selected to achieve the maximal surface area exposed to the reaction medium while allowing gas to bubble through, and will be readily apparent to anyone skilled in the use of metallic or other solid-phase catalysts in a liquid-phase or gas-phase reaction.
- One example of a wire size is 1 mm in diameter. Using individual wires of each of four metals, such as for example cobalt, nickel, aluminum, and tungsten, two pounds of each metal wire can be used per ring, or eight pounds total per ring.
- the number of rings can vary, and will in most cases be limited only by the size of the reactor, the gas flow rate into the reactor, the desirability of maintaining little or minimal pressure drop across the rings, and economic factors such as the cost of materials.
- seven rings are used, each wound with the same number and weight of wires.
- the reaction can also be enhanced by placing screens of wire mesh between adjacent plates to assure that the gas bubbles contacting the catalyst wires are of a small size. Screens that are 40-mesh (U.S. Sieve Series) of either stainless steel or aluminum will serve this purpose.
- Product gas is drawn from the head space 14 of the reaction vessel 11 and passed through a supplementary catalyst bed of the same catalyst material as the catalyst rings 25 of the reaction vessel.
- the supplementary catalyst can be in the form of metallic wire screens, grids, or perforated plates similar to those of the catalyst grids 25 in the reactor vessel 11.
- the supplementary catalyst promotes the same reaction that occurs in the reaction vessel 11 for any unreacted materials that have been carried over with the product gas drawn from the reaction vessel.
- Product gas emerging from the supplementary catalyst beds is passed through a condenser 33 and the resulting condensate 34 is directed to the product vessel 12 where it is introduced under the liquid level.
- the liquid level in the product vessel 12 is controlled by a level control 41 which is actuated by a pair of float valves inside the vessel and governs a motor valve 42 on a liquid product outlet line 43 at the base of the vessel.
- a level control 41 which is actuated by a pair of float valves inside the vessel and governs a motor valve 42 on a liquid product outlet line 43 at the base of the vessel.
- Above the liquid level is a packed bed 44 of conventional tower packings. Examples are Raschig rings, Pall rings, and Intalox saddles; other examples will be readily apparent to those familiar with distillation towers and column packings.
- the packing material is inert to the reactants and products of the system, or at least substantially so, and serves to entrap liquid droplets that may be present in the gas phase and return the entrapped liquid back to the bulk liquid in the lower portion of the vessel.
- Unreacted gas 45 is withdrawn from the head space 46 above the packed bed by a gas pump 47.
- the pump outlet is passed through a check valve 48 and then directed to the reaction vessel 11 where it enters through the gas distributor 24 positioned between the resistance heater 23 and the catalyst grids 25.
- any known type of condenser can be used to condense the vaporized product from the reaction vessel.
- types of condensers are shell-and-tube condensers and plate-and- frame condensers, and among the shell- and-tube condensers are horizontal tube condensers and vertical tube condensers.
- Either co- current or counter-current condensers can be used, and the condensers can be air-cooled, water- cooled, or cooled by organic coolant media such as automotive anti-freeze (for example, 50% pre-diluted ethylene glycol) and other gly col-based coolants.
- organic coolant media such as automotive anti-freeze (for example, 50% pre-diluted ethylene glycol) and other gly col-based coolants.
- Alternatives to the resistance heater are heating jackets, heating coils using steam or other heat-transfer fluids, and radiation heaters.
- Heating of the reaction vessel can also be achieved, either in part or in whole, by recirculation of heat transfer fluid between the coolant side of the condenser and the reaction vessel.
- the gas distributors for the inlet feed and the recycle gas can be any of a variety of types known in the art. Examples are perforated plates, cap-type distributors, and pipe distributors.
- the liquid level controls can likewise be any of a variety of mechanisms known in the art. Examples are float-actuated devices, devices measuring hydrostatic head, electrically actuated devices such as those differentiating liquid from gas by electrical conductivity or dielectric constant, thermally actuated devices such as those differentiating by thermal conductivity, and sonic devices based on sonic propagation characteristics.
- This example illustrates the use of the present invention in a processing system in which the biogas is hydrogen and the reaction medium is mineral oil.
- a catalyst material was prepared by placing the following between two pads of steel wool: aluminum wire, cobalt wire (an alloy containing approximately 50% cobalt, 10% nickel, 20% chromium, 15% tungsten, 1.5% manganese, and 2.5% iron), nickel wire, tungsten wire, and cast iron granules. The material was placed in a reaction vessel over a perforated aluminum plate, and the vessel was charged with heavy mineral oil, submerging the catalyst material.
- cobalt wire an alloy containing approximately 50% cobalt, 10% nickel, 20% chromium, 15% tungsten, 1.5% manganese, and 2.5% iron
- the vessel contents were then heated to approximately 320-370°F (approximately 160-190°C), and hydrogen gas was bubbled through the vessel at a continuous rate of 60-80 cubic feet per hour (measured at ambient temperature of approximately 25 0 C), while the pressure in the reactor was maintained at or below 2 psig (approximately 115 KPa).
- the reaction was continued for five hours, after which time the reaction medium had reduced in volume from 3 parts by volume to 2 parts by volume, and had produced 2.5 parts by volume of condensed product.
- Hydrocarbon Composition (% by weight): 25.01 29.97 34.46 22.24 21.7 Total Paraffins 60.59 59.63 59.74 59.86 63.7 Naphthenes 14.4 10.4 5.8 17.9 14.6 Aromatics
- This example illustrates the use of the present invention in a processing system in which the biogas is methane and the reaction medium is mineral oil. Except for the substitution of methane for hydrogen, the test was conducted in the same manner as that of Example 1, using the same materials and operating conditions. The results, measured as in Example 1, are listed in Table II below. TABLE II: Test Results for Methane and Mineral Oil
- Hydrocarbon Composition (% by weight): 25.01 31.12 36.6 18.87 23.13 Total Paraffins 60.59 59.08 63 64.83 63.57 Naphthenes 14.4 9.8 0.4 16.3 13.3 Aromatics
- This example illustrates the use of the present invention in a processing system in which the biogas is 50% hydrogen and 50% carbon monoxide (by volume) and the reaction medium is mineral oil. Except for the substitution of the hydrogen/carbon monoxide mixture, the test was conducted in the same manner as that of Example 1, using the same materials and operating conditions. The results, measured as in Example 1, are listed in Table III below.
- Hydrocarbon Composition (% by weight): 25.01 25.51 32.01 17.95 21.63 Total Paraffins 60.59 63.49 67.89 65.35 63.87 Naphthenes 14.4 11 0.1 16.7 14.5 Aromatics
- This example illustrates the use of the present invention in a processing system in which the feed biogas was methane and the liquid petroleum fraction used in the reaction vessel was diesel fuel.
- the equipment was a pilot version of the plant set forth in the Figure and described above, with a catalyst bed of aluminum wire, cobalt wire (an alloy containing approximately 50% cobalt, 10% nickel, 20% chromium, 15% tungsten, 1.5% manganese, and 2.5% iron), nickel wire, tungsten wire, and cast iron granules.
- the reaction vessel was 19 inches (0.5 meter) in diameter and initially charged with ten gallons (39 liters) of diesel fuel.
- the diesel fuel was maintained at a temperature of 240-250°F (116- 121 0 C) and a pressure of 3 psig (122 kPa) as the methane was bubbled through the reactor. After startup, the reactor was run for ten hours, then continued for another 2.5 hours during which time product was collected for analysis. The volume of product collected was 5.6 liters, and upon completion of the collection, the volume of liquid reaction medium remained at 8-10 gallons (30-39 liters). The product was analyzed by standard ASTM protocols and the results are listed in Table IV.
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- Processing Of Solid Wastes (AREA)
- Preparation Of Compounds By Using Micro-Organisms (AREA)
- Apparatus Associated With Microorganisms And Enzymes (AREA)
- Catalysts (AREA)
Priority Applications (11)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP09730699.7A EP2268379A4 (en) | 2008-04-07 | 2009-03-04 | METHOD FOR CONVERTING BIOGAS IN LIQUID FUEL |
| EA201001602A EA201001602A1 (ru) | 2008-04-07 | 2009-03-04 | Способ превращения биогаза в жидкое топливо |
| NZ588113A NZ588113A (en) | 2008-04-07 | 2009-03-04 | Process for conversion of biogas to liquid fuel by passing it through a heated petroleum fraction with a transition metal catalyst |
| CN2009801125637A CN102006920A (zh) | 2008-04-07 | 2009-03-04 | 将生物气转化为液体燃料的方法 |
| MX2010010995A MX2010010995A (es) | 2008-04-07 | 2009-03-04 | Proceso para conversion de biogas a combustible liquido. |
| US12/682,511 US20110000128A1 (en) | 2008-04-07 | 2009-03-04 | Process For Conversion of Biogas to Liquid Fuels |
| AU2009234105A AU2009234105A1 (en) | 2008-04-07 | 2009-03-04 | Process for conversion of biogas to liquid fuel |
| UAA201013194A UA98225C2 (uk) | 2008-04-07 | 2009-03-04 | Спосіб конверсії біогазу в рідке паливо |
| BRPI0910440A BRPI0910440A2 (pt) | 2008-04-07 | 2009-03-04 | processo para conversão de biogás para combustível líquido |
| ZA2010/06621A ZA201006621B (en) | 2008-04-07 | 2010-09-15 | Process for conversion of biogas to liquid fuel |
| MA33324A MA32361B1 (fr) | 2008-04-07 | 2010-11-03 | Procede pour la conversion de biogaz en combustible liquide |
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US12/098,513 | 2008-04-07 | ||
| US12/098,513 US20090249682A1 (en) | 2008-04-07 | 2008-04-07 | Conversion of biogas to liquid fuels |
| US12/171,801 | 2008-07-11 | ||
| US12/171,801 US7880044B2 (en) | 2008-04-07 | 2008-07-11 | Conversion of biogas to liquid fuels |
| US12/212,968 US7897124B2 (en) | 2008-09-18 | 2008-09-18 | Continuous process and plant design for conversion of biogas to liquid fuel |
| US12/212,968 | 2008-09-18 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2009126379A1 true WO2009126379A1 (en) | 2009-10-15 |
Family
ID=41162186
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/US2009/036054 WO2009126379A1 (en) | 2008-04-07 | 2009-03-04 | Process for conversion of biogas to liquid fuel |
Country Status (19)
| Country | Link |
|---|---|
| US (1) | US20110000128A1 (uk) |
| EP (1) | EP2268379A4 (uk) |
| KR (1) | KR20110036697A (uk) |
| CN (1) | CN102006920A (uk) |
| AR (1) | AR070939A1 (uk) |
| AU (1) | AU2009234105A1 (uk) |
| BR (1) | BRPI0910440A2 (uk) |
| CL (1) | CL2009000564A1 (uk) |
| CO (1) | CO6310969A2 (uk) |
| EA (1) | EA201001602A1 (uk) |
| EC (1) | ECSP10010595A (uk) |
| GE (1) | GEP20125688B (uk) |
| MA (1) | MA32361B1 (uk) |
| MX (1) | MX2010010995A (uk) |
| NZ (1) | NZ588113A (uk) |
| PE (1) | PE20100038A1 (uk) |
| UA (1) | UA98225C2 (uk) |
| WO (1) | WO2009126379A1 (uk) |
| ZA (1) | ZA201006621B (uk) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2012022841A1 (en) * | 2010-08-20 | 2012-02-23 | Timo Nylander | Method for producing fuel from organic material and a gasification plant |
| EP2507348A1 (en) * | 2009-11-30 | 2012-10-10 | Conocophillips Company | A blended fuel composition having improved cold flow properties |
| US8658026B2 (en) | 2011-12-22 | 2014-02-25 | Iogen Corporation | Method for producing fuel with renewable content having reduced lifecycle greenhouse gas emissions |
| US8753854B2 (en) | 2011-12-22 | 2014-06-17 | Iogen Corporation | Method for producing renewable fuels |
| US11760630B2 (en) | 2021-04-15 | 2023-09-19 | Iogen Corporation | Process and system for producing low carbon intensity renewable hydrogen |
| US11807530B2 (en) | 2022-04-11 | 2023-11-07 | Iogen Corporation | Method for making low carbon intensity hydrogen |
| US11946001B2 (en) | 2021-04-22 | 2024-04-02 | Iogen Corporation | Process and system for producing fuel |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7897124B2 (en) * | 2008-09-18 | 2011-03-01 | Gunnerman Rudolf W | Continuous process and plant design for conversion of biogas to liquid fuel |
| US8226817B2 (en) * | 2010-01-04 | 2012-07-24 | Gunnerman Rudolf W | Non-fractionation process for production of low-boiling fuel from crude oil |
| US9109177B2 (en) * | 2011-12-12 | 2015-08-18 | Ensyn Renewables, Inc. | Systems and methods for renewable fuel |
| US8715488B1 (en) | 2013-01-07 | 2014-05-06 | Clean Global Energy, Inc. | Method and apparatus for making hybrid crude oils and fuels |
| DE102014209216B4 (de) * | 2014-05-15 | 2018-08-23 | Glatt Gmbh | Katalytisch wirksames poröses Element und Verfahren zu seiner Herstellung |
| US10416729B2 (en) * | 2016-09-27 | 2019-09-17 | Seagate Technology Llc | Mounting structure for hard disk drives |
| CN106823750A (zh) * | 2017-03-24 | 2017-06-13 | 华北电力大学（保定） | 一种用于镁法脱硫中亚硫酸盐氧化与协同脱汞的装置 |
| KR102068337B1 (ko) * | 2018-04-03 | 2020-01-20 | 한국기계연구원 | 바이오매스와 합성수지의 혼합 열분해를 위한 바이오 원유 제조 시스템 |
| JP7226898B2 (ja) | 2019-02-20 | 2023-02-21 | カラ テクノロジーズ インコーポレイテッド | 触媒構造物、および触媒構造物の存在下で炭化水素をアップグレードする方法 |
| CN112717839B (zh) * | 2020-12-25 | 2022-05-03 | 江苏新河农用化工有限公司 | 一种流化反应装置及其用于间二甲苯氨氧化的方法 |
| CZ310054B6 (cs) | 2022-07-06 | 2024-06-26 | Dereroy & Co., a.s | Metoda homolytického a heterolytického rozbíjení vazeb v molekulách plynů a kapalin s primárním uvolněním vazebné energie, využití této energie ke změně vnitřní geometrické architektury některých molekul vedoucí k syntéze nových chemických sloučenin a zařízení pro její realizaci |
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- 2009-03-04 GE GEAP200911994A patent/GEP20125688B/en unknown
- 2009-03-04 UA UAA201013194A patent/UA98225C2/uk unknown
- 2009-03-04 NZ NZ588113A patent/NZ588113A/en not_active IP Right Cessation
- 2009-03-04 EP EP09730699.7A patent/EP2268379A4/en not_active Withdrawn
- 2009-03-04 EA EA201001602A patent/EA201001602A1/ru unknown
- 2009-03-04 KR KR1020107024698A patent/KR20110036697A/ko not_active Application Discontinuation
- 2009-03-04 CN CN2009801125637A patent/CN102006920A/zh active Pending
- 2009-03-04 AU AU2009234105A patent/AU2009234105A1/en not_active Abandoned
- 2009-03-04 WO PCT/US2009/036054 patent/WO2009126379A1/en active Application Filing
- 2009-03-04 US US12/682,511 patent/US20110000128A1/en not_active Abandoned
- 2009-03-04 BR BRPI0910440A patent/BRPI0910440A2/pt not_active IP Right Cessation
- 2009-03-04 MX MX2010010995A patent/MX2010010995A/es not_active Application Discontinuation
- 2009-03-10 CL CL2009000564A patent/CL2009000564A1/es unknown
- 2009-04-06 PE PE2009000486A patent/PE20100038A1/es not_active Application Discontinuation
- 2009-04-06 AR ARP090101215A patent/AR070939A1/es unknown
-
2010
- 2010-09-15 ZA ZA2010/06621A patent/ZA201006621B/en unknown
- 2010-10-07 CO CO10124683A patent/CO6310969A2/es not_active Application Discontinuation
- 2010-11-03 MA MA33324A patent/MA32361B1/fr unknown
- 2010-11-05 EC EC2010010595A patent/ECSP10010595A/es unknown
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Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2507348A4 (en) * | 2009-11-30 | 2014-12-10 | Conocophillips Co | MIXED FUEL COMPOSITION HAVING ENHANCED COLD FLOW PROPERTIES |
| EP2507348A1 (en) * | 2009-11-30 | 2012-10-10 | Conocophillips Company | A blended fuel composition having improved cold flow properties |
| WO2012022841A1 (en) * | 2010-08-20 | 2012-02-23 | Timo Nylander | Method for producing fuel from organic material and a gasification plant |
| RU2570456C2 (ru) * | 2010-08-20 | 2015-12-10 | Тимо НЮЛАНДЕР | Способ производства топлива из органического материала и установка газификации |
| US10093540B2 (en) | 2011-12-22 | 2018-10-09 | Iogen Corporation | Method for producing renewable fuels |
| US8945373B2 (en) | 2011-12-22 | 2015-02-03 | Iogen Corporation | Method for producing renewable fuels |
| US9040271B2 (en) | 2011-12-22 | 2015-05-26 | Iogen Corporation | Method for producing renewable fuels |
| US8753854B2 (en) | 2011-12-22 | 2014-06-17 | Iogen Corporation | Method for producing renewable fuels |
| US8658026B2 (en) | 2011-12-22 | 2014-02-25 | Iogen Corporation | Method for producing fuel with renewable content having reduced lifecycle greenhouse gas emissions |
| US10421663B2 (en) | 2011-12-22 | 2019-09-24 | Iogen Corporation | Method for producing renewable fuels |
| US10723621B2 (en) | 2011-12-22 | 2020-07-28 | Iogen Corporation | Method for producing renewable fuels |
| US10981784B2 (en) | 2011-12-22 | 2021-04-20 | Iogen Corporation | Partially renewable transportation fuel |
| US11873220B2 (en) | 2011-12-22 | 2024-01-16 | Iogen Corporation | Method for producing renewable fuels |
| US12122673B2 (en) | 2011-12-22 | 2024-10-22 | Iogen Corporation | Method for producing renewable fuels |
| US11760630B2 (en) | 2021-04-15 | 2023-09-19 | Iogen Corporation | Process and system for producing low carbon intensity renewable hydrogen |
| US11946001B2 (en) | 2021-04-22 | 2024-04-02 | Iogen Corporation | Process and system for producing fuel |
| US11807530B2 (en) | 2022-04-11 | 2023-11-07 | Iogen Corporation | Method for making low carbon intensity hydrogen |
Also Published As
| Publication number | Publication date |
|---|---|
| CO6310969A2 (es) | 2011-08-22 |
| AR070939A1 (es) | 2010-05-19 |
| KR20110036697A (ko) | 2011-04-08 |
| ECSP10010595A (es) | 2011-03-31 |
| NZ588113A (en) | 2012-05-25 |
| ZA201006621B (en) | 2012-02-29 |
| EA201001602A1 (ru) | 2011-06-30 |
| CN102006920A (zh) | 2011-04-06 |
| MA32361B1 (fr) | 2011-06-01 |
| PE20100038A1 (es) | 2010-02-02 |
| GEP20125688B (en) | 2012-11-12 |
| AU2009234105A1 (en) | 2009-10-15 |
| EP2268379A1 (en) | 2011-01-05 |
| EP2268379A4 (en) | 2014-01-22 |
| US20110000128A1 (en) | 2011-01-06 |
| MX2010010995A (es) | 2011-03-01 |
| BRPI0910440A2 (pt) | 2015-09-29 |
| CL2009000564A1 (es) | 2009-11-13 |
| UA98225C2 (uk) | 2012-04-25 |
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