AU2009234105A1 - Process for conversion of biogas to liquid fuel - Google Patents
Process for conversion of biogas to liquid fuel Download PDFInfo
- Publication number
- AU2009234105A1 AU2009234105A1 AU2009234105A AU2009234105A AU2009234105A1 AU 2009234105 A1 AU2009234105 A1 AU 2009234105A1 AU 2009234105 A AU2009234105 A AU 2009234105A AU 2009234105 A AU2009234105 A AU 2009234105A AU 2009234105 A1 AU2009234105 A1 AU 2009234105A1
- Authority
- AU
- Australia
- Prior art keywords
- liquid
- biogas
- gas
- product
- vessel
- 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.)
- Abandoned
Links
- 239000007788 liquid Substances 0.000 title claims description 77
- 238000006243 chemical reaction Methods 0.000 title claims description 50
- 238000000034 method Methods 0.000 title claims description 31
- 239000000446 fuel Substances 0.000 title claims description 18
- 239000007789 gas Substances 0.000 claims description 55
- 239000000047 product Substances 0.000 claims description 51
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 38
- 239000003208 petroleum Substances 0.000 claims description 20
- 229910052723 transition metal Inorganic materials 0.000 claims description 20
- 150000003624 transition metals Chemical class 0.000 claims description 20
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 18
- 239000003921 oil Substances 0.000 claims description 18
- 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
- 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
- 239000002283 diesel fuel Substances 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
- 239000003345 natural gas Substances 0.000 claims description 4
- 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 description 27
- 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
- 239000004215 Carbon black (E152) Substances 0.000 description 5
- 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
- 229930195733 hydrocarbon Natural products 0.000 description 5
- 150000002430 hydrocarbons Chemical class 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
- 239000012263 liquid product Substances 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
- 239000005416 organic matter Substances 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- 230000029087 digestion Effects 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
- 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
- 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
- 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
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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
- B01J23/70—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
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/30—Tungsten
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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
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- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
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- C10G2300/1055—Diesel having a boiling range of about 230 - 330 °C
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- C—CHEMISTRY; METALLURGY
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- 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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- C10G2300/1059—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
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Description
WO 2009/126379 PCT/US2009/036054 PROCESS FOR CONVERSION OF BIOGAS TO LIQUID FUEL BACKGROUND OF THE INVENTION 1. Field of the Invention 5 [00011 This invention lies in the field of biogas and its use as a source of energy and its conversion to liquid fuel. 2. Description of the Prior Art [00021 Alternative sources of energy are in ever increasing demand as crude oil fluctuates in price and as governments and the public at large become increasingly concerned over adverse 10 environmental impacts of gaseous emissions from the processing of crude oil. A major group of alternatives to crude oil are the gases commonly known as "biogas" which 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 15 of biodegradable materials such as biomass, manure, sewage, municipal waste, and energy crops. The decomposition can also occur naturally in geological formations. Depending on its source, 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. SUMMARY OF THE INVENTION 20 [0003] It has now been discovered that 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. The term "clean-burning" when used to describe a liquid fuel means a liquid fuel that 1 WO 2009/126379 PCT/US2009/036054 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 5 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. When the process is operated on a continuous basis, the product is produced in a volume that far exceeds the starting volume of the reaction medium. [00041 A preferred design for a chemical plant in which the process of this invention is 10 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 15 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 20 from the reaction vessel. Further features of the plant design are described below. [00051 The reaction medium in the gas-liquid reaction vessel is a liquid petroleum fraction, and 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 25 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. 2 WO 2009/126379 PCT/US2009/036054 [0006] These and other objects, advantages, and features of the invention are included in the descriptions below. BRIEF DESCRIPTION OF THE DRAWING [0007] The Figure is a process flow diagram embodying an example of an implementation of 5 the invention. DETAILED DESCRIPTION OF THE INVENTION AND PREFERRED EMBODIMENTS [0008] The term "biogas" is used herein to include any non-inert gas that can be produced by the biological degradation of organic matter. As noted above, prime examples of biogas are 10 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. One example is methane associated with coal, commonly known as "coal bed methane," "coal mine 15 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. [0009] The petroleum fraction in the liquid reaction medium in the process of this invention 20 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 25 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 3 WO 2009/126379 PCT/US2009/036054 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. Examples of such fractions are light straight-run naphtha, heavy straight-run naphtha, light steam-cracked naphtha, 5 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 10 oil, naphtha, kerosene, gas oil, and gasoline. [0010] 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 15 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. [00111 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 20 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 25 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. When wires are used, individual cobalt, nickel, aluminum, and tungsten wires, for example, of approximately equal diameter and length, and be strung across a frame of cast iron to form an open-mesh network which can then be supported inside the reactor. A reactor can contain a single frame strung with wires in this manner or two 30 or more such frames, depending on the size of the reactor. A still further variation of the catalyst 4 WO 2009/126379 PCT/US2009/036054 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. As mentioned above in the "SUMMARY OF THE INVENTION," the reaction vessel will typically contain one or more gas distributors for incoming gas, and in certain embodiments of the invention as explained below, 5 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. The term "metallic grid" is 10 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. 15 [00121 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 250'C. In certain 20 embodiments, 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 0 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 25 are those within the range of 1 atmosphere to 2 atmospheres. [00131 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. In the supplementary vessel, however, the grid is not submerged in a liquid but instead supported 30 within the vessel in the path of the vaporized product emerging from the gas-liquid reaction 5 WO 2009/126379 PCT/US2009/036054 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. [0014] 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 5 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 10 line 17 at the base of the vessel. [00151 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 15 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 20 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). 25 [0016] 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. Of the variety of metals that can be used for the ring and the pegs, one example is a cast iron ring and chromium pegs. The sizes of the wires 30 and the total length of each wire will be selected to achieve the maximal surface area exposed to 6 WO 2009/126379 PCT/US2009/036054 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 5 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. In a preferred embodiment, seven rings are used, each wound with the same number and weight of wires. The reaction can also be enhanced by placing 10 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. [00171 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 15 reaction vessel. In the diagram shown, two such catalyst beds 31, 32 of identical construction and catalyst composition are arranged in parallel. 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 20 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. [0018] 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 25 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 30 entrapped liquid back to the bulk liquid in the lower portion of the vessel. Unreacted gas 45 is 7 WO 2009/126379 PCT/US2009/036054 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. 5 [0019] Alternatives to the units described above and shown in the Figure will be readily apparent to the skilled chemical engineer. For example, any known type of condenser can be used to condense the vaporized product from the reaction vessel. Examples of 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 10 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 glycol-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 15 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 20 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. EXAMPLE 1 [0020] This example illustrates the use of the present invention in a processing system in 25 which the biogas is hydrogen and the reaction medium is mineral oil. [0021] 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 8 WO 2009/126379 PCT/US2009/036054 plate, and the vessel was charged with heavy mineral oil, submerging the catalyst material. 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'C), while the pressure in the reactor was 5 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. Values of the kinematic viscosity (taken at 50*C using the protocol of ASTM D 445), flashpoint (by the Pensky-Martens closed-cup method using the protocol of ASTM D 93a), hydrocarbon 10 composition (using the Robinson Modified Method of ASTM D 3239-2425), lubricity (using the high-frequency reciprocating rig method at 60'C with the protocol of ASTM D 6049), vapor pressure (using the dry vapor pressure equivalent method with the protocol of ASTM D 5191), and gross heat of combustion (measured according to the protocol of ASTM D 240) were taken on the reaction medium at the start of the test (mineral oil) and at one and five hours after the 15 start of the test, and on the condensed gaseous product at one and five hours after the start of the test. The results are listed in Table I below. 9 WO 2009/126379 PCT/US2009/036054 TABLE I: Test Results for Hydrogen and Mineral Oil ------------- Reaction Medium-------- -- Condensed Product-- Start of Test at 1 hour at 5 hours at 1 hour at 5 hours Kinematic Viscosity 4.524 15.27 4.506 4.499 4.512 (centistokes) Flashpoint ('C) 126.5 151.5 168 74 132 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 Lubricity (mm) 0.15 0.24 0.16 0.33 0.3 Vapor Pressure (psi) 0.25 0.25 0.25 1.06 0.48 Gross Heat of 19,572 19,577 19,536 19,505 19,693 Combustion (BTU/lb) ' [00221 The product was fed to a VAL6 Infrared Oil Heater (Shizuoka Seiki Co., Ltd., Japan) where it burned readily in air. An attempt to use the liquid reaction medium at the start of the test (mineral oil) in the same oil heater was made, and the result was negative, i.e., the medium 5 would not burn. EXAMPLE 2 [0023] 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 10 the same materials and operating conditions. The results, measured as in Example 1, are listed in Table II below. 10 WO 2009/126379 PCT/US2009/036054 TABLE II: Test Results for Methane and Mineral Oil ----------- Reaction Medium----------- ---Condensed Product-- Start of Test at 1 hour at 5 hours at 1 hour at 5 hours Kinematic Viscosity 4.524 15.11 26.79 4.201 5.967 (centistokes) Flashpoint ('C) 126.5 157 172.5 115 253.5 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 Lubricity (mm) 0.15 0.23 0.19 0.34 0.16 Vapor Pressure (psi) 0.25 0.25 0.25 0.25 0.25 [0024] The product was fed to a VAL6 Infrared Oil Heater (Shizuoka Seiki Co., Ltd., Japan) where it burned readily in air. As in Example 1, the liquid reaction medium at the start of the test (mineral oil) would not burn in the same oil heater. 5 EXAMPLE 3 [00251 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 10 operating conditions. The results, measured as in Example 1, are listed in Table III below. 11 WO 2009/126379 PCT/US2009/036054 TABLE III: Test Results for Hydrogen/Carbon Monoxide and Mineral Oil ----------- Reaction Medium----------- ---Condensed Product-- Start of Test at 1 hour at 5 hours at 1 hour at 5 hours Kinematic Viscosity 4.524 16.84 57.37 4.274 5.797 (centistokes) Flashpoint (*C) 126.5 327.5 0 141 126.5 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 Lubricity (mm) 0.15 0.18 0.17 0.24 0.14 Vapor Pressure (psi) 0.25 0.25 0.25 0.25 0.25 [00261 The product was fed to a VAL6 Infrared Oil Heater (Shizuoka Seiki Co., Ltd., Japan) where it burned readily in air. As in Examples 1 and 2, the liquid reaction medium at the start of the test (mineral oil) would not burn in the same oil heater. 5 EXAMPLE 4 [00271 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 10 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 (1 16-121'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 15 hours, then continued for another 2.5 hours during which time product was collected for analysis. 12 WO 2009/126379 PCT/US2009/036054 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. TABLE IV: Product Test Results Protocol Result Flash Point ASTM D 93 202-F (94-C) API Gravity at 60'F (15.6'C) ASTM D 287 34.80 Distillation at 760 mm Hg (1 atm) ASTM D 86 Percent Recovered: Result Initial b.p. 423 0 F (217-C) 5 452.5 0 F (234-C) 10 464.7-F (240 0 C) 20 475.5-F (246-C) 30 485.4 0 F (252-C) 40 495.1-F (257-C) 50 505.2-F (263-C) 60 516.0-F (269-C) 70 527.5 0 F (275-C) 80 541.6-F (283-C) 90 560.8*F (294-C) 95 580.3-F (305-C) End 597.9 0 F (314 0 C) Recovery 98.1% Residue 1.0% Loss 0.9% Pressure 765 mm Hg Estimated hydrogen content ASTM D 3343 13.38 weight % Particulate Matter ASTM D 2276 2-0.8tm filters 8.5 mg/gal Volume 0.26 gal Vacuum 28.3 in. Hg Time 10 min Total Aromatics ASTM D 1319 18.0 volume % Sediment and Water ASTM D 2709 0 volume % Ash ASTM D 482 0.002 weight % 13 WO 2009/126379 PCT/US2009/036054 Copper Corrosion ASTM D 130 la (3 hours at 122'F, 50*C) Ramsbottom Carbon Residue, ASTM D 524 0.07 weight % 10% Bottoms Ramsbottom Carbon Residue ASTM D 524 0 weight % Lead ASTM D 3605 <0.1 ppm Vanadium ASTM D 3605 <0.1 ppm Calcium ASTM D 3605 <0.1 ppm Sodium, Potassium, Lithium ASTM D 3605 <0.1 ppm Demulsification ASTM D 1401 5 minutes Sulfur by X-ray ASTM D 2622 0.0005 weight % Cetane Number ASTM D 613 46.4 Gross Heat of Combustion ASTM D 240 19,547 BTU/lb, 138,490 BTU/gal [0028] The product was fed to a VAL6 Infrared Oil Heater (Shizuoka Seiki Co., Ltd., Japan) where it burned readily in air, emitting neither odor nor smoke. EXAMPLE 5 [0029] This example illustrates the use of the present invention in a processing system in 5 which the feed biogas was natural gas and the liquid petroleum fraction used in the reaction vessel was kerosene. Using equipment of a similar design and layout as that of Example 4 and a catalyst of the same composition, liquid product was formed. The product was tested in both a diesel engine and a gasoline engine, and both engines started cold and ran effectively on the product. 10 [0030] In the claims appended hereto, the term "a" or "an" is intended to mean "one or more." The term "comprise" and variations thereof such as "comprises" and "comprising," when preceding the recitation of a step or an element, are intended to mean that the addition of further steps or elements is optional and not excluded. All patents, patent applications, and other 14 WO 2009/126379 PCT/US2009/036054 published reference materials cited in this specification are hereby incorporated herein by reference in their entirety. Any discrepancy between any reference material cited herein and an explicit teaching of this specification is intended to be resolved in favor of the teaching in this specification. This includes any discrepancy between an art-understood definition of a word or 5 phrase and a definition explicitly provided in this specification of the same word or phrase. 15
Claims (17)
1. A process for producing liquid fuel from a biogas, said method comprising: (a) passing said biogas through a liquid petroleum fraction at a temperature of about 800C or above but below boiling, while contacting said biogas and said liquid petroleum fraction with a transition metal to produce a gaseous effluent; and (b) condensing said effluent to liquid form.
2. The process of claim 1 wherein said transition metal is a metal with an atomic number from 23 to 79.
3. The process of claim 1 wherein said transition metal is a metal with an atomic number from 24 to 74.
4. The process of claim 1 wherein step (a) is performed while contacting said biogas and said liquid petroleum fraction with a plurality of transition metals in metallic form.
5. The process of claim 4 wherein said transition metals comprise cobalt, nickel, and tungsten.
6. The process of claim 4 wherein said transition metals comprise cobalt, nickel, tungsten, and iron.
7. The process of claim 1 wherein said liquid petroleum fraction is a member selected from the group consisting of mineral oil, diesel oil, naphtha, kerosene, gas oil, and gasoline.
8. The process of claim 1 wherein step (a) is performed at a temperature of from about 100°C to about 250°C.
9. The process of claim 1 wherein step (a) is performed at a pressure of from about 1 atmosphere to about 2 atmospheres.
10. The process of claim 1 wherein said biogas is a member selected from the group consisting of hydrogen, carbon monoxide, methane, and mixtures thereof.
11. The process of claim 1 wherein said biogas is natural gas.
12. The process of claim 1 wherein: step (a) comprises feeding biogas to a reaction vessel partially filled with said liquid petroleum fraction to a first externally controlled liquid level to cause said biogas to bubble through said liquid petroleum fraction and through a metallic grid of said transition metal immersed in said liquid; and step (b) comprises performing the following steps continuously and simultaneously with step (a): (i) drawing said effluent from a head space in said reaction vessel above said liquid level through a condenser to convert said gaseous reaction product mixture to liquid condensate and uncondensed gas; (ii) passing said liquid condensate and uncondensed gas into a product vessel having a second externally controlled liquid level, to separate said liquid condensate from said uncondensed gas; and (iii) drawing said liquid condensate so separated from said product vessel, as said liquid fuel, while recycling said uncondensed gas from said product vessel to said reaction vessel by directing said uncondensed gas below said first liquid level and through said first metallic grid.
13. The process of claim 12 wherein said metallic grid in said reaction vessel is defined as a first metallic grid, said process further comprising passing said gaseous reaction product mixture through a second metallic grid of at least one transition metal prior to said condenser.
14. The process of claim 13 wherein said second metallic grid is external to said reaction vessel and said product vessel.
15. The process of claim 12 further comprising passing said uncondensed gas through a fixed bed of inert packing material to recover entrained liquid therein prior to recycling said uncondensed gas to said reaction vessel.
16. The process of claim 13 wherein said at least one catalytic transition metal constituting said first metallic grid and said at least one catalytic transition metal constituting said second metallic grid are both pluralities of metals comprising cobalt, nickel, and tungsten.
17. The process of claim 1 wherein: said a reaction vessel is equipped with a first liquid level control means to define minimum and maximum liquid levels, heating means for heating liquid, an inlet gas distributor, a metallic grid of said transition metal, and a vaporized product outlet port, said inlet gas distributor and said first metallic grid positioned below said minimum liquid level, and said vaporized product outlet port positioned above said maximum liquid level; said condenser is arranged to receive said vaporized product emerging from said vaporized product outlet port; and said product vessel is equipped with a second liquid level control means to define minimum and maximum liquid levels.
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US12/098,513 US20090249682A1 (en) | 2008-04-07 | 2008-04-07 | Conversion of biogas to liquid fuels |
US12/098,513 | 2008-04-07 | ||
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 | 2008-09-18 | ||
US12/212,968 US7897124B2 (en) | 2008-09-18 | 2008-09-18 | Continuous process and plant design for conversion of biogas to liquid fuel |
PCT/US2009/036054 WO2009126379A1 (en) | 2008-04-07 | 2009-03-04 | Process for conversion of biogas to liquid fuel |
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US7897124B2 (en) * | 2008-09-18 | 2011-03-01 | Gunnerman Rudolf W | Continuous process and plant design for conversion of biogas to liquid fuel |
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US10416729B2 (en) * | 2016-09-27 | 2019-09-17 | Seagate Technology Llc | Mounting structure for hard disk drives |
CN106823750A (en) * | 2017-03-24 | 2017-06-13 | 华北电力大学(保定) | It is a kind of to be aoxidized for magnesium processes desulfurization sulfite salt and the device for cooperateing with demercuration |
KR102068337B1 (en) * | 2018-04-03 | 2020-01-20 | 한국기계연구원 | System for producing bio-oil from pyrolysis of biomass and plastics |
WO2020170042A1 (en) | 2019-02-20 | 2020-08-27 | Kara Energy Services Inc. | Catalyst structure and method of upgrading hydrocarbons in the presence of the catalyst structure |
CN112717839B (en) * | 2020-12-25 | 2022-05-03 | 江苏新河农用化工有限公司 | Fluidized reaction device and method for oxidizing m-xylene by using same |
CA3214940A1 (en) | 2021-04-15 | 2022-10-20 | Iogen Corporation | Process and system for producing low carbon intensity renewable hydrogen |
WO2022221954A1 (en) | 2021-04-22 | 2022-10-27 | 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 |
CZ310054B6 (en) | 2022-07-06 | 2024-06-26 | Dereroy & Co., a.s | A method of homolytic and heterolytic breaking of bonds in molecules of gases and liquids with primary release of the binding energy, use of such energy to change the internal geometric architecture of some molecules leading to a synthesis of new chemical compounds and an equipment to implement the method |
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UA98225C2 (en) | 2012-04-25 |
MX2010010995A (en) | 2011-03-01 |
GEP20125688B (en) | 2012-11-12 |
CN102006920A (en) | 2011-04-06 |
EA201001602A1 (en) | 2011-06-30 |
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BRPI0910440A2 (en) | 2015-09-29 |
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