NZ617115B2 - Method of operation of process to produce syngas from carbonaceous material - Google Patents
Method of operation of process to produce syngas from carbonaceous material Download PDFInfo
- Publication number
- NZ617115B2 NZ617115B2 NZ617115A NZ61711512A NZ617115B2 NZ 617115 B2 NZ617115 B2 NZ 617115B2 NZ 617115 A NZ617115 A NZ 617115A NZ 61711512 A NZ61711512 A NZ 61711512A NZ 617115 B2 NZ617115 B2 NZ 617115B2
- Authority
- NZ
- New Zealand
- Prior art keywords
- syngas
- carbonaceous material
- cooler
- produce
- cooled
- Prior art date
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- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 105
- 238000000034 method Methods 0.000 title claims abstract description 75
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 52
- CURLTUGMZLYLDI-UHFFFAOYSA-N carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000002309 gasification Methods 0.000 claims description 120
- MYMOFIZGZYHOMD-UHFFFAOYSA-N oxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 98
- 229910001882 dioxygen Inorganic materials 0.000 claims description 61
- 229910052760 oxygen Inorganic materials 0.000 claims description 30
- 239000001301 oxygen Substances 0.000 claims description 30
- 238000007792 addition Methods 0.000 claims description 22
- 230000003647 oxidation Effects 0.000 claims description 22
- 238000007254 oxidation reaction Methods 0.000 claims description 22
- 230000001603 reducing Effects 0.000 claims description 12
- 238000006722 reduction reaction Methods 0.000 claims description 6
- 241000282619 Hylobates lar Species 0.000 claims description 5
- 150000001768 cations Chemical class 0.000 claims description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 57
- 229910002091 carbon monoxide Inorganic materials 0.000 description 57
- 239000007789 gas Substances 0.000 description 38
- 238000004519 manufacturing process Methods 0.000 description 32
- 239000001569 carbon dioxide Substances 0.000 description 27
- 239000000428 dust Substances 0.000 description 27
- 238000010438 heat treatment Methods 0.000 description 26
- 239000000463 material Substances 0.000 description 22
- 238000004140 cleaning Methods 0.000 description 20
- 239000011269 tar Substances 0.000 description 20
- 239000000047 product Substances 0.000 description 19
- 239000002699 waste material Substances 0.000 description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 18
- 239000000126 substance Substances 0.000 description 18
- 229910052799 carbon Inorganic materials 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 238000001816 cooling Methods 0.000 description 11
- 239000007787 solid Substances 0.000 description 11
- 150000002500 ions Chemical class 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 238000010586 diagram Methods 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 230000002829 reduced Effects 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 8
- -1 tires Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000004033 plastic Substances 0.000 description 6
- 229920003023 plastic Polymers 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000003245 coal Substances 0.000 description 5
- 239000000356 contaminant Substances 0.000 description 5
- 230000003247 decreasing Effects 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 239000002440 industrial waste Substances 0.000 description 5
- 229920000139 polyethylene terephthalate Polymers 0.000 description 5
- 239000005020 polyethylene terephthalate Substances 0.000 description 5
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 4
- 239000004744 fabric Substances 0.000 description 4
- 238000005755 formation reaction Methods 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 230000002194 synthesizing Effects 0.000 description 4
- 241000196324 Embryophyta Species 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000010828 animal waste Substances 0.000 description 3
- 239000000571 coke Substances 0.000 description 3
- 238000011143 downstream manufacturing Methods 0.000 description 3
- 239000002921 fermentation waste Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000010419 fine particle Substances 0.000 description 3
- 235000013305 food Nutrition 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 3
- 229920005610 lignin Polymers 0.000 description 3
- 244000144972 livestock Species 0.000 description 3
- 244000005700 microbiome Species 0.000 description 3
- 239000010813 municipal solid waste Substances 0.000 description 3
- 239000003345 natural gas Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 239000004458 spent grain Substances 0.000 description 3
- 239000002023 wood Substances 0.000 description 3
- 239000002916 wood waste Substances 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000004035 construction material Substances 0.000 description 2
- 230000000875 corresponding Effects 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000000855 fermentation Methods 0.000 description 2
- 230000004151 fermentation Effects 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 238000002536 laser-induced breakdown spectroscopy Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000010908 plant waste Substances 0.000 description 2
- 244000144977 poultry Species 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 238000004611 spectroscopical analysis Methods 0.000 description 2
- 239000002918 waste heat Substances 0.000 description 2
- 235000003625 Acrocomia mexicana Nutrition 0.000 description 1
- 244000202285 Acrocomia mexicana Species 0.000 description 1
- 239000004788 BTU Substances 0.000 description 1
- 238000010744 Boudouard reaction Methods 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 241000229754 Iva xanthiifolia Species 0.000 description 1
- 210000003800 Pharynx Anatomy 0.000 description 1
- 210000002381 Plasma Anatomy 0.000 description 1
- 229940035295 Ting Drugs 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 210000004027 cells Anatomy 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000000567 combustion gas Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 238000011068 load Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 239000002906 medical waste Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006011 modification reaction Methods 0.000 description 1
- 230000001590 oxidative Effects 0.000 description 1
- 239000003348 petrochemical agent Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000010801 sewage sludge Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 239000004071 soot Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000000629 steam reforming Methods 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/025—Processes for making hydrogen or synthesis gas containing a partial oxidation step
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/08—Methods of heating or cooling
- C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/08—Methods of heating or cooling
- C01B2203/0872—Methods of cooling
- C01B2203/0877—Methods of cooling by direct injection of fluid
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/08—Methods of heating or cooling
- C01B2203/0872—Methods of cooling
- C01B2203/0888—Methods of cooling by evaporation of a fluid
- C01B2203/0894—Generation of steam
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/14—Details of the flowsheet
- C01B2203/142—At least two reforming, decomposition or partial oxidation steps in series
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/14—Details of the flowsheet
- C01B2203/142—At least two reforming, decomposition or partial oxidation steps in series
- C01B2203/143—Three or more reforming, decomposition or partial oxidation steps in series
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
- C01B3/36—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using oxygen or mixtures containing oxygen as gasifying agents
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2200/00—Details of gasification apparatus
- C10J2200/09—Mechanical details of gasifiers not otherwise provided for, e.g. sealing means
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2200/00—Details of gasification apparatus
- C10J2200/15—Details of feeding means
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
- C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
- C10J2300/0953—Gasifying agents
- C10J2300/0956—Air or oxygen enriched air
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
- C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
- C10J2300/0953—Gasifying agents
- C10J2300/0959—Oxygen
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
- C10J2300/16—Integration of gasification processes with another plant or parts within the plant
- C10J2300/1603—Integration of gasification processes with another plant or parts within the plant with gas treatment
- C10J2300/1606—Combustion processes
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
- C10J2300/18—Details of the gasification process, e.g. loops, autothermal operation
- C10J2300/1846—Partial oxidation, i.e. injection of air or oxygen only
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
- C10J2300/18—Details of the gasification process, e.g. loops, autothermal operation
- C10J2300/1861—Heat exchange between at least two process streams
- C10J2300/1884—Heat exchange between at least two process streams with one stream being synthesis gas
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
- C10J3/72—Other features
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
- C10J3/72—Other features
- C10J3/721—Multistage gasification, e.g. plural parallel or serial gasification stages
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
- C10J3/72—Other features
- C10J3/723—Controlling or regulating the gasification process
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
- C10J3/72—Other features
- C10J3/726—Start-up
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
- C10J3/72—Other features
- C10J3/82—Gas withdrawal means
- C10J3/84—Gas withdrawal means with means for removing dust or tar from the gas
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
- C10J3/72—Other features
- C10J3/86—Other features combined with waste-heat boilers
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K1/00—Purifying combustible gases containing carbon monoxide
- C10K1/02—Dust removal
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K1/00—Purifying combustible gases containing carbon monoxide
- C10K1/04—Purifying combustible gases containing carbon monoxide by cooling to condense non-gaseous materials
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K3/00—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide
- C10K3/001—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide by thermal treatment
- C10K3/003—Reducing the tar content
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K3/00—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide
- C10K3/001—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide by thermal treatment
- C10K3/003—Reducing the tar content
- C10K3/005—Reducing the tar content by partial oxidation
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K3/00—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide
- C10K3/001—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide by thermal treatment
- C10K3/003—Reducing the tar content
- C10K3/008—Reducing the tar content by cracking
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F22—STEAM GENERATION
- F22B—METHODS OF STEAM GENERATION; STEAM BOILERS
- F22B1/00—Methods of steam generation characterised by form of heating method
- F22B1/02—Methods of steam generation characterised by form of heating method by exploitation of the heat content of hot heat carriers
- F22B1/18—Methods of steam generation characterised by form of heating method by exploitation of the heat content of hot heat carriers the heat carrier being a hot gas, e.g. waste gas such as exhaust gas of internal-combustion engines
- F22B1/1838—Methods of steam generation characterised by form of heating method by exploitation of the heat content of hot heat carriers the heat carrier being a hot gas, e.g. waste gas such as exhaust gas of internal-combustion engines the hot gas being under a high pressure, e.g. in chemical installations
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/30—Fuel from waste, e.g. synthetic alcohol or diesel
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/32—Hydrogen storage
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/10—Internal combustion engine [ICE] based vehicles
- Y02T10/12—Improving ICE efficiencies
Abstract
process for producing syngas, the process comprising: gasifying carbonaceous material to provide a first syngas having a CO to CO2 molar ratio of less than about 0.5 until the first syngas reaches a first target temperature; upon reaching the first target temperature, gasifying carbonaceous material to provide a second syngas having a CO to CO2 ratio of greater than the first syngas; and passing at least a portion of the second syngas to a syngas cooler at a linear velocity of greater than about 24 meters per second. al to provide a second syngas having a CO to CO2 ratio of greater than the first syngas; and passing at least a portion of the second syngas to a syngas cooler at a linear velocity of greater than about 24 meters per second.
Description
METHOD OF OPERATION OF PROCESS TO PRODUCE SYNGAS FROM
CARBONACEOUS MATERIAL
This application claims the benefit of U.S. Provisional Application Nos.
61/516,646, 61/516,704 and 61/516,667 all filed April 6, 2011, all of which are
incorporated in their entirety herein by reference.
A process is provided for gasification of aceous materials to produce
producer gas or synthesis gas or syngas comprising carbon monoxide and hydrogen. More
specifically, the s is ive for producing cooled syngas for ream use. The
s utilizes gasification of carbonaceous materials to produce a syngas ed by
cooling of said syngas to produce cooled syngas and optionally cleaning said cooled
syngas to e a clean syngas for several downstream processes.
BACKGROUND
Gasification of carbonaceous materials to produce producer gas or sis gas or
syngas comprising carbon monoxide and hydrogen is well known in the art. Typically,
such a gasification process involves a partial oxidation or starved-air oxidation of
carbonaceous material in which a snb—stoiehiometric amount of oxygen is supplied to the
gasification process to promote production of carbon monoxide as disclosed in PCT Patent
Application No. W0 93/018341. Gaseous products produced by partial oxidation of
carbonaceous materials are often treated in a high temperature heat treatment unit, e. g. for
destruction of tar. See for example W0 2009/ 1 54788 that discloses a two stage gasifier in
which carbonaceous material is fed to the first stage in which air, oxygen—enriched air or
pure oxygen can be injected at controlled rate. The first stage temperature and oxygen
input is controlled such that only partial ion of carbonaceous al occurs. The
s product from the first stage moves to the second stage (heat ent unit). Pure
oxygen is introduced into the second stage in order to accomplish cracking and partial
oxidation of any tar contained in the gaseous stream from the first stage. Product syngas is
removed from the second stage.
Syngas produced by gasification processes described in the art can be hot and
needs cooling prior to downstream sing. Recovery and use of this heat content of
hot syngas can be very important for process economics. Hot syngas comprising carbon
monoxide generated in gasification apparatus, is cooled in a heat exchanger or waste heat
boiler downstream of the gasification apparatus. See for example US Patent No. 6,435,139;
US Patent No. 7,587,995 and US Patent No. 7,552,701.
At high temperature reducing environment carbon monoxide is a stable product.
However when carbon monoxide is cooled, carbon de may oxidize into carbon
dioxide, and produce carbon ite) that precipitates as soot:
2CO (g) C02 (g) + C (s)
This reaction is generally known as Boudouard reaction and is believed to take place
at or below about 760°C. Fouling of heat transfer surface caused by deposit of carbon can
cause disruption in operation of a syngas cooler. It is, therefore, important to ate or
reduce fouling of the syngas cooler.
Sulfur in carbonaceous matter transforms to H2S in reductive mode of operation, to
SO2 in oxidative mode of operation. It is advantageous to make SO2 during start-up so that it
can be scrubbed easily prior to disposal.
There is a need for method of operation of a process comprising gasifying
carbonaceous material in a gasification apparatus to produce syngas comprising carbon
monoxide (CO) and carbon dioxide (CO2) and g said syngas in a syngas cooler in a
way that fouling or carbon deposit ion is reduced or eliminated.
SUMMARY
In a first aspect, the present invention provides a process for producing syngas, the
process comprising:
gasifying carbonaceous material to provide a first syngas having a CO to CO2 molar
ratio of less than about 0.5 until the first syngas reaches a first target ature, wherein at
least a portion of the first syngas is passed to a syngas cooler at a linear velocity of r
than about 24 meters per second and/or at least a portion of the first syngas is passed to a
thermal oxidation unit;
upon reaching the first target temperature, gasifying carbonaceous material to provide
a second syngas having a CO to CO2 ratio of greater than the first syngas; and passing at least
a portion of the second syngas to a syngas cooler at a linear ty of greater than about 24
meters per .
In a second aspect, the t invention provides a process to produce , said
process comprising:
(a) adding carbonaceous material and molecular oxygen to a gasification
apparatus to produce a first syngas with CO/CO2 molar ratio less than 0.5;
10445274_1
(b) passing at least a portion of the first syngas to a syngas cooler and/or passing
at least a portion of the first syngas to a thermal oxidation unit;
(c) measuring temperature of said first syngas downstream of said gasification
apparatus; and
(d) upon said temperature of said first syngas prior to entry in said syngas cooler
attaining a first target temperature, reducing the addition of molecular oxygen per unit mass
of carbonaceous material in said gasification apparatus to produce a second syngas with
CO/CO2 molar ratio greater than that of said first syngas,
wherein a flow of syngas through the syngas cooler is maintained at a linear velocity
of greater than about 24 meters per second.
In a third aspect, the present invention provides a s comprising ing
aceous material in a gasification apparatus to produce a syngas, said method
comprising:
(a) adding aceous material and adding molecular oxygen in said
gasification apparatus to produce a first syngas with CO/CO2 molar ratio less than 0.5;
(b) passing at least a portion of said first syngas h a syngas cooler at a
linear velocity of greater than about 24 meters per second to produce a cooled first syngas;
(c) passing at least a portion of said cooled first syngas through a dust collection
system to produce a cleaned syngas;
(d) measuring a temperature of said d syngas at an exit of the dust
collection system; and
(e) upon said temperature of cleaned syngas ing a second target temperature,
reducing addition of molecular oxygen per unit mass of carbonaceous material in said
gasification apparatus to produce a second syngas with CO/ CO2 molar ratio r than that
of said first syngas.
A s is provided for producing syngas that is effective for use in downstream
processes. The process for producing syngas includes operating a gasification apparatus in a
up mode until the cation apparatus and equipment downstream of the gasification
apparatus are adequately warmed up to a first target temperature. Upon reaching a first target
temperature, the process is then operated in a production mode to produce a second syngas
with a higher CO/CO2 molar ratio. Operation in a start-up mode until reaching a first target
temperature es a process that is effective for reducing fouling in downstream
equipment and for providing a second syngas can be more effectively cooled and cleaned.
10445274_1
The second syngas with a higher CO/CO2 molar ratio that is cooled and cleaned is especially
useful for fermentation processes.
The process for producing syngas includes gasifying aceous material to provide
a first syngas having a CO to CO2 molar ratio of less than about 0.5 until the first syngas
reaches a first target ature. Upon reaching the first target temperature, carbonaceous
material is gasified to provide a second syngas having a CO to CO2 molar
10445274_1
ratio of greater than the first syngas. Gasifying of carbonaceous material occurs in a
gasification apparatus and molecular oxygen is introduced at a rate of about 0 to about 100
lb-mole per ton of carbonaceous material on a dry basis to provide the first syngas. The
temperature of the first syngas may be measured at one or more points inside and/or
downstream of the gasification apparatus. When the temperature of the first syngas at one
or more points inside and/or outside the gasification apparatus reaches the first target
temperature, molecular oxygen is introduced at a rate of a rate of 0 to about 100 Ib~mole
per ton of carbonaceous al on a dry basis to provide the second syngas. In this
aspect, the first target temperature is about 700° C to about 1000°C.
In one aspect, at least a portion of the first syngas is passed through a syngas cooler
to produce a cooled first syngas and at least a portion of the second syngas is passed
through a syngas cooler to produce a cooled second syngas. In this aSpect, syngas is
passed through the syngas cooler at a linear velocity of greater than about 24 meters per
second. At least a n of the first syngas is provided to a thermal oxidation unit until
the first syngas s the first target temperature.
In another aspect, a process is provided to e syngas that includes adding
carbonaceous material and molecular oxygen to a ation apparatus to produce a first
syngas with CO/COZ molar ratio less than 0.5. The temperature of the first syngas is
measured downstream of the gasification apparatus. Temperature may be measured prior
to entry into a syngas cooler or downstream of a syngas cooler. Once the syngas reaches a
first ature prior to entry into a syngas cooler, addition of molecular oxygen is
reduced per unit mass of aceous material in the gasification apparatus to produce a
second syngas with CO/COZ molar ratio greater than that of said first syngas. The first
target temperature is about 700°C to about lOOO°C. Reduction of addition of molecular
oxygen per unit mass of carbonaceous material may be lished by increasing rate of
addition of carbonaceous material. Alternatively, reduction of addition of molecular
oxygen per unit mass of carbonaceous material may be accomplished by sing rate of
addition of lar oxygen.
At least a portion of the first syngas may be passed through the syngas cooler to
produce a cooled first syngas and at least a n of the second syngas may be passed
through a syngas cooler to produce a cooled second syngas. At least a n of the
cooled first syngas may be mixed with a portion of the first syngas prior to its passing
through said syngas cooler to produce the cooled first syngas. At least a portion of the
cooled second syngas may be mixed with at least a portion of the second syngas prior to
passing through the syngas cooler to produce the cooled second syngas. The e of the
cooled first syngas and the first syngas flowing through the syngas cooler may have a
linear velocity of greater than about 24 meter/second. The mixture of the cooled second
syngas and the second syngas flowing through the syngas cooler may have a linear
velocity of greater than about 24 meten’second.
In r aspect, one or more of steam and C02 may be added to the gasification
apparatus prior to reduction of the addition of molecular oxygen per unit mass of
carbonaceous material or prior to ng a first target temperature. When additions are
made prior to reaching a first target temperature, less than about 50 lb-mole steam per ton
of carbonaceous material on a dry basis or less than about 50 lb—mole C02 per ton of
carbonaceous material on a dry basis is added.
In another aSpect, a process is provided that includes ing carbonaceous
material in a gasification apparatus to produce a clean syngas. The method es adding
carbonaceous material and adding molecular oxygen in the gasification apparatus to
produce a first syngas with CO/CO; molar ratio less than 0.5. At least a portion of the first
syngas is passed h the syngas cooler to produce a cooled first syngas. At least a
portion of the first cooled syngas is passed through a dust collection system to produce a
clean syngas. The temperature of the clean syngas is measured at an exit of the dust
collection system. Upon the temperature of clean syngas attaining a second target
temperature, reducing addition of lar oxygen per unit mass of carbonaceous
material in the gasification apparatus is reduced to produce a second syngas with CEO/C02
molar ratio greater than that of the first . In this aspect, the second target
temperature is about 100°C to about 200°C. The process is effective for providing a syngas
having less than about 10 ppm tars.
In another aspect, a process is provided for cooling syngas. The s includes
passing a syngas h a syngas cooler to produce a cooled syngas; and recycling at
least a portion of the cooled syngas to an inlet of the syngas cooler to maintain a
temperature at the inlet of the syngas cooler of 760°C or less and a linear velocity through
the syngas cooler of at least 24 meters per second.
BRIEF DESCRIPTION OF FIGURES
The above and other aspects, features and advantages of several aspects of the
s will be more apparent from the following drawings.
Figure l is a schematic diagram of an aspect of a process that includes gasification
of carbonaceous material by treating with molecular oxygen in a gasification apparatus to
produce a hot syngas and subsequent cooling of said hot syngas in a syngas cooler to
produce a cooled .
Figure 2 is a schematic diagram of an aspect of a process that es gasification
of carbonaceous material by treating with molecular oxygen in a gasification tus to
produce a hot syngas and subsequent cooling of said hot syngas in a syngas cooler to
produce a cooled syngas; wherein at least a part of said cooled syngas is recycled and
mixed with said hot syngas prior to entry into syngas cooler.
Figure 3 is a schematic diagram of an aspect of a process that includes gasification
of carbonaceous material by ng with molecular oxygen in a gasification apparatus to
produce a hot syngas and subsequent cooling of said hot syngas in a syngas cooler to
e a cooled syngas; wherein at least a part of said cooled syngas is recycled and
mixed with said hot syngas prior to entry into syngas cooler; and wherein the gasification
apparatus includes two reaction zones, e.g., a gasification zone and a heat treatment zone
connected through a connecting zone.
Figure 4 is a schematic diagram of an aspect of a process that includes gasification
of carbonaceous material by ng with molecular oxygen in a ation apparatus to
produce a hot syngas and subsequent cooling of said hot syngas in a syngas cooler to
e a cooled syngas; n at least a part of said cooled syngas is recycled and
mixed with said hot syngas prior to entry into syngas cooler; n at least a portion of
one or more of hot and cooled syngas can be sent to a thermal oxidation unit; and wherein
at least a portion of said cooled syngas can be processed in a bag—house.
Corresponding reference characters indicate corresponding components throughout
the several views of the drawings. Skilled artisans will appreciate that elements in the
figures are illustrated for simplicity and clarity and have not necessarily been drawn to
scale. For example, the dimensions of some of the elements in the figures may be
exaggerated relative to other ts to help to improve understanding of s aspects
of the present process and apparatus. Also, common but well-understood elements that are
useful or necessary in commercialiy feasible aspects are often not depicted in order to
facilitate a less obstructed view of these various s.
DETAILED DESCRIPTION
Definitions
Unless otherwise defined, the following terms as used throughout this specification
for the present disclosure are defined as follows and can include either the singular or
plural forms of ions below :
The term “about” modifying any amount refers to the variation in that amount
encountered in real world conditions, e.g., in the lab, pilot plant, or production facility. For
it) example, an amount of an ingredient or measurement ed in a mixture or quantity
when ed by “about” includes the variation and degree of care typically employed in
measuring in an experimental condition in production plant or lab. For example, the
amount of a component of a product when modified by “about” includes the variation
between batches in a multiple experiments in the plant or lab and the variation nt in
the analytical method. Whether or not modified by “about,” the amounts incinde
equivalents to those amounts. Any ty stated herein and modified by “about” can also
be employed in the present disclosure as the amount not modified by “about”.
The term “bag—house” or “baghouse” means process or equipment designed for the
use of engineered fabric filter tubes, envelopes or cartridges for capturing, tion or
filtering of solid particles (fine particles, dust) contained in a gas. Dust—laden or solid-
laden gases enter the bag-house and pass through fabric bags that act as filters. The bags
can be of woven or felted , synthetic, or glass—fiber material in either a tube or
envelope shape. Common types of bag-houses include mechanical shaker, reverse air, and
reverse jet.
“Carbonaceous al” as used herein refers to carbon rich material such as coal,
and petrochemicals. However, in this specification, carbonaceous material includes any
carbon material whether in solid, liquid, gas, or plasma state. Among the numerous items
that can be considered carbonaceous material, the present disclosure contemplates:
aceous material, carbonaceous iiquid product, carbonaceous industrial liquid
recycie, carbonaceous municipal solid waste (MSW or msw), carbonaceous urban waste,
carbonaceous agricultural material, carbonaceous forestry material, carbonaceous wood
waste, carbonaceous construction al, carbonaceous vegetative material,
aceous industrial waste, carbonaceous fermentation waste, carbonaceous
petrochemical co products, carbonaceous alcohol tion co—products, carbonaceous
coal, tires, plastics, waste plastic, coke oven tar, ft, lignin, black liquor, polymers,
waste polymers, hylene terephthalate (PETA), polystyrene (PS), sewage ,
animal waste, crop es, energy crops, forest processing residues, wood processing
residues, livestock wastes, poultry wastes, food processing residues, fermentative process
wastes, ethanol co-products, spent grain, spent microorganisms, or their combinations.
The term “dust collector” or “dust collection system” means process or equipment
designed for capturing, separation or filtering of solid particles (fine particles, dust)
contained in a gas. A dust tion system generally consists of a blower, dust filter, a
filter-cleaning system, and a dust receptacle or dust removal system. Principal types of
industrial dust collectors include inertial separators, fabric filters or bag-houses, wet
scrubbers, ostatic precipitators, and unit collectors.
The term “fibersoft” or “Fibersoft” or “fibrosoft” or “fibrousoft” means a type of
i5 carbonaceous material that is produced as a result of softening and concentration of
various nces; in an example carbonaceous material is produced Via steam
autociaving of various substances, In another example, the ft can include steam
autoclaving of municipal, industrial, commercial, and medical waste ing in a fibrous
mushy material.
The term “municipal solid waste” or “MSW” or “msw” means waste that may
include household, commercial, industrial and/or residual waste.
The term “syngas” or “synthesis gas” means synthesis gas which is the name given
to a gas mixture that contains varying s of carbon monoxide and hydrogen.
Examples of production methods include steam reforming of natural gas or hydrocarbons
to e hydrogen, the gasification of coal and in some types of waste-to—energy
ation faciiities. The name comes from their use as intermediates in creating
synthetic natural gas (SNG) and for producing ammonia or methanol. Syngas comprises
use as an intermediate in producing synthetic petroleum for use as a fuel or lubricant via
Fischer-Tropsch synthesis and previously the Mobil methanol to gasoline process. Syngas
consists primarily of en, carbon monoxide, and some carbon dioxide, and has less
than half the energy density (i.e., BTU content) of natural gas. Syngas is combustible and
is often used as a fuel source or as an intermediate for the production of other chemicals.
“Ton” or “ton” refers to U.S. short ton, i.e. about 907.2 kg (2000 lbs).
As used herein, the term "tar" includes, without limitation, a gaseous tar, a liquid
tar, a solid tar, a tar—forming substances, or mixtures thereof, which generally comprise
arbons and derivatives thereof. A large number of well known tar measurement
methods exist that may be utilized to measure tar. One large family of techniques includes
analytical s based on liquid or gas phase chromatography coupled with a detector.
The most frequent detectors in the case of measurement of tars are the flame-ionization
detector (FID) and the mass spectrometer. Another family of techniques includes
spectrometric methods, which inciude detecting and analyzing a spectrum. This is for
e infrared, ultraviolet (UV) or luminescence spectrometry, and LIBS (Laser—
Induced Breakdown Spectroscopy) technique. Another technique for monitoring of
combustion gases is FTIR (Fourier Transform InfraRed) infrared spectrometry.
Miscellaneous documents mention this technique, such as for e W020060l5660,
0480 and U.S. Pat. No. 5,984,998.
There exist other known electronic s which allow continuous monitoring of
tars. These techniques include detectors with electrochemical cells and sensors with
nductors. Various gravimetric techniques may also be utilized for tar
measurements. In one aspect, the amount of tar may be-expressed as equivalent ppm of
carbon. In this aspect, the hydrocarbon may be benzene or an alcohol, such as methanol. In
this aspect, a tar concentration equivalent or tar equivaients most preferably corresponds to
as equivalent ppm (molar) of benzene. The tar concentration is usefully measured at the
outlet of the gasification apparatus and upstream of any substantial cooling of the syngas.
Detailed Description
The following description is not to be taken in a limiting sense, but is made merely
for the purpose of describing the l principles of exemplary embodiments. The scope
of the invention should be determined with reference to the claims.
A gasification process for ing syngas is provided that includes gasifying
carbonaceous al in a gasification apparatus to produce syngas that includes carbon
monoxide (CO) and carbon dioxide (€02) and g said syngas in a syngas cooler or
waste heat boiler and ally further treating the cooled syngas with chemicals to
remove contaminants and then further treating the chemical ning syngas in a dust
collection , e.g. a bag-house. The process includes operating the gasification
apparatus in a start—up mode with a reduced rate of feed, optionally with a high oxygen
input per unit mass of carbonaceous material (e.g., stoichiometric or near stoichiometric or
above stoichiometric amount of oxygen) to produce a first syngas with low CO content i.e.
with low CO/C02 ratio, eg. CO/CO; molar ratio less than about 0.5. The process includes
operating the gasification apparatus in a production mode, i.e. with a low oxygen input per
unit mass of carbonaceous material (e.g., oichiometric amount of oxygen) in order to
preferentially promote production of carbon monoxide and to produce a second syngas
with high CO t i.e. with high CO/CO; ratio, cg. CO/C02 molar ratio greater than
that of first syngas. In one embodiment, CO/CO; molar ratio in the second syngas is
greater than about 1.0.
The process es operating the gasification apparatus in a start—up mode until
the gasification apparatus and equipment downstream of the gasification apparatus are
adequately warmed up. The process, therefore, includes measuring temperatures of at one
or more points (locations) inside and downstream of the gasification apparatus. In one
aspect, the s includes measuring temperatures of syngas (eg. first syngas) at one or
more points (locations) inside and downstream of the gasification apparatus. According to
the s, operation of the gasification apparatus transitions from start-up mode to
production mode after one or more points (locations) inside and downstream of the
gasification apparatus attain target temperatures. In one , operation of the
gasification apparatus transitions from start-up mode to production mode after temperature
of syngas (first syngas) prior to entering syngas cooler attains a first target temperature. In
one , operation of the gasification apparatus transitions from start—up mode to
production mode after temperature of syngas (first syngas) at exit of dust—collection
system (e. g. bag—house) attains a second target ature.
Until the temperature of first syngas attains the first target temperature, all or part
of the first syngas produced during this start-up mode of operation can be passed through
the syngas cooler to e a cooled first syngas. Alternatively, all or part of the first
syngas produced during this start-up mode of operation can be sent to a thermal oxidation
unit for processing and disposal. In one embodiment, all or a part of first syngas is sent to
a l oxidation unit until temperature of first syngas at entry of said syngas cooler
attains the first target ature. In one aspect, all or a part of first syngas is sent to a
thermal oxidation unit during ion of gasification apparatus in start-up mode.
In one aspect, ion of the gasification apparatus transitions to production
mode after the temperature of first syngas at syngas cooler entry s a first target
temperature. In one aspect, operation of the gasification apparatus transitions to production
mode after the temperature of first syngas at exit of dust collection system (eg. bag-house)
attains a second target temperature. Addition of carbonaceous material and molecular
oxygen into the ation apparatus is continued, however, addition of molecular
oxygen per unit mass of carbonaceous material in said gasification tus is reduced in
order to produce a second syngas with high CO content or with high CO/COZ ratio, e.g,
CO/CO; moiar ratio greater than that of first syngas. For example, in one embodiment,
CO/CO; molar ratio in the second syngas is greater than about 1.0. Ail or part of the first
syngas produced during this production mode of Operation can be passed through the
syngas cooler to produce a cooled second . Optionally, all or part of the second
syngas produced during this production mode of operation can be sent to a thermal
ion unit for processing and disposal.
It is desirable to have iittle or no CO and mostly C02 in the first syngas. In one
aspect, the process is effective for providing a COa’COz molar ratio in said first syngas of
less than about 0.5. In one aspect, the COICO; molar ratio in said first syngas is iess than
about 0.25. In another aspect, the CO/COg molar ratio in said first syngas is less than about
0.1. It is desirable to have more CO and less C02 in the second syngas. In one aSpect, the
process is effective for providing a CO/COZ molar ratio in said second syngas of greater
than about 1.0. In one aspect, the COICO; molar ratio in said second syngas is greater than
about 1.5.
A sub-stoichiometric amount of oxygen is supplied to the gasification apparatus in
order to promote production of carbon monoxide during ion in production mode.
Therefore, in one aspect, during operation in production mode, the ratio of amount of
molecuiar oxygen input to total amount of molecular oxygen ed to completely
oxidize ail carbon ned in aceous material feed to carbon dioxide is in a range
of 0.i to 0.9, in one aspect 0.1 to 0.8, in another aspect 0.1 to 0.7, and in another aspect 0.2
to 0.45. In one aspect, during operation in start-up mode, the ratio of amount of moiecular
oxygen input to total amount of molecular oxygen required to completely oxidize all
carbon contained in carbonaceous material feed to carbon dioxide is in a range of 0.5 to
2.0. In one aspect, during operation in start—up mode, the ratio of amount of molecular
oxygen input to total amount of molecular oxygen required to completely oxidize all
carbon ned in carbonaceous material feed to carbon dioxide is in a range of 0.75 to
1.5. In one aspect, during operation in start-up mode, the ratio of amount of molecular
oxygen input to total amount of molecular oxygen required to completely oxidize all
carbon contained in carbonaceous material feed to carbon dioxide is in a range of 0.9 to
1.1.
The target temperatures are selected in a way that occurrence of fouling or deposit
formation inside and downstream of the ation apparatus can be avoided or reduced.
The first target temperature can be about 700°C to about 1000°C. In one aspect, the first
target temperature can be about 750°C to about 850°C. The second target temperature at an
exit of the dust collection system can be about 100°C to about 200°C. In one , the
second target temperature can be about 100°C to about 150°C.
The reduction of the rate of addition of lar oxygen per unit mass of
carbonaceous material can be accomplished by increasing the rate of addition of
aceous material. For example in one aspect, for start—up mode of operation, the rate
of addition of carbonaceous material feed is kept significantly lower than that for
production mode of operation While keeping the rate of on of molecular oxygen at
the same level as in each mode of ion. The reduction of the rate of addition of
molecular oxygen per unit mass of carbonaceous material can be lished by
decreasing rate of addition of molecular oxygen. For example in one aspect, the rate of
addition of carbonaceous material feed is kept the same for start-up mode of operation and
the production mode of ion but the rate of addition of molecular oxygen is
decreased. In one aspect, the rate of addition of lar oxygen is decreased as the
mode of operation is changed‘from start-up mode to production mode while rate of
addition of carbonaceous material is increased.
Occurrence of fouling or deposit formation can be avoided or reduced in the
syngas cooler by taking an additional measure of assuring a high enough linear velocity of
gas flowing through the syngas cooler. A linear velocity measured at the inlet of the
syngas cooler is greater than about 15 meters/second, in another aspect, greater than about
20 /second, and in another aspect, about 24 meters/second is ble. In another
aspect, the linear velocity measured at an inlet of the syngas cooler is between about 15 to
about 30 meters/second, and in another aspect, about 22 to about 26 meters/second.
Increased linear velocity can be accomplished by increasing the volumetric flow rate of
gas and/or decreasing the cross sectional area of flow. The volumetric flow rate can be
increased by recycling all or part of the gas exiting the syngas cooler back to the syngas
cooler inlet. For e in one aspect, an increased linear velocity is attained by mixing
at least a n of the cooled first syngas with at least a portion of first syngas prior to
passing through said syngas cooler. In another aspect, an increased linear velocity is
attained by mixing at least a portion of cooled second syngas with at least a portion of
second syngas prior to passing through said syngas cooler. sed volumetric flow rate
can also be obtained by increasing the inert content of the gas. The use of recycled cooled
syngas enables optimum exchanger velocities to be maintained when the syngas
production rate is d for er reason, including during start—up, shut-down and
feedstock transitions. Thus in one aspect, an increased linear velocity is attained by using
air as a molecular oxygen source especially during start—up mode of operation.
The gasification apparatus may include any gasification equipment bed in
prior art such as, but not limited to moving bed, fixed bed, fluidized bed, entrained flow,
counter—current ("up draf "), co—current ("down draf "), counter—current fixed bed, co—
current fixed bed, counter—current moving bed, co—current moving bed cross draft, ,
cross flow, cross flow moving bed, or a part f. In one aspect, the gasification
apparatus comprises a cross flow unit. In one embodiment, the gasification apparatus
comprises a cross flow moving bed unit.
in one aspect, the gasification apparatus includes a gasification zone wherein
carbonaceous material is contacted with oxygen containing gas at a vely low
ature (e.g. below the ash fusion ature) to produce a raw syngas and a heat
treatment zone wherein the raw syngas undergoes heat treatment or conditiorring in the
presence of an additional amount of oxygen at a higher temperature (e. g. above the ash
fusion temperature) to produce a hot syngas. In one , for example during start—up,
pressure is atmospheric or greater than atmospheric. In another aspect, for example during
start-up mode, air leakage may be allowed.
In one aspect, the gasification apparatus or the gasification zone includes multiple
sections or gasification hearths for contacting said carbonaceous material with a first
molecular oxygen-containing gas and optionally with one or more of steam and C02 to
gasify a n of said carbonaceous al and to produce a first gaseous product. In
various aspects, the ation apparatus or gasification zone ses 1, 2, 3, 4, 5, 6, 7,
8, 9, or 10 sections or gasification hearths. Gas inlets for uction of molecular oxygen
can be attached to the gasification apparatus or gasification zone or one or more hearths
contained therein. Steam or C02 may also be introduced through one or more of these gas
inlets. In one aspect, one or more of molecuiar oxygen, steam and C02 are pre—mixed prior
to suppiying to the gas inlets attached to the gasification apparatus or the gasiiication zone
or to one or more hearths contained therein.
The heat treatment zone may accomplish one or more of cracking and partial
oxidation of any tar contained in raw syngas. The heat treatment zone can be a horizontal
or a vertical chamber with circular or square or rectangular or any other cross section. The
heat treatment zone can be ed to the horizontal or vertical direction. In one ,
the heat treatment zone is connected to the gasification zone through one or more
ting zones. A gas inlet can be attached ly to the heat treatment zone. One or
more gas inlets can be attached to one or more connecting zones (throats). Molecular
oxygen containing gas can be introduced directly into the heat treatment zone. Molecular
oxygen ning gas can be introduced into the heat treatment zone through one or more
gas iniets attached to one or more connecting zones.
Undesirable hot spots might be created in said gasification—apparatus or in the
gasification zone or hearths contained therein due to uneven distribution of molecular
Oxygen containing gas in said carbonaceous material feed. This may produce poor y
syngas. ion of hot spots can be reduced or ted by injecting one or more of
steam and carbon dioxide into one or more of said gasification apparatus. Thus, in order to
prevent undesirable hot spots, carbonaceous material feed may be treated with steam along
with molecular oxygen in the gasification apparatus. Carbonaceous material feed may be
treated with 002 gas along with molecular oxygen in the gasification apparatus. However,
during operation in start-up mode wherein an objective can be rapid heating of the process,
ding steam or C02 may not be advantageous. (Io-feeding steam or C02 may be
advantageous and important during operation in production mode.
The source of molecular oxygen can be one or more of air, oxygen enriched air or
pure oxygen. The total amount of molecular oxygen uced in the ation
apparatus during operation in production mode can be about 0 to about 75 lb-moles per ton
of carbonaceous material on a dry basis, in another aspect about 0 to about 50 lb—moles per
ton of carbonaceous material on a dry basis, and in another aspect about 40 to about 60 lb-
moles per ton of carbonaceous material on a dry basis. The total amount of molecular
oxygen introduced in the gasification apparatus during operation in up mode can be
in a range of about 0 to about 125 lbvmoles per ton of carbonaceous material on a dry
basis, in r aspect about 0 to about 100 lb-moies per ton of carbonaceous materiai on
a dry basis, and in r aspect about 0 to about 50 lb-moles per ton of aceous
material on a dry basis. The totai amount of steam introduced in the gasification apparatus
can be about 0 to about 50 Ila-moles per ton of carbonaceous al feed on a dry basis.
The total amount of carbon dioxide gas introduced in the gasification apparatus can be
about 0 to about 50 lb-moles per ton of carbonaceous al feed on a dry basis. In one
aspect, both steam and carbon dioxide gas are uced in the gasification apparatus.
The carbonaceous material fed to the gasifier may include carbonaceous material,
carbonaceous liquid product, carbonaceous industrial iiquid recycle, carbonaceous
municipal solid waste (msw), carbonaceous urban waste, carbonaceous agricultural
al, carbonaceous forestry material, carbonaceous wood waste, carbonaceous
construction material, carbonaceous vegetative material, carbonaceous industrial waste,
carbonaceous fermentation waste, carbonaceous petrochemical co-products, carbonaceous
alcohol production ducts, carbonaceous coal, tires, plastics, waste plastic, coke oven
tar, fibersoft, lignin, black liquor, polymers, waste polymers, polyethylene terephthalate
(PETA), polystyrene (PS), sewage , animal waste, crop residues, energy crops,
forest processing residues, wood processing residues, livestock wastes, y wastes,
food processing residues, fermentative process wastes, ethanol co—products, spent grain,
spent microorganisms, or their combinations. In one embodiment of the present sure
the carbonaceous al fed to the gasifier comprises a plurality of carbonaceous
materials selected from carbonaceous material, carbonaceous liquid t, carbonaceous
industrial liquid recycle, carbonaceous pal solid waste (msw), carbonaceous urban
waste, carbonaceous agricultural material, carbonaceous forestry material, carbonaceous
wood waste, carbonaceous construction material, carbonaceous vegetative material,
carbonaceous industrial waste, carbonaceous fermentation waste, carbonaceous
petrochemical co—products, carbonaceous alcohol production co—products, carbonaceous
coal, tires, plastics, waste plastic, coke oven tar, fibersoft, lignin, black liquor, polymers,
waste polymers, polyethylene terephthalate (PETA), yrene (PS), sewage sludge,
animal waste, crop residues, energy crops, forest processing residues, wood processing
residues, livestock , poultry wastes, food processing residues, fermentative process
wastes, ethanol co-products, spent grain, spent microorganisms, or their combinations.
In one aspect, said carbonaceous material includes water. In one aspect, said
carbonaceous material includes less than about 50 wt% water. In one aspect, said
carbonaceous material includes less than about 25 wt% water. In one aspect, said
aceous material includes less than about 15 wt% water. In one , the moisture
content of said carbonaceous material is decreased by pre-drying. In one aspect, said
carbonaceous material includes greater than about 25 wt% carbon on a dry or water free
IO basis. In one aspect said carbonaceous material includes greater than about 50 wt% carbon
on a dry or water free basis. In one , said carbonaceous material includes about 0 to
about 50 Wt% oxygen on a dry or water free basis. In one aspect said carbonaceous
material includes about 0 to about 25 wt% hydrogen on a dry or water free basis. In one
aspect, said carbonaceous material includes less than about 25 wt% ash on a dry or water
free basis, In one aspect said carbonaceous al es less than about 15 wt% ash
on a dry or water free basis.
As described above, syngas produced by the gasification apparatus can be cooled
in a syngas cooler to produce a cooled syngas for downstream use, e.g. fermentation to
produce chemicals such as acetic acid, ethanol, etc. The syngas cooler may be heat
exchange equipment or a heat exchanger known in the art. For example a syngas cooler
can be a selection from: and-tube heat ger, plate heat exchanger, plate-and—
frame heat exchanger, tubular heat exchanger, double-pipe heat exchanger, hair-pin heat
exchanger, single-pass heat ger, multi—pass heat exchanger, plate—fin heat
exchanger, spiral heat ger, and combinations thereof.
Cooled syngas may contain contaminants that should be removed prior to
downstream use. Removal of contaminants can be accomplished by treating cooled syngas
with chemical agents. Thus, one or more chemical agents may be added to cooled syngas
to produce a chemical containing cooled syngas. The chemical containing cooled syngas
may be processed in a dust collection system (eg. a bag-house) to remove chemical
residues to thus produce a clean cooled syngas. Clean cooled syngas may be sent to a
down stream processing or to a thermal oxidation unit. The clean cooled syngas can be
optionally r cooled in a quench tower prior to downstream use.
The dust collection system is effective for capturing, separation or filtering of solid
particles (fine particles, dust) from the gas. The dust collection system may include one or
more of a blower, a dust filter, a filter-cleaning system, and a dust receptacle or dust
removal system. The dust collection system can be an inertial separator type dust collector,
a fabric filter type dust collector ouse), a wet scrubber, an electrostatic precipitator,
or a unit tor In one aspect, the dust collection system is a bag-house.
For a gasification apparatus that es a gasification zone and a heat treatment
zone, the heat treatment zone may be cold during start—up and may be prone to fouling or
deposit formation or may bute to fouling or deposit formation in the downstream
piping or syngas cooler. It is, therefore, often preferred that the gasification apparatus is
operated in start~up mode until the heat ent zone is adequately warmed up. For
example in one aspect, the gasification tus is operated in start—up mode until the
heat treatment zone attains a ature of about 900°C. Operation in production mode is
not started until the heat treatment zone attains at least about 900°C temperature.
Optionally, all or part of the first syngas produced is sent to a thermal oxidation unit until
the heat treatment zone s at least about 900°C temperature. In one embodiment, the
gasification apparatus is operated in a start-up mode until the heat treatment zone attains a
temperature of about 1000°C. Operation in production mode is not started until the heat
treatment zone s at least about . Optionally, all or part of the first syngas
produced is sent to a thermal oxidation unit until the heat treatment zone attains at least
about 1000°C.
In one aspect, at least a portion of syngas exiting the syngas cooler is recycled back
to the gasification apparatus in order to cool the syngas cooler inlet temperature and/or
se the linear velocity of gas entering syngas cooler. In one aspect, at least a portion
of syngas exiting the syngas cooler is recycled back to the connecting zone of a
gasification apparatus in order to increase the linear velocity of gas entering syngas cooler
as well as through the connecting zone wherein the gasification zone includes a
ation zone and a heat treatment zone connected by a connecting zone.
Figures 1 to 4 illustrates various aspects of the process. Figure l is a schematic
diagram of one aspect of a process comprising gasification of carbonaceous material by
treating with molecular oxygen in a gasification apparatus to produce a hot syngas and
uent cooling of said hot syngas in a syngas cooler to produce a cooled syngas.
Referring now to Figure 1, a carbonaceous material feed (100) is introduced in the
gasification-apparatus (200). A molecular oxygen containing gas (150) is supplied to the
gasification apparatus and thus the carbonaceous material feed is treated with molecular
oxygen in order to initiate and facilitate chemical transformation of carbonaceous material.
At least a portion of the carbonaceous material feed is gasified in the gasification
apparatus to produce a gaseous product or syngas (250). Supply of oxygen into the
gasification-apparatus can be controlled in order to control ve amounts of carbon
monoxide (CO) and carbon dioxide (C02) produced from gasification of the carbonaceous
material. Hot syngas is subsequently cooled in a syngas cooler (300) to e a cooled
syngas (350). A stream of ash (220) is removed from the gasification tus.
Figure 2 is a schematic diagram of an aspect of a process including gasification of
carbonaceous material by treating with molecular oxygen in a ation apparatus to
produce a hot syngas and subsequent g of said hot syngas in a syngas cooler to
produce a cooled ; wherein at least a part of said cooled syngas is recycled and
mixed with said hot syngas prior to entry into syngas cooler. Referring now to Figure 2, a
carbonaceous al feed (lOO) is introduced in the gasification-apparatus (200). A
molecular oxygen containing gas (150) is supplied to the gasification apparatus and thus
the carbonaceous al feed is treated with molecular oxygen in order to initiate and
facilitate chemical transformation of carbonaceous material. At least a portion of the
carbonaceous material feed is gasified in the gasification apparatus to produce a gaseous
product or syngas (250). Supply of oxygen into the gasification—apparatns can be
controlled in order to control ve amounts of carbon monoxide (CO) and carbon
dioxide (C02) produced from gasification of the carbonaceous material. Hot syngas is
subsequently cooled in a syngas cooler (300) to produce a cooled syngas (350). At least a
part of said cooled syngas (450) is recycled and mixed with said hot syngas prior to entry
into syngas cooler. A compressor (400) is used to facilitate recycle of cooled syngas. A
stream of ash (220) is removed from the gasification apparatus.
Figure 3 is a tic diagram of an aspect of a process that includes gasification
of carbonaceous material by treating with molecular oxygen in a gasification tus to
produce a hot syngas and subsequent cooling of said hot syngas in a syngas cooler to
produce a cooled syngas; n at least a part of said cooled syngas is recycled and
mixed with said hot syngas prior to entry into syngas cooler; and wherein the gasification
tus comprises two reaction zones, e.g., a gasification zone and a heat treatment zone
ted through a connecting zone. Referring now to Figure 3, a carbonaceous material
feed (100) is introduced in the ation zone (201) of said gasification—apparatus. A
molecular oxygen containing gas (150) is supplied to the gasification zone of said
gasification apparatus and thus the carbonaceous material feed is treated with molecular
of carbonaceous material.
oxygen in order to initiate and facilitate chemical ormatiou
At least a portion of the carbonaceous material feed is gasified in the ation zone to
produce a raw syngas passes through the
gaseous product (raw ). The raw
connecting zone (203). Molecular oxygen (202) is introduced in the connecting zone to be
mixed with said raw syngas. Mixture comprising raw syngas and molecular oxygen enters
the heat ent zone (204). Molecular oxygen can also be uced in the heat
treatment zone. Raw syngas undergoes heat treatment in the heat treatment zone to
produce a hot syngas (250). Supply of oxygen into the gasification—apparatus (one or more
of cation zone, connecting zone and heat treatment zone) can be controlled in order
to control relative amounts of carbon monoxide (CO) and carbon dioxide (C02) produced
from gasification of the carbonaceous material. Hot syngas is subsequently cooled in a
least a part of said cooled syngas
syngas cooler (300) to produce a cooled syngas (350). At
(450) is recycled and mixed with said hot syngas prior to entry into syngas cooler. A
is used to facilitate recycle of cooled syngas. A stream of ash (220) is compressor (400)
removed from the gasification tus.
Figure 4 is a schematic diagram of a process that includes gasification of
aceous material by treating with molecular oxygen in a gasification apparatus to
produce a hot syngas and subsequent cooling of said hot syngas in a syngas cooker to
produce a cooled syngas; wherein at least a part of said cooled syngas is recycled and
mixed with said hot syngas prior to entry into syngas cooler; wherein at least a portion of
one or more of hot and cooled syngas can be sent to a thermal oxidation unit; and wherein
at least a n of said cooled syngas can be processed in a bag-house. Referring now to
Figure 4, a carbonaceous material feed (100) is introduced in the gasification-apparatus
(200). A iar oxygen containing gas (150) is supplied to the gasification apparatus
and thus the carbonaceous material feed is treated with molecular oxygen in order to
initiate and facilitate chemical transformation of carbonaceous material. At least a portion
of the carbonaceous material feed is gasified in the gasification apparatus to produce a
gaseous product or syngas (250). Supply of oxygen into the gasification-apparatus can be
controlled in order to control relative amounts of carbon monoxide (CO) and carbon
dioxide (C02) ed from gasification of the carbonaceous material. Hot syngas is
subsequently cooled in a syngas cooler (300) to produce a cooled syngas (350). At least a
part of said cooled syngas (450) is recycled and mixed with said hot syngas prior to entry
into syngas cooler. A compressor (400) is used to facilitate recycle of cooied syngas. At
least a portion of hot syngas can be sent to a thermal oxidation unit (700) for sing
and disposal (750). At least portion of cooled syngas can be sent to a thermal oxidation
unit. Cooled syngas. may contain contaminants that should be removed prior to
ream use. Removal of contaminants can be accomplished by adding chemical
agents. Thus one or more chemical agents (500) can be added to cooled syngas to produce
a chemical containing cooled syngas (550). The chemical containing cooled syngas is
sed in a bag—house (600) to remove chemical residues (chemical agents with
inants) and to produce a clean cooled syngas (650) that is either sent to down
stream sing or to thermal oxidation unit. The clean cooled syngas can be optionally
further cooled in a quench tower prior to downstream use (not shown on diagram). A
stream of ash (220) is removed from the gasification apparatus.
EXAMPLES
Example 1: Solid Load of Syngas Produced by Gasification in Production Mode
The gasification apparatus was operated in a up mode by providing
carbonaceous materials to the gasifier at a feed rate of about half as much as that used in a
production mode. Oxygen was supplied to the gasifier at a feed rate of about 40 to 50 lb—
mole ton of carbonaceous material on a dry basis. As described previously, some air
leakage into the gasifier was d that increase oxygen bility.
Upon starting up a gasifier under start-up mode as described above to obtain a first
target temperature in a range of about 700 °C to about 1000 °C, a carbonaceous material
feed rate was sed into the gasification apparatus. A molecular oxygen containing gas
was supplied to the gasification apparatus at the rate of about 50 to about 90 lb-moles per
ton of water-free carbonaceous material. The gasifier was also fed a stream of carbon
dioxide at the rate of about 10 to about 15 lb-moles per ton of water—free carbonaceous
material.
Hot syngas is produced during this operation is subsequently cooled in a syngas
cooler to produce a cooled syngas. Cooled syngas is processed in a bag—house to remove
solid residues and to produce a clean cooled syngas. The clean cooled syngas comprised
CO in the range of about 25 to about 35 mole%, C02 in the range of about 30 to about 40
mole%, Hz in the range of about 10 to about 20 mole%, N2 in the range of about 15 to
about 25 mole% and small amount of CH4. The bag-house removed about 1.5 to about 3.5
lbs solid per hour per 1000 lbs per hour clean cooled syngas produced.
Analysis of Residue from use
Start—up Mode: Low level of solid residue in ; operation in production modecan
follow.
Production Mode: Operable level of solid residue in syngas (3 fold increase of
solids over start-up mode)
While the invention herein disclosed has been described by means of specific
embodiments, examples and applications thereof, numerous modifications and variations
could be made thereto by those skilled in the art t ing from the scope of the
invention set forth in the claims.
Claims (19)
1. A process for producing syngas, the process comprising: ing carbonaceous material to provide a first syngas having a CO to CO2 molar ratio of less than about 0.5 until the first syngas reaches a first target temperature, wherein at least a n of the first syngas is passed to a syngas cooler at a linear velocity of greater than about 24 meters per second and/or at least a n of the first syngas is passed to a thermal oxidation unit; upon reaching the first target temperature, gasifying carbonaceous material to provide a second syngas having a CO to CO2 ratio of greater than the first syngas; and passing at least a portion of the second syngas to a syngas cooler at a linear velocity of greater than about 24 meters per second.
2. The process of claim 1 wherein the gasifying of carbonaceous material occurs in agasification apparatus.
3. The process of claim 1 wherein molecular oxygen is introduced at a rate of about 0 to about 100 lb-mole per ton of carbonaceous material on a dry basis to e the first syngas.
4. The process of claim 2 wherein the temperature of the first syngas is measured at one or more points inside and/or ream of the cation apparatus.
5. The process of claim 4 n when the temperature of the first syngas at one or more points inside and/ or e the gasification apparatus reaches the first target temperature, molecular oxygen is introduced at a rate of about 0 to about 100 lb-mole per ton of carbonaceous material on a dry basis to provide the second syngas.
6. The process of claim 1 wherein the first target temperature is about 700° C. to about 1000° C.
7. The process of claim 1 wherein at least a portion of the first syngas is passed through a syngas cooler to produce a cooled first syngas and wherein at least a portion of the second syngas is passed through a syngas cooler to produce a cooled second syngas.
8. The process of claim 1 wherein at least a portion of the first syngas is ed to a thermal oxidation unit until the first syngas reaches the first target temperature.
9. A process to produce syngas, said process comprising: (a) adding carbonaceous material and molecular oxygen to a gasification apparatus to produce a first syngas with CO/CO2 molar ratio less than 0.5; (b) passing at least a portion of the first syngas to a syngas cooler and/or passing at least a portion of the first syngas to a thermal oxidation unit; 10445274_1 (c) measuring temperature of said first syngas downstream of said gasification apparatus; and (d) upon said temperature of said first syngas prior to entry in said syngas cooler attaining a first target temperature, reducing the addition of molecular oxygen per unit mass of carbonaceous al in said gasification apparatus to produce a second syngas with CO/CO2 molar ratio greater than that of said first syngas, wherein a flow of syngas through the syngas cooler is maintained at a linear ty of greater than about 24 meters per second.
10. The process of claim 9 wherein the temperature of said first syngas is ed prior to entry into a syngas cooler.
11. The process of claim 9 wherein the temperature of said first syngas is measured downstream of a syngas cooler.
12. The process of claim 9 wherein at least a portion of said first syngas is passed through said syngas cooler to produce a cooled first syngas and at least a portion of said second syngas passed through said syngas cooler to e a cooled second syngas.
13. The process of claim 9 wherein a source of molecular oxygen in step (a) is selected from the group consisting of air, oxygen enriched air, pure oxygen, and ations thereof.
14. The process of claim 9 wherein a source of molecular oxygen in step (c) is selected from the group consisting of air, oxygen ed air, pure oxygen, and combinations thereof.
15. The process of claim 9 wherein the source of lar oxygen in step (a) comprises air.
16. The process of claim 9 wherein the source of molecular oxygen in step (c) comprises pure oxygen.
17. The process of claim 9 wherein said first target temperature is about 700° C. to about 1000° C.
18. The process of claim 9 wherein said first target temperature is about 750° C. to about 850° C.
19. The process of claim 9 wherein reduction of on of molecular oxygen per unit mass of carbonaceous material is accomplished by increasing rate of addition of carbonaceous material. 10445274
Applications Claiming Priority (9)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US201161516646P | 2011-04-06 | 2011-04-06 | |
US201161516667P | 2011-04-06 | 2011-04-06 | |
US201161516704P | 2011-04-06 | 2011-04-06 | |
US61/516,646 | 2011-04-06 | ||
US61/516,667 | 2011-04-06 | ||
US61/516,704 | 2011-04-06 | ||
US13/427,247 US20120256131A1 (en) | 2011-04-06 | 2012-03-22 | Method of Operation of Process to Produce Syngas from Carbonaceous Material |
US13/427,247 | 2012-03-22 | ||
PCT/US2012/032168 WO2013032537A1 (en) | 2011-04-06 | 2012-04-04 | Method of operation of process to produce syngas from carbonaceous material |
Publications (2)
Publication Number | Publication Date |
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NZ617115A NZ617115A (en) | 2015-09-25 |
NZ617115B2 true NZ617115B2 (en) | 2016-01-06 |
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