CN101918305A - 利用甲醇生产氢气和燃料，生产氢气和燃料的方法及设备 - Google Patents

利用甲醇生产氢气和燃料，生产氢气和燃料的方法及设备 Download PDF

Info

Publication number
CN101918305A
CN101918305A CN2008801239991A CN200880123999A CN101918305A CN 101918305 A CN101918305 A CN 101918305A CN 2008801239991 A CN2008801239991 A CN 2008801239991A CN 200880123999 A CN200880123999 A CN 200880123999A CN 101918305 A CN101918305 A CN 101918305A
Authority
CN
China
Prior art keywords
biological
hydrogen
biofuel
unit
methanol
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN2008801239991A
Other languages
English (en)
Inventor
P·库科宁
P·克努蒂拉
P·约凯拉
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
UPM Kymmene Oy
Original Assignee
UPM Kymmene Oy
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=39386023&utm_source=***_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=CN101918305(A) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Priority claimed from FI20075794A external-priority patent/FI20075794L/fi
Application filed by UPM Kymmene Oy filed Critical UPM Kymmene Oy
Publication of CN101918305A publication Critical patent/CN101918305A/zh
Pending legal-status Critical Current

Links

Images

Classifications

    • 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
    • C01B3/323—Catalytic reaction of gaseous or liquid organic compounds other than hydrocarbons with gasifying agents
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
    • C01B13/02—Preparation of oxygen
    • C01B13/0229—Purification or separation processes
    • C01B13/0248—Physical processing only
    • 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
    • C01B3/38—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 catalysts
    • C01B3/382—Multi-step processes
    • 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
    • C01B3/48—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 followed by reaction of water vapour with carbon monoxide
    • 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
    • C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
    • C01B3/52—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with liquids; Regeneration of used liquids
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • 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
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
    • C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
    • C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C10G3/50—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids in the presence of hydrogen, hydrogen donors or hydrogen generating compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/58—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K1/00—Purifying combustible gases containing carbon monoxide
    • C10K1/08—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors
    • C10K1/10—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with aqueous liquids
    • C10K1/101—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with aqueous liquids with water only
    • 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
    • C10K3/02—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 catalytic treatment
    • C10K3/04—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 catalytic treatment reducing the carbon monoxide content, e.g. water-gas shift [WGS]
    • 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
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C11/00—Regeneration of pulp liquors or effluent waste waters
    • D21C11/06—Treatment of pulp gases; Recovery of the heat content of the gases; Treatment of gases arising from various sources in pulp and paper mills; Regeneration of gaseous SO2, e.g. arising from liquors containing sulfur compounds
    • 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
    • C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
    • C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
    • C01B2203/0233—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a steam reforming 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
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
    • C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
    • C01B2203/0244—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being an autothermal reforming step, e.g. secondary reforming processes
    • 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
    • C01B2203/0283—Processes for making hydrogen or synthesis gas containing a CO-shift step, i.e. a water gas shift 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
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0415—Purification by absorption in liquids
    • 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
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/042—Purification by adsorption on solids
    • C01B2203/043—Regenerative adsorption process in two or more beds, one for adsorption, the other for regeneration
    • 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
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0465—Composition of the impurity
    • 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
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0465—Composition of the impurity
    • C01B2203/048—Composition of the impurity the impurity being an organic compound
    • 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
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0465—Composition of the impurity
    • C01B2203/049—Composition of the impurity the impurity being carbon
    • 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
    • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1205—Composition of the feed
    • C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
    • C01B2203/1217—Alcohols
    • C01B2203/1223—Methanol
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2210/00—Purification or separation of specific gases
    • C01B2210/0043—Impurity removed
    • C01B2210/0046—Nitrogen
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/34—Organic compounds containing oxygen
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/02—Non-contaminated water, e.g. for industrial water supply
    • C02F2103/023—Water in cooling circuits
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/16—Nature of the water, waste water, sewage or sludge to be treated from metallurgical processes, i.e. from the production, refining or treatment of metals, e.g. galvanic wastes
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/26—Nature of the water, waste water, sewage or sludge to be treated from the processing of plants or parts thereof
    • C02F2103/28—Nature of the water, waste water, sewage or sludge to be treated from the processing of plants or parts thereof from the paper or cellulose industry
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
    • C02F2103/36—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds
    • C02F2103/365—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds from petrochemical industry (e.g. refineries)
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00—Biological treatment of water, waste water, or sewage
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1003—Waste materials
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1011—Biomass
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0913—Carbonaceous raw material
    • C10J2300/0916—Biomass
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0953—Gasifying agents
    • C10J2300/0959—Oxygen
    • 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
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/16—Integration of gasification processes with another plant or parts within the plant
    • C10J2300/164—Integration of gasification processes with another plant or parts within the plant with conversion of synthesis gas
    • C10J2300/1656—Conversion of synthesis gas to chemicals
    • C10J2300/1659—Conversion of synthesis gas to chemicals to liquid hydrocarbons
    • 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
    • C10J2300/1678—Integration of gasification processes with another plant or parts within the plant with air separation
    • 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
    • C10J2300/169—Integration of gasification processes with another plant or parts within the plant with water treatments
    • 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
    • C10L2200/00—Components of fuel compositions
    • C10L2200/04—Organic compounds
    • C10L2200/0461—Fractions defined by their origin
    • C10L2200/0469—Renewables or materials of biological origin
    • 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
    • C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
    • C10L2290/42—Fischer-Tropsch steps
    • 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
    • C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
    • C10L2290/54—Specific separation steps for separating fractions, components or impurities during preparation or upgrading of a fuel
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C11/00—Regeneration of pulp liquors or effluent waste waters
    • D21C11/0007—Recovery of by-products, i.e. compounds other than those necessary for pulping, for multiple uses or not otherwise provided for
    • 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
    • Y02E20/00—Combustion technologies with mitigation potential
    • Y02E20/16—Combined cycle power plant [CCPP], or combined cycle gas turbine [CCGT]
    • 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
    • Y02E20/00—Combustion technologies with mitigation potential
    • Y02E20/16—Combined cycle power plant [CCPP], or combined cycle gas turbine [CCGT]
    • Y02E20/18—Integrated gasification combined cycle [IGCC], e.g. combined with carbon capture and storage [CCS]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/30—Fuel from waste, e.g. synthetic alcohol or diesel
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/141—Feedstock
    • Y02P20/145—Feedstock the feedstock being materials of biological origin
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Combustion & Propulsion (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Analytical Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Processing Of Solid Wastes (AREA)
  • Liquid Carbonaceous Fuels (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Preparation Of Compounds By Using Micro-Organisms (AREA)
  • Paper (AREA)

Abstract

本发明涉及利用来自纸浆工业的生物甲醇生产生物氢。优选的生物甲醇包含经过纯化的由黑液得到的生物甲醇。本发明还涉及由回收自黑液的粗生物甲醇生产生物氢的方法，并且涉及利用这种生物氢作为氢源生产烃生物燃料的方法。本发明还涉及由生物氢和生物烃生产燃料的一种生产生物燃料的装置，并且本发明还涉及这样所制得的生物燃料。本发明使生产一种其原料百分之百出自非化石来源的生物燃料成为可能。

Description

利用甲醇生产氢气和燃料，生产氢气和燃料的方法及设备
发明领域
本发明涉及利用来自纸浆工业的生物甲醇生产生物氢。优选的生物甲醇包含经过纯化的由黑液得到的生物甲醇。本发明还涉及由来自黑液的生物甲醇生产生物氢的方法，并且涉及利用这种生物氢作为氢源生产烃生物燃料的方法。最后，本发明涉及由生物氢和生物烃生产燃料的生物燃料生产装置，并且本发明还涉及这样所制得的生物燃料。
本发明改进了通过生成烃的过程，诸如费-托反应(Fischer-Tropsch)和加氢脱氧反应，利用生物材料来生产生物燃料的已知的方法。本发明的生物氢可用于将中间产物烃提升至具有理想化学和物理性质的最终产物。所有以上提到的反应过程都需要氢气作为反应剂，许多反应优选在氢气压力下发生。
本发明给木材加工业带来的益处在于它促进了其一种低价值的副产品即生物甲醇的利用率。利用生物甲醇来生产生物氢意味着烃生物燃料产品的生产完全具有生物的特性。在目前的工艺中，生物燃料的生产通常依赖于外来的氢气，它通常通过天然气的蒸汽重整来生产。
发明背景
日益减少的化石燃料资源以及利用化石燃料时排放出的有害气体提高了利用生物原料，尤其是由不可食用的，可再生的资源来生产能替代化石燃料的液体燃料的兴趣。先前已知有几个从生物起始物质生产液体燃料的工艺。一个已经成功商业化的工艺包含通过源自生物质的油类与醇类的酯交换反应来生产生物柴油(FAME)。
生物燃料也成功地从由费-托合成法将生物质气化产物制成的烃类，以及通过生物来源的甘油三酸酯和脂肪酸的加氢脱氧反应制成的烃类来获得。另外，从生物原料生产的醇类，如乙醇和甲醇，已被提议用作内燃机的化石燃料的替代品。
甲醇是醇类中最简单的一种，它的化学式为CH3OH。它被用作溶剂，用作工业化学品来制造范围广泛的原料，包括甲醛，甲基叔丁基醚(MTBE)，乙酸，对苯二甲酸二甲酯(DMT)，甲基丙烯酸甲酯(MMA)，甲胺类，防冻剂等。甲醇也已被提议用于生产非化石燃料，诸如脂肪酸甲酯(FAME)，二甲醚(DME)，甲醇制汽油(MTG)，甲醇制烯烃(MTO)。另外，甲醇已被提议作为燃料电池的氢源。
甲醇也被称为”木醇”，因为它原先是作为木材干馏的副产品被制得的。现今，绝大部分的甲醇是通过多步的合成工艺过程制得的，其中天然气与蒸汽在反应炉中被转化，生成氢和一氧化碳。然后在加压下，氢气与一氧化碳气体在催化剂的存在下反应，生成甲醇。
生物甲醇，即生物来源的甲醇，可以从各种不同的来源制得。典型地，它通过生物质，诸如各种农作物或林作物残渣，动物和人类排出的废弃物，城市废弃物和回填物，制糖甜菜浆，甘油等的厌氧消化来生产。
硫酸盐制浆过程(Kraft pulping process)中形成的黑液已被提议作为原料来生产用作非化石燃料的生物甲醇。此时，黑液被气化，生成氢与一氧化碳的混合物(合成气)，然后再被转化为甲醇。
在制木浆的过程中，生物甲醇也作为直接的副产品产出。在硫酸盐制浆过程中，不希望发生的硫化钠与各种木组分的副反应的结果形成了大量的不同的有机硫化合物。在蒸发黑液的过程中，获得了含有生物甲醇的冷凝液。但是，生物甲醇被所述的硫化合物所污染，具有十分臭的气味。传统上，被污染的甲醇在工厂中被焚烧，回收能量，破坏臭味组分。
从黑液得到的甲醇的纯化方法已在先前的技术中描述过。美国专利5,450,892公开了一种黑液冷凝液汽提塔尾气洗气工艺。碱性洗气去除了诸如硫化氢，甲硫醇，二甲硫和二甲基二硫醚那样的气体，使大部分的甲醇留在经过洗气的气体中。这些气体然后被焚烧掉。
美国专利5,718,810公开了利用萃取蒸馏从硫基木浆工艺中回收甲醇的方法。根据该方法，从至少含有甲醇和二甲硫的制浆过程蒸气中回收甲醇。该蒸气分两步或三步蒸馏，得到纯度接近100％的甲醇。
在生产烃基生物燃料时，典型的起始原料是生物质，生物质被气化，制得合成气。接着，将合成气导入费-托(FT)反应器，制得生物烃。合适的生物质源的例子包括林区废料，城市废木，造纸工业的副产品和废料，废木材，木屑，锯末，稻草，柴薪，农业残渣，粪等。
气化器已经被研究了一个多世纪，已经开发了许多不同类型的气化器。但生物质气化器的一个缺点还是存在，即它们不能产生具有约为2的最佳H2/CO比例，用于效率最高的钴基费-托三相淤浆合成的稳定的合成气流。为了校正产自生物质的合成气的氢与一氧化碳的比例，需要补充氢气。
另一种生产烃基生物燃料的可能性是利用生物甘油三酸酯(生物油类)或生物脂肪酸(生物酸类)作为起始原料。为了生产生物燃料，通过加氢脱氧工艺(HDO)来处理起始原料。在催化HDO过程中，氢与氧结合形成水，这样使所需要的石蜡生物烃主链释放出来进行化学处理。
在生产生物燃料的过程中，在FT或HDO之后紧接着的阶段包含生物烃产物的改质。改质工艺通常包含裂化和/或需要氢的异构化过程。采用一维分子筛催化剂，例如Pt/丝光沸石，Pt-SAPO类，或者Pt-ZSM-23，22或相当的催化剂会有助于得到合适的，柴油范围分子长度的生物烃，有助于提供能决定所需的浊点和十六烷值的侧链结构。典型地，这些改质工艺采用较高的氢压而并不消耗大量的氢气。
天然气的水蒸汽重整是工业上大量生产氢最普通的方法。它也是最便宜的方法。它是基于这样一个概念，即在高温下(700-1100℃)和有镍基催化剂存在时，水蒸汽与甲烷根据反应方程式发生反应，生成氢。
CH4+H2O→CO+3H2
利用与生成的一氧化碳发生的温度较低的水煤气变换反应可以回收更多的氢气。
也可以由产自生物质的合成气，和由生物燃料分级时的尾气来生产补充用的氢气。获得更多氢的一个标准步骤是熟知的水煤气变换(WGS)反应(CO+H2O→CO2+H2)。但是，WGS反应有其缺点。WGS反应是一催化过程，难控制，对合成气中的杂质很敏感。而且，由于WGS反应要用掉作为合成气一部分的一氧化碳，它降低了整个过程***的总的碳转化率。
因此，为了生产生物燃料，有需要来提供另一可供选择的氢源。为了提供100％生物的非化石燃料，需要一种成本合理的生物氢产物。生物氢的提供应该最好不用掉WGS反应的一氧化碳，因为一氧化碳是一个形成生物烃燃料结构单元的组分。本发明致力于满足该需要。本发明从纸浆工业的废产物，即从生物甲醇来提供生物氢。
发明概述
本发明涉及利用来自纸浆工业的生物甲醇生产生物氢。该生物甲醇通常包含经过纯化的由废制浆液或黑液得到的生物甲醇。生物甲醇可以通过，例如蒸馏和/或汽提从黑液中回收。生物甲醇的纯化在它用于生产生物氢之前进行。生物氢可以在用于生产生物烃燃料之前进一步纯化。
在一个实施方式中，该生物氢被用于与纸浆厂和/或造纸厂整合在一起的生产生物燃料的装置中。
本发明还涉及生产生物氢的方法，其中，对回收自黑液的粗生物甲醇进行纯化和重整，然后回收生物氢。纯化过程除去了恶臭的硫杂质，它污染了产自硫酸盐木纸浆的粗生物甲醇。
本发明还涉及生产烃生物燃料的方法，它包括以下步骤，其中
a)回收自黑液的粗生物甲醇被纯化和重整以提供生物氢，回收经过纯化的生物氢；
b)通过选自利用产自生物质的合成气的费-托反应，生物甘油三酸酯或脂肪酸的加氢脱氧反应，以及它们的组合的方法来产生生物烃流，其中
c)所述步骤b)的生物烃流生产包括至少一个选自以下的工艺步骤：调节合成气的氢与一氧化碳的比例，费-托合成过程中得到的石蜡的裂化/异构化，所述生物甘油三酸酯或脂肪酸的加氢脱氧，正石蜡的加氢异构化，以及催化剂的还原；和
d)所述纯化过的在步骤a)中回收到的生物氢在步骤c)中所定义的至少一个工艺步骤中被用作氢源，所制得的生物烃流被分离成馏分，从至少一个所述的馏分中回收得到生物燃料。
生物甲醇可以与气体流一起被重整，这些气体流来源于所述生物燃料生产过程的一个或多个工艺步骤，它们含有能通过重整生成氢的气体组分。所得到的生物氢通常被直接用于生物燃料的生产。
本发明还涉及整合在一起的纸浆/生物燃料生产装置，它包括提供黑液的硫酸盐纸浆厂；从所述黑液中回收粗生物甲醇的回收单元；对所述粗生物甲醇进行纯化，产生纯化了的生物甲醇的甲醇纯化单元；将所述纯化了的生物甲醇重整，生成含有生物氢的气体混合物的重整单元；将所述气体混合物纯化，提供纯化了的生物氢的氢气纯化单元；从所述生物氢和从生物质生产生物烃基生物燃料的生物燃料生产设备。
在本发明的一个实施方式中，生物质包含硫酸盐纸浆厂的生物废物和/或副产品，诸如林产品废渣，林区废料，树皮，木屑，黑液，妥尔油和妥尔油脂肪酸等。纸浆厂和生物燃料生产设备优选通过一个或更多个单元整合在一起。
本发明的一个最终产物是由木材加工业的废料和/或副产品所生产的生物燃料，该生物燃料是由生物烃构成，生物烃由产自硫酸盐纸浆厂的生物废物和/或副产品，以及产自黑液的生物氢制成。
附图简要说明
图1为利用来自纸浆生物甲醇的生物氢来生产生物燃料的流程示意图。
图2为从纸浆工艺过程中的粗生物甲醇生产生物氢的流程示意图。
图3为利用在与生物燃料生产设备整合在一起的纸浆厂中产出的生物氢的流程示意图。
发明详述
本发明涉及用于生产生物燃料的生物氢的生产。在一个实施方式中，本发明涉及一个整合的工业的概念，其中生物燃料生产设备利用毗连的纸浆厂的生物废物和/或副产品来生产可替代化石燃料的有价值的生物燃料。
在本申请说明书和权利要求书中，下述术语的意义定义如下。
术语“生物甲醇”指的是产自生物来源的，即是可再生的生物的(非化石)来源的甲醇CH3OH。典型地，本发明中的生物甲醇产自纸浆废液(黑液)。
术语“生物氢”和“生物烃”分别指的是产自生物来源的，即是可再生的生物的(非化石)来源的氢和烃。
术语“生物”，“生物材料”和“生物来源的”指的是种类繁多的自植物，动物和/或鱼获得的物质，即相对于化石来源而言是生物可再生的来源。
术语“生物质”包括任何种类的源自生物的材料，它们适合于被气化制成合成气，和/或它们含有适合于生产烃类的甘油三酸酯和/或脂肪酸。典型地，生物质选自植物，动物和/或鱼来源的原始材料和废料物质，诸如城市废弃物，工业废物或副产品，农业废物或副产品(也包括粪)，木材加工业的废料或副产品，食品工业的废料或副产品，海洋植物(如藻类)和它们的组合。生物质材料优选自非食用的资源，诸如非食用的废物和非食用的植物性材料，包括油类，脂肪和蜡。
根据本发明的说明书和权利要求书，一种特定的生物质材料包含“木材加工业的生物废物和/或副产品”。这种从木材获得的生物质包括林区废料，砍伐后的废木，树皮，城市废木，废木材，木屑，锯末，稻草，柴薪，木料，纸，纸浆，造纸业或木材业的副产品，黑液，妥尔油和妥尔油脂肪酸等。
术语“木材加工业”指的是任何使用木头作为其原料的工业。典型地，木材加工业包含纸浆厂和造纸厂，锯木厂，面板公司，柴薪生产商，木造粒机等。
术语“硫酸盐纸浆厂生物废物和/或副产品”指的是在硫酸盐纸浆造浆过程中所产生的任何生物废物和/或副产品，并且，它们可以用于制烃。典型地，该术语指的是林区废料，砍伐后的废木，树皮，木屑和黑液，以及妥尔油和妥尔油脂肪酸。
术语“生物燃料”指的是主要或完全由生物来源的原料生产的燃料。本发明的生物燃料实际上不含氧。
术语“生物柴油”在本说明书中指的只是那些传统的生物燃料产品，它们是由生物质获得的油类与醇进行酯交换反应所制得的，它们含氧。
术语“纸浆废液”或”黑液”是木质素残渣，半纤维素，和硫酸盐纸浆造浆过程中所使用的无机化学品的水溶液。
术语“中间馏分”指的是一种烃馏分，其中烃基本上由碳链长度为11至20的烃组成。
术语“重馏分”指的是一种烃馏分，其中烃基本上由碳链长度超过20的烃组成。
术语“石脑油馏分”指的是一种馏出烃馏分，其中烃基本上由碳链长度为5至10的烃组成。
术语“轻馏分”指的是一种烃馏分，其中，烃链长度为1至4。根据获得轻馏分工艺的不同，轻馏分还包括诸如氢和一氧化碳那样的其他气体组分。
术语“合成气”指的是一种气体混合物，它是含碳物质气化时生成的，它含有的一氧化碳和氢的量是变化的。生物物质气化所提供的氢与一氧化碳的比例接近2。在加入一些额外的氢气后，该气体适合于利用费-托合成来生产烃。
术语“生物质制液体”BTL指的是由生物质生产液体生物燃料的多步骤的工艺过程。该过程利用整个设备来改善CO2的平衡和提高产率。用于BTL的主要工艺是费-托过程。
术语“费-托”(FT)合成是一催化化学反应，在该反应中，氢和一氧化碳(合成气)被转化成基本高斯分布的各种长度的烃链。所采用的典型催化剂是基于铁和钴的。
术语“催化加氢脱氧”(HDO)用在本说明书和权利要求书中指的是在催化条件下，利用氢气处理生物甘油三酸酯(油，脂肪，蜡)和/或脂肪酸进料的催化处理过程，在该过程中发生了以下反应：甘油三酸酯的结构被断裂，以水的形式脱氧或将氧去除，以及加氢使双键饱和。本发明优选的HDO还除去了不希望有的杂质，如以硫化氢的形式将硫脱除，以氨的形式将氮脱除。可用的HDO催化剂是例如US 7232935中所述的适用于HDO步骤的催化剂。
术语“异构化”和“加氢异构化”指的是在催化和氢的帮助下，将短链的(典型的是甲基)支链引入到正石蜡烃中。
用于本发明的HDO烃物流的术语“非裂化加氢异构化”指的是一种异构化反应，该反应在已知几乎不会或完全不会使所述的烃裂化的催化剂作用下进行。典型的非裂化催化剂包含中等孔径大小的硅铝磷酸盐分子筛(SAPO)催化剂。例如，可用的非裂化异构化催化剂是在美国专利7,232,935中提到的用于所述异构化步骤的那些催化剂。
根据本发明，用于产自FT的石蜡的术语“催化裂化/异构化”指的是按照所谓的碳阳离子机理(G.A.Olah等，<超酸>，Wiley-Interscience，1985，第5章)，同时发生裂化与加氢异构化步骤。典型的异构化催化剂兼具加氢-脱氢(Pt，Pd)和酸性功能(分子筛)。反应过程是在氢气和兼具裂化与异构化性质的催化剂存在下进行的。典型的裂化/异构化催化剂包括在美国专利4,222,855，4,229,282和4,247,388中描述的用于如费-托蜡那样的石蜡原料的选择性裂化和异构化的ZSM沸石催化剂，例如ZSM-5和ZSM-23催化剂。
术语“自热重整”(ATR)指的是通过结合部分氧化与蒸汽重整，由诸如烃和甲醇那样的原料催化制氢的过程。
术语“水煤气变换”(WGS)指的是水与一氧化碳反应生成二氧化碳与氢的无机化学反应(水裂解)。
术语“回收”用在本发明的说明书和权利要求书中与生物甲醇和生物氢联系在一起，并非一定意指上述的甲醇或氢被分离出来成为其自身产物。该术语也用来表示将所获得的甲醇或氢分别直接用于后续的过程中。
术语“整合的过程”这样一种过程，其中将两种或更多种能独立进行的相关功能组合，使得这两种过程具有至少一个共同的重要工艺步骤。
术语“十六烷值”与柴油燃料的点火性质有关。该值通过将待分析燃料与具有已知十六烷值的燃料或掺混物进行标准化的比较而获得。参比的燃料正十六烷(C16)的十六烷值为100。
本发明特别感兴趣的实施方式涉及从黑液中回收甲醇。可以通过对黑液进行汽提和/或蒸馏来回收粗生物甲醇，或者，粗生物甲醇可以作为妥尔油蒸馏时的副产品被回收，妥尔油是在黑液酸化时生成的。
生物甲醇是纸浆生产时的一种低价值的副产品，通常它是被烧掉以产生能量。但是依照本发明，由黑液获得的生物甲醇被用作生物氢的来源，通过重整工艺用于FT和/或HDO过程。
从黑液获得的生物甲醇含有许多源自纸浆造浆过程化学品的氮化合物和硫化合物。某些氮化合物也源自纸浆造浆过程中木蛋白的脱氨基过程。
包含在粗生物甲醇中各种各样的化合物，尤其是氮化合物和硫化合物，会损害用于生产生物燃料的转化催化剂，所以需要另外的纯化步骤来使生物甲醇在经历催化反应步骤时不含硫。
粗生物甲醇可以通过各种方法步骤来纯化，诸如洗涤，洗气，汽提，液-液分离，蒸馏，催化转化，离子交换，吸收和吸附。市场上可以买到各种吸附剂，离子交换剂、催化剂和清洁装置。
已经发现在氮化合物中最多的是氨，而硫化合物中最多的是诸如硫化氢，二甲硫，二甲基二硫醚和甲硫醇那样的硫化物。所有这些化合物都是气体或者低沸点液体，可以通过汽提和/或蒸馏去除掉。生物甲醇还含有硫醇化合物，在它们的分子中有巯基(-SH)。它们被认为是纸浆生物甲醇有臭味的原因。经过汽提的和/或蒸馏的生物甲醇仍然含有一些较高分子量的杂质，可以通过例如吸附的方法除去。合适的吸附剂在市场上有售。需要时，可以将吸附剂，洗涤剂，催化剂等结合起来使用。
例如，ZnO基的吸附剂材料能吸附有机硫化合物，它可以用来将生物甲醇纯化至可接受的程度。某些硫化合物，以及尤其是二氧化碳，可以用一种纯化方法除去，该方法包括使粗生物甲醇物流在高压下经受冷甲醇(refrigerated methanol)的处理。冷甲醇作为一种物理溶剂，吸收了生物甲醇中的杂质。接着，通过降低压力和/或蒸汽汽提，被吸收的杂质从物理溶剂中被除去。依赖化学反应来去除杂质的溶剂，和使杂质降解的催化剂也可用于本发明中来纯化生物甲醇。在上述美国专利5,450,892和5,718,810中概述的方法也可在本发明中用于生物甲醇的纯化。将不同的纯化方法结合起来达到了最佳的结果。
经过纯化的生物甲醇可能仍然含有一些高分子量的硫化合物和氮化合物。这些化合物将与生物甲醇一起进入重整器，在那里降解成更小的化合物，最后变成氨和硫化氢，它们可以被压力变动吸附(PSA)分子筛吸附剂所吸附。
经过纯化的生物甲醇通常在自热重整(ATR)过程中经历重整。也可以采用带单独热源的蒸汽重整过程。ATR转化单元是一项业内人士熟知的技术，市场上有售。蒸汽重整的原理也是业内人士所熟知的。
大家都知道，除了自热重整方法，甲醇还可以通过其他各种方法被重整为氢。但由于该重整是吸热反应，需要有外部的能源来维持反应的进行。除非可以便宜地得到来自外部的燃料，利用部分的甲醇原料作为燃料来维持最佳的重整反应温度是合理的，提供自给重整。
甲醇自热重整是甲醇部分氧化放热反应与水煤气变换由一氧化碳生成二氧化碳和氢的吸热反应的结合。
4CH3OH+3H2O→4CO2+11H2
这个想法是在二十世纪八十年代后期由Johnson-Matthey提出的，该反应的净反应焓变为零。因此，一旦达到了反应温度，该过程的反应器就不需要外部的加热。根据300℃下的化学计量，在产物气体中最高可获得的氢含量为65％。
重整之后，所得到的生物氢再进一步被恰当地纯化，与产生的二氧化碳分离。压力变动吸附(PSA)装置或类似的手段适用于纯化和分离过程。得到的经过纯化的生物氢随时可以进一步利用。
产自黑液的生物氢适宜用于生产烃生物燃料的过程中。
生产生物燃料的生物烃可通过生物质气化得到的合成气的费-托(FT)反应，或者通过生物甘油三酸酯或脂肪酸的加氢脱氧(HDO)反应来生产。当然，生物烃也可以通过掺混产自这两种反应过程的烃来得到。
任何适合于生产合成气的生物质材料都可以用作用于气化的生物质材料。在本发明一个优选的实施方式中，生物质包含木材加工业的生物废物和/或副产品。在本发明的一个实施方式中，木材加工业包含硫酸盐纸浆厂，生物质包含该纸浆厂的生物废物和/或副产品。
在生物质原料被气化后，利用FT反应从合成气的氢和一氧化碳生产烃。依照本发明，产自生物甲醇的生物氢被用来将产出的合成气的H2/CO比例调整至2左右以适应于FT反应。FT反应生成了不同链长度的生物烃。
除去尾气后，剩下的生物烃再经历裂化/异构化反应来缩短链长度。在这个反应过程中，本发明的生物氢可以再被用来提供足够的氢压。裂化反应提高了生物烃物流中C11-C20石蜡的比例。同时，异构化反应生成了支链烃，它改善了最终产物燃料的浊点。
用于加氢脱氧(HDO)反应过程的生物质可以是任意的甘油三酸酯或脂肪酸物质，它适合于通过HDO反应过程来生成烃。这样的物质通常包括诸如麻风油，蓖麻油，妥尔油或妥尔油脂肪酸(TOFA)等非食用性油类。在本发明一个优选的实施方式中，生物质含有木材加工业的生物副产品，如妥尔油或妥尔油脂肪酸。产自生物甲醇的生物氢可用于HDO反应过程，这样一来，得到富含16和18个碳原子链的生物烃的饱和正石蜡物流。
HDO处理也使任何不饱和的链饱和。通常，正石蜡被加氢异构化以提高生物烃流中异石蜡的比例。本发明的生物氢提供了合适的氢进料，为非裂化加氢异构化催化剂提供了所需要的氢压。加氢异构化反应可以在单独的一个异构化反应器内进行，或者，它可以与加氢脱氧反应一起在同一个反应器内进行。
用于生物燃料生产过程各个步骤中的催化剂不时需要用氢气来还原再生。这也可以利用本发明的生物氢来实施。利用氢气再生催化剂有两个方面的作用：首先，将活性金属还原回零价的金属状态，其次，将最终会堵塞催化剂***的重质蜡组分吹洗出去。
接着，来自FT和/或HDO反应过程的加氢了的和/或异构化了的生物烃流被分割成适合于生物燃料用途的馏分。典型的馏分包括轻馏分，石脑油馏分，中间馏分，和重馏分。中间馏分包含所需的烃生物燃料，这是由于它具有理想的沸点范围，良好的十六烷值和浊点，它可以替代化石柴油燃料。
在本发明一个有利的实施方式中，生物燃料生产装置与纸浆厂和/或造纸厂整合在一起。在这样的情形下，工厂的生物废物和/或副产品适合用作生物质经过气化生成合成气。当该工厂包括硫酸盐纸浆车间时，黑液通常作为生物甲醇的来源，妥尔油或妥尔油脂肪酸可以作为HDO过程的原料。
典型的经整合的纸浆/生物燃料生产装置包括硫酸盐纸浆车间，该车间提供含生物甲醇的黑液。整合的装置包括所述生物甲醇的回收单元，纯化单元和重整单元，以及纯化和回收所生成的生物氢的单元。提供了生物燃料生产设备，它由生物氢和包括硫酸盐纸浆厂生物废物和/或副产品的生物质来生产基于生物烃的燃料。
生物甲醇回收单元包括一个或多个汽提单元和/或蒸馏单元以回收粗生物甲醇。由于纸浆生物甲醇有恶臭味，而且含有对催化剂有害的杂质，所以可设置各种单元来纯化粗生物甲醇。这些单元包括选自以下的手段：洗气单元，洗涤单元，汽提单元，吸附单元，吸收单元，催化反应器单元，以及它们的组合。
经过纯化之后，生物甲醇被重整生成氢。虽然还可以采用蒸汽重整单元，但最有利的重整单元是自热重整单元。
重整反应器中生成的气体包含杂质，即除了生物氢之外还有其他气体，因此，设备要包括纯化生物氢的手段。氢气纯化单元通常包括压力变动吸附(PSA)单元，它能提供加压的，经纯化的生物氢。
本发明的生物燃料设施的生物燃料或BTL设备是大家所熟知的设计，它包括FT反应器或HDO反应器，或二者都有。生物燃料的分离和回收以大家熟知的方式来进行。
依照本发明的一个实施方式，一种生物燃料产物由木材加工业的废物和/或副产品来生产。该生物燃料有利地由产自硫酸盐纸浆厂的生物废物和/或副产品的生物烃与由来自黑液的生物甲醇产生的生物氢制得。
下述实施例进一步来说明本发明，但无意限制本发明的范围。
实施例1
图1为与一座硫酸盐纸浆厂和造纸厂(未示出)紧密衔接并整合在一起的一个生物质制液体(BTL)过程的流程示意图。该BTL过程利用由纸浆生物甲醇获得的生物氢来生产生物燃料。
生物质制液体的过程包括将生物质1进料至原料预处理单元2，然后，原料被加至气化及气体调节单元3以生产合成气。该气化及气体调节单元3包括洗气单元和水煤气变换(WGS)单元。单元3与生产氧气的空气分离装置(ASU)4连接在一起。在费-托(FT)合成单元6之前，气体在气体加工和纯化单元5中作处理。
在自热重整(ATR)单元7中由回收自硫酸盐纸浆厂的经过纯化的生物甲醇16生产生物氢。来自BTL过程的尾气14和尾气15被加至ATR单元7进行重整。所得到的生物氢在压力变动吸附(PSA)单元8中被纯化和分离。经过纯化的生物氢被加至FT合成单元6以调整反应气体的H2/CO比例至2左右。
将FT合成单元6的产物气体导入产物改质单元11。分别从FT合成单元6和产物改质单元11回收FT尾气14和尾气15，将它们导入ATR单元7。从改质单元11中获得作为FT产物气体馏分的石脑油9和中间馏分10。
实施例2
按照图2所示的流程，从回收自硫酸盐制浆过程的粗生物甲醇生产生物氢。
产自硫酸盐造浆过程的粗生物甲醇在回收单元12中经蒸馏和/或汽提，然后被引入甲醇纯化单元13，该单元可以除去硫化合物。在该示出的实施方式中，纯化单元13包括两个吸附塔，每个吸附塔都置有吸附床。吸附塔交替使用，一个在吸附中，而另一个则在再生。需要时还可以添加另外的纯化手段，诸如洗气塔，洗涤塔，吸收塔，和催化反应器。
经过纯化了的生物甲醇被引入至自热重整(ATR)单元7，空气也被引入该单元。ATR单元7生成了一种气体混合物，该混合物含有生物氢，二氧化碳，氮，氨和硫化氢。该气体还含有少量分子量较高的有恶臭气味的硫化合物。该气体混合物与循环生物氢H2混合，接着，被送往包含有压力变动吸附(PSA)床的氢气纯化单元8。在吸附塔中气体被纯化，回收得到纯度超过99％的加压了的生物氢17。
实施例3
图3为一流程示意图，说明如何利用产自硫酸盐纸浆厂19的生物氢，该纸浆厂19与生物燃料生产设备20整合在一起。
纸浆厂19买进木料，在木料供料装置18中对木料进行处理，用作纸浆生产的原料。装置18在处理木料过程中回收到的树皮在纸浆厂19的锅炉(未示出)中被焚烧以产生能量。有能量的木料(主要是林区废料)1从公用木料供料装置18被加到生物质制液体(BTL)设备20。
在该实施例中，约2.1TWh/a(太瓦小时/年)或约1Mio m3/a(百万立方米/年)的林区废料被加进该BTL设备20。该BTL工艺生产出65,000-88,000吨/年的中间馏分和20,000-27,000吨/年的石脑油。该硫酸盐纸浆过程生产出约600,000-700,000吨/年的纸浆。
从硫酸盐纸浆厂19产生的黑液中，通过汽提和蒸馏在回收单元12中回收到约20,000吨/年的粗生物甲醇。粗纸浆生物甲醇在吸收塔13中被预纯化，当BTL过程内部产生的氢不够多时，全部或部分的经预纯化的粗生物甲醇被送往BTL设备20的ATR单元去生产补充生物氢气。
除了上述的木料原料和生物甲醇的给料之外，整合在一起的纸浆/造纸厂19和BTL设备20还适宜有其他整合在一起的过程。这样一来，蒸汽，电力，气体和水可以在各个过程之间输送，和/或在整合的装置中进行处理。图3给出进一步整合水纯化装置21的例子。在该情形之下，BTL过程在其费-托合成反应中采用了钴催化剂，因此，该BTL过程产生了被醇污染的水。被污染的水用来自纸浆和造纸厂19的水稀释，然后在共用的生物纯化过程单元21中加以处理。来自纸浆和造纸厂19的被污染的水在同一个废水纯化单元21中被纯化。
至此，本发明已经参考特定的实施方式加以了说明。但是，对于业内人士而言，这些过程方法无疑可以在权利要求书的范围之内有所变动。

Claims (21)

1.来自纸浆工业的生物甲醇在生产生物氢中的应用。
2.如权利要求1所述的应用，其特征在于，所述生物甲醇包含经过纯化的由黑液得到的生物甲醇。
3.如权利要求1所述的应用，其特征在于，所述生物甲醇是通过蒸馏和/或汽提从黑液中回收的。
4.如权利要求1，2或3所述的应用，其特征在于，所述生物氢用于生产烃生物燃料。
5.如权利要求4所述的应用，其特征在于，所述生物氢用于生产生物燃料的工艺步骤，所述工艺步骤选自以下步骤：调节合成气的氢与一氧化碳的比例，费-托石蜡的裂化/异构化，天然油的加氢脱氧，正石蜡的加氢异构化，催化剂的还原，以及这些步骤的组合。
6.如权利要求5所述的应用，其特征在于，所述步骤都在与纸浆厂和/或造纸厂整合在一起的生物燃料生产装置中进行。
7.一种生产生物氢的方法，其特征在于，对从黑液回收的粗生物甲醇进行纯化和重整，然后回收生物氢。
8.如权利要求7所述的方法，其特征在于，所述纯化过程包括选自以下的步骤：洗涤，洗气，汽提，液-液分离，蒸馏，催化转化，离子交换，吸收和吸附。
9.如权利要求7或8所述的方法，其特征在于，所述重整包括自热重整或蒸汽重整。
10.如权利要求7-9中任一项所述的方法，其特征在于，所述生物氢是通过在压力变动吸附单元中将其与二氧化碳分离而回收的。
11.一种生产烃生物燃料的方法，其特征在于，
a)对从黑液回收的粗生物甲醇进行纯化和重整以提供生物氢，回收经过纯化的生物氢；
b)通过选自以下的过程来生产生物烃物流：产自生物质的合成气的费-托反应，生物甘油三酸酯或脂肪酸的加氢脱氧反应，以及它们的组合，其中，
c)所述步骤b)的生物烃物流的生产包括至少一个选自以下的工艺步骤：调节合成气的氢与一氧化碳的比例，费-托石蜡的裂化/异构化，所述生物甘油三酸酯或脂肪酸的加氢脱氧，正石蜡的加氢异构化，以及催化剂的还原；和
d)所述纯化过的在步骤a)中回收的生物氢在步骤c)中所定义的至少一个工艺步骤中用作氢源，所产生的生物烃物流被分离成馏分，从至少一个所述馏分中回收生物燃料。
12.如权利要求11所述的方法，其特征在于，所述生物质包含木材加工业的生物废物或者副产品。
13.如权利要求11或12所述的方法，其特征在于，所述甘油三酸酯或脂肪酸包含妥尔油或者妥尔油脂肪酸。
14.如权利要求11所述的方法，其特征在于，所述生物甲醇与气体流一起被重整，这些气体流来源于所述生物燃料生产过程的一个或多个工艺步骤，它们含有能通过重整生成氢的气体组分。
15.一种生产生物燃料的装置，其特征在于，该装置包括：
-硫酸盐纸浆厂(19)，它提供黑液；
-回收单元(12)，用于从所述黑液中回收粗生物甲醇；
-甲醇纯化单元(13)，用于将所述粗生物甲醇纯化，产生纯化了的生物甲醇；
-重整单元(7)，用于将所述纯化了的生物甲醇重整，生成含有生物氢的气体混合物；
-氢气纯化单元(8)，用于将所述气体混合物纯化，提供纯化了的生物氢；和
-生物燃料生产设备(20)，该设备从所述生物氢和从生物质产生生物烃基的生物燃料。
16.如权利要求15所述的生产生物燃料的装置，其特征在于，所述生物质包含所述硫酸盐纸浆厂的生物废物和/或副产品。
17.如权利要求15所述的生产生物燃料的装置，其特征在于，用于所述生物甲醇的所述回收单元(12)包括选自以下的装置：汽提单元和蒸馏单元以及它们的组合。
18.如权利要求15所述的生产生物燃料的装置，其特征在于，用于纯化生物甲醇的所述甲醇纯化单元(13)包括选自以下的装置：洗气单元，洗涤单元，汽提单元，吸附单元，吸收单元，催化反应器单元以及它们的组合。
19.如权利要求15-18中任一项所述的生产生物燃料的装置，其特征在于，所述重整单元(7)包括自热重整单元或者蒸汽重整单元。
20.如权利要求15-19中任一项所述的生产生物燃料的装置，其特征在于，所述氢气纯化单元(8)包括至少一个吸附单元。
21.由木材加工业的废物和/或副产品制得的生物燃料，其特征在于，所述生物燃料由产自硫酸盐纸浆厂的生物废物和/或副产品的生物烃以及产自黑液的生物氢制得。
CN2008801239991A 2007-11-09 2008-10-29 利用甲醇生产氢气和燃料，生产氢气和燃料的方法及设备 Pending CN101918305A (zh)

Applications Claiming Priority (7)

Application Number Priority Date Filing Date Title
FI20075794A FI20075794L (fi) 2007-11-09 2007-11-09 Integroitu prosessi diesel-polttoaineen valmistamiseksi biologisesta materiaalista ja prosessiin liittyvät tuotteet, käyttötavat ja laitteisto
FI20075794 2007-11-09
FI20085400 2008-04-30
FI20085400A FI20085400A0 (fi) 2007-11-09 2008-04-30 Menetelmä jäteveden integroidulle käsittelylle
FI20085697 2008-07-04
FI20085697A FI20085697A0 (fi) 2007-11-09 2008-07-04 Metanolin käyttö vedyn ja polttoaineen valmistuksessa, menetelmät ja laitokset vedyn ja polttoaineen valmistamiseksi
PCT/EP2008/064675 WO2009059920A2 (en) 2007-11-09 2008-10-29 Use of methanol in the production of hydrogen and fuel, processes and plants for the production of hydrogen and fuel

Publications (1)

Publication Number Publication Date
CN101918305A true CN101918305A (zh) 2010-12-15

Family

ID=39386023

Family Applications (2)

Application Number Title Priority Date Filing Date
CN2008801155093A Active CN101939264B (zh) 2007-11-09 2008-07-18 包括合成气生产和整体化工厂设施的生物质液化工艺的废水处理
CN2008801239991A Pending CN101918305A (zh) 2007-11-09 2008-10-29 利用甲醇生产氢气和燃料，生产氢气和燃料的方法及设备

Family Applications Before (1)

Application Number Title Priority Date Filing Date
CN2008801155093A Active CN101939264B (zh) 2007-11-09 2008-07-18 包括合成气生产和整体化工厂设施的生物质液化工艺的废水处理

Country Status (8)

Country Link
US (3) US8591737B2 (zh)
EP (2) EP2238084B1 (zh)
CN (2) CN101939264B (zh)
BR (2) BRPI0819176A2 (zh)
CA (2) CA2705064C (zh)
FI (2) FI20085400A0 (zh)
RU (2) RU2480425C2 (zh)
WO (2) WO2009059819A1 (zh)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103146413A (zh) * 2011-12-07 2013-06-12 Ifp新能源公司 在源于非化石资源的氢气存在下由直接液化和间接液化结合的杂化途径转化碳基材料的方法
CN103443355A (zh) * 2011-02-03 2013-12-11 斯塔诺阿埃索澳吉有限公司 由得自硫酸盐纸浆工艺的液化馏分制备纯化的甲醇的方法
CN110168153A (zh) * 2016-11-01 2019-08-23 柯利亚·库赛 以二氧化碳为原料结合整体生产方法制造可再生或部分可再生碳纤维
CN115385300A (zh) * 2022-07-04 2022-11-25 西北农林科技大学 一种自农林废弃物生产氨的工艺
US11898309B2 (en) * 2018-06-11 2024-02-13 Valmet Ab Method and a system for obtaining methanol from foul condensate of a pulping process

Families Citing this family (66)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FI20085400A0 (fi) 2007-11-09 2008-04-30 Upm Kymmene Oyj Menetelmä jäteveden integroidulle käsittelylle
US7982076B2 (en) 2007-09-20 2011-07-19 Uop Llc Production of diesel fuel from biorenewable feedstocks
US7999142B2 (en) 2007-09-20 2011-08-16 Uop Llc Production of diesel fuel from biorenewable feedstocks
US7982078B2 (en) 2007-09-20 2011-07-19 Uop Llc Production of diesel fuel from biorenewable feedstocks with selective separation of converted oxygen
US7982077B2 (en) 2007-09-20 2011-07-19 Uop Llc Production of diesel fuel from biorenewable feedstocks with selective separation of converted oxygen
US7999143B2 (en) 2007-09-20 2011-08-16 Uop Llc Production of diesel fuel from renewable feedstocks with reduced hydrogen consumption
US8003834B2 (en) 2007-09-20 2011-08-23 Uop Llc Integrated process for oil extraction and production of diesel fuel from biorenewable feedstocks
US7982075B2 (en) 2007-09-20 2011-07-19 Uop Llc Production of diesel fuel from biorenewable feedstocks with lower hydrogen consumption
US7915460B2 (en) 2007-09-20 2011-03-29 Uop Llc Production of diesel fuel from biorenewable feedstocks with heat integration
US8742183B2 (en) 2007-12-21 2014-06-03 Uop Llc Production of aviation fuel from biorenewable feedstocks
US8193399B2 (en) 2008-03-17 2012-06-05 Uop Llc Production of diesel fuel and aviation fuel from renewable feedstocks
US8039682B2 (en) 2008-03-17 2011-10-18 Uop Llc Production of aviation fuel from renewable feedstocks
US8198492B2 (en) 2008-03-17 2012-06-12 Uop Llc Production of transportation fuel from renewable feedstocks
US8058492B2 (en) 2008-03-17 2011-11-15 Uop Llc Controlling production of transportation fuels from renewable feedstocks
US8193400B2 (en) 2008-03-17 2012-06-05 Uop Llc Production of diesel fuel from renewable feedstocks
US8329967B2 (en) 2008-04-06 2012-12-11 Uop Llc Production of blended fuel from renewable feedstocks
US8324438B2 (en) 2008-04-06 2012-12-04 Uop Llc Production of blended gasoline and blended aviation fuel from renewable feedstocks
WO2009126508A2 (en) 2008-04-06 2009-10-15 Uop Llc Fuel and fuel blending components from biomass derived pyrolysis oil
US8329968B2 (en) 2008-04-06 2012-12-11 Uop Llc Production of blended gasoline aviation and diesel fuels from renewable feedstocks
US8304592B2 (en) 2008-06-24 2012-11-06 Uop Llc Production of paraffinic fuel from renewable feedstocks
US8766025B2 (en) 2008-06-24 2014-07-01 Uop Llc Production of paraffinic fuel from renewable feedstocks
AU2009270687B2 (en) * 2008-07-17 2015-07-23 Intercat Equipment, Inc. Material delivery system to one or more units and methods of such delivery
US8146414B2 (en) * 2008-09-05 2012-04-03 Intercat Equipment, Inc. Material withdrawal apparatus and methods of regulating material inventory in one or more units
US7982079B2 (en) 2008-09-11 2011-07-19 Uop Llc Integrated process for production of diesel fuel from renewable feedstocks and ethanol denaturizing
US8921627B2 (en) 2008-12-12 2014-12-30 Uop Llc Production of diesel fuel from biorenewable feedstocks using non-flashing quench liquid
US8471079B2 (en) 2008-12-16 2013-06-25 Uop Llc Production of fuel from co-processing multiple renewable feedstocks
US8314274B2 (en) 2008-12-17 2012-11-20 Uop Llc Controlling cold flow properties of transportation fuels from renewable feedstocks
US8283506B2 (en) 2008-12-17 2012-10-09 Uop Llc Production of fuel from renewable feedstocks using a finishing reactor
US8236247B2 (en) 2008-12-23 2012-08-07 Intercat Equipment, Inc. Material withdrawal apparatus and methods of regulating material inventory in one or more units
US10471384B2 (en) 2009-04-22 2019-11-12 The Babcock & Wilcox Company System and method for reducing halogen levels necessary for mercury control, increasing the service life and/or catalytic activity of an SCR catalyst and/or control of multiple emissions
US8471081B2 (en) 2009-12-28 2013-06-25 Uop Llc Production of diesel fuel from crude tall oil
WO2012054812A2 (en) * 2010-10-21 2012-04-26 Packaging Corporation Of America Method for biological treatment of hydrolyzate from pulp washing by balancing chemical oxygen demand
FI20115038L (fi) * 2011-01-14 2012-07-15 Vapo Oy Menetelmä btl-tehtaassa muodostuvien kaasujen sisältämän lämpöenergian hyödyntämiseksi
ES2641640T3 (es) 2011-02-08 2017-11-10 Neste Oyj Método de lavado de gas en dos etapas
FI123086B (fi) * 2011-02-28 2012-10-31 Aalto Korkeakoulusaeaetioe Menetelmä kemikaalien talteenottamiseksi
WO2012122622A1 (en) * 2011-03-17 2012-09-20 Nexterra Systems Corp. Control of syngas temperature using a booster burner
US8900443B2 (en) 2011-04-07 2014-12-02 Uop Llc Method for multi-staged hydroprocessing using quench liquid
SE535947C2 (sv) * 2011-04-26 2013-03-05 Chemrec Ab Förgasning av alkaliinnehållande energirika vattenhaltiga lösningar från massabruk
ES2785988T3 (es) * 2011-05-30 2020-10-08 Neste Oyj Procedimiento de producción de una composición de hidrocarburo
WO2012175796A1 (en) * 2011-06-23 2012-12-27 Upm-Kymmene Corporation Integrated biorefinery plant for the production of biofuel
ES2746912T3 (es) * 2011-06-30 2020-03-09 Neste Oyj Método para ajustar la relación de hidrógeno a monóxido de carbono en un gas de síntesis
EP2561916A1 (en) * 2011-08-24 2013-02-27 Neste Oil Oyj Method for naphthalene removal
EP2564918B1 (en) 2011-08-31 2018-03-07 Neste Oyj A two-stage gas washing method applying sulfide precipitation and alkaline absorption
US8546629B2 (en) * 2011-09-23 2013-10-01 Uop Llc Methods for co-production of alkylbenzene and biofuel from natural oils
CN102703107B (zh) * 2012-06-26 2015-04-01 武汉凯迪工程技术研究总院有限公司 一种由生物质生产的合成气制造液态烃产品的方法
US9533899B2 (en) 2013-03-12 2017-01-03 General Electric Company Gasification waste water treatment using air separation unit oxygen
SI24343A (sl) * 2013-04-03 2014-10-30 Univerza V Ljubljani Procedura za odstranjevanje cianida iz onesnaĹľenih vod in produkcija bioplina iz cianida
AU2014311701B2 (en) * 2013-08-08 2018-08-02 The Babcock & Wilcox Company System and method for reducing halogen levels necessary for mercury control
AU2014332576B2 (en) 2013-10-11 2018-02-22 Andritz Oy Process for removal of sulphur from raw methanol
CN105084506B (zh) * 2014-05-14 2017-10-27 中国石油化工股份有限公司 湿式氧化降低废水中cod的方法
CN105084505B (zh) * 2014-05-14 2017-10-27 中国石油化工股份有限公司 多相湿式氧化处理工业废水的方法
CN104150578B (zh) * 2014-07-10 2016-01-13 唐国民 臭氧催化氧化水处理装置
JP6404024B2 (ja) * 2014-07-30 2018-10-10 積水化学工業株式会社 化学品製造装置及び化学品製造方法
WO2016036698A1 (en) * 2014-09-01 2016-03-10 Rachid Taha Hydrotreatment catalyst regeneration
CN104449846A (zh) * 2014-12-09 2015-03-25 贵州开阳化工有限公司 煤粉的制备及输送方法及装置
RU2605714C1 (ru) * 2015-06-26 2016-12-27 Федеральное государственное бюджетное образовательное учреждение высшего образования "Воронежский государственный университет инженерных технологий" (ФГБОУ ВО "ВГУИТ"). Способ получения загрузки биофильтра с иммобилизационными свойствами
WO2017180880A1 (en) 2016-04-13 2017-10-19 Northwestern University Efficient catalytic greenhouse gas-free hydrogen and aldehyde formation from alcohols
US10260005B2 (en) 2016-08-05 2019-04-16 Greyrock Technology LLC Catalysts, related methods and reaction products
RU2658404C1 (ru) * 2016-12-23 2018-06-21 Федеральное государственное бюджетное научное учреждение Федеральный научный агроинженерный центр ВИМ (ФГБНУ ФНАЦ ВИМ) Способ очистки сточных вод от растворенных органических загрязнений
SE542659C2 (en) * 2018-07-10 2020-06-23 Stora Enso Oyj Method for desulfurization of methanol
WO2020074095A1 (en) * 2018-10-12 2020-04-16 Upm-Kymmene Corporation Process for the production of hydrogen
EP3863962B1 (en) * 2018-10-12 2023-10-04 UPM-Kymmene Corporation Process for the production of hydrogen
CN110357366B (zh) * 2019-08-13 2022-02-11 南京工业大学 一种费托合成废水生化处理方法
CN110486989B (zh) * 2019-08-27 2021-02-02 安徽省智慧产业研究院股份有限公司 一种生物质气化炉冷电联产***
KR102425227B1 (ko) * 2020-05-22 2022-07-26 한국화학연구원 바이오오일 부산물로부터 합성가스를 제조하는 방법 및 제조장치
CN112480971B (zh) * 2020-10-28 2022-10-11 中石化宁波工程有限公司 一种掺烧高浓度有机废液的粉煤气化工艺的控制方法

Family Cites Families (46)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5344184B2 (zh) 1974-10-16 1978-11-27
FI52710C (fi) * 1976-04-22 1977-11-10 Kemi Oy Menetelmä sulfaattiprosessin lauhteista erotetun metanolin puhdistamis eksi.
US4188260A (en) * 1977-05-05 1980-02-12 Erco Envirotech Ltd. Low effluent pulp mill, bleach plant operation
US4222855A (en) * 1979-03-26 1980-09-16 Mobil Oil Corporation Production of high viscosity index lubricating oil stock
US4229282A (en) * 1979-04-27 1980-10-21 Mobil Oil Corporation Catalytic dewaxing of hydrocarbon oils
US4247388A (en) * 1979-06-27 1981-01-27 Mobil Oil Corporation Hydrodewaxing catalyst performance
US4592762A (en) * 1981-10-22 1986-06-03 Institute Of Gas Technology Process for gasification of cellulosic biomass
US4648956A (en) 1984-12-31 1987-03-10 North American Philips Corporation Electrode configurations for an electrophoretic display device
US4906671A (en) * 1985-08-29 1990-03-06 Mobil Oil Corporation Fischer-tropsch process
GB8702199D0 (en) 1987-01-31 1987-03-04 Man Oil Ltd Liquefaction of cellulose
US4968325A (en) * 1987-08-24 1990-11-06 Centre Quebecois De Valorisation De La Biomasse Fluidized bed gasifier
US4992325A (en) * 1987-12-15 1991-02-12 The Dexter Corporation Inorganic whisker containing impact enhanced prepregs and formulations formulations
US4992605A (en) * 1988-02-16 1991-02-12 Craig Wayne K Production of hydrocarbons with a relatively high cetane rating
FR2631949B1 (fr) * 1988-05-27 1990-09-14 Inst Francais Du Petrole Procede de production d'hydrogene de haute purete par reformage catalytique du methanol
US5450892A (en) * 1993-03-29 1995-09-19 Alliedsignal Inc. Alkaline scrubber for condensate stripper off-gases
DK171701B1 (da) * 1993-07-06 1997-04-01 Topsoe Haldor As Fremgangsmåde til genvinding af brugt syrekatalysator fra alkylering af carbonhydrider
RU2101273C1 (ru) * 1994-04-27 1998-01-10 Коваленко Владимир Васильевич Способ выделения метанола из смесей с углеводородами с4 или с5
CA2149685C (en) * 1994-06-30 1999-09-14 Jacques Monnier Conversion of depitched tall oil to diesel fuel additive
SE503351C2 (sv) * 1994-09-06 1996-05-28 Ahlstroem Oy Förfarande för rening av sekundära kondensat vid indunstning av avlutar
US5833837A (en) * 1995-09-29 1998-11-10 Chevron U.S.A. Inc. Process for dewaxing heavy and light fractions of lube base oil with zeolite and sapo containing catalysts
US6090312A (en) * 1996-01-31 2000-07-18 Ziaka; Zoe D. Reactor-membrane permeator process for hydrocarbon reforming and water gas-shift reactions
FI100248B (fi) 1996-02-05 1997-10-31 Fortum Oil Oy Keskitisleen valmistus
US5718810A (en) * 1996-03-19 1998-02-17 The Dow Chemical Company Methanol recovery using extractive distillation
US20020007595A1 (en) * 1997-06-24 2002-01-24 Uli Maier-Roeltgen Method for reforming hydrocarbons autothermally
AU779487B2 (en) * 1999-08-17 2005-01-27 Battelle Memorial Institute Chemical reactor and method for catalytic gas phase reactions
US6533945B2 (en) * 2000-04-28 2003-03-18 Texaco Inc. Fischer-Tropsch wastewater utilization
US20020045010A1 (en) 2000-06-14 2002-04-18 The Procter & Gamble Company Coating compositions for modifying hard surfaces
DE10049377C2 (de) 2000-10-05 2002-10-31 Evk Dr Oberlaender Gmbh & Co K Katalytische Erzeugung von Dieselöl und Benzinen aus kohlenwasserstoffhaltigen Abfällen und Ölen
RU2189968C1 (ru) * 2001-01-23 2002-09-27 Открытое акционерное общество "Акрон" Способ получения метанола
CN1151955C (zh) 2001-03-07 2004-06-02 中国科学院山西煤炭化学研究所 一种甲醇裂解制氢的方法
JP4259777B2 (ja) 2001-07-31 2009-04-30 井上 斉 バイオマスのガス化方法
US6656387B2 (en) * 2001-09-10 2003-12-02 Texaco Inc. Ammonia injection for minimizing waste water treatment
US6924399B2 (en) * 2001-12-28 2005-08-02 Mitsubishi Heavy Industries, Ltd. Method of manufacturing dimethyl ether
AU2003252192B8 (en) 2002-06-18 2009-05-07 Sasol Technology (Pty) Ltd Method of purifying Fischer-Tropsch derived water
US7279018B2 (en) * 2002-09-06 2007-10-09 Fortum Oyj Fuel composition for a diesel engine
US7232935B2 (en) * 2002-09-06 2007-06-19 Fortum Oyj Process for producing a hydrocarbon component of biological origin
EP1403216B1 (en) * 2002-09-26 2011-03-23 Haldor Topsoe A/S Process for the preparation of synthesis gas
US20040102315A1 (en) * 2002-11-27 2004-05-27 Bailie Jillian Elaine Reforming catalyst
DE10346892B4 (de) * 2002-12-23 2007-03-01 Bernd Rüdiger Kipper Verfahren und Vorrichtung zur Aufbereitung von organische Bestandteile enthaltenden festen und flüssigen Abfallgemischen
WO2005018034A1 (en) * 2003-08-19 2005-02-24 Hydrogenics Corporation Method and system for distributing hydrogen
AU2005261096B2 (en) * 2004-07-12 2010-01-21 Sumitomo Seika Chemicals Co., Ltd. Hydrogen production system and reforming apparatus
AU2006257007A1 (en) 2005-06-09 2006-12-14 Lignosol Gmbh & Co. Kg Method for producing fuel from biogenous raw materials, and installation and catalyst composition for carrying out said method
US7754931B2 (en) * 2005-09-26 2010-07-13 Her Majesty The Queen In Right Of Canada As Represented By The Minister Of Natural Resources Production of high-cetane diesel fuel from low-quality biomass-derived feedstocks
US20070209966A1 (en) * 2006-03-07 2007-09-13 Syntroleum Corporation Catalytic distillation process for hydroprocessing Fischer-Tropsch liquids
WO2007112314A2 (en) * 2006-03-24 2007-10-04 Wisconsin Alumni Research Foundation Method for producing bio-fuel that integrates heat from carbon-carbon bond-forming reactions to drive biomass gasification reactions
FI20085400A0 (fi) 2007-11-09 2008-04-30 Upm Kymmene Oyj Menetelmä jäteveden integroidulle käsittelylle

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103443355A (zh) * 2011-02-03 2013-12-11 斯塔诺阿埃索澳吉有限公司 由得自硫酸盐纸浆工艺的液化馏分制备纯化的甲醇的方法
CN103443355B (zh) * 2011-02-03 2017-02-15 斯塔诺阿埃索澳吉有限公司 由得自硫酸盐纸浆工艺的液化馏分制备纯化的甲醇的方法
CN103146413A (zh) * 2011-12-07 2013-06-12 Ifp新能源公司 在源于非化石资源的氢气存在下由直接液化和间接液化结合的杂化途径转化碳基材料的方法
CN110168153A (zh) * 2016-11-01 2019-08-23 柯利亚·库赛 以二氧化碳为原料结合整体生产方法制造可再生或部分可再生碳纤维
US11898309B2 (en) * 2018-06-11 2024-02-13 Valmet Ab Method and a system for obtaining methanol from foul condensate of a pulping process
CN115385300A (zh) * 2022-07-04 2022-11-25 西北农林科技大学 一种自农林废弃物生产氨的工艺

Also Published As

Publication number Publication date
BRPI0819109A2 (pt) 2019-09-24
CN101939264B (zh) 2012-11-28
FI20085697A0 (fi) 2008-07-04
FI20085400A0 (fi) 2008-04-30
CA2704999A1 (en) 2009-05-14
US10407304B2 (en) 2019-09-10
US20100317905A1 (en) 2010-12-16
WO2009059819A1 (en) 2009-05-14
CA2704999C (en) 2015-12-29
CN101939264A (zh) 2011-01-05
WO2009059920A3 (en) 2009-11-05
CA2705064A1 (en) 2009-05-14
WO2009059920A2 (en) 2009-05-14
BRPI0819176A2 (pt) 2015-05-05
EP2229339B1 (en) 2012-08-01
RU2480425C2 (ru) 2013-04-27
EP2238084B1 (en) 2014-12-24
US20100317749A1 (en) 2010-12-16
US8591737B2 (en) 2013-11-26
EP2238084A1 (en) 2010-10-13
RU2489348C2 (ru) 2013-08-10
EP2229339A2 (en) 2010-09-22
CA2705064C (en) 2016-09-06
RU2010119343A (ru) 2011-12-20
US20160083252A1 (en) 2016-03-24
EP2229339B2 (en) 2021-09-01
RU2010119341A (ru) 2011-12-20

Similar Documents

Publication Publication Date Title
CN101918305A (zh) 利用甲醇生产氢气和燃料，生产氢气和燃料的方法及设备
AU2010222913B2 (en) Controlling the synthesis gas composition of a steam methane reformer
DE102007038760B3 (de) Verfahren und Anlage zur Herstellung von Synthesegas aus Biogas
Ptasinski Thermodynamic efficiency of biomass gasification and biofuels conversion
AU2007275752B2 (en) Controlling the synthesis gas composition of a steam methane reformer
US20100317903A1 (en) Integrated Process for Producing Diesel Fuel from Biological Material and Products, Uses and Equipment Relating to Said Process
US20110155631A1 (en) Integrated Process for Producing Diesel Fuel from Biological Material and Products and Uses Relating to Said Process
Kumar et al. Thermochemical conversion routes of hydrogen production from organic biomass: processes, challenges and limitations
WO2015101713A1 (en) Integrated process for producing hydrocarbons
US20240109827A1 (en) Biogas conversion to mixed alcohols
CN102712847B (zh) 生物精炼方法
Pandey et al. Syngas production via biomass gasification
EP4105171A1 (en) Process for the production of hydrogen
KR100519386B1 (ko) 제지슬러지를 이용한 합성가스 제조방법
Halmenschlager et al. PRODUCTION OF BIOFUELS FROM WASTE BIOMASS VIA FISCHER-TROPSCH SYNTHESIS
CA3218821A1 (en) Process for producing synthetic hydrocarbons from biomass
WO2023201413A1 (en) Process for enhancing production of biofuels from biomass
Halmenschlager et al. Production of Biofuels from Waste Biomass Via Fischer-Tropsch Synthesis an Overview

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C02 Deemed withdrawal of patent application after publication (patent law 2001)
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20101215