TWI293944B - Production of hydrogen - Google Patents

Production of hydrogen Download PDF

Info

Publication number
TWI293944B
TWI293944B TW091119535A TW91119535A TWI293944B TW I293944 B TWI293944 B TW I293944B TW 091119535 A TW091119535 A TW 091119535A TW 91119535 A TW91119535 A TW 91119535A TW I293944 B TWI293944 B TW I293944B
Authority
TW
Taiwan
Prior art keywords
less
sulfur
content
hydrogen
fuel
Prior art date
Application number
TW091119535A
Other languages
English (en)
Inventor
Graham Hodges Michael
Original Assignee
Bp Plc
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
Application filed by Bp Plc filed Critical Bp Plc
Application granted granted Critical
Publication of TWI293944B publication Critical patent/TWI293944B/zh

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32Production 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
    • C01B3/34Production 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
    • C01B3/38Production 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
    • C01B3/386Catalytic partial combustion
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32Production 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
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32Production 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
    • C01B3/34Production 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
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32Production 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
    • C01B3/34Production 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
    • C01B3/36Production 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
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32Production 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
    • C01B3/34Production 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
    • C01B3/38Production 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
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32Production 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
    • C01B3/34Production 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
    • C01B3/38Production 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
    • C01B3/382Multi-step processes
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G29/00Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
    • C10G29/20Organic compounds not containing metal atoms
    • C10G29/205Organic compounds not containing metal atoms by reaction with hydrocarbons added to the hydrocarbon oil
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02Processes for making hydrogen or synthesis gas
    • C01B2203/0205Processes for making hydrogen or synthesis gas containing a reforming step
    • C01B2203/0211Processes for making hydrogen or synthesis gas containing a reforming step containing a non-catalytic reforming step
    • C01B2203/0216Processes for making hydrogen or synthesis gas containing a reforming step containing a non-catalytic reforming step containing a non-catalytic steam reforming step
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02Processes for making hydrogen or synthesis gas
    • C01B2203/0205Processes for making hydrogen or synthesis gas containing a reforming step
    • C01B2203/0227Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
    • C01B2203/0233Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a steam reforming step
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02Processes for making hydrogen or synthesis gas
    • C01B2203/0205Processes for making hydrogen or synthesis gas containing a reforming step
    • C01B2203/0227Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
    • C01B2203/0244Processes 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
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02Processes for making hydrogen or synthesis gas
    • C01B2203/025Processes for making hydrogen or synthesis gas containing a partial oxidation step
    • C01B2203/0255Processes for making hydrogen or synthesis gas containing a partial oxidation step containing a non-catalytic partial oxidation step
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02Processes for making hydrogen or synthesis gas
    • C01B2203/025Processes for making hydrogen or synthesis gas containing a partial oxidation step
    • C01B2203/0261Processes for making hydrogen or synthesis gas containing a partial oxidation step containing a catalytic partial oxidation step [CPO]
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02Processes for making hydrogen or synthesis gas
    • C01B2203/0283Processes for making hydrogen or synthesis gas containing a CO-shift step, i.e. a water gas shift step
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0435Catalytic purification
    • C01B2203/044Selective oxidation of carbon monoxide
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0465Composition of the impurity
    • C01B2203/047Composition of the impurity the impurity being carbon monoxide
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/06Integration with other chemical processes
    • C01B2203/066Integration with other chemical processes with fuel cells
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/08Methods of heating or cooling
    • C01B2203/0805Methods of heating the process for making hydrogen or synthesis gas
    • C01B2203/0838Methods of heating the process for making hydrogen or synthesis gas by heat exchange with exothermic reactions, other than by combustion of fuel
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/08Methods of heating or cooling
    • C01B2203/0805Methods of heating the process for making hydrogen or synthesis gas
    • C01B2203/0838Methods of heating the process for making hydrogen or synthesis gas by heat exchange with exothermic reactions, other than by combustion of fuel
    • C01B2203/0844Methods of heating the process for making hydrogen or synthesis gas by heat exchange with exothermic reactions, other than by combustion of fuel the non-combustive exothermic reaction being another reforming reaction as defined in groups C01B2203/02 - C01B2203/0294
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10Catalysts for performing the hydrogen forming reactions
    • C01B2203/1005Arrangement or shape of catalyst
    • C01B2203/1023Catalysts in the form of a monolith or honeycomb
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041Composition of the catalyst
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041Composition of the catalyst
    • C01B2203/1047Group VIII metal catalysts
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041Composition of the catalyst
    • C01B2203/1047Group VIII metal catalysts
    • C01B2203/1052Nickel or cobalt catalysts
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041Composition of the catalyst
    • C01B2203/1047Group VIII metal catalysts
    • C01B2203/1064Platinum group metal catalysts
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041Composition of the catalyst
    • C01B2203/1082Composition of support materials
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/12Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1205Composition of the feed
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/12Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1205Composition of the feed
    • C01B2203/1211Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
    • C01B2203/1235Hydrocarbons
    • C01B2203/1247Higher hydrocarbons
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/12Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1258Pre-treatment of the feed
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/12Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1258Pre-treatment of the feed
    • C01B2203/1264Catalytic pre-treatment of the feed
    • C01B2203/127Catalytic desulfurisation
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/12Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1276Mixing of different feed components
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/12Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1288Evaporation of one or more of the different feed components
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/14Details of the flowsheet
    • C01B2203/142At least two reforming, decomposition or partial oxidation steps in series
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/16Controlling the process
    • C01B2203/1614Controlling the temperature
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/16Controlling the process
    • C01B2203/1642Controlling the product
    • C01B2203/1647Controlling the amount of the product
    • C01B2203/1652Measuring the amount of product
    • C01B2203/1666Measuring the amount of product the product being carbon dioxide
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/80Aspect of integrated processes for the production of hydrogen or synthesis gas not covered by groups C01B2203/02 - C01B2203/1695
    • C01B2203/82Several process steps of C01B2203/02 - C01B2203/08 integrated into a single apparatus
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00Fuel cells; Manufacture thereof
    • H01M8/06Combination of fuel cells with means for production of reactants or for treatment of residues
    • H01M8/0606Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants
    • H01M8/0612Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants from carbon-containing material
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00Fuel cells; Manufacture thereof
    • H01M8/06Combination of fuel cells with means for production of reactants or for treatment of residues
    • H01M8/0662Treatment of gaseous reactants or gaseous residues, e.g. cleaning
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30Hydrogen technology
    • Y02E60/50Fuel cells

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Hydrogen, Water And Hydrids (AREA)

Description

1293944 五、發明說明(3) 液態烴進料包含一個烷化劑。如此的烷化劑可能是被 添加的或者是在進料原本就有的。適當的烷化劑包含 有烯煙、醇類(舉例來說,一級、二級和三級醇)及其 等之混合物。該烷化劑可以包含3到2〇個碳原子, 更佳地為3到1 〇個碳原子。 在本發明的較佳具體例中,一或更多的烯係被用來作 為院化劑。適當的烯煙包含有環烯烴類、取代的環烯 烴類與化學式為R1R2C=CR2R2的烯烴,其中Rl是一 烴基基團’且每個R2係各別地為氫或—烴基基團。 較佳的烯烴包含.3到15個碳原子,更佳地為4到 10個碳原子’舉例來說,5到7個碳原子。此種稀 蜢可月匕疋實際上存在於液態烴進料中,或者可以特意 地加入該進料中。 〜 適當的f稀煙和取代的環稀烴之範例包含有環戍稀、 ·· 4 已烯、1_甲基環己烯、3·甲基環己烯、 甲基W埽、環庚烯、環辛烯和"基 ==學式為RlR2C=CR2R2之範例包含有丙稀、2_ 丁^、2 丁埽、2·丁婦、2_甲基小U·甲基-卜 13 7 甲基-1-丁烯、:二丁:;2·乙基 2- f A 1 Λ 土 丁烯、1_戊烯、2-戊烯、 = “戊稀、4·甲“戊稀、2,‘ Κ己烯、2_己稀、3_己烯、1,3-己二烯、 6 1293944
7 1293944 五、發明說明(6) 係被回收以作為該烴燃料組成物。這個烴燃料組成物 然後被轉換為用於一燃料電池中的氫。 較佳地該烷基化步驟減少烴進料的硫含量、芳香族含 量和烯烴含量之一或更多。該烷基化步驟可以增加烴 進料的石蠟鏈烷烴含量。因此,催化裂解醇類可以被 變得更適於一燃料電池之氫的生產。 在一較佳的具體例中,自烧基化步驟中回收的烴燃料 組成物具有: 一小於40 wt%的烯烴含量,其係較佳地少於 30wt%,更佳地少於20wt%且係最佳地少於1〇 wt% ; 一小於35 wt%的芳香族含量%,其係較佳地少於25 wt%且係更佳地少於5 wt% ; 一低於215°C的最終沸點(fbp),更佳地為少於18〇 °C,舉例來說,界於1〇〇和175°c之間;以及 小於60 ppm的硫含量,較佳地少於1〇 ppm,更佳地 少於5 ppm,最佳地少於2 ppm。 该烴燃料組成物也可以有小於5 wt%的苯含量,較佳 地少於1 wt%。該組成物的二烯烴含量也可以是少於 5 wt%,較佳地少於1 wt%,更佳地少於〇1 wt〇/〇。 如上所述,一較高沸點部份可自烷基化反應中分離。 這比較南沸點部份係典型地包含有高沸點成分,其包 括有芳香族的化合物和含硫雜質。部分的這些高濟點 成分在烷基化步驟中可能在其他成分還未已烷基化時
1293944
五、發明說明(7) 就已經烷基化。未烷基化的雜質包含多取代的噻吩、 苯并噻吩以及經取代的苯并噻吩。 忒較鬲沸點部份可藉由在烷基化條件下與一酸催化劑 接觸而將該部份進一步烷基化。任擇地,一額外的烷 化劑可已被加入該反應中,以幫助該第二烷基化步 驟。烷基化作用會將至少一部分的較高沸點部份轉變 為較高沸點成分。這些較高沸點成分可以藉由例如分 餾作用來分離。一第二較低沸點部份也可以自此一第 二烧基化步驟中回收。 此第二較低沸點部份通常具有較低濃度的含硫雜質及/ 或芳香族化合物。該第二較低沸點部份可被回收以做 為烴燃料組成物’並轉換成為應用於燃料電池的氫。 將第二較低沸點部份與第一較低沸點部份混合以產生 適合於轉換成氫的烴燃料組成物是有可能的。 该烷基化步驟可以在該第二個以及之後的較高沸點部 伤中重複’以產生第三個和之後的較高的與比較低沸點 部份。 任何的適當酸催化劑可能在本發明的烷基化步驟中被 雇用。適當的酸催化劑係被詳細地描述在美國專利第 5863419號、美國美國專利第6〇25534號、美國專利 第6048451號和美國美國專利第6〇59962號中,其 等係在被併入以供參考。此種酸包含了布忍斯特酸, 例如磷酸、硫酸、硼酸、氫氟酸、氟磺酸、三氟甲烷 續酸和二經敗爛酸。例如BF3、BCl3、AlCl3、AlBr3、 1293944
五、發明說明(〇
FeCl2、FeCl3、ZnCl2、SbFs、北⑶以及 Alcl3 和 HC1 的組合物之路易斯酸也是適合的。該酸催化劑可以被 支撐或不被支撐。在一較佳的具體例中,使用了一個 固態的磷酸催化劑。 5亥烧基化反應可以在較高的溫度下進行。舉例來說, 超過50C的溫度,較佳地超過1〇(rc,且更佳地超 過125C。在較佳的具體例中,該烷基化反應係較佳 地在100到350 c下進行,較佳地在125到250 C。在進行多重烷基化步驟時,該烷基化溫度可以與 後來的每個烷基化步驟不同。 反應壓力係界於0_01到200 atm,較佳地在1到 100 atm。適當的烷基化條件之進一步細節係被描述在 美國專利第5863419號、美國專利第6〇25534號、 美國專利第6 048 451號和美國6 059 962號中。 在一較佳的具體例中,本發明的方法更進一步包含一 加氩脫硫步驟。這個加氫脫硫反應可以在烷基化步驟 之前、同時或之後進行。在一較佳的具體例中,該自 烷基化反應中回收的烴燃料組成物係被加氫脫硫以進 一步減少它的硫濃度。傳統的及/或選擇性的加氫脫硫 方法可以被使用。一旦被加氫脫硫之後,該烴燃料組 成物可以轉變成氫。 除了加氫脫硫步驟之外或是其之替代方法,可能是將 整個的或任何該烴燃料組成物的子部份通過例如一硫 陷阱的脫硫裝置。此種裝置可能是一液體、液體/液體 11 1293944 五、發明說明(9 或以固體為基礎的牵播,0 _ ,… ㈣糸統,且係可以被用來藉由例如吸 附作用、吸收作用或其它方式,的自煙燃料 =任何的含硫雜質。硫陷牌可能對於在烴燃料組成 物中移除硫化物和硫醇雜質是特別有效果的。 烴燃料組成物可具有一至少8〇的馬達辛炫值 _N),以及—至少%的研究辛院值(刪)。較佳 地’該燃料組成物具有至少85 # MC)N,以及至少 的 RON 〇 該烴燃料組成物可以具有一高達100的雷德蒸氣麼力 (RVP),較佳地為35到1〇〇,更佳地為45到1〇〇 kPa。 煙燃料組成物的密度可以大於G4gW,較佳地大於 〇.5gW棒’更佳地大於G 7g/em3,且最佳地在〇 7 和〇·8 g/cm3之間。 ·· 本發明的方法可以更進-步地包含在烴燃料組成物被 轉變成氫之前,將一或更多的添加劑加入至該烴燃料組 成物的步驟。i§當的添加劑包含在傳統的内燃機汽油中 使用的添加劑。此種的添加劑包含有界面活化劑、穩定 性添加劑、抗氧化劑和金屬去活化劑,以及任何可以使 該烴燃料能夠被用來做為内燃機的燃料之其他的添加 劑。該烴燃料組成物可以使用任何適當的技術來轉變成 氫。舉例來說,可以使用部份氧化作用及/或重組作用。 典型地,該烴燃料組成物係被轉變成一包含有氫,以及 一氧化碳及/或二氧化碳的產物流。通常,一氧化碳和 12 1293944 五、發明說明(10 氧化厌都會產生。舉例來說,在該產物流中二氧化碳 相對於一氧化碳的莫爾比例係為10:1至〇.1:1。 在本發明的一個具體例中,該煙燃料組成物係藉由將 該組成物在蒸氣的重組條件之下與蒸氣反應而轉變成 氫’來產生氫和-氧化碳及/或二氧化碳。蒸氣重組作 用可以在具有與不具有催化劑的情況下進行。適當的 催化劑係在此技藝中已知的。其包含有過渡金屬催化 劑’例如錢、錄、録、始、紐、釕和錶。可以使用傳 統的蒸氣重組作用溫度和壓力。 在本發明的另一個具體例中,烴燃料組成物係在部分 氧化作用條件下藉由將組成物與氧反應而轉變成氫, 來產生氫和一氧化碳及/或二氧化碳。部分氧化作用可 以在具有與不具有部分氧化催化劑的情況下進行。適 δ的部分氧化催化劑係在此技藝中已知的。其包含有 過渡金屬催化劑,例如铑、鎳、鈷、鉑、鈀、釕和錶。 ·· 可以使用傳統的部分氧化作用溫度和壓力。 當烴燃料組成物被轉變成氫的時候,通常也會產生一 氧化碳。在本發明的一具體例中,一氧化碳係藉由氧 化作用而自產物流中移除。該反應會將一氧化碳轉變 成二氧化碳,在該過程中會放出熱。這個熱可以用來 驅使烴燃料組成物轉化成氫。 除此之外或任擇地,一氧化碳可藉由一水汽轉換 (water shift)反應來移除。在一水汽轉換反應中,一氧 化碳係在催化劑存在下與水反應而產生二氧化碳和 13 1293944 五、發明說明(11 適當的水氣轉換催化劑包含有一氧化鐵和三價絡 氧物在水A轉換反應中產生的氫可以與由烴燃料 、、且成物轉化產生的氫結合,並且被導入至一燃料電池。 在本發明的方法中產生之氫係被導入至一燃料電池, 較佳地為一用於提供動力給例如車輛、卡車、台車、 體育運動車車輛或公車之交通工具的燃料電池。氫可 以被直接地進料到燃料電池或在被導入燃料電池内之 前儲存在例如一儲存單元中。當氫在被導入至燃料電 池之别係被儲存的時候,該錯存單元可以設置在一以 燃料電池作為能量的交通工具上及/或在一靜止的儲存 位置。 當燃料電池被用來提供一交通工具能量的時候,其可 已用來產生實質上所有必需的能量,以符合該交通工 具的能量需求。然而,在某些情況中燃料電池可能不 適合產生1 〇〇%的能量。因此,其他的能量來源可能 是必需的。此種的能量來源包含有傳統的電化電池、 太陽能電池和内燃機。當一個内燃機被使用的時候, 烴燃料組成物可以被直接地導入内燃機内並燃燒產生 能量。 要注意的是,發明所使用的烴燃料組成物也可以作為 内燃機的汽油。本發明現在將會被參照接下來的實驗 來例示說明。 實施例 14 1293944 五、發明說明(12 ) 一光催化裂輕油的樣本係被烷基化、分餾且較低沸點 部份係被苛性萃取以產生一不具有二烯烴、低硫含量 之還原芳族化合物與浠烴燃料,表1。 表1 欲烷基化 之進料 烷基化 產物 烧基化產 物 Bp<100C 烷基化產物 Bp<100C 鹼 洗 石躐%wt 33 37 59 59 環烧%wt 10 8 9 9 烯烴%wt 37 34 28 28 環烯烴 %wt 6 3 1 1 芳族化合 物%wt 13 12 2 2 硫醇S ppm wt S 74 21 15 <2 噻吩S ppm wt S 7 7 1 1 總 S ppm wt S 81 98 13 <3 15 1293944 五、發明說明(l3) RON 94 94 91 MON 80 82 82 (R+M)/2 87 88 87 RVP PRVR GRAB (Kpa) 98 81 92 IBP 27.2 29.6 30.0 28.4 T50 59.4 77.8 52.8 53.3 T90 113.3 165.4 78.3 77.9 T95 130.0 190.2 84.4 83.8 FBP 152.9 216.7 109.4 110.8 實施例2 一進一步的光催化裂輕油樣本係被烷基化、酸洗並分 餾以得到一低硫含量之還原芳族化合物與烯烴燃料, 表2 〇 16 1293944 五、發明說明(l4) 表2 欲烷基 化之進 料 烷基化 產物 烧基化產 物 Bp<160C 烧基化產物 Bp<100C 鹼 洗 石躐%wt 33.3 34.1 38.0 48.0 環烧%wt 11.1 12.3 13.0 11.8 晞烴%wt 37.3 34.2 32.9 34.4 環烯烴%wt 5.7 3.3 3.2 1.7 芳族化合物 %wt 12.4 6.0 12.7 4.1 硫醇S ppm wt S 6 13 4 6 口塞吩S ppm wt S 146 200 68 16 硫化物s ppm wt S 58 7 10 6 總 S ppm wt S 210 210 82 27 1293944 五、發明說明(l6) 所有的實驗係在一自熱重組器(ATR)設備中進行,該 裝置係由水份汽化器、燃料汽化器、石英反應器(quartz reactor)和氣體取樣系統所組成。燃料、水和空氣最初 係在19,000hr_1的氣體時空速度(GHSV)、標記為 0.9的氧與碳的莫耳數比例(0/C)以及標記為0.5的 蒸氣與碳的莫耳數比例(0/C)的條件下,以氣體反應 物流供給到石英反應器。在第一組的條件下一小時之後 以一快速的步驟轉換成標記為0.09的蒸氣與碳的莫 耳數比例(0/C),同時將氣體時空速度(GHSV)維持 在19,000hy且將氧與碳的莫耳數比例(0/C) 維持 在標記為0.9的第二組的條件。該實驗更進一步的該 第二組條件下進行另一個小時。該重組催化劑係使用一 載入有2% wt始和1 % wt铑的以氧化铭修補基面塗 層的堇青石,且其係由Johnson Matthey所提供的。該 圓筒形催化劑係為30毫米長且直徑為27mm ,且在 每平方吋中具有900個通道(PCI)。 一個燃料進料流與一空氣/水進料流係以被選定之可以 提供在氣體反應物流中必需0/C與S/C以及GHSV 的速率而以幫浦打進個別之汽化器中。該汽化的燃料 流係被注入從空氣/水之進料流汽化所產生的空氣與蒸 氣之混合物内,以產生該氣體的反應物流。燃料和空 氣/水的進料流之迅速汽化和完全混合,係藉由在汽化 器中提供大的表面積以供熱轉移與使用許多的混合管 來達成。該氣體的反應物流係直接地供給至一石英反
·· 19 1293944 五、發明說明(17 ) 應器内。其係由垂直設置的3〇〇mm長的反應器進料管 所組成,該等僅料管係向外開口以形成直徑為 的反應區,而在其底部具有燒結。該圓筒形的催化劑 係在其之周圍附近以一適當的密封材料包裝,並載入 至反應區内,因此其會接觸該燒結物。該氣體反應物 流的預熱溫度,係藉由以一與該燒結物接觸之熱偶所 控制第一管爐來加熱反應器進料f,而被維持在3〇〇 °C。該石英反應器的反應區係密封在第二管爐裡。其 之溫度係以熱化學資料為基礎而被設定在預定的催化 劑出口溫度-即為s/c=0.5下為839t而s/c=〇〇7 下為88(TC。一絨毛狀石英栓塞,係被插入反應區内 於催化劑之上,使催化劑的輻射損失減至最小。 一從催化劑來的氣體產物流係在催化劑的上表面的 l〇mm之上被採樣,且其之組成物係以線上和離線氣相 色層分析法(GC)來檢測。在採樣的氣體產物流中的 ·· ,分濃度,係運用該GC資料而以物料衡算特性来計 算,且然後用於這些結果的標準化。 在每個二小時之實驗的最後,燃料和空氣/水進料流係 被停止,啟動一通過石英反應器的氮清洗作用,且該 第一(預熱)個和第二(反應區)爐係被減弱能量。在 催化劑從反應區中移走之前,其可以被冷卻。 在每個長達一小時的實驗之後,在催化劑上累積的碳 係以溫度預計氧化作(ΤΡ())來確定。該催化劑係在氧 /氦流中以2〇t/min的速率從室溫加熱到85(rc,而 20 1293944 五、發明說明(is) 在這個階段中所涉及的二氧化碳濃度中係使用一質譜 儀來測量。 在實施例2中之樣本的結果係如表3中所示。這些 結果係以許多參數作為基礎來表示,即氫的生產、非 曱烧烴臨界點(non_methane hydrocarbon breakthrough) 以及在該催化劑上的積碳(催化劑碳),該烷基化產物 在ATR中的效能較烴進料佳。此外,在相同參數的基 礎下,該<100C烷基化產物在ATR中的效能係較該 <160C的烷基化產物佳。 表3 ATR裝置的結果 樣本 操作 編號 0/C (莫 耳) S/C (莫 耳) 碳轉 化率 (%C1) H2產生 量 (g/100g 進料) NMHC* (ppm wt/wt) 催化 劑碳 (毫 克) 欲烷基 A1 0. 88 0.49 100 18.2 未取得 - 化之進 33.0 料 A2 0.89 0.07 99 15.0 103 烷基化 B1 0.89 0.49 100 18.7 未取得 產物 22.0 Bp<160C B2 0.89 0.07 99 15.0 25 烷基化 C1 0.89 0.50 101 19.3 未取得 產物 15.9 Bp<100C C2 0.90 0.07 100 15.8 16 * NMHC =在C1的基礎上的非甲烷烴臨界點值。
·· 21 93· 6. 25 1293944 五、發明說明(1) 氫的製造方法 本發明係與一燃料電池的產生氫之方法有關。 燃料電池是-種結合氣燃料和來自空氣的氧以產 生電、熱和水的電化學裝置。燃料電池的操作沒有姆 燒現象,使其成為一乾淨的和有效率的能量來源。對 於使用燃料電池作為交通工具的能量來源具有一逐漸 成長的興趣。 在燃料電池中使用的氫可以被直接地儲存或在原 t上生產’舉例來說,藉由把—個煙轉換成氫和一氧化 碳及[或]二氧化碳。轉化過程可以在具有或不具有催 化劑的情況下藉著部份地將煙類氧化來進行。任擇 地,該烴燃料可以選擇性地在一個催化劑存在下藉由 蒸氣重組作用轉變成氫。 已經嘗試著將傳統馬達汽油重組成用於燃料電池 的氫。然而,此種嘗試會產生例如煤焦之會損害重組 催化劑之副產物。除此之外,汽油中存在的硫會導致 重組催化劑和燃料電池堆兩者的效能退化。 見在發現種可以減輕這些問題的烴燃料組成物。 依據本發明’其提供—種用於自—烴燃料組成物產 生用於燃料電池之氫的方法,該方法包含以下步驟: 、提供一煙燃料組成物,其係藉由將一包含有炫化劑 之液態烴進料與一酸催化劑在一能有效地炫基化至少 一部分的烴進料之條件下接觸; 4 1293944 93. 6. 25 五、發明說明(2) 將烴燃料轉變成氫;並選擇性地將所生產的氫引入 一燃料電池内。 在一較佳的具體例中,該方法包含有: 將一包含有烷化劑之液態烴進料與一酸催化劑在 一能有效地烷基化至少一部分的液態烴進料之條件下 接觸; 回收至少一部分的來自烷基化步驟之產物以產生 一煙燃料組成物, 將烴燃料組成物轉變成氫,並將所生產的氫引入一 燃料電池内。 該液態烴進料可以在10到345°C的範圍中沸 騰,較佳地,在10到249°C的範圍中。此種進料可 以在石油的提煉過程中以及從煤的液化和石油頁岩與 焦油砂的加工處理之產物的精煉過程中取得。此種進 料係典型地包含有烴類的複雜混合物。適當進料的例 子包含有輕油、重油、汽油、煤油、減黏裂解汽油、 催化裂解醇類、焦化汽油和輕循環油。該進料可在例 如其被烷基化之前或之後被選擇性地加氫處理。在本 發明的較佳具體例中,來自一催化裂解過程的輕油或 一選擇性加氫處理(例如一催化裂解程序)過的輕油 係被用來作為液態烴進料。適當的進料係被被詳細地 描述在美國專利第5 863419號、美國專利第6〇25 534號和美國專利第6 048 451號中,其等之内容在 此處被併入以供參考。
1293944 93. 6. 25 五、發明說明(5 ) 在烷基化步驟中可以被烷基化的物種的例子包含 有含硫雜質和芳香族化合物。此種可烷基化的物種係 被烧基化成更重的取代物,且因此係為較高分子量產 物。舉例來說,噻吩可以被烷基化以產生一烷基化噻 吩’而硫醇可以被烷基化以產生較高分子量的硫化物 種類。當然,可以理解的是單一的與多-烷基化反應兩 者都有可能發生。烷基化反應係被更詳細地描述在美 國專利第5863419號、美國專利第6025534號和美 國專利第6048451號中,其之内容在此被併入以供參 考0 由於燒基化產物傾向於具有較未烷基化的對應物 高的沸點,因此部分的液態烴進料係在烷基化步驟中 被轉變為具有較高沸點的產物。這些較高沸點的產物 可藉由例如蒸餾來分離出一較高沸點部份。該最後的 較高沸點部份之沸點可能比l7〇t:更大,較佳地大於 2〇〇°C,且更佳地大於22(rc。一較低沸點部份也可以 自燒基化步驟中藉著例如蒸餾作用而回收。這個較低 沸點部份可能具有小於215它的最終沸點,更佳地小 於180°C,舉例來說,在1〇〇和175。〇之間。 該較低沸點部份可以包含有烴類以及濃度減低的 έ石瓜雜貝及/或芳香族化合物。在較低沸點部份的該稀 烴濃度也可能會減少,因為本來存在於液態烴進料中的 烯烴,可能也已經涉及了烷基化反應及/或被聚合以形 成較尚沸點成分。一較佳具體例中,這個較低沸點部分 1293944 93· 6. 25 五、發明說明(15) RON 90.8 9.5 88.7 MON 80 79.3 80.1 (R+M)/2 85.4 84.4 84.4 RVP 61 63.6 密度 0.7152 0.7325 0.7177 0.6889 IBP 38.9 41.6 42.2 40.9 T50 84.9 102.3 91.7 69.8 T90 135.0 171.4 130.3 90.3 T95 148.1 211.5 137.3 94.6 FBP 157.4 137.1 147.1 103.8
實施例3 下述來自實施例2的表2的樣本係在一自熱重組器 中當作烴燃料來加以測試: 樣本A :欲烧基化之進料 樣本B:烷基化產物Bp<160C 樣本C:烷基化產物Bp<100C 18

Claims (1)

1293944 六、申 公告本 第91 119535號專利申請案申請專利範圍修正本 修正曰期·· 93年6月 込燃料組成物中產生用於燃料電池的氫之方法,該方法 包含以下步驟: ^ L燃料組成物,該組成物係藉由將一包含有烧化劑之 =丄進料與—酸催化劑在_可有效地烧基化至少—部分的煙 ;條件下接觸而獲得,其中該液態烴進料係選自於由輕油、 重油、A油、煤油、減黏裂解汽油、催化裂解醇類、焦化汽油、 ^裒/由來自催化裂解過程的輕油及一選擇性加氫處理過的輕 油,該烷化劑係選自於烯烴、醇類及其等之混合物,且其中 該烷化反應係在l〇〇°C至350°c下及0.01至200大氣壓力下 進行, 將煙燃料轉變成氫;以及 選擇性地,將所生產的氫引入一燃料電池内。 . 2.如申請專利範圍第1項之方法,其中該液態烴進料更包含有含硫 雜質’其至少一部分係在烷基化步驟期間被烷基化。 3·如申請專利範圍第2項之方法,其中在烷基化步驟期間超過 30%的含硫物種係被烷基化。 4.如申請專利範圍第3項之方法,其中在烷基化步驟期間超過 50%的含硫物種係被烷基化。 5·如申請專利範圍第4項之方法,其中在烷基化步·驟期間超過 9 0 %的含硫物種係被烧基化。 ~---- -22- 1293944 六、申請專利範圍 6·如申明專利章巳圍第!項之方法,其中該液態烴進料更包含有在烷 基化步驟中被烧基化之芳香族化合物。 7.=申請專利範圍第i項之方法,其中—較低沸點部份包含有烴和 |度減低的含硫雜質’且/或該芳香族化合物係自烧基化步驟回收 以作為燃料組成物。 8·如中請專利範圍第7項之方法,其中該較低彿點部份是藉由蒸 餾作用來回收。 9·如申請專利範圍第7項或第8項之方法,其中該較低彿點部份 具有一低於215°C的最終沸點。 1〇.如申請專利範圍第9項之方法,其中該較低沸點部份具有-低 於180°C的最終沸點。 u.如申請專利範圍第1G項之方法,其中該較低彿點部份具有-介 於100和之間的最終滞點。 12·如申請專利㈣第μ之方法,其中自絲化步驟回收的㈣ 料纽成物具有: ·… 一小於40 wt%的烯烴含量; Φ 一小於35 wt%的芳香族含量; 一低於215〇C的最終沸點(fbp);以及 小於60 ppm的硫含量。 請專利範圍第12項之方法,其中該稀烴含量少於3〇wt%。 .如申請專利範圍第η項之方法,其中該_含量少於2_%。 15·如申請專利範圍第14項 ^ “申請專利範圍第12項之二 = 含:… 17,如_ 含量少於25wt%。 月專圍苐16項之方法,其中該芳香族含量少於5 wt%。
-23- 1293944 申請專利範圍 18·如申請專利範圍第12 + ΐ9·如申浐衷朱卜々 員之方法,其中該最終沸點少於18(rc。· 175。、圍第18項之方法,其中該最終彿點介於100和 L之間。 20.如申請專利範圍第12 甘士 ★ *人曰, 21 ,. 貝之方法,其中該硫含篁少於l〇ppm〇 21·如申請專利範圍第20項之方土 , ΡΡ 90 , 貝之方法,其中該硫含量少於5 ppm。 .如申請專利範圍第21項之大、土甘士外戌八曰, 2 貝之方法,其中该硫含置少於2 ppm。 士申。月專利粑圍第1項之方法,其中該煙燃料組成物呈有一至 Li) (m〇n)5^^^ 90 24·如申請專利範圍第23項之方法,其中該燃料組成物具有至少Μ 的Μ〇Ν,以及至少95的R〇N。 ^ 25·—如中^專利範圍第丨項之方法,其包含在煙燃料組成物轉變成 氫之前,將一或更多的添加劑導入烴燃料組成物中的步驟。义 •24-
TW091119535A 2001-09-11 2002-08-28 Production of hydrogen TWI293944B (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
GBGB0121871.8A GB0121871D0 (en) 2001-09-11 2001-09-11 Hydrogen production

Publications (1)

Publication Number Publication Date
TWI293944B true TWI293944B (en) 2008-03-01

Family

ID=9921832

Family Applications (1)

Application Number Title Priority Date Filing Date
TW091119535A TWI293944B (en) 2001-09-11 2002-08-28 Production of hydrogen

Country Status (10)

Country Link
US (1) US7294420B2 (zh)
EP (1) EP1425243A1 (zh)
JP (1) JP2005502983A (zh)
AU (1) AU2002321554B2 (zh)
GB (1) GB0121871D0 (zh)
MY (1) MY140937A (zh)
RU (1) RU2311339C2 (zh)
TW (1) TWI293944B (zh)
UA (1) UA77694C2 (zh)
WO (1) WO2003022735A1 (zh)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030162060A1 (en) * 2000-12-21 2003-08-28 Graham Butler Dual use hydrocarbon fuel composition
WO2004035468A1 (en) * 2002-10-14 2004-04-29 Shell Internationale Research Maatschappij B.V. A process for the catalytic conversion of a gasoline composition
CA2672626A1 (en) * 2006-12-21 2008-07-03 The Lubrizol Corporation Lubricant for hydrogen-fueled engines
US8003073B2 (en) * 2007-04-16 2011-08-23 Air Products And Chemicals, Inc. Autothermal hydrogen storage and delivery systems
US8211583B2 (en) * 2008-05-08 2012-07-03 Bloom Energy Corporation Derivation of control parameters of fuel cell systems for flexible fuel operation

Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3965252A (en) * 1973-01-20 1976-06-22 Ashland Oil, Inc. Hydrogen production
US4205196A (en) * 1979-04-05 1980-05-27 Phillips Petroleum Company Acid-type hydrocarbon alkylation with acid recycle streams at spaced points of a vertically-disposed elongated reactor
US4929800A (en) * 1986-10-22 1990-05-29 University Of Florida Hydrocarbon conversion and polymerization catalyst and method of making and using same
US5707923A (en) * 1995-05-01 1998-01-13 Stratco, Inc. Method of and apparatus for controlling an alkylation process
US5863419A (en) 1997-01-14 1999-01-26 Amoco Corporation Sulfur removal by catalytic distillation
US6048451A (en) 1997-01-14 2000-04-11 Bp Amoco Corporation Sulfur removal process
AR017317A1 (es) * 1997-10-14 2001-09-05 Shell Int Research Proceso de oxidacion parcial catalitica, un metodo y disposicion para generar energia electrica por medio de dicho proceso, y medio de transporteprovisto con dicha disposicion
US5938800A (en) * 1997-11-13 1999-08-17 Mcdermott Technology, Inc. Compact multi-fuel steam reformer
EP1060791B1 (en) * 1998-03-04 2004-06-23 Japan Energy Corporation Solid acid catalyst, method for preparing the same and reaction using the same
US6025534A (en) 1998-04-07 2000-02-15 Bp Amoco Corporation Olefin polymerization process
US6348278B1 (en) * 1998-06-09 2002-02-19 Mobil Oil Corporation Method and system for supplying hydrogen for use in fuel cells
US6059962A (en) 1998-09-09 2000-05-09 Bp Amoco Corporation Multiple stage sulfur removal process
JP2001262163A (ja) * 2000-03-23 2001-09-26 Idemitsu Kosan Co Ltd 内燃機関用及び燃料電池用兼用燃料油
US20030162060A1 (en) 2000-12-21 2003-08-28 Graham Butler Dual use hydrocarbon fuel composition

Also Published As

Publication number Publication date
US7294420B2 (en) 2007-11-13
US20040213735A1 (en) 2004-10-28
EP1425243A1 (en) 2004-06-09
RU2004111010A (ru) 2005-10-10
JP2005502983A (ja) 2005-01-27
GB0121871D0 (en) 2001-10-31
MY140937A (en) 2010-02-12
UA77694C2 (en) 2007-01-15
RU2311339C2 (ru) 2007-11-27
WO2003022735A1 (en) 2003-03-20
AU2002321554B2 (en) 2007-07-12

Similar Documents

Publication Publication Date Title
JP2003518155A (ja) 燃料電池電力設備用のガソリンまたはディーゼル燃料の脱硫方法
MY116750A (en) Hydrocarbon conversion
EA012632B1 (ru) Способ получения катализатора переходного металла и применение катализатора в способе получения неочищенного продукта
JPH0513882B2 (zh)
TWI293944B (en) Production of hydrogen
WO2001070914A1 (fr) Gazole utilisable dans les moteurs thermiques et dans les piles a combustible
WO2002031090A1 (fr) Combustible a double fonction pour automobile a essence et systeme de pile a combustible, et systeme de stockage et/ ou de distribution de combustible a double fonction
JP2004516628A (ja) 併用炭化水素燃料組成物
EP0679709B1 (fr) Procédé de conversion du gaz naturel en hydrocarbures
CA2457139A1 (en) Method for desulfurization and reforming of hydrocarbon
US6958117B2 (en) Fuel for use in a fuel cell system
AU2002321554A1 (en) Production of hydrogen
EP1273651A1 (en) Fuel for use in fuel cell system
US6939459B2 (en) Fuel for use in fuel cell system
Halasi et al. Production of hydrogen from dimethyl ether over supported rhodium catalysts
US6837909B2 (en) Fuel for use in a fuel cell system
JP2001279271A (ja) 燃料電池用燃料油及び燃料電池用水素の製造方法
US6962650B2 (en) Fuel for use in a fuel cell system
US5012025A (en) Molecular restructuring catalyst
JP4227927B2 (ja) 水素製造用炭化水素油および水素製造システム
JPWO2002046334A1 (ja) 混合ガソリン、並びにその貯蔵及び/または供給システム
CN1648112A (zh) 制备含硫的蒸汽裂化器原料的方法
KR101115663B1 (ko) 수소제조용 탄화수소유 및 수소제조 시스템
FR2845372A1 (fr) Procede de recuperation d'hydrogene dans un effluent hydrocarbone gazeux par reaction chimique
JP2001279276A (ja) 燃料電池用燃料油及び燃料電池用水素の製造方法

Legal Events

Date Code Title Description
MM4A Annulment or lapse of patent due to non-payment of fees