CN102325858B - Low-pressure fischer-tropsch process - Google Patents

Low-pressure fischer-tropsch process Download PDF

Info

Publication number
CN102325858B
CN102325858B CN200980157057.XA CN200980157057A CN102325858B CN 102325858 B CN102325858 B CN 102325858B CN 200980157057 A CN200980157057 A CN 200980157057A CN 102325858 B CN102325858 B CN 102325858B
Authority
CN
China
Prior art keywords
fischer
tropsch
catalyst
cobalt
promotor
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.)
Expired - Fee Related
Application number
CN200980157057.XA
Other languages
Chinese (zh)
Other versions
CN102325858A (en
Inventor
康芮·爱亚沙
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.)
Canada Chemical Corp
Original Assignee
Canada Chemical Corp
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
Priority claimed from US12/318,106 external-priority patent/US8053481B2/en
Priority claimed from PCT/CA2008/002306 external-priority patent/WO2010071967A1/en
Application filed by Canada Chemical Corp filed Critical Canada Chemical Corp
Publication of CN102325858A publication Critical patent/CN102325858A/en
Application granted granted Critical
Publication of CN102325858B publication Critical patent/CN102325858B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8913—Cobalt and noble metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/889—Manganese, technetium or rhenium
    • B01J23/8896—Rhenium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/31—Density
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/615—100-500 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/635—0.5-1.0 ml/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • 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
    • 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
    • C01B3/38—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
    • C01B3/384—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 the catalyst being continuously externally heated
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
    • C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
    • C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
    • C10G2/33—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used
    • C10G2/331—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals
    • C10G2/332—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals of the iron-group
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/04—Liquid carbonaceous fuels essentially based on blends of hydrocarbons
    • C10L1/08—Liquid carbonaceous fuels essentially based on blends of hydrocarbons for compression ignition
    • 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
    • C01B2203/025—Processes for making hydrogen or synthesis gas containing a partial oxidation step
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0405—Purification by membrane separation
    • 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
    • C01B2203/0495—Composition of the impurity the impurity being water
    • 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
    • C01B2203/06—Integration with other chemical processes
    • C01B2203/062—Hydrocarbon production, e.g. Fischer-Tropsch process
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/08—Methods of heating or cooling
    • C01B2203/0872—Methods of cooling
    • C01B2203/0877—Methods of cooling by direct injection of fluid
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/08—Methods of heating or cooling
    • C01B2203/0872—Methods of cooling
    • C01B2203/0883—Methods of cooling by indirect heat exchange
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/08—Methods of heating or cooling
    • C01B2203/0872—Methods of cooling
    • C01B2203/0888—Methods of cooling by evaporation of a fluid
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/08—Methods of heating or cooling
    • C01B2203/0872—Methods of cooling
    • C01B2203/0888—Methods of cooling by evaporation of a fluid
    • C01B2203/0894—Generation of steam
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/12—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
    • C01B2203/1235—Hydrocarbons
    • C01B2203/1241—Natural gas or methane
    • 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
    • C01B2203/1258—Pre-treatment of the feed
    • 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
    • C01B2203/1288—Evaporation of one or more of the different feed components
    • C01B2203/1294—Evaporation by heat exchange with hot process stream
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/40—Characteristics of the process deviating from typical ways of processing
    • C10G2300/4025—Yield
    • 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
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/04—Diesel oil
    • 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
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Inorganic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

A Fischer-Tropsch process for producing diesel fuel or diesel blending stock with a high cetane number, in a concentration of 65-90wt% at pressures below 200 psia, using a cobalt catalyst with a rhenium and/or ruthenium promoter. The catalyst is a cobalt catalyst with crystallites having an average diameter greater than 16 nanometers, and the resulting hydrocarbon product after a rough flash, contains less than 10wt% waxes (>C23).

Description

Low-pressure fischer-tropsch process
Technical field
The present invention relates to a kind of for carbon monoxide and hydrogen being changed into the low-pressure fischer-tropsch process of raw material for diesel oil fuel or diesel oil blending by and large.
Background technology
For carbon monoxide and hydrogen being changed into the fischer-tropsch (Fischer-Tropsch of liquid motor fuel and/or wax; FT) method is just known from the twenties in 20th century.
During World War II, in Germany, by coal gasification, supply the hydrogen of 1: 1 ratio and carbon monoxide to change into fuel hydrocarbon, thereby manufacture combined diesel oil.Due to the shortage of trade sanction and Sweet natural gas, make South Africa further via the gasification process of synthetic gas, develop coal, and use fixed bed iron Fischer-Tropsch catalyst.Iron catalyst very enlivens for water gas shift reaction, and described water gas shift reaction is removed gaseous constituent from hydrogen in shortage, so more approach approximately 2.0 best H 2/ CO ratio.When developing a large amount of natural gas supplies, using steam reformer and autothermal reformer is to use the slurry state bed FT reactor of cobalt or iron catalyst to produce raw material of synthetic gas.
At cyclostrophic liquid (Gas-To-Liquids; GTL), in factory, must between liquid product yield and factory's operation and investment cost, trade off.For example, if there is electricity market, can select so steam reformer design, because technology for this reason produces a large amount of used heat: use " economizer " and steam turbine can change into electric power by stack gas heat.If the preservation of gas material and low investment cost are primary, it is favourable using so the self-heating of air or partial oxidation reformer.
Another factor of selecting best reformer type is the character of reformer hydrocarbon feed gases.If gas is rich in CO 2, this situation can be for favourable, because after this can directly realize desired H in reformer gas so 2/ CO ratio, and do not need to remove excessive hydrogen, and CO 2in some be converted to CO, thereby increase the potential amount of issuable liquid hydrocarbon product.In addition, reduce the amount of the steam needing, this measure reduces processes energy requirement.
The market of fischer-tropsch (FT) method has large-scale " world-class scale " factory of the gas material speed that is greater than 200,000,000 scfd because considerable scale economics concentrates on.These factories are in the lower operation of high pressure (about 450psia), and the extensive circulation of use tail gas in FT reactor.For example, Norsk Hydro plant design has approximately 3.0 recycle ratio.Focus on realizing maximum wax productive rate.With regard to product slate, these integrated mills seek the maximum output of Fischer-Tropsch process synthetic wax, to minimize the formation of C1-C5 product.After this, wax is hydrocracking into and is mainly diesel oil mark and petroleum naphtha mark.Regrettably, in this process, also formed light hydrocarbon.Reformer uses the self-heating recapitalization of the use oxygen of some forms conventionally, and described oxygen produces from air in low temperature mode, and it is expensive technique that the low temperature mode of take produces oxygen with regard to process cost and investment cost from air.Scale economics proves, use, the tail gas that the use of high working pressure, oxynatural are reformed be extensively circulated to FT reactor for increase synthetic gas transform and control heat removes and the hydrocracking of product wax for be proper.Up to now, also do not have for thering is the FT plant design of midget plant's exploiting economy of the capacity that is less than 100,000,000 scfd.
Carbon monoxide is carried out to catalytic hydrogenation to produce from methane to heavy hydrocarbon (up to C 80higher) and the various products of the scope of oxygenation hydrocarbon be commonly referred to Fischer-Tropsch synthesis.High molecular hydrocarbon product mainly comprises n-paraffin, and described n-paraffin can not directly be used as motor spirit, because the cold property of described n-paraffin and described motor spirit is inconsistent.After further hydrotreatment, fischer-tropsch hydrocarbon product can be transformed into the product having compared with high additive value, such as, diesel oil fuel, rocket engine fuel or kerosene.Therefore, wish directly to maximize the output of high value liquid hydrocarbon, make to carry out component separation or hydrocracking.
The VIII of catalytic activity family (being especially iron, cobalt and nickel) is used as to Fischer-Tropsch catalyst; Cobalt/ruthenium is a catalysis system in prevailing catalysis system.In addition, catalyzer contains loaded metal and metal and promotor conventionally, for example, and rhenium.
Summary of the invention
According to an aspect of the present invention, provide fischer-tropsch (FT) method having containing the cobalt catalyst of crystallite, wherein said crystallite has the mean diameter that is greater than 16 nanometers.Described method produces liquid hydrocarbon product, and described liquid hydrocarbon product contains wax (the > C that is less than 10 % by weight 23) and be greater than the diesel oil (C of 65 % by weight 9-C 23).Described method can have the FT support of the catalyst for described cobalt catalyst, and wherein said support of the catalyst is the freely following support of the catalyst group forming of choosing: aluminum oxide, zirconium white, titanium dioxide and silicon-dioxide.Described cobalt catalyst can have the catalyst cupport that is greater than 10 % by weight.Working pressure for described Fischer-Tropsch process can be for being less than 200psia.In this method, can utilize promotor, in this case, promotor is the freely following group forming of choosing: ruthenium, rhenium, rhodium, nickel, zirconium, titanium and its mixture.Can in described method, implement flash distillation to reduce naphtha fraction.Described method can be used FT reactor, and described FT reactor is not used circulation of tail gas.Described method can also be used reformer, and described reformer uses air as oxygen source.Described reactor can be fixed bed FT reactor or slurry state bubbling bed FT reactor.
According to another aspect of the present invention, a kind of FT method is provided, described FT method operates being less than under 200psia, described FT method is used air autothermal reformer, and described FT method has at least 65% CO turnover ratio, and in one way FT reactor, provide the diesel yield that is greater than 60 % by weight with cobalt catalyst.Described catalyzer has the cobalt metal load that is greater than 5 % by weight and the rhenium load that is less than 2 % by weight on catalyst support material, and described catalyst support material is to be selected from the catalyst support material group that comprises following material: aluminum oxide, zirconium white and silicon-dioxide.Described cobalt catalyst is the form of crystallite, and wherein said crystallite has the mean diameter that is greater than 16 nanometers.Described FT catalyst support material can be comprised of aluminum oxide.This method can have unstripped gas, wherein with selective membrane or molecular sieve, from unstripped gas, removes hydrogen.Or described cobalt catalyst load can be for being greater than 6 % by weight, and working pressure can be for being less than 100psia.Described reactor can further have promotor, and wherein said promotor comprises the freely promotor of the following promotor group forming of choosing: ruthenium and rhenium or its mixture.
According to a further aspect of the invention, a kind of FT method is provided, described FT method operates being less than under 200psia, described FT method is used oxygen autothermal reformer, and described FT method has at least 65% CO turnover ratio, and in FT reactor, provide with cobalt catalyst the diesel yield that is greater than 60 % by weight.Described catalyzer has the cobalt metal load that is greater than 5 % by weight and the rhenium load that is less than 2 % by weight in support of the catalyst, and described support of the catalyst is the support of the catalyst group that the freely following material of choosing forms: alumina material, zirconia material and earth silicon material.Described cobalt catalyst is the form of crystallite, and described crystallite has the mean diameter that is greater than 16 nanometers.Described FT support of the catalyst can be comprised of aluminum oxide.Described method can comprise the tail gas from described reformer, wherein makes described tail gas partly be circulated to described reformer.Described method can also comprise unstripped gas, wherein with selective membrane or molecular sieve, from described gas, removes hydrogen.Or described cobalt catalyst load can be for being greater than 6 % by weight, and described working pressure can be for being less than 100psia.Described reactor can further have promotor, and wherein said promotor comprises the freely promotor of the following promotor group forming of choosing: ruthenium or rhenium or its mixture.
According to a further aspect of the invention, a kind of FT method is provided, described FT method operates being less than under 200psia, described FT method is used steam oxygen reformer, and described FT method has at least 65% CO turnover ratio, and use cobalt catalyst that the diesel yield that is greater than 60 % by weight is provided in FT reactor, described cobalt catalyst has the cobalt metal load that is greater than 5 % by weight and the rhenium load that is less than 2 % by weight in support of the catalyst, described support of the catalyst is the freely following support of the catalyst group forming of choosing: alumina material, zirconia material or earth silicon material or its mixture.Described cobalt catalyst is the form of crystallite, and wherein said crystallite has the mean diameter that is greater than 16 nanometers.Described FT support of the catalyst can be comprised of aluminum oxide.Described method can comprise unstripped gas, wherein with selective membrane or molecular sieve, from described unstripped gas, removes hydrogen.Described method may further include the tail gas from reformer, and the some or all of tail gas that wherein burns is to provide heat to described reformer.Or described cobalt catalyst load can be for being greater than 6 % by weight, and described working pressure can be for being less than 100psia.Described reactor can further have promotor, and wherein said promotor comprises the freely promotor of the following promotor group forming of choosing: ruthenium or rhenium or its mixture.
According to a further aspect of the invention, a kind of FT method is provided, described FT method operates being less than under 200psia, described FT method is used air or oxygen partial oxidation reformer, and described FT method has the CO turnover ratio that is greater than 65%, and with cobalt catalyst, in FT reactor, provide the diesel yield that is greater than 60 % by weight, described cobalt catalyst has the cobalt metal load that is greater than 5 % by weight and the rhenium load that is less than 2 % by weight in FT support of the catalyst, described FT support of the catalyst is to be selected from the support of the catalyst group that comprises following material: alumina material, zirconia material and earth silicon material.Described cobalt catalyst is the form of crystallite, and described crystallite has the mean diameter that is greater than 16 nanometers.Described FT support of the catalyst can be comprised of aluminum oxide.Described method can comprise unstripped gas, wherein with selective membrane or molecular sieve, from described unstripped gas, removes hydrogen.Described method may further include the tail gas from reformer, and the some or all of tail gas that wherein burns is to provide heat to described reformer.Or described cobalt catalyst load can be for being greater than 6 % by weight, and described working pressure can be for being less than 100psia.Described reactor can further have promotor, and wherein said promotor comprises the freely promotor of the following promotor group forming of choosing: ruthenium or rhenium or its mixture.
Accompanying drawing explanation
Fig. 1 is the process flow sheet of specific embodiment of the present invention;
Fig. 2 is the schema for flash separation petroleum naphtha mark and diesel hydrocarbon mark as the subsequent step of Fischer-Tropsch process;
The chart of the C5+ carbon number distribution of the catalyzer (trilobes) that Fig. 3 is displaying example 3 at 190 ℃;
Fig. 4 is for showing the chart of pressure on the impact of the catalyst performance of example 4;
Fig. 5 is the chart of the C5+ carbon number distribution of the catalyzer of example 7 under 190 ℃, 70psia;
Fig. 6 is the chart of the C5+ carbon number distribution of the catalyzer (LD-5) of example 8a under 200 ℃, 70psia;
Fig. 7 is the chart of the C5+ carbon number distribution of the catalyzer (F-220) of example 9 under 190 ℃, 70psia;
Fig. 8 is the chart of the C5+ carbon number distribution of the catalyzer of the example 10 of use ruthenium promotor;
Fig. 9 is the chart of C5+ carbon number distribution of the catalyzer (Aerolyst 3038 silicon-dioxide) of example 11;
Figure 10 is the chart of the relation of the wax content of displaying cobalt catalyst crystallite size and C5+FT product; And
Figure 11 is for showing the chart of catalyst carbon distribution and the comparison that traditional Anderson-Shultz-Flory distributes of use in example 9.
*in all figure of chart that show carbon number, petroleum naphtha is by large square expression, and diesel oil is represented by rhombus, and light wax is represented by little square.
Embodiment
Introduce
In Fischer-Tropsch process, such as the activity of the various parameter influence supported cobalt catalysts of the size and shape of cobalt crystallite.The size of microcrystalline is controlled quantity and the reducing degree to the effective reactive site of reduction (dispersity).
Under some pre-treatment and activation condition, the strong interaction between cobalt metal and oxide carrier forms bad cobalt-carrier structure (for example, cobalt aluminate), and described cobalt-carrier structure may need high reduction temperature.High reduction temperature may cause sintered cobalt crystallite and form large-scale cobalt metal cluster.Not only Temperature Treatment, and cobalt metal precursor and metal load and metallic promoter agent also can affect the size of cobalt crystallite.Low cobalt metal load may produce high metal dispersity and little crystallite, but promoted, causes the metal-carrier of bad reductibility and low catalyst activity to interact.
Use the hydrogenization of carbon monoxide and the cobalt atom amount of exposure of cobalt-supported catalyst to be directly proportional.Therefore, in logic, the cobalt metal dispersity increasing on Oxide-supports just can be promoted catalyst activity and C5+ selectivity.Yet little cobalt crystallite and oxide carrier interact consumingly, thereby form unreducible cobalt-carrier system.Strong correlation meeting between cobalt microcrystalline and reductibility affects catalyst activity, and may produce bad product.Under typical Fischer-Tropsch reaction condition, cobalt crystallite size scope (9-200nm) and dispersity scope (11-0.5%) have less impact to C5+ selectivity.Yet less cobalt crystallite suffers serious inactivation.In fact, the people such as Barbie have studied the dependency between inactivation rate and cobalt crystallite size for 2000, and observe peak value at 5.5nm place.
Embodiments of the invention
Embodiments of the invention described herein relate to low-pressure fischer-tropsch process and produce the catalyzer of high diesel oil mark productive rate.Processing pressure can be lower than 200psia.Catalyzer is for being deposited on cobalt on gamma aluminum oxide (optionally depositing) to be greater than 5 % by weight together with the rhenium of 0.01-2 % by weight or ruthenium, and described catalyzer has the crystallite that mean diameter is greater than 16 nanometers.Have been found that, it is very effective that this class catalyzer under low pressure changes into synthetic gas in diesel oil with high yield, thereby produce, contains the wax (> C23) that is less than 10 % by weight and the liquid hydrocarbon product that is greater than the diesel oil (C9-C23) of 65 % by weight.The embodiment of the present invention is especially well suited for the low-pressure gas that contains low molecular weight hydrocarbon to change into FT liquid.The example of application is landfill gas, solution gas of oil field and from the low-pressure gas in the field of going to calm the anger.Under all these situations, in traditional F T factory, will need multistage gas compression and air compressing.The high-level efficiency of FT catalyzer of the present invention makes to realize high CO transformation efficiency, and produces and contain the product flow up to the diesel oil of 90+ % by weight in one way.In natural gas reformer, use air that the synthetic gas of the nitrogen that contains about 50% is provided, this measure promotes in FT reactor as the removing of the heat of sensible heat, and improves gas velocity and heat transfer efficiency, makes not need circulation of tail gas.Can petroleum naphtha is separated with hydrocarbon product part by flash distillation cheaply, to generate purer diesel product.It is cooling that this measure is also used to provide some products.For being in harmonious proportion to increase cetane value with petrifaction diesel and reducing for sulphur content, liquid hydrocarbon product is splendid.
The embodiment of the present invention not only can be applied to the cyclostrophic liquid factory of world scale, and can be applied to use the small-sized FT factory be less than 100,000,000 scfd.When the embodiment of the present invention is applied to small-sized FT factory, the optimal economic meaning that the described embodiment of the present invention is sought to focus on simplification and minimized investment cost, may take efficiency as cost.Be below existing FT technology is compared with the embodiment of the present invention when being applied to small-sized FT factory comparison:
The existing FT technology embodiment of the present invention
In order to use oxygen blast reformer synthetic gas to operate FT method under high conversion, described method must be with at high proportion---based on fresh feed gas with 3.0 or larger ratio carry out recycled offgas.Secondary benefit is, live gas is diluted in carbon monoxide, and this measure reduction removes the needed speed of heat from FT reactor, reduces local heating and also improves product slate.Yet circulation of tail gas is energy and capital-intensive movable.From air separation oxygen, it is also energy and capital-intensive movable.
The means that adopt in the inventive method will be used air in reformer, and this measure produces and contains about 50% nitrogen as the synthetic gas of inert diluent, thereby eliminate, circulation of tail gas be removed to the needs of requirement to relax FT reactor heat.In FT method, use the additive method that blows air synthetic gas by a plurality of FT reactors of continuous use, to realize desired high CO transformation efficiency, this measure needs high capital cost and complicated operation.The inventive method realizes high CO transformation efficiency in simple one way, and realizes high diesel oil distillate by the special catalyst using as below more clearly describe.
Catalyzer is in one embodiment used the alumina supporter with high cobalt concentration, promotes catalyst reduction together with low-level rhenium.High cobalt concentration improves catalyst activity, thereby makes to realize high one way synthetic gas transformation efficiency.Make catalyzer there is relatively large average cobalt crystallite size, and this measure is substantially selectivity the product of diesel oil.
The theoretical prophesy of Anderson-Shultz-Florey, FT hydrocarbon covers carbon number range (from 1 to 60) very widely, and optimal product is diesel oil fuel (C 9-C 23, Chevron definition).For " loss " that reduce CO is to produce C 1-C 5hydrocarbon, common method is to strive for the main wax of producing in FT reactor, then, strives for wax to be hydrocracking into and to be mainly diesel oil and petroleum naphtha in lock out operation.Unexpectedly, the method for the embodiment of the present invention and catalyzer are directly produced diesel oil with high yield (reaching 90 % by weight) in FT reactor, thereby avoid the needs to expensive and complicated hydrocracking facility.
Because eliminated oxygen purification, high pressure compressed, circulation of tail gas and hydrocracking, so can apply economically the inventive method in being considered to so far for FT technology as much smaller factory of possible factory.
Fig. 1 shows the process flow sheet of the FT method of the embodiment of the present invention, and wherein alphabetical A-K represents following content:
The unprocessed gas containing hydrocarbon of A
B hydrocarbon gas conditioning equipment
C reformer
D water
E oxidizing gas
F water cooler
G separator
H hydrogen removes (optional)
I Fischer-Tropsch reaction device
J back pressure controller
K product is cooling and reclaim (2-option)
Letter A represents unprocessed hydrocarbonaceous processing unstripped gas.This hydrocarbonaceous is processed unstripped gas can be from each provenance: for example, and from natural-gas field, bury facility (biogas), petrolize facility (solution gas), etc.Pressure for the gas of the inventive method can change widely, from atmospheric pressure change to 200psia or higher.Single-stage compression or two stages of compression be may need, source pressure and desired processing working pressure depended on.For example, for landfill gas, pressure is conventionally close to barometric point, and use gas blower is sent to gas in combustion equipment.Also solution gas (being generally flash of light) must be compressed to processing working pressure.Also have many have for accept to in pipeline low pressure before exploitation and be the natural gas field in later stage, described natural gas field can produce possible raw material for the inventive method.May be in trouble and maybe may not be in trouble other gas sources of (fail to lead to pipeline) may be desired processing working pressure place or more than, and these gas sources are also candidate.Another candidate is for too high such as the inert gas content of nitrogen so that can not meet the Sweet natural gas of pipeline specifications.
Letter b represents hydrocarbon gas conditioning equipment.Gas may need to purify to remove the component that will destroy reformer or FT catalyzer.These examples that will destroy the component of reformer or FT catalyzer are mercury, hydrogen sulfide, silicone resin and organic chloride.Such as being found in the organic chloride of burying in gas, in reformer, produce hydrochloric acid, may cause heavy corrosion like this.Silicone resin forms and is coated in the continuous silicon-dioxide on catalyzer, thereby blocks pore.Hydrogen sulfide is powerful FT catalyzer poison, and hydrogen sulfide is removed to 1.0ppm or lower conventionally.Some gases from low-sulfur gas field may be without any need for regulating (purification).
The economy that hydrocarbon concentration affects in unprocessed gas is processed, because the unstripped gas for by same volume forms less hydrocarbon product.Yet, method can (for example) use bury gas 50% or lower methane concentration under operate.Even may there is the finance reason of working method at a loss: for example, for meeting greenhouse gases management or enterprise's emission standard.Method can operate with the unstripped gas that only contains methane hydrocarbon or contain natural gas liquids by applying known reformer technology.Carbonic acid gas is present in unstripped gas for favourable.
Letter C represents reformer, and described reformer can be some types, depends on the composition of unstripped gas.The remarkable interests of low pressure reformer operation be Brouard reaction compared with the minimizing of low rate and metallic dust.
Partial oxidation reformer is conventionally in the lower operation of very high pressure (that is, 450psia or larger), and therefore described partial oxidation reformer is not the suitableeest for low pressure FT method.Partial oxidation reformer is high energy poor efficiency, and can easily produce coal smoke, yet described partial oxidation reformer does not need water, and produces with H 2/ CO ratio approaches 2.0 synthetic gas, described synthetic gas for FT catalyzer for the best.Partial oxidation reformer can be used in the inventive method.
Steam reformer investment is expensive, and in integrated mill, needs stack gas heat recuperation with maximum efficiency.Because synthetic gas contains relatively low-level rare gas element (such as, nitrogen), so being controlled at, the temperature in FT reactor there is no circulation of tail gas in the situation of FT reactor may be for difficulty.Yet low-level rare gas element makes some tail gas can be circulated to reformer side pipe, thus supplemental natural gas raw material, or described low-level rare gas element makes some tail gas can be circulated to side shell, so that heat to be provided.Should keep it in mind, under any circumstance, FT tail gas must burn before discharging, and these energy can or be utilized better for generating, and so that reformer heat to be provided, otherwise described reformer heat will be provided by gas-firing.For small-sized FT factory, steam reformer is feasible selection.Steam reformer can be used in the inventive method.
Self-heating recapitalization is effective processing with relatively low investment cost, and described self-heating recapitalization is used moderate temperature and appropriate vapour concentration to use low CO 2gas material produces with H 2/ CO approximately 2.5 without coal smoke synthetic gas, H 2the H that/CO approximately 2.5 produces than steam reformation 2/ CO is closer to desired ratio.Yet, for most of gas material, still need to remove some hydrogen.If unstripped gas contains the CO that is greater than approximately 33% 2(landfill gas raw material is exactly so conventionally) can realize 2.0 H so without any cycling stream in the situation that 2/ CO ratio, and can reduce the use of water.This is the reformer that low pressure FT method of the present invention is wished the type that obtains most.
Letter D represents as the optional water in steam injection reformer.All reformer technology except partial oxidation reformer all need injecting steam.
Letter e represents oxidizing gas, and described oxidizing gas can be air, oxygen or oxygen-rich air.
Letter F represent for by reformer temperature out from being greater than 700 ℃ of water coolers that are reduced to close to surrounding temperature.Although can carry out coolingly in some stages, preferably carry out cooling in the single stage.Can realize with shell-tube type or board frame type heat-exchanger coolingly, and can utilize the energy of recovery to carry out pre-thermal reforming device unstripped gas, as known in industry.The another kind of mode of cooled reformer tail gas is by water injection stream or by making stream through the water of container by direct.
Letter G represents separator, and described separator is for separating of reformer synthetic gas and water of condensation, to make to enter the water yield minimum of upstream device.
Letter H represents optional hydrogen removing device, such as, the Prism being sold by Air Products tMhydrogen selective film, or from the Cynara film of Natco.
Some reformer method produces the too much synthetic gas of hydrogen content, must remove some hydrogen to realize best FT reactor performance.Desirable H 2/ CO ratio is 2.0-2.1, and unprocessed synthetic gas may have 3.0 or higher ratio.High hydrogen concentration causes larger CO loss, thereby produces methane, rather than desired motor spirit or such as the motor spirit precursor of petroleum naphtha.
Letter I represents typical FT reactor, and described typical FT reactor has fixed bed or slurry state bubbling type, and can use any one in both.Yet fixed bed is preferred in midget plant, because it is simple to operate and be easy to expand.
Letter J represents to set the back pressure controller of processing pressure.Described back pressure controller can be placed in other positions, depend on the possible part separating treatment that product reclaims and uses.
Letter K represents that product is cooling and reclaims.Conventionally to realize product cooling for the exchange by heat and cold water, and the cooling preheating water that is used for of described product, for the elsewhere in FT factory, uses.Separation is to realize in the separated separator vessel designing for oil/water.Yet second is chosen as flash cooling FT reactor product before aforementioned water cooler-separator as shown in Figure 2.This measure provides two objects---and first reduces product temperature and second makes it possible to the petroleum naphtha component in separated the produced hydrocarbon product of part, thus the remaining liq in enrichment diesel component.
Fig. 2 illustrates the programchart of flash separation petroleum naphtha and diesel hydrocarbon, wherein:
1 is fixed bed Fischer-Tropsch reaction device.
2 for approximately at 190-240 ℃ and pressure be greater than the mixture of gas, water, petroleum naphtha, diesel oil and light wax under normal atmosphere.
3 is pressure bleed valve.
4 is the stream 2 at the temperature reducing due to gas expansion and under 14.7psia.
5 is flash tank container.
6 streams 2 of serving as reasons deduct the vapor phase that diesel oil and light wax form.
7 is water cooler.
8 is the stream 6 with liquid phase petroleum naphtha and water.
9 for holding the container of petroleum naphtha and water.
10 is the waste tail gas stream being mainly comprised of rare gas element and light hydrocarbon.
FT product 2 flows through pressure bleed valve 3 and flows in flash tank 5.Rare gas element and compared with low boiling hydrocarbon, water and petroleum naphtha atop as steam from flash tank out, and through water cooler 7.Diesel oil and light wax are collected in container 5.Water and petroleum naphtha condense in water cooler 7, and are collected in container 9.Residual gas flows out from flowing 10 atop, and burned (sometimes having energy recovery) conventionally, or is used for generating.
Example
The support of the catalyst of using
The physical property of table 1. support of the catalyst
Example 1
Catalyze and synthesize is by implementing as the common components of being implemented by the affiliated learned personnel in field.Support of the catalyst is the aluminum oxide trilobal extrudate (hereinafter referred to as ' trilobe ') obtaining from Sasol Germany GmbH.Extrudate is of a size of the length of diameter and the 4.1mm of 1.67mm.By carrier in air with 500 ℃ of roastings 24 hours.By just wet impregnation method, the solution mixture of Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES and perrhenic acid is added into carrier, to realize 5 % by weight cobalt metals and the 0.5 % by weight rhenium metal in finished catalyst (catalyzer 1).Oxide catalyst in following three steps:
Step 1: catalyzer is heated to 85 ℃, and is incubated 6 hours;
Step 2: make temperature rise to 100 ℃ with 0.5 ℃ of per minute, and be incubated 4 hours;
Step 3: make temperature rise to 350 ℃ with 0.3 ℃ of per minute, and be incubated 12 hours.
The drying rate of moist catalysis depends on the size of catalyst particle to a certain extent.Compared with small-particle, will compare macroparticle dry sooner, and the size of the crystal forming can change with crystallization rate in pore.The oxide catalyst that is 29cc by volume is placed on 1/2 inch of external diameter (outside diameter; OD) in pipe, described pipe has outer ring space, and temperature control water flows through described outer ring space under pressure, to remove reaction heat.In fact, FT reactor is with the shell and tube heat exchanger that is placed on the catalyzer in side pipe.Inlet gas and water are all in goal response temperature.Catalyst reduction is realized by following program:
H in reducing gas flow rate (cc/ minute)/nitrogen 2(%)/temperature (℃)/the time (hour):
1.386/70/200/4, pre-heating stage
2.386/80/ to 325/4, the slow heating phase
3.386/80/325/30, the fixed temperature stage
During fischer-tropsch katalysis, to the total gas couette of FT reactor, be 1000hr -1gas volume air speed (Gaseous hourly space velocity; GHSV).Gaseous constituent represents air autothermal reformer gas: 50% nitrogen, 33.3%H2 and 16.7%CO.The air-dry methane production that reduces with catalyzer.This measure is by making temperature of reactor locate to keep first within 24 hours, to realize at 170 ℃.By inference, this process produces the carbonylation on cobalt surface and the FT of raising activity.Under all temps between between 190 ℃ and 220 ℃, measure CO transformation efficiency and liquid yield.
Example 2
Except cobalt metal load is 10 % by weight, the catalyzer using in this example (catalyzer 2) is identical with the catalyzer using in example 1.
Example 3
Except cobalt metal load is 15 % by weight, the catalyzer using in this example (catalyzer 3) is identical with the catalyzer using in example 1.
Example 4
Except cobalt metal load is 20 % by weight, the catalyzer using in this example (catalyzer 4) is identical with the catalyzer using in example 1.
Example 5
Except cobalt metal load is 26 % by weight, the catalyzer using in this example (catalyzer 5) is identical with the catalyzer using in example 1.
Example 6
Except cobalt metal load is 35 % by weight, the catalyzer using in this example (catalyzer 6) is identical with the catalyzer using in example 1.
Example 7
Except alumina supporter is the CSS-350 obtaining from Alcoa, and cobalt load is outside 20 % by weight, and the catalyzer using in this example (catalyzer 7) is identical with the catalyzer of use in example 1.This carrier is to have diameter spherical of 1/16 inch.
Example 8a, 8b, 8c and 8d
Except following difference, the catalyzer using in these examples (catalyzer 8a, 8b, 8c and 8d) is identical with the catalyzer using in example 1: except the LD-5 of alumina supporter for obtaining from Alcoa, and cobalt load is outside 20 % by weight, and catalyzer 8a is consistent with catalyzer 1.This carrier is to have mean value particle distribution spherical of 1963 microns.Example 8a is used former state size of particles mixture.Some in progenitor are worn into less screening size: catalyzer 8b, 8c and 8d be made into have respectively 214 microns, the particle of the diameter of 359 microns and 718 microns.Example 8b, 8c are consistent with catalyzer 8a with the cobalt load in 8d.
Example 9
Except alumina supporter is the F-220 obtaining from Alcoa, and cobalt load is outside 20 % by weight, and the catalyzer using in this example (catalyzer 9) is identical with the catalyzer of use in example 1.F-220 has the ball type carrier that 7/14 mesh size distributes.
Example 10
Except promotor is ruthenium rather than rhenium, the catalyzer using in this example (catalyzer 10) is identical with catalyzer 4.
Example 11
Except replacing aluminum oxide, use the Aerolyst 3038 SiO 2 catalyst carriers from Degussa, the catalyzer using in this example (catalyzer 11) is identical with catalyzer 3.
Example 12
During catalyzing and synthesizing, the oxidising process hold-time doubles, the catalyzer using in this example (catalyzer 12) is consistent with catalyzer 8d, has same catalyst carrier, size of particles and catalyst cupport.That is to say, for 3 oxidation steps of describing for catalyzer 1, temperature hold-time reaches respectively 12 hours, 8 hours and 24 hours.The intention of the slower catalyst oxidation speed of small catalyst 12 particles is, compares with the crystallite size (15.72) under the very fast crystallization condition of catalyzer 8d, realizes larger cobalt crystallite size (21.07nm) in the pore of vectorette particle.Be used for controlling the method for drying rate and catalyst cobalt crystallite size herein and do not mean that getting rid of any other method that realizes larger crystallite size.For example, can change the relative humidity of kiln or pressure to control catalyzer drying rate, and therefore control cobalt crystallite size.
Catalyst characterization
Use Chembet 3000 (Quantachrome Instruments) TPR/TPD analyzer to analyze average crystallite dimension (d (CoO), dispersity (D%) and the reducing degree (DOR) of above catalyzer.At 325 ℃, reduce H 2catalyzer in stream, and calculate cobalt dispersity, suppose that a hydrogen molecule covers two cobalt surface atoms.At 325 ℃, after reducing catalyst, at 380 ℃, use a series of (O through catalyzer 2/ He) oxygen chemisorption is measured in pulse.Determine uptake oxygen molar weight, and calculate reducing degree, suppose that all cobalt metals are reoxidized Co 3o 4.According to following formula, calculate cobalt crystallite size:
d(CoO)＝(96/D％)DOR
D%: dispersity
The assessment of FT catalyzer
(i) impact of cobalt load
With example 1-6, test the impact of Co load on catalyst performance, and the results are shown in table 2.
The impact of the catalyst cupport of table 2. example 1-6 (trilobes) under 70psia on performance
Implement at various temperatures the test for each of example 1-6, and list the temperature of the hydrocarbon product that produces maximum.Obviously, 5% cobalt is not enough to provide the liquid hydrocarbon of consumption; Optimum concn is 20 % by weight Co, and 20 % by weight Co concentration produce the liquid hydrocarbon of 1.03ml/h.Under 10 % by weight cobalts or higher cobalt load, in hydrocarbon product, the concentration of diesel range hydrocarbons is 75.3-92.5%.Use has the trilobal carrier of 20% cobalt and under 70psia, realizes the highest diesel production speed (0.78ml/h).
The performance data of catalyzer 1 at 202.5 ℃ is showed in table 8.The level of the wax on C5+ liquid (C > 23) is only 6.8%, and diesel oil mark is 73.5% (C9-C23).It is found that, for all tested crystallite mean diameters, be greater than 16 how for the catalyzer of rice, C5+ wax is less than 10 % by weight, thereby makes product can directly be used as diesel oil blending material.
The carbon number distribution of catalyzer 3 (trilobe) in Fig. 3 illustrative example 3 at 190 ℃.Obtain very narrow distribution, there is no pyroparaffine.Diesel oil is 90.8%, and petroleum naphtha is 6.1%, and light wax is 3.1%.Cetane value is very high, is 88.In the chart of all carbon numbers, petroleum naphtha is by large square expression, and diesel oil is represented by rhombus, and light wax is represented by little square.
The impact of pressure
Catalyzer 4 in example 4 is in standard test equipment as above, to turn round under various pressure, at the temperature of 202.5 ℃.Result in table 3 and Fig. 4 shows, is being low to moderate under the low pressure of 70psia for significant, and obtains optimum at the pressure between 70psia and 175psia for generation of the productivity of the catalyzer of liquid hydrocarbon.Preferred pressure is 70-450psia, and most preferably pressure is from 70psia to 175psia.The diesel oil mark that surpasses that pressure range is suitably constant in 70.8-73.5 % by weight.As shown in table 8, with the average crystallite dimension of the catalyzer 4 of 20% cobalt, be 22.26 nanometers, and C5+ wax mark is 6.8 % by weight, thereby makes product can be used as diesel oil blending material.
Table 3. pressure is on the impact of catalyst performance (4,202.5 ℃ of catalyzer)
Catalyzer 7
Seen in table 4, at 215 ℃ and realize maximum diesel production speed under 70psia.Compare with catalyzer 4, catalyzer 7 is at lower lower diesel production speed, the still higher diesel oil mark of generation of producing of optimum temps (215 ℃) of catalyzer 7.Fig. 5 is shown in the narrow carbon number range having at 190 ℃ in 89.6% product liquid in diesel range.Cetane value is 81.Yet as shown in table 8, crystallite size is 18.26 nanometers, and wax mark is 7.2%, thereby makes product can be used as diesel oil blending material.
Table 4. is the performance of catalyzer 7 (CSS-350) at various temperatures
Catalyzer 8a, 8b, 8c and 8d
Test-results is showed in table 5.The Co metal dispersity that catalyzer 8b, 8c and 8d are shown is higher than catalyzer 8a.Contain the Co lower than 16 nanometers 0the catalyzer of average crystallite dimension produces the wax distillate of 17.6-19.3 % by weight in FT product, and contains the Co that is greater than 16 nanometers 0the catalyzer 8a of crystallite and catalyzer 12 produce in C5+ liquid and are respectively the lower wax slop of 6.6 % by weight and 7.8 % by weight, thereby make product can be used as diesel oil blending material.Although it should be noted that catalyzer 8a and catalyzer 12 have very different size of particles, catalyzer 8a and catalyzer 12 produce similar low wax slop.This shows, what control low wax change in concentration is crystallite size, rather than size of particles.
The performance of table 5. catalyzer 8a-8d and catalyzer 12 under 70psia
Catalyzer 9
Under 70psia, test catalyst 9.As shown in table 6 and Fig. 7,190 ℃ of hydrocarbon products contain 99.1% " petroleum naphtha adds diesel oil " diesel oil originally as 93.6%.There is considerably less light wax.Cetane value is 81.As shown in table 8, crystallite size is 22.22 nanometers, and wax mark is 2.3%, thereby makes product can directly be used as diesel oil fuel.
The performance of table 6. catalyzer 9 (F-220) under all temps (pressure 70psia)
Catalyzer 10
Data display in table 7 and Fig. 8, replaces rhenium to use ruthenium catalyst promotor also to provide having 74.42% narrow hydrocarbon in the diesel range with total cetane value 78 to distribute.As shown in table 8, crystallite size is 20.89 nanometers, and wax mark is 3.73%, thereby makes product can be used as diesel oil blending material.
The performance of table 7. catalyzer 10 (ruthenium promotor, LD-5 alumina supporter)
Catalyzer 11
For catalyzer 11, at 210 ℃, hydrocarbon liquid throughput rate is 0.55ml/h.Carbon distribution curve shown in Fig. 9 is shown the narrow distribution with high diesel oil distillate.As shown in table 8, crystallite size is 33.1nm, and wax mark is 5.2%, thereby makes product can be used as diesel oil blending material, perhaps after flashing off petroleum naphtha mark.
The summary of table 8. cobalt crystallite size on the impact of C5+ wax concentration
Catalyzer 1 in this announcement to catalyzer 12 (except catalyzer 8b, 8c and 8d) shows, when FT catalyzer has the cobalt crystallite that is greater than 16nm, acquisition has the narrow distribution of the hydrocarbon (mainly in diesel range) of low wax content (< 10 % by weight), as shown in Figure 10 (large square is not the part of this embodiment).For example, in the situation of small catalyst particle (, catalyzer 12), be necessary crystallization control speed, to obtain desired crystallite size.
Figure 11 is this result and expected value from the Anderson-Shultz-Flory based on chainpropagation (A-S-F) carbon number distribution relatively.A-S-F distributes provides the only diesel oil mark of 50 % by weight, and the embodiment of the present invention provides the diesel oil mark of > 65 % by weight.
The liquid hydrocarbon product of catalyzer of the present invention is more valuable than the product of extensive A-S-F type, because the liquid hydrocarbon product of catalyzer of the present invention can directly be used as diesel oil blending raw material, and do not need hydrocracking to increase cetane value and to reduce the sulphur content of petrifaction diesel.Because the inventive method can be simple single pass method, so the inventive method can need low investment cost.
Although the preferred embodiments of the present invention are described and are illustrated in this announcement, it should be understood that, the invention is not restricted to these specific embodiments.Those skilled in the art now expects many variations and modification.About complete definition of the present invention and its desired extent, by consult with announcement herein and graphic together with summary of the invention and the claims of enclosing of reading and thinking over.

Claims (39)

1. for generation of comprising diesel oil fuel or the diesel oil blending Fischer-Tropsch process with the liquid hydrocarbon of raw material, described method produces and contains the liquid hydrocarbon product that is less than 10 % by weight waxes and is greater than 65% diesel oil, and described wax is >C 23wax, described diesel oil is C 9-C 23diesel oil, described Fischer-Tropsch process comprises:
Under the pressure lower than 200psia, operate; And
Use cobalt catalyst, described cobalt catalyst comprises Fischer-Tropsch catalyst carrier, and described Fischer-Tropsch catalyst carrier has cobalt microcrystalline thereon, and described cobalt microcrystalline has the mean diameter that is greater than 16 nanometers.
2. method according to claim 1, wherein said Fischer-Tropsch catalyst carrier is the support of the catalyst being selected from by the support of the catalyst group forming below: aluminum oxide, zirconium white, titanium dioxide, silicon-dioxide and its mixture.
3. method according to claim 2, wherein said aluminum oxide is gamma aluminum oxide.
4. method according to claim 1, wherein said cobalt catalyst has cobalt metal load, and wherein said cobalt metal load is at least 15 % by weight.
5. method according to claim 1, wherein the transformation efficiency of the CO in unstripped gas is at least 60%.
6. according to the method described in any one in claim 1 to 5, wherein in described method, use promotor, and described promotor is the free following promotor group forming of choosing: ruthenium, rhenium, rhodium, nickel, zirconium and titanium with and composition thereof.
7. according to the method described in any one in claim 1 to 5, wherein implement flash distillation to reduce light fractions, described light fractions has the boiling point lower than diesel oil.
8. method according to claim 1, wherein said method usage charges-tropsch reactors, described Fischer-Tropsch reaction device does not use circulation of tail gas.
9. according to the method described in any one in claim 1 to 5 or 8, wherein said method is used reformer, and described reformer uses air as oxygen source.
10. according to the method described in any one in claim 1 to 5 or 8, the Fischer-Tropsch reaction device wherein using in described Fischer-Tropsch process is fixed bed Fischer-Tropsch reaction device or slurry state bubbling bed Fischer-Tropsch reaction device.
11. 1 kinds of Fischer-Tropsch processes, described Fischer-Tropsch process operates being less than under 200psia, described Fischer-Tropsch process is used air autothermal reformer, and described Fischer-Tropsch process has at least 60% CO transformation efficiency and the diesel yield that is greater than 65 % by weight is provided in one way fare-tropsch reactors, and described Fischer-Tropsch process comprises following steps:
Use cobalt catalyst, described catalyzer has the cobalt metal load of at least 15 % by weight and is less than the rhenium load of 2 % by weight, described cobalt catalyst has the freely catalyst support material of the following catalyst support material group forming of choosing: aluminum oxide, zirconium white, silicon-dioxide and its mixture, and described cobalt catalyst has cobalt microcrystalline thereon, described cobalt microcrystalline has the mean diameter that is greater than 16 nanometers.
12. methods according to claim 11, wherein said Fischer-Tropsch catalyst solid support material is comprised of gamma aluminum oxide.
13. methods according to claim 11, described method has fischer-tropsch unstripped gas, wherein uses selective membrane or molecular sieve to remove hydrogen from described fischer-tropsch unstripped gas.
14. methods according to claim 11, wherein said working pressure is 40psia at least, and the temperature in described Fischer-Tropsch reaction device is at least 190 ℃.
15. methods according to claim 11, wherein said working pressure is for being less than 100psia.
16. Fischer-Tropsch processes according to claim 11, described cobalt catalyst further has promotor, and wherein said promotor comprises the freely promotor of the following promotor group forming of choosing: ruthenium, rhenium and its mixture.
17. 1 kinds of Fischer-Tropsch processes, described Fischer-Tropsch process has at least 60% CO transformation efficiency, and described Fischer-Tropsch process provides the diesel yield that is greater than 65 % by weight in Fischer-Tropsch reaction device, and described Fischer-Tropsch process comprises following steps:
Operate being less than under the pressure of 200psia;
Use oxygen autothermal reformer; And
Use cobalt catalyst, described catalyzer has the cobalt metal load of at least 15 % by weight and is less than the rhenium load of 2 % by weight on Fischer-Tropsch catalyst solid support material, described Fischer-Tropsch catalyst solid support material is the freely following catalyst support material group forming of choosing: aluminum oxide, zirconium white, silicon-dioxide and its mixture, wherein said cobalt catalyst is the form of cobalt microcrystalline, and described crystallite has the mean diameter that is greater than 16 nanometers.
18. methods according to claim 17, wherein said Fischer-Tropsch catalyst carrier is comprised of aluminum oxide.
19. methods according to claim 17, described method has the tail gas from fischer-tropsch reformer, wherein makes described tail gas partly be circulated to described reformer.
20. methods according to claim 17, described method further has Fischer-Tropsch reaction device unstripped gas, wherein uses selective membrane or molecular sieve to remove hydrogen from described unstripped gas.
21. methods according to claim 17, wherein said working pressure is 40psia at least, and the temperature in described Fischer-Tropsch reaction device is at least 190 ℃.
22. methods according to claim 17, wherein said working pressure is not more than 100psia.
23. Fischer-Tropsch processes according to claim 17, described reactor further has promotor, and wherein said promotor comprises the freely promotor of the following promotor group forming of choosing: ruthenium, rhenium and its mixture.
24. 1 kinds of Fischer-Tropsch processes for Fischer-Tropsch reaction device, described Fischer-Tropsch process comprises following steps:
Operate being less than under the pressure of 200psia;
Use steam oxygen reformer;
There is at least 60% CO transformation efficiency and the diesel yield that is greater than 65 % by weight is provided; And
Use cobalt metal catalyst, described cobalt metal catalyst has the cobalt metal load of at least 15 % by weight and is less than the rhenium load of 2 % by weight on Fischer-Tropsch catalyst solid support material, described Fischer-Tropsch catalyst solid support material is the freely following catalyst support material group forming of choosing: aluminum oxide, zirconium white, silicon-dioxide and its mixture, on wherein said catalyst support material, load has cobalt microcrystalline, and described crystallite has the mean diameter that is greater than 16 nanometers.
25. methods according to claim 24, wherein said Fischer-Tropsch catalyst carrier is comprised of gamma aluminum oxide.
26. methods according to claim 24, described method further has Fischer-Tropsch reaction device unstripped gas, wherein uses selective membrane or molecular sieve to remove hydrogen from described unstripped gas.
27. according to the method described in any one in claim 24 to 26, and described method has the tail gas from described reformer, and the some or all of described tail gas wherein burning in described tail gas is to provide heat to described reformer.
28. according to the method described in any one in claim 24 to 26, and wherein said working pressure is 40psia at least, and described temperature is at least 190 ℃.
29. according to the method described in any one in claim 24 to 26, and wherein said working pressure is less than 100psia.
30. according to the Fischer-Tropsch process described in any one in claim 24 to 26, and described reactor further has promotor, and wherein said promotor comprises the freely promotor of the following promotor group forming of choosing: ruthenium, rhenium and its mixture.
31. 1 kinds of Fischer-Tropsch processes, described Fischer-Tropsch process has and is greater than 60% CO transformation efficiency and the diesel yield that is greater than 65 % by weight is provided, and described Fischer-Tropsch process comprises:
Operate being less than under 200psia;
Use air or oxygen partial oxidation reformer; And
Usage charges-tropsch reactors, described Fischer-Tropsch reaction utensil has cobalt catalyst, described cobalt catalyst has the cobalt metal load that is greater than 15 % by weight and the rhenium load that is less than 2 % by weight on Fischer-Tropsch catalyst solid support material, described Fischer-Tropsch catalyst solid support material is the freely following catalyst support material group forming of choosing: aluminum oxide, zirconium white and silicon-dioxide with and composition thereof, wherein said cobalt catalyst is the form of microcrystalline, and described crystallite has the mean diameter that is greater than 16 nanometers.
32. methods according to claim 31, wherein said Fischer-Tropsch catalyst carrier is comprised of aluminum oxide.
33. according to the method described in claim 31 or 32, and described method has Fischer-Tropsch reaction device unstripped gas, wherein uses selective membrane or molecular sieve to remove hydrogen from described unstripped gas.
34. methods according to claim 31, wherein said working pressure is 40psia at least, and described temperature is at least 190 ℃.
35. methods according to claim 31, wherein said working pressure is less than 100psia.
36. Fischer-Tropsch processes according to claim 31, described reactor further has promotor, and wherein said promotor comprises the freely promotor of the following promotor group forming of choosing: ruthenium, rhenium and its mixture.
37. according to the method described in any one in claim 1,11,17,24 or 31, and the described temperature in wherein said Fischer-Tropsch reaction device is at least 190 ℃.
38. according to the method described in any one in claim 1,11,17,24 or 31, described temperature in wherein said Fischer-Tropsch reaction device is at least 190 ℃, described working pressure is 40psia at least, wherein in described method, use promotor, described promotor is the freely following promotor group forming of choosing: ruthenium, rhenium, rhodium, nickel, zirconium, titanium or its mixture; And wherein said CO transformation efficiency is greater than 65%.
39. according to the method described in claim 38, and wherein said CO transformation efficiency is greater than 65%.
CN200980157057.XA 2008-12-22 2009-12-21 Low-pressure fischer-tropsch process Expired - Fee Related CN102325858B (en)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
US12/318,106 US8053481B2 (en) 2006-11-08 2008-12-22 Low-pressure Fischer-Tropsch process
US12/318,106 2008-12-22
PCT/CA2008/002306 WO2010071967A1 (en) 2008-12-22 2008-12-22 Low-pressure fischer-tropsch process
CAPCT/CA2008/002306 2008-12-22
PCT/CA2009/001862 WO2010071989A1 (en) 2008-12-22 2009-12-21 Low-pressure fischer-tropsch process

Publications (2)

Publication Number Publication Date
CN102325858A CN102325858A (en) 2012-01-18
CN102325858B true CN102325858B (en) 2014-10-22

Family

ID=42286824

Family Applications (1)

Application Number Title Priority Date Filing Date
CN200980157057.XA Expired - Fee Related CN102325858B (en) 2008-12-22 2009-12-21 Low-pressure fischer-tropsch process

Country Status (9)

Country Link
EP (1) EP2379676A4 (en)
CN (1) CN102325858B (en)
AR (1) AR074831A1 (en)
AU (1) AU2009329785B2 (en)
CA (1) CA2748216C (en)
MX (1) MX2011006743A (en)
MY (1) MY160250A (en)
RU (1) RU2487159C2 (en)
WO (1) WO2010071989A1 (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2527372A (en) * 2014-06-21 2015-12-23 Inventure Fuels Ltd Synthesising hydrocarbons
RU2725983C2 (en) * 2017-01-17 2020-07-08 Андрей Владиславович Курочкин Autothermal reactor

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1436097A (en) * 2000-06-12 2003-08-13 萨索尔技术(控股)有限公司 Cobalt catalysts
CN1723087A (en) * 2002-11-13 2006-01-18 斯塔特石油公开有限公司 Fischer-tropsch catalysts
CA2567425A1 (en) * 2006-11-08 2008-05-08 Canada Chemical Corporation Simple low-pressure fischer-tropsch process

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DZ2370A1 (en) * 1996-12-13 2002-12-28 Shell Int Research Process for the preparation of hydrocarbons
EA005420B1 (en) * 2000-05-19 2005-02-24 Джонсон Мэтти Плс Catalysts with high cobalt surface area
US7452844B2 (en) * 2001-05-08 2008-11-18 Süd-Chemie Inc High surface area, small crystallite size catalyst for Fischer-Tropsch synthesis
US7541310B2 (en) * 2003-10-16 2009-06-02 Conocophillips Company Silica-alumina catalyst support, catalysts made therefrom and methods of making and using same
US8053481B2 (en) * 2006-11-08 2011-11-08 Wm Gtl, Inc. Low-pressure Fischer-Tropsch process

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1436097A (en) * 2000-06-12 2003-08-13 萨索尔技术(控股)有限公司 Cobalt catalysts
CN1723087A (en) * 2002-11-13 2006-01-18 斯塔特石油公开有限公司 Fischer-tropsch catalysts
CA2567425A1 (en) * 2006-11-08 2008-05-08 Canada Chemical Corporation Simple low-pressure fischer-tropsch process

Non-Patent Citations (7)

* Cited by examiner, † Cited by third party
Title
&amp *
&Oslash
G.Lendert Bezemer.Cobalt Particle Effects in the Fischer-Tropsch Reaction Studied with Carbon Nanofiber Supported Catalysts.《J.AM.CHEM.SOC.》.2006,第128卷(第12期),全文. *
Oslash *
yvind Borg.Fischer–Tropsch synthesis over γ -alumina-supported cobalt catalysts:.《JOURNAL OF CATALYSIS》.2007,第248卷全文.
yvind Borg.Fischer–Tropsch synthesis over γ-alumina-supported cobalt catalysts:.《JOURNAL OF CATALYSIS》.2007,第248卷全文. *
代小平.费-托合成制液态烃研究进展.《化学进展》.2000,第12卷(第3期),全文. *

Also Published As

Publication number Publication date
RU2487159C2 (en) 2013-07-10
MY160250A (en) 2017-02-28
CN102325858A (en) 2012-01-18
AU2009329785B2 (en) 2012-11-08
EP2379676A4 (en) 2012-06-20
RU2011130432A (en) 2013-01-27
CA2748216A1 (en) 2010-07-01
CA2748216C (en) 2016-06-07
EP2379676A1 (en) 2011-10-26
WO2010071989A1 (en) 2010-07-01
AU2009329785A1 (en) 2011-08-11
MX2011006743A (en) 2011-10-06
AR074831A1 (en) 2011-02-16

Similar Documents

Publication Publication Date Title
US8053481B2 (en) Low-pressure Fischer-Tropsch process
AU2006271760B2 (en) Multi stage Fischer-Tropsch process
US20150031922A1 (en) Process and catalyst system for the production of high quality syngas from light hydrocarbons and carbon dioxide
US20230295517A1 (en) Process for synthesising hydrocarbons
US20090111900A1 (en) Simple low-pressure fischer-tropsch process
RU2577547C2 (en) Fischer-tropsch process improvement for production of hydrocarbon fuel in conditions of gas-to-liquids technology
CN104508091B (en) The enhancing for the fischer-Te Luopuxi technique prepared in GTL environment for hydrocarbon fuel
WO2021185869A1 (en) Production of hydrocarbons
JP5107234B2 (en) Liquid fuel synthesis system
AU2002362693B2 (en) System for power generation in a process producing hydrocarbons
CN101928600A (en) Method for producing diesel oil or diesel oil blending component
US7001574B2 (en) Apparatus for producing high molecular weight liquid hydrocarbons from methane and/or natural gas
AU2002362693A1 (en) System for power generation in a process producing hydrocarbons
CN102325858B (en) Low-pressure fischer-tropsch process
US20230340334A1 (en) Processes for the production of liquid fuels from carbon containing feedstocks, related systems and catalysts
CN101432393B (en) Method for start-up of liquid fuel synthesis system, and liquid fuel synthesis system
WO2010038395A1 (en) Method for synthesizing liquid fuel and apparatus for synthesizing liquid fuel
CA2567425A1 (en) Simple low-pressure fischer-tropsch process
JP7483718B2 (en) Method for producing liquid hydrocarbons by a Fischer-Tropsch process integrated into a refinery
CN102165041B (en) Hydrocarbon synthesis reaction apparatus, hydrocarbon synthesis reaction system, and hydrocarbon synthesis method
WO2010071967A1 (en) Low-pressure fischer-tropsch process
WO2008055353A1 (en) Low pressure fixed bed fischer-tropsch process and apparatus
CN118256266A (en) Method for producing liquid fuel from carbon-containing raw material, related system and catalyst

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20141022