WO2007003959A1 - Production d'hydrocarbures liquides - Google Patents

Production d'hydrocarbures liquides Download PDF

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Publication number
WO2007003959A1
WO2007003959A1 PCT/GB2006/050145 GB2006050145W WO2007003959A1 WO 2007003959 A1 WO2007003959 A1 WO 2007003959A1 GB 2006050145 W GB2006050145 W GB 2006050145W WO 2007003959 A1 WO2007003959 A1 WO 2007003959A1
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WIPO (PCT)
Prior art keywords
hydrocracking
reactor
catalyst
hydrocarbons
hydrogen
Prior art date
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PCT/GB2006/050145
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English (en)
Inventor
Michael Joseph Bowe
Original Assignee
Compactgtl Plc
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Publication date
Application filed by Compactgtl Plc filed Critical Compactgtl Plc
Publication of WO2007003959A1 publication Critical patent/WO2007003959A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
    • 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
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/24—Stationary reactors without moving elements inside
    • B01J19/248—Reactors comprising multiple separated flow channels
    • B01J19/249—Plate-type reactors
    • 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
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    • 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
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G49/00—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00
    • C10G49/002—Apparatus for fixed bed hydrotreatment processes
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    • B01J2219/0004—Processes in series
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
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    • B01J2219/2461—Heat exchange aspects
    • B01J2219/2462—Heat exchange aspects the reactants being in indirect heat exchange with a non reacting heat exchange medium
    • 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
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    • B01J2219/2401—Reactors comprising multiple separate flow channels
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    • B01J2219/2476—Construction materials
    • B01J2219/2477—Construction materials of the catalysts
    • B01J2219/2479—Catalysts coated on the surface of plates or inserts
    • 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
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
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    • B01J2219/2476—Construction materials
    • B01J2219/2483—Construction materials of the plates
    • B01J2219/2485—Metals or alloys
    • 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
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
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    • B01J2219/2491—Other constructional details
    • B01J2219/2497—Size aspects, i.e. concrete sizes are being mentioned in the classified document
    • 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
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    • 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
    • C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
    • C01B2203/0811—Methods of heating the process for making hydrogen or synthesis gas by combustion of fuel
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/08—Methods of heating or cooling
    • C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
    • C01B2203/0811—Methods of heating the process for making hydrogen or synthesis gas by combustion of fuel
    • C01B2203/0822—Methods of heating the process for making hydrogen or synthesis gas by combustion of fuel the fuel containing hydrogen
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    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/08—Methods of heating or cooling
    • C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
    • C01B2203/0811—Methods of heating the process for making hydrogen or synthesis gas by combustion of fuel
    • C01B2203/0827—Methods of heating the process for making hydrogen or synthesis gas by combustion of fuel at least part of the fuel being a recycle stream
    • 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
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C01B2203/1047—Group VIII metal catalysts
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    • 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
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C01B2203/1047—Group VIII metal catalysts
    • C01B2203/1052—Nickel or cobalt catalysts
    • C01B2203/1058—Nickel catalysts
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    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
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    • C01B2203/1064—Platinum group metal catalysts
    • C01B2203/107—Platinum catalysts
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    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
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    • 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
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    • C01B2203/1288—Evaporation of one or more of the different feed components
    • C01B2203/1294—Evaporation by heat exchange with hot process stream
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    • C01B2203/14—Details of the flowsheet
    • C01B2203/142—At least two reforming, decomposition or partial oxidation steps in series
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    • C01B2203/80—Aspect of integrated processes for the production of hydrogen or synthesis gas not covered by groups C01B2203/02 - C01B2203/1695
    • C01B2203/84—Energy production
    • 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
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    • Y02P20/00—Technologies relating to chemical industry
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Definitions

  • This invention relates to a chemical process to produce liquid hydrocarbons, and to a plant including a catalytic reactor suitable for use in performing the process .
  • a process is described in WO 01/51194 and WO 03/048034 (Accentus pic) in which methane is reacted with steam, to generate carbon monoxide and hydrogen in a first catalytic reactor; the resulting gas mixture is then used to perform Fischer-Tropsch synthesis in a second catalytic reactor.
  • the overall result is to convert methane to hydrocarbons of higher molecular weight, which are usually liquids or waxes under ambient conditions.
  • the two stages of the process, steam/methane reforming and Fisher-Tropsch synthesis require different catalysts, and catalytic reactors are described for each stage.
  • the catalytic reactors enable heat to be transferred to or from the reacting gases, respectively, as the reactions are respectively endothermic and exothermic; the heat required for steam/methane reforming may be provided by combustion.
  • the product includes hydrocarbons ranging between about C5 and C40, about half of the product (by weight) being in the range C5 - C19 (and typically a liquid) , and just under a third in the range C20 - C29 (typically low molecular weight waxes) . Consequently the product is waxy, and is preferably stored at an elevated temperature to ensure it remains liquid; alternatively it may, in some situations, be possible to blend this Fischer- Tropsch product with crude oil.
  • a further problem of the process described in the above patent applications is that the synthesis gas produced in the first stage provides a higher proportion of hydrogen than is required by the Fischer-Tropsch synthesis of the second stage, so that the tail gases from the Fischer-Tropsch synthesis inevitably contain significant quantities of excess hydrogen.
  • this hydrogen- containing tail gas may be utilised for generating electrical power in a turbine, but with larger capacity offshore or remote plants it is more difficult to find an economic use for this excess hydrogen.
  • a process for processing natural gas to generate longer- chain hydrocarbons comprising reacting the methane to generate a mixture of carbon monoxide and hydrogen, and subjecting this mixture to Fischer-Tropsch synthesis to generate longer-chain hydrocarbons, wherein the longer-chain hydrocarbons from the Fischer-Tropsch synthesis are reacted with hydrogen in a compact catalytic reactor at a substantially constant elevated temperature and an elevated pressure above 80 atmospheres so as to perform hydrocracking, the reactor comprising a stack of plates bonded together and defining flow channels for the hydrocracking reaction alternating in the stack with flow channels for heat removal, the flow channels for the hydrocracking reaction containing a removable catalyst insert with a metal substrate.
  • This hydrocracking step preferably uses hydrogen from the tail gas.
  • the tail gas may be sufficiently hydrogen-rich that it may be used for this purpose without additional processing.
  • the hydrocracking reaction is at a pressure above 90 atmospheres, for example 100 atmospheres or above, and at a temperature preferably in the range 400° to 450°C.
  • the product stream from the hydrocracking reaction is subsequently subjected to a separation process such as distillation, to produce a liquid product fraction (which would be liquid at ambient conditions), a light hydrocarbon gas fraction, and a waxy product fraction (which would be waxy at ambient conditions) .
  • a separation process such as distillation
  • the hydrocracking process is exothermic, and reaction conditions are preferably substantially isothermal in order to avoid thermal instability, coking, and the production of short chain (C1-C5) hydrocarbons.
  • a compact catalytic reactor can provide sufficiently good heat transfer to ensure substantially isothermal operation. This may utilise, as a cooling medium, the waxy product fraction produced by the separation process, and/or the waxy product feed.
  • the compact catalytic reactor comprises a stack of plates, and the flow channels for reactants and for coolant are defined between successive plates, the plates being stacked and then bonded together.
  • the flow channels may be defined by grooves in the plates.
  • the flow channels may be defined by thin metal sheets that are castellated and stacked alternately with flat sheets; the edges of the flow channels may be defined by sealing strips.
  • the stack of plates forming the reactor is bonded together for example by diffusion bonding, brazing, or hot isostatic pressing.
  • the reactor must also be provided with headers to supply the fluids to the flow channels.
  • Each header for the reactant channels preferably comprises a chamber attached to the outside of the reactor and communicating with a plurality of channels, such that after removal of a header, the corresponding catalyst structures in the flow channels are removable. This ensures that the catalysts can easily be replaced when they become spent.
  • the catalyst structure preferably incorporates a ceramic coating to carry the catalytic material.
  • the metal substrate for the catalyst structure is a steel alloy that forms an adherent surface coating of aluminium oxide when heated, for example an aluminium- bearing ferritic steel such as iron with 15% chromium, 4% aluminium, and 0.3% yttrium (eg Fecralloy (TM)) .
  • TM yttrium
  • this metal is heated in air it forms an adherent oxide coating of alumina, which protects the alloy against further oxidation and against corrosion.
  • the ceramic coating is of alumina, this appears to bond to the oxide coating on the surface.
  • the substrate may be a wire mesh or a felt sheet, but the preferred substrate is a thin metal foil for example of thickness less than 100 ⁇ m, and the substrate may be corrugated, pleated or otherwise shaped so as to define a multiplicity of flow paths.
  • the metal substrate of the catalyst structure within the flow channels enhances heat transfer within the catalyst structure, preventing hot spots or cold spots, enhances catalyst surface area, and provides mechanical strength.
  • the metal substrate is preferably coated with a stabilised gamma-alumina support, in which is a nickel tungsten catalyst.
  • the catalyst structure may for example be a single shaped foil.
  • the catalyst structure may comprise a plurality of such shaped foils separated by substantially flat foils; the shaped foils and flat foils may be linked to each other, for example by projecting lugs locating in corresponding slots, or alternatively may be inserted as separate items.
  • the reactant channels are preferably less than 20 mm deep, and more preferably less than 10 mm deep, and may be less than 5 mm deep. But the channels are preferably at least 1 mm deep, or it becomes difficult to insert the catalyst structures, and engineering tolerances become more critical.
  • the temperature within the channels is maintained uniformly across the channel width, within about 2-4 0 C, and this is more difficult to achieve the larger the channel becomes.
  • the plates forming the reactor may each be of width in the range 0.1 m to 0.8 m and of length in the range 0.3 m to 1.5 m.
  • Reactors of this type provide short diffusion path lengths, so that the heat and mass transfer rates can be high, and so the rates of chemical reactions can be high. Such a reactor can therefore provide a high power density. In the present context it enables a comparatively small and lightweight plant to be used for hydrocracking, leading to a hydrocarbon product which is potentially more valuable and is easier to store and transport .
  • the invention also provides a plant incorporating one or more compact catalytic reactors for performing such a process.
  • Figure 1 shows graphically the range of chain lengths produced by the Fischer-Tropsch synthesis
  • Figure 2 shows a flow diagram of a chemical process of the invention
  • Figure 3 shows a diagrammatic cross-section of a reactor suitable for use in this process.
  • the invention relates to a chemical process for converting natural gas (primarily methane) to longer chain hydrocarbons.
  • the natural gas typically contains higher hydrocarbons say C2 - CIl at up to 10 % v/v depending on its source.
  • the natural gas is mixed with steam, and passed, at a temperature of about 45O 0 C, through an adiabatic pre-reformer containing a nickel or a platinum/rhodium based methanation catalyst.
  • the higher hydrocarbons react with the steam to form methane and CO.
  • the next stage involves steam reforming, that is to say the reaction:
  • This reaction may be catalysed by a platinum/rhodium catalyst at about 800 0 C, and the necessary heat produced by catalytic combustion of an inflammable gas in adjacent gas flow channel.
  • the resulting mixture of carbon monoxide and hydrogen may be referred to as synthesis gas.
  • the synthesis gas is then cooled and used to perform a Fischer-Tropsch synthesis to generate longer chain hydrocarbons, that is to say:
  • the preferred catalyst for the Fischer-Tropsch synthesis comprises a support of gamma-alumina, with about 10-40% cobalt (by weight compared to the alumina) , and with a promoter such as ruthenium, platinum or gadolinium which is less than 10% the weight of the cobalt.
  • the reactors for the steam reforming and the synthesis reaction are each compact catalytic reactors as described above, with appropriate catalysts.
  • Mn is the mass fraction of a carbon chain of length n.
  • the value of ⁇ is affected by the reaction temperature, and by the pressure. For example, with Fischer-Tropsch carried out between about 204° and 22O 0 C and pressure about 2.0 MPa, the value of ⁇ is in the range between about 0.80 and 0.85. Operation at these conditions minimises formation of methane, while maximising the conversion of carbon monoxide to hydrocarbons, so that it provides a good yield of products. However, inevitably a significant proportion are of chain length above about C20, and are therefore waxy at ambient conditions.
  • the natural gas feed 5 consists primarily of methane with a small proportion of higher hydrocarbons C 2 to Cn. It is mixed with steam, for example in a fluidic vortex mixer 14.
  • the gas/steam mixture is heated in a heat exchanger 16 using the hot exhaust gas from catalytic combustion so that the gas mixture is at a temperature of 500 0 C.
  • the mixture enters an adiabatic fixed bed pre-reformer 18 where it contacts a nickel or a platinum/rhodium based methanation catalyst.
  • the higher hydrocarbons react with the steam to form methane and carbon monoxide.
  • the gas mixture typically leaves the pre-reformer 18 at about 45O 0 C, and is supplied to a reformer 20 which is a compact catalytic reactor made from a stack of plates (castellated plates alternating with flat plates) which define flow paths for endothermic and exothermic reactions which are in good thermal contact, and which contain appropriate catalysts on corrugated metal foil supports.
  • the reformer channels in the reformer 20 contain a platinum/rhodium catalyst, and the steam and methane react to form carbon monoxide and hydrogen.
  • the temperature in the reformer increases from 45O 0 C at the inlet to about 800-850 0 C at the outlet.
  • the heat for the endothermic reactions in the reforming reactor 20 is provided by the catalytic combustion of a mixture of short chain hydrocarbons and hydrogen which is the tail gas 22 from the Fischer-
  • the combustion takes place over a palladium/platinum catalyst within adjacent flow channels within the reforming reactor 20.
  • the combustion gas path is co-current relative to the reformer gas path.
  • the catalyst may include gamma-alumina as a support, coated with a palladium/platinum mixture 3:1, which is an effective catalyst over a wide temperature range.
  • the synthesis gas may be further cooled in another heat exchanger (not shown) , and any excess water separated from it.
  • the synthesis gas is then compressed by one or more compressors 28 to about 20 atmospheres, and is then fed to a catalytic Fischer-Tropsch reactor 30a, this again being a compact catalytic reactor formed from a stack of plates as described above; the reactant mixture flows through one set of channels, while a coolant flows through the other set .
  • the reaction products from the Fischer-Tropsch synthesis are cooled to about 80-90 0 C by passage through a heat exchanger 32a and supplied to a separating chamber 34 in which the gases and condensed liquids separate.
  • the gases primarily short-chain hydrocarbons and unreacted synthesis gas, are heated back to the reaction temperature (say 200 0 C) in a heat exchanger 33 and then supplied to a second Fischer-Tropsch reactor 30b, so that still more of the carbon monoxide undergoes the synthesis reaction.
  • the outflow from the reactor 30b is passed through a second cooling heat exchanger 32b, so it is cooled to a temperature of about 80-90 0 C, and supplied to a first stage separator 35.
  • the liquid phase from the separating chamber 34 is also fed into this separator 35.
  • the gas phase is passed through another cooling heat exchanger 36, to cool it to a temperature of about 2O 0 C, and supplied to a second stage separator 38.
  • the gas phase emerging from this separator 38 consists of the non-condensed hydrocarbons and excess hydrogen gas which constitute the Fischer-Tropsch tail gases 22; these are collected and split.
  • a proportion passes through a pressure reduction valve 39 to provide the fuel for the catalytic combustion process in the reformer 20 (as described above) .
  • Some of the tail gases may be fed to a gas turbine (not shown) to generate electricity.
  • a major part of the final tail gas stream 22 is compressed to 100 atmospheres by a compressor 40.
  • the longer-chain hydrocarbon stream 42 from the first stage separator 35 (which consists of the waxy hydrocarbons that condense at about 8O 0 C) is also raised to this pressure by a pump 44.
  • the hydrocarbon stream 42 is then passed through a heat exchanger 46 in which it is preheated by catalytic combustion in the adjacent channels, the combustion being of part of the tail gas stream 22 combined with air.
  • the catalyst for the combustion can be the same as that in the combustion channels of the reforming reactor 20.
  • the hot hydrocarbon stream 42 at a temperature of about 400 0 C is then mixed with the tail gas stream 22 at a mixer 48, and the mixture is then passed in succession through two hydrocracking reactors 50 and 52.
  • the reaction channels contain a nickel tungsten catalyst on a stabilised gamma alumina support coated on a corrugated Fecralloy foil insert.
  • the resulting hydrocarbons are supplied to a high-pressure separator vessel 54, and unreacted hydrogen emerges through a duct 56 and is returned to the mixer 48 to be recycled through the reactors 50 and 52.
  • the liquid phase from the separator 54 is then supplied to a distillation column 58. This separates the hydrocarbons into three fractions.
  • a light fraction (C5 and below) consists of hydrocarbons that are gaseous under ambient conditions; this is fed back to the mixer 14 so that it is subjected to pre-reforming again.
  • a middle fraction whose boiling point at atmospheric pressure would be in the range about 20° to 35O 0 C, constituting hydrocarbons between about C6 and C18, is similar to diesel fuel, and is the desired hydrocarbon product 60 of the plant 10.
  • the waxy fraction 62 whose boiling point at atmospheric pressure would be above 35O 0 C, constituting hydrocarbons above about C19, is recycled to be combined with the hydrocarbon stream 42 and subjected to hydrocracking again .
  • the recycled waxy fraction 62 is used as the cooling medium in the hydrocracking reactors 50 and 52, typically being provided at a temperature of about 35O 0 C.
  • the intention is to maintain the reaction temperature in the range 410° to 42O 0 C, despite the exothermic nature of the reaction, and to heat the waxy fraction up to about 400 0 C in the process.
  • the flow rate of the waxy fraction 62 through the coolant channels of the reactors 50 and 52 can be adjusted using valves 64 in a bypass, to maintain the required reaction temperature profile.
  • a significant aspect of the present invention is the use of a compact catalytic reactor for the hydrocracking reactors 50 and 52.
  • These reactors may be made of stainless steel castellated plates.
  • the reaction channels extend straight through the reactor, aligned vertically so that the reactants flow from top to bottom.
  • a reactor 70 suitable for use as the reactor 50 (or 52) is constructed from a stack of flat plates alternating with castellated plates, with the orientations of the channels defined by the castellations being orthogonal in alternate castellated plates.
  • the channels (not shown in figure 3) for the hydrocracking reaction contain catalyst-carrying foils, and extend straight through the reactor between appropriate headers (not shown) , the flow along these channels being indicated by the arrows F.
  • the coolant channels are constructed from a long strip of 1 mm thick sheet formed into castellations running along its length. As shown, the castellated strip is cut into lengths 71 and these are laid side-by-side to define flow paths 72 transverse to the direction of the arrows F, three such lengths 71 of castellated strip forming a rectangle, with edge strips 74 along the edges, so as to provide paths between an inlet port 75 and an outlet port 76. The ends of the castellated strip next to the inlet port 75 and the outlet port 76 are cut square, while the other ends are cut at 45°, and triangular pieces 77 of the castellated strip provide links between the flow paths 72.
  • edge strips 74 are also provided between side-by-side edges of the lengths 71 of castellated strip.
  • the stack is assembled as described above, and then bonded together for example by high-temperature brazing.
  • the flow of the coolant indicated by the arrows G, follows a zigzag path which overall is countercurrent to that of the reactants (arrows F) .
  • Heat transfer into and across the coolant channels 72 may be enhanced by inserting corrugated foils (not shown) , similar to the foils that would be used in a reaction channels but not incorporating a catalyst, and not needing to be removable. Such inserted foils may be perforated.
  • the castellations defining the flow channels 72 might not follow straight paths along the length of the strip, but might follow a sinuous or zigzag path, and might also be perforated.
  • the reactor 70 allows the coolant to pass three times across the width of the hydrocracking reaction channels, in passing between the inlet 75 and the outlet 76; alternatively the coolant might pass more than three times.
  • the steel plates forming the reactor 70 must be sufficiently strong to withstand the pressures to which they are exposed. However, it will be understood that the entire reactor assembly shown in figure 3 may instead be enclosed within a conventional pressure vessel.

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Abstract

L'invention concerne un procédé dans lequel du gaz naturel est traité pour produire des hydrocarbures à chaînes longues, consistant à faire réagir (20) le méthane pour produire un mélange de monoxyde de carbone et d'hydrogène, puis à soumettre le mélange obtenu à une synthèse de Fischer-Tropsh (30) pour produire des hydrocarbures à chaînes longues. Ce procédé permet de produire des hydrocarbures à chaînes longues, y compris des hydrocarbures paraffineux. Le procédé consiste ensuite à faire réagir le produit liquide issu de la synthèse de Fischer-Tropsch avec de l'hydrogène dans un réacteur catalytique compact (50, 52) à une température sensiblement constante comprise entre 400 °C et 450 °C et à une pression élevée supérieur à 80 atmosphères afin qu'il subisse un hydrocraquage. Les gaz restants sont recyclés (56) dans le réacteur d'hydrocraquage et le produit liquide est traité pour retirer une fraction paraffinique résiduelle. Cette fraction paraffinique résiduelle (62) peut être réutilisée dans le réacteur d'hydrocraquage comme élément de refroidissement pour le procédé d'hydrocraquage.
PCT/GB2006/050145 2005-07-01 2006-06-08 Production d'hydrocarbures liquides WO2007003959A1 (fr)

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GBGB0513484.6A GB0513484D0 (en) 2005-07-01 2005-07-01 Producing liquid hydrocarbons

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8207132B2 (en) 2004-07-28 2012-06-26 National Research Council Of Canada Recombinant vaccines against caligid copepods (sea lice) and antigen sequences thereof
EP3421122A1 (fr) * 2017-06-28 2019-01-02 Commissariat à l'Energie Atomique et aux Energies Alternatives Module de reacteur-echangeur a au moins deux circuits de fluide realise par empilement de plaques, applications aux reactions catalytiques exothermiques ou endothermiques

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0967262A1 (fr) * 1998-06-25 1999-12-29 AGIP PETROLI S.p.A. Procédé de préparation d'hydrocarbures à partir de gaz de synthèse
WO2003033131A1 (fr) * 2001-10-12 2003-04-24 Gtl Microsystems Ag Reacteur catalytique
WO2003033133A1 (fr) * 2001-10-18 2003-04-24 Gtl Microsystems Ag Reacteur catalytique
WO2003048035A1 (fr) * 2001-12-05 2003-06-12 Gtl Microsystems Ag Procede et appareil pour le reformage vapeur - methane
WO2003048034A1 (fr) * 2001-12-05 2003-06-12 Gtl Microsystems Ag Procede et appareil de reformage vapeur du methane
WO2004050799A1 (fr) * 2002-12-02 2004-06-17 Gtl Microsystems Ag Reacteur catalytique et procede associe

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0967262A1 (fr) * 1998-06-25 1999-12-29 AGIP PETROLI S.p.A. Procédé de préparation d'hydrocarbures à partir de gaz de synthèse
WO2003033131A1 (fr) * 2001-10-12 2003-04-24 Gtl Microsystems Ag Reacteur catalytique
WO2003033133A1 (fr) * 2001-10-18 2003-04-24 Gtl Microsystems Ag Reacteur catalytique
WO2003048035A1 (fr) * 2001-12-05 2003-06-12 Gtl Microsystems Ag Procede et appareil pour le reformage vapeur - methane
WO2003048034A1 (fr) * 2001-12-05 2003-06-12 Gtl Microsystems Ag Procede et appareil de reformage vapeur du methane
WO2004050799A1 (fr) * 2002-12-02 2004-06-17 Gtl Microsystems Ag Reacteur catalytique et procede associe

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8207132B2 (en) 2004-07-28 2012-06-26 National Research Council Of Canada Recombinant vaccines against caligid copepods (sea lice) and antigen sequences thereof
EP3421122A1 (fr) * 2017-06-28 2019-01-02 Commissariat à l'Energie Atomique et aux Energies Alternatives Module de reacteur-echangeur a au moins deux circuits de fluide realise par empilement de plaques, applications aux reactions catalytiques exothermiques ou endothermiques
FR3068263A1 (fr) * 2017-06-28 2019-01-04 Commissariat A L'energie Atomique Et Aux Energies Alternatives Module de reacteur-echangeur a au moins deux circuits de fluide realise par empilement de plaques, applications aux reactions catalytiques exothermiques ou endothermiques

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