WO2017093130A1 - Procédé pour la préparation d'un gaz de synthèse - Google Patents

Procédé pour la préparation d'un gaz de synthèse Download PDF

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Publication number
WO2017093130A1
WO2017093130A1 PCT/EP2016/078773 EP2016078773W WO2017093130A1 WO 2017093130 A1 WO2017093130 A1 WO 2017093130A1 EP 2016078773 W EP2016078773 W EP 2016078773W WO 2017093130 A1 WO2017093130 A1 WO 2017093130A1
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WO
WIPO (PCT)
Prior art keywords
methane
gas
syngas
steam
preheated
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PCT/EP2016/078773
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English (en)
Inventor
Ruben SMIT
Gerald Sprachmann
Robert Schouwenaar
Hubert Willem Schenck
Original Assignee
Shell Internationale Research Maatschappij B.V.
Shell Oil Company
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Application filed by Shell Internationale Research Maatschappij B.V., Shell Oil Company filed Critical Shell Internationale Research Maatschappij B.V.
Publication of WO2017093130A1 publication Critical patent/WO2017093130A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/38—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
    • 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
    • C01B2203/12—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
    • C01B2203/1258—Pre-treatment of the feed
    • C01B2203/1264—Catalytic pre-treatment of the feed
    • C01B2203/127—Catalytic desulfurisation
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/14—Details of the flowsheet
    • C01B2203/142—At least two reforming, decomposition or partial oxidation steps in series
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency
    • Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines

Definitions

  • the present invention relates to a process for the preparation of a syngas comprising hydrogen and carbon monoxide from a methane comprising gas and to a process for the production of hydrocarbon products from such syngas by means of a Fischer-Tropsch process.
  • syngas refers to synthesis gas, which is a common term to refer to gas mixtures comprising carbon monoxide and hydrogen.
  • the present invention specifically relates to a process for the preparation of syngas using an
  • ATR autothermal reformer
  • the heat contained in the hot raw syngas can be recovered for use in the process by indirect heat exchange against water to produce steam (e.g. in a waste heat boiler) and/or by heat exchange against other process streams.
  • the syngas side of the heat exchanger used is consequently prone to metal dusting corrosion. This can cause serious damage to the heat exchanger.
  • the alloys used for such heat exchangers typically comprise metals such as iron, nickel and/or cobalt.
  • the metal dust produced as a result of metal dusting corrosion will accordingly comprise these metals which are known to catalyse the methanation reaction.
  • Methanation is the formation of methane from hydrogen and carbon oxides and is an undesired side reaction in the production of syngas, not only because it reduces the amount of hydrogen and carbon monoxide in the syngas, but also because methanation is a strongly exothermic reaction and may cause local damage or failure of the syngas side of the heat exchanger if too much heat is accumulated. Such local heat accumulation may initiate further metal dusting, which in return will again promote methanation .
  • One way to reduce the problem of metal dusting corrosion is by the addition of sulphur to the feed stream entering the ATR or to the hot raw syngas stream exiting the ATR before it enters a waste heat boiler or other type of heat exchanger, such as, for example, disclosed in US20040063797 and WO2000009441.
  • the sulphur may poison the reforming catalyst used in the ATR.
  • it generally needs to be removed from the syngas formed before such syngas can be used in subsequent catalytic operations, such as a
  • Fischer-Tropsch synthesis process In many of such operations catalysts are used which would be prone to deactivation and/or reduced selectivity when exposed to sulphur .
  • Yet another solution to prevent metal dusting may be to apply a coating to the metal surface inside the heat exchanger which is in direct contact with the hot raw syngas.
  • a coating is, for example, disclosed in
  • WO2010009718 metal alloys specifically developed to withstand aggressive conditions may be used.
  • applying a coating or using a specific metal alloy are expensive measures which will add substantially to the cost of the heat exchanger to be used, whilst their effect under the aggressive conditions caused by the hot raw syngas may still be limited.
  • EPA2233433 discloses a process for producing carbon dioxide in concentrated form and electricity from a hydrocarbon feedstock comprising methane.
  • the process comprises converting a methane comprising feed with an oxygen-containing feed in an ATR into a syngas stream, converting the syngas in a shift converter unit into additional carbon dioxide and hydrogen, passing the shift converted stream to a carbon dioxide separation unit to obtain the concentrated carbon dioxide and a hydrogen- rich stream and finally combusting at least part of the hydrogen-rich stream in a gas turbine which drives an electric generator thereby producing electricity.
  • the methane comprising feed to the ATR is first desulphurised and may subsequently be subjected to prereforming to convert the C2+ hydrocarbons into methane. Steam is added to the feed to the prereformer.
  • Preheating of the feed to the ATR takes place in two different stages.
  • the feed to the desulphurisation unit is preheated to a temperature of 180 to 420°C (suitably against the shift converted stream) and secondly the feed to prereforming unit is preheated to a temperature of 400 to 650°C (suitably against the ATR effluent stream after this stream is cooled in a waste heat boiler to produce steam) .
  • the present invention is not so much aimed at producing concentrated carbon dioxide and electricity, but, more importantly, has no separate preheating step between desulphurisation and prereforming. This results in a simpler process line-up and hence in a more energy efficient and cost effective overall process.
  • the present invention aims to provide a syngas manufacturing process which effectively deals with problems of metal dusting and methanation.
  • the present invention thus aims to avoid any reduced carbon
  • the present invention relates to a process for the preparation of a syngas comprising hydrogen and carbon monoxide from a methane comprising gas, which process comprises the steps of:
  • step (b) desulpurising the preheated methane comprising gas resulting from step (a) ;
  • step (c) prereforming the preheated, desulphurised methane comprising gas resulting from step (b) in a prereformer;
  • step (d) reacting the prereformed product stream resulting from step (c) with an oxidising gas in an
  • step (e) cooling the hot raw syngas resulting from step (d) to obtain the syngas
  • step (i) the methane comprising gas is preheated in step (a) to a temperature not exceeding 400°C;
  • step (ii) steps (a) and (e) are combined in that step (e) comprises cooling the hot raw syngas by indirect heat exchange against the methane comprising gas used in step (a) , and
  • methane comprising gas resulting from step (b) before it enters the prereformer in step (c) in such amount that the steam to carbon (as
  • the present process makes the use of preheating furnaces, which are typically used in conventional ATR processes, redundant. This saves both fuel and equipment and hence is beneficial from both a capital expenditure and operating cost perspective.
  • the methane comprising gas used as the feed to the syngas manufacturing process is first preheated to a temperature not exceeding 400°C.
  • the preheating is first preheated to a temperature not exceeding 400°C.
  • This preheating temperature should be sufficiently high to enable the endothermic prereforming in step (c) to take place, but not too high as that would require the hot raw syngas at the syngas side of the feed/effluent heat exchanger to have a higher temperature resulting in higher skin temperatures of the metal tubes at the syngas side in the feed/effluent heat exchanger.
  • Such higher temperatures of the hot raw syngas favour corrosive conditions, which in return may induce metal dusting and methanation to occur. Therefore, it is important to control the preheating temperature to the levels indicated.
  • Preheating is achieved by indirect heat exchange against the hot raw syngas produced in the authothermal reformer (ATR) in step (d) . This will be described in more detail below.
  • the methane comprising gas used as the feedstock to step (a) of the present process should contain a
  • methane substantial amount of methane, i.e. more than 75% volume percent (%vol), preferably more than 90%vol and more preferably more than 94%vol of methane.
  • methane comprising gas could be natural gas or associated gas.
  • Very suitably natural gas is used as the methane
  • Prereforming catalysts used for prereforming step (c) are generally highly sensitive to sulphur. Therefore, in step (b) of the present process the sulphur present in the preheated methane comprising feed gas is first removed to levels of below 100 ppb, suitably below 10 ppb, before the methane comprising gas is subjected to a steam reforming treatment in prereforming step (c) .
  • Desulphurisation treatments are well known in the art. For example, at high sulphur levels the removal of sulphur could be performed by contacting the methane comprising gas with a liquid mixture of a physical and chemical absorbent, typically in two steps: a first step to selectively remove H 2 S and a second step to remove remaining acid gases.
  • the sulfolane extraction process is an example of such process.
  • step (b) of the present process the sulphur present in the preheated methane comprising feed gas is first removed to levels of below 100 ppb, suitably below 10 ppb, before
  • small amounts of sulphur may be removed by passing the methane comprising gas through one or more beds of a suitable adsorbent, for example zinc oxide, to adsorb any H 2 S present.
  • a suitable adsorbent for example zinc oxide
  • adsorption treatment is preceded by a hydrogenation treatment, wherein the methane comprising gas is passed through a hydrogenation reactor to convert organic sulphur compounds into H 2 S.
  • Prereforming step (c) can be carried out by methods known in the art.
  • the prereforming of the methane comprising gas is carried out by means of a steam reforming treatment.
  • steam is added to the methane comprising gas, both are mixed and, if needed, heated to a temperature in the range of from 300 to 500°C, suitably 350 to 450°C, and the resulting natural gas/steam mixture is
  • the pressure at which the prereforming treatment is performed is suitably between 20 and 60 bar and more suitably in the same range as the pressure in the ATR, that is, the pressure at which step (d) is performed.
  • prereformer step (c) The addition of steam to the prereformer is not only important to allow the steam reforming reactions in prereformer step (c) to take place, but also to ensure that sufficient steam remains present in the subsequent oxidation/steam reforming step (d) in the ATR. This steam will subsequently cause a dilution of the hot raw syngas formed in the ATR which, in combination with the
  • the amount of steam added should be such that the steam to carbon ratio (as hydrocarbon) in the prereformer is suitably between 0.3 and 1.5, more suitably between 0.4 and 1.2 and even more suitably between 0.5 and 1.0.
  • the steam could be saturated steam or superheated steam (i.e. steam heated to a temperature above the temperature that corresponds with the saturated steam pressure), but superheated steam is preferred.
  • Typical steam pressures would be between 25 and 70 bar,
  • steam pressure would typically be kept higher than the pressure of the methane comprising feed gas to the prereformer to enable in ection/mixing and to avoid leakage of methane into the steam system.
  • Suitable prereforming catalysts for use in the prereformer are known in the art . Typically such
  • catalysts comprise at least one metal of the group consisting of nickel, platinum, palladium, ruthenium, iridium and cobalt on a refractory oxide support
  • Suitable catalyst are nickel on alumina catalysts and ruthenium on alumina, which are commercially available from several suppliers .
  • the prereforming is suitably performed adiabatically .
  • the mix of steam and the preheated and desulphurised methane comprising gas feed is passed through a bed of the steam reforming catalyst .
  • the C2+ hydrocarbons in the methane comprising gas feed will react with steam to give carbon oxides and hydrogen.
  • methanation of the carbon oxides with the hydrogen takes place to form methane.
  • the net result is that the C2+ hydrocarbons are converted into methane with the formation of some hydrogen and carbon oxides.
  • the heat required for the reforming of the C2+ hydrocarbons is provided by the exothermic methanation of carbon oxides (formed by the steam reforming of methane and C2+ hydrocarbons), but also from the sensible heat of the preheated and desulphurised methane comprising gas feed and from the steam fed to the prereformer.
  • the exit temperature will therefore be determined by the temperature and composition of the feedstock/steam mixture and may be above or below the inlet temperature. In general, the conditions should be selected such that the exit temperature is lower than the limit set by the de-activation of the prereforming catalyst. Generally, most prereforming catalysts start deactivating at temperatures above about 500°C. For the purpose of the present invention, however, the exit temperature of the prereformed gas will suitably be between 350 and 450°C and more suitably between 360 and 420°C.
  • the autothermal reforming step (d) can be carried out according to methods and with equipment known in the art. Autothermal reforming is a well known process. In autothermal reforming the methane comprising gas reacts with the oxidising gas to produce syngas.
  • the oxidising gas is suitably oxygen or an oxygen-containing gas .
  • suitable gases include air (containing about 21 volume percent of oxygen) and oxygen-enriched air, which may contain at least 60 volume percent (%vol) oxygen, more suitably at least 80%vol and even at least 98%vol of oxygen.
  • air containing about 21 volume percent of oxygen
  • oxygen-enriched air which may contain at least 60 volume percent (%vol) oxygen, more suitably at least 80%vol and even at least 98%vol of oxygen.
  • Such pure oxygen is preferably obtained in a cryogenic air separation process or by so-called ion transport membrane processes.
  • the oxidising gas may also be steam. If an oxygen-containing gas is used, steam may be added in such amount that the steam to carbon (as hydrocarbon) molar ratio is suitably between 0.5 and 3.
  • An autothermal reformer or ATR typically comprises a burner, a combustion chamber and a catalyst bed in a refractory lined pressure shell.
  • the burner is placed at the top of the pressure shell and extends into the combustion chamber which is located in the top section of the pressure shell.
  • the catalyst bed is arranged below the combustion chamber. Examples of autothermal reforming processes and ATRs are e.g. disclosed in WO2004041716, EPA1403216 and US20070004809.
  • the ATR used in step (d) may be any of the well-known ATRs which are commercially used.
  • Such catalysts typically comprise a
  • catalytically active metal suitably nickel
  • a refractory oxide support such as ceramic pellets .
  • Pellets, rings or other shapes of refractory oxide materials like zirconia, alumina or titania could also be used as support material. Further examples of suitable reforming catalysts are disclosed in US20040181313 and US20070004809.
  • the feed gas to the ATR in step (d) is the
  • prereformed product gas from step (c) which also still contains a substantial amount of steam.
  • the amount of steam is such that the steam to carbon (as hydrocarbon) molar ratio of the prereformed product stream entering step (d) is in the range of from 0.3 to 1.5, preferably 0.4 to 1.2 and more preferably 0.5 to 1.0.
  • the temperature of the prereformed product stream entering the ATR is suitably between 350 and 450°C and more suitably between 360 and 420°C. This is lower than in typical ATR processes.
  • the (wet) raw syngas leaving the ATR unit in the process of the present invention suitably has a temperature in the range of from 750 to
  • Operating pressures in the ATR are typically between 20 and 60 bar, more suitably between 20 and 50 bar.
  • Cooling in step (e) is effected by a cooling process that comprises indirect heat exchange of the hot (and wet) raw syngas produced in step (d) against the methane comprising gas used in step (a) .
  • a suitable heat exchanger in this case also referred to as a feed/effluent heat exchanger.
  • suitable feed/effluent heat exchangers would be shell and tube heat exchangers, plate and shell heat exchangers or plate fin heat exchangers.
  • a shell and tube-type feed/effluent heat exchangers is preferred, although the use of other types of heat exchangers is not excluded.
  • Feed/effluent heat exchangers generally are expensive pieces of equipment, particularly if the syngas entering this heat exchanger has a high temperature and hence is corrosive. In such case the internals of the heat exchanger should be made of special alloys with a high corrosion resistance and resistance to metal dusting. Such special alloys are extremely expensive.
  • An advantage of the process of the present invention is that the feed for prereforming step (c) can have a lower temperature than would typically be used and hence the hot raw syngas entering the feed/effluent heat exchanger to preheat such feed can also have a low temperature. This enables the use of less expensive materials at the syngas side of the feed/effluent heat exchanger. This adds to benefits of the present process.
  • Waste heat boilers are well known and commercially available from several suppliers. A few examples of waste heat boilers are described in
  • step (e) comprises passing the hot raw syngas resulting from step (d) through a waste heat boiler to produce saturated steam before further cooling the raw syngas by indirect heat exchange against the methane comprising gas used in step (a) .
  • the heat efficiency and carbon efficiency of the syngas manufacturing process are further improved.
  • the present invention also relates to a process for the preparation of a Fischer-Tropsch synthesis product from a syngas produced according to the process described above, which process comprises the further steps of :
  • step (f) performing a Fischer-Tropsch synthesis using the syngas resulting from step (e) as the feed;
  • step (g) separating the Fischer-tropsch synthesis product obtained in step (f) into a product stream
  • step (g) obtained in step (g) to step (d) .
  • EPA2594527 discloses a process for producing syngas for subsequent use in a Fischer-Tropsch process, wherein the syngas is produced by autothermal reforming in an ATR. The tail gas produced in the Fischer-Tropsch process is recycled to the ATR but not before it is first hydrogenated .
  • Fischer-Tropsch tail gas has the effect of reducing or even completely eliminating metal dusting in the ATR, in particular in the burner parts thereof.
  • the present invention focuses on preventing, or anyhow significantly reducing, metal dusting corrosion in the heat exchange equipment used for cooling the hot raw syngas. This is a different focus requiring different measures.
  • the result consequently, is a combination of features relating to process conditions, sequence of process steps and heat integration as described above which is not disclosed in EPA2594527.
  • the Fischer-Tropsch (FT) synthesis process is well known in the art as a catalytic process for synthesizing longer chain hydrocarbons from carbon monoxide and hydrogen. It may be operated in a single pass mode ("once through") or in a recycle mode and could involve a multi- stage conversion process, which may involve, two, three, or more conversion stages .
  • Fischer-Tropsch catalysts for use in the fixed bed catalyst beds of the syngas conversion reactor are known in the art, and typically include a Group 8 or 9 metal component, preferably Co, Fe and/or Ru, more preferably
  • Such support material could be a porous inorganic refractory oxide material, such as alumina, silica, titania, zirconia or mixtures thereof, but could also be an alternative support structure.
  • the Fischer-Tropsch synthesis is preferably carried out at a temperature in the range from 125 °C to 350 °C, more preferably 175 °C to 275 °C, most preferably 200 °C to 260 °C.
  • the pressure may range from 5 to 150 bar, while preferred pressures are typically in the range of from 50 to 80 bar.
  • Step (f) involves carrying out the Fischer-Tropsch synthesis reaction in a suitable reactor.
  • Fischer-Tropsch reactor is first treated to remove any nitrogen components, such as ammonia and hydrogencyanide . Any excess if water or steam still present will then also be removed.
  • the H 2 /CO molar ratio of the resulting syngas stream can then optionally be adjusted to the desired value, if needed. This can, for instance, be achieved by passing the syngas stream through a membrane which selectively removes a certain amount of hydrogen from the syngas stream, thereby lowering the H 2 /CO molar ratio. Obviously such treatment would only be needed, if the amount of hydrogen in the syngas is too high for a
  • the amount of light stream recycled in step (h) to step (d) is suitably such that the H 2 /CO ratio of the hot raw syngas produced in step (d) is in the range of from 1.7 to 2.2, more preferably in the range of from 1.8 to 2.0.
  • Products of the Fischer-Tropsch synthesis may range from methane to heavy paraffinic waxes.
  • the production of methane is minimised and a substantial portion of the hydrocarbons produced have a carbon chain of at least 5 carbon atoms.
  • C5+ hydrocarbons is at least 60% by weight of the total product, more preferably, at least 70% by weight, even more preferably, at least 80% by weight, most preferably, at least 85% by weight.
  • Table 1 also indicates the steam to carbon (as
  • hydrocarbon hydrocarbon molar ratios in the prereformer feed (S/C ratio) that correspond with the indicated steam contents in the syngas .
  • Table 1 also shows a clear trend that at increasing steam contents, and hence increasing S/C ratios in the prereformer feed, the temperature at which metal dusting is induced increases. So at S/C ratios of 0.5 and above the temperature at which metal dusting is induced will anyhow be higher than 510°C. Consequently, the

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Abstract

L'invention concerne un procédé pour la préparation d'un gaz de synthèse comprenant de l'hydrogène et du monoxyde de carbone à partir d'un gaz comprenant du méthane, un gaz comprenant du méthane préchauffé désulfuré étant soumis à un préreformage dans un préreformeur et à une oxydation dans un reformeur autothermique, après quoi le gaz de synthèse brut chaud ainsi obtenu est refroidi. Dans ce procédé : (i) le gaz comprenant du méthane est préchauffé à une température inférieure ou égale à 400 °C ; (ii) les étapes de préchauffage et de refroidissement sont combinées en ce que ladite étape de refroidissement du gaz de synthèse brut chaud comprend un échange thermique indirect avec le gaz comprenant du méthane qui est préchauffé, et (iii) de la vapeur d'eau est ajoutée au gaz comprenant du méthane préchauffé désulfuré avant son entrée dans le préreformeur en une proportion telle que le rapport molaire entre la vapeur d'eau et le carbone (sous la forme d'hydrocarbures) de ce gaz comprenant du méthane préchauffé désulfuré est situé dans la plage allant de 0,3 à 1,5 lorsqu'il entre dans le préreformeur. L'invention concerne également un procédé pour la préparation de produits hydrocarbonés dans lequel un gaz de synthèse d'alimentation est préparé au cours du procédé tel que décrit ci-dessus suivi d'un procédé de synthèse de Fischer-Tropsch.
PCT/EP2016/078773 2015-12-04 2016-11-25 Procédé pour la préparation d'un gaz de synthèse WO2017093130A1 (fr)

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EP15198091.9 2015-12-04
EP15198091 2015-12-04

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004096952A1 (fr) * 2003-05-02 2004-11-11 Johnson Matthey Plc Production d'hydrocarbures par reformage a la vapeur et reaction de fischer-tropsch
EP2233433A1 (fr) * 2009-03-24 2010-09-29 Hydrogen Energy International Limited Procédé pour la génération d'électricité et pour la séquestration de dioxyde de carbone
WO2013033812A1 (fr) * 2011-09-08 2013-03-14 Steve Kresnyak Amélioration du procédé fischer-tropsch pour une formulation d'hydrocarbure combustible dans un environnement de transformation du gaz en liquide
EP2594527A1 (fr) * 2011-11-16 2013-05-22 Haldor Topsøe A/S Procédé de reformage d'hydrocarbures

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004096952A1 (fr) * 2003-05-02 2004-11-11 Johnson Matthey Plc Production d'hydrocarbures par reformage a la vapeur et reaction de fischer-tropsch
EP2233433A1 (fr) * 2009-03-24 2010-09-29 Hydrogen Energy International Limited Procédé pour la génération d'électricité et pour la séquestration de dioxyde de carbone
WO2013033812A1 (fr) * 2011-09-08 2013-03-14 Steve Kresnyak Amélioration du procédé fischer-tropsch pour une formulation d'hydrocarbure combustible dans un environnement de transformation du gaz en liquide
EP2594527A1 (fr) * 2011-11-16 2013-05-22 Haldor Topsøe A/S Procédé de reformage d'hydrocarbures

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