WO2014180888A1 - Procédé de préparation de gaz de synthèse - Google Patents

Procédé de préparation de gaz de synthèse Download PDF

Info

Publication number
WO2014180888A1
WO2014180888A1 PCT/EP2014/059314 EP2014059314W WO2014180888A1 WO 2014180888 A1 WO2014180888 A1 WO 2014180888A1 EP 2014059314 W EP2014059314 W EP 2014059314W WO 2014180888 A1 WO2014180888 A1 WO 2014180888A1
Authority
WO
WIPO (PCT)
Prior art keywords
syngas
gas
carbon dioxide
methane
process according
Prior art date
Application number
PCT/EP2014/059314
Other languages
English (en)
Inventor
Hubert Willem Schenck
Frans Hans GHIJSEN
Ruben SMIT
Thomas Paul Von Kossak-Glowczewski
Original Assignee
Shell Internationale Research Maatschappij B.V.
Shell Oil Company
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shell Internationale Research Maatschappij B.V., Shell Oil Company filed Critical Shell Internationale Research Maatschappij B.V.
Publication of WO2014180888A1 publication Critical patent/WO2014180888A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—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
    • 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
    • C01B3/36—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 oxygen or mixtures containing oxygen as gasifying agents
    • 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
    • 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
    • C10G2/50—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon dioxide with hydrogen
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K3/00—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide
    • C10K3/02—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide by catalytic treatment
    • C10K3/026—Increasing the carbon monoxide content, e.g. reverse water-gas shift [RWGS]
    • 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
    • C01B2203/06—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
    • 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

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.
  • syngas Processes for the preparation of syngas are well known in the art. Typically a feed gas comprising methane is contacted with an oxidizing gas and the methane reacts with the oxidizing gas to form a syngas.
  • Such POX process can take place in the presence of a suitable reforming catalyst or in the absence of a catalyst.
  • a suitable reforming catalyst or in the absence of a catalyst.
  • methane reacts with oxygen in an exothermic reaction to form carbon monoxide and hydrogen.
  • both processes can be integrated.
  • the steam reforming process can be used to prereform a hydrocarbon feed, thereby converting C2+ hydrocarbons in the hydrocarbon feed into methane and part of the methane into carbon monoxide and hydrogen, after which the effluent of this steam reforming reaction is subjected to a POX process.
  • the heat generated in the exothermic POX process may be, in whole or in part, used to provide the reaction heat for the endothermic steam reforming reaction. Examples of such integrated processes are, for example, disclosed in WO-A-2004/041716.
  • a POX process and a steam reforming process can also be combined by carrying out these processes in parallel and subsequently mixing the respective syngas streams produced in each process. Examples of such processes are disclosed in US-A-2007/0004809 and WO-A-2010/122025.
  • H 2 /CO hydrogen/carbon monoxide
  • This H 2 /CO molar ratio is typically controlled by adjusting the feed streams to the syngas producing reactor.
  • the steam to carbon molar ratio and the carbon dioxide to carbon molar ratio (with moles of carbon as moles of hydrocarbon in the methane comprising feed) are important parameters in this respect.
  • the present invention aims to provide a process for the production of syngas which enables the adjustment of the H 2 /CO molar ratio of the syngas produced to the desired level, while cooling the syngas. This will allow the production of more syngas at the desired 3 ⁇ 4/CO molar ratio for a given oxygen demand and hence is more
  • 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) cooling the gas mixture resulting from step (b) to obtain the syngas.
  • a further advantage of the process according to the present invention is that some of the carbon dioxide produced in the syngas production and/or possible subsequent Fischer- Tropsch synthesis can be effectively re-used in the process .
  • the carbon dioxide added in step (b) can be in the form of any gas stream comprising a substantial amount of carbon dioxide.
  • carbon dioxide containing gas stream should comprise at least 90 mole%, preferably at least 95 mole% and more preferably at least 99 mole% of carbon dioxide.
  • a substantially pure carbon dioxide stream would be most preferred.
  • step (b) The amount of carbon dioxide added in step (b) will to a large extent be determined by the target 3 ⁇ 4/CO molar ratio of the syngas to be obtained, which in return is determined by the envisaged application of the syngas.
  • the 3 ⁇ 4/CO molar ratio of the syngas should suitably be in the range of from 1.6 to 2.2, more
  • step (b) Another factor that plays a role in determining the amount of carbon dioxide to be added is the overall integration of process streams, notably carbon dioxide recycle. It was found, however, that the amount of carbon dioxide added in step (b) is such that the ratio of the moles of syngas (3 ⁇ 4 + CO) present in the hot syngas stream before addition of the carbon dioxide relative to carbon dioxide added in step (b) [ (H 2 +CO) /CO 2 molar ratio] should typically be in the range of from 3.5 to 50.0, preferably 5.0 to 35.0 and more preferably 10.0 to 30.0. So, per 100 moles of syngas (H 2 + CO) present in the hot syngas stream 2 to 28.5 moles of carbon dioxide are typically added. Preferably 3 to 20 moles and more preferably 3.3 to 10 moles of carbon dioxide are added per 100 moles of syngas (3 ⁇ 4 + CO) present in the hot syngas stream.
  • the conditions under which the carbon dioxide is added should be such that the reaction between at least part of the carbon dioxide added and hydrogen present in the hot raw syngas will take place to the desired extent, that is, to such extent that the syngas eventually obtained has the desired 3 ⁇ 4/CO molar ratio.
  • temperature of the gaseous reaction mixture of carbon dioxide and the hot raw syngas is suitably at least 750 °C and preferably at least 800 °C.
  • the upper temperature is determined by the type of oxidation reaction used in step (a) as will be described in more detail hereinafter.
  • the temperature of the carbon dioxide added is not critical. Because of the relatively high temperature of the hot raw syngas, the carbon dioxode will typically be added at a temperature below the temperature of the hot raw syngas. The lower temperature of the carbon dioxide added will also have a (physical) cooling effect in addition to the chemical cooling effect. However, this physical cooling effect will be limited, because of the relatively low amount of carbon dioxide added relative to the amount of hot raw syngas. Furthermore, the reaction between carbon dioxide and hydrogen is favoured at higher temperatures, so that it is beneficial that the
  • step (a) comprises the use of a furnace (e.g. for feed preheat), as will be described in more detail below, then preheating of the carbon dioxide may also take place by using heat generated in such furnace, for example, in a separate coil in such furnace.
  • a furnace e.g. for feed preheat
  • Adding the carbon dioxide to the hot raw syngas can be performed by ways known in the art, for example by injecting the carbon dioxide into the hot raw syngas stream.
  • catalytically active metal catalytically active metals
  • suitable catalytically active metals are metals from the d-block (Groups 3 to 12) of the Periodic Table of Elements, also commonly referred to as transition metals.
  • suitable metals are chromium, iron, cobalt, copper, nickel, zinc, ruthenium and palladium.
  • Particularly suitable metals are chromium, iron and copper. If a catalytically active metal is used in step
  • At least one of chromium, iron and copper is preferably used.
  • the reaction mixture of carbon dioxide and the hot raw syngas can be contacted with a suitable catalytically active metal in various ways.
  • the reaction mixture of carbon dioxide and hot raw syngas obtained is passed over a catalyst bed consisting of catalyst particles comprising at least one catalytically active metal catalyzing the reaction between carbon dioxide and hydrogen.
  • the catalytically active metal will suitably be in the form of an oxide (e.g. iron (III) oxide, Fe2 ⁇ 0 3 ) or be supported on a porous inorganic refractory oxide material, such as alumina, silica, titania,
  • zirconia or mixtures thereof.
  • reaction mixture of carbon dioxide and hot raw syngas obtained is passed through a heat exchanger or boiler with the inner wall of the tubes of such heat exchanger or boiler comprising at least one catalytically active metal catalyzing the reaction between carbon dioxide and hydrogen.
  • the catalytically active metal (s) can be in the form of the alloy forming the inner wall of the tube. Part of the reaction between the carbon dioxide added and the
  • Reacting the methane comprising gas with an oxidising gas to obtain a hot raw syngas in step (a) of the present process can be performed by processes known in the art as generally described above.
  • the methane comprising gas used as the feedstock to the present process may be natural gas, associated gas or a mixture of C 1 -4 hydrocarbons.
  • the feed comprises mainly, i.e. more than 90 volume percent (% v/v) , especially more than 94% v/v, C 1 -4 hydrocarbons, and especially comprises at least 60% v/v methane, preferably at least 75% v/v, more preferably at least 90% v/v.
  • Very suitably natural gas or associated gas is used.
  • the oxidising gas used in step (a) may be oxygen or an oxygen-containing gas.
  • gases include air (containing about 21 percent of oxygen) and oxygen enriched air, which may contain at least 60 volume percent oxygen, more suitably at least 80 volume percent and even at least 98 volume percent of oxygen.
  • oxygen enriched air Such pure oxygen is preferably obtained in a cryogenic air
  • the oxidising gas may also be steam.
  • Suitable processes to prepare the hot raw syngas in step (a) include catalytic and non-catalytic partial oxidation (POX) processes and steam reforming processes as well as combinations of two or more of these
  • a suitable process to prepare syngas using oxygen or an oxygen-containing gas as the oxidising agent is carried out in a partial oxidation reactor.
  • This can be a catalytic or non-catalytic POX process.
  • such partial oxidation reactor typically comprises a burner placed at the top in a reactor vessel with a refractory lining. The reactants are introduced at the top of the reactor. In the reactor a flame from the burner is maintained in which the methane comprising feed gas reacts with the oxygen or oxygen-containing gas to form a syngas.
  • Reactors for catalytic POX processes usually comprise a burner at the top and one or more fixed beds of suitable catalyst to react the methane in the feed with the oxygen added to the top of the reactor to form a syngas.
  • Non-catalytic POX processes are well known.
  • the syngas produced typically has a temperature of between
  • the pressure at which the syngas product is obtained may be between 3 and 10 MPa and suitably between 5 and 7 MPa.
  • steam may also be added.
  • step (c) of the present process is suitably performed by indirect heat exchange between the gas mixture
  • step (b) on the one hand and water and/or the methane comprising gas on the other hand.
  • the gas mixture resulting from step (b) is first cooled in a boiler or other type of heat exchanger against water to produce steam and subsequently is further reduced in temperature by indirect heat exchange against the methane comprising gas used as a feed to step (a) .
  • the methane comprising feed gas can be preheated in a heat-efficient manner.
  • Suitable heat exchangers are well known in the art and include, for example, shell-tube heat exchangers .
  • the non-catalytic POX process as described above may be combined with a preceding steam pre-reforming step.
  • the methane comprising gas used as a feed to the POX process of step (a) is then produced in this pre- reforming step.
  • Such pre-reforming is preferably
  • the gaseous hydrocarbon feed to the pre-reformer comprising methane and C2+ hydrocarbons
  • steam are heated to the desired inlet temperature and passed through a bed of a suitable steam reforming catalyst.
  • Higher hydrocarbons having 2 or more carbon atoms 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 higher hydrocarbons are converted to methane with the formation of some hydrogen and carbon oxides.
  • hydrocarbons is provided by heat from the exothermic methanation of carbon oxides (formed by the steam
  • 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.
  • the conditions should be selected such that the exit temperature is lower than the limit set by the de-activation of the catalyst. While some reformer catalysts commonly used are deactivated at temperatures above about 550 °C, other catalysts that may be employed can tolerate temperatures up to about 700°C. Preferably the outlet temperature is between 350 and 530°C.
  • step (a) of the present process can also be suitably carried out in an auto-thermal reformer (ATR) unit.
  • ATR auto-thermal reformer
  • hydrocarbon hydrocarbon
  • hydrocarbon hydrocarbon
  • the ATR unit may be the well-known ATR units as commercially used.
  • Suitable reforming catalysts and arrangements for such which can be used in the ATR unit are known in the art.
  • Such catalysts typically comprise a catalytically active metal on a suitable support material.
  • suitable reforming catalysts are disclosed in US-A- 2004/0181313 and US-A-2007/0004809.
  • the methane comprising gas feed to the ATR unit suitably has a temperature in the range of up to 850°C, suitably from 500 to 850°C, more suitably 650 to 800°C, whilst the raw syngas leaving the ATR unit typically has a temperature in the range of from 950 to 1200°C , more suitably 970 to 1100°C.
  • Operating pressures are typically between 2 and 6 MPA, more suitably between 2 and 5 MPa.
  • the ATR unit can be used as the sole oxidation unit in step (a) , but in another suitable embodiment the ATR unit can also be integrated with a heat exchange reformer
  • the methane comprising gas feed to the ATR unit in step (a) of the present process is obtained by steam reforming of a gaseous methane comprising feed in such a HER unit.
  • the cooling step (c) comprises feeding the gas mixture obtained in step (b) to the HER unit where it provides the necessary heat for the steam reforming of the gaseous methane comprising feed to the HER unit by indirect heat exchange.
  • the HER unit preferably is a tube and shell reactor wherein the steam reforming reaction takes place inside the tubes in the presence of a
  • reaction is suitably provided by passing the hot effluent of the ATR unit to the shell side of the reactor tubes.
  • the catalyst and process conditions as applied in the steam reformer reactor tubes of the HER unit are known in the art and hence may be those known by the skilled person in the field of steam reforming. Suitable
  • catalysts for example, comprise nickel, optionally applied on a refractory oxide carrier material, for example alumina.
  • a refractory oxide carrier material for example alumina.
  • suitable catalyst are disclosed in WO-A-2004/041716.
  • the steam to carbon (as hydrocarbon) molar ratio is preferably from 0 up to 2.5 and more preferably below 1 and most preferably from 0.5 up to 0.9.
  • the product gas as it leaves the tubes of the HER unit preferably has a temperature of from 600 up to
  • the operating pressure at the tube side is preferably between 2 and 6 MPa, more preferably between 2.5 and 5 MPa.
  • the ATR unit is typically operated at a slightly lower pressure to avoid recompression of the syngas from the HER unit before feeding to the ATR unit. This means that in the HER unit the pressure at the shell side will suitably be at a slightly lower level than in the ATR unit.
  • step (a) is a steam reforming reaction.
  • the oxidising gas in step (a) is steam and the reaction between the methane comprising gas and steam takes place in the presence of a steam reforming catalyst.
  • Suitable steam reforming catalysts and process conditions applied in such steam reforming step are well known in the art. If steam reforming is the sole or primary methane
  • the temperature will usually be slightly higher than in a HER unit which is integrated with an ATR unit. Accordingly, the raw syngas leaving a steam methane reforming unit will typically have a temperature of from 800 to 1000°C, more suitably 850 to 950°C, and be at a pressure of from 0.5 to 8 MPa, more suitably 2 to 4 MPa.
  • the present invention also relates to a process for the preparation of hydrocarbon products comprising the steps of:
  • the Fischer-Tropsch (FT) 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
  • 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 Co, on a suitable catalyst support material.
  • a suitable catalyst 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 preferably ranges from 0.5 to 15 MPa, more preferably from 0.5 to 8 MPa.
  • 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.
  • the amount of 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.
  • the hot raw syngas effluent of the ATR had a
  • Boiler outlet temperature of the raw syngas was 400 °C.
  • t-moles refers to "tonne- moles” which is equal to 1,000 kmoles or 10 s moles.
  • tonne refers to 1,000 kg.
  • Example 1 was repeated except that carbon dioxide at a temperature of 300 °C and a pressure of 50 bar was added to the natural gas feed prior to entering the ATR unit.
  • the ATR effluent had a temperature of 1040 °C and was passed through a boiler for indirect heat exchange against boiler feed water to produce steam.
  • Boiler outlet temperature of the raw syngas was 400 °C.
  • Example 1 was repeated except that carbon dioxide at a temperature of 300 °C and a pressure of 50 bar was added to the effluent of the ATR unit.
  • the ATR effluent had a temperature of 1040 °C, which after the addition of and reaction with carbon dioxide was reduced to 900 °C before it was passed through the boiler to produce steam. Boiler out let temperature of the raw syngas was 400 °C.
  • Example 3 illustrates the invention, whereas Examples 1 and 2 are included for comparative purposes.
  • C02 conversion is calculated on the basis of C02 added; the amount of C02 present in the natural gas feed (6.5 tmoles/d) and the amount of C02 generated in the oxidation reaction that takes place in the ATR (137 tmoles/d) is not taken into account.
  • Example 1 results in a syngas with a H2/CO molar ratio which is significantly higher (2.36) than the H2/CO molar ratio of the syngas produced in the example according to the invention
  • Example 3 2.0 at equal natural gas use. This is undesired for, for example, Fischer-Tropsch synthesis.
  • Example 2 a syngas with the same 3 ⁇ 4/CO molar ratio as in Example 3 is produced, but as can be seen from Table 1 the process according to the present invention as illustrated in Example 3 has a lower oxygen consumption and hence a lower energy consumption to produce syngas with the same 3 ⁇ 4/CO molar ratio.
  • the absolute amount of syngas produced is slightly lower in the process
  • the present invention which implies that there is more unconverted methane present in the syngas produced.
  • This unconverted methane is suitably recycled to the ATR unit, when the syngas is used in a Fischer-Tropsch synthesis process.
  • the lower oxygen consumption for the same amount of natural gas resulting in a syngas with the same 3 ⁇ 4/CO molar ratio means that in a plant with a fixed oxygen production capacity, more natural gas can be processed with the same equipment resulting in a higher syngas yield of the same H2/CO molar ratio. This is beneficial from an economic perspective .
  • Table 1 also shows that the duty available for steam recovery in Example 3 is lower than in Examples 1 and 2. That implies that heat available in the hot raw syngas is used chemically in the endothermic reaction between hydrogen and carbon dioxide and in fact ends up in the syngas product. Hence, heat generated in the process is used more effectively in the process according to the present invention than would be the case when converting it into steam via indirect heat exchange in a boiler.

Landscapes

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

Abstract

La présente invention concerne un procédé de préparation d'un gaz de synthèse comprenant de l'hydrogène et du monoxyde de carbone à partir d'un gaz comprenant du méthane, ledit procédé comprenant les étapes consistant à : (a) faire réagir le gaz comprenant du méthane avec un gaz oxydant afin d'obtenir un gaz de synthèse brut chaud comprenant du monoxyde de carbone et de l'hydrogène ; (b) ajouter du dioxyde de carbone au gaz de synthèse brut chaud dans des conditions telles qu'au moins une partie du dioxyde de carbone ajouté réagisse avec l'hydrogène présent dans le gaz de synthèse brut chaud ; et (c) refroidir le mélange gazeux obtenu à l'étape (b) afin d'obtenir le gaz de synthèse. L'invention concerne également un procédé de préparation de produits hydrocarbonés, un gaz de synthèse d'alimentation étant préparé par le biais du procédé tel que décrit ci-dessus et étant ensuite converti en produits hydrocarbonés par le biais d'un procédé de Fischer-Tropsch.
PCT/EP2014/059314 2013-05-08 2014-05-07 Procédé de préparation de gaz de synthèse WO2014180888A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP13167111 2013-05-08
EP13167111.7 2013-05-08

Publications (1)

Publication Number Publication Date
WO2014180888A1 true WO2014180888A1 (fr) 2014-11-13

Family

ID=48444089

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2014/059314 WO2014180888A1 (fr) 2013-05-08 2014-05-07 Procédé de préparation de gaz de synthèse

Country Status (1)

Country Link
WO (1) WO2014180888A1 (fr)

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2644869C2 (ru) * 2016-07-21 2018-02-14 Федеральное государственное бюджетное учреждение науки Институт проблем химической физики Российской академии наук (ИПХФ РАН) Способ получения синтез-газа
WO2019110268A1 (fr) * 2017-12-08 2019-06-13 Haldor Topsøe A/S Installation et procédé de production de gaz de synthèse
WO2019110265A1 (fr) * 2017-12-08 2019-06-13 Haldor Topsøe A/S Procédé et système de reformage d'un gaz d'hydrocarbure
WO2019110267A1 (fr) * 2017-12-08 2019-06-13 Haldor Topsøe A/S Procédé et système de production de gaz de synthèse
WO2019110269A1 (fr) * 2017-12-08 2019-06-13 Haldor Topsøe A/S Système et procédé pour la production de gaz de synthèse
CN111465448A (zh) * 2017-10-05 2020-07-28 彼得里奥-巴西石油公司 具有对在没有还原剂的情况下因蒸汽通过而失活的抗性的预重整催化剂的制备方法、和预重整催化剂
WO2020174056A1 (fr) * 2019-02-28 2020-09-03 Haldor Topsøe A/S Installation chimique dotée d'une section de reformage et procédé de production d'un produit chimique
WO2021244980A1 (fr) * 2020-06-01 2021-12-09 Shell Internationale Research Maatschappij B.V. Procédé flexible de conversion de dioxyde de carbone, d'hydrogène et de méthane en gaz de synthèse
US11213794B2 (en) 2016-06-10 2022-01-04 Haldor Topsøe A/S CO rich synthesis gas production
CN114516618A (zh) * 2020-11-18 2022-05-20 乔治洛德方法研究和开发液化空气有限公司 二氧化碳缓冲容器工艺设计
GB2612647A (en) * 2021-11-09 2023-05-10 Nordic Electrofuel As Fuel generation system and process
US11905173B2 (en) 2018-05-31 2024-02-20 Haldor Topsøe A/S Steam reforming heated by resistance heating
US11964872B2 (en) 2018-12-03 2024-04-23 Shell Usa, Inc. Process and reactor for converting carbon dioxide into carbon monoxide
KR102672526B1 (ko) 2017-12-08 2024-06-10 토프쉐 에이/에스 합성 가스의 제조를 위한 플랜트 및 방법

Citations (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0168892A2 (fr) 1984-07-18 1986-01-22 Shell Internationale Researchmaatschappij B.V. Production de mélanges gazeux contenant de l'hydrogène et du monoxyde de carbone
GB2168718A (en) * 1984-10-29 1986-06-25 Humphreys & Glasgow Ltd Producing synthesis gas
EP0291111A1 (fr) 1987-05-12 1988-11-17 Shell Internationale Researchmaatschappij B.V. Procédé d'oxydation partielle d'un combustible gaseux hyrdrocarboné
WO1996003345A1 (fr) 1994-07-22 1996-02-08 Shell Internationale Research Maatschappij B.V. Procede de fabrication d'un gaz de synthese par oxydation partielle d'un combustible contenant un hydrocarbure gazeux a l'aide d'un bruleur co-annulaire a orifices multiples
EP0742172A2 (fr) * 1995-04-10 1996-11-13 Air Products And Chemicals, Inc. Procédé intégré de reformation à vapeur de méthane pour la production de monoxyde de carbone et d'hydrogène
WO1996039354A1 (fr) 1995-06-06 1996-12-12 Shell Internationale Research Maatschappij B.V. Procede de stabilisation de flamme dans un processus de preparation de gaz de synthese
WO1997022547A1 (fr) 1995-12-18 1997-06-26 Shell Internationale Research Maatschappij B.V. Procede de preparation d'un gaz de synthese
US5714657A (en) * 1994-03-11 1998-02-03 Devries; Louis Natural gas conversion to higher hydrocarbons
FR2806073A1 (fr) * 2000-03-07 2001-09-14 Air Liquide Procede de production de monoxyde de carbone par retroconversion inverse avec un catalyseur adapte
WO2003070629A1 (fr) * 2002-02-25 2003-08-28 Air Products And Chemicals, Inc. Procede et appareil de production d'un gaz de synthese
EP1403216A1 (fr) 2002-09-26 2004-03-31 Haldor Topsoe A/S Procédé pour la préparation de gaz de synthèse
WO2004041716A1 (fr) 2002-11-07 2004-05-21 Johnson Matthey Plc Production d'hydrocarbures
US20040181313A1 (en) 2003-03-15 2004-09-16 Conocophillips Company Managing hydrogen in a gas to liquid plant
US20070004809A1 (en) 2005-06-29 2007-01-04 Lattner James R Production of synthesis gas blends for conversion to methanol or fischer-tropsch liquids
WO2010122025A1 (fr) 2009-04-22 2010-10-28 Shell Internationale Research Maatschappij B.V. Production d'un mélange de gaz de synthèse et son utilisation dans un procédé de fischer-tropsch

Patent Citations (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0168892A2 (fr) 1984-07-18 1986-01-22 Shell Internationale Researchmaatschappij B.V. Production de mélanges gazeux contenant de l'hydrogène et du monoxyde de carbone
GB2168718A (en) * 1984-10-29 1986-06-25 Humphreys & Glasgow Ltd Producing synthesis gas
EP0291111A1 (fr) 1987-05-12 1988-11-17 Shell Internationale Researchmaatschappij B.V. Procédé d'oxydation partielle d'un combustible gaseux hyrdrocarboné
US5714657A (en) * 1994-03-11 1998-02-03 Devries; Louis Natural gas conversion to higher hydrocarbons
WO1996003345A1 (fr) 1994-07-22 1996-02-08 Shell Internationale Research Maatschappij B.V. Procede de fabrication d'un gaz de synthese par oxydation partielle d'un combustible contenant un hydrocarbure gazeux a l'aide d'un bruleur co-annulaire a orifices multiples
EP0742172A2 (fr) * 1995-04-10 1996-11-13 Air Products And Chemicals, Inc. Procédé intégré de reformation à vapeur de méthane pour la production de monoxyde de carbone et d'hydrogène
WO1996039354A1 (fr) 1995-06-06 1996-12-12 Shell Internationale Research Maatschappij B.V. Procede de stabilisation de flamme dans un processus de preparation de gaz de synthese
WO1997022547A1 (fr) 1995-12-18 1997-06-26 Shell Internationale Research Maatschappij B.V. Procede de preparation d'un gaz de synthese
FR2806073A1 (fr) * 2000-03-07 2001-09-14 Air Liquide Procede de production de monoxyde de carbone par retroconversion inverse avec un catalyseur adapte
WO2003070629A1 (fr) * 2002-02-25 2003-08-28 Air Products And Chemicals, Inc. Procede et appareil de production d'un gaz de synthese
EP1403216A1 (fr) 2002-09-26 2004-03-31 Haldor Topsoe A/S Procédé pour la préparation de gaz de synthèse
WO2004041716A1 (fr) 2002-11-07 2004-05-21 Johnson Matthey Plc Production d'hydrocarbures
US20040181313A1 (en) 2003-03-15 2004-09-16 Conocophillips Company Managing hydrogen in a gas to liquid plant
US20070004809A1 (en) 2005-06-29 2007-01-04 Lattner James R Production of synthesis gas blends for conversion to methanol or fischer-tropsch liquids
WO2010122025A1 (fr) 2009-04-22 2010-10-28 Shell Internationale Research Maatschappij B.V. Production d'un mélange de gaz de synthèse et son utilisation dans un procédé de fischer-tropsch

Cited By (34)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11213794B2 (en) 2016-06-10 2022-01-04 Haldor Topsøe A/S CO rich synthesis gas production
RU2644869C2 (ru) * 2016-07-21 2018-02-14 Федеральное государственное бюджетное учреждение науки Институт проблем химической физики Российской академии наук (ИПХФ РАН) Способ получения синтез-газа
CN111465448A (zh) * 2017-10-05 2020-07-28 彼得里奥-巴西石油公司 具有对在没有还原剂的情况下因蒸汽通过而失活的抗性的预重整催化剂的制备方法、和预重整催化剂
CN111465448B (zh) * 2017-10-05 2023-06-20 彼得里奥-巴西石油公司 具有对在没有还原剂的情况下因蒸汽通过而失活的抗性的预重整催化剂的制备方法、和预重整催化剂
JP7365341B2 (ja) 2017-12-08 2023-10-19 トプソー・アクチエゼルスカベット 合成ガスを生産するためのプラントと方法
WO2019110265A1 (fr) * 2017-12-08 2019-06-13 Haldor Topsøe A/S Procédé et système de reformage d'un gaz d'hydrocarbure
KR102678026B1 (ko) * 2017-12-08 2024-06-26 토프쉐 에이/에스 탄화수소 가스를 개질하기 위한 방법 및 시스템
KR102668169B1 (ko) * 2017-12-08 2024-05-23 토프쉐 에이/에스 합성 가스 제조를 위한 방법 및 시스템
US11447389B2 (en) 2017-12-08 2022-09-20 Haldor Topsøe A/S System and process for production of synthesis gas
JP2021505515A (ja) * 2017-12-08 2021-02-18 ハルドール・トプサー・アクチエゼルスカベット 炭化水素ガスを改質するための方法および装置
JP2021505517A (ja) * 2017-12-08 2021-02-18 ハルドール・トプサー・アクチエゼルスカベット 合成ガスを生産するためのプラントと方法
KR102672526B1 (ko) 2017-12-08 2024-06-10 토프쉐 에이/에스 합성 가스의 제조를 위한 플랜트 및 방법
WO2019110269A1 (fr) * 2017-12-08 2019-06-13 Haldor Topsøe A/S Système et procédé pour la production de gaz de synthèse
WO2019110267A1 (fr) * 2017-12-08 2019-06-13 Haldor Topsøe A/S Procédé et système de production de gaz de synthèse
KR102674399B1 (ko) 2017-12-08 2024-06-14 토프쉐 에이/에스 합성 가스의 제조를 위한 시스템 및 방법
CN111247091A (zh) * 2017-12-08 2020-06-05 托普索公司 用于生产合成气的方法和系统
KR20200096755A (ko) * 2017-12-08 2020-08-13 할도르 토프쉐 에이/에스 합성 가스 제조를 위한 방법 및 시스템
US11591214B2 (en) 2017-12-08 2023-02-28 Haldor Topsøe A/S Process and system for producing synthesis gas
JP7332597B2 (ja) 2017-12-08 2023-08-23 トプソー・アクチエゼルスカベット 炭化水素ガスを改質するための方法および装置
US11649164B2 (en) 2017-12-08 2023-05-16 Haldor Topsøe A/S Plant and process for producing synthesis gas
US11932538B2 (en) 2017-12-08 2024-03-19 Haldor Topsøe A/S Process and system for reforming a hydrocarbon gas
CN111247091B (zh) * 2017-12-08 2023-05-30 托普索公司 用于生产合成气的方法和系统
WO2019110268A1 (fr) * 2017-12-08 2019-06-13 Haldor Topsøe A/S Installation et procédé de production de gaz de synthèse
US11905173B2 (en) 2018-05-31 2024-02-20 Haldor Topsøe A/S Steam reforming heated by resistance heating
US11964872B2 (en) 2018-12-03 2024-04-23 Shell Usa, Inc. Process and reactor for converting carbon dioxide into carbon monoxide
WO2020174056A1 (fr) * 2019-02-28 2020-09-03 Haldor Topsøe A/S Installation chimique dotée d'une section de reformage et procédé de production d'un produit chimique
CN115697895B (zh) * 2020-06-01 2024-03-01 国际壳牌研究有限公司 用于将二氧化碳、氢气和甲烷转化为合成气的灵活工艺
CN115697895A (zh) * 2020-06-01 2023-02-03 国际壳牌研究有限公司 用于将二氧化碳、氢气和甲烷转化为合成气的灵活工艺
WO2021244980A1 (fr) * 2020-06-01 2021-12-09 Shell Internationale Research Maatschappij B.V. Procédé flexible de conversion de dioxyde de carbone, d'hydrogène et de méthane en gaz de synthèse
EP4001210A1 (fr) * 2020-11-18 2022-05-25 L'Air Liquide - Société Anonyme pour l'Etude et l'Exploitation des Procédés Georges Claude Conception de processus de récipient de tampon de dioxyde de carbone
CN114516618A (zh) * 2020-11-18 2022-05-20 乔治洛德方法研究和开发液化空气有限公司 二氧化碳缓冲容器工艺设计
WO2023083661A1 (fr) * 2021-11-09 2023-05-19 Nordic Electrofuel As Système et procédé de production d'un combustible
GB2612647A (en) * 2021-11-09 2023-05-10 Nordic Electrofuel As Fuel generation system and process
GB2612647B (en) * 2021-11-09 2024-04-24 Nordic Electrofuel As Fuel generation system and process

Similar Documents

Publication Publication Date Title
WO2014180888A1 (fr) Procédé de préparation de gaz de synthèse
US5252609A (en) Synthesis gas production
AU742314B2 (en) Steam reforming
KR102060451B1 (ko) 탄화수소 개질 방법
EP1991639B1 (fr) Procédé pour préparer un produit par synthese de fischer tropsch
EP3658496B1 (fr) Procédé de préparation d'un gaz de synthèse
AU728230B2 (en) Production of methanol
ZA200510336B (en) Reforming process
CN105820036B (zh) 使用部分氧化生产甲醇的方法和系统
KR20120127454A (ko) 탄화수소 개질 방법
AU2006224604B2 (en) Process to prepare a mixture of carbon monoxide and hydrogen
CA2500645A1 (fr) Processus d'amelioration du prereformage et du reformage des gaz naturels contenant davantage d'hydrocarbures ainsi que du methane
EP2736840B1 (fr) Procédé de production de mélanges gazeux riches en hydrogène
CA3138720A1 (fr) Procede de synthese de methanol
KR20120054632A (ko) 메탄올 생산을 위한 복합 개질 방법
KR20200096755A (ko) 합성 가스 제조를 위한 방법 및 시스템
US9701535B2 (en) Process for producing a syngas intermediate suitable for the production of hydrogen
WO2012084135A1 (fr) Procédé pour le reformage d'hydrocarbures
EP3362405B1 (fr) Procédé de production et unité de production de méthanol
ZA200400794B (en) Production of hydrocarbons.
WO2017093130A1 (fr) Procédé pour la préparation d'un gaz de synthèse

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 14721883

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 14721883

Country of ref document: EP

Kind code of ref document: A1