WO2014114931A1 - Exploitation d'un processus de reformage et installation - Google Patents

Exploitation d'un processus de reformage et installation Download PDF

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Publication number
WO2014114931A1
WO2014114931A1 PCT/GB2014/050168 GB2014050168W WO2014114931A1 WO 2014114931 A1 WO2014114931 A1 WO 2014114931A1 GB 2014050168 W GB2014050168 W GB 2014050168W WO 2014114931 A1 WO2014114931 A1 WO 2014114931A1
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duct
plant
reforming
reactor
threshold value
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PCT/GB2014/050168
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English (en)
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Thomas Westermann
Alexander Karpenko
Robert Peat
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Compactgtl Limited
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Publication of WO2014114931A1 publication Critical patent/WO2014114931A1/fr

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    • B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
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    • 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
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    • C01B2203/142—At least two reforming, decomposition or partial oxidation steps in series
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Definitions

  • This invention relates to a process for operating a catalytic plant for performing a steam reforming reaction, and a plant for performing this process.
  • WO 2005/10251 1 GTL Microsystems AG
  • 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 reforming reaction is typically carried out at a temperature of about 800°C, and the heat required may be provided by catalytic combustion in channels adjacent to those in which reforming is carried out, the combustion channels containing a catalyst which may comprise palladium or palladium/platinum on an alumina support in the form of a thin coating on a metallic substrate.
  • An inflammable gas mixture such as a mixture of methane and air is supplied to the combustion channels. Combustion occurs at the surface of the catalyst without a flame.
  • WO 2009/101434 (CompactGTL pic) describes a module for performing this steam methane reaction in two stages.
  • a process for operating a steam reforming plant for reforming a hydrocarbon comprising a pre- reforming reactor, and a steam reforming reactor, wherein a stream of hydrocarbon is passed through pre-reforming reactor and then through a duct to the steam reforming reactor, wherein the plant also includes a carbonyl trap upstream of the pre-reforming reactor, the carbonyl trap being held at a temperature between a lower threshold value and an upper threshold value, wherein the process also comprises maintaining the entire length of the duct in a state in which metal carbonyls are not formed.
  • the present invention provides a steam reforming plant for reforming a hydrocarbon, the plant comprising a pre-reforming reactor, and a steam reforming reactor, a duct for supplying gases output from the pre-reforming reactor to the steam reforming reactor, a carbonyl trap upstream of the pre-reforming reactor, with means to hold the carbonyl trap at a temperature between a lower threshold value and an upper threshold value, and means to ensure that metal carbonyls are not formed throughout the length of the duct.
  • the inner surface of the duct is of a material which does not form metal carbonyl.
  • the metals that can form metal carbonyls are V, Cr, Mn, Fe, Co, Ni, Mo, Tc, Ru, Rh, W, Re, Os and Ir, so that a suitable material would be a metal or metal alloy that does not contain any of these elements, for example brass.
  • Another suitable material would be a ceramic that does not contain any of those elements, for example alumina or zirconia.
  • the temperature along the entire length of the duct is maintained at above the lower threshold value.
  • the carbonyl trap may for example consist of a guard bed containing particulate zeolite, or containing particulate alumina.
  • the lower threshold value is the temperature above which metal carbonyl is unstable. This may for example be about 120°C, as regards iron carbonyl, and may be somewhat higher, for example about 220°C or 250°C, if nickel carbonyl is of concern. At low temperatures, for example below 80°C, any carbon monoxide in the gas stream will react readily with metals such as iron and nickel in the pipework, forming metal carbonyls which are vapours. At a temperature above the lower threshold value, metal carbonyls are unstable and break down to form the metal, and carbon monoxide gas.
  • the metal deposited by breakdown of a metal carbonyl is raised to a still higher temperature, above the temperature referred to herein as the upper threshold value, it does not remain trapped. It is hypothesised that the deposited metal may react with a hydrocarbon such as methane, possibly forming molecules of iron carbide in the vapour phase.
  • This upper threshold value may be no higher than 500°C, and may be no higher than 400°C.
  • the steam reforming reactor may be a compact catalytic reactor in the form of a reactor block defining a multiplicity of first and second flow channels arranged alternately within the block to ensure thermal contact between the first and second flow channels. Reforming would be carried out in one set of channels, and heat would be provided from the other set of channels. Heat may be provided by catalytic combustion within those channels.
  • the first flow channels and the second flow channels may extend in parallel directions, and the combustible gas mixture and the steam reforming mixture flow in the same direction (co-flow) during operation.
  • each channel which is intended for a chemical reaction contains a catalyst.
  • the catalyst may be coated onto the channel walls, or provided on one or more supports within the channels.
  • the catalyst may be in the form of a removable catalyst structure with a metal substrate, and incorporating an appropriate catalytic material.
  • Each such catalyst structure may be shaped so as to subdivide the flow channel into a multiplicity of parallel flow sub-channels.
  • Each catalyst structure may include a ceramic support material on the metal substrate, to provide a support for the catalyst.
  • the metal substrate provides strength to the catalyst structure and enhances thermal transfer by conduction.
  • the metal substrate may be of a steel alloy that forms an adherent surface coating of aluminium oxide when heated, for example a ferritic steel alloy that incorporates aluminium (eg Fecralloy (TM)).
  • the substrate may be a foil, a wire mesh or a felt sheet, which may be corrugated, dimpled or pleated; a suitable substrate is a thin metal foil for example of thickness typically between 50 ⁇ and 200 ⁇ , for example 100 ⁇ , which is corrugated to define the longitudinal subchannels.
  • Each reactor block may comprise a stack of plates.
  • the first and second flow channels may be defined by grooves in respective plates, the plates being stacked and then bonded together.
  • 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.
  • both the first and the second gas flow channels may be between 10 mm and 2 mm high (in cross-section); and each channel may be of width between about 3 mm and 25 mm.
  • the stack of plates forming the reactor block is bonded together for example by diffusion bonding, brazing, or hot isostatic pressing.
  • Figure 1 shows a schematic flow diagram of a gas-to-liquid plant, including a steam/reforming reactor.
  • the steam reforming reaction of methane may be brought about by mixing steam and methane, and contacting the mixture with a suitable catalyst at an elevated temperature so the steam and methane react to form carbon monoxide and hydrogen (which may be referred to as synthesis gas or syngas).
  • the steam reforming reaction is endothermic, and the heat may be provided by catalytic combustion, for example of methane mixed with air.
  • the combustion may take place over a combustion catalyst within adjacent flow channels within a reforming reactor.
  • the steam/methane mixture is preheated, for example to over 600°C, before being introduced into the reactor.
  • the temperature in the reformer reactor therefore typically increases from about 600°C at the inlet to about 750-800°C at the outlet. 1 .
  • alloys such as Inconel 625 and 800HT (trade marks), which are high-temperature stainless steel alloys, are typically used.
  • process leading to deactivation of the catalyst involves formation of metal carbonyls, at a low-temperature region in which the metal carbonyls are stable; the deposition of metal by breakdown of the metal carbonyls in a high- temperature region; and then the formation of another metal compound in the vapour form (possibly a metal carbide) in the high-temperature region.
  • another metal compound in the vapour form possibly a metal carbide
  • the formation of the other metal compound in the vapour form requires a temperature above an upper temperature threshold of about 400°C or possibly 500°C.
  • the deposited metal formed by the breakdown of the metal carbonyls is in a fine particulate form, and so is potentially very reactive.
  • the invention is applicable in a chemical plant and process for converting natural gas (primarily methane) to longer chain hydrocarbons.
  • long chain hydrocarbons refers to hydrocarbons that contain more than one carbon atom, that is to say C2+ hydrocarbons, which may be aliphatic or cyclic. Hydrocarbons between about C5 and C16 are typically liquid at ambient conditions, whereas C17 and above are waxy.
  • the plant is suitable for treating associated gas, which is natural gas that is produced along with crude oil, and is then separated from the crude oil.
  • the first stage of the chemical process involves the formation of synthesis gas. This may be achieved for example by steam reforming, by a reaction of the type:
  • This reaction is endothermic, and may be catalysed by a rhodium or platinum/rhodium catalyst in a first gas flow channel.
  • the heat required to cause this reaction may be provided by catalytic combustion of a gas such as methane or hydrogen, which is exothermic, in an adjacent channel, or by heat exchange with exhaust gases from a separate combustion reactor.
  • the combustion may be catalysed by a palladium catalyst, and the catalyst may be on a stabilised-alumina support which forms a coating typically less than 100 ⁇ thick on a metallic substrate.
  • the catalyst may be applied to the walls of the flow channels or may be provided as pellets within the flow channel.
  • the heat generated by the combustion would be conducted through the metal sheet separating the adjacent channels.
  • the resulting syngas H 2 /CO ratio is 3.0, although the exact value depends on reactor conditions, and on the ratio of steam to methane provided to the reactor, and for example the ratio may be 3.5 if a higher proportion of steam is provided.
  • the gas mixture produced by the steam/methane reforming is then, in this example, used to perform a Fischer-Tropsch synthesis to generate longer chain hydrocarbons, that is to say: n CO + 2n H 2 ⁇ (CH 2 ) n + n H 2 0 (2) which is an exothermic reaction, occurring at an elevated temperature, typically between 190°C and 280°C, for example 230°C, and an elevated pressure typically between 1 .8 MPa and 2.7 MPa (absolute values), in the presence of a catalyst.
  • Fischer-Tropsch synthesis produces hydrocarbons with a range of different chain lengths, for example between C4 and C24.
  • the exact range of chain lengths depends upon the catalyst and the reaction conditions.
  • Fe based catalysts can be used, metallic Co promoted with precious metals such as Pd, Pt, Ru or Re doped to 1 wt% are preferred when operating at lower temperatures as they have enhanced stability to oxidation.
  • the active metals are impregnated to 10-40 wt% into refractory support materials such as Ti0 2 , Al 2 0 3 or Si0 2 which may be doped with rare earth and transition metal oxides to improve their hydrothermal stability.
  • a hydrogen-rich gas stream can therefore be separated either from the synthesis gas stream before performing Fischer-Tropsch synthesis, or from the tail gases that remain after performing Fischer-Tropsch synthesis. Such a separation may use a membrane separator.
  • a natural gas feed 5 consists primarily of methane, but with small proportions of other gaseous hydrocarbons, hydrocarbon vapours, and water vapour.
  • the gas feed 5 may for example be at a pressure of 4.0 MPa (40 atmospheres) and 35°C, following sea water cooling from an initial temperature of 90°C, and may constitute associated gas from a well that produces crude oil.
  • the natural gas feed 5 is supplied to a pretreatment system 25, in which it is subjected to treatment which may comprise one or more of the following: changing its pressure; changing its temperature; and removing impurities such as sulphur or mercury. This produces clean natural gas 12. It is then mixed with hot steam in a mixer 26.
  • the gas/steam mixture preferably at a temperature of about 450°C, is then fed into a catalytic reactor 28 acting as a pre-reformer in which any ethane or other higher hydrocarbons are converted to methane.
  • a catalytic reactor 28 acting as a pre-reformer in which any ethane or other higher hydrocarbons are converted to methane.
  • the resultant gas mixture consisting predominantly of steam and methane, is then fed into a steam/methane reformer 30.
  • the steam/methane reformer 30 consists of a compact catalytic reactor formed from a stack of plates defining two sets of channels arranged alternately.
  • One set of channels 31 are for the reforming reaction, and contain a suitable catalyst, which may be on removable corrugated metal foil supports, while the other set of channels 32 are for the provision of heat.
  • the heat is provided by combustion, over a platinum/palladium catalyst, in the channels 32 for the provision of heat within the steam/methane reformer 30.
  • the reactor 30 would have a multiplicity of reforming channels 31 alternating with heat- providing channels 32, but only one of each are shown.
  • a reformer catalyst for example a platinum/rhodium catalyst, and so the steam and methane react to form carbon monoxide and hydrogen.
  • the heat for the steam/methane reforming reaction in the reformer 30 is provided by combustion in the heat-providing channels 32 of a fuel gas in a stream of combustion air.
  • the fuel gas is primarily methane, but as explained below it may also include hydrogen and other flammable compounds.
  • the combustion air may be preheated in a heat exchanger (not shown) taking heat from the hot exhaust gases from the combustion which emerge from the heat-providing channels 32. The exhaust gases may then be vented through a stack.
  • a mixture of carbon monoxide and hydrogen at above 800°C emerges from the reformer 30, and is quenched by passing it through a steam-raising heat exchanger 36 which may be a thermosiphon, arranged to generate steam.
  • the resulting steam is supplied to the mixer 26.
  • the gas mixture which is a form of synthesis gas, is then subjected to further cooling in a heat exchanger 38. It is then subjected to compression using two successive compressors 40 (only one is shown) preferably with cooling and liquid- separation stages (not shown) after each compressor 40.
  • the compressors 40 raise the pressure to about 2.6 MPa (26 atm) (absolute).
  • Fischer-Tropsch Synthesis The stream of high pressure carbon monoxide and hydrogen is then fed through a heat exchanger 46 to a catalytic Fischer-Tropsch reactor 50.
  • the Fischer- Tropsch reactor 50 is a compact catalytic reactor formed from a stack of plates as similar to that described above, with multiple channels for a coolant fluid alternating with channels for the Fischer-Tropsch synthesis (only one of each being shown).
  • a catalyst within each of the channels for Fischer-Tropsch synthesis is a catalyst, which may be provided as a removable catalytic insert (not shown) consisting of a corrugated 50 ⁇ thick foil (typically of thickness in the range from 20-200 ⁇ ) with a ceramic coating acting as a support for the catalytic material; instead of a single foil, the insert may consist of a stack of shaped foils.
  • the reactant mixture flows through the reaction channels of the reactor 50, while a coolant flows through the other channels.
  • the coolant is circulated through a heat exchanger 52. Initially, when the catalyst is new, the Fischer-Tropsch reaction takes place at about 210°C, and the coolant is circulated at such a rate that the temperature varies by less than 10 K on passage through the reactor 50.
  • the reaction products from the Fischer-Tropsch synthesis predominantly water and hydrocarbons such as paraffins, are cooled in a heat exchanger 60 and fed to a separating chamber 62 in which the three phases water, hydrocarbons and tail gases separate.
  • the aqueous phase contains water with about 1 -2% oxygenates such as ethanol and methanol which are formed by the Fischer-Tropsch synthesis. At least some of the aqueous phase is fed as process water through the heat exchanger 52, and hence through a pressure-drop valve 64, so it can be used to provide the steam to the mixer 26.
  • the arrangement for separating the reaction products may be more complex than shown in figure 1 .
  • the vapour and gas phase from the separating chamber 62 may be fed through successive cooling heat exchangers to a lower temperature, so as to condense more of the hydrocarbon product.
  • the remaining vapour phase which is at the same pressure as the Fischer- Tropsch reactor 50, may be passed through a throttle valve (not shown) to expand adiabatically into a lower pressure region, with no significant heat input from the surroundings, so as to cool the gas further, and then fed into a phase separating vessel.
  • a throttle valve not shown
  • This may increase the amount of water and light hydrocarbon product that is obtained, that is to say hydrocarbons between about C4 and C8.
  • This tail gas 66 comprises unreacted hydrogen and carbon monoxide, and gaseous hydrocarbons such as methane and ethane.
  • a commercial plant may include several steam/methane reformers 30 operating in parallel, and may also include several Fischer-Tropsch reactors 50 operating in parallel.
  • natural gas mixed with steam is subjected to pre-reforming in a pre-reformer 28, at a temperature of about 400°C or 450°C, to convert longer hydrocarbons to methane. It is then subjected to reforming in the reformer 30, which is at a temperature above 750°C.
  • the mixture of steam and natural gas is passed through a guard bed 70 containing a bed of particulate zeolite held at a temperature of 260°C.
  • This guard bed 70 ensures that any metal carbonyls that may be present in the gas mixture undergo thermal decomposition, forming metal which is trapped on the zeolite.
  • the temperature of the guard bed 70 is controlled, to ensure it does not exceed 300°C. This ensures that the deposited metal does not undergo any alternative reactions that could lead to metal transport.
  • the resulting gas mixture flows through a duct 71 leading to the pre-reformer
  • the duct 71 is held at a temperature between 260°C and 400°C along its entire length; and similarly the duct 72 is held at a temperature between 400°C and 600°C along its entire length. This may be achieved in each case merely by the provision of thermal insulation, because the ends of the ducts 71 and 72 are at suitable temperatures.
  • the pre-reformer 28 forms some carbon monoxide as a result of the reaction between steam and higher hydrocarbons, the temperature within the pre- reformer 28 is too high for formation of metal carbonyls. As long as the duct 72 remains at a temperature of above about 120°C along its entire length, metal carbonyls cannot form within the duct 72. Hence the provision of the guard bed 70, and control of the temperatures of the duct 71 and 72, prevents transport of metal from the pipework to the catalysts in the reforming channels 31 of the reformer 30.
  • the plant 10 may also include a preheater (not shown) within the duct 71 , to heat the gas mixture from about 260°C up to about 400°C. In this temperature range there is no risk of formation of metal carbonyls.

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Abstract

L'invention concerne une installation de reformage à la vapeur, destinée à reformer un hydrocarbure, qui comprend un réacteur (28) de pré-reformage et un réacteur (30) de reformage à la vapeur. Un flux d'hydrocarbure est amené à passer par le réacteur (28) de pré-reformage, puis par une conduite (72) jusqu'au réacteur (30) de reformage à la vapeur. L'installation comprend également un piège (70) à carbonyle, en amont du réacteur (28) de pré-reformage, le piège (70) à carbonyle étant maintenu à une température comprise entre des valeurs de seuil inférieure et supérieure. Toute la longueur de la conduite (72) est telle que les métaux carbonyle ne se forment pas. La paroi interne de la conduite (72) peut être constituée d'un matériau qui ne forme pas de métaux carbonyle ou la conduite (72) peut être maintenue à une température supérieure à la valeur de seuil inférieure, de sorte que les métaux carbonyle ne soient pas stables. Il a été constaté que cela permettait de supprimer la contamination et la désactivation des catalyseurs de reformage.
PCT/GB2014/050168 2013-01-23 2014-01-22 Exploitation d'un processus de reformage et installation WO2014114931A1 (fr)

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Cited By (1)

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WO2023001521A1 (fr) * 2021-07-22 2023-01-26 Topsoe A/S Catalyseur de reformage à la vapeur pour charges d'hydrocarbures lourds

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EP0239111A2 (fr) * 1986-03-27 1987-09-30 Union Carbide Corporation Procédé d'élimination de métaux carbonyles de courants gazeux
WO1994025142A1 (fr) * 1993-04-23 1994-11-10 Den Norske Stats Oljeselskap A.S. Procede pour reduire la quantite de carbonyles de metal contenue dans des courants gazeux
WO2012032324A1 (fr) * 2010-09-09 2012-03-15 Johnson Matthey Public Limited Company Passivation de métal d'un échangeur thermique exposé à un gaz de synthèse
WO2012062338A1 (fr) * 2010-11-08 2012-05-18 Haldor Topsøe A/S Procédé pour la préparation sélective d'isopropnaol, d'isobutanol et d'autres alcools en c3+ à partir de gaz de synthèse et de méthanol

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EP0239111A2 (fr) * 1986-03-27 1987-09-30 Union Carbide Corporation Procédé d'élimination de métaux carbonyles de courants gazeux
WO1994025142A1 (fr) * 1993-04-23 1994-11-10 Den Norske Stats Oljeselskap A.S. Procede pour reduire la quantite de carbonyles de metal contenue dans des courants gazeux
WO2012032324A1 (fr) * 2010-09-09 2012-03-15 Johnson Matthey Public Limited Company Passivation de métal d'un échangeur thermique exposé à un gaz de synthèse
WO2012062338A1 (fr) * 2010-11-08 2012-05-18 Haldor Topsøe A/S Procédé pour la préparation sélective d'isopropnaol, d'isobutanol et d'autres alcools en c3+ à partir de gaz de synthèse et de méthanol

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023001521A1 (fr) * 2021-07-22 2023-01-26 Topsoe A/S Catalyseur de reformage à la vapeur pour charges d'hydrocarbures lourds

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