EP2825502A1 - Procédé pour produire du co et/ou h2 en fonctionnement alterné entre deux types de fonctionnement - Google Patents

Procédé pour produire du co et/ou h2 en fonctionnement alterné entre deux types de fonctionnement

Info

Publication number
EP2825502A1
EP2825502A1 EP13708492.7A EP13708492A EP2825502A1 EP 2825502 A1 EP2825502 A1 EP 2825502A1 EP 13708492 A EP13708492 A EP 13708492A EP 2825502 A1 EP2825502 A1 EP 2825502A1
Authority
EP
European Patent Office
Prior art keywords
heating
reactor
reaction
group
fluid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP13708492.7A
Other languages
German (de)
English (en)
Inventor
Alexander Karpenko
Kristian VOELSKOW
Emanuel Kockrick
Albert TULKE
Daniel Gordon Duff
Stefanie Eiden
Oliver Felix-Karl SCHLÜTER
Vanessa GEPERT
Ulrich Nieken
René KELLING
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bayer AG
Bayer Intellectual Property GmbH
Original Assignee
Bayer Technology Services GmbH
Bayer Intellectual Property GmbH
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 Bayer Technology Services GmbH, Bayer Intellectual Property GmbH filed Critical Bayer Technology Services GmbH
Publication of EP2825502A1 publication Critical patent/EP2825502A1/fr
Withdrawn legal-status Critical Current

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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/24—Stationary reactors without moving elements inside
    • B01J19/248—Reactors comprising multiple separated flow channels
    • B01J19/2485—Monolithic reactors
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
    • C01B3/384—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
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    • B01J12/00—Chemical processes in general for reacting gaseous media with gaseous media; Apparatus specially adapted therefor
    • B01J12/007—Chemical processes in general for reacting gaseous media with gaseous media; Apparatus specially adapted therefor in the presence of catalytically active bodies, e.g. porous plates
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    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/32—Manganese, technetium or rhenium
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    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
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    • B01J8/0453—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 the fluid passing successively through two or more beds the flow within the beds being predominantly vertical in two or more cylindrical beds the beds being superimposed one above the other
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    • B01J8/04—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 the fluid passing successively through two or more beds
    • B01J8/0496—Heating or cooling the reactor
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    • 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
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    • 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
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    • Y02P20/10—Process efficiency
    • Y02P20/133—Renewable energy sources, e.g. sunlight
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

  • the present invention relates to a process for the production of synthesis gas in the interplay of an endothermic reaction, electrical heating and an exothermic reaction. Due to the increased expansion of renewable energies, a fluctuating supply of energy in the power grid is created. In phases of favorable electricity prices results for the operation of reactors for carrying out endothermic reactions, preferably for the production of synthesis gas, the possibility of an economical and economically meaningful operation taking advantage of renewable energies when they are electrically heated. In phases in which no regeneratively generated electrical energy is available, then another form of energy supply of the endothermic reactions must be selected.
  • synthesis gas is produced by steam reforming of methane. Due to the high heat demand of the reactions involved, they are carried out in externally heated reformer tubes. Characteristic of this method is the limitation by the reaction equilibrium, a heat transport tempering and, above all, the pressure and temperature limitation of the reformer tubes used (nickel-based steels). Temperature and pressure side results in a limitation to a maximum of 900 ° C at about 20 to 40 bar.
  • An alternative method is autothermal reforming.
  • a portion of the fuel is burned by the addition of oxygen within the reformer, so that the reaction gas is heated and the expiring endothermic reactions are supplied with heat.
  • DE 10 2007 022 723 A1 and US 2010/0305221 describe a process for the production and conversion of synthesis gas, which is characterized in that it has a plurality of different operating states, which essentially consist of the alternating (i) daytime operation and (ii) night-time operation, day-to-day operations (i) being mainly dry reforming and steam reforming with the supply of renewable energy and night-time operation (ii) mainly comprising the partial oxidation of hydrocarbons and wherein the produced synthesis gas is used for the production of value products.
  • WO 2007/042279 A1 deals with a reformer system with a reformer for the chemical conversion of a hydrocarbon-containing fuel into a hydrogen-rich reformate gas, and electrical heating means by which the reformer heat energy for producing a reaction temperature required for the feed can be supplied, wherein the reformer system further comprises a capacitor has, which can supply the electric heating means with electric current.
  • WO 2004/071947 A2 / US 2006/0207178 AI relate to a system for the production of hydrogen, comprising a reformer for generating hydrogen from a hydrocarbon fuel, a compressor for compressing the generated hydrogen, a renewable energy source for converting a renewable resource into electrical Energy for driving the compressor and a storage device for storing the hydrogen from the compressor.
  • the object of the present invention is to provide such a method.
  • it has set itself the task of specifying a method for the production of synthesis gas, which is suitable for alternating operation between two different modes of operation.
  • This object is achieved according to the invention by a process for the preparation of carbon monoxide and / or hydrogen-containing gas mixtures, comprising the steps: - Providing a flow reactor, which is adapted for the reaction of a fluid comprising reactants, wherein the reactor comprises at least one heating level, which is electrically heated by means of one or more heating elements, wherein the heating level can be traversed by the fluid and wherein arranged on at least one heating element, a catalyst is and is heated there;
  • the amount of heat Q2 is the amount of heat released by the electric heating of the reactor. In particular, it is the amount of heat that raises the temperature of the reactants in the reactor.
  • the amount of heat Q3 is calculated.
  • the well-known in the field of chemical engineering procedures are suitable. This is considered to be the endothermic reaction of C0 2 with the other starting materials in the composition, which is present in the reactor.
  • the heat quantity Q3 necessary for an equilibrium yield Y of> 90% is derived therefrom.
  • a reaction in the reactor can be a yield, based on the carbon dioxide used, due to thermodynamic limitations of 58%. 90% of 58% equals 52.2%, which is used to calculate Q3 heat demand.
  • Q3 is selected so that an equilibrium yield Y> 90% to ⁇ 100% and more preferably> 92% to ⁇ 99.99% is achieved.
  • the production of the products takes place in a reactor which is heated both autothermally and by means of electrical energy made available.
  • Methane with water or C0 2 can preferably be used as starting materials.
  • the reverse water gas shift reaction is another way to produce preferably CO.
  • high temperatures of> 700 ° C are desirable in order to maximize yields.
  • An autothermal reaction regime makes it possible to provide the required energy input, in particular very endothermic reactions such as dry reforming (+ 247 kJ / mol) or steam reforming (+ 206 kJ / mol).
  • the autothermal reaction is carried out by the oxidation of preferably methane and / or hydrogen as well as part of the resulting products (eg CO).
  • the oxidation takes place on the one hand at the entrance of the reactor, whereby the inlet temperature can be quickly brought to a high level and so-called "cold spots" are avoided by the endothermy of the reactions.
  • the gas feed takes place laterally along the reactor length in order to reduce the fuel gas concentrations in the inlet region and thus the theoretically maximum possible adiabatic temperature increase.
  • the side feed can bring the temperature level to values above the inlet temperature. This heating concept is coupled with the additional possibility of feeding in electrical energy, preferably in the middle and at the end of the reactor.
  • optimal temperature profiles can be set along the reactor, for example an increasing temperature ramp along the reactor length, which positively influences the thermodynamics of the endothermic reactions.
  • the reaction is optimized in terms of CO / H 2 - yield.
  • the feeding of electrical energy can originate, for example, from renewable sources. Due to the increased expansion of renewable energies, a fluctuating supply of energy in the power grid is created. In phases of favorable electricity prices results for the operation of Reactors for the production of synthesis gas (endothermic reactions) the possibility of an economically and economically meaningful operation taking advantage of renewable energies with the simultaneous saving of methane / hydrogen, which are then less necessary for heating. On the other hand, there are phases of high electricity prices, in which the supply of electrical energy necessary for carrying out the processes should be minimized. However, the share of regenerative energy in the grid also determines the eco-efficiency of the process. As will be described further below, the process management of the endothermic synthesis gas production with regard to the energy demand can be designed so that economically and ecologically meaningful operating points can be set depending on the price of electricity and the proportion of regenerative energy in the power grid.
  • the energy supply in the process described above takes place within the reactor by oxidation of a portion of the feed gas supplied, methane in DRM or SMR and / or hydrogen in RWGS, and / or by electrical heating. Both ways can be used for all mentioned reactions.
  • part of the methane supplied (in the case of DR and SMR) or hydrogen (in the case of RWGS) is partially oxidized by additionally introduced oxygen.
  • the resulting heat of combustion is then used for both the respective endothermic reaction and for further heating of the reaction gas.
  • this makes sense in order to absorb the endotherm of the reaction and to avoid so-called "cold spots". Also, this can be used to bring the reaction gas to a desired inlet and outlet temperature.
  • intermediate gas feeds can also be made an energy input for the reaction and / or heating of the reaction gas and a temperature profile can be adjusted, which are achieved in thermodynamically limited reforming higher CO / H 2 yields.
  • the fuel gas concentration in the inlet area is also reduced by the side feed and thus the theoretically possible adiabatic temperature increase is reduced.
  • the necessary oxygen addition can take place both continuously and discontinuously.
  • the addition of oxygen takes place in the upper explosion range and can be realized in the following forms: addition of pure oxygen, addition of air and / or in admixture with one of the otherwise occurring in the reactor species (CH 4 , H 2 , C0 2 , H 2 0, N 2 ). An oxygen / air mixture together with C0 2 and / or H 2 0 is sought.
  • Another advantage of this reactor concept lies in the flexible switching of the heating modes from oxidation to electrical and / or driving in alternating operation between strong (DR, SMR) and weak endothermic reactions (RWGS).
  • the same reactor is used for both reaction types (endothermic and exothermic), so that it is not necessary to switch the reactant streams to separate apparatuses. Rather, there is the possibility of a gradual start of the other reaction by continuously reducing the supply of methane while increasing the hydrogen supply to the reactor and vice versa. It is therefore also a mixed form of both reactions to-casual.
  • a metered addition of water is also possible in this concept, so that operation as a steam reformer (SMR, +206 kJ / mol) or a mixed form results from the three abovementioned reactions.
  • SMR steam reformer
  • +206 kJ / mol a mixed form
  • C0 2 reacts with hydrocarbons, H 2 O and / or H 2 to form (inter alia) CO.
  • the hydrocarbons involved in the endothermic and exothermic reactions are preferably alkanes, alkenes, alkynes, alkanols, alkenols and / or alkynols.
  • alkanes methane is particularly suitable, among the alkanols methanol and / or ethanol are preferred.
  • hydrocarbons CO and / or hydrogen are used as starting materials. They react with each other or with other reactants in the reactor.
  • OCM methane
  • the combustion of hydrogen can be used. It is both possible that the combustion of hydrogen in the RWGS reaction by metering of 0 2 in the educt gas (ideally a locally distributed or lateral metering) takes place, as well as possible that hydrogen-rich residual gases (for example, PSA exhaust gas), such They can be incurred in the purification of the synthesis gas, recycled and burned together with 0 2 , which then the process gas is heated.
  • hydrogen-rich residual gases for example, PSA exhaust gas
  • An advantage of the oxidative mode of operation is that soot deposits formed by dry reforming or steam reforming can be removed and thus the catalyst used can be regenerated. Moreover, it is possible to regenerate passivation layers, the heating conductor or other metallic internals in order to increase the service life.
  • endothermic reactions are heated from the outside through the walls of the reaction tubes. Opposite is the autothermal reforming with 0 2 -addition.
  • the endothermic reaction can be efficiently internally supplied with heat via an electrical heating within the reactor (the undesired alternative would be electrical heating via radiation through the reactor wall). This type of reactor operation is particularly economical if the excess supply resulting from the expansion of renewable energy sources can be used cost-effectively.
  • FIG. 1 shows schematically a flow reactor in an expanded representation.
  • the endothermic reaction is selected from: methane dry reforming, methane methane reverse gas reforming, reverse gas shift, coal gasification and / or methane pyrolysis
  • the exothermic reaction is selected from: partial oxidation of methane, autothermal reforming, Boudouard reaction, methane combustion, CO oxidation, hydrogen oxidation, oxidative coupling of methane and / or Sabatier methanation (C0 2 and CO to methane).
  • the proportion of the quantity of heat Q2 increases downstream in the reactor. In a further embodiment of the method according to the invention, this further comprises the steps:
  • Threshold Sl for the cost of the electric current available for the flow reactor and / or a threshold value S2 for the relative proportion of electrical energy from regenerative
  • the first threshold S 1 relates to the electricity cost of the reactor, in particular the cost of electrically heating the reactor by the heating elements in the heating levels. Here it can be determined up to which height the electric heating is still economically reasonable.
  • the second threshold S2 relates to the relative proportion of electrical energy from regenerative sources available to the reactor and, in particular, to the electrical heating of the reactor by the heating elements in the heating levels.
  • the relative proportion is in this case based on the total electrical energy of the electric current available for the flow reactor and can of course vary over time. Examples of regenerative sources from which electrical energy can be obtained are wind, solar, geothermal, wave and hydro.
  • the relative share can be determined by providing information to the energy supplier. If, for example, a factory site owns its own regenerative energy sources such as solar plants or wind turbines, this relative energy share can also be indicated via performance monitoring.
  • the threshold value S2 can be understood as a requirement to use renewable energies to the greatest possible extent.
  • S2 may mean that from a proportion of 5%, 10%, 20% or 30% of electrical energy from renewable sources, the electrical heating of the reactor should take place.
  • a comparison of the desired values with the actual values in the method can now reach the conclusion that electrical energy is available inexpensively and / or enough electrical energy is available from renewable sources. Then, the flow reactor is operated so that the exothermic reaction is carried out to a lesser extent and / or more electrically heated.
  • the system can be coupled with a water electrolysis unit for hydrogen production.
  • the operating strategy of water electrolysis is also linked to the parameters 'electricity price' and 'proportion of regenerative energy in the grid'. The entire system may therefore have at least one hydrogen storage if required.
  • the flow reactor comprises: seen in the flow direction of the fluid, a plurality of heating levels which are electrically heated by heating elements and wherein the heating levels are permeable by the fluid, wherein a catalyst is arranged on at least one heating element and is heatable there , Wherein furthermore at least once an intermediate plane between two heating planes is arranged and wherein the intermediate plane is also traversed by the fluid.
  • FIG. 1 schematically shown flow reactor used according to the invention is flowed through by a fluid comprising reactants from top to bottom, as shown by the arrows in the drawing.
  • the fluid may be liquid or gaseous and may be single-phase or multi-phase.
  • the fluid is gaseous. It is conceivable that the fluid contains only reactants and reaction products, but also that additionally inert components such as inert gases are present in the fluid.
  • the reactor has a plurality of (four in the present case) heating levels 100, 101, 102, 103, which are electrically heated by means of corresponding heating elements 110, 111, 112, 113.
  • the heating levels 100, 101, 102, 103 are flowed through by the fluid during operation of the reactor and the heating elements 110, 111, 112, 113 are contacted by the fluid.
  • At least one heating element 110, 111, 112, 113, a catalyst is arranged and is heated there.
  • the catalyst may be directly or indirectly connected to the heating elements 110, 111, 112, 113 so that these heating elements constitute the catalyst support or a support for the catalyst support.
  • the heat supply of the reaction takes place electrically and is not introduced from the outside by means of radiation through the walls of the reactor, but directly into the interior of the reaction space. It is realized a direct electrical heating of the catalyst.
  • thermoistor alloys such as FeCr Al alloys are preferably used.
  • electrically conductive Si-based materials particularly preferably SiC.
  • This has the effect of homogenizing the fluid flow.
  • additional catalyst is present in one or more intermediate levels 200, 201, 202 or other isolation elements in the reactor. Then an adiabatic reaction can take place.
  • the intermediate levels may act as flame arresters as needed, especially in reactions where oxygen delivery is provided.
  • the material forms an Al 2 O 3 protective layer by the action of temperature in the presence of air / oxygen.
  • This passivation layer can serve as a basecoat of a washcoat, which acts as a catalytically active coating.
  • the direct resistance heating of the catalyst or the heat supply of the reaction is realized directly through the catalytic structure.
  • the formation of other protective layers such as Si-OC systems.
  • the pressure in the reactor can take place via a pressure-resistant steel jacket.
  • suitable ceramic insulation materials it can be achieved that the pressure-bearing steel is exposed to temperatures of less than 200 ° C and, if necessary, less than 60 ° C.
  • the electrical connections are shown in FIG. 1 only shown very schematically. They can be routed in the cold area of the reactor within an insulation to the ends of the reactor or laterally from the heating elements 110, 111, 112, 113, so that the actual electrical connections can be provided in the cold region of the reactor.
  • the electrical heating is done with direct current or alternating current.
  • heating elements 110, 111, 112, 113 are arranged, which are constructed in a spiral, meandering, grid-shaped and / or reticulated manner.
  • At least one heating element 110, 111, 112, 113 may have a different amount and / or type of catalyst from the other heating elements 110, 111, 112, 113.
  • the heating elements 110, 111, 112, 113 are arranged so that they can each be electrically heated independently of each other.
  • the individual heating levels can be individually controlled and regulated.
  • In the reactor inlet area can be dispensed with a catalyst in the heating levels as needed, so that only the heating and no reaction takes place in the inlet area. This is particularly advantageous in terms of starting the reactor.
  • a temperature profile adapted for the respective reaction can be achieved. With regard to the application for endothermic equilibrium reactions, this is, for example, a temperature profile which achieves the highest temperatures and thus the highest conversion at the reactor outlet.
  • the (for example ceramic) intermediate levels 200, 201, 202 or their contents 210, 211, 212 comprise a material resistant to the reaction conditions, for example a ceramic foam.
  • the material of the content 210, 211, 212 of an intermediate level 200, 201, 202 comprises oxides, carbides, nitrides, phosphides and / or borides of aluminum, silicon and / or zirconium.
  • SiC silicon and / or zirconium.
  • cordierite is an example of this.
  • the intermediate level 200, 201, 202 may include, for example, a loose bed of solids. These solids themselves may be porous or solid, so that the fluid flows through gaps between the solids. It is preferred that the material of the solid bodies comprises oxides, carbides, nitrides, phosphides and / or borides of aluminum, silicon and / or zirconium. An example of this is SiC. Further preferred is cordierite. It is also possible that the intermediate plane 200, 201, 202 comprises a one-piece porous solid. In this case, the fluid flows through the intermediate plane via the pores of the solid. This is shown in FIG. 1 shown. Preference is given to honeycomb monoliths, as used for example in the exhaust gas purification of internal combustion engines. Another conceivable possibility is that one or more of the intermediate levels are voids.
  • the average length of a heating level 100, 101, 102, 103 is viewed in the direction of flow of the fluid and the average length of an intermediate level 200, 201, 202 in the direction of flow of the fluid is in a ratio of> 0.01: 1 to ⁇ 100: 1 to each other. Even more advantageous are ratios of> 0.1: 1 to ⁇ 10: 1 or 0.5: 1 to ⁇ 5: 1.
  • Suitable catalysts may, for example, be selected from the group comprising:
  • A, A 'and A are independently selected from the group: Mg, Ca, Sr, Ba, Li, Na, K, Rb, Cs, Sn, Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Tl, Lu, Ni, Co, Pb, Bi and / or Cd;
  • B, B 'and B are independently selected from the group: Cr, Mn, Fe, Bi, Cd, Co, Cu, Ni, Sn, Al, Ga, Sc, Ti, V, Nb, Ta, Mo, Pb , Hf, Zr, Tb, W, Gd, Yb, Mg, Li, Na, K, Ce and / or Zn; and
  • A, A 'and A are independently selected from the group: Mg, Ca, Sr, Ba, Li, Na, K, Rb, Cs, Sn, Sc, Y, La, Ce, Pr, Nd, Sm, Eu , Gd, Tb, Dy, Ho, Er, Tm, Yb, Tl, Lu, Ni, Co, Pb and / or Cd;
  • B is selected from the group: Cr, Mn, Fe, Bi, Cd, Co, Cu, Ni, Sn, Al, Ga, Sc, Ti, V, Nb, Ta, Mo, Pb, Hf, Zr, Tb, W , Gd, Yb, Bi, Mg, Cd, Zn, Re, Ru, Rh, Pd, Os, Ir and / or Pt; B 'is selected from the group: Re, Ru, Rh, Pd, Os, Ir and / or Pt;
  • B is selected from the group: Cr, Mn, Fe, Bi, Cd, Co, Cu, Ni, Sn, Al, Ga, Sc, Ti, V, Nb, Ta, Mo, Pb, Hf, Zr, Tb, W, Gd, Yb, Bi, Mg, Cd and / or Zn, and 0 ⁇ w ⁇ 0.5, 0 ⁇ x ⁇ 0.5, 0 ⁇ y ⁇ 0.5, 0 ⁇ z ⁇ 0.5, and 1 ⁇ delta ⁇ 1;
  • Ml and M2 are independently selected from the group: Re, Ru, Rh, Ir, Os, Pd and / or Pt;
  • M3 is selected from the group: Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and / or Lu;
  • M is selected from the group: Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Zn, Cu , Ag and / or Au;
  • L is selected from the group: Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Sc, Y, Sn, Pb, Mn, In, Tl, La, Ce, Pr, Nd, Sm, Eu, Gd , Tb, Dy, Ho, Er, Tm, Yb and / or Lu; and 4 ⁇ z ⁇ 9;
  • a metal Ml and / or at least two different metals Ml and M2 on and / or in a carrier wherein the carrier comprises a carbide, oxycarbide, carbonitride, nitride, boride, silicide, germanide and / or selenide of metals A and / or B is;
  • Ml and M2 are independently selected from the group: Cr, Mn, Fe, Co, Ni, Re, Ru, Rh, Ir, Os, Pd, Pt, Zn, Cu, La, Ce, Pr, Nd, Sm, Eu , Gd, Tb, Dy, Ho, Er, Tm, Yb, and / or Lu;
  • a and B are independently selected from the group: Be, Mg, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Y, Zr, Nb, Mo, Hf, Ta, W, La, Ce , Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and / or Lu;
  • (VIII) a catalyst comprising Ni, Co, Fe, Cr, Mn, Zn, Al, Rh, Ru, Pt and / or Pd; and or
  • reaction products includes the catalyst phases present under reaction conditions.
  • the reactor can be modular.
  • a module may include, for example, a heating level, an insulation level, the electrical contact and the corresponding further insulation materials and thermal insulation materials.
  • the individual heating elements 110, 111, 112, 113 are operated with a respective different heating power.
  • the reaction temperature in the reactor is at least in places> 700 ° C to ⁇ 1300 ° C. More preferred ranges are> 800 ° C to ⁇ 1200 ° C and> 900 ° C to ⁇ 1100 ° C.
  • the average (mean) contact time of the fluid to a heating element 110, 111, 112, 113 may be, for example,> 0.01 seconds to ⁇ 1 second and / or the average contact time of the fluid to an intermediate level 110, 111, 112, 113 may be, for example > 0.001 seconds to ⁇ 5 seconds.
  • Preferred contact times are> 0.005 to ⁇ 1 second, more preferably> 0.01 to ⁇ 0.9 seconds.
  • the reaction can be carried out at a pressure of> 1 bar to ⁇ 200 bar.
  • the pressure is> 2 bar to ⁇ 50 bar, more preferably> 10 bar to ⁇ 30 bar.
  • the H 2 / CO ratio changes from 1: 1 to 2: 1 when changing from C0 2 reforming to POX. Modifications by adding H 2 0 or C0 2 to the SMR are also possible. When changing from Dry Reforming to POX, however, the H 2 / CO ratio changes from 1: 1 to 2: 1.
  • the main target product may be CO or H 2 .
  • the characteristic value Sl has fallen below and / or the characteristic value S2 has been exceeded.
  • the endothermic operation that is, steam reforming or dry reforming, wherein in addition C0 2 is used as Cl source, which is reflected in a saving of methane, preferred.
  • C0 2 is used as Cl source
  • two moles of CO and two moles of H 2 are obtained per mole of methane.
  • the educt ratio of C0 2 / CH 4 is> 1.25.
  • the C0 2 present in the product gas is separated off in subsequent process steps and recycled to the reactor.
  • the mode of operation is changed over from the endothermic operation to the exothermic operation.
  • methane is fed with 02 to the reactor.
  • C0 2 can be further added during the switching phase and used as a kind of inert component until the POX reaction is stabilized and a new stationary state is reached.
  • the separated in the following steps C0 2 can be temporarily stored in order to start the endothermic reaction used as starting material.
  • the reactant streams or the throughput of methane and oxygen are adjusted so that a constant amount of CO or H 2 amount is available for subsequent processes.
  • the target product is CO.
  • the characteristic value Sl has fallen below and / or the characteristic value S2 has been exceeded.
  • endothermic operation that is, performance of the rWGS reaction using C0 2 as the Cl source, is preferred.
  • one mole of CO and one mole of water will be contained per mole of CO 2 .
  • the educt ratio of H 2 / CO 2 is> 1.25.
  • the C0 2 present in the product gas is separated off in subsequent process steps and recycled to the reactor.
  • the Characteristic value S 1 is exceeded and / or the characteristic value S2 is exceeded, the mode of operation is changed over from the endothermic operation to the exothermic operation.
  • methane is fed with 0 2 to the reactor.
  • C0 2 can be further added during the switching phase and used as a kind of inert component until the POX reaction is stabilized and a new stationary state is reached.
  • Part of the hydrogen produced during POX operation can be cached and used to operate the rWGS reaction.
  • the reactant streams or the throughput of methane and oxygen are adjusted in such a way that a constant amount of CO is available for subsequent processes.
  • the saving of methane in carrying out the electrically heated C0 2 reforming which uses C0 2 as Cl source, is weighed against the cost of electric heating.
  • the switching to the exothermic mode of operation takes place in order to react on soot formation during the endothermic operation.
  • the 0 2 operation can also be used to regenerate passivation layers within the reactor.
  • the electrical heating elements can be used in the region of the reactor inlet for the starting process.
  • a rapid heating of the reactant stream is possible, which reduces coking when carrying out the endothermic reforming reactions and, when carrying out the POX, allows a locally defined ignition of the reaction and thus enables safe reactor operation.
  • the present invention relates to a control unit which is set up for the control of the method according to the invention.
  • This control unit can also be distributed to a plurality of modules which communicate with one another or can then comprise these modules.
  • the controller may include a volatile and / or non-volatile memory containing machine-executable instructions associated with the method of the invention. In particular, these may be machine-executable instructions for detecting the threshold values, for comparing the threshold values with the currently prevailing conditions and for controlling control valves and compressors for gaseous reactants.

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Abstract

L'invention concerne un procédé de production de gaz de synthèse en fonctionnement alterné entre deux types de fonctionnement. Ce procédé comprend les étapes suivantes : préparation d'un réacteur à écoulement, réaction endothermique entre du dioxyde de carbone et des hydrocarbures, de l'eau et/ou de l'hydrogène dans le réacteur à écoulement, le produit formé étant au moins du monoxyde de carbone, un chauffage électrique au moyen d'un ou de plusieurs élément(s) de chauffage (110, 111, 112, 113) étant réalisé ; et simultanément réaction exothermique entre des hydrocarbures, du monoxyde de carbone et/ou de l'hydrogène en tant matières de départ dans le réacteur à écoulement. La réaction exothermique libère une quantité de chaleur Q1, le chauffage électrique du réacteur libère une quantité de chaleur Q2 et la réaction exothermique ainsi que le chauffage électrique du réacteur sont réalisés de manière que la somme de Q1 et Q2 est supérieure ou égale à la quantité de chaleur Q3 qui est requise pour atteindre un rendement équilibré Y de la réaction endothermique ≥ à 90%.
EP13708492.7A 2012-03-13 2013-03-12 Procédé pour produire du co et/ou h2 en fonctionnement alterné entre deux types de fonctionnement Withdrawn EP2825502A1 (fr)

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US20150129805A1 (en) 2015-05-14
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AU2013231342A1 (en) 2014-10-16
WO2013135707A1 (fr) 2013-09-19
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CN104169210A (zh) 2014-11-26
HK1204316A1 (en) 2015-11-13
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