WO2025190857A1 - Process for converting chemical compounds by using a membrane reactor - Google Patents

Process for converting chemical compounds by using a membrane reactor

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Publication number
WO2025190857A1
WO2025190857A1 PCT/EP2025/056449 EP2025056449W WO2025190857A1 WO 2025190857 A1 WO2025190857 A1 WO 2025190857A1 EP 2025056449 W EP2025056449 W EP 2025056449W WO 2025190857 A1 WO2025190857 A1 WO 2025190857A1
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WIPO (PCT)
Prior art keywords
membrane
chemical compounds
catalyst
reactor
hydrogen
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PCT/EP2025/056449
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French (fr)
Inventor
Stephan Schunk
Piyush Ingale
Ivana JEVTOVIKJ
Sebastian Weber
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BASF SE
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BASF SE
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Publication of WO2025190857A1 publication Critical patent/WO2025190857A1/en
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen; Reversible storage of hydrogen
    • C01B3/02—Production of hydrogen; Production of gaseous mixtures containing hydrogen
    • C01B3/04—Production of hydrogen; Production of gaseous mixtures containing hydrogen by decomposition of inorganic compounds
    • C01B3/047—Decomposition of ammonia
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/02—Inorganic material
    • B01D71/022—Metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/02—Inorganic material
    • B01D71/024—Oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/02—Inorganic material
    • B01D71/024—Oxides
    • B01D71/0271—Perovskites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/24—Stationary reactors without moving elements inside
    • B01J19/2475—Membrane reactors
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/008—Details of the reactor or of the particulate material; Processes to increase or to retard the rate of reaction
    • B01J8/009—Membranes, e.g. feeding or removing reactants or products to or from the catalyst bed through a membrane
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    • 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; Reversible storage of hydrogen
    • C01B3/02—Production of hydrogen; Production of gaseous mixtures containing hydrogen
    • C01B3/06—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen with inorganic reducing agents
    • C01B3/12—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen with inorganic reducing agents by reaction of water vapour with carbon monoxide
    • C01B3/16—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen with inorganic reducing agents by reaction of water vapour with carbon monoxide using catalysts
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    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen; Reversible storage of hydrogen
    • C01B3/02—Production of hydrogen; Production of gaseous mixtures containing hydrogen
    • C01B3/22—Production of hydrogen; Production of gaseous mixtures containing hydrogen by decomposition of gaseous or liquid organic compounds
    • C—CHEMISTRY; METALLURGY
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    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen; Reversible storage of hydrogen
    • C01B3/50—Separation of hydrogen or hydrogen-containing gases from gaseous mixtures, e.g. purification
    • C01B3/501—Separation of hydrogen or hydrogen-containing gases from gaseous mixtures, e.g. purification by diffusion
    • C01B3/503—Separation of hydrogen or hydrogen-containing gases from gaseous mixtures, e.g. purification by diffusion characterised by membranes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
    • C07C1/12—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon dioxide with hydrogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
    • C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
    • C07C5/333—Catalytic processes
    • C07C5/3335—Catalytic processes with metals
    • C07C5/3337—Catalytic processes with metals of the platinum group
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2311/00—Details relating to membrane separation process operations and control
    • B01D2311/26—Further operations combined with membrane separation processes
    • B01D2311/263—Chemical reaction
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2311/00—Details relating to membrane separation process operations and control
    • B01D2311/26—Further operations combined with membrane separation processes
    • B01D2311/2696—Catalytic reactions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2313/00—Details relating to membrane modules or apparatus
    • B01D2313/42—Catalysts within the flow path
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/10—Catalysts being present on the surface of the membrane or in the pores
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/02—Inorganic material
    • B01D71/022—Metals
    • B01D71/0223—Group 8, 9 or 10 metals
    • B01D71/02231—Palladium
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    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0266—Processes for making hydrogen or synthesis gas containing a decomposition step
    • C01B2203/0277—Processes for making hydrogen or synthesis gas containing a decomposition step containing a catalytic decomposition step
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    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0405—Purification by membrane separation
    • C01B2203/041—In-situ membrane purification during hydrogen production
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
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    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/06—Integration with other chemical processes
    • C01B2203/061—Methanol production
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    • 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
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    • C01B2203/06—Integration with other chemical processes
    • C01B2203/063—Refinery processes
    • C01B2203/065—Refinery processes using hydrotreating, e.g. hydrogenation, hydrodesulfurisation
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    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/08—Methods of heating or cooling
    • C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
    • C01B2203/085—Methods of heating the process for making hydrogen or synthesis gas by electric heating
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
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    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1005—Arrangement or shape of catalyst
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    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1005—Arrangement or shape of catalyst
    • C01B2203/1011—Packed bed of catalytic structures, e.g. particles, packing elements
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    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1005—Arrangement or shape of catalyst
    • C01B2203/1035—Catalyst coated on equipment surfaces, e.g. reactor walls
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    • C01B2203/1041—Composition of the catalyst
    • C01B2203/1082—Composition of support materials
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    • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1205—Composition of the feed
    • C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
    • C—CHEMISTRY; METALLURGY
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    • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1205—Composition of the feed
    • C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
    • C01B2203/1217—Alcohols
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    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1205—Composition of the feed
    • C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
    • C01B2203/1235—Hydrocarbons
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    • C01B2203/80—Aspect of integrated processes for the production of hydrogen or synthesis gas not covered by groups C01B2203/02 - C01B2203/1695
    • C01B2203/82—Several process steps of C01B2203/02 - C01B2203/08 integrated into a single apparatus

Definitions

  • the present invention relates to a process for converting chemical compounds by using a membrane reactor whereby the process is based on the coupling of two different reaction processes which are conducted in different reaction areas which are separated by a hydrogen permeable membrane.
  • Example is given the publication by Verves et al. which discloses the use of a PdAg-membrane for the dehydrogenation of propane to propene (see Int. Journal of Hydrogen Energy Vol. 50 Part A (2024) p. 409 - 419; Sciencedirect.com under https://doi.Org/10.1016/j.ijhydene.2023.06.202).
  • a publication of Binazadeh et al. covers the use of membrane reactors to produce hydrogen via membrane separation (see Int. J. of hydrogen energy 48 (2023) p. 39225 - 39253). Aspects of the publications are the use of different membrane materials as well as different types of membrane reactors.
  • Sattler et al. have published a study on the dehydrogenation reaction of ethane by using a membrane reactor and compared results to traditional fixed bed reactor technology by simulating different conversions degrees based on the use of different gas compositions (see Energy Environ. Sci., 2022, 15, 2120-2129).
  • WO 2018/13097 Al discloses a process for alkane dehydrogenation in a membrane reactor in which an alkane dehydrogenation catalyst is coupled to a hydrogen permeable polysiloxane-silica ceramic membrane.
  • the dehydrogenation process is performed at a temperature of 350 to 500 ° C and the alkane selectivity is in the range of 85% or above.
  • US 2012/0190904 Al discloses a method in which a hydrocarbon containing feed is dehydrogenated in the presence of steam within a traditional reactor whereby the resulting product feed is passed through a membrane separator which is arranged downstream of the dehydrogenation reactor.
  • US 11,465,114 B2 discloses a membrane reactor which is used for decomposition of ammonia whereby the dehydrogenation catalyst includes ruthenium as an active component.
  • the membrane reactor comprises a hydrogen selective metal membrane whereby hydrogen is transported through the membrane to the permeate side of the membrane. At the permeate side the hydrogen is removed by sweep gas and in a preferred embodiment the hydrogen sweep is fed to fuel cell which is arranged downstream of the membrane reactor.
  • US 11,090,628 B2 discloses a catalytic membrane reactor which is used for dehydrogenation reactions of ammonia and which comprises different layers of materials whereby a macro- porous base layer is covered by a mesoporous metal catalyst layer and the mesoporous metal catalyst layer is covered by a dense metallic film.
  • the membrane reactor is used for dehydrogenation of ammonia in order to produce hydrogen with a high purity.
  • Brune et al. discloses the use of membrane reactors for the oxidative and thermal dehydrogenation of propane using porous ceramic membranes (see Brune et al., Chemie Ingenieurtechnik, Wiley VCH-Verlag, Vol. 91, No. 5, p. 645 - 650). Brune et al. compares different concepts for the coupling of reactions which are conducted in connection with membrane reactors. This includes an example combining the thermal dehydrogenation of propane with the reverse water gas shift reaction using a porous gamma-alumina based membrane.
  • Hirota et al. disclosed the use of carbon membranes in a membrane reactor with the intention to use cycloalkanes as hydrogen storage molecules, (see Y. Hirota et al., Journal of Membrane Science 440 (2013) 134 - 139). Diffusion of different molecules through carbon membranes that have continuous micropores whereby the transport properties had been modified by post-treatment.
  • the structure is scalable and can also be arranged in modules which can be switched on or off depending on availability of the renewable power source.
  • modules can be organized in stacks.
  • tubular membranes and resulting membrane reactors such modules can be organized as tubular bundle reactors.
  • a process is preferred in which the membrane reactor is heated at a temperature in the range of 100 to 1000 ° C, preferably the membrane reactor is heated at a temperature in the range of 300 to 800 ° C, more preferably the membrane reactor is heated at a temperature in the range of 450 to 750 ° C; whereby the membrane reactor is operated at a pressure in the range of 0.1 to 100 bara, preferably in the range of 0.5 to 10 bara, more preferably in the range of 0.9 to 7 bara.
  • the unit bara or bar(a) denotes the absolute pressure.
  • the proton conducting ceramic material is preferably from the group of mixed ionic electronic conductors (MI EC) offering simultaneous conductivity for electrons and protons; more preferably the MI EC material is from the group of lanthanum tungstates La 6.x WO 12.5 (LWO) with 0.2 ⁇ x ⁇ 0.8, Mo-doped lanthanum tungstates La ⁇ Wj-yMOyOj ⁇ (LWO-Mo) with y ⁇ 0.4, SrTi x Fe, X O 3 (STF) with 0.5 ⁇ x ⁇ 1, Ba 0 5 Sr 05 Cu 0 oFe 02 0 3 5 (BSCF) and La 06 Sr 04 Cu 02 Fe 08 O 3.5 (LSCF).
  • Such membranes can additionally be surface-promoted with a promoting-catalyst, none limiting examples are given by platinum or nickel as promoting elements.
  • a further aspect of the invention is a method for producing the membrane unit according to the invention.
  • the supporting structure is made by use of an additive manufacturing process. All features, advantages and properties of the membrane unit described above is valid for the manufacturing process analogous and vice versa.
  • a dehydrogenation catalyst which is used on the retentate side which comprises at least one metal element on a carrier which preferably contains an oxide support or a refractory oxide whereby the at least one metal element is present in oxidic or metallic form or mixed form of metal and oxide.
  • the metal component comprises at least one noble metal from the group Ru, Rh, Pt, Pd, Au, Ag, Cu.
  • the catalyst comprises a mixture of metal element and noble metal whereby the metal element is selected from the group Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Zn, Y, Zr, Nb, Mo, Hf, Ta, W, Re, Os, Ir, Hg, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, B, Al, Si, Ga, Ge, I n, Sn and the noble metal is selected from the group Rh, Pt, Pd, Au, Ag, Cu whereby the metal elements are present in the metallic or oxidic form and mixture of metal and noble metal is present on a carrier which preferably contains an oxide support or a refractory oxide.
  • the metal element is selected from the group Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Sc, Ti, V, Cr, M
  • the dehydrogenation catalyst includes one or more promoting elements selected from the group of alkaline elements, earth alkaline elements, transition metal elements, rare-earth elements and/or main group elements whereby it is most preferred that the promoting elements include one or more elements from the group Sn, Zn, Ga, K, Mg, Ca, Co.
  • the noble metal content of the catalyst is in the range of 0.01 to 10 wt-% based on total amount of the catalyst, preferably the noble metal content is in the range of 0.1 to 5 wt-% based on total amount of the catalyst.
  • the content of metal elements in the range of 1 to 45 wt-%, preferably in the range from 2 to 30 wt-% whereby the ratio is given here in relation to the total amount of the catalyst.
  • the specification can refer to the oxidic form or the metallic form of the metal.
  • the hydrogen which is transported through the membrane in step (2) accounts for 5 to 95 vol.-% of the hydrogen formed in step (1) of the process, preferably the hydrogen which is transported through the membrane in step (2) accounts for 10 to 90 vol.-% of the hydrogen which is formed in step
  • step (2) accounts for 15 to 50 vol.-% of the hydrogen which is formed in step (1).
  • the process is characterized in that a hydrogenation catalyst used at the permeate side which comprises at least one metal element on a carrier which preferably contains an oxide support or a refractory oxide whereby the at least one metal element is present in oxidic or metallic form or mixed form of metal and oxide.
  • a hydrogenation catalyst used at the permeate side which comprises at least one metal element on a carrier which preferably contains an oxide support or a refractory oxide whereby the at least one metal element is present in oxidic or metallic form or mixed form of metal and oxide.
  • the catalyst comprises at least one metal element from the group of Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, N b, Mo, Ru, Rh, Pd, Ag, Cd, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, Al, Si, P, Ga, Ge, As, In, Sn, Sb, Sr, Mg, Ba, Ca.
  • the catalyst comprises one or more special metal elements which are selected from the group of Ce, Cu, Zn, Al, Fe, Cr, Co, I n, M n, Ni, Zr, Si, Sr, Mg, Ba, Ca. Even more preferably the catalyst comprises an active metal element which is selected from Pt, Pd, Au, Rh, Ru, Cu, Ni, Re, Co, Fe, Mo.
  • the catalyst comprises one or more special metal elements selected from the group Ce, Cu, Zn, Al, Fe, Cr, Co, In, Mn, Ni, Zr, Si, Sr, Mg, Ba, Ca in the presence of one or more active metal elements which are selected from the group of Pt, Pd, Au, Rh, Ru, Cu, Ni, Re, Co, Fe, Mo. More preferably the combination of special metal elements and active metal elements described here is in the presence of one or more promoting elements which are selected from the group of alkaline elements, earth alkaline elements, transition metal elements, rare-earth elements and/or main group elements.
  • the metal content is in the range of 0.01 to 50 wt.% based on the total amount of catalyst which is given by the sum of metal and carrier, preferably the metal content in the range of 0.3 to 30 wt-%, more preferably 0.5 to 10 wt.% based on the sum of metal and carrier.
  • the metals within the catalyst material can be either present in the elemental form or in the oxidic form. Depending on the form of the catalyst, the specification of the ratios can refer to the oxidic form or the metallic form of the metal.
  • the chemical compounds are supplied in the presence of dilution fluid which comprises inert gas or inert gas in the presence of side feed, whereby the volume of chemical compounds to total fluid given by sum of dilution feed and chemical compounds is in the range from 5 to 90 vol.-%, preferably in the range from 10 to 80 vol.-%, preferably the amount of side feed is in the range of 0.05 to 5 vol.-%, more preferably the amount of side feed is in the range from 0.1 to 4 vol.%.
  • a preferred process set-up comprises a separation unit which is arranged downstream of the retentate side of the membrane reactor whereby product fluid stream obtained under step (1) is fed to the separation unit in which a separation is carried out leading to product stream, chemical compounds of the starting compounds and hydrogen, preferably the part which contain the chemical compounds of the starting material is fed back to step (2) of the process.
  • the process includes a step in which the material the catalyst is subjected to a regeneration treatment, preferably the regeneration treatment in the presence of an oxygen or water or hydrogen containing feed in combination with a thermal regeneration at a temperature which is > 50° C than the operation temperature under step (1) to (3), preferably the thermal regeneration is at a temperature > 100° C than the operation temperature under step (1) to (3).
  • a regeneration treatment preferably the regeneration treatment in the presence of an oxygen or water or hydrogen containing feed in combination with a thermal regeneration at a temperature which is > 50° C than the operation temperature under step (1) to (3), preferably the thermal regeneration is at a temperature > 100° C than the operation temperature under step (1) to (3).
  • the process set-up comprises a fuel cell which is arranged downstream of the retentate side of the membrane reactors whereby the product fluid is fed to the fuel cell in which hydrogen is removed; preferably a separation unit is also present in the set-up which is arranged downstream of the fuel cell whereby the product stream is separated from remaining fluid; more preferably the remaining fluid which contains chemical molecules of the starting material under step (1) is fed back to process step (1).
  • the present invention relates to the use of a process for converting chemical compounds according to one of the embodiments which are described within the description whereby basic chemicals are produced on the retentate side which are selected from the group ethene, propene, butenes, butadiene, iso-butene and/or mixtures thereof.
  • the present invention relates to a process control unit which is used to conduct the process according to the invention which is described herein whereby the set-up comprises one or more sensor elements which are arranged on the downstream side of the membrane reactor and which are used to monitor and control the composition of the product fluid streams whereby the control of the regeneration process is based on the result of the sensor measurement which is carried out on the product fluid stream.
  • the process according to the invention is combined with a process for the conversion of the olefins to polymers or synthesis gas to chemical molecules.
  • the olefins and the synthesis gas which are obtained from a membrane process according to the embodiments are converted to polymers and the synthesis gas is converted to chemical molecules.
  • the process according to the invention is preferably followed by a separation step.
  • the process according to the invention relates to the conductance of a dehydrogenation reaction in a membrane reactor whereby a membrane reactor must be provided as a prerequisite. As further prerequisite a first and a second fluid stream must be provided as educt fluid streams which are different in their composition.
  • the process according to the invention relates to a coupling of two reaction processes which comprise a dehydrogenation process and a simultaneous removal of the formed hydrogen and the utilization of the formed hydrogen in a hydrogen consuming reaction process. Therefore, the process according to the invention comprises three different steps which are given by a step (1) in the form of dehydrogenation reaction, a step (2) in the form of a separation of hydrogen via a membrane process, and a step (3) in the form of hydrogen reaction process.
  • the process relates to the dehydrogenation of chemical molecules which are listed in Table 1.
  • the process according to the invention is associated with a synergistic effect which is given by the coupling and utilization of hydrogen in the reaction process which is providing an energy efficient way of the process since it is an enablement to convert carbon dioxide containing feeds versus an emission into the atmosphere.
  • emission of greenhouse gas is prevented by utilization of carbon dioxide in the educt feed under the step (3) and at the same time the provision of the two reactions that the thermal energy which is required under step (1) can largely be preserved and temper the process under step (3).
  • the different process steps are adjusted with each other in terms of temperature level. Therefore, it is not necessary to heat up fluids in separate reactions.
  • the membrane reactor is heated by electrical power which is supplied by a renewable energy source.
  • Dehydrogenation catalysts can have all types and forms that are known to person who is skilled in the art.
  • Dehydrogenation catalysts are provided as solid state catalysts which are given in the form of powders, shaped bodies, coatings, or films.
  • H 2 transport mechanisms in membranes which are given by diffusion, molecular sieving or solution-diffusion. Solutiondiffusion which occurs in dense films is associated with the dissociation of hydrogen molecules into hydrogen atoms or protons and electrons.
  • the hydrogen atoms or protons or protons and electrons are transported through the membrane and finally recombine at the membrane-permeate interface to produce molecular hydrogen.
  • the transport mechanism is determined by the material that forms the membrane.
  • dense membranes the hydrogen transport is controlled by solid state-diffusion.
  • Dense membranes which either comprise metallic or ceramic materials have lower permeability over porous membranes. The use of dense membranes in the process according to the invention is favored due to the fact that their hydrogen selectivity is higher over porous membranes.
  • the catalyst material in contact with the permeate side is a solid-state catalyst which can have different shapes and forms as in the case of the dehydrogenation catalyst.
  • a 5 wt.% Ru/ y -AI 2 O 3 catalyst was prepared via incipient wetness impregnation (Cat. 2).
  • An aqueous solution of Tri-nitrato-nitrosyl- ruthenium-(ll) was impregnated on a Puralox TM100/150 support.
  • Puralox TM100/150 is a y -AI 2 O 3 which is produced by SASOL.
  • the catalyst was dried at 120 ° C for 6 h and subsequently calcined at 400 ° C for 4 h under clean dry air.
  • 13 mm tablets with a catalyst mass of 0.5 g were prepared by pressing.
  • Cat. 1 Based on the horizontal orientation of the membrane surface the Cat. 1 could be loaded as self-supporting powder on the upper side of the membrane plate whereas Cat. 2 was positioned in proximity below the bottom side of the membrane.
  • the hydrogenation catalyst (Cat. 2) was attached underneath the membrane as described by the membrane configurations which are given in Table 1 (hereafter called the simple catalyst configuration).
  • dehydrogenation catalyst (Cat. 1) was positioned on the upper side and hydrogenation catalyst (Cat. 2) was positioned on the bottom side as depicted in Table 2.
  • the material was converted into tablets by using a tablet press. Several tablets were prepared, each tablet having a weight of 0.5 g and a diameter of 13 mm.
  • the experiments were characterized by good reproducibility due to the good mixing condition within the membrane reactor.
  • a characteristic feature is the central fluid inlet and several tubes around the central fluid inlet.
  • the Pd membrane was fixed in the membrane reactor and the sealed membrane reactor was inserted in the testing apparatus which was subjected to the following testing conditions:
  • Table 1 Summary of the hydrogen permeation experiments performed for the 75 pm thick Pd foil membrane. Inlet gas flow of 80 mL min -1 of 10 vol.% H 2 , 10 vol.% Ar in N 2 on the retentate side. Total pressure of 2 bara on retentate and permeate sides. On the permeate side the Ru/AI 2 O 3 catalysts was used in 13 mm tablets of each 0.5 g.
  • Example 3.4 and Example 6.4 show selectivities in the conversion of CO 2 to CO of about 100 %.
  • the same selectivity trends are also observed for Experiments 7.1 to 10.3 using a diluted CO 2 feed with a smaller ration of CO 2 vs. permeated H2 leading to generally higher conversion of CO 2 .
  • Example 2.3 compared with Example 3.4
  • Example 8.3 compared with Example 9.3 and Example 10.3
  • the increase in H 2 conversion on the permeate side increases the amount of permeated H 2 highlighting the control of H 2 permeation by the CO 2 hydrogenation reaction on the permeate side, e.g. as shown comparing Example 8.3 and Example 10.3.
  • the 75 pm thick Pd foil was used as a membrane as in the examples above which il lustrate the hydrogen permeation effect in combination with the reaction step (3).
  • the flow rate was varied between 80 and 241 mL min -1 with a gas composition of 90 vol.% CO 2 and 10 vol.% N 2 and total pressure of 2 bara.
  • no (C2, C4) or 0.5 g of the Ru/AI 2 O 3 hydrogenation catalyst (C3, 05) was used. Without catalyst on the permeate side the CO 2 /N 2 mixture acts as a sweep gas and does not react.
  • the reaction temperature was varied from 450 to 550 ° C.
  • the data which were obtained for the membrane configuration MC6-C2 as comparative example is based on the state of the art for a sweep gas method in order to generate a concentration gradient as driving force for the hydrogen transportation over the membrane.
  • a sweep gas method in order to generate a concentration gradient as driving force for the hydrogen transportation over the membrane.
  • An increase in conversion was 3.2 % which means that the relative increase due to the integration of the membrane was in the range of 40 to 50% to the comparative examples were the catalyst activity was compared to the activity of a membrane reactor with a sweep gas present on the permeate side.
  • Example 14.3 example according to the invention
  • Example 13.3 comparative example at 510° C
  • the coupled process conditions of dehydrogenation on the retentate side with the syngas production on the permeate side showed a beneficial effect on the conversion increase.
  • Fig. l.a shows a schematic illustration of process according to the invention with step (1): dehydrogenation of A to B, process step (2) removing H 2 over selective membrane, and process step (3) with reaction C + H 2 to D.
  • Fig. 2 shows a schematic illustration of an embodiment of the process in which the catalysts are immobilized on both sides of the membrane, i.e. on the retentate side (34) and on the permeate side (36).
  • Fig. 3 shows a schematic illustration of an embodiment of the process according to the invention which has a gas separation unit (51) downstream of the retention side of the membrane chamber.
  • Fig. 4 shows a schematic illustration of an embodiment of the process according to invention whereby the configuration comprises a recycle of chemical molecules to the process under step (1) and means for catalyst regeneration.
  • Fig. 5. a shows a schematic depiction of a membrane reactor whereby a flat catalyst holders or supporting structures are attached to each side of the membrane surfaces.
  • the supporting structure serves to take up particulate catalyst material whereby the upper part is filled with catalyst particles.
  • Fig. 5.b shows a schematic depiction of a membrane reactor which is equipped with a membrane holder for particulate catalyst on the retentate side of the membrane and a catalyst coating on the permeate side of the membrane whereby the fluid flow is directed in a co-current flow through both chambers.
  • Fig. 5.c shows a schematic depiction of a membrane reactor which is equipped with packed beds of catalyst material on each side of the membrane whereby the catalyst beds are fixed with pressing elements.
  • Fig. 6 shows the activity in terms of ethane conversion for the experiments MC5 - Cl to MC7 - C3 summarized in Table 3. The ethane conversion is compared with the blind activity of only the Pd-foil and the calculated equilibrium conversion of ethane.
  • particulate hydrogenation catalyst / reforming catalyst 26 either fixed bed or fluidized bed of hydrogenation catalyst
  • PCMEP PCMEP - proton conducting ceramic material which is used as electrochemical proton pump

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Abstract

The invention relates to a process for converting chemical compounds by using a membrane reactor or an integrated membrane reactor which is equipped with a hydrogen permeable membrane whereby the process is characterized by the following steps: (1) dehydrogenating chemical compounds on the retentate side of the membrane reactor; (2) transferring part of the formed H2 from the retentate side to permeate side; and (3) hydrogenating chemical compounds on the permeate side of the membrane reactor. The reaction enthalpy balance of step (1) and step (3) is focused on endothermic reactions. Embodiments of the process according to the invention in particularly preferred embodiments are provided in the dependent claims 2 to 15. A synergistic effect is achieved by coupling of two different reactions which are conducted in different reactions spaces whereby the reaction spaces are separated by a hydrogen permeable membrane. Thus, the process according to invention provides a very flexible process that can be operated within a large operating window means to save energy and preferably powered by renewable energy and processing of residues.

Description

Process for converting chemical compounds by using a membrane reactor
The present invention relates to a process for converting chemical compounds by using a membrane reactor whereby the process is based on the coupling of two different reaction processes which are conducted in different reaction areas which are separated by a hydrogen permeable membrane.
Membrane based processes have gained a considerable attention over the past decades and are established in many different areas of process and separation technology. The particular importance can be seen from the fact that there are large numbers of publications, both in specialist literature and in patent literature. There are also separate specialized journals for the field of membrane science and application. The following part provides an overview of relevant publications in the field of membrane reactor technology.
Example is given the publication by Verves et al. which discloses the use of a PdAg-membrane for the dehydrogenation of propane to propene (see Int. Journal of Hydrogen Energy Vol. 50 Part A (2024) p. 409 - 419; Sciencedirect.com under https://doi.Org/10.1016/j.ijhydene.2023.06.202).
A publication of Binazadeh et al. covers the use of membrane reactors to produce hydrogen via membrane separation (see Int. J. of hydrogen energy 48 (2023) p. 39225 - 39253). Aspects of the publications are the use of different membrane materials as well as different types of membrane reactors.
A publication of Mamivand et al. provides an overview of the use of membrane reactor technology in industrial hydrogen producing reactions (see J. of Ind. And Engineering Chem. 104 (2021) p. 212 - 230. Different processes and different reactions are covered.
Sattler et al. have published a study on the dehydrogenation reaction of ethane by using a membrane reactor and compared results to traditional fixed bed reactor technology by simulating different conversions degrees based on the use of different gas compositions (see Energy Environ. Sci., 2022, 15, 2120-2129).
Shelepova et al. have published an article on the mathematical modeling of the propane dehydrogenation process in the catalytic membrane reactor (Chem. Eng. J. 176 - 177 (2011) p. 151 - 157). One way to remove the hydrogen on the permeate side is given by the addition of oxygen on the sweep side which is converted to water.
Deibert et al. have published an article reviewing potential applications for mixed ionic electronic conducting dense ceramic membranes (J. Mem. Sci. 54 (2017) p- 79-97). They also highlight the different types of ion conducting membranes including proton conducting ceramics, mixed ionic conducting ceramics, mixed ionic electronic conducting ceramics. Ceramics without significant electron conduction (proton conducting ceramics, mixed ionic conducting ceramics) required an external circuit (electrochemical potential) for a continuous ion current and are thus also called proton pump membranes. Mixed ionic electronic membranes (MIEC) do not require an external circuit for a continuous ion current, a chemical potential (partial pressure difference) on both sides of the membrane is required.
Other publications which pick up the use of membrane reactors in connection with the performance of dehydrogenation reactions are given by Yu et al. or by Meng et al. Yu et al examines the conversion of ethylbenzene to styrene (see Separation and Purification Technology 78 (2011) p. 249 - 252). Meng et al. covers the dehydrogenation of methylcyclohexane to toluene (see AIChE Journal Vol 61 No. 5 (2015) p 1628 - 1638).
WO 2018/13097 Al discloses a process for alkane dehydrogenation in a membrane reactor in which an alkane dehydrogenation catalyst is coupled to a hydrogen permeable polysiloxane-silica ceramic membrane. The dehydrogenation process is performed at a temperature of 350 to 500 ° C and the alkane selectivity is in the range of 85% or above.
US 2012/0190904 Al discloses a method in which a hydrocarbon containing feed is dehydrogenated in the presence of steam within a traditional reactor whereby the resulting product feed is passed through a membrane separator which is arranged downstream of the dehydrogenation reactor.
US 11,465,114 B2 discloses a membrane reactor which is used for decomposition of ammonia whereby the dehydrogenation catalyst includes ruthenium as an active component. The membrane reactor comprises a hydrogen selective metal membrane whereby hydrogen is transported through the membrane to the permeate side of the membrane. At the permeate side the hydrogen is removed by sweep gas and in a preferred embodiment the hydrogen sweep is fed to fuel cell which is arranged downstream of the membrane reactor.
US 11,090,628 B2 discloses a catalytic membrane reactor which is used for dehydrogenation reactions of ammonia and which comprises different layers of materials whereby a macro- porous base layer is covered by a mesoporous metal catalyst layer and the mesoporous metal catalyst layer is covered by a dense metallic film. In a preferred embodiment the membrane reactor is used for dehydrogenation of ammonia in order to produce hydrogen with a high purity.
A publication by Brune et al. which discloses the use of membrane reactors for the oxidative and thermal dehydrogenation of propane using porous ceramic membranes (see Brune et al., Chemie Ingenieur Technik, Wiley VCH-Verlag, Vol. 91, No. 5, p. 645 - 650). Brune et al. compares different concepts for the coupling of reactions which are conducted in connection with membrane reactors. This includes an example combining the thermal dehydrogenation of propane with the reverse water gas shift reaction using a porous gamma-alumina based membrane.
Abo-Ghander et al. had used a modelling approach to illustrate the behavior of membrane reactor in which the dehydrogenation of ethylbenzene to styrene was coupled with hydrogenation of nitrobenzene to aniline (see N. S. Abo-Ghander et al., Chemical Engineering Science 63 (2008) 1817 - 1826). This means that the membrane reactor was used to combine an endothermic reaction on the permeate side with an exothermic reaction on the retentate side.
Hirota et al. disclosed the use of carbon membranes in a membrane reactor with the intention to use cycloalkanes as hydrogen storage molecules, (see Y. Hirota et al., Journal of Membrane Science 440 (2013) 134 - 139). Diffusion of different molecules through carbon membranes that have continuous micropores whereby the transport properties had been modified by post-treatment.
Itoh et al. disclosed a carbon containing membrane reactor (see N. Itoh et al., Catalysis Today 56 (2000) 103 - 111). The disclosure relates to the transport properties of molecules through porous carbon membranes due to size exclusion and molecular size.
EP 3 265 437 Bl discloses a dehydrogenation process which is performed in a multi-stage process with a first stage which consists of a dehydrogenation reaction in a dehydrogenation reactor and with a second stage which consists of membrane separation which is performed downstream of the first stage. In a preferred embodiment the dehydrogenation process is carried out in the presence of steam.
One of the objectives which had to be solved by the present invention was to provide a process for the production of olefins by an energy saving way which provides an alternative over the state of the art. Another objective was to provide a process which contributes to reduction of greenhouse gas emissions.
The objective mentioned here and many other objectives which are not mentioned here were solved by the provision of a process for converting different chemical compounds by using a membrane reactor which is equipped with a hydrogen permeable membrane whereby the process is characterized by the following steps:
(1) supplying a first educt fluid stream to the retentate side of the membrane reactor and dehydrogenating chemical compounds which are contained therein;
(2) transferring part of the formed hydrogen from the retentate side to permeate side; and
(3) supplying a second educt fluid stream to the permeate side of the membrane reactor and hydrogenating chemical compounds which are contained therein; whereby the process is in such a way that step (1) and step (3) comprise endothermic reactions; preferably step (1) consists of an endothermic reaction and step (3) includes an endothermic reaction, more preferably step (1) consists of an endothermic reaction and step (3) includes an endothermic reaction and the total reaction enthalpy in step (3) is A RH > 0 whereby the total reaction enthalpy is given in kJ/mol; whereby the hydrogen permeable membrane contains a dense film which comprises a metallic or a ceramic material, or at least a metallic and a ceramic material or a proton conducting ceramic material or a proton conducting ceramic material which is used as electrochemical proton pump and powered by an electric supply.
The coupling of two endothermic reactions within the membrane reactor according to the invention offers the user an operation in a wide process window. In addition to that the coupling of endothermic reactions is possible via heating and thus better to handle over coupling endothermic dehydrogenation with an exothermic reaction. Coupling with an exothermic reaction may require cooling and is limited to a small process window.
In a preferred embodiment of the process the chemical compounds which are being contained in the first educt fluid stream under step (1) are selected from the group of alkanes, alcohols, aldehydes, ammonia, more preferably the chemical compounds are selected from the group of ethane, propane, butane, iso-butane, methanol, ethanol, propanol, butanol, pentanol, aldehydes, more preferably the chemical compounds are selected from the group of ethane, propane, butane, iso-butane. Preferably, valuable products are produced. Preferably from short-chain alkanes whereby short-chain alkanes means a hydrocarbon compound with C2 to C4 carbon atoms.
Preferably the chemical compounds which are being contained in the first educt fluid stream under step (1) contains a hydrocarbon which is derived from a renewable source of energy, or which is derived from reprocessing waste material by a circular process, preferably waste material from polymeric waste which is obtainable by pyrolysis.
Alternatively, the chemical compounds which are being contained in the first educt fluid may be of biogenic origin. Technical requirements are such that the process can be carried out in small units in comparison to traditional reactors since there are special advantages of lower temperature and pressure.
It is preferred that the reaction being carried out under step (3) is selected from the group of CO2 hydrogenation to CO or mixtures of CO/H2, CO2 hydrogenation to CH3OH, CO2 hydrogenation to CH4, O2 hydrogenation to H2O, preferably the reaction carried out under step (3) is selected from the group CO2 hydrogenation to CO or mixtures of CO/H2, CO2 hydrogenation to CH3OH, CO2 hydrogenation to CH4, more preferably the reaction carried out under step (3) is selected from the group CO2 hydrogenation to CO or mixtures of CO/H2. Here the process offers the advantage of processing carbon dioxide containing waist gases and converting them into a valuable synthesis gas. The CO2 containing gases can come from different sources and origins. They may come from biogenic sources or fossil sources, or from direct air capture. Without restricting the invention in any way there are indications that addition of small amounts of oxygen or water can be beneficial, as an enhancer which reduces the tendency of coking of the catalyst. Small amounts are maybe less than 10 vol.% or preferably less than 5 vol.-% of O2 or H2O as co-feed. However, amount is so small that the process is predominantly characterized by endothermic reactions.
In a preferred embodiment of the process the performance characteristics of the catalyst on the retentate side is given by a space-time-yield - which is given in mol per m3 and per s i.e. [mol, rrr3, s’1] - in the range from 0.1 to 10 and the performance characteristics of the membrane is given by an area-time-yield - which is given in mol per m2 and per s i.e. [mol.m’ Ts’1] - in the range from 0.001 to 1.
Furthermore, it is preferred that the configuration of the membrane reactor is characterized by the ratio of membrane surface Amem to reactor volume Vreact which is in the range from 10 rrr1 to 10000 m’1, whereby the reactor volume Vreact is given by the sum of the volume of the reactor on the retentate side and the permeate side. Preferably the membrane reactor comprises two different chambers and the way as the catalyst is present in the chambers is in the form of a fluidized or moving catalyst bed, packed catalyst bed, packed particles bed in a holder, coating, impregnation, film growth on the membrane surface whereby the form of the catalyst may be identical in both chambers or different in chambers, preferably the catalyst is present in the form packed catalyst bed, packed particles bed in a holder, coating, impregnation, film growth on the membrane surface; in case that the catalyst is present in the form of packed particles in a holder then it is preferred that the holder is manufactured by 3D- pri nti ng process.
Preferably the membrane is planar. In particular, the membrane is flat. Though, in an embodiment the membrane can be curved, for example tubular, therefore formed as tube.
In a preferred embodiment of the process the heating of the membrane reactor is based on a) resistive heating, preferably using renewable energy via built-in heating elements in the reactor or the membrane or the reactor and the membrane; b) additionally heating with waste heat from the electrochemical proton pumps in the case of ceramic proton pump membranes. Providing the electrical heating in a membrane process according to the invention is much easier from a technical point of view in comparison to the operation of a traditional reactor system since the parts are small and the housing is very close to catalyst and membrane. Preferably, the electrical energy provided to operate the process according to the invention is generated via a renewable energy source such as solar power, wind power, hydroelectric power, bio-mass based energy. One reason is also that the structure is scalable and can also be arranged in modules which can be switched on or off depending on availability of the renewable power source. In the case of a flat membranes and resulting flat membrane reactors such modules can be organized in stacks. In the case of tubular membranes and resulting membrane reactors such modules can be organized as tubular bundle reactors.
A process is preferred in which the membrane reactor is heated at a temperature in the range of 100 to 1000 ° C, preferably the membrane reactor is heated at a temperature in the range of 300 to 800 ° C, more preferably the membrane reactor is heated at a temperature in the range of 450 to 750 ° C; whereby the membrane reactor is operated at a pressure in the range of 0.1 to 100 bara, preferably in the range of 0.5 to 10 bara, more preferably in the range of 0.9 to 7 bara. The unit bara or bar(a) denotes the absolute pressure.
The pressure difference between the retentate side and permeate side is either balanced or the pressure on the retentate side may be higher over the pressure on the permeate side. Higher pressure means that the transmembrane pressure difference is 0.1 bar or higher, preferably 0.5 bar or higher This creates the conditions that additionally promote hydrogen flow across the membrane.
Preferred embodiment of the invention foresees that the membrane comprises a metallic or a metallic and ceramic component, preferably the metallic component is present in its pure form or as a mixture with other metals, more preferably the metal comprises Pd, or mixtures of Pd with other metals, more preferably a mixture of Pd with Ag; the thickness of the membrane is in the range from 1 to 250 pm, preferably in the range from 5 to 100 pm. The membrane can be either supported with a ceramic or metallic carrier or without a carrier whereby the specification of the membrane thickness does not include the carrier material. Such carrier materials are typically porous and can be made from metals or refractory oxides with palladium being present as particles in interstitial voids.
I n an embodiment the membrane comprises a material or the membrane is made of a material which is selected from the group of hydrogen conducting metals, particularly Pd, or Pd- containing alloys like Pd-Ag or others, or ceramic supported Pd and Pd-alloys containing membranes or metallic supported Pd and Pd-alloys containing membranes.
Another preferred embodiment includes membranes from materials of the group of ceramic proton conductors: the proton conducting ceramic material is preferably from the group of mixed ionic electronic conductors (MI EC) offering simultaneous conductivity for electrons and protons; more preferably the MI EC material is from the group of lanthanum tungstates La6.xWO12.5 (LWO) with 0.2 < x <0.8, Mo-doped lanthanum tungstates La^Wj-yMOyOj^ (LWO-Mo) with y <0.4, SrTixFe, XO3 (STF) with 0.5 < x < 1, Ba0 5Sr05Cu0oFe0203 5 (BSCF) and La06Sr04Cu02Fe08O3.5 (LSCF). Such membranes can additionally be surface-promoted with a promoting-catalyst, none limiting examples are given by platinum or nickel as promoting elements.
Another preferred embodiment includes membranes from materials of the group of ceramic proton conductors used as electrochemical pump: Preferably the membrane comprises a ceramic material which is proton conducting, more preferably the proton conduction is increased by application of an external electrical circuit characterized as electron pumping, preferably the proton conducting ceramic material is from the group of proton conducting oxides including BaZrxCeyYzO3 (BZCY) with x+y+z=l or BaZrxYyO3 with x+y=l or SrZrxCeyYzO3 with x+y+z=l. Such membranes can additionally be surface-promoted with a promoting- catalyst, none limiting examples are given by platinum or nickel as promoting elements.
A further aspect of the invention is a method for producing the membrane unit according to the invention. The supporting structure is made by use of an additive manufacturing process. All features, advantages and properties of the membrane unit described above is valid for the manufacturing process analogous and vice versa.
It is preferred that a dehydrogenation catalyst which is used on the retentate side which comprises at least one metal element on a carrier which preferably contains an oxide support or a refractory oxide whereby the at least one metal element is present in oxidic or metallic form or mixed form of metal and oxide. I n a preferred embodiment the metal component comprises at least one noble metal from the group Ru, Rh, Pt, Pd, Au, Ag, Cu. In a more preferred embodiment, the catalyst comprises a mixture of metal element and noble metal whereby the metal element is selected from the group Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Zn, Y, Zr, Nb, Mo, Hf, Ta, W, Re, Os, Ir, Hg, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, B, Al, Si, Ga, Ge, I n, Sn and the noble metal is selected from the group Rh, Pt, Pd, Au, Ag, Cu whereby the metal elements are present in the metallic or oxidic form and mixture of metal and noble metal is present on a carrier which preferably contains an oxide support or a refractory oxide. It is preferred that the dehydrogenation catalyst includes one or more promoting elements selected from the group of alkaline elements, earth alkaline elements, transition metal elements, rare-earth elements and/or main group elements whereby it is most preferred that the promoting elements include one or more elements from the group Sn, Zn, Ga, K, Mg, Ca, Co.
It is preferred that the noble metal content of the catalyst is in the range of 0.01 to 10 wt-% based on total amount of the catalyst, preferably the noble metal content is in the range of 0.1 to 5 wt-% based on total amount of the catalyst. The content of metal elements in the range of 1 to 45 wt-%, preferably in the range from 2 to 30 wt-% whereby the ratio is given here in relation to the total amount of the catalyst. Depending on the form of the catalyst, the specification can refer to the oxidic form or the metallic form of the metal.
According to the process of the present invention it is preferred that the hydrogen which is transported through the membrane in step (2) accounts for 5 to 95 vol.-% of the hydrogen formed in step (1) of the process, preferably the hydrogen which is transported through the membrane in step (2) accounts for 10 to 90 vol.-% of the hydrogen which is formed in step
(1), even more preferably the hydrogen which is transported through the membrane in step
(2) accounts for 15 to 50 vol.-% of the hydrogen which is formed in step (1).
Preferably the process is characterized in that a hydrogenation catalyst used at the permeate side which comprises at least one metal element on a carrier which preferably contains an oxide support or a refractory oxide whereby the at least one metal element is present in oxidic or metallic form or mixed form of metal and oxide. I n a preferred embodiment the catalyst comprises at least one metal element from the group of Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, N b, Mo, Ru, Rh, Pd, Ag, Cd, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, Al, Si, P, Ga, Ge, As, In, Sn, Sb, Sr, Mg, Ba, Ca. More preferably the catalyst comprises one or more special metal elements which are selected from the group of Ce, Cu, Zn, Al, Fe, Cr, Co, I n, M n, Ni, Zr, Si, Sr, Mg, Ba, Ca. Even more preferably the catalyst comprises an active metal element which is selected from Pt, Pd, Au, Rh, Ru, Cu, Ni, Re, Co, Fe, Mo. Preferably the catalyst comprises one or more special metal elements selected from the group Ce, Cu, Zn, Al, Fe, Cr, Co, In, Mn, Ni, Zr, Si, Sr, Mg, Ba, Ca in the presence of one or more active metal elements which are selected from the group of Pt, Pd, Au, Rh, Ru, Cu, Ni, Re, Co, Fe, Mo. More preferably the combination of special metal elements and active metal elements described here is in the presence of one or more promoting elements which are selected from the group of alkaline elements, earth alkaline elements, transition metal elements, rare-earth elements and/or main group elements.
It is preferred that the metal content is in the range of 0.01 to 50 wt.% based on the total amount of catalyst which is given by the sum of metal and carrier, preferably the metal content in the range of 0.3 to 30 wt-%, more preferably 0.5 to 10 wt.% based on the sum of metal and carrier.
The metals within the catalyst material can be either present in the elemental form or in the oxidic form. Depending on the form of the catalyst, the specification of the ratios can refer to the oxidic form or the metallic form of the metal. In a preferred embodiment of the process the chemical compounds are supplied in the presence of dilution fluid which comprises inert gas or inert gas in the presence of side feed, whereby the volume of chemical compounds to total fluid given by sum of dilution feed and chemical compounds is in the range from 5 to 90 vol.-%, preferably in the range from 10 to 80 vol.-%, preferably the amount of side feed is in the range of 0.05 to 5 vol.-%, more preferably the amount of side feed is in the range from 0.1 to 4 vol.%.
Furthermore, a preferred process set-up comprises a separation unit which is arranged downstream of the retentate side of the membrane reactor whereby product fluid stream obtained under step (1) is fed to the separation unit in which a separation is carried out leading to product stream, chemical compounds of the starting compounds and hydrogen, preferably the part which contain the chemical compounds of the starting material is fed back to step (2) of the process.
In another preferred embodiment the process includes a step in which the material the catalyst is subjected to a regeneration treatment, preferably the regeneration treatment in the presence of an oxygen or water or hydrogen containing feed in combination with a thermal regeneration at a temperature which is > 50° C than the operation temperature under step (1) to (3), preferably the thermal regeneration is at a temperature > 100° C than the operation temperature under step (1) to (3).
In another embodiment the process set-up comprises a fuel cell which is arranged downstream of the retentate side of the membrane reactors whereby the product fluid is fed to the fuel cell in which hydrogen is removed; preferably a separation unit is also present in the set-up which is arranged downstream of the fuel cell whereby the product stream is separated from remaining fluid; more preferably the remaining fluid which contains chemical molecules of the starting material under step (1) is fed back to process step (1).
The present invention relates to the use of a process for converting chemical compounds according to one of the embodiments which are described within the description whereby basic chemicals are produced on the retentate side which are selected from the group ethene, propene, butenes, butadiene, iso-butene and/or mixtures thereof.
In another aspect the present invention relates to a process control unit which is used to conduct the process according to the invention which is described herein whereby the set-up comprises one or more sensor elements which are arranged on the downstream side of the membrane reactor and which are used to monitor and control the composition of the product fluid streams whereby the control of the regeneration process is based on the result of the sensor measurement which is carried out on the product fluid stream.
In a preferred embodiment the process according to the invention is combined with a process for the conversion of the olefins to polymers or synthesis gas to chemical molecules.
This means that the olefins and the synthesis gas which are obtained from a membrane process according to the embodiments are converted to polymers and the synthesis gas is converted to chemical molecules. In the case of further processing, it is also preferred that the process according to the invention is preferably followed by a separation step.
The membrane reactor technology offers several advantages over the traditional chemical production plants with respect to energy and scale. The membrane based process is easy to use and easy to be powered by electricity. Particularly suitable for such a combination with the production plants for the production of polymers from olefins or chemical compounds from synthesis gas. Thus, the membrane reactor based process provides a foundation for the future development of decentralized production units in chemical industries. Example is given by coastal production site with algae as biomass and wind power on the coast. Or the building of CO2 converting technology in the proximity of a plant for carbon dioxide direct air capture (DAC) technology. Smaller size and easy handling also enable a modular design and movable units.
Detailed description of the process according to the invention which is reflected in the embodiments which are listed in the claims. The process according to the invention relates to the conductance of a dehydrogenation reaction in a membrane reactor whereby a membrane reactor must be provided as a prerequisite. As further prerequisite a first and a second fluid stream must be provided as educt fluid streams which are different in their composition.
The process according to the invention relates to a coupling of two reaction processes which comprise a dehydrogenation process and a simultaneous removal of the formed hydrogen and the utilization of the formed hydrogen in a hydrogen consuming reaction process. Therefore, the process according to the invention comprises three different steps which are given by a step (1) in the form of dehydrogenation reaction, a step (2) in the form of a separation of hydrogen via a membrane process, and a step (3) in the form of hydrogen reaction process. In a preferred embodiment the process relates to the dehydrogenation of chemical molecules which are listed in Table 1.
The process according to the invention is associated with a synergistic effect which is given by the coupling and utilization of hydrogen in the reaction process which is providing an energy efficient way of the process since it is an enablement to convert carbon dioxide containing feeds versus an emission into the atmosphere. Thus, emission of greenhouse gas is prevented by utilization of carbon dioxide in the educt feed under the step (3) and at the same time the provision of the two reactions that the thermal energy which is required under step (1) can largely be preserved and temper the process under step (3). The different process steps are adjusted with each other in terms of temperature level. Therefore, it is not necessary to heat up fluids in separate reactions. Preferably the membrane reactor is heated by electrical power which is supplied by a renewable energy source.
The retentate side is in contact with a dehydrogenation catalyst or the retentate chamber is equipped with a dehydrogenation catalyst. Dehydrogenation catalysts can have all types and forms that are known to person who is skilled in the art. Dehydrogenation catalysts are provided as solid state catalysts which are given in the form of powders, shaped bodies, coatings, or films. With respect to the membrane it is noted that there are different H2 transport mechanisms in membranes which are given by diffusion, molecular sieving or solution-diffusion. Solutiondiffusion which occurs in dense films is associated with the dissociation of hydrogen molecules into hydrogen atoms or protons and electrons. The hydrogen atoms or protons or protons and electrons are transported through the membrane and finally recombine at the membrane-permeate interface to produce molecular hydrogen. The transport mechanism is determined by the material that forms the membrane. In dense membranes the hydrogen transport is controlled by solid state-diffusion. Dense membranes which either comprise metallic or ceramic materials have lower permeability over porous membranes. The use of dense membranes in the process according to the invention is favored due to the fact that their hydrogen selectivity is higher over porous membranes.
An alternative to permeation of hydrogen atoms in the form of protons through ceramic membranes is given by the permeation of protons through ceramic membranes which can additionally be stimulated or excited by an electrical voltage that is applied to the outer surface of certain ceramic membrane materials which can conduct protons and provide a significant increase the permeability compared to other dense membrane material.
To illustrate the caloric conditions of the process step (1), the data for selected reactions are given here:
In a preferred embodiment the reaction being carried out under step (3) is selected from the following group of chemical reactions:
The term endothermic reaction means that the enthalpy of the system increases, so that A RH is positive whereby the enthalpy is given in kJ/mol (kilojoules per mole). According to the invention the step (3) that A RH > 0, preferably step (3) has a A RH > 5 kJ/mol, more preferably step (3) has a A RH > 10 kJ/mol.
Preferably the membrane is characterized by a thickness which is in the range from 0.5 to 250 pm, more preferably the thickness of the membrane is in the range from 1 to 100 pm. On the one hand, a thin membrane is good in terms of high permeability and on the other hand a thin membrane is bad in terms of mechanical stability. Therefore, a compromise must be made in respect to the respective material and composition. It is noted that ceramic membranes have a higher thickness in comparison to metallic membranes. The thickness of metallic membranes may be in the range from 0.5 to 100 pm, more preferably from 1 to 50 pm. Ceramic membranes may have a thickness in the range from 10 to 250 pm, preferably 30 to 200 pm. Depending on the embodiment it may be possible that the thickness may be higher or lower than the values which are mentioned here.
Embodiments are possible and preferred in which the membrane is protected by a protective element as support structure which prevents a mechanical damage of the membrane ensuring a long lifetime given by a reusability.
As far as the material composition is concerned the catalyst material in contact with the permeate side is a solid-state catalyst which can have different shapes and forms as in the case of the dehydrogenation catalyst.
Assuming a catalyst density in the range from 1-3 g/cm3 it is possible to derive that 1 to 6 kg of catalyst are required to have surface coating for one square meter of membrane surface. The application of 1 to 6 kg catalysts results in a catalyst coating in the range from 500 to 2000 pm. Nevertheless, it is not excluded in any way that the thickness of the catalyst coating is below 500 pm or higher than 2000 pm.
Characterizing features of the performance characteristics of the process according to the invention are provided by the reaction rates which are given by the space-time-yields as well as the area-time-yield of the membrane transport process.
In a preferred embodiment of the process includes the use of a membrane unit which the membrane and the catalyst are formed by separate physical objects whereby the catalyst is arranged in a catalyst holder. In a further embodiment such catalyst holder has been prepared by a high precision manufacturing process. It is preferred that the catalyst is filled and replaced by the provision of a setup procedure for filling and replacing catalysts as well as assembling the membrane unit. In a preferred embodiment the holder is manufactured by using an additive manufacturing process.
In a preferred embodiment of the process, a membrane holder is used to hold the catalyst material which is used in the membrane chambers. Preferably, the structure of the catalysts is adjusted to the membrane holder or the membrane holder geometry is adjusted to the structure of the catalysts which ensures good fit and easy handling. Preferably the holder is fabricated by a 3D- printing process. Fixation of the catalyst provides a high precision whereby a catalyst exchange of spent catalyst is possible whereby in a preferred embodiment the membrane is reusable. An advantage is that industrially manufactured catalyst materials can be used that already exist off the shelf vis-a-vis the use of sensitive and fragile membrane coatings that may result in severe wear of the membrane. The production of the membrane is a very energy-intensive process. Therefore, this improvement is of particular importance and a special aspect of this embodiment of the process of the invention which is preferred.
The use of a customized holder provides another advantage which is given by easy way of filling and emptying. For example, filling and emptying can be performed by using air stream or fluid streams for the transportation of the particulate catalyst.
Examples To illustrate the process according to the invention a series of examples were carried out which will be described in more detail below. These examples do not represent any restrictions on the claimed invention. A membrane reactor was used to carry out the examples, whereby the membrane reactor was integrated into a set-up which was operated as a laboratory setup. The membrane reactor was equipped with a membrane holder had a diameter of 4 cm. Detailed description of the structure of the membrane reactor is given in the EP-application EP- A 4 197 625. Plate like membranes could be fixed on the holder in such way that approximately eight square centimeters (approximately 8 cm2) of freely accessible membrane surface area could be provided for the testing experiments. The membranes were fixed on the holder in a nondetachable form.
To obtain the catalytic membranes, the different membranes had to be coated with different particulate catalyst materials. The membrane material used here was a palladium foil with a thickness of 75 pm from Alfa Aesar (having a purity of 99.5 %), and an iron-chromium steel plate as hydrogen impermeable reference material for comparison purpose. The steel plate and Pd membrane did not show any signs of wear or aging could be reused multiple times in the experiments.
Description of the experimental test set-up which was employed for testing the materials in the membrane reactor. The membrane loaded membrane reactor was inserted into a testing apparatus which was equipped with feed supply lines, automatically controlled control valves, heating, exit lines to an exhaust line as well as an online GC (Agilent 8890, equipped with two FID and two TCD detectors) and mass spectrometer (HPR-20 R&D) as analytical unit. Ar and N2 were used as internal standards for the experiments on the retentate and permeate side, respectively. The various elements of the testing apparatus were connected with a common process control unit. By use of the process control unit, it was possible to conduct the experiments automatically and record the measurement data as well as carry out regular analyses on the product fluid streams.
Preparation of catalysts which were used in the examples:
Prior to the testing experiments in the membrane reactor a set of two different catalyst materials had been prepared. The dehydrogenation catalyst was based on a Pt-Zn formulation which was coated on silica particles whereby the resulting catalyst had the composition of 1 wt.% PtZn/SiO2 (Cat. 1). The catalyst was prepared by incipient wetness impregnation. Pt(NO3)2 and Zn(NO3)2 ■ 6H2O were used as metal precursors in an aqueous solution and were impregnated on a Cariact Q20C (315 to 500 pm) support material (SiO2). For 15 g of the support, 0.297 g Pt precursors and 1.025 g Zn precursor were dissolved in 17.4 mL of H2O. After impregnation the sample was dried for 24 h at 70 ° C and subsequently calcined at 500 ° C under clean dry air for 2 h and a final reductive treatment under 5 vol.% H2 in N2 at 600 ° C for 1 h before cooling to room temperature. The final catalyst was sieved into a fraction of 250 to 500 pm for the later testing on the Pd membrane or steel plate.
For the hydrogenation of carbon dioxide, a 5 wt.% Ru/ y -AI2O3 catalyst was prepared via incipient wetness impregnation (Cat. 2). An aqueous solution of Tri-nitrato-nitrosyl- ruthenium-(ll) was impregnated on a Puralox TM100/150 support. Puralox TM100/150 is a y -AI2O3 which is produced by SASOL. After impregnation the catalyst was dried at 120 ° C for 6 h and subsequently calcined at 400 ° C for 4 h under clean dry air. Of the resulting catalyst 13 mm tablets with a catalyst mass of 0.5 g were prepared by pressing.
Based on the horizontal orientation of the membrane surface the Cat. 1 could be loaded as self-supporting powder on the upper side of the membrane plate whereas Cat. 2 was positioned in proximity below the bottom side of the membrane. In a first set of experiments the hydrogenation catalyst (Cat. 2) was attached underneath the membrane as described by the membrane configurations which are given in Table 1 (hereafter called the simple catalyst configuration). In a second set of experiments dehydrogenation catalyst (Cat. 1) was positioned on the upper side and hydrogenation catalyst (Cat. 2) was positioned on the bottom side as depicted in Table 2. To have the Cat. 2 in a form which was good to handle, the material was converted into tablets by using a tablet press. Several tablets were prepared, each tablet having a weight of 0.5 g and a diameter of 13 mm. The experiments were characterized by good reproducibility due to the good mixing condition within the membrane reactor. A characteristic feature is the central fluid inlet and several tubes around the central fluid inlet.
Hydrogen permeation studies of the Pd membrane
The Pd membrane was fixed in the membrane reactor and the sealed membrane reactor was inserted in the testing apparatus which was subjected to the following testing conditions:
(i) variation of the flow rate of a sweep gas on the permeate side and
(ii) hydrogenation reaction of carbon dioxide with the 5 wt.% Ru/AI2O3 catalyst on the permeate side to consume the permeated hydrogen.
The experiments are summarized in Table 1. For the experiments 80 mL min-1 of a 10 vol.% H2, 10 vol.% Ar in N2 mixture were dosed as feed on the retentate side with a total pressure of 2 bara. The 5 wt.% Ru/AI2O3 catalyst was applied on the permeate side in form of tablets due to the reactor configuration. The absolute pressure on the permeate side was equal to the retentate side with 2 bara. For the experiments the amount of catalyst, total permeate flow rate and gas composition of the permeate feed were varied according to Table 1. The hydrogen permeation was studied in a temperature range from 450 to 550 ° C.
Table 1 (Cat.2 configurations without Cat. 1 on the retentate side) Summary of the hydrogen permeation experiments performed for the 75 pm thick Pd foil membrane. Inlet gas flow of 80 mL min-1 of 10 vol.% H2, 10 vol.% Ar in N2 on the retentate side. Total pressure of 2 bara on retentate and permeate sides. On the permeate side the Ru/AI2O3 catalysts was used in 13 mm tablets of each 0.5 g.
The results of the hydrogen permeation studies depending on the endothermic reaction of the permeated hydrogen with CO2 to CO on the permeate side are summarized in Table 2. For CO2 conversion below 2 % the calculated selectivity towards methane (SCH4) and carbon monoxide (Sco) have a large error and can only be discussed qualitatively. In the different examples the membrane configurations (listed in Table 1) were tested at various temperature levels whereby the composition of the exhaust gas stream was continuously analyzed while the temperature level was maintained constant for a duration of one hour. The temperature was then further increased to the next stage by using a temperature ramp of 5 ° C/min.
A significant influence due to the presence of the catalyst material in the step (2) is noticeable since nearly no conversion is detected without the catalyst which can be seen in the Example 1.1 - Example 1.4; Example 4.1 to Example 4.4; Example 7.1 to Example 7. Absence of a catalyst showed negligible turnover even at different temperatures.
A significant contrast to this is represented by the results in the presence of larger amounts of Cat. 2 whereby a pronounced effect was visible at high flow and at low flow conditions as can be seen by the data which are given in Example 3.1 to Example 3.3; Example 6.1 to Example 6.4; Example 10.1 to Example 10.3. The highest CO2 selectivities as well as CO2 conversion was obtained for the catalysts at 550 ° C. Example 3.4 and Example 6.4 show selectivities in the conversion of CO2 to CO of about 100 %. The same selectivity trends are also observed for Experiments 7.1 to 10.3 using a diluted CO2 feed with a smaller ration of CO2 vs. permeated H2 leading to generally higher conversion of CO2. This highlights the favor towards selective CO formation on the permeate side with higher reaction temperatures. With increased specific residence time of the catalyst on the permeate side, e.g., Example 2.3 compared with Example 3.4, or Example 8.3 compared with Example 9.3 and Example 10.3, showed increase conversion of the permeated H2 as quantified with the ration of permeated amount of hydrogen and converted hydrogen (hH2Tp/hH2TCoriv). The increase in H2 conversion on the permeate side increases the amount of permeated H2 highlighting the control of H2 permeation by the CO2 hydrogenation reaction on the permeate side, e.g. as shown comparing Example 8.3 and Example 10.3.
Table 2 Results of the hydrogen permeation experiments ratio of the amount of hydrogen on the retentate side vs the permeate amount (hH2,R/hH2,p), ratio of permeated amount of hydrogen and converted hydrogen (hH2,p/hH2,conv), hydrogen amount permeated (fiH2,p), conversion of CO2 (XC02), conversion of the permeated hydrogen (XH2) , selectivity towards methane (SCH4) and carbon monoxide (Sco).
Examples: Dehydrogenation of ethane
Experiments in the catalytic dehydrogenation of ethane towards ethylene on the retentate side were carried out using the PtZn/SiO2 dehydrogenation catalyst. The set-up of the membrane and the test conditions of the dehydrogenation experiments are summarized in Table 3. Catalytic experiments were performed without Pd membrane on a gas tight steel membrane in Cl as reference experiment without membrane (designated as membrane configuration MC5 in Table 3). For the experiments 0.5 g of the PtZn/SiO2 (250-500 pm sieve fraction) catalyst were distributed as layer on the Pd membrane/steel plate on the upper side (i.e. the retentate side). Before each catalytic test, the catalyst was in situ activated at 500
C for 1 h under 80 mL min-1 of a 10 vol.% H2, 10 vol.% Ar in N2. For the catalytic experiments 80 mL min-1 of a 10 vol.% C2H6, 10 vol.% Ar in N2 mixture were dosed as feed on the retentate side with a total pressure of 2 bara.
For combined experiments with membrane (C2-C5 or MC6 to MC7 respectively) the 75 pm thick Pd foil was used as a membrane as in the examples above which il lustrate the hydrogen permeation effect in combination with the reaction step (3). On the permeate side the flow rate was varied between 80 and 241 mL min-1 with a gas composition of 90 vol.% CO2 and 10 vol.% N2 and total pressure of 2 bara. On the permeate side no (C2, C4) or 0.5 g of the Ru/AI2O3 hydrogenation catalyst (C3, 05) was used. Without catalyst on the permeate side the CO2/N2 mixture acts as a sweep gas and does not react. The reaction temperature was varied from 450 to 550 ° C.
Table 3 Summary of the hydrogen permeation experiments performed for the 75 pm thick Pd foil membrane. I nlet gas flow of 80 mL min-1 of 10 vol.% C2H6, 10 vol.% Ar in N2 on the retentate side. Total pressure of 2 bara on retentate and permeate sides. In case of membrane configuration MC5 (or Cl): a gas tight steel plate was used instead of the 75 pm Pd foil.
The results of the catalytic ethane dehydrogenation experiments are summarized in Table 4 in terms of the achieved ethane conversion (XC2H6) and ethylene yield (YC2H4). The results for the ethane conversion are also illustrated in Figure 6 together with the calculated equilibrium conversion of ethane. The equilibrium conversion was calculated for condition MC5 - Cl. The Example 12. 1 to Example 12.4 showed the activity of the reactor cell with Cat.-l which was equipped with a hydrogen impermeable stopper in the form of the steel plate representing the base case of the catalytic performance of Cat.-l.
However, exceptionally high conversion and selectivity could be obtained in the presence of the catalysts within the membrane reactor and according to the use of the two different reactions steps (1) and (2) what can be seen from the examples in Example 16.1 to Examples 16.4 as well as the examples which are given in Example 14.1 to 14.4.
It is noted that special testing conditions had been used by the set-up which was characterized by the highly efficient mixing and low conversion. The membrane itself had no effect as can be seen in Figure 6 by the curve at the bottom which is marked with the rhomb symbol (blind activity). The tests which are shown in Figure 6 were carried out in a temperature range from 450° C to 550° C and there was higher conversion above 480° C than at 450° C. The fact that the dehydrogenation catalyst material was highly active can be seen from the comparative example MC5-C1 in Figure 6 (triangle symbols standing on top). It is also noteworthy that the supplement of the palladium membrane delivers the improvement as the comparative example shows in the case of the curve which shows the measuring points MC6-C2 in Figure 6 (square symbols). The data which were obtained for the membrane configuration MC6-C2 as comparative example is based on the state of the art for a sweep gas method in order to generate a concentration gradient as driving force for the hydrogen transportation over the membrane. Here we can see an improvement from 6.8 % ethane conversion (obtained in Example 12.4) to an ethane conversion of 10.0 % (in Example 13.4). An increase in conversion was 3.2 % which means that the relative increase due to the integration of the membrane was in the range of 40 to 50% to the comparative examples were the catalyst activity was compared to the activity of a membrane reactor with a sweep gas present on the permeate side. The examples according to the invention for membrane configuration MC7-C3 in Figure 6 (symbols with standing triangles on the side) show that compared to the state of the art a further enhancement is obtained by the addition of the hydrogenation catalyst to the permeate side. The ethane conversion in Example 14.4 was 15.7 % and the ethane conversion in the comparative example (Example 13.4) was 10.0 % which means a total increase of 5.7% which corresponds to a relative increase in more than 50% higher conversion at 550° C. Surprisingly, such strong increases occur at low temperatures such as shown in Example 14.3 (example according to the invention) in comparison to Example 13.3 (comparative example at 510° C) given by 6% higher ethane conversion in absolute numbers and 50% higher ethane conversion in relative numbers. Therefore, it is clearly illustrated that the coupled process conditions of dehydrogenation on the retentate side with the syngas production on the permeate side showed a beneficial effect on the conversion increase.
Table 4 provides a summary of the results of the catalytic ethane dehydrogenation experiments as summarized in Table 3.
Short description of the figures: Fig. l.a shows a schematic illustration of process according to the invention with step (1): dehydrogenation of A to B, process step (2) removing H2 over selective membrane, and process step (3) with reaction C + H2 to D.
Fig. l.b shows a schematic illustration of an embodiment of the process whereby the catalysts which are employed on the retentate side (24) and permeate side (26) of the membrane are either present as fixed bed or as fluidized bed.
Fig. 2 shows a schematic illustration of an embodiment of the process in which the catalysts are immobilized on both sides of the membrane, i.e. on the retentate side (34) and on the permeate side (36). Fig. 3 shows a schematic illustration of an embodiment of the process according to the invention which has a gas separation unit (51) downstream of the retention side of the membrane chamber.
Fig. 4 shows a schematic illustration of an embodiment of the process according to invention whereby the configuration comprises a recycle of chemical molecules to the process under step (1) and means for catalyst regeneration.
Fig. 5. a shows a schematic depiction of a membrane reactor whereby a flat catalyst holders or supporting structures are attached to each side of the membrane surfaces. The supporting structure serves to take up particulate catalyst material whereby the upper part is filled with catalyst particles.
Fig. 5.b shows a schematic depiction of a membrane reactor which is equipped with a membrane holder for particulate catalyst on the retentate side of the membrane and a catalyst coating on the permeate side of the membrane whereby the fluid flow is directed in a co-current flow through both chambers.
Fig. 5.c shows a schematic depiction of a membrane reactor which is equipped with packed beds of catalyst material on each side of the membrane whereby the catalyst beds are fixed with pressing elements.
Fig. 6 shows the activity in terms of ethane conversion for the experiments MC5 - Cl to MC7 - C3 summarized in Table 3. The ethane conversion is compared with the blind activity of only the Pd-foil and the calculated equilibrium conversion of ethane.
List with reference signs
01 membrane reactor
5 membrane, H2-permeabel
7 chamber on the retentate side of the membrane
9 chamber on the permeate side of the membrane
10 reforming catalyst
11 supply line to the retentate chamber
13 exit line to discharge product from the chamber
15 supply line to the permeate chamber
17 exit line from the permeate chamber
19 catalyst holder or supporting structure on the side of the retentate chamber
21 catalyst holder or supporting structure on the side of the permeate chamber
23 particulate dehydrogenation catalyst
24 either fixed bed or fluidized bed of dehydrogenation catalyst
25 particulate hydrogenation catalyst / reforming catalyst 26 either fixed bed or fluidized bed of hydrogenation catalyst
27 pressing element or holder
29 dehydrogenation catalyst as fixed bed
31 hydrogenation catalyst as fixed bed
33 pressing element or holder
34 immobilized dehydrogenation catalyst
36 immobilized hydrogenation catalyst
50 electrical power supply for membrane
51 separation unit
53 exit line for product compound
55 return line for educt compound
57 exit line for hydrogen
60 regeneration unit
61 catalyst transfer line from the retentate chamber to regeneration unit
63 catalyst transfer line from the regeneration unit to retentate chamber
Abbreviations
MIEC - mixed ionic electronic conductors
PCM - proton conducting ceramic material
PCMEP - proton conducting ceramic material which is used as electrochemical proton pump
The present invention is further illustrated by the following set of embodiments and combinations of embodiments resulting from the indicated dependencies and references.

Claims

Claims
1. Process for converting different chemical compounds by using a membrane reactor which is equipped with a hydrogen permeable membrane whereby the process characterized by the following steps:
(1) supplying a first educt fluid stream to the retentate side of the membrane reactor and dehydrogenating chemical compounds which are contained therein;
(2) transferring part of the formed hydrogen from the retentate side to permeate side; and
(3) supplying a second educt fluid stream to the permeate side of the membrane reactor and hydrogenating chemical compounds which are contained therein; whereby the process is in such a way that each of step (1) and step (3) comprise an endothermic reaction; and whereby hydrogen permeable membrane is including a dense film which comprises at least a metallic material or a ceramic material or combination of metallic and ceramic material.
2. Process for converting chemical compounds according to claim 1 whereby the chemical compounds which are being contained in the first educt fluid stream under step (1) are selected from the group of alkanes, alcohols, aldehydes, ammonia and whereby the reaction being carried out under step (3) is selected from the group CO2 hydrogenation to CO or CO2 hydrogenation to mixtures of CO and H2, CO2 hydrogenation to CH3OH, CO2 hydrogenation to CH4.
3. Process for converting chemical compounds according to claim 1 or claim 2 whereby the chemical compounds which are being contained in the first educt fluid stream under step (1) contains a hydrocarbon compound which is derived from a renewable source of energy or which is derived from reprocessing waste material by a circular process.
4. Process for converting chemical compounds according to one of the claims 1 to 3 whereby a dehydrogenation catalyst on the retentate side which comprises at least one metal element on a carrier which preferably contains an oxide support or a refractory oxide whereby the at least one metal element is present in oxidic or metallic form or mixed form of metal and oxide.
5. Process for converting chemical compounds according to one of the claims 1 to 4 whereby a hydrogenation catalyst which comprises at least on metal element metal element on a carrier which preferably contains an oxide support or a refractory oxide and the metal element is selected from the group the group of Sc, Ti, V, Cr, M n, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Ru, Rh, Pd, Ag, Cd, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, Al, Si, P, Ga, Ge, As, In, Sn, Sb, Sr, Mg, Ba, Ca whereby the metal is present as metal element or metal oxide or both.
6. Process for converting chemical compounds according to one of the claims 1 to 5 whereby the performance characteristics of the catalyst on the retentate side is given by a space-time-yield in the range from 0.1 moLm’Ts’1 to 10 moLm’Ts’1 and the performance characteristics of the membrane is given by an area-time-yield in the range from 0.001 mol. m’2. s’1 to 1 mol. m’2. s’1; and/or whereby the configuration of the membrane reactor is characterized by the ratio of membrane surface Amem to reactor volume Vreact which is in the range from 10 to 10000 m’1, whereby the reactor volume Vreact is given by the sum of the volume of the reactor on the retentate side and the permeate side.
7. Process for converting chemical compounds according to one of the claims 1 to 6 whereby the membrane reactor is heated at a temperature in the range of 100 to 1000
C; and/or whereby the membrane reactor is operated at a pressure in the range of 0.1 to 100 bara.
8. Process for converting chemical compounds according to one of the claims 1 to 7 whereby the membrane reactor comprises two different chambers and the way as the catalyst is present in the chambers is in the form of a fluidized catalyst bed, packed catalyst bed, packed particles bed in a holder, coating, impregnation, film growth on the membrane surface whereby the form of the catalyst may be identical in both chambers or different in chambers; and/or whereby the thickness of the membrane is in the range from 1 to 250 pm.
9. Process for converting chemical compounds according to one of the claims 1 to 8 whereby the hydrogen which is transported through the membrane in step (2) accounts for 5 to 95 vol.-% of the hydrogen formed in step (1) of the process; and/or whereby the chemical compounds are supplied in the presence of dilution fluid which comprises inert gas or inert gas in the presence of side feed, whereby the volume of chemical compounds to total fluid given by sum of dilution feed and chemical compounds is in the range from 5 to 90 vol.-%.
10. Process for converting chemical compounds according to one of the claims 1 to 9 whereby the membrane comprises a metallic material which is selected from the group of hydrogen conducting metals, in particular Pd, or alloys of Pd with other metals like Pd-Ag or others, or ceramic supported Pd or alloys of Pd with other metals containing membranes.
11. Process for converting different chemical compounds according to claim 1 to claim 9 whereby the hydrogen permeable membrane contains a ceramic material which is either a proton conducting ceramic material (PCM) or proton conducting ceramic material which is used as electrochemical proton pump (PCMEP) and powered by an electric supply, whereby a proton conducting ceramic material is preferably from the group of mixed ionic electronic conductors (MI EC) offering simultaneous conductivity for electrons and protons; more preferably the M IEC material is from the group of lanthanum tungstates La6.xWO12.5 (LWO) with 0.2 < x <0.8, Mo-doped lanthanum tungstates La^Wj-yMOyOj^ (LWO-Mo) with y <0.4, SrTixFe1.xO3 (STF) with 0.5 < x < 1, Ba05Sr05Cu0 8Fe02O3- (5 (BSCF) and La06Sr04Cu02Fe0 gO3- (5 (LSCF) and whereby a proton conducting ceramic material which is used as electrochemical proton pump comprises a ceramic material which is proton conducting, more preferably the proton conduction is increased by application of an external electrical circuit characterized as electron pumping, preferably the proton conducting ceramic material is from the group of proton conducting oxides including BaZrxCeyYzO3 (BZCY) with x+y+z=l or BaZrxYyO3 with x+y=l or SrZrxCeyYzO3 with x+y+z=l.
12. Process for converting chemical molecules compounds according to one of the claims 1 to 11 whereby the heating of the membrane reactor based on resistive heating, preferably using renewable energy via built-in heating elements in the reactor or the membrane or in the reactor and the membrane; in the case that a PCM EP material is used as membrane at least part of the waste heat is used as heating source.
13. Process for converting chemical compounds for co-producing olefins and syngas by using an electrically heated membrane reactor whereby the process includes one or more of the embodiments according to the claims 1 to 12 whereby basic chemicals are produced on the retentate side which are selected from the group ethene, propene, butenes, iso-butene, benzene, toluene, styrene, preferably selected from the group ethene, propene, butenes, iso-butenes or mixtures thereof; more preferably the process according to one of the claims 1 to 12 includes one or more of the following steps: (4) separation process, which is downstream of the membrane reactor, (5) recycling separated educt component to the educt fluid of process step (1), (6) regeneration of the catalyst material, preferably during the ongoing process using a circular regeneration process.
14. Process comprising the production olefins and synthesis gas according to one of the claims 1 to 13 and the conversion of the olefins to polymers or synthesis gas to chemical molecules.
15. Process for converting olefins to polymers and synthesis gas to chemicals whereby the olefins and the synthesis gas are obtained from a membrane process according to claims 1 to 13.
PCT/EP2025/056449 2024-03-11 2025-03-10 Process for converting chemical compounds by using a membrane reactor Pending WO2025190857A1 (en)

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