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WO2025002620A1 - Conversion de dioxyde de carbone en produits chimiques à valeur ajoutée à l'aide de catalyseurs à base de zéolite - Google Patents

Conversion de dioxyde de carbone en produits chimiques à valeur ajoutée à l'aide de catalyseurs à base de zéolite Download PDF

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WO2025002620A1
WO2025002620A1 PCT/EP2024/060292 EP2024060292W WO2025002620A1 WO 2025002620 A1 WO2025002620 A1 WO 2025002620A1 EP 2024060292 W EP2024060292 W EP 2024060292W WO 2025002620 A1 WO2025002620 A1 WO 2025002620A1
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catalyst
zeolite
hours
gme
gmelinite
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Søren KEGNÆS
Jerrik MIELBY
Dimitra ILTSIOU
Christian Sander PETERSEN
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Danmarks Tekniske Universitet
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Danmarks Tekniske Universitet
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    • 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
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/064—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof containing iron group metals, noble metals or copper
    • B01J29/072—Iron group metals or copper
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • B01J29/10—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing iron group metals, noble metals or copper
    • B01J29/14—Iron group metals or copper
    • B01J29/146—Y-type faujasite
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
    • C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
    • C07C29/153—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used
    • C07C29/154—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used containing copper, silver, gold, or compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
    • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • C07C2529/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65
    • C07C2529/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65 containing iron group metals, noble metals or copper
    • C07C2529/76—Iron group metals or copper

Definitions

  • the present invention relates to the field of carbon dioxide (CO2) utilization and more specifically the conversion of CO2 into value-added chemicals through hydrogenation.
  • CO2 carbon dioxide
  • the present invention thus provides methods and catalysts for efficient and selective conversion of CO2 into value-added chemicals through hydrogenation, as well as systems implementing both of these.
  • CO2 carbon dioxide
  • zeolites have emerged as highly promising candidates for addressing the challenges associated with CO2 capture and conversion.
  • Zeolites are crystalline, macro-/meso-/ and microporous materials with well-defined structures, characterized by a network of interconnected channels and cages. These unique structures provide an ideal platform for catalytic processes, making zeolites exceptionally versatile in a wide range of applications.
  • the present invention aims to address at least some of the aforementioned limitations and challenges associated with synthesis of ethanol from CO2 in catalytic hydrogenation reactions.
  • a second aspect of the present invention is to provide a system for the catalytic conversion of CO2 into ethanol in a hydrogenation reaction, the system comprising: a. a reaction chamber equipped with a zeolite catalyst; b. a reaction chamber inlet for CO2, H 2 and optionally H 2 O provided together or separately; c. a heating source; and d. a product outlet; wherein the reaction chamber is a plug-flow reactor and wherein the zeolite catalyst is a gmelinite (GME) based catalyst.
  • GME gmelinite
  • a third aspect of the present invention is to provide a solid zeolite catalyst selected from the group consisting of gmelinite potassium (K-GME), gmelinite sodium (Na- GME), and gmelinite calcium (Ca-GME), characterized in comprising 1-2 wt% (based on total catalyst weight) of at least one auxiliary non-noble transition metal.
  • K-GME gmelinite potassium
  • Na- GME gmelinite sodium
  • Ca-GME gmelinite calcium
  • GME refers to a crystalline synthetic form of the mineral compound gmelinite.
  • Gmelinite is a zeolite with an aluminosilicate framework comprising the repeating unit ⁇ (SisAI 4 )O24- 11 H 2 O ⁇ 4- .
  • the structure of the interconnected tetrahedra results in channels and pores within the framework with exposed active sites that can be targeted either for the purpose of catalysis, or for adsorbing a chemical entity such as a metal ion into the channel structure.
  • the negative charge of the aluminosilicate framework may be in principle be balanced by any cationic material or metal.
  • K-GME potassium, calcium and sodium forms of GME are highlighted, and referred to as K-GME, Ca-GME and Na-GME respectively.
  • Exemplary K-GME refers to K ⁇ SisADOs ⁇ l 1 H 2 O
  • Ca-GME Ca2(Si8Al4)O24-11 H2O.
  • the identifier (K-Ca)-GME refers to mixtures of K-GME and Ca- GME, such as those obtained by ion exchange of Na-GME using both K and Ca as exchange ions.
  • Other zeolite abbreviations used herein which are well known to those skilled in the art include CHA (Chabazite), FAU (Faujasite), and ANA (analcime).
  • the symbols 7’ such as used in relation to zeolites, e.g., in H-Cu/FAU or K-Cu/GME refers to the situation where Cu (or another metal) was added in the zeolite structure by an adsorption process like incipient wetness impregnation or ion exchange.
  • the term such as used for K-Cu@GME refers to the situation where a zeolite which already contained Cu was transformed and/or recrystallized (such as by inter-zeolite transformation) into another framework/structure which now also contains Cu adsorbed and/or doped and/or incorporated into the pores of the zeolite framework as an auxiliary metal framework without affecting the aluminosilicate structure.
  • the same terminology may be used for other metals and other zeolite structures.
  • V such as used in relation to silylated zeolites 0.5h 4 ⁇ K- Cu@GME refers to a catalyst obtained by the reaction between silylating agent h 4 and the zeolite K-Cu@GME.
  • the ‘0.5h4’ in 0.5h4 ⁇ K-Cu@GME refers to the reaction stoichiometry between silylating agent h 4 and K-Cu@GME, and identifies that 0.5 mmol h4 per gram K-Cu@GME zeolite was employed in the reaction. The same nomenclature may be used for other silylating agents and zeolite systems.
  • AFI refers to a zeolite of a specific structural type.
  • the AFI- framework is originally identified in the material abbreviated ‘AIPO-5’ which is an aluminophosphate known to those skilled in the art of heterogeneous catalysis.
  • the AFI framework resembles the GME framework in the crystallographic ab-plane with big 12-membered channels with an aperture of 7.3 A, but only has these parallel nonintersecting channels as opposed to the GME framework which also features intersecting 8-membered channels.
  • one-pot or “one-step” in relation to catalytic hydrogenation reaction refers to a process wherein successive chemical reaction steps are performed in one reaction chamber or reaction vessel without isolation, separation or purification of any intermediates. In such reactions, the only separation of the intermediate and/or product mixture is performed in isolation of the final desired product.
  • One-pot reactions are particularly advantageous for scale-up as they require less physical interventions.
  • the term “one-pot reaction” and/or “one-step reaction” is a well-known term in the field of chemicals synthesis.
  • Figure 1 The effect of water addition in the CO2 conversion and selectivity of the CO2 hydrogenation catalyzed by the K-Cu@GME zeolite as prepared following Example 1 . Testing was performed in a temperature range from 200°C to 350 °C under H2/CO2 volume ratio of 5 and a pressure of 2.0 MPa. The H2O/CO2 molar ratio was varied as being A) 0, B) 0.35, C) 0.5 and D) 0.4. The shown data is for a Cu-loading of 1 wt% in K-Cu@GME.
  • Figure 2 The influence of pressure in the CO2 hydrogenation towards ethanol production under H2/CO2 volume ratio of 5 and a H2O/CO2 molar ratio of 0.4 at 250°C.
  • the shown data is for a Cu-loading of 1 wt% in K-Cu@GME as prepared following Example 1 .
  • Figure 3 The effect of the Cu loading in the direct synthesis of ethanol from CO2 under H2/CO2 ratio of 5 and a H2O/CO2 ratio of 0.4 at 250°C and 2.0 MPa using the catalyst system K-xCu@GME, x referring to the wt% of Cu (based on total catalyst weight) as illustrated on the principal axis and prepared following Example 1 .
  • Figure 4 Selectivity and CO2 conversion from the stability test of Ca-Cu@GME under H2/CO2 volume ratio of 5 and a H2O/CO2 molar ratio of 0.4 at 250°C and 2.0 MPa.
  • the shown data is for a Cu-loading of 1 wt% in K-Cu@GME as prepared following Example 1.
  • Figure 5 X-ray d iff ractog rams of K-Cu@GME reacted with varying amounts of the silylating agent trichloromethylsilane (hi). Obtained at room temperature using Cu-Ka radiation.
  • Figure 6 X-ray d iff ractog rams of K-Cu@GME reacted with 0.5 mmol of silylating agent per 1 gram of zeolite.
  • Employed silylating agents are trimethylchlorosilane (h 2 ), trimethoxymethylsilane (h 3 ) and hexadecyltrimethoxysilane (h 4 ). Obtained at room temperature using Cu-Ka radiation.
  • Figure 7 Structural and catalytic investigation of mixed (K-Ca)-Cu@GME catalyst.
  • A Selectivity and CO2 conversion from the stability test of (K-Ca)-Cu@GME under H2/CO2 volume ratio of 5 and a H2O/CO2 molar ratio of 0.4 at 250°C and 2.0 MPa.
  • the shown data is for a nominal Cu-loading of 1 wt% in (K-Ca)-Cu@GME.
  • the dotted line represents CO2 conversion as indicated on the right y-axis, while the bar charts display selectivities on the left y-axis.
  • the shown data is for a nominal Cu-loading of 1 wt%.
  • the dotted line represents CO2 conversion as indicated on the right y-axis, while the bar charts display selectivities on the left y-axis.
  • the shown data is for a nominal Cu-loading of 1 wt%.
  • the dotted line represents CO2 conversion as indicated on the right y-axis, while the bar charts display selectivities on the left y-axis.
  • Figure 10 Selectivity and CO2 conversion from the stability test of silylated 0.5h 4 ⁇ (K- Ca)-Cu@GME under H2/CO2 volume ratio of 5 and a H2O/CO2 molar ratio of 0.4 at 250°C and 2.0 MPa.
  • the shown data is for a nominal Cu-loading of 1 wt%.
  • the dotted line represents CO2 conversion as indicated on the right y-axis, while the bar charts display selectivities on the left y-axis. Stable operation and ethanol production is observed for the full 50 hours duration of the test.
  • the present invention is directed to a new method for catalytic hydrogenation of CO2 which involves chemical manipulation of CO2 and H 2 by solid heterogeneous catalysts into value-added chemicals such as ethanol, thereby allowing for utilization of CO2 in carbon cycling for the advancement of circular economy.
  • One embodiment of the present disclosure is to provide a method for the catalytic hydrogenation of CO2 into ethanol, the method comprising contacting a feed stream containing CO2 and H 2 with a solid heterogeneous catalyst in a reaction chamber, wherein the H2/CO2 volume ratio in the feed stream is from 1 :1 to 10:1 .
  • the feed stream may preferably be a gaseous feed stream.
  • the hydrogenation may preferably be operated continuously or in cycles.
  • the present inventors have surprisingly identified a catalyst composition and process method which when subjected to appropriate feed stream compositions and reaction parameters produce value-added chemicals such as ethanol with sufficiently high selectivity and conversion rate to be industrially relevant.
  • the H2/CO2 volume ratio in the feed stream is from 1 :1 to 10:1 , such as 1 :1 , such as 2:1 , such as 3:1 , such as 4:1 , such as 5:1 , such as 6:1 , such as 7:1 , such as 8:1 , such as 9:1 , such as 10:1 or any 0.5 increment therein between.
  • the molar ratio of H2 and CO2 in the feed stream is from 4:1 to 6:1 , such as 4.5:1 to 5.5:1 , such as 5:1 .
  • the reaction chamber is selected from the group consisting of plug-flow reactor, multi-tubular reaction, fluidised bed reactor and void reactor.
  • the reaction chamber is a plug-flow reactor.
  • the examples of the present disclosure makes use of a plug-flow reactor comprising a stainless steel reactor with an inner diameter of 4 mm, wherein the active catalyst is fixed between two sections of quartz wool. It will be immediately apparent to the skilled person that other types of plug-flow reactors of different type and dimensions would be equally suitable for use in the method of the present disclosure, thus it is also within the scope of the present disclosure to cover such embodiments.
  • the majority of solid heterogeneous catalysts employed industrially are solid acid catalysts.
  • the solid heterogeneous catalyst is an acidic catalyst.
  • Solid acid catalyst is generally considered as any type of acid which is not soluble in the reaction medium. This may for some reactions include organic acids such as oxalic acid, tartaric acid, but for most purposes refer to metal oxides such as titania, zirconia, alumina, niobia and mixed silicoaluminates (or aluminosilicates) including zeolites.
  • the catalyst is a zeolitebased catalyst.
  • zeolites lie in their exceptional catalytic properties.
  • the inherent porosity of zeolites allows for high surface areas, providing numerous active sites for catalytic reactions. This enables efficient adsorption and activation of CO2 molecules, facilitating subsequent conversion reactions.
  • the well-defined and uniform pore sizes of zeolites also contribute to their selectivity, allowing for precise control over reaction pathways and product distributions.
  • zeolites can be tailored and modified to enhance their catalytic performance.
  • zeolites can be customized to exhibit specific catalytic properties, such as improved CO2 adsorption capacity, enhanced stability, and increased reaction rates. This tunability makes zeolites adaptable to various CO2 conversion processes and enables the optimization of reaction conditions to achieve desired product yields and selectivities.
  • the catalyst is a zeolite-based catalyst selected from the group consisting of gmelinite (GME), chabazite (CHA), faujasite (FAU), and analcime (ANA), preferably, the zeolite-based catalyst is based on gmelinite (GME).
  • GME Gmelinite
  • CHA chabazite
  • the presently disclosed method is suitable to produce GME structures of very high purity, such as of more than 90% purity, such as substantially devoid and/or free of any CHA.
  • the catalyst has a Si/AI ratio between 2.0 and 4.0, such as between 2.0 and 2.5, such as between 2.5 and 3.0, such as between 3.0 and 3.5, such as between 3.5 and 4.0, preferably between 3.0 and 4.0, such as 3.1 , 3.2, 3.3, 3.4, 3.5, 3,6, 3.7, 3.8, 3.9, 4.0, or any 0.01 increment therein between.
  • Gmelinite zeolites are sometimes referred to by their cation constituents, such as gmelinite potassium being characterized by the repeating unit K 4 (Si 8 AI 4 )O2 4 -11 H 2 O.
  • gmelinite potassium being characterized by the repeating unit K 4 (Si 8 AI 4 )O2 4 -11 H 2 O.
  • other cationic species can be used in combination with the aluminosilicate, and may in some embodiments be one or more elements selected from main group 1 or 2 of the periodic table, ie the cation of gmelinite may in some embodiments be one or more selected from the group consisting of lithium, sodium, potassium, rubidium, caesium, francium, beryllium, magnesium, calcium, strontium, barium and radium.
  • the catalyst is preferably selected from the group consisting of gmelinite sodium (Na-GME), gmelinite potassium (K-GME) and gmelinite calcium (Ca-GME) or a gmelinite wherein the cation is a mixture of at least two cations selected from sodium, potassium and calcium. In one embodiment, the at least two cations are potassium and calcium. In one embodiment, the gmelinite catalyst always comprise potassium, alone or in combination with another cation.
  • the catalyst unit cell comprises a repeating unit selected from the group consisting of Na 4 (Si 8 AI 4 )O2 4 -1 1 H 2 O, K 4 (Si 8 AI 4 )O 24 - 11 H 2 O, and Ca 2 (Si 8 AI 4 )O 24 -1 1 H 2 O.
  • Potassium and calcium cations have higher ionic radii than sodium cations, therefore, they are expected to be more strongly linked to the zeolite framework. As a result, the structure is more stable and can resist greater temperatures without collapsing or losing crystallinity. Furthermore, the presence of these exchangeable cations can result in a more rigid structure, which improves the zeolite's thermal stability. As a result, K- GME and Ca-GME zeolites are preferred over Na-GME zeolites for high-temperature applications including catalysis and gas separation as in the present disclosure.
  • the operando and/or in situ lifetime of the hydrogenation catalyst can be significantly improved by reaction with silylating agents bearing hydrophobic groups.
  • this improved stability is believed to arise as a result of a hydrophobic layer protecting the zeolite framework from highly hydrophilic molecules during reaction, allowing with preference less polar molecules such as hydrogen, carbon dioxide, alkanes and alcohols to pass the layer.
  • deactivation of the catalyst is postponed evidenced in a stable product mixture for a longer period of continuous operation, such as of more than 20, 30 or even 50 hours.
  • silylating agent can be added in only very small quantities of approximately 0.5 mmol pr gram of zeolite in order to obtain the effect, and likely also with even lower loadings. This could not be predicted based on the available prior art where usually up to 10 mmol (20 timers higher silylation loading) is needed for a significant improvement in stability and substrate conversion.
  • the catalyst comprises a hydrophobic layer, such as a hydrophobic layer obtained by silylation of zeolite OH-groups using a silylating agent.
  • the catalyst is a silylated heterogenous catalyst such as a silylated zeolite-based catalyst, or is a catalyst having been subjected to a step of silylation using a silylating agent.
  • the catalyst is a silylated Cu-doped gmelinite based catalyst such as silylated K-GME, Ca-GME or (K-Ca)-GME, obtained by the reaction with a silylating agent selected from the group consisting of trichloromethylsilane (hi), trimethylchlorosilane (hs), trimethoxymethylsilane (hs) and hexadecyltrimethoxysilane (h 4 ).
  • a silylating agent selected from the group consisting of trichloromethylsilane (hi), trimethylchlorosilane (hs), trimethoxymethylsilane (hs) and hexadecyltrimethoxysilane (h 4 ).
  • the silylating agent is trichloromethylsilane (hi). In one embodiment, the silylating agent is trimethylchlorosilane (hs) - In one embodiment, the silylating agent is trimethoxymethylsilane (h 3 ). In one embodiment, the silylating agent is hexadecyltrimethoxysilane (h 4 ).
  • the catalyst is a silylated Cu-doped gmelinite based catalyst such as K-GME, Ca-GME or (K-Ca)-GME obtained by the reaction with hexadecyltrimethoxysilane (h4), preferably in an amount of 0.5 mmol silylating agent per gram of zeolite.
  • a silylated Cu-doped gmelinite based catalyst such as K-GME, Ca-GME or (K-Ca)-GME obtained by the reaction with hexadecyltrimethoxysilane (h4), preferably in an amount of 0.5 mmol silylating agent per gram of zeolite.
  • the catalyst is a silylated Cu-doped gmelinite based catalyst obtained by the reaction of Cu-doped K-GME or (K-Ca)-GME with hexadecyltrimethoxysilane (h4).
  • the silylated zeolite catalyst comprise and/or is obtained by reaction with 0.1 mmol to 20 mmol silylating agent per gram of zeolite, such as 0.5 mmol to 10 mmol silylating agent per gram of zeolite, such as 0.5 mmol silylating agent per gram of zeolite, such as 1 .0 mmol silylating agent per gram of zeolite, such as 2.5 mmol silylating agent per gram of zeolite, such as 5.0 mmol silylating agent per gram of zeolite, such as 7.5 mmol silylating agent per gram of zeolite, such as 10.0 mmol silylating agent per gram of zeolite.
  • the silylated catalyst comprise 0.4 mmol to 0.6 mmol silylating agent per gram of zeolite, such as 0.5 mmol silylating agent per gram
  • the catalyst further comprises at least one auxiliary transition metal, such as a non-noble transition metal.
  • the catalyst may in some embodiments comprise from 0.5 to 5.0 wt% (based on total catalyst weight) of at least one auxiliary transition metal, such as non-noble transition metal.
  • the at least one auxiliary transition metal is present in an amount (based on total catalyst weight) from 0.5 wt% to 2.5 wt%, such as from 0.5 wt% to 2.0 wt%, such as from 0.8 wt% to 2.2 wt%, such as from 0.5 wt% to 1 .5 wt%, such as from 1 .0 wt% to 1 .5 wt%, such as from 1 .0 wt% to 2.0 wt%.
  • the catalyst may comprise 0.8 wt% to 2.2 wt% (based on total catalyst weight) of at least one auxiliary non-noble transition metal, such as selected from Cu, Fe, Co, Mn, Cr or any two-element mixture thereof, such as 0.8 wt% to 0.9 wt%, such as 0.9 wt% to 1 .0 wt%, such as 1 .0 wt% to 1.1 wt%, such as 1 .1 wt% to 1 .2 wt%, such as 1 .2 wt% to 1 .3 wt%, such as 1 .3 wt% to 1 .4 wt%, such as 1 .4 wt% to 1 .5 wt%, such as 1 .5 wt% to 1 .6 wt%, such as 1 .6 wt% to
  • auxiliary non-noble transition metal such as selected from Cu, Fe, Co, Mn, Cr or any two-element mixture thereof.
  • the non-noble transition metal is selected from the group consisting of Cu, Fe, Ni, Co, Mn, Cr, or any two-element mixture thereof, but is preferably comprising Cu, such as consisting essentially of Cu, more preferably zero-valent Cu.
  • One embodiment of the presently disclosed method further comprises a step of introducing water into the reaction chamber.
  • Water may be introduced together with H 2 and CO 2 in the feed stream or separately through a dedicated water-inlet using a pump, such as an HPLC pump.
  • Water may in one embodiment be introduced so as to provide a H2O/CO2 molar ratio between 0.1 and 1 .0.
  • Water as a reactant, participates in the well-known water-gas shift reaction (WGSR), by reacting with CO to produce H 2 and CO 2 .
  • WGSR water-gas shift reaction
  • This exothermic reaction is thermodynamically favored at elevated temperatures, typically exceeding 400°C, and requires a catalyst, such as copper or iron, to proceed to great extent.
  • the present inventors contemplated that by facilitating the conditions for the water-gas shift reaction, the production of CO (observed e.g., in Fig. l a when no water is added) could be avoided because the produced CO is further reacted in the process, thereby increasing the ethanol yield and selectivity.
  • the molar ratio of H2O and CO2 is between 0.1 and 1 .0, such as 0.1 , such as 0.2, such as 0.3, such as 0.4, such as 0.5, such as 0.6, such as 0.7, such as 0.8, such as 0.9, such as 1 .0 but is preferably 0.4 or 0.5, more preferably the molar ratio of H 2 O and CO2 0.4.
  • the H2O/CO2 molar ratio is between 1 :10 and 1 :1 , such as 1 :10, such as 2:10, such as 3:10, such as 4:10, such as 5:10, such as 6:10, such as 7:10, such as 8:10, such as 9:10, such as 1 :1 but is preferably 4:10 or 5:10, more preferably H2O/CO2 molar ratio is 4:10.
  • One embodiment of the present disclosure is to provide a method for the catalytic hydrogenation of CO2 into ethanol in the presence of a zeolite catalyst, the method comprising contacting a feed stream containing CO2 and H 2 with the catalyst and a source of water such as to achieve a H2O/CO2 ratio of from 0.4 to 0.5, wherein the source of water is provided periodically for one every three consecutive hours; preferably wherein the zeolite catalyst is a silylated Cu-doped GME catalyst, such as obtained by the reaction between Cu-doped GME and a silylating agent.
  • the feed stream may in some embodiments comprise other reagents and/or molecules than only carbon dioxide and hydrogen, that is to say the feed stream may in one embodiment comprise CO2, H 2 and at least one further reagent such as carbon monoxide.
  • the combination of CO2 and CO with H2 will generally result in higher conversion of CO2, thereby increasing the yield of value-added chemicals produced from the reaction.
  • the CO/CO2 molar ratio is between 1 :10 and 1 :1 , such as 1 :10, such as 2:10, such as 3:10, such as 4:10, such as 5:10, such as 6:10, such as 7:10, such as 8:10, such as 9:10, such as 1 :1. More preferably the CO/CO2 molar ratio is below 4:10, such as below 3:10, such as below 2:10, such as between 5:100 and 2:10.
  • the catalytic hydrogenation is carried out at non-ambient pressure.
  • the catalytic hydrogenation is carried out at a pressure between 0.5 MPa and 5 MPa, such as between 1 .0 MPa and 4 MPa, such as between 1 .5 MPa and 3 MPa, such as between 1 .5 MPa and 2.5 MPa, such as between 1 .7 MPa and 2.3 MPa, such as between 1 .8 MPa and 2.2 MPa, such as between 1 .9 MPa and 2.1 MPa, such as 2.0 MPa
  • the conversion rate of CO2 gradually increases with pressure, ranging from approximately 6.1 % at 1 .5 MPa to approximately 8.5% at 3.0 MPa.
  • the selectivity towards ethanol production does not follow the same trend and instead displays an optimum at 2.0 MPa of pressure.
  • ethanol selectivity increases to a significant 63% at 2.0 MPa (corresponding to 7.33% CO2 conversion) before again dropping down to modest but still relevant 44% and 39% at 2.5 MPa and 3.0 Mpa respectively.
  • the catalytic hydrogenation is carried out at a pressure a or above 1 .8 MPa, such as at or above 1 .9 MPa, such as at or above 2.0 MPa.
  • the catalyst is brought into contact with the feed stream at a temperature of at least 200 °C, such as at least 250 °C, such as at least 300 °C, such as at least at least 350 °C.
  • the catalyst is brought into contact with the feed stream at a temperature from 200 °C to 500 °C, such as from 200 °C to 400 °C, such as from 250 °C to 350 °C, such as from 275 °C to 325 °C, but preferably at a temperature ranging from 250 °C to 300 °C.
  • the method provides continuous CO2 conversion above 6.0 % for at least 8 hours of continuous operation and/or hydrogenation, such as for at least 15 hours, such as for at least 25 hours, such as for at least 40 hours, such as for at least 50 hours.
  • the method provides continuous CO2 conversion above 7.0 % for at least 8 hours of continuous operation and/or hydrogenation, such as for at least 15 hours, such as for at least 25 hours, such as for at least 40 hours, such as for at least 50 hours.
  • the method provides continuous CO2 conversion above 8.0 % for at least 8 hours of continuous operation and/or hydrogenation, such as for at least 15 hours, such as for at least 25 hours, such as for at least 40 hours, such as for at least 50 hours.
  • the method is for catalytically producing ethanol from CO2 hydrogenation reaction with a selectivity of at least 30% during continuous operation for at least 8 hours, such as for at least 15 hours, such as for at least 25 hours, such as for at least 40 hours, such as for at least 50 hours.
  • the method provides continuous ethanol selectivity is above 30 % for at least 8 hours of continuous operation and/or hydrogenation, such as for at least 15 hours, such as for at least 25 hours, such as for at least 40 hours, such as for at least 50 hours.
  • the method is for catalytically producing ethanol from CO2 hydrogenation reaction with a selectivity of at least 40% during continuous operation for at least 8 hours, such as for at least 15 hours, such as for at least 25 hours, such as for at least 40 hours, such as for at least 50 hours.
  • the method provides continuous ethanol selectivity is above 40 % for at least 8 hours of continuous operation and/or hydrogenation, such as for at least 15 hours, such as for at least 25 hours, such as for at least 40 hours, such as for at least 50 hours.
  • said method provides ethanol selectivity which is stable or which does not decrease for at least 8 hours of continuous operation, such as for at least 15 hours, such as for at least 25 hours, such as for at least 40 hours, such as for at least 50 hours.
  • a system for the catalytic conversion of CO2 into ethanol in a hydrogenation reaction comprising: a. a reaction chamber equipped with a zeolite catalyst; b. a reaction chamber inlet for CO2, H 2 and optionally H 2 O provided together or separately; c. a heating source; and d. a product outlet; wherein the reaction chamber is a plug-flow reactor and wherein the zeolite catalyst is a gmelinite (GME) based catalyst.
  • GME gmelinite
  • the catalyst is selected from the group consisting of gmelinite sodium (Na-GME), gmelinite potassium (K-GME) and gmelinite calcium (Ca-GME), and/or the catalyst unit cell comprises a repeating unit selected from the group consisting of Na 4 (Si8AI 4 )O 24 -11 H 2 O, K 4 (Si8AI 4 )O2 4 -11 H 2 O, and Ca2(Si8AI 4 )O24- 11 H2O.
  • the catalyst is a mixed gmelinite potassium/calcium catalyst (K-Ca)-GME.
  • K-Ca mixed gmelinite potassium/calcium catalyst
  • the potassium and calcium is present in K/Ca ratio ranging from 0.4 to 4, more preferably ranging from 0.5 to 2.0, more preferably from 1 .0 to 1 .5.
  • the catalyst may be a silylated catalyst obtained by the reaction between a gmelinite or Cu-doped gmelinite catalyst and a silylating agent, such as selected from the group consisting of trichloromethylsilane (hi), trimethylchlorosilane (h 2 ), trimethoxymethylsilane (hs) and hexadecyltrimethoxysilane (h 4 ).
  • silylated catalysts catalysts obtained by said reaction
  • for catalytic hydrogenation of CO2 into value-added chemicals such as ethanol.
  • the catalyst may further comprise at least one auxiliary transition metal, such as comprise from 0.5 to 5 wt% (based on total catalyst weight) of at least one auxiliary transition metal.
  • the transition metal is preferably a non-noble transition metal and may in one embodiment be selected from the group consisting of Cu, Fe, Ni, Co, Mn, Cr, or any two-element mixture thereof, but is preferably comprising Cu, such as consisting essentially of Cu, more preferably zero-valent Cu.
  • the catalyst of the disclosed system may in some embodiments comprise from 0.5 to 5.0 wt% (based on total catalyst weight) of the at least one auxiliary transition metal, such as non-noble transition metal.
  • the at least one auxiliary transition metal is present in an amount (based on total catalyst weight) from 0.5 wt% to 2.5 wt%, such as from 0.8 wt% to 2.2 wt%, such as from 0.5 wt% to 2.0 wt%, such as from 0.5 wt% to 1 .5 wt%, such as from 1 .0 wt% to 1 .5 wt%.
  • a solid zeolite catalyst selected from the group consisting of gmelinite potassium (K-GME), gmelinite sodium (Na-GME), and gmelinite calcium (Ca-GME), characterized in comprising 0.5 wt% to 2.5 wt% (based on the total catalyst weight) of at least one auxiliary non-noble transition metal.
  • the at least one auxiliary non-noble transition metal is present in an amount (based on total catalyst weight) from 0.8 wt% to 2.2 wt%, such as from 1 .0 wt% to 2.0 wt%, such as from 1 .0 wt% to 1 .5 wt%.
  • the auxiliary non-noble transition metal of the presently disclosed zeolite catalyst is preferably a non-noble transition metal, and may in one embodiment be selected from the group consisting of Cu, Fe, Ni, Co, Mn, Cr, or any two-element mixture thereof, but is preferably comprising Cu, such as consisting essentially of Cu, more preferably zero- valent Cu.
  • the catalyst as provided hereinabove for the catalytic hydrogenation of CO2 into a value- added chemical, such as wherein the chemical is selected from the group consisting of ethanol, methanol, methane, methanal, and ethanal (CH 3 CHO), preferably ethanol.
  • the use is of a Cu-doped zeolite catalyst obtained by reaction such as K-GME, Ca-GME or (K-Ca)-GME obtained by the reaction with a silylating agent selected from the group consisting of trichloromethylsilane (hi), trimethylchlorosilane (hs), trimethoxymethylsilane (hs) and hexadecyltrimethoxysilane (h 4 ).
  • a silylating agent selected from the group consisting of trichloromethylsilane (hi), trimethylchlorosilane (hs), trimethoxymethylsilane (hs) and hexadecyltrimethoxysilane (h 4 ).
  • the use is of a silylated catalyst obtained by the method comprising: a. providing a gmelinite based zeolite selected from potassium gmelinite, sodium gmelinite, calcium gmelinite or a mixture thereof such as mixed potassium/calcium gmelinite; b. dispersing said zeolite into an organic non-polar solvent, preferably toluene to provide a first solution; c. preparing a second solution by dissolving a silylating agent in an organic non-polar solvent, preferably toluene; d. mixing the first solution with the second solution and stirring the resulting mixture for at least 8 hours, more preferably 24 hours; and e. recovering the silylated gmelinite-based catalyst from the mixture.
  • said gmelinite based zeolite is doped with from 0.8 to 2.2 wt% Cu (based on total catalyst weight before silylation) in order to ensure sufficient catalytic hydrogenation properties of the resulting catalyst.
  • catalysts referred to as H-Cu/FAU, K- Cu@GME, Na-Cu@GME and Ca-Cu@GME refer to zeolites with a 1 wt% (based on the total catalyst weight) Cu-loading.
  • the Cu-loading (unless specified otherwise) also refers to 1 wt% (based on the total catalyst weight) prior to reaction with the silylating agent.
  • X- was carried out by using a HUBER G670 Gionier camera in transmission mode with Cu-Ka radiation. The powders were measured with 0.005° steps for 1 hour.
  • the powders Prior to the measurements, the powders were degassed at 400 °C overnight under vacuum.
  • the Brunauer-Emmett-Teller (BET) method was used to estimate the surface area.
  • the pore volume of the materials was estimated by a single point adsorption at 0.95 relative pressure.
  • the t-plot method (Galarneau, A. et al.) was used to calculate the micropore volume, an alternative methodology could follow ASTM D4365.
  • the Barrett-Joyner-Halenda (BJH) method on the desorption brand was used for the pore size distribution.
  • Scanninq electron was done on a Quanta 200 ESEM FEG operated at 20 kV.
  • the samples were loaded on carbon tape and coated with gold for 60 seconds at 20 nA current in argon atmosphere. was performed on a micromeritics ASAP 2020. Initially, the samples were heated to 500 °C in a flow of N 2 . The temperature was then decreased to 150 °C and subsequently, the gas was changed to an NH 3 flow for 30 minutes to get the NH 3 to chemisorp on the catalyst, before the catalyst was flushed with N 2 for 3 hours to remove physically adsorbed NH 3 . The desorption of NH 3 took place when the temperature was increased at 600 °C with a ramp of 5°C/min.
  • X-ray Fluorescence was done in a PANanalytical Epsilon 3X. Prior to the measurement, the powders (250 mg) were mixed with the non-wetting agent Li Br (0.60 g) and Lithium Borate Flux (10.5 g). A Claisse LaNEO FLuxer was used to melt the mixture at 1050 °C and poured into a mold to create glass discs for the XRF measurements.
  • the 27 AI-MAS-NMR spectra were obtained using one-pulse experiments with a 0.5 ps TT/1 2 excitation pulse, an interscan delay of 0.5 s, and a spinning frequency of 8 kHz.
  • the 29 Si-MAS-NMR spectra were obtained using one-pulse experiments with a 4.75 ps TT/2 excitation pulse, an interscan delay of 60 s, and a spinning frequency of 5 kHz.
  • High-power 1 H decoupling was applied during the acquisition of both 27 AI- and 29 Si-MAS-NMR.
  • Electron resonance (EPR) spectroscopy was done using an ER 4102ST resonance cavity, at a microwave frequency of 9.46 GHz and microwave power of 6.67 mW on a Broker CW X-band EMX spectrometer. Electromagnets consisting of two large water-cooled copper coils were utilized to generate magnetic fields ranging from 220 mT to 300 mT. The EPR spectra had a modulation frequency of 100 kHz and a modulation amplitude of 5.2 G.
  • H-FAU commercial H-FAU
  • the CU(NO 3 ) 2 aqueous solution was added drop-wise to the plastic bottle while stirring, and was subsequently left stirring for a minimum of 8 hours.
  • the light blue powder was washed with deionized H 2 O, dried at 80 °C for a minimum of 8 hours, and was calcined at 550 °C for 5 hours with a temperature ramp of 3 hours to form the material denoted as H-Cu/FAU.
  • the sodium ions were exchanged with potassium ions, calcium ions or a mix of both.
  • K-ion exchange 1 .0 g Na-Cu@GME was added to a beaker containing an 80 mL solution of KNO3 in demineralized H 2 O. The beaker with a magnetic stirrer, was then placed in an oil bath and maintained at 80°C for at least 8 hours. The amount of potassium ions in the KNO3 solution was three times that of the sodium ions in the sample Na-Cu@GME, assuming that all the sodium from the added NaOH came to be in the zeolite.
  • the powder was isolated by centrifugation.
  • the resulting precipitate was washed with demineralized H 2 O and placed in a drying oven at 80°C for at least 8 hours.
  • the precipitate was calcined for 5 hours at 550 °C (with a ramp time of 3 hours) to result the material denoted as K-Cu@GME.
  • a sample denoted Ca-Cu@GME was synthesized in an analogous way from Na- Cu@GME employing Ca(NO3)2 in the ion-exchange reaction rather than KNO3.
  • a sample denoted (K-Ca)-Cu@GME was also synthesized in an analogous way from Na- Cu@Gme employing a mix of K and Ca nitrates. For this, the amount of potassium and calcium ions in the aqueous nitrate solution was three times that of the sodium ions in the sample Na-GME, i.e. (n K + n Ca )/nNa equal to 3, assuming that all the sodium from the added NaOH came to be in the Na-GME zeolite.
  • K and Ca are not very important for the final product, as ion exchange will be governed by ionic radii of the exchanged ions, allowing potassium to preferentially migrate and exchange within larger channels, while calcium due to it’s smaller size can exchange in the smaller zeolite channels of GME.
  • K:Ca ratio may vary from 10:1 to 1 :10 in the solution used for ion exchange.
  • a variety of Cu-loadings can be achieved by varying the amount of Cu which is impregnated on the commercial H-FAU zeolite in the first step of the synthesis.
  • GME catalysts with Cu-loadings of 0 (K-GME), 0.5 wt%, 1 .0 wt%, 1 .5 wt%, 2.0 wt% and 2.5 wt% were produced.
  • Synthesis of the zeolites of the present invention may be done via different methodologies.
  • the catalyst presented herein may be prepared by initially converting H-FAU to Na-GME via interzeolite conversion using NaOH and subsequently ion-exchanged with K and/or Ca and/or Cu to achieve Cu- doped gmelinite type catalysts.
  • the skilled person can produce catalysts following this alternative methodology following the procedure outlined in Mielby, J. et al. (2001 ) without undue burden.
  • the powder samples Prior to testing of synthesized samples in the catalytic reaction, the powder samples were reduced under a flow of 5 vol.% H 2 /N 2 at 350 °C for 2 hours with a temperature ramp of 5 °C/min in a plug flow reactor.
  • the parent zeolite H-Cu/FAU exhibited a considerably higher surface area at around 549 m 2 /g and a total pore volume of 0.36 cm 3 /g, while the daughter zeolite Na- Cu@GME displayed lower surface area and total pore volume (42 m 2 /g, and 0.051 cm 3 /g, respectively).
  • Several factors are known to cause zeolites synthesized via interzeolite transformation to exhibit a lower pore volume and surface area than those synthesized via the conventional hydrothermal route.
  • the original zeolite framework is initially dissolved, and then recrystallized to another structure, leading to the formation of crystals with reduced surface area and pore volume.
  • conventional hydrothermal synthesis typically yields crystals with a greater surface area and pore volume that are larger and better defined.
  • the interzeolite transformation process involves the migration of cations between the parent and daughter zeolites, which can potentially lead to changes in the crystal structure and pore size distribution, resulting in a decrease in the final product's overall surface area and pore volume.
  • the surface area (14 m 2 /g) and total pore volume (0.037 cm 3 /g ) of K-Cu@GME is lower than the corresponding Na-Cu@GME.
  • Table 1 Surface area and pore volumes for various zeolites of the present invention calculated from N 2 -physisorption at 77 K. Numbers in sample name indicate Cu- loadings in the range of 0.1 to 2.5 wt% as achieved by incipient wetness impregnation of H-FAU followed by interzeolite transformation as described here above. a Estimated by the t-plot method, b estimated from a single point adsorption of 0.95 relative pressure, c estimated by the BET method.
  • the synthesis procedure is exemplified using K-Cu@GME wherein the FAU to GME interzeolite transformation was performed in a calcination step at 400 °C for 5 with a ramp time of 4 hours.
  • the K-Cu@GME may however also be calcined at other temperatures in the range of 300 to 550 °C without significantly impacting the resulting properties.
  • 1g of the K-Cu@GME catalyst was dispersed in 20 ml of toluene.
  • the dispersion of the catalyst was achieved with the use of an ultrasonic bath for approximately 30 minutes.
  • another solution was prepared containing the respective silylating agent and 20 ml toluene. Varying amounts of the silylating agent were assessed, ranging from a minimum of 0.5 mmol per gram of zeolite to a maximum of 10 mmol per 1 gram of zeolite.
  • the solution with the silylating agent was combined with the dispersed zeolite in toluene solution and the mixture was left to stir for 24 hours at room temperature while covered with aluminum foil.
  • the diffractogram of 0.5hi ⁇ K-Cu@GME closely resembles non-silylated K-Cu@GME, with well-defined GME peaks.
  • the zeolites silylated with more than 2.5 mmol of trichloromethylsilane pr 1 gram zeolite exhibit two significantly more intense peaks, indicating altered signals and a reduction in the GME signal intensity.
  • Silylation involves the reaction of silane compounds with zeolite surface hydroxyl groups. Without wishing to be bound by theory, this process is believed to potentially introduce organic moieties, modifying the structure to make it more hydrophobic and potentially impacting the crystal lattice. The degree of impact on the diffractograms of Fig. 5 appear to be proportional to the concentration of the silylating agent.
  • Fig. 6 the four investigated silylating agents are reacted with K-Cu@GME in the lowest evaluated concentration (0.5 mmol per 1 gram zeolite). It can be seen that the specific silylating agent employed had no discernible effect on the catalysts structure.
  • N 2 physisorption provided estimates of surface area and total pore volume for the silylated catalysts, with results detailed in Table 2.
  • silylation consistently increased both BET surface area and pore volume compared to non-silylated K- Cu@GME contradicting what has generally been known in the art such as in Vu et.,(2018) where post-synthetic silylation methods lead to a reduction in pore volume.
  • the increase was particularly pronounced when the concentration of the silylating agent trichloromethylsilane (hi) was increased, leading to significant enhancements in both parameters.
  • the surface area increased from 14 m 2 g 1 in K-Cu@GME to 95.18 m 2 g 1 in 7.5hi ⁇ K-Cu@GME.
  • this increase be attributed to the interaction of chlorine in trichloromethylsilane with zeolite OH groups, resulting in HCI production during silylation.
  • This presence of HCI could potentially induce dealumination, creating additional micropores and boosting overall porosity.
  • the treatment also enriched silicon in the zeolite framework, fostering the development of new silica domains and further enhancing porosity.
  • Example 2 initial catalytic testing for production of ethanol from CO2
  • the catalysts as produced above were tested under flow conditions, by using the Micromeritics plug flow reactor FR-50.
  • the stainless steel reactor had an inner diameter of 4 mm, and it was loaded with 100 mg of the fractionated catalyst (150-355 pm) mixed with roughly 900 mg of fractionated quartz (150-355 pm).
  • the solids were fixed between two pieces of quartz wool.
  • the temperature of the reaction was regulated using a thermocouple placed in the middle of the reactor.
  • K-Cu@GME was first reduced in situ at 350 °C under a flow of H 2 (5 mL/min) and N 2 (45 mL/min) for 120 min.
  • the reduced K-Cu(1 )@GME was in a first setup tested under 2.0 MPa and at the temperature range 200 °C to 350 °C.
  • the reactant gas flow volume ratios (H 2 /CO 2 ) varied from 4:1 to 6:1 .
  • H 2 O was investigated in the reactant gas mixture by adding H 2 O to the reaction chamber with an HPLC pump.
  • the H 2 O/CO 2 molar ratio varied from 0.35 to 0.7 while CO 2 was fed in the reactor with a constant flow of 10 mL/min, and H 2 with a constant flow of 50 mL/min.
  • the catalysts exemplified in the tables above were all subjected to the same testing regime including a prolonged stability test to evaluate the continuous operation performance of the catalyst.
  • Exemplary for Ca-Cu@GME this data can be seen in Fig. 4.
  • the catalyst displays are very high stability, maintaining CO 2 conversion above 10% and ethanol selectivity above 45% for the first 8 hours of continuous operation.
  • For the mixed potassium/calcium gmelinite catalyst (denoted (K- Ca)-Cu@GME) data obtained under similar conditions can be seen in Fig. 7A.
  • Fig. 7B is XRD data showing that the structure of the zeolite does not change with mixing potassium and calcium, the shown diffractograms are essentially superimposable with parent Na-GME except for intensity differences.
  • the mixed gmelinite catalyst displays a good CO 2 conversion above 10% with stable and high production (selectivity of approximately 60%) of EtOH for the first 13 hours of continuous operation.
  • the quantification of products was done using an online GC with an FID detector equipped with PoraBond U polar column, and a TCD detector equipped with two DB-1 non-polar capillary column. Calibration of the GC was performed by creating standard curves through direct injection of commercial analogues of the analytes with known concentrations. From the constructed calibration curves, a calibration equation was determined for each analyte. Unless specified otherwise, the catalytic results shown in Table 3 to Table 9 here below were quantified based on GC measurements performed after 1 hour of operation under the specified conditions.
  • Fig. 1 a shows the production of carbon monoxide, methane (CH 4 ), methanol (CH 3 OH), formaldehyde (CH 2 O), and ethanol (EtOH) at 350°C.
  • the CO 2 conversion rate (3.16%) and ethanol selectivity (1 1%) were observed to be too low for feasible industrial applications.
  • the selectivity towards CO at 350°C was notably high (70%).
  • Fig. 1 b shows the experimental results when adding water to the feed stream at a H 2 O/CO 2 ratio of 0.35. The addition of water resulted in a reduction in CO production and an increase in ethanol production, which was observed at 250°C with higher conversion and selectivity.
  • Table 5 Catalytic results for K-Cu@GME at 2.0 Mpa, H2/CO2 at 5, H2O/CO2 at 0.4
  • Table 6 Catalytic results for K-Cu@GME at 2.0 Mpa, H2/CO2 ratio of 4, and a H2O/CO2 ratio of 0.4.
  • the optimal conditions for the CO2 hydrogenation using K-Cu@GME were determined to be a H2/CO2 ratio of 5 and a H2O/CO2 ratio of 0.4 at 250°C and 2.0 Mpa.
  • a H2O/CO2 at 0.5 was also found to perform very well for this system.
  • Example 3 effects of pressure on CO2 conversion and ethanol selectivity.
  • Table 8 Catalytic results showing the influence of pressure in the CO2 hydrogenation for K-Cu@GME at 2.0 Mpa, 250 °C, H2/CO2 ratio of 5, and H2O/CO2 ratio of 0.4.
  • Example 4 effects of Cu-loading on CO2 conversion and ethanol selectivity.
  • the Cu loading referring to the amount or concentration of copper (Cu) in the catalyst, has a significant impact on the CO2 hydrogenation process for ethanol production.
  • Fig. 3 presents the CO2 conversion and selectivities of methane, methanol and ethanol at 250 °C, 2.0 Mpa, with a H2/CO2 ratio of 5 and H2O/CO2 ratio of 0.4 with varying the Cu- loading in the catalyst between 0 and 2.5 wt% (see also Table 9).
  • Cu serves as an active site for the hydrogenation reaction, facilitating the conversion of CO2 to ethanol. This is demonstrated in Fig. 3, where the absence of Cu loading (K- GME) results in the production of methane as the only detectable product, while the conversion of CO2 remains low, measuring only 1.29%. Higher Cu loading is expected to provide more available active sites, leading to increased reaction rates and improved ethanol production.
  • Cu loading can however also influence the reaction mechanism of CO2 hydrogenation and this is evident when the Cu loading increases at 2 wt% and 2.5 wt%.
  • the presence of Cu modifies the adsorption and activation of CO2 and H 2 , influencing the reaction intermediates and subsequent steps.
  • Higher Cu loading can alter the reaction pathways and favor the formation of specific products, like methanol and methane.
  • a Cu loading of 2 wt% both the CO2 conversion rate and the selectivity towards ethanol reach 7.49% and 59% respectively. These values are comparable to the CO2 conversion rate of 7.33% and the selectivity towards ethanol of 63% observed at a Cu loading of 1 wt%.
  • Fig. 3 illustrates that a loading between 1 and 2 wt% of Cu in this type of zeolites constitutes a surprising optimum.
  • Table 9 Catalytic results for K-Cu@GME with different Cu loadings at 2.0 Mpa, H2/CO2 ratio of 5, and a H2O/CO2 ratio of 0.4. K-GME is also included for reference.
  • Example 5 effects of silylation on CO2 conversion, ethanol selectivity and stability.
  • the catalytic experiments were conducted using the respective silylated catalysts under identical reaction conditions as the standard K-Cu@GME catalysts namely 20 bar and 250 °C, with a volumetric H2/CO2 ratio of 5, and a molar H2O/CO2 ratio of 0.4.
  • Fig. 8A-8D The results illustrating the performance variations of catalysts silylated by different amounts of trichloromethylsilane (hi) are shown in Fig. 8A-8D, while Fig. 9A-9C illustrates the performance of K-Cu@GME catalysts silylated using 0.5 mmol of various silylating agents (h 2 , h 3 and h 4 ) per 1 gram zeolite. From both sets of figures it is clear to see that the in situ stability and/or operando lifetime is drastically increased for all systems, generally increasing from 8 hours of stable operation up to 20 hours and above.
  • Table 10 Stability test for (K-Ca)-Cu@GME at 2.0 MPa, H2/CO2 ratio of 5, and a H2O/CO2 ratio of 0.4.
  • Table 11 - Stability test for 0.5hi ⁇ K-Cu@GME at 2.0 MPa, H2/CO2 ratio of 5, and a H2O/CO2 ratio of 0.4.
  • Table 13 Stability test for 0.5h 3 ⁇ K-Cu@GME at 2.0 MPa, H2/CO2 ratio of 5, and a H2O/CO2 ratio of 0.4.
  • Table 14 Stability test for 0.5h 4 ⁇ K-Cu@GME at 2.0 MPa, H2/CO2 ratio of 5, and a H2O/CO2 ratio of 0.4.
  • Example 6 effects of cycled water addition on operation stability.
  • a method for the catalytic hydrogenation of CO2 into at least one value-added chemical comprising contacting a feed stream containing CO2 and H 2 with a solid heterogeneous catalyst in a reaction chamber, wherein the H2/CO2 volume ratio in the feed stream is from 1 :1 to 10:1 .
  • the H2/CO2 volume ratio in the feed stream is from 1 :1 to 10:1 , such as 1 :1 , such as 2:1 , such as 3:1 , such as 4:1 , such as 5:1 , such as 6:1 , such as 7:1 , such as 8:1 , such as 9:1 , such as 10:1 or any 0.5 increment therein between.
  • the at least one value-added chemical is one or more selected from the group consisting of ethanol, methanol, methane, methanal, and ethanal.
  • reaction chamber is a plug-flow reactor 6.
  • catalyst is an acidic catalyst.
  • the catalyst is a zeolite-based catalyst selected from the group consisting of gmelinite (GME), chabazite (CHA), faujasite (FAU), and analcime (ANA).
  • GME gmelinite
  • CHA chabazite
  • FAU faujasite
  • ANA analcime
  • the catalyst has a Si/AI ratio between 2.0 and 4.0, such as between 2.0 and 2.5, such as between 2.5 and 3.0, such as between 3.0 and 3.5, such as between 3.5 and 4.0, preferably between 3.0 and 4.0, such as 3.1 , 3.2, 3.3, 3.4, 3.5, 3,6, 3.7, 3.8, 3.9, 4.0, or any 0.01 increment therein between.
  • the catalyst is selected from the group consisting of gmelinite sodium (Na-GME), gmelinite potassium (K-GME) and gmelinite calcium (Ca-GME).
  • the catalyst unit cell comprises a repeating unit selected from the group consisting of Na 4 (Si 8 AI 4 )O 24 -11 H 2 O, K 4 (Si 8 AI 4 )O 24 - 11 H 2 O, and Ca 2 (Si 8 AI 4 )O 24 -11 H 2 O.
  • the catalyst further comprises at least one auxiliary transition metal.
  • the catalyst comprises from 0.5 to 5.0 wt% (based on total catalyst weight) of at least one auxiliary transition metal, such as from 0.5 to 2.5 wt%, from 0.8 to 2.2 wt%, from 1 .0 to 2.0 wt%.
  • the at least one auxiliary transition metal is a non-noble transition metal.
  • the catalyst comprises 1 .0 wt% (based on total catalyst weight) of at least one auxiliary non- noble transition metal.
  • non-noble transition metal is selected from the group consisting of Cu, Fe, Ni, Co, Mn, and Cr.
  • the molar ratio of H 2 O and CO2 is between 0.1 and 1 .0, such as 0.1 , such as 0.2, such as 0.3, such as 0.4, such as 0.5, such as 0.6, such as 0.7, such as 0.8, such as 0.9, such as 1 .0 but is preferably 0.4 or 0.5, more preferably the molar ratio of H 2 O and CO20.4.
  • the method according to any one of the preceding items, wherein the catalytic hydrogenation is carried out at non-ambient pressure The method according to any one of the preceding items, wherein the catalytic hydrogenation is carried out at a pressure between 0.5 MPa and 5 MPa, such as between 1 .0 MPa and 4 MPa, such as between 1 .5 MPa and 3 MPa, such as between 1 .5 MPa and 2.5 MPa, such as between 1 .7 MPa and 2.3 MPa, such as between 1 .8 MPa and 2.2 MPa, such as between 1 .9 MPa and 2.1 MPa, such as 2.0 MPa.
  • 0.5 MPa and 5 MPa such as between 1 .0 MPa and 4 MPa, such as between 1 .5 MPa and 3 MPa, such as between 1 .5 MPa and 2.5 MPa, such as between 1 .7 MPa and 2.3 MPa, such as between 1 .8 MPa and 2.2 MPa, such as between 1 .9 MPa and 2.1 MP
  • the method according to any one of the preceding items wherein the catalyst is brought into contact with the feed stream at a temperature of at least 200 °C, such as at least 250 °C, such as at least 300 °C, such as at least at least 350 °C.
  • a system for the catalytic conversion of CO2 into ethanol in a hydrogenation reaction comprising: a. a reaction chamber equipped with a zeolite catalyst; b. a reaction chamber inlet for CO2, H 2 and optionally H 2 O provided together or separately; c. a heating source; and d. a product outlet; wherein the reaction chamber is a plug-flow reactor and wherein the zeolite catalyst is a gmelinite (GME) based catalyst.
  • GME gmelinite
  • the catalyst is selected from the group consisting of gmelinite sodium (Na-GME), gmelinite potassium (K-GME) and gmelinite calcium (Ca-GME).
  • the catalyst unit cell comprises a repeating unit selected from the group consisting of Na 4 (Si 8 AI 4 )O 24 -11 H 2 O, K 4 (Si 8 AI 4 )O 24 - 11 H 2 O, and Ca 2 (Si 8 AI 4 )O 24 -1 1 H 2 O.
  • the catalyst comprises from 0.5 to 5 wt% (based on total catalyst weight) of at least one auxiliary transition metal, such as from 0.5 to 2.5 wt%, from 0.8 to 2.2 wt%, from 1 .0 to 2.0 wt%.
  • non-noble transition metal is selected from the group consisting of Cu, Fe, Ni, Co, Mn, and Cr.
  • a solid zeolite catalyst selected from the group consisting of gmelinite potassium (K-GME), gmelinite sodium (Na-GME), and gmelinite calcium (Ca- GME), characterized in comprising 0.5-2.5 wt% (based on total catalyst weight) of at least one auxiliary non-noble transition metal, such as from 0.8 to 2.2 wt%, from 1 .0 to 2.0 wt%.
  • the catalyst according to item 40 wherein the at least one non-noble transition metal is selected from the group consisting of Cu, Fe, Ni, Co, Mn, and Cr.
  • the catalyst according to any one of items 40 to 41 wherein the catalyst comprises 1 .0 wt% (based on total catalyst weight) of at least one auxiliary non- noble transition metal.
  • the catalyst according to any one of items 40 to 41 wherein the catalyst comprises 2.0 wt% (based on total catalyst weight) of at least one auxiliary non- noble transition metal.
  • the catalyst according to any one of items 40 to 43, wherein the non-noble transition metal is Cu.
  • the catalyst according to item 44, wherein the Cu is in the form of zero-valent Cu.
  • a method for the catalytic hydrogenation of CO2 into at least one value-added chemical selected from the group consisting of ethanol, methanol, methane, methanal, and ethanal comprising contacting a feed stream containing CO2 and H 2 with a solid heterogeneous catalyst in a reaction chamber, wherein the H2/CO2 volume ratio in the feed stream is from 4:1 to 6:1 .
  • reaction chamber is a plug-flow reactor.
  • the catalyst is a gmelinite (GME) based catalyst selected from the group consisting of gmelinite sodium (Na-GME), gmelinite potassium (K-GME) and gmelinite calcium (Ca-GME).
  • GME gmelinite
  • Na-GME gmelinite sodium
  • K-GME gmelinite potassium
  • Ca-GME gmelinite calcium
  • the catalyst unit cell comprises a repeating unit selected from the group consisting of Na 4 (Si 8 Al4)O24-11 H 2 O, K 4 (Si 8 Al4)O24-11 H 2 O, and Ca 2 (Si 8 AI 4 )O24-1 1 H 2 O.
  • the catalyst further comprises at least one auxiliary transition metal.
  • the catalyst comprises from 0.8 wt% to 2.2 wt% (based on total catalyst weight) of at least one non-noble transition metal selected from the group consisting of Cu, Fe, Ni, Co, Mn, and Cr .
  • a system for the catalytic conversion of CO2 into ethanol in a hydrogenation reaction comprising: a. a reaction chamber equipped with a zeolite catalyst; b. a reaction chamber inlet for CO2, H 2 and optionally H 2 O provided together or separately; c. a heating source; and d. a product outlet; wherein the reaction chamber is a plug-flow reactor and wherein the zeolite catalyst is a gmelinite (GME) based catalyst selected from the group consisting of gmelinite sodium (Na-GME), gmelinite potassium (K-GME) and gmelinite calcium (Ca-GME),
  • GME gmelinite
  • a solid zeolite catalyst selected from the group consisting of gmelinite potassium (K-GME), gmelinite sodium (Na-GME), and gmelinite calcium (Ca- GME), characterized in comprising 1 .0-2.0 wt% (based on total catalyst weight) of Cu.

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Abstract

La présente invention concerne le domaine de l'utilisation de dioxyde de carbone (CO2) et plus spécifiquement la conversion de CO2 en produits chimiques à valeur ajoutée par hydrogénation. La présente invention concerne ainsi des procédés et des catalyseurs pour une conversion efficace et sélective de CO2 en produits chimiques à valeur ajoutée par hydrogénation, ainsi que des systèmes mettant en oeuvre à la fois ceux-ci.
PCT/EP2024/060292 2023-06-30 2024-04-16 Conversion de dioxyde de carbone en produits chimiques à valeur ajoutée à l'aide de catalyseurs à base de zéolite Pending WO2025002620A1 (fr)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017211237A1 (fr) * 2016-06-08 2017-12-14 Basf Corporation Gmelinite à promoteur de cuivre et son utilisation dans la réduction catalytique sélective de no x
WO2020092113A1 (fr) * 2018-10-31 2020-05-07 Basf Corporation Composition catalytique comprenant un composant de piégeage de cuivre ajouté pour une réduction des nox
CA3180719A1 (fr) * 2020-05-29 2021-12-02 Johannis Alouisius Zacharias Pieterse Catalyseur multifonctionnel pour la conversion de dioxyde de carbone

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017211237A1 (fr) * 2016-06-08 2017-12-14 Basf Corporation Gmelinite à promoteur de cuivre et son utilisation dans la réduction catalytique sélective de no x
WO2020092113A1 (fr) * 2018-10-31 2020-05-07 Basf Corporation Composition catalytique comprenant un composant de piégeage de cuivre ajouté pour une réduction des nox
CA3180719A1 (fr) * 2020-05-29 2021-12-02 Johannis Alouisius Zacharias Pieterse Catalyseur multifonctionnel pour la conversion de dioxyde de carbone

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GALARNEAU, A ET AL.: "Langmuir", 2014, AMERICAN CHEMICAL SOCIETY, article "Validity of the t-Plot Method to Assess Microporosity in Hierarchical Micro/Mesoporous Materials"
MICHIEL DE PRINS ET AL: "Structural parameters governing low temperature activity of small pore copper zeolites in NH3-SCR", JOURNAL OF CATALYSIS, vol. 390, 12 August 2020 (2020-08-12), US, pages 224 - 236, XP055736716, ISSN: 0021-9517, DOI: 10.1016/j.jcat.2020.08.003 *
MIELBY, J ET AL.: "A shortcut to high-quality gmelinite through steam-assisted interzeolite transformation", MICOPOROUS AND MESOPOROUS MATERIALS, 2022, Retrieved from the Internet <URL:https://doi.org/10.1016/j.micromeso.2021.111606>
VU, H.-T. ET AL.: "Silylated Zeolites With Enhanved Hydrothermal Stability for the Aqueous-Phase Hydrogenation of Levulinic Acid to y-Valerolactone", FRONT. CHEM., vol. 6, 2018, pages 143, XP055833717, DOI: 10.3389/fchem.2018.00143

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