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    • 专利摘要:
    A method for conducting a catalytic reaction on a catalyst layer 121 supported on a surface 10A of a porous material 10 is provided. In the method, a reactive compound 1 is directed into a confined reaction space 201 through the porous material 10 towards the supported catalyst layer 121 to yield, into said reaction space 201, a product compound 2 formed as a result of catalytic reactions at the catalyst layer.
    公开号:FI20195480A1
    申请号:FI20195480
    申请日:2019-06-06
    公开日:2020-12-07
    发明作者:Marko Pudas
    申请人:Picosun Oy；
    IPC主号:
    专利说明:

    METHOD FOR CONDUCTING CATALYTIC REACTION
    FIELD OF THE INVENTION The present invention generally relates to methods and systems for conducting chemical reactions on solid-state porous catalysts. In particular, the invention concerns a method and related system, in where catalytic reactions occur at catalyst layers or films supported on surfaces of essentially solid porous materials.
    BACKGROUND Porous solid-state or solid-phase catalysts have gained popularity in the field of organic chemistry due to providing additional selectivity in terms of size and/or shape of the molecules, such as reactants, intermediates and products. Conventional porous catalysts are produced by functionalizing the internal pore network of the porous carrier with predetermined catalytic substances. Commercial solid-state porous catalysts can be provided as shape-selective articles tailored to meet the needs of various industrial processes. Such articles are established by a porous carrier, such as zeolites, porous ceramics, porous metals, for example, deposited with catalytic substance(s) throughout its entire structure. Chemical deposition processes, such as chemical vapor deposition (CVD), atomic layer deposition (ALD) and modifications thereof, have gained popularity in manufacturing porous catalysts in view of capability of these methods to generate porous structures impregnated with a variety of chemicals, as precursor gas(es) flow through the porous substrate and completely coat insides of the pores. Such catalysts can be manufactured in relatively fast timeline, as in conventional ALD processes, precursor gases absorb > into certain porous substrates to a depth of about I mm in approximately 1 second. N At present, solid-state porous catalysts produced by chemical deposition methods or by O any other methods are hindered by a number of drawbacks that generally reduce life- © time of the catalyst and naturally incur additional costs to the consumer. The major I problem pertains to fouling of the catalyst due to pore clogging. Clogging can be = affected by various factors, such as excessive amount of intermediates / products > produced on the catalyst, release of side products, improper selection of reactants and/or & product design in view of catalyst pore size, ageing of the catalyst, etc. Clogging of pore > network reduces the catalysts’ ability to transport reactant and product molecules therethrough. If the process cannot be stopped for some reasons and the reactant is kept delivered onto the clogged catalyst, reactant molecules experience hindrances to assess catalytic sites in blocked pores, whereby activity of such catalyst is markedly reduced, which results in substantially decreased reaction yields. Regeneration of conventional solid-state porous catalysts, such as zeolite catalysts, often requires withdrawal of the catalyst from a catalytic reactor due to incapacity of many reactors to withstand regeneration conditions (500 degrees Celsius in presence of air). In this regard, an update in the field of technology that concerns conducting chemical reactions on solid-state porous catalysts is still desired, in view of addressing challenges associated with formation of clogs in porous catalyst materials in the course of catalytic processes.
    SUMMARY OF THE INVENTION An objective of the present invention is to solve or to at least alleviate each of the problems arising from the limitations and disadvantages of the related art. The objective is achieved by various embodiments of a method and related system for conducting a catalytic reaction on a catalyst layer supported on a surface of a porous material. Thereby, in one aspect of the invention a method for conducting a catalytic reaction provided, in accordance to what is defined in the independent claim 1. In preferred embodiment, the method for conducting a catalytic reaction on a catalyst layer supported on a surface of a porous material is provided, in which method at least one reactive compound is directed into a confined reaction space through the porous material towards the supported catalyst layer to yield, into said reaction space, at least one product compound formed as a result of catalytic reactions at the catalyst layer. = In embodiments, the reactive compound is an organic compound comprising at least one N carbon atom.
    S O In embodiments, the reactive compound is a hydrocarbon compound comprising at least x two carbon atoms. In some embodiments, the reactive compound is an unsaturated S hydrocarbon compound. In some embodiments, the reactive compound is a hydrocarbon > compound selected from the group consisting of an alkene compound, an alkyne S compound and a diene compound. In some embodiments, the reactive compound is > ethylene.
    In embodiments, the catalyst layer supported on the surface of the porous material comprises an at least one metal.
    In some embodiments, said catalyst layer comprises a metal selected from the group consisting of palladium, platinum and ruthenium.
    In embodiments, the catalyst layer is formed by a polymerization catalyst compound supported on the surface of the porous material.
    In some embodiments, the catalyst layer is formed by a Phillips-type catalyst compound supported on the surface of the porous material.
    In embodiments, the catalyst layer is formed by a hydrogenation catalyst compound supported on the surface of the porous material.
    In embodiments, the porous material is selected from the group consisting of porous metal, porous ceramics and porous polymer.
    In some embodiments, the porous material is established by a fibrous substrate or a particulate substrate.
    In another aspect, a system for conducting a catalytic reaction on a catalyst layer supported on a surface of a porous material is provided, according to what is defined in the independent claim 14. In said system, at least one reactive compound is directed into a confined reaction space through the porous material towards the supported catalyst layer to yield, into said reaction space, at least one product compound formed as a result of catalytic reactions at the catalyst layer.
    In some embodiments, the system is configured as a chemical deposition reactor.
    In still further aspect, a catalyst comprising a porous material with a catalyst layer supported on a surface of said porous material is provided, according to what is defined in the independent claim 16. Said catalyst is configured to receive at least one reactive compound into the porous material and to propagate said reactive compound through > the porous material towards the supported catalyst layer, at which catalyst layer the N reactive compound undergoes a catalytic reaction, whereupon at least one product S compound is formed.
    Use of said catalyst is further provided for polymerization of O olefins according to what is defined in the independent claim 17. = a The utility of the present invention arises from a variety of reasons depending on each 2 particular embodiment thereof.
    The invention provides a robust, versatile and highly D tailorable tool for synthesizing a variety of new useful compounds on supported porous > catalysts.
    In the system and the method disclosed hereby, the catalyst layer is deposited on the surface of the porous carrier material in a manner that promotes flow of reaction products directly into the reaction space.
    Although the reactive substances are allowed to enter the reaction space via the porous catalyst, catalytic reaction(s) do not occur until said reactive substances reach the catalyst layer. By such an arrangement, clogging of porous carrier(s) can be effectively avoided. The invention enables synthesis of essentially solid products, such as polyethylene compounds, for example. This is attained by selectively inducing electron excitation in the catalyst layer. The term “catalyst” is indicative of a compound that triggers reactions between starting substances causing molecules, contained in said starting substances, to interact and/or that further accelerates the reaction between starting substances, without being consumed or altered. The expression “a number of” refers in the present disclosure to any positive integer starting from one (1), e.g. to one, two, or three. The expression “a plurality of” refers herein to any positive integer starting from two (2), e.g. to two, three, or four.
    BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 schematically illustrate various embodiments of a method and a system, according to the aspects of the present invention. Fig. 2 schematically illustrates a process of preparation of a solid-state catalyst, according to some aspect of the present invention.
    DETAILED DESCRIPTION OF THE DRAWINGS Detailed embodiments of the present invention are disclosed herein with the reference to D accompanying drawings. The same reference characters are used throughout the O . . oo N drawings to refer to same members. Following citations are used for the members: © 2 1 — a reactive compound for conducting catalytic reaction on a solid-state catalyst 200; O 2 — a product compound obtained upon conducting catalytic reaction on a solid-state E catalyst 200; a . . 10, 10A — a porous substrate and a surface at which a catalyst layer is formed, O . % accordingly; S 11, 12 — inert and reactive fluids, accordingly, used in preparation of the catalyst 200; > 31, 101 — eguipment used in preparation of the catalyst 200; 110 — a system for preparation of the solid state catalyst 200; 121 — a catalyst layer;
    200 — a solid state catalyst; 201 — a reaction space for conducting chemical reaction on a solid state catalyst 200; 202 — an intake volume for reactive compound 1; 203 — an energy source; 210 — a system for conducting catalytic reaction on the solid-state catalyst 200. Fig. 1 illustrates a concept underlying a method for conducting chemical reactions on a catalyst supported on a porous material, in accordance to various embodiments. In the method, a porous support material 10 is provided with a surface 10A, referred to hereafter, as a target surface, is deposited with a catalyst layer 121. Formation of the catalyst layer or film 121 pertains strictly to surface of the porous material. The expression “a target surface” is hereby indicative of an exterior surface of the porous material deposited with the catalyst layer 121 forming a catalytic surface. The porous material 10 and the catalyst layer 121 formed on the surface of said porous material together establish a catalyst 200. The catalyst 200 is a finite item of solid material (a solid-state catalyst) comprising a porous carrier with a catalytic layer established on a surface thereof. The catalytic surface 121 can be provided as a simple one-layer structure or as a multilayer structure (a so called stack). In the stack, the layers differ from one another in terms of composition and optionally structural parameters, such as layer thickness, for example. The layered catalyst structure can be prepared by the method described in the Example 1. In exemplary embodiments, in the catalyst 200 the porous support 10, typically 1-10 mm thick (thickness being a subject of adjustment), can be deposited with the catalyst o layer 121 having thickness within a range of 0,1 nm — 1 mm, or more preferably 1nm- > 100 um, or more preferably 10 nm — 10 um or more preferably or more preferably 100 O nm - 1 um. Thickness of the catalyst layer 121 is advantageously adjusted to meet 2 demands of a predetermined chemical process. Thus, provision of solid-state catalysts 9 200 comprising catalytic surfaces established layers with thickness exceeding 1 mm, is E not excluded.
    O 2 The catalyst 200 is placed, at least in part, into a confined reaction space 201. The 3 confined reaction space 201 is a reaction chamber (an interior thereof) of a reactor N device configured for conducting a predetermined reaction or reactions. The catalyst layer 121 and the solid-state catalyst 200 are tailored to assist in a variety of catalytic conversion (transformation) processes, such as combination (synthesis), substitution,
    metathesis, isomerization, decomposition, etc., by thorough selection of catalytic compounds and/or the porous carrier. In the method, an at least one reactive compound 1 is directed into said confined reaction space 201 through the porous material 10. The reactive compound, preferably provided in fluidic form, propagates, in said porous material, towards the supported catalyst layer 121. The reactive compound 1 is preferably provided in a gaseous form. In some other instances, the reactive compound can be provided in a liquid form or as a vapor (vaporized liquid). A variety of porous materials can be utilized as porous carrier(s) including, but not limited to metals, ceramics, polymers, composites and semiconductor materials (e.g. silicon). Cellular solids, such as metal foams and ceramic foams, can further be exploited. The porous material can be further established by a fibrous substrate or a particulate substrate. In the latter case, pores are formed by air gaps established between particles, fibers or any other related particulate matter. The invention sets no restrictions on the nature of the porous material; nevertheless, for the one skilled in the art it is clear that selection of the substrate depends on ability of potential substrate materials to withstand reaction conditions, such as temperature and pressure, and on compatibility of the predetermined reactive compounds with said substrate material. In some instances, the porous material 10 is selected from the group consisting of porous metal, porous ceramics and porous polymer. Provision of the catalyst 200 in regard the reaction space 201 is such that the reactive compound 1 is allowed to propagate into the reaction space at least partly via said catalyst. In some instances, the compound 1 is allowed to propagate into the reaction o space solely via the catalyst. In some configurations, the catalyst layer 121 is enclosed, O in its entirety, in the reaction space 201. The reactive compound 1 is supplied into the > reaction space 201 via an intake volume 202.
    O O The intake volume 202 can be configured as an essentially hollow, enclosed space =E having a predetermined volume (7), through which an unhindered flow of the reactive > compound or compounds 1 can be established. The intake volume 202 is essentially X isolated from the reaction space 201 such, that fluid communication (fluid flow) 3 between the intake volume 202 and the reaction space 201 occurs solely via the solid- state catalyst 200. It is preferred that the catalyst 200 is received, at least in part, inside the intake volume 200.
    Fig. 1 shows a layout, in which the intake volume 202 adjoins the reaction space 202. The catalyst 200 is thus accommodated in between mentioned zones. In an event the reaction space 201 is established by a reaction vessel, for example, an aperture can be provided in a sidewall or in a lid of said vessel to accommodate the solid-state catalyst
    200. The intake volume 202 can thus be configured as an essentially tubular member with or without an expansion (forming a separate compartment) at an end adjoining the reaction space 201 to accommodate the catalyst 200. In basic configurations, the intake volume 202 can be established by a feedline or feedlines, via which the reactive compound 1 is directed into the reaction space 201. The reactive compound propagating through the porous catalyst 200 (viz., through the porous material 10 towards the supported catalyst layer 121), undergoes a catalytic reaction undergoes resulting in a formation of an at least one product compound 2. The product compound is formed as a result of a catalytic reaction or reactions at the catalyst layer. Fluidic flow through the catalyst structure 200 can be controlled by pressure difference generated across said structure 200 by an evacuation pump, mass-flow controller(s) and/or a number of gas flow meters, for example (not shown). Other control means include conventional appliances, such as gas- and pressure sensors, and/or valves. The apparatus 210 advantageously comprises a control system, implemented as a computer unit, for example, and comprising at least one processor and a memory with an appropriate computer program or software. In some embodiments, the reactive compound 11 is an organic compound comprising at > least one carbon atom. Said organic compound can be a hydrocarbon compound (a N compound consisting of carbon- and hydrogen atoms, such as methane, CH) or an S organic compound additionally comprising (other) heteroatom(s), such as oxygen and/or 8 nitrogen. For clarity, the term “heteroatom” is utilized hereby to refer to non-carbon E atoms other than hydrogen. > In some exemplary embodiments, the reactive compound 1 is an aldehyde compound, O such as formaldehyde (CHO) or and/acetaldehyde (CH;COH).
    O N In some embodiments, the reactive compound 1 is a hydrocarbon compound comprising at least two carbon atoms in its carbon chain (aka main chain). The method is advantageously rendered to assist catalytic reactions, in which the reactive compound 1 is an unsaturated hydrocarbon compound or compounds with 2-12 carbons in the carbon chain (C2-C12). Hydrocarbons with even longer carbon chains can be utilized as reactive compounds 1 to the extent of their capacity to penetrate through the porous material 10.
    In some embodiments, the reactive compound 1 is a low molecular weight hydrocarbon compound provided in a gaseous form. Examples of gaseous hydrocarbons (carbon number C2-C4) are ethylene, propylene, butylene (alkenes), acetylene (alkyne), propadiene and butadiene (dienes).
    In some embodiments, the reactive compound 1 is alkene (olefin) compound having general formula C,Han. The alkene compound can be represented by linear alkenes, such as ethylene, propylene, butylene etc., or by branched alkenes, such as isobutylene, for example. In some instances, utilization of alpha-olefins (having double carbon-carbon bond at alpha-position) can be preferred due to enhanced reactivity thereof.
    In preferred configurations, the reactive compound 1 is a lower olefin (ethylene, propylene and butylene) or a mixture thereof. An isomer mixture of a predetermined compound can be provided, in which all isomers have the same carbon number (e.g.
    butene isomers). Alternatively, a mixture of alkene compounds with different carbon number can be provided (e.g. mixtures of ethylene and propylene).
    In some instances, the reactive compound(s) 1 can be provided as mixtures of lower olefins (C2-C4) with higher olefins (C5 and higher), such as hexene or octene, for example.
    In some other embodiments, the reactive compound 1 is an alkyne compound (with = general chemical formula with the general chemical formula C:H2n2). In some N instances, the reactive compound is acetylene.
    S O In further embodiments, the reactive compound 1 is a diene compound, preferably, a I linear diene compounds, such as butadiene or propadiene.
    a a 3 In some exemplary embodiments, the reactive compound 1 is a saturated hydrocarbon > compound, preferably, acyclic alkane, with 2-22 carbon atoms in its’ main chain, or a 2 mixture of such compounds. In some instances, the reactive compound 1 is represented N by optionally pre-gasified naphtha (light fraction C5-C6 and/or heavy fraction C6-C12) and/or other fractions typically obtainable upon petroleum refining. The method described hereby allows for conducting thermal decomposition, viz. cracking, of mentioned compounds at the catalyst 200. In some embodiments, the catalyst layer 121 comprises an at least one (elemental) metal compound. In some configurations, the metal is a platinum group metal (a transition metal) selected from the group consisting of palladium, platinum, ruthenium, iridium, osmium and rhodium. In preferred configurations, the metal is selected from the group consisting of palladium, platinum and ruthenium. Other metals, such as nickel, iron, copper, zinc, chromium, aluminum, titanium and wolfram, can be utilized. In further configurations, the catalyst layer can be established by an alloy film comprising at least two metal components. A non-limiting example includes formation of ZnO-Al;03 alloy film on the porous material. Mentioned combination is known from 1930’s as a catalyst for ethanol-to-butadiene conversion (Lebedev process, GB 331482). In some preferred embodiments, the catalyst layer 121 is formed by a polymerization catalyst supported on the porous material 10. By the term “polymerization”, we refer to a process, in which low molecular weight monomer molecules combine to produce oligomers and polymers. Upon oligomerization, unsaturated hydrocarbons with carbon number 4-20 are typically produced; whereas polymerization results in chains with carbon number typically exceeding 20. Fig. 1 schematically depicts a method for production ethylene polymer(s) (compound 2) on the catalyst layer 121 supported on the porous material 10 that together form the solid-state catalyst 200. Polymerization reactions proceeding via addition or condensation mechanisms can be realized. o < In some embodiments, the catalyst layer is formed by a Ziegler-Natta type catalyst, O based on complexes of transition metal salts (hereby, metals of groups IV-VIII, such as © titanium, zirconium, hafnium, nickel, vanadium, etc.) with organoaluminum I compounds. Typical transition metals salts include TiCls, TiCls, VC14, VOC, ZrCla & and NiCb. An organometallic component typically includes aluminum trialkyl 2 compound (AIR3), such as triethylaluminum (AIlEt;), or other derivatives based on
    O O group I-III metals (e.g. AIR:CI, ZnR>, RMgCI, wherein R = alkyl). Exemplary systems > for polymerization of ethylene include AIR3-TiCl4 and AIR>CI.
    In some embodiments, the catalyst layer 121 is formed by a Phillips type catalyst (chromium catalyst) supported on the surface of the porous material. Polymerization reactions, in particular, involving the Phillips-type catalyst, typically proceed at 65 — 180 °C and pressure about 2 MPa (20 bar). In some further embodiments, the catalyst layer 121 is formed by a hydrogenation catalyst, supported on the surface of the porous material. Polymerization catalysts for heteroatom compounds include, but are not limited to metal oxide films, such as tungsten trioxide (WOs3), for example, supported on platinum or any other platinum group metal (production of paraformaldehyde and polyacetaldehyde); and aluminum oxide Al20O3 (production of polyacetaldehyde). In another aspect, a system 210 is provided for conducting a catalytic reaction or reactions on the catalyst layer 121 supported on the surface 10A of the porous material 10 according to the embodiments of the method described hereinabove. The system advantageously comprises the reaction space 201 and at least one reactive fluid intake space 202. In the system, the at least one reactive compound 1 is directed into said confined reaction space 201 through the porous material 10 towards the supported catalyst layer 121 to yield, into said reaction space 201, an at least one product compound 2 formed as a result of catalytic reactions at the catalyst layer. The system 210 is thus configured as a reactor or a reactor assembly designed for conducting various types of chemical reactions, in particular, catalytic chemical reactions. Mentioned catalytic processes, include, but are not limited to chemical deposition, polymerization, hydrogenation, in particular, pyrolysis (cracking). In some instances, the apparatus 210 can be configured as an ALD or CVD reactor, = similar to that described in Example 1.
    N O In some embodiments, the system 210 comprises at least one energy source 203 (Fig. 1) O configured to cause electron excitation to the solid-state catalyst 200 and/or to the I catalyst layer 121 (Fig. 1). For the reasons described hereinbelow it is preferred that & excitation is induced solely in the catalyst layer 121.
    O s The source or sources 203 can be provided at least partly inside the reaction space 201 2 (Fig. 1). Additionally or alternatively, the source(s) 203 can be provided within the N intake volume 202 or as an auxiliary appliance outside the reactor device (not shown).
    In some embodiments, said at least one source 203 is configured as an electromagnetic (EM) radiation source. EM radiation is used to deliver photons onto the solid-state catalyst 200 and to induce photoexcitation in the catalytic surface 121 and/or in the porous carrier 10 (in case the latter being porous metal, for example). It is still preferred that said source(s) 203 is configured, in terms of irradiation intensity, wavelength range, etc., to effect solely the catalytic surface 121. Ultraviolet radiation (100 nm — 400 nm), visible light (400 nm — 800 nm), infrared radiation (over 800 nm), or microwave radiation (1 mm — 1 m) can be utilized. The solid-state catalyst 200 can be exposed to electromagnetic radiation of at least one wavelength within a predetermined wavelength range to a predetermined period of time. EM radiation source(s) can be positioned, at least partly, within the reaction space 201 to direct radiation to the catalyst layer 121 and/or outside said reaction space (within the intake volume 202, for example). In the latter case, EM radiation is allowed to penetrate through the porous material 10 prior it reaches the catalytic surface 121. The latter configuration is particularly advantageous when radiation of a predetermined wavelength is utilized, e.g. infrared. Additionally or alternatively the at least one energy source 203 can be configured to generate / induce an electric field to cause excitation to electrons (in catalyst molecules), utilizing principles of electromagnetic induction. In similar manner as described above, inductive coupling can be induced from the inside- and/or from the outside the reaction space 201. In still further configurations, the energy source 203 can be configured as a source of thermal energy disposed, at least partly, in the reaction space 201 and/or outside said reaction space. Electron excitation is attained when atoms in the heated catalyst layer o 121 produce collisions there between. & & Inducing electron excitation in the catalytic surface 121 by the methods described above 2 or by any other appropriate method, enables fine-tuning of chemical activity within the © catalyst layer 121.
    I a > In an event of inducing excitation in the catalyst layer only (via heating, for example), X selective heating of the catalyst layer 121 can be attained. Heat transfer through said 3 catalyst layer 121 is lower as compared to the same through the support material 10. At the same time heating of the catalyst layer can be faster due to smaller surface volume (thickness) occupied by the latter.
    Hence, higher temperature can be selectively attained at the catalyst layer 121 (e.g. 100 °C) in comparison to that at the porous support 10 and in the reaction space 201 (for 10 and 201, temperature regime remains essentially the same, e.g. 20 °C). Selective heating of the catalyst layer 121 allows for liguefying reaction products around the catalyst, which is essential for catalytic reactions yielding substantially solid products, such as polyethylene, for example.
    Additionally, by selective heating of the catalyst layer with regard to the ambient (viz. 10, 201), production of a number of chemicals can be enabled, which are typically unstable at high temperatures (e.g. catalyst temperatures) due to a fact that said chemicals are immediately released into the reaction space 201. Overall, temperature control can be implemented by independently adjusting (via heating or cooling) temperature in any one of: a) feedline(s) or related appliances (for gaseous media entering the reaction space); b) the reaction chamber (gaseous media in the reaction space); and c) the catalyst layer or layers.
    Adjustment for “a” and *b” can be implemented by conventional devices, such as heating jackets, heaters installed in conjunction with a reaction chamber, and associated controllers; whereas adjustment for “c” can be implemented by means of the energy source 203 and/or by any suitable temperature control device with heating and/or cooling function.
    The latter can be provided as a number of separate fluid channels inside the porous material (not shown). Liquefaction described herein above is beneficial for facilitating removal of substance(s) clogging the pores.
    Example 1. Preparation of the solid-state catalyst 200 (Fig. 2). The porous material 10 is obtained as described hereinabove.
    Formation of the catalyst layer 121 on the surface of said porous material is implemented in an exemplary reactor o 110 configured to exploit principles of vapor-deposition based techniques.
    N In terms of an overall implementation, the reactor 110 may be based on an ALD S (Atomic Layer Deposition) installation described in the US patent no. 8211235 8 (Lindfors), for example, or on the installation trademarked as Picosun R-200 Advanced E ALD system available from Picosun Oy, Finland. 2 Nevertheless, the features underlying a concept of the present invention can be D incorporated into any other chemical deposition reactor embodied as an ALD, MLD > (Molecular Layer Deposition) or CVD (Chemical Vapor Deposition), for example.
    In the context of this application, the term ALD comprises all applicable ALD based technigues and any eguivalent or closely related technologies, such as, for example the following ALD sub-types: plasma-assisted ALD, for example PEALD (Plasma Enhanced Atomic Layer Deposition) and photon-enhanced Atomic Layer Deposition (known also as photo-ALD or flash enhanced ALD). The reactor 110, implemented, hereby, as an atomic layer deposition (ALD) reactor comprises a reaction chamber 101 configured to receive, at least in part, a porous material 10 with a target surface 10A to be deposited with the catalyst layer. In the method, shown on Fig. 2, a series of predetermined precursor compounds have been directed into the reaction chamber 101 in a flow of reactive fluid 12 such that reactive fluid 12 directed into the reaction chamber comprises one precursor compound at a time. Inert fluid 11 possessing essentially zero reactivity towards the precursors (reactants) and the reaction products has been continuously directed (from a volume 31) through the porous material 10 towards the target surface 10A. At said surface, a flow of inert fluid 11 has encountered a flow of reactive fluid 12 and the catalyst layer 121 has been formed at the target surface 10A of the porous material by sequential reactions between the precursor compounds. Thus, aluminum oxide (A1203) can be deposited on porous substrates, such as, silicon oxide, for example, from trimethylaluminum (TMA, Al(CH3)3) used as a first precursor and water used as a second precursor. By further depositing palladium (5%) on said a- Al, Os, a solid-state catalyst 200 can be obtained for production of ethane from ethylene via addition of molecular hydrogen at carbon — carbon double bond. Reaction chamber 101 has been purged with inert fluid 11 after deposition of each precursor compound. During each ALD cycle (e.g. precursor 1 followed by purge; precursor 2 followed by o purge) a layer of material is formed on the substrate. The catalyst layer 121 can thus be > formed in a single ALD cycle or during a number of cycles, whereby the multilayer O structure (stack) is obtained.
    O O The solid-state catalyst 200 prepared as described hereinabove has been transferred =E from the ALD reactor 110 (the reaction chamber 101) into a system 210 for conducting - chemical reaction, according to some aspect of the present invention. Provision of the s catalyst 200 with the system for conducting chemical reaction is shown on Fig. 1.
    O > It is emphasized, that the reactor devices 110 and 210 schematically depicted on Figs. 1 and 2 are distinct apparatuses.
    The apparatus 110 (Fig. 1) can be further utilized to clear the pores and/or to charge or regenerate the catalyst 200 (apart from or in addition to liquefaction procedure described for the system 210). Hence, a used catalyst 200 can be withdrawn from the apparatus 210 (used for conducting catalytic reactions) and transferred (back) to the apparatus 110 (initially used for preparation of said catalyst by ALD or CVD methods). By directing gaseous media, such as oxygen gas (02) or ozone (Os), for example, into the reaction chamber 101 at elevated temperatures, organic clogging materials or any other organic contaminants residing on the target surface(s) can be oxidized (‘burned’) to form carbon dioxide. Oxidation can be followed by reductive process(es), by using hydrogen gas (Hz), for example, to decrease metal oxidation state on the catalyst surface, as reduced metal oxidation state is beneficial for catalytic reaction conditions in terms of activity and selectivity of the catalyst. Example 2. Polymerization reactions 2a. Solid-state catalyst 200 has been obtained comprising palladium chloride supported on porous material. An essentially low molecular weight oligomer has been produced from framns-butadiene. 2b. Solid-state catalyst 200 has been obtained comprising copper (Cu) supported on porous material. Acetylene polymer has been produced from acetylene at 250-300 °C. Example 3. Addition of molecular hydrogen at carbon — carbon double bond — production of ethane (C2Hc) from ethylene (C2H4). 3a. The solid-state catalyst 200 has been obtained comprising palladium supported on the porous material. Hydrogenation reaction has been conducted at a temperature within a range of 100-300 °C, with pressure about 18.9 kPa. In some instances, the reaction has = been conducted at 188-190 °C.
    N O 3b. The solid-state catalyst 200 has been obtained comprising palladium supported on O silicon dioxide (S102). Hydrogenation reaction has been conducted at 90 °C (Ho : C:H4 - =2: 1) with conversion rate 93-100%.
    a a 3 Example 4. Addition of molecular hydrogen at carbon — carbon double bond — > production of octane (CsH1s) from 1-octene (CsH16).
    O N The solid-state catalyst 200 has been obtained comprising palladium supported on the porous material. Hydrogenation reaction has been conducted at 25 *C with conversion rate 100% in 28 min.
    Example 5. Addition of molecular hydrogen at carbon — carbon triple bond — production of ethane from acetylene The solid-state catalyst 200 has been obtained comprising a layer of aluminum oxide (Al1203) further deposited with palladium. Hydrogenation reaction has been conducted at 100 — 250 °C and pressure 0,7 — 3,55 MPa. It shall be appreciated by those skilled in the art that the embodiments set forth in the present disclosure may be adapted and combined as desired. The disclosure is thus intended to encompass any possible modifications of the device and the deposition method, recognizable by those of ordinary skill in the art, within a scope of appended claims.
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    权利要求:
    Claims (17)
    [1] 1. A method for conducting a catalytic reaction on a catalyst layer (121) supported on a surface (10A) of a porous material (10), in which method at least one reactive compound (1) is directed into a confined reaction space (201) through the porous material (10) towards the supported catalyst layer (121) to yield, into said reaction space (201), at least one product compound (2) formed as a result of catalytic reactions at the catalyst layer.
    [2] 2. The method of claim 1, wherein the reactive compound (1) is a hydrocarbon compound comprising at least two carbon atoms.
    [3] 3. The method of any one of claims 1 or 2, wherein the reactive compound (1) is an unsaturated hydrocarbon compound.
    [4] 4. The method of any preceding claim, wherein the reactive compound (1) is a hydrocarbon compound selected from the group consisting of an alkene compound, an alkyne compound and a diene compound.
    [5] 5. The method of any preceding claim, the reactive compound (1) is any one of ethylene, propylene or butylene or a mixture thereof.
    [6] 6. The method of any preceding claim, wherein the catalyst layer (121) comprises an at least one metal.
    [7] 7. The method of claim 7, wherein the catalyst layer (121) comprises a metal selected from the group consisting of palladium, platinum and ruthenium.
    [8] o 8. The method of any preceding claim, wherein the catalyst layer (121) is formed by a O polymerization catalyst supported on the surface of the porous material.
    [9] N S 9. The method of any preceding claim, wherein the catalyst layer (121) is formed by a S Phillips-type catalyst supported on the surface of the porous material.
    [10] I & 10. The method of any preceding claims 1-8, wherein the catalyst layer (121) is formed > by a Ziegler-Natta catalyst.
    [11] LO 2 11. The method of any one of claims 1-7, wherein the catalyst layer (121) is formed by N a hydrogenation catalyst supported on the surface of the porous material.
    [12] 12. The method of any preceding claim, wherein the porous material (10) is selected from the group consisting of porous metal, porous ceramics and porous polymer.
    [13] 13. The method, further comprising delivery of energy to the catalyst layer (121) by an at least one energy source (203), wherein said energy is delivered in the form of electromagnetic radiation, electromagnetic induction and/or thermal energy.
    [14] 14. A system (210) for conducting a catalytic reaction on a catalyst layer (121) supported on a surface (10A) of a porous material (10), in which system at least one reactive compound (1) is directed into a confined reaction space (201) through the porous material (10) towards the supported catalyst layer (121) to yield, into said reaction space (201), at least one product compound (2) formed as a result of catalytic reactions at the catalyst layer.
    [15] 15. The system of claim 13 configured as a chemical deposition reactor.
    [16] 16. A catalyst (200) comprising a porous material (10) with a catalyst layer (121) supported on a surface of said porous material (10), which catalyst (200) is configured to receive at least one reactive compound (1) into the porous material (10) and to propagate said reactive compound (1) through the porous material towards the supported catalyst layer (121), at which catalyst layer the reactive compound (1) undergoes a catalytic reaction, whereupon at least one product compound (2) is formed.
    [17] 17. Use of the catalyst (200) as defined in claim 14 in polymerization of olefins.
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