Process for preparing catalytically active scaffolds

Abstract

The present disclosure relates generally to a process for preparing a catalytically active scaffold from a scaffold material, and in particular to activating the surface of the scaffold by chemically removing sacrificial material from the surface of the scaffold to provide catalytically reactive sites on the surface of the scaffold.

Description

[Technical Field]

[0001] The present disclosure relates generally to a process for preparing a catalytically active scaffold from a scaffold material, and in particular to activating the surface of the scaffold by chemically removing sacrificial material from the surface of the scaffold to provide catalytically reactive sites on the surface of the scaffold. [Background technology]

[0002] A continuous flow chemical reactor generally comprises a tubular reaction chamber into which a reactant fluid is continuously fed to undergo a chemical reaction and continuously form a product that exits the reaction chamber. The reaction chamber is typically immersed in a heating / cooling fluid to facilitate the transfer of heat to / from the reaction, e.g., in a shell-and-tube heat exchanger configuration.

[0003] Continuous flow reactors used for catalytic reactions typically employ packed-bed reaction chambers, in which the reaction chamber is packed with solid catalyst particles that provide a catalytic surface on which chemical reactions can occur. Static mixers are used to premix fluid streams prior to contact with the packed-bed reaction chambers and downstream of these chambers to transfer heat between the central and outer regions of the reactor tube. Static mixers contain solid structures that disrupt fluid flow to promote mixing of reactants prior to reaction in the packed-bed reaction chambers and to promote desired patterns of heat transfer downstream of these chambers.

[0004] There is a need for alternative or improved processes for preparing catalytically active scaffolds, particularly static mixer scaffolds, which can provide various desirable properties such as the flexibility and utility of catalytic static mixer technology, which can provide more efficient mixing of reactant chemistries and / or electrochemical reactants, heat transfer, and catalytic reactions. Summary of the Invention

[0005] The present inventors have undertaken significant research and development of alternative methods for the preparation of catalytically active scaffolds and have determined that a catalytic surface can be provided on the surface of a scaffold, for example a static mixer scaffold, such that the resulting static mixer scaffold can be used in a continuous flow chemical reactor.

[0006] In one aspect, there is provided a catalytically active static mixer comprising a scaffold material comprising an active catalytic material and, optionally, an inert material, the catalytically active scaffold material being in the form of a lattice of interconnected segments that are periodically repeated along a longitudinal axis of the scaffold, each segment configured to define a plurality of pores and passages in a non-line-of-sight configuration, the plurality of passages being spaced apart from one another at intervals of 200 m , corresponding to a number of times within a predetermined length along the longitudinal axis of the catalytically active scaffold material. -1 The present invention is configured to disperse and mix one or more fluid reactants during flow and reaction by redistributing fluid across the flow by changing local flow direction or splitting the flow, the plurality of passages being defined by a plurality of pores, the pores including one or more subpores within the pores, the pores being at least about 100 times larger than the subpores. The pore size of the one or more pores within the pores ranges from about 0.1 μm to 500 μm. The catalytically active scaffold material is in the form of a catalytic static mixer or a catalytically active monolithic porous insert. The catalytically active scaffold material including subpores within the pores has a surface area that is at least about 30% larger than the surface area of ​​a scaffold without subpores. The mass loss of the catalytically active scaffold ranges from about 0.5 wt% to 60 wt% when compared to the total mass of the scaffold without subpores.

[0007] In one embodiment, the active catalytic material may be selected from the group including palladium, platinum, nickel, ruthenium, copper, rhodium, gold, silver, cobalt, iridium, osmium, rhenium, chromium, or mixed metal alloys or metal oxides thereof, zeolites, and metal organic frameworks. For example, the active material may be palladium, platinum, nickel, ruthenium, copper, nickel, cobalt, silver, or mixed metal alloys or metal oxides thereof.

[0008] In one embodiment, the scaffolding material can be one or more of nickel, titanium, aluminum, tungsten, niobium, molybdenum, steel, stainless steel, copper, cobalt chromium, titanium-based alloys, nickel-based alloys, palladium-based alloys, nickel-aluminum-based alloys, platinum-based alloys, ruthenium-based alloys, rhodium-based alloys, gold, platinum, palladium, and silver.

[0009] In another embodiment, the catalytically active scaffold has a surface area of ​​about 0.5 m 2 / g~750m 2 In some embodiments, the catalytically active scaffold has a total pore volume of about 0.2 cm 3 / g~10cm 3 / g.

[0010] In one embodiment, the catalytically active static mixer has an aspect ratio (L / d) of at least 75.

[0011] In another aspect, a process is provided for preparing a catalytically active scaffold from a scaffold material, the scaffold material being in the form of a lattice of interconnected segments that are periodically repeated along a longitudinal axis of the scaffold, each segment configured to define a plurality of passages and pores in a non-line-of-sight configuration, the plurality of passages being spaced apart from one another at intervals of 200 m , corresponding to a number of times within a predetermined length along the longitudinal axis of a static mixer. -1The present invention is configured to disperse and mix one or more fluid reactants during flow and reaction by redistributing fluid across the flow by changing local flow direction or splitting the flow, the scaffold material comprising an active catalytic material and an inactive material, the process including: (i) activating the surface of the scaffold material by chemically removing at least about 0.5 wt.% of the inactive material from the surface of the scaffold material to provide the catalytically active static mixer with catalytically active sites on the surface of the scaffold material and one or more subpores within the pores of the scaffold material, the surface of the scaffold material being activated using a selective or non-selective chemical process. In another embodiment, the scaffold material may further comprise an inactive material. For example, the selective chemical process may be chemical leaching to remove at least about 0.5 wt.% of a sacrificial material from the scaffold material, the sacrificial material being an inactive material. The chemical leaching process may include the use of a leaching solution. In another example, the non-selective chemical process can be chemical etching to remove at least about 0.5% by weight of sacrificial material from the scaffold material, where the sacrificial material is an active catalytic material, a non-active material, an optional inert material, or a combination thereof. The chemical etching process can include the use of an etching solution.

[0012] In one embodiment, the pores may be at least about 100 times larger than the subpores. For example, the pores may be at least about 1000 times larger than the subpores.

[0013] In one embodiment, the mass loss of the sacrificial material from the catalytically active scaffold can range from about 0.5% to 60% by weight, based on the total mass of the scaffold material.

[0014] In another embodiment, the surface area of ​​the catalytically active static mixer may be increased by at least about 30% when compared to the surface area of ​​a scaffolding material without subpores.

[0015] In one embodiment, the active catalyst material may be selected from the group including palladium, platinum, nickel, ruthenium, copper, rhodium, gold, silver, cobalt, iridium, osmium, rhenium, chromium, or their metal oxides, zeolites, and metal organic frameworks. The inactive material may be selected from the group including chromium, titanium, copper, iron, zinc, aluminum, nickel, or their metal oxides, and carbon-based materials. The inactive material may be selected from the group including magnesium, or its metal oxides, silicon, silicone, polymers, ceramics, and metal oxides.

[0016] The scaffold material can be titanium, aluminum, tungsten, niobium, molybdenum, steel, stainless steel, copper, cobalt chromium, titanium-based alloys, nickel-based alloys, palladium-based alloys, nickel-aluminum-based alloys, platinum-based alloys, ruthenium-based alloys, rhodium-based alloys, gold, platinum, palladium, and silver. For example, the scaffold material can be a nickel-based alloy. In another example, the scaffold material can be a nickel metal foam.

[0017] In another embodiment, the catalytically active static mixer has a surface area of ​​about 0.5 m 2 / g~750m 2 In another embodiment, the total pore volume of the catalytically active static mixer can be in the range of about 0.2 cm 3 / g~10cm 3 / g, In yet another embodiment, the pore size of the subpores may range from about 0.05 μm to 500 μm.

[0018] In another embodiment, the process comprises a further activation step ii) to remove metal oxide impurities by contacting the surface of the catalytically active scaffold with hydrogen gas. [Brief explanation of the drawings]

[0019] Preferred embodiments of the present disclosure will now be further described and illustrated, by way of example only, with reference to the accompanying drawings, in which:

[0020] [Figure 1]1 shows a general route to prepare catalytically active scaffolds via (a) chemical leaching process and (b) chemical etching process. [Figure 2A] 1 shows scanning electron micrograph (SEM) images of (a) untreated Monel scaffold and (b) Monel catalytic static mixer treated using a chemical leaching process. [Figure 2B] 1 shows scanning electron micrograph (SEM) images of (a) untreated Monel scaffold and (b) Monel catalytic static mixer treated using a chemical leaching process. [Figure 3A] 1 shows scanning electron micrograph (SEM) images of (a) an untreated Inconel scaffold and (b) an Inconel catalytic static mixer that has been treated using a chemical etching process. [Figure 3B] 1 shows scanning electron micrograph (SEM) images of (a) an untreated Inconel scaffold and (b) an Inconel catalytic static mixer that has been treated using a chemical etching process. [Figure 4A] 1 shows scanning electron micrograph (SEM) images of (a) untreated nickel foam and (b) nickel foam treated using a chemical etching process. [Figure 4B] 1 shows scanning electron micrograph (SEM) images of (a) untreated nickel foam and (b) nickel foam treated using a chemical etching process. [Figure 5A] Scatter plots of vinyl acetate conversion versus liquid flow rate (a) and (c) and hydrogen to substrate molar ratio (H / S ratio) (b) are shown for the reduction of vinyl acetate to ethyl acetate in ethanol over each set of CSMs. The reactions were run at p = 20 bar, T = 120 °C, c(vinyl acetate) = 2 M for (a) and (b), 0.5 M for (c), VG,N(H2) = 50 mL N / min for (a) and (b), and variable VG,N(H2) for (c). [Figure 5B]Scatter plots of vinyl acetate conversion versus liquid flow rate (a) and (c) and hydrogen to substrate molar ratio (H / S ratio) (b) are shown for the reduction of vinyl acetate to ethyl acetate in ethanol over each set of CSMs. The reactions were run at p = 20 bar, T = 120 °C, c(vinyl acetate) = 2 M for (a) and (b), 0.5 M for (c), VG,N(H2) = 50 mL N / min for (a) and (b), and variable VG,N(H2) for (c). [Figure 5C] Scatter plots of vinyl acetate conversion versus liquid flow rate (a) and (c) and hydrogen to substrate molar ratio (H / S ratio) (b) are shown for the reduction of vinyl acetate to ethyl acetate in ethanol over each set of CSMs. The reactions were run at p = 20 bar, T = 120 °C, c(vinyl acetate) = 2 M for (a) and (b), 0.5 M for (c), VG,N(H2) = 50 mL N / min for (a) and (b), and variable VG,N(H2) for (c). [Figure 6] Figure 1 shows a scatter plot of coumarin conversion versus liquid flow rate at a constant H / S = 5. The liquid and gas flow rates were varied in tandem to maintain a constant H / S ratio. [Figure 7] Figure 1 shows the product composition for the hydrogenation of cinnamaldehyde over three sets of CSM at a liquid flow rate of 2 mL / min and H / S=5. [Figure 8] 1 shows the product composition for the hydrogenation of linalool over two sets of CSM at a liquid flow rate of 2 mL / min and H / S=5. [Figure 9] 1 shows the hydrogenation conversion for 2,5-dichloronitrobenzene over two sets of CSM at a liquid flow rate of 2 mL / min and H / S=5. DETAILED DESCRIPTION OF THE INVENTION

[0021] The present disclosure describes various non-limiting embodiments below, which relate to research conducted to identify alternative or improved processes for preparing catalytically active scaffolds of static mixers (CSMs) that can provide various desirable properties, such as the flexibility and utility of catalytic static mixer technology, which can provide more efficient mixing, heat transfer, and catalytic reactions of chemical and / or electrochemical reactants. It has surprisingly been found that chemically removing sacrificial material from the surface of a scaffold, such as a static mixer, can provide efficient mixing, heat transfer, and catalytic reactions of reactants in a continuous-flow chemical reactor. It will be understood that the techniques described by the present invention may depend on the application and the type of catalyst and / or scaffold used. The inventors have also surprisingly determined that chemically removing sacrificial material from the surface of a scaffold, as described herein, provides an improved technique for catalytically active complex three-dimensional structures, such as static mixer scaffolds.

[0022] The static mixers of the present invention have been shown to offer various advantages over current heterogeneous catalyst systems, such as packed beds. While allowing flexibility in redesign and configuration of the static mixer, they present other difficulties and challenges in providing a robust, commercially viable platform that can be catalytically activated to operate under the specific operational performance parameters of a continuous flow chemical reactor, for example, providing desirable mixing and flow conditions within a continuous flow reactor, and providing enhanced heat and mass transfer characteristics and reduced backpressure compared to packed bed systems.

[0023] Chemical removal of sacrificial material from the surface of a scaffold by selective or non-selective chemical processes has been found to be surprisingly suitable for catalytically activating the surface of a scaffold, such as the surface of a static mixer scaffold, and is suitable for applications using a wide variety of scaffold materials.

[0024] For example, the static mixer scaffold can be configured as a scaffold that provides an insert for use with an in-line continuous flow reactor system. The static mixer scaffold can also provide a wide range of heterogeneous catalysis, which is critical to chemical manufacturing, including the production of fine and specialty chemicals, pharmaceuticals, food and pesticides, consumer products, and petrochemicals.

[0025] General terminology Throughout this specification, unless specifically stated otherwise or the context requires otherwise, reference to a single step, composition of matter, group of steps, or group of compositions of matter should be construed to encompass one and a plurality (i.e., one or more) of that step, composition of matter, group of steps, or group of compositions of matter. Thus, as used herein, the singular forms "a," "an," and "the" include plural aspects unless the context clearly dictates otherwise. For example, reference to "a" includes the singular as well as two or more; reference to "an" includes the singular as well as two or more; reference to "the" includes the singular as well as two or more, etc.

[0026] Those skilled in the art will understand that the disclosure herein is susceptible to variations and modifications other than those specifically described. The present disclosure is to be understood to include all such variations and modifications. The present disclosure also includes, individually or collectively, all of the steps, features, compositions, and compounds referred to or shown in this specification, as well as any and all combinations of such steps or features, or any two or more of such steps or features.

[0027] Each example of the present disclosure described herein applies mutatis mutandis to each and every other example of the disclosure unless otherwise specified. The present disclosure should not be limited in scope by the specific examples described herein, which are for illustrative purposes only. Functionally equivalent products, compositions, and methods are clearly within the scope of the present disclosure as described herein.

[0028] The term "and / or," e.g., "X and / or Y," shall be understood to mean either "X and Y" or "X or Y," and shall be interpreted as providing explicit support for both meanings or either meaning.

[0029] Throughout this specification the word "comprise" or modifications such as "comprises" or "comprising" will be understood to mean the inclusion of a stated scaffold, integer or step, or group of scaffolds, integers or steps, but not the exclusion of any other scaffold, integer or step, or group of scaffolds, integers or steps.

[0030] Specific terms The term "catalytically active static mixer" shall be understood to mean a catalytically active scaffold prepared from a scaffold material comprising active catalytic material and non-active material.

[0031] The term "active catalytic material" shall be understood to mean a material capable of providing catalytic activity.

[0032] The term "non-active material" may optionally include inert material, and it is understood that non-active material may be fully or partially sacrificed during the substrate manufacturing processes described herein.

[0033] The terms "sacrificed component" or "sacrificed material" or "sacrificial material" shall be understood to mean a material (at least a portion thereof) that is selectively or non-selectively removed from the surface of the static mixer scaffold. In a chemical etching (non-selective) process, the sacrificial material as defined herein can be either (1) an active catalytic material or (2) a combination of an active catalytic material and an inactive material. In a chemical leaching (selective) process, the sacrificial material as defined herein can be an inactive material.

[0034] The term "inert material" comprises materials that are not catalytically active and do not participate as active catalytic materials. It is understood that inert materials, as defined herein, may or may not be dissolved during the substrate manufacturing process (i.e., the chemical leaching or chemical etching process). In other words, inert materials can be dissolved during chemical etching or chemical leaching. Alternatively, inert materials are defined as materials that may remain undissolved during chemical etching or chemical leaching, but are non-catalytic and optionally present.

[0035] Although several prior art publications are referred to in this specification, it will be expressly understood that this reference does not constitute an admission that any of these documents form part of the common general knowledge in the art in Australia or any other country.

[0036] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention, suitable methods and materials are described below. In case of conflict, the present specification, including definitions, will control. Furthermore, the materials, methods, and examples are illustrative only and are not intended to be limiting.

[0037] Process for preparing catalytically active scaffolds The present inventors have discovered an effective and scalable method for the preparation of catalytically active scaffolds (eg, catalytically active static mixers) for use in continuous flow reactors in heterogeneous catalytic applications.

[0038] The inventors have surprisingly determined that a catalytically active scaffold (e.g., catalytic static mixer, CSM) can be formed by using subtractive manufacturing methods, such as chemical etching or leaching, to remove at least a portion of the inactive material from a preformed scaffold (e.g., static mixer scaffold) comprising a combination of active and inactive materials. Additive manufacturing processes (3D printing) can be used to form static mixers having a line-of-sight configuration comprising a plurality of passages defined by a plurality of pores. By activating the surface of the scaffold using either chemical etching or chemical leaching, a static mixer can be formed with a surface area of ​​200 mm, corresponding to a number of times within a given length along the longitudinal axis of the static mixer. -1 By redistributing fluid across the flow by changing local flow direction or splitting the flow by a factor of 10, a catalytic static mixer having a non-line-of-sight configuration is created, with a plurality of passages configured for dispersing and mixing one or more fluid reactants during flow and reaction of the reactants, the plurality of passages being defined by a plurality of pores, the pores containing one or more subpores within the pores. The pores of the catalytic static mixer are at least about 100 times larger than the subpores.

[0039] Surprisingly, it has been found that the surface area of ​​the scaffold is increased as a result of the chemical leaching or etching process, providing the surface of the catalytically active scaffold or catalytically active static mixer scaffold with increased surface activity so that more active material can be exposed to the environment, e.g., to one or more fluid reactants during reactant flow and reaction.

[0040] It will be understood that the static mixers described herein can be prepared from scaffold materials that include active catalytic materials and inactive materials. The inactive materials can optionally include inactive materials. The inactive materials are sacrificed fully or partially during the substrate fabrication process. The sacrificed components can be referred to as sacrificial materials. The inactive materials consist of materials that are not catalytically active and do not participate as active catalytic materials. The inactive materials may or may not be dissolved during the substrate fabrication process.

[0041] Once formed, the catalytically active static mixer comprises active catalytic material and optionally inactive material. Depending on the amount of inactive material sacrificed, the catalytically active static mixer may also comprise inactive material.

[0042] The active catalytic material can be oxidized to form metal oxides on the surface of the catalytically active static mixer, which can be reactivated by hydrogenation of the metal oxides that form.

[0043] The resulting catalytically active scaffold or catalytically active static mixer scaffold has a) tailored mixing properties as a result of the design created by 3D printing or other manufacturing process, and b) a high active surface area containing catalytically active metals such as nickel as a result of the etching / leaching process.

[0044] It will be appreciated that if the scaffold formed is not catalytically active or has low catalytic activity, subtractive methods of chemically etching or leaching out the sacrificial material can then facilitate the formation of a catalytically active scaffold or catalytically active static mixer scaffold with high porosity and surface area, resulting in effective catalytic activity. It will be appreciated that the processes described herein aid in the performance of the catalytically active scaffold or catalytically active static mixer scaffold in chemical synthesis. For example, the catalytically active static mixer scaffold can be used in tubular or duct reactor systems for a range of suitable heterogeneous catalytic applications, such as hydrogenation, oxidation, and others.

[0045] chemical leaching It will be understood from the present disclosure that static mixers undergoing chemical leaching include active catalytic materials, inactive catalytic materials that are sacrificed during the chemical leaching process, and, optionally, inactive materials. Chemical leaching can selectively remove at least a portion of the inactive materials (sacrificial materials) from the surface of the static mixer scaffold, leaving behind the active catalytic materials. It should be understood that, depending on the conditions used, the inactive materials may or may not be dissolved. The resulting surface of the catalytically active static mixer scaffold contains subpores within the catalytically active pores. For example, chemical leaching may selectively remove the sacrificial metal phase (i.e., inactive materials) from the printed alloy matrix by dissolving the sacrificial metal phase (i.e., inactive materials) while leaving the "desired" catalytically active metal species (e.g., active catalytic material, nickel) intact. In certain instances, selective removal of copper from Monel (nickel-based alloy scaffold material) in higher amounts than nickel can be applied during the chemical leaching process as described herein. It will be understood that nickel and copper are the two major components of Monel, by weight. The resulting leached material (i.e., catalytically active static mixer) may be porous, nickel-rich, and copper-depleted.

[0046] In some embodiments or examples, the selective chemical process can be a chemical leaching process to remove sacrificial material. It will be understood that the sacrificial material in the chemical leaching process can be the selective removal of non-active material present in the scaffold material. The selective enrichment of the active catalytic species is at least two-fold compared to the sacrificial material.

[0047] In embodiments, the selective chemical process can be chemical leaching to remove at least about 0.5% by weight of the sacrificial material from the scaffold material, where the sacrificial material is a non-active material.

[0048] In some embodiments or examples, the weight percent mass loss of the sacrificial material in the starting scaffold material can range from about 0.5 weight percent to about 60 weight percent. For example, the weight percent mass loss can range from about 0.5 weight percent to about 40 weight percent. The weight percent mass loss of the sacrificial material can be less than about 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 10, 5, 1, or 0.5. The weight percent mass loss of the sacrificial material can be at least about 0.5, 1, 10, 20, 30, 40, 50, or 60. The weight percent mass ratio of the sacrificial material in the starting scaffold material can be in a range provided by any two of these upper and / or lower limits.

[0049] The chemical leaching process may include subjecting a scaffold described herein to a leaching solution described herein to provide a catalytically active scaffold or a catalytically active static mixer scaffold comprising subpores within the pores that define a plurality of passages.

[0050] Chemical etching It will be understood from the present disclosure that the static mixer that undergoes chemical etching is composed of active and inactive catalytic materials, which may be the same or different, and optionally an inactive material. The chemical etching process can non-selectively remove some species from the surface of the scaffold by dissolving them from the surface. In some embodiments or examples, the active and inactive materials are the same, meaning they are made from a single active catalytic material, and the chemical etching results in a catalytically active static mixer prepared from the active catalytic material. In this case, the sacrificial material becomes the active catalytic material. Such a static mixer may or may not contain an inactive material. The etching process may sacrifice both the active and inactive catalytic materials. In another example, the active and inactive materials are different, and the chemical etching results in a catalytically active static mixer prepared from the non-selective removal of both the inactive and active materials. In this case, the sacrificial material includes both the active and inactive materials. Such a static mixer may or may not contain an inactive material. The etching process may sacrifice both the active and inactive catalytic materials. In both examples, the resulting surface of the scaffold contains catalytically active material. The surface of the catalytically active static mixer scaffold contains subpores within the pores that define multiple passageways. In one example, non-selective removal of nickel and chromium from Inconel (a nickel-chromium based alloy scaffold material). Nickel and chromium are the two major components (by weight) of Inconel. The resulting etched layer may be porous but may not be significantly enriched in nickel or chromium. In another example, in nickel foam or other scaffold materials containing only one metallic element (with negligible amounts of impurities), the etching process described herein may dissolve the surface layer of the scaffold, providing a highly porous surface that is catalytically active.

[0051] It will be appreciated that sacrificial materials in a chemical etching process may be the non-selective removal of inactive materials and / or active catalytic materials present in the scaffold material.

[0052] In one embodiment, the non-selective chemical process can be chemical etching to remove at least about 0.5% by weight of sacrificial material from the scaffold material, where the sacrificial material is an active catalytic material, a non-active material, an optional inert material, or a combination thereof.

[0053] In some embodiments or examples, the weight percent mass loss of the sacrificial material in the starting scaffold material can range from about 0.5 weight percent to about 60 weight percent. For example, the weight percent mass loss can range from about 0.5 weight percent to about 40 weight percent. The weight percent mass loss of the sacrificial material can be less than about 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 10, 5, 1, or 0.5. The weight percent mass loss of the sacrificial material can be at least about 0.5, 1, 10, 20, 30, 40, 50, or 60. The weight percent mass ratio of the sacrificial material in the starting scaffold material can be in a range provided by any two of these upper and / or lower limits.

[0054] The chemical etching process may include subjecting a scaffold described herein to an etching solution described herein to provide a catalytically active scaffold or a catalytically active static mixer scaffold.

[0055] Further activation Once the catalytically active static mixers are formed using the subtractive processes referred to herein, the active catalyst material can be further activated by contacting the surfaces of the catalytically active static mixers with hydrogen gas to remove metal oxides that form on the surfaces of the catalytically active static mixers.

[0056] Chemical Leaching and Etching Solutions In some embodiments or examples, the chemical leaching process may include the use of a leaching solution. In some embodiments or examples, the chemical etching process may include the use of an etching solution.

[0057] For example, the leaching and etching solutions may be selected from acidic, basic, oxidizing, or any other leaching / etching solutions known in the art. It will be appreciated that the leaching and etching solutions may be selected based on the type of scaffold material used.

[0058] For example, the basic solution may include persulfate and ammonia in a highly alkaline aqueous solution. It will be appreciated that the strong base activates the persulfate ions that generate highly reactive molecular oxygen in situ. It will be appreciated that the basic solution may include one of many bases. In one example, the basic solution may be selected from potassium persulfate, sodium persulfate, ammonium persulfate, potassium sulfate, sodium sulfate, ammonium sulfate, sodium hydroxide, potassium hydroxide, ammonium hydroxide, calcium hydroxide, magnesium hydroxide, barium hydroxide, aluminum hydroxide, cesium hydroxide, strontium hydroxide, lithium hydroxide, rubidium hydroxide, or a combination thereof. For example, the basic solution may be selected from potassium persulfate, sodium persulfate, ammonium persulfate, potassium sulfate, sodium sulfate, ammonium sulfate, or a combination thereof.

[0059] It will be appreciated that the acidic solution may include one of many acids. In one example, the acidic solution may be selected from, but is not limited to, ASTM No. 30, Adler Etchant, Kalling's No. 2, Keller's Etch, Klemm's Reagent, Kroll's Reagent, Nital, Marble's Reagent, Murakami's, Picral, Vilella's Reagent, Jewitt-Wise etch, hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, aqua regia, ferric chloride, acetic acid, hydrofluoric acid, ceric ammonium nitrate, hydrobromic acid, chromic acid, or a combination thereof. For example, the acidic solution may be selected from, but is not limited to, ASTM No. 30, Adler Etchant, Nital, Marble's reagent, hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, ferric chloride, or a combination thereof.

[0060] With respect to oxidative dissolution of species from the surface of a scaffolding material, it will be understood that the leaching or etching solution may contain at least one oxidizing agent (to oxidize the species), an optional solvent (aqueous or non-aqueous) to dissolve the oxidizing agent, and an optional complexing agent to adjust the redox potential and / or solubility of the species. In one example, the oxidizing agent may be selected from, but is not limited to, dissolved oxygen, hydrogen peroxide (H2O2), free chlorine, potassium chromate (K2Cr2O7), potassium permanganate (KMnO4), or combinations thereof.

[0061] Composition of catalytically active scaffolds In some embodiments, a catalytically active static mixer is provided that includes a scaffold material comprising an active catalytic material and an optional inert material, the scaffold material being in the form of a lattice of interconnected segments that are periodically repeated along a longitudinal axis of the scaffold, each segment configured to define a plurality of passages and pores in a non-line-of-sight configuration, the plurality of passages being spaced apart from one another at intervals of 200 m , corresponding to a number of times within a predetermined length along the longitudinal axis of the catalytically active static mixer. -1 The device is configured to disperse and mix one or more fluid reactants during flow and reaction of the reactants by redistributing fluid across the flow by changing local flow direction or splitting the flow, the plurality of passages being defined by a plurality of pores, the pores including one or more subpores within the pores, the pores being at least about 100 times larger than the subpores, and the pore size of the one or more pores within the pores can be in the range of about 0.1 μm to 500 μm.

[0062] In some other embodiments or examples, a process is provided for preparing a catalytically active static mixer from a scaffold material, the scaffold material being in the form of a lattice of interconnected segments that are periodically repeated along a longitudinal axis of the scaffold, each segment being configured to define a plurality of passages and pores in a non-line-of-sight configuration, the plurality of passages being spaced apart from one another at intervals of 200 m or more corresponding to a predetermined number of times within a predetermined length along the longitudinal axis of the static mixer. -1The present invention relates to a catalytically active static mixer configured to disperse and mix one or more fluid reactants during flow and reaction by redistributing fluid across the reactants by changing local flow direction or splitting the flow, the plurality of passages being defined by a plurality of pores, the scaffold material comprising an active catalytic material and an inactive material, the process including (i) activating the surface of the scaffold material by chemically removing at least about 0.5 wt. % of the inactive material from the surface of the scaffold material to provide catalytically active sites on the scaffold material, the scaffold material being activated using a selective or non-selective chemical process, the activation step resulting in catalytically active subpores within the pores of the scaffold material. The activation step is described herein as a subtractive manufacturing process, such as chemical leaching or chemical etching.

[0063] It will be appreciated that in some embodiments or examples, there may be an overlap between active catalytic materials, non-active materials, and inert materials.

[0064] active catalyst material It will be appreciated that the active catalytic material described herein can provide catalytic activity to the surface of the scaffold. The active catalytic material can be selected from the group including palladium, platinum, nickel, ruthenium, copper, rhodium, gold, silver, cobalt, iridium, osmium, rhenium, chromium, or mixed metal alloys or metal oxides thereof, zeolites, and metal-organic frameworks. For example, the active catalytic material can be palladium, platinum, nickel, ruthenium, copper, nickel, cobalt, silver, or mixed metal alloys or metal oxides thereof.

[0065] Zeolites are understood to be hydrated aluminosilicate minerals made up of interconnected tetrahedra of alumina (AlO4) and silica (SiO4). The structure of a zeolite can be a three-dimensional crystalline structure built from the elements aluminum, oxygen, and silicon, with alkali or alkaline earth metals (e.g., sodium, potassium, and magnesium) and water molecules trapped in the gaps between them. Zeolites are formed by many different crystalline structures with regularly arranged open pores.

[0066] It will be understood that a MOF is a one-, two-, or three-dimensional structure provided by a metal-organic polymer framework that includes multiple metal ions or clusters, each coordinated to one or more organic ligands. MOFs can provide porous structures that include multiple pores. It will be understood that a MOF can be crystalline or amorphous, e.g., a one-, two-, or three-dimensional MOF structure can be amorphous or crystalline.

[0067] inert material It will be understood that the non-active materials described herein may be dissolved from the surface of the scaffold in a chemical leaching or chemical etching solution. It will be understood that in some embodiments or examples, there may be some overlap between the active catalytic materials and the non-active materials. For example, it will be understood that the active catalytic material may be a sacrificial material, i.e., both the active catalytic material and the non-active material may be dissolved from the surface of the scaffold material during a non-selective chemical etching process.

[0068] The inactive material may be selected from the group including chromium, titanium, copper, iron, zinc, aluminum, nickel, silver or their metal oxides, polymers, and carbon.

[0069] Examples of polymers that can be used include, but are not limited to, polycarbonate, polymethyl methacrylate, polypropylene, polyethylene, polyamide, polyacrylamide, polyvinyl chloride, or copolymers thereof, or any combination thereof.

[0070] Examples of carbon-based materials that can be used include, but are not limited to, carbon nanotubes, carbon nanofibers, graphene nanosheets, graphene quantum dots, graphene nanoribbons, graphene nanoparticles, and derivatives thereof.

[0071] inert material It will be understood that the inert material described herein refers to a material that may be present in the scaffold material but is not required or used as a catalytically active material in the catalytically active static mixer. When present, the inert material may be at least partially subject to chemical etching or chemical leaching. The inert material may also resist corrosion and oxidation in moist air. The inert material may have minimal chemical reactivity when the catalytic static mixer is used for catalytic reactions. It will be understood that the inert material may remain intact when the scaffold is exposed to the chemical processes described herein.

[0072] In some embodiments or examples, the inert material may be selected from the group including aluminum, iron, copper, zinc, chromium, titanium, magnesium, silver, oxides of these metals, silicon, silicone, polymers, ceramics, zeolites, and metal organic frameworks.

[0073] Examples of polymers that can be used include, but are not limited to, polycarbonate, polymethyl methacrylate, polypropylene, polyethylene, polyamide, polyacrylamide, polyvinyl chloride, or copolymers thereof, or any combination thereof. In some embodiments or examples, any polyester (including poly(alpha-hydroxy esters)), polyether (including polyethylene oxide), polystyrene, and polymethyl methacrylate can be used to form the scaffold. In other embodiments or examples, thermoplastic resins can be used to form the scaffold. In yet other embodiments, non-biodegradable and biodegradable polymers are contemplated for forming the scaffold.

[0074] Surface characterization of scaffold materials and catalytically active scaffolds The catalytically active static mixers and processes for making catalytically active static mixers described herein have been shown to advantageously improve catalytic activity and increase the surface area of ​​the catalytically active scaffold or catalytically active static mixer scaffold.

[0075] In some embodiments or examples, the mass ratio (wt%) of sacrificial material to active material in the starting scaffold material can be in the range of about 1:100 to 50:1. The ratio of sacrificial material can be less than about 50, 45, 40, 35, 30, 25, 20, 15, 10, 5, or 1. The ratio of active material can be at least 1, 10, 20, 30, 40, 50, 60, 70, 80, 90, or 100. The mass ratio (wt%) of sacrificial material to active material in the starting scaffold material can be within a range provided by any two of these upper and / or lower limits.

[0076] In some embodiments or examples, the weight percent mass loss ratio in the catalytically active scaffold may provide an active material to sacrificial material ratio of about 20:80 to 80:20. The sacrificial material range may be less than about 80, 70, 60, 50, 40, 30, 20, or 10. The active material range may be at least 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, or 85. The weight percent mass loss ratio in the catalytically active scaffold may be within a range provided by any two of these upper and / or lower limits.

[0077] In some embodiments or examples, the surface of the starting scaffolding material may comprise at least about 30% (by weight) of an active material selected from a catalytically active metal. It will be understood that the catalytically active metal may be selected from any one of the active materials described herein. The surface of the scaffolding material may comprise at least about 30%, 40%, 50%, 60%, 70%, or 80% (by weight) of the active material. The surface of the scaffolding material may comprise less than about 95%, 85%, 75%, 65%, 55%, 45%, or 35% (by weight) of the active material. The surface of the scaffolding material may comprise a weight percent active material in a range provided by any two of these upper and / or lower limits.

[0078] In some embodiments or examples, the mass loss of the catalytically active scaffold (e.g., static mixer) can be in the range of about 0.5% to 60% by weight when compared to the total mass of the scaffold material without subpores. For example, the mass loss of the catalytically active scaffold (e.g., static mixer) can be in the range of about 0.5% to 40% by weight when compared to the total mass of the scaffold material without subpores.

[0079] When a scaffold material undergoes a chemical leaching process as described herein, the mass loss of the catalytically active scaffold (e.g., static mixer) can range from about 0.5 wt% to 60 wt% when compared to the total mass of the scaffold material without subpores. For example, the mass loss (wt%) can range from about 0.5 wt% to about 40 wt%. For example, the mass loss (wt%) of the sacrificial material can be less than about 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 10, 5, 1, or 0.5. The mass loss (wt%) of the sacrificial material can be at least about 0.5, 1, 5, 10, 20, 30, 40, 50, or 60. The mass ratio (wt%) of the sacrificial material in the starting scaffold material can be in a range provided by any two of these upper and / or lower limits.

[0080] When a scaffold material is subjected to a chemical etching process as described herein, the mass loss of the catalytically active scaffold (e.g., static mixer) can range from about 0.5 wt% to 60 wt% when compared to the total mass of the scaffold material without subpores. For example, the mass loss (wt%) can range from about 0.5 wt% to about 40 wt%. For example, the mass loss (wt%) of the sacrificial material can be less than about 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 10, 5, 1, or 0.5. The mass loss (wt%) of the sacrificial material can be at least about 0.5, 1, 5, 10, 20, 30, 40, 50, or 60. The mass ratio (wt%) of the sacrificial material in the starting scaffold material can be in a range provided by any two of these upper and / or lower limits.

[0081] The chemical etching process may include subjecting a scaffold described herein to an etching solution described herein to provide a catalytically active scaffold or a catalytically active static mixer scaffold.

[0082] In some embodiments or examples, the surface area of ​​the catalytically active scaffold (eg, static mixer) may be at least about 30% greater when compared to the surface area of ​​a scaffold material that does not have subpores.

[0083] In some embodiments or examples, the surface area of ​​the catalytically active scaffold (e.g., static mixer) is about 0.5 m 2 / g~750m 2 / g. Surface area (m 2 / g) can be less than about 750, 700, 650, 600, 550, 500, 450, 400, 350, 300, 250, 200, 150, 100, 50, 25, 10, 5, or 1. 2 / g) can be at least about 0.5, 1, 5, 10, 20, 40, 50, 80, 100, 150, 200, 250, 300, 350, 400, 450, 500, 550, 600, 650, or 700. The surface area of ​​the catalytically active scaffold can be in a range provided by any two of these upper and / or lower limits.

[0084] In some embodiments or examples, the total pore volume of the catalytically active scaffold (e.g., static mixer) is about 0.2 cm 3 / g~10cm 3 / g. Total pore volume (cm 3 / g) can be less than about 10, 9, 8, 7, 6, 5, 4, 3, 2, 1, 0.5, or 0.2. 3 / g) can be at least about 0.2, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10. The total pore volume of the catalytically active scaffold can be in a range provided by any two of these upper and / or lower limits.

[0085] The inventors have surprisingly found that the catalytically active static mixers described herein contain one or more subpores within the pores. In one embodiment, the pores may be at least about 100 times larger than the subpores. For example, the pores may be at least about 1000 times larger than the subpores. For example, the scaffold material contains a plurality of passages that can be defined as pores, and these pores may have pore sizes ranging from about 1 mm to about 10 mm. It has unexpectedly been found that subpores, as defined herein, can be provided within the pores by a chemical leaching / etching process.

[0086] In some embodiments or examples, the pore size of one or more pores within the pore ranges from about 0.05 μm to 500 μm. For example, the pore size of the subpores can range from about 0.05 μm to 500 μm. The pore size (μm) can be less than 500, 450, 400, 350, 300, 250, 200, 150, 100, 75, 50, 25, 10, 5, 1, 0.5, 0.1, or 0.05. The pore size (μm) can be at least 0.05, 0.1, 0.5, 1, 2, 5, 7, 10, 20, 50, 70, 100, 150, 200, 250, 300, 350, 400, 450, or 500. The pore size of the subpores can be in the range provided by any two of these upper and / or lower limits.

[0087] Scaffolding and scaffolding materials In an embodiment or example, the scaffold may be applied to any device or apparatus. In another embodiment or example, the scaffold may be a complex 3D structure. The complex 3D structure may be porous. In an embodiment or example, the scaffold may be suitable for a continuous flow process. In an embodiment or example, the scaffold may be a static mixer or an integral porous insert. In an embodiment or example, the scaffold may be a static mixer.

[0088] The static mixer scaffold can be prepared from a scaffold material. The scaffold material is in the form of a lattice of interconnected segments that are periodically repeated along the longitudinal axis of the scaffold, with each segment configured to define a plurality of passages and pores in a non-line-of-sight configuration. The plurality of passages is configured to disperse and mix one or more fluid reactants during reactant flow or mixing. The scaffold material can include or consist of at least one of a metal, a metal alloy, a cermet, a calcium phosphate or polymer, a carbon-based material, or silicon carbide. The scaffold material can be formed from a metal, a metal alloy, or other known printable polymer-metal composite. For example, the metal or metal alloy can be titanium, nickel, aluminum, tungsten, niobium, molybdenum, steel, stainless steel, copper, cobalt chromium, titanium-based alloys, nickel-based alloys, palladium-based alloys, nickel-aluminum-based alloys, platinum-based alloys, ruthenium-based alloys, rhodium-based alloys, gold, platinum, palladium, and silver. In another example, the metal or metal oxide may be a nickel-based alloy, a palladium-based alloy, or a nickel-aluminum-based alloy. In another example, the metal may be a nickel-based alloy. Examples of usable polymers include, but are not limited to, polycarbonate, polymethyl methacrylate, polypropylene, polyethylene, polyether ether ketone, polyethylene terephthalate, polylactic acid, polyolefin, polyamide, polyimide, polyacrylamide, polyvinyl chloride, copolymers thereof, or any combination thereof. Examples of usable carbon-based materials include, but are not limited to, carbon nanotubes, carbon nanofibers, graphene nanosheets, graphene quantum dots, graphene nanoribbons, graphene nanoparticles, and derivatives thereof.

[0089] The scaffolding material may include active catalytic materials, non-active materials, and optionally inactive materials, as described herein.

[0090] The scaffold material can be prepared from materials suitable for additive manufacturing (i.e., 3D printing). The scaffold material can be prepared from materials suitable for further surface modification to provide or enhance catalytic reactivity, such as metals including nickel, titanium, palladium, platinum, gold, copper, aluminum, or alloys thereof, and other metals including metal alloys such as stainless steel. In one embodiment, the scaffold material can comprise or consist of titanium, stainless steel, and alloys of cobalt and chromium. In another embodiment, the scaffold material can comprise or consist of titanium, aluminum, or stainless steel. In another embodiment, the scaffold material can comprise or consist of stainless steel and cobalt-chromium alloys. In another embodiment, the scaffold material can comprise or consist of nickel-based alloys, palladium-based alloys, nickel-aluminum-based alloys. Using additive manufacturing techniques, namely 3D metal printing, scaffolding materials can be specifically designed to perform two main tasks: a) act as a substrate for catalytic materials or catalyst materials, and b) act as a flow guide for optimal mixing performance during chemical reactions and subsequently aid in the transfer of heat dissipation to the walls of the reactor tube (single-phase liquid stream or multi-phase stream) inside the reactor.

[0091] In one embodiment, the scaffolding material comprises a catalytically active surface. In another embodiment, the scaffolding material comprises titanium, nickel, aluminum, stainless steel, cobalt, chromium, any alloy thereof, or any combination thereof. Further advantages may be provided when the scaffolding material comprises or consists of nickel or a nickel-based alloy.

[0092] Static mixers are used in continuous flow chemical reaction systems and processes. The process can be an in-line continuous flow process. The in-line continuous flow process can be a recycle loop or a single pass process. In one embodiment, the in-line continuous flow process is a single pass process.

[0093] As mentioned above, chemical reactors including static mixer scaffolds are capable of continuously conducting heterogeneous catalytic reactions. Chemical reactors can use single-phase or multi-phase feed and product streams. In one embodiment, the substrate feed (including one or more reactants) can be provided as a continuous fluid stream, for example, as a liquid stream containing either a) the substrate as a solute in a suitable solvent, or b) a liquid substrate with or without a co-solvent. It will be understood that the fluid stream can be provided by one or more gas streams, for example, hydrogen gas or a source thereof. The substrate feed is pumped into the reactor using pressure-driven flow, for example, by means of a piston pump.

[0094] The % volume displacement of the static mixer relative to the reactor chamber to contain the mixer ranges from 1 to 60, 2 to 50, 3 to 40, 4 to 22, 5 to 15, or 40 to 60. The % volume displacement of the static mixer relative to the reactor chamber to contain the mixer can be less than 60%, 50%, 40%, 35%, 30%, 25%, 20%, 15%, 10%, or 5%.

[0095] The static mixer configuration can be provided to enhance cross-sectional microscopic turbulence. Such turbulence can arise from a variety of sources, including the geometry of the CSM or microscopic roughness of the CSM surface resulting from the 3D printing process. For example, the turbulence length scale can be reduced to provide better mixing. The turbulence length scale can be, for example, a microscopic length scale.

[0096] The static mixer configuration can provide enhanced heat transfer characteristics in the reactor, such as reduced temperature differentials at the exit cross section. The heat transfer of the CSM can provide, for example, a cross-sectional or transverse temperature profile having a temperature differential of less than about 20° C. / mm, 15° C. / mm, 10° C. / mm, 9° C. / mm, 8° C. / mm, 7° C. / mm, 6° C. / mm, 5° C. / mm, 4° C. / mm, 3° C. / mm, 2° C. / mm, or 1° C. / mm.

[0097] The scaffolding can be configured so that, in use, the pressure drop (or back pressure) (Pa / m) across the static mixer ranges from about 0.1 to 1,000,000 Pa / m (or 1 MPa / m), including any value or range of values ​​therebetween. For example, the pressure drop (or back pressure) (Pa / m) across the static mixer can be less than about 500,000, 250,000, 100,000, 50,000, 10,000, 5,000, 1,000, 750, 500, 250, 100, 75, 50, 25, 20, 15, 10, or 5 Pa / m. The static mixer can be configured to provide a lower pressure drop for a particular flow rate. In this regard, the static mixers, reactors, systems, and processes described herein can be provided with parameters suitable for industrial applications. The above pressure drops can be maintained when the volumetric flow rate is at least 0.1, 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 6, 7, 8, 9, 10, 20, 30, 40, 50, 100, 500, 1000 mL / min.

[0098] The catalytically active scaffold or catalytically active static mixer scaffold may require a chemical or physical (heat) activation process step, for example, for hydrogen activation by exposing the catalytically active scaffold or catalytically active static mixer scaffold to molecular hydrogen or a hydrogen source. In some embodiments or examples, the processes described herein for preparing the catalytically active scaffold or catalytically active static mixer scaffold may include a further activation step (step ii) to remove metal oxide impurities by contacting the surface of the catalytically active scaffold with hydrogen gas. In some embodiments or examples, the catalytically active scaffold or catalytically active static mixer scaffold may be activated by contacting it with an activation fluid (e.g., hydrogen gas) for at least 1, 2, 5, 10, 15, 20, 25, or 30 hours, for example, at a temperature gradient of 20°C to 800°C. Activation may occur for less than 30, 25, 20, 15, 10, 5, 2, or 1 hour. Activation may occur between any two of the above time ranges.

[0099] The catalytic reaction can be a hydrogen insertion reaction involving the use of a hydrogenation catalyst. The hydrogen insertion or hydrogenation catalyst promotes the intramolecular bond of a reactant, for example, the insertion of hydrogen into a carbon-oxygen bond, the conversion of an unsaturated bond to a saturated bond, the removal of a protecting group such as the conversion of an O-benzyl group to a hydroxyl group, or the reaction of a nitrogen triple bond to form ammonia or hydrazine or mixtures thereof, forming the oxygen-containing organic material described above. The hydrogen insertion or hydrogenation catalyst can be selected from the group consisting of cobalt, ruthenium, osmium, nickel, palladium, platinum, and alloys, compounds, and mixtures thereof. In one embodiment, the hydrogen insertion or hydrogenation catalyst comprises or consists of platinum or titanium. In ammonia synthesis, the catalyst can promote the dissociative adsorption of hydrogen and nitrogen species sources for subsequent reactions. In a further embodiment, the hydrogen insertion or hydrogenation catalyst is activated by leaching or etching.

[0100] It will be understood that the static mixer can provide a monolithic scaffold for a chemical reactor chamber. A static mixer scaffold for a continuous-flow chemical reactor chamber can include a catalytically active scaffold defining a plurality of passages configured to disperse and mix one or more fluid reactants during flow and reaction of the reactants through the mixer. It will be understood that at least a substantial portion of the surface of the scaffold can include catalytically reactive sites. A catalytically active scaffold or catalytically active static mixer scaffold can be prepared by activating the surface of the scaffold by chemically removing sacrificial material from the surface of the scaffold to provide catalytically reactive sites on the surface of the scaffold.

[0101] The static mixer may be provided as one or more scaffolds, each configured for insertion into a continuous flow chemical reactor or its reactor chamber. The static mixer scaffold may be configured as a modular insert for construction into a continuous flow chemical reactor or its chamber. The static mixer scaffold may be configured as an insert for an in-line continuous flow chemical reactor or its chamber. The in-line continuous flow chemical reactor may be a recycle loop reactor or a single pass reactor. In one embodiment, the in-line continuous flow chemical reactor is a single pass reactor.

[0102] The static mixer scaffold can be configured to enhance mixing and heat transfer characteristics to redistribute fluids across the main flow, e.g., radially and tangentially or azimuthally relative to the central longitudinal axis of the static mixer scaffold. The static mixer scaffold can be configured for at least one of: (i) ensuring that the largest possible catalyst surface area is presented to the flow to activate a near-maximum number of reaction sites; and (ii) improving flow mixing so that (a) reactant molecules contact the surface of the static mixer scaffold more frequently and (b) heat is efficiently transferred away from or to the fluid. The static mixer scaffold can have various geometric configurations or aspect ratios to correlate with specific applications. The static mixer scaffold allows the fluid reactants to mix and be in close proximity to the catalytic material for activation. The static mixer scaffold can be configured for use with turbulent flow rates, for example, to enhance turbulence and mixing even on or near the interior surface of a reactor chamber housing. It will also be appreciated that the static mixer scaffolding can be configured to enhance heat and mass transfer characteristics for both laminar and turbulent flow.

[0103] The configuration may also be designed to enhance the efficiency, extent of chemical reaction, or other characteristics, such as pressure drop (while maintaining a given or desired flow rate), residence time distribution, or heat transfer coefficient. As previously mentioned, conventional static mixers have not been developed to specifically address the enhanced heat transfer requirements that may result from the catalytic reaction environment provided by the present static mixers.

[0104] The configuration of the scaffold or static mixer can be determined using computational fluid dynamics (CFD) software that can be used to enhance the configuration for mixing reactants to enhance contact and activation of the reactants or their reactive intermediates at the catalytically reactive sites of the scaffold. Determining the configuration by CFD is described in more detail in the following section.

[0105] The static mixer scaffold can be formed by additive manufacturing. The static mixer can be an additively manufactured static mixer. Additive manufacturing of the static mixer and subsequent catalytic reactive sites on the surface of the scaffold can provide a static mixer configured for efficient mixing (of reactants in a continuous flow chemical reactor), heat transfer, and catalytic reaction, which can be physically tested for reliability and performance and, optionally, further redesigned and reconfigured using additive manufacturing (e.g., 3D printing) techniques. Additive manufacturing provides flexibility in preliminary design and testing, and further redesign and reconfiguration of the static mixer to facilitate the development of more commercially viable and durable static mixers.

[0106] The static mixer scaffold may be provided in a configuration selected from one or more of the following general non-limiting example configurations: open configuration with spirals, Open configuration with blades, Corrugated plates, ·Multi-layer design, Closed configurations with channels or holes.

[0107] The static mixer scaffold may be provided in a mesh configuration having a plurality of integral units defining a plurality of passageways configured to facilitate mixing of one or more fluid reactants.

[0108] The static mixer scaffold may include a scaffold provided by a lattice of interconnected segments configured to define a plurality of pores to promote mixing of fluids flowing through the reactor chamber. The scaffold may also be configured to promote both heat transfer as well as fluid mixing.

[0109] In various embodiments, the geometric shape or configuration can be selected to enhance one or more properties of the static mixer scaffold selected from a particular surface area, volumetric displacement rate, strength and stability for high flow rates, suitability for processing using additive manufacturing, and can be selected to achieve one or more of a high degree of chaotic advection, turbulent mixing, catalytic interaction, and heat transfer.

[0110] In some embodiments, the static mixer scaffold may be configured to enhance chaotic advection or turbulent mixing, for example, cross-sectional, transverse (relative to the flow), or localized turbulent mixing. The geometry of ..., for example, cross-sectional, transverse, transverse, transverse, transverse, transverse, transverse, transverse, transverse, transverse, transverse, transverse, transverse, transverse, transverse, transverse, transverse, transverse, transverse, transverse, transverse, transverse, transverse, transverse, transverse, transverse, transverse, transverse, transverse, transverse, transverse, trans -1 More than, optionally, 400m -1 More than, optionally, 800m -1 exceeding, optionally 1500m -1 exceeding, optionally 2000m -1 exceeding, optionally 2500m -1 exceeding, optionally 3000m -1 exceeding, optionally 5000m -1 The geometry or configuration of the static mixer scaffold can be configured to redirect or split the local flow more than a certain number of times within a given volume of the static mixer, e.g., 100 m -3 exceeding, optionally 1000m -3greater than, optionally 1 × 10 4 m -3 greater than, optionally 1 × 10 6 m -3 greater than, optionally 1 × 10 9 m -3 greater than, optionally 1 × 10 10 m -3 The flow dividing structure may include more than one flow dividing structure.

[0111] The geometry or configuration of the static mixer scaffold can be substantially tubular or linear. The static mixer scaffold can be formed from or include multiple segments. Some or all of the segments can be straight segments. Some or all of the segments can include polygonal prisms, such as rectangular prisms. The static mixer scaffold can include multiple planar surfaces. The straight segments can be angled relative to each other. The straight segments can be arranged at several different angles, for example, at two, three, four, five, or six different angles, relative to the longitudinal axis of the scaffold. The static mixer scaffold can include repeating structures. The static mixer scaffold can include multiple similar structures that are periodically repeated along the longitudinal axis of the scaffold. The geometry or configuration of the static mixer scaffold can be consistent along the length of the scaffold. The geometry of the static mixer scaffold can vary along the length of the static mixer scaffold. The straight segments can be connected by one or more curved segments. The scaffold can include one or more helical segments. The static mixer scaffold may generally define a helical surface. The static mixer scaffold may include a helical surface that includes a plurality of pores on a surface of the helical surface.

[0112] The dimensions of the static mixer can vary depending on the application. The static mixer, or reactor containing the static mixer, can be tubular. The static mixer or reactor tube can have a diameter (mm) ranging from 1 to 5000, 2 to 2500, 3 to 1000, 4 to 500, 5 to 150, or 10 to 100. The static mixer or reactor tube can have a diameter (mm) of, for example, at least about 1, 5, 10, 25, 50, 75, 100, 250, 500, or 1000. The static mixer or reactor tube can have a diameter (mm) of, for example, less than about 5000, 2500, 1000, 750, 500, 250, 200, 150, 100, 75, or 50. The aspect ratio (L / d) of the static mixer scaffold, or the reactor chamber containing the static mixer scaffold, can be provided in a range suitable for industrial-scale flow rates for a particular reaction. The aspect ratio can be, for example, in the range of about 1 to 1000, 2 to 750, 3 to 500, 4 to 250, 5 to 100, or 10 to 50. The aspect ratio can be, for example, less than about 1000, 750, 500, 250, 200, 150, 100, 75, 50, 25, 20, 15, 10, 9, 8, 7, 6, 5, 4, 3, or 2. The aspect ratio can be, for example, greater than about 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 15, 20, 25, 50, 75, or 100. It is understood that aspect ratio refers to the ratio of length to diameter (L / d) of a single unit or scaffold.

[0113] The static mixer scaffold or reactor generally has a high specific surface area (i.e., the ratio of the internal surface area to the volume for the static mixer scaffold and reactor chamber). The specific surface area may be lower than that provided by a packed bed reactor system. The specific surface area (m 2 m -3 ) can be in the range of 100 to 40,000, 200 to 30,000, 300 to 20,000, 500 to 15,000, or 12,000 to 10,000. 2 m -3) can be at least 100, 200, 300, 400, 500, 750, 1000, 2000, 3000, 4000, 5000, 7500, 10000, 12500, 15000, 17500, or 20000. It will be appreciated that specific surface areas are measured by several techniques including the BET isotherm technique.

[0114] Static mixer substrates can be configured to enhance properties such as mixing and heat transfer for laminar or turbulent flow rates. For a Newtonian fluid flowing inside a hollow pipe, the correlation between laminar and turbulent flow and the Reynolds number (Re) value is typically such that for Re < 2300 it is laminar flow, for 2300 < Re < 4000 it is transitional flow, and generally for Re > 4000 it is turbulent flow. Static mixer substrates can be configured for laminar or turbulent flow rates to provide enhanced properties selected from one or more of mixing, degree of reaction, heat transfer, and pressure drop. It will be appreciated that specific considerations are required to further enhance a particular type of chemical reaction.

[0115] Static mixer substrates can generally be configured to operate at a Re of at least 0.01, 0.1, 1, 5, 50, 100, 150, 200, 250, 300, 350, 400, 550, 600, 650, 700, 750, 800, 850, 900, 950, 1000, 1100, 1200, 1300, 1400, 1500, 1600, 1700, 1800, 1900, 2000, 2500, 3000, 3500, 4000, 4500, 5000, 5500, 6000, 6500, 7000, 7500, 8000, 8500, 9000, 9500, 10000. Static mixer substrates can be configured to operate in a generally laminar Re range of about 0.1 to 2000, 1 to 1000, 10 to 800, or 20 to 500. Static mixer substrates can be configured to operate in a generally turbulent Re range of about 1000 to 15000, 1500 to 10000, 2000 to 8000, or 2500 to 6000.

[0116] The % volume displacement of the static mixer relative to the reactor chamber to contain the mixer ranges from 1 to 40, 2 to 35, 3 to 30, 4 to 25, 5 to 20, or 10 to 15. The % volume displacement of the static mixer relative to the reactor chamber to contain the mixer can be less than 40%, 35%, 30%, 25%, 20%, 15%, 10%, or 5%.

[0117] Static mixer configurations can be provided to enhance cross-sectional microscopic turbulence. Such turbulence can arise from a variety of sources, including the geometry of the CSM or microscopic roughness of the CSM surface resulting from surface coatings and / or 3D printing processes. For example, the turbulence length scale can be reduced to provide better mixing. The turbulence length scale can be, for example, in the microscopic length scale range.

[0118] The static mixer configuration can provide enhanced heat transfer characteristics in the reactor, such as reduced temperature differentials at the exit cross section. The heat transfer of the CSM can provide, for example, a cross-sectional or transverse temperature profile having a temperature differential of less than about 20° C. / mm, 15° C. / mm, 10° C. / mm, 9° C. / mm, 8° C. / mm, 7° C. / mm, 6° C. / mm, 5° C. / mm, 4° C. / mm, 3° C. / mm, 2° C. / mm, or 1° C. / mm.

[0119] The scaffolding can be configured so that, in use, the pressure drop (i.e., pressure differential or back pressure) (Pa / m) across the static mixer ranges from about 0.1 to 1,000,000 Pa / m (or 1 MPa / m), including any value or range of values ​​therebetween. For example, the pressure drop (Pa / m) across the static mixer can be less than about 500,000, 250,000, 100,000, 50,000, 10,000, 5,000, 1,000, 750, 500, 250, 100, 75, 50, 25, 20, 15, 10, or 5 Pa / m. The static mixer can be configured to provide a lower pressure drop for a particular flow rate. In this regard, the static mixers, reactors, systems, and processes described herein can be provided with parameters suitable for industrial applications. The above pressure drops can be maintained when the volumetric flow rate is at least 0.1, 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 6, 7, 8, 9, 10, 20, 30, 40, 50 mL / min.

[0120] Process for preparing a static mixer The static mixer scaffold can be provided by additive manufacturing, such as 3D printing. Additive manufacturing of the static mixer and subsequent catalytic reactive sites on the surface of the scaffold can provide a static mixer configured for efficient mixing (of reactants in a continuous flow chemical reactor), heat transfer, and catalytic reaction, which can be physically tested for reliability and performance and, optionally, further redesigned and reconfigured using additive manufacturing (e.g., 3D printing) techniques. Following the original design and development using additive manufacturing, the static mixer can be prepared using other manufacturing processes, such as casting (e.g., investment casting). Additive manufacturing offers flexibility in preliminary design and testing, and further redesign and reconfiguration of the static mixer to facilitate the development of more commercially viable and durable static mixers.

[0121] The static mixer scaffold can be fabricated by additive manufacturing (i.e., 3D printing) techniques. For example, electron beam 3D printers or laser beam 3D printers may be used. The additive material for 3D printing can be, for example, titanium alloy-based powder (e.g., in the diameter range of 45 to 105 micrometers) or cobalt-chromium alloy-based powder (e.g., FSX-414), or stainless steel, aluminum-silicon alloy, titanium-based alloy, nickel-based alloy, palladium-based alloy, platinum-based alloy, nickel-aluminum-based alloy, ruthenium-based alloy, or rhodium-based alloy. In one embodiment, the additive material for 3D printing can be a nickel-based alloy, palladium-based alloy, or nickel-aluminum-based alloy. The diameter of the powders associated with laser beam printers is typically smaller than that used in electron beam printers.

[0122] 3D printing is a well-understood process that involves sequentially depositing material onto a powder bed via fusion, facilitated by heat delivered by a beam or by processes based on extrusion and sintering. 3D-printable models are typically created in computer-aided design (CAD) packages. Before printing a 3D model from an STL file, it is typically inspected for manifold errors and applied corrections. Once this is done, the STL file is processed by software called a "slicer," which converts the model into a series of thin layers and generates a G-code file containing instructions tailored to a specific type of 3D printer. The 3D printing process is advantageous for use in preparing static mixer scaffolds because it eliminates the limitations on product design imposed by traditional manufacturing routes. Therefore, the design freedom inherited from 3D printing allows the static mixer geometry to be optimized for performance more than with other methods.

[0123] Catalytically active scaffolds can be prepared by chemically removing sacrificial material from the surface of the scaffold material to provide catalytic reaction sites on the surface of the scaffold.

[0124] In some embodiments, the process may involve first forming a scaffold using an additive manufacturing process such as 3D printing. [Example]

[0125] The present disclosure is further illustrated by the following examples. It should be understood that the following descriptions are merely for the purpose of illustrating particular embodiments and are not intended to be limiting on the above description.

[0126] The present disclosure provides an effective and scalable process for preparing catalytically active scaffolds or catalytically active static mixer scaffolds by chemically removing sacrificial and / or active materials from the surface of the scaffold to activate the surface of the scaffold and provide catalytically reactive sites on the surface of the scaffold or static mixer scaffold. Referring to FIG. 1 , the process can include a selective chemical process or a non-selective chemical process. The selective chemical process can be a chemical leaching process to remove the sacrificial material, and the non-selective chemical process can be a chemical etching process to remove the sacrificial and / or active materials. The chemical process used can be determined by the type of scaffold or static mixer scaffold.

[0127] Example 1: General process for preparing catalytically active scaffolds from 3D printed scaffolds using leaching method: Static mixer scaffolds were printed from metal or metal oxide powders and then subjected to one or more leaching solutions containing ammonium sulfate or ammonium persulfate.

[0128] Ni-based catalytic static mixers were prepared from Monel (Alloy 400) powder with a composition of approximately 61% Ni, 35% Cu, 2.2% Fe, 1.3% Mn, and 0.5% Si according to the general process described above. This process selectively removes copper from the scaffold and enriches the surface of the scaffold with nickel, forming a catalytically active static mixer scaffold.

[0129] The Ni / Cu ratio at the surface of the catalytically active static mixer was 4–8 after chemical leaching treatment compared to 1.77 for the untreated sample.

[0130] It will be appreciated that after the activation process, the Ni-based catalytically active static mixer scaffold can be used as a Ni[0] type catalyst for catalytic reactions, for example, hydrogenation reactions.

[0131] Example 1a. Ni-based CSM prepared from Monel 400 by chemical leaching In the example, a Monel static mixer scaffold was added to 450 mL of an aqueous solution of 2 M ammonium sulfate and 5 M ammonia, left for 10 days, and sonicated for at least 1 hour per day. Approximately 30 mL of aqueous ammonia was added every 3 days to replace the lost ammonia as a gas. The mixture was observed to turn pale green. The mixer was then washed in water and added to another 450 mL solution of 2 M ammonium persulfate and 5 M ammonia, and the same protocol was applied, leaving the mixer for 12 days. The mixture was found to be [Cu(NH3)(OH2)2] 2+ The color of the Monel static mixer was observed to change to sapphire blue. The catalytically active static mixer scaffold was then washed. As shown by the SEM images (Figure 2), there are visible differences between the untreated (Figure 2a) and treated (Figure 2b) Monel static mixers. For example, the surface area of ​​the Monel static mixer is at least about 30% greater when compared to the surface area of ​​the scaffold material without subpores.

[0132] The mass loss of the Monel static mixer is 5 wt. % when compared to the total mass of the scaffold material without subpores.

[0133] The pore size of one or more pores within the pore is about 0.1 μm.

[0134] The XPS results showing the change in Ni:Cu ratio before and after treatment are shown in Table 1 below. As can be seen from the XPS results, the selective enrichment of nickel (i.e., the active catalytic species) is at least two times greater than that of copper (i.e., the sacrificial material). This depends on the leaching agent and leaching time. For example, when ammonium persulfate is used as the leaching agent after a leaching time of 7 days, the selective enrichment of nickel is about seven times greater than that of copper. [Table 1]

[0135] Example 2: General process for preparing catalytically active scaffolds from 3D printed scaffolds using the etching method: Static mixer scaffolds were printed from Inconel powder with a composition of approximately 61% Ni, 16% Cr, 8.5% Co, 3.4% Al, 3.4% Ti, 2.6% W, 1.8% Ta, 1.8% Mo, and lesser amounts of Fe, C, B, Zr, Mn, Si, and S. The static mixer scaffolds were then subjected to a chemical etching solution: Marble's reagent, [1 M] copper sulfate in [4.4 M] aqueous hydrochloric acid. The chemical etching process provides a non-selective surface etching and oxidation process of metal species, particularly Ni, Cr, and other metal species within the alloy material, thereby forming a chemically active static mixer scaffold and providing a surface of the static mixer scaffold with increased porosity and surface area.

[0136] It will be appreciated that after an additional reduction / activation procedure to reduce the Ni-oxide to Ni[0], the catalytically active static mixer scaffold can be used as a Ni[0] type catalyst for hydrogenation reactions.

[0137] Example 2a Ni-based CSM prepared from Inconel 738 by chemical etching In the example, an Inconel static mixer scaffold was prepared according to the general procedure described above, and the static mixer scaffold was immersed in 250 mL of Marble's reagent (1 M copper sulfate in 4.4 M aqueous hydrochloric acid) to which 10 drops of pure sulfuric acid had been added. The mixer was left for 24 hours, and the solution was observed to turn opaque black. The mixer was then removed and washed thoroughly with water.

[0138] As shown by SEM images (Figure 3), there are visible differences between the untreated (Figure 3a) and treated (Figure 3b) Inconel static mixers. For example, the surface area of ​​the Inconel static mixer is at least about 30% greater when compared to the surface area of ​​the scaffold material without subpores.

[0139] The mass loss of the Inconel static mixer is 5 wt. % when compared to the total mass of the scaffold material without subpores.

[0140] The pore size of one or more pores within the pore is about 0.1 μm.

[0141] Example 3 General process for preparing catalytically active scaffolds from metal foam scaffolds using an etching method: The nickel foam was subjected to one or more etching solutions containing hydrochloric acid, nitric acid, ferric chloride, or Marble's reagent. This process removes some of the nickel from the foam, enriching the surface of the foam and forming a catalytically active static mixer scaffold.

[0142] It will be appreciated that after the activation process, the Ni-based catalytically active static mixer scaffold can be used as a Ni[0] type catalyst for catalytic reactions, for example, hydrogenation reactions.

[0143] Example 3a Ni-based CSM prepared from nickel foam by chemical etching In one example, nickel foam was prepared according to the general procedure described above in Example 3, and the nickel foam static mixer was immersed in 30 mL of 30 wt % ferric chloride for 1 minute. The mixer was then removed and washed thoroughly with water.

[0144] As shown by SEM images (Figure 4), there are visible differences between the untreated (Figure 4a) and treated (Figure 4b) nickel foam static mixers. For example, the surface area of ​​the nickel static mixer is at least about 30% greater when compared to the surface area of ​​the scaffold material without subpores.

[0145] The mass loss of the nickel foam static mixer is 50 wt% when compared to the total mass of the scaffold material without subpores.

[0146] The pore size of one or more pores within the pore is about 0.1 μm.

[0147] Example 4 Preparation of catalytically active static mixer scaffolds: Catalytically active static mixer scaffolds were prepared according to the general procedure described above and tested for a series of hydrogenation reactions. CSMs were printed into the mixer design disclosed in previous work (see WO2017 / 106916) with an outer diameter of 6 mm and a length of 150 mm. CSM volume V CSM and the remaining reactor volume V R was calculated using the displacement of water in a length of standard glass tube. [Table 2]

[0148] Example 5 Catalyst Activation: Each set of CSMs was activated using hydrogen after storage in air. The activation process reduces catalytically inactive metal oxides formed by aerobic passivation. To identify the necessary conditions, a temperature-programmed reduction (TPR) was performed on a small cutoff of CSMs. This process involves passing a constant stream of 95% N2 / 5% H2 over the catalyst in a furnace with a steady temperature gradient from 20 °C to 800 °C, recording the decrease in the thermal conductivity of the gas mixture. The protocol for activating each CSM is detailed in the table below. [Table 3]

[0149] Example 6 Performance Evaluation: Hydrogenation of vinyl acetate to ethyl acetate: Vinyl acetate hydrogenation reactions (Scheme 1) were carried out in a Mark II hydrogenation reactor packed with an active CSM and eight blanks for each experiment (see WO2017 / 106916 and Hornung et al., Org. Process Res. Dev. 2017, 21, 9, 1311-1319 for a detailed description of the reactor and reaction protocol). The CSM was conditioned before each reaction according to the condition parameters. Multiple product fractions were collected from which steady-state measurements could be made. Conversion and selectivity data were reported as follows: 1 Calculations were performed using H NMR spectra and GC-MS. [ka]

[0150] Input variables were pressure, temperature, liquid residence time, and H / S ratio. Unless otherwise noted, all reactions were carried out at p = 24 bar and T = 120 °C, and substrates were used as [0.5 M] solutions in ethyl acetate. All solvents were obtained from Merck.

[0151] Figures 5a and 5b show the conversion results for leached Monel CSM and etched Inconel CSM at 2 M vinyl acetate, demonstrating superior performance compared to untreated Inconel CSM and Monel CSM. The treated Monel CSM showed 95% conversion at 1 mL / min, compared to 30% conversion for the untreated sample, and the treated Inconel CSM showed 55% conversion at the same flow rate, compared to 8% for the untreated sample. Figure 5c shows the conversion results for the etched nickel foam sample at 0.5 M vinyl acetate, also demonstrating significant improvement in activity compared to the untreated sample. The treated nickel foam CSM showed 88% conversion at 2 mL / min, compared to 47% conversion for the untreated sample. This demonstrates the effectiveness of the chemical etching and leaching process for creating catalysts with high surface area and, therefore, catalytic activity. Advantageously, the leached and etched CSM performs better as hydrogen availability (H / S) and residence time increase (ie, as liquid flow rate decreases).

[0152] Hydrogenation of Coumarin: The performance of leached Monel CSM was also tested for the hydrogenation of coumarin (see Scheme 2). [ka]

[0153] As can be seen in Figure 6, the leached Monel CSM performed well with high conversion rates. Coumarin conversion was higher at longer residence times and lower liquid flow rates, as expected.

[0154] Hydrogenation of cinnamaldehyde, linalool, and 2,5-dichloronitrobenzene: Further test reactions were performed to compare the selectivity of leached Monel CSM. The hydrogenation of cinnamaldehyde, linalool, and 2,5-dichloronitrobenzene is shown in Schemes 3, 4, and 5 below: [ka] [ka] [ka]

[0155] In the above cases of Schemes 3 and 4, both substrates have two reactive moieties that can be reduced, so selectivity towards three possible hydrogenation products (two semi-hydrogenated intermediate species and one fully hydrogenated species) must be considered; in the case of cinnamaldehyde, these are the C-C double bond and the carbonyl group, and in the case of linalool, they are the terminal C-C double bond and the internal C-C double bond. Figure 7 shows that the leached Monel CSM primarily hydrogenated the C-C double bonds, resulting in the hydrocinnamaldehyde intermediate as the major product, followed by smaller amounts of fully hydrogenated 3-phenyl-1-propanol and other unidentified by-products. No cinnamyl alcohol was produced.

[0156] When using the leached Monel catalyst to reduce linalool (Figure 8), surprising selectivity was observed. While strong selectivity for the reduction of either of the two C-C double bonds was not observed for Ni / Al2O3 or the other Ni, Pd, or Ru-type catalysts we tested, the leached Monel catalyst reduced the terminal C-C double bond to 1,2-dihydrolinalool, but not to 6,7-dihydrolinalool or 3,7-dimethyloctan-3-ol (a small amount of unreacted starting material remained). This 100% selectivity for the reduction of the terminal double bond was an unexpected beneficial effect and was believed to be a result of the alloy type and nature of the catalyst prepared in this disclosure, which contains Cu and other metal species within a Ni-enriched matrix.

[0157] Figure 9 shows the conversion rates for the hydrogenation of 2,5-dichloronitrobenzene to 2,5-dichloroaniline over leached and untreated Monel CSM. Again, the treated sample performs significantly better with a conversion rate of 80% versus 24% for untreated CSM.

Claims

1. 1. A catalytically active static mixer comprising a scaffold material comprising an active catalytic material and a non-active material, the scaffolding material is in the form of a lattice of interconnected segments that are periodically repeated along a longitudinal axis of the scaffolding material, each segment configured to define a plurality of passages and pores in a non-line-of-sight configuration, the plurality of passages being spaced apart from one another at intervals of 200 m, corresponding to a number of times within a predetermined length along the longitudinal axis of the catalytically active static mixer. －１ configured to disperse and mix one or more fluid reactants during flow and reaction of the reactants by redistributing fluid across the flow by changing local flow direction or splitting the flow; the plurality of passages are defined by a plurality of pores; the pores contain one or more catalytically active subpores within the pores; A catalytically active static mixer wherein said pores are at least about 100 times larger than said catalytically active subpores.

2. 2. The catalytically active static mixer of claim 1, wherein the active catalyst material is selected from the group comprising palladium, platinum, nickel, ruthenium, copper, rhodium, gold, silver, cobalt, iridium, osmium, rhenium, chromium, or metal alloys or oxides thereof, zeolites, and metal organic frameworks.

3. 3. The catalytically active static mixer of claim 1 or 2, wherein the pore size of the one or more pores within the pores ranges from about 0.05 μm to 500 μm.

4. 4. The catalytically active static mixer of claim 1, wherein the inactive material is selected from the group comprising magnesium or its metal oxides, silicon, silicone, polymers, ceramics, and metal oxides.

5. 5. The catalytically active static mixer of any one of claims 1-4, wherein the scaffold material is one or more of nickel, titanium, aluminum, tungsten, niobium, molybdenum, steel, stainless steel, copper, cobalt chromium, titanium-based alloys, nickel-based alloys, palladium-based alloys, nickel-aluminum-based alloys, platinum-based alloys, ruthenium-based alloys, rhodium-based alloys, gold, platinum, palladium, and silver.

6. The surface area of ​​the catalytically active scaffold is approximately 0.5 m ２ / g~750m ２ A catalytically active static mixer according to any one of claims 1 to 5, wherein the mixing ratio is in the range of 1 / g.

7. The catalytically active scaffold has a total pore volume of about 0.2 cm ３ / g to 10cm ３ A catalytically active static mixer according to any one of claims 1 to 6, wherein the mixing ratio is in the range of 1 / g.

8. A catalytically active static mixer according to any one of claims 1 to 7, wherein the catalytically active static mixer has an aspect ratio (L / d) of at least 75.

9. 1. A process for preparing a catalytically active static mixer from a scaffold material, the scaffold material being in the form of a lattice of interconnected segments that are periodically repeated along a longitudinal axis of the scaffold material, each segment configured to define a plurality of passages and pores in a non-line-of-sight configuration, the plurality of passages being spaced apart from one another at intervals of 200 m corresponding to a number of times within a predetermined length along the longitudinal axis of the catalytically active static mixer. －１ 1. A process for dispersing and mixing one or more fluid reactants during flow and reaction of the reactants by redistributing fluid across a flow by changing local flow direction or splitting the flow by a factor of 10, wherein the plurality of passages are defined by a plurality of pores, and the scaffold material comprises active catalytic material and inactive material, the process comprising: (i) activating the surface of the scaffold material by chemically removing at least about 0.5 wt. % of inactive material from the surface of the scaffold material to provide the catalytically active static mixer with catalytically active sites on the scaffold material and catalytically active subpores within the pores of the scaffold material, wherein the scaffold material is activated using a selective or non-selective chemical process.

10. The process of claim 9 , wherein the scaffolding material further comprises an inert material.

11. 11. The process of claim 9 or 10, wherein the selective chemical process is a chemical leaching process to remove at least about 0.5 wt% of a sacrificial material from the scaffold material, the sacrificial material being the non-active material.

12. 12. The process of claim 9 or 11, wherein the non-selective chemical process is a chemical etching process to remove at least about 0.5 wt. % of sacrificial material from the scaffolding material, wherein the sacrificial material is the active catalytic material, the non-active material, an optional inert material, or a combination thereof.

13. The process of claim 12 , wherein the chemical etching process comprises the use of an etching solution.

14. The process of claim 11 , wherein the chemical leaching process comprises the use of a leaching solution.

15. The process of any one of claims 9 to 14, wherein the pores are at least about 100 times larger than the catalytically active subpores.

16. 16. The process of any one of claims 9 to 15, wherein the pores are at least about 1000 times larger than the catalytically active subpores.

17. 17. The process of any one of claims 9 to 16, wherein the mass loss of the sacrificial material from the catalytically active scaffold ranges from about 0.5% to 60% by weight, based on the total mass of the scaffold material.

18. 18. The process of any one of claims 9 to 17, wherein the active catalytic material is selected from the group comprising palladium, platinum, nickel, ruthenium, copper, rhodium, gold, silver, cobalt, iridium, osmium, rhenium, chromium, or alloys or oxides of these metals, zeolites, and metal organic frameworks.

19. 19. The process of any one of claims 9 to 18, wherein the inactive material is selected from the group comprising chromium, titanium, copper, iron, zinc, aluminum, nickel, silver, or oxides of these metals, and carbon-based materials.

20. The process of any one of claims 9 to 19, wherein the inert material is selected from the group comprising magnesium or its metal oxides, silicon, silicone, polymers, ceramics, and metal oxides.

21. 21. The process of any one of claims 9 to 20, wherein the scaffold material is one or more of nickel, titanium, aluminum, tungsten, niobium, molybdenum, steel, stainless steel, copper, cobalt chromium, titanium-based alloys, nickel-based alloys, palladium-based alloys, nickel-aluminum-based alloys, platinum-based alloys, ruthenium-based alloys, rhodium-based alloys, gold, platinum, palladium, and silver.

22. 22. The process of any one of claims 9 to 21, wherein the surface area of ​​the catalytically active static mixer is increased by at least about 30% when compared to the surface area of ​​the scaffolding material without catalytically active subpores.

23. The surface area of ​​the catalytically active scaffold is approximately 0.5 m ２ / g~750m ２ The process of any one of claims 9 to 22, wherein the hydroxyl group is in the range of / g.

24. The catalytically active scaffold has a total pore volume of about 0.2 cm ３ / g to 10cm ３ The process of any one of claims 9 to 23, wherein the hydroxyl group is in the range of / g.

25. 25. The process of any one of claims 9 to 24, wherein the pore size of the catalytically active subpores ranges from about 0.05 μm to 500 μm.

26. 26. The process of any one of claims 9 to 25, wherein the catalytically active static mixer has an aspect ratio (L / d) of at least 75.

27. 27. The process of any one of claims 9 to 26, wherein the process comprises a further activation step to remove metal oxide impurities by step ii) contacting the surface of the catalytically active static mixer with hydrogen gas.

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