FI20186003A1 - A porous body, method for manufacturing it and its use for catalysis - Google Patents
A porous body, method for manufacturing it and its use for catalysis Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
- B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/56—Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional monoliths
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
- B29C64/10—Processes of additive manufacturing
- B29C64/141—Processes of additive manufacturing using only solid materials
- B29C64/153—Processes of additive manufacturing using only solid materials using layers of powder being selectively joined, e.g. by selective laser sintering or melting
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y10/00—Processes of additive manufacturing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y80/00—Products made by additive manufacturing
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Abstract
Keksinnön kohteena on yksinkertainen, monipuolinen ja uudelleen käytettävä katalyytti, joka perustuu 3D-lasertulostettuun huokoiseen kappaleeseen. Esineiden muoto, huokoisuus ja aktiivinen ainesosa voidaan säätää helposti tuottamaan tehokas katalyytti erilaisia reaktioita, kuten hydratointia ja C-C-sidoksen muodostusta varten.The present invention relates to a simple, versatile and reusable catalyst based on a 3D laser printed porous body. The shape, porosity and active ingredient of the articles can be easily adjusted to produce an effective catalyst for various reactions such as hydration and C-C bond formation.
Description
FOR CATALYSIS Field of invention This invention relates to catalysis using a laser 3D printed porous body made of at least one compound having catalytically active component, to its application as a catalyst in batch and flow processes and to a method for manufacturing said porous body. Background and prior art The research around 3D printing has reached a phase where functional properties of the objects, such as catalysis for chemical reactions are actively developed instead of physical properties that have traditionally been the main area of interest of the industry.' Techniques like direct ink writing, fused deposition modeling and stereolithography have been used in preparation of different catalytically active materials and reaction vessels.” However, the material generated by above methods requires often demanding post-processing to activate or even insert the catalytically active species and/or the objects are not porous allowing higher surface (reaction) © area and effective catalytic processes such as continuous flow systems.
O N 20 Patent US 9278338B2 presents 3D printing of catalyst, where ALM method is a disclosed. The ALM method, which is also known as layer manufacturing, may be
N r applied to catalyst design using known techniques. In order that the shaped unit has Ao 0 structural integrity, the powder material is bound or fused together as the layers are 3 deposited. The process of layer deposition and binding or fusion is repeated until a > 25 robust shaped unit is generated. Several ALM binding and fusion fabricationtechniques are available, notably 3D printing and laser sintering techniques. Any of the techniques may however be used. Chinese document CN103751852A presents a preparation method of a three- dimensional artificial random porous structure tissue engineering scaffold, belonging to the technical field of biomaterials. The document aims to solve the design and manufacturing problems of the bionic structure of tissue engineering scaffold, provides a design method for constructing a random distributed scaffold porous structure with a bionic shape under expected porosity and pore size requirements, and molds by using a 3D additive manufacturing method to produce tissue substitute. The porosity of the structure is described by the aperture size being in a range of 1000 - 1500 um. WO application WO2016188606A1 presents devices for substance separation prepared using 3D printed monolithic objects. The invention aims produce monolithic sorbents for chromatography or sample preparation. Chromatography is a technique where single components can be separated from a mixture. Column chromatography, where the monoliths described in the document are principally used, is based on stationary materials that retards components of a mixture to certain extent when the mixture is pushed through a column together with carrier solution (eluent). Importantly, the materials commonly utilized in chromatography © 20 and in the above application, will retard the substances for a certain time but are S eventually eluted out of the material by the eluent. This limits the usability of this - material to only chromatographic applications where the interactions between N substrate and stationary phase are generally physical and reasonably weak. : WO application WO2013121230A1 describes reaction vessels, potentially
O 3 25 containing catalytically active materials, obtained by 3D-printing methods. The > document does not specify the 3D printing method to be used but it is clear for aperson skilled in art that the technique intended to use is based on extrusion. Typically, this type of 3D printing does not produce porous materials. Furthermore, the document does not indicate that any part of the reaction vessels is made porous by 3D printing.
Summary of the invention The object of the invention is to present a porous body, method for manufacturing it and its use in catalysis. These objects are achieved by the features presented accompanying claims. Particularly the polymer particles in the porous body are connected to each other and they form themselves a uniform porous structure and said active component can act as a catalyst in a chemical reaction. One of the principal processes described in the invention is an approach in heterogeneous catalysis, where the catalytically active component containing porous body can be utilized as fully functional catalyst in both batch and flow processes. Important feature of said body is that it has a permanent self-channeling structure, created by careful tuning of the 3D printing parameters. The structure allows fluid flow through the object without any traditional, pre-designed macroscopic channels enabling highly efficient interaction between the substrate and catalytically active 2 20 component. - The invention discloses laser 3D printed, preferably manufactured using selective N laser sintering (SLS) technigue, catalytically active porous objects, which act as E catalyst. Importantly, the catalytically active component is mixed to the polymer S powder and the porous body, after 3D printing, can act as fully functional catalyst 3 25 without any chemical or physical post-processing of the material.
Particularly, a method for manufacturing catalytically active component containing, self-channeling, SLS 3D printed porous body and utilizing it in catalysis, has been developed. The porous body A porous body with catalytically active component is provided according to claim
1. The polymer particles are connected to each other and form themselves a self- channeling, uniform porous structure. In a preferred embodiment, said particles are mainly untouched and connected to each other by only a small fraction of the total surface forming a lattice resembling structure. In addition to a designed mesh structure or flow channels, proper control of the SLS-device can create a uniform, self-channeling porous structure having a porosity (excluding any designed hollow areas such as channels), defined as volume of voids over total volume, between 10 and 70 %. The powder is heated only to such extent, where the particles are smelted slightly in order to connect them to each other. The contact surface to each next particle in only a small fraction of the total surface of a particle (typically 1 - 50 %, preferably 5 — 30 %). According to advantageous but non-essential features of the invention, the porous body incorporates one or more of the following characteristics: e Said body has thickening forms solid walls encompassing the porous portion. = 20 A fluid may flow, be absorbed, poured or pumped through the object. 2 e Said polymer has the particle size in a range of 10 - 200 um, preferably in a © range of 15 - 100 um and most preferably in a range of 20-80 um. E e The particles have optimum shape of a spherical body, but in practice there 2 are deviations of dimensions in a range of 5 - 200 %, preferably 60 - 140 % 3 25 of the average diameter of particles. N e Said body is composed of a polymer and a catalytically active component.
e Said polymer belongs to class of polyolefins, polyamides, polyimides, polyarylates, polyesters, vinyl polymers, polystyrenes, polyacrylates or a mixture of two or more of these.
e Said body is composed of a ceramic material and a catalytically active 5 component.
e Said ceramic material can be composed of one or more inorganic compounds, clay, glass, porcelain, main group oxides, main group nitrides or pure main group compounds.
e Said body is composed of a metal and a catalytically active component.
e Said metal belongs to d- or f-block elements and can be in pure form or an alloy of one or more metals.
e Said body contains 0.01-100 %, preferably 1-50 % and more preferably 5-30 % of catalytically active component that belongs to group of d-, f- or p-block metals.
e Said catalytically component belongs to a group noble metals (Cu, Ru, Rh, Pd, Ag, Re, Os, Pt, Au, Hg).
e Said catalytically active component belongs to the noble metals (Cu, Ru, Rh, Pd, Ag, Re, Os, Ir, Pt, Au and Hg) when catalysts for hydrogenation reactions are targeted.
© 20 e Said catalytically active component belongs to the platinum group metals S (Ru, Rh, Pd, Os, Ir, Pt) when catalysts for coupling reactions are targeted.
= e Said body has a maximum dimension limited only by printer capacity. N Currently typical printable bodies range of 5 - 500 mm in the transverse E direction of through flow and in a range of 5 - 500 mm in the direction of S 25 through flow.
Ne Said body may have interlocking members or connections for tubing to form an assembly of bodies or connect the body to pumping system. e Said body may have designed interior channels or mesh to improve the flow and reduce the back pressure.
In another embodiment a porous body has an essentially defined structure achieved by the laser printing of seguential layers, each having a defined layout. Thus, porosity of inner and outer layers can be adjusted accurately.
In another embodiment are integral walls encompassing a porous center portion. The walls have a non-porous structure and thus they form a channel for a liguid.
The properties of the porous body are efficiently controllable in a macroscopic using computer-aided design (CAD) and in a microscopic scale by fine tuning the parameters of the 3D printer.
The macroscopic control includes the design of shape, inner and outer structure of the body, size and functional parts, such as connections only limited by the available 3D printer.
The microscopic control includes design of the porosity and chemical properties of the body limited only by the intrinsic physical and chemical properties of the raw materials such as particle size and shape, melting/glass transition temperature and © chemical functionality. O . a N 20 The porous body can be reused under both batch and continuous flow conditions. v The flow properties of the object can be adjusted by designing interior flow
O - channels and/or by adjusting the printing parameters. a a JN Inactivated inner surface of the porous can be reactivated simply by removing the
O 2 inactivated layer revealing fresh active surface. Removal of the inactivated surface 0 > 25 can be carried out by using mineral acid or acid mixtures, typically nitric acid atconcentrations of 0.5-8 M. Also, organic solvents such as alcohols, typically methanol or ethanol, can be used for removal of the inactivated layer. If the body is mechanically damaged beyond use, it can be grinded into powder with particle size of 20-80 um and used again as printing material.
Method for manufacturing the porous body Method for manufacturing a chemically functional porous body for heterogeneous catalysis is described, where the selective body is manufactured by SLS 3D printing using at least one compound giving said catalytic properties and at least one substance forming structure for the body in 3D printing.
The polymer powder has the particle size preferably in a range of 10 - 200 um, more preferably in the range of 20 - 80 um. With smaller particle size, smaller channels and larger reactive surface area is achieved.
According to one embodiment of the invention the polymer is a part of a mixture having other substances such as soluble inorganic or organic salts. A salt may be used which can be dissolved after 3D printing leading to even higher porosity structure.
In another embodiment the walls encompassing a porous center portion are manufactured integrally in the porous body. This is achieved preferably so, that said SLS 3D printing parameters are adjusted to melt polymer powder fully in the 00 > 20 area of walls (18) representing 100 % power of laser and to use 15 - 80 %, = preferably 30 - 70 % power for porous center portion (13). The temperature of the N chamber was 2 - 25 °C, preferably 5-20 °C below the melting point. E It was found that to obtain impermeable, solid material, the printing temperature
O S was selected to be 2-25 *C, preferably 5-20 *C below the melting temperature (or
O = 25 in certain cases glass transition temperature) of the printable polymer and 100 %
Nlaser power and laser speed between 400-1200 mm s' was used. In contrast, to obtain porous material the laser power was lowered to 30-70 % and the rate was increased to 1600-2560 mm s" while the temperature remained in the same range. The most of particles (usually 70 - 100%, preferably 90 - 100%) are partly sintered so that they are connected to each other by only a small fraction of the total surface and they form a lattice like structure. The mechanical strength of the porous body, particularly inside integral walls has not been an issue even in the lightest, i.e. the most porous body. This forms an efficient method to achieve coarsely a lattice like structure for industrial use. The thickness of the wall in commercial solutions is preferably 0.1 - 7 % and more preferably 0.3 - 4 %, of the diameter of the porous portion. The density of a porous body can be defined as percentage compared to the impermeable, solid material (fully melted) as inverse of the porosity which in turn is defined as volume of voids (excluding the designed macroporous channels) over total volume of the object. Hence, the density of the porous body is commonly 30- 90 % of the density of fully melted material, such as impermeable walls as described above. The absolute density values are dependent on the materials used, namely sinterable polymer and chemically active component. The density of a body with porosity of © 20 30 %, mainly composed of standard polymer, such as polyamide or polypropylene, N is preferably between 0.3 - 0.8 g/cm’ and more preferably 0.4 - 0.6 g/cm’. The 7 density of the fully melted material of standard polymers is 1.01 g/cm’ and 0.946 2 g/cm’ for polyamide and polypropylene, respectively. The test bodies were N measured and following density values of porous body were found: polyamide 3 25 (PA): 0.45-0.6 g/cm’ and polypropylene (PP): 0.35-0.65 g/cm”
Method for converting source material to other substance using catalytically active porous body, Above described catalytically active SLS 3D printed porous body can be used to convert initial substances fed to the printed object to another chemical compounds or ions and eluted through the body or collected by the body. According to advantageous but non-essential features of the invention, the method incorporates one or more of the following characteristics: e Substances fed to a porous body are converted to another chemical compounds or ions. e Conversion of substance ions and molecules is due to interaction and/or chemical reaction with the chemical functionality in said body. e Said catalytically active component is preferably elemental transition metal, elemental main group metal, metal ion or complex or organic molecule. e Said catalytically active component can be a single element/compound or a mixture of several functional materials. e Said catalytically active component is available and active without any chemical or physical post-processing of the porous body. e Said porous body can be used in a batch reaction by adding the object into the reaction mixture. = 20 e Said porous body can be used in continuous flow system where the reaction 2 mixture is passed through the body © e Said porous body can be used in an inverse flow system where the object is E passed through the reaction mixture
O S 25 Chemically active component can be mixed with the printing material that can be = polymer, ceramic or metal, to get chemically, photochemically or biologically
Nactive hybrid material containing metals or metal compounds such as Ni, Zr or platinum group metals like Pt, Pd or Rh. The typical concentration of the added metal or metal compound range from 0.01-30%. The chemical reaction is performed in the object in a continuous flow or batch process resulting in products converted from the original compounds to other substances. The effectivity of the laser 3D printed object is based on high and adjustable surface area and porosity of the object.
A method, where carbon-carbon (C-C) bond formation is occurring inside the porous body, characterized that said chemical functionality is preferably, a platinum group metal (Ru, Rh, Pd, Os, Ir, Pt) bound to mesoporous carrier such as activated carbon, graphite, silica or alumina.
A method, where carbon-element (C-E; E is preferably N, O, P, S, As, Se) bond formation is occurring inside the porous body, characterized that said chemical functionality is preferably, a platinum group metal (Ru, Rh, Pd, Os, Ir, Pt) bound to mesoporous carrier such as graphite or silica.
A method, where hydrogenation is occurring inside the porous body, characterized that said chemical functionality is preferably, platinum group metal (Ru, Rh, Pd, Os, Ir, Pt) bound to mesoporous carrier such as graphite or silica.
A method, where said chemical functionality is preferably an elemental transition = 20 metal selected from Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Ru, Rh, = Pd, Ag, Cd, La, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, preferable from Ti, Fe, Co, Ni, © Nb, Ru, Rh, Pd, Ag, Hf, Re, Os, Ir, Au and most preferably from Ru, Rh, Pd, Os, x Ir, Pt.
3 A method, where said chemical functionality is an organic compound. 5
A method for converting source material to another chemical compound by flow process where one or more porous bodies are utilized in a column or tube form.
A method for converting source material to another chemical compound by inverse flow process where said porous body containing selected active component is forced through the source material as fluid (solution or gas) by magnetic or mechanical force.
A method for converting source material to another chemical compound by inverse flow process where said porous body containing active component is in a form of a replaceable cover of a stirring device such as magnetic stir bar (Fig. 5a).
A method for converting source material to another chemical compound by inverse flow process where said porous body containing active component is a replaceable part of the stirring device such as mechanical stirrer blade (Fig. 5b).
A method for converting source material to another chemical compound by placing the said porous body containing the active component in the source material (a reaction mixture). A method for performing multiple catalytic reactions simultaneously using porous body containing two or more different catalytically active components. A method for performing multiple catalytic reactions simultaneously using separate © porous objectives with different catalytically active components.
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Brief Description of the Several Views of the Drawing The Invention is further illustrated by reference to the Figures in which; Figures 1a and 1b present SLS 3D printed flow through object Figure 1c presents the 3D printed mesh with integrated walls Figures 2a and 2b present helium ion microscope (HIM) images of the break surface of 3D printed catalyst Figure 3a presents X-ray tomographic image of a cylinder shaped SLS 3D printed porous object Figure 3b presents air structure diameter (pore size) distribution of the object SLS 3D printed porous body.
Figures 4a - 4c present HIM images taken from objects printed with SLS technique using Nylon 12 powder (50 um particle size), and wherein the effect of low (porous materials, 4a and 4b) and high laser power (impermeable material, 4c) are visible.
Figure Sa depicts a porous body with an active component 3D printed to a form of a replaceable cover of a magnetic stir bar.
Figure 5b depicts a porous body with an active component 3D printed to a form of replaceable part of a mechanical stirrer blade.
00 > Figure 6a depicts the performance (conversion and product distribution) and = 20 reusability of the catalyst in styrene hydrogenation reaction.
© N Figure 6b depicts the performance (conversion and product distribution) of the E catalyst in phenyl acetylene hydrogenation reaction.
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Detailed Description of the Invention Example 1 A porous body with catalytic activity is manufactured using selective laser sintering (SLS) 3D printing with Sharebot SnowWhite 3D printer. A mixture of polypropylene (AdSint PP flex by ADVANC3D Materials&) and supported Pd/SiO>, (5 % of Pd) is prepared by thorough mechanical stirring. This material is placed to Sharebot SnowWhite 3D printer and printed to desired shape using 0.1 mm layer thickness, laser power of 40 % of the maximum power with the laser rate of 2560 mm s". Build plate temperature of 119-123 °C was used. For computer aided design (CAD) and slicing, FreeCad v. 0.16 and Slic3r v 1.2.9 were used, respectively. Figure la presents SLS 3D printed flow through object (10) with 3D printed hose connectors (11), and figure 1b presents a split body showing the interior structure with impermeable walls (12), highly porous interior for catalytic reaction (13) and flow channels for the fluid (14). The whole object is printed as a single object using Nylon 12. Instead of arbitrary structure, a well-organized mesh can be manufactured by 3D printing as in figure 1c. It has thickening in an outer circle forming walls 142 encompassing a channel of a porous portion 141. The funnel 16 at the bottom = 20 restricts the flow, and the mesh 14 (here length 35 mm, diameter 27 mm) works as NN the functional part of the collector. The reservoir 12 at the top is used to load the © sample into the system. E Figure 2a presents a helium ion microscope (HIM) images of the break surface of S 3D printed catalyst with overall porous structure and figure 2b presents tightly ©
NNattached catalytically active material (Pd/SiO,) is shown as sharp-edged, light- coloured particles 21. Figure 3a presents X-ray tomographic image of a cylinder shaped SLS 3D printed porous object and figure 3b presents air structure diameter (pore size) distribution of the SLS 3D printed porous body. Figure 4a presents a zoom in view on a porous object showing that the printing material has retained its particle-like structure in printing with low laser and high rate in normal temperature (30 %, 2560 mm/s and 166 °C, respectively). Separate particles 21 are clearly visible and their minimal contact to each other. Figure 4b presents a break surface of a porous object (taken from the inside of a cylinder-shaped object) printed with low laser and high rate in normal temperature (30 %, 2560 mm/s and 166 °C, respectively). Figure 4c presents an image of a low-porosity wall of an object printed with high laser power and slow rate in normal temperature (100 %, 1200 mm/s and 166 °C, respectively) using SLS 3D printer (for example Sharebot SnowWhite). Figure 5 demonstrates the potential laboratory and industrial applications and the versatility of the claimed catalytically active porous object. Figures 6a and 6b reveal good performance of the porous body in palladium © catalyzed hydrogenation reactions.
O N 20 Example 2 © A porous body with chemical functionality and solid walls is manufactured from = Nylon 12 (AdSint PA12 by ADVANC3D Materials®) by placing the polymer to 2 Sharebot SnowWhite 3D printer and printing it to desired shape using 0.1 mm layer 3 thickness. The outer layers (3-15, the number depends on the complexity of the design) are defined during the slicing of the CAD model. For these layers, formingthe impermeable walls, laser power of 100 % of the maximum power with the laser rate of 800-1200 mm s" is used. The porous interior structure (all areas that were not defined as outer layers during the slicing of the CAD model), is available to be used for chemical reaction, laser power of 30-40 % of the maximum power with the laser rate of 2400-2560 mm s" is used. Build plate temperature of 158-163 °C was used. For CAD and slicing, FreeCad v. 0.16 and Slic3r v 1.2.9 were used, respectively. Example 3 In a Teflon& autoclave, about 7 mmol of styrene, 2 ml of methanol and a stir bar covered with 3D printed porous body with an Pd/SiO, active component. The amount of styrene in each reaction was adjusted to correspond to a total Pd-loading of 0.1 mol-%. At room temperature, 10 bar of hydrogen gas was introduced to the vessel and the mixture was stirred for 2 hours. The conversion and product distribution were examined using gas chromatography. Example 4 In a Teflon® autoclave, about 7 mmol of phenyl acetylene, 2 ml of methanol and a stir bar covered with 3D printed porous body with an Pd/SiO> active component. The amount of phenyl acetylene in each reaction was adjusted to correspond to a total Pd-loading of 0.1 mol-%. At room temperature, 10 bar of hydrogen gas was = 20 introduced to the vessel and the mixture was stirred for 2 hours. The conversion
N v and product distribution were examined using gas chromatography. N Example 5 E To a reaction vessel, 1 mmol of aryl halide, 1.2 mmol of phenyl boronic acid and
O S 1.5 mmol of K,CO3 were weighted. Solvent was added, the mixture was brought to
O = 25 reflux and the porous object containing chemical functionality was added as
Nreplaceable covers for magnetic stir bar (0.5 mol-% of Pd). The reaction was followed using thin layer chromatography. After completion (1 hour with 4- iodoanisol for example), object was removed and washed with water and dried using pressurized air for further use. The product was purified using flash chromatography and characterized with NMR. References and Notes:
1. (a) Hurt, C. et al., Catal. Sci. Technol. 2017, 7, 3421-3439; (b) Parra-Cabrera, C.; Achille, C.; Kuhn, S.; Ameloot, R. Chem. Soc. Rev. 2018, 47, 209-230.
2. (a) Xintong, Z.; Chang jun, L. Adv. Funct. Mater. 2017, 27, 1701134. (b) Diaz-Marta, A. S. et al. ACS Catal. 2018, 8, 392—404. (c) Manzano, J. S.; Weinstein, Z. B.; Sadow, A. D.; Slowing, I. I. ACS Catal. 2017, 7, 7567-7577. (d) Kitson, P. J. et al. Science 2018, 359, 314-319. (e) Avril, A. et al. React. Chem. Eng. 2017, 2, 180-188.
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Claims (15)
1. A porous body (10), manufactured using laser 3D printing from at least one polymer, ceramic or metal powder and at least one active component providing catalytic properties for the object without any post-processing, characterized in that the particles (21) are forming a uniform, lattice resembling structure, allowing flow of fluid (liquid or gas) through the entire body solely via connected voids in between the sintered particles.
2. A porous body according to claim 1, characterized in that pressure and flow control channels are produced inside the structure during 3D printing process
3. A porous body according to claim 1 or 2, characterized in that said polymer powder belongs to class of polyolefins, polyamides, polyimides, polyarylates, polyesters, vinyl polymers, polystyrenes, polyacrylates or a mixture of two or more of these.
4. A porous body according to claim 1 or 2, characterized in that said powder is itself said active component. ® & v
5. A porous body according to claim 1 or 2, characterized that said body contains © 0.01-100 %, preferably 1-50 % and more preferably 5-30 % of said active E component. 3 25 e
6. A porous body according to claim 1 or 2, characterized that said active 2 component belongs to group of d-, f- or p-block metals.
7. A porous body according to claim 1 or 2, characterized in that the active component is belonging to a group of transition metals.
8. A porous body according to claim 1 or 2, characterized that said active component belongs to a group noble metals (Cu, Ru, Rh, Pd, Ag, Re, Os, Pt, Au, Hg).
9. A porous body according to claim 1 or 2, characterized that said active component is supported on a mesoporous material.
10. A porous body according to claim 1 or 2, characterized that said active component is an inorganic compound containing one or more d-, f- or p-block metals.
11. A porous body according to any of claims 1 - 10, characterized in that there are integral walls (18) encompassing a porous center portion (13), the walls having a non-porous structure and thus forming a channel for a liquid.
12. Method for manufacturing a porous body (10) with catalytic properties for = converting a source material to another compound, characterized in that the NN porous body is manufactured by SLS 3D printing using at least one sinterable © powder forming the structure for the body and at least one component providing the E catalytic activity. 2 25 3
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13. A method according to claim 12, characterized in that walls (18) encompassing a porous center portion (13) are manufactured integrally in the porous body (10).
14. A method to convert source material to another chemical compound, characterized in that a porous body according to any of claims 1 - 11, is used in a system where the object is passed through the reaction mixture.
15. A method for performing multiple catalytic reactions in a single vessel or column using one or more porous bodies according to any of claims 1-11, containing one or more different catalytically active components, in a system where the object is passed through the reaction mixture. 00
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FI20186003A FI20186003A1 (en) | 2018-11-26 | 2018-11-26 | A porous body, method for manufacturing it and its use for catalysis |
| PCT/FI2019/050839 WO2020109658A1 (en) | 2018-11-26 | 2019-11-25 | A porous body, method for manufacturing it and its use for catalysis |
| FI20215683A FI131236B1 (en) | 2018-11-26 | 2019-11-25 | POROUS ARTICLE, METHOD FOR ITS PREPARATION AND USE IN CATALYSIS |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FI20186003A FI20186003A1 (en) | 2018-11-26 | 2018-11-26 | A porous body, method for manufacturing it and its use for catalysis |
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| FI20186003A1 true FI20186003A1 (en) | 2020-05-27 |
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| Application Number | Title | Priority Date | Filing Date |
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| FI20186003A FI20186003A1 (en) | 2018-11-26 | 2018-11-26 | A porous body, method for manufacturing it and its use for catalysis |
| FI20215683A FI131236B1 (en) | 2018-11-26 | 2019-11-25 | POROUS ARTICLE, METHOD FOR ITS PREPARATION AND USE IN CATALYSIS |
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| FI20215683A FI131236B1 (en) | 2018-11-26 | 2019-11-25 | POROUS ARTICLE, METHOD FOR ITS PREPARATION AND USE IN CATALYSIS |
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| FI (2) | FI20186003A1 (en) |
| WO (1) | WO2020109658A1 (en) |
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| DE102021116862A1 (en) * | 2021-06-30 | 2023-01-05 | Rheinisch-Westfälische Technische Hochschule (RWTH) Aachen, Körperschaft des öffentlichen Rechts | Process for the additive manufacturing of porous, gas-permeable shaped bodies with controllable porosity |
| CN114749216B (en) * | 2022-03-31 | 2023-01-31 | 西安交通大学 | Monolithic catalyst porous structure based on 3D printing and bionic preparation method thereof |
| DE102022116221A1 (en) * | 2022-06-29 | 2024-01-04 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung eingetragener Verein | Method for producing a catalyst element for use in a chemical reactor, catalyst element and chemical reactor |
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|---|---|---|---|---|
| GB201014950D0 (en) * | 2010-09-08 | 2010-10-20 | Johnson Matthey Plc | Catalyst manufacturing method |
| US9421523B2 (en) * | 2011-04-07 | 2016-08-23 | Asemblon, Inc. | Processes for producing controlled porous catalysts for the dehydrogenation of organic compounds |
| EP2979752A1 (en) * | 2014-07-29 | 2016-02-03 | Nederlandse Organisatie voor toegepast- natuurwetenschappelijk onderzoek TNO | A catalyzing reactor, a method for producing a catalyzing reactor and a use of catalyzing reactor |
| GB201506325D0 (en) * | 2015-04-14 | 2015-05-27 | Johnson Matthey Plc | Shaped catalyst particle |
| EP3512619A1 (en) * | 2016-09-13 | 2019-07-24 | Stichting Energieonderzoek Centrum Nederland | Method for additive manufacturing of a 3d structure |
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- 2018-11-26 FI FI20186003A patent/FI20186003A1/en not_active Application Discontinuation
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2019
- 2019-11-25 WO PCT/FI2019/050839 patent/WO2020109658A1/en not_active Ceased
- 2019-11-25 FI FI20215683A patent/FI131236B1/en active
Also Published As
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|---|---|
| FI20215683A1 (en) | 2021-06-11 |
| WO2020109658A1 (en) | 2020-06-04 |
| FI131236B1 (en) | 2024-12-20 |
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