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    • 专利摘要:
    Preparation of heterogeneous metal ceramic catalysts with three-dimensional structure obtained by 3D printing. The present invention refers to a new type of heterogeneous catalysts formed by a three-dimensional metal-ceramic structure (cermet), obtained by direct writing techniques (3D Printing). One or more metals and one or more ceramic compounds are used in suitable proportions, with which a paste (ink) is made, whose rheological properties allow its extrusion by 3D printing, to form a pre-designed three-dimensional structure. After its conformation, the structure is thermally processed to obtain the consolidated cermet, with catalytically active metallic phases in its mass and on its surface. (Machine-translation by Google Translate, not legally binding)
    公开号:ES2824324A1
    申请号:ES201930983
    申请日:2019-11-08
    公开日:2021-05-11
    发明作者:Rivera Francisco Guitian；Gonzalez Alvaro Gil；Tubio María Del Carmen Rial；Perez Eddy Sotelo；Coton José Alberto Coelho
    申请人:Universidade de Santiago de Compostela；
    IPC主号:
    专利说明:

    [0004] TECHNICAL SECTOR
    [0005] The present invention refers to heterogeneous catalysts formed by a three-dimensional structure obtained by 3D printing of a metal-ceramic composition (cermet). The invention also relates to the process of obtaining and uses.
    [0007] BACKGROUND OF THE INVENTION
    [0008] Cermets are composite materials made up of ceramics and metals. They are a type of materials that are characterized by combining the characteristic properties of ceramic materials and metals. Like ceramic materials, they resist high temperatures while being lighter than metal alloys. The combination of ceramic and metallic components in a material makes it have great resistance and hardness, as well as high resistance to temperature, wear and corrosion. These characteristics vary according to the composition of the cermet, its heat treatment and its final microstructure. From a mechanical point of view, the ceramic component mainly provides hardness and resistance to wear and tear and the metal contributes, among other properties, toughness. These physical properties have led cermets to be used in friction parts and tools for cutting and drilling materials for years.
    [0009] Cermets are applied in all types of industries such as sectors related to gas, oil, mining, pulp, chemical and petrochemical industries and all in which parts that are subject to attack or service are required. wear. Some of the most notable applications are:
    [0010] -In resistors and capacitors that withstand high temperatures.
    [0011] -In vacuum tubes for hot water systems.
    [0012] -In mechanical seals to isolate electrical sections of turbine generators designed to operate with liquid metal or corrosive vapors.
    [0013] -In bioceramics, since many cermets are biocompatible.
    [0014] -In dentistry for implants and prostheses.
    [0015] -In the transport sector, for friction materials such as brakes and clutches. -In cutting tools for machining.
    [0016] -In valve seats, pumps (both in bodies and especially in rotors), cyclones (mainly in their mouths), tubes interspersed in pipes of all kinds, heat exchangers (inlet and outlet, tubes, etc.), turbine parts, nozzles, gears, injectors, furnace supports, magnetic separators, etc.
    [0018] Cermet manufacturing.- Most cermet manufacturing processes are based on powder metallurgy techniques. Metal and ceramic powders are mixed and ground together in a ball mill or attrition mill. A lubricant or humectant is often added to facilitate shaping operations. In many cases, after grinding, a suspension is prepared with the raw materials, which is atomized to obtain fine, homogeneous and spherical particles.
    [0019] The pieces are formed by compacting the powder by cold pressing, cold isostatic pressing, or hot isostatic pressing. Except in the latter case, the pieces already formed are thermally processed for sintering at high temperatures in continuous or discontinuous furnaces, with or without controlled atmospheres, depending on the case.
    [0021] Heterogeneous catalysts with metallic active centers.
    [0022] Transition metal catalyzed reactions occupy an important place among the synthetic methodologies of modern Organic Chemistry. These transformations allow the efficient assembly of complex molecules, using mild and environmentally friendly experimental conditions. Much of the progress made in this area is a consequence of the development of catalytic systems available today (homogeneous or heterogeneous), which have different advantages and disadvantages. In homogeneous catalysis, the catalyst is dispersed in the reaction medium, which usually translates into greater efficiency of the catalytic process and high selectivity. Despite these advantages, heterogeneous catalysis is preferred on an industrial scale, mainly because of the possibility of recovering and reusing the catalyst. However, and despite the enormous potential of this type of transformation, its application in areas such as the pharmaceutical and agrochemical industries remains limited by the inability to efficiently satisfy the rigorous controls established by regulatory agencies in relation to the quantities of metals present in medicines and phytosanitary products. Most heterogeneous catalysts are metals, metal oxides, or acids. The most common metallic catalysts are Fe, Co, Ni, Pt, Cr, Mn, W, Ag and Cu (generally transition metals with partially unoccupied d orbitals). Metal oxides commonly used as catalysts are AhO3, C2O3, V2O5, ZnO, NiO, and Fe2O3. The most common catalytic acids are H3PO4 and H2SO4.
    [0023] The development of new heterogeneous catalytic systems allows efficient catalysis, by offering the catalytic species a different environment that serves as a support and that, depending on the structure of the latter, chemically stabilizes it. Additionally, the use of these materials facilitates the processes of purification, recovery and reuse of the catalyst.
    [0024] A highly appreciated strategy in the synthesis of heterogeneous catalytic materials is surface functionalization using a solid support. This strategy consists of the heterogenization of catalytic species by attachment to polymeric materials of an organic nature (eg polystyrene) or inorganic (eg silica, zeolites) using mostly chemical methods.
    [0025] The most common supports are silica gel (SiO2), alumina (Al2O3), carbon (in the form of activated carbon) and diatomaceous earth. The support can be inert or contribute to catalytic activity.
    [0026] The fixation of the catalytic species to the support is currently carried out by precipitation / absorption on the support, fixation of the metal by chelating, exchange of metal species or surface functionalization by fixation to spacers of an organic nature (in the case of inorganic matrices such as alumina or silica).
    [0027] The aforementioned fixation strategies have in common that surface functionalization uses chemical methods and, in many cases, require pre-conditioning or pre-functionalization of the support, which implies greater laboriousness and synthesis steps. A further drawback of the fixation of metal species by surface functionalization by chemical methods is that it allows leaching of the metal. During this type of functionalization, it is common for variable amounts of the metal to go into solution, reducing the charge of the metal on the functionalized surface (and its recyclability) and contaminating the products obtained during the synthesis (which disables the material for applications in synthesis of drugs).
    [0029] Manufacture of metal ceramic catalysts (cermets) by 3D printing.
    [0030] According to an exhaustive review published at the end of 2017 (Xintong Zhou, DOI: 10.1002 / adfm.201701134), the state of the art in 3D printing applications to catalysis includes: a) the use of polymeric structures with dispersed phases of metals or salts metallic; b) carbon materials with or without other active phases; c) metallic or metallic oxide structures; and d) structures based on zeolites.
    [0031] Similarly, a review of the SciFinder database (May 2018) indicates the existence of 10 publications or patents with the concepts metal / ceramic / 3d printing / catalyst, and none of them refer to a cermet catalyst manufactured by 3d print. Likewise, a search carried out in "Web of Science" did not return any reference to "3D printing cermet catalyzer" or "3D printing metal ceramic catalyzer!" The only publications found, referring to materials of this type are the following:
    [0032] - 3D Printing of a Heterogeneous Copper-Based Catalyst . Journal of Catalysis. DOI:
    [0033] 10.1016 / j.jcat.2015.11.019; 2015 .: describes a 3D Printing catalyst composed of a biphasic Al2O3 and CuO ceramic. The x-ray spectra provided in the article (Figure 2, page 113) demonstrate unequivocally that there is no metallic phase in the structure. The copper present is in the form of Cu2 + (copper oxide, CuO).
    [0034] - An efficient and recyclable 3D printed -AI2O3 catalyst for the multicomponent assembly of bioactive heterocycles . Applied Catalysis A: General 530 (2017) 203 210. (2017): describes the fabrication, characterization and uses of a single-phase aluminum oxide ceramic catalyst.
    [0035] - Three-Dimensional Printing in Catalysis: Combining 3D Heterogeneous Copper and Palladium Catalysts for Multicatalytic Multicomponent reactions . ACS. Catal.
    [0036] 8,392-404. (2018): documents a catalyst based on a single-phase ceramic structure obtained by 3D Printing, and composed only of silica (SiO2). This structure is functionalized on its surface (by silanization) and metal-organic compounds of copper and palladium are incorporated.
    [0037] - 3D-printed graphene-A h O 3 composites with complex mesoscale architecture .
    [0038] Ceramics International. DOI: 10.1016 / j.ceramint.2017.12.234. (2018): describes the manufacture of monolithic hybrid structures by 3D Printing, composed of Alumina.Graphene, with possible catalytic applications.
    [0039] - 3D Printed Composites of Copper-Aluminum Oxides. 3D Printing and additive manufacturing. Volume 5, Number 1 ,; DOI: 10.1089 / 3dp.2017.0101. (2018): the preparation of inks for heterogeneous ceramic-type catalysts, and more specifically, compounds of CuO and Al2O3 was studied in detail.
    [0040] - Porous ceramic matrix AhO 3 / Al composites as supports and precursors for catalysts and permeable materials. Metal ceramic and polymeric composites for various uses. Ed. IntechOpen. DOI: 10.5772 / 1428. (2011): proposes obtaining metal-ceramic materials without a defined structure by hydrothermal oxidation treatment of aluminum-metal compacts.
    [0041] DESCRIPTION OF THE INVENTION
    [0042] The present invention develops a new type of heterogeneous metal-ceramic catalysts (cermets). In them, the "support" structure and the catalytically active species are integrated en masse: the proposed catalyst is formed by a hybrid structure of one or more metals and one or more ceramic phases, conformed together in a pre-designed 3D structure. Shaping may vary from one case to another, but direct writing techniques ( 3D Printing) are proposed as more suitable. In a manufacturing technology of this type, the preparation of the catalyst consists of three steps. Once the raw materials have been selected, (a metal salt or combination of metal salts and the support ceramic or combination of ceramics) that are going to make up the catalyst, with suitable granulometries, a paste (ink) is made with them that meets the appropriate rheological conditions so that it can be extruded by means of the 3D printing technique. In a second phase, the ink is extruded to produce the pre-designed three-dimensional structure. Finally, the structure obtained is thermally processed to eliminate additives added to the ink and to sinter the structure so that it reaches the appropriate rigidity and toughness to be used.
    [0043] The temperature of the thermal treatment is determined by two procedures: a) the decomposition temperature of the metallic salts and the pyrolysis of the organic compounds is determined with a previous thermal analysis of the ink (Differential Thermal Analysis and Thermogravimetric); and b) the sintering temperature of the cermet is determined in light of the phase equilibrium diagrams of the metal-ceramic systems involved.
    [0044] Thus shaped and sintered, the catalyst has certain properties useful in catalysis, which differentiate it from the catalysts developed to date and existing on the market:
    [0045] a) The metal, the active phase in the catalysis, is homogeneously distributed in the mass of the ceramic support, and therefore also on its surface, so it is easily accessible by the reactants of the reaction to be catalyzed.
    [0046] b) The metal, which is provided in the raw materials as micro or nanometric powder, or in the form of metallic salt in solution, is immersed in a mass of ceramic particles, also very fine. Therefore, if the dispersion of these metal particles in the ceramic matrix is good, there are few metal-metal contacts, which is why it is not possible to grow these metal particles in sintering.
    [0047] c) The porosity, and therefore, the specific surface of the catalyst is designable, both at the level of the macropores, which depend on the 3D structure built, and on the micro and nanopores, which depend on the sintering of the material ( strut porosity). Thus, for example, an Alumina-Palladium catalyst, with 4% palladium content, sintered at 1400 ° C has a total porosity of 67% by volume, made up of 54% macropores (size> 100 microns) and 13% micropores (size> 3 microns). The specific surface of a material of this type ( "struts"), discounting the macropores, varies with the sintering temperature, as shown in Figure 1 and Table 1.
    [0048] d) The metallic particles are firmly integrated into the ceramic matrix, so there will be no release (leaching) during the catalytic process.
    [0049] e) For these reasons, the catalysts are recyclable infinitely many times, and do not contaminate the products of the catalyzed reaction.
    [0051] Figures
    [0053] These and other characteristics and advantages of the invention will become more apparent from the detailed description that follows of a preferred embodiment, given solely by way of illustrative and non-limiting example, with reference to the accompanying figures. .
    [0055] Figure 1: Variation of the Specific Surface (S.E.) in m2 / g with the sintering temperature in a heterogeneous metal-ceramic catalyst (cermet) Alumina-Palladium
    [0056] Figure 2: Part of a heterogeneous metal-ceramic (cermet) Alumina-Palladium catalyst after undergoing heat treatment.
    [0058] Figure 3: Results of elemental chemical analysis by means of X-ray energy dispersion (EDS) of a heterogeneous metal-ceramic (cermet) alumina-palladium catalyst.
    [0060] Figure 4: Part of a heterogeneous metal-ceramic (cermet) Alumina-Copper catalyst before undergoing heat treatment.
    [0062] Figure 5: Results of elemental chemical analysis by means of X-ray energy dispersion (EDS) of a heterogeneous metal-ceramic (cermet) alumina-copper catalyst.
    [0064] Figure 6: Results of elemental chemical analysis by X-ray energy dispersion (EDS) Palladium-Copper-Alumina.
    [0065] Detailed description of the invention
    [0067] Unless otherwise stated, all scientific terms used herein have the meaning that is commonly understood by the person skilled in the art to whom this description is directed. In the present invention, singular forms include plural forms unless otherwise indicated. In particular, definite (el, la, lo) or indeterminate (un, uno, una) singular pronouns do not limit to a cardinal number and can refer to more than one element (for example, one, two, three or more) . This is particularly relevant in the present invention when referring for example to "heterogeneous metal ceramic catalyst".
    [0068] In the scope of the present invention, the term "cermet" is directed to a composite material formed by ceramic and metal; also referred to in the present application as "metal-ceramic material", or simply "metal-ceramic".
    [0070] The main object of the present invention is to provide a method for preparing heterogeneous metal-ceramic catalysts (cermets) with a three-dimensional structure obtained by 3D printing, wherein said heterogeneous metal-ceramic catalyst comprises a ceramic material and at least one metal in a zero oxidation state. The method of preparation of the present invention is characterized in that it comprises the steps of:
    [0071] a) mixing at least one metal salt, at least one ceramic compound, a viscosity modifier and a gelling agent in a liquid to produce an ink,
    [0072] b) extruding the ink obtained in step (a) by 3D printing to obtain a three-dimensional structure; Y
    [0073] c) heat treating the three-dimensional structure obtained in step (b).
    [0075] In a preferred embodiment, the liquid from step (a) is water.
    [0077] In another preferred embodiment, the metal salt of step (a) is a metal chloride, a metal nitrate, or any other metal salt that can decompose at high temperature, or combinations thereof. Non-limiting examples of salts that decompose at high temperature and that can be used in the method of the present invention are metal sulfates, nitrates, chlorides, and acetates. The person skilled in the art would be able to select suitable metal salts for the method of the present invention. In a particular embodiment, the metal of the metal salts of the present invention can be selected from any of the metals with catalytic activity proposed in the present invention; in particular of palladium, copper, cobalt, platinum, ruthenium, gold, nickel or their combinations. In a further embodiment In particular, the metal salt of step (a) is selected from metal chlorides, metal nitrates, metal sulfates, metal acetates, and combinations thereof.
    [0079] In another preferred embodiment, the ceramic compound in step (a) is added in a range between 10 and 70% v / v, with respect to the total volume of the mixture.
    [0081] In another preferred embodiment, the viscosity modifier in step (a) is added in a range between 0 and 3% by weight with respect to the total weight of the ceramic compound.
    [0083] In another preferred embodiment, the viscosity modifier in step (a) is hydroxypropylmethylcellulose or any other compound with a similar effect. Non-limiting examples of viscosity modifiers that can be used in the present invention are methylcellulose, hydroxypropylmethylcellulose (HPMC), carboxymethylcellulose (CMC), polyvinylpyrrolidone (PVP), bentonite magma, xanthan gum, gum tragacanth, guar gum, sodium alginate, pectin , starch, gelatin or combinations thereof. The person skilled in the art would be able to select the suitable viscosity modifier for the method of the present invention. In a more particular embodiment, the viscosity modifier of step (a) is selected from cellulose, cellulose derivatives, bentonite magma, gums, sodium alginate, pectin, starch, gelatin and combinations thereof.
    [0085] In another preferred embodiment, the gelling agent in step (a) is added in a range between 0 and 3% by weight with respect to the total weight of the ceramic compound. In a particular embodiment, no gelling agent is added (0%). In a more particular embodiment, gelling agent is added between 0.001 and 3% by weight with respect to the total weight of the ceramic compound.
    [0087] In another preferred embodiment, the gelling agent in step (a) is polyethyleneimine, or any other compound with similar effects. Non-limiting examples of gelling agents that can be used in the present invention are polyethyleneimine, sodium alginate, sodium carrageenan, locust bean gum, acacia, pectin or combinations thereof; preferably polyethyleneimine. The person skilled in the art would be able to select the suitable gelling agent for the method of the present invention. In a more particular embodiment, the gelling agent of step (a) is selected from the group comprising polyethyleneimine, sodium alginate, sodium carrageenan, locust bean gum, acacia, pectin and combinations thereof.
    [0088] In a particular embodiment, the heat treatment of step (c) is carried out under an oxidizing atmosphere. The term "oxidizing atmosphere" refers to an atmosphere that contains molecules with oxygen as the predominant ingredient.
    [0089] In another particular embodiment, the heat treatment of step (c) is carried out under a reducing atmosphere. The term "reducing atmosphere" refers to an atmosphere free of oxygen and other oxidizing gases or vapors, and with significant amounts of reducing gases, such as hydrogen, ammonia or methane; particularly it refers to an atmosphere of hydrogen, ammonia or methane.
    [0091] In another particular embodiment, the heat treatment in step (c) comprises a heat treatment under an oxidizing atmosphere and subsequently a heat treatment under a reducing atmosphere.
    [0093] The temperature of the heat treatment in step (c) when carried out under an oxidizing atmosphere is preferably between 1000 ° C and 1700 ° C.
    [0095] The temperature of the heat treatment in step (c) when carried out under a reducing atmosphere is preferably between 1000 ° C and 1700 ° C.
    [0097] In a particular embodiment, the method of the present invention comprises a drying step prior to step (c), preferably at room temperature.
    [0099] In a particular embodiment, the method for preparing the heterogeneous metal-ceramic catalyst comprises a previous stage of designing its three-dimensional structure; in particular a pre-design stage; whereby the three-dimensional structure is preset based on computer design or other methods.
    [0101] Another aspect of the present invention is directed to a heterogeneous metal-ceramic catalyst with a three-dimensional structure comprising a ceramic material and at least one metal in a zero oxidation state, obtainable by the preparation method as defined above. A person skilled in the art will be able to pre-design said three-dimensional structure of the present invention depending on its application.
    [0103] In a particular embodiment, the three-dimensional structure of the heterogeneous metal-ceramic catalyst is a monolith, piece or structure of any geometric shape. Non-limiting examples of three-dimensional structures of the heterogeneous metal-ceramic catalyst (cermet) of the present invention are both solid and porous monoliths, solid or porous cylinders, solid and porous n-sided polygonal-based prisms (with n values between 4 and 20 ). In a particular embodiment, the three-dimensional structure of the heterogeneous metal-ceramic catalyst is a monolith, particularly a porous monolith.
    [0104] The person skilled in the art would be able to select the suitable three-dimensional structure for the present invention.
    [0106] In another particular embodiment, the three-dimensional structure of the heterogeneous metal-ceramic catalyst has a porosity comprised between 10 and 80%.
    [0108] In a particular embodiment, the metal-ceramic heterogeneous catalyst obtainable by the preparation method of the present invention has a pore size of between 0.1 and 5 microns.
    [0110] In a preferred embodiment, the ceramic material of the heterogeneous metal-ceramic catalyst is aluminum oxide, silicon oxide or any other ceramic oxide with similar characteristics, or their combinations.
    [0112] In a particular embodiment, the ceramic material of the heterogeneous metal-ceramic catalyst is selected from aluminum oxide, silicon oxide, zirconium oxide, titanium oxide, triaxial porcelains or their combinations. More particularly it is selected from the group consisting of AhO3, SiO2, ZrO2, ZnO, TiO2, or combinations thereof; even more particularly it is selected from the group consisting of AhO3 and SiO2.
    [0114] In another preferred embodiment, the metal in the zero oxidation state of the heterogeneous metal-ceramic catalyst is a metal with catalytic capacity. In a particular embodiment, the metal in the zero oxidation state of the heterogeneous metal-ceramic catalyst of the invention is selected from palladium, copper, cobalt, platinum, ruthenium, gold, nickel or their combinations; in particular palladium, copper, cobalt, platinum, ruthenium, gold and nickel; more particularly palladium and copper.
    [0116] In another preferred embodiment, the metal in the zero oxidation state is present in the heterogeneous metal-ceramic catalyst in an amount between 0.1 and 10% by weight relative to the total weight of the ceramic material.
    [0118] Another aspect of the present invention is directed to a heterogeneous metal-ceramic catalyst with a three-dimensional structure comprising a ceramic material and at least one metal in a zero oxidation state, obtainable by the preparation method of the invention. In a particular embodiment, said heterogeneous metal-ceramic catalyst has the three-dimensional structure of a monolith, piece or structure of any geometric shape. In a more particular embodiment, said heterogeneous metal-ceramic catalyst It has a three-dimensional structure with a porosity between 10 and 80%. In a more particular embodiment, the ceramic material of said heterogeneous metal-ceramic catalyst is aluminum oxide, silicon oxide or any other ceramic oxide with similar characteristics, or their combinations. In a more particular embodiment, the metal of said heterogeneous metal-ceramic catalyst is copper, palladium, a combination thereof, or any other metal with catalytic capacity. In an even more particular embodiment, said metal is present in an amount between 0.1 and 10% by weight with respect to the total weight of the ceramic material.
    [0120] Another aspect of the invention is directed to the use of the heterogeneous metal-ceramic catalyst of the invention as a heterogeneous catalyst for reactions capable of being catalyzed by metals with a catalytic effect; in particular coupling reactions. In a particular embodiment, the present invention is directed to the use of the heterogeneous metal-ceramic catalyst (cermet) obtainable by the method of the present invention as a heterogeneous catalyst in Suzuki reactions (reaction between an organic derivative of boron R'-BY and a halide alkyl to form an alkyl); Sonogashira reaction (reaction between a terminal alkyne and an aryl or vinyl halide to form a substituted alkyne) or Stille reaction (reaction between an organic derivative of tin and an alkyl halide to form an alkyl) and Ullmann (reaction between two alkyl halides catalyzed by copper to form a substituted alkyl).
    [0122] Another aspect of the present invention is directed to a process for the coupling of hydrocarbons that comprises reacting at least two hydrocarbons in the presence of a catalytic amount of the heterogeneous metal-ceramic catalyst (cermet) of the present invention, and in the presence of a solvent.
    [0124] Another aspect of the present invention is directed to the use of the heterogeneous metal-ceramic catalyst (cermet) as defined above as a heterogeneous catalyst for reactions capable of being catalyzed by metals with a catalytic effect. In a particular embodiment, the metal with a catalytic effect of the invention is selected from palladium, copper, cobalt, platinum, ruthenium, gold, nickel or their combinations; in particular palladium, copper, cobalt, platinum, ruthenium, gold and nickel; more particularly palladium and copper.
    [0126] A final aspect of the present invention is directed to the use of the heterogeneous metal-ceramic catalyst (cermet) of the present invention in the biological, medical, pharmaceutical or agrochemical sector.
    [0127] EXAMPLE 1
    [0128] Example of a CERMET Alumina-Palladium catalyst: A CERMET 3D printing catalyst is proposed as an example. The material is composed of Palladium (Pd) and Alumina (AI2O3) with a palladium content of 5% by weight.
    [0129] Manufacturing procedure: 4.43 grams of PdCh are mixed with 12.63 mL deionized water and stirred vigorously. Then 50 g of micronized AhO3 powder (50% by volume) are added. It is stirred vigorously until complete homogenization and 0.065 g of hydroxypropylmethylcellulose (HPMC, 0.13 wt% with respect to AhO3) are added. The mixture is stirred again and allowed to stand for one hour. The suspension is then gelled by adding 0.12 mL of polyethyleneimine (PEI, 0.25 wt% with respect to AhO3) and stirring for the necessary time until a homogeneous mixture is obtained.
    [0130] The structures are printed by means of a 3D printing device equipped with an extrusion system with an adequate pressure to print pulverulent materials dispersed in a liquid support (aqueous or organic solvent).
    [0131] Once the structure is printed, it is dried for 12 hours at room temperature, and then calcined and sintered at 1500 ° C for two hours using a temperature ramp of 10 ° C / min in an oxidizing atmosphere.
    [0132] The specific surface area (SE) in m2 / g varies with the sintering temperature as can be observed in Table 1. The specific surface area of the invention has been measured by the adsorption technique using the BET isotherm developed by Brunauer, Emmett and Teller , which makes it possible to determine the surface of a solid based on the adsorption of an inert gas, generally N2, at low temperature.
    [0134] Table 1.- Variation of the specific surface with sintering (B.E.T.).
    [0136]
    [0139] Figure 2 shows the piece obtained after having been subjected to heat treatment. The image shows one of the many designs that can be made by 3D printing, in this case a porous cylindrical structure.
    [0140] Figure 3. Elemental chemical analysis by X-ray Energy Dispersion (EDS) of the sample in Figure 2 confirming the presence of Pd in the AhO3 structures. The The presence of Au is due to the surface metallization process of the sample for analysis. X-ray Diffration Spectrometry confirms that the only species present are alpha-alumina and palladium metal.
    [0142] Reactivity of the Pd (0) CERMET catalyst in catalytic processes: several processes catalyzed by a CERMET catalyst of Alumina-Palladium metal, formed by 3D Printing, are presented below. The catalyst is effective in conventional reactions, but its maximum effectiveness is observed when it is used in microwave reactions. Its 3D design has been adjusted to the morphology of the walls of the microwave vial. CERMET-Pd is effective in the following catalytic processes for the formation of carbon-carbon bonds, described in scheme 1:
    [0146] Scheme 1: C-C bond formation reactions catalyzed by CERMET-Pd (0).
    [0148] Process 1: Heck reaction catalyzed by a CERMET-Pd (0) monolith catalyst: In a typical example, a CERMET-Pd (0) monolith (dimensions 0.5 / 1 / 0.5 cm) and subsequently iodobenzene (5 mmol) is dissolved, the Corresponding alkene (5.1 mmol), base (triethylamine, 15 mmol) in acetonitrile (8 mL). The reaction is monitored by TLC at 10 min intervals. Most reactions take 30 minutes-1 hour. The reaction mixture is allowed to cool and the crystallized product on the walls of the vial is collected by filtration, washed and recrystallized.
    [0149] As an example, the yields obtained in representative reactions (three replications) using iodobenzene (X = I) and the following alkenes are indicated below: styrene (R = Ph) = 90%, methyl acrylate (R = COOMe) 95% , acrylonitrile (R = CN) 95%.
    [0151] Process 2: Sonogashira reaction catalyzed by a CERMET-Pd (0) monolith catalyst: In a typical example, a CERMET-Pd (0) monolith (dimensions 0.5 / 1 / 0.5 cm) and subsequently iodobenzene (5 mmol), the corresponding alkyne (5.2 mmol), CuI (0.26 mmol) and the base (triethylamine, 15 mmol) are dissolved in DMF (8 mL), at 100 ° C. The reaction is monitored by TLC at 10 min intervals. Most reactions take 30 minutes-1 hour. The reaction mixture is allowed to cool and the crystallized product on the walls of the vial is collected by filtration, washed and recrystallized.
    [0152] As an example, the yields obtained in representative reactions (three replications) using iodobenzene (X = I) and the following terminal alkynes are indicated below: phenylacetylene (R = Ph) = 90%, methyl propriolate (R = COOMe) 92 %, propargyl alcohol (R = OH) 85%.
    [0154] Process 3: Suzuki reaction catalyzed by a CERMET-Pd (0) monolith catalyst:
    [0155] In a typical example, a CERMET-Pd (0) monolith (dimensions 0.5 / 1 / 0.5 cm) is introduced into a microwave vial of (20 mL) and subsequently iodobenzene (5 mmol) is dissolved, the Corresponding boronic acid (5.1 mmol), and the base (potassium carbonate, 16 mmol) in an EtOH / H2O mixture (4: 4 mL), at 100 ° C. The reaction is monitored by TLC at 10 min intervals. Most reactions take 30 minutes-1 hour. The reaction mixture is allowed to cool and the crystallized product on the walls of the vial is collected by filtration, washed and recrystallized.
    [0157] As an example, the yields obtained in representative reactions (three replicates) using iodobenzene (X = I) and the following boronic acids are indicated below: phenylboronic acid (R = Ph) = 97%, 4-methoxycarbonylphenylboronic acid (R = COOMe ) 95%, 4-cyanophenylboronic acid (R = CN) 98%.
    [0158] Process 4: Stille reaction catalyzed by a CERMET-Pd (O) monolith catalyst: In a typical example, a CERMET-Pd (0) monolith (dimensions 0.5 / 1 / 0.5 cm) and subsequently iodobenzene (5 mmol), the corresponding organostannan (5.1 mmol) are dissolved in toluene (8 mL), at 100 ° C. The reaction is monitored by TLC at 10 min intervals. Most reactions take 30 minutes-1 hour. The reaction mixture is allowed to cool and the crystallized product on the walls of the vial is collected by filtration, washed and recrystallized.
    [0160] By way of example, the yields obtained in representative reactions (three replications) using iodobenzene (X = I) and the following stannanes are indicated below: tributylphenylstannane (R = Ph) = 97%, tributylvinylstannane (R = CH = CH2) 92% , tributylphenylethynylstannane (R = CC-Ph) 95%.
    [0162] EXAMPLE 2
    [0163] Example of a CERMET Alumina-Copper catalyst: The new catalytic material claimed in this section differs (conceptually and experimentally) from a system previously published by our group (Journal of Catalysis 2016, 334, 110-115). In this work we documented a catalytic material that contains AhO3 as a ceramic support and Cu2 + (in the form of CuO) as a catalytic species. The new material claimed here contains metallic copper [Cu (0)] as a catalytically active species. In order to obtain this new catalytic system, the experimental procedure used in the manufacture of the prototypes has been modified (use of a reducing atmosphere).
    [0165] An example is a CERMET 3D printing catalyst composed of metallic copper [Cu (0)] and alumina (AhO3) with a copper content of 5% by weight.
    [0167] Manufacturing procedure: 9.54 g of (NO3) 2Cu are added to 12.63 mL deionized water and stirred vigorously. Then 50 g of micronized AhO3 powder (50% by volume) are added. It is stirred vigorously until complete homogenization and 0.065 g of hydroxypropylmethylcellulose (HPMC, 0.13 wt% with respect to AhO3) are added. The mixture is stirred again and allowed to stand for one hour. The suspension is then gelled by adding 0.12 mL of polyethyleneimine (PEI, 0.25 wt% with respect to AhO3) and stirring the necessary time until a homogeneous mixture is obtained.
    [0168] The structures are printed by means of a 3D printing device equipped with an extrusion system with an adequate pressure to print pulverulent materials dispersed in a liquid support (aqueous or organic solvent).
    [0170] Once the structure is printed, it is dried at room temperature for 12 hours, and subsequently it is subjected to heat treatment in two stages, both with heating rates of 10 ° C / minute: a) treatment up to 550 ° C in an oxidizing atmosphere to eliminate the matter organic, and transform the nitrate ion to oxide; and b) treatment from 550 ° C to 1200 ° C in a slightly reducing atmosphere, to achieve the sintering of the cermet and the reduction of the copper oxide to copper metal.
    [0172] Figure 4 shows a newly formed piece of AhO3 / Cu cermet, before subjecting it to heat treatment.
    [0174] Figure 5: Elemental chemical analysis by X-ray Energy Dispersion (EDS) of the sample of Figure 4 sintered at 1200 ° C, confirming the presence of Cu in the AhO3 structure. As in example 1, the presence of Au is due to the surface metallization process of the sample for analysis. X-ray diffraction confirms the presence of alpha-alumina and copper metal as the only species present.
    [0176] CERMET Copper-alumina catalyst reactivity in catalytic processes:
    [0177] N-arylation (Ullmann) reaction between heterocyclic amines and aryl chlorides catalyzed by a CERMET-Cu (0) -alumina monolith catalyst: Ullmann reaction catalyzed by a CERMET-Cu (0) -Alumina monolith catalyst: In a typical example , in a microwave vial of (20 mL) a CERMET-Cu-alumina monolith (dimensions 0.5 / 1 / 0.5 cm) is introduced and then the chloroaryl (5 mmol), the amine corresponding (5.2 mmol) and the base (potassium carbonate, 15 mmol) in DMF (8 mL), at 150 ° C. The reaction is monitored by TLC at 30 min intervals. Most reactions take 2-3 hours. The reaction mixture is allowed to cool and the crystallized product on the walls of the vial is collected by filtration, washed and recrystallized.
    [0179] Scheme 2 shows the experimental conditions and typical reaction times, the yields range between 84-95%. By way of example (Figure 2) the yields obtained in representative reactions (three replicates) using imidazole and chlorobenzene derivatives are indicated.
    [0180]
    [0183] Scheme 2.- Reactions catalyzed by CERMET Al2O3-Cu
    [0185] EXAMPLE 3
    [0186] Example of a CERMET Palladium-Copper-Alumina catalyst: An example is a CERMET 3D printing catalyst composed of Palladium [Pd (0)], Copper [Cu (0)] and Alumina (AI2O3) as support. Said catalytic material contains a proportion of palladium of 2.5% by weight and of copper of 2.5% by weight.
    [0187] Procedure: 2.124 grams of PdCh and 4.65 g of (NO3) 2Cu are added to 12.63 mL deionized water and stirred vigorously. Then 50 g of AhO3 powder (50% by volume) are added. It is stirred vigorously until complete homogenization and 0.065 g of hydroxypropylmethylcellulose (HPMC, 0.13 wt% with respect to AhO3) are added. The mixture is stirred again and allowed to stand for one hour. The suspension is then gelled by adding 0.12 mL of polyethyleneimine (PEI, 0.25 wt% with respect to AhO3) and stirring for the necessary time until a homogeneous mixture is obtained.
    [0189] The structures are printed using 3D printing devices equipped with an extrusion system with adequate pressure to print powdery materials dispersed in an aqueous or organic solution.
    [0191] Once the structure is printed, it is dried at room temperature for 12 hours, and subsequently it is subjected to heat treatment in two stages, both with heating rates of 10 ° C / minute: a) treatment up to 550 ° C in an oxidizing atmosphere to eliminate the matter organic and chloride and nitrate ions; and b) treatment from 550 ° C to 1200 ° C in a slightly reducing atmosphere, to achieve the sintering of the cermet, the reduction to copper metal, and the permanence of palladium, also as metal.
    [0192] Figure 6: Elemental chemical analysis by X-ray Energy Dispersion (EDS) of a structure described according to example 3 that confirms the presence of Cu and Pd in the structure of AhO3. As in example 1, the presence of Au is due to the surface metallization process of the sample for analysis. Again X-ray Diffraction is used to confirm that the only species present in sintered CERMET are alpha-alumina and the metals copper and palladium.
    [0194] Reactivity of the Palladium-Copper-Alumina CERMET catalyst in catalytic processes: Sonogashira reaction catalyzed by a CERMET-Pd (0) -Cu (0) monolith: In a typical example, in a microwave vial of (20 mL) it is introduced a CERMET-Pd / Cu monolith (dimensions 0.5 / 1 / 0.5 cm) and subsequently iodobenzene (5 mmol), the corresponding alkyne (5.2 mmol) and the base (triethylamine, 15 mmol) are dissolved in DMF (8 mL), at 120 ° C. The reaction is monitored by TLC at 10 min intervals. Most reactions take 1 hour. The reaction mixture is allowed to cool and the crystallized product on the walls of the vial is collected by filtration, washed and recrystallized.
    [0196]
    [0199] Scheme 3.- Reaction catalyzed by the CERMET Al2O3-Pd-Cu catalyst
    [0201] As an example, the yields obtained in representative reactions (three replications) using iodobenzene (X = I) and the following terminal alkynes are indicated below: phenylacetylene (R = Ph) = 95%, propiolic acid (R = CO2H) = 80 %, propargyl alcohol (R = CH2OH) 84%.
    [0203] EXAMPLE 4.
    [0205] Reuse of the catalytic systems described in examples 1-3. In order to evaluate whether it is possible to reuse the materials described in examples 1-3, the catalytic efficiency of each of them was determined in a model reaction. For the alumina-Pd (0) catalyst the Heck reaction (iodobenzene and methyl acrylate) was used, for the alumina-Cu (O) catalyst the Ullman reaction (4-nitrochlorobenzene and imidazole) was used and and for the alumina-Pd (0) -Cu (0) catalyst was used the Sonogashira reaction (iodobenzene and propargyl alcohol). In all cases, an analogous experimental protocol was followed: once the reaction had finished, the catalyst was recovered from the reaction medium, washed 3 times (10 mL) with the solvent used in the reaction and subsequently with water (2x10 mL) and dried. under vacuum (8 hours). This same catalyst is used in at least 5 analogous experiments. In the three cases evaluated, a significant decrease in its catalytic efficiency was not observed (evaluated based on the yields of the products obtained in each transformation). As an example, the yields obtained during the 5 replications of each transformation are indicated: Heck reaction: 95%, 95%, 95%, 94%, 94%, Ullman reaction: 97%, 97% 97%, 96% , 95%, Sonogashira Reaction: 84%, 84%, 84%, 83%, 83%, 84%.
    [0207] EXAMPLE 5.
    [0209] In laboratory tests we have demonstrated the feasibility of preparing by 3D printing cermet structures similar to those described in examples 1, 2 and 3 using SiO2, Fe2O3, C 2O3, ZnO ceramics and others, with metals such as Fe, Co, Ni, Pt, Cr, Mn, W, Ag and Au.
    [0210] Although the catalytic effectiveness of these materials has not yet been experimentally studied, the possibility of their manufacture by the procedures proposed in this document has been demonstrated.
    权利要求:
    Claims (26)
    [1]
    1. - Preparation method of a heterogeneous metal-ceramic catalyst (cermet), with a three-dimensional structure obtained by 3D printing, where said heterogeneous metal-ceramic catalyst comprises a ceramic material and at least one metal in a zero oxidation state, the method characterized in that it comprises the steps from:
    a) mixing at least one metal salt, at least one ceramic compound, a viscosity modifier and a gelling agent in a liquid to produce an ink; b) extruding the ink obtained in step (a) by 3D printing to obtain a three-dimensional structure; Y
    c) heat treating the three-dimensional structure obtained in step (b).
    [2]
    2. - Method of preparation of the heterogeneous metal-ceramic catalyst according to claim 1, where the liquid in step (a) is water.
    [3]
    3. - Method of preparation of the heterogeneous metal-ceramic catalyst according to any of claims 1 or 2, where the metal salt in step (a) is a metal chloride, a metal nitrate, or any other metal salt that can decompose at high temperature, or their combinations.
    [4]
    4. - Method of preparation of the heterogeneous metal-ceramic catalyst according to any of claims 1 to 3, where the ceramic compound in step (a) is added in a range between 10 and 70% v / v with respect to the total volume of the mixture.
    [5]
    5.- Preparation method of the heterogeneous metal-ceramic catalyst according to any of claims 1 to 4, where the viscosity modifier in step (a) is added in a range between 0 and 3% by weight with respect to the total weight of the compound ceramic.
    [6]
    6. - Method of preparation of the heterogeneous metal-ceramic catalyst according to any of claims 1 to 5, where the viscosity modifier in step (a) is hydroxypropylmethylcellulose or any other compound with a similar effect.
    [7]
    7. Method of preparation of the heterogeneous metal-ceramic catalyst according to any of claims 1 to 6, wherein the gelling agent in step (a) is added in a range between 0 and 3% by weight with respect to the total weight of the ceramic compound.
    [8]
    8. - Method of preparation of the heterogeneous metal-ceramic catalyst according to any of claims 1 to 7, where the gelling agent in step (a) is polyethyleneimine, or any other compound with similar effects.
    [9]
    9. - Method of preparation of the heterogeneous metal-ceramic catalyst according to any of claims 1 to 8, where the heat treatment of stage (c) is carried out under an oxidizing atmosphere.
    [10]
    10. - Method of preparation of the heterogeneous metal-ceramic catalyst according to any of claims 1 to 9, where the heat treatment in step (c) is carried out under a reducing atmosphere.
    [11]
    11. - Method for preparing the heterogeneous metal-ceramic catalyst according to any of claims 1 to 10, wherein the heat treatment in step (c) comprises a heat treatment under an oxidizing atmosphere and subsequently a heat treatment under a reducing atmosphere.
    [12]
    12. - Method of preparation of the heterogeneous metal-ceramic catalyst according to claims 9 or 11 where the heat treatment under an oxidizing atmosphere is carried out between 1000 ° C and 1700 ° C.
    [13]
    13. - Method of preparation of the heterogeneous metal-ceramic catalyst according to claims 10 or 11, where the heat treatment under a reducing atmosphere is carried out between 1000 ° C and 1700 ° C.
    [14]
    14. - Method of preparation of the heterogeneous metal-ceramic catalyst according to any of claims 1 to 13, comprising a drying stage prior to stage (c), preferably at room temperature.
    [15]
    15. Method of preparation of the heterogeneous metal-ceramic catalyst according to any of claims 1 to 14, which comprises a pre-design step of its three-dimensional structure.
    [16]
    16. - Heterogeneous metal-ceramic catalyst with a three-dimensional structure comprising a ceramic material and at least one metal in a zero oxidation state, obtainable by the preparation method according to any of claims 1 to 15.
    [17]
    17. - Heterogeneous metal-ceramic catalyst according to claim 16, where the three-dimensional structure is a monolith, piece or structure of any geometric shape.
    [18]
    18. - Heterogeneous metal-ceramic catalyst according to any of claims 16 or 17, where the three-dimensional structure has a porosity between 10 and 80%.
    [19]
    19. - Heterogeneous metal-ceramic catalyst according to any of claims 16 to 18, where the ceramic material is aluminum oxide, silicon oxide or any other ceramic oxide with similar characteristics, or their combinations.
    [20]
    20. - Heterogeneous metal-ceramic catalyst according to any of claims 16 to 19, where the metal in the zero oxidation state is a metal with catalytic capacity.
    [21]
    21. - Heterogeneous metal-ceramic catalyst according to any of claims 16 to 20, where the metal in the zero oxidation state is copper, palladium, a combination thereof, or any other metal with catalytic capacity.
    [22]
    22. - Heterogeneous metal-ceramic catalyst according to any of claims 16 to 21, wherein the metal in the zero oxidation state is present in an amount between 0.1 and 10% by weight with respect to the total weight of ceramic material.
    [23]
    23. - Use of the heterogeneous metal-ceramic catalyst according to any of claims 16 to 22 in coupling reactions.
    [24]
    24. - Process for the coupling of hydrocarbons that comprises reacting at least two hydrocarbons in the presence of a catalytic amount of the heterogeneous metal-ceramic catalyst according to any of claims 16 to 22, and in the presence of a solvent.
    [25]
    25. Use of the heterogeneous metal-ceramic catalyst according to any of claims 16 to 22 as a heterogeneous catalyst for reactions capable of being catalyzed by metals with a catalytic effect.
    [26]
    26. Use of the heterogeneous metal-ceramic catalyst according to any of claims 16 to 22 in the biological, medical, pharmaceutical or agrochemical sector.
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    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US20160289469A1|2015-04-02|2016-10-06|Taiwan Green Point Enterprises Co., Ltd.|Catalyst for a catalytic ink and uses thereof|
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