PROCEDURE FOR THE MANUFACTURE OF A GAS SEPARATION MEMBRANE (Machine-translation by Google Translate,

专利摘要:
Procedure for the manufacture of a gas separation membrane. The present invention refers to a process for manufacturing ceramic gas separation membranes that comprises effecting the deposition of the inks developed in aqueous base that make up the layers of a gas separation membrane, by means of the ink jet printing technique plus specifically, it comprises at least the following stages: (a) formed of a porous support (i); compatible with a functional separation layer, (b) deposition on the support (i), by means of the ink jet technique of at least one functional separation layer (ii) made up of at least two inks and (c) at least one heat treatment, leading to sintering, in which the functional separation layer (ii) is deposited in a way that gives rise to a surface: - with gradients - with patterns, or - combinations of both, - and to a gas separation membrane manufactured with the procedure described. (Machine-translation by Google Translate, not legally binding)
公开号:ES2852058A1
申请号:ES202030189
申请日:2020-03-04
公开日:2021-09-10
发明作者:Alfaro José Manuel Serra；Cardona Isaac Herraiz；Villanueva Juan Uso；Pedro Juan Carlos Gallart；Soliva Francisco José Ferrando
申请人:Kerionics S L；Ferro Spain SA；
IPC主号:

专利说明:

[0001] Procedure for the manufacture of a gas separation membrane
[0003] Field of the invention
[0005] The present invention belongs to the field of gas separation membranes. Specifically, it refers to the manufacturing process using gases based on ceramic materials inkjet technologies (inkjet) permeable membranes. The invention also provides the configuration of the membrane and its use in different applications in the energy sector and chemical process industry. In the case of the use of mixed electronic and ionic conductive ceramic materials, the use of the membrane is mainly oriented to oxidation and oxy-fuel processes in which a flow enriched in oxidizer (oxygen) is used to obtain high flame temperatures, improve the combustion or to avoid the contact of O2 or N2 with the products of the industrial oxidation process in which the membrane is used. An example is the use in oxy-fuel power plants in which the combustion gases can be used as entrainment streams in the membrane module. This thermal power plant concept makes it possible to minimize CO2 and NOx emissions.
[0007] Background of the invention
[0009] Currently, there are many decoration systems used in the manufacture of ceramic wall and floor tiles that provide ceramic surfaces with certain aesthetic properties: screen printing, intaglio, flexography, gravure, etc .; however, there are many characteristics of digital ink jet (also called inkjet) printing technology that make it especially interesting for this purpose. This application process has its beginning in the years 1999 - 2000 with the introduction in the sector of the first digital printer that used soluble inks, which were formulated from organic complexes of metals.
[0011] In recent years, ceramic surface decoration processes using digital printing systems such as ink jet have become very important, not only to increase the aesthetic properties of the decorations, but also to provide other properties that until now were impossible. get with the rest of decoration techniques.
[0012] The main advantages of inkjet systems are: the absence of contact between the applicator and the surface to be printed, avoiding ruptures in crude oil and defects caused by friction; the high resolution of the image; the reduction in the number of operations to be carried out during the printing process; easy sourcing of personalized products; the economy of the process, both in small and large batches; and the great versatility of the technology by allowing the printing of any topography that the piece presents. The above advantages make inkjet technology an ideal decoration method to increase the added value of ceramic substrates, a key aspect in the manufacture of traditional ceramics, which has been possible thanks to the great evolution that technology has undergone. in all areas: machinery, heads, software, inks, ink preparation processes, etc ...
[0014] Regarding machinery and heads, there has been considerable progress: from the first heads used that allowed a deposition of less than 10 g / m2 of material and limited the particle size of solids (D99) around 1 ^ m, until now we can have high deposition heads, around 100 g / m2 per bar, in which ink with solids at a D99 of up to 3 ^ m can be used, for piezoelectric heads, and 20 ^ m, for valve heads.
[0016] There has also been an evolution in the type of printing mode that can be performed with the heads. At first, a binary printing mode was used, which with the passage of time went to grayscale mode, and today it is possible to deposit even in high-droplet size mode.
[0018] The development of inks has advanced considerably in the sense of including solids in the formulation of the ink. In this sense, different types of inkjet inks have been developed that are characterized by using inorganic pigments, inorganic raw materials and / or frits as a solid component that provides the desired aesthetic effect, and organic solvents as a liquid component.
[0020] There are many inkjet ink formulations on the market prepared from combinations of different organic solvents such as esters, glycol ethers, hydrocarbons, etc. Their use is due to the fact that they give the ink low evaporation speeds, so that they have little tendency to dry out in the heads, which are usually found at temperatures between 30 - 50 ° C and a Newtonian behavior required to be able to be applied with heads high definition.
[0021] As regards the present invention, the ink layer that must be deposited on the support to constitute the membrane is of the order of 30 µm once sintered, that is, 6 times higher than that currently applied for the ceramic tile decoration. This high thickness of ink to be deposited makes it difficult to use inks formulated with the aforementioned solvents. This is due to the fact that they have a very slow evaporation temperature and also a very high decomposition temperature, which causes very high part drying times and the appearance of defects in the fired layer.
[0023] For this reason, work has been done on formulating the necessary inks using water and water-miscible liquids such as glycols as liquids. Thus, the novelty in the formulation of inks resides in the use of inorganic compounds of a ceramic nature as solid components and in the use of water and glycols and / or mixtures of both as liquid components.
[0025] From the application point of view, the novelty of the present invention resides in the use of digital printing technology to effect the deposition of the inks developed in aqueous base that make up the layers of a gas separation membrane. It is understood that the necessary modifications of the configuration and position of the heads adapting them to the different geometric shapes of the membranes to be coated are evident to a person skilled in the art.
[0027] According to their structural characteristics, inorganic membranes capable of gas separation can be divided into two categories, which can have a significant impact on their performance as separators and / or reactors: dense membranes and porous membranes. The latter are characterized by the presence of pores or voids that can be straight through the thickness of the membrane or can be interconnected with high tortuosity, which is directly influenced by the preparation method. Both dense and porous membranes can be deposited on porous supports, in order to reduce the thickness of the membrane and increase the mechanical resistance. When the separation layer and the designed support present a homogeneous structure and composition in the direction of the thickness of the membrane, they take the name of symmetrical membranes (they also take this name when they are self-supporting, that is, there is no porous support). Alternatively, if the The membrane layer and the support structure have different microstructure and / or composition, we speak of asymmetric membranes.
[0028] The main characteristics of the different types of gas separation membrane used are detailed below:
[0029] a) Porous inorganic membranes: These types of membranes include: (1) mesoporous membranes (25 nm> pore radius> 2 nm), which present Knudsen-type separation at high temperature and which is proportional to (M1 / M2) 05, where M1 and M2 are the molecular weights of the species to be separated; and (2) microporous membranes (pore radius <1 nm), where the separation depends on the size and shape of the pore, on the interaction between the molecules and the pore surface.
[0031] In silica membranes, separation is achieved mainly thanks to the sieving effect that occurs through irregular pores defined mainly by six connected SiO2 tetrahedra with an average size of about 3 Á. Currently, the interest in this type of membranes is focused on the separation of H2 and pervaporation, where it is possible to simultaneously achieve high values of flux and selectivity (in operation at temperatures between 200 and 600 ° C), although they present serious stability problems of materials under hydrothermal conditions.
[0033] Zeolite-based membranes which, by definition, are crystalline microporous aluminosilicates composed of TO4 where T = Si, Al with primary tetrahedral units with oxygen atoms connecting neighboring tetrahedra, are garnering considerable interest due to their extraordinary hydrothermal stability and potential. to achieve high selectivities and H2 permeation values at working temperatures between 200 and 600 ° C. The main drawback of these membranes is the reduction in permeability and selectivity values caused by microstructural imperfections and the difficulty in reducing the membrane thickness. The present invention solves this problem posed since membranes are achieved that do not have imperfections and the thickness is more controllable.
[0035] b) Dense metallic membranes for hydrogen separation: Many metals have high hydrogen permeability, particularly the transition metals of groups IV, V and Pd. For example, hydrogen transport across Pd membranes can be divided into different stages: (1) hydrogen diffusion to the metal surface of the membrane on the feed side; (2) adsorption of hydrogen on the surface; (3) dissociation of hydrogen molecules and incorporation into the metal; (4) diffusion of the protons in the structure and of the electrons in the electronic bands; (5) regeneration of hydrogen molecules on the permeate side; (6) desorption of hydrogen molecule; (7) diffusion of the hydrogen molecule from the surface, assuming a porous support. Hydrogen flux is strongly limited by membrane thickness. Therefore, research efforts are focused on the development of the deposition of thin layers of Pd (and its alloys) on a porous support, which confers the required mechanical resistance. Pd alloys increase H2 permeation and prevent hydrogen embrittlement phenomenon. Some of the materials used in alloys are Ru, Rh, Ni, Cu, and Ag.
[0037] c) Dense ionic ceramic membranes : This type of membrane is based on mixed ionic conductors, which are capable of simultaneously transporting electrons and ions through their structure, or in mixtures of two types of crystalline phases, one that predominantly carries ions and the other It predominantly carries electrons or electronic holes. Among the constituent materials of these membranes we can find: (1) ionic oxygen conductors: they conduct oxygen ions compensated by the transport in the opposite direction of electrons and, (2) proton conductors: they are capable of transporting protons through their structure, and electroneutrality is achieved by conducting electrons and, in some cases, oxygen ions. The advantage of this type of membranes over the previous ones is that they have infinite permselectivity.
[0039] The present invention describes a process for the manufacture of membranes based on digital ink jet printing. It has been discovered that using this technology it is possible to manufacture functional layers with a configuration that maximizes gas permeation, given the improved diffusivity of the gas to be separated through said structured functional layers. In the case of membranes based on mixed ionic and electronic conductors, porous interlayers can also be introduced that allow maximizing the catalytic activity for gas exchange, so that the total permeability of the membrane is improved. Likewise, this technology, thanks to the unique combination and structuring of various materials during digital printing, makes it possible to improve the chemical stability of the membrane against interaction and degradation in operation with industrial gases.
[0040] Next, the mechanism of operation of two types of membranes based on ionic conductors is offered in greater detail: (a) protons, for the separation of hydrogen; (b) of oxygen ions, for the separation of gaseous oxygen. Likewise, examples of constituent materials and industrial processes that can accommodate the technology based on ceramic membrane modules are provided:
[0041] (a) Dense ionic ceramic membranes for hydrogen separation
[0043] Hydrogen separation can be carried out using membranes whose functional layer is a dense layer composed of ceramic materials capable of conducting protons through their crystal lattice at high temperatures (300-1000 ° C). If the membrane only has proton transport capacity and not electronic carriers, the separation can be carried out by applying an electric potential between both sides of the membrane. On the other hand, if the membrane has proton and electronic transport capacity, the driving force for separation may be a pressure or chemical potential gradient. There are few materials reported as mixed conductors of electrons and protons, and in all cases there is a notable deficiency in both the ambivalent conductivity (a¡on • ael) / (a¡on ael) and the stability against reaction with CO2 to produce carbonates. The known materials with the best mixed conduction properties are: BaCe0.9Yb0.1O3, La6WO i2 and Ca0.05Nd0.95NbO4. Another alternative with greater potential is the use of mixtures of materials (composites or composites) that have, separately, high electronic conductivity and high proton conductivity, and present, as a whole, high thermochemical stability and compatibility. (Reference: T. Scherb et at. Journal of Membrane Science 444 (2013) 276-284). Examples of said composites are the combinations Ce0.8Eu0.2O2-s with BaCe0.8Eu0.2O3-s; or Ce0.8Y0.2O2-s with BaCe0.8Y0.2O3-s, as electronic and proton conductors, respectively. (Reference ME Ivanova et al, Scientific Reports 6 (Nov.
[0044] 2016) 34773).
[0045] The hydrogen transport mechanism in mixed proton conductors comprises a sequence of elementary steps (Figure 5.a). In the first place, the adsorption of water in the vacancies of the crystal lattice is necessary to form OH species in different positions of the same, and the transport of the protons is carried out by means of the jump of the proton to neighboring oxygens. The flow of protons is accompanied by a flow of electrons or electronic holes in the same direction. The surface processes of oxidation / reduction and dissociation of hydrogen are catalyzed by noble metals and other metals, (generally highly sensitive to the presence of sulfur compounds) and ceramic materials in the form of nanometric particles.
[0046] This type of membrane allows the separation of hydrogen from gaseous streams, such as hydrocarbon reforming, with theoretical selectivities of 100% with respect to CO and CO2.
[0047] (b) Dense ionic ceramic membranes for oxygen separation
[0049] The non-porous functional separation layer (ii) in this type of ceramic dense membranes is generally composed of a mixed conductor material of electrons and oxygen ions in solid state, including in its crystalline structure alkaline earth elements, rare earths and transition metals such as iron and cobalt. These oxides are oxygen deficient in their structure and, thanks to these oxygen vacancies in their network, the oxygen ion diffusion mechanism through the crystalline structure is possible. The materials most used today for this application have a crystalline structure of the perovskite type, with compositions such as Lao.6Sro.4Feo.8Coo.2O3-5 or Bao.5Sro.5Feo.2Coo.8O3-5. However, the great problem with this type of material is its low stability when subjected to oxygen concentration gradients for long periods of time and, mainly, when subjected to the presence of CO2 under operating conditions, generally producing carbonates. alkaline earth elements (carbonation phenomenon). With respect to membranes made up of two types of crystalline phases, one that predominantly carries oxygen ions and the other that predominantly carries electrons or electronic holes, it has recently been reported that the combination of gadolinium-doped cerium oxide with a cobalt-free spinel and alkaline earth metals, such as Fe2NiO4, has given rise to a promising material in terms of its activity for the separation of oxygen (J. Caro et al., Angewandte Chemie International Edition 2oi 1, 5o, 759.).
[0050] In the dense layer of ceramic membranes, the oxygen transport (and separation) phenomenon occurs in the following consecutive stages, outlined in Figure 5.b: Initially, molecular oxygen (O2) is adsorbed on the membrane surface and then it is reduced and dissociated to form adsorbed atomic species of reduced oxygen. The adsorbed oxygen (O-2) ion is incorporated into an oxygen vacancy in the crystal lattice and diffuses by hopping to neighboring oxygen vacancies in the lattice. This diffusion of the anion is accompanied by a counter-diffusion of electrons in the opposite direction. Finally, the oxygen ions are oxidized and recombined into molecular oxygen at the other interface of the membrane, and finally the O2 is released and incorporated into the permeate stream.
[0051] The intracrystalline transport of oxygen demands temperatures above 65o ° C, and the balance of charges produced by the transport of electrons or oxygen vacancies requires that the material has sufficient electronic conductivity under the operating conditions of the membrane. The driving force responsible for oxygen transport across the membrane is the partial pressure difference of oxygen between both sides. membrane. This pressure gradient can be achieved by applying a vacuum on the permeate side of the membrane or by using a stripping gas. Thus, the flow of oxygen through a membrane is determined by the temperature and the partial pressure difference of oxygen, in addition to the thickness of the membrane.
[0052] Another crucial step in the oxygen separation process in ion transport membranes is gas exchange. The different stages of transport can be limiting and cause a decrease in permeation flux through the membrane. Among the different possible reasons we can highlight the following: (1) the thickness of the selective separation layer is very small, so that the diffusion through the solid is much faster than the gas exchange. Typically, this critical dimension is called "characteristic length" and is the quotient between the diffusion coefficient and the kinetic constant of the surface gas exchange reaction under the operating conditions and composition of gases in contact with the membrane surface; ( 2) The membrane surface does not have appreciable catalytic activity for the oxygen activation reaction; (3) Gaseous atmospheres in contact with the membrane surface or surfaces discourage the adsorption / desorption of molecular oxygen and its evolution through the reaction O2 2e- -o- O ^-2 .
[0053] Ceramic oxygen separation membranes are assembled in modules that can be fed from the waste heat generated in industries with thermal combustion or oxidation processes. In particular, the simulations carried out on the integration of this technology in oxy-fuel processes indicate an overall energy efficiency of the plant much higher than that currently available with conventional oxygen supply technologies. Oxy-combustion consists of injecting a stream of high purity O2 as an oxidizer in the furnace burners instead of air, as is done in conventional combustion processes, thus reaching higher flame temperatures with less fuel consumption. fuel and thus achieving higher performance. The use of oxidizers rich in oxygen makes it possible to obtain combustion gases with a composition consisting mainly of CO2 and water vapor. The high concentration of CO2 in the exhaust gases in the oxy-fuel process facilitates its potential separation. Therefore, this process has the advantage of facilitating the separation and capture of CO2, which can later be liquefied, transported and stored or used in other industrial processes. This combustion process concept makes it possible to reduce CO2 and NO ^x emissions to a minimum, as well as to substantially increase the energy efficiency of the process. Examples of energy-intensive industries that use oxygen are the glass industry, incinerators, manufacture of frits, enamels and colorifices, metallurgy, steel, chemical, refining and petrochemical industries. One of the industrial sectors in which the use of oxygen makes oxy-fuel combustion possible is glass melting and the manufacture of frits, enamels and ceramic colors. In this type of industry, the need to reach temperatures above 1500 ° C inside the furnaces, in order to melt the mixture of raw materials that is introduced, is achieved by using oxygen instead of air in the gas burners. natural.
[0054] Oxygen membranes can also be applied in air enrichment, so that the oxygen concentration is increased from 21% to higher values, typically above 24%. This increase in concentration is necessary in certain combustion or chemical conversion processes in which the calorific value of the product to be treated, generally a fuel, is insufficient to maintain adequate operating conditions. A typical example of enrichment is the use in cement plants that use alternative fuels or incinerate residues during the manufacture of clinker.
[0055] Oxy-fuel combustion aims to be one of the most economical technologies for capturing CO2, its main drawback being the high demand for O2 it presents and the cost that obtaining it entails. The great challenge of this technology lies in the production of O2 in order to supply the high quantities required. Currently, the only technologies available on an industrial scale capable of producing large volumes of O2 are cryogenic distillation of air and absorption installations in solid absorbent columns (PSA-VPSA), the latter with lower production capacities and, generally, with oxygen purities less than 95% by volume. The drawback of cryogenic air distillation is its high energy consumption. In the case of a thermal power plant, this consumption can amount to 15% of its electricity production, penalizing the overall efficiency of the plant by 10%. Therefore, the technology of dense ceramic membranes based on conductors of the oxygen ion is postulated as a particularly interesting alternative with which it is expected to reduce the overall efficiency loss in the oxy-fuel plant up to 5%, with a theoretical oxygen purity of 100%.
[0056] Publications that describe types of gas separation membranes in general include: Ind. Eng. Chem. Res. 2009, 48, 10, 4638-4663, April 22, 2009. Membrane Gas Separation: A Review / State of the Art:
[0057] https://pubs.acs.org/doi/full/10.1021/ie8019032 src=recsys
[0058] Publications describing porous gas separation membranes include: Interceram - International Ceramic Review, July 2018, Volume 67, Issue 4, pp 16-21 Microporous Inorganic Membranes for Gas Separation and Purification:
[0059] https://link.springer.com/artide/10.1007/s42411-018-0023-2
[0060] Publications describing dense gas separation membranes include: Chemical Communications 39,2011. Dense ceramic catalytic membranes and membrane reactors for energy and environmental applications:
[0061] 5 https://pubs.rsc.org/en/content/articlelanding/2011/cc/c1cc13001c#!divCitation
[0063] Advantages of ink jet technology for the deposition of functional layers on ceramic gas separation membranes.
[0065] The present invention refers to a new process for manufacturing ceramic membranes using, among others, the ink jet technique , so that improved configurations and functionalities can be obtained. Therefore, it provides a solution to improve the gas separation membrane manufacturing process, as well as its performance (permeate flow) under industrial operating conditions and, consequently, to overcome the drawbacks of the state of the art; Also using materials that have high chemical stability and high performance in the separation of gases. Specifically, the digital application by inkjet of the electroceramic functional layers makes it possible: (a) the reduction of thickness, the fine adjustment of the microporous structure of the system and the improvement of its final performance, thanks to the 0 high resolution; (b) the application on non-flat and raised supports, improving the design and functionality of the device, and minimizing the number of defective parts as it is a non-contact deposition, (c) the automation of the production process, and (d) the manufacturing in environmentally friendly conditions, by allowing the use of water-based inks.
[0066] 5
[0067] Description of the invention
[0069] The dense (non-porous) or porous gas separation membranes of a ceramic nature (such as the examples described in the background section, at a and c) that are obtained according to the process of the present invention, comprise, for their practical use, the following basic configuration consisting of at least the following components:
[0070] (i) - A porous support (i), compatible with a separating functional layer, where compatible means that both components - support and functional layer - have a similar expansion profile as a function of temperature and that a reaction does not take place between both phases at high temperatures (800-1500 ° C) to give rise to third phases, which generally cause degradation and rupture of the membrane.
[0072] - at least one functional separation layer, dense or porous, located on the porous support made up of 2 or more inks, (ii).
[0074] That the materials present a similar expansion profile means that they expand (expand and contract) in an aligned way to avoid cracks, breaks, buckling (warping) or other defects, in the final membranes. If two materials do not have the same thermal expansion or expansion profile, then their bond is unstable and the assembly breaks during heating or cooling.
[0076] Additionally, the membranes prepared by the process of the invention may comprise the following layers, among others:
[0078] (iii) A porous catalytic layer, deposited on the functional separation layer (ii), which allows improving the processes of incorporation and elimination of gaseous products, (iv) A porous interlayer, deposited between the porous support (i) and the functional separation layer (ii), which has the objective of improving the gas exchange stages, especially when the porous support (i) does not possess catalytic activity nor does it allow to carry out ionic transport.
[0080] The basic membrane architecture comprises layers (i) and (ii) (Figure 1). The geometry of the membrane in the final module can be flat, tubular or of any other complex geometry that improves the performance of the module, that is, the thermofluid dynamics, resistance to pressure, heat exchange and proper sealing of the system.
[0082] According to a further embodiment, a membrane prepared by the process of the invention comprises layers (i), (ii), (iii) and (iv) in the order of sequence (i), (iv), (ii) and ( iii) (Figure 2). Generally, the properties of layer (ii), (iii) and (iv) are quite similar, although in general the specific surface area of layers (iii) and (iv) is considerably higher than that of layer (ii ).
[0084] According to a further embodiment, optionally, in a membrane prepared by the process of the invention, another layer called the porous compositional damping interlayer may also be necessary, (v), located between the support (i) and the catalytic layer porous (iv), as an intermediate link that dampens the compositional change, favoring the deposition and stability of the following layers, as seen in Figure 3.
[0086] According to a particular embodiment, in a membrane prepared by the process of the invention another additional non-porous layer (vi) may be necessary. This layer is located between the functional separation layer (ii) and the porous catalytic activation layer (iii), and serves to protect the layers (ii) and (iii) against possible interactions or degradation reactions in contact with the layer (iii) or with the operating gases in contact with layer (ii) (Figure 4). The additional non-porous layer (vi) must allow ionic and electronic transport, while being thermo-chemically compatible with the adjacent layers and with the gases with which it is in contact. Figure 4 shows a diagram of a membrane in which the architecture and sequence between (i), (ii), (iii), (iv), (v) and (vi) are presented.
[0088] Of the possible constitutive layers of the membrane obtained by the process of the invention:
[0089] - layer (ii) can be dense or porous.
[0090] - layers (iii), (iv) and (v) are always porous.
[0091] - the layer (vi) is dense.
[0093] In this specification the expression "sintered layer" refers to each of the constituent layers of a membrane in its final state, that is, as it is obtained after the applications of the corresponding inks and a heat treatment that produces sintering at a minimum temperature of at least 600 ° C in the case of a layer such as layer (iii) and porous membranes, or 800 ° C in the case of dense membranes.
[0095] Thus, the present invention relates to a process for the manufacture of ceramic gas separation membranes that comprises deposition on a porous support (i); by means of the ink jet technique of at least one functional separation layer (ii) made up of at least two inks, and at least one heat treatment, which produces sintering of the layer.
[0097] The present invention relates, more specifically, to a process for the manufacture of ceramic gas separation membranes that comprises, at least, the following steps:
[0098] (a) formed of a porous support (i) compatible with a functional separation layer (ii),
[0099] (b) deposition on the support (i), by means of the ink jet technique, of at least one functional separation layer (ii) made up of at least two inks and
[0100] (c) at least one heat treatment, leading to sintering,
[0101] wherein the separating functional layer (ii) is deposited in a way that gives rise to a surface:
[0102] - with gradients
[0103] - with patterns, or
[0104] with combinations of both.
[0106] "Compatible" means that both components - support and functional layer - have a similar expansion profile as a function of temperature and that a reaction between both phases does not take place at high temperatures to give rise to third phases, which generally produce defects and / or membrane rupture.
[0108] The term "gradient" has in this specification its usual meaning, that is, a smooth or progressive transition effect between different colors, or also a smooth transition effect in a scale of shades of the same color, such as a gray scale.
[0110] Gradients can be obtained in image, that is, two-dimensional, 2D. When using several inks, there is a “drawing-pattern” on the surface (2D) for each pass or application of ink. If you also want to have a pattern in the plane perpendicular to the surface, (3D), you have to make more than one pass or ink application. For this purpose, the texture (rheology) of the inks must be similar. After sintering, each ink can evolve differently and it is possible that the "sintered layer" has different textures or reliefs at the point where they are applied.
[0112] The term "pattern" refers to any type of image or drawing, with geometric patterns with repeating geometric shapes, such as a 2D checkerboard with cross-sectional phase interconnectivity, fractal pattern, spiral pattern, and combinations thereof. .
[0114] "Interconnectivity of phases in section" means that, by making a cut in the thin membrane, or in one of the layers that compose it, it can be seen that the crystalline phases -which can be separated at the surface level-, are connected inside between them.
[0116] It is possible to obtain a gradient or pattern by depositing the inks so that different geometries are obtained. For example, when using the inkjet printing technique Ink, by depositing the inks, making the print heads follow a predetermined movement, the desired geometry is obtained.
[0118] According to particular embodiments, step b) of the method comprises deposition of at least one fluid layer made up of at least two inks that covers - without leaving ink-free gaps - a complete area of the surface of the porous support (i), and so that the two inks are applied simultaneously.
[0120] According to a particular embodiment, step b) of the process further comprises a step of deposition of at least one porous catalytic activation layer (iii) on the functional separation layer (ii). The technique used for the deposition of the layer (iii) on the functional separation layer (ii) can be selected between dip coating, spin coating, roller coating or screen printing. ; physical vapor deposition, sputtering, electron beam, atomized; airbrushing; spraying of suspensions; and / or thermal spraying, including plasma spraying and pyrolysis spray; 3D printing, stereolithography, injection, inkjet printing (inkjet) and combinations thereof, preferably inkjet (inkjet).
[0122] According to another particular embodiment, stage b) of the process further comprises an additional stage in which a porous catalytic layer (iv) located between the porous support (i) and the separating functional layer (ii) is deposited. The technique used for the deposition of layer (iv) between the porous support (i) and layer (ii) can be selected from the techniques mentioned above for the preparation of layer (iii). Preferably the technique for depositing the porous catalytic layer (iv) is ink jet printing .
[0124] According to another particular embodiment, stage b) of the process further comprises another stage in which a porous compositional damping interlayer (v) is deposited between the functional separation layer (ii) and the porous catalytic layer (iv). The technique used for the deposition of layer (v) between the functional separation layer (ii) and the porous catalytic layer (iv) can be selected from the techniques mentioned above for the preparation of layer (iii) or (iv) , and preferably the technique for depositing the porous compositional damping interlayer (v) is inkjet.
[0126] According to another particular embodiment, step b) of the described process may further comprise the deposition of another additional non-porous layer (vi) (Figure 4). This layer (vi) is designed for the particular case of membranes based on dense separation layers (ii) made of mixed ionic-electronic conductors. This layer (vi) is located, if present, between the functional separation layer (ii) and the porous catalytic activation layer (iii), and serves to protect layers (ii) and (iii) against possible interactions or degradation reactions in contact with layer (iii) or with operating gases in contact with layer (ii). The additional non-porous layer (vi) must allow ionic and electronic transport, while being thermo-chemically compatible with the adjacent layers and with the gases with which it is in contact. This layer is usually more stable and with lower ionic conductivity than the functional separation layer (ii), which implies that its thickness must normally be less.
[0127] The technique used for the deposition of the additional non-porous layer (vi) between the functional separation layer (ii) and the porous catalytic activation layer (iii), can be selected from the techniques mentioned above for the preparation of the layer. (iii) or (iv), and is preferably ink jet .
[0129] According to a further embodiment, a membrane prepared by the process of the invention comprises layers (i) and (ii) and one or more of layers (iii), (iv), (v) and / or (vi).
[0131] Each optional layer that may be forming part of the membrane, for example, layer (iii), (iv), (v) and / or (vi) can be deposited in a way that results in a pattern, gradients or combinations of them, different from the patterns or gradients or combinations obtained or foreseen for the other layers.
[0132] According to a particular embodiment of the procedure described, in step b), in each application of each of the layers (ii), (iii), (iv) and (v) and / or (vi) at least 2 different inks, in this way the desired patterns and / or gradients are obtained.
[0134] According to particular embodiments, step b) of the procedure comprises a single application or identical applications of the inks that make up the layer or layers of the membrane ("identical applications" are those that maintain the drawing or pattern of the previously made application), that is that is, layer (ii) and, optionally, one of layers (iii), (iv), (v) and / or (vi). In this case, after a heat treatment, the gradient or pattern obtained gives rise to a distribution of the different crystalline phases and / or a distribution of porosity, for example, between 2D checkerboard, mosaic with interconnectivity of phases in section, fractal pattern, spiral pattern and combinations thereof.
[0135] According to a further particular embodiment, step b) of the procedure comprises the deposition of inks following a model of different applications ("different applications" are those that give rise to a drawing different from the drawing or pattern of the previous application). In this case a different pattern is obtained in each ink application in layers (ii), (iii), (iv) and (v) and / or (vi) after a heat treatment, and a 3D gradient is obtained along the z-axis (perpendicular to the printing plane), with geometry, for example, based on pyramidal patterns, conical patterns, or based on regular porous systems such as those found in zeolites or coordination polymers (MFOs).
[0137] According to additional particular embodiments, step b) of the process comprises the deposition of inks with different applications that give rise to gradients or patterns that comprise areas with different porosity in the same layer or from one layer to another.
[0139] According to additional particular embodiments, step b) of the process comprises the deposition of inks following the model of different applications (as defined above) that give rise to gradients or patterns that comprise areas with different ionic and / or electronic conductive capacity.
[0141] These areas can be in the form of, for example, individual lines, grids, segments, mosaics, spirals, and / or pillars.
[0143] According to additional particular embodiments, step b) of the process comprises the deposition in certain areas of inks that comprise two or more different ionic conductors.
[0145] According to particular embodiments, step c) of the process comprises a heat treatment at a temperature of at least 800 ° C (minimum temperature for a layer to sinter), for example, at temperatures between 850 and 1650 ° C.
[0147] Optionally, it is possible to carry out a heat treatment after each ink application in each of the layers mentioned above.
[0148] Preferably, the heat treatment is carried out only after depositing a complete layer and not after one or more applications or "passes" with inks.
[0149] At least one heat treatment of one layer of the membrane must be capable of sintering said layer.
[0150] In addition, an intermediate heat treatment, eg drying, may be necessary between about 50-120 ° C in air.
[0151] Regardless of whether heat treatments have been carried out during the production of the membrane, at least one final heat treatment is always necessary. This treatment is carried out, for example, typically in air or inert gas in the maximum temperature range during the treatment between 800 and 1650 ° C, with heating and cooling ramps, for example, between 3 and 15 ° C / min.
[0152] How a heat treatment is carried out depends on the furnace, the load, among other parameters. A heat treatment according to the invention can be carried out by any known technique, preferably it can be selected from treatment in an electric oven, gas oven, induction oven, microwave treatment, laser treatment or combinations thereof. It is normally carried out in an electric or gas oven, in which the heat transfer is carried out mainly by radiation and convection. Heat treatments after each ink application can be carried out in a conventional way, for example in a temperature range between 800 and 1650 ° C (preferably between 1000 and 1500 ° C), with a heating ramp depending on the type furnace, load and other parameters.
[0154] According to a particular embodiment, the porous catalytic activation layer (iii) is deposited after at least one heat treatment has occurred, and after its deposition another heat treatment is applied again. These treatments (for layer (iii)) can be carried out in the temperature range between 600 and 1100 ° C, to have a greater control of the size, pore morphology and connectivity between them.
[0156] According to the process of the present invention, the shaping of the porous support (i) can be carried out by a technique selected from uniaxial or isostatic pressing, extrusion or calendering, tape casting, conventional casting, dip coating. ), spin coating, rollercoating or screen printing, physical vapor deposition, sputtering, electron beam, suspension spraying , and / or thermal projection ( thermal spraying), including plasma spraying and pyrolysis spray; 3D printing, stereolithography, injection, inkjet printing (inkjet) and combinations thereof, preferably uniaxial pressing, extrusion, calendering, inkjet (inkjet) and combinations thereof.
[0157] According to preferred embodiments, the shaping of the porous support (i) is carried out in such a way as to obtain a porous support (i) with porosity between 10 and 60% with respect to the volume. Total support, measured by the liquid pore saturation method based on Archimedes' principle, preferably between 30 and 50%, and a thickness of less than 2.5 mm, preferably between 0.1 and 2mm.
[0158] The constituent materials of the porous support (i) used, which must be resistant to high temperatures, such as sintering temperatures, and mechanically and chemically compatible with the constituent materials of the functional separation layer (ii), can be selected, for For example, between magnesium oxide, aluminum and magnesium spinels, cerium oxide doped with at least one lanthanide metal, zirconium oxide doped with at least one of the following elements: Y, Mg, Sc or a lanthanide metal; titanium oxide, aluminum nitride, refractory alloys / superalloys, materials containing crystalline phases including clays or aluminum silicates, magnesium silicate, iron silicate, titanium silicate or silicates of alkali or alkaline earth elements, iron perovskites and combinations thereof, preferably magnesium oxide, doped cerium oxide, doped zirconium oxide, magnesium silicates and iron perovskite.
[0160] Furthermore, according to a particular embodiment of the process for obtaining the ceramic membranes, it may comprise a stage of heat treatment at temperatures between 600 and 1200 ° C (specific for the porous support) after shaping the porous substrate (i), with the in order to eliminate the organic matter present in the deposited layers, and to sinter and chemically connect the ceramic particles to each other. Sintering in this context means thermally compressing through recrystallization mechanisms at high temperature, whereby it is achieved with heat treatment at the appropriate temperature. The heat treatment after the initial shaping of the porous substrate (i) is optional, but in the end all the inks must have undergone at least one heat treatment, which is necessary to activate and structure the inks.
[0162] Preferably, the functional separation layer (ii) of the process described in the present invention has a thickness of less than 50 µm, preferably between 2 and 50 µm, and more preferably between 2 and 30 µm.
[0164] In particular, for the constitution of the functional separation layers (ii) - both dense and porous, it is necessary to deposit a minimum of two inks of different composition that comprise, at least:
[0165] a) an inorganic solid,
[0166] b) a liquid component and
[0167] c) a conditioning additive (such as dispersants, preservatives, binders, surfactants, etc.).
[0169] In the case of dense membranes, the inorganic solids constituting layer (ii) are always crystalline solids.
[0170] Layer (ii) in the case of dense membranes can comprise a mixture of 2 or more inorganic solids (crystalline phases). In a typical example, the functional layer (ii) is dense and has 2 crystalline phases with different conductivities, one is ionic and the other electronic.
[0172] In the manufacture of ceramic membranes ionic dense gas separation, low ionic conductivity l of the functional layer (ii) is 1 mS / cm and electronic conductivity is low 5mS / cm at a temperature of 850 ° C.
[0174] According to a particular embodiment, in the manufacture of dense ionic ceramic gas separation membranes, the functional separation layer (ii) is a non-porous layer, where the inorganic solids (a) of the inks can be selected from:
[0175] - those that give rise to conductive layers of the oxygen ion,
[0176] - conductors of protons or of the hydride anion (H-),
[0177] - conductors of the carbonate ion,
[0178] - conductive alkali metals,
[0179] - electronic conductors type n or p,
[0180] and combinations thereof,
[0181] preferably oxygen ion conductive layers, protons, n or p type electronic conductors and combinations thereof.
[0183] Some of these solids are solids that, once sintered, give rise to a majority crystalline phase selected from fluorite, perovskite, spinel, pyrochlor and combinations thereof.
[0185] According to a particular embodiment, in the manufacture of porous inorganic gas separation membranes, the functional separation layer (ii) is a porous layer, where the inorganic solids (a) of the inks can be selected so as to obtain functional layers (ii) porous selected from ceramic porous matrices with selectivity to H2, CO, O2, water, hydrocarbons (such as methane) and combinations thereof. According to particular embodiments, these solids are based on SiO2, TiO2, ZrO2, AI2O3, SiC, Nb2O3, silico-aluminates (zeolites), MgO, carbon and combinations thereof.
[0187] In the case of porous membranes, clear crystalline phases do not form and are known as amorphous microporous membranes - with the exception of zeolitic membranes. In a particular preferred embodiment, once the functional separation layer (ii) has been deposited, it is subjected to a heat treatment (sintering) of between 800 and 1500 ° C, which gives rise to a layer with a thickness of less than 30 µm, sintered and chemically connected to the underlying layers. In the case of porous membranes, the minimum sintering heat treatment temperature may be 600 ° C.
[0189] According to a preferred embodiment, a heat treatment is carried out after depositing a complete layer, instead of carrying out a treatment after one or more applications or "passes" with inks.
[0191] According to the present invention, each of the inks used for layers (iii), (iv) and (v) comprises, at least:
[0192] - (c) a liquid component, and
[0193] - (d) a conditioning additive AA; (such as dispersants, preservatives, binders, surfactants, etc.),
[0194] and optionally comprises
[0195] (a) an inorganic solid SO,
[0196] (b) a fugitive additive, AF, which is a compound that decomposes during the sintering stage, giving rise to the desired porous structure
[0197] or comprises both (a) and (b).
[0199] Components (c) and (d) are always present in the formulation of each of the constituent inks of layers (iii), (iv) and (v), while components (a) and (b) may be present both at the same time or only one of them, that is, the fugitive additive (b) can be mixed in the ink containing the inorganic solid (a), or it can constitute a new ink together with the liquid component and the conditioning additive / s. Preferably, the fugitive additive comprises materials selected from graphite, starch, polymethylmethacrylate (PMMA), cellulose, PVA (polyvinyl alcohol) PVB (Polyvinyl Butyral), nylon, ammonium bicarbonate and combinations thereof, preferably PMMA and graphite, with particle sizes selected between 0.1 and 5.0 µm, preferably between 0.1 and 3.0 µm. These fugitive additives are commercial products.
[0200] The fugitive additive is a pore former, generally a polymeric, carbonaceous, vegetable solid or the like. This additive is used to give porosity to porous layers. This fugitive additive is not a conditioning additive.
[0202] The fugitive additive (b) can be removed with a heat treatment between 400 and 1100 ° C. According to a particular embodiment, the fugitive additive (b) can be removed with a heat treatment between 400 and 1100 ° C, with heating and cooling ramps between 3 and 15 ° C / min.
[0204] According to the present invention, for the case of dense ionic ceramic membranes, each of the inks used for the additional non-porous layer (vi) comprises at least: a) an inorganic solid,
[0205] b) a liquid component, and
[0206] c) a conditioning additive (such as dispersants, preservatives, binders, surfactants, etc.).
[0208] The inorganic solids (a) of the inks of the additional non-porous layer (vi) are selected from the same inorganic solids constituting the functional separating layer (ii).
[0210] The chemical composition of the layers comprises, for example, metal oxides, metal oxides doped with different elements, so that the crystalline phases have the desired structure, as explained for the majority crystalline phase in the layers (ii) , (vi), etc.
[0212] According to particular embodiments, each of the layers (ii), (iii), (iv), (v) and (vi) after sintering comprises at least 2 different inorganic crystalline phases, they are selected from fluorite, perovskite, spinel, pyrochloro and combinations thereof.
[0214] In the process of the invention, the solid component of the inks is present in a percentage by weight between 20 and 55%, preferably between 25 and 45% with respect to the total weight of the ink.
[0215] As described in the present invention, in the cases in which the porous layers (iii), (iv) and (v) described above are deposited, these deposited layers have a porosity between 20 and 60% with respect to the volume of each of the layers, preferably between 20 and 40% with respect to the volume of each of the layers, made up of pores with an average size between, preferably 0.1 and 5 µm, and a thickness in each layer between 5 and 100 µm, preferably between 20 and 60 jm. Optionally, and preferably, a last stage of heat treatment can be carried out on the final membrane after the deposition of all the layers at temperatures between 650 and 1500 ° C. In the final membrane, the particles that form the porous structure of the membrane (a membrane, even if it is a dense membrane, has or can have a porous structure, since - if present-, the layers (iii), (iv) and (v) they are porous) they can have an average grain size preferably between 0.05 and 2.0 µm, and the membrane can have a thickness of between 20 and 60 µm after sintering heat treatment. All deposited layers need to be subjected to at least one heat treatment. Said treatment depends on the type of furnace, the load and the size and geometry of the membrane, as well as the layer to be sintered (for example, normally, layer (iii) is brought to 1000 ° C, while the functional layers are brought to higher temperatures.
[0217] According to particular embodiments, layer (iii) is applied after having sintered the rest of the membrane, and its layers, at maximum temperature. Therefore, the sintering temperature of layer (iii) is generally substantially lower than the maximum sintering temperature of layer (ii).
[0219] According to the process of the invention, the liquid component of the inks, for any of the layers, can be selected from among water, glycol, glycol ether, aliphatic solvents (for example, esters with a carbon number greater than 10 (preferably between 10 and 35). ) and combinations thereof, and is preferably water.
[0221] The liquid component of the inks is present in a percentage by weight between 15 and 80%, preferably between 25% and 70% with respect to the total weight of the ink.
[0223] According to the process of the invention, the ink conditioning additives, which comprise dispersants, preservatives, binders, surfactants and / or combinations thereof, are present in a percentage by weight between 0.5 and 25%, preferably between 2 and 20% with respect to the total ink.
[0225] According to the present invention, for the case of dense ionic ceramic membranes, there may be an additional step in the procedure for the preparation of the porous layers (iii), (iv) and (v), which improves its functionality. According to a possible embodiment, the process for obtaining the catalytic activation layer (iii) may comprise, at least, one step of incorporation - after step c) - of a catalyst on the surface of the particles of the previously porous layer prepared, preferably, by inkjet application.The deposition is done by immersing the final membrane, already sintered (after the thermal treatment / s) in a solution with a precursor, which accesses all the porous layers (therefore that the catalyst would be included in all the porous layers). The catalyst is introduced by a technique selected from impregnation or infiltration of liquid solutions of precursors of the metals comprised in the final catalyst composition; infiltration of a dispersion of nanoparticles of the catalyst; Vapor phase deposition by PVD or CVD techniques and combinations thereof.
[0226] This stage of incorporation of the catalyst can be carried out in 2 steps, that is, introducing a first element (metal), and then, consecutively, other metals or combinations of them using the techniques stated in the previous paragraph. It is common practice to carry out a drying heat treatment (T between 100-200 ° C, between 0.5-8 h) after the incorporation of the first element and before the incorporation of the second. Doing it in 2 steps can be advantageous in some cases since it can allow to preferentially modify or promote the surface of the nanoparticles of the compound based on the first element without producing any effect inside said nanoparticles. Furthermore, according to a particular embodiment, the process for obtaining a catalytic activation layer may further comprise a second stage of heat treatment at temperatures between 450 and 1100 ° C. This is another specific heat treatment of this catalytic activation. The atmosphere can vary between air, inert or H2 and the time between 0.5 and 36h.
[0228] The application of the different layers requires sintered thicknesses of the order of 30 ^ m, that is, 6 times higher than those currently applied for the decoration of ceramic tiles (figure 6). Said thickness determines the type of liquid component that can be used, and it is necessary to avoid solvents with very slow evaporation and with very high decomposition temperatures, which cause long parts drying times and the appearance of defects in the sintered layer. For this reason, in a preferred embodiment, the inks applied by ink jet printing technology are formulated using water, glycols, glycol ether or combinations of both as the liquid component, since they are miscible.
[0229] By way of example, the composition of the ceramic membranes can be as follows: (a) Ionic dense ceramic membranes for oxygen separation. Any of the porous and dense layers that make up the O2 separation ceramic membranes can be formed at least of mixtures of particles that have two different crystalline compositions and phases (mixed ionic conductive composites):
[0230] a.1) a first phase consisting of zirconium oxide or cerium oxide, partially substituted - zirconium or cerium -, preferably between 10-30% molar, by at least one element selected from Y, Sc, Gd , Pr, Sm, Nd, Er, Tb and combinations thereof, preferably Y, Gd, Sm, Tb and combinations thereof, said first phase has a fluorite-type crystalline structure, and has an ionic conductivity greater than 0.001 S / cm at 850 ° C;
[0231] a.2) a second phase comprising a mixed oxide with a spinel-type structure, comprising at least one element selected from Fe, Ni, Co, Al, Cr, Mn and combinations thereof, preferably Fe, Ni, Co, Mn and combinations thereof, and has a total conductivity greater than 0.05 S / cm at 850 ° C.
[0233] Another example of membranes for the same application: (b) (dense ionic ceramic membranes for oxygen separation), each of the porous and dense layers can be formed at least of mixtures of particles that have two different crystalline compositions and phases:
[0234] b.1) a first phase comprising zirconium oxide or cerium oxide, partially substituted (10-30% molar) for cerium or zirconium by at least one element selected from Y, Sc, Gd, Pr, Sm, Nd, Er, Tb and combinations thereof, preferably Y, Gd, Sm, Tb and combinations thereof, said first phase has a crystalline structure of the fluorite type, and has an ionic conductivity greater than 0.001 S / cm at 850 ° C;
[0235] b.2) a second phase comprising a mixed oxide with a perovskite-type structure, comprising at least one metal selected from lanthanides, Fe, Ni, Co, Cr, Mn and combinations thereof, preferably from Fe, Mn and combinations thereof, and has a total conductivity greater than 0.05 S / cm at 850 ° C.
[0237] Composites can also be used in the constituent layers of ceramic H2 separation membranes. An example of a H2 separation membrane is, as indicated in the particular embodiment of application (c) (dense ionic hydrogen separation ceramic membrane):
[0238] c.1) a first phase comprising barium cerate or zirconate doped (15-20% molar) by at least one element selected from Gd, Y, Eu, Yb and combinations of the themselves. and has a crystalline structure of the perovskite type and a proton conductivity greater than 0.01 S / cm at 600 ° C,
[0239] c.2) a second phase comprising an oxide of cerium or zirconium, partially substituted (10-30% molar) by at least one element selected from Y, Gd, Sm and combinations of both, and has a crystalline structure of the fluorite type, and has a total conductivity greater than 0.05 S / cm under operating conditions.
[0241] The high resolution of inkjet technology makes it possible to make patterns with different inks, with different materials that confer specific functions, or ink mixtures, which allow progressive gradients, for example, in order to achieve selectivities to different products in a certain way. integrated and / or maximize permeability, respectively. These gradients are obtained after one or more applications of the inks. These applications (or past), can be identical applications (same drawing or pattern) obtaining patterns in 2D (see figure 8) or they can be several different applications, thus obtaining patterns in 3D (see figure 9) and thanks to the different crystalline phases and / or porosity of the layers where they are applied. These patterns achieve greater membrane permeation as it maximizes the ambipolar conductivity of the membrane as a whole.
[0243] For example, for oxygen membranes based on mixed ionic conductive composites , in the dense separation functional layer, (ii), it is possible to make patterns that maximize the amount of the ionic conductive phase (which ultimately determines the total permeability) to the Once they ensure connectivity and good distribution of the electronic conducting phase, so that the total permeability is optimized. Figure 8.a shows a pattern in which, on an ink matrix composed of an ionic conductor (eg Ce0.9Gd0.2O1.95) lines have been drawn with an ink of an electronic conductor (eg . La0.85Sr0.15MnO3). In the same way, it would be possible to make other types of traces on the ionic conductive matrix, such as grids, segments ( Journal of Membrane Science, 486 (2015) 222-228), mosaics, spirals and / or individual pillars with the electronic conductive ink or with mixtures of the two inks, so as to guarantee the continuity of both phases and, therefore, the ionic and electronic exchange. This same type of pattern can be made in the rest of the layers that make up the membrane.
[0245] Another type of example for these membranes is the possibility of achieving ink distributions that give rise to patterns and / or gradients according to the intended use of the membranes. A particular embodiment comprises deposition in areas determined from two or more different ionic conductors, such as, for example, an oxygen ion preferential conductor and a proton preferential conductor, in a checkerboard-like ink distribution (Figure 8.b), or fractals (Figure 8. c). The following conductors or type of selective material can be combined (normally two or three on the same membrane):
[0246] - Oxygen ion conductor, proton conductor, carbonate ion conductor, alkali metal conductor
[0247] - Electronic conductor type n or p
[0248] - Non-oxide ceramics (eg titanium nitrides) or hydrogen permeable alloys (eg Pd, V, Nb, Ta alloys)
[0249] - Porous ceramic matrices (after sintering the layer) with selectivity to: H2, CO, CO2, water, methane or certain hydrocarbons (olefins, paraffins, aromatics, etc.). This type of combination makes it possible to precisely adjust the mixed selectivity of the separating membranes, allowing a distribution of the type of conductor or selective material along the membrane to adapt to the needs of the process, for example, in membrane reactors where injection / exhaust gas should be adjusted along the length of it.
[0251] * Examples of 3D layer volume resolution *
[0253] Because the inkjet technique is a layer-by-layer deposition system, a different type of pattern can be made in each of the ink applications (that is, in each "pass" of the inkjet heads). , it is possible to manufacture very well defined multilayer structures in micrometric 3D layers, to obtain tight properties of conduction in solid state or diffusion by porous media. Figure 9 shows an example of multilayer pyramidal compositional architecture made with different applications ("passes") of ink heads, which can be achieved by modifying the design pattern in each of the applied layers.
[0255] Today's existing inkjet technology and heads allow the obtaining of layers with a fired thickness between 3 and 15 | jm for each "pass" with a maximum resolution of 400 * 1800 dpi.
[0257] The same type of strategy can be used to adjust the porosity characteristics with lateral (2D - XY) or depth (3D -z) resolution, so that in layers (iii, iv and v) can be made gradients (in cross sections of the membrane) and with specific variations in the 2D planes.
[0259] This type of 3D structure by sequential deposition of layers with different patterns (drawings) of inks, allows to adjust the composition of the surfaces in the volume, so that the composition of the membrane is defined (progressively) depending on the gases or conditions. present on both sides of the membrane. The purpose of this can be variable, for example, improve permeability to different gases or selectivity, improve stability, adjust catalytic properties, avoid pore blocking or irreversible adsorption or selective promotion of electronic conductivity type n or p.
[0261] Throughout the description and claims the word "comprise" and its variants are not intended to exclude other technical characteristics, additives, components or steps. For those skilled in the art, other objects, advantages and characteristics of the invention will emerge in part from the description and in part from the practice of the invention.
[0263] With the process of the invention, membranes of mixed conductivity are achieved (based on ionic conductors) and the permeability of the membrane is considerably increased with respect to known membranes. This is achieved because with the inkjet technique it is possible to make layers that achieve these functionalities in 2D and 3D.
[0265] Brief description of the figures
[0266] Figure 1. Shows a simplified representation of a membrane with: (i) a porous support, (ii) a separating functional separation layer;
[0267] Figure 2. Shows a simplified representation of a membrane with (i) a porous support, (iv) an intermediate porous catalytic layer, (ii) a functional separation layer and (iii) an upper porous catalytic catalytic activation layer;
[0268] Figure 3 . Shows a simplified representation of a membrane with:
[0269] - (i) a porous support,
[0270] - (v) a porous compositional buffer interlayer, (iv) a porous catalytic layer, (ii) a functional non-porous separation layer, and (iii) a catalytic activation top layer;
[0271] Figure 4. shows a diagram of a membrane in which the architecture and sequence between (i), (ii), (iii), (iv), (v) and (vi) are presented.
[0272] Figure 5. a) Representation of hydrogen separation through dense ceramic-based membranes with proton and carrier transport capacity electronics at high temperature. b) Representation of the separation of oxygen through dense membranes based on ceramics with the capacity to transport oxygen ions and electronic carriers at high temperature.
[0273] Figure 6. Scanning electron microscope image of a cross section of an oxygen permeable ceramic membrane having (i) a porous support, (iv) a porous catalytic layer, (ii) a non-porous functional separation layer.
[0274] Figure 7. Shows a scanning electron microscopy image of an oxygen-permeable ceramic membrane that presents components (i), (ii), (iii) and (iv), the last three layers being made up of a material composed of two crystalline phases, one that primarily conducts oxygen ions and another that conducts primarily electronic carriers.
[0275] Figure 8. Examples of functional layer design made with inkjet printing technology : a) Electrical conductive lines on ionic conductive matrix; b) Arrangement on a chessboard of different mixed conductors; cdef) Fractal arrangement of different mixed conductors.
[0277] Figure 9. Example of multilayer design with 3D pyramidal architecture.
[0279] Figure 10. Scanning electron microscope image of a cross section of an ionic oxygen-permeable ceramic membrane prepared using inkjet technology, in which a 3-stage degradation of the dense functional layer (ii) obtained by mixing two distinct crystalline phases.
[0281] Figure 11. Scanning electron microscope images of a cross section of an ionic oxygen-permeable ceramic membrane prepared using inkjet technology, in which a 3D pattern is observed in the location of the grains of two different crystalline phases (spinel and fluorite) along the axis parallel to the printing plane.
[0283] The present invention is illustrated by the following examples which are not intended to be limiting thereof.
[0285] Examples
[0287] Example 1 . Preparation of materials and inks
[0288] On a porous advanced ceramic (porous support (i) made of ytrium-doped zirconium oxide with PMMA pore former, which has undergone a heat treatment of 1000 ° C (2h), ramp 1 ° C / min), which acts as a support for the membrane and does not present catalytic activity, the inks T1 and T2 have been deposited, which originate the porous (iv) and dense (ii) layers after sintering, respectively. Both printable inks are obtained from the combination of three inks (A, B and C).
[0290] The liquid components used for inks A, B and C have been water and long chain glycol. As conditioning agents (dispersants, preservatives, binders, surfactants, etc.), a specific additive system has been used for water-based work, which has allowed to regulate the properties of the ink, facilitating its application in high thicknesses. (required for the application) without defects of adhesion to the substrate, cracks or formation of surface irregularities, achieving uniform and smooth layers on the ceramic support.
[0291] As examples of dispersants or a mixture thereof, there are on the market, produced and distributed by LUBRIZOL, such as Solsperse 13940, Solsperse 36000, Solsperse 32500, Solsperse 28000, Solsperse 19000, Solsperse 16000, Solsperse 39000 or their respective assigned co-dispersants, such as for example Solsperse 22000 and 5000.
[0293] Other additives: glycols such as diethylene glycol, glycerin, 1,4-butanediol, 1,4-cyclohexanedimethanol, 1,5-pentanediol, 1,6-hexanediol, polycarboxylic acids
[0295] Preservative: they can be antioxidants such as ascorbic acid.
[0297] Examples of binders: emulsified polymers such as butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, decyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate and polyglycols, triethanolamine, methylpyrrolidone, polyvinylpyrrolidone.
[0299] Conventional surfactants: anionic and / or nonionic emulsifiers such as, for example, alkali metal or ammonium salts of alkyl, aryl, alkylaryl sulfates, sulfonates or phosphates; alkyl sulfonic acids; sulfosuccinate salts; fatty acids; ethylenically unsaturated surfactant monomers, and ethoxylated alcohols or phenols.
[0301] Defoamers can be, for example, block copolymers based on ethylene and propylene oxide, e.g. Pluronic 127, Pluronic 123, Pluronic L61.
[0303] The composition of each of the inks A, B and C is as follows:
[0304] Ink A is composed of an organic solid with a high specific surface area, the composition being the following:
[0305] Table 1
[0306]
[0308] Glycols PEG 200 (polyethylene glycol 200), DEG 15-35 (diethylene glycol)
[0309] Dispersant: Acrylic polymer 2 - 20 Defoamer: Polymers and copolymers of 0.1-2
[0310] alkoxanes
[0311] Surfactant: Siloxane modified with polyether 0.05-2 Preservative: Isothiazolone derivatives solution 0.01-0.05
[0313] • Ink B has a high-density ceramic oxide composition, its composition being the following:
[0314] Table 2
[0318] Defoamer: Polymers and copolymers of 0.1-2
[0319] alkoxanes
[0320] Surfactant: Siloxane modified with 0.05-2
[0321] polyether
[0322] Preservative: Dissolution of derivatives of 0.01-0.05
[0323] Isothiazolones
[0325] • Finally, ink C has in its composition a pigment based on metallic oxides -electronic conductive crystalline phase- of low density, its composition being the following:
[0326] Table 3
[0327] Ink C
[0329] Pigment
[0330] Glycols PEG 200 15-35
[0331] (polyethylene glycol 200), DEG
[0332] (diethylene glycol)
[0333] Water 15-35
[0334] Dispersant: Polymer 1 - 20
[0335] acrylic
[0336] Defoamer: Polymers 0.1-2
[0337] and alkoxane copolymers
[0338] Surfactant: Siloxane 0.05-2
[0339] modified with polyether
[0340] Preservative 0.01-0.05 dissolution
[0341] Isothiazolone derivatives
[0343] Each of these inks has been prepared using a microbead mill of the kind commonly used in the manufacture of inkjet inks. To obtain the catalytic inks T1 and T2, the established amount of each of the preparations A, B and C has been dosed, in the percentages listed in Table 4, and an integration and homogenization process has been carried out ( for example, stirring and grinding with ceramic micro-balls).
[0345] Table 4. Percentage by weight of the preparations that make up the catalytic inks
[0350] Below, Table 5 specifies the approximate composition of both functional inks, as well as their main characteristics:
[0351] Table 5. Composition and properties of catalytic inks T1 and T2
[0354] Solid Content 25- 45% with respect to weight
[0355] total composition
[0357] Liquid Content 25-70%
[0365] Viscosity in Conditions of 13-18 cP
[0366] Shooting
[0368] Particle size 0.8 - 1.5 ^ m
[0372] Inkjet application of functional layers:
[0374] The prepared inks were deposited on flat supports made of advanced zirconium oxide ceramics doped with 3 molar% yttrium oxide that present high porosity (40%) and permeability to the passage of gases as a consequence of the combustion of the fugitive agent (microspheres PMMA) present in the formulation in a previous heat treatment at 1100 ° C.
[0375] These inks can be applied with different piezoelectric heads designed to withstand water as the main solvent, such as Dimatix 1024 M, L, HF, PQRL. Also the new print heads from Seiko and Kiocera are suitable for these inks. In this way it is possible to apply an amount of ink around 100 gr / m2 per head bar. Considering that nowadays both single pass machines and plotters can be installed up to 12 bars, it is possible to get an idea of the amount of ink that can be discharged.
[0376] Example 2. Deposition process (machinery, heads, deposition parameters, passes, etc)
[0378] First, the T1 ink was applied to the available ceramic substrate using an HF head from Dimatix. In total, 225 g / m2 were applied, for which it was necessary to make a total of 3 passes of 75 g / m2 each.
[0379] Next, a total of 375 g / m2 of the T2 ink was applied, for which it was necessary to make a total of 5 passes of 75 g / m2 each. After a drying process at 100 ° C, a thermal treatment is carried out at 1450 ° C, obtaining a sintered membrane, to which finally a deposition was made using the T1 ink (to obtain the catalytic layer (iii)) and after drying, sintering at 1100 ° C.
[0381] Example 3. Sample prepared in the same way as that described in example 2, but to which a 1M aqueous solution of Pr and Ce nitrate has infiltrated the porous substrate. The membrane obtained is in accordance with the present invention and has a porous support (i), a non-porous separation functional layer about 100 µm thick (ii) and an upper porous catalytic activation layer (iii), according to the scheme shown in Figure 2.
[0383] To evaluate the oxygen separation properties of the compounds under study, an experimental setup built in quartz is available in which to analyze the behavior of different ceramic membranes.
[0385] The quartz assembly consists of a tube with two chambers separated by a ceramic membrane, there being no communication point between the two chambers due to the density (absence of porosity) of the membrane and the sealing made with O-rings. On one side an oxygen-rich stream is fed, while on the other side a stripping gas is circulated or a vacuum is induced. This difference in oxygen content conditions serves as a driving force for oxygen diffusion from the feed-reject side to the permeate side to occur. By quantifying the oxygen content in the permeate stream using a gas chromatograph, the oxygen flux that permeates through the membrane is determined under different temperature conditions, oxygen content in the feed chamber and aggressive atmospheres in the permeate (presence CO2 and SO2).
[0387] Oxygen permeation was studied in the membrane described above. The permeation tests and the catalytic studies were carried out on membranes with the shape of 15 mm diameter disc and approximately 1 mm thick. The reaction temperature is controlled by a thermocouple close to the membrane. The permeate gas stream was analyzed using a Varian CP-4900 micro-CG equipped with three analysis modules: Molsieve5A, PoraPlot-Q and CP-Sil. Table 6 shows the oxygen permeation obtained in milliliters (normal conditions) per minute and square centimeter (Nml-min "1cm-2) as a function of temperature. The results show that the membrane according to the present invention has a much higher oxygen permeation than a membrane prepared by uniaxial pressing of the same composition as layer (ii) of the membrane prepared according to the present invention and sintered at 1450 ° C.
[0389] Table 6
[0391]

权利要求:
Claims (34)
[1]
1. A process for the manufacture of ceramic gas separation membranes comprising:
the deposition on a porous support (i); by means of the ink jet technique of at least one functional separation layer (ii) made up of at least two inks and
at least one heat treatment, which produces sintering of the layer.
[2]
2. A process according to claim 1, comprising at least the following steps:
(a) formed of a porous support (i); compatible with a functional separation layer,
(b) deposition on the support (i), by means of the ink jet technique of at least one functional separation layer (ii) made up of at least two inks and
(c) at least one heat treatment, leading to sintering,
wherein the separating functional layer (ii) is deposited in a way that gives rise to a surface:
- with gradients, or
- with patterns, or
- with combinations of both.
[3]
A process according to claim 1 or 2, characterized in that it further comprises a step of deposition of at least one porous catalytic activation layer (iii) on the functional separation layer (ii).
[4]
4. A process according to any one of the preceding claims, characterized in that it further comprises a stage in which a porous catalytic layer (iv) located between the porous support (i) and the separating functional layer (ii) is deposited.
[5]
5. A process according to any one of claims 1 to 4, characterized in that it further comprises a step in which a porous compositional damping interlayer (v) is deposited between the support (i) and the porous catalytic layer (iv ).
[6]
6. A process according to any one of claims 1 to 5, characterized in that it further comprises the deposition of an additional non-porous layer (vi) of protection between the functional separation layer (ii) and the porous catalytic activation layer (Ni).
[7]
A method according to one of claims 3 to 6, characterized in that it comprises applying one or more of:
- the porous catalytic activation layer (iii) when present
- the porous catalytic layer (iv) when present,
- the compositional damping porous interlayer (v) when present
- the additional non-porous layer (vi) when present,
It is deposited using a technique selected from dip coating, spin coating, roller coating or screen printing; physical vapor deposition, sputtering, electron beam., atomized; airbrushing; spraying of suspensions; and / or thermal spraying, including plasma spraying and pyrolysis spray; 3D printing, stereolithography, jetting, ink jet printing and combinations thereof, preferably ink jet.
[8]
A method according to one of the preceding claims, characterized in that the shaping of the porous support (i) is carried out by a technique selected from uniaxial or isostatic pressing, extrusion or calendering, tape casting, conventional casting, coating dip coating, spin coating, roller coating or screen printing, physical vapor deposition, sputtering, electron beam ,, spraying of suspensions, and / or thermal spraying, including plasma spraying and pyrolysis spray; 3D printing, stereolithography, injection, inkjet printing and combinations thereof.
[9]
9. A process according to any one of the preceding claims, characterized in that the porous support (i) comprises materials resistant to sintering temperatures and mechanically and chemically compatible with the materials of the separating functional layer (ii).
[10]
10. A process according to any one of the preceding claims, characterized in that the constituent materials of the porous support (i) are selected from magnesium oxide, aluminum and magnesium spinels, cerium oxide doped with at least one lanthanide metal, zirconium oxide doped with at least one of the following elements: Y, Mg, Sc or a lanthanide metal; titanium oxide, aluminum nitride, refractory alloys / superalloys, materials based on clays or aluminum silicates, magnesium silicate, iron, titanium or alkaline or alkaline earth elements, iron perovskites and combinations thereof.
[11]
11. A process according to any one of the preceding claims 1, 2, 9 or 10, characterized in that the porous support (i) has a porosity between 10 and 60% with respect to the total volume of the support, measured by the pore saturation method with liquid based on Archimedes' principle and a thickness between 0.1 and 2.5 mm.
[12]
12. A method according to claim 1 or 2, characterized in that the separating functional layer (ii) comprises inks that are composed of, at least:
(a) an inorganic solid,
(b) a liquid component, and
(c) a conditioning additive.
[13]
A method according to claim 12, characterized in that the functional separation layer (ii) is a non-porous layer.
[14]
A process according to claim 13, characterized in that the inorganic solids are selected from solids that result in a minimum ionic conductivity of the sintered functional layer (ii) of 1mS / cm and a minimum electronic conductivity is 5mS / cm at a temperature 850 ° C.
[15]
15. A process according to claim 14, characterized in that the inorganic solids are selected so as to obtain non-porous separation functional layers (ii) selected from conducting oxygen ion, conducting proton, conducting hydride anion, conducting carbonate ion , alkali metal conductors, nop type electronic conductors, and combinations thereof.
[16]
16. A process according to one of claims 14 or 15, characterized in that the inorganic solids (a) consist of a majority crystalline phase with a structure selected from fluorite, perovskite, spinel, pyrochlor and combinations thereof.
[17]
17. A method according to claim 12, characterized in that the functional separation layer (ii) is a porous layer.
[18]
18. A process according to claim 17 characterized in that the inorganic solid (a) is selected in such a way that porous functional layers (ii) are obtained selected from ceramic porous matrices with selectivity to H2, CO, O2, water, hydrocarbons and combinations of the The same, preferably, said inorganic solids are based on SiO2, TiO2, ZrO2, AhO3, SiC, Nb2O5, silico-aluminates (zeolites), MgO, carbon and combinations thereof.
[19]
19. A process according to any one of the preceding claims 1, 2, 12 or 13, characterized in that the functional separation layer (ii) has a thickness between 2 and 50 µm.
[20]
20. A method according to any one of the preceding claims, characterized in that the set of inks that give rise to layers (iii), (iv) and (v) is composed of, at least:
(a) an inorganic solid,
(b) a fugitive additive,
(c) a liquid component, and
(d) a conditioning additive;
where components (c) and (d) are always present in the formulation of each of the constituent inks, while components (a) and (b) can be present both at the same time or only one of them.
[21]
21. A process according to claim 20, characterized in that the fugitive additive (b) comprises materials selected from graphite, starch, PMMA, PVA, cellulose, PVB, nylon, ammonium bicarbonate and combinations thereof.
[22]
22. A process according to one of claims 20 or 21, characterized in that the particle size of the fugitive additive (b) is between 0.1 and 5.0. ^ M.
[23]
23. A process according to one of claims 20 to 22, characterized in that the fugitive additive (b) is removed with a heat treatment between 400 and 1100 ° C, with heating and cooling ramps between 3 and 15 ° C / min.
[24]
24. A process according to any one of the preceding claims, characterized in that the porosity of the layers (iii), (iv) and (v) is between 20 and 60% with respect to the total volume of the layer and the thickness of each layer between 5 and 100 ^ m.
[25]
25. A process according to any one of the preceding claims, characterized in that the set of inks that give rise to the additional non-porous layer (vi) comprises, at least:
a) an inorganic solid,
b) a liquid component and
c) a conditioning additive.
[26]
26. A process according to claim 25, characterized in that the inorganic solids (a) are selected such that the majority crystalline phase constituting the sintered layer has a structure selected from fluorite, perovskite, spinel, pyrochlor and combinations thereof.
[27]
27. A process according to claim 26, characterized in that the inorganic solids are selected from those that give rise to layers that conduct the oxygen ion, that conduct protons, that conduct the carbonate ion, that of alkali metals, that are electronic conductors of the nop type, non-oxidic ceramics or hydrogen permeable alloys and combinations thereof.
[28]
28. A process according to any one of the preceding claims, characterized in that the solid component of the inks is present in a percentage by weight between 20 and 55%, preferably between 25 and 45% with respect to the total weight of the ink.
[29]
29. A process according to any one of the preceding claims, characterized in that the liquid component of the inks for any one of the layers is selected from water, glycol, glycol-ether, aliphatic solvents and combinations thereof, in a percentage by weight between 15 and 80%, preferably between 25% and 70% with respect to the total ink.
[30]
30. A process according to any one of the preceding claims, characterized in that the ink conditioning additives, comprising dispersants, preservatives, binders, surfactants and / or combinations thereof, are present in a percentage by weight between 0.5 and 25%, preferably between 2 and 20% with respect to the total ink.
[31]
31. A process according to any one of the preceding claims, characterized in that each of the layers (ii), (iii), (iv), (v) and (vi) after sintering comprises at least 2 different inorganic crystalline phases, selected from fluorite, perovskite, spinel, pyrochlor and combinations thereof.
[32]
32. A method according to any one of the preceding claims, characterized in that it comprises generating a gradient or a pattern after an identical application or applications, in layers (ii), (iii), (iv) and (v) and (vi) after a heat treatment that has a distribution in the different crystalline phases and / or porosity selected between 2D chessboard, mosaic with interconnectivity of phases in section, fractal pattern, spiral pattern and combinations thereof.
[33]
33. A process for the manufacture of ceramic gas separation membranes, according to any of the preceding claims, characterized in that the gradient or pattern that is generated, after more than one application with a different pattern, in the layers (ii), (iii ), (iv) and (v) after a heat treatment is a gradient with 3D architectures selected from conic, pyramidal, spiral and combinations of them.
[34]
34. A ceramic membrane obtained by the process defined in any one of the preceding claims.

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