• 专利附录
  • 专利说明
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    • 专利摘要:
    The present invention relates to a tangential flow separation element of a fluid medium to be treated in a filtrate and a retentate, said separating element comprising a porous rigid monolithic support (2) of rectilinear structure, in which are arranged several channels (3 ) for the circulation of the fluid medium to be treated between an inlet (6) and an outlet (7) for the retentate, in order to recover a filtrate at the outer surface (5) of the support. According to the invention, the porous rigid monolithic support (2) delimits, from the internal walls (31) of said channels, obstacles (9) to the circulation of the fluid to be treated which have an identity and a continuity of material and texture porous with the support.
    公开号:FR3024664A1
    申请号:FR1457744
    申请日:2014-08-11
    公开日:2016-02-12
    发明作者:Jerome Anquetil
    申请人:Technologies Avancees et Membranes Industrielles SA；
    IPC主号:
    专利说明:

    [0001] The present invention relates to the technical field of tangential flow separation elements of a fluid medium to be treated into a filtrate and a retentate, commonly called filtration membranes. More specifically, the invention relates to novel geometries of porous multichannel support for reducing or even eliminating clogging problems, as well as a method of manufacturing by additive method of such supports and tangential flow separation elements comprising them. Separation processes using membranes are used in many sectors, particularly in the environment for the production of drinking water and the treatment of industrial effluents, in the chemical, petrochemical, pharmaceutical, food and beverage industries. biotechnology. A membrane constitutes a selective barrier and makes it possible, under the action of a transfer force, to pass or stop certain components of the medium to be treated. The passage or the stop of the components results from their size compared to the size of the pores of the membrane which then behaves like a filter. Depending on the pore size, these techniques are called microfiltration, ultrafiltration or nanofiltration. There are membranes of different structures and textures. The membranes are, in general, constituted by a porous support which provides the mechanical strength of the membrane and also gives the shape and thus determines the filtering surface of the membrane. On this support, one or more layers of a few microns thick ensuring the separation and said separating layers, filter layers, separation layers, or active layers, are deposited. During the separation, the transfer of the filtered fluid is through the separator layer, and then this fluid flows into the porous texture of the support to point toward the outer surface of the porous support. This part of the fluid to be treated having passed through the separation layer and the porous support is called permeate or filtrate and is recovered by a collection chamber surrounding the membrane. The other part is called retentate and is most often reinjected into the fluid to be treated upstream of the membrane, thanks to a circulation loop.
    [0002] In a conventional manner, the carrier is first made to the desired shape by extrusion, then sintered at a temperature and for a time sufficient to provide the required strength, while maintaining in the resulting ceramic the desired open and interconnected porous texture. . This process requires obtaining one or more rectilinear channels within which the at least one separating layer is then deposited and sintered. The supports are traditionally tubular and have one or more rectilinear channels arranged parallel to the central axis of the support. In general, the inner surface of the channels is smooth and has no irregularities. However, it has been found that filtration membranes made from supports having such geometries face clogging problems and thus have limited performance in terms of flow. Indeed, small particles and macromolecules can be adsorbed on the surface of the separator layer or deposited therein forming a gel or deposit, they can even penetrate the porosity and block certain pores. The principle of any tangential separation using filtration elements resides in a selective transfer whose efficiency is dependent on the selectivity of the membrane (the active layer) and the permeability (flux) of the filtration element considered. in its entirety (support + active layer). The selectivity and permeability are not only determined by the characteristics of the active layer and the filter element since they can be reduced or limited by the appearance of polarization of concentration, deposition and a blockage of the pores. The concentration polarization phenomenon operates during a filtration operation when the macromolecules present in the liquid to be treated concentrate at the membrane / solution interface where they exert an osmotic counterpressure opposite to the separation force or backscatter in the heart of the liquid to be treated according to Fick's law. The polarization concentration phenomenon results from the accumulation of the compounds retained in the vicinity of the membrane because of the permeation of the solvent. Deposition occurs during a filtration operation when the particle concentration on the surface of the membrane increases to cause the appearance of a condensed phase in the form of a gel or cohesive deposit inducing resistance. hydraulic additional to that of the membrane. The pore blockage occurs when intrusions of particles smaller than or equal to those of the pores occur, resulting in a reduction of the filter surface. Clogging, its reversibility or irreversibility, are complex phenomena that depend on the filter element and in particular the separating layers, the liquid to be treated and operating parameters.
    [0003] Clogging is a major impediment to the economic attractiveness of filtration because it leads, when sizing filtration plants, to increase the installed surface to meet the volume requirements to be treated on the one hand and it makes it necessary to implementation of specific technical means for post-erection remediation, such as cleaning cycles using detergents or periodic backflushing on the other hand. In the prior art, it has already been proposed to reduce the clogging phenomenon by creating a turbulent flow regime inside the channel of a filter element.
    [0004] First of all, it has been proposed to introduce in the tubular filter elements devices intended to create turbulence. In particular, see M.M. Krstic et al., Journal of Membrane Science 208 (2002) 303-314. These devices make it possible to improve the flow of permeate, and consequently the efficiency of the filtration, by limiting the clogging.
    [0005] However, the placement and fixation of these devices in the tubular elements is difficult and complex. In addition, they cause annoying vibrations that affect the reliability of the equipment.
    [0006] Other fairly complex systems have also been proposed by M.Y. Jaffrin in Journal of Membrane Science 324 (2008) 7-25 and use circular membranes and a central module that rotate relatively to create turbulence. However, this work has shown that the high shear rate obtained makes it possible to reduce clogging. Other solutions consist in modifying the geometry of the tubular element. Patent FR 2,503,615 describes cylindrical tubes for the filtration of gaseous mixtures introduced under pressure, the internal wall of which has imprints intended to create turbulences which prevent the accumulation of one of the gaseous phases on the wall of the tube and improve gas diffusion separation. These impressions are formed by passing the tubes out of the extrusion die, between rollers or tools that locally deform the tube over the entire thickness of its wall. Patent FR 2 503 616 describes a method of the same principle, consisting in deforming the wall of the tube at the outlet of the extrusion die by applying knobs arranged face to face on either side of the tube, or in alternating positions. In these two documents, after the prior extrusion step of the single-channel tube, a final shaping step is therefore carried out by plastic deformation for obtaining impressions inside the single channel by the pressure of a rotary punch or the like on the outer surface of the tube. Obtaining these "fingerprints" will be more or less easy depending on the ductility of the material, that is to say its ability to undergo a permanent deformation without breaking. However, pastas used for the manufacture of ceramic membranes do not have good ductility: they are easily shaped by extrusion but generally have an elongation at break of less than 5%. In addition, with such techniques only small impressions can be obtained. Finally, the deformations made over the entire thickness of the tube cause significant stresses in the material and the risk of cracking, which therefore greatly affects the mechanical strength.
    [0007] Another application is FR 2,736,843, which proposes porous tubes comprising a single channel whose walls include indentations, while the peripheral wall of the support is smooth. For this, the porous tube is shaped by means of an extrusion die which has a cylindrical pin disposed along its axis, the spindle or the output matrix of the die being rotatably mounted and non-circular section. Again, this manufacturing technique is limited to certain types of indentations, ie indentations which are continuous from one end to the other of the separating element and which can not cause any variation of the passage section. of the canal. In addition, it can not be transposed to the manufacture of separation element comprising a series of internal channels. However, multichannel separation elements are more and more sought after because they make it possible to increase the filtering surface and thus improve performance.
    [0008] In this context, the present invention proposes to provide new filtration elements and a manufacturing technique adapted to their production, which have a multichannel structure and a geometry adapted to reduce or eliminate clogging phenomena. It is an object of the invention to provide novel filter elements whose geometry can be modulated in a manner to create high wall shear stresses and intense turbulence within the channels without the disadvantages of prior solutions. . To achieve such an objective, the invention relates to a monolithic tangential flow separation element of a fluid medium to be treated in a filtrate and a retentate, said separation element comprising a porous rigid monolithic support of rectilinear structure, in which are arranged several channels for the circulation of the fluid medium to be treated between an inlet and an outlet for the retentate, in order to recover a filtrate at the outer surface of the support.
    [0009] According to the invention, the monolithic rigid porous support delimits, from the internal walls of said channels, obstacles to the circulation of the fluid to be treated which have an identity and continuity of material and porous texture with the support. In addition, the element according to the invention may additionally comprise in combination at least one and / or the following additional characteristics: at least one separating layer continuously deposited on the inner walls of the channels and coming to cover entirely the obstacles; the number, shape and dimensions of the obstacles are adapted to promote turbulent flows and to reveal shears and recirculations sufficient to reduce or even eliminate the deposits and clogging of the pores of the filter layer at the level of internal walls of the channels; the obstacles generate variations in the passage sections of the channels; The obstacles correspond to discontinuous reliefs arranged on the internal walls of the channels; the obstacles correspond to reliefs arranged on the inner walls of the channels, which extend continuously between the inlet and the outlet; The obstacles correspond to reliefs arranged on the internal walls of the channels, which extend continuously between the inlet and the outlet, and generate no variation of the passage sections of the channels; the obstacles have their contact surface for the fluid to be filtered situated towards the inlet which is inclined in the direction of circulation of the fluid to be treated; The obstacles have a greater height generate variations in the passage section of the channel if at least one of the following three criteria varies namely, the area of the cross section, the shape of the cross section, the dimensions of the right section of the canal; the porous support is made of an organic or inorganic material; a porous support and at least one separating layer continuously deposited on the inner walls of the channels and completely covering the obstacles, each consisting of a ceramic chosen from oxides, nitrides, carbides or other ceramic materials and mixtures thereof, and in particular, titanium oxide, alumina, zirconia or a mixture thereof, titanium nitride, aluminum nitride, boron nitride, silicon carbide optionally mixed with another ceramic material; the support has an average pore diameter in the range from 4 μm to 40 μm; the average pore diameter corresponds to the value d50 of the volume distribution, for which 50% of the total pore volume corresponds to the pore volume of diameter less than this d50; the volume distribution being obtained by mercury penetration, for example according to the technique described in standard 150 15901-1: 2005; the outer surface of the porous support has a constant profile.
    [0010] Another object of the invention is to provide a method for producing monolithic separation elements in accordance with the invention. The method of manufacturing a tangential flow separation element according to the invention in which the three-dimensional structure of the support is formed by forming superimposed elementary layers and bonded successively with each other, so as to progressively increase the desired three-dimensional shape. In addition, the element according to the invention may further consist in combination of at least one and / or the following additional features: - to achieve the dimensional structure, by repetition of the following steps: - realization of a continuous bed of a material for forming the porous support, the bed being of constant thickness along a surface greater than the section of said porous support taken at the level of the stratum; Localized consolidation, in a pattern determined for each stratum, of a portion of material made to create the elementary stratum, and simultaneous binding of the elementary stratum thus formed to the preceding stratum; - to achieve a continuous bed of a solid material in the form of an organic or inorganic powder; Forming a continuous bed of a medium in the form of a photopolymerizable liquid precursor in which an inorganic powder has been disposed; each stratum is produced by continuous or discontinuous melting of a wire of a hot melt solid precursor which is either a hot-melt organic polymer used alone to produce an organic support and an organic layer, or is a mixture of a hot-melt organic polymer and an inorganic ceramic powder, for producing a carrier of inorganic nature; to successively create strings of material by spraying a melted powder into the beam of a laser. The present invention also relates to tangential flow separation elements obtained by the method defined in the context of the invention. The fact that the growth of the three-dimensional structure of the support has been carried out in accordance with the invention can be demonstrated by the visualization of the different strata by optical microscopy or scanning electron microscopy. Of course, it will be sought that the demarcation between the different strata is as tenuous as possible. The description which follows, with reference to the appended figures, makes it possible to better understand the invention.
    [0011] Figure 1 is a perspective view of a separating element according to the invention comprising eight circulation channels for the fluid to be treated and provided with oblong or rice grain localized parietal barriers. Figure 2A is a perspective view of a separating element 30 according to the invention showing another embodiment of obstacles in the form of low walls arranged inside eight circulation channels for the fluid to be treated.
    [0012] Figure 2B is a longitudinal sectional view of the separating member illustrated in FIG.
    [0013] 2A. Figure 3 is a perspective view of a separating element according to the invention showing another embodiment of the obstacles in the form of sticks arranged within seven circulation channels for the fluid to be treated. Figure 4 is a perspective view of a separating element according to the invention showing another embodiment of the obstacles in the form of a continuous parietal propeller arranged within eight circulation channels for the fluid. treat. As a preliminary, some definitions of terms used in the context of the invention will be given. By mean grain size is meant the value d50 of a volume distribution for which 50% of the total volume of the grains corresponds to the volume of the grains of diameter less than this d50. The volume distribution is the curve (analytical function) representing the frequencies of grain volumes as a function of their diameter. The d50 corresponds to the median separating into two equal parts the area under the frequency curve obtained by particle size, by laser diffraction which is the reference technique used in the context of the invention for measuring the average diameter of the particles. grains. In particular, for the measurement technique of the d50, reference is made to: - ISO 13320: 2009, with regard to the laser granulometry measurement technique; 25 - 1SO 14488: 2007, with regard to sampling techniques for the powder analyzed; 150 14887: 2000, with regard to a reproducible dispersion of the powder sample in the liquid before measurement by laser granulometry.
    [0014] By average pore diameter is meant the value d50 of a volume distribution for which 50% of the total pore volume corresponds to the volume of pore diameter smaller than this d50. The volume distribution is the curve (analytical function) representing the frequencies of the pore volumes as a function of their diameter. The d50 corresponds to the median separating into two equal parts the area under the frequency curve obtained by mercury penetration, for average diameters of the order of a few nm or, in the case of a smaller pore diameter , by adsorption of gas, and especially N2, these two techniques being used as references in the context of the invention for measuring the average pore diameter. In particular, the techniques described in 150 - 15901-1: 2005 can be used for the mercury penetration measurement technique; - Standards 150 15901-2: 2006 and ISO 15901-3: 2007, for the gas adsorption measurement technique. The invention proposes tangential flow separation elements of a fluid medium to be treated into a filtrate and a retentate, which comprises a multi-channel monolithic porous support whose geometry is selected to delimit, from the internal walls of the channels, obstacles to the circulation of the fluid to be filtered. Such monolithic supports whose obstacles are an integral part of the monolithic porous structure can not be realized, either by the techniques proposed in the prior art for single-channel supports comprising turbulence promoters, or by the traditional extrusion technique used. for the manufacture of multichannel elements. In the context of the invention, it is proposed to produce such porous monolithic supports, or even the entire separation element (and thus including the separating layers), by additive technique. In the context of the invention, the aim is separation elements of a fluid medium by tangential filtration, commonly called filtration membranes. Such separating elements comprise a porous support in which different circulation channels for the fluid to be filtered are arranged. Conventionally, the support is of tubular form. These traffic channels have an entrance and an exit. In general, the inlet of the circulation channels is positioned at one of the ends, this end acting as an inlet zone for the fluid medium to be treated and their outlet is positioned at the other end of the playing support. the role of exit zone for the retentate.
    [0015] In such separating elements, the body constituting the support has a porous texture. This porous texture is characterized by the average pore diameter deduced from their distribution measured by mercury penetration porometry. The porous texture of the support is opened and forms an interconnected pore network, which allows the fluid filtered by the filtration separator layer to pass through the porous support and be recovered at the periphery. It is customary to measure the water permeability of the support to qualify the hydraulic resistance of the support. Indeed, in a porous medium, the stationary flow of an incompressible viscous fluid is governed by Darcy's law. The fluid velocity is proportional to the gradient of the pressure and inversely proportional to the dynamic viscosity of the fluid, via a characteristic parameter called permeability which can be measured, for example, according to the French standard NF X 45-101 of December 1996. The permeate is, for its part, recovered on the peripheral surface 20 of the porous support. The wall of the channels is continuously covered by, at least, a filtering separator layer which ensures the filtration of the fluid medium to be treated. The filter separating layers, by definition, must have an average pore diameter less than that of the support. The separating layers delimit the surface of the tangential flow separation element intended to be in contact with the fluid to be treated and on which the fluid to be treated will flow. Fig. 1 illustrates an example of such a tangential flow separation element 1 of tubular geometry in which a series of channels have been arranged, but many other forms could be constructed with the method according to the invention. The tangential flow separation element 1 comprises a porous support 2 made in an elongate shape extending along a central longitudinal axis A, which is why the structure of this porous support 3024664 12 is described as rectilinear. The porous support 2 illustrated in FIG. I has a circular cross section and thus has a peripheral or cylindrical outer surface, but the transverse cross section could be arbitrary or for example polygonal. According to one characteristic of the invention, the outer or peripheral surface 5 of the support has a constant profile. In other words, the outer surface 5 has no surface unevenness other than that caused by the intrinsic porosity of the material or that caused by a surface roughness inherent in the forming process proper. Thus, the outer surface 5 has no deformation or fingerprints. The porous support 2 is arranged to include a series of channels 3 which extend parallel to the axis A of the support. In the example illustrated in FIG. 1, these channels are eight in number. Of course, the number of channels 3 arranged in the porous support 2 may be different. Similarly, the cross section of the channels 3 may have various identical or different shapes. In the example illustrated in FIG. 1, seven peripherally disposed channels 3 have a triangular transverse cross section and a central channel 3 has a circular cross section 20. The channels 3 each have a surface covered by at least one separating layer 4 intended to be in contact with the fluid medium to be treated, circulating inside the channels 3. Part of the fluid medium passes through the separating layer 4 and the porous support 2, so that this treated part of the fluid, called permeate, flows through the outer surface 5 of the porous support. The fluid to be filtered flows between an inlet zone and an outlet zone. In the illustrated example, the inlet zone 6 is located at one end of the tubular support and the outlet zone 7 at the other end. The thicknesses of the filter separating layers typically vary from 1 to 100 μm in thickness. Of course, to ensure its separation function, and serve as an active layer, the separator layers have an average pore diameter less than the average pore diameter of the support. Most often, the average pore diameter of the filter separating layers is at least 3-fold less, and preferably at least 5-fold higher than that of the support. The notions of microfiltration separation layer, ultrafiltration and nanofiltration are well known to those skilled in the art. It is generally accepted that: the microfiltration separation layers have an average pore diameter of between 0.1 and 2 μm; the ultrafiltration separator layers have an average pore diameter of between 0.1 and 0.01 μm; the nanofiltration separation layers have an average pore diameter of between 0.5 and 2 nm. It is possible for this so-called active layer of micro or ultrafiltration layer to be deposited directly on the porous support (in the case of a monolayer separation layer), or on an intermediate layer with a smaller average pore diameter, itself. deposited directly on the porous support (in the case of a monolayer separation layer). The separation layer may, for example, be based on, or consist exclusively of, one or more metal oxide, carbide or nitride or other ceramics.
    [0016] In particular, the separation layer will be based on, or consist exclusively of, TiO 2, Al 2 O 3 and ZrO 2, alone or in admixture. According to an essential characteristic of the invention, the support is shaped to comprise a series of obstacles 9, starting from the internal walls 31 of the channels 3 which are capable of generating disturbances in the flow and amplitude shear forces. sufficient to reveal recirculations, thus limiting, or even completely avoiding, clogging phenomena. The obstacles 9 form an integral part of the monolithic porous support, that is to say that they result from the same geometry given to the porous support and are in no way added elements. The support and obstacles assembly forms a single porous monolithic, without connection, interface or joint of any kind. There is an identity and continuity of porous material and texture between the obstacles and the porous support. Thus, the obstacles 9 are mechanically and chemically solid of equal strength as the support 2. The obstacles 9 are entirely covered by the separating layer, so that they do not reduce, but rather increase, the filtering surface of the filter. separating element. The obstacles have the role of being in the path of the fluid flowing inside the channels 3. The obstacles 9 obstruct or disrupt the passage of the fluid to be treated, forcing their bypass, appearing between two positions taken along the axis longitudinal A of the channel. Obstacles 10 thus cause increases in the speed of circulation of the liquid to the right of each of them generating high wall shear stresses and areas of turbulence where clogging phenomena are reduced or even eliminated. Obstacles play the role of promoters of turbulence. The number, shape, and dimensions of the obstacles 9 are adapted to promote turbulent flows and reveal shears and recirculations sufficient to reduce or eliminate the deposits and clogging of the pores at the inner walls of the walls. canals. Preferably, in order to promote an adequate deposition of the separating layer on the obstacle 9, the latter will have a rounded shape. In particular, the obstacle will originate on the wall either perpendicular to the wall, or with a connection angle of less than 90 °, or thanks to connection fillers having radii of curvature between 0.1 times and 0.9 times the height of the obstacle 9.
    [0017] The obstacles 9 may be present at regular or irregular intervals. Two or more obstacles 9, when their morphology and size allow, may be present at the same cross section of the channel. The novel support geometries envisaged in the present invention have a repetition of one or more obstacles starting from the wall of each channel of which they are integral. In particular, the inner walls of the channels integrating the obstacles 9 may comprise reliefs such as hollows, bumps, grooves, striations and / or any other morphology capable of acting as obstacles acting as promoters of turbulence during the flow of fluid within said channels. According to an alternative embodiment, the obstacles 9 generate variations of the passage sections of the channels making it possible to increase the turbulences. In the context of the present invention, a passage section of a channel is defined as being the cross section of said channel taken perpendicularly to the longitudinal axis of the channel. This straight section of the channel is considered variable along its longitudinal axis if at least one of the following three criteria varies - area of the right section of the channel; - shape of the cross section of the canal; dimensions of the cross section of the canal.
    [0018] For example, the obstacles 9 generate a decrease in the area of the passage section of the channel 3, relative to the maximum passage section of between 1% and 50%. For example, the obstacles 9 have a height taken in a diametrical direction perpendicular to the longitudinal axis A which is greater than their width divided by two (the width being taken in the other diametrical direction perpendicular to the longitudinal axis A). 1 to 4 show examples of embodiments of obstacles 9 arranged in channels 3 made in a separating element 1. Of course, the number and the shape of the channels 3 are given by way of illustrative example but it is clear that the number and shape of the channels may be different from the illustrated examples In the example illustrated in Fig. 1, the obstacles 9 are protrusions projecting from the inner wall 31 of the support and having a half-ovoid or half-grain shape of rice The obstacles 9 are successively arranged in several rows of three in the illustrated example, extending parallel to the longitudinal axis Preferably, the obstacles 9 of the rows are offset along the longitudinal axis of the channel, so that the obstacles are not positioned opposite each other. Figs.
    [0019] 2A and 2B illustrate another alternative embodiment, in which each channel 3 of the support 2 comprises obstacles 9 extending radially from the inner wall 31 of the support, being distributed along the longitudinal axis A in accordance with a distribution determined. In the example illustrated in FIGS.
    [0020] 2A, 2B, the obstacles 9 are arranged along the longitudinal axis of the channel 3 in an alternation of 180 °. Of course, an alternation of different values, for example equal to 90 ° or 45 ° may be considered. Each obstacle 9 is made by a wall, wall or embossed, with a disc sector profile. Preferably, the height of the obstacle 9 is smaller than the half-diameter of the channel 3. In the example illustrated in FIG. 3, the support 2 comprises seven channels 15 in which obstacles 9 are made in the form of bars or rods extending diametrically inside the channels 3 from two parts of the wall located opposite . The obstacles 9 are arranged inside the channels 3 along the longitudinal axis of the channels, at regular intervals for example, being offset between them by a constant determined angular value. For example, the obstacles 9 are angularly offset from each other by a value equal to 90 °. Of course, the angular alternation between the obstacles 9 may have a different value. Similarly, the pitch between the obstacles 9 taken along the longitudinal axis of the channel may be variable.
    [0021] In the illustrated example, each bar 9 has a substantially constant cross section over most of its length and is connected to the inner wall 31 at each of its ends by a portion flaring to the inner wall . Of course, there may be provided an embodiment of the bars 30 which extend only a portion of the diameter being connected by a single end to the inner wall 31 of the support.
    [0022] In the same sense, these diametrical obstacles 9 can take different forms such as spherical, ovoid or oblong, for example. Fig. 4 illustrates another alternative embodiment of a support 2 with eight channels 3 of circular section, having in each channel, an obstacle 9 5 in the form of a helix arranged on the inner wall 31 of the support. For example, the obstacles 9 in the form of a helix are made continuously from one end to the other of the support or in a discontinuous manner so as to reveal sections in the form of a helix. It should be noted that it is possible to provide in each channel 3, several 10 continuous or discontinuous propellers, angularly offset between them. In the case where the obstacles 9 correspond to reliefs arranged on the inner walls of the channels, extending continuously between the inlet and the outlet of the support, these obstacles 9 do not generate any variation of the passage sections of the channels.
    [0023] In the various exemplary embodiments illustrated in the drawings, the obstacles 9 are arranged identically for all the channels 3. According to another variant embodiment, the obstacles 9 made in at least two channels 3 are different. Different obstacles 9 are different obstacles depending on their shape and / or size and / or number and / or orientation and / or distribution along the longitudinal axis. According to this variant embodiment, it may be envisaged to modulate in the channels the role of the turbulence promoters to allow, for example, to homogenize the stresses inside the support or to take into account the pressure difference occurring between the 25 channels in the event of circulation of the fluid in loop inside the support. In the context of the invention, the production of the porous support, or even of the tangential flow separation element in its entirety, is carried out by means of an additive technique. The method according to the invention consists in producing the three-dimensional structure of the support by forming superimposed elementary layers superimposed on each other so as to progressively increase the three-dimensional structure of the support.
    [0024] The method has the advantage, compared with prior art, of producing the support in a single production step that does not require tools or machining, and thus allows access to a wider range of products. support geometries and allows to vary the shapes and dimensions of obstacles in the channels. In the case of the use of a solid material such as a powder, the thickness of the powder bed and therefore of each layer successively consolidated is relatively small to allow its connection to the lower layer, by application of the contribution of energy or projection of the liquid. In particular, a thickness of 20 μm to 200 μm of powder will be deposited, this thickness being a function of the selected additive technique. It is the repetition of the binary sequence that allows, stratum after stratum, to build the desired three-dimensional shape. The reason for consolidation may vary from one stratum to another. The growth of the desired three-dimensional shape is carried out along a chosen growth axis. The particle size of the deposited powder is one of the factors which determines the minimum thickness of each powder bed, as well as the final average pore diameter obtained. In particular, a powder of the material intended to constitute the support, for example a metal oxide powder, or even a powder of one of its precursors, will be used. The deposited powder will have, for example, an average grain size of the order of 35 μm to obtain an average pore diameter in the ceramic support of the order of 10 μm. The Applicant has found that the adjustment of various parameters such as the choice of material and, for a given material, the average grain size of the powder used, and, for a given material and granularity, the thickness of the layer of powder repeated layer after layer on the one hand and the setting of various parameters specific to the technology chosen for consolidation allows the obtaining and control of a residual porous texture interconnected within the consolidated monolith. This residual porous texture is the result of controlled sintering of the powder grains leaving interleaved inter-granular voids.
    [0025] In the case of the use of a beam of energy, the main parameters, on which it is possible to act, are its focus, that is to say the beam diameter at the impact level. with the powder bed, the sweep rate of the powder bed by the photon or electron beam or the rate of overlap of the impact surfaces of the energy beam when forming a stratum. In the case of the use of a liquid projection, the main parameters on which it is possible to act are the weight of the drops, their frequency, the sweeping speed of the powder bed by the "jet" of drops. 10 or the recovery rate during each pass. The Applicant has also found that it is possible, by modulating the various parameters described above, to adjust the pore size distribution and, for each given pore population, to control their number and their tortuosity.
    [0026] Once the powder has been agglomerated in the selected areas, the non-agglomerated material is removed by any suitable technique. The initial fluidity of the powder used facilitates this operation. It is also possible to use waterjet techniques or vibrations to get rid of the last traces of powder remaining on the surface of the formed shape.
    [0027] The final consolidation of the filter element and the final state of the porous texture are, for the most part, obtained by one or more heat post-treatments which are intended to eliminate binders (debinding) and / or to sinter. of the material itself. The temperature chosen for such a final sintering will be a function of the nature of the inorganic material used and the average grain size of the powder used. The support, or even the tangential flow separation element in its entirety, is thus produced stratum after stratum. For this, upstream, using computer design software, the three-dimensional structure of the support or the tangential flow separation element to be produced is sliced. The three-dimensional virtual object to be produced is thus cut into two-dimensional slices of very thin thickness. These thin slices will then be made one by one in the form of superimposed and superposed elementary strata so as to progressively increase the desired three-dimensional shape. This three-dimensional structure is achieved: either by the repetition of the following steps: production of a bed of a solid material (organic or inorganic powder) or liquid (organic or liquid precursor in which is dispersed a powder which can be organic or inorganic) intended to form the porous support, the bed being of constant thickness along a surface greater than the section of said porous support taken at the level of the stratum; Localized consolidation, according to a pattern determined for each stratum, of a portion of material produced to create the elementary stratum, and simultaneous binding of the elementary stratum thus formed to the preceding stratum; or by the successive creation of cords of material formed following the fusion of an organic or inorganic powder projected into the beam of a laser according to the predetermined pattern for each stratum; or by continuous or discontinuous (drop) melting of a wire of a hot melt solid precursor. When the precursor is a hot-melt organic polymer used alone the support is organic in nature and immediately usable for the deposition of a layer of organic nature. When the precursor is a mixture of a hot-melt organic polymer and an inorganic ceramic or metallic powder, the support is, after removal of the binder polymer and after sintering of the grains of the inorganic powder, of inorganic nature.
    [0028] In general, in the first case, the material used is either solid or liquid and the consolidation of the elementary strata is carried out by a supply of energy or by spraying a liquid into fine droplets. The localized supply of energy can be done with a directed beam of light (LED or LASER) or a directed electron beam, or with any source of energy allowing its focusing and a scanning of the bed of powder according to the pattern selected by CAD. The energy-material interaction then leads to either a sintering or a melting / solidification of the material, or else to a photopolymerization or photo-crosslinking of the material, depending on its nature and that of the source of the material. energy used. The localized supply of liquid on a bed of powder can be done with microdroplets created using a piezoelectric system, possibly loaded and directed in an electrostatic field. The liquid will be a binder or an activating agent of the binder previously added to the ceramic powder. The use of an additive technique envisaged in the context of the invention makes it possible to obtain, in relation to prior art techniques, on the one hand, a gain in terms of reliability and production rate, and on the other hand a great variability in the choice of support shapes and shapes and reliefs that can be shaped in the channel or channels inside the support. Various additive techniques that can be used in the context of the invention for the design of the three-dimensional shape are detailed below: SLS (English Selective Laser Sintering) or SLM (Selective Laser English) Meltino) With this technique, a powder of the material intended to constitute the support or the tangential flow separation element, an organic powder or, preferably, a powder of an inorganic metal or ceramic material of the oxide, nitride type or carbide, or a powder of one of its precursors, is deposited to form a continuous bed. The beam of a powerful laser is then applied locally according to the selected pattern and makes it possible to agglomerate the powder to form the layer corresponding to the support or the separation element, by tangential flow and to bind it to the previous layer by sintering. . Under the effect of the localized energy supply, the grains of the powder partially fuse and weld together, which gives its cohesion to the stratum, thus achieving a pre-sintering of the shape in progress. A new bed of powder is then spread and the process starts again.
    [0029] The laser beam scans the surface of the powder so as to consolidate the material according to the desired pattern, stratum per stratum. This scanning can be performed by moving the laser along parallel paths. It may be advantageous if there is overlap of the impact surface of the laser between two successive parallel paths. The amount of energy received by the powder bed at the location of the impact of the laser beam must be such that the melting of the grains of powder remains partial or in any case that each grain merges sufficiently to bind with its more close neighbors without closing the porous texture.
    [0030] The settings of the machine will therefore depend, in particular, on the intrinsic characteristics of the powder bed and the nature of the material determining the efficiency of the photon / material interaction. As an indication, the conditions corresponding to the ranges presented in TABLE 1 below may be used TABLE 1 Min Max 100 μm 200 μm 1000 W 10 m / s Average grain size of the ceramic powder 10 μm Thickness of the powder bed 40 pm Laser power 100 w Laser displacement speed 0.5 m / s By locally adjusting the laser beam focus and / or the beam displacement speed, it is possible to adjust the amount of energy received by the laser beam. powder bed and thus adjust the densification of the ceramic material obtained and, therefore, its porous texture. It is thus possible to obtain, in some places, a porous texture corresponding to that desired for the filtration separator layer, and to others, that desired for the support. Although the sintering is carried out as and when the support or the tangential flow separation element is designed, by application of the laser, a final sintering step can be advantageously carried out, a 23 times the growth of the support or tangential flow separation element completed, in order to release the residual mechanical stresses and to homogenize the porous texture. The temperature chosen for such a final sintering will be a function of the nature of the inorganic material used and the average grain size of the powder used; for example, a temperature of 1300 ° C to 1500 ° C will be used in the case of titanium oxide. It should be noted that the selective melting of the powder described above can be obtained analogously by an electron beam corresponding to EBM (Electron Beam Melting) technique. 3D printing The principle remains the same, but in this case, the deposited layers may correspond to a mixture of organic or inorganic powder, ceramic or metallic, the material constituting the support, or even one of its precursors, with a binder itself in the form of a powder or coating the inorganic powder itself. Preferably, this mixture will be homogeneous and the powder particles of the material constituting the support, or even one of its precursors, and those of the binder will have similar sizes. By way of examples of binders, mention may be made of furanic, phenolic and other aminoplast resins. The mass percentage of binder will be between 1 and 25% depending on its nature and the average diameter of the powder used. Then, a binder activating agent is sprayed in the form of very fine droplets according to the selected pattern and causes local agglomeration of the powder. The activating agent may be a solvent for the binder, which, after almost instantaneous drying, allows the inorganic particles to be adhesively bonded to one another or trapped inside a solid network. It is also possible to deposit only an organic or inorganic powder, ceramic or metal, the material intended to constitute the support, or even a powder of one of its precursors, to form a continuous bed and then to locally spray a binder. which will then be a quick-drying liquid glue or a thermosetting liquid resin.
    [0031] The projection of binder or activating agent which is in liquid form is carried out according to any suitable device, in particular a piezoelectric system used in inkjet type printers with a scanning which can be achieved by moving the print head in parallel paths. It may be advantageous if there is an overlap of the impact surface of the drops between two successive parallel paths. After removing the unagglomerated powder, the binder is removed during the sintering heat treatment, this debinding being most often completed before 500 ° C.
    [0032] 3D printing makes it possible, with average grain sizes of the ceramic powder of between 30 and 100 μm, to produce thicknesses of the powder bed between 80 and 300 μm and to achieve linear construction speeds of the desired shape included. The LCM is a technique for which the ceramic powder is premixed with a photopolymerizable resin, the consolidation by polymerization being obtained with a source. LED light or LASER. As for the previously described techniques, it is necessary to remove the uncrosslinked powder before the thermal sintering cycle which allows debinding, that is to say the removal of the photopolymerizable resin and then the sintering itself. The use of LCM is limited by the fact that the powder grains must be transparent at the wavelengths considered for volume polymerization under and around the light impact. FDM (Fused Deposition Modelino) FDM is a technique using a thermofusible solid organic polymer to which an inorganic powder is optionally added. This technique aims to create successive deposits of material beads from a wire or ribbon. The bead of material is made by softening or continuous melting (extrusion) or discontinuous (drip) of the end of the wire or ribbon. In contrast to the preceding techniques, there is no formation of a bed of prior material. Consolidation of strata or cords of material is achieved by heating. According to an alternative to this technique, it can be expected to project an inorganic powder to ensure the successive creation of material cords, this powder projected into a beam of a laser merging before impact. Stereolithography Aobaratus SLA This technique, similar in principle to the above techniques, uses a liquid material such as a photocurable liquid precursor in which an inorganic powder is incorporated. The photon beam (LED or laser) scans the liquid layer and polymerizes it locally. In the case of 3D printing or LCM, the filtration separator layer (s) will be deposited once the support is constituted, after the final sintering operation. The deposition of a separating layer, in particular on the surface of the channels and obstacles in these channels of the support will consist in depositing thereon a suspension containing at least one sinterable composition intended, after firing, to constitute a filtering layer. Such a composition has a constitution conventionally used in the production of inorganic filtration membranes. This composition contains at least one oxide, nitride, carbide, or other ceramic material or a mixture thereof, with oxides, nitrides and metal carbides being preferred. The sinterable composition is suspended, for example, in water. To eliminate the risk of aggregates and to optimize the dispersion of the grains in the liquid, the suspension obtained is milled to destroy the aggregates and to obtain a composition composed essentially of elementary particles. The rheology of the suspension is then adjusted with organic additives to meet the hydrodynamic requirements of penetration into the channels of the supports. Once deposited, the layer is dried and then sintered at a temperature which depends on its nature, the average size of its grains and the target cut-off point.
    [0033] In the case of SLS or SLM, the filtration separator layer (s) can be generated simultaneously with the growth of the support or subsequently deposited according to conventional deposition methods used in membrane production. Again, the filtration separator layer or layers may be deposited from suspensions of particles of the inorganic material to be deposited, or one of its precursors. Such suspensions are conventionally used in the production of ceramic filtration elements. This or these layers are subjected after drying to a sintering operation which allows them to be consolidated and bonded to the surface on which they are deposited. The particle size of the particles present in the suspension will be a function of the desired porous texture ultimately for the filter separation layer. The examples below, illustrate the invention, but have no limiting character.
    [0034] Tangential flow separation tubular elements of the type shown in the Figures are manufactured in accordance with the invention. The support is in the form of a tube 300 mm to 1200 mm long, whose transverse cross section is circular, and has a diameter of 10 mm to 42 mm and in which several rectilinear channels parallel to the axis 20 of the tube are arranged. Exempt 1 SLS / support only Material Average grain size of the powder Thickness of the powder bed Focus (diameter of the laser beam at the point of impact with the powder) Chamber atmosphere Laser power Laser displacement speed% overlap between two passes of the laser Final sintering temperature Bearing time at 1380 ° C Average pore diameter obtained Titanium oxide 20-22 μm 40 μm 50 μm Air 500 W 2.5 m / s 20- 25% 1380 ° C 2 hours 6 Example 2: SIS / support + layer Material Titanium oxide Average grain size of the powder Thickness of the powder bed 20-22 μm 40 μm Focus (diameter of the laser beam 1 at the point of impact with the powder ) 50 pm Air Room Atmosphere Laser Power 500 W Laser Movement Speed Support Layer% overlap between two separator laser passes 1 m / s 20 - 25% 1380 ° C 2 hours Final sintering temperature Duration of step at 1380 ° C T1I 4-1 5 pm 6-7 pm Dia average pore meter obtained Silicon carbide Example 3: SILS / support only Material 75-80 pm 120 pm 100 pm 25-30 pm Average pore diameter obtained Average grain size of the powder Thickness of the powder bed Focusing (beam diameter laser at the point of impact with the powder) Chamber atmosphere Laser power Laser cover displacement velocity between two laser passes Argon 500 W 1.2 m / s 30 - 35% 5 In this case, no final sintering is not necessary.
    [0035] EXAMPLE 4 3D printing Average pore diameter obtained 10-12 μm In the case of Examples 1, 3 and 4, the production of the tangential flow separation element is completed by the deposition of a separating layer on the channel surface made from the following suspension. Preparation of suspension by ball milling Material 20% 30 mm / h Bearing time at 1500 ° C 6 hours Material Average grain size of the powder Thickness of the powder bed Binder type Titanium oxide-35 -40 pm 80 pm Furanic resin% binder Linear construction speed of the form Final sintering temperature 1500 ° C Titanium oxide Average grain size of the powder before grinding Ratio Titanium oxide / water Grinding time Average grain size powder after milling 3.6 pm 0.4 5 hours 1 pm Adding water for rheology setting 200 to 400 centipoise A microfiltration separator layer having a cut-off of 1.4 μm is obtained after a direct deposit on the rack in the following manner. The suspension is pumped into the channels to bring it into contact with the surface of the channels. The driving mechanism of the deposit is the attraction of the liquid of the suspension by the porosity of the porous support. The thickness of the deposition of titanium oxide particles at the surface and therefore the mass deposited per unit area depends on the residence time of the suspension in the channels of the support. Residence time of the suspension in the channels 1 deposited mass The operation is repeated twice for a final deposited mass of about 110 g / m 2. Baking cycle for sintering the layer 30 seconds 50 to 60 g / m2 100 ° C / hour 1 hour Heating rate up to 1200 ° C Duration of the stage at 1200 ° C Natural cooling 10 The manufacture of elements Microfiltration tangential flow separation with cutoff thresholds of less than 1.4 μm and separation elements, by tangential flow of ultrafiltration and nanofiltration will be obtained by successive deposition on such a first layer from thinner suspensions. with suitable thermal cycles. The invention is not limited to the examples described and shown because various modifications can be made without departing from its scope. 20
    权利要求:
    Claims (21)
    [0001]
    CLAIMS1 - Tangential flow separation element of a fluid medium to be treated in a filtrate and a retentate, said separating element comprising a porous rigid monolithic support (2) of rectilinear structure, in which are arranged several channels (3) for the flow of the fluid medium to be treated between an inlet (6) and an outlet (7) for the retentate, in order to recover a filtrate at the outer surface (5) of the support, characterized in that the porous rigid monolithic support ( 2) delimits, from the internal walls (3j) of said channels, obstacles (9) to the circulation of the fluid to be treated which have an identity and continuity of material and porous texture with the support.
    [0002]
    2 - tangential flow separation element according to claim 1, characterized in that it comprises at least one separating layer (4) continuously deposited on the inner walls (31) of the channels (3) and coming to completely cover the obstacles (9). ).
    [0003]
    3 - tangential flow separation element according to claim 1 or 2, characterized in that the number, shape and dimensions of the obstacles (9) are adapted to promote turbulent flows and show shears and recirculations sufficient to reduce or even eliminate the deposits and clogging of the pores of the filter layer at the inner walls of the channels.
    [0004]
    4 - Tangential flow separation element according to any one of claims 1 to 3, characterized in that the obstacles (9) generate variations of the passage sections of the channels.
    [0005]
    5 - Tangential flow separation element according to claim 3 or 4, characterized in that the obstacles (9) correspond to discontinuous reliefs arranged on the inner walls of the channels.
    [0006]
    6 - tangential flow separation element according to claim 3 or 5, characterized in that the obstacles (9) correspond to reliefs 30 arranged on the inner walls of the channels, which extend continuously between the inlet (6) ) and the output (7). 3024664 31
    [0007]
    7 - tangential flow separation element according to any one of claims 1 to 3, characterized in that the obstacles (9) correspond to reliefs arranged on the inner walls of the channels, which extend continuously between the input and output, and generate no variation of channel passage sections.
    [0008]
    8 - tangential flow separation element according to one of claims 1 to 7, characterized in that the obstacles (9) have their contact surface for the fluid to be filtered towards the inlet which is inclined in the direction of circulation fluid to be treated. 10
    [0009]
    9 - tangential flow separation element according to one of claims 1 to 6, characterized in that the obstacles (9) generate variations of the passage section of the channel if at least one of the following three criteria varies namely , the area of the cross section, the shape of the cross section, the dimensions of the cross section of the channel. 15
    [0010]
    10 - Tangential flow separation element according to one of claims 1 to 9, characterized in that the porous support (2) is made of an organic or inorganic material.
    [0011]
    11 - tangential flow separation element according to one of claims 1 to 10, characterized in that it comprises a porous support (2) 20 and at least one separating layer (4) continuously deposited on the inner walls (31) channels (3) which completely cover the obstacles, each consisting of a ceramic selected from oxides, nitrides, carbides or other ceramic materials and mixtures thereof, and in particular titanium oxide, of alumina, zirconia or a mixture thereof, titanium nitride, aluminum nitride, boron nitride, silicon carbide optionally mixed with another ceramic material.
    [0012]
    12 - tangential flow separation element according to one of claims 1 to 11, characterized in that the support has an average pore diameter in the range of 4 pm to 40 pm.
    [0013]
    13 - tangential flow separation element according to claim 12, characterized in that the average pore diameter corresponds to the value d50 of the volume distribution, for which 50% of the total volume of the pores 3024664 32 correspond to the volume of the pores of diameter less than this d50; the volume distribution being obtained by mercury penetration, for example according to the technique described in standard 150 15901-1: 2005.
    [0014]
    14 - tangential flow separation element according to one of claims 1 to 13, characterized in that the outer surface (5) of the porous support has a constant profile.
    [0015]
    Tangential flow separation element according to one of claims 1 to 14, characterized in that the obstacles (9) made in at least two channels are different. 10
    [0016]
    16 - A method of manufacturing a tangential flow separation element according to one of claims 1 to 15, wherein the three-dimensional structure of the support is formed by forming superimposed elementary strata and successively linked together, so as to grow gradually the desired three-dimensional shape. 15
    [0017]
    17 - Process according to claim 16, characterized in that it consists in carrying out the dimensional structure, by repetition of the following steps: - realization of a continuous bed of a material intended to form the porous support, the bed being of constant thickness in a surface greater than the section of said porous support taken at the level of the stratum; Localized consolidation, in a pattern determined for each stratum, of a portion of material produced to create the elementary stratum, and simultaneous binding of the elementary stratum thus formed to the preceding stratum.
    [0018]
    18 - Manufacturing process according to one of claims 16 to 17, characterized in that it consists in producing a continuous bed of a solid material in the form of an organic or inorganic powder.
    [0019]
    19 - Manufacturing process according to claim 16, characterized in that it consists in producing a continuous bed of a medium in the form of a photopolymerizable liquid precursor in which an inorganic powder has been disposed.
    [0020]
    20 - Manufacturing process according to claim 16, characterized in that each stratum is made by continuous or discontinuous fusion of a son of a hot melt solid precursor which is either a hot melt organic polymer used alone with an organic support and a organic layer, or a blend of a hot melt organic polymer and an inorganic ceramic powder, with a carrier of inorganic nature.
    [0021]
    21 - Manufacturing method according to claim 16, characterized in that it consists in successively creating strings of material by spraying a melted powder into the beam of a laser.
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    同族专利:
    公开号 | 公开日
    RU2017107769A3|2019-02-04|
    ES2860927T3|2021-10-05|
    HUE054244T2|2021-08-30|
    RU2017107769A|2018-09-13|
    JP6815989B2|2021-01-20|
    CN107155312A|2017-09-12|
    EP3180109B1|2021-02-24|
    PL3180109T3|2021-07-12|
    FR3024664B1|2020-05-08|
    CN107155312B|2021-03-23|
    JP2017532187A|2017-11-02|
    DK3180109T3|2021-05-17|
    PT3180109T|2021-04-20|
    US20170232393A1|2017-08-17|
    EP3180109A1|2017-06-21|
    RU2692723C2|2019-06-26|
    WO2016024056A1|2016-02-18|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    FR2503615A1|1978-11-27|1982-10-15|Commissariat Energie Atomique|METHOD FOR MANUFACTURING CERAMIC CYLINDRICAL TUBES HAVING LOCALIZED IMPRESSIONS AND DEVICE FOR CARRYING OUT SAID METHOD|
    GB2223690A|1988-10-17|1990-04-18|Roger Stanley White|Filter tubes|
    EP0813445A1|1995-03-10|1997-12-29|Isis Innovation Limited|Filter comprising one or more ducts|
    WO2012032325A1|2010-09-08|2012-03-15|Johnson Matthey Public Limited Company|Catalyst manufacturing method|
    WO2013144399A1|2012-03-30|2013-10-03|Asociación De Investigación De La Industria Del Juguete, Conexas Y Afines|Method for the production of monolithic carbonaceous or ceramic systems|
    EP2832708A1|2012-03-30|2015-02-04|Asociación De Investigación De La Industria Del Juguete, Conexas Y Afines|Method for the production of monolithic carbonaceous or ceramic systems|FR3060410A1|2016-12-21|2018-06-22|Technologies Avancees Et Membranes Industrielles|TANGENTIAL FLOW SEPARATION ELEMENT INTEGRATING FLEXIBLE CHANNELS|
    FR3088831A1|2018-11-27|2020-05-29|Technologies Avancees Et Membranes Industrielles|Manufacturing process by adding material of inorganic filtration media from a hot-melt filament and obtained membrane|
    FR3088832A1|2018-11-27|2020-05-29|Technologies Avancees Et Membranes Industrielles|Manufacturing process by adding material of inorganic filtration media and membrane obtained|FR2503616A1|1978-11-27|1982-10-15|Commissariat Energie Atomique|Ceramic tubes with irregular flow cross=section - produced by indentation of extruded tube|
    JPS6220601U|1985-07-23|1987-02-07|
    FR2736843B1|1995-07-19|1997-09-26|Centre Nat Rech Scient|POROUS IMPRESSION TUBE FOR TANGENTIAL FILTRATION|
    CN100393399C|2001-09-17|2008-06-11|日本碍子株式会社|DDR type zeolite membrane, and composite ddr type zeolite membrane, and method for preparation thereof|
    MXPA04002508A|2001-09-17|2004-05-31|Ngk Insulators Ltd|Method for preparing ddr type zeolite film, ddr type zeolite film, and composite ddr type zeolite film, and method for preparation thereof.|
    RU2287358C1|2005-06-08|2006-11-20|Николай Яковлевич ЗАЙЦЕВ|Separating filter element for cleaning and drying gases|
    GB0906751D0|2009-04-18|2009-06-03|Fairey Filtration Systems Ltd|Filter|
    EP2714354B1|2011-06-01|2019-04-17|BAM Bundesanstalt für Materialforschung und -prüfung|Method for producing a moulded body and device|
    KR101320467B1|2011-10-26|2013-10-22|주식회사 부강테크|Filtering Apparatus having Fixed-Type Chaos-Flow Inducer|FR3024665B1|2014-08-11|2020-05-08|Technologies Avancees Et Membranes Industrielles|TANGENTIAL FLOW SEPARATION ELEMENT INCLUDING TRAFFIC OBSTACLES AND MANUFACTURING METHOD|
    FR3024663B1|2014-08-11|2020-05-08|Technologies Avancees Et Membranes Industrielles|NOVEL GEOMETRIES OF TANGULAR FLOW SEPARATION SINGLE-CHANNEL TUBULAR ELEMENTS INCLUDING TURBULENCE PROMOTERS AND MANUFACTURING METHOD|
    US10089416B1|2015-03-12|2018-10-02|Stratasys, Inc.|Self-supporting internal passageways for powder metal additive manufacturing|
    WO2018235210A1|2017-06-21|2018-12-27|エム・テクニック株式会社|Filtration membrane module and filtration method|
    DE102018003063A1|2018-04-14|2019-10-17|Linde Aktiengesellschaft|Method for the generative production of a three-dimensional membrane-like component, and such a three-dimensional membran component|
    DE102020121547A1|2020-08-17|2022-02-17|InnoSpire Technologies GmbH|Monolithic ceramic membrane filters|
    WO2022038093A1|2020-08-17|2022-02-24|InnoSpire Technologies GmbH|Monolithic membrane filter|
    DE102020121549A1|2020-08-17|2022-02-17|InnoSpire Technologies GmbH|Monolithic membrane filter|
    法律状态:
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    优先权:
    申请号 | 申请日 | 专利标题
    FR1457744A|FR3024664B1|2014-08-11|2014-08-11|NOVEL GEOMETRIES OF TANGENTIAL FLOW SEPARATION MULTI-CHANNEL TUBULAR ELEMENTS INCLUDING TURBULENCE PROMOTERS AND MANUFACTURING METHOD|
    FR1457744|2014-08-11|FR1457744A| FR3024664B1|2014-08-11|2014-08-11|NOVEL GEOMETRIES OF TANGENTIAL FLOW SEPARATION MULTI-CHANNEL TUBULAR ELEMENTS INCLUDING TURBULENCE PROMOTERS AND MANUFACTURING METHOD|
    US15/502,547| US20170232393A1|2014-08-11|2015-07-21|Novel shapes for tangential flow seperation multichannel tubular elements incorporating turbulence promoters, and method of fabrication|
    JP2017507691A| JP6815989B2|2014-08-11|2015-07-21|New shape of multi-channel tubular element for tangential flow separation with built-in turbulence promoting means and its manufacturing method|
    HUE15753393A| HUE054244T2|2014-08-11|2015-07-21|Novel geometries of multichannel tubular elements intended for separation via tangential flow and having built-in turbulence promoters, and manufacturing method|
    ES15753393T| ES2860927T3|2014-08-11|2015-07-21|New geometries of tangential flow separation multichannel tubular elements that integrate turbulence promoters and manufacturing process|
    PT157533936T| PT3180109T|2014-08-11|2015-07-21|Novel geometries of multichannel tubular elements intended for separation via tangential flow and having built-in turbulence promoters, and manufacturing method|
    PCT/FR2015/051998| WO2016024056A1|2014-08-11|2015-07-21|Novel geometries of multichannel tubular elements intended for separation via tangential flow and having built-in turbulence promoters, and manufacturing method|
    RU2017107769A| RU2692723C2|2014-08-11|2015-07-21|Novel geometric shapes of multichannel tubular elements intended for tangential separation, having built-in turbulence amplifiers, and method of their production|
    DK15753393.6T| DK3180109T3|2014-08-11|2015-07-21|New geometries for multichannel tubular elements intended for separation via tangential flow and with built-in turbulence promoters and manufacturing method|
    CN201580043464.3A| CN107155312B|2014-08-11|2015-07-21|Shape and manufacturing method of a multichannel tubular element incorporating turbulence promoters for tangential flow separation|
    PL15753393T| PL3180109T3|2014-08-11|2015-07-21|Novel geometries of multichannel tubular elements intended for separation via tangential flow and having built-in turbulence promoters, and manufacturing method|
    EP15753393.6A| EP3180109B1|2014-08-11|2015-07-21|Novel geometries of multichannel tubular elements intended for separation via tangential flow and having built-in turbulence promoters, and manufacturing method|
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