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    • 专利摘要:
    The invention relates to a monolithic element for tangential flow separation of a fluid medium to be treated comprising a rectilinear rigid porous support (2) of three-dimensional structure inside which is arranged at least one channel (3) for the circulation of the medium. fluid to be treated in order to recover a filtrate at the peripheral surface of the support. The porous rigid monolithic support (2) comprises, from the inner wall of the channel (s), obstacles (9) to the circulation of the fluid to be filtered, having an identity and continuity of material and porous texture with the support, these obstacles (9) hindering or disturbing the passage of the fluid, forcing their bypass, appearing between a first (P1) and second (P2) positions taken along the longitudinal axis of the channel.
    公开号:FR3024665A1
    申请号:FR1457745
    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 support is first produced in 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 to remedy posteriorly, such 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. 3affrin 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. It is also possible to cite the application 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 pin or the output matrix of the die being rotatably mounted and non-circular section. Again, this manufacturing technique is limited to certain types of imprints, namely 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.
    [0007] In this context, the present invention proposes to provide new filtration elements and a manufacturing technique adapted to their production, which have a single-channel or multichannel structure and a geometry adapted to reduce or eliminate clogging phenomena. The object of the invention is 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 separating element comprising a porous rigid rectilinear support of three-dimensional structure inside. which is arranged at least one channel for the circulation of the fluid medium to be treated in order to recover a filtrate on the outer surface of the support, the outer surface of the support having a constant profile.
    [0008] According to the invention, the monolithic rigid porous support comprises, from the inner wall of the channel (s), obstacles to the circulation of the fluid to be filtered, having an identity and continuity of material and porous texture with the support. these obstacles hindering or disturbing the passage of fluid, forcing their bypass, appearing between a first and second positions taken along the longitudinal axis of the channel. 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 obstacle of a channel generates a sudden narrowing or a convergent in the flow direction of the fluid to be treated in said channel; At least one obstacle of a channel generates a cross section that is locally narrower at the location of said obstacle, this cross section perpendicular to the longitudinal axis of said channel and having a different shape with respect to portions of the channel located downstream and upstream of said obstacle; 15 - between a portion of the canal situated upstream of the narrowest cross section and the narrowest cross section, one of the following criteria remains unchanged while the other criteria vary, the criteria being taken from shape, area, wet perimeter and hydraulic diameter; 20 - between a portion of the canal located upstream of the narrowest cross section and the narrowest crossing section, all the criteria taken from the following list remain invariable, namely the shape, the area, the wet perimeter and the hydraulic diameter; at least one obstacle of a channel has a straight passage section perpendicular to the longitudinal axis of said channel, this straight passage section rotating about the longitudinal axis of said channel, between two positions taken along this longitudinal axis of the channel; ; at least one obstacle in a channel has a straight passage section rotating about the longitudinal axis of said channel, discontinuously between the ends of said channel; The element comprises at least one separating layer continuously deposited on the inner walls of the channels and completely covering the obstacles; the porous support is made of an organic or inorganic material; the separating layers or even intermediate layers are made of an organic or inorganic material; the three-dimensional structure of the porous support has different layers that can be demonstrated by optical microscopy or scanning electron microscopy. Another object of the invention is to provide a method for producing the monolithic separation elements according to the invention. The method of manufacturing a tangential flow separation element according to the invention consists in producing the three-dimensional structure of the support 15 by forming superimposed elementary strata and successively bonded to each other so as to progressively increase the desired three-dimensional shape. In addition, the method according to the invention may further consist in combination of at least one and / or the following additional characteristics: - to realize 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 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, a portion of material made to create the elementary stratum, and simultaneous binding of the elementary stratum thus formed to the previous stratum; Producing solid continuous beds in the form of a powder or a liquid material such as photopolymerizable resins; - to realize 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; in that 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 for producing a hot melt. organic hot-melt polymer and inorganic ceramic powder, with a carrier of inorganic nature; to successively create strings of material by projecting a melted powder into the beam of a laser. The tangential flow separation elements obtained by the process defined in the context of the invention leads to a growth of the three-dimensional structure of the support. It should be noted that this structure 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 layers is as tenuous as possible. Various other characteristics appear from the description given below with reference to the accompanying drawings which show, by way of non-limiting examples, embodiments of the subject of the invention. Figure 1A is a longitudinal sectional view of a support illustrating an embodiment of an obstacle. Figures 1B and 1C are cross sections of the support taken respectively at the obstacle and upstream of the obstacle in consideration of the flow direction of the fluid. Figure 2 is a longitudinal section of a carrier showing an obstacle causing a sharp narrowing and a converging. Figures 3A and 3B are the cross-sections of a support taken respectively upstream and at the level of the obstacle, illustrating the variation of the passage section of a channel while its area does not vary. Figures 4A and 4B are the cross sections of a support 5 taken respectively upstream and at the obstacle, illustrating the variation of the passage section of a channel while the wet perimeter does not vary. Figures 5A and 5B are the cross-sections of a support taken respectively upstream and at the level of the obstacle, illustrating the variation of the passage section of a channel while the hydraulic diameter does not vary. Figures 6A and 6B are sectional views respectively longitudinal and transverse of a support illustrating the invariability of the shape of the passage section of the channel while its dimensions vary.
    [0009] Figures 7A and 7B are respectively longitudinal and transverse sectional views of a support illustrating the invariable character of the passage section of the channel with invariable dimensions. Figure 8 is a longitudinal partial sectional view of a support illustrating the rotation of a locally invariable passage section.
    [0010] 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 (analytic 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 the measurement of the average diameter of the particles. grains. In particular, reference will be made to the measurement technique of d50: - 150 13320: 2009, with regard to the laser granulometry measurement technique; - standard 150 14488: 2007, as regards the sampling techniques of the powder analyzed; 5 - to the standard ISO 14887: 2000, with regard to a reproducible dispersion of the powder sample in the liquid before measurement by laser granulometry. By mean 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 (analytic 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 mean 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: 1SO 15901-1: 2005 can be used for the mercury penetration measurement technique; - Standards 150 15901-2: 2006 and 150 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 monolithic or multichannel monolithic porous support whose geometry is selected to delimit, from the inner walls of the channels. , obstacles to the circulation of the fluid to be filtered. Such monolithic supports whose obstacles form an integral part of the monolithic porous structure 30 are produced by the additive techniques as will be explained in the following description.
    [0011] In the context of the invention, it is intended separation elements of a fluid medium by tangential filtration, commonly called filtration membranes. Such separating elements comprise a porous support in which one or more 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 entry zone for the fluid medium to be treated and their outlet is positioned at the other end of the support serving the role. output zone 10 for the retentate. In such separation 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.
    [0012] The porous texture of the support is opened and forms a network of interconnected pores, which allows the fluid filtered by the filter 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 45401 of December 1996.
    [0013] Permeate is, for its part, recovered on the peripheral surface 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.
    [0014] 3024665 12 FIG. 1 illustrates an example of such a tangential flow separation element 1 of tubular geometry in which a channel has 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 is described as rectilinear. The porous support 2 illustrated in FIG. 1 has a circular cross-section and thus has a cylindrical outer surface, but the cross-section may be arbitrary or 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 actual forming process. Thus, the outer surface 5 has no deformation or fingerprints. The porous support 2 is arranged to include at least one channel 3 and, in the example illustrated in FIG. 1, a channel 3 and, in the example illustrated in FIG. 2, two channels 3. Each channel 3 extends parallel to the axis A of the support along a longitudinal axis T which is advantageously confused with the axis A of the support in the case of a single channel support. 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 portion 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 a direction of circulation represented by the arrow f. In the illustrated example, the inlet zone 6 is located at one end of the tubular support and the exit zone 7 at the other end. The thicknesses of the filtration separator layers typically vary between 1 μm and 100 μm in thickness. Of course, to ensure its separation function, and serve as an active layer, the separating layers have an average pore diameter smaller than the average pore diameter of the support, most often the average pore diameter of the filtration separator layers. is at least a factor of 3, and preferably at least a factor of 5 relative to that of the support. The notions of microfiltration separation layer, ultrafiltration and nanofiltration are well known to those skilled in the art. art. It is generally accepted that the microfiltration separator 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.
    [0015] It is possible that this layer of micro or ultrafiltration, called the active layer, is deposited directly on the porous support (in the case of a monolayer separation layer), or on an intermediate layer with a mean pore diameter less than - even deposited directly on the porous support (case of a monolayer separation layer).
    [0016] The separating layer may, for example, be based on, or consist exclusively of, one or more metal oxides, carbides or nitrides or other ceramics; ceramics including all non-metallic inorganic materials. In particular, the separating layer will be based on or consisting exclusively of TiO 2, Al 2 O 3 and ZrO 2, alone or in admixture. The separation layer may also, for example, be based on, or consist exclusively of, a collodion of a polymer deposited on a porous support of organic nature. The separation layer may, for example, be based on, or consist exclusively of, a metal deposited on a porous support of a metallic nature. According to an essential characteristic of the invention, the support is shaped to comprise at least one and in a general manner a series of obstacles 9 starting from the internal walls 31 of the channels and which are capable of generating disturbances in the flow and shear forces of sufficient magnitude to reveal recirculations, thus limiting, or even completely avoiding, clogging phenomena. The obstacles 5 form an integral part of the monolithic porous support, that is to say that it results 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 material and porous texture between the obstacles 9 and the porous support 2. Thus, the obstacles 9 are mechanically and chemically solid of equal strength as the support. The obstacles 9 are entirely covered by the separating layer, so that they do not reduce, but instead increase the filtering surface of the separating element.
    [0017] The obstacles have the role of being in the path of the fluid circulating inside the channels. The obstacles 9 obstruct or disturb the passage of the fluid to be treated, forcing their bypass, appearing between a first position P1 and a second position P2 taken along the longitudinal axis T of the channel. Thus, the first position P1, as defined by the sectional view C-C of the channel (FIG.
    [0018] 1C), is taken immediately upstream of the obstacle 9 in the direction of the flow of the fluid to be treated illustrated by the arrow f while the second position P2, as defined by the sectional view B-B of the channel (Fig.
    [0019] 1B) is taken at the location of the obstacle 9, located downstream of the first position P1, according to the flow direction f of the fluid to be treated. The obstacles 9 thus cause increases in the speed of circulation of the liquid to the right of each of them, generating high wall shear stresses and turbulence zones where clogging phenomena are reduced or even eliminated. Obstacles play the role of promoters of turbulence.
    [0020] The obstacles 9 generally have a length L taken along the longitudinal axis A of the channel and a height h taken in a direction perpendicular to the longitudinal axis A and from the inner wall 31 of the channel. . In the example illustrated in FIG. 1, the channel 3 has the same diameter D upstream and downstream of the obstacle 9. The obstacles 9 may be present at regular or irregular intervals. The new 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 incorporating the obstacles 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. In general, it should be considered that an obstacle 9 generates a cross-sectional cross section that is locally modified in terms of its shape, its area, its wet perimeter or its hydraulic or locally offset diameter, or being rotated at the location of the channel 3 relative to portions of the channel located downstream and upstream of said obstacle, this cross section for the fluid being taken perpendicular to the longitudinal axis T of said channel. As is more particularly apparent from FIG. 2, an obstacle 9 generates, in the flow direction of the fluid in the channel represented by the arrow f, a sudden narrowing or a convergent as illustrated in the respectively up and down channels of FIG. 2. The sudden narrowing has a radial wall 9a which extends perpendicularly to the longitudinal axis T, from the inner wall of the channel. The convergent 25 has a wall 9a inclined with respect to the longitudinal axis T, at an angle a strictly greater than 0 ° and less than 90 °. Of course, this radial wall or inclined 9a can be connected to the inner wall of the channel with or without connecting fillet. Of course, the obstacles 9 may have very diversified geometries to hinder or disturb the passage of the fluid. The following examples describe various geometries of the obstacles 9 appearing between a portion of the channel located upstream of the smallest cross-section of the passage and the smallest cross-section of passage, corresponding respectively to a first position and a second position. Figs.
    [0021] 3A and 3B illustrate a first embodiment in which the shape of the passage section of the channel varies between the first and second positions while the area of the passage section remains invariable. At the first position, the channel has a square cross section of side a so that the area of this cross section is equal to a2 (Fig.
    [0022] 3A). At this position, the channel has a hydraulic diameter Dh D = 4A / P, with A the area of the passage section of the channel and P the wet perimeter of this passage section. According to this example, the area A is equal to a2 and the wet perimeter is equal to 4a so that the hydraulic diameter Dh = a. The channel has at the second position, a square obstacle 91 side a / 2 and a complementary obstacle 92 recessed (Fig.
    [0023] 3B). The area A of the crossing straight section at this second position is equal to A = a.2 '. (A / 2) 2+ (a / 2) 2 = a2. The area of the right section of the canal does not vary. On the other hand, the hydraulic diameter varies since it is equal to Dh = 4a2 / 6a = 2 / 3a, with the wet perimeter P = 6a which also varies.
    [0024] Figs.
    [0025] 4A and 4B illustrate a second embodiment in which the shape of the passage section of the channel varies while the wet perimeter P remains invariable, the hydraulic diameter Dh and the area A of the passage section of the channel being variable. According to this example, the channel 3 has at a first position illustrated in FIG.
    [0026] 4A, a square cross-section 3a, an area A equal to 9a2, a wet perimeter P = 12a and a hydraulic diameter Dh = 3a. The channel 3 has at the second position, an obstacle constituted by four portions 91 of square cross section a side placed at each corner of the channel section. (Fig.
    [0027] 4B). At this second position, the wet perimeter P is equal to 12a and does not change while the area A = 5 a2 varies as well as the hydraulic diameter Dh = 5 / 3a.
    [0028] Figs.
    [0029] 5A and 5B illustrate a third embodiment in which the shape of the passage section of the channel varies while the hydraulic diameter Dh does not vary, although the area A and the wet perimeter P of the channel section vary. According to this example, the channel has 5 at the first position illustrated in FIG.
    [0030] 5A, a square cross section of side a, an area A = a2, a wet perimeter P = 4a and a hydraulic diameter Dh = 4 a2 / 4a = a. The channel has at the second position (Fig.
    [0031] 5B), a circular cross section of radius r = a / 2, so that the area A = i r2 = Tra2 / 4, the wet perimeter P = rra and the hydraulic diameter Dh = rt a2hc a = a. Thus, the hydraulic diameter remains invariable while the shape of the section of the channel varies. It should be noted that between the first and second positions, the dimensions vary without rotation of the section and without eccentricity with respect to the central axis of the support, but it is clear that the section can be rotated and / or or an eccentricity with respect to the central axis of the support. Figs.
    [0032] 6A, 6B illustrate a fourth embodiment in which the shape of the channel section is invariable while the area, the wet perimeter and the hydraulic diameter of the channel section vary.
    [0033] The channel has in a first position Pl, a rectangular shape and in a second position P2, a reduced cross section of rectangular shape. It should be noted that between the first and second positions, the dimensions vary without rotation of the section and without eccentricity with respect to the central axis of the support, but it is clear that a rotation of the section and / or or an eccentricity with respect to the central axis of the support. In the foregoing examples, one of the criteria taken from the following list remains invariable while the other criteria vary, the criteria being taken from the form, the area, the wet perimeter and the hydraulic diameter. In the example illustrated in FIGS.
    [0034] 7A, 7B the shape of the passage section of the channel 3 remains invariable as well as the area, the wet perimeter and the hydraulic diameter of the passage section of the channel. The channel has in a first position Pi, a circular shape and a second position P2, a circular shape of the same size but offset from the passage section taken at the first position. The obstacle 9 is generated by the eccentricity of the circular passage section. Of course, the shape of the passage section may be any. It should be noted that the same function of generating an obstacle 9 can be obtained by rotating a non-circular passage section. This is the case, for example for a passage section of the channel 3 made in the form of an isosceles triangle whose shape remains invariable as well as the area, the wet perimeter and the hydraulic diameter of the passage section of the channel. . The channel thus has, in a first position, a triangular shape and in a second position, a triangular shape but angularly offset by a given value, for example equal to 900.
    [0035] FIG. 8 illustrates another embodiment in which the orientation of the obstacle 9 inside the channel 3 is involved. According to this example, the obstacle 9 has a cross-section perpendicular to the longitudinal axis T of the channel, this cross section running about the longitudinal axis T of the channel, between two positions P1, P2, taken according to FIG. this longitudinal axis T. This passage cross section rotates discontinuously between the ends of the channel, that is to say that the length of the obstacle is less than the length of the channel. For example, the obstacle 9 is in the form of at least one parietal helix so that helical sections appear between the inlet and the outlet of the channel.
    [0036] In the context of the invention, the manufacture 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 strata and successively bonded to each other so as to progressively increase the three-dimensional structure of the support. The method has the advantage, compared with prior art techniques, of producing the support in a single production step that does not require tooling or machining, and thus to allow access to a larger surface area. range of support geometries and makes it possible to vary the shapes and dimensions of the 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 successively consolidated stratum is relatively small to allow it to be bonded to the lower stratum, by application of the supply 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.
    [0037] It is the repetition of the binary sequence which makes it possible, stratum after stratum, to construct the desired three-dimensional shape. The consolidation pattern may vary from one layer to another. The growth of the desired three-dimensional shape is carried out along a selected 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 adjustment of various parameters specific to the technology chosen for consolidation allows 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 intergranular voids. 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 sweeping speed of the powder bed by the photon or electron beam or the degree of overlap of the impact surfaces of the energy beam during the formation of a layer.
    [0038] 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 or the recovery rate during each pass. The Applicant has also found that it is possible, by modulating the various parameters previously described, to adjust the pore size distribution and, for each given pore population, to control their number and their tortuosity. Once the powder is agglomerated in the selected areas, the unagglomerated 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. 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 have the objective of eliminating binders (debinding) and / or sintering. of the material itself. The temperature chosen for such a final sintering will depend on 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 formed stratum after stratum. For this, upstream, using a computer design software, the three-dimensional structure of the support or tangential flow separation element to achieve, 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 elementary strata bonded together, so as to progressively increase the desired three-dimensional shape.
    [0039] 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 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; or by successively creating strings of material formed following the fusion of an organic or inorganic powder projected in 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 of organic 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 a ceramic or metallic inorganic powder, the support is, after removal of the binder polymer and after sintering of the grains of the inorganic powder, of inorganic nature. 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 local energy supply 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 powder bed according to the pattern selected by CAD. The energy-material interaction then leads to either sintering or melting / solidification of the material, or to photo-polymerization or photo-crosslinking of the material, depending on its nature and that of the source of the material. energy used.
    [0040] The localized supply of liquid on a bed of powder can be done with microdroplets created using a piezoelectric system, possibly charged and directed in an electrostatic field. The liquid will be a binder or activator 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 techniques, on the one hand, a gain in terms of reliability and production rate, and on the other hand a great deal of variability in the choice of support shapes and shapes and reliefs that may be formed in the channel (s) within 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 Sinterinq) or SLM (English Selective Laser) Melting) 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 25 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 form in progress. A new bed of powder is then spread and the process starts again.
    [0041] 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 an 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 powder grains remains partial or in any case that each grain merges sufficiently to bond with its nearest neighbors without closing the porous texture. The machine settings 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 a guide, the conditions corresponding to the ranges presented in TABLE 1 below may be used TABLE 1 Min Average grain size of the ceramic powder Thickness of the powder bed Laser power Laser moving speed 10 μm 40 μm 100 W 0.5 m / s Max 100 μm 200 μm 1000 W 10 By locally adjusting the focusing of the laser beam and / or the beam displacement speed, it is possible to adjust the amount of energy received by the powder bed and thus to adjust the densification of the ceramic material obtained. and, because of this, 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 design of the support or the tangential flow separation element, by application of the laser, a final sintering step can be advantageously carried out, once the growth of the support or the 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 depend on 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.
    [0042] 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 10 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. As examples of binders, mention may be made of furanic resins, phenolic resins and other aminoplasts. The mass percentage of binder will be between 1 and 25% depending on its nature and the average diameter of the powder used. Subsequently, a binder activating agent is sprayed in the form of very fine droplets according to the selected pattern and locally causes agglomeration of the powder. The activating agent may be a solvent for the binder, which, after almost instantaneous drying, makes it possible to bond the inorganic particles together by sticking them together or traps them inside a solid network. It is also possible to deposit only an organic or ceramic, ceramic or metallic powder, 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. 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 head printing according to 3024665 25 parallel paths. It may be advantageous if there is an overlap of the impact surface of the drops between two successive parallel paths. After removal of the unagglomerated powder, the binder is removed during the sintering heat treatment, this debinding being terminated most often before 500 ° C. 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 between 25 and 100 mm / hour. LCM (Lithography-based Ceramic Manufacturinu) LCM is a technique for which the ceramic powder is premixed with a photopolymerizable resin, the consolidation by polymerization being obtained with a LED or LASER light source.
    [0043] 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 Modeling) The FDM is a technique using a thermofusible solid organic polymer to which an inorganic powder is optionally added.
    [0044] This technique aims at creating successive deposits of material cords 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. Unlike the previous techniques, there is no formation of a bed of prior material. Consolidation of strata or strings 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 Apparatus (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 carrier is formed 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 on the latter 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, a nitride, a carbide, or another ceramic material or a mixture thereof, the 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 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 slurry is then adjusted with organic additives to meet the hydrodynamic requirements for penetration into the media channels. Once deposited, the layer is dried and then sintered at a temperature that depends on its nature, the average size of its grains and the target cutoff threshold. In the case of SLS or SLM, the filtration separator layer (s) can be generated simultaneously with the growth of the support 30 or subsequently deposited according to conventional deposition methods used in membrane production. Here again, the filtration separator layer (s) may be deposited from suspensions of particles of the inorganic material to be deposited, or from 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 consolidates them and binds them 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.
    [0045] Tangential flow separation tubular elements, of the type shown in the figures, are manufactured according to the invention. The support is in the form of a tube 300 mm to 1200 mm long, the transverse cross section is circular, and has a diameter of 10 mm to 42 mm and in which one or more rectilinear channels 15 parallel to the tube axis are arranged. Example 1 SLS / support only Material 1 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 cover displacement velocity between two passes of the laser Final sintering temperature Bearing time at 1380 ° C 2 hours Titanium oxide Average pore diameter obtained 6-7 pm 3024665 28 Example 2: SLS / support + layer Material Titanium oxide Average grain size of the powder 20-22 pm Powder bed thickness 40 μm Focus (diameter of the laser beam at the point of impact with the powder) Room Atmosphere Laser power 50 μm Air 500 W Laser displacement speed% overlap between two passes Support Separating layer 5 m / s 1 m / s 20 - 25% of the laser Final sintering temperature Bearing time at 1380 ° C Average pore diameter obtained Example 3: SLS / medium only Material Average size of powder grains 1380 ° C 2 hours 6-7 pm 11.4-, 5 pm Silicon carbide 75-80 pm Thickness of the powder bed 120 pm Focusing (diameter of the laser seal at 100 pm point of impact with the powder) 1 Atmosphere of the chamber Argon Power of the laser 500 W Laser displacement speed, 2 m / s% overlap between two passages of the 30 - 35% laser Average pore diameter obtained In this case, no final sintering is possible necessary.
    [0046] EXAMPLE 4 3D Printing In the case of Examples 1, 3 and 4, the fabrication of the tangential flow separation element is completed by the deposition of a separating layer on the surface of the channels made from the following suspension. Preparation of the slurry by ball milling Material Average grain size of the powder Thickness of the powder bed Type of binder% of binder Furan resin 20% Linear construction speed of the form Final sintering temperature Duration of the bearing at 1500 ° C Average pore diameter obtained 30 mm / h 1500 ° C 6 hours 10-12 pm Material Average grain size of the powder before grinding Ratio Titanium oxide / water 0.4 Titanium oxide, 6 pm Grinding time 5 hours Size average grain size of the powder after grinding 1 μm Addition of water for rheology setting 200 to 400 centipoise A microfiltration separation layer having a cut-off point of 1.4 μm is obtained after a direct deposit on the support of the following way. 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 from the suspension by the porosity of the porous support. The thickness of the deposition of surface titanium oxide particles and thus the deposited mass per unit area depends on the residence time of the suspension in the support channels. Residence time of the suspension in the channels 50 seconds deposited mass 50 to 60 g / m The operation is repeated twice for a final deposited mass of about 110 g / m 2. Baking cycle for sintering of the layer rSpeed of temperature rise up to 1200 ° C 100 ° C / hour Duration of the bearing at 1200 ° C Cooling 10 The production of microfiltration tangential flow separation elements with thresholds of cuts below 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 slower 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.
    权利要求:
    Claims (18)
    [0001]
    CLAIMS1 - Monolithic tangential flow separation element of a fluid medium to be treated in a filtrate and a retentate, said separation element comprising a rectilinear rigid porous support (2) of three-dimensional structure within which is arranged at least one channel (3) for the circulation of the fluid medium to be treated in order to recover a filtrate on the outer surface (5) of the support, the outer surface (5) of the support having a constant profile, characterized in that the porous rigid monolithic support ( 2) comprises from the inner wall of the channel or channels, obstacles (9) to the flow of the fluid to be filtered, having an identity and continuity of material and porous texture with the support, these obstacles (9) annoying or disrupting the passage of the fluid, forcing their bypass, appearing between a first (P1) and second (P2) positions taken along the longitudinal axis (T) of the channel.
    [0002]
    2 - monolithic tangential flow separation element according to claim 1, characterized in that at least one obstacle (9) of a channel (3) generates a sudden narrowing or a convergent in the direction of flow of the fluid to be treated in said channel.
    [0003]
    3 - monolithic tangential flow separation element according to claims 1 or 2, characterized in that at least one obstacle (9) of a channel (3) generates a cross section of the local passage narrowest at the location of said obstacle, this crossing cross section being perpendicular to the longitudinal axis (T) of said channel and having a different shape with respect to portions of the channel located downstream and upstream of said obstacle.
    [0004]
    4 - monolithic tangential flow separation element according to claim 3, characterized in that between a portion of the channel (3) upstream of the narrowest cross section and the narrowest cross section, the one of the criteria in the following list remains invariable while the other criteria vary, the criteria being taken from the form, the area, the wet perimeter and the hydraulic diameter.
    [0005]
    5 - monolithic tangential flow separation element according to claim 3, characterized in that between a portion of the channel located upstream of the narrowest cross section of the narrowest passage section and all the criteria taken from the following list remain invariable namely the shape, the area, the wet perimeter and the hydraulic diameter.
    [0006]
    6 - tangential flow separation monolith element according to one of claims 1 to 5, characterized in that at least one obstacle (9) of a channel (3) has a straight passage section perpendicular to the axis longitudinal (T) of said channel, this straight passage section rotating about the longitudinal axis of said channel, between 2 positions taken along this longitudinal axis of the channel. 10
    [0007]
    7 - monolithic tangential flow separation element according to claim 6, characterized in that at least one obstacle (9) of a channel (3) has a straight passage section rotating about the longitudinal axis of said channel, discontinuously between the ends of said channel.
    [0008]
    8 - monolithic tangential flow separation element according to one of claims 1 to 7, characterized in that it comprises at least one separating layer (4) continuously deposited on the inner walls (31) of the channels (3) and completely covering the obstacles (9).
    [0009]
    9 - tangential flow separation monolith element according to one of claims 1 to 8, characterized in that the porous support (2) is made of an organic or inorganic material.
    [0010]
    10 - tangential flow separation monolith element according to one of claims 8 or 9, characterized in that the separating layers or intermediate layers are made of an organic or inorganic material. 25
    [0011]
    11 - monolithic tangential flow separation element according to one of claims 1 to 10, characterized in that the three-dimensional structure of the porous support (2) has different layers that can be demonstrated by optical microscopy or scanning electron microscopy.
    [0012]
    12 - A method of manufacturing a separation element (1) by tangential flow according to one of claims 1 to 11, wherein the three-dimensional structure of the support is formed by forming superimposed elementary layers and bound together successively , so as to progressively increase the desired three-dimensional shape.
    [0013]
    13 - Process according to claim 12, characterized in that it consists in producing the dimensional structure, by repetition of the following steps: 5 - production of a continuous bed of a material intended to form the porous support, the bed being constant thickness in 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 part of material produced to create the elementary stratum, and simultaneous binding of the elementary stratum thus formed to the preceding stratum.
    [0014]
    14 - Manufacturing process according to claim 13, characterized in that it consists in producing continuous beds of solid material in the form of a powder or of a liquid material such as photopolymerizable resins.
    [0015]
    15 - The manufacturing method according to one of claims 12 to 14, characterized in that it consists in producing a continuous bed of a solid material in the form of an organic or inorganic powder.
    [0016]
    16 - Manufacturing method according to claim 12, characterized in that it consists in producing a continuous bed of a medium in the form of a photopolymerizable liquid precursor in which has been disposed an inorganic powder.
    [0017]
    17 - Manufacturing method according to claim 12, 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 to produce an organic support and a organic layer, or a mixture of a thermofusible organic polymer and an inorganic ceramic powder, for producing a carrier of inorganic nature. 30
    [0018]
    18 - manufacturing method according to claim 12, 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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    PT3180111T|2021-05-06|
    PH12017500256A1|2017-07-03|
    CA2957159A1|2016-02-18|
    AU2015303084B2|2020-04-30|
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    RU2017107791A|2018-09-13|
    ES2865110T3|2021-10-15|
    EP3180111B1|2021-02-24|
    DK3180111T3|2021-05-17|
    PL3180111T3|2021-08-09|
    RU2693159C2|2019-07-01|
    MX2017001785A|2017-05-23|
    CN107155311B|2019-12-20|
    US10293307B2|2019-05-21|
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    JP6783226B2|2020-11-11|
    KR20170071476A|2017-06-23|
    BR112017002656A2|2017-12-12|
    CN107155311A|2017-09-12|
    US20170239622A1|2017-08-24|
    FR3024665B1|2020-05-08|
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    AU2015303084A1|2017-03-16|
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    法律状态:
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    优先权:
    申请号 | 申请日 | 专利标题
    FR1457745|2014-08-11|
    FR1457745A|FR3024665B1|2014-08-11|2014-08-11|TANGENTIAL FLOW SEPARATION ELEMENT INCLUDING TRAFFIC OBSTACLES AND MANUFACTURING METHOD|FR1457745A| FR3024665B1|2014-08-11|2014-08-11|TANGENTIAL FLOW SEPARATION ELEMENT INCLUDING TRAFFIC OBSTACLES AND MANUFACTURING METHOD|
    CN201580043489.3A| CN107155311B|2014-08-11|2015-07-21|Tangential flow separation element incorporating a flow barrier and method of manufacture|
    US15/502,267| US10293307B2|2014-08-11|2015-07-21|Tangential flow separator element incorporating flow obstacles, and method of fabrication|
    PCT/FR2015/052000| WO2016024058A1|2014-08-11|2015-07-21|Element intended for separation via tangential flow and having built-in flow obstacles, and manufacture method|
    BR112017002656-2A| BR112017002656B1|2014-08-11|2015-07-21|MONOLITHIC ELEMENT FOR SEPARATION BY TANGENTIAL FLOW AND MANUFACTURING PROCESS OF SUCH ELEMENT|
    HUE15753395A| HUE054157T2|2014-08-11|2015-07-21|Element intended for separation via tangential flow and having built-in flow obstacles, and manufacture method|
    PL15753395T| PL3180111T3|2014-08-11|2015-07-21|Element intended for separation via tangential flow and having built-in flow obstacles, and manufacture method|
    AU2015303084A| AU2015303084B2|2014-08-11|2015-07-21|A tangential flow separator element incorporating flow obstacles, and method of fabrication|
    ES15753395T| ES2865110T3|2014-08-11|2015-07-21|Separation element through tangential flow that integrates obstacles to circulation and manufacturing procedure|
    RU2017107791A| RU2693159C2|2014-08-11|2015-07-21|Element for tangential separation, containing built-in obstacles for flow, and method of its manufacturing|
    KR1020177006919A| KR20170071476A|2014-08-11|2015-07-21|A tangential flow separator element incorporating flow obstacles, and method of fabrication|
    JP2017507694A| JP6783226B2|2014-08-11|2015-07-21|Tangential flow separation element with built-in flow obstacle and its manufacturing method|
    PT157533951T| PT3180111T|2014-08-11|2015-07-21|Element intended for separation via tangential flow and having built-in flow obstacles, and manufacture method|
    MX2017001785A| MX2017001785A|2014-08-11|2015-07-21|Element intended for separation via tangential flow and having built-in flow obstacles, and manufacture method.|
    CA2957159A| CA2957159A1|2014-08-11|2015-07-21|Element intended for separation via tangential flow and having built-in flow obstacles, and manufacture method|
    DK15753395.1T| DK3180111T3|2014-08-11|2015-07-21|Element for separation, via tangential flow and with built-in flow barriers as well as manufacturing method|
    EP15753395.1A| EP3180111B1|2014-08-11|2015-07-21|Element intended for separation via tangential flow and having built-in flow obstacles, and manufacture method|
    PH12017500256A| PH12017500256A1|2014-08-11|2017-02-10|Element intended for separation via tangential flow and having built-in flow obstacles, and manufacturing method|
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