EP3389833A1 - Filtre monolithique - Google Patents
Filtre monolithiqueInfo
- Publication number
- EP3389833A1 EP3389833A1 EP16825511.5A EP16825511A EP3389833A1 EP 3389833 A1 EP3389833 A1 EP 3389833A1 EP 16825511 A EP16825511 A EP 16825511A EP 3389833 A1 EP3389833 A1 EP 3389833A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- filter
- support
- channels
- filter according
- membrane
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 239000012528 membrane Substances 0.000 claims abstract description 63
- 238000001914 filtration Methods 0.000 claims abstract description 22
- 230000002093 peripheral effect Effects 0.000 claims abstract description 19
- 239000007788 liquid Substances 0.000 claims abstract description 18
- 229910010272 inorganic material Inorganic materials 0.000 claims abstract description 12
- 239000011147 inorganic material Substances 0.000 claims abstract description 12
- 238000011144 upstream manufacturing Methods 0.000 claims abstract description 11
- 230000035699 permeability Effects 0.000 claims abstract description 10
- 238000000605 extraction Methods 0.000 claims description 4
- 238000000746 purification Methods 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 3
- 239000003814 drug Substances 0.000 claims 1
- 239000011148 porous material Substances 0.000 description 32
- 239000002245 particle Substances 0.000 description 22
- 238000003754 machining Methods 0.000 description 19
- 238000000034 method Methods 0.000 description 18
- 229910010271 silicon carbide Inorganic materials 0.000 description 17
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 230000008021 deposition Effects 0.000 description 12
- 238000000151 deposition Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 8
- 239000000706 filtrate Substances 0.000 description 8
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 8
- 229910052753 mercury Inorganic materials 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 239000012530 fluid Substances 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 239000011230 binding agent Substances 0.000 description 6
- 238000009826 distribution Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 239000001913 cellulose Substances 0.000 description 4
- 229920002678 cellulose Polymers 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 238000010191 image analysis Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910003564 SiAlON Inorganic materials 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 238000010411 cooking Methods 0.000 description 2
- 230000001186 cumulative effect Effects 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052575 non-oxide ceramic Inorganic materials 0.000 description 2
- 239000012466 permeate Substances 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000001033 granulometry Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000007750 plasma spraying Methods 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 238000002459 porosimetry Methods 0.000 description 1
- 239000012465 retentate Substances 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000009718 spray deposition Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D63/00—Apparatus in general for separation processes using semi-permeable membranes
- B01D63/06—Tubular membrane modules
- B01D63/066—Tubular membrane modules with a porous block having membrane coated passages
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D63/00—Apparatus in general for separation processes using semi-permeable membranes
- B01D63/06—Tubular membrane modules
- B01D63/061—Manufacturing thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
- B01D71/0215—Silicon carbide; Silicon nitride; Silicon oxycarbide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2315/00—Details relating to the membrane module operation
- B01D2315/10—Cross-flow filtration
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/20—Specific permeability or cut-off range
Definitions
- the invention relates to the field of filtering structures made of inorganic material intended for the filtration of liquids, in particular structures coated with a membrane in order to separate particles or molecules from a liquid, more particularly from water, especially from production water from oil extraction or shale gas.
- Filters have long been known using ceramic or non-ceramic membranes to effect the filtration of various fluids, especially polluted water. These filters can operate according to the principle of frontal filtration, this technique involving the passage of the fluid to be treated through a filter medium, perpendicular to its surface. This technique is limited by the accumulation of particles and the formation of a cake on the surface of the filter medium, and gives rise to a rapid drop in performance and a decrease in the filtration level.
- the tangential filtration is used, which, on the contrary, makes it possible to limit the accumulation of particles, thanks to the longitudinal circulation of the fluid on the surface of the membrane.
- the particles remain in the flow of circulation whereas the liquid can cross the membrane under the effect of a pressure difference.
- This technique ensures a stable performance and level of filtration. It is more particularly recommended for the filtration of highly charged fluids particles and / or molecules.
- the strengths of tangential filtration are its ease of implementation, its reliability through the use of porosity membranes adapted to perform said filtration, and its continuous operation.
- the tangential filtration uses little or no adjuvant and provides two separate fluids that can be both valuable: the concentrate (also called retentate) and the filtrate (also called permeate): it is a clean process that respects the environment.
- These filters are made from monolithic structures or tubular supports made of a porous inorganic material formed of walls delimiting longitudinal channels parallel to the axis of said supports, through which the liquid to be filtered passes. The purified liquid of its particles or molecules is then discharged through the peripheral surface of the porous support.
- This membrane comprises, or even consists essentially of, a porous inorganic material, the nature and morphology of which are adapted to stop the molecules or particles insofar as their size is close to or greater than the median pore diameter of said membrane.
- US 4069157 discloses a multichannel structure whose surface, channel density and porosity of the support are optimized to increase the flow while minimizing the size of the filter.
- US 4781831, US 5855781, US 6077436, US Pat. EP 1457243, EP 1607129 In order to reduce the hydraulic resistance of the filter, it has been proposed to provide slits or evacuation channels according to different geometries (US 4781831, US 5855781, US 6077436, US Pat. EP 1457243, EP 1607129).
- the slots can be made by machining on the filter after cooking or during extrusion as is more particularly proposed by US 2001/0020756.
- the Applicant has noted that it was still possible to maximize the flow of filtrate on monolithic filtering structures comprising evacuation slots taking into account the physical characteristics of the support and the membrane to determine the geometry of the filter.
- the present invention proposes to choose a configuration of slots so as to respect an average distance of travel of the liquid to be filtered. through the support before being discharged in the form of filtrate, this mean distance of course being determined not only according to the geometric characteristics of the support but also according to the physical characteristics of the support and the membrane, in particular according to their permeability and the thickness of the membrane.
- the present invention relates to a monolithic membrane filter for the filtration of liquids, in particular tangential filtration, comprising: a support formed of a porous permeable inorganic material K s , said support having a generally tubular shape having a main axis, an upstream base, a downstream base, a peripheral surface and an internal part;
- At least one slot formed in the inner part of the support and opening on the peripheral surface of the support so that the filter has an outer surface formed by the peripheral surface of the support and the surface of said at least one slot;
- a is a coefficient within a range of 0.0008 to 0.0012
- 0 C is the average hydraulic diameter of the channels
- 0 f is the hydraulic diameter of the filter
- pi is the average thickness of the internal walls.
- the quantities are classically expressed in the units of the international system, namely in meters (m) for quantities D, t m , 0 C , pi and 0 f , and in square meters (m 2 ) for sizes K s and K m .
- the open porosity and the median pore diameter of the support according to the present invention are determined in known manner by mercury porosimetry.
- the porosity corresponding to the pore volume, is measured by mercury intrusion at 2000 bar using a mercury porosimeter such as the Autopore IV series 9500 Micromeritics porosimeter, on a 1 cm 3 sample taken from a block of support, the skin-excluding sample region typically extending up to 500 microns from the block surface.
- the applicable standard is ISO 15901-1.2005 part 1.
- the increase in pressure up to high pressure leads to "push" the mercury into pores of smaller and smaller size.
- the intrusion of mercury is conventionally done in two stages.
- a mercury intrusion is carried out at low pressure up to 44 psia (about 3 bar), using air pressure to introduce mercury into the larger pores (> 4 ⁇ ).
- a high-pressure intrusion is carried out with oil up to the maximum pressure of 30000 psia (about 2000 bar).
- a mercury porosimeter thus makes it possible to establish a pore size distribution by volume.
- the median pore diameter of the support corresponds to the threshold of 50% of the population by volume.
- the porosity of the membrane, corresponding to the total pore volume in the membrane, and the median pore diameter of the membrane are advantageously determined according to the invention using a scanning electron microscope.
- the porosity obtained for the membrane by this method can be likened to open porosity.
- sections of a wall of the support are made in cross section so as to visualize the entire thickness of the coating over a cumulative length of at least 1.5 cm.
- the acquisition of the images is performed on a sample of at least 50 grains, preferably at least 100 grains.
- the area and the equivalent diameter of each of the pores are obtained from the images by conventional image analysis techniques, possibly after a binarization of the image to increase the contrast.
- a distribution of equivalent diameters is thus deduced, from which the median diameter of pores is extracted.
- the porosity of the membrane is obtained by integrating the distribution curve of equivalent pore diameters.
- this method can be used to determine a median size of the particles constituting the membrane layer.
- An example of determination of the median pore diameter or the median size of the particles constituting the membrane layer comprises the succession of the following steps, conventional in the field:
- a series of SEM images is taken from the support with its observed membrane layer in a cross-section (i.e. throughout the thickness of a wall). For more clarity, the pictures are taken on a polished section of the material. The acquisition of the image is performed over a cumulative length of the membrane layer at least equal to 1.5 cm, in order to obtain values representative of the entire sample.
- the images are preferably subjected to binarization techniques, well known in image processing techniques, to increase the contrast of the particle or pore contour.
- a measurement of its area is carried out.
- An equivalent diameter of pore or grain is determined, corresponding to the diameter of a perfect disk of the same area as that measured for said particle or for said pore (this operation may possibly be performed using a dedicated software including Visilog® marketed by Noesis).
- a size distribution of particles or grains or pore diameter is thus obtained according to a conventional distribution curve and a median particle size and / or a median pore diameter constituting the membrane layer are thus determined, this median size or median diameter respectively corresponding to the equivalent diameter dividing said distribution into a first population comprising only particles or pores of equivalent diameter greater than or equal to this median size and a second population comprising particles of equivalent diameter less than this median size or this median diameter.
- the hydraulic diameter of the filter or of a channel is conventionally defined by the formula 4 * S / P, S being the area of the overall section (that is to say without taking into account locally the the loss of section related to the area of the slot or walls) of the filter perpendicular to the main axis, or the area of the channel section perpendicular to the main axis, and P being the perimeter of this section.
- the shape of the support defines the general shape of the filter. It has an elongate tubular shape along a major axis and includes an upstream base, a downstream base, a peripheral surface, and an inner portion.
- the upstream and downstream bases can be of varied shape, for example square, hexagonal or circular. They are preferably circular.
- the downstream base is intended to be positioned on the side of the incoming liquid flow (liquid to be filtered) and the upstream base opposite the flow of incoming liquid.
- the support typically has a hydraulic diameter f 0 of 50 to 300 mm, preferably 80-230 mm, and a length of 200 to 1500 mm.
- the support is formed of a porous inorganic material, in particular a non-oxide ceramic material, such as SiC, in particular recrystallized SiC, SiO 3 N 4 , SiO 2 ON 2 , SiAlON, BN or a combination thereof.
- Its porosity is typically from 20 to 70%, preferably from 40 to 50%, and the median pore diameter from 5 nm to 50 ⁇ m, preferably from 100 nm to 40 ⁇ m, more preferably from 5 to 30 ⁇ m.
- Permeability K s support is preferably between 1.0x10 "15 and 1.0x10" 12, preferably between 6,9.10 "15 and 3,4.10" n m 2.
- a plurality of channels parallel to the main axis of the support is formed in the inner portion of the support.
- These channels also called filter channels, are preferably not plugged at their ends and open on each of the bases of the support.
- the shape of the channels is not limited and they may have a polygonal section, in particular pentagonal or hexagonal or square, or circular but preferably have a circular or square section.
- the average hydraulic diameter of the channels 0 C is generally 1 to 5 mm, preferably 2 to 4 mm.
- the filter can include several categories of channels.
- a category of channels is defined by a set of channels having the same shape and a hydraulic diameter identical to +/- 5%.
- the filter may comprise a first category of channels consisting of channels located near the peripheral surface of the filter and a second category consisting of channels located in the center of the filter, the channels of the first category having a hydraulic diameter greater than those of the second category.
- the filter comprises only one category of channels.
- the channels are separated from each other by internal walls formed by the porous inorganic material of the support.
- the average thickness of the internal walls p is typically 0.3 to 2 mm, preferably 0.4 to 1.2 mm.
- the filter also includes a membrane covering the inner surface of the channels. It is formed of a porous inorganic material, in particular a non-oxide ceramic material, such as SiC, in particular recrystallized SiC, SiO 3 N 4 , SiO 2 ON 2 , SiAlON, BN or a combination thereof. Its porosity is typically 10 to 70% and the median pore diameter 10 nm to 5 ⁇ .
- the permeability of the membrane K m is preferably from 10 -19 to 10 -14 m 2 . It typically has an average thickness t m from 0.1 to 300 ⁇ , preferably from 1 to 200 ⁇ , more preferably from 10 to 80 ⁇ .
- the ratio K s * m / K m is in general 0.01 to 100, preferably 0.1 to 10, more preferably 0.1 to 5.
- the filter according to the invention comprises at least one slot formed in the inner part of the filter and opening on the peripheral surface.
- the outer surface of the filter is formed on the one hand by the surface of said at least one slot, and on the other hand by the peripheral surface of the support.
- slot in the sense of the present invention, the space formed on the one hand by a cavity, created by machining the support or formed during the shaping of the support in place of a portion of the channels in the inner part of the support, and opening on the peripheral surface of the support; and secondly by the channels directly connected to this cavity, that is to say that are not separated from the cavity by an inner wall of the support.
- the channels connected directly to the cavities of the slots also called evacuation channels as opposed to the filter channels described above, contribute to improving the evacuation of the filtrate by draining it to the cavities opening out of the filter.
- the evacuation channels In order to preserve the filtration capacity of the filter, the evacuation channels must of course be plugged on each of the bases of the support.
- the slots make it possible to facilitate extraction and evacuation of the filtrate at the periphery of the filter by decreasing the hydraulic resistance of the filter.
- the shape of the cavities which determines the shape of the slits, is in theory not limited. However, for manufacturing constraints and / or mechanical strength, the cavities are preferably rectilinear.
- a rectilinear cavity is defined as a cavity in a plane parallel to the main axis, preferably substantially parallelepipedal, the length of which extends parallel to the main axis, the depth and width extending perpendicular to the main axis .
- the width of a cavity preferably corresponds to the width of a fixed number of channels, preferably to the width of a channel, for example 0.5 and 5 mm, or even 1 to 3 mm.
- the length of a cavity is obviously at most equal to the length of the filter. To maintain good mechanical strength, however, the length of a cavity is preferably between 1 and 20% of the length of the filter, for example from 1 to 20 cm, or even 3 to 15 cm.
- the depth of the cavity is obviously at most equal to the width of the filter in the plane, parallel to the main axis, of the cavity in question.
- a cavity may in particular be through, that is to say open at both ends in the direction of the depth on the peripheral surface of the support. This configuration has the advantage of maximizing the evacuation surface provided by the cavity.
- a cavity may also be blind, or non-through, that is to say, opening at only one of its ends in the direction of the depth on the peripheral surface of the support.
- the depth of the cavity is preferably 25 to 40% of the width of the filter in the plane, parallel to the main axis, of the cavity in question.
- at least one cavity is blind.
- all the cavities are blind. This configuration maximizes the mechanical strength of the filter while maintaining a maximum of filter channels and a sufficient evacuation surface.
- the number of slots and their configurations are determined so as to obtain an average distance of course D satisfying the relation (1) defined above, in which the coefficient a is equal to 0.0008 to 0.0012, preferably 0, 0009 to 0.0011, ideally about 0.001.
- the minimum distance d between the center of each channel and the outer surface of the filter is preferably such that the ratio ⁇ / D is less than 0.65, or even less than 0.6 or even less than 0.55.
- D is the average distance of travel as defined above
- ⁇ is F standard deviation of the distances d relative to the average distance of travel D.
- the filter generally comprises a plurality of slots.
- the slots are generally distributed relatively homogeneously in the inner part of the filter, for example so that the distances between each of the slots and its direct neighbors are as constant as possible.
- the slots are preferably each disposed in a plane parallel to the main axis.
- They may be arranged radially, that is to say all being arranged in a plane parallel to the main axis and passing through it. They can also be arranged in planes parallel to each other and to the main axis and preferably equidistant from each other. It is understood that, for a given filter, a plurality of slot configurations may make it possible to obtain the same average distance of path D according to the invention.
- FIG. 1 illustrates a filter comprising a support 1 of cylindrical shape having a main axis (X), an upstream base 2 and a downstream base 3.
- a plurality of channels parallel to the main axis (X) are formed in the inner part of the support and separated from each other by internal walls, comprising filtering channels 4 and discharge channels 5.
- the filter channels 4, opening on each of the upstream 2 and downstream 3 bases, are covered on their inner surface by a membrane (not shown).
- the evacuation channels 5 are plugged at the level of the upstream base 2 and the downstream base 3.
- the filter also comprises two through cavities 6a and 6b perpendicular to each other and positioned at different levels along the filter.
- the average distance of travel D is the arithmetic mean of the set of minimum distances d, between each filtering channel c; and the outer surface of the filter.
- the distance d is measured for each filter channel c; by considering a plane section perpendicular to the main axis on which are reported, by projection, all the slots.
- the slots extending over the entire length of the filter (either in the form of cavity or in the form of evacuation channels), the minimum distance d for a given filter channel will be the same whatever the section plan considered. For example, considering the filter shown in FIG. 1, FIGS.
- FIGS. 2A and 2B respectively represent sections of the filter at the plane sections A and B perpendicular to the main axis (X) shown in dashed lines in FIG. 1.
- the recessed portions represent the cavities 6a and 6b and the hatched portions represent the discharge channels 5a, connected to the cavity 6a, and 5b, connected to the cavity 6b.
- the outer surface of the filter as defined in the present invention is shown in thick lines in FIGS. 2A and 2B and comprises on the one hand the peripheral surface of the support, and on the other hand the surface of the slots, that is to say the internal surfaces of the cavities and evacuation channels.
- the filter according to the invention can be obtained by any technique well known to those skilled in the art.
- a typical manufacturing process generally comprises the following main steps:
- the support is preferably obtained by extruding a paste through a die and followed by drying and baking to sinter the support material and obtain the porosity and mechanical strength characteristics necessary for the support. application.
- a recrystallized SiC support it may in particular be obtained according to the following manufacturing steps:
- the mixture also comprises an organic binder of the cellulose derivative type. Water is added and kneaded to obtain a homogeneous paste whose plasticity allows extrusion, the die being configured to obtain the monoliths according to the invention.
- the filter support is then coated with a membrane.
- the membrane may be deposited according to various techniques known to those skilled in the art: deposition from suspensions or slips, chemical vapor deposition (CVD) or thermal spray deposition, for example plasma projection (plasma spraying).
- CVD chemical vapor deposition
- plasma spraying plasma projection
- the membrane layers are deposited by coating from slips or suspensions.
- the membrane can be obtained by the deposition of several successive layers.
- the membrane generally comprises a first layer, called a primary layer, deposited in direct contact with the substrate.
- the primary acts as a layer of attachment.
- the slurry used for the deposition of the primer comprises 50% by weight of SiC grains having a median diameter of 10 to 30 ⁇ and 50% by weight of deionized water.
- the membrane also comprises a separating layer deposited on the primer layer. It is in this separating layer that the porosity is controlled in order to give the filter its selectivity.
- the slip used for the deposition of the separating layer comprises 50% by mass of SiC grains having a median diameter of 0.1 to 2 ⁇ and 50% by weight of deionized water.
- the viscosity of the slips is typically from 0.05 to 0.5 Pa.s, preferably from 0.01 to 0.3 Pa.s, measured at 22 ° C. under a shear rate of 1 s -1 according to DIN -53019-1: 2008.
- the slips can typically comprise from 0.1 to 1% of the water mass of thickening agents preferably chosen from cellulose derivatives, They can typically comprise from 0.1 to 5% of the mass of SiC powder of selected binding agents of Preferably, the slip may also comprise from 0.01 to 1% of the SiC powder mass of dispersing agents preferably chosen from ammonium polymethacrylate.
- a slip layer typically makes it possible to obtain a membrane with a thickness of 0.1 to 80 ⁇ , but thicker membranes, typically from 100 to 300 ⁇ , can be obtained by the deposition of several successive layers of slip.
- the thus coated support is then dried at room temperature typically for at least 30 minutes and then at 60 ° C for at least 24 hours.
- the supports thus dried are sintered at a firing temperature of typically between 1000 and 2200 ° C. under a non-oxidizing atmosphere, preferably under argon so as to obtain a membrane porosity measured by image analysis of 10 to 70% by volume and a median equivalent pore diameter measured by image analysis from 10 nm to 5 ⁇ .
- the slots are then made by machining the cavities in the support and plugging the evacuation channels at the upstream and downstream base.
- the slots are created by machining the cavities by sawing the support, usually before baking on the dried support. Before or after machining, the evacuation channels connected to the cavity are plugged according to well-known techniques, for example described in application WO2004 / 065088, on each of the downstream and upstream bases of the support, generally before cooking thereof.
- the support is sintered reference once the machining and capping operations performed and before the deposition of the membrane.
- the filter according to the invention can be used for various applications for the purification of liquids and / or the separation of particles or molecules from a liquid.
- the filter according to the invention makes it possible to maximize the flow of filtrate independently of the viscosity of the liquid to be filtered.
- the present invention relates in particular to the use of a filter as described. above for the purification of production water from oil extraction or shale gas, and is also applicable in various industrial processes for the purification and / or separation of liquids in the field of chemistry, pharmaceutical, food, agri-food or bioreactors,
- Examples 1A and 1B A support was carried out according to the techniques well known to those skilled in the art by shaping silicon carbide honeycomb. To do this, mix in a kneader:
- the support is extruded from this paste using a die to obtain a cylindrical green cylindrical block 150 mm in diameter and length 300 mm whose inner portion has a plurality of square section channels.
- the shape of the die is adapted to obtain channels having a hydraulic diameter of 4 mm and internal walls of average thickness of 1.2 mm.
- the raw monolith obtained is then dried by microwave for a time sufficient to bring the water content not chemically bound to less than 1% by weight, and then baked to a temperature of at least 2050 ° C which is maintained during 5 hours.
- the support obtained has an open porosity of 50% and a median pore diameter of approximately 10 ⁇ m.
- a membrane is then deposited on the inner surface of the channels.
- the deposition of the membrane is carried out by coating of slip.
- a first primer layer is deposited from a slurry comprising 50% by weight of SiC grains having a median diameter of about 20 ⁇ and 50%> deionized water.
- a separating layer is then deposited on the primer layer from a slurry comprising 50% by weight of SiC grains having a median diameter of approximately 1 ⁇ and 50% of deionized water.
- the viscosity of the slips measured at 22 ° C. under a shear rate of 1 s -1 according to DIN-53019-1: 2008, is adjusted to 0.1 Pa.s using well-known additives. the skilled person.
- the primer and the membrane are deposited according to the same process.
- the slurry is introduced into a stirred tank at 20 rpm. After a light vacuum de-aeration phase, typically 25 mbar, while maintaining stirring, the tank is placed in a slight overpressure of about +1 bar in order to coat the inside of the support from the bottom to the top . This operation takes only a few seconds for a 300 mm long stand. The slip comes to coat the inner wall of the channels of the support and the excess is then discharged by gravity immediately after deposition.
- the coated support is then dried at ambient temperature for 30 minutes and then at 60 ° C. for 30 hours.
- the thus dried coated support is then sintered at a temperature of 1350 ° C under an Argon atmosphere for 4 hours to obtain a membrane porosity of 40% with a median pore diameter of 200 nm.
- Cavities have been machined in the dried support and the evacuation channels connected to the cavities have been plugged according to well-known techniques as described in WO2004 / 065088 in order to create slots, before the sintering of the support.
- the slots were arranged so as to obtain an average path distance D satisfying the relation (1) according to the invention, that is to say a distance D of between 5.7 and 8.5 mm in the case examples 1A and 1B.
- Example 1A four through cavities 50 mm in length equal to one channel (4 mm), parallel to each other and to the main axis, are machined according to the diagram shown in FIG. 3.
- the slots are arranged regularly between them, that is to say that the number of channels between two adjacent slots is constant to plus or minus one channel.
- Example 1B 10 blind slots of length 50 mm, parallel to each other and to the main axis, are machined according to the diagram shown in FIG. 4.
- FIGs. 3 and 4 Representing filter section planes according to Examples 1A and 1B respectively, the recessed portions represent the slots without distinction between the cavities and the discharge channels.
- Comparative Example C1 A filter was prepared identically to that of Example 1A except that only 2 slots were made by machining in the support 2 through cavities, parallel to each other and to the main axis according to the illustrated diagram. in FIG. 5.
- a filter was prepared in a manner identical to that of Example 1A with the difference that the shape of the die is adapted to obtain channels having a hydraulic diameter of 2 mm and internal walls of average thickness of 1.2 mm. ; and 5 slots were made by machining in the support 5 through cavities, parallel to each other and to the main axis.
- the cavities have a length of 50 mm and a thickness equal to one channel (2 mm).
- a filter was prepared identically to that of Example 2 except that 3 slots were made by machining in the support 3 through cavities, parallel to each other and to the main axis.
- the cavities have a length of 50 mm and a thickness equal to one channel (2 mm).
- Example 3 A filter was prepared in a manner identical to that of Example 1A with the difference that the shape of the die is adapted to obtain channels having a hydraulic diameter of 4 mm and internal walls of average thickness of 0.4 mm. ; and 7 slots were made by machining in the support 7 through cavities, parallel to each other and to the main axis.
- the cavities have a length of 50 mm and a thickness equal to one channel (4 mm).
- a filter was prepared in the same manner as in Example 3 except that 10 slots were made by machining in the support 10 through cavities, parallel to each other and to the main axis.
- the cavities have a length of 50 mm and a thickness equal to one channel (4 mm).
- a filter was prepared in the same manner as in Example 1A except that the dried coated support was sintered at a temperature of 1300 ° C. under an Argon atmosphere for 4 hours to obtain a membrane porosity of 40%. with a median pore diameter of 125 nm; and 3 slots were made by machining in the support 3 through cavities, parallel to each other and to the main axis.
- the cavities have a length of 50 mm and a thickness equal to one channel (4 mm).
- Comparative Example C4 A filter was prepared in the same manner as in Example 4 except that 7 slots were made by machining in the support 7 parallel through cavities. between them and the main axis The cavities have a length of 50 mm and a thickness equal to one channel (4 mm).
- a filter was prepared in the same manner as in Example 1A except that the slip used for the deposition of the membrane comprises 12.3% by mass of SiC grains having a median diameter of approximately 0.5 ⁇ . 64.4% deionized water, 23.1% PVA and 0.2% deflocculant with reference to Example 2 of EP0219383;
- the coated and dried support is sintered at a temperature of 1050 ° C under a nitrogen atmosphere for 4 hours of dwell to obtain a membrane porosity of 25% with a median pore diameter of 200 nm; and 2 slots were made by machining in the support 2 through cavities, parallel to each other and to the main axis.
- the cavities have a length of 50 mm and a thickness equal to one channel (4 mm).
- a filter was prepared in a manner identical to that of Example 5 except that 1 slot was made by machining in the support 1 through cavity, parallel to the main axis.
- the cavity has a length of 50 mm and a thickness equal to one channel (4 mm).
- a filter was prepared identically to that of Example 1A, with the difference that a longer contact time between the suspension and the support is chosen to obtain a membrane having an average thickness of 200 ⁇ , this thickness being obtained accumulating 4 layers of 50 ⁇ with the deposition and drying process described in Example 1 A;
- the support thus coated and dried is sintered in the same conditions as Example 1A; and 3 slots were made by machining in the support 3 through cavities, parallel to each other and to the main axis.
- the cavities have a length of 50 mm and a thickness equal to one channel (4 mm).
- Comparative Example C6 A filter was prepared in a manner identical to that of Example 6 except that 6 slots were made by machining in the support 6 through cavities, parallel to each other and to the main axis.
- the cavities have a length of 50 mm and a thickness equal to one channel (4 mm).
- Example 7 A filter was prepared in the same way as in Example 1A except that the mixture used to make the support comprises:
- a filter was prepared in the same manner as in Example 7 except that 4 slots were made by machining in the support 4 parallel through cavities. between them and at the main axis.
- the cavities have a length of 50 mm and a thickness equal to one channel (4 mm).
- the ratio ⁇ / ⁇ is determined, in which ⁇ is characteristic flow of the filter and ⁇ 0 is the characteristic flow of an identical filter having no slot.
- the characteristic flow of a filter was evaluated according to the following method: at a temperature of 25 ° C., a fluid consisting of demineralised water fed the filters to be evaluated at a transmembrane pressure of 0.5 bar and a circulation velocity in the channels of 2 m / s. The permeate is recovered at the periphery of the filter.
- the measurement of the characteristic flow of the filter is expressed in L / h / m / bar after 20 hours of filtration.
- Table 1 The results obtained as well as the dimensional characteristics of the filters thus obtained are summarized in Table 1 below.
- Nf number of slots ⁇ through or blind
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Filtering Materials (AREA)
Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR1562810A FR3045398A1 (fr) | 2015-12-18 | 2015-12-18 | Filtre monolithique |
PCT/FR2016/053422 WO2017103473A1 (fr) | 2015-12-18 | 2016-12-14 | Filtre monolithique |
Publications (1)
Publication Number | Publication Date |
---|---|
EP3389833A1 true EP3389833A1 (fr) | 2018-10-24 |
Family
ID=55806484
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP16825511.5A Withdrawn EP3389833A1 (fr) | 2015-12-18 | 2016-12-14 | Filtre monolithique |
Country Status (4)
Country | Link |
---|---|
US (1) | US20180361321A1 (fr) |
EP (1) | EP3389833A1 (fr) |
FR (1) | FR3045398A1 (fr) |
WO (1) | WO2017103473A1 (fr) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR3066924B1 (fr) * | 2017-05-31 | 2019-07-12 | Saint-Gobain Centre De Recherches Et D'etudes Europeen | Structure filtrante a membrane |
FR3074060B1 (fr) * | 2017-11-30 | 2023-04-28 | Saint Gobain Ct Recherches | Structure filtrante membranaire monolithique |
Family Cites Families (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH01503265A (ja) * | 1987-04-02 | 1989-11-02 | モトローラ・インコーポレーテッド | 小型パーソナル通信機用アンテナ・チューニング装置 |
JP3277918B2 (ja) * | 1999-06-15 | 2002-04-22 | 住友電気工業株式会社 | セラミック多孔体を用いた濾過器 |
JP3868391B2 (ja) * | 2003-04-10 | 2007-01-17 | 日本碍子株式会社 | セラミックスハニカムフィルタ及びその製造方法 |
JP2006006998A (ja) * | 2004-06-22 | 2006-01-12 | Ngk Insulators Ltd | セラミックフィルタ |
KR101048461B1 (ko) * | 2005-06-30 | 2011-07-12 | 메타워터 가부시키가이샤 | 여과 장치 |
JP5409053B2 (ja) * | 2008-04-02 | 2014-02-05 | 日本碍子株式会社 | ハニカム構造体 |
CN103501879B (zh) * | 2011-04-25 | 2016-12-07 | 日本碍子株式会社 | 陶瓷过滤器的清洗方法 |
EP2832426B1 (fr) * | 2012-03-30 | 2017-05-10 | NGK Insulators, Ltd. | Corps poreux en céramique en forme de nid d'abeilles, son procédé de fabrication, et structure de membrane de séparation en céramique en forme de nid d'abeilles |
JP2015140273A (ja) * | 2014-01-28 | 2015-08-03 | イビデン株式会社 | ハニカム構造体 |
FR3021231B1 (fr) * | 2014-05-22 | 2018-02-16 | Saint-Gobain Centre De Recherches Et D'etudes Europeen | Filtres tangentiels |
US10350545B2 (en) * | 2014-11-25 | 2019-07-16 | ADA-ES, Inc. | Low pressure drop static mixing system |
-
2015
- 2015-12-18 FR FR1562810A patent/FR3045398A1/fr not_active Withdrawn
-
2016
- 2016-12-14 EP EP16825511.5A patent/EP3389833A1/fr not_active Withdrawn
- 2016-12-14 WO PCT/FR2016/053422 patent/WO2017103473A1/fr unknown
- 2016-12-14 US US16/061,940 patent/US20180361321A1/en not_active Abandoned
Also Published As
Publication number | Publication date |
---|---|
US20180361321A1 (en) | 2018-12-20 |
FR3045398A1 (fr) | 2017-06-23 |
WO2017103473A1 (fr) | 2017-06-22 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP3233252B1 (fr) | Filtres comprenant des membranes en sic incorporant de l'azote | |
WO2021009084A1 (fr) | Filtre comprenant une couche separatrice en carbure de silicium | |
EP3233253B1 (fr) | Filtres comprenant des membranes a base de sic appauvri en oxygene | |
EP3471863B1 (fr) | Filtres comprenant des couches separatrices a base de beta-sic | |
CA2947124C (fr) | Filtre tangentiel avec un element support comprenant un ensemble de canaux | |
EP3389833A1 (fr) | Filtre monolithique | |
EP3233251A1 (fr) | Filtres a membranes composites sic-nitrure ou sic-oxynitrure | |
EP3288669A1 (fr) | Filtres assembles pour la filtration de liquides | |
FR3066924B1 (fr) | Structure filtrante a membrane | |
EP3717106A1 (fr) | Structure filtrante membranaire monolithique | |
EP3887025A1 (fr) | Dispositif de filtration dynamique avec plaque poreuse ceramique de carbure de silicium |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
17P | Request for examination filed |
Effective date: 20180718 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |
|
AX | Request for extension of the european patent |
Extension state: BA ME |
|
DAV | Request for validation of the european patent (deleted) | ||
DAX | Request for extension of the european patent (deleted) | ||
17Q | First examination report despatched |
Effective date: 20190816 |
|
RAP1 | Party data changed (applicant data changed or rights of an application transferred) |
Owner name: SAINT-GOBAIN CENTRE DE RECHERCHES ET D'ETUDES EUROPEEN |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN |
|
18D | Application deemed to be withdrawn |
Effective date: 20200103 |