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WO2018156039A1 - Dispositif de filtration centrifuge et procédé de concentration de mélanges liquides - Google Patents

Dispositif de filtration centrifuge et procédé de concentration de mélanges liquides Download PDF

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Publication number
WO2018156039A1
WO2018156039A1 PCT/PT2018/050006 PT2018050006W WO2018156039A1 WO 2018156039 A1 WO2018156039 A1 WO 2018156039A1 PT 2018050006 W PT2018050006 W PT 2018050006W WO 2018156039 A1 WO2018156039 A1 WO 2018156039A1
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WIPO (PCT)
Prior art keywords
filtration
chamber
concentrate
permeate
centrifugal
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.)
Ceased
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PCT/PT2018/050006
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English (en)
Portuguese (pt)
Inventor
Vitor Manuel Geraldes FERNANDES
Viriato Sérgio DE ALMEIDA SEMIÃO
Miguel Ângelo Joaquim RODRIGUES
Carlos Duarte DA SILVA COMPLETO
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Universidade de Lisboa
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Universidade de Lisboa
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Publication of WO2018156039A1 publication Critical patent/WO2018156039A1/fr
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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
    • B01D63/08—Flat membrane modules
    • B01D63/087—Single membrane modules
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D21/00—Separation of suspended solid particles from liquids by sedimentation
    • B01D21/26—Separation of sediment aided by centrifugal force or centripetal force
    • B01D21/262—Separation of sediment aided by centrifugal force or centripetal force by using a centrifuge
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
    • B01D61/08—Apparatus therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/14—Ultrafiltration; Microfiltration
    • B01D61/18—Apparatus therefor
    • 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
    • B01D63/16—Rotary, reciprocated or vibrated modules
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01L—CHEMICAL OR PHYSICAL LABORATORY APPARATUS FOR GENERAL USE
    • B01L3/00—Containers or dishes for laboratory use, e.g. laboratory glassware; Droppers
    • B01L3/50—Containers for the purpose of retaining a material to be analysed, e.g. test tubes
    • B01L3/502—Containers for the purpose of retaining a material to be analysed, e.g. test tubes with fluid transport, e.g. in multi-compartment structures
    • B01L3/5021—Test tubes specially adapted for centrifugation purposes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01L—CHEMICAL OR PHYSICAL LABORATORY APPARATUS FOR GENERAL USE
    • B01L2200/00—Solutions for specific problems relating to chemical or physical laboratory apparatus
    • B01L2200/06—Fluid handling related problems
    • B01L2200/0684—Venting, avoiding backpressure, avoid gas bubbles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01L—CHEMICAL OR PHYSICAL LABORATORY APPARATUS FOR GENERAL USE
    • B01L2300/00—Additional constructional details
    • B01L2300/06—Auxiliary integrated devices, integrated components
    • B01L2300/0681—Filter
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01L—CHEMICAL OR PHYSICAL LABORATORY APPARATUS FOR GENERAL USE
    • B01L2300/00—Additional constructional details
    • B01L2300/08—Geometry, shape and general structure
    • B01L2300/0832—Geometry, shape and general structure cylindrical, tube shaped
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N15/00—Investigating characteristics of particles; Investigating permeability, pore-volume or surface-area of porous materials
    • G01N15/08—Investigating permeability, pore-volume, or surface area of porous materials
    • G01N2015/084—Testing filters
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A20/00—Water conservation; Efficient water supply; Efficient water use
    • Y02A20/124—Water desalination
    • Y02A20/131—Reverse-osmosis

Definitions

  • the present invention relates to a centrifugal filtration device and a method for concentration, fractionation, purification, and / or desalination of small volume liquid samples using reverse osmosis, nanofiltration or ultrafiltration membranes.
  • the centrifugal filtration device is particularly suitable for nanofiltration or reverse osmosis of liquid samples with high osmotic pressures.
  • Liquid mixtures may be fractionated using pressure difference driven membrane separation processes, taking into account the molecular weight of the components of the liquid mixtures and the molecular exclusion limit of the membrane.
  • microfiltration, ultrafiltration, nanofiltration and reverse osmosis membranes can be used, which operate at different pressure ranges.
  • tangential membrane filtration is generally the best alternative for concentrating such mixtures, as tangential flow minimizes concentration bias.
  • centrifugal filtration As its name implies, with this technique the difference in transmembrane pressure is created by centrifugal acceleration inside a centrifuge.
  • centrifugal filtration Compared to the front membrane filtration processes, centrifugal filtration has the advantage of propelling the denser fluid elements that accumulate on the membrane surface away from the axis of rotation under the effect of centrifugal force. With proper membrane orientation, the concentration boundary layer that forms near the membrane can be removed from the membrane by centrifugal force, providing a self-cleaning mechanism, reducing concentration bias and maintaining high filtration flow.
  • centrifugal filtration devices There are several centrifugal filtration devices described in the literature, but all of them have been developed for microfiltration and / or ultrafiltration.
  • This patent describes various embodiments of a centrifugal filtration device wherein the angle between the centrifugal force vector and the membrane surface is preferably less than 15 ° to ensure efficient removal of the concentrated layer in the vicinity of the membrane.
  • the main drawback of this device is that it does not prevent filtration from continuing to complete concentrate dryness.
  • the same problem occurs in centrifugal filtration devices disclosed in U.S. Pat. No. 4,683,058 issued to GF Lyman and G. Mathus, and in U.S. Pat. EP 0298513, issued to A. Szabados, a Since these devices do not have locations where concentrate can accumulate without drying.
  • centrifugal filtration devices comprising a concentrate chamber receiving the concentrate.
  • the concentrate chamber is located at the outermost radial level to maximize the dragging of the heavier and more concentrated fluid elements into that chamber.
  • Examples of devices with this type of concentrate chamber are described in the following patents: Pat. US 4,722,792 issued to T. Miyagi et al. , US 5,647,990, issued to V. Vassarotti, US 6,357,601, issued to WF Bowers et al. , US 8,747,670 issued to L. Bon Subscribe et al.
  • An interesting centrifugal filtration device has been disclosed in U.S. Pat. US 6,719,896 issued to P. Clark, in which the final volume of concentrate is adjusted by the user by clearance of permeate ducts. These permeate ducts are prepared in the device manufacturing process and the user only needs to uncover the ducts corresponding to the desired final concentrate volume.
  • Another significant factor that may influence filtration performance is the angle between the membrane surface and the centrifugal force vector. For a given centrifugal filtration device, this angle varies with the centrifuge rotor type. In a tilting rotor centrifuge the device rotates horizontally, while in a fixed angle rotor centrifuge the device rotates at a given inclination relative to the axis of rotation. Many configurations with different angles between the membrane surface and the axis of the centrifugal filtration device have been disclosed in previous inventions.
  • the membrane In this type of centrifugal filtration device, the membrane is usually placed at the base of a piston that presses against the liquid mixture to be filtered. The permeate passes through the membrane into an internal permeate chamber (inside the piston) and the concentrated fluid is drawn away from the membrane due to centrifugal force (see, for example, the devices disclosed in US Patent 3,661,265, to DJ Greenspan). , US 3,960,727, to HT Hochstrasser, US 4,522,713, to D. Nussbaumer et al., US 4,832,851, to WF Bowers and DB Tiffany, US 5,490,927, to AE Herczeg, and US 6,302,919 to B Chambers et al.
  • Patent 4,632,761 issued to WF Bowers and PN Rigopulos, US Pat. 5,501,841, issued to YC Lee et al., and US Pat. 8,747,670, issued to L. Bon Subscribe et al.).
  • Ultrafiltration membrane devices have a molecular exclusion limit typically between 1 kDa and 1000 kDa. This means that centrifugal filtration devices can now be applied to concentrate or purify viruses, bacteria or macromolecules such as proteins.
  • centrifugal filtration devices For a molecular weight of less than 1 kDa in the range of nanofiltration and reverse osmosis there are no commercially available centrifugal filtration devices. This means that there are no centrifugal filtration devices capable of concentrating small peptides, drugs, toxins, biomarkers, etc. These small molecules can only be concentrated by nanofiltration or reverse osmosis membranes. However, with such membranes, to achieve reasonable filtration flows and solute rejections, as well as high concentration factors, it is necessary to operate at pressures typically between 5 and 80 bar.
  • centrifugal filtration devices to operate at high pressure is not simple.
  • the supply pressure begins to decrease rapidly as soon as the liquid level in the sample chamber decreases. This poses a serious problem as it is at the end of the concentration cycle that the supply pressure must be raised to compensate for the osmotic pressure of the concentrated solution, which is maximum at this final concentration phase.
  • Increasing centrifugal acceleration too much does not adequately solve this problem as nanofiltration and reverse osmosis membranes can compact. irreversibly at high pressures. In fact, when the maximum pressure recommended by membrane manufacturers is far exceeded, severe irreversible membrane compaction is observed (McConnon, 2015), which causes the permeation flow to decrease dramatically throughout the concentration process.
  • An object of the invention is a centrifugal filtration device and a method for the fractionation, purification, concentration and / or desalination of liquid sample mixtures over a wide molecular weight range, including molecular weights below 1 kDa.
  • the device of the invention enables the fractionation, purification, concentration and / or desalination of liquid samples of substance mixtures over a wide range of molecular weights, including the particular case of high osmotic pressure liquid samples, also using nanofiltration and reverse osmosis to perform separation.
  • the pressure can be maintained at high levels throughout the filtration process, which allows to reach higher concentration factors and reduce the filtration time.
  • the centrifugal filtration devices described above have a large part of their volume occupied by the sample chamber extending to the membrane region. However, as the sample is filtered, its volume decreases and the liquid pressure decreases to practically zero. Since the pressure generated by the centrifugal force varies quadratically with the distance from the air / liquid interface of the sample to the membrane, after some time has elapsed since the filtration process began, the low liquid level and the pressure and flow values of permeate are reduced to a small fraction of their initial values. Thus, to achieve a high concentration factor, the filtration time needs to be greatly increased. Low flow operation also results in reduced solute rejection, as rejection tends to decrease with decreasing permeate flow.
  • the filtration pressure can of course be increased by gradually increasing the centrifuge's rotation speed throughout the test.
  • controlling the spin speed of the centrifuge is difficult or even impossible to implement because the liquid level in the sample chamber is not known in real time.
  • a centrifugal filtration device that maintains high pressure throughout most of the filtration process is described herein.
  • the liquid sample in order to maintain the high pressure near the membrane for most of the filtration process, is placed as far as possible from the membrane in terms of radial distance.
  • the liquid sample is placed in a chamber, hereinafter referred to as the sample chamber, located as far as possible from the chamber from which the membrane is located, here designated as a filtration chamber, and both chambers are connected. by a channel as thin as possible, which is called a narrow neck.
  • the sample chamber located as far as possible from the chamber from which the membrane is located, here designated as a filtration chamber, and both chambers are connected. by a channel as thin as possible, which is called a narrow neck.
  • most of the initial liquid sample volume is confined to the sample chamber to ensure an always high liquid height during the filtration cycle.
  • the centrifugal filter device also has a chamber for collecting the sample elements. concentrates moving out of the membrane by centrifugal force. This chamber is called a concentrate chamber.
  • the supply pressure can be advantageously increased by increasing the centrifuge speed, provided this does not compromise the mechanical integrity of the centrifugal filtration device.
  • the liquid sample may be further concentrated to the point where the osmotic pressure of the concentrated solution is reached or the permeate flow tends to zero due to membrane compaction.
  • the centrifugal filtration device of the invention comprises, but is not limited to, a housing comprising a sample chamber, a filtration chamber, a concentrate chamber, a permeate chamber, a narrow neck connecting the sample chamber to the chamber. and a cap to prevent liquid from spilling out of the device.
  • the body of the centrifugal filtration device described above may be made of one piece or several pieces depending on the embodiments of the invention.
  • the system also includes chamber ventilation channels to prevent pressure imbalance between the permeate chamber and the filtration chamber after the centrifuge is stopped.
  • the operating mode of the device is briefly described below.
  • the centrifugal filtration device rotates about the axis of rotation in a In the centrifuge, the filtration process takes place in the filtration chamber, which is fed fresh liquid from the sample chamber through the narrow neck.
  • the centrifugal force scans the heaviest elements of fluid that accumulate on the membrane surface located inside the filtration chamber. This self-cleaning mechanism minimizes concentration polarization in the membrane.
  • the liquid solution permeating through the membrane flows into the permeate chamber through at least one narrow permeate channel or porous support.
  • the method for fractionation, purification, concentration and / or desalination of liquid samples of substance mixtures consists of three main steps.
  • the first step is the introduction of the liquid sample to be processed in the centrifugal filtration device.
  • filtration is performed by placing the centrifugal filtration device in a centrifuge at a rotational speed that creates the desired transmembrane pressure difference, typically between 0 and 10 bar for ultrafiltration and microfiltration, between 10 bar and 60 bar for nanofiltration and between 20 bar and 80 bar for reverse osmosis.
  • the spin speed of the centrifuge can be increased at the end of the step to increase transmembrane pressure and thereby increase the final concentration of concentrated liquid.
  • the separated fluids are removed from the centrifugal filtration device. Removal of the permeate is easy because access to the permeate chamber below the membrane is sufficient.
  • the concentrate can be removed by suctioning it through a thin tube that enters the narrow neck into the filtration chamber. In Alternatively, the concentrate may be returned to the sample chamber through the narrow neck, reversing the position of the centrifugal filtration device and turning the centrifuge at low speed.
  • Table 1 Method for fractionation, purification, concentration and / or desalination of liquid samples of substance mixtures.
  • Step 1 Place the sample into the sample chamber of the centrifugal filtration device.
  • removal of the concentrate may be by suction, using a flexible thin tube through the narrow neck, or by centrifugation at low rotation speed of the inverted centrifugal filtration device.
  • FIG. 1 is a schematic of a generic centrifugal filtration device according to the object of the invention.
  • FIG. 2 is the schematic of the centrifugal filtration device during the filtration process outlining the operating fundamentals.
  • FIG. 3 is the isometric view of the object of the invention according to certain embodiments (in particular with embodiments 1 and 2).
  • FIG. 4 is an exploded view of the object of the invention according to embodiment 1.
  • FIG. 5 is a top view of the object of the invention according to embodiment 1.
  • FIG. 6 is a sectional view of the object of the invention at level A-A of FIG. 5 according to embodiment 1.
  • FIG. 7 is a sectional view of the object of the invention at section level AA of FIG. 5 according to embodiment 1 when placed in a centrifuge at a certain angle with the axis of rotation.
  • FIG. 8 is a sectional view of the object of the invention at section AA level of FIG. 5 according to embodiment 1 when placed in a centrifuge at a given angle with the axis of rotation prior to filtration with a liquid sample in the feed reservoir.
  • FIG. 9 is a cross-sectional view of the object of the invention at section A-A of FIG. 5 according to embodiment 1 when placed in a centrifuge at a certain angle with the axis of rotation at the end of filtration with the permeated liquid already in the permeate chamber.
  • FIG. 10 is an exploded view of the two parts of embodiment 2 differing from embodiment 1 of the object of the invention.
  • FIG. 11 is a top view of the object of the invention according to embodiment 2.
  • FIG. 12 is a sectional view of the object of the invention at section level B-B of FIG. 11 according to embodiment 2.
  • FIG. 13 is the enlarged view of the object of the invention in section C defined in FIG. 12 according to embodiment 2.
  • FIG. 14 is the isometric view of the object of the invention according to embodiment 3.
  • FIG. 15 is an exploded view of the object of the invention according to embodiment 3.
  • FIG. 16 is a top view of the object of the invention according to embodiment 3.
  • FIG. 17 is a cross-sectional view of the object of the invention at section D-D of FIG. 16 according to embodiment 3.
  • FIG. 18 is a cross-sectional view of the object of the invention at section level E-E of FIG. 16 according to embodiment 3.
  • FIG. 19 is a cross-sectional view of the object of the invention at section D-D of FIG. 16 when an extra reservoir is used to collect the concentrate by centrifuging with the inverted centrifugal filtration device according to embodiment 3.
  • FIG. 20 is a graph of a sucrose solution filtration result set obtained with a centrifugal filtration device according to embodiment 1.
  • the present invention relates to a centrifugal filtration device (1) for concentrating liquid mixtures to be inserted into the rotor of a centrifuge comprising: a housing which comprises a sample chamber (2, 102, 302) with at least one vent (123, 312); a permeate chamber (6, 106, 306) with at least one vent (145, 351); at least one filtration chamber (4, 104, 304) with at least a semipermeable membrane (5, 105, 205, 305); a concentrate chamber (7,107,307) downstream of the filtration chamber (4,104,304); and at least one neck (3, 103, 303) connecting the sample chamber (2, 102, 302) to the filtration chamber (4, 104, 304) and whose volume is less than the volume contained in the concentrate chamber (7). , 107, 307) and the filtration chamber (4,104,304).
  • the volume of the neck (33,103,303) is less than 1/5 of the volume contained in the concentrate and filtration chambers.
  • the cross-sectional area of the neck (3,103,303) is less than 1 mm 2 .
  • a long narrow neck between the sample chamber, which is closest to the spin axis of the centrifuge, and the filtration chamber, which is farthest from said axis of rotation preferably a neck with a volume of less than 1/5 of the volume contained in the concentrate and filtration chambers, and a cross-sectional area preferably less than 1 mm 2 , can maintain the pressure at high levels throughout the filtration process, allowing for greater factors to be achieved. concentration and reduce the filtration time.
  • the housing further comprises a concentrate removal channel (133, 333) that connects the sample chamber (102, 302) to the concentrate chamber (107, 307), and through which it can be insert a flexible tube to remove the liquid mixture concentrated.
  • This channel also allows to easily eliminate air pockets in the filtration and concentrate chambers at the beginning of centrifugation.
  • the device further comprises at least one permeate channel (144, 237, 346, 347) which connects the permeate side of the filtration membrane to the permeate chamber and permits the permeate flow to be conducted. to the permeate chamber.
  • the normal vector on the active side of the membrane is at an angle of approximately 90 ° with the centrifugal acceleration vector to maximize the self-cleaning action of the concentration boundary layer.
  • the centrifugal filtration device comprises two filtration chambers (304a, 304b) with two semipermeable membranes (305a, 305b) facing each other on opposite sides of the filtration chamber. 304, and a neck 303 leading into two independent conduits 303a, 303b, which in turn flow into the filtration chambers 304a and 304b.
  • the semipermeable membranes (5, 105, 205, 305) have a molecular exclusion limit in the range of reverse osmosis and nanofiltration, i.e. between 100 Da and 1000 Da.
  • a molecular exclusion limit in the range of reverse osmosis and nanofiltration, i.e. between 100 Da and 1000 Da.
  • membranes nanofiltration or reverse osmosis to achieve reasonable filtration flows and solute rejections, as well as high concentration factors, it is necessary to operate at pressures typically between 5 and 80 bar. THE The device of the invention avoids the rapid decrease of the supply pressure as soon as the liquid level in the sample chamber decreases, keeping the pressure at high levels throughout the filtration process, which allows to reach higher concentration factors and reduce the filtration time. .
  • the semipermeable membranes (5, 105, 205, 305) have a molecular exclusion limit in the range of ultrafiltration or microfiltration, i.e. between 1 kDa and 1000 kDa.
  • the invention further relates to a method for concentrating a liquid mixture comprising the following steps: a) providing a centrifugal filtration device (100, 200 or 300) according to claims 1 to 8;
  • step e) of said method the spin speed of the centrifuge is set to gradually increase from a given starting value to a given ending value throughout the filtration process.
  • FIG. 1 shows a generic sketch of a centrifugal filtration device. This figure is used herein to describe and explain the fundamentals of operation of the object of the invention.
  • Centrifugal filtration device 1 comprises a sample chamber (2), at least one narrow neck (3) connecting the sample chamber (2) to a filtration chamber (4), a semipermeable membrane (5) which allows permeate passage from the filtration chamber (4) to a permeate chamber (6), and a concentrate chamber (7). All components are placed inside a housing and in this case it is assumed that centrifugal acceleration acts horizontally from left to right.
  • FIG. 2 shows the general sketch of the centrifugal filtration device 1 shown in FIG. 1 during operation.
  • the centrifugal filtration device (1) rotates at an angular velocity ⁇ about the axis of rotation of the centrifuge.
  • the liquid sample (2a) placed in the sample chamber (2) flows into the narrow neck (3). From this neck it then flows into the filtration chamber (4) where permeation occurs. Part of the concentrated sample then accumulates in the concentrate chamber (7). As the process A portion of the liquid sample permeates through the membrane (5) and is collected as permeate (6a) in the permeate chamber (6).
  • the centrifugal force creates a self-cleaning mechanism that causes the fluid elements concentrates the membrane deviate from this in the radial direction.
  • the more concentrated fluid elements are projected toward the concentrate chamber (7), which ends up being largely concentrated in the liquid sample (7b).
  • the angle ⁇ between the wall surface (2c) and the centrifugal force vector must be between 90 ° and 180 °.
  • the narrow neck (3) allows the high transmembrane pressure difference to be maintained throughout most of the filtration cycle.
  • the centrifugal filtration device is designed so that the level of the sample feed reaches the narrow neck inlet when the desired concentration factor has already been reached. That way, transmembrane pressure never decays much throughout the filtration cycle.
  • FIG. 3 shows an isometric sketch of embodiment 1, or embodiment 2, of the centrifugal filtration device of the invention.
  • the housing of centrifugal filter device 100 (or 200 for embodiment 2) is comprised of several parts.
  • the cap (110) fits into a hole in the upper surface (121) of the upper part (120).
  • the bottom edge surface of the upper part 120 connects to the membrane support part 140 (240) for embodiment 2 which in turn connects to the bottom part 150 which preferably has , a hemispherical shape, suitable for insertion into typical centrifuge rotors.
  • the support portion (140) has a porous plate or a micro channel surface beneath the membrane to allow the permeate to flow into the permeate chamber (106) within the bottom portion (150) (see FIG. 4).
  • Embodiment 1 uses a single membrane (105) glued by its edges to the upper surface (141) of the membrane support portion (140).
  • the adhesive for bonding the membrane edges to the upper surface (141) must be compatible with the liquid sample solvent and the upper surface material (141).
  • epoxy or polyurethane based adhesives may be used.
  • the membrane support portion 140 is secured between the upper portion 120 and the bottom portion 150.
  • Two o-rings (142 and 143) ensure fluid tightness in the filtration (104), concentrate (107) and permeate (106) chambers.
  • At least one narrow permeate channel (144) interconnects the surface (141) of the membrane support (140) to the permeate chamber (106) at the bottom (150) of the centrifugal filtration device.
  • the upper surface (141) may have a porous plate or a set of grooves to facilitate permeate flow towards the narrow permeate channel (144).
  • the filtration chamber (104) is defined as the void space between the membrane (105) and the lower surface of the inner block (130).
  • the height of the filtration chamber (104) is determined by the height of the edge (132) of the lower surface of the inner block (130). For this reason, the effective membrane area is smaller than the upper surface area (141) of the membrane support (140) and depends on the edge dimensions (132). A clearer description of edge 132 can be seen in FIG. 10.
  • the camera The sample (102) is bounded between the upper part of the inner block (130) and the inner surface of the upper part (120).
  • the sample chamber 102 should be located as far away from the filtration chamber as possible and as close as possible to the axis of rotation.
  • the inner block (130) there are grooved narrow channels connecting the sample chamber (102) to the filtration (104) and concentrate (107) chambers.
  • One of the grooved channels is the narrow neck (103), which corresponds to the narrow neck (3) outlined schematically in FIG. 1.
  • Narrow neck 103 which is not visible in FIG. 3, but is visible in FIG. 6 connects the sample chamber (102) to the filtration chamber (104), allowing the liquid sample to be fed to the filtration chamber.
  • a flexible capillary tube can be inserted into the narrow channel (133) (concentrate removal channel) and thereby sucked out the concentrate from the concentrate chamber (107).
  • the narrow channel (133) (concentrate removal channel) also facilitates the passage of the liquid sample into the filtration chamber at the initial stage of centrifugation, allowing any air pockets to be eliminated.
  • a first vent hole (123) connected to the sample chamber (102). This prevents the occurrence of vacuum at the end of the filtering cycle, which could damage the membrane.
  • a second vent (145) is located in the membrane support portion (140) and connects to the permeate chamber (106). Finally, the upper part 120 may be closed with the lid (110), which has a sealing o-ring (111).
  • FIG. 5 The top view of embodiment 1 of the invention is in FIG. 5 showing the location of the cross-section A-A to be used in FIGS. 6, 7, 8 and 9.
  • FIG. 6 shows the sectional view of embodiment 1 of the invention according to section A-A defined in FIG. 5.
  • the connections between the various chambers and the two ventilation holes are visible in FIG. 6.
  • the narrow neck (103) connects the sample chamber (102) to the filtration chamber (104).
  • the narrow neck (103) is formed by a groove in the inner block (130).
  • the sample chamber (102) is defined as the void space between the inner block (130) and the top part (120).
  • the surface (131) of the inner block (130), which defines the sample chamber, makes an angle ⁇ to the vertical axis of the centrifugal filtration device.
  • FIG. 7 shows a cross-sectional view of embodiment 1 of the invention according to section AA defined in FIG. 5, when the centrifugal filtration device is placed within the fixed angle rotor of a centrifuge with angle ⁇ .
  • angle ⁇ should preferably be between 90 ° and 180 °
  • angle a should preferably be close to angle ⁇ of the rotor so that the membrane is aligned with centrifugal acceleration.
  • FIGs. 8 and FIG. 9 show that of embodiment 1 of the centrifugal filter device positioned in the same configuration shown in FIG. 7, but in two different filtration phases.
  • FIG. 8 shows the initial phase, prior to filtration, where the liquid sample (102a) fills the entire space defined by the sample chamber (102), the narrow neck (103), the second narrow channel (133) (concentrate removal channel). ), the filtration chamber (104) and the concentrate chamber (107).
  • FIG. 9 illustrates the final phase of the filtration process, where permeate chamber 106 already contains most of the permeate liquid 106a that has permeated through the membrane, while concentrated liquid 107a is trapped in the concentrate chamber (10). 107).
  • Embodiment 2 of the invention is similar to embodiment 1 already described, but includes an additional membrane in the filtration chamber. This doubles the membrane area and halves the time required to concentrate the fluid sample.
  • This embodiment 2 of the centrifugal filtration device is illustrated in FIG. 10.
  • the additional membrane (205b) is disposed on the lower surface of the inner block (230) and the second permeate channel (237) connects the permeate side of the membrane (205b) to the permeate chamber (106).
  • the second permeated channel (237) comprises two sections: a channel section (238) within the inner part of the block (230) and another section (246) within the membrane support part (240).
  • the perforated rod (236) connects the channel section (238) in the inner block (230) to the channel section (246) in the membrane holder (240).
  • the second membrane 205b is glued to the lower surface of the inner block 230 using the same type of bonding as previously described for gluing the first membrane.
  • FIG. 11 The top view of embodiment 2 of the invention is shown in FIG. 11 which shows the location of the cross section BB to be used in FIG. 12. Cut section BB changes direction in position aligned with the center of the permeate channel (144) to pass through the middle of the perforated rod (236). The region defined by the dashed line C is enlarged in FIG. 13.
  • the permeated channel 237 is shown in FIG. 13 as a tube with bends. However, sections 238 and 246 of permeate channel 237 may be straight channels made by perforation.
  • FIG. 14 shows an isometric perspective sketch of embodiment 3 of the centrifugal filtration device of the invention.
  • the external portion of the centrifugal filtration device (300) comprises an outer part (350) and a lid (310) at the top thereof. There are also two holes to prevent pressure imbalance at the end of filtration and to prevent membranes from rupturing. On the side surface of the outer part 350 is the hole 351 connected to the permeate chamber. On the top surface of the cap (310) is the hole (312) connected to the sample chamber.
  • the shape of the centrifugal filtration device (300) should preferably be designed so that this device can be inserted into standard centrifuge rotors.
  • FIG. 15 shows the exploded isometric view of embodiment 3 of the invention. All internal parts of centrifugal filtration device (300) are supported on edge (352) of outer part (350).
  • the novelty of embodiment 3 of the invention is the use of an inner block (330) separating the sample chamber (302) from the filtration chamber (304).
  • the membrane 305a is supported in the slot 342, while the membrane 305b is supported in a similar slot on the opposite side.
  • the surfaces of these grooves should preferably have a set of protrusions or porous surfaces to facilitate passage of permeate flow to permeate reservoir (306).
  • Each of the membrane support pieces (340 and 341) has at least one permeate channel (346 and 347), respectively, to conduct permeate flow into the permeate chamber (306).
  • the permeate chamber (306) is defined by the inner walls of the outer shell (350).
  • the membrane support pieces (340 and 341) are attached to the edges (361a and 361b) of the inner part (360).
  • the assembly comprising the parts (340, 341 and 360) is capped by the lid (310) and fits within the outer part (350), the edge (362) of the inner part (360) being supported at the edge (352) of the outside (350).
  • the inner block (330) fits into the inner part (360), creating the filtration chambers (304a and 304b) that lie between the inner block (330) and the membranes (305a and 305b). .
  • the thickness of the filtration channels is determined by the dimensions of the rod (339) of the inner block (330).
  • Inner block (330) is supported by lip engagement (338) at end (363) of inner part (360).
  • the sample chamber (302) is created by a cavity in the top of the inner block (330).
  • the neck 303 connects the deepest part of the sample chamber 302 to the filtration chambers 304a and 304b through the auxiliary narrow channels 303a and 303b.
  • a narrow channel (333) concentrate removal channel
  • This channel also allows to easily eliminate air pockets in the filtration chambers at the beginning of centrifugation.
  • Embodiment 3 of the invention can be further understood using the sectional sections DD and EE outlined in FIG. 16 illustrating the top view of embodiment 3 of the invention.
  • Section DD is seen from the front in FIG. 17.
  • fresh sample liquid flows from the sample chamber (302) into the narrow neck (303).
  • the narrow neck then flows into the ducts (303a and 303b) which in turn flow into the filtration chambers (304a and 304b), where are the membranes (305a and 305b).
  • the concentrated sample is collected in the concentrate chamber of (307).
  • the permeate passes through the channels 346 and 347 and is collected in the permeate chamber 306.
  • FIG. 18 shows the cross-sectional view of embodiment 3 of the invention along section E-E defined in FIG. 16.
  • the narrow channel (333) concentrate removal channel
  • in the center of the device may be used to withdraw concentrated sample at the end of filtration or to facilitate the elimination of air pockets that may initially exist in the filtration chambers.
  • Another option for removing the concentrate from embodiment 3 of the invention is to detach the lid (310) and the outer part (350) from the assembly, insert a reservoir (370) through the opening of the inner block part (330) and perform a low speed spin with the inverted device.
  • This procedure is best understood with the aid of FIG. 19.
  • the additional reservoir (370) is inserted into the top of the inner block (330) and the new assembly is inverted and centrifuged at a low rotational speed. .
  • the concentrated liquid that was in the concentrate chamber 307 flows into the chamber 371, where it can be collected as the concentrated sample 307a, after separating the reservoir 370 from the device.
  • the centrifugal filtration device may utilize reverse osmosis membranes, nanofiltration membranes with a molecular exclusion limit that is typically between 100 Da and 1 kDa, or ultrafiltration membranes with a molecular exclusion limit between 1 kDa and 1000 kDa.
  • centrifugal filtration device To evaluate the performance of the centrifugal filtration device disclosed in this invention, various centrifugal filtration experiments were performed with aqueous sucrose solutions using embodiment 1 of the object of the invention, with an angle ⁇ of 30 ° and an angle ⁇ of 34 °. .
  • the prototype used has a height of 103 mm and a width of 28.7 mm and was manufactured from an aluminum light alloy (with the exception of the Teflon inner block 130 and the polyinitrile o-rings 111, 142 and 143).
  • sample chamber 102 has a volume of about 3.2 mL.
  • Sucrose was selected as the reference solute because it has a molecular weight of 342.3 g / mol which is in the range of nanofiltration molecular exclusion limit.
  • concentration factor CF
  • C a the concentration factor
  • An apparent rejection close to 1 indicates that the membrane prevents the passage of solute to the permeate.
  • NFX nanofiltration membrane manufactured by Synder Filtration (Vacaville, USA) was used.
  • the membrane which according to the manufacturer has a limit of Nominal molecular exclusion between 150 and 300 Da was bonded to the backing using two epoxy resins: Ceys Araldite Standard (Spain) and Omega Omegabond OB-101 (USA).
  • the membrane was glued to the surface (141) of the membrane support portion as described below.
  • a surface-shaped membrane piece (141) was cut from a new membrane sheet.
  • a thin wire (about 1 mm) of Omegabond OB-101 blend was scattered about 2 mm from the edges of either the surface (141) of the centrifugal filter device or the surface of the membrane polyester support (105).
  • the surface of the membrane polyester support (105) was brought into contact with the surface (141) of the membrane support part (140) and the time required for curing the adhesives was waited according to the manufacturers' instructions. glues. After the adhesives were cured, a thin layer of Araldite Standard mixture was spread to about 3 mm from the membrane edge (105) (including the lip) to ensure their sealing. After curing of the glue, the filtration device according to embodiment 1 was fit for use.
  • the permeate and concentrate sucrose concentrations at the end of filtration were determined using the Atago DD-5 differential refractometer (Japan). In all examples a Sorvall RC6 centrifuge with a fixed angle F10-6x500y rotor was used. An adapter was attached to this rotor such that the angle ⁇ was 34 °.
  • the sample chamber volume was about 3.2 mL
  • the narrow neck length was 1.9 cm
  • the volume contained in the narrow neck was 0.018 mL
  • the volume contained in the sample chambers Concentration and filtration was 0.1 mL in Examples 1 and 2 and 0.4 mL in Example 3.
  • the ratio between the volume of the neck and the volume contained in the concentrate and filtration chambers was then always less than 1/5 (this ratio is 0.18 in examples 1 and 2 and 0.04 in example 3).
  • the cross-sectional area of the narrow neck was 1 mm 2 .
  • a 3.2 mL volume of aqueous sucrose solution with a concentration of 7.7 g / l was filtered according to the present method disclosed in the invention (see Table 1).
  • the height of the filtration chamber ie the distance from the membrane surface 105 to the lower surface of the inner part of the block 130, was 0.2 mm.
  • the membrane Prior to filtration of the sample itself, the membrane was washed with water to remove the preservative and protective substances from the membrane placed by the membrane manufacturer. To this end, 3.2 mL of deionized water was filtered into the centrifugal filtration device at a rotation speed of 6000 rpm for 30 minutes and the process repeated once. Under these conditions, the average pressure in the filtration chamber 104 at the beginning of the filtration cycle is 16 bar. After washing the membrane, 3.2 ml of sucrose solution was filtered over 45 minutes at a rotation speed of 6000 rpm. This filtration time was sufficient for all the solution contained in the feed chamber to be filtered.
  • the permeate was removed from the permeate reservoir and the concentrated liquid sample was suctioned from the device using a flexible capillary tube and syringe according to the method described in the present invention. Under these conditions, it was possible to extract from the centrifugal filtration device about 105 ⁇ concentrate, which had an average concentration of 117 g / l sucrose. The apparent rejection obtained in this assay was 97%.
  • this example proves that through embodiment 1 of the object of the invention it is possible to concentrate 3.2 ml of an aqueous sucrose solution with a concentration of 7.7 g / l to obtain 105 ⁇ of concentrated solution to give a concentration factor of 15, with an apparent rejection of 97%.
  • FIG. 20 shows the evolution of the average permeate flow rate at each time interval and the sucrose concentration in the concentrate at the end of each interval.
  • the average permeate flow rate is the average permeate volume that crosses the membrane per unit time and was obtained by determining the accumulated permeate volume in the permeate chamber 106 at the different time intervals shown in FIG. 20.
  • centrifugal filtration device disclosed in this invention achieves high repeatability between assays, and the membrane used in the different assays was always the same, it was possible to determine the average permeate volume between two generic t1 and t2, ie in the time interval [tl, t2], calculating the accumulated permeate volume difference in centrifugal filtration tests with different filtration times tl and t2. Thus, for each interval [tl, t2] a filtration time test t2 was performed always starting from

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Abstract

La présente invention concerne un dispositif de filtration centrifuge et un procédé pour la concentration, le fractionnement, la purification et/ou le dessalement d'échantillons liquides de petit volume, au moyen de membranes d'osmose inverse, par nanofiltration ou par ultrafiltration. Le dispositif comprend une enveloppe, laquelle comprend une chambre d'échantillon (102) présentant au moins un orifice de ventilation (123) ; une chambre de perméat (106) présentant au moins un orifice de centilation (145) ; une chambre de filtration (104) présentant au moins une membrane semi-perméable (105) ; une chambre de concentré (107) en aval de la chambre de filtration (104) ; et au moins un col (103) qui relie la chambre d'échantillon (102) à la chambre de filtration (104) et dont le volume est inférieur au volume contenu dans les chambres de concentré (107) et de filtration (104). Le dispositif est particulièrement approprié pour effectuer la nanofiltration ou l'osmose inverse d'échantillons liquides à des pressions osmotiques élevées. La filtration se produit sous l'action de la rotation du dispositif de filtration centrifuge autour d'un axe de rotation dans une centrifugeuse. En utilisant un col long et étroit entre la chambre d'échantillon, qui est plus proche de l'axe de rotation de la centrifugeuse, et la chambre de filtration, qui est plus éloignée dudit axe de rotation, on parvient à maintenir la pression à des niveaux élevés pendant tout le processus de filtration, ce qui permet d'obtenir de plus grands facteurs de concentration et de réduire le temps de filtration.
PCT/PT2018/050006 2017-02-24 2018-02-23 Dispositif de filtration centrifuge et procédé de concentration de mélanges liquides Ceased WO2018156039A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP4317400A4 (fr) * 2021-03-24 2025-02-12 Hitachi High-Tech Corporation Cartouche de filtration centrifuge et procédé de test microbien
WO2025034126A1 (fr) 2023-08-10 2025-02-13 Instituto Superior Técnico Dispositifs de filtration turbo-centrifuges et procédé de caractérisation de membrane, de concentration ou de purification d'échantillon par ultrafiltration, nanofiltration, et osmose inverse

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
PT118865A (pt) * 2023-08-10 2025-02-10 Inst Superior Tecnico Dispositivos turbo-centrífugos de filtração e método para filtração de líquidos, purificação por ultrafiltração, nanofiltração e osmose inversa de alto desempenho

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4722792A (en) * 1985-02-09 1988-02-02 Kurashiki Boseki Kabushiki Kaisha Filter for centrifugal separator
US5647990A (en) * 1993-05-21 1997-07-15 Vassarotti; Vincenzo Centrifugal method for concentrating macromolecules from a solution and device for carrying out said method
US6344140B1 (en) * 1997-08-11 2002-02-05 Peter Zuk, Jr. Centrifugal filtration apparatus
US7141167B2 (en) * 2001-04-23 2006-11-28 N F T Nanofiltertechnik Gmbh Filter device

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US573344A (en) * 1896-12-15 mustain
US463276A (en) * 1891-11-17 Wagon end-gate

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4722792A (en) * 1985-02-09 1988-02-02 Kurashiki Boseki Kabushiki Kaisha Filter for centrifugal separator
US5647990A (en) * 1993-05-21 1997-07-15 Vassarotti; Vincenzo Centrifugal method for concentrating macromolecules from a solution and device for carrying out said method
US6344140B1 (en) * 1997-08-11 2002-02-05 Peter Zuk, Jr. Centrifugal filtration apparatus
US7141167B2 (en) * 2001-04-23 2006-11-28 N F T Nanofiltertechnik Gmbh Filter device

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
COMPLETO CARLOS ET AL: "Centrifugal nanofiltration for small-volume samples", JOURNAL OF MEMBRANE SCIENCE, ELSEVIER BV, NL, vol. 540, 27 June 2017 (2017-06-27), pages 411 - 421, XP085177587, ISSN: 0376-7388, DOI: 10.1016/J.MEMSCI.2017.06.069 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP4317400A4 (fr) * 2021-03-24 2025-02-12 Hitachi High-Tech Corporation Cartouche de filtration centrifuge et procédé de test microbien
WO2025034126A1 (fr) 2023-08-10 2025-02-13 Instituto Superior Técnico Dispositifs de filtration turbo-centrifuges et procédé de caractérisation de membrane, de concentration ou de purification d'échantillon par ultrafiltration, nanofiltration, et osmose inverse

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