FLUIDIC FLUID PURIFYING DEVICE AND ASSOCIATED PURIFYING METHOD
20200277205 · 2020-09-03
Assignee
Inventors
Cpc classification
B01J19/0093
PERFORMING OPERATIONS; TRANSPORTING
B01J2219/00783
PERFORMING OPERATIONS; TRANSPORTING
B01J2219/00837
PERFORMING OPERATIONS; TRANSPORTING
C02F1/283
CHEMISTRY; METALLURGY
International classification
B01D71/38
PERFORMING OPERATIONS; TRANSPORTING
Abstract
The invention relates to a fluidic purifying device designed to clean a fluid of at least one pollutant, comprising a fluidic purification network, characterized in that the fluidic purification network comprises a plurality of microfluidic channels, each microfluidic channel being defined by one or more fluidttight walls, each microfluidic channel comprising at least one zone on the interior surface of said microfluidic channel that exhibits at least one autonomous purifying agent and each microfluidic channel exhibiting, in such a zone, a height less than 60 m in a direction normal to the main direction of flow of the fluid, the purifying agent or agents, and the sizing of said zones, being configured in such a way as to allow at least 10% of the pollutants to be captured and/or broken down by said zones, for at least one flow rate of the fluid that is to be purified.
Claims
1. A fluidic purification device (1) adapted to purify a fluid (2) of at least one pollutant (3), comprising a fluidic purification network (8), characterized in that the fluidic purification network is a three-dimensional array of microfluidic channels (9), each microfluidic channel (9) being defined by one or more fluid-tight walls (2), each microfluidic channel (9) comprising at least one zone (13) on the inner surface of said microfluidic channel (9) having at least one self-contained purification agent (11) and each microfluidic channel (9) having at such a zone (13) a height of less than 60 m in a direction normal to the main direction of flow (12) of the fluid, the self-contained purification agent or agents and the dimensioning of said zones (13) being configured to allow capture and/or degradation of at least 10% of the pollutants (3) by said zones, for at least one flow of the fluid to be purified, the device comprising a plurality of distribution channels (40) and a plurality of collection channels (41), the fluidic purification network (8) connecting the distribution channels and the collection channels and being implemented at least by an array of microfluidic channels (9) connected in parallel.
2. A fluidic device (1) in which a three-dimensional array of microfluidic channels (9) comprising a superposition of two-dimensional arrays of microfluidic channels (9), the fluidic purification network (8) connecting the distribution channels (40) and the collection channels (41).
3. The device as claimed in claim 1, comprising at least three stacked layers (17, 18), at least two sides of one or more layers having, facing at least two Layers, a depression pattern configured to form at least two two-dimensional arrays of microfluidic channels (9) when the at least three layers are stacked.
4. The fluidic device (1) as claimed in one of claims 1 to 3, wherein the hydrodynamic resistance of the distribution channel(s) and the collection channel(s) is strictly lower than the hydrodynamic resistance of the fluidic purification network.
5. The device as claimed in claim 4, comprising at least three stacked layers (17, 18), at least two sides of one or more layers having, facing at least two layers, a depression pattern configured to form at least two two-dimensional arrays of microfluidic channels (9) when the at least three layers are stacked, wherein one said pattern is configured to form at least in part one or more distribution channels (40), and at Least in part one or more collection channels (41).
6. The device as claimed in one of claims 3 to 5, comprising at least one primary channel (19) passing through a plurality of adjacent layers (17, 18) and opening into at least one distribution channel (40) and/or at least one collection channel (41) formed between two layers (17, 18).
7. The device as claimed in one of claims a to 6, wherein the stack (14) comprises a superposition of sub-stacks each formed of two layers (17, 18), said two layers being of different materials.
8. The device as claimed in one of claims 3 to 6, wherein the stack (14) comprises a superposition of sub-stacks each formed of three consecutive layers (17, 18), the two layers on either side of the sub-stack being of the same material.
9. The device as claimed in one of claims 3 to 8 wherein the material of a second layer (18) has a mass fraction of self-contained purification agent (11) greater than 0.15.
10. The device as claimed in one of claims 3 to 9 wherein the material of a layer (17, 18) comprises a polycondensate of cyclodextrins.
11. The device as claimed in one of claims 3 to 10 wherein the material of a layer (17, 18) comprises an ethylene-vinyl alcohol copolymer.
12. The device as claimed in one of claims 3 to 11 wherein the material of at least two layers (17, 18) in contact, comprises a block copolymer, the block copolymer having a glass transition temperature below 0 C. and the material having a Young's modulus of less than 10 MPa.
13. The device as claimed in one of claims 3 to 12 wherein the material of a layer (17, 18) comprises a styrenic thermoplastic elastomer.
14. The device as claimed in one of claims 1 to 13, wherein the material of a layer is at least selected from glass and silicon.
15. The device as claimed in one of claims 1 to 14, wherein a self-contained purification agent (11) is adapted to capture the pollutant (3) and is at least one selected from cyclodextrin, activated carbon, calixarene, activated alumina, silica get, graphite, clay and zeolite.
16. The device as claimed in one of claims 1 to 15, wherein a self-contained purification agent (11) is adapted to degrade the pollutant (3) and is at Least one selected from laccase, horseradish peroxidase, lignin peroxidase, manganese peroxidase, tyrosinase, potassium permanganate, persulfate and a fungal enzyme.
17. The device as claimed in one of claims 1 to 16, wherein at least one wall of a microfluidic channel (9) has a plurality of reliefs (38) extending in at least one direction different from the main direction of flow (12) of the fluid.
18. The device as claimed in claim 17, wherein the reliefs are in the form of striations and/or chevrons.
19. A purification assembly adapted to purify a fluid (2) of at least one pollutant (3), comprising a plurality of fluidic devices (1), each fluidic device (1) comprising a fluidic purification network (8), said fluidic purification network being a three-dimensional array of microfluidic channels (9), each microfluidic channel (9) being defined by one or more fluid-tight walls (2), each microfluidic channel (9) comprising at least one zone (13) on the inner surface of said microfluidic channel (9) having at least one self-contained purification agent (11) and each microfluidic channel (9) having at such a zone (13) a height of less than 60 m in a direction normal to the main direction of flow (12) of the fluid, the self-contained purification agent or agents and the dimensioning of said zones (13) being configured to allow (11) a capture and/or degradation of at least 10% of the pollutants (3) by said zones, for at least one flow of the fluid to be purified, the device comprising a plurality of distribution channels (40) and a plurality of collection channels (41), the fluidic purification network (8) connecting the distribution and collection channels and being implemented at least by an array of microfluidic channels (9) connected in parallel, the fluidic devices (1) being fluidically connected in series and/or in parallel.
20. A purification system comprising at least one fluidic purification device (1) adapted to purify a fluid (2) of at least one pollutant (3), each fluidic device (1) comprising a fluidic purification network (8), said fluidic purification network being a three-dimensional array of microfluidic channels (9), each microfluidic channel (9) being defined by one or more fluid-tight walls (2), each microfluidic channel (9) comprising at least one zone (13) on the inner surface of said microfluidic channel (9) having at least one self-contained purification agent (11) and each microfluidic channel (9) having at such a zone (13) a height of less than 60 m in a direction normal to the main direction of flow (12) of the fluid, the self-contained purification agent or agents and the dimensioning of said zones (13) being configured to allow (11) a capture and/or degradation of at least 10% of the pollutants (3) by said zones, for at least one flow of the fluid to be purified, the device comprising a plurality of distribution channels (40) and a plurality of collection channels (41), the fluidic purification network (8) connecting the distribution channels and the collection channels and being implemented at least by a array of microfluidic channels (9) connected in parallel, the system also comprising a device for conditioning the temperature of a microfluidic channel (9).
21. The purification system as claimed in claim 20, which is portable and/or electrically self-contained.
22. The purification system as claimed in one of claim 20 or 21 comprising at least one ultrasonic radiation source (25).
23. A purification process adapted to purify a fluid (2) of at least one pollutant (3), comprising a step wherein the fluid (2) is passed through a three-dimensional fluidic purification network (8) of microfluidic channels (9) at a flow rate of the fluid to be purified, each microfluidic channel (9) comprising at least one zone (13) on the inner surface of said microfluidic channel (9) having at least one self-contained purification agent (11) and each microfluidic channel (9) having at such a zone (13) a height of Less than 60 m in a direction normal to the main direction of flow (12) of the fluid, the self-contained purification agent or agents and the dimensioning of said zones (13) being configured to allow (11) a capture and/or degradation of at least 10% of the pollutants (3) by said zones during the flow of the fluid (2) at said flow rate in the array of microfluidic channels (9), comprising controlling a pressure difference between the inlet (4) and the outlet (5) of a device (1) so as to cause said fluid flow (2) into said device (1), the device (2) comprising a plurality of distribution channels (40) connected to the inlet (4) and a plurality of collection channels (41) connected to the outlet (5), the fluidic purification network (8) connecting the distribution channels and the collection channels, the hydrodynamic resistance of the distribution channel or channels and the collection channel or channels being strictly lower than the hydrodynamic resistance of the fluidic purification network and the absolute value of the pressure difference being less than 5 bar.
24. The process as claimed in claim 23, wherein the flow rate is such that the Peclet number of the pollutant (3) in the flow of the fluid (2) passing through the length of the purification zones (13) in the direction of flow is less than 10.sup.4.
25. The process as claimed in one of claims 23 to 24 wherein the fluid (2) is recirculated in the microfluidic channels (9).
26. The process as claimed in one of claims 23 to 25, wherein, for the purification of a pollutant (3) selected from a metallic element and an organic molecule having an octanol/water partition coefficient LogK.sub.ow, greater than 1.5, the self-contained purification agent (11) is a cyclodextrin.
27. The process as claimed in one of claims 23 to 26, comprising a step in which a washing and/or regeneration fluid is passed through the microfluidic channels (9).
28. A process for manufacturing a fluidic purification device (1) adapted to purify a fluid (2) of at least one pollutant (3), comprising a fluidic purification network (8), the fluidic purification network being a three-dimensional array of microfluidic channels (9), each microfluidic channel (9) being defined by one or more walls fluid-tight to the fluid (2), each microfluidic channel (9) comprising at least one zone (13) on the inner surface of said microfluidic channel (9) having at least one self-contained purification agent (11) and each rnicrofluidic channel (9) haying at such a zone (13) a height of less than 60 m in a direction normal to the main direction of flow (12) of the fluid, the self-contained purification agent(s) and the dimensioning of said zones (13) being configured to allow (11) a capture and/or degradation of at least 10% of the pollutants (3) by said zones, for at least one flow of the fluid to be purified, the fluidic device 1 also comprising at least three stacked layers (17, 18), at least two sides of one or more layers having, facing at least two layers, a depression pattern configured to form at least one two-dimensional array of microfluidic channels (9) when the two layers are stacked, the material of each of the layers (17, 18) having a glass transition temperature below 0 C., the bonding between two layers being achieved solely by bringing the two layers into contact at a temperature between 0 C. and 50 C.
Description
PRESENTATION OF THE FIGURES
[0072] Other features and advantages will also emerge in the following description, which is purely illustrative and non-limiting, and should be read in conjunction with the appended figures, among which:
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DETAILED DESCRIPTION
Theoretical Elements
[0091] The Stokes-Einstein relationship, described by formula (1), relates the diffusion coefficient D of a pollutant 3 in a fluid to its mobility , to the absolute temperature T and to the Boltzmann constant k.sub.B.
D=k.sub.BT (1)
[0092] Unlike large-diameter pollutants, which can for example be removed from water by sedimentation, many micropollutants have a high diffusion coefficient. Lead, for example, has a diffusion coefficient of about 5.Math.10.sup.10 m.sup.2.Math.s.sup.1 in water at 20 C.
[0093] Thus, in a confined environment, for example with a characteristic size of less than 100 m and in a short time, for example less than 5 seconds, the pollutant 3 can meet the limits of the confined environment by diffusion with a high probability, for example more than 95%.
[0094] The Pclet number Pe (or Pclet mass number) is used to characterize the ratio between the transport of a pollutant 3 by convection and by diffusion, for example in a microfluidic channel. It can be defined by the formula (2):
where L.sub.c is the characteristic length, and v is the advection velocity of the pollutant 3. The characteristic length is considered during the implementation of the invention to be equal to the length l, i.e. the length of a zone 13 having self-contained purification agents within a microfluidic channel 4 in the main direction of fluid flow.
General Architecture of the Device
[0095] With reference to
Remediation of a Pollutant
[0096] With reference to
[0097] The microfluidic channel 9 has a zone 13 on the inner surface of said microfluidic channel, with self-contained purification agents 11. For example, this zone 13 may correspond to a wall 11 with a self-contained purification agent 11 within the microfluidic channel 9, illustrated in
TABLE-US-00001 TABLE 1 Diffusion coeffi- cients D Diffusion time in water at 20 C. Pollutants 3 m.sup.2 .Math. s.sup.1 1 cm 1 mm 100 m 10 m Carbamazepine 4 .Math. 10.sup.10 6.9 h 4.2 min 2.5 s 0.03 s (CBZ, Tegretol) Diuron 5 .Math. 10.sup.10 5.6 h 3.3 min 2.0 s 0.02 s Chlordecone 2 .Math. 10.sup.10 138.9 h 83.3 min 50.0 s 0.50 s Heavy metals 10.sup.9 27.8 h 16.7 min 10.0 s 0.10 s (low limit) Heavy metals .sup.10.sup.10 277.8 h 166.7 min 100 s 1.00 s (high limit)
[0098] Thus, as shown in the central part of
[0099] For example, for pollutants 3 such as carbamazepine, diuron, chlordecone and some heavy metals, the time required to interact with a self-contained purification agent 11 is less than one second in a microfluidic channel 9 with a height of 10 m. In comparison, this time is of the order of 100 minutes and several hundred hours in channels with a height of 1 mm and 1 cm respectively. The quadratic reduction of this time with the height of the microfluidic channel 9 makes a purification of the fluid 2 possible by diffusion.
[0100] Thus, the flow of the fluid 2 in the confined microfluidic channels 9 with a height of less than 100 m, preferentially 80 m and preferentially 60 m, purifies the fluid 2 by taking advantage of the effects of the diffusion of the pollutants 3, which, in known methods, has a purifying effect only in a negligible volume of the fluid 2.
[0101] The fluidic purification network 8 is a three-dimensional array of microfluidic channels 9, each microfluidic channel 9 having at least one self-contained purification agent 11 inside the microfluidic channel 9. Thus, it is possible to run the purification implemented by a single microfluidic channel 9 in parallel in order to achieve a flow rate compatible with industrial applications, for example greater than 10 L/h and preferentially 1000 L/h, contrary to the prejudices of the prior art (Wang et al., IV, Discussion, [it] may not be used directly for practical water purification application). In all the embodiments of the invention, the purification agent(s) 11 being self-contained, no light stimulation (or more generally no external stimulation) is required to capture and/or degrade a pollutant 3. Thus, it is possible to make the microfluidic channels 9 parallel in each dimension of space, regardless, for example, of the light absorption of the material forming the microfluidic channels 9.
[0102] With reference to
[0103] With reference to
[0104] The length of the distribution channel(s) 40 and/or the collection channel(s) 41 may be between 0.4 cm and 40 cm, preferentially between 2 cm and 10 cm and preferentially between 4 cm and 6 cm. The width of the distribution channels) 40 and/or the collection channel(s) 41 may be between 10 m and 1 mm, preferentially between 50 m and 200 m and preferentially between 100 m and 150 m. Finally, the height of the distribution channel(s) 40 and/or the collection channel(s) 41 may be between 50 m and 500 m, preferentially between 100 m and 300 m and preferentially between 150 m and 200 m. The length of the microfluidic channels 9 of the fluidic purification network 8 can be between 50 m and 100 mm, preferentially between 500 m and 10 mm and preferentially between 1 mm and 3 mm. The width of the microfluidic channels 9 can be between 10 m and 1 mm, preferentially between 50 m and 200 m and preferentially between 100 m and 150 m. The height of the microfluidic channels 9 of the fluidic purification network 8 can be between 1 m and 500 m, preferentially between 5 m and 100 m and preferentially between 10 m and 60 m. A microfluidic channel 9 can have several heights: a wall of the microfluidic channel 9 can, for example, have chevron-shaped reliefs.
[0105] With reference to
[0106] A first layer 17 can for example be made of thermoplastic elastomeric material (for example polystyrene-b-poly(ethylene-butylene)-b-polystyrene or SEBS, of polystyrene-b-polybutadiene-b-polystyrene or SBS, of syndiotactic polystyrene or SPS, of Kraton, registered trademark, or of Flexdym).
[0107] A second layer 18 may for example comprise a mixture of multiphase polymers of ethylene and vinyl alcohol (EVOH) and polycondensate of cyclodextrin(s) (PCCD), a thin layer of polypropylene, SEBS, SBS, SPS, Kraton (registered trademark) or Flexdym (registered trademark). A second layer 18 can also be partially functionalized by fungal laccases.
[0108] In general, a layer 17,18 can also be made of PDMS, PFPE, PMMA or any other known material suitable for microfabrication of microfluidic channels 9.
[0109] The fluidic device 1 may comprise one comprising at least one primary channel passing through a plurality of adjacent layers to open respectively into at least one distribution channel 40 and/or at least one collection channel 41 formed between two layers 17, 18. Aligned apertures through the different adjacent layers may form a primary channel 19. It is possible to compare a primary channel 19 with a via structure in microelectronics by analogy between the electric current and the flow of the fluid 2. A primary channel 19 can be included in the fluidic distribution network 6, and allow fluid 2 to be routed to the part of the fluidic distribution network 6 at the interface of a first layer 17 and a second layer 18. A primary channel 19 can also be included in the fluidic collection network 7 and allow the purified fluid 2 to be discharged from the part of the fluidic collection network 7 at the interface of a first layer 17 and a second layer 18. In general, a primary channel 19 can fluidly connect all parts of the fluidic distribution network 6 and/or all parts of the fluidic connection network 7.
[0110] The area of a section of a primary channel 19, normal to the main direction of flow, may be between 0.01 mm.sup.2 and 100 mm.sup.2, preferentially between 0.1 mm.sup.2 and 10 mm.sup.2 and preferentially between 0.8 mm.sup.2 and 5 mm.sup.2.
[0111]
[0112] With reference to
[0113] Panel A in
[0114] Preferentially, the second layer 18 is made using a polycondensate of cyclodextrin(s), or a composition comprising at least one polycondensate of cyclodextrin(s) obtained by the reaction of the following compounds (A) to (C):
[0115] (A) at Least one cyclodextrin,
[0116] (B) at Least one Linear, branched and/or cyclic, saturated, unsaturated or aromatic polycarboxylic acid, and (C) at least one thermoplastic polymer polyol. The thermoplastic polymer polyol (C) is a copolymer of ethylene and vinyl alcohol (EVOH) and the polycondensate of cyclodextrin(s) thus obtained, or a composition comprising at least this polycondensate of cyclodextrin(s), is the self-contained purification agent 11 present on the surface of the second layer 18 and on the surface of a wall 10.
The term polycondensate refers to any polymer obtained by stepwise polymerization, where each step is a condensation reaction, which is carried out with removal of water, Monomers with two or more functional groups react to form first dimers, then longer trimers and oligomers, and then tong-chain polymers. The polycondensate of cyclodextrin(s) has a porous network which combines super-absorbent sponge-like properties with the ability to form inclusion complexes in the cavities of the cyclodextrin(s) immobilized within the polymer network, thereby allowing the capture of substances having an affinity with said polymer network. The polycondensate of cyclodextrin(s) allows the capture of, for example, metals or metallic elements, noted M, in their oxidation state 0 (M(0)), as well as substances such as medicines and pesticides. The polycondensate of cyclodextrin(s) is also obtainable by the reaction of the following compounds (A) to (C): (A) at least one cyclodextrin, (B) a linear or branched saturated aliphatic polycarboxylic acid, and (C) a copolymer of ethylene and vinyl alcohol (EVOH). The cyclodextrin (A) used is a compound of general structure (3) below, or one of the derivatives of this compound such as methyl, hydroxyalkyl, sulfoalkyl, sulfate or sugar-substituted cyclodextrins:
##STR00001##
[0117] The cyclodextrin (A) can be selected from -cyclodextrin, -cyclodextrin and -cyclodextrin. The polycondensate of cyclodextrin is obtained by the reaction of compounds (A) to (C) using only a cyclodextrin (A). The polycondensate of cyclodextrins can also be obtained by the reaction of compounds (A) to (C) using a mixture of cyclodextrins (A), for example a mixture of two, three or more cyclodextrins (A). When this mixture of cyclodextrins (A) comprises two cyclodextrins, one of these two cyclodextrins is advantageously the -cyclodextrin. Such a mixture of cyclodextrins (A) may in particular comprise, relative to the total mass of the said mixture, the following proportions by mass: [0118] 10% to 60% of -cyclodextrin, and [0119] 40% to 90% of -cyclodextrin or -cyclodextrin.
[0120] In this particular mixture of two cyclodextrins (A), the mass proportion of -cyclodextrin can advantageously be between 20% to 50% and preferentially between 25% to 40% of the total mass of the cyclodextrin mixture. In this particular mixture of two cyclodextrins (A), the proportion by mass of -cyclodextrin or -cyclodextrin may be between 50% and 80% and preferentially between 60% and 75% of the total mass of said mixture of cyclodextrins.
[0121] The compound (B) used may be a linear, branched or cyclic, saturated, unsaturated or aromatic polycarboxylic acid. Such polycarboxylic acid(s), which comprise at least two carboxyl groups COOH, may be linear, branched and/or cyclic. They can also be saturated, unsaturated or aromatic. This or these polycarboxylic acid(s) may comprise from 2 to 50, advantageously from 3 to 36, preferentially from 4 to 18 and even more preferentially from 4 to 12 carbon atoms. Compound (B) may, for example, be a saturated linear or branched aliphatic polycarboxylic acid, and/or selected from malic acid, citric acid, aconitic acid, 1,2,3-propanetricarboxylic acid, 1,2,3,4-butanetetracarboxylic acid, oxydisuccinic acid and thiodisuccinic acid. The compound (C) is a copolymer of ethylene and vinyl alcohol, known by the abbreviation EVOH. The polycondensate of cyclodextrin(s) used may be in the form of a solid compound that can be advantageously processed, for example in the form of pebbles, granules, powder or nanotubes. Being a solid compound, the polycondensate of cyclodextrin(s) can also be molded. The polycondensate of cyclodextrin(s) is obtainable by the reaction of the following compounds (A) to (C): (A) at least one cyclodextrin, (B) at least one linear, branched and/or cyclic, saturated, unsaturated or aromatic polycarboxylic acid, and (C) at least one copolymer of ethylene and vinyl alcohol (EVOH). In addition, the composition may include one or more other compound(s), which may impart properties complementary to those of the polycondensate of cyclodextrin(s), such as magnetic properties. Such compounds may include activated carbon, paints, magnetic compounds and antibacterial agents (for example silver or copper microparticles). Thus, this polycondensate of cyclodextrin(s) alone, or in admixture with one or more other compounds in a composition, enables a substance or a mixture of substances to be trapped within its structure, to immobilize it and/or to delay its release to the outside.
[0122] The polycondensate of cyclodextrin(s) and/or the composition comprising one or more polycondensate of cyclodextrin(s) can be used as a capture agent for at least one substance selected from a metallic element and an organic molecule.
[0123] Where the substance is a metallic element, this metallic element M may in particular be selected from aluminum, silver, iron, boron, tin, copper, zinc, lead, nickel, cadmium, chromium, mercury and gold.
[0124] When the substance is an organic molecule, this organic molecule has an octanol/water partition coefficient, denoted LogK.sub.ow greater than or equal to 1.5. The polycondensate of cyclodextrin(s) and the composition can be used as a capture agent for at least one organic molecule having a LogK.sub.ow, of between 1.5 and 10 and preferentially between 5 and 8.
[0125] The pollutant 3 may be an organic molecule chosen from a herbicide such as diuron, a drug, for example an anticonvulsant drug such as carbamazepine, an endocrine disruptor such as polychlorinated biphenyls (PCBs or pyralenes), phthalates and polycyclic aromatic hydrocarbons (PAHs) such as benzopyrene, these organic molecules being known to be particularly difficult to clean up environments containing them.
[0126] In particular, the polycondensate of cyclodextrin(s) according to the invention is particularly effective as a capture agent for the congeners of polychlorinated phenyls known by the abbreviations PCB 28, PCB 52, PCB 101, PCB 118, PCB 138, PCB 153 and PCB 180.
[0127] Alternatively, the polycondensate is obtainable by the reaction in which the compound (A) is selected from hydroxypropyl--cyclodextrin (HPCD), methyl--cyclodextrin (MCD) and carboxymethyl--cyclodextrin (CMCD).
[0128] Panel B in
[0129] Panel C in
Parallelization
[0130] The parallelization of the microfluidic channels 9 increases the total flow of the fluidic device 1. With reference to
[0131] With reference to
[0132] With reference to
[0133] The surface occupied, in the projection onto the principal plane of the interface between two superimposed layers, by the distribution channel or channels 40 and by the collection channel or channels 41 on the side of a layer is advantageously between 20% and 45% of the total surface of said side, preferentially between 6% and 25% of the total surface of said side and preferentially between 13% and 17% of the total surface of said side.
[0134] The surface area occupied, in the projection onto the principal plane f the interface between two superimposed layers, by the microfluidic channel or channels 9 on the side of a layer is advantageously between 20% and 70% of the total surface area of said side and preferentially between 40% and 50% of the total surface area of said side.
[0135] Thus, the layout of the fluidic distribution network 6, the fluidic collections network 7 and the fluidic purification network 8 is optimized to meet two criteria: on the one hand, to minimize the ratio between the hydrodynamic resistance of the fluidic distribution network 6 and the fluidic collection network 7 in relation to the hydrodynamic resistance of the fluidic purification network 8, and on the other hand, to maximize the surface density occupied by the fluidic purification network 8 on a layer.
[0136] With reference to
[0137] The thickness of the first layers 17 can be between 0.05 mm and 1 cm, preferentially between 0.5 mm and 2 mm and preferentially between 1 mm and 1.5 mm.
[0138] The primary channels 19 make it possible, in the case of a stack 14 of several first layers 17 and several second layers 18 to distribute or collect the fluid 2 in the channels present at each interface between a first layer 17 and a second layer 18. The dashed tines show channels at the interface of the two layers 17, 18 allowing the primary channels 19 to be connected to the other channels at the interface.
[0139] With reference to
[0140] In general, at Least three layers are stacked, at least two sides of one or more layers having, facing at least two layers, a depression pattern configured to form at least two two-dimensional arrays of microfluidic channels when the at least three layers are stacked. Thus, it is possible to parallelize the two-dimensional arrays of microfluidic channels 9 formed between two layers so as to form a three-dimensional array of micro-fluidic channels 9. Thus, the high degree of parallelization of the microfluidic channels 9 makes it possible to reduce the hydrodynamic resistance of the fluidic purification network 8 and thus to circulate fluid 2 by controlling or monitoring the system and/or the purification network 8 with a pressure variation between inlet and outlet of less than 5 bar, and preferentially less than 1 bar.
[0141] With reference to
[0142] With reference to
[0143] With reference to
[0144] The distribution connector 22 and collection connector 23 can be made of polydimethylsiloxane (PDMS) and produced by soft lithography. They can also be made of thermoplastic elastomers and structured by hot printing lithography, injection molding, 3D printing, or stereolithography. Materials such as polystyrene, polycarbonate, polyimide or other thermoplastic elastomeric materials such as polyurethane or blockamide materials can also be used. The distribution connector 22 and collection connector 23 can also be made of silicon, glass or metallic material (for example Ni, NiCo alloy, aluminum, stainless steel): thus, the fluidic device 1 can mechanically and chemically resist an organic fluid flow 2. The distribution connector 22 and collection connector 23 can be manufactured, using these materials, by 3D printing, micromachining, electroplating, wet etching and/or reactive ion etching.
Washing and Regeneration of the Fluidic Device 1
[0145] Washing fluids and/or regeneration fluids for the self-contained purification agents can be introduced into the fluidic device 1. Washing fluid means a fluid for removing impurities trapped in a fluidic device 1. Regeneration fluid means a fluid that allows the release of the pollutants 3 captured by the self-contained purification agents 11, or allows the self-contained purification agents 11 to degrade the pollutants 3 with an efficiency substantially equal to the sensitivity to the initial time at which the fluid 2 is introduced into the fluidic device 1. A combination of cleaning and regeneration fluids can be introduced into the fluidic device 1, for example at a flow rate between 0.01 L/min and 250 L/min, preferentially between 1 L/min and 2 L/min, and preferentially between 0.7 mL/min and 3 mL/min. A flow of washing and/or regeneration fluid can be coupled with thermal conditioning. For example, the temperature of the fluid 2 can be conditioned before it is introduced into a fluidic device 1. The circulation of washing and/or regeneration fluid may be discontinuous, open or closed Loop. A 5% citric acid solution can be used as a washing and regeneration solution. An oxidizing O.sub.2 plasma can also be used. This plasma can circulate, in a closed Loop, at a flow rate between 0.1 L/min and 0.5 L/min.
[0146] The washing and/or regeneration fluids may be recirculated in the same direction or in, the opposite direction to the flow of the fluid 2. In addition, the circulation and/or recirculation of the washing and/or regeneration fluid may be pulsed, i.e. the flow rate is periodic and variable, for example in slots.
General Architecture of a Purification System
[0147]
[0148] A temperature conditioning device 27 is adapted to condition the temperature inside the frame 28. Another temperature conditioning device 27 can be adapted to condition the temperature of the fluidic device 1. The temperatures of the frame and/or fluidic device 1 can be adjusted by the temperature conditioning devices between 20 C. and 250 C. For example, temperature conditioning devices may include temperature sensors to maintain a setpoint temperature by closed-loop temperature control. Thus, it is possible to adjust the purification efficiency of the fluid 2 passing through the fluidic device 1: according to the Stokes-Einstein equation, the diffusion constant of a pollutant 3 changes Linearly with temperature. An increase in temperature thus makes it possible to increase the speed at which a pollutant 3 is likely to encounter a wall with a self-contained purification agent 11.
[0149] A pump 30 is used to control the flow 16 of the fluid 2 in the purification system. Pump 30 is suitable to drive a fluid flow rate in the purification system between 0.01 L/min and 2500 L/min.
[0150] A pressure controller 31 can control a pressure inside the frame 28 whose absolute value is less than 5 bar and preferentially less than 1 bar. A pressure controller can also be adapted to control a fluid flow rate by pressure difference in the fluidic device 1. The pressure difference between inlet and outlet can be negative to attract the fluid 2 to the outlet or positive to push the fluid 2 to the outlet.
[0151] A first fluidic detection unit 32 can be fluidly connected downstream of the fluidic device 1. The fluidic detection unit 32 can measure the pollutant concentration 3 of the fluid 2 at the outlet of the fluidic device 1.
[0152] A second fluidic detection unit 33 can be fluidly connected downstream of the fluidic device 1. The second fluidic detection unit 33 allows specific analysis of washing and/or regeneration liquids.
[0153] A first outlet manifold 34 and a second outlet manifold 35 are fluidly connected to the fluidic device 1. The first outlet manifold 34 is used to collect the fluid 2 purified or partially purified by the fluidic device 1. The second manifold 35 allows to collect the regenerating fluid or the washing fluid downstream of the fluidic device 1. Fluids can be selectively conveyed to one or other of the manifolds for example by means of a valve controlled by a control unit 26.
[0154] A collection unit for regenerating fluids and/or washing fluids 37 is connected to the second outlet manifold 35.
[0155] A control unit 26 is electrically connected to the pump 30, pressure controller 31, selector valve 38, temperature conditioning devices 27, first and second outlet manifolds 34 and 35. The control unit can be a computer comprising a microprocessor and a memory. Data communication between the central unit and the other components of a purification system can be implemented via one or more wireless links. The different manifolds and/or valves can be adapted to redirect the different fluids upstream of the fluidic device 1 to allow recirculation of the fluid 2.
[0156] The detection units 32,33 may include sensors, microsystems or lab-on-a-chip to perform various fluid analyses downstream of the fluidic device 1, and transmit these analyses to the control unit. This data allows closed-loop control of recirculation in the purification system. Control units can also include fluid turbidity sensors and/or UV spectrometers. More generally, the system is adapted to purify the fluid 2 by implementing at least one recirculation of the fluid 2 in the microfluidic channel array.
[0157] The various arrows illustrate possible fluid flows in the system, the continuous lines illustrate fluid connections in the system, the dashed lines illustrate connections allowing heat transfer and the gray lines illustrate a network allowing pressure control at the ends of the network.
[0158] With reference to
[0159]
[0160] With reference to
[0161] In Step 181, a fluid 2 is passed through a microfluidic channel array 9 at a flow rate of the fluid to be purified. The speed of the fluid flow 2 or its rate of flow may be controlled by a pump 30 or a pressure controller 31, and selected to allow the self-contained purification agents 11 capture and/or degradation of at least 10%, preferentially at least 40% and preferentially at least 90% and preferentially 100% of the pollutants 3, at the flow rate of the flow. The proportion of the pollutants 3 can be measured by the first detection unit 32 downstream of the device 1. The formula (2) is used to calculate the Pclet number Pe corresponding to a pollutant 3 in the flow. The diffusion coefficient D and the length l are known values. The value of the flow rate can be calculated according to the geometry of the different channels of the system and according to the pressure applied to the system. Thus, in step 181 a fluid flow 2 is controlled in which Pe is less than 10.sup.4, preferentially less than 10 and preferentially less than 1. The flow velocity of the fluid 2 can also be chosen so that the Pclet number of the pollutant 3 in fluid 2 is between 10.sup.2 and 10.sup.4, preferentially between 10.sup.1 and 10 and preferentially between 1 and 10.sup.2 and: thus the diffusion can allow the pollutants 3 of a fluid 2 to be partially or totally captured or degraded by one or more self-contained purification agents 11, while corresponding to a flow rate sufficient for industrial applications of the purification process. In order to purify a fluid 2 with the same pollutant 3 abatement rate, it is possible to circulate the fluid in the fluidic device 1 only once at a low Pclet number of the pollutant 3, for example less than 10 and preferentially less than 1, or to carry out recirculation of the fluid 2 at a higher flow rate and therefore at a higher Pclet number of the pollutant 3, for example less than 10000 and preferentially less than 1000, and more preferentially less than 1000.
[0162] In step 182, the microfluidic channels are washed or regenerated as described above. This step may be followed by step 181. Thus, it is possible to purify a large volume of the fluid 2 by interrupting the flow of the fluid 2 by washing or regeneration of the self-contained purification agents 11.
[0163] In step 183, the fluid 2 is recirculated. Step 183 can be performed in parallel with step 181. Recirculation can be implemented by recirculating the fluid 2 in the same direction as the first circulation of the fluid 2, or in the opposite direction. In addition, the circulation and/or recirculation of the fluid 2 may be pulsed, i.e. the flow rate is not constant and is periodic. Pulsed recirculation can optimize the interaction between a pollutant 3 and a self-contained purification agent 11.
General Microfabrication Elements
[0164] The manufacture of the microfluidic channels 9, and more generally, of the channels of the fluidic distribution network 6, the fluidic connection network 7 and the fluidic purification network 8, can be implemented using microfabrication techniques using for example a substrate made of silicon, glass, but also thin, thick, rigid or flexible polymer material. A substrate can be molded, etched or micromachined. A mechanically robust substrate can present 2D and 3D microfluidic elements. The channels of the different fluidic networks can also be made by a low-cost lithographic microfabrication process using hot printing. For example, it is possible to thermomould a CD made of thermoplastic elastomeric material (similar to a plastic audio/video CD) so as to produce a plurality of interconnected microchannels, a plurality of interconnected fluid reservoirs and other dosing and mixing units.
Examples of Purifications
[0165] The purification of previously polluted water by a purification system comprising a fluidic purification device 1 was implemented.
[0166] Flows 16 of water previously polluted by various pollutants 3 were controlled in a fluidic device 1 comprising a stack 14 of 23 sub-stacks comprising a first layer 17 and a second layer 18. A controlled pressure difference of 175 Pa between the inlet and outlet of the purification system results in a fluid flow rate 2 of 2.3 L/min. The first layers 17 of thermoplastic elastomer (Flexdym, registered trademark) have a thickness of 1.3 mm and recessed structures produced by printing lithography on one side 21, using a mold microstructured with epoxy type resin. The second purification layers 18 are 0.5 mm thick. The material of the second layers 18 is an EVOH/PCCD mixture, the mass concentration of PCCD being approximately 38%. The second layers 18 are manufactured beforehand by an extrusion process, The height of the microfluidic channels 9 is 10 m.
[0167] Table 2 shows the development of the abatement rate of pollutant 3 with the flow rate of fluid 2 controlled in the purification system. Water polluted with lead at a mass concentration of 0.1 g/L is initially introduced into the purification system. Purification is carried out at room temperature (20 C.), at a continuously controlled flow rate, without washing the system and without the release of the pollutants 3 by the self-contained purification agents 11.
TABLE-US-00002 TABLE 2 Flow rate 50 L/min 20 L/min 5 L/min 1 L/min Abatement rate 30% 62% 85% 93%
[0168] Table 3 shows the development of the abatement rate of pollutant 3 with the flow rate of fluid 2 controlled in the purification system. Water polluted with carbamazepine at a mass concentration of 0.1 g/L.sup.0 is initially introduced into the purification system. Purification is carried out at room temperature (20 C.), at a continuously controlled flow rate, without washing the system and without the release of the pollutants 3 by the self-contained purification agents 11.
TABLE-US-00003 TABLE 3 Flow rate 50 L/min 20 L/min 5 L/min 1 L/min Abatement rate 14% 31% 56% 87%