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WO2017096414A1 - Puces microfluidiques et leurs utilisations - Google Patents

Puces microfluidiques et leurs utilisations Download PDF

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Publication number
WO2017096414A1
WO2017096414A1 PCT/AU2016/000391 AU2016000391W WO2017096414A1 WO 2017096414 A1 WO2017096414 A1 WO 2017096414A1 AU 2016000391 W AU2016000391 W AU 2016000391W WO 2017096414 A1 WO2017096414 A1 WO 2017096414A1
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WIPO (PCT)
Prior art keywords
liquid
gas
microfluidic chip
immiscible
channel
Prior art date
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PCT/AU2016/000391
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English (en)
Inventor
Craig Ian Priest
Frederik Hermanus KRIEL
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Adelaide University
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University of South Australia
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Filing date
Publication date
Priority claimed from AU2015905059A external-priority patent/AU2015905059A0/en
Application filed by University of South Australia filed Critical University of South Australia
Publication of WO2017096414A1 publication Critical patent/WO2017096414A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D11/00—Solvent extraction
    • B01D11/04—Solvent extraction of solutions which are liquid
    • B01D11/0496—Solvent extraction of solutions which are liquid by extraction in microfluidic devices
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N1/00—Sampling; Preparing specimens for investigation
    • G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
    • G01N1/40—Concentrating samples
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N1/00—Sampling; Preparing specimens for investigation
    • G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
    • G01N1/40—Concentrating samples
    • G01N1/4055—Concentrating samples by solubility techniques
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N1/00—Sampling; Preparing specimens for investigation
    • G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
    • G01N1/40—Concentrating samples
    • G01N1/4055—Concentrating samples by solubility techniques
    • G01N2001/4072—Concentrating samples by solubility techniques membraneless transfer of a component between two parallel laminar flows of fluid

Definitions

  • the present disclosure relates to microfluidic chips suitable for use in solvent-solvent or solvent-gas phase transfer applications.
  • microfluidics typically involves the manipulation of picolitre to microlitre volumes of fluid(s) in channels having height and width that is typically in the range of hundreds of nanometres to hundreds of micrometres.
  • Microfluidic chips incorporating microfluidic channels have been used in a variety of applications, including microreactors, separators, inkjet printers, biochemical assays, chemical synthesis, drug screening, environmental and health monitoring, and immuno specific processes.
  • Microfluidic devices and processes are becoming increasingly popular as they offer a number of advantages over conventional macro-scale devices and processes, such as compact size, automatability, reduced sample volumes, reduced processing times, integratability, increased utility, and ability to perform several processes simultaneously.
  • microfluidic chips are laminates consisting of two or more substrate plates bonded together.
  • the elements that form the fluid networks, such as channels, chambers, wells and the like through which fluids flow are disposed between the substrate plates.
  • 6,322,753 (Lindberg et al.) and U.S. Patent No. 5,932,3 15 (Lum et al.) each describes a microfluidic chip composed of juxtaposed plates that are bonded together, wherein one or more of the plates has an etched pattern of grooves on the surface facing the other plate so as to form sealed microchannels when the plates are bonded together.
  • the plates are typically bonded together using an adhesive and/or by thermal bonding.
  • Microfluidic chips can be used in a range of applications, including solvent-solvent extraction, solvent-gas extraction, phase transfer reactions, microreactions, assays, etc.
  • an analyte e.g. a metal ion or complex
  • the process includes passing the analyte-containing fluid phase along a first fluid microchannel of a microfluidic extraction device and passing an extractant fluid phase that is at least partially immiscible with the analyte-containing fluid phase along a second fluid microchannel of the microfluidic extraction device.
  • the process results in extraction of the analyte from one phase into another and has some advantages over conventional, "bulk” extraction processes.
  • different reagents and/or reactants may each be included in immiscible phases and the immiscible phases brought into contact with one another in a microfluidic device in order to bring about a reaction or interaction between the reagent(s) or reactant(s) in each phase.
  • microfluidic devices and processes have been slow.
  • One reason for this is that microfluidic devices can be difficult and costly to produce due to the high levels of precision required in order to accurately and reliably reproduce the various microscale features of the devices.
  • Other problems with microfluidic devices and processes include clogging of the channels and accumulations of air bubbles that interfere with proper microfluidic system operation.
  • microfluidic devices that can be used for solvent-solvent extraction, solvent-gas extraction and/or phase transfer applications that are relatively easy to use and/or are scalable and suitable for use on an industrial scale.
  • a microfluidic chip suitable for use in liquid-liquid or liquid-gas phase transfer applications, the microfluidic chip comprising a contact zone comprising a high aspect ratio channel in fluid connection with at least one liquid or gas inlet whereby, in use, at least two immiscible or partially immiscible liquid and/or gas streams exiting the at least one liquid or gas inlet flow adjacent one another and in contact with one another through the contact zone under conditions to allow transfer of at least some of a chemical entity from one stream to the other before the streams exit the high aspect ratio channel at a microchip outlet.
  • a microfluidic chip suitable for use in liquid- liquid or liquid-gas phase transfer applications, the microfluidic chip comprising: one or more liquid or gas inlet(s), each inlet configured to receive one or more liquids and/or gases; a contact zone comprising a high aspect ratio channel in fluid communication with the one or more liquid or gas inlet(s), said channel having a length and defining a flow path along the length of the channel, the channel being configured to receive at least two immiscible or partially immiscible liquid and/or gas streams from the one or more liquid or gas inlet(s) such that, in use, the at least two immiscible or partially immiscible liquids and/or gases flow in contact with one another along the flow path under conditions to allow transfer of at least some of a chemical entity from one of the liquids or gases to the other liquid or gas; and an outlet configured to allow the at least two immiscible or partially immiscible liquids and/
  • the high aspect ratio channel has a width and a depth and is configured such that each liquid or gas stream formed in the channel has a width to depth ratio of > 1.
  • multiple streams of each of the two immiscible or partial ly immiscible liquids and/or gases flow in contact with one another in the contact zone or flow path.
  • Streams of each immiscible or partially immiscible liquid and/or gas may alternate with one another across the width of the channel.
  • streams of each immiscible or partially immiscible liquid and/or gas do not need to alternate in type or composition across the width of the channel and, for example, two aqueous streams (which are miscible) could meet between organic streams (which are immiscible or partially immiscible with the aqueous stream) for an aqueous phase reaction to occur and the product of the reaction may then transfer immediately into the organic stream.
  • multiple liquid or gas streams may be used provided at least one of the streams is immiscible or partially immiscible with the other stream(s).
  • the microfluidic chip further comprises a collection chamber in fluid connection with the outlet, the collection chamber configured to receive the at least two immiscible or partially immiscible liquids and/or gases exiting the microfluidic chip.
  • the immiscible or partially immiscible liquids and/or gases may separate or disengage into separate phases in the collection chamber.
  • the microfluidic chip further comprises an inlet channel zone comprising a plurality of microchannels with each microchannel in fluid connection with a liquid or gas inlet and with the high aspect ratio channel.
  • microchannels are substantially parallel to one another immediately adjacent the contact zone.
  • the plurality of microchannels are configured so that the
  • a microfluidic device comprising one or more microfluidic chip(s) according to either the first or the second aspect, a housing containing said microfluidic chip(s), connection means for connecting said microfluidic chip(s) with one another, at least one inlet for the at least two immiscible liquids and/or gases, and an outlet.
  • a process for extracting a chemical entity from a first liquid or gas containing the chemical entity comprising: passing the first liquid or gas through at least one liquid or gas inlet of a microfluidic chip of either the first aspect or the second aspect; passing a second liquid or gas that is immiscible or partially immiscible with the first liquid or gas through at least one liquid or gas inlet of the microfluidic chip of either the first aspect or the second aspect; allowing the first liquid or gas and the second liquid or gas to contact one another in the contact zone to allow transfer of at least some of the chemical entity from the first liquid or gas to the second liquid or gas; and separating the second liquid or gas from the first liquid or gas.
  • the first liquid or gas and the second liquid or gas may each be an organic solution, an aqueous solution, an ionic liquid solution or a gas provided that the two liquids or gases are immiscible.
  • the second liquid or gas may comprise an extractant, or it may comprise the substantially no extractant (relying, instead, on a preferential solubility of the chemical entity in the second liquid or gas).
  • a microfluidic chip of the first or second aspects or a microfluidic device of the third aspect in a solvent extraction or an ion exchange process.
  • Figure 1 is a plan view of a prior art microfluidic chip 10 as described in WO 2010/022441 ;
  • Figure 2 is a plan view of an embodiment of a microfluidic chip 20 of the present disclosure containing 25 organic and 24 aqueous inlets/streams and a single high aspect ratio outlet;
  • Figure 3 is a plan view of another embodiment of a microfluidic chip 20 of the present disclosure containing 25 organic and 24 aqueous inlets/streams and a single high aspect ratio outlet;
  • Figure 4 is a side view of the embodiment of the microfiuidic chip 20 shown in Figure 3;
  • Figure 5 shows images of flow in the chip design of the present disclosure visualised with blue dye in water and organic solvent (left) and for precious metal feed solution and secondary amine extractant in organic solvent (right);
  • Figure 6 shows images showing the widths of the organic (colourless) and aqueous (brown) streams for various aqueous inlet pressures and fixed organic inlet pressure (50 kPa).
  • the aqueous inlet pressures were (a) 30, (b) 35, (c) 40, (d) 42.5, (e) 45, (f) 47.5, (g) 50, (h) 55, (i) 60, (j) 65, and (k) 70 kPa;
  • Figure 7 shows: Left: Calculated organic/aqueous flow rate ratio, R, plotted against the inlet pressure ratio. Inset images are taken from Figure 6. The horizontal dotted line corresponds to the condition R ⁇ when the pressure ratio is 1 . Right: Measured stream widths plotted against the measured R, showing good agreement with the theoretical prediction ( ⁇ aqueous, organic, - theoretical);
  • Figure 8 shows plots of the concentration of platinum group metal left in solution after extraction plotted against R for bulk SX (variable R), a Y-Y chip with symmetrical channels (R ⁇ 0.56), and the chip design of the present disclosure ('same P' means R ⁇ 0.56; 'variable P' means that the relative inlet pressures were altered to vary R) ( ⁇ Bulk, A Symmetrical Y-Y, ⁇ Asymmetric Y-Y, ⁇ New chip design (fixed P), * New chip design (variable P)) ;
  • Figure 10 shows an illustration of a counter-current circuit using the chip design of the present disclosure
  • Figure 11 shows (a) vials containing the aqueous phase: loaded (before extraction, A), after one extraction stage (B), and after two stages (C). (b) Vials containing the organic phase: fresh (before extraction, D), after one stage extraction (C), and after two stages extraction (B); and
  • Figure 12 shows aqueous platinum group metal concentrations in a two-stage counter-current microSX circuit using the chip design of the present disclosure. DESCRIPTION OF EMBODIMENTS
  • microfluidic solvent-solvent and solvent-gas extraction processes to industrial extractions and, particularly, in solvent-solvent and solvent-gas extraction processes used in mineral processing industries, such as in the extraction of leach solutions.
  • solvent-solvent and solvent-gas extraction processes used in mineral processing industries, such as in the extraction of leach solutions.
  • illustrated embodiments that are suitable for use in such microfluidic solvent extraction processes.
  • the disclosure herein is not limited to any one specific application and the person skilled in the art will appreciate that the microfluidic chips, devices and processes described herein can also be used in other processes that exploit microfluidic technology, for example, extraction of particulate biomaterials, extraction of environmental samples, synthetic chemistry, and immunospecific and other biological purification processes.
  • liquid-liquid extraction processes refer to liquid-liquid extraction processes but the present disclosure is equally applicable to liquid-gas or gas-gas extraction processes in which the liquid and gas, or the two gases are immiscible or partially immiscible.
  • the microfluidic chips, devices and processes described herein could be used for two phase reactions where a different reagent is present in each immiscible or partially immiscible liquid or gas. Such applications are collectively referred to herein as “liquid-liquid phase transfer applications” or “solvent-gas phase transfer applications”.
  • Liquid-liquid extraction also known as “solvent extraction” or “SX" is a process that is commonly used for the recovery or removal of analytes or solutes from solution.
  • Typical solvent extraction processes involve contacting an analyte-containing aqueous phase with an organic liquid phase having an affinity for a solute and mixing the two phases to distribute small droplets of one phase in the other phase, and subsequently separating the two phases by gravity. When the phases are mixed, there is diffusive transfer of solute from the small droplets into the other phase or vice versa.
  • solvent extraction is usually carried out using a large volume, two stage vessel known as a mixer-settler.
  • the two immiscible liquid phases are mutually dispersed under turbulent flow conditions so that the chemical entity of interest can transfer by diffusion from one liquid into the second liquid.
  • the mutually dispersed phases then flow into the settler where they are allowed to coalesce and settle by gravity whereupon at least a portion of the chemical entity is dispersed in the second liquid.
  • Solvent extraction is used in a number of areas, including the extraction of metals from leach solutions and environmental samples, as well as in synthetic chemistry.
  • Mineral processing in particular, is a widely used application of solvent extraction. Many mineral processing plants utilise
  • hydrometallurgical processes as part of an extractive metallurgical operation and solvent extraction is an important step in the recovery of economically significant metals from ores.
  • a typical solvent extraction process in this context entails preferentially removing a target metal or metal complex (i.e. a chemical entity of interest) from an aqueous phase, and transferring it to an organic phase so that the metal can ultimately be recovered.
  • a target metal or metal complex i.e. a chemical entity of interest
  • solvent extraction processes one or more metal species present in an aqueous solution may be removed so that the aqueous solution itself can be re-used.
  • Solvent extraction processes of this type are used in the remediation of contaminated soils, tannery effluent, and galvanic sludge, which contain harmful levels of heavy metals, such as chromium.
  • an analyte-containing fluid phase is passed along a first fluid microchannel 12 and an extractant fluid phase that is at least partially immiscible with the analyte-containing fluid phase is also passed along a second fluid microchannel 14.
  • the analyte-containing fluid phase and the extractant fluid phase contact one another at a contact zone 16 formed between the first and second fluid microchannels 12 and 14 so that the solute is able to diffuse from the analyte-containing fluid phase into the extractant fluid phase.
  • the chip 10 is particularly effective at separations from particle laden phases but is less suitable for use in some applications.
  • the present disclosure relates to an improved microfluidic chip 20.
  • the chip 20 is suitable for use in solvent extraction but could also be used in other liquid-liquid phase transfer applications or liquid-gas phase transfer applications, as described previously.
  • the microfluidic chip 20 comprises a contact zone 22 comprising a high aspect ratio channel 24 in fluid connection with at least one liquid or gas inlet 26.
  • a contact zone 22 comprising a high aspect ratio channel 24 in fluid connection with at least one liquid or gas inlet 26.
  • at least two immiscible or partially immiscible liquid and/or gas streams 28 and 30 exiting the at least one liquid or gas inlet 26 flow adjacent one another and in contact with one another through the contact zone 22 under conditions to allow transfer of at least some of a chemical entity from one stream to the other before the streams exit the high aspect ratio channel 24 at a microchip outlet 32.
  • the at least two immiscible or partially immiscible liquid and/or gas streams 28 and 30 can be any combination of organic liquids, aqueous liquids, ionic liquids or gases provided that at least two of the liquids or gases are not miscible or are only partially miscible with one another.
  • the at least two immiscible or partially immiscible liquid and/or gas streams 28 and 30 may be two liquid streams, two gas streams or a liquid stream and a gas stream, provided they are not miscible or are only partially miscible with one another.
  • liquids and/or gases can be used with two of the liquids or gases miscible with one another and two of the liquids or gases immiscible.
  • immiscible and variants thereof, as used throughout the specification means that two phases, if mixed together, will separate and not form a homogeneous mixture.
  • partially immiscible and variants thereof, as used throughout the specification means that two phases may have some (albeit relatively low) solubility of one phase in the other phase.
  • two liquids can be considered “partially miscible” if shaking equal volumes of the liquids together results in a meniscus visible between two layers of liquid, but the volumes of the layers are not identical to the volumes of the liquids originally mixed.
  • the high aspect ratio channel 24 has a length 34 and defines a flow path along the length of the channel 24.
  • the channel 24 is configured to receive the at least two immiscible or partially immiscible liquids and/or gases 28 and 30 such that, in use, the at least two immiscible or partially immiscible liquids and/or gases 28 and 30 flow in contact with one another along the flow path under conditions to allow transfer of at least some of a chemical entity from one of the liquids or gases to the other liquid or gas.
  • the term "high aspect ratio channel” means a channel that is configured such that each liquid or gas stream 28 or 30 formed in the channel 24 has a width to depth ratio of more than 1. These conditions apply to all streams but some streams may be much wider than others.
  • the depth of the high aspect ratio channel 24 is either 32 or 34 ⁇ m and the width of each stream 28 or 30 formed in the channel is larger than 32 or 34 ⁇ and smaller than 268 or 266 ⁇ giving the contact zone a total width of ⁇ 7.3 mm (ie. width to depth ratios of more than 1 for each stream formed).
  • the microfluidic chip 20 may comprise one liquid or gas inlet 26 through which both liquid streams 28 and 30 enter the high aspect ratio channel 24.
  • the microfluidic chip 20 may comprise a plurality of liquid or gas inlets 26.
  • a plurality of first liquid stream inlets 44 are alternately disposed between a plurality of second liquid stream inlets 46 at an upstream end of the high aspect ratio channel 24.
  • first and second liquid streams are formed across the width of the high aspect ratio channel 24.
  • first and second liquid streams could meet between second liquid streams 46 which are immiscible with the first liquid streams.
  • a phase reaction may occur when the two miscible streams 44a and 44b combine and mix and the product thus formed can then transfer into the second liquid stream 46.
  • aqueous streams having different pH could mix and initiate a reaction and then the reaction product could transfer to an immiscible or partially immiscible liquid.
  • the first liquid and second liquid can be transferred from a source of each liquid to the at least one liquid or gas inlet 26 using any suitable method.
  • a channel may be in fluid connection with a reservoir of liquid and the one or more inlets 26 or a reservoir of liquid may be in direct fluid connection with one or more liquid or gas inlets 26.
  • the liquid or gas inlets 26 can take any suitable form.
  • the inlets 26 are in the form of apertures or openings in an end wall of the high aspect ratio channel 24. It is contemplated that one or more of the inlets 26 could be located in a top or bottom wall of the high aspect ratio channel 24 provided said inlets 26 are generally located at an upstream end of the high aspect ratio channel 24 (ie. an end of the high aspect ratio channel 24 that is most distant from the outlet 32).
  • the chip 20 comprises a substrate 36 comprising an inlet channel zone 38 comprising at least two microchannels 40 with each microchannel 40 in fluid connection with a liquid or gas inlet 26.
  • the inlet channel zone 38 may comprise a plurality of first liquid stream microchannels 44 each in fluid connection with a first liquid stream inlet 26a and a plurality of second liquid stream microchannels 46 each in fluid connection with a second liquid stream inlet 26b, wherein the first liquid and second liquid are immiscible with one another.
  • the first liquid stream may be an aqueous stream and the second liquid stream may be an organic stream.
  • the first liquid stream microchannels 44 and the second liquid stream microchannels 46 are substantially parallel to one another and are configured so that the first liquid stream microchannels 44 and the second liquid stream microchannels 46 are alternately disposed in the inlet channel zone 38 with each microchannel 44 and 46 configured to form discrete streams within each microchannel.
  • Each microchannel 44 and 46 comprises an outlet 48 adjacent to and upstream of the contact zone 22.
  • microfluidic means that the chip, device, apparatus, substrate or related apparatus contains fluid control features that have at least one dimension that is sub-millimetre and, typically less than 100 ⁇ , and greater than 1 ⁇ .
  • microchannel means a channel having at least one dimension that is sub- millimetre and, typically less than 100 ⁇ , and greater than I ⁇ m.
  • microfluidic extraction means an extraction in which the volume of fluids involved in the liquid-liquid contact stage of an extraction are in the picolitre, nanolitre or microlitre range.
  • a network of microfluidic chips and/or devices can be connected together in series and/or parallel and used to process large volumes (millilitres to litres) of fluids using continuous throughput processing.
  • the substrate 36 may take any suitable form and be made from any suitable material.
  • the substrate is formed from plates 50 and 52 that are held together in a face to face manner to form the microfluidic chip 20.
  • the plates 50 and 52 are thin, rectangular plates that are formed from a suitable material.
  • Materials suitable for the manufacture of plates for microfluidic chips are known in the art and may be chosen based on considerations such as cost, inertness or reactivity toward fluids and other materials that will be in contact with the chip, etc.
  • suitable substrate materials include glass, quartz, metal (e.g. stainless steel, copper), silicon, and polymers.
  • the substrate is a glass substrate.
  • Pyrex glass microfluidic chips may be suitable.
  • Suitable polymeric substrates include polydimethylsiloxane (PDMS), polytetrafluoroethylene (PTFE), other perfluoropolyether (PFPE) based elastomers, polymethylmethacrylate (PMMA), silicone, and the like.
  • PDMS polydimethylsiloxane
  • PTFE polytetrafluoroethylene
  • PFPE perfluoropolyether
  • PMMA polymethylmethacrylate
  • silicone silicone, and the like.
  • the plates 50 and 52 in the illustrated embodiments are rectangular in plan view but it is envisaged that they can be other shapes in plan view, such as circular, square, etc.
  • the plates 50 and 52 have a thickness adequate for maintaining the integrity of the microfluidic chip assembly. In the illustrated embodiments, the plates 50 and 52 are about 1.1 mm thick.
  • the first liquid stream microchannels 44 and the second liquid stream microchannels 46 are formed on the plate 50 and that plate is then capped with the second plate 52 to form covered
  • microchannels Methods for forming fluid microchannel networks are known in the art.
  • the microchips can be fabricated using standard photolithographic and etching procedures including soft lithography techniques (e.g. see Shi J., et al., Applied Physics Letters 91 , 153 1 14 (2007); Chen Q., et al., Journal of Microelectromechanical Systems, 16, 1 193 (2007); or Duffy et al, Rapid Prototyping of Microfluidic Systems in Poly(dimethylsiloxane), Anal.
  • soft lithography techniques e.g. see Shi J., et al., Applied Physics Letters 91 , 153 1 14 (2007); Chen Q., et al., Journal of Microelectromechanical Systems, 16, 1 193 (2007); or Duffy et al, Rapid Prototyping of Microfluidic Systems in Poly(dimethylsiloxane), Anal.
  • Direct machining or forming techniques may also be used as suited to the particular chip. Such techniques may include hot embossing, cold stamping, injection moulding, direct mechanical milling, laser etching, chemical etching, reactive ion etching, physical and chemical vapour deposition, and plasma sputtering. The particular methods used will depend on the function of the particular microfluidic network, the materials used as well as ease and economy of production.
  • the first liquid stream microchannels 44 may be formed from or lined with a first material and the second liquid stream microchannels 46 may be formed from or lined with a second material, the first and second materials being different.
  • the materials may be hydrophilic materials or hydrophobic materials.
  • the first material may be glass which provides a relatively hydrophilic surface in the microchannels 44 suitable for use with an aqueous stream and the second material may be polytetrafluoroethylene which provides a relatively hydrophobic surface in the microchannels 46 suitable for use with an organic stream.
  • a plurality of the first liquid stream microchannels 44 and a plurality of the second liquid stream microchannels 46 together form the inlet channel zone 38.
  • the first liquid stream microchannels 44 and the second liquid stream microchannels 46 are substantially parallel to one another immediately prior to connecting with the high aspect ratio channel 24.
  • substantially parallel means that the microchannels 44 and 46 are mutually aligned and generally disposed with the same orientation with respect to one another.
  • a longitudinal axis of one microchannel may be angled slightly (e.g. at an angle of less than about 5°) with respect to an adjacent microchannel without affecting the operation of the microfluidic chip 20.
  • the microchannels 44 and 46 prior to the microchannels 44 and 46 becoming substantially parallel to one another immediately prior to connecting with the high aspect ratio channel 24 the microchannels 44 and 46 can be any arrangement, configuration, shape and/or angle with respect to one another.
  • the first liquid stream microchannels 44 and the second liquid stream microchannels 46 are alternately disposed in the inlet channel zone 38.
  • the inlet channel zone 38 comprises alternate first liquid 44 and second liquid 46 stream microchannels.
  • n microchannels for the stream that contains the solute ie. first liquid or second liquid depending on the solute
  • «+ / microchannels for the other stream there may be n aqueous stream microchannels 44 and n+J organic stream microchannels 46.
  • each aqueous stream is flanked by an organic stream in the contact zone 22, although this is not a necessary condition.
  • n may be an integer from 1 to 1000.
  • Each microchannel 44 and 46 is configured to form a discrete liquid stream within each microchannel. As described previously, the microchannels 44 and 46 are formed in one of the plates 50 and then capped by the second plate 52 to form enclosed microchannels 44 and 46.
  • the microchannels 44 and 46 may have a depth (ie. height) of 1 to 500 ⁇ m, such as 10 to 50 ⁇ m . In the illustrated embodiments, the microchannels 44 and 46 have a height of 32 ⁇ m or 34 ⁇ m .
  • Each first liquid stream microchannel 44 is in fluid connection with a first liquid stream inlet 26a and each second liquid stream microchannel 46 is in fluid connection with a second liquid stream inlet 26b.
  • the inlets 26a and 26b may be in the form of holes or apertures in the top of the microfluidic chip 20.
  • the aqueous first liquid inlets 26b may be in fluid connection with a first liquid phase reservoir 54.
  • the second liquid stream inlets 56 may be in fluid connection with a second liquid phase reservoir 56.
  • the reservoirs 54 and 56 may be any suitable form. In the illustrated embodiments the reservoirs are cut out sections formed on top of the microfluidic chip 20.
  • Each reservoir 54 and 56 can be connected to inlet tubing (not shown) and fed with the first liquid and second liquids on a continuous basis, as required.
  • the inlet microchannels may be from 1 ⁇ to 1000 ⁇ in depth or width.
  • the size of the microchannels may also differ from one another in both dimensions.
  • An inner surface of one or more of the microchannels 42 and 44 may be modified to minimise or prevent adsorption of particles to the surface.
  • the inner surface may be modified with a chemical agent.
  • Suitable chemical agents include, for example, poly(ethylene glycol), chlorosilanes, methoxysilanes, hydroxysilanes, and their amine, hydroxy, fluorine, carboxylic, derivatives, amine compounds, polyelectrolytes such as poly(methacrylic acid), poly(allylamine), poly(N- vinylpyrrolidone) etc.
  • an inner surface of one or more of the microchannels 42 and 44 may be modified with nanostructures, such as nanoprotrusion or nanoholes. Methods for modifying microchannels are known in the art.
  • the aqueous and organic streams flow in the first liquid stream microchannels 44 and the second liquid stream microchannels 46, respectively, until they reach an inlet 26 adjacent to and upstream of a contact zone 22.
  • the streams in each microchannel 44 and 46 are initially separate streams (e.g. aqueous and organic) in the inlet channel zone 38 until they reach the inlets 26 adjacent to and upstream of a contact zone 22.
  • the first and second liquid streams exiting the respective microchannels 44 and 46 then flow alongside one another and in contact with each adjacent stream(s) through the contact zone 22.
  • the streams 44 and 46 are free to broaden or narrow at the entrance of the contact zone 22 depending on flow conditions.
  • phase disengagement occurs when the first and second (immiscible) streams exit the microchip 20 at the outlet 32. Both phases can be collected in a collection chamber 58, such as a settler, after which the phases can be separated in the normal manner.
  • the microfluidic chip 20 further comprises a collection chamber 58 configured to receive the at least two immiscible liquids exiting the microfluidic chip.
  • solvent extraction such as liquid-liquid extraction
  • extraction of all of the chemical entity present in one liquid into the other liquid may occur completely in the contact zone 22. If extraction is not complete in the contact zone 22 there may also be some off-chip extraction that takes place in the collection chamber 58.
  • the processing steps are carried out under continuous flow conditions.
  • a range of processing parameters can be precisely controlled by adjusting flow rate alone, e.g. volumetric throughput, extraction efficiency, and extraction time.
  • Typical flow rates for either the first liquid or the second liquid may be between 1 ⁇ L/h to 100 mL/h per stream.
  • the first and second liquids may be transferred to the inlets 26 and along the contact zone 22 under positive pressure provided by a suitable pump (in which case the first liquid and second liquid can be delivered independently of one another and their respective flow rates may be different), by drawing the liquids through the chip 20 under vacuum, or by gravity feed.
  • a suitable pump in which case the first liquid and second liquid can be delivered independently of one another and their respective flow rates may be different
  • Devices for transferring liquids and gases to and through microfluidic networks are known in the art.
  • the extraction efficiency can be determined using any suitable technique. UV-visible spectroscopy (off-line or on-line analysis), ICP (off-line), and/or thermal lens microscopy (online analysis) may be suitable.
  • the microfluidic chip and device described herein can be used in processes where a physical or chemical reaction takes place between reagents that are initially separate in immiscible or partially immiscible liquids (a phase- transfer reaction), processes where a physical or chemical reaction takes place in one of the liquids (which may be one or more merged miscible or immiscible streams) and the product transfers to another immiscible liquid, extraction/mass transfer or transfer of reaction products from one phase to another.
  • the product is referred to herein as a "chemical entity”.
  • the either the first liquid or the second liquid contains a chemical entity to be extracted.
  • the chemical entity may be referred to as a solute.
  • the first liquid may be an aqueous phase comprising an ore sample (or more specifically a leach solution derived therefrom), mineral tailings, a refinery waste stream, a tannery waste stream, an aqueous soil sample, etc containing metal ions of interest.
  • the extraction process may be used to recover the metal ions (such as in mineral processing) or to remove the metal ions from the aqueous stream so that it can be further processed (such as in remediation of soil or tannery waste streams).
  • the first liquid or the second liquid may or may not comprise an extractant.
  • the metal ion may be selected from one or more ions of the group of metals consisting of: Be, Mg, Al, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, As, Se, Rb, Sr, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, In, Sn, Sb, Te, Cs, Ba, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, Tl, Pb, Bi, Po, At, Rn, Fr, Ra, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Er, Tm, Yb, Lu, Ac, Th, Pr, U, Np, Pu, Am, Cm, Bk, and Cf.
  • the metal ion may be selected from one or more ions of the group of metals consisting of: Be, Mg, Al, Sc, Ti, V, Cr, Mn, Fe,
  • the metal ion will be partitioned when it is in the form of a metal complex.
  • the metal complex may be formed by treating the aqueous solution with a ligand for the metal of interest.
  • a sample containing Pt 4 may be treated with a solution of HCl to form an aqueous solution containing [PtCl 6 ] 2- which is then subjected to the extraction process described herein.
  • a sample containing Cu 2 may be treated with a solution of 2-hydroxy-5-nonylacetophenone oxime (LIX) to form an aqueous solution containing Cu(LIX) 2 which is then subjected to the extraction process described herein.
  • LIX 2-hydroxy-5-nonylacetophenone oxime
  • the organic phase may contain the ligand so that when the aqueous phase (containing the metal ion of interest) and the organic phase come in to contact at the contact zone 22 the ligand is able to diffuse into the aqueous phase or to the liquid-liquid interface where it can form a complex with the metal ion of interest.
  • the metal complex thus formed may then diffuse in to organic phase.
  • the ligand used will depend on the metal ion of interest but may be selected from the group consisting of (but not limited to): alkyl sulfides, alkyl phosphates, alkyl amines, alkyl phosphoric acids, ketoximes, aldoximes, and derivatives of any of the aforementioned.
  • the organic phase is a non-aqueous fluid phase that is at least partially immiscible with the aqueous phase.
  • the organic phase is chloroform.
  • the organic phase is a hydrocarbon liquid.
  • solvents could also be used including: alkanes, alkenes, alkynes, alcohols, aldehydes, ketones, acids, esters, aromatics and their halogen, sulfur, phosphorous, and nitrogen-containing derivatives, silicone oils and their halogen, sulfur, phosphorous, and nitrogen- containing derivatives, petroleum (all commercial grades) and petroleum-based products, and mixtures thereof.
  • the solubility of the metal or metal complex in a particular solvent may guide the choice of solvent.
  • the solubility of the metal ligand complex in the aqueous phase is strongly dependent on the metal ion. This enables selective separation of low solubility metal complexes, e.g. Cr and Be. Selectivity can also be achieved by selective metal ligand complex formation.
  • the ligand might bind to only one (or a few) of the metal ions.
  • the process may also include a further step of recovering the solute from the organic or aqueous phase, as required.
  • use of the methods of the present disclosure may lead to reduced footprints for solvent extraction unit operations and, because the microchannels are closed systems, greater potential for recycling of volatile liquids and reduced human and environmental exposure to potentially hazardous chemicals.
  • the microfluidic chip 20 may be part of a microfluidic device comprising one or more microfluidic chips 20, a housing containing said microfluidic chip(s) 20, connection means for connecting said microfluidic chip(s) with one another, at least one inlet for the at least two immiscible liquids and/or gases, and an outlet.
  • the microfluidic device further comprises a collection chamber in fluid connection with the outlet, the collection chamber configured to receive the at least two immiscible liquids and/or gases exiting the microfluidic chip.
  • the microfluidic device may further comprise at least one flow controller for introducing the first liquid and/or the second liquid to the microfluidic chip 20.
  • the flow controller may include one or more valves, flow diverters, or fluid diodes.
  • the microfluidic device may further comprise a flow detector or sensor. There may be a feedback loop between the flow detector or sensor and the flow controller whereby the flow detector or sensor is configured to produce a signal which is transmitted to the flow controller in order to control the flow rate of the first liquid and/or second liquid via the flow controller.
  • the microfluidic device may be used, for example, in an apparatus for extracting an analyte from a sample.
  • Also provided herein is process for extracting a chemical entity from a first liquid or gas containing the chemical entity comprising: passing the first liquid or gas through at least one liquid or gas inlet of a microfluidic chip of either the first aspect or the second aspect; passing a second liquid or gas that is immiscible or partially immiscible with the first liquid or gas through at least one liquid or gas inlet of the microfluidic chip of either the first aspect or the second aspect; allowing the first liquid or gas and the second liquid or gas to contact one another in the contact zone to allow transfer of at least some of the chemical entity from the first liquid or gas to the second liquid or gas; and separating the second liquid or gas from the first liquid or gas.
  • microfluidic chip 20 or a microfluidic device comprising at least one microfluidic chip 20 in a solvent extraction process is also provided herein.
  • Example 1 Preparation and use of microfluidic chip
  • FIG. 3 An embodiment of a microfluidic chip 20 of the present disclosure is shown in Figure 3.
  • Inlet tubing (not shown) is connected to rectangular reservoirs 54 and 56 which, in turn, feed twenty five organic phase inlets 26a and twenty four aqueous phase inlet holes 26b located in the plate 50.
  • the extra organic inlet hole 26a (and therefore stream within the chip) is required to ensure that each aqueous phase stream is flanked by an organic phase stream in the contact zone 22.
  • FIG. 5 shows two examples of the parallel streams that form in the contact zone (indicated in the figure).
  • the only preferred criterion for effective extraction is continuous (unbroken) streams, which occurs when the stream width is greater than the channel height 1 , so the variability of the width of the streams shown in the figures is unimportant.
  • An advantage of the microfluidic chip design is the ability to vary the flow rate ratio using a single chip. In this case, the streams adjust their relative widths according to the relative flow rate and relative viscosity.
  • the contact zone under consideration is rectangular and the flow is in the x-axis direction.
  • the total channel width (W) is in the y-axis, while the channel height (h) is in the z-axis.
  • the analytical and numerical models are reduced to two dimensions.
  • the width of the aqueous and organic channels are w a and w o , respectively. Due to the large channel aspect ratio, W/h > 2000, the flow behaviours can be described by a Hele-Shaw cell approximation. If one examine the bulk of any of the liquid streams away from an interface or wall, the Napier-Stokes equation reduces to: 2-5
  • A is the cross-sectional area. As the height is equal for all streams, the relationship
  • the width of the respective organic and aqueous streams are determined by the flow rate ratio and viscosity ratio.
  • the aqueous stream widens from a very thin stream at low aqueous:organic inlet pressure ratio (30 kPa : 50 kPa) to a wide aqueous stream (narrow organic stream) at high inlet pressure ratio (70 kPa : 50 kPa).
  • the organic phase inlet pressure was kept constant at 50 kPa throughout these experiments.
  • FIG. 1 1 shows the collected samples.
  • the fully loaded aqueous phase is shown to the left of picture (a).
  • the fresh organic phase is shown to the right of picture (b).
  • the aqueous and organic phase outputs from the chips at positions B and C are shown in separate vials (see figure caption for details).
  • the platinum concentration of each aqueous solution is plotted in Figure 12. After one stage the concentration of platinum is reduced to approximately 40% of the original concentration after one stage and to approximately 8 % of original after two stages.
  • a new microfluidic chip was designed and prepared, which enables tuning of R, greater flow stability, higher volumetric throughput, and can operate in continuous flow. Furthermore, the extraction appears to be very efficient, giving an equilibrium concentration of platinum closer to that expected based on bulk SX experiments. Finally, a two-stage counter-current coupling of microSX chips was achieved.

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  • Extraction Or Liquid Replacement (AREA)

Abstract

L'invention concerne une puce microfluidique pouvant être utilisée dans des applications de transfert de phase liquide-liquide ou liquide-gaz. La puce microfluidique comprend une zone de contact comprenant un canal à facteur de forme élevé en communication fluidique avec au moins une entrée de liquide ou de gaz, grâce à quoi, en service, au moins deux flux de gaz et/ou de liquides non miscibles ou partiellement non miscibles sortant de ladite entrée de liquide ou de gaz s'écoulent de manière adjacente l'un à l'autre et en contact l'un avec l'autre par la zone de contact dans des conditions permettant le transfert d'au moins une partie d'une entité chimique d'un flux à l'autre avant que les flux sortent du canal à rapport de forme élevé vers une sortie de micropuce.
PCT/AU2016/000391 2015-12-07 2016-12-07 Puces microfluidiques et leurs utilisations Ceased WO2017096414A1 (fr)

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CN114450077A (zh) * 2019-09-26 2022-05-06 香奈儿香水美妆品公司 用于从植物油中微流体萃取的方法

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CN108707536A (zh) * 2018-04-10 2018-10-26 广东顺德墨赛生物科技有限公司 液滴生成方法和系统
US20210229094A1 (en) * 2018-07-09 2021-07-29 Hewlett-Packard Development Company, L.P. Microfluidic devices
US11813610B2 (en) * 2018-07-09 2023-11-14 Hewlett-Packard Development Company, L.P. Microfluidic devices
CN109967146A (zh) * 2019-04-16 2019-07-05 中国工程物理研究院材料研究所 一种微流控层流芯片及其制备方法
CN114450077A (zh) * 2019-09-26 2022-05-06 香奈儿香水美妆品公司 用于从植物油中微流体萃取的方法
CN112858177A (zh) * 2019-11-26 2021-05-28 武汉理工大学 一种基于微流控萃取技术的重金属离子在线检测芯片
CN111504406A (zh) * 2020-05-15 2020-08-07 大连理工大学 一种超微小流量液体的流量检测芯片及检测方法
CN113484496A (zh) * 2021-04-27 2021-10-08 合肥工业大学 一种基于微流控芯片观测絮体污泥的装置及方法
CN113484496B (zh) * 2021-04-27 2024-01-09 合肥工业大学 一种基于微流控芯片观测絮体污泥的装置及方法

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