WO2003082429A2 - Separation liquide/liquide - Google Patents

Separation liquide/liquide Download PDF

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Publication number
WO2003082429A2
WO2003082429A2 PCT/GB2003/001421 GB0301421W WO03082429A2 WO 2003082429 A2 WO2003082429 A2 WO 2003082429A2 GB 0301421 W GB0301421 W GB 0301421W WO 03082429 A2 WO03082429 A2 WO 03082429A2
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WO
WIPO (PCT)
Prior art keywords
channels
phases
liquid
liquid phases
junction
Prior art date
Application number
PCT/GB2003/001421
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English (en)
Other versions
WO2003082429A3 (fr
Inventor
Kai Friedrich Hoettges
Derek Stevenson
Kevin Peter Homewood
Russell Mark Gwilliam
Original Assignee
University Of Surrey
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by University Of Surrey filed Critical University Of Surrey
Priority to AU2003214475A priority Critical patent/AU2003214475A1/en
Publication of WO2003082429A2 publication Critical patent/WO2003082429A2/fr
Publication of WO2003082429A3 publication Critical patent/WO2003082429A3/fr

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Classifications

    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D17/00—Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
    • B01D17/02—Separation of non-miscible liquids
    • B01D17/0202—Separation of non-miscible liquids by ab- or adsorption
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D17/00—Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
    • B01D17/02—Separation of non-miscible liquids
    • B01D17/04—Breaking emulsions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D17/00—Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
    • B01D17/08—Thickening liquid suspensions by filtration
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00781—Aspects relating to microreactors
    • B01J2219/00819—Materials of construction
    • B01J2219/00837—Materials of construction comprising coatings other than catalytically active coatings
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01L—CHEMICAL OR PHYSICAL LABORATORY APPARATUS FOR GENERAL USE
    • B01L3/00—Containers or dishes for laboratory use, e.g. laboratory glassware; Droppers
    • B01L3/50—Containers for the purpose of retaining a material to be analysed, e.g. test tubes
    • B01L3/502—Containers for the purpose of retaining a material to be analysed, e.g. test tubes with fluid transport, e.g. in multi-compartment structures
    • B01L3/5027—Containers for the purpose of retaining a material to be analysed, e.g. test tubes with fluid transport, e.g. in multi-compartment structures by integrated microfluidic structures, i.e. dimensions of channels and chambers are such that surface tension forces are important, e.g. lab-on-a-chip
    • 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
    • G01N2001/4061—Solvent extraction
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N2030/009—Extraction

Definitions

  • the present invention relates to the separation of two liquid phases from each other and is particularly useful for the separation, isolation, purification or analysis of compounds dissolved in either or both of the liquid phases.
  • a particular compound dissolves in a particular liquid i.e. the solubility of a potential solute in a potential solvent
  • ionic compounds usually dissolve well in aqueous liquids
  • polar organic compounds dissolve well in polar organic liquids
  • non-polar organic compounds dissolve well in non-polar organic liquids.
  • Mixtures of liquids or solutions may consist of separate liquid phases, each of which is a substantially homogeneous, physically distinct and mechanically separable portion of the mixture. Where two liquid phases are present, then given sufficient time and/or mixing, a compound or mixture of compounds (potential solutes) will partition between the two phases according to the solubility of each compound in each phase.
  • the differential partitioning of compounds between two liquid phases forms the basis of a wide range of useful chemical techniques.
  • Preparative and analytical methods often require compounds to be separated from mixtures.
  • Many types of mixtures (to name just a few: crude reaction products; biological fluids such as urine, saliva and plasma; and fluids which are important to analyse for environmental reasons such as waste water and river water) can be purified, separated or analysed on the basis of compounds' differing solubility in different phases.
  • the partitioning may result in a desired compound being effectively the only solute in a phase, or it may result in a partial but nevertheless useful separation of solutes.
  • the organic compound can often be isolated by partitioning the mixture between an aqueous phase and an organic phase, separating off the organic phase and removing the organic solvent. Further purification steps may be carried out if necessary.
  • liquid-liquid extraction or partitioning between phases is often used to partially clean up a sample or produce a solution in a suitable solvent prior to further analysis, for example by chromatography or mass spectrometry.
  • the principle is not only useful for isolation or clean up purposes but also in its own right for characterization purposes since the extent to which a compound partitions between two phases provides useful information about the compound's properties; for example, octanol-water partition coefficients are important parameters to measure.
  • Gravity-based separation is by far the most common method of separation and relies on the fact that two phases often differ in density.
  • the classical separating funnel allows each layer to be tapped off separately.
  • Lipophilic and or hydrophilic inserts have also been used to enhance gravity- based separation.
  • Teflon fibre bundles and strips have been used to help direct the organic phase to the desired outlet.
  • Membrane phase separators have also been used.
  • An article by Kuban - "Liquid-liquid extraction flow injection analysis", Critical Reviews in Analytical Chemistry 1991, 22(6), 11-511 - discusses on pages 501-513 some phase separators that have been used. However, such arrangements have their disadvantages.
  • Gravity-based separation may not work well if the layers do not separate easily, for example, if their densities are not very different.
  • separators using lipophilic or hydrophilic inserts are complex to fabricate, and where more than one of these separators is used, the cost and complexity is multiplied. Teflon inserts need to be cleaned frequently, hydrophilic/lipophilic filters often require frequent replacement, and membrane phase separators often suffer in terms of stability and ease of operation.
  • the present invention seeks to provide an improved apparatus and method for separating liquid phases which is adaptable for use on a miniaturised scale.
  • the invention provides an apparatus for separating two liquid phases, comprising a junction, said junction branching into at least two channels, said channels having surfaces whose surface properties differ from each other whereby the phases are separated on the basis of their respective affinities to the respective surfaces.
  • the invention provides a method of separation of two liquid phases comprising flowing the liquid phases into a junction branching into at least two channels, said channels having surfaces whose surface properties differ from each other whereby the phases are separated on the basis of their respective affinities to the respective surfaces.
  • the present invention is based on the differential affinity of liquids for solid surfaces. Liquids differ in the extent to which they have an affinity for solid surfaces. For example, polar liquids have a greater affinity to polar surfaces and non-polar liquids have a greater affinity to non-polar surfaces.
  • separation may occur on the basis of phases' differing affinities for surfaces within the junction, so that regardless of what the surface properties are outside the junction, a degree of separation occurs inside the junction so that the respective phases are preferentially directed into one or other of the channels.
  • the invention provides an apparatus for separating two liquid phases, comprising a junction, said junction branching into two channels and having two regions, said regions having surfaces whose surface properties differ from each other whereby the phases are separated on the basis of their respective affinities to the respective surfaces and accordingly are preferentially directed down one or the other channel.
  • the invention provides a method of separation of two liquid phases comprising flowing the liquid phases into a junction branching into two channels and having two regions, said regions having surfaces whose surface properties differ from each other whereby the phases are separated on the basis of their respective affinities to the respective surfaces and accordingly are preferentially directed down one or the other channel.
  • the respective channel surfaces and/or surfaces of regions within junctions have differing polarities.
  • one channel's surface is preferably more polar than the other, and/or one region's surface is preferably more polar than the other.
  • the more polar surface is an inorganic compound, for example glass, acid-activated glass or silicon, or a polar organic polymer, for example polyethylene glycol.
  • Metals could also be considered, for example titanium.
  • the less polar surface is a non-polar organic compound for example an organic polymer or silicone.
  • Suitable silicones are dimethylsiloxane, octadecylsilane or polymers thereof.
  • Other suitable polymers for the less polar surface include trichloro octadecylsilane, polyethylene and polypropylene.
  • Each channel's entire surface may have the same surface properties, but that is not essential. What is important is that the channels should present different resistance to the flow of the respective liquid phases, or alternatively or additionally that the regions within the junctions, through their differing affinities for each phase, should differentially direct the flow of the respective liquid phases.
  • the channels and junctions are sufficiently small for the differences in affinity to allow the separation of the two liquid phases to occur.
  • the channels are capillary channels.
  • the width and depth of the channels are within the range 0.1-2000 ⁇ m, more preferably 1-1000 ⁇ m, more preferably 5-500 ⁇ m, most preferably 5-100 ⁇ m.
  • the dimensions of the junctions are within the range 0.1-4000 ⁇ m, more preferably 1-2000 ⁇ m, more preferably 5-1000 ⁇ m, most preferably 5-200 ⁇ m.
  • a junction may be T-shaped, or more preferably generally Y-shaped, as this gives reduced resistance to flow and improved separation.
  • the separation may be partial or complete: for many applications a partial separation is sufficient. While the invention in its broadest terms covers separation occurring at a single junction, this may not in some circumstances produce a sufficient degree of separation.
  • the apparatus comprises a plurality of interconnected junctions.
  • the output of a channel leading from a first junction may itself be input to a second junction, whereby further separation can take place at the second junction, and so on.
  • junctions are arranged such that outlet channels from two preceding junctions flow into the junction.
  • the channels flowing into the junction are those having different surface properties.
  • the junction may have a generally X-shaped configuration.
  • the sets of channels intersect each other thereby providing an interconnected array of channels, with junctions formed where the channels intersect.
  • the channels in a set are arranged parallel to each other.
  • each of the two sets of channels is configured such that the separated flows in said channels are directed into respective single outlet channels. This considerably facilitates collection of the separated phases.
  • the channels and junctions may be formed in any suitable manner. Preferably, however, they are formed at the interface between two substrate surfaces. In this way, for example, a groove in one surface may cooperate with the opposed surface to form a channel. This provides a simple and effective way of fabricating a complex array of channels, such as the intersecting array of channels discussed above and avoids the need for micro fabrication.
  • the invention also extends to a method of manufacture of apparatus suitable for separating two liquid phases, comprising forming a set of grooves in a surface of a first substrate, and locating said surface against a surface of a second substrate so as to define a set of channels therebetween.
  • the grooves may be formed on just one substrate surface, but preferably they are formed on both substrate surfaces as this facilitates the provision of differing surface properties in the grooves.
  • the grooves formed in one substrate may have a first surface property and those in the second substrate a second surface property.
  • one side of each channel will be of the 'wrong' surface chemistry.
  • the majority of the channel surface will be of the "right" surface chemistry, so that at the entry junction to the channels, the two phase liquid will see one channel with predominantly one property and another with predominantly the other property and will separate accordingly.
  • the cross-sectional profile of the grooves may be of any form. They may, for example, be straight sided for example rectangular, trapezoid or N-shaped, or rounded, for example semi-circular or elliptical.
  • the grooves may be prepared by any suitable method including photolithography, etching (for example with hydrofluoric acid), reaction moulding, injection moulding, embossing, cutting, precision milling, laser ablation and fast prototyping.
  • the surface chemistries of the sets of grooves differ by virtue of the fact that sets of grooves are formed on two substrates with different chemistries.
  • one substrate could be glass and the other an organic material.
  • Metals and semi-conductors might also be possible materials.
  • one or both substrate surfaces can be provided with a suitable coating, either before or after groove formation.
  • suitable methods of coating include, for example, spin coating, evaporative coating, sputtering or chemical vapour deposition.
  • the coating may be applied directly to the substrate or there may be an intermediate layer for improving adhesion of the coating to the substrate.
  • the surface may be vinylised (e.g. by reaction with vinyl trichlorosilane) and then coated (e.g. spin-coated) with a further substance such as a mixture which will bind to the vinyl layer and result in the desired surface properties (e.g. a silicon monomer mix comprising vinyl-terminated dimethylsiloxane, methylhydrosiloxane-dimethylsiloxane copolymer and a polymerisation catalyst).
  • a further substance such as a mixture which will bind to the vinyl layer and result in the desired surface properties
  • the two substrates are bonded together.
  • at least one of the substrates is coated with or formed from a substance which functions as a bonding medium, for example when the two substrates are pressed together and the substance is allowed to react (e.g. heat is applied so that the substance polymerises and simultaneously bonds the two substrates together).
  • the bonding coating is the groove surface coating, whereby the need for a separate bonding coating is avoided.
  • Direct bonding of the two substrates may be achieved by activating them, bringing them together and annealing them: for example, glass or silicon substrates can be hydrophilically or hydrophobically activated (an example of the former is the formation at the surface of silanol groups which initially bond the two substrates together by hydrogen bonds and Van der Waals forces) and then annealed at elevated temperatures to form Si-O-Si bonds between the layers.
  • Anodic bonding can be used, for example, to bond a glass substrate to a silicon substrate.
  • Bonding with spin-on glass a solution of silicon hydroxide
  • An example of bonding with an intermediate polymer layer has been described above. For some materials simple mechanical clamping may suffice.
  • a large array of separation junctions can be formed on a substrate for example in the manner described above.
  • a plurality of arrays can be joined together in parallel.
  • individual separators may be stacked one upon the other and supplied with liquid to be separated from a common source.
  • supply and/or outlet channels may be formed, e.g. drilled, to extend through the stack, communicating with the inlets and/or outlets of each individual separator. This will provide a particularly compact construction.
  • the present invention is particularly suited for use in liquid-liquid extraction, particularly on a miniaturised scale.
  • the invention extends to cover liquid-liquid extraction apparatus incorporating separation apparatus in accordance with the invention and also a method of separating, purifying, isolating or analysing compounds by extraction between liquid phases followed by separation of the liquid phases by a method in accordance with the invention.
  • the extraction apparatus further comprises means for bringing two liquid phases together and allowing extraction or partitioning between the two phases prior to the separator stage.
  • the two liquid phases are introduced into a channel where they proceed in the form of a slug flow, rather than a laminar flow.
  • Slug flows are associated with internal circulation (see for example Burns et al., "The intensification of rapid reactions in multiphase systems using slug flow in capillaries", Lab on a Chip 2001, /, 10-15) and improve contacting between the liquid phases such that compounds are more easily partitioned between the two.
  • the length of the channel is such that sufficient partitioning or extraction occurs.
  • the contacting channel is preferably of generally the same dimensions as the separation channels discussed above.
  • the two liquid phases are brought together at a T junction to form a slug flow.
  • the flow rate is such as to allow the desired extent of separation.
  • the flow rate is less than 100 ⁇ l per minute, more preferably between 0.1 and 10 ⁇ l per minute.
  • Fast flow rates may be associated with less efficient separation.
  • the slug flow arrangement above is better able to cope with variations in flow rates and noisy pumping systems.
  • the flow rate of one liquid phase may be different to the flow rate of the other liquid phase; this allows one phase (e.g. an organic phase) to be more concentrated than a second phase (e.g. an aqueous phase).
  • one phase e.g. an organic phase
  • a second phase e.g. an aqueous phase
  • the extraction apparatus may also comprise a detector (e.g. a spectrophotometer) or further separation device (e.g. a chromatographic device such as an HPLC or GC device) downstream from the separator to allow for more detailed analysis or separation.
  • a detector e.g. a spectrophotometer
  • further separation device e.g. a chromatographic device such as an HPLC or GC device
  • the invention also extends to an apparatus which comprises a plurality of the above-mentioned apparatus stacked together in parallel such that all the inlets are joined together and all the outlets are joined together. This allows separations to be carried out on larger scales.
  • FIG. 1 shows, schematically, a liquid-liquid extraction apparatus incorporating a separator in accordance with the invention
  • Figure 2 shows, schematically, a detail of the apparatus of Figure 1;
  • Figure 3 shows, schematically, a detail of Figure 2
  • Figure 4 shows, schematically, a further detail of Figure 2.
  • Figure 5 shows a sectional view along the line N-V of Figure 4.
  • the separator 12 comprises an inlet channel 18 and two outlet channels 20, 22.
  • the inlet channel 18 enters a junction 24 from which leave outlet channels 26, 28.
  • the inlet channel 18 and outlet channels 26, 28 are arranged in a generally Y shaped configuration.
  • a first set of parallel passages 30 extend from the outlet passage 28 to the outlet channel 20 and a second set of parallel channels 32 extend from the channel 26 to the outlet channel 22.
  • the channel 26, outlet channel 20 and the set of parallel channels 30 have a predominantly non- polar surface while the channels 28, 22 and 32 have a predominately polar surface.
  • the channels 30 and 32 intersect with each other forming generally X shaped junctions 34 at their points of intersection; in this particular embodiment there are 16 such junctions 34.
  • the channels 30 and 26 also intersect with the channel 28, and the channels 32 and 28 with the channel 26, forming generally Y-shaped junctions 24 at their points of intersection; in this particular embodiment there are 9 such junctions 24.
  • a mixture of a polar liquid phase and a non-polar liquid phase which enters the inlet 18 will arrive at the junction 24 and due to the relative affinity of the liquids for the polar and non-polar surfaces of the channels 28, 26, they will be separated at least partially at that junction 24. As the partially separated liquid travels up the passages 26, 28, it will reach further Y junctions 24 and separate further and also X junctions 34 separating further still. As a result, the polar component of the mixture will flow towards to the outlet channel 22 and the non-polar towards the channel 20.
  • the respective liquids may be then removed from the apparatus and, if desired, subjected to further examination or analysis.
  • the separator may be used in a liquid-liquid extraction device 2.
  • liquids which may contain solutes to be partitioned between the liquids are introduced into the inlets 4, 6 and mixed together, preferably in a slug formation at the T junction 8.
  • the two phase liquid mixture then passes along the extraction channel 10 into the inlet junction 18 of the separation device, where the liquid components, with solute, are separated as described above for analysis.
  • the separation device and indeed the other components shown in figure 1 are all formed on a "chip" which typically may be 20mm wide by 40mm long.
  • the chip is formed in two layer 42, 44. Each of these layers is typically 0.25 - 2mm thick.
  • each junction comprises a polar surface region 48 towards which a polar phase will be drawn and a non-polar surface region 46 towards which a non-polar phase will be drawn.
  • the lower layer 44 is formed from a glass material in to which has been etched or otherwise suitably formed the grooves 48.
  • the upper layer 42 comprises a glass substrate 50 whose surface is acid-activated and then vinylised by reaction with vinyltrichlorosilane to form a vinyl layer 52 bonded onto the glass surface.
  • a non-polar layer 54 is then deposited on the vinyl layer 52 in order to provide the groove 46 with the appropriate surface chemistry.
  • the non- polar layer comprises a silicon monomer mix comprising vinyl-terminated dimethylsiloxane (about 95% by weight), methylhydrosiloxane- dimethylsiloxane copolymer (about 5% by weight) and a catalyst (platinum carbonyl cyclovinylmethylsiloxane complex, about 0.15% by weight). This coating is spin coated onto the vinyl layer.
  • the layers are pressed together face-to-face and polymerisation initiated by heating the composite to 100°C. This acts to bond the layers together and produce a silicone coating on the upper layer 42. Once bonded, the two layers together define the desired pattern of intersecting channels.
  • the non-coated glass acts as a polar surface and the coated glass acts as a non-polar surface.
  • the extraction channel 10, mixing junction 8 and the passages leading from inlets 4 and 6 may also be formed in this manner in the chip.
  • the pump was operated in such a manner that the respective phases entered the extraction channel 10 in a slug flow. After passing through the separator 2, it was found that the outlet 14 contained 99.3% iso-octane and 0.7% water by volume while the other outlet contained 96% water and 3.9% iso-octane. This demonstrates the efficiency of the separation procedure and of course further separation could take place to completely separate the phases.
  • separable liquid phase systems are: (i) one phase being aqueous and the other organic; (ii) one phase being polar and the other non-polar; and (iii) one phase being water and the other octanol.
  • the invention is applicable to the analysis, separation, purification or isolation of many compounds and mixtures, and these include, but are not limited to, crude reaction products, pesticides (e.g. organochlorines, phenylureas), drugs (e.g. morphine, clenbuterol, propanolol, tamoxifen), biological fluids (e.g.
  • the invention provides a method of separating two liquid phases comprising flowing the liquid phases along a flow passage for example a junction or channel having wall regions having surfaces whose surface properties differ, whereby the phases are separated on the basis of their respective affinities to the respective surfaces.

Abstract

Cette invention a trait à un procédé de séparation de deux phases liquides, lequel procédé consiste à faire s'écouler les phases liquides par un circuit d'écoulement, notamment une voie de jonction ou un canal, dont les parois comportent des zones ayant des surfaces présentant des propriétés différentes. De la sorte, les phases se séparent selon leur affinités pour ces surfaces. L'invention porte également sur un appareil permettant de séparer deux phases liquides, sur un appareil extrayant deux phases liquides ou les partageant avant la séparation liquide/liquide. Elle concerne également un procédé permettant de séparer, de purifier, d'isoler ou d'analyser un ou plusieurs composés par extraction ou partage de deux phases liquides avant leur séparation.
PCT/GB2003/001421 2002-04-02 2003-04-01 Separation liquide/liquide WO2003082429A2 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2003214475A AU2003214475A1 (en) 2002-04-02 2003-04-01 Liquid-liquid separation

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GBGB0208766.6A GB0208766D0 (en) 2002-04-02 2002-04-02 Liquid-liquid separation
GB0208766.6 2002-04-02

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WO2003082429A2 true WO2003082429A2 (fr) 2003-10-09
WO2003082429A3 WO2003082429A3 (fr) 2004-03-04

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GB (1) GB0208766D0 (fr)
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CN102784854A (zh) * 2011-05-17 2012-11-21 长春旭阳富维江森汽车座椅骨架有限责任公司 双头自动钢丝折弯机
WO2013021067A1 (fr) * 2011-08-11 2013-02-14 Dsm Ip Assets B.V. Injecteur de chromatographie en phase gazeuse multimode
WO2014190768A1 (fr) * 2013-05-27 2014-12-04 北京华阳利民仪器有限公司 Dispositif d'extraction solide-liquide automatique
WO2014190767A1 (fr) * 2013-05-27 2014-12-04 北京华阳利民仪器有限公司 Appareil d'extraction liquide-liquide entièrement automatique, très efficace et générant un faible émulsionnement
WO2014195662A1 (fr) * 2013-06-07 2014-12-11 Blacktrace Holdings Limited Systèmes et procédés de séparation et d'analyse

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WO2001078893A2 (fr) * 2000-04-14 2001-10-25 Nanostream, Inc. Barrieres d'ecoulement des fluides dans un systeme microfluidique
WO2001089693A1 (fr) * 2000-05-23 2001-11-29 Merck Patent Gmbh Dispositif d'emulsification et de separation pour des phases liquides
WO2002011888A2 (fr) * 2000-08-07 2002-02-14 Nanostream, Inc. Melangeur fluidique pour systeme microfluidique

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US5804022A (en) * 1994-10-19 1998-09-08 Hewlett-Packard Company Method for making miniaturized planar columns in novel support media for liquid phase analysis
WO1998049548A1 (fr) * 1997-04-25 1998-11-05 Caliper Technologies Corporation Dispositifs microfluidiques a geometrie de canaux amelioree
WO2000004390A2 (fr) * 1998-07-14 2000-01-27 Zyomyx, Inc. Microdispositifs servant a cribler des biomolecules
WO2001078893A2 (fr) * 2000-04-14 2001-10-25 Nanostream, Inc. Barrieres d'ecoulement des fluides dans un systeme microfluidique
WO2001089693A1 (fr) * 2000-05-23 2001-11-29 Merck Patent Gmbh Dispositif d'emulsification et de separation pour des phases liquides
WO2002011888A2 (fr) * 2000-08-07 2002-02-14 Nanostream, Inc. Melangeur fluidique pour systeme microfluidique

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102784854A (zh) * 2011-05-17 2012-11-21 长春旭阳富维江森汽车座椅骨架有限责任公司 双头自动钢丝折弯机
WO2013021067A1 (fr) * 2011-08-11 2013-02-14 Dsm Ip Assets B.V. Injecteur de chromatographie en phase gazeuse multimode
WO2014190768A1 (fr) * 2013-05-27 2014-12-04 北京华阳利民仪器有限公司 Dispositif d'extraction solide-liquide automatique
WO2014190767A1 (fr) * 2013-05-27 2014-12-04 北京华阳利民仪器有限公司 Appareil d'extraction liquide-liquide entièrement automatique, très efficace et générant un faible émulsionnement
WO2014195662A1 (fr) * 2013-06-07 2014-12-11 Blacktrace Holdings Limited Systèmes et procédés de séparation et d'analyse

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