EP3863745A1 - Procédé et dispositif de transfert de matière en continu à contre-courant entre deux phases fluides - Google Patents
Procédé et dispositif de transfert de matière en continu à contre-courant entre deux phases fluidesInfo
- Publication number
- EP3863745A1 EP3863745A1 EP19831781.0A EP19831781A EP3863745A1 EP 3863745 A1 EP3863745 A1 EP 3863745A1 EP 19831781 A EP19831781 A EP 19831781A EP 3863745 A1 EP3863745 A1 EP 3863745A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- phase
- solute
- fluid
- liquid
- called
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
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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
- B01D11/0476—Moving receptacles, e.g. rotating receptacles
- B01D11/048—Mixing by counter-current streams provoked by centrifugal force, in rotating coils or in other rotating spaces
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
- B01D15/08—Selective adsorption, e.g. chromatography
- B01D15/10—Selective adsorption, e.g. chromatography characterised by constructional or operational features
- B01D15/18—Selective adsorption, e.g. chromatography characterised by constructional or operational features relating to flow patterns
- B01D15/1892—Selective adsorption, e.g. chromatography characterised by constructional or operational features relating to flow patterns the sorbent material moving as a whole, e.g. continuous annular chromatography, true moving beds
-
- 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
- B01D11/00—Solvent extraction
- B01D11/04—Solvent extraction of solutions which are liquid
- B01D11/0403—Solvent extraction of solutions which are liquid with a supercritical fluid
- B01D11/0407—Solvent extraction of solutions which are liquid with a supercritical fluid the supercritical fluid acting as solvent for the solute
-
- 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
- B01D11/0484—Controlling means
-
- 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
- B01D11/0488—Flow sheets
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
- B01D15/08—Selective adsorption, e.g. chromatography
- B01D15/10—Selective adsorption, e.g. chromatography characterised by constructional or operational features
- B01D15/18—Selective adsorption, e.g. chromatography characterised by constructional or operational features relating to flow patterns
- B01D15/1807—Selective adsorption, e.g. chromatography characterised by constructional or operational features relating to flow patterns using counter-currents, e.g. fluidised beds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
- B01D15/08—Selective adsorption, e.g. chromatography
- B01D15/10—Selective adsorption, e.g. chromatography characterised by constructional or operational features
- B01D15/18—Selective adsorption, e.g. chromatography characterised by constructional or operational features relating to flow patterns
- B01D15/1864—Selective adsorption, e.g. chromatography characterised by constructional or operational features relating to flow patterns using two or more columns
- B01D15/1871—Selective adsorption, e.g. chromatography characterised by constructional or operational features relating to flow patterns using two or more columns placed in series
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B04—CENTRIFUGAL APPARATUS OR MACHINES FOR CARRYING-OUT PHYSICAL OR CHEMICAL PROCESSES
- B04B—CENTRIFUGES
- B04B11/00—Feeding, charging, or discharging bowls
- B04B11/04—Periodical feeding or discharging; Control arrangements therefor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B04—CENTRIFUGAL APPARATUS OR MACHINES FOR CARRYING-OUT PHYSICAL OR CHEMICAL PROCESSES
- B04B—CENTRIFUGES
- B04B5/00—Other centrifuges
- B04B5/06—Centrifugal counter-current apparatus
-
- 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
- B01D11/0403—Solvent extraction of solutions which are liquid with a supercritical fluid
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D11/00—Solvent extraction
- B01D2011/002—Counter-current extraction
Definitions
- the invention relates to a process for transferring, continuously exchanging material against the current between two fluid phases.
- the invention relates to a process for exchanging, transferring, material continuously against the current between a first fluid phase and a second fluid phase.
- this transfer, material exchange method uses a single device, which is a Centrifugal Partition Chromatography (CPC) device or a device whose mechanical and hydraulic operation is similar to that of a Centrifugal Sharing Chromatography (CPC).
- CPC Centrifugal Partition Chromatography
- the invention also relates to a device for implementing this method.
- the technical field of the invention can, in general, be defined as that of the exchange of material between two fluid phases, that is to say two phases which are not solid.
- These fluid phases can be chosen in particular independently of one another, from among all the fluid phases such as the liquid, gas, and supercritical phases.
- the exchange of material can in particular be a liquid / liquid extraction operation during which a chemical compound, called solute, being in a liquid phase called the feed phase is transferred to another liquid phase called the solvent phase.
- the food phase thus depleted in solute obtained is called raffinate.
- the solvent phase enriched in solute obtained is called extract.
- the two initial liquid phases are immiscible, but may be partially miscible
- the counter-current consists in circulating against the current from one another the feed phase containing the solute and the solvent phase. It is a method of contact making it possible to maximize the potential for the exchange of material between the two fluid phases, therefore the yield of solute extraction or of purification of the raffinate, for a given solvent flow rate.
- These devices include a zone for stirring the two liquid phases (step for passing the solute from one liquid phase to another) and a gravity settler (step for separating the two liquid phases). They are simple, robust and easy to extrapolate. Just multiply the number of devices to get high NET values. It is also sufficient to increase the agitation and decantation volumes in order to be able to process large, even very large, flows, for example greater than 150 m 3 / h. Such flows are typically encountered in the mining industry. This multiplication of the number of devices nevertheless has the consequence of high investment costs and footprint, a high immobilization of volumes of the feed and solvent phases, as well as high maintenance costs due especially the large number of pumps and pipes.
- liquid phases present have a sufficient density difference, of the order of 50 kg / m 3 or more, and / or that they do not have tendency to emulsify, because the mechanical separation of the phases is carried out under the action of the earth's gravitational force.
- a disadvantage of this technology is also the long time to reach a continuous regime.
- liquid phases present have a sufficient density difference, of the order of 50 kg / m 3 and more, and / or that the liquid phases present do not have not tend to emulsify, because the mechanical separation of the phases is carried out by the force of terrestrial gravity.
- a disadvantage of this technology is also the long time to reach a continuous regime.
- CPC centrifugal partition chromatography
- the centrifugal sharing chromatography (CPC) technology stems from the Counter-Current Centrifugal Chromatography (CCC) technology developed by Y. ITO in the sixties and seventies.
- CCC Counter-Current Centrifugal Chromatography
- the first CCC devices were originally built in Japan to perform size segregation of suspended solid particles and for the separation of solute in a solvent system. These first CCC devices operated on the principle of a variable gravitational field produced by a mechanism with two gyratory axes but without actually carrying out counter-current flows of the two liquid phases. In 1982, the first prototype CPC (centrifugal partition chromatography) device was built.
- CPC devices differ from early CCC devices in that they use a constant gravitational field, created by a single axis of rotation.
- a CPC device is in the form of a stack of discs or cartridges in which are engraved several tens or hundreds of cells linked together by small diameter channels. These cells can be cylindrical, rectangular, spherical, or ovoid in shape. They can be symmetrical or asymmetrical with respect to the plane of rotation of the CPC device.
- a column of CPC makes it possible to carry out a separation of the chromatographic type between solutes initially contained in a mobile liquid phase. Thanks to a circulation pump, this mobile liquid phase circulates through the CPC apparatus via channels which connect all the cells of the CPC column to each other.
- the stationary phase is immobilized in the cells by the centrifugal force field and by the difference in density which exists between the two phases.
- the mobile phase is therefore injected into the cells in which this stationary phase is already present.
- the solutes are then divided between the mobile phase and the stationary phase.
- the mobile phase passes successively from cell to cell.
- the stationary phase is the light phase, the latter is positioned towards the axis of rotation of the device.
- the mobile phase which is therefore the heavy phase, is propelled radially by centrifugal force and moves away from the axis of rotation.
- the stationary phase is maintained in the cells while the mobile phase crosses it in the form of droplets or jets.
- the flow of circulation (and the incompressibility of liquids) then forces the mobile phase to pass through the channels in order to supply the next cell.
- the stationary phase is the heavy phase and the mobile phase is the light phase which is then eluted in each cell in a centripetal movement.
- the transition from one elution mode to the other is carried out by pumping the other of the two phases through the other end of the column.
- FIGS. 1 and 2 The principle of Centrifugal Partition Chromatography is illustrated in FIGS. 1 and 2, according to which a stationary liquid phase is immobilized in the cells by centrifugal force and a mobile mobile phase percolates through this stationary phase.
- the mobile phase which is the light phase (13), for example an organic phase charged with solute
- a reservoir (14) contrary to the centrifugal force field (arrow g) and it passes through the stationary phase, which is the heavy phase (15), for example an aqueous phase, immobilized in the cells (11, 12).
- the mobile phase which is the heavy phase (15), for example an aqueous phase
- the stationary phase which is the light phase (13)
- the saturated solvent is removed and replaced by the solvent from the cell (12).
- Document FR-A1-2856933 relates to a process for the separation of the constituents of a charge in liquid solution from at least two constituents (A, B) of different partition coefficients, such that they are driven at unequal speeds respectively by a light solvent and a heavier solvent, in a device comprising at least one liquid-centrifugal liquid chromatography column constituted by the interconnection in series of at least one set of separation cells.
- This process includes the following steps:
- the process of this document is characterized by a continuous injection of A, B at a point between the ends of the chromatographic column, by an alternative elution in the two ascending and descending modes, with a frequency defined by the operator , by collecting the fractions at the two ends of the chromatographic column, alternatively with a frequency f defined by the operator, and finally by simultaneous filling of the chromatographic column with the two phases according to a ratio defined by the operator.
- an sCPC device comprises at least one rotor with numerous metal disks on which there are more than a thousand separation chambers (i.e. cells) connected in series.
- the stationary liquid phase is passed through (continuously) by a mobile phase.
- a separation of the two liquid phases in each of the chambers Under the action of centrifugal force and due to the difference in density occurs a separation of the two liquid phases in each of the chambers.
- the sample or mixture of substances can be injected into the rotor.
- the sample or the mixture of substances is preferably injected at an intermediate point of the rotor.
- two or more rotors can be coupled.
- FIG. 1 A block diagram of a cycle is shown in Figure 1 of this document. Note that in this Figure, the device comprises two rotors 1 and 2 and that the load (“Feed”) is injected between these two rotors.
- the invention of this document therefore relates to a process for the separation and / or purification of natural substances from plant extracts, comprising at least a liquid-liquid chromatography step, during which a change continuous (tilting) from stationary phase to mobile phase and vice versa occurs, characterized in that one or more fractions are separated.
- Example 1 paragraph [0028] the device used is a “True-Moving-Bed” liquid-liquid chromatograph (TM B) with two rotors.
- TM B True-Moving-Bed liquid-liquid chromatograph
- the sample or the mixture of substances is injected continuously, gradually, into the two rotors, and the components of the sample are separated with an appropriate two-phase solvent system, according to their polarity and of their liquid-liquid partition coefficient K.
- the object of the present invention is inter alia to meet the needs previously listed above for a material exchange process between two fluid phases, such as a liquid / liquid extraction process.
- a continuous material exchange process by bringing into contact against the current a first fluid phase and a second fluid phase, not totally miscible, characterized in that the contacting is carried out in a single apparatus, which is an apparatus of the centrifugal sharing chromatography apparatus type (CPC) in which only the first fluid phase and the second fluid phase are introduced, at the exclusion of any other phase, said apparatus comprising a plurality of cells, with a stationary phase immobilized in each of the cells and a mobile phase passing through the stationary phase, and in that the following steps a), b) and c) are carried out successively: a) Step in which the mobile phase consists of the first phase fluid, and the stationary phase immobilized in the cells is constituted by the second fluid phase;
- CPC centrifugal sharing chromatography apparatus type
- step c) Repeating the succession of steps a) and b); step b) being carried out immediately after step a), and step c) being carried out immediately after step b).
- CPC Centrifugal Sharing Chromatography
- the apparatus which is an apparatus of the CPC apparatus type (column) implemented in the method according to the invention, comprises only two inputs for introducing phases into the apparatus, namely a first input by which the first fluid phase is introduced into the apparatus and a second inlet by which the second fluid phase is introduced into the apparatus, and if the apparatus furthermore optionally includes one or more other input (s), this input (these inputs) is not (are not) used to introduce one or more other phase (s) (other than the first fluid phase and the second fluid phase) into the apparatus.
- the first entry is preferably located at a first end of the device (column) and the second entry is preferably located at a second end of the column. When one of these two inputs is used to introduce a fluid phase, the second input is used to draw a fluid phase outside the device.
- the apparatus of the CPC apparatus type implemented in the process of the invention does not include, in addition to the two inputs for each of the fluid phases brought into contact, other input (s), in particular in an intermediate point, in particular for another phase, such as a charge, the constituents of which must be separated as is the case in the document FR-A1-2856933 since, according to the invention, no chromatographic separation is carried out but an extraction against the current of a solute contained in a fluid by another fluid containing an extraction solvent.
- this device may include and which are generally intended to introduce another phase such as a load to be separated, in addition to the two aforementioned phases, are not used and / or are closed.
- the density of the first fluid phase is lower than the density of the second fluid phase, and step a) is then a step called step in ascending mode, and step b) is then a step called step in descending mode; or else, the density of the first fluid phase is greater than the density of the second fluid phase, and step a) is then a step called step in descending mode, and step b) is then a step called step in ascending mode.
- CPC Centrifugal Sharing Chromatography
- not completely miscible generally means that the first fluid phase and the second fluid phase are not miscible in all proportions with one another.
- the first fluid phase and the second fluid phase may thus be immiscible with each other in all proportions, or the first fluid phase and the second fluid phase may be partially miscible with one another.
- the switch between a step a) and a step b) or between a step b) and a step a) is very rapid, instantaneous, and that the start-up is immediate. More precisely, by immediately, we generally mean a duration less than or equal to one second, for example of the order of a second, in particular a duration of one second.
- the first fluid phase and the second fluid phase can be chosen independently from the liquid phases (including ionic liquids or solvents with deep eutectics), gas phases, and supercritical phases.
- the first phase can be a liquid phase
- the second phase can be a liquid phase or a supercritical phase, or vice versa.
- the first phase and the second phase can be liquid phases, or can be a liquid phase and a supercritical phase.
- the first phase may be a liquid phase and the second phase may be a liquid phase, or the first phase may be a liquid phase and the second phase a supercritical phase, or the first phase may be a supercritical phase and the second phase can be a liquid phase.
- the first phase can be a liquid phase containing a solute and the second phase can be a liquid phase containing a solvent for extracting the solute or a supercritical phase playing the role of solvent for extracting the solute , and at the end of step a) a so-called liquid phase is recovered raffinate depleted in solute, and recovering at the end of step b) a liquid phase called extract enriched in solute or a supercritical phase called extract extracted enriched in solute; either the first phase can be a liquid phase containing a solvent for extracting a solute or a supercritical phase playing the role of solvent for extracting a solute and the second phase can be a liquid phase containing the solute, and thus recovering at the end of step a) a liquid phase called extract enriched in solute or a supercritical phase called extract enriched in solute, and recovering at the end of step b) a liquid phase called depleted raffinate in solute.
- the supercritical phase playing the role of solvent for extracting the solute can be constituted by a pure fluid in the supercritical state, or else it can comprise said fluid in the supercritical state and one or more co-solvents. (s), the phase formed by the fluid and the cosolvent (s) being generally in the supercritical state.
- the first phase can be a supercritical phase containing a solute and the second phase can be a liquid phase containing a solvent for extracting the solute, and thus is recovered at the end of the step a) a supercritical phase called raffinate depleted in solute, and recovering at the end of step b) a liquid phase called extract enriched in solute; or else the first phase can be a liquid phase containing a solvent for extracting a solute and the second phase can be a supercritical phase containing a solute, and a liquid phase is thus recovered at the end of step a) said extract enriched in solute and recovering at the end of step b) a supercritical phase called raffinate depleted in solute.
- the supercritical phase containing a solute can be constituted by a pure fluid in the supercritical state and one or more solute (s), the phase formed by the fluid and the solute (s) being overall in a supercritical state.
- the supercritical fluid can be chosen from carbon dioxide CO; sulfur hexafluoride; nitrous oxide NO; linear or branched alkanes, preferably linear or branched alkanes of 1 to 10 carbon atoms, especially from 1 to 5 carbon atoms, such as methane, propanes, butanes, and pentanes; cyclic alkanes, preferably cyclic alkanes of 3 to 10 carbon atoms; linear or branched alkenes, of preferably linear or branched alkenes of 2 to 10 carbon atoms, especially from 2 to 5 carbon atoms, such as ethylene and propylene; alcohols, preferably aliphatic alcohols of 1 to 5 carbon atoms such as methanol, ethanol and butanols; and their mixtures; in particular, the fluid can be chosen from mixtures of carbon dioxide CO2 and from at least one other fluid chosen from the fluids listed above.
- the preferred fluid is carbon dioxide CO2.
- carbon dioxide has in particular the advantage of a relatively easy implementation, because it is inexpensive, non-toxic, non-flammable and has easily accessible critical conditions (critical pressure: Pc of 7.3 MPa and temperature critical 31.1 ° C).
- the co-solvent can be chosen from water; aqueous solutions; alcohols, preferably aliphatic alcohols of 1 to 5 carbon atoms such as methanol, ethanol, and butanols; ketones, preferably linear or branched ketones of 3 to 10 carbon atoms such as acetone or methyl ethyl ketone, or cyclic ketones; terpenes; hydrofluoroethers; cyclohexanes; and their mixtures.
- alcohols preferably aliphatic alcohols of 1 to 5 carbon atoms such as methanol, ethanol, and butanols
- ketones preferably linear or branched ketones of 3 to 10 carbon atoms such as acetone or methyl ethyl ketone, or cyclic ketones
- terpenes hydrofluoroethers
- cyclohexanes and their mixtures.
- said aqueous solutions can be chosen from detergent solutions such as anionic and / or cationic surfactants; solutions of complexing agents or chelating agents; and their mixtures.
- the cosolvent can be added to the fluid in an amount of 0.01 to 30%, by mass, preferably in an amount of 1 to 10% by mass.
- the first fluid phase may be a liquid phase and the second fluid phase may be a gas phase, or vice versa, and the transfer of a compound from one of the phases to the other phase is carried out.
- the apparatus of the Centrifugal Sharing Chromatography (CPC) type apparatus can comprise from 100 to 2000 cells.
- the cells can be symmetrical or asymmetrical.
- the cells are symmetrical.
- Each of the cells can be divided into several sub-cells, for example, into two or three "sub-cells", linked together by a channel.
- the cells are linked together by a single channel. More specifically, two consecutive cells of the plurality of cells of the device are connected by a single channel, which simplifies the manufacture of the device and allows use of a CPC device in a completely new mode, know an extraction with two fluids against the current.
- the succession of steps a) and b) can be repeated as many times as is necessary to carry out the treatment of an entire volume of a feeding phase, for example of a feeding phase which is sought. to extract the solute.
- the succession of steps a) and b) is repeated from 1 to 300,000 times, more preferably from 1 to 100,000 times, better from 1 to 10,000 times, better still from 1 to 1,000 times.
- the duration of step a) can be from 10 seconds to 120 seconds, preferably from 30 to 60 seconds and the duration of step b) can be from 10 seconds to 120 seconds, preferably from 30 to 60 seconds.
- the duration of step a) is equal to the duration of step b).
- sequence time This duration, also called sequence time, has a significant impact on the number of NET theoretical plates or stages generated by the column. In fact, the more the time of a sequence decreases, the more the NET increases.
- the method according to the invention differs fundamentally from the methods of the prior art firstly in that it uses a Centrifugal Sharing Chromatography (CPC) apparatus comprising a plurality of cells to carry out a continuous material exchange by contacting against the current between a first fluid phase and a second fluid phase that are not completely miscible.
- Centrifugal Partition Chromatography (CPC) devices are known devices, but which have so far only been used to carry out separations of several solutes by the principle of chromatography. The use of these CPC devices to carry out a continuous exchange of material against the current between a first fluid phase and a second fluid phase which are not totally miscible has never been described or suggested in the prior art and is totally surprising. .
- the method according to the invention is then fundamentally characterized by the fact that (due to the fact that, surprisingly, there is a continuous material exchange of a solute against the current between only a first fluid phase and a second fluid phase and not the separation of the constituents of a third phase) only, only the two fluid phases brought into contact against the current are introduced into the single device (column) of device type ( column) of CPC implemented in the method according to the invention, and that no other phase, such as a charge, the constituents of which must be separated, is furthermore introduced into the apparatus of CPC apparatus type, as is the case in document FR-A1-2856933 since, according to the invention, a separation by chromatographic effect is not carried out but rather, in an original manner, a continuous exchange of material against the current (otherwise says an extraction operation) between a first fluid phase and a second fluid phase.
- a material exchange is carried out continuously by contacting against the current between a first fluid phase and a second fluid phase which are not completely miscible and not the separation of several constituents, such as solutes, present in a third phase by the principle of chromatography, only, only the two fluid phases brought into contact against the current are introduced into the single device (column) of device type (column) of CPC work in the process according to the invention, and no other phase, phase, such as a filler whose constituents must be separated, is introduced into the apparatus.
- the method according to the invention is also fundamentally distinguished from the methods of the prior art in that it comprises a specific series of specific steps a) and b) which follow one another quickly, and in that these steps a) and b) are repeated. Such a specific series of specific steps and their repetition has never been described or suggested in the prior art.
- the method according to the invention consists in using in an original way a Centrifugal Partition Chromatography (CPC) apparatus by very quickly reversing the mobile phase and the stationary phase to produce a true continuous counter-current flow (in the generally accepted sense for the term counter-current in particular in the field of liquid-liquid extraction, and not in the inappropriate sense given to this term in the field of chromatography) of the first fluid phase and of the second fluid phase.
- CPC Centrifugal Partition Chromatography
- a continuous exchange of material is carried out against the current between a first fluid phase and a second fluid phase by performing cyclically, in a CPC apparatus, a rapid succession of steps a) and b), repeated, in particular a rapid succession of an ascending mode and a descending mode, repeated.
- the apparatuses of CPC are used either in ascending mode, or in descending mode and one does not carry out the immediate succession, fast, of an ascending mode and a descending mode repeated.
- a conventional centrifugal sharing chromatography (CPC) apparatus for example a commercially available common CPC apparatus, is thus transformed for example into a working counter-current liquid-liquid contactor. continuously allowing the extraction and purification of liquid mixtures, using an immiscible (or partially miscible) liquid solvent as a separating agent.
- An apparatus specifically designed and constructed to operate according to the principle of principle of the method according to the invention, and not a current CPC apparatus, can also be used.
- the method according to the invention is fundamentally different from the method which is the subject of document FR-A1-2956933, in that the method according to the invention is a continuous material exchange method while the method of document FR-A1- 2956933 is a process for separating the constituents of a liquid charge.
- the method according to the invention does not include, like the method of document FR-A1-2956933, a step of injecting an additional phase, namely the charge comprising at least two constituents to be separated, into a intermediate point of a liquid-centrifugal liquid chromatography column, in other words at a point located between the ends of the chromatographic column.
- the apparatus of the CPC apparatus type implemented in the method of the invention does not include, in addition to the two inputs for each of the fluid phases brought into contact, other input (s), in particular at a point intermediate, in particular for a load whose constituents must be separated as is the case in the document FR-A1- 2856933.
- the method according to the invention is even more different from the method and device of the document by Johannes Goll because instead of a single device, in the document by Johannes Goll, two columns are used.
- the method according to the invention is even more different from the method and device of document EP-A1-3409339 because instead of a single device, it is, in document EP-A1-3409339, two columns which are placed implemented.
- the method according to the invention does not have the drawbacks, defects, limitations and disadvantages of the methods of the prior art, as they have been described above in particular, and it provides a solution to the problems which arose in the methods of the prior art, in particular in known liquid-liquid extraction processes.
- the method according to the invention has a unique combination of advantages compared to the methods of the prior art and in particular compared to the liquid-liquid extraction methods of the prior art, namely:
- the method according to the invention makes it possible in particular to treat systems with two aqueous phases.
- the extraction systems with two aqueous phases are mainly composed of water added for example with polymers and / or salts. These two aqueous phases are immiscible and make it possible to obtain phase separation during decantation.
- the method according to the invention makes it possible to treat low feed rates, for example less than 30 L / h, or even less than 20 L / h, or even even less than 10 L / h, for which the gravity columns are not suitable.
- the number of theoretical stages obtained with the method according to the invention is generally greater than or equal to 5, even greater than or equal to 20, and even greater than or equal to 30, and it can go up to one or more hundreds of theoretical stages.
- each elementary cell of the CPC apparatus can be assimilated to a theoretical stage.
- the size of the single device used in the method according to the invention is much smaller than that of the devices used in existing technologies treating equivalent flow rates.
- the apparatus used in the method according to the invention is also advantageous compared to gravity columns which cannot, because of the wall effects, treat low feed rates.
- the process according to the invention makes it possible to obtain continuous setting up much faster, generally less than a minute, while the other two processes have warm-up times greater than 15 minutes and rather of the order of an hour.
- the method according to the invention therefore makes it possible to reduce the level of solvent by approaching the theoretical minimum value. This induces reduced operating costs, since the costs related in particular to the purchase of the solvent, to its regeneration, and to pumping are all the more reduced.
- the method according to the invention can be used for "ultra-recoveries", where a very high solute recovery rate (ie> 99% by mass) must be obtained.
- This second application is extremely interesting in particular in the context of recovery of species with high added value, for example in biotechnology or hydrometallurgy.
- the method according to the invention makes it possible in particular to carry out an exchange with a high NET and / or to use low flow rates of extraction solvents.
- Another important advantage of the process according to the invention is also the capacity to treat all kinds of systems, and in particular “difficult” liquid phases with for example a small density difference. between the phases, and / or a surfactant effect inducing a low interfacial tension between the liquid phases causing risks of emulsification.
- the process according to the invention surprisingly combines the advantages of processes with centrifugal extractors and processes with multi-stage columns with a large number of stages.
- the invention also relates to a device for implementing the method according to the invention, as described above, comprising:
- CPC Centrifugal Sharing Chromatography
- a first pipe provided with a first pump, and with a first valve, connecting the first reservoir to a first inlet of the apparatus of the Centrifugal Sharing Chromatography apparatus type;
- a second pipe provided with a second pump, and with a second valve, connecting the second tank to a second inlet of the apparatus of the type of Centrifugal Sharing Chromatography apparatus;
- a third pipe fitted with a third valve, connecting the second inlet of the apparatus of the centrifugal partition chromatography apparatus type to a reservoir intended to collect the first fluid phase, such as a so-called liquid phase raffinate, having passed through the apparatus of the Centrifugal Sharing Chromatography apparatus;
- a fourth pipe provided with a fourth valve, connecting the first inlet of the apparatus of the type of centrifugal sharing chromatography apparatus to a reservoir intended to collect the second fluid phase, such as a liquid phase called extract, having passed through the apparatus of the Centrifugal Sharing Chromatography type;
- control means for actuating the opening and closing of the valves, actuating the operation and stopping of the pumps, synchronizing the operation of the pumps and valves, controlling the opening and closing times of the valves and the operating times and stop pumps.
- the device according to the invention comprises a device of the Centrifugal Sharing Chromatography device type (single) which is equipped with a specific set of piping tanks, valves, pumps and control means, which has never been described or suggested in the prior art, and which transforms this apparatus of the Centrifugal Sharing Chromatography type apparatus, designed to perform chromatographic separations, into an apparatus capable of implementing the method according to the invention, namely capable of carrying out an exchange of material by continuously contacting against the current between a first fluid phase and a second fluid phase, by cyclically carrying out in this apparatus a step a) and a step b) repeated, in particular an ascending mode and a descending mode or a repeat mode and repeat mode.
- the apparatus of the Centrifugal Sharing Chromatography (CPC) type of the device according to the invention comprises only two inputs for introducing phases into the apparatus, namely a first input by which the first fluid phase is introduced into the device, and a second input through which the second fluid phase is introduced into the device.
- the apparatus of the Centrifugal Sharing Chromatography (CPC) type could also be called a column of the Centrifugal Sharing Chromatography (CPC) column.
- the apparatus (column) of CPC apparatus type (column) implemented in the device according to the invention generally comprises only two inputs for introducing phases into the apparatus, namely a first input by which the first fluid phase is introduced in the device and a second input through which the second fluid phase is introduced into the device, and if the device also optionally includes one or more other inputs, these inputs are not used to introduce one or more other phases ( s) (other than the first fluid phase and the second fluid phase) in the device.
- the first entry is preferably located at a first end of the device (column) and the second entry is preferably located at a second end of the column.
- the apparatus of the CPC apparatus type implemented in the device according to the invention does not include, in addition to the two inputs for each of the fluid phases brought into contact, other input (s), in particular at a point intermediate, in particular for a filler whose constituents must be separated as is the case in document FR-A1-2856933 since, according to the invention, no separation is carried out.
- the device according to the invention does not include, like the device in document FR-A1-2856933, a PI pump for injecting the sample, charging it at an intermediate point of the column ( Figures 1, 2), or even on the conduit which separates two drums.
- the claimed device differs even more from the device of EP-A1-3409339 because instead of one device are, in EP-A1-3409339 Two columns are implemented.
- the device according to the invention inherently has all the advantages of the process which it implements and which have already been explained above.
- control means comprise a programmable automaton which allows alternating and timed operation between:
- a first mode for example an ascending mode, preferably of a fixed duration, in which the first pump is in operation, the first valve is open, and the third valve is open, while the second pump is stopped, the second valve is closed and the fourth valve is closed and;
- a second mode for example a descending mode, preferably of a fixed duration, in which the second pump is in operation, the second valve is open and the fourth valve is open while the first pump is stopped, the first valve is closed, and the third valve is closed.
- the third and / or the fourth pipe is (are) provided with detection and / or analysis means such as UV, IR or Raman detectors.
- detection and / or analysis means make it possible in particular to analyze the composition of the liquid phases in these pipes, for example to continuously monitor the concentration of solute in these liquid phases.
- the cells are linked together by a single channel. More specifically, two consecutive cells of the plurality of cells of the device are connected by a single channel, which simplifies the device and lowers costs.
- Figure 1 is a schematic view which illustrates the principle of CPC Centrifugal Sharing Chromatography in ascending mode, as well as the first step a) of the method according to the invention, called step in ascending mode.
- Figure 2 is a schematic view which illustrates the principle of the second step b) of the method according to the invention, called step in descending mode.
- Figure 3 is a schematic view of an embodiment of the device according to the invention, for the implementation of the method according to the invention.
- Figures 4A and 4B are a schematic view of another embodiment of the device according to the invention for implementing the method according to the invention.
- Figures 4A and 4B also illustrate the operation in descending mode (Figure 4A) and in ascending mode ( Figure 4B) of steps a) and b) of the device of these figures for the implementation of the method according to the invention.
- FIG. 3 An embodiment of the device according to the invention, for implementing the method according to the invention, is described in a simplified manner in FIG. 3.
- This device includes:
- a Centrifugal Sharing Chromatography apparatus such as a CPC column (31); a first reservoir (32) containing the first fluid phase (33), for example a liquid phase called the feed phase or rich phase (in solutes) which is for example an aqueous liquid phase, such as an aqueous solution containing a compound to be extracted , solute, such as a pollutant;
- a first fluid phase for example a liquid phase called the feed phase or rich phase (in solutes) which is for example an aqueous liquid phase, such as an aqueous solution containing a compound to be extracted , solute, such as a pollutant;
- a second pipe (310), provided with a second pump (not shown), and a second valve R3 (311), connecting, via a pipe (312), the second tank (34) to a second inlet (313 ) of the apparatus of the Centrifugal Sharing Chromatography apparatus (31);
- the raffinate is the feeding phase which has been purified of the compound to be extracted, in solute, from which the solute has been extracted;
- the extract is the solvent phase enriched in product to be extracted, in solute.
- an apparatus, contactor, of CPC is equipped with a set of controlled RI (37), R2 (319), R3 (311), R4 (315) valves. automatically to allow cyclical operation against the current of the CPC apparatus (31).
- the first liquid phase that is to say the solute-rich feed phase
- the second liquid phase that is to say the fresh solvent phase.
- valves RI and R4 are closed and the valves R2 and R3 are open, while in the descending mode, the valves R2 and R3 are closed and the valves RI and R4 are open.
- the operation is reversed: in the ascending mode, the valves RI and R4 are open and the valves R2 and R3 are closed, while in the descending mode, the R2 and R3 valves are open and the RI and R4 valves are closed.
- the originality of the invention is in the control of the cyclic operation (in particular cycle time) to reproduce an operation against the current with the number of theoretical stages desired for a given separation.
- a programmable controller (not shown) is used to control the tilting of the valves and to synchronize the operation of the pumps and valves.
- FIG. 4 Another embodiment of the device according to the invention, for implementing the method according to the invention, is described in a simplified manner in FIG. 4.
- the feed phase has a density greater than that of the solvent phase.
- This device includes:
- Centrifugal Sharing Chromatography type apparatus also called a CPC contactor (41);
- a liquid phase called feed phase F or rich phase (in solutes) or heavy phase which is for example an aqueous liquid phase, such as an aqueous solution containing a compound to be extracted, solute, such as a pollutant;
- the second fluid phase (45) for example a liquid phase called the solvent phase S ′ or lean phase (in solutes) or light phase, this phase can for example be fresh solvent for extracting the solutes from the feeding phase;
- the first three-way valve (48) is connected to a first inlet (49) of the Centrifugal Sharing Chromatography apparatus (41) by a pipe (410);
- the three-way valve (413) is connected to a second inlet (414) of the Centrifugal Sharing Chromatography apparatus (41) by a pipe (415);
- the raffinate R is the feed phase which has been purified of the compound to be extracted, that is to say into the solute.
- the extract (421) is the solvent phase enriched in product to be extracted, that is to say in solute.
- UV detector for example Raman, IR or UV detectors (UV1 detector (422)
- UV1 detector (422) can be provided on the pipes (416) (UV1 detector (422)) and (419) (UV2 detector (423)) for continuously analyze the solute concentration in the raffinate R and in the extract E.
- a programmable controller (not shown) is used to control the tilting of the valves and to synchronize the operation of the pumps and these valves.
- the PI pump (47) makes it possible to send the Supply phase F (43) into the CPC contactor (41).
- the P2 pump (412) allows the extraction solvent S '(45) to be sent from the reservoir (44) into the CPC contactor (41).
- the Supply F which is depleted in solute B becomes the Raffinate phase R and the extraction solvent S 'which is enriched in solute B becomes the Extract phase E.
- the raffinate phase R leaves the CPC contactor (41) through the inlet (414) then the pipe (415), the valve (413) and the pipe (416).
- the extracted phase leaves the CPC contactor (41) through the inlet (49), the pipeline (410), the valve (48), and the pipeline (419).
- the contactor of CPC (41) contains a number of cells Y.
- start of contactor the part of the contactor located on the side of the entry of the phase Supply (49) and on the side of the exit of the Extract phase (49) (above in Figures 4A and 4B).
- the part of the contactor located on the inlet side of the solvent phase (414) and on the outlet side of the raffinate phase (414) will be designated by “end of contactor” (bottom in FIGS. 4A and 4B). .
- the CPC contactor (41) is first filled with extraction solvent S 'by the pump P2 (412).
- the contactor is rotated to the value of desired setpoint, and the PI pump (47) is then used to fill the CPC contactor with a given quantity of supply phase (43) containing no solute.
- those skilled in the art can adjust the ratio of solvent and supply phases present in the contactor by varying the speed of rotation and the flow rate of the supply phase used.
- the quantity of solvent S 'expelled due to the filling of the CPC contactor (41) by the supply phase can be collected in a specific recipe or else in the main Extract recipe (reservoir 420).
- phase F is therefore the mobile phase supplying the CPC contactor.
- this first cycle is done in descending mode.
- the EV1 valve (48) is positioned so as to allow the passage of the aforementioned volume F1 into the CPC contactor (41) through the pipe (410), and the EV2 valve (413) is positioned so as to send via the pipes (415) and (416) a phase volume Fl ', contained at the end of the CPC contactor, equivalent (or almost equivalent) to the volume Fl.
- This phase volume Fl' is thus expelled from the CPC contactor (41) to the Raffinât recipe (417) via the pipes (415) and (416).
- a number XI of cells of the CPC contactor (41) is therefore crossed at the start of the contactor by a supply volume F1 containing solute.
- the pump PI (47) is stopped, and the pump P2 (412) is put into operation.
- This pump P2 (412) then sends, during a cycle time T'cyclel, a given volume SI of extraction solvent S '(45) from the reservoir (44) at the end of the CPC contactor.
- the EV2 valve (413) is positioned so as to allow the passage of an equivalent (or almost equivalent) volume to the volume SI in the CPC contactor (41), and the EV1 valve (48) is positioned so to allow the passage of a volume of solvent phase SI 'contained at the start of contactor CPC (41), equivalent (or almost equivalent) to volume SI.
- This volume of solvent phase is thus expelled from the CPC contactor (41) to the Extract recipe (420) via the pipes (410) and (419).
- the Solvent phase S 'therefore becomes the mobile phase in the CPC and the supply phase becomes the stationary phase.
- the volume SI of solvent (421) expelled from the CPC contactor contains solute which has been extracted from the feeding phase present in the XI cells.
- the device therefore operates in ascending mode, that is to say with the mobile phase which is lighter than the stationary phase.
- the PI pump (47) then fills X2 CPC cells (X2 can be equal to or different from XI depending on the programming of the PLC) with supply phase F pushing towards the end of the CPC contactor, phase d power already present in the XI cells of the CPC contactor and having undergone an extraction during T'cyclel.
- this alternative operation makes it possible to simulate a countercurrent flow of the phases F and S '. This alternative operation lasts until the entire supply volume F has been processed.
- the influential input parameters which can feed the program of the control automaton are in particular: the volumes of F and S 'sent successively by the pumps, the operating times Tcycle and T' cycle (possibility of having variable times during handling), the speed of rotation, the geometry and the number of cells, the volume of the contactor, the initial stationary phase / phase ratios the thermodynamics of the system (partition coefficient of the solute, density and viscosity of the phases, interfacial tension, etc.).
- the input parameters and the operation of the CPC contactor then define a value for the number of theoretical extraction stages (NET), a solute purification rate of the supply phase, and a solute extraction rate of the Solvent phase.
- NET number of theoretical extraction stages
- the feed phase can be lighter than the solvent phase.
- the principle of the invention remains valid except that the supply phase is sent in ascending mode when it becomes the mobile phase and that the solvent phase is sent in descending mode when it becomes the mobile phase.
- the CPC contactor in another operating configuration of the invention, can be initially thermodynamically balanced using a supply phase F containing solute.
- the installation used in the examples is analogous to that described in Figures 1 and 2.
- This installation includes a system of two Gl / 8 valves available from the company Bürkert ® , Germany, controlled by an automaton (controlled by Labview ® ) . These valves are placed as close as possible to the rotary joints of the CPC device.
- CPC CPC device Two AP-100 pumps, available from Armen ® , France, allow the charge and solvent to arrive in the CPC contactor.
- the contactor of CPC CPC device, used is an EPC 300 column, available from the company Kromaton ®, France, with a volume of 280 ml and containing 231 asymmetrical cells.
- the raffinate and the extract are recovered at the end of each test and were assayed by UV spectrophotometry at 280 nm, using a spectrophotometer Jasco ® V630 dual beam.
- phase system tested is as follows: acetone (solute), heptane and water.
- the feed phase F consists of the heptane phase which contains the acetone to be extracted.
- the extraction solvent S '(solvent phase) is water.
- the operating conditions are as follows:
- Rotation speed N of the CPC device 800 rpm
- the column, CPC contactor is first of all hydrodynamically balanced with this liquid phase system.
- T Cycle are respectively 120 s., 60 s., And 30 s., For examples 1, 2, and 3.
- partition coefficient of acetone K (that is to say the partition coefficient for Examples 1, 2, and 3) between the organic phase (feed phase) and the aqueous phase ( solvent phase) is considered to be constant.
- This partition coefficient K is given by the formula below (Foucault, AP Chromatographie Science Sériés In Centrifugal Partition Chromatography; Marcel Dekker: New York, 1995; Vol. 68): kg acetone / L of feeding phase
- NET (X F -X n ) / X n .
- the CPC contactor makes it possible to carry out between 17 and 42 theoretical extraction stages (extraction rate of the solute relative to the feed between 94% by mass and 97% by mass).
- the use of short cycle times allows the contactor to operate under conditions increasingly close to a real counter current continuously.
- Using a CPC contactor with more cells would achieve even higher NET values.
- phase system tested is as follows: acetone (solute), heptane and water.
- the feed phase F is now constituted by the Water phase which therefore contains acetone, and the extraction solvent S '(solvent phase) is then pure heptane.
- the operating conditions are as follows:
- the CPC contactor is hydrodynamically balanced with this liquid phase system.
- the retention obtained is 40%, that is to say that 40% of the volume of the contactor is occupied by the stationary heptane phase.
- T Cycle are respectively 120 s., 60 s., And 30 s., For examples 1, 2, and 3.
- T Cycle cycle times 120 s., 60 s., And 30 s., For Examples 1, 2, and 3.
- NET (X F -X n ) / X n .
- the CPC contactor makes it possible to carry out between 6 and 8.5 theoretical extraction stages (extraction rate of the solute relative to the feed between 86% by mass and 89% by mass).
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Abstract
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FR1860505A FR3088219B1 (fr) | 2018-11-14 | 2018-11-14 | Procede et dispositif de transfert de matiere en continu a contre-courant entre deux phases fluides |
PCT/FR2019/052711 WO2020099796A1 (fr) | 2018-11-14 | 2019-11-14 | Procédé et dispositif de transfert de matière en continu à contre-courant entre deux phases fluides |
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US1651328A (en) | 1923-09-19 | 1927-11-29 | Edeleanu Lazar | Arrangement for refining heavy mineral oils |
EP1178308A4 (fr) * | 1999-11-02 | 2005-01-19 | Daicel Chem | Dispositif de simulation d'un lit mobile |
FR2856933B1 (fr) * | 2003-07-02 | 2005-08-19 | Inst Francais Du Petrole | Procede et dispositif de separation des constituants d'une charge liquide par chromatographie liquide-liquide centrifuge |
FR2883770B1 (fr) * | 2005-04-01 | 2007-06-08 | Kromaton Sarl Sarl | Dispositif ameliore de chromatographie de partage centrifuge a cellules |
FR2907686B1 (fr) * | 2006-10-26 | 2009-01-23 | Kromaton Sarl Sarl | Dispositif et procede de chromatographie a contre courant vrai |
GB0813579D0 (en) * | 2008-07-24 | 2008-09-03 | Univ Brunel | counter-current chromatographic arrangement |
FR2956933A1 (fr) | 2010-03-01 | 2011-09-02 | Inside Contactless | Circuit integre protege contre une analyse par canal auxiliaire horizontale |
FR2967082B1 (fr) * | 2010-11-09 | 2016-12-09 | Nicolas Sebastien Fauquet | Procede de separation par chromatographie continue a haut debit |
EP3409339A1 (fr) * | 2017-05-29 | 2018-12-05 | Bionorica Ethics GmbH | Procédé de séparation de mélanges de matières naturelles à l'aide de scpc |
-
2018
- 2018-11-14 FR FR1860505A patent/FR3088219B1/fr active Active
-
2019
- 2019-11-14 WO PCT/FR2019/052711 patent/WO2020099796A1/fr unknown
- 2019-11-14 EP EP19831781.0A patent/EP3863745A1/fr active Pending
- 2019-11-14 US US17/294,010 patent/US20220016546A1/en not_active Abandoned
- 2019-11-14 CA CA3119417A patent/CA3119417A1/fr active Pending
Also Published As
Publication number | Publication date |
---|---|
CA3119417A1 (fr) | 2020-05-22 |
US20220016546A1 (en) | 2022-01-20 |
FR3088219A1 (fr) | 2020-05-15 |
WO2020099796A1 (fr) | 2020-05-22 |
FR3088219B1 (fr) | 2023-11-10 |
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