A PULSED FLOW REACTOR AND USE THEREOF
20210205776 ยท 2021-07-08
Assignee
Inventors
- Bert D F Metten (Lokeren, BE)
- Koen Toye (Bissegem, BE)
- Koen Jeanne Alfons Van Aken (Kuurne, BE)
- Wouter Debrouwer (Beernem, BE)
Cpc classification
B01J19/0093
PERFORMING OPERATIONS; TRANSPORTING
B01J2219/00783
PERFORMING OPERATIONS; TRANSPORTING
B01J2219/00074
PERFORMING OPERATIONS; TRANSPORTING
B01J2219/00837
PERFORMING OPERATIONS; TRANSPORTING
B01J2219/0086
PERFORMING OPERATIONS; TRANSPORTING
International classification
Abstract
A planar flow reactor includes a straight planar process channel, a flow generator, and a plurality of static mixing elements disposed within the process channel. The flow generator is configured to generate a pulsatile flow within the process channel, and the static mixing elements are configured to locally split and recombine the flow. The straight planar process channel enables the generation of a flow pattern that is largely independent of the width of the process channel, meaning that the throughput may be increased by increasing the width without significantly affecting the residence time distribution or the flow behavior. Furthermore, by creating a pulsatile flow within the process channel, turbulence and/or chaotic fluid flows may be generated even at low net flow rates, i.e. low net Reynolds numbers.
Claims
1. A flow reactor comprising: a straight planar process channel having a longitudinal direction and being delimited by a bottom wall, a top wall, two side walls, a first end wall, and a second end wall opposite to said first end wall along said longitudinal direction, the process channel comprising at least one inlet at said first end wall configured to introduce at least one feed stream into said process channel and at least one outlet at said second end wall configured to discharge at least one product stream from said process channel; a flow generator configured to generate a pulsatile flow within said process channel, the pulsatile flow comprising a unidirectional net flow component through said process channel along said longitudinal direction and an oscillatory flow component superposed on said net flow component; and a plurality of static mixing elements disposed within said process channel and configured to locally split and recombine the pulsatile flow.
2. The flow reactor according to claim 1, wherein said flow generator is configured to generate said pulsatile flow with a normalized oscillatory Reynolds number that is at least 5v, where v is a kinematic viscosity of a material in the process channel.
3. The flow reactor according to claim 1, wherein said flow generator is configured to generate said pulsatile flow with a velocity ratio of at least 1, where the velocity ratio is the ratio of an oscillatory Reynolds number to a net Reynolds number and is given by 2fx.sub.0/u where u is a velocity of the net flow component, f is a frequency of the oscillatory flow component and x.sub.0 is a center-to-peak amplitude of the oscillatory flow component.
4. The flow reactor according to claim 1, wherein said flow generator is configured to generate said pulsatile flow with a normalized net Reynolds number that is at most 200v, where v is a kinematic viscosity of a material in the process channel.
5. The flow reactor according to claim 1, wherein said mixing elements are further configured to generate vertical vortices within said pulsatile flow.
6. The flow reactor according to claim 1, wherein said top wall comprises at least one transparent part.
7. The flow reactor according to claim 6, wherein a transparent protective cover is disposed on an inside of said top wall, said protective cover protecting at least one of said at least one transparent part.
8. The flow reactor according to claim 6, wherein the flow reactor further comprises at least one irradiation source configured to irradiate a material inside the process channel through said transparent part.
9. The flow reactor according to claim 1, further comprising a heat exchanger in thermal connection with said process channel.
10. The flow reactor according to claim 9, wherein said bottom wall comprises a material having a thermal conductivity of at least 5 W/mK, the bottom wall being part of said heat exchanger.
11. The flow reactor according to claim 10, wherein said bottom wall is provided with a plurality of channels configured to circulate a fluid therethrough, said channels being connected to a heat controller configured to at least one of add heat to and extract heat from said fluid.
12. The flow reactor according to claim 10, wherein said heat exchanger further comprises at least one thermally controlled support element configured to support said process channel with said bottom wall being in thermal contact with said support element, said support element comprising a plurality of channels configured to circulate a fluid therethrough, said channels being connected to a heat controller configured to at least one of add heat to and extract heat from said fluid.
13. The flow reactor according to claim 1, wherein at least one of said side walls comprises a plurality of deflector elements configured to locally deflect said pulsatile flow.
14. The flow reactor according to claim 1, wherein at least said top wall of the process channel is removably attached to the side walls and the end walls of the process channel.
15. The flow reactor according to claim 1, wherein one or more of said top wall, said bottom wall, said side walls, said first end wall, said second end wall and said mixing elements are provided with a coating.
16. The flow reactor according to claim 1, wherein the flow reactor comprises a plurality of inlets distributed along said first end wall and a plurality of outlets distributed along said second end wall.
17. The flow reactor according to claim 1, wherein said mixing elements are formed by at least one removable inlay disposed within the process channel.
18. The flow reactor according to claim 1, wherein said flow generator comprises an oscillator configured to generate said oscillatory flow component with an oscillation frequency of at least 0.01 Hz and of at most 400 Hz, and with an oscillation center-to-peak amplitude within the process channel of at least 1 m and at most 5 cm.
19. The flow reactor according to claim 1, wherein said mixing elements are provided in said process channel in a density of at least 0.1 mixing element per cm.sup.2, and wherein said density is at most 100 mixing elements per cm.sup.2.
20. The flow reactor according to claim 1, wherein said process channel has an internal volume, said mixing elements filling up at least 5% of said internal volume and at most 60% of said internal volume.
21. The flow reactor according to claim 1, wherein the mixing elements are separated by a shortest distance from an adjacent mixing element of at least 0.1 mm, said shortest distance being less than 8 mm.
22. The flow reactor according to claim 1, wherein said process channel has a height measured between said top wall and said bottom wall, said mixing elements having a height that is at most equal to said process channel height.
23. The flow reactor according to claim 1, wherein said process channel has an average height measured between said top wall and said bottom wall of at least 0.1 mm, said average height being at most 10 mm.
24. The flow reactor according to claim 1, wherein said process channel has a longest length measured between said first end wall and said second end wall of at least 1 cm, said length being at most 10 m.
25. The flow reactor according to claim 1, wherein said process channel is provided with at least one further inlet connected to a gas chamber, said at least one further inlet comprising a semipermeable membrane.
26. The flow reactor according to claim 1, wherein the mixing elements are distributed throughout the entire process channel.
27. The flow reactor according to claim 1, wherein said process channel further comprises a single straight channel.
28. A method for producing a product stream using the flow reactor according to claim 1, wherein the method comprises the steps of: providing the flow reactor; continuously introducing a feed stream into the flow reactor; generating a pulsating flow within said process channel; and removing a product stream from said flow reactor.
29. The method according to claim 28, wherein the step of generating a pulsating flow within said process channel comprises generating said pulsatile flow with a normalized oscillatory Reynolds number that at least 5v, where v is a kinematic viscosity of a material in the process channel.
30. The method according to claim 28, wherein the step of generating a pulsating flow within said process channel comprises generating said pulsatile flow with a velocity ratio at least 1, where the velocity ratio is the ratio of an oscillatory Reynolds number to a net Reynolds number and is given by 2fx.sub.0/u u where u is a velocity of the net flow component, f is a frequency of the oscillatory flow component and x.sub.0 is a center-to-peak amplitude of the oscillatory flow component.
31. The method according to claim 28, wherein the step of generating a pulsating flow within said process channel comprises generating said pulsatile flow with a normalized net Reynolds number that is at most 200v, where v is a kinematic viscosity of a material in the process channel.
32. The method according to claim 28, wherein the step of generating a pulsating flow within said process channel comprises generating said oscillatory flow component with an oscillation frequency of at least 0.01 Hz, and with an oscillation center-to-peak amplitude of at least 1 m and of at most 100 cm.
33. The method according to claim 28, wherein the step of generating a pulsating flow within said process channel further comprises generating a plurality of vertical vortices within said pulsating flow.
34. The method according to claim 28, further comprising one of the steps of: heating a material in said process channel and cooling the material in said process channel.
35. The method according to claim 28, wherein the method further comprises irradiating a material in said process channel.
36. The method according to claim 35, wherein the material is irradiated in said process channel to obtain a photochemical reaction.
37. (canceled)
Description
BRIEF DESCRIPTION OF THE DRAWINGS
[0054] The invention will be further explained by means of the following description and the appended figures.
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DESCRIPTION OF THE INVENTION
[0068] The present invention will be described with respect to particular embodiments and with reference to certain drawings but the invention is not limited thereto but only by the claims. The drawings described are only schematic and are non-limiting. In the drawings, the size of some of the elements may be exaggerated and not drawn on scale for illustrative purposes. The dimensions and the relative dimensions do not necessarily correspond to actual reductions to practice of the invention.
[0069] Furthermore, the terms first, second, third and the like in the description and in the claims, are used for distinguishing between similar elements and not necessarily for describing a sequential or chronological order. The terms are interchangeable under appropriate circumstances and the embodiments of the invention can operate in other sequences than described or illustrated herein.
[0070] Moreover, the terms top, bottom, over, under and the like in the description and the claims are used for descriptive purposes. The terms so used are interchangeable under appropriate circumstances and the embodiments of the invention described herein can operate in other orientations than described or illustrated herein.
[0071] Furthermore, the various embodiments, although referred to as preferred are to be construed as exemplary manners in which the invention may be implemented rather than as limiting the scope of the invention.
[0072] The present invention relates to a flow reactor assembly, generally indicated with reference number 1, that may be used for a wide variety of reactions and/or processes. Specifically, the reactor 1 is suitable for processing fluids or mixtures of fluids, including multiphase mixtures of fluids which may include solids or dissolved gases. These processes may involve continuous reactions, temperature adjustment, (re-)mixing, separation, extraction, crystallization or precipitation, leaching, absorption, stripping or adsorption. The processing may include a biological process, a physical process or a chemical reaction, i.e. a process that results in the interconversion of organic, inorganic or both organic and inorganic species. In particular, the reactor 1 is suitable for mixtures of reactants and/or products, suspensions, emulsions and dispersions comprising solids, liquids and (dissolved) gases.
[0073] In an embodiment, the reactor 1 is suitable for a wide variety of thermal syntheses or disintegrating (e.g. waste treatment) reactions, which may optionally be catalysed (homogeneously, heterogeneously, enzymatic). The following non-limiting list of reactions may be performed with the reactor 1: oxidation; reduction; substitution; elimination; addition rearrangements; radical reactions; ligand exchange; metal exchange; and ion exchange. More specifically, any one of the reactions of the following non-limiting list may be performed with the reactor 1: polymerization; alkylation; dealkylation; nitration; peroxidation; sulfoxidation; epoxidation; ammoxidation; hydrogenation; dehydrogenation; organometallic reactions; precious metal chemistry/homogeneous catalyst reactions; carbonylation; thiocarbonylation; alkoxylation; halogenation; dehydrohalogenation; dehalogenation; hydro formylation; carboxylation; decarboxylation; amination; arylation; peptide coupling; aldol condensation; cyclocondensation; dehydrocyclization; esterification; amidation; heterocyclic synthesis; dehydration; alcoholysis; hydrolysis; ammonolysis; etherification; enzymatic synthesis; ketalization; saponification; isomerisation; quaternization; formylation; phase transfer reactions; silylations; nitrile synthesis; phosphorylation; ozonolysis; azide chemistry; metathesis; hydrosilylation; coupling reactions; cycloadditions; radical generation; radical reaction; biradical reaction and enzymatic reactions.
[0074] Furthermore, in certain embodiments, the reactor 1 is also suitable for reactions initiated and/or maintained by non-thermal activation technologies, such as electromagnetic radiation (e.g. radio, microwave, infrared, visible light, ultraviolet, X-rays and gamma rays), potential differences using electrodes in contact with reactor matrix (i.e. electrochemistry), external electric fields, external magnetic fields, or sound waves (e.g. ultrasound). These activation technologies can applied either in isolation or in combination (e.g. photoelectrochemistry)
[0075] As illustrated in
[0076] As used herein, the term feed stream is intended to mean all components, including liquids, gases and solids, that are introduced in the process channel 2 through the inlet(s) 10 in order to perform the desired reaction and/or process.
[0077] As used herein, the term product stream is intended to mean all components, including liquids, gases and solids, that are discharged from the process channel 2 through the outlet(s) 11 as a result of the desired reaction and/or process.
[0078] It will be readily appreciated that, although the inlet 10 and outlet 11 are illustrated in the figures as being in the bottom wall 4 of the process channel 2, in other embodiments, the inlet 10 and/or the outlet 11 may be provided in respective ones of the first end wall 8 and/or the second end wall 9. Furthermore, it will be appreciated that one or more additional inlets and/or outlets may be provided between the first end wall 8 and the second end wall 9, for example near the middle of the process channel 2. Moreover, multiple inlet tubes 12 may be connected to a single inlet 10 in which case the feed stream is formed by mixing of the streams from the multiple inlet tubes within the flow reactor assembly 1 before reaching the inlet 10.
[0079] The process channel 2 is typically assembled from a variety of different parts as illustrated in
[0080] It will be readily appreciated that the bottom half 22 and top half 25 may be joined together by other means besides the bolts 26. For example, external clamps may be provided to clamps these halves 22, 25 together. Alternatively, the halves 22, 25 may be permanently joined together, although a removable top half 25 is preferred as this makes it much easier to clean the interior of the process channel 2 and/or replace parts.
[0081] Preferably, a protective sheet (not shown) may be applied on the side of the cover plate 23 that forms the top wall 5, in which case the protective sheet forms the top wall 5. Such a protective sheet is advantageous as it is suitable to protect the cover plate 23 from fouling by material deposition and/or aggressive media (e.g. strong bases and sources of fluorides) which can attack the material from which the cover plate 23 is manufactured. Furthermore, this protective sheet can be easily replaced in case it degrades during use. The protective sheet is preferably manufactured from chemically resistant materials, such as polyfluorinated polymers.
[0082] The halves 22, 25, the mixing elements 15 and the cover plate 23 may be manufactured from a whole variety of materials. However, chemically resistant materials are preferred. Such materials may include (poly)fluorinated polymers (e.g. PTFE, FKM, FPM, FFKM, FFPM, etc.), graphite, rubber, fibre and glass (e.g. borosilicate, Pyrex, Vycor, etc.) or other transparent materials. However, Incalay, Monel, Hastelloy, Inconel, Durimet, Si, SiC, steel, stainless steel and any other corrosion resistant metals or alloys are preferred. Moreover, these components may be manufactured using different machining processes, such as milling, etching processes, laser medium processing, micro spark erosion, 3D printing, etc.
[0083] The process channel 2 may be designed to be operated under pressure, in which case the thickness and/or the mechanical strength of the halves 22, 25, the mixing elements 15, the cover plate 23, the seal 24, etc. is chosen for the desired pressure. A typical pressure within the process channel 2 is between 1 and 11 bar and preferably between 2 and 5 bar. However, it will be readily appreciated that a pressure below 1 bar (i.e. an underpressure) may also be used in the process channel 2.
[0084] A separate inlay for the mixing elements 15 as in
[0085] The interior of the process channel 2 may optionally be coated to add additional functionalities. The coating can serve as an extra protective layer (e.g. when aggressive and/or corrosive media are used), have catalytic properties (e.g. for catalytic and photocatalytic solid-liquid reactions), modify the flow properties by changing surface tension and/or surface roughness, or change reflection properties.
[0086] A protective coating advantageously comprises materials such as a functionalized mixture of amorphous silicon, oxygen and carbon (e.g. Dursan), tantalum, PTFE, ceramics, glass, etc.
[0087] One type of photocatalytic coating comprises a metal chalcogenide, such as a metal oxide (for example TiO.sub.2, ZnO or SrTiOs, CdS, CdSe, Fe.sub.2O.sub.3, Cu.sub.2O, Fe.sub.2TiO.sub.3, Bi.sub.2O.sub.3, etc.) or a polymer (e.g. poly(methyl)methacrylate) which can serve as anchor point to covalently bind photocatalysts, acids, bases, ligands (with or without metals), organic ions (tetraalkylammonium, sulfonates, zwitterions etc.), organocatalysts or enzymes or has photoredox properties (Graphene, (doped) graphitic nitride, etc.). Another type of catalytic coating may comprise and/or may be bounded with an enzyme, a peptide, a peptidomimetic or other biocatalytic based species.
[0088] The surface layer of a catalytic coating may be porous or fibrous which can be inert (e.g. microfibrous glass) or catalytic (e.g microfibrous copper) in which other catalytic species can be entrapped. In other words, the surface of the coating has a microstructure which includes a number of pores, depressions and holes therein. This porosity serves to increase the surface area available to make contact with the fluid in the process channel 2.
[0089] Furthermore, the nature of the coating may influence the adsorption of specific molecules and/or materials in the fluid carried through the process channel 2, which further modify the activity of the flow reactor 1.
[0090] The coating can be applied by a variety of methods, such as sol-gel methods, dipping, sputtering, anodic oxidation, electrodeposition, immobilized nanoparticles, chemical vapor deposition (CVD), Physical Vapor Deposition (PVD), anodic oxidation under spark discharge (ANOF), etc.
[0091] As illustrated in
[0092] As used herein, the term pulsatile flow is intended to mean the resultant periodic flow of the superposition of a unidirectional net flow along said process channel and a periodic oscillatory flow, irrespective of the amplitude of the oscillatory flow. In particular, the maximum oscillatory velocity may be less than the net flow velocity, meaning that the flow always has a positive velocity. Alternatively, the maximum oscillatory velocity may be more than the net flow velocity, meaning that the flow at times has a negative velocity. Preferably, said net flow has a substantially constant flow rate.
[0093] Moreover, the process channel 2 is further provided with a plurality of static mixing elements 15 configured to locally split and recombine said flow as illustrated in
[0094] It has been found that combining a process channel 2 having static mixing elements 15 disposed therein, preferably being distributed along the entire length and width of the process channel 2, with the pulsatile flow generated by the flow generator 14 leads to the generation of sufficient turbulence and/or mixing of the fluid within the process channel 2 even at low net flow rates. In particular, in the absence of an oscillating flow component, the mixing elements 15 do not hinder the development of a laminar flow behaviour for a low net flow rate where the split flow 16R, 16L does not mix as intensely with left-handed, respectively right-handed flow components from adjacent mixing elements 15, meaning that there is not sufficient turbulence and/or mixing of the fluid within the process channel 2. However, the oscillating flow component alleviates this issue as the oscillating behaviour locally creates sufficiently high flow rates such that the flow is impinged on the mixing elements 15 with a high enough velocity such that the split flow components 16R, 16L indeed mix with left-handed, respectively right-handed flow components from adjacent mixing elements 15.
[0095] It will be readily appreciated that the pulsatile flow may be damped in the product stream, i.e. the oscillatory component is damped in order to obtain a net flow in the outlet tube 13. Having only a net flow outside the flow reactor assembly 1 is preferred especially in case one or more measuring and/or monitoring appliances are connected. Such a damping may be achieved in different ways, e.g. by using a hydraulic accumulator, a cyclone, a buffer, etc.
[0096] In some embodiments the flow generator 14 may generate the unidirectional flow by any different number of means which are known to the person skilled in the art, such as natural convection, forced convection, gravity, pressurized feed vessels, mass flow controlled (liquefied) gases, slurry dosage, etc. In particular, in the case of forced convection, pumps (e.g. a peristaltic pump, a gear pump, a diaphragm pump, a piston pump, a centrifugal pump, a syringe pump, etc.) may be used. Moreover, in the case of net flow due to gravity, it will be readily appreciated that the orientation of the process channel 2 is different from the horizontal orientation illustrated in the figures. In other words, the reactor 1 may be set up in different orientations, including tilted and/or vertical orientations, depending on the specific circumstances.
[0097] In some embodiments the flow generator 14 may include an oscillator (not shown) configured to generate the oscillating flow component. In particular, said oscillator may be configured to generate said oscillatory flow component with an oscillation frequency of at least 0.01 Hz, preferably at least 0.1 Hz and more preferably at least 0.5 Hz and of at most 400 Hz, preferably at most 100 Hz, more preferably at most 50 Hz and most preferably at most 25 Hz, and with an oscillation centre-to-peak amplitude of at least 1 m, preferably at least 10 m, more preferably at least 0.1 mm and most preferably at least 0.5 mm and at most 100 cm, preferably at most 20 cm, more preferably at most 5 cm, most preferably at most 1 cm, advantageously at most 5 mm and more advantageously at most 2 mm.
[0098] Moreover, it is advantageous when the generated centre-to-peak amplitude of the oscillatory flow is of at least the same order of magnitude as the distance between subsequent mixing elements 15, i.e. mixing elements which are adjacent to one another along the longitudinal direction 3. In other words, the centre-to-peak amplitude is ideally at least half of the distance between subsequent mixing elements as this ensures that, for each periodic oscillation cycle, a fluid parcel is displaced over a distance in the longitudinal direction that it is at least equal to the distance between subsequent mixing elements, meaning that, for each periodic oscillation cycle, the fluid parcel normally is split by a mixing element 15.
[0099] The oscillator may be in the form of a modified membrane pump or a piston pump where the check valves have been removed or altered. Alternatively, a custom made piston or bellows directly connected to the process volume, e.g. the feed stream, is possible too. Furthermore, a first pump, e.g. a membrane pump, may be used to generate the net flow component and a second pump, e.g. a modified membrane pump, may be used to generate the oscillatory flow component.
[0100] It will be readily appreciated that, in practice, the flow generator 14 may have different settings, meaning that the flow generator 14 may be capable of generating net flows across a range of flow velocities and/or oscillatory flows across a range of oscillation amplitudes and/or oscillation frequencies.
[0101] In general, for a pulsatile flow, the net and oscillatory Reynolds numbers are defined in order to characterise the flow. The net Reynolds number is given by R.sub.n=uL/v, where u is the velocity of the net flow component, L is a characteristic length which is typically taken as the hydraulic diameter of the process channel 2 and v is the kinematic viscosity of the fluid. The oscillatory Reynolds number is given by R.sub.o=2fx.sub.0L/v, where f is the frequency of the oscillatory flow component and x.sub.0 is the centre-to-peak amplitude of the oscillatory flow component. Using both Reynolds numbers it is also possible to define the velocity ratio
Furthermore, as both Reynolds numbers are dependent on the characteristics of the medium within the process channel 2 through the kinematic viscosity, it is useful to define normalised Reynolds numbers. Specifically, the normalised net Reynolds number is given by =R.sub.nv=uL, and the normalised oscillatory Reynolds number is given by
=R.sub.ov=f.Math.2.Math.x.sub.0L.
[0102] It has been found that a normalised oscillatory Reynolds number that is at least 5v, preferably at least 25v, more preferably at least 50v, advantageously at least 75v and most advantageously at least 100v leads to sufficient turbulence and/or chaotic motions even for relatively low net flow rates as described above. In some embodiments, said pulsatile flow has a velocity ratio of at least 1, preferably at least 5, more preferably at least 10, advantageously at least 15 and most advantageously preferably at least 20. Similarly, said pulsatile flow has a normalised net Reynolds number that is preferably at most 200v, preferably at most 100v, more preferably at most 50v, most preferably at most 20v, advantageously at most 10v, more advantageously at most 5v, and most advantageously at most 0.5v. Such low net Reynolds numbers are advantageous as it enables a long residence time of the fluid within a short process channel 2, meaning the flow reactor 1 may be very compact and may thus be easily used in a laboratory for example.
[0103] In calculating the Reynolds numbers, the hydraulic diameter of the process channel 2 is used. This hydraulic diameter is typically dependent on the cross-sectional area of the process channel, i.e. its height H and its width W, and on the area that is filled by the mixing elements 15
[0104] As used herein, the term height of the process channel is intended to mean the average distance between the bottom wall 4 and the top wall 5 of the process channel 2.
[0105] As used herein, the term length of the process channel is intended to mean the average distance between the first end wall 8 and the second end wall 9 of the process channel 2.
[0106] As used herein, the term width of the process channel is intended to mean the average distance between the side walls 6, 7 of the process channel 2.
[0107] In an example of the flow reactor, the planar process channel 2 has a cross-section with a high aspect ratio (e.g. at least 3, in particular at least 5 and more in particular at least 10), where the aspect ratio is the ratio of the width to the height of the process channel.
[0108] In certain embodiments, the height H of the process channel 2 is at least 0.1 mm, preferably at least 0.5 mm, more preferably at least 1 mm and most preferably at least 2 mm, said height H being at most 10 mm, preferably at most 7.5 mm, more preferably at most 5 mm and most preferably at most 3 mm. Such a limited height H is especially advantageous for photochemistry as described below as the radiation is then able to penetrate to the bottom wall 4 thus irradiating sufficiently all of the fluid within the process channel 2.
[0109] In certain embodiments, the length L of the process channel 2 is at least 1 cm, preferably at least 5 cm, more preferably at least 10 cm, advantageously at least 25 cm and most advantageously at least 50 cm, said length being at most 10 m, preferably at most 5 m, more preferably at most 2 m and most preferably at most 1 m. Such a range of lengths ensures that both long residence times and short residence times are feasible depending on the reaction and/or process in combination with low net flow rates which are known to have a lower pressure drop along the length of the process channel 2.
[0110] Moreover, the width W of the process channel 2 is typically decided based on the desired production capacity, i.e. the wider the process channel 2, the larger the internal volume thereof and the larger the volume of the product stream. In other words, the width W of the process channel 2 may cover several orders of magnitude in size range. For example, in some embodiments, the width W may be at least 5 mm, preferably at least 1 cm and more preferably at least 2 cm and at most 10 m, preferably at most 1 m, more preferably at most 50 cm and most preferably at most 10 cm.
[0111] It will be appreciated that when the width W of the process channel 2 is increased, increasing the number of inlets 10 and outlets 11 is also recommended as illustrated in the flow reactor assembly 1 shown in
[0112] In some embodiments, the distance between adjacent inlets 10 and/or outlets 11 is at most 10 cm, preferably at most 5 cm and more preferably at most 2 cm. Such a small distance aids in avoiding dead volumes between the inlets 10 and outlets 11.
[0113] In some embodiments, the mixing elements 15 are provided in the process channel 2 in a density of at least 0.1 mixing element per cm.sup.2, more preferably with at least 1 mixing element per cm.sup.2 and most preferably with at least 5 mixing elements per cm.sup.2 and with a density of at most 100 mixing elements per cm.sup.2, more preferably with at most 50 mixing elements per cm.sup.2 and most preferably with at most 10 mixing elements per cm.sup.2. Moreover, the process channel 2 has an internal volume, i.e. a volume without any mixing elements 15 being disposed within the process channel 2. In some embodiments, the mixing elements 15 fill up at least 5% of said internal volume, preferably at least 10% of said internal volume and more preferably at least 15% of said internal volume and at most 60% of said internal volume, preferably at most 50% of said internal volume, more preferably at most 40% of said internal volume, most preferably at most 30% of said internal volume and advantageously at most 20% of said internal volume.
[0114] It has experimentally been found that such a distribution of mixing elements 15 within the process channel 2 enables to provide a desired mixing level for a whole range of Reynolds numbers for different reactions and/or processes.
[0115] Furthermore, it is advantageous, especially at very low net Reynolds numbers, i.e. very low net flow rates, to provide smaller openings between adjacent mixing elements 15. As such, it has been found that it is beneficial when the mixing elements 15 are separated by a shortest distance from an adjacent mixing element 15 of at least 0.1 mm, preferably at least 0.5 mm, more preferably at least 1 mm and most preferably at least 1.5 mm, said shortest distance being preferably less than 8 mm, more preferably less than 5 mm, advantageously less than 3 mm and more advantageously less than 2.5 mm.
[0116] It will be readily appreciated that the mixing elements 15 may exist in various shapes and/or sizes. A number of examples of differently shaped mixing elements 15 are shown in
[0117] Furthermore, although the mixing elements 15 may have surfaces that are perpendicular with respect to the bottom wall 4, these surfaces may also be inclined with respect to the bottom wall 4 as in
[0118] Preferably, the mixing elements 15 are set up in a periodic pattern, i.e. a repeating pattern along the longitudinal direction 3 of the process channel. Furthermore, it is advantageous when the mixing elements 15 are set up in a symmetrically ordered periodic pattern, meaning that the mixing elements 15 are mirrored with respect to the vertical longitudinal centre plane of the process channel 2. Such patterns typically result in repeating flow patterns which improve the RTD.
[0119] As illustrated in
[0120] In the embodiment illustrated in
[0121] As illustrated in
[0122] In particular, in cooling mode, a cooled fluid is pumped into the heat exchanger 17 via tube 18 to inlet 19 which opens onto one or more channels (not shown) within the metal plate 17. Due to the thermal contact between the channels within the metal plate 17 and the process channel 2, the cooled fluid is heated while the process channel 2 is cooled. The heated fluid then exits the metal plate 17 via outlet 20 into tube 21. Tube 21 is then typically connected to a further heat exchanger (not shown) which cools the heated fluid and injects the cooled fluid again into tube 18. In heating mode the same principle applies but the fluid entering the inlet 19 is now hotter than the fluid within the process channel 2. It will be readily appreciated that the roles of the inlet 19 and outlet 20 may also be reversed. In other words, cooled or heated fluid may be inserted through outlet 20 to create a counter-current heat exchanger.
[0123] As the heat needs to be supplied to or removed from the process channel 2, it is advantageous when the bottom wall 4, formed by the lower half 22 of the flow reactor 1 (see
[0124] Furthermore, it is also advantageous when the static mixing elements 15 form a part of the heat exchanger 17 as this dramatically increases the contact surface area between the fluid within the process channel 2 and the heat exchanger 17. In the embodiment illustrated in
[0125] It will be appreciated that other types of heat exchangers 17 may be used, such as heat exchangers operating on electrical heating or Peltier elements. Moreover, other heat exchangers are known to the person skilled in the art and may readily be applied in combination with the flow reactor assembly 1 of the present invention.
[0126] Moreover, it will be appreciated that the heat exchanger 17 may be integrated within the lower half 22 of the flow reactor 1, which lower half 22 also comprises the bottom wall 4, as illustrated in
[0127] The operating temperature of the process channel 2 is typically dependent on the reaction and/or process for which the flow reactor 1 is being used. In some embodiments, the operating temperature is at least 100 c., preferably at least 30 C. and more preferably at least 20 C. and at most 400 C., preferably at most 200 C. and more preferably at most 100 C.
[0128] In some embodiments, the flow reactor 1 may be provided by an at least partly transparent top wall 5 in the appended figures. In other words, one or more parts of the cover plate 23 are transparent. In this way the flow reactor 1 may be used for photochemistry, i.e. reactions requiring irradiation as a trigger, such as photo initiated polymerizations.
[0129] Furthermore, the flow reactor 1 can be used in combination with an irradiation source 32 (shown in
[0130] As used herein, the term irradiation is intended to mean electromagnetic emission with a wavelength suitable for photochemistry. Typically, the electromagnetic emission has a wavelength between 100 nm and 1 m.
[0131] In case of photochemistry, it is advantageous when the top part of the internal process channel 2 is unobstructed, i.e. when the mixing elements 15 do not extend entirely to the top wall 5. In this way, the mixing elements 15 results in a decreased shade, meaning that the irradiated volume is increased. Furthermore, the generation of vertical vortices due to mixing elements 15 as shown in
[0132] In some embodiments, at least one cooling means (not shown) is provided configured to cool the irradiation source 32 and/or the region between the irradiation source 32 and the cover plate 23, and the cover plate 23 itself. In this way the irradiation source 32 may be operated at its desired operating temperature increasing its efficiency. Moreover, cooling the region between the irradiation source 32 and the cover plate 23, or the cover plate itself, aids in controlling the temperature within the process channel 2.
[0133] An additional benefit of the transparent cover plate 23 is that the radiation from the irradiation source 23 does not need to penetrate through thermal oil layers, as is the case in some known flow reactors, which causes loss of efficiency especially during long irradiation times and/or limits the available wavelengths that may be used.
[0134] A spectral filter (not shown) can be placed on top of the transparent cover plate 23, e.g. in the form of a sheet. The spectral filter may be a short-pass, long-pass, band-pass or interference filter in order to select the appropriate wavelengths depending on the reaction and/or process for which the flow reactor 1 is being used. Furthermore, an infrared filter can be applied in order to minimise undesired heating of the fluid within the process channel 2 by infrared portions of the irradiation source 32. Moreover, the spectral filter may also be a hot mirror or a cold mirror.
[0135] Moreover, to broaden the spectrum of possible wavelengths (especially in the ultraviolet region), the material of the transparent cover plate 23 may be, quartz, fused silica, Al.sub.2O.sub.3(Sapphire), Alon, BaF.sub.2, BK7 glass, CaF.sub.2, Germanium, KRS5, LiF, MgF.sub.2, Silica glass, ZnS (FLIR), ZnSe, Aluminium oxynitride (AlON), MgAl.sub.2O.sub.4 (Spinel), polymeric materials (polymethylmethacrylate, polystyrene, cyclic olefin copolymers (COC, Topas), polydimethylsiloxane, polycarbonate, light absorbing/emitting materials, luminescent (solar) concentrators, etc.
[0136] A known problem in flow reactors for photochemistry is a decreasing transparency of a polymeric material over time, since this process is uncontrollable and decreases the performance of a flow reactor. However, due to the simple design of the flow reactor 1, this problem may be alleviated as the various transparent cover plate 23 and/or the protective sheet applied thereto may be easily cleaned and/or replaced.
[0137] Photochemical reactions can be initiated by direct activation through irradiation or via use of a photomediator (i.e. a photoinitiator, a photocatalyst or a photosensitizer). The photomediator can be present homogeneously in the feed stream, as a solid particle in the feed stream or as part of an internal coating of the process channel 2. In case of a photochemical gas-liquid reaction (e.g. generation of a singlet oxygen), the photosensitizer may also be present in a semi-permeable membrane 36 as described below with respect to
[0138] Moreover, as described above, the internal coating may also increase reflection of the irradiation thus increasing the performance of the flow reactor 1 as the reflecting light from the bottom wall 4 leads to a more efficient use of the photons.
[0139] A non-limiting list of photochemical reactions includes photoisomerizations, photorearrangements, photoreductions (e.g. of CO.sub.2, photooxidation (e.g. photo fenton reaction), cyclizations, [2+2] cycloadditions (e.g. Paterno-Buchi), [4+2] cycloadditions, [4+4] cycloadditions, 1,3-dipolar cycloadditions, sigmatropic shifts, photocleavage of protecting groups or linkers, photohalogenations (photofluorination, photochlorinations, photobrominations, photoiodination), photosulfochlorinations, photosulfoxidations, photopolymerizations, photonitrosations, photodecarboxylations, photosynthesis of previtamin D, decomposition of azo-compounds, Norrish type reactions, Barton type reactions, photoredox reactions, Photogeneration of active species (e.g. singlet oxygen), photo (homo) dimerization of alkynes, photoaddtions (e.g. thiol-ene coupling) phototri (or di)fluoromethylation, perfluoroalkylations, photoalkylation, photohydroxymethylation, photoacylation, photodeuteration and tritiation, dehydrogenative photooxidation, photo beta-oxidation of amines, photo beta functionalisation of carbonyl compounds, photo alpha functionalisation of amines, photo alpha functionalisation of aldehydes, acylation of ethers, carbon addition on double bonds, synergistic photocatalysis (with metals, organocatalyst and enzymes), photo cross-coupling reaction (carbon or heteroatom) (sp3-sp3, sp3-sp2, sp2-sp2), photo cascade reaction, photo aza-Henry reaction, photodehalogenations, photo halogen exchange reactions, and ATRA (atom transfer radical additions).
[0140] It will be readily appreciated that one or more sensors and/or analytic tools may be integrated within the process channel 2, within one or more walls 4, 5, 6, 7, 8, 9 thereof, in or near the inlet(s) 10 and/or outlet(s) 11 to provide readings on a host of process parameters, such as pressure, temperature, viscosity, flow rate, etc.
[0141] Additionally, monitoring tools may be able to operate through the transparent cover plate 23 (e.g. Raman, IR, NIR, UV-VIS, etc.). Using fused silica or quartz to manufacture the cover plate 23 has the advantage (over the use of common laboratory glass, e.g. borosilicate, Pyrex, Vycor) that these materials are translucent in the required wavelength regions. This enables spectroscopic analysis during operation of the flow reactor 1.
[0142] Besides for multiphasic reactions and/or processes involving combinations of (immiscible) liquids and solids, the flow reactor 1 can also be used for multiphasic reactions involving (dissolved) gases. The existence of separate gas phases in the reaction fluid is not recommended as the gas bubbles attenuate the superposed oscillating flow component due to their compressibility. However, when pre-saturating the feed stream under a positive pressure this attenuation may be largely avoided.
[0143]
[0144] The supply of the gases will be dependent of the overpressure, the nature of the semipermeable membrane 36 and its pore size. Typical gases are oxygen, carbon dioxide, carbon monoxide, hydrogen, nitrogen oxides, trifluoromethyliodide, etc.
[0145] Also degassing of the reaction medium within the process channel 2 is feasible using an additional raster or a more rigid membrane 36 and applying a reduced pressure. In this way, undesirable gases can be removed from reaction medium (e.g. oxygen) in a pre-processing step or the equilibrium can be shifted in processes in which removal from gases (decarboxylation, nitrogen, ethene, . . . ) are involved. Alternatively, an overpressure of an inert gas may be used to remove other gases from the solution.
[0146] As illustrated in
[0147] As a first example,
[0148] A second example is shown in
[0149]