EP1796829A1

EP1796829A1 - Microcapillary reactor and method for controlled mixing of non homogeneously mixable fluids using said microcapillary reactor

Info

Publication number: EP1796829A1
Application number: EP05798042A
Authority: EP
Inventors: Yücel ÖNAL; Martin Lucas; Peter Claus
Original assignee: Technische Universitaet Darmstadt
Current assignee: Technische Universitaet Darmstadt
Priority date: 2004-10-11
Filing date: 2005-10-06
Publication date: 2007-06-20
Also published as: DE102004049730B4; JP2008515627A; CA2583834A1; US20080080306A1; DE102004049730A1; WO2006039895A1

Abstract

The invention relates to a microcapillary reactor (1) containing at least one first static mixer, comprising at least one first static mixer (2), comprising at least one first capillary supply line (4) for a first fluid, at least one second capillary supply line for a second fluid which is not substantially homogeneously mixable with the first fluid, wherein the first and second capillary supply lines flow into a region which is the point of departure for at least one transport line, wherein the first (6) and second (8) capillary supply lines are dimensioned in such a way that the first and second fluids can be respectively transported in laminary flow conditions and can be displaced in the form of alternatingly successive discrete liquid phase sections (plugs). The invention is characterized by at least one second static mixer(1), comprising at least one third supply line (12), particularly a capillary supply line, for a gaseous third fluid which flows into the first capillary transport line (10) downstream from the first mixer (2). The invention also relates to a multi-microcapillary reactor. The invention further relates to a method for controlled mixing of at least two fluids which substantially cannot be mixed in a homogeneous manner and at least one gaseous fluid, using said microcapillary reactor. The inventive method makes it possible to catalytically hydrogenate, for example, unsaturated aldhehydes, hydroformulate olefins and homogeneously catalytically oxidize organic compounds.

Description

Microcapillary reactor and method for controlled mixing of non-homogeneously miscible fluids using this microcapillary reactor

The present invention relates to a microcapillary reactor comprising at least a first static mixer comprising at least a first capillary feed line for a first liquid fluid, at least one second capillary feed line for a second liquid fluid which is substantially non-homogeneously miscible with the first fluid, wherein the first and second capillary supply lines open in a region which is the starting point for at least one first transport line, the first and second capillary supply lines being dimensioned such that at least the first and second fluids can each be transported under laminar flow conditions and transported in Form alternately successively following discre¬ ter liquid phase sections (plugs) are forwarded. Furthermore, the present invention relates to a process for the controlled mixing of at least two substantially immiscible liquid fluids and at least one gaseous fluid. Finally, the invention relates to the use of the microcapillary reactor according to the invention for the hydrogenation, hydroformylation, carbonylation and oxidation of organic compounds.

Microcapillary reactors are known, for example, from WO 01/64332 A1. This Mikrokapillarre¬ actuator is basically a T-mixer with two leads and a derivative. Two liquids which are essentially immiscible with one another are preferably supplied frontally to one another via the two feed lines, with the result that the liquids mixed with one another are continued in the common discharge of the microcapillary reactor in the form of alternately sequential, miniaturized fluid blocks (plugs). This results in a high degree of common phase interface between the non-mixed-phase ren fluid components created at the example diffusion-controlled chemical reactions can take place. However, care must be taken to ensure that the diameter of discharge or supply lines is chosen as small as possible and in particular does not exceed the value of 1000 μm. According to WO 01/64332 A1, liquid / gaseous, solid / liquid / liquid and solid / liquid / gaseous reactions can be carried out with the microcapillary reactor found. The solid phase can be provided, for example, as a coating on the inner wall of the discharge. With the microcapillary reactor according to WO 01/64332 Al, for example, the Ni¬ tration of benzene and toluene succeed.

In addition to the previously described variant for the intimate mixing of immiscible liquids via two capillary streams which impact one another head-on in a T-mixer, which has also already been described in general terms in US Pat. No. 5,921,678, the most effective possible contact of two liquids which can not be mixed with one another can be achieved via parallel Liquid flows, as disclosed in WO 97/39814 and WO 99/22858, accomplish conditions. In this case, the mass transfer between the substantially parallel flowing next to each other, immiscible fluids by diffusion takes place at the phase boundary surface perpendicular to the direction of flow.

The use of Y-shaped microcapillary reactors for the nitration of benzene or toluene in liquid / liquid systems can also be found in G. Dummann et al., Catalysis Today 79-80 (2003) 433-439.

According to EP 1 329 258 A2, it is also possible to use microcapillary reactors in the form of plates or plate stacks for carrying out continuous processes, on the surfaces of which there are miniaturized functional spaces or channels in which the liquid phase is at least partially absorbed by gravity and / or by capillary forces a uninterrupted capillary thread flows. With this device, chemical reactions and physical processes should be carried out, with resulting liquid or gaseous constituents and reaction products from the liquid phase being able to be continuously removed in a controlled manner.

Although the microreactor technology is still very young, it has already been recognized that it is suitable not only for analytical purposes but also for commercial synthesis processes (see O. Wörz, et al., Chemical Engineering Science 56 (2001) 1029- 1033). In this In connection with this, it is advantageous that very large surface / volume ratios can be set in the microreactors mentioned, so that even very fast and very exothermic reactions can be carried out under substantially isothermal conditions.

Improvements in microreactors, in particular in microcapillary reactors, would be equally desirable in order to be able to further expand their application potential and make better use of it.

It is therefore an object of the present invention to provide a microcapillary reactor which does not suffer from the disadvantages of the prior art, which allows a wider application in analytical and synthetic terms and which moreover also involves the controlled mixing and reaction of liquid / liquid / gaseous systems allowed in a very effective way.

A further object of the invention was to make available a process for the controlled mixing of liquid / liquid / gaseous systems, with which multiphase reactions, e.g. catalytically controlled multiphase reactions, can be carried out effectively.

Accordingly, a microcapillary reactor has been found, characterized by at least one second static mixer, comprising at least one, in particular capillary, third supply line for a gaseous third fluid, which flows downstream into the first capillary transport line to the first mixer. In this case, extension lines may also be provided for the first, second and / or third supply line and / or from or in the first transport line.

In one embodiment, the first and / or second mixers can in each case represent uniform material blocks, for example made of a plastic material or of metal, into which the first, second or third supply lines and first transport lines have been incorporated by means of bores. Of course, these static mixers may also be molded plastic or cast metal components. Furthermore, it is possible in a further embodiment that the first and second static mixers are present or coupled in a unitary block of material or directly adjacent to one another. Selbstver- Of course, the first and second mixers can also be spatially separated, and the first transport line, optionally with the interposition of an extension line, can connect both mixers. For the purpose of feeding the fluids into these static mixers, it is possible to resort to corresponding first, second and third extension lines which are sealingly connected to the first, second and third supply lines, respectively. Advantageously, the extension lines have substantially the same inner diameter as the leads to which they are connected. Furthermore, the first transport line can also be connected after exiting the second mixer with a fourth extension line ver¬. It is also possible to interpose a fifth extension line between the first transport line which carries out the first mixer and the first transport line leading into the second mixer. Again, it is advantageous if the inner diameter of these fourth and fifth extension lines substantially coincide with the inner diameter of the first transport line.

The first mixer of the microcapillary reactor according to the invention is based on the functional principle of the static mixer described in WO 01/64332 A1. The immiscible liquids are accordingly transferred in the first and second capillary Zuleitun¬ gene in the manner in a common transport line, that alternate, non-homogeneously mogenbare fluid blocks while maintaining or training a coherent fluid flow_resultieren. For this purpose, the term alternate plug-flow system is used.

With the second mixer it is possible to selectively feed the gaseous third fluid into the plugs of only the first or the second fluid. In these fluid blocks, a gas bubble is generally present in each case. Preferably, this gas bubble oscillates within a fluid block between the phase interfaces of adjacent immiscible fluid blocks.

In a particularly preferred embodiment it is provided that at least the Innen¬ wall of the first transport line and / or at least the inner wall of the first, second and / or third supply line and / or the extension lines to the first, second and / or third supply line and / or The first transport line is at least partially equipped with a polarity or are, which has a greater affinity to the first or the second fluid. It has surprisingly been found that if the polarity of at least the inner wall of the first transport line of that of one of the used, not mixed Baren fluid is adapted, the gaseous third fluid is particularly controlled and selectively introduced into those fluid blocks / plugs having an identical or similar polarity as the inner wall of the transport line. In this way it can be controlled via the choice of the material of the first transport line, in which fluid blocks or segments the gaseous fluid is to be entered. Surprisingly, it has been shown that the result according to the invention of the controlled, selective entry of the gas phase into fluid blocks of uniform polarity also sets in if at least the inner wall of the section of the first transport line adjoining the second mixer and / or or the fourth extension line is or are at least partially equipped with a polarity that has a greater affinity for the first or the second fluid, for example, based on or consisting of a plastic such as Teflon.

Particular preference has been given to microcapillary reactors according to the invention in which the inner wall of the first transport line is partially or completely, e.g. in which adjoining the second mixer section, at least partially equipped non-polar. Unpolar or a non-polar surface in the sense of the present invention should be understood to mean one which, with water as the test liquid, has a contact angle, e.g. determined by the sessile drop method, of> 90 °. Preferred nonpolar surfaces have a contact angle> 90 °.

It can be provided in particular that at least the first transport line, in particular its inner wall, at least partially a preferably non-polar plastic, in particular Teflon comprises.

In principle, it is possible to use those polymer materials which do not react with the fluid components and / or are dissolved or dissolved by them. In addition to polytetrafluoroethylene (PTFE, Teflon), polyolefin materials, for example polyethylene or polypropylene, polyamides, polyoxyalkylenes, for example POM, polystyrenes, styrene-co-polymers, for example ABS, ASA or SAN, polyphenylene ethers or polyesters, for example PET or PBT are also used , considering. With a non-polar polymer material, such as Teflon, it is readily possible to introduce hydrogen as the third fluid via the second static mixer of the microcapillary reactor according to the invention into the organic, non-polar fluid plugs. One particular advantage of the microcapillary reactor according to the invention is, inter alia, that, preferably in coordination of the polarity of the inner wall of the first transport line with the polarity of the first or second fluid, the gaseous fluid is controlled even with continuous feed and reproducible only in the fluid plugs only first or second fluid passes. If the gaseous third fluid represents, for example, a reaction gas such as hydrogen, oxygen or carbon monoxide or a hydrogen / carbon monoxide mixture, this can be introduced selectively into nonpolar organic solvent plugs, in which the educt component can then also be present in solution. A reaction generally takes place along the phase boundary surfaces of the liquid / liquid system, for example if a homogeneously dissolved hydrogenation catalyst is present in the aqueous phase.

Of course, it is also possible that the first transport line, in particular the inner wall, at least partially metal and / or glass.

According to the invention may also be provided in an alternative embodiment that the first transport line before and in particular behind the mouth of the third supply line is thermostatable. The first transport line in the context of the present invention is understood to mean a line in which not only one fluid component but at least one two-phase mixture and after entry of the third fluid component a three-phase mixture are transported. In this first transport line or in an extension line of this transport line, after addition of the third fluid component in the second static mixer, the chemical reaction takes place at the phase boundary surfaces of the liquid fluid segments. In particular over the length of the first transport line or an extension line adjoining this first transport line after the third feed line has merged into the second mixer, the reaction time can be controlled as a function of the flow rate.

In this case, e.g. be provided that the length of the portion of the first transport line, with or without extension line, which begins behind the junction of the third supply line of the second mixer, in the range of 0.1 to 50 m.

To generate and maintain alternating fluid segments, it is particularly favorable that the first, second and / or third supply line and / or the first transport line and / or at least one extension line, at least in sections, has a diameter of not more than 1000 μm, in particular in the range of 50 to 1000 μm, or aurwei¬ sen. Suitable cross-sectional sizes are for example in the range of 400, 500 or 750 microns. The flow in capillaries with small channel diameters of <1000 microns is usually different from normal flow profiles in conventional tubular reactors. Usually, the flow in these capillaries is in the form of a laminar flow. Basically, such lines are suitable, with which preferably over the entire length of a laminar flow can be maintained. Suitable flow rates for these laminar flows in the lines of the reactor according to the invention are in the range of about 6 to 15,000 μl / min.

The generation of alternating fluid segments is also promoted by the fact that the first and second leads of the first mixer with their respective mouth areas are oriented substantially in opposite directions. The frontally overlapping liquid first and second fluids are passed on in segments, as described above, in a first transport line extending perpendicularly to the first and second supply lines.

Alternatively it can be provided that the first and second supply lines meet with their Mün¬ training sections substantially at a right angle.

Furthermore, it is possible for the first and second supply lines to meet with their respective coin sections at an angle between 90 and 180 ° or at an angle between 0 and 90 °. For example, the first and second supply lines and the first transport line can be configured Y-shaped.

The above-described arrangements of supply and discharge lines can also be realized in the second static mixer. For example, a preferred embodiment provides that the third supply line and the first transport line present in the second mixer collide in opposite directions at an angle of approximately 180 °. Furthermore, it is possible that the third supply line of the second mixer in its mouth region opens substantially perpendicularly or at an angle between 0 and 90 ° or at an angle between 90 and 180 ° in the first transport line. Regularly, it has proved sufficient to design the lines of the second mixer as T or Y pieces. loading Particularly preferably, the mouth section of the third supply line forms a substantially right angle with the section of the first transport line which leads the alternating two-phase mixture. Advantageously, the first transport line changes its direction in the contact area with the mouth section of the third supply line, in particular by approximately 90 °, so that the section of the first transport line forms an angle of approximately 180 ° behind the contact area and at least the mouth section of the third line ,

Particularly preferably, the first and / or second mixers each represent T-mixers.

The microcapillary reactor according to the invention can be used not only for analytical purposes or for product screening, but is also suitable for the commercial production of chemical products, in particular high-quality fine chemicals. It can be provided that the first transport line opens into at least one Produktaufnahmebe- ratio. Of course, several microcapillary reactors according to the invention can be operated parallel to one another in order to increase the product quantity. If, for example, The first mixer of a microcapillary reactor in a uniform block of material, a multi-Mikrokapillarreaktorverbund invention can be obtained by the fact that not only a first mixer, but at the same time two or more such first mixer are incorporated in this uniform block of material. Likewise, a plurality of juxtaposed second static mixers may be incorporated in the same or another unitary block of material, e.g. by drilling. At the output of each second mixer is followed by a separate fourth extension line and / or a separa¬ ter section of the first transport line. In a multi-microcapillary reactor assembly, all individual reactors may be run under the same conditions, e.g. in terms of pressure, temperature or flow rate. Alternatively, individual conditions can be set for each reactor. This last-mentioned embodiment of the multi-microcapillary reactor according to the invention makes possible, for example, a very efficient rapid screening, e.g. of different reaction conditions and / or Katalysato¬ ren for a particular chemical reaction. Accordingly, the multi-microcapillary reactor according to the invention is suitable for use in combinatorial chemistry.

According to a further aspect, the object underlying this invention is essentially not achieved by a method for the controlled mixing of at least two homogeneously miscible liquid fluids with at least one gaseous fluid solved by bringing together a first liquid fluid via at least a first supply line of a first static mixer and a second liquid fluid via at least one second supply line of the first static mixer in a range, the starting point at least one The first transport line is, wherein the first and second capillary feed lines and the transport line are dimensioned such that the first and second fluids each transported under laminar flow conditions and in the form of successively fol¬ gender, discrete liquid phase portions (plugs) weiterge¬ in the first transport line The gaseous, third fluid is fed via a third, in particular capillary, supply line of a second static mixer into the first transport line downstream of the first mixer.

The erfϊndungsgemäße method is particularly suitable for the catalytic hydrogenation of reducible organic compounds, the catalytic oxidation of organic compounds, for hydroformylation and carbonylation in liquid / liquid / gas multiphase systems. For this purpose, water-soluble catalysts are preferably used.

Suitable starting materials for the hydrogenation reactions according to the invention are, for example, olefins, such as mono- or diolefins, and α, β-unsaturated aldehydes. Suitable water-soluble cata- talysatorkomplexe for these hydrogenations are well known in the art. In the reactions mentioned, for example, it is possible to work with hydrogen pressures in the range from 1 to 200 bar. The hydroformylation of olefins, for example 1-alkenes such as 1-octene, aldehydes can be obtained. Suitable catalysts are also known to the person skilled in the art. A catalyst system which is based on a rhodium complex chelated with biphephos ligands may be mentioned by way of example. Such a catalyst can be obtained, for example, from [Rh (acac) (CO) ₂ ] and biphephos ligands in propylene carbonate as solvent. The hydrogen / carbon monoxide mixture used for the hydroformylation reaction is also known by the term synthesis gas. Carbonylation reactions of alkenes and alkynes in the presence of carbon monoxide, for example in the sense of a repeat carbonylation, can furthermore be carried out in the microcapillary reactor according to the invention. The present invention was thus based on the surprising finding that gaseous products can be introduced in a controlled manner into already mixed liquid / liquid systems. In this case, it is particularly advantageous that the gaseous reactant component can be deliberately introduced into the first or the second liquid phase by selective selection of the capillary material. For example, the catalytic chemoselective hydrogenation of α, β-unsaturated aldehydes by means of hydrogen with very high chemoselectivities and surprisingly good conversions succeeds in this way. Even with reaction times of only about two to three minutes, which can be set, for example, with first transport lines having lengths of 3 to 12 m, the conversion is already above 10%. By combining several microcapillary reactors according to the invention into reactor clusters or multi-microcapillary reactor systems, product quantities which permit commercial production of, for example, high-quality fine chemicals can also be obtained, in particular in continuous operation. Advantageous in this case also has the effect that the safety measures can be reduced to a minimum and that can also be dispensed with complex cooling systems in the case of exothermic reactions.

In addition, a defined flow behavior of a three-phase mixture (liquid / liquid / gaseous) can be controlled and reproducibly produced with the microcapillary reactor according to the invention.

In addition, it is possible to adjust the length of the individual plugs and the specific exchange surface between the phases with great accuracy. Average plug lengths are in the range of 0.1 to 3 mm. As flow rates and droplet or Plug¬ sizes, the u.a. are also specified by the capillary diameter, can be precisely controlled, the microcapillary reactor according to the invention provides an excellent In¬ instrument to the influence of mass transfer on the reaction rate and the Selek¬ tivity to investigate and model.

Further advantages, features and possible applications of the present invention will become apparent from the following description of a preferred embodiment in conjunction with the accompanying drawings. In these show:

FIG. 1 shows a circuit diagram for a microcapillary reactor according to the invention; FIG. 2 shows an alternative circuit diagram for a microcapillary reactor according to the invention;

FIG. 3 shows a schematic longitudinal section through the transport line of the microcapillary reactor according to the invention; and

FIG. 4 shows a flow chart of a microcapillary reactor system according to the invention.

1 shows an embodiment of a microcapillary reactor 1 according to the invention, comprising a first mixer 2 and a second mixer 4, which are arranged in series. The first mixer 2 comprises a first supply line 6 and a second supply line 8, which converge towards one another at an angle of 180 ° and which both open into the first transport line 10 or pass over. The inner diameter of the lines 6, 8 and 10 is in the illustrated embodiment at about 0.75 mm. The first transport line 10 is eben¬ if part of the second mixer 4 and essentially represents the first supply line of this second mixer. In the second mixer 4, a gaseous component is introduced into the transport line 10 via the third supply line 12. In the illustrated embodiment, the angle between the third supply line and the first transport line 10 present in the second mixer 4 is 180 °, so that the gaseous component hits the liquid / liquid volume flow head-on. The first transport line 10 is then continued in the second mixer 4 at a right angle. In one embodiment, the first, second, and third leads may be connected to first, second, and third extension leads 14, 16, and 18, respectively. In such an embodiment, e.g. the first, second and third supply line in each case essentially in the first or second mixer before and are connected via suitable coupling pieces 30 a, b and 32 c with the extension lines ver¬. Of course, in the present between the first and second mixers 2 and 4 section of the first transport line 10 via the coupling pieces 30 c and 32 a, a fourth extension line 20 are inserted. As extension line 20 of the first transport line 10, the section adjoining the second mixer can also be considered.

FIG. 2 illustrates an alternative circuit diagram for a microcapillary reactor 1 according to the invention. The two T-shaped first and second mixers 2 and 4 are arranged substantially mirror-inverted. The configuration and the flow paths of the first mixer are identical to the first mixer according to FIG. 1. In the second mixer 4, the arrangement of the first transport line 10 with that of the second mixer 4 according to FIG. gur 1 match. However, in the second mixer 4, the mouth section of the third supply line 18 for the gaseous third fluid is brought perpendicularly to the first transport line 10 entering the second mixer 4. This type of feeding of the gaseous fluid component is preferred in many cases.

FIG. 3 shows a longitudinal section through a section of the first transport line 10, after which the gaseous component has been introduced into the second mixer 4 via the third supply line 12. It can be seen from FIG. 2 that FIUID blocks or plugs 34 and 36 of aqueous or organic phase occur alternately in the first transport line 10. Depending on the flow rate, the individual plugs have a length of about 1.3 mm at a capillary inner diameter of 0.75 mm. The generation of such a flow pattern is already described in WO 01/64332 A1. Although hydrogen is continuously introduced into the two-phase volume flow of the first transport line 10 in the second mixer 4, it is possible with the device according to the invention to produce the gaseous phase 38, e.g. between two successive aqueous phase blocks in ei¬ nem organic phase block with small bubble size to arrange or store. This is achieved, in particular, in that at least the inner wall of the section of the first transport line 10 extending in the second mixer 4 has a greater affinity for the organic phase than for the aqueous phase. In the present in the first transport line 10 after addition of the gaseous phase three-phase mixture can then proceed readily at the phase boundaries a desired chemical reaction.

FIG. 4 shows the structure of a microcapillary reaction system 100 according to the invention in a schematic representation. The core of this plant is the microcapillary reactor 1 according to the invention, comprising a first mixer 2 and a second mixer 4, which are connected to one another via the first transport line 10. Via the first extension line 14, the liquid organic phase containing educt material in dissolved form is introduced from a storage container 42 into the first supply line 6 of the first mixer 2 by means of an HPLC pump 22. In the same way, the aqueous phase containing, for example, a homogeneously dissolved catalyst, is fed from a storage container 24 via an extension line 16 into the second supply line 8 of the first mixer 2 with the aid of a piston or syringe pump. As described above with reference to FIG. 1, in the mixer 2 a controlled mixing of the immiscible organic and aqueous phases is carried out to form an alternating plug-flow system. Via a third supply line 12, the gas shaped component in the second mixer 4 fed into the first transport line 10. This may be, for example, pure hydrogen from a hydrogen storage container 44 or an H ₂ / Ar mixture. Argon is added via a separate storage container 46 via a mixing station 48. In general, argon is used to remove oxygen from the first and second fluids by repeated gasification with argon prior to pressurization with hydrogen. The first transport line 10 is led out of the second mixer 4 and can then extend over a longer section which, as shown, can be kept at a constant temperature by means of a heater 40. Via a branch from the first transport line 10, the multiphase mixture is preferably randomly supplied to a sample analysis 26, for example in the form of a gas chromatograph. The first transport line opens into the product collection container 28. The reaction mixture obtained can then be processed and the desired reaction product isolated. Via the line 52, a pressure is set in the Produktam¬ meibehältnis which corresponds substantially to the pressure in the transport line.

In the following, the use of the microcapillary reactor according to the invention will be discussed in detail by way of example with reference to the chemoselective hydrogenation of the α, β-unsaturated aldehydes citral and prenal.

For this purpose, a microcapillary reaction plant as shown in FIG. 4 was essentially used. As first and second mixers T-pieces of the company Valco were used. The first transport line 10 is a PTFE (polytetrafluoroethylene) capillary with an inner diameter of 750 μm. The organic phase was fed via a first Zulei¬ device with the same inner diameter using a HPLC pump Gynkotek M480 at a flow rate of 250 ul / min, while the metered addition of the aqueous phase via the second supply line of the first mixer via a piston pump with a För¬ amount <600 ul / min was carried out. The two liquid phases mixed in the first transport line after leaving the first mixer were brought into contact with hydrogen in the second mixer in the form of a T-piece from Valco. The continuous hydrogen stream was regulated by a conventional mass flow controller (MFC) and the hydrogen partial pressure was set to 2.0 MPa. The adjoining the second mixer section of the first transport line was adjusted by means of a water heater to a constant 60 ⁰ C. The organic solvent was n-hexane or toluene resorted. The hydrogenation catalyst used was a Ru (II) -TPPTS complex (TPPTS: triphenylphosphine trisulfonate). The hydrogenation catalyst was prepared in the presence of hydrogen _(H 2 P = 2.0 MPa) (prepared at a temperature of 5O ⁰ C and a reaction time of one hour from RuCl ₃ and TPPTS _RU C = 0.005, C _TP PTS ⁼ 0.05 M ). In the preparation of the hydrogenation catalyst, a pH of 7.0 was ensured with the aid of a buffer. Prenal (3-methyl crotonaldehyde) was used as a 0.5 M solution in n-hexane and citral as a 0.25 M solution in toluene. These solutions were degassed in the ultrasonic bath for about 15 minutes before use in the microcapillary reactor in order to minimize the proportion of oxygen dissolved in the mixture.

By increasing the volume flow of the catalyst phase of 0.19 ml / min to 0.51 ml / min was found to increase the reaction rate by 60% (from 0.15 to 0.24 x 10 ^"2 mol / ^{L" 1} min ^"1 An even more pronounced effect was observed for the reduction in the inner diameter of the capillary from 1000 to 500 μm (increase in the reaction rate from 0.10 to 0.25 × 10 -4 mol / L ^-1 min ^-1 ) As a result of the higher affinity of the organic phase, it is to be assumed that the mass transport at the liquid / liquid phase interface controls the reaction kinetics a surface material with a low surface energy, eg Teflon, a frictional force opposite the direction of flow is expected at the edges of the organic plug, as a consequence of these shearing forces, which are associated with small stress As the inside diameter of the capillaries becomes relatively more noticeable, internal circulation within the plug results. As set with a reduction of the Kapillarinnendurchmessers increased reaction rates, it is believed that the internal circulation affects the mass transfer or accelerated.

The features of the invention disclosed in the foregoing description and the drawings as well as in the claims may be essential for the realization of the invention in its various embodiments both individually and in any arbitrary combination. Bezuεszeichenliste

Microcapillary reactor first mixer second mixer first feed second feed

Transport line third feed line first extension line second extension line third extension line fourth extension line

HPLC pump

Storage container for aqueous phase

sample analysis

Product holding a, b, c Coupling a, b, c Coupling Aqueous fluid block Organic fluid block Gaseous phase

heater

Eduktvorratsbehältnis

Hydrogen storage container

Ar-storage container

mixing station

piston pump

branch line

Mikrokapillarreaktionsanlage

Claims

claims

A microcapillary reactor (1) comprising at least one first static mixer (2), comprising at least one first capillary feed line (6) for a first liquid fluid, at least one second capillary feed line (18) for a second liquid fluid connected to the first Fluid is substantially not homogeneously miscible, wherein at least the first and second capillary leads (6, 8) open in a region which is the starting point of at least one first transport line (10), wherein at least the first and second capillary leads (6, 8) are dimensioned such that the first and second fluids are transportable under laminar flow conditions and in the form of alternating successively following, discrete liquid phase portions (plugs), characterized by at least one second static mixer (4), comprising at least one, in particular capillary , Third supply line (12) for a gaseous third fluid, in the he ¬ capillary transport line (10) downstream of the first mixer (2) opens.

2. microcapillary reactor (1) according to claim 1, characterized by extension lines (14, 16, 18, 20) for the first, second and / or third supply line (6, 8, 12) and / or from the first transport line (10).

3. microcapillary reactor (1) according to claim 1 or 2, characterized in that at least the inner wall of the first transport line (10) and / or at least the inner wall of the first, second and / or third supply line (6, 8, 12) and / or the extension lines (14, 16, 18) to the first, second and / or third supply line and / or the extension line (20) of the first transport line (10) at least be¬ equipped with a polarity having a greater affinity to the first or the having second fluid.

4. microcapillary reactor (1) according to claim 3, characterized in that at least the inner wall of the first transport line (10), in particular in which the second mixer (4) downstream section, at least partially equipped non-polar.

5. microcapillary reactor (1) according to claim 3 or 4, characterized in that at least the first transport line (10), in particular the inner wall, minde¬ least partially sections a preferably non-polar plastic, in particular Teflon comprises.

6. microcapillary reactor (1) according to claim 3, characterized in that the first transport line (10), in particular the inner wall, at least partially cut metal and / or glass.

7. microcapillary reactor (1) according to any one of the preceding claims, characterized gekenn¬ characterized in that the first transport line (10) before and / or behind the junction of the third Zulei¬ device (12) is thermostatable.

8. microcapillary reactor (1) according to any one of the preceding claims, characterized gekenn¬ characterized in that the first, second and / or third supply line (6, 8, 12) and / or the first Transportlei¬ device (10) and / or at least one Extension line (14, 16, 18, 20) at least partially has a diameter not above 1000 microns or auf¬ wise.

9. microcapillary reactor (1) according to any one of the preceding claims, characterized gekenn¬ characterized in that the length of the behind the junction of the third supply line (12) of the second mixer (4) beginning portion of the first transport line (10), with or without Verlänge¬ in the range of 0.1 to 50 m.

10. microcapillary reactor (1) according to any one of the preceding claims, characterized gekenn¬ characterized in that the first and second supply lines (6, 8) of the first mixer (2) are oriented with their respective mouth portions substantially in opposite directions.

11. microcapillary reactor (1) according to one of claims 1 to 9, characterized in that the first and second leads (6, 8) meet with their respective mouth portions substantially at a right angle.

12. microcapillary reactor (1) according to any one of claims 1 to 9, characterized in that the first and second supply lines (6, 8) meet with their respective mouth portions at an angle between 90 and 180 ° or at an angle between 0 and 90 ° ,

13. microcapillary reactor (1) according to any one of the preceding claims, characterized gekenn¬ characterized in that the third supply line (12) of the second mixer (4) and the first transport line (10), in particular whose downstream to the mouth of the third supply line (12) extending section, in opposite directions at an angle of about 180 ° Seinandersto¬ Shen.

14. microcapillary reactor (1) according to one of claims 1 to 12, characterized in that the third supply line (12) of the second mixer (4) with its mouth portion substantially perpendicular or at an angle between 0 and 90 ° or in a Win¬ kel between 90 and 180 ° in the leading the first and second fluid leading portion of the first transport line (10) opens.

15. microcapillary reactor (1) according to any one of the preceding claims, characterized gekenn¬ characterized in that the first and / or second mixer (2, 4) represent a T or Y mixer.

16. microcapillary reactor (1) according to one of the preceding claims, characterized by at least one product receptacle (28) into which the first transport line (10) opens.

17. A multi-microcapillary reactor comprising at least two microcapillary reactors according to one of the preceding claims.

18. A method for the controlled mixing of at least two substantially non-homogeneously miscible liquid fluids and at least one gaseous fluid, wherein a first liquid fluid via at least a first supply line of a first static mixer and a second liquid fluid via at least one second Zulei¬ device of the first static mixer in a region which is the starting point of at least one first transport line, wherein the first and second capillary supply lines and the transport line are dimensioned such that the first and second fluids each transported under laminar flow conditions and alternating in shape successively following, discrete liquid phase portions (plugs) in the first transport line to be forwarded, characterized in that the gaseous, third fluid via at least a third, in particular capillary, Zulei¬ direction of a second static mixer in the e first transport line downstream to the first mixer is fed.

19. The method according to claim 18, characterized in that therein at least one microcapillary reactor according to one of claims 1 to 16 or a multi-microcapillary reactor according to claim 17 is used.

20. The method according to claim 18 or 19, characterized in that at least the inner wall of the first transport line and / or at least the inner wall of the first, second and / or third supply line is at least partially equipped with a polarity having a greater affinity to the first or having second fluid.

21. The method according to any one of claims 18 to 20, characterized in that at least the first transport line, in particular the inner wall, in particular in the adjoining the second mixer downstream section, wenig¬ least sections a plastic, in particular Teflon comprises.

22. The method according to any one of claims 18 to 21, characterized in that the first fluid comprises an organic phase and the second fluid comprises an aqueous phase.

23. The method according to any one of claims 18 to 22, characterized in that the first, second and / or third feed line and / or the first transport line and / or at least one extension line at least partially has a diameter not greater than 1000 microns or have.

24. The method according to any one of claims 18 to 23, characterized in that the length of the behind the junction of the third supply line of the second mixer be¬ starting section of the first transport line, with or without Verlängerungslei¬ device, in the range of 0.1 to 50 m is located.

25. The method according to any one of claims 18 to 24, characterized in that the first and second supply lines of the first mixer are oriented in opposite directions substantially with their je¬ respective mouth portions.

26. The method according to any one of claims 18 to 24, characterized in that the first and second supply lines meet with their mouth portions substantially at a right angle.

27. The method according to any one of claims 18 to 24, characterized in that the first and second supply lines meet with their mouth sections at an angle between 90 and 180 ° or at an angle between 0 and 90 °.

28. The method according to any one of claims 18 to 24, characterized in that the third supply line of the second mixer with its mouth portion in wesentli Chen perpendicular or at an angle between 0 and 90 ° or at an angle zwi¬'s 90 and 180 ° in the first and second fluid leading portion of the first transport line opens.

29. A method according to any one of claims 18 to 24, characterized in that the first and / or second mixer represent a T or Y mixer.

30. The method according to any one of claims 18 to 29, characterized in that the gaseous third fluid comprises hydrogen, oxygen, carbon monoxide or a hydrogen / carbon monoxide mixture.

31. The method according to any one of claims 18 to 30, characterized in that the flow rates of the first and second fluid in the first and second Zu¬ line and / or the multiphase mixture in the first transport line in the range of 6 to 15000 ul / min.

32. The method according to any one of claims 18 to 31, characterized in that the plugs of the aqueous and / or the organic phase have a length in the range of 0.1 to 3 mm.

33. The method according to any one of claims 18 to 32, characterized in that the first fluid is an organic phase having at least one dissolved therein organi¬ and reducible by hydrogen educt, in particular α, ß-unsaturated aldehydes, the second fluid an aqueous Phase with a homogeneously dissolved Hydrierka¬ talysator and the gaseous third fluid hydrogen, or that the first fluid is an organic phase having at least one olefin dissolved therein, the second fluid is an aqueous phase with a homogeneously dissolved hydroformylation and the gaseous third fluid is a hydrogen / carbon monoxide Mixture, or that the first fluid is an organic phase having at least one dissolved therein and oxygen-oxidisable starting material, the second fluid is an aqueous phase with a homogeneously dissolved oxidation catalyst and the gaseous third fluid oxygen, or that the first fluid with an organic phase at least one there dissolved organic and carbon monoxide carbonyl educt, the second fluid ei¬ ne aqueous phase with a homogeneously dissolved carbonylation catalyst and the gaseous third fluid carbon monoxide include.

34. Use of the microcapillary reactor according to one of claims 1 to 16 or of the multi-microcapillary reactor according to claim 17 for the catalytic hydrogenation, hydroformylation, oxidation or carbonylation in liquid / liquid / gas multiphase systems.