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WO2002049737A1 - Utilisation d'un canal de micro-reaction avec element piezo-electrique - Google Patents

Utilisation d'un canal de micro-reaction avec element piezo-electrique Download PDF

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Publication number
WO2002049737A1
WO2002049737A1 PCT/EP2001/013872 EP0113872W WO0249737A1 WO 2002049737 A1 WO2002049737 A1 WO 2002049737A1 EP 0113872 W EP0113872 W EP 0113872W WO 0249737 A1 WO0249737 A1 WO 0249737A1
Authority
WO
WIPO (PCT)
Prior art keywords
reaction
piezo element
frequency
flow
miniaturized
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.)
Ceased
Application number
PCT/EP2001/013872
Other languages
German (de)
English (en)
Inventor
Hanns Wurziger
Guido Pieper
Michael Schmelz
Norbert Schwesinger
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Merck Patent GmbH
Original Assignee
Merck Patent GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Merck Patent GmbH filed Critical Merck Patent GmbH
Priority to AU2002227951A priority Critical patent/AU2002227951A1/en
Publication of WO2002049737A1 publication Critical patent/WO2002049737A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/0093—Microreactors, e.g. miniaturised or microfabricated reactors
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F33/00—Other mixers; Mixing plants; Combinations of mixers
    • B01F33/30—Micromixers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00781—Aspects relating to microreactors
    • B01J2219/00819—Materials of construction
    • B01J2219/00835—Comprising catalytically active material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00781—Aspects relating to microreactors
    • B01J2219/00873—Heat exchange
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00781—Aspects relating to microreactors
    • B01J2219/00889—Mixing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00781—Aspects relating to microreactors
    • B01J2219/0095—Control aspects
    • B01J2219/00984—Residence time

Definitions

  • the present invention relates to the construction of a microreaction channel system in interconnected silicon wafers, which is connected to a ceramic bimorph or a piezo element.
  • the invention also relates to the use of this construction for performing phase transfer catalytic reactions.
  • Phase transfer reactions between two immiscible phases have particular problems for the person skilled in the art in comparison to reactions in homogeneous phase, which result from the fact that a reaction only starts when the system adds a small amount of a catalytically active substance which unites one the reactants, usually an anion extracted through the interface from one phase to the other.
  • a catalytically active substance which unites one the reactants, usually an anion extracted through the interface from one phase to the other.
  • Such catalytically active substances serve as solubilizers.
  • the phases in the reactors are brought into contact at high stirring speed.
  • phase transfer catalysis is usually distinguished by a high selectivity
  • the phase transfer catalysts used are usually unstable at higher temperatures.
  • quaternary ammonium or phosphonium salts decompose at temperatures from 120 to 150 ° C. Others even decompose at lower temperatures. Separation, recovery and use can also be problematic. Factors such as price, toxicity and disposal of contaminated chemicals and the high energy requirements are also often problems.
  • the object of the present invention was therefore to provide both a system and a method by means of which phase transfer reactions can be carried out in a simple and inexpensive manner without causing the disadvantages indicated above. Since all the reactants in the reactions described above are in solution, miniaturized flow-through reactors were investigated for their applicability due to their outstanding mixing properties.
  • a particular advantage of these reactors is that there are only small amounts of reaction mixture in the reactor at all times. This type of reactor is therefore suitable for reactions that have to be carried out using particularly aggressive or environmentally hazardous chemicals.
  • phase transfer reactions can be carried out in miniaturized flow reactors.
  • Such reactors are produced by connecting thin silicon structures to one another. However, it is also possible to use comparable reactors which are made from other materials which are inert to the reaction media. What these miniaturized reactors have in common is that they have very thin channels, which in themselves are very light
  • FIG. 1 shows a drawing of such a piezo element with its electrical connections in connection with a silicon chip.
  • the special design of the flow reactor used is a channel system of 30 cm length produced by anisotropic etching in silicon with a total volume of 80 ⁇ L with external dimensions of 2.7 x 4.1 x 0.1 cm, on which a ceramic one Bimorph was glued on to generate sound.
  • phase transfer-catalyzed N-, C-, 0- and S-alkylations and etherifications can be carried out in flow without having the disadvantages listed above.
  • the phases are intensely mixed by the introduction of ultrasound energy, forming large interfaces over which the mass transfer is accelerated very quickly, without the phases having to be brought into contact with one another with high stirring speed and high energy consumption, as is customary.
  • all alkylations and etherifications per se can be carried out with the reagents and solvents customary in the literature:
  • Chlorinated hydrocarbons as water-immiscible solvents
  • Carrying out the alkylations and etherifications in the microfluid systems according to the invention has advantages in comparison to the reaction systems usually used in the form of better mass and heat transport, improved control of the reaction times and increased safety when dealing with dangerous substances. This is due in particular to the very small amounts of reagent in the system. The very good mixing of the reagents and the continuous procedure contribute significantly to better control of the reaction conditions.
  • the piezo element shown in FIG. 1, which has been used for the tests carried out, has a frequency control which enables an adjustment in the range from 750 to 16000 Hz.
  • Suitable solvents for this purpose are those from the group of water-immiscible hydrocarbons, chlorinated hydrocarbons, such as. B. dichloromethane, trichloromethane and carbon tetrachloride, it being assumed that there is only sodium hydroxide in the aqueous phase and the catalyst used in the second phase.
  • the reactants are initially introduced in liquid or dissolved form and, under the conditions described, are reacted with one another in the miniaturized reaction system under the influence of the ultrasound energy introduced.
  • the solutions are prepared in such a way that the molar ratio of the reactants to one another is in the range from 1: 2.1 to 1: 3.
  • Solutions are preferably used in which the ratio is between 1: 2.3 to 1: 2.7, in particular those with an educt ratio of 1: 2.5.
  • the chosen ratio has to be matched to the reactivity of the reactants used and the optimal value can therefore be very different.
  • the external conditions in the microreaction system have a decisive influence on the result. These factors are flow rate, energy introduced by ultrasound, temperature, the catalyst used, but also the pressure generated in the microreactor.
  • the yield achieved is generally significantly influenced, in particular, by the reaction temperature. While the model reaction at room temperature already leads to good results, it may be necessary to carry out other comparable reactions at higher temperatures.
  • a heatable microreactor known from the literature can be used, which is connected to a miniaturized flow reactor with piezo element described above. In this way, corresponding reactions which only take place at a higher temperature can also be carried out in the system according to the invention.
  • the product yield can be optimized by variation of the flow rate as well as the temperature and the ultrasound frequency and, if necessary, the formation of by-products can also be reduced. It is possible for a person skilled in the art to optimally set these parameters in accordance with the respective reaction.
  • a variation of the miniaturized flow reactor used also means that, on the one hand, an increased number of the individual structures making up the flow reactor can be connected to one another, as a result of which the length of the thin channels located in the flow reactor is increased. It is readily possible for the person skilled in the art to achieve an extension by changing the position of the channels in the structures connected to one another. Various solutions to this problem are known from the patent literature.
  • miniaturized flow reactors are particularly suitable whose channels have a diameter of at least 25 ⁇ m. It is even possible to use microreactors whose channels have a diameter of 1 mm, since the advantages described above can also be demonstrated here.
  • the flow-through rate must be adjusted, as already indicated above, so that the residence time of the reaction mixture in the reactor is so long that the desired reaction can be ended, and one optimal product yield can be achieved.
  • a tight connection of the individual parts or structures forming the microreactor is provided both inside and outside, so that the channels carrying liquid are separated from one another and no liquid can escape to the outside,
  • model examples are given below with reference to a model reaction which are within the scope of the present invention but are not suitable for restricting the invention to these examples.
  • those embodiments of the invention which are carried out using static micromixers and miniaturized flow reactors which are also known to the person skilled in the art, but the flow reactors used for producing larger amounts of product in can allow larger flow rates for the same unit of time and furthermore ensure both uniform temperature control and homogeneous mixing in each volume element of the reactor, or allow an input of ultrasonic energy in another way. example
  • syringes are each connected to a suitable pump (Harvard Apparatus pump 22) and connected to a miniaturized static silicon mixer, which in turn is connected to an indwelling element in the form of a miniaturized flow reactor, which is located on a silicon chip.
  • This continuous reactor consists of a capillary of 100 cm in length and has a holding volume of 80 ⁇ l of liquid.
  • a piezo crystal is attached to the chip as an ultrasonic generator, the frequency of which can be set in the range from 750 to 16,000 Hz.
  • the present miniaturized system was first calibrated with regard to the dwell time as a function of the pump power.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physical Or Chemical Processes And Apparatus (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

La présente invention concerne la construction d'un système de micro-canal dans une plaquette de silicium reliée à un bimorphe céramique. L'invention concerne également l'utilisation de cette construction pour la mise en oeuvre de réactions chimiques.
PCT/EP2001/013872 2000-12-18 2001-11-28 Utilisation d'un canal de micro-reaction avec element piezo-electrique Ceased WO2002049737A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2002227951A AU2002227951A1 (en) 2000-12-18 2001-11-28 Use of a microreaction channel with a piezo element

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10063027.8 2000-12-18
DE10063027A DE10063027A1 (de) 2000-12-18 2000-12-18 Verwendung eines Mikroreaktionskanals mit Piezoelement

Publications (1)

Publication Number Publication Date
WO2002049737A1 true WO2002049737A1 (fr) 2002-06-27

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2001/013872 Ceased WO2002049737A1 (fr) 2000-12-18 2001-11-28 Utilisation d'un canal de micro-reaction avec element piezo-electrique

Country Status (4)

Country Link
AU (1) AU2002227951A1 (fr)
DE (1) DE10063027A1 (fr)
TW (1) TW508267B (fr)
WO (1) WO2002049737A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100579991C (zh) * 2005-03-04 2010-01-13 诺瓦提斯公司 制备聚合物材料的连续方法

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7118920B2 (en) 2002-10-22 2006-10-10 Battelle Memorial Institute Multiphasic microchannel reactions
DE102005025248B4 (de) * 2005-06-02 2009-07-30 Forschungszentrum Karlsruhe Gmbh Fluidführungssystem

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB417453A (en) * 1932-03-29 1934-09-28 Bruno Claus Improvements in and relating to methods of producing photographic emulsions, and apparatus therefor
US3775058A (en) * 1965-06-04 1973-11-27 Adler Auto Precision Ltd Method and apparatus for mixing liquids
DE2924086A1 (de) * 1979-06-15 1981-01-08 Stuttgart Instgemeinschaft Ev Verfahren zur bestimmung der konzentration von reaktionsloesungen
DE19511603A1 (de) * 1995-03-30 1996-10-02 Norbert Dr Ing Schwesinger Vorrichtung zum Mischen kleiner Flüssigkeitsmengen
DE19611270A1 (de) * 1996-03-22 1997-09-25 Gesim Ges Fuer Silizium Mikros Mikromischer zur Handhabung kleinster Flüssigkeitsmengen
WO1998037397A1 (fr) * 1997-02-21 1998-08-27 University Of Washington Dispositif de melange commande par actionneur piezo-ceramique
DE19917148A1 (de) * 1999-04-16 2000-10-26 Inst Mikrotechnik Mainz Gmbh Verfahren und Mikrovermischer zur Herstellung einer Dispersion
WO2001021291A2 (fr) * 1999-09-21 2001-03-29 University Of Hawaii Micromalaxeur a ondes sonores utilisant des actionneurs a secteur annulaire de fresnel

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB417453A (en) * 1932-03-29 1934-09-28 Bruno Claus Improvements in and relating to methods of producing photographic emulsions, and apparatus therefor
US3775058A (en) * 1965-06-04 1973-11-27 Adler Auto Precision Ltd Method and apparatus for mixing liquids
DE2924086A1 (de) * 1979-06-15 1981-01-08 Stuttgart Instgemeinschaft Ev Verfahren zur bestimmung der konzentration von reaktionsloesungen
DE19511603A1 (de) * 1995-03-30 1996-10-02 Norbert Dr Ing Schwesinger Vorrichtung zum Mischen kleiner Flüssigkeitsmengen
DE19611270A1 (de) * 1996-03-22 1997-09-25 Gesim Ges Fuer Silizium Mikros Mikromischer zur Handhabung kleinster Flüssigkeitsmengen
WO1998037397A1 (fr) * 1997-02-21 1998-08-27 University Of Washington Dispositif de melange commande par actionneur piezo-ceramique
DE19917148A1 (de) * 1999-04-16 2000-10-26 Inst Mikrotechnik Mainz Gmbh Verfahren und Mikrovermischer zur Herstellung einer Dispersion
WO2001021291A2 (fr) * 1999-09-21 2001-03-29 University Of Hawaii Micromalaxeur a ondes sonores utilisant des actionneurs a secteur annulaire de fresnel

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100579991C (zh) * 2005-03-04 2010-01-13 诺瓦提斯公司 制备聚合物材料的连续方法

Also Published As

Publication number Publication date
TW508267B (en) 2002-11-01
DE10063027A1 (de) 2002-06-20
AU2002227951A1 (en) 2002-07-01

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