CA2180864A1 - Apparatus for carrying out chemical reactions and use thereof - Google Patents
Apparatus for carrying out chemical reactions and use thereofInfo
- Publication number
- CA2180864A1 CA2180864A1 CA 2180864 CA2180864A CA2180864A1 CA 2180864 A1 CA2180864 A1 CA 2180864A1 CA 2180864 CA2180864 CA 2180864 CA 2180864 A CA2180864 A CA 2180864A CA 2180864 A1 CA2180864 A1 CA 2180864A1
- Authority
- CA
- Canada
- Prior art keywords
- reaction space
- reaction
- container
- ultrasonic
- liquid
- 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.)
- Abandoned
Links
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
- B01J19/26—Nozzle-type reactors, i.e. the distribution of the initial reactants within the reactor is effected by their introduction or injection through nozzles
-
- 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
- B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
- B01J19/10—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing sonic or ultrasonic vibrations
-
- 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
- B01J19/24—Stationary reactors without moving elements inside
-
- 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
- B01J19/24—Stationary reactors without moving elements inside
- B01J19/2455—Stationary reactors without moving elements inside provoking a loop type movement of the reactants
- B01J19/2465—Stationary reactors without moving elements inside provoking a loop type movement of the reactants externally, i.e. the mixture leaving the vessel and subsequently re-entering it
-
- 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
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
- B01J8/20—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles with liquid as a fluidising medium
- B01J8/22—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles with liquid as a fluidising medium gas being introduced into the liquid
-
- 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
- B01J2219/00049—Controlling or regulating processes
- B01J2219/00051—Controlling the temperature
- B01J2219/00054—Controlling or regulating the heat exchange system
- B01J2219/00056—Controlling or regulating the heat exchange system involving measured parameters
- B01J2219/00058—Temperature measurement
-
- 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
- B01J2219/00049—Controlling or regulating processes
- B01J2219/00051—Controlling the temperature
- B01J2219/00074—Controlling the temperature by indirect heating or cooling employing heat exchange fluids
- B01J2219/00087—Controlling the temperature by indirect heating or cooling employing heat exchange fluids with heat exchange elements outside the reactor
- B01J2219/00094—Jackets
-
- 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
- B01J2219/00049—Controlling or regulating processes
- B01J2219/00164—Controlling or regulating processes controlling the flow
-
- 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
- B01J2219/19—Details relating to the geometry of the reactor
- B01J2219/194—Details relating to the geometry of the reactor round
- B01J2219/1941—Details relating to the geometry of the reactor round circular or disk-shaped
- B01J2219/1946—Details relating to the geometry of the reactor round circular or disk-shaped conical
Abstract
There is described an apparatus for carrying out chemical re-actions between liquid or gaseous and solid reactants under the influence of ultrasound. The apparatus comprises a fun-nel-shaped reaction space (3) and a subsequently disposed container (13), where the reaction space (3) has the shape of a truncated cone, on whose smaller basal surface (4) the ul-trasonic source (5, 6) is disposed, and where in the vicinity of the ultrasonic source (5, 6) at least one nozzle (2a, 2b) is provided, through which the liquid and gaseous reactants are supplied to the reaction space (3). Furthermore, it is proposed to use said apparatus for carrying out organometal-lic reactions, in particular the Grignard reaction.
Description
2l8o8~
Description This invention relates to an apparatus for carrying out chemical reactions between liquid or ga6eous and solid reac-tants under the influence of ultra60und. The invention also relates to the use of such apparatus.
Ultrasound is known to produce a number of mechanical, chemi-cal and biological effects- For instance, by means of ultra-sonic pulses soiled textiles or soiled metal articles can be cleaned. Furthermore, due to high pressure diiferences pro-duced on a minimum of spaCe, ultra80nic osCillations provide for extremely fine mixing and grinding operations, the pro-duction of extremely fine dispersions, the degassing of liq-uids and melts, the coagul~tion of aerosols, the production of alloys from otherwise non-alloyable metals, the dispersion of immiscible liquids, and the atomization of liquids for the production of aerosols. Finally, ultrasound destroys oxide layers on aluminium, iron and copper. Meanwhile, a branch of chemistry, the sonochemi5try, deals with the effects of ul-trasound on chemical reactions. It was found that the main effects of the sonochemical reactions preferably carried out in liquid phase are based on cavitations, where actually high temperatures and pressures in the micro-range are observed.
Organic molecules are, for instance, broken down under the influence of ultrasound, polymers are depolymerized and mono-mers are polymerized (acrylonitrile). Even the execution of the Grignard reaction under the influence of ultrasound has already been suggested, where by means of the ultrasound in particular the reaction ra1~e is increased and the induction period, i.e. the start of l:he reaction, is reduced.
Ultrasound is understood to be the sound whose frequency lies above the human range of hearing, i . e . above about 20 kHz .
For the generation of ultrasound mechanical or electrical os-cillators ( electroacoustical transducers ) are used . In par-,-- 21808~4 ticular piezoelectrical oscillators are utilized, which are made of quartz or a ceramic material. As regards mechanical impact and energy, ultrasound is by far superior to ordinary sound. In addition, ultrasound can easily be focussed. How-ever, the medium for the transport of ultrasound plays an im-portant role. Since the absorption of sound generally in-creases with increasing frequency, the ultrasound is attenu-ated at a f aster rate than ordinary sound on its way through a medium. Since gases greatly attenuate the ultrasound, pro-cesses taking place under the influence of ultrasound are preferably carried out in liquid media. The absorption of the ultrasound effects a local heating of the medium.
For the execution of chemical reactions on a technical scale, the use of ultrasound has not yet gained acceptance, as on the one hand only a small number of possible applications was examined, and on the other hand the development of suitable reactors has only started. It is therefore the object of the invention to provide an apparatus for carrying out chemical reactions between liquid or gaseous and solid reactants under the influence of ultrasou~d, which is also applicable on a technical scale, ensures a high operational safety, and sig-ni~icantly increases in p~rticular the reaction rate.
The object underlying the invention is solved by creating an apparatus comprising a funnel-shaped reaction space and a subsequently disposed container, where the reaction space has the shape of a truncated cone, on whose small basal surface the ultrasonic source is arranged, and where adjacent the ul-trasonic source at least one nozzle is provided, through which the liquid and gaseous reactants are supplied to the reaction space . Since the ef fect of ultrasound in the liquid phase is better than in the gaseous phase, the liquid reac-tants are either used as such or in the form of solutions. In the form of solutions - possibly under pressure -, the gaseous reactants reach the reaction spaCe, or are supplied as such to the reaction space in the pre88urized condition.
In the reaction 8pace, there i8 thu8 in any ca6e present a liquid phase, which po88ibly contain8 ga8 bubbles, and in which the solid phase i8 su8pended in particular under the influence of the ultra80und- Due to the effect of the ultra-sound and the supply of the liquid and ga8eoUs reactants in the vicinity of the ultrasonic source it is achieved that the solid phase is properly di3tributed in the liquid phase and always is in a vortical state. Moreover, on and adjacent the ultrasonic source solids are not deposited, so that the ul-trasound can unimpededly enter the reaction space. Due to the inventive shape of the reaction space, in particular disad-vantageous superpositions and cancellations of the sound waves are avoided, which results in an optimum and uniform tran~ ; on of energy to the reactants.
In accordance with a further a8pect of the invention the re-action space has a cone angle ~ of 7 to 35 , a volume of 0 . 5 to 100 1, and a ratio between maximum diameter and height of 0 .1 to 1. 7 . These features advantageously lead to the forma-tion of planar sound waves, a good intensity distribution in the reaction space, and the usability of the apparatuS both on a semi-technical and on a technical scale. Even with a volume of 100 1, there are not observed macroscopically local overheatings or local fluctuations of the concentratiOn of the reactants in the reaction space, so that there are no safety problems. In accordance with the invention, a reaction space with a volume of 0.5 to 10 1 is particularly useful, as it can also be operated with great safety over an extended period .
In accordance with a further aspect of the invention the re-action space and/or the container have a cooling jacket. Via the cooling jacket heat is d ssipated in exothermal reac-218086~
.
tions, and in endothermal reactions heat is supplied, so that the optimum reaction temperature can saf ely be maintained .
The ultrasonic source used in the inventive apparatus com-prises an electroacoustical tran8ducer and a sound amplifier, where as electroacoustical transduc~r a piezoelectrical transducer i9 used, and as sound amplifier a sonotrode or a horn is used. By means of 'the sonotrode or the horn it is achieved that the ultrason ic source emits the ultrasound al-most uniformly over the sound inlet diameter.
In accordance with a further aspect of the invention the ul-trasonic source emits sound wave8 with a frequency of 20 kHz to 10 MHz almost uniformly into the reaction space and gener-ates an ultrasonic intensi-ty of 0.1 to 1000 W/cm . The maxi-mum value of the ultrasonic intensity of 0.1 to 1000 W/cm2 is reached at the 60und-emitting surface of the sonotrode or the horn. With these features the reaction rate is increased con-siderably without the reactor getting out of control; there will in particular not be an uncontrolled evolution of heat in the reaction space.
In accordance with the invention it was found to be particu-larly advantageous that the reaction products present in the liquid phase are transferred from the upper part of the reac-tion space to the container, and the solid reactants are sup-plied to the upper part of the reaction space. The container is dimensioned such that it provides for a long enough secon-dary reaction time and acts as buffer. The container is ad-vantageously designed as stirred vessel. The cooperation of reaction space and container in particular provides for the continuous execution of the chemical reactions by circulating the liquid phase.
It is furthermore possible to select the material of the in-ner wall of the reaction space such that the sound field for 21808~
the intended reaction is advantageously influenced; acousti-cally hard materials promo~te the formation of plane waves, and acoustically soft materials promote the formation of spherical waves.
To avoid that coarser particles of the solid reactants are transferred to the container, it is expedient in accordance with the invention to provide a f ilter element between reac-tion space and container. With this feature it is ensured that the major part of the reaction work is effected in the reaction space, and in the container merely the secondary re-action takes place.
In accordance with the invention it is finally provided that through the nozzles disposed adjacent the ultrasonic source an inert gas is introduced into the reaction space in addi-tion to the liquid and gaseous reactants. In this way, the cavitation ef fects of the ultrasound are supported and the vortical state of the solid reactants is improved.
In accordance with the invention it is particularly advanta-geous to use the apparatus for the execution of organometal-lic reactions, in particular the Grignard reaction.
The Grignard reaction R -- X + Mg ----> R -- Mg - X
R = alkyl or aryl residue; X = Cl, Br, J
is generally carried out in an ether as solvent. On a techni-cal scale, problems occur in the execution of the Grignard reaction because the reaction rate is comparatively low, and the reaction does frequently not start as desired. Under the inf luence of ultrasound the reaction rate can be increased and the induction period can be reduced, which is particu-larly advantageous in the execution of the Grignard reaction _ . .. . ... . . _ _ _ _ 218086~
on a technical scale. It was found that the Grignard reaction can be mastered particularly well on a technical scale, when it is carried out in the apparatus in accordance with the in-vention. Moreover, due to the increase of the reaction rate and the reduction of the induction period, a continuOus op-eration, which is extremely economic, is also possible on a technical scale in the apparatu8 in accordance with the in-vention. The apparatus in accordance with the invention can advantageously also be u8ed for the generation of alkyl and aryl compounds of lithium.
The subject-matter of the invention will subsequently be ex-plained in detail with reference to the drawing, a calcula-;
tion program, and an embodiment. The drawing shows a sche-matic representation of the apparatus in accordance with the invention .
From the reservoir 1 the liquid or gasePux reactants, which are possibly dissolved in a solVent, are supplied in the form 20 of a liquid phase via line 2 and a plurality of nozzles 2a, 2b to the reaction space 3. From the reservoir 20 an inert gas is additionally metered via line 21 into line 2. The noz-zles 2a, 2b are provided in the bottom 4 of the reaction space 3 and are disposed in the vicinity of the ultrasonic source. The bottom 4 is formed by the small basal surface of the reaction space 3, which has the shape of a truncated cone. The ultrasonic source disposed in the bottom 4 consists of the electroacoUstical tran8ducer 6 and the sonotrode 5 and emits almost uniform ultrasonic waves into the reaction space 30 3. From the reservoir 7 t~le comminuted solid reactants are introduced into the upper part of the reaction space 3 via line 8. The reaction temperature is adjusted in the reaction space 3 via the cooling jacket 9 as well as the temperature measuring device 10.
2I~08~4 Both the solid reactants and the reactants present in the liquid and/or gaseous pha8~e and the inert gas are introduced continuously into the reaction 8pace 3- By means of the gas or liquid jet, which is generated by the nozzles 2a, 2b, and by means of the ultra80und emitted by the ultrasonic source an optimum mixing of the reactant8 is achieved in the reac-tion space 3, where the solid reactants are in the vortical state and are not deposited on the bottom 4 or on the ultra-sonic source 5, 6. The liquid phaBe, which also contains the reaction products, i8 continuou81y discharged from the upper part of the reaction space 3 via line 11 into the stirred vessel 13, in which a stirrer 14 is provided. The stirred vessel 13 is equipped with a cooling jacket lS, by means of which the reaction temperature is also maintained in the stirred vessel 13. The gas liberated in the stirred vessel 13 ~ inert gas and unreacted gaseous reactants ) is discharged via line 22 and, possibly after a treatment, recirculated to the reaction space 3, which is not repre8ented in the drawing. In line 11 a filter element 16 is provided, which retains the solid particles from the liquid phase supplied to the stirred vessel 13.
Via line 17, part of the liquid phase is continuously with-drawn from the stirred vessel 13. A partial stream thereof is returned to the reaction space 3 through the pump 12 as well as the lines 18 and 2, so as to convert the reactants still pre~ent in the liquid phase. A second partial stream flows through line 19 for product recovery.
The height, the cone angle 1', the maximum diameter, the ratio between maximum diameter and height, and the volume of the reaction space 3 as well as the diameter, the frequency and the ultrasonic intensity of the ultrasonic source 5, 6 are in particular dependent on the reaction rate of the chemical re-action, the absorption behaviour of the multi-phase content of the reaction space wit~l respect to the sound waves, the .~
design of the sonotrode 5 and the performance characteristics of the electroacoustical tran8ducer 6- The 8election of the ultrasonic source and the design of the reactiOn space 3 will be made depending on the respective application of the i,uven-tive apparatus by utilizin.g a calculation program based on Webster's differential equ.ation, which is generally used for the calculation of sound funnels- The dimensioning of the stirred vessel 13 is effected such that it ensures a suffi-cient secondary reaction E'erid and has sufficient buffer ca-pacity. To avoid secondary reactions care should, however, be taken that the volume of the stirred vessel 13 is not chosen too large.
Subsequently, the calculation program used for designing the reaction 6pace 3 will be explained- Webster's differential equation reads as follows:
~r J~n~r ~1 ~r (~) ~xL d~ t~
For the case of a conical funnel the equation for the vari-able cross-sectional area of the funnel reads as follows:
,~ ( x I = ~
and the above-stated differentia1 equation is transferred to:
- t k (~ C ~) clx~ 8 218~86~
with the wave number:
k= ~
c = speed of sound in the reaction mixture;
o~ = angular frequency of the oscillations;
The solutions of these differential equations for the pres-sure and the speed of sound read as follows:
Xx I e,~r(~ Yr ( 'kX) (~J
and 2~ yLX ) - ~ c ` ,~ . e~(r ( ~ c.i t ~ ` ~Xr ~~ ~k x~ '('I ~ ~ kX ) ( S
Accordingly, the radiation impedance for the conical funnel at the coordinate o~ the piston-type source is equal to:
--f~ T~x~ ;kxI ~) ~r VT lxl ) ,1 ~-kxr For the emission of energy as compression wave the imaginary part must disappear, i.e. the real part of the radiation im-pedance ZR~ the radiation resistance R~.~, must become large.
The maximum possible value is equal to p c, and the ratio:
218~86~
,~
h ~ T ~l (kXT ~
A I J~ ( K X, ~ ) ~
should approach one. With a given wave number k for the me-dium, the coordinate XT of the piston-type source in the ~Eun-nel should be calculated such that a predetermined value i6 reached. ~or the piston-type source in the free medium with the same amplitude, half the piston diameter should be in-serted in equation (7) inEtead of the coordinate ~T/ so that the transmitted sound energy is constantly decreasing with very small values of k dT/2. Together with the diameter of the piston-type source dT the opening angle of the funnel can then be determined to be:
~/ u r ~ f a '` ( x ) ( ~)) The coordinate ~L of the reactor output should be chosen such that its maximum diameter dL is larger than the wave length in the medium. A reflection of the wave is thus prevented, and an unimpeded propagation into the f urther reaction space is made possible:
X ~ q) ta.l( r) A reflection and thus the formation of a standing wave field can be controlled by adjusting the filling level of the reac-tion space. By making use of the funnel geometry the emitted acoustic performance can be increased as against the perform-21~86~
ance of the piston-type source oscillating in the free me-dium. The radiation resistance of the used piston-type source in the free medium is equal to:
~, (k ~ 9 (/¦o S -1 ~ ( K 1 ~ I
As technically realizable dimensions of a production reactor the folLowing assumptions 3rust be made:
1. Maximum diameter of the sonotrode: dT = 30 mm 2. Wave numbers of the operating media k = ~o/c The smallest value is given at a frequency of 20 kHz and water with c = 1500 m/s. Organic solvents generally have a value of c < 1000 m/s, so that wave numbers between 0 .1257 1/mm 2 k 2 0 . 0838 1/mm can occur.
Description This invention relates to an apparatus for carrying out chemical reactions between liquid or ga6eous and solid reac-tants under the influence of ultra60und. The invention also relates to the use of such apparatus.
Ultrasound is known to produce a number of mechanical, chemi-cal and biological effects- For instance, by means of ultra-sonic pulses soiled textiles or soiled metal articles can be cleaned. Furthermore, due to high pressure diiferences pro-duced on a minimum of spaCe, ultra80nic osCillations provide for extremely fine mixing and grinding operations, the pro-duction of extremely fine dispersions, the degassing of liq-uids and melts, the coagul~tion of aerosols, the production of alloys from otherwise non-alloyable metals, the dispersion of immiscible liquids, and the atomization of liquids for the production of aerosols. Finally, ultrasound destroys oxide layers on aluminium, iron and copper. Meanwhile, a branch of chemistry, the sonochemi5try, deals with the effects of ul-trasound on chemical reactions. It was found that the main effects of the sonochemical reactions preferably carried out in liquid phase are based on cavitations, where actually high temperatures and pressures in the micro-range are observed.
Organic molecules are, for instance, broken down under the influence of ultrasound, polymers are depolymerized and mono-mers are polymerized (acrylonitrile). Even the execution of the Grignard reaction under the influence of ultrasound has already been suggested, where by means of the ultrasound in particular the reaction ra1~e is increased and the induction period, i.e. the start of l:he reaction, is reduced.
Ultrasound is understood to be the sound whose frequency lies above the human range of hearing, i . e . above about 20 kHz .
For the generation of ultrasound mechanical or electrical os-cillators ( electroacoustical transducers ) are used . In par-,-- 21808~4 ticular piezoelectrical oscillators are utilized, which are made of quartz or a ceramic material. As regards mechanical impact and energy, ultrasound is by far superior to ordinary sound. In addition, ultrasound can easily be focussed. How-ever, the medium for the transport of ultrasound plays an im-portant role. Since the absorption of sound generally in-creases with increasing frequency, the ultrasound is attenu-ated at a f aster rate than ordinary sound on its way through a medium. Since gases greatly attenuate the ultrasound, pro-cesses taking place under the influence of ultrasound are preferably carried out in liquid media. The absorption of the ultrasound effects a local heating of the medium.
For the execution of chemical reactions on a technical scale, the use of ultrasound has not yet gained acceptance, as on the one hand only a small number of possible applications was examined, and on the other hand the development of suitable reactors has only started. It is therefore the object of the invention to provide an apparatus for carrying out chemical reactions between liquid or gaseous and solid reactants under the influence of ultrasou~d, which is also applicable on a technical scale, ensures a high operational safety, and sig-ni~icantly increases in p~rticular the reaction rate.
The object underlying the invention is solved by creating an apparatus comprising a funnel-shaped reaction space and a subsequently disposed container, where the reaction space has the shape of a truncated cone, on whose small basal surface the ultrasonic source is arranged, and where adjacent the ul-trasonic source at least one nozzle is provided, through which the liquid and gaseous reactants are supplied to the reaction space . Since the ef fect of ultrasound in the liquid phase is better than in the gaseous phase, the liquid reac-tants are either used as such or in the form of solutions. In the form of solutions - possibly under pressure -, the gaseous reactants reach the reaction spaCe, or are supplied as such to the reaction space in the pre88urized condition.
In the reaction 8pace, there i8 thu8 in any ca6e present a liquid phase, which po88ibly contain8 ga8 bubbles, and in which the solid phase i8 su8pended in particular under the influence of the ultra80und- Due to the effect of the ultra-sound and the supply of the liquid and ga8eoUs reactants in the vicinity of the ultrasonic source it is achieved that the solid phase is properly di3tributed in the liquid phase and always is in a vortical state. Moreover, on and adjacent the ultrasonic source solids are not deposited, so that the ul-trasound can unimpededly enter the reaction space. Due to the inventive shape of the reaction space, in particular disad-vantageous superpositions and cancellations of the sound waves are avoided, which results in an optimum and uniform tran~ ; on of energy to the reactants.
In accordance with a further a8pect of the invention the re-action space has a cone angle ~ of 7 to 35 , a volume of 0 . 5 to 100 1, and a ratio between maximum diameter and height of 0 .1 to 1. 7 . These features advantageously lead to the forma-tion of planar sound waves, a good intensity distribution in the reaction space, and the usability of the apparatuS both on a semi-technical and on a technical scale. Even with a volume of 100 1, there are not observed macroscopically local overheatings or local fluctuations of the concentratiOn of the reactants in the reaction space, so that there are no safety problems. In accordance with the invention, a reaction space with a volume of 0.5 to 10 1 is particularly useful, as it can also be operated with great safety over an extended period .
In accordance with a further aspect of the invention the re-action space and/or the container have a cooling jacket. Via the cooling jacket heat is d ssipated in exothermal reac-218086~
.
tions, and in endothermal reactions heat is supplied, so that the optimum reaction temperature can saf ely be maintained .
The ultrasonic source used in the inventive apparatus com-prises an electroacoustical tran8ducer and a sound amplifier, where as electroacoustical transduc~r a piezoelectrical transducer i9 used, and as sound amplifier a sonotrode or a horn is used. By means of 'the sonotrode or the horn it is achieved that the ultrason ic source emits the ultrasound al-most uniformly over the sound inlet diameter.
In accordance with a further aspect of the invention the ul-trasonic source emits sound wave8 with a frequency of 20 kHz to 10 MHz almost uniformly into the reaction space and gener-ates an ultrasonic intensi-ty of 0.1 to 1000 W/cm . The maxi-mum value of the ultrasonic intensity of 0.1 to 1000 W/cm2 is reached at the 60und-emitting surface of the sonotrode or the horn. With these features the reaction rate is increased con-siderably without the reactor getting out of control; there will in particular not be an uncontrolled evolution of heat in the reaction space.
In accordance with the invention it was found to be particu-larly advantageous that the reaction products present in the liquid phase are transferred from the upper part of the reac-tion space to the container, and the solid reactants are sup-plied to the upper part of the reaction space. The container is dimensioned such that it provides for a long enough secon-dary reaction time and acts as buffer. The container is ad-vantageously designed as stirred vessel. The cooperation of reaction space and container in particular provides for the continuous execution of the chemical reactions by circulating the liquid phase.
It is furthermore possible to select the material of the in-ner wall of the reaction space such that the sound field for 21808~
the intended reaction is advantageously influenced; acousti-cally hard materials promo~te the formation of plane waves, and acoustically soft materials promote the formation of spherical waves.
To avoid that coarser particles of the solid reactants are transferred to the container, it is expedient in accordance with the invention to provide a f ilter element between reac-tion space and container. With this feature it is ensured that the major part of the reaction work is effected in the reaction space, and in the container merely the secondary re-action takes place.
In accordance with the invention it is finally provided that through the nozzles disposed adjacent the ultrasonic source an inert gas is introduced into the reaction space in addi-tion to the liquid and gaseous reactants. In this way, the cavitation ef fects of the ultrasound are supported and the vortical state of the solid reactants is improved.
In accordance with the invention it is particularly advanta-geous to use the apparatus for the execution of organometal-lic reactions, in particular the Grignard reaction.
The Grignard reaction R -- X + Mg ----> R -- Mg - X
R = alkyl or aryl residue; X = Cl, Br, J
is generally carried out in an ether as solvent. On a techni-cal scale, problems occur in the execution of the Grignard reaction because the reaction rate is comparatively low, and the reaction does frequently not start as desired. Under the inf luence of ultrasound the reaction rate can be increased and the induction period can be reduced, which is particu-larly advantageous in the execution of the Grignard reaction _ . .. . ... . . _ _ _ _ 218086~
on a technical scale. It was found that the Grignard reaction can be mastered particularly well on a technical scale, when it is carried out in the apparatus in accordance with the in-vention. Moreover, due to the increase of the reaction rate and the reduction of the induction period, a continuOus op-eration, which is extremely economic, is also possible on a technical scale in the apparatu8 in accordance with the in-vention. The apparatus in accordance with the invention can advantageously also be u8ed for the generation of alkyl and aryl compounds of lithium.
The subject-matter of the invention will subsequently be ex-plained in detail with reference to the drawing, a calcula-;
tion program, and an embodiment. The drawing shows a sche-matic representation of the apparatus in accordance with the invention .
From the reservoir 1 the liquid or gasePux reactants, which are possibly dissolved in a solVent, are supplied in the form 20 of a liquid phase via line 2 and a plurality of nozzles 2a, 2b to the reaction space 3. From the reservoir 20 an inert gas is additionally metered via line 21 into line 2. The noz-zles 2a, 2b are provided in the bottom 4 of the reaction space 3 and are disposed in the vicinity of the ultrasonic source. The bottom 4 is formed by the small basal surface of the reaction space 3, which has the shape of a truncated cone. The ultrasonic source disposed in the bottom 4 consists of the electroacoUstical tran8ducer 6 and the sonotrode 5 and emits almost uniform ultrasonic waves into the reaction space 30 3. From the reservoir 7 t~le comminuted solid reactants are introduced into the upper part of the reaction space 3 via line 8. The reaction temperature is adjusted in the reaction space 3 via the cooling jacket 9 as well as the temperature measuring device 10.
2I~08~4 Both the solid reactants and the reactants present in the liquid and/or gaseous pha8~e and the inert gas are introduced continuously into the reaction 8pace 3- By means of the gas or liquid jet, which is generated by the nozzles 2a, 2b, and by means of the ultra80und emitted by the ultrasonic source an optimum mixing of the reactant8 is achieved in the reac-tion space 3, where the solid reactants are in the vortical state and are not deposited on the bottom 4 or on the ultra-sonic source 5, 6. The liquid phaBe, which also contains the reaction products, i8 continuou81y discharged from the upper part of the reaction space 3 via line 11 into the stirred vessel 13, in which a stirrer 14 is provided. The stirred vessel 13 is equipped with a cooling jacket lS, by means of which the reaction temperature is also maintained in the stirred vessel 13. The gas liberated in the stirred vessel 13 ~ inert gas and unreacted gaseous reactants ) is discharged via line 22 and, possibly after a treatment, recirculated to the reaction space 3, which is not repre8ented in the drawing. In line 11 a filter element 16 is provided, which retains the solid particles from the liquid phase supplied to the stirred vessel 13.
Via line 17, part of the liquid phase is continuously with-drawn from the stirred vessel 13. A partial stream thereof is returned to the reaction space 3 through the pump 12 as well as the lines 18 and 2, so as to convert the reactants still pre~ent in the liquid phase. A second partial stream flows through line 19 for product recovery.
The height, the cone angle 1', the maximum diameter, the ratio between maximum diameter and height, and the volume of the reaction space 3 as well as the diameter, the frequency and the ultrasonic intensity of the ultrasonic source 5, 6 are in particular dependent on the reaction rate of the chemical re-action, the absorption behaviour of the multi-phase content of the reaction space wit~l respect to the sound waves, the .~
design of the sonotrode 5 and the performance characteristics of the electroacoustical tran8ducer 6- The 8election of the ultrasonic source and the design of the reactiOn space 3 will be made depending on the respective application of the i,uven-tive apparatus by utilizin.g a calculation program based on Webster's differential equ.ation, which is generally used for the calculation of sound funnels- The dimensioning of the stirred vessel 13 is effected such that it ensures a suffi-cient secondary reaction E'erid and has sufficient buffer ca-pacity. To avoid secondary reactions care should, however, be taken that the volume of the stirred vessel 13 is not chosen too large.
Subsequently, the calculation program used for designing the reaction 6pace 3 will be explained- Webster's differential equation reads as follows:
~r J~n~r ~1 ~r (~) ~xL d~ t~
For the case of a conical funnel the equation for the vari-able cross-sectional area of the funnel reads as follows:
,~ ( x I = ~
and the above-stated differentia1 equation is transferred to:
- t k (~ C ~) clx~ 8 218~86~
with the wave number:
k= ~
c = speed of sound in the reaction mixture;
o~ = angular frequency of the oscillations;
The solutions of these differential equations for the pres-sure and the speed of sound read as follows:
Xx I e,~r(~ Yr ( 'kX) (~J
and 2~ yLX ) - ~ c ` ,~ . e~(r ( ~ c.i t ~ ` ~Xr ~~ ~k x~ '('I ~ ~ kX ) ( S
Accordingly, the radiation impedance for the conical funnel at the coordinate o~ the piston-type source is equal to:
--f~ T~x~ ;kxI ~) ~r VT lxl ) ,1 ~-kxr For the emission of energy as compression wave the imaginary part must disappear, i.e. the real part of the radiation im-pedance ZR~ the radiation resistance R~.~, must become large.
The maximum possible value is equal to p c, and the ratio:
218~86~
,~
h ~ T ~l (kXT ~
A I J~ ( K X, ~ ) ~
should approach one. With a given wave number k for the me-dium, the coordinate XT of the piston-type source in the ~Eun-nel should be calculated such that a predetermined value i6 reached. ~or the piston-type source in the free medium with the same amplitude, half the piston diameter should be in-serted in equation (7) inEtead of the coordinate ~T/ so that the transmitted sound energy is constantly decreasing with very small values of k dT/2. Together with the diameter of the piston-type source dT the opening angle of the funnel can then be determined to be:
~/ u r ~ f a '` ( x ) ( ~)) The coordinate ~L of the reactor output should be chosen such that its maximum diameter dL is larger than the wave length in the medium. A reflection of the wave is thus prevented, and an unimpeded propagation into the f urther reaction space is made possible:
X ~ q) ta.l( r) A reflection and thus the formation of a standing wave field can be controlled by adjusting the filling level of the reac-tion space. By making use of the funnel geometry the emitted acoustic performance can be increased as against the perform-21~86~
ance of the piston-type source oscillating in the free me-dium. The radiation resistance of the used piston-type source in the free medium is equal to:
~, (k ~ 9 (/¦o S -1 ~ ( K 1 ~ I
As technically realizable dimensions of a production reactor the folLowing assumptions 3rust be made:
1. Maximum diameter of the sonotrode: dT = 30 mm 2. Wave numbers of the operating media k = ~o/c The smallest value is given at a frequency of 20 kHz and water with c = 1500 m/s. Organic solvents generally have a value of c < 1000 m/s, so that wave numbers between 0 .1257 1/mm 2 k 2 0 . 0838 1/mm can occur.
3. Efficiencies (according to equation 10):
They lie between 90 and 99%, so that the product k xT
is between 10 2 k XT 2 3.
They lie between 90 and 99%, so that the product k xT
is between 10 2 k XT 2 3.
4. Maximum diameter dL: I~ is larger than the wave length in the medium. This condition is satisfied in any case, when the maximum diameter i~ larger than the wave length in water at 20 kHz, as in organic liquids smaller wave lengths are measured, ~uch as dL 2 75 mm.
With these general conditions, the geometrical limit cases can be determined for the different wave numbers. When de-signing the reaction space 3, there should, however, also be made considerations as to process technology.
218Q~
Example:
In the following, the apparatus in accordance with the inven-tion and its use for the execution of a Grignard reaction will be explained in detail- For carrying out a Grignard re-action, which takes place in tetrahydrofuran, uses 2-chloro-butane as liquid reactant and magnesium with a particle sizr~
of 1. 8 to 1. 4 mm as solid reactant, a reaction space is cre-ated by mean6 of the calculation program, which has a cone angle ~ of 7, a height of 200 mm, a volume of 0.5 l, a maxi-mum diameter of 80 mm, a ratio between maximum diameter and height of 0.4, and a bottom diameter of 30 mm. The ultrasonic source comprises an electroacoustical transducer, which emits an ultrasound with a frequency of 20 kHz and an intensity of 20 W/cm2. The sonotrode of the ultrasonic source has a diame-ter of 13 mm. The Grignard reaction is carried out at a tem-perature of 23 C and an excess pressure of 0 .1 MPa. 2 . 2 ml/min of a 1-molar 2-chlorobutane solution in tetrahydrofu-ran are supplied continuously to the reaction space. Subse-quent to the reaction space, a stirred vessel having a volume of 3 l is provided. The reaction space contains 10 g magne-sium .
It was noted that the speed of the Grignard reaction is in-creased by 300 % under the influence of ultrasound. Hence it follows that when using said reaction in a continuous plant, the same conversion can be achieved in a third of the time otherwise required. It was also found that under the influ-ence of ultrasound at 5 C the Grignard reaction takes place at the same speed as the Grignard reaction without ultrasound at a reaction temperature of 23OC. Hence it follows that the secondary reactions under the inf luence of the ultrasound can be restrained due to the possible reduction of the reaction temperature. 12
With these general conditions, the geometrical limit cases can be determined for the different wave numbers. When de-signing the reaction space 3, there should, however, also be made considerations as to process technology.
218Q~
Example:
In the following, the apparatus in accordance with the inven-tion and its use for the execution of a Grignard reaction will be explained in detail- For carrying out a Grignard re-action, which takes place in tetrahydrofuran, uses 2-chloro-butane as liquid reactant and magnesium with a particle sizr~
of 1. 8 to 1. 4 mm as solid reactant, a reaction space is cre-ated by mean6 of the calculation program, which has a cone angle ~ of 7, a height of 200 mm, a volume of 0.5 l, a maxi-mum diameter of 80 mm, a ratio between maximum diameter and height of 0.4, and a bottom diameter of 30 mm. The ultrasonic source comprises an electroacoustical transducer, which emits an ultrasound with a frequency of 20 kHz and an intensity of 20 W/cm2. The sonotrode of the ultrasonic source has a diame-ter of 13 mm. The Grignard reaction is carried out at a tem-perature of 23 C and an excess pressure of 0 .1 MPa. 2 . 2 ml/min of a 1-molar 2-chlorobutane solution in tetrahydrofu-ran are supplied continuously to the reaction space. Subse-quent to the reaction space, a stirred vessel having a volume of 3 l is provided. The reaction space contains 10 g magne-sium .
It was noted that the speed of the Grignard reaction is in-creased by 300 % under the influence of ultrasound. Hence it follows that when using said reaction in a continuous plant, the same conversion can be achieved in a third of the time otherwise required. It was also found that under the influ-ence of ultrasound at 5 C the Grignard reaction takes place at the same speed as the Grignard reaction without ultrasound at a reaction temperature of 23OC. Hence it follows that the secondary reactions under the inf luence of the ultrasound can be restrained due to the possible reduction of the reaction temperature. 12
Claims (17)
1. An apparatus for carrying out chemical reactions between liquid or gaseous and solid reactants under the influence of ultrasound, characterized in that the apparatus com-prises a funnel-shaped reaction space (3) and a subse-quently disposed container (13), where the reaction space (3) has the shape of a truncated cone, on whose smalller basal surface (4) the ultrasonic source (5, 6) is dis-posed, and where in the vicinity of the ultrasonic source (5, 6) at least one nozzle (2a, 2b) is provided, through which the liquid and gaseous reactants are supplied to the reaction space (3).
2. The apparatus as claimed in claim 1, characterized in that the reaction space (3) has a cone angle .gamma. of 7 to 35°, a volume of 0.5 to 100 1, and a ratio between maxi-mum diameter and height of 0.1 to 1.7.
3. The apparatus as claimed in claim 2, characterized in that the reaction space (3) has a volume of 0.5 to 10 1.
4. The apparatus as claimed in claim 1, characterized in that the reaction space (3) or the container (13) have a cooling jacket (9, 15).
5. The apparatus as claimed in claim 1, 2, 3 or 4, characterized in that the ultrasonic source comprises an electroacous-tical transducer (6) and a sound amplifier (5), where as electroacoustical transducer a piezoelectrical transducer and as sound amplifier a sonotrode or a horn is used.
6. The apparatus as claimed in claim 1, 2, 3 or 4, characterized in that the ultrasonic source (5, 6) emits sound waves with a frequency of 20 kHz to 10 MHz almost uniformly into the reaction space (3) and produces an ultrasonic intensity of 0.1 to 1000 W/cm2.
7. The apparatus as claimed in claim 1, 2, 3 or 4, characterized in that the reaction products present in the liquid phase are transferred from the upper part of the reaction space (3) to the container (13), and that the solid reactants are supplied to the upper part of the reaction space (3).
8. The apparatus as claimed in claim 1, 2, 3 or 4, characterized in that between reaction space (3) and container (13) a filter element (16) is provided.
9. The apparatus as claimed characterized in that through the nozzles (2a, 2b) disposed in the vi-cinity of the ultrasonic sources (5, 6) an inert gas is introduced into the reaction space (3) in addition to the liquid and gaseous reactants.
10. The apparatus as claimed in claim 2 or 3, characterized in that the reaction space (3) and the container (13) have a cooling jacket (9, 15).
11. The apparatus as claimed in claim 10, characterized in that the ultrasonic source comprises an electroacous-tical transducer (6) and a sound amplifier (5), where as electroacoustical transducer a piezoelectrical transducer and as sound amplifier a sonotrode or a horn is used.
12. The apparatus as claimed in claim 11, characterized in that the ultrasonic source (5, 6) emits sound waves with a frequency of 20 kHz to 10 MHz almost uniformly into the reaction space (3) and produces an ultrasonic intensity of 0.1 to 1000 W/cm2.
13. The apparatus as claimed in claim 12, characterized in that the reaction products present in the liquid phase are transferred from the upper part of the reaction space (3) to the container (13), and that the solid reactants are supplied to the upper part of the reaction space (3).
14. The apparatus as claimed in claim 13, characterized in that between reaction space (3) and container (13) a filter element (16) is provided.
15. The apparatus as claimed in claim 14, characterized in that through the nozzles (2a, 2b) disposed in the vi-cinity of the ultrasonic sources (5, 6) an inert gas is introduced into the reaction space (3) in addition to the liquid and gaseous reactants.
16. Use of the apparatus as claimed in claim 1, 2, 3 or 4, for car-rying out organometallic reactions.
17. Use of the apparatus as claimed in claim 11, 12, 13, 14 or 15, for carrying out a Grignard reaction.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE1995124712 DE19524712C2 (en) | 1995-07-11 | 1995-07-11 | Device for carrying out chemical reactions |
| DE19524712.4 | 1995-07-11 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2180864A1 true CA2180864A1 (en) | 1997-01-12 |
Family
ID=7766215
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2180864 Abandoned CA2180864A1 (en) | 1995-07-11 | 1996-07-09 | Apparatus for carrying out chemical reactions and use thereof |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0755715A1 (en) |
| JP (1) | JPH0924270A (en) |
| CA (1) | CA2180864A1 (en) |
| DE (1) | DE19524712C2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1152823B2 (en) † | 1999-02-17 | 2006-10-11 | Protensive Limited | Process for the conversion of a fluid phase substrate by dynamic heterogeneous contact with a solid agent |
| CN109071376A (en) * | 2016-04-13 | 2018-12-21 | 弗劳恩霍夫应用研究促进协会 | For producing the continuation method of grignard adduct and implementing the equipment of this method |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19808239C1 (en) * | 1998-02-27 | 1999-04-08 | Ulrich Dr Ing Kunz | Organometallic compounds and Grignard reagents |
| DE19946649A1 (en) * | 1999-09-29 | 2001-04-19 | Marc Breitbach | Fluidizing a solid charge and stabilizing a fluidized bed, used in biotechnology for water preparation, and enzyme catalysis, comprises using pressure waves |
| GB0022016D0 (en) * | 2000-09-08 | 2000-10-25 | Aea Technology Plc | Chemical process plant |
| DE10050315C2 (en) * | 2000-10-10 | 2003-08-21 | Uhde Gmbh | Process for dissolving salts in 1,2-dichloroethane by means of ultrasound and device for carrying out the process |
| DE10200149A1 (en) * | 2002-01-04 | 2003-07-10 | Gruenenthal Gmbh | Process for the preparation of Grignard compounds |
| DE102009031106B4 (en) * | 2009-06-29 | 2022-02-17 | Khs Gmbh | Process and device for degassing a liquid |
| EP3057701A2 (en) | 2013-10-14 | 2016-08-24 | Coldharbour Marine Limited | Apparatus and method |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB447159A (en) * | 1935-04-08 | 1936-05-13 | Iwao Seto | A method of effecting continuous hydrogenation and other catalytic reactions |
| US2662091A (en) * | 1950-09-25 | 1953-12-08 | William W Odell | Process and means of promoting chemical reactions |
| US2800444A (en) * | 1953-02-09 | 1957-07-23 | Standard Oil Co | Alkylation process utilizing ultrasonics |
| DE1442761A1 (en) * | 1963-12-07 | 1969-01-23 | Licencia Talalmanyokat | Method and device for carrying out reactions between gases and liquids or suspensions under pressure |
| FR2338073A1 (en) * | 1976-01-16 | 1977-08-12 | Bertin & Cie | Chemical reactor for two immiscible liquids - has emulsifier, e.g. using ultrasonic waves, at inlet replacing mechanical agitators |
| EP0173219B1 (en) * | 1984-08-30 | 1988-05-11 | Ruhrchemie Aktiengesellschaft | Process for making aldehydes |
| ES2032649T3 (en) * | 1988-12-21 | 1993-02-16 | Hoechst Aktiengesellschaft | PROCEDURE FOR PREPARING PHOSPHORED ORGANIC DERIVATIVES OF 2,4-DI-T-BUTYLPHENOL, THE COMPOUNDS OF 4,4'-DIHALOGENOMAGNESIUM OF BIPHENYL, AND THE USE OF PHOSPHORINATED ORGANIC DERIVATIVES, SPECIAL MOLESOLES, SPECIAL |
| DE3902665A1 (en) * | 1989-01-30 | 1990-08-02 | Harald Garbe | Process for upgrading inorganic nonmetallic fibres, in particular ceramic fibres, and also an apparatus for carrying out this process |
| CA2086616C (en) * | 1990-07-02 | 1996-02-27 | Manfred Bohshar | 6-aryl-6h-dibenzo[c,e][1,2] oxaphosphorines, a process for their preparation, and their use for stabilizing plastics, in particular polyolefin molding compositions |
| DE4228618A1 (en) * | 1992-08-28 | 1994-03-03 | Hoechst Ag | Reactor for carrying out chemical reactions |
-
1995
- 1995-07-11 DE DE1995124712 patent/DE19524712C2/en not_active Expired - Fee Related
-
1996
- 1996-05-11 EP EP96107549A patent/EP0755715A1/en not_active Withdrawn
- 1996-07-09 CA CA 2180864 patent/CA2180864A1/en not_active Abandoned
- 1996-07-11 JP JP20129396A patent/JPH0924270A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1152823B2 (en) † | 1999-02-17 | 2006-10-11 | Protensive Limited | Process for the conversion of a fluid phase substrate by dynamic heterogeneous contact with a solid agent |
| US7247202B1 (en) | 1999-02-17 | 2007-07-24 | Protensive Limited | Process for the conversion of a fluid phase substrate by dynamic heterogeneous contact with a solid agent |
| CN109071376A (en) * | 2016-04-13 | 2018-12-21 | 弗劳恩霍夫应用研究促进协会 | For producing the continuation method of grignard adduct and implementing the equipment of this method |
| CN109071376B (en) * | 2016-04-13 | 2022-02-25 | 弗劳恩霍夫应用研究促进协会 | Continuous process for the production of a grignard adduct and apparatus for carrying out the process |
| US11667653B2 (en) | 2016-04-13 | 2023-06-06 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Continuous method for producing Grignard adducts and a device for carrying out same |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0755715A1 (en) | 1997-01-29 |
| JPH0924270A (en) | 1997-01-28 |
| DE19524712A1 (en) | 1997-01-16 |
| DE19524712C2 (en) | 1997-07-03 |
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