WO2019035145A1 - An improved continuous flow stirred multiphase reactor - Google Patents
An improved continuous flow stirred multiphase reactor Download PDFInfo
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- WO2019035145A1 WO2019035145A1 PCT/IN2018/050535 IN2018050535W WO2019035145A1 WO 2019035145 A1 WO2019035145 A1 WO 2019035145A1 IN 2018050535 W IN2018050535 W IN 2018050535W WO 2019035145 A1 WO2019035145 A1 WO 2019035145A1
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- 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
- B01J19/18—Stationary reactors having moving elements inside
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- 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
- B01J19/0053—Details of the reactor
- B01J19/0066—Stirrers
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- 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
- B01J4/00—Feed or outlet devices; Feed or outlet control devices
- B01J4/008—Feed or outlet control devices
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- 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
- B01J4/00—Feed or outlet devices; Feed or outlet control devices
- B01J4/02—Feed or outlet devices; Feed or outlet control devices for feeding measured, i.e. prescribed quantities of reagents
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- 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
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- 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
Definitions
- the invention provides an improved multiphase continuous flow reactor. More preferably, the present invention provides a continuous flow stirred multiphase reactor to carry out a two/three phase chemical reaction under controlled and independent agitation rate of each phase.
- the said controlled and independent agitation speed for each phase leads to maximum mass transfer rate and provide higher conversion of substrate. Reactions could be carried out to attain desired selectivity under either mass transfer controlled or Idnetically controlled or mass transfer with chemical reaction controlled mechanism
- the present invention also provides a means for circulation or means for continuous flow of all phases liquid so that catalyst phase is reused continuously without any treatment or loss.
- Multiphase reactions such as liquid-liquid-liquid phase reactions in a tank reactor, which are carried out at the interlace of two immiscible liquids to form a new product, can be advantageous in terms of improved reaction kinetics, higher yields, and selectivity.
- the presence of the third liquid phase between liquid- liquid interface can accelerate the reaction, the interface between hydrophilic and hydrophobic liquids can be used to combine immiscible reaction agents or to protect sensitive reagents, from hydrolysis for example or a phase-transfer catalyst is employed to transfer the locale of the reaction in either organic or aqueous phase (liquid-liquid-liquid three phase reaction).
- phase transfer catalyst is a special type of catalyst used to conduct multiphase reactions, Where PTC enables the reaction in a heterogeneous system (different liquid phases) between general organic compounds soluble in upper layer organic solvents and compounds soluble in water in the bottom layer.
- multiphase FTC reaction contains upper organic phase, middle catalyst rich phase and lower aqueous phase.
- the middle phase is the catalyst-rich phase, with two interfaces on either side, namely, aqueous phase-middle catalyst phase and organic- middle phase.
- the formation of the middle phase occurs between the aqueous phase and organic phase.
- the formation and stability of the middle phase depend on the phase equiUbrium-hydrophilic and lipophilic balance, density difference, nature of reactants, ionic strength and temperature.
- the middle phase contains a majority of the catalyst along with some of the organic solvent, aqueous nucleophile and trace quantity of water.
- the operating conditions for the formation of middle phase include type and quantity of phase transfer catalyst, type and quantity of aqueous reactants, reactant and product in organic phase, quantity of base, quantity of inorganic salts and reaction temperature.
- Such liquid-liquid-liquid (L-L-L) three phase reactions which are carried out in presence of a liquid catalyst (middle phase) at the interface of upper and bottom immiscible liquids to form a new product, wherein the middle catalyst phase is the main locale of the reaction into which both aqueous and organic phase reagents are transferred from both the upper and the bottom phase.
- This middle phase not only intensifies the rates of reaction but also prohibit direct contact of aqueous and organic phases which results in improving the selectivity of the desired product as aqueous-phase promoted reactions are totally suppressed, leading to economic and environmental benefits.
- Newmann et aL (1984) discovered role of polyethylene glycol as a phase transfer catalyst for the isomerization of allyl anisole under triphasic reaction conditions.
- Another objective of the present invention is to design continuous flow stirred tank reactor for multiphase PTC reaction to reuse aqueous phase and to continuously reuse middle catalyst phase without any treatment
- another objective of the invention is to keep all three phase steady for mass transfer study.
- the inventors of the present invention have developed a multiphase continuous flow reactor with three concentric stirrers to aghate each phase independently with the independent speed of agitation.
- the present invention provides a continuous flow stirred multiphase reactor for conducting reaction in two or more immiscible phases which is having three concentric stirrers to agitate each phase independently with the independent speed of agitation.
- the present invention provides a modified continuous flow stirred reactor for multiphase reaction involving liquid-liquid, fluid-liquid and gas-liquid immiscible phase reactions, the reactor comprising of: an inlet ports (IS, 16,17) disposed on the reactor wall into which an immiscible phase are supplied into the reactor, an outlet ports (IS', 16' and 16') disposed opposite the inlet ports; a hollow jacket (18), a concentric stirrers (IF, 12' and 13') placed at the centre of reactor controlled and independent agitation speed for each phase, an agitation controlling means (11, 12, 13) for said stirrer; characterized in that, the immiscible phases supplied from the respective inlet ports in the reactor allows conducting a multiphase reaction at interface formed in the reactor without creating an emulsion but allows an online replenish and
- the technical advantage of the present invention includes three concentric stirrers to agitate each phase independently with the independent speed of agitation, which results in proper mixing of reactant without micro-emulsion formation.
- Design and working of reactor prohibit direct contact of aqueous and organic phases which results in improving the selectivity of the desired product as aqueous-phase promoted reactions are totally suppressed, leading to economic and environmental benefits.
- the aqueous phase is also reused after making up reactant concentration with fresh reactants.
- the overall design of reactor makes all phases stable and steady, prevent formation of micro- emulsion and loss of catalyst, which in turn allow continuous reuse of middle phase with steady conversion and high selectivity.
- Figure No. 1 Depict a schematic view a continuous flow stirred multiphase reactor for three phase reaction as per present invention.
- Figure No. 2 Illustrate a side cross view of a continuous flow stirred multiphase reactor for three phase reaction as per present invention.
- Figure No. 3 Illustrate a top cross-view of a continuous flow stirred multiphase reactor for three phase reaction as per present invention.
- the present invention provides an improved multiphase continuous flow reactor for carrying out at least two liquid phase chemical reaction under different agitation speed using one or more concentric stirrer.
- the present invention further provides a continuous flow stirred multiphase reactor for carrying out three liquid phase chemical reaction under different agitation speed using three concentric stirrers.
- the present invention allows continuous reuse of catalyst without any disturbance or shutdown of the reaction process.
- all phases stirred independently using three independent stirrers which result in proper mixing of reactants and control mass transfer.
- the present invention provides a multiphase continuous flow reactor comprising; at least two concentric stirrers, a means for circulating at least one liquid phases, a means for controlling the temperature of reactor, a means for detection of temperature.
- the present invention provides a modified continuous flow stirred reactor for multiphase reaction cornprising of:
- the immiscible phases supplied from the respective inlet ports in the reactor allows conducting a multiphase reaction at interface formed in the reactor without creating an emulsion but allows an online replenish and recirculation of phase to carry out continuous process.
- the reactor comprises of feeding and withdrawing ports.
- Each phase in reactor is preferably continuously coming into the reactor at desired feed rate through a respective port disposed as per the layer thickness in a reactor and going out from the opposite port to the separate reservoirs.
- the distance between the ports along the length of the reactor is preferably from 10 to 40% of the average height of the reactor.
- the size of the port or the width of the port is preferably chosen to provide a minimal flow rate within the entire volume of the reactor and to avoid jet flow /wobbling of feeding reaction medium.
- the said reactor is further configured to metering valve (4, 5, 6) means to control the residence time of reaction phases.
- the reactor is further configured to pumps (21, 22 and 23) to feed reaction phases and reservoirs (24, 25 and 26) to hold each reaction phase.
- it provides a modified continuous flow multiphase reaction reactor with inlet and outlet ports connected to plurality of conduits configured to circulate phases to said reservoir and recirculation back to inlet port. Further it comprising of additional temperature sensors (10), top feeder (9), bottom empty valve (19), over flow valves (8) and metering valve (20).
- the present invention of continuous flow reactor is comprising of at least two inlet and two outlet ports for two phase reactions selected from liquid-liquid, gas-liquid, fluid-liquid reaction.
- the present invention of continuous flow reactor is comprising of at least three inlet and three outlet ports for three phase reactions selected from liquid- liquid-liquid, gas-liquid-liquid, fluid-liquid-liquid reaction.
- the density of organic phase is lower than that of the aqueous phase, while that of the catalyst middle phase is in between.
- the reactor is designed in such a way that the organic phase admitted from the top and the aqueous phase entered from the bottom while middle phase would reside in middle part of reaction.
- the arrangement was made to circulate middle phase when required.
- the outlet for organic phase kept at upper end and that of aqueous at lower end of reactor.
- the reactor is made up of glass with jacket for temperature control.
- Three or more concentric stirrers with a desired shape impeller and adjustable in height are installed to agitate each phase independently with independent speed of agitation. Separate motors are used to controlled agitation of each stirrer and three or more pumps are configured to pump each phase in reactor.
- thermometer, overflow tube and adjustable sample tube were installed at top. To control flow rate metering valves were installed at inlet of middle phase and outlet of each phase. At lower end of reactor drain valve was installed.
- the lower aqueous phase is selected from group of aqueous phase reactant, base, inorganic salt, small amount of catalyst and water.
- Base used is any water soluble alkali preferably sodium hydroxide (NaOH), potassium hydroxide (KOH) and inorganic salt like sodium chloride (NaCl), sodium bromide(NaBr), potassium chloride (KCl)and potassium bromide (KBr).
- the upper organic phase is selected from group organic phase reactant, organic solvents.
- Solvent should be immiscible preferably toluene, cyclohexane and lchlorooctane.
- the middle catalyst phase is selected from group ammonium salts like tetra butyl ammonium bromide (TBAB), tetra methyl ammonium bromide (TMAB),butyl triethyl ammonium chloride (BTEAC1), Polyethylene glycol (PEG3000-20000), crown ether, phosphonium salts like ethyl triphenylphosphonium bromide (ETPB), Tetra Phenyl Phosphonium Bromide(TPPB) are used as phase transfer catalyst.
- group ammonium salts like tetra butyl ammonium bromide (TBAB), tetra methyl ammonium bromide (TMAB),butyl triethyl ammonium chloride (BTEAC1)
- PEG3000-20000 Polyethylene glycol
- crown ether phosphonium salts like ethyl triphenylphosphonium bromide (ETPB), Tetra Phenyl Phosphonium Bromide(TPPB)
- the reactor disclosed in the present invention can be useful to conduct various PTC reactions like displacement reaction, C-alkylation reaction, O-alkylation reaction, N-alkylation reaction, S-alkylation reaction, oxidation reaction, reduction reaction, isomerization reaction, dehydrohalogenation reaction, Halex reaction.
- the present invention provides a method of operation of multiphase continuous flow reactor for carrying out at least two liquid phase chemical reaction under different agitation speed using one or more concentric stirrer.
- the method to conduct a multiphase reaction in present invention reactor includes following steps: a) Preparation of solution mixture comprising of water, aqueous phase reactant, base, inorganic salt, catalyst,
- Continuous flow is achieved by means of controlling pump operated to feed or withdraw aqueous, catalyst and/or organic phase.
- the pump flow rate and metering valve is adjusted in such way that it maintains all three phases in steady condition.
- a technical advantage of the present invention includes three concentric stirrers to agitate each phase independently with the independent speed of agitation, which results in proper mixing of reactant without micro-emulsion formation.
- Design and working of reactor prohibit direct contact of aqueous and organic phases which results in improving the selectivity of the desired product as aqueous-phase promoted reactions are totally suppressed, leading to economic and environmental benefits.
- mass transfer coefficients cannot be determined in the presence of microemulsion, while in current reactor mass transfer coefficients can be determined with individual phase agitation.
- the aqueous phase is also reused after making up reactant concentration with fresh reactants.
- the overall design of reactor make all phases stable and steady, prevent formation of micro-emulsion and loss of catalyst, which in turn allow continuous reuse of middle phase with steady conversion and high selectivity.
- the economic potential of the present invention includes continuous reuse catalyst without any treatment and continuous process for conducting multiphase PTC reaction. It should be understood that the invention is not restricted to the embodiment which has been described herein but covers all variants immediately accessible to a man skilled in the art
- the method and the installation according to the invention can be used for the carrying out of any two or more phase chemical reaction under pressure in the presence of a gas phase, a liquid phase and a third phase which may, according to the case, be a liquid or a solid.
- the hydrophilic or hydrophobic can be placed at the interlace of liquid phase if desired for particular reaction. The invention is further explained by way of giving example to carry out the reaction and check its performance.
- the reactor was made up of glass. Three concentric stirrers were installed to agitate each phase independently with independent speed of agitation. Flat (paddle) impellers were used. All stirrers were adjustable in height The position of upper organic phase stirrer was such that it resides in organic phase. The position of lower aqueous phase stirrer was such that it resides in aqueous phase and the position of middle phase stirrer remains in middle phase. No baffles were used in reactor to maintain steady state phases. Three separate motors were used to controlled agitation of each stirrer and three pumps were used to pump each phase in reactor. Jacketed heating system was used for heating. Depending on temperature either water or oil was used in jacket as heating medium.
- Thermowell was provided for thermocouple to monitor temperature of reaction mixture.
- Overflow tube and adjustable sample tube were installed at top.
- To control flow rate metering valves were installed at inlet of middle phase and outlet of each phase. At lower end of reactor drain valve was installed. Flow rate of inlet and outlet and speed of agitation of stirrers were set in such way that it maintains steady three phases during reaction. Adjustments were made to keep middle phase either stationary or in continuous recirculation.
- Typical reactions were conducted in continuous flow stirred tank reactor with 0.1 mol 2-Methoxyphenol, 0.2 mol sodium hydroxide, 0.616 mol sodium chloride and 0.137 mol Tetra-n-butylammonium bromide as the catalyst were dissolved in water to make up volume of aqueous phase to 150 cm 3 and 0.1 mol 2- (Chloromethyl)oxirane, 0.0281 mol n-ndecane as internal standard dissolved in toluene with to make the volume of organic phase to 150 cm 3 . The mixture was stirred which formed three phases after settlement.
- aqueous phase feed prepared with 0.1 mol 2-Methoxyphenol, 0.2 mol sodium hydroxide, 0.616 mol sodium chloride were dissolved in water to make up volume of aqueous phase to 150 cm 3
- the organic phase feed prepared with 0.1 mol 2-(Chloromethyl)oxirane, 0.0281 mol n-ndecane as internal standard dissolved in toluene with to make the volume of organic phase to 150 cm 3 .
- aqueous, middle catalyst phase and organic phases were pumped to the continuous flow stirred tank reactor through separate inlet, flow rate of the aqueous, middle catalyst phase and organic phase were 0.5ml/min, and a typical reaction was conducted at 313K.
- the speed of agitation kept 60 rpm for all three phases.
- Final product was analysed by GC analysis.
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Abstract
The invention provides an improved multiphase continuous flow stirred reactor having an inlet ports (15, 16,17) disposed on the reactor wall into which an immiscible phase are supplied into the reactor, an outlet ports (15', 16' and 16') disposed opposite the inlet ports, a concentric stirrers (11', 12' and 13') placed at the centre of reactor and independent agitation controlling means (11, 12, 13) for said stirrer to control agitation rate of each phase. The controlled and independent agitation speed for each phase resulting in maximum mass transfer rate and provide higher conversion of substrate. There is a precise control on the locale of the reaction phase. The present invention also provides a means for circulation or means for continuous flow of all phases liquid so that catalyst phase is reused continuously without any treatment or loss.
Description
TITLE OF THE INVENTION:
AN IMPROVED CONTINUOUS FLOW STIRRED MULTIPHASE REACTOR FIELD OF INVENTION:
The invention provides an improved multiphase continuous flow reactor. More preferably, the present invention provides a continuous flow stirred multiphase reactor to carry out a two/three phase chemical reaction under controlled and independent agitation rate of each phase. The said controlled and independent agitation speed for each phase leads to maximum mass transfer rate and provide higher conversion of substrate. Reactions could be carried out to attain desired selectivity under either mass transfer controlled or Idnetically controlled or mass transfer with chemical reaction controlled mechanism The present invention also provides a means for circulation or means for continuous flow of all phases liquid so that catalyst phase is reused continuously without any treatment or loss.
BACKGROUND OF THE INVENTION:
Multiphase reactions, such as liquid-liquid-liquid phase reactions in a tank reactor, which are carried out at the interlace of two immiscible liquids to form a new product, can be advantageous in terms of improved reaction kinetics, higher yields, and selectivity. The presence of the third liquid phase between liquid- liquid interface can accelerate the reaction, the interface between hydrophilic and hydrophobic liquids can be used to combine immiscible reaction agents or to protect sensitive reagents, from hydrolysis for example or a phase-transfer catalyst is employed to transfer the locale of the reaction in either organic or aqueous phase (liquid-liquid-liquid three phase reaction). There are many types of reactions that can be conducted at the interface or within the thin film between two immiscible liquids, either in a static environment or mechanically stirred. The phase transfer catalyst (PTC) is a special type of catalyst used to conduct multiphase reactions, Where PTC enables the reaction in a heterogeneous system
(different liquid phases) between general organic compounds soluble in upper layer organic solvents and compounds soluble in water in the bottom layer. Thereby, multiphase FTC reaction contains upper organic phase, middle catalyst rich phase and lower aqueous phase. The middle phase is the catalyst-rich phase, with two interfaces on either side, namely, aqueous phase-middle catalyst phase and organic- middle phase. When the catalyst concentration is beyond a critical concentration, the formation of the middle phase occurs between the aqueous phase and organic phase. The formation and stability of the middle phase depend on the phase equiUbrium-hydrophilic and lipophilic balance, density difference, nature of reactants, ionic strength and temperature. The middle phase contains a majority of the catalyst along with some of the organic solvent, aqueous nucleophile and trace quantity of water. Thus, the operating conditions for the formation of middle phase include type and quantity of phase transfer catalyst, type and quantity of aqueous reactants, reactant and product in organic phase, quantity of base, quantity of inorganic salts and reaction temperature.
Such liquid-liquid-liquid (L-L-L) three phase reactions which are carried out in presence of a liquid catalyst (middle phase) at the interface of upper and bottom immiscible liquids to form a new product, wherein the middle catalyst phase is the main locale of the reaction into which both aqueous and organic phase reagents are transferred from both the upper and the bottom phase. This middle phase not only intensifies the rates of reaction but also prohibit direct contact of aqueous and organic phases which results in improving the selectivity of the desired product as aqueous-phase promoted reactions are totally suppressed, leading to economic and environmental benefits. Newmann et aL (1984) discovered role of polyethylene glycol as a phase transfer catalyst for the isomerization of allyl anisole under triphasic reaction conditions. They obtained three phase reaction mixture by using 60% aqueous KOH with toluene and catalytic amount of PEG-400. Weng et aL ( 1988) studied the role played by middle liquid phase in L-L-L phase transfer catalysis and observed that addition
of phase transfer catalyst beyond a critical amount leads to a sharp increase in the reaction rate.
Yadav and coworkers studied several L-L-L FTC systems which include n- butoxylation of p-chloro-nitrobenzene (Yadav G.D. and Reddy C.A., 1999), alkylation of 2'-hydroxyacetophenone with 1-bromopentane (Yadav G.D. and Desai N.M, 2006), synthesis of benzyl phenyl ether (Yadav G.D. and Badure O.V.,2007), synthesis of 3-(Phenyl methoxy)phenol from resorcinol and benzyl chloride (Yadav G.D. and Badure O.V., 2008), etherification of p-hydroxybiphenyl with benzyl chloride to 1, 1 -biphenyl-4-(phenyl methoxy) (Y adav G.D. and Badure O.V., 2008), Also various oxidation and reduction reactions have been explored such as oxidation of methyl mandelate to methyl phenyl glyoxalate
(Yadav G.D. and Motirale B.G., 2010), reduction of 4-nitro-o-xylene by sodium sulphide to give 4-amino-o-xylene (Yadav G.D. and Lande S.V., 2007), selective reduction of substituted nitroaromatics (Yadav G.D. and Lande S.V., 200S). In multiphase reactors, the only physical process influencing the efficiency of chemical conversion is the mechanical stirring, which creates micro-emulsion. Numerous multiphase batch or continuous flow reactors are reported in prior art wherein mechanical stirring is achieved by placing stirrer with stirring rate of more than lOOOrpm. A preliminary study on a continuous flow stirred vessel reactor for tri-liquid phase Phase Transfer Catalysis by Hung-Shan Weng et aL (1997). This reactor was designed in such way that the third liquid phase was kept in the reactor while both aqueous and organic phases flowed through.
Ultrasound-assisted third-liquid phase-transfer catalyzed esterification of sodium salicylate in a continuous two-phase-flow reactor by Hung-Ming Yang et aL (2010), discloses three-liquid phase-transfer operated in a continuous two phase flow with catalyst layer stationary mode.
In above continuous flow reactors (also disclosed by Weng et aL 1997 and Yang et aL 2010, 2011), counter current flow of phases causes contact of organic phase reactant with basic aqueous phase, which results in hydrolysis of organic phase reactant. In addition to that, it has single stirrer and high rpm causes rippling of interlaces and formation of microemulsion. Such vigorous mixing could distribute middle catalyst phase in aqueous and organic phase, which flows out of reactor. Overall, it results in loss of reusable and active catalyst due to degradation of catalyst phase.
Recovering of the active and stable catalyst phase would reduce production costs significantly. Furthermore, to discard large volumes of liquid waste such as catalyst containing environment hazardous agents and costly substance, the waste must be post-treated for proper disposal. By recovering such pure catalyst phase after completion of multiphase reaction can be achieved by modification in reactor, and thus add further economic and ecological benefit to the overall multiphase processes. Hence, since recovery of catalytic organic/aqueous phase from multiphase mixture is highly desirable and requirement of the chemical industries.
It has been observed that in multiphase tank batch/continuous reactors, the situation is much more complex, because the objective is not only the reacting components must be efficiently mixed, but also conditions have to be created to transport those components efficiently across the interlaces between the phases, such as across the layer of phase transfer catalyst. The most important is to achieve maximum mass transport rate across the interface. The mass transfer coefficient depends primary on the hydrodynamic conditions and the physicochemical properties of the phases involved. As one can see from above consideration, basic steps that can be undertaken in order to improve the mass transfer rate from one phase to another phase is to intensify hydrodynamics along with avoiding microemulsion of phases.
Hence, it is an objective of the present invention to provide improvements in batch or continuous multiphase reactor to achieve maximum mass transfer rate by improving the hydrodynamics of three phases and to keep all three phase steady for
effective separation of phases and recirculation of active catalyst phase back to reactor. Another objective of the present invention is to design continuous flow stirred tank reactor for multiphase PTC reaction to reuse aqueous phase and to continuously reuse middle catalyst phase without any treatment Further, another objective of the invention is to keep all three phase steady for mass transfer study.
The inventors of the present invention have developed a multiphase continuous flow reactor with three concentric stirrers to aghate each phase independently with the independent speed of agitation.
The discussion of documents, acts, materials, devices, articles and the like is included in tins specification solely for the purpose of providing a context for the present invention. It is not suggested or represented that any or all of these matters formed part of the prior art base or were common general knowledge in the field relevant to the present invention as it existed before the priority date of each claim of this application. SUMMARY OF THE INVENTION:
The present invention provides a continuous flow stirred multiphase reactor for conducting reaction in two or more immiscible phases which is having three concentric stirrers to agitate each phase independently with the independent speed of agitation. Accordingly, the present invention provides a modified continuous flow stirred reactor for multiphase reaction involving liquid-liquid, fluid-liquid and gas-liquid immiscible phase reactions, the reactor comprising of: an inlet ports (IS, 16,17) disposed on the reactor wall into which an immiscible phase are supplied into the reactor, an outlet ports (IS', 16' and 16') disposed opposite the inlet ports; a hollow jacket (18), a concentric stirrers (IF, 12' and 13') placed at the centre of reactor controlled and independent agitation speed for each phase, an agitation controlling means (11, 12, 13) for said stirrer; characterized in that, the immiscible phases supplied from the respective inlet ports in the reactor allows conducting a multiphase reaction at interface formed in the reactor without creating an emulsion
but allows an online replenish and recirculation of phase to carry out continuous process. The said controlled and independent agitation speed for each phase leads to maximum mass transfer rate and provide higher conversion of substrate. Reactions could be carried out to attain desired selectivity under either mass transfer controlled or kinetically controlled or mass transfer with chemical reaction controlled mechanism.
Accordingly, the technical advantage of the present invention includes three concentric stirrers to agitate each phase independently with the independent speed of agitation, which results in proper mixing of reactant without micro-emulsion formation. Design and working of reactor prohibit direct contact of aqueous and organic phases which results in improving the selectivity of the desired product as aqueous-phase promoted reactions are totally suppressed, leading to economic and environmental benefits. The aqueous phase is also reused after making up reactant concentration with fresh reactants. The overall design of reactor makes all phases stable and steady, prevent formation of micro- emulsion and loss of catalyst, which in turn allow continuous reuse of middle phase with steady conversion and high selectivity.
BRIEF DESCRIPTION OF DRAWINGS:
For a more complete understanding of the features and advantages of the present invention, reference is now made to the detailed description of the invention along with the accompanying figures and in which:
Figure No. 1 : Depict a schematic view a continuous flow stirred multiphase reactor for three phase reaction as per present invention.
Figure No. 2: Illustrate a side cross view of a continuous flow stirred multiphase reactor for three phase reaction as per present invention.
Figure No. 3: Illustrate a top cross-view of a continuous flow stirred multiphase reactor for three phase reaction as per present invention.
DETAILED DESCRIPTION OF THE INVENTION:
While the making and using of various embodiments of the present invention are discussed in detail below, it should be appreciated that the present invention provides many applicable inventive concepts that can be embodied in a wide variety of specific contexts. The specific embodiments discussed herein are merely illustrative of specific ways to make and use the invention and do not delimit the scope of the invention.
To facilitate the understanding of this invention, a number of terms are defined below. Terms defined herein have meanings as commonly understood by a person of ordinary skill in the areas relevant to the present invention. Terms such as "a", "an" and "the" are not intended to refer to only a singular entity, but include the general class of which a specific example may be used for illustration. The terminology herein is used to describe specific embodiments of the invention, but their usage does not delimit the invention, except as outlined in the claims. The present invention provides an improved multiphase continuous flow reactor for carrying out at least two liquid phase chemical reaction under different agitation speed using one or more concentric stirrer.
The present invention further provides a continuous flow stirred multiphase reactor for carrying out three liquid phase chemical reaction under different agitation speed using three concentric stirrers.
The present invention allows continuous reuse of catalyst without any disturbance or shutdown of the reaction process. In present reactor all phases stirred independently using three independent stirrers which result in proper mixing of reactants and control mass transfer. In accordance to one embodiment, the present invention provides a multiphase continuous flow reactor comprising; at least two concentric stirrers, a means for circulating at least one liquid phases, a means for controlling the temperature of reactor, a means for detection of temperature.
With reference to accompanied figure no. 1, the present invention provides a modified continuous flow stirred reactor for multiphase reaction cornprising of:
-an inlet ports (15, 16,17) disposed on the reactor wall into which an immiscible phases are supplied into the reactor,
-an outlet ports (15', 16' and 17') disposed opposite the inlet ports;
-a hollow jacket ( 18),
-a concentric stirrers (1 1', 12' and 13') placed at the centre of reactor, -an agitation controlling means (11, 12, 13) for said stirrer;
Characterized in thai; the immiscible phases supplied from the respective inlet ports in the reactor allows conducting a multiphase reaction at interface formed in the reactor without creating an emulsion but allows an online replenish and recirculation of phase to carry out continuous process.
With reference to accompanied figure no.2 and 3, representing a cross section and top view of said reactor respectively, and as reflected in that, the concentric stirrer (11', 12', 13') provided with different speed of agitation with the help of independently connected agitation controlling means (11, 12, 13). The hollow jacket (18) preferably have openings for circulation of temperature controlling medium. Accordance to a preferred embodiment of the invention, the reactor comprises of feeding and withdrawing ports. Each phase in reactor is preferably continuously coming into the reactor at desired feed rate through a respective port disposed as per the layer thickness in a reactor and going out from the opposite port to the separate reservoirs. The distance between the ports along the length of the reactor is preferably from 10 to 40% of the average height of the reactor.
The size of the port or the width of the port is preferably chosen to provide a minimal flow rate within the entire volume of the reactor and to avoid jet flow /wobbling of feeding reaction medium.
The said reactor is further configured to metering valve (4, 5, 6) means to control the residence time of reaction phases. The reactor is further configured to pumps (21, 22 and 23) to feed reaction phases and reservoirs (24, 25 and 26) to hold each reaction phase. In accordance to present invention, it provides a modified continuous flow multiphase reaction reactor with inlet and outlet ports connected to plurality of conduits configured to circulate phases to said reservoir and recirculation back to inlet port. Further it comprising of additional temperature sensors (10), top feeder (9), bottom empty valve (19), over flow valves (8) and metering valve (20). In accordance to one more embodiment, the present invention of continuous flow reactor is comprising of at least two inlet and two outlet ports for two phase reactions selected from liquid-liquid, gas-liquid, fluid-liquid reaction.
Further, the present invention of continuous flow reactor is comprising of at least three inlet and three outlet ports for three phase reactions selected from liquid- liquid-liquid, gas-liquid-liquid, fluid-liquid-liquid reaction.
While conducting multiphase reaction involving an organic phase and aqueous phase, the density of organic phase is lower than that of the aqueous phase, while that of the catalyst middle phase is in between. Therefor the reactor is designed in such a way that the organic phase admitted from the top and the aqueous phase entered from the bottom while middle phase would reside in middle part of reaction. The arrangement was made to circulate middle phase when required. The outlet for organic phase kept at upper end and that of aqueous at lower end of reactor.
The following but not limiting, the disclosure gives the parameters of a specific reactor which may be constructed in accordance with the present invention. The reactor is made up of glass with jacket for temperature control. Three or more concentric stirrers with a desired shape impeller and adjustable in height are installed to agitate each phase independently with independent speed of agitation. Separate motors are used to controlled agitation of each stirrer and three or more
pumps are configured to pump each phase in reactor. In addition to that, thermometer, overflow tube and adjustable sample tube were installed at top. To control flow rate metering valves were installed at inlet of middle phase and outlet of each phase. At lower end of reactor drain valve was installed. The lower aqueous phase is selected from group of aqueous phase reactant, base, inorganic salt, small amount of catalyst and water. Base used is any water soluble alkali preferably sodium hydroxide (NaOH), potassium hydroxide (KOH) and inorganic salt like sodium chloride (NaCl), sodium bromide(NaBr), potassium chloride (KCl)and potassium bromide (KBr).
The upper organic phase is selected from group organic phase reactant, organic solvents. Solvent should be immiscible preferably toluene, cyclohexane and lchlorooctane.
The middle catalyst phase is selected from group ammonium salts like tetra butyl ammonium bromide (TBAB), tetra methyl ammonium bromide (TMAB),butyl triethyl ammonium chloride (BTEAC1), Polyethylene glycol (PEG3000-20000), crown ether, phosphonium salts like ethyl triphenylphosphonium bromide (ETPB), Tetra Phenyl Phosphonium Bromide(TPPB) are used as phase transfer catalyst.
The reactor disclosed in the present invention can be useful to conduct various PTC reactions like displacement reaction, C-alkylation reaction, O-alkylation reaction, N-alkylation reaction, S-alkylation reaction, oxidation reaction, reduction reaction, isomerization reaction, dehydrohalogenation reaction, Halex reaction.
In accordance to second embodiment, the present invention provides a method of operation of multiphase continuous flow reactor for carrying out at least two liquid phase chemical reaction under different agitation speed using one or more concentric stirrer.
The method to conduct a multiphase reaction in present invention reactor includes following steps:
a) Preparation of solution mixture comprising of water, aqueous phase reactant, base, inorganic salt, catalyst,
b) Addition of organic phase reactant,
c) Settling down to separate the phases namely organic, middle catalyst and aqueous phase,
d) Attending and maintaining the desired temperature of reaction vessel using jacketed system,
e) Conducting the reaction by selecting speed of agitation of each stirrer in order to avoid formation of micro-emulsion,
f) Continuous flow is achieved by means of controlling pump operated to feed or withdraw aqueous, catalyst and/or organic phase.
Wherein, the pump flow rate and metering valve is adjusted in such way that it maintains all three phases in steady condition.
A technical advantage of the present invention includes three concentric stirrers to agitate each phase independently with the independent speed of agitation, which results in proper mixing of reactant without micro-emulsion formation. Design and working of reactor prohibit direct contact of aqueous and organic phases which results in improving the selectivity of the desired product as aqueous-phase promoted reactions are totally suppressed, leading to economic and environmental benefits. In conventional batch reactor mass transfer coefficients cannot be determined in the presence of microemulsion, while in current reactor mass transfer coefficients can be determined with individual phase agitation. The aqueous phase is also reused after making up reactant concentration with fresh reactants. The overall design of reactor make all phases stable and steady, prevent formation of micro-emulsion and loss of catalyst, which in turn allow continuous reuse of middle phase with steady conversion and high selectivity.
The economic potential of the present invention includes continuous reuse catalyst without any treatment and continuous process for conducting multiphase PTC reaction.
It should be understood that the invention is not restricted to the embodiment which has been described herein but covers all variants immediately accessible to a man skilled in the art In particular, the method and the installation according to the invention can be used for the carrying out of any two or more phase chemical reaction under pressure in the presence of a gas phase, a liquid phase and a third phase which may, according to the case, be a liquid or a solid. In addition, the hydrophilic or hydrophobic can be placed at the interlace of liquid phase if desired for particular reaction. The invention is further explained by way of giving example to carry out the reaction and check its performance.
Example 1:
The objective of this work was to carry out reaction in continuous mode. Another objective was to reuse middle catalyst phase without any treatment
The reactor was made up of glass. Three concentric stirrers were installed to agitate each phase independently with independent speed of agitation. Flat (paddle) impellers were used. All stirrers were adjustable in height The position of upper organic phase stirrer was such that it resides in organic phase. The position of lower aqueous phase stirrer was such that it resides in aqueous phase and the position of middle phase stirrer remains in middle phase. No baffles were used in reactor to maintain steady state phases. Three separate motors were used to controlled agitation of each stirrer and three pumps were used to pump each phase in reactor. Jacketed heating system was used for heating. Depending on temperature either water or oil was used in jacket as heating medium. Thermowell was provided for thermocouple to monitor temperature of reaction mixture. Overflow tube and adjustable sample tube were installed at top. To control flow rate metering valves were installed at inlet of middle phase and outlet of each phase. At lower end of reactor drain valve was installed. Flow rate of inlet and outlet and speed of agitation of stirrers were set in such way that it maintains steady three phases during reaction. Adjustments were made to keep middle phase either stationary or in continuous recirculation.
A. Synthesis of 2-[(2-Methoxyphenoxy)methyl]oxirane in continuous flow stirred multiphase reactor as per present invention:
The reaction of 2-Methoxyphenol and 2-(Chloromethyl)oxirane leads to the formation of 2-[(2-Methoxyphenoxy)methyl]oxirane and reaction is depicted in following scheme I:
SCHEME I
Typical reactions were conducted in continuous flow stirred tank reactor with 0.1 mol 2-Methoxyphenol, 0.2 mol sodium hydroxide, 0.616 mol sodium chloride and 0.137 mol Tetra-n-butylammonium bromide as the catalyst were dissolved in water to make up volume of aqueous phase to 150 cm3 and 0.1 mol 2- (Chloromethyl)oxirane, 0.0281 mol n-ndecane as internal standard dissolved in toluene with to make the volume of organic phase to 150 cm3. The mixture was stirred which formed three phases after settlement.
The aqueous phase feed prepared with 0.1 mol 2-Methoxyphenol, 0.2 mol sodium hydroxide, 0.616 mol sodium chloride were dissolved in water to make up volume of aqueous phase to 150 cm3
The organic phase feed prepared with 0.1 mol 2-(Chloromethyl)oxirane, 0.0281 mol n-ndecane as internal standard dissolved in toluene with to make the volume of organic phase to 150 cm3.
The aqueous, middle catalyst phase and organic phases were pumped to the continuous flow stirred tank reactor through separate inlet, flow rate of the aqueous, middle catalyst phase and organic phase were 0.5ml/min, and a typical reaction was conducted at 313K.
Following scheme II depict a reaction mechanism in three phases [ Organic top, Catalyst middle and aqueous Bottom].
The speed of agitation kept 60 rpm for all three phases. In another example speed of agitation of aqueous phase stirrer kept at 40 rpm, middle phase stirrer kept at 80
rpm and organic phase stirrer kept at 60 rpm. Final product was analysed by GC analysis.
Table no 1: Selectivity and Conversion data in synthesis of 2-[(2- Methoxyphenoxy)methyl] oxlrane
By recovering such pure catalyst phase after completion of multiphase reaction can be achieved by a modified multiphase reactor as per present invention, and thus add further economic and ecological benefit to the overall multiphase processes.
Claims
1. A modified continuous flow stirred reactor for multiphase reaction involving at least two immiscible chemical phases, the reactor comprising of:
-an inlet ports (15, 16, 17) disposed on the reactor wall through which an immiscible phase is supplied into the reactor,
-an outlet ports (IS', 16' and 17') disposed opposite the inlet ports;
-a hollow jacket (18),
-a concentric stirrers (11', 12' and 13') placed at the centre of reactor, -an agitation controlling means (11, 12, 13) for said stirrers;
Characterized in thai; the immiscible phases supplied from the respective inlet ports in the reactor allows conducting a multiphase reaction at interface formed in the reactor without creating an emulsion but allows an online replenish and recirculation of phase to carry out continuous multiphase reaction process.
2. The modified continuous flow stirred reactor as claimed in claim 1, wherein the each concentric stirrer (11 ', 12', 13') provides different speed of agitation with the help of independently connected agitation controlling means (11,12, 13).
3. The modified continuous flow stirred reactor as claimed in claim 1, wherein the reactor is further configured to flow controlling means (4, 5 and 6) to control the residence time of reaction phases.
4. The modified continuous flow stirred reactor as claimed in claim 1, wherein the reactor is further configured to pumps (21, 22 and 23) to feed reaction phases.
5. The modified continuous flow stirred reactor as claimed in claim 1, wherein the reactor is further configured to reservoirs (24, 25 and 26) to hold each reaction phase separated.
6. The modified continuous flow stirred reactor as claimed in claim 1, wherein each port is having plurality of conduits configured to circulate phases to said reservoir and recirculation back to inlet port.
7. The modified continuous flow stirred reactor as claimed in claim 1, wherein the hollow jacket (18) is having externally an opening for circulation of temperature controlling medium.
8. The modified continuous flow stirred reactor as claimed in claim 1, wherein the said continuous reactor is comprises of at least two inlet and two outlet ports for two phase reactions selected from liquid-liquid, gas- liquid, fluid-liquid reaction.
9. The modified continuous flow stirred reactor as claimed in claim 1, wherein the said continuous reactor is comprises of at least three inlet and three outlet ports for three phase reactions selected from liquid-liquid- liquid, gas-liquid-liquid, fluid-liquid-liquid reaction.
10. The modified continuous flow stirred reactor as claimed in claim 1, wherein the distance between the ports along the length of the reactor is preferably from 10 to 40% of the average height of the reactor.
11. The modified continuous flow stirred reactor as claimed in claim 1, wherein the reactor is further comprising of temperature sensors (10), top feeder (9), bottom empty valve (19), over flow valves (8) and metering valve (20).
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US20170106345A1 (en) * | 2014-04-22 | 2017-04-20 | Bayer Aktiengesellschaft | Multi-stage stirred reactor having reduced back mixing |
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US11718801B2 (en) * | 2019-09-16 | 2023-08-08 | Saudi Arabian Oil Company | Apparatus to simulate biocide performance in crude pipeline conditions |
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