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Process Intensification using Tri – Liquid Phase Transfer Catalysis

Submitted in partial fulfilment of the requirements

of the degree of

(Bachelor of Engineering)
By

1) Sahil Latke /UID – 122CH3018A/ Roll no. 14


2) Raviraj Patil /UID – 122CH3019A /Roll no. 21
3) Monali Mandavkar/UID – 122CH3017B/Roll no.16

T.E. Chemical Engineering Sem. V A.Y. 2023-2024


Supervisor:

(Dr. Cyrus K. Mistry)

(Chemical Engineering Department)


(Subject – Mini Project 2 B)

MGM’s College of Engineering affiliated to Mumbai University

1
(2023-24)

CERTIFICATE

This is to certify that the project entitled “Process Intensification


using Tri – Liquid Phase Transfer Catalysis” is a bonafide work of
“Sahil Latke, Raviraj Patil, Monali Mandavkar” (Roll No.
14,21,16) submitted to the University of Mumbai in partial fulfilment
of the requirement for the award of the undergraduate degree in
“Chemical Engineering”.

(Name and sign)


Supervisor/Guide

(Name and sign) (Name and sign)


Head of Department Director

2
Mini Project Report Approval for T. E.

This project report entitled Process Intensification using Tri – Liquid

Phase Transfer Catalysis by Sahil Latke, Raviraj Patil, Monali


Mandavakar is approved for the partial fulfilment of the undergraduate degree

of Chemical Engineering as Mini Project 2B.

Examiners

1.---------------------------------------------

2.---------------------------------------------

Date:

Place:

3
Declaration
I declare that this written submission represents my ideas in my own words
and where others' ideas or words have been included, I have adequately cited
and referenced the original sources. I also declare that I have adhered to all
principles of academic honesty and integrity and have not misrepresented
or fabricated or falsified any idea/data/fact/source in my submission. I
understand that any violation of the above will be cause for disciplinary action
by the Institute and can also evoke penal action from the sources which have
thus not been properly cited or from whom proper permission has not been
taken when needed.

-----------------------------------------
(Signature)

-----------------------------------------
(Name of student and Roll No.)

Date:

4
Content
Sr.No Content Page No.
.
1. Introduction on Phase Transfer Catalysis 6

2. Types of Phase Transfer Catalysis 7

3. Classification of Phase Transfer Catalysis 8

4. What is process intensification of tri phase S-L-L transfer catalysis 9

5. Types of S-L-L tri phase transfer catalysis 10

6. Examples of tri phase S-L-L transfer catalysis 11

7. Advantages and Disadvantages 12

8. Literature Review : 13-16

9. Difference between Process Intensification of Tri Phase Transfer 17


Catalysis of L-L-L and S-L-L.

10. References 18

5
Introduction on Phase Transfer Catalysis
Phase transfer catalysis (PTC) is a chemical technique used to facilitate reactions between
substances that are present in different phases, typically between a solid and a liquid or
between two immiscible liquids. This catalytic method has found widespread application in
organic synthesis, helping to increase the efficiency and yield of various chemical reactions.
In PTC, a catalyst, often referred to as a phase transfer catalyst, acts as a mediator between
reactants that would not normally interact effectively due to their differing solubilities or
phases. The phase transfer catalyst is typically a compound with both hydrophilic (water-
attracting) and lipophilic (organic-solvent-attracting) properties, allowing it to shuttle
reactants between the phases and promote their interaction. The key to the success of phase
transfer catalysis is the ability of the catalyst to create a microenvironment where reactants
can come into close proximity and react with each other.
Here are some key aspects of phase transfer catalysis:
1.Catalyst Selection: The choice of an appropriate phase transfer catalyst is crucial, as it
should be compatible with the reactants and the specific reaction conditions. Common phase
transfer catalysts include quaternary ammonium salts, crown ethers, and phosphonium
compounds.
2.Reaction Types: Phase transfer catalysis is commonly used in various types of reactions,
such as nucleophilic substitution, alkylation, oxidation, and polymerization. It is especially
valuable when one of the reactants is a solid or an immiscible liquid, and the other is in a
different phase.
3.Advantages: PTC offers several advantages, including enhanced reaction rates, improved
selectivity, and increased yields. It also often eliminates the need for toxic or hazardous
organic solvents, making reactions more environmentally friendly.
4.Applications: Phase transfer catalysis is employed in the synthesis of a wide range of
organic compounds, including pharmaceuticals, agrochemicals, and specialty chemicals. It
has also been used in green chemistry initiatives to reduce the environmental impact of
chemical processes.
5.Challenges: While PTC can be highly effective, there are some challenges associated with
this technique. Catalyst poisoning, product separation, and waste management are among the
considerations that researchers need to address.
In summary, phase transfer catalysis is a powerful tool in the field of organic synthesis that
enables the efficient and selective transformation of reactants by bridging the gap between
different phases. Its versatility and environmental benefits have made it a valuable approach
in the toolbox of chemists, enabling the development of innovative solutions to various
chemical challenges.

6
Types of Phase Transfer Catalysis
Phase transfer catalysis (PTC) is a versatile technique, and various types of phase transfer
catalysts are employed to facilitate reactions between different phases. Here are some
common types of phase transfer catalysts:
1.Quaternary Ammonium Salts: Quaternary ammonium salts are among the most widely used
phase transfer catalysts. They typically consist of a positively charged nitrogen atom attached
to four alkyl or aryl groups and a negatively charged counterion. These catalysts are known
for their ability to transfer anions between the organic and aqueous phases, facilitating
various nucleophilic substitution reactions.
2.Phosphonium Salts: Similar to quaternary ammonium salts, phosphonium salts have a
positively charged phosphorus atom bonded to four alkyl or aryl groups. These salts can also
act as effective phase transfer catalysts, enabling reactions that involve anionic species to
proceed in biphasic systems.
3.Crown Ethers: Crown ethers are cyclic polyethers with a structure that allows them to
complex with cations. They are commonly used as phase transfer catalysts in reactions
involving cationic species. Crown ethers are highly selective and can help transport cations
from one phase to another, promoting the desired reactions.
4.Polyethylene Glycols (PEGs): Polyethylene glycols are water-soluble, high molecular
weight polymers that can serve as phase transfer catalysts in certain applications. PEGs can
create a microenvironment that enhances the solubility of organic compounds in the aqueous
phase, making them useful in reactions where a solid reactant or an immiscible organic phase
needs to be transferred into the aqueous phase.
5.Cryptands: Cryptands are a class of macrocyclic compounds that are similar to crown ethers
in their ability to complex with cations. They have been employed as phase transfer catalysts
in reactions involving cations, and their high selectivity can lead to efficient and selective
transformations.
6.Cyclodextrins: Cyclodextrins are cyclic oligosaccharides that can form inclusion complexes
with organic molecules. They are often used as phase transfer catalysts in reactions involving
nonpolar or poorly water-soluble organic compounds, allowing them to become more
accessible to reactions in aqueous phases.
7. Surfactants: Some surfactants, particularly those with both hydrophilic and hydrophobic
portions, can function as phase transfer catalysts. They can help solubilize organic reactants
in water or enhance the transport of species between immiscible phases.
These are just a few examples of the types of phase transfer catalysts commonly used in
various PTC applications. The choice of a specific catalyst depends on the nature of the
reactants, the desired reaction, and the conditions under which the reaction is carried out.
Each type of catalyst has its own advantages and limitations, and selecting the appropriate
catalyst is crucial for the success of phase transfer catalysis in a given reaction.

7
Classification of Phase Transfer Catalysis
Phase transfer catalysis (PTC) can be classified into various categories based on the number
of phases involved in the reaction system. Two of the most common classifications are
biphase catalysis and triphase catalysis.
1.Biphase Catalysis:
Biphase Catalysis involves a system with two immiscible phases: typically an aqueous phase
and an organic phase. In such systems, a phase transfer catalyst (PTC) helps facilitate the
transfer of reactants between these two phases, enabling reactions that would otherwise be
challenging or impossible due to the immiscibility of the reactants. Biphase catalysis is
widely used in various nucleophilic substitution reactions, alkylation reactions, and other
processes where one of the reactants is soluble in the organic phase, and the other is soluble
in the aqueous phase.
2.Triphase Catalysis:
Triphase Catalysis extends the concept of phase transfer catalysis to systems with three
phases. In addition to the aqueous and organic phases, a third phase is introduced, which can
be a solid phase or a different immiscible liquid phase. Triphase catalysis is particularly
useful when the reaction involves solid reactants or when two immiscible liquid phases need
to be bridged for a reaction to occur. The phase transfer catalyst aids in transferring reactants
from one phase to another, facilitating reactions that would be otherwise challenging to
conduct.
Both biphase and triphase catalysis offer significant advantages in organic synthesis,
including improved reaction selectivity, higher yields, and the ability to reduce the use of
hazardous or environmentally harmful solvents. The choice between these two classifications
depends on the specific requirements of the reaction and the phases involved. Researchers
carefully consider factors such as reactant solubilities and the nature of the desired
transformation when selecting the appropriate type of phase transfer catalysis for a given
synthesis.
Tri-liquid phase transfer catalysis (L-L-L PTC) is a specialized variation of phase transfer
catalysis (PTC) in which three immiscible liquid phases are employed in a chemical reaction.
In a typical tri-liquid phase transfer catalysis system, these three phases may consist of water,
an organic solvent, and a second organic solvent or a reagent phase. The purpose of
introducing the third liquid phase is to create a unique environment for specific chemical
transformations.

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What is process intensification of tri phase S-L-L transfer catalysis
Process intensification refers to the design and implementation of chemical processes that
lead to significant improvements in efficiency, productivity, and sustainability. In the context
of tri-phase (solid-liquid-liquid) transfer catalysis, process intensification aims to enhance the
efficiency of the catalytic reaction occurring between the phases involved.
Here's how process intensification principles can be applied to tri-phase transfer catalysis:
1. Enhanced Mass Transfer: One of the key challenges in tri-phase catalysis is ensuring
efficient mass transfer of reactants between the solid catalyst and the liquid phases. Process
intensification techniques such as the use of structured catalysts, microreactors, or membrane
reactors can enhance mass transfer rates, thereby improving overall reaction kinetics.
2. Optimized Reactor Design: Traditional batch reactors may not be efficient for tri-phase
catalysis due to limitations in mass transfer and heat transfer. Continuous flow reactors, such
as trickle-bed reactors or fixed-bed reactors with appropriate internals, can improve mass
transfer and reaction selectivity. Moreover, advanced reactor configurations like oscillatory
flow reactors or spinning disk reactors can further enhance mixing and mass transfer.
3. Selective Catalysis: Process intensification involves the development and use of selective
catalysts that can promote the desired reaction while minimizing undesired side reactions.
Tailoring the catalyst properties (e.g., surface area, pore size distribution, active sites) can
enhance selectivity and yield.
4. Integration of Separation Processes: Separation of products from the reaction mixture is
often a significant challenge in tri-phase catalysis. Process intensification strategies involve
the integration of separation processes such as membrane separation, liquid-liquid extraction,
or adsorption directly into the reaction system. This integration reduces the number of unit
operations, leading to a more compact and efficient process.
5. Controlled Reaction Conditions: Maintaining optimal reaction conditions (e.g.,
temperature, pressure, pH) is crucial for maximizing the efficiency of tri-phase catalysis.
Process intensification involves the development of advanced control strategies and
automation systems to ensure precise control over reaction parameters, leading to improved
product quality and yield.
6. Resource Efficiency: Process intensification aims to minimize resource consumption (e.g.,
energy, raw materials, catalysts) and waste generation. This can be achieved through the
design of closed-loop systems, recycling of reactants and solvents, and integration of
renewable energy sources.
Overall, process intensification of tri-phase transfer catalysis involves a holistic approach that
combines innovative reactor design, advanced catalyst development, efficient mass transfer
techniques, and integrated separation processes to achieve significant improvements in
reaction efficiency, selectivity, and sustainability.

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Types of S-L-L tri phase transfer catalysis
Tri-phase (solid-liquid-liquid) transfer catalysis involves reactions where a solid catalyst
facilitates the transfer of reactants between two liquid phases. These reactions can be
classified into different types based on the nature of the catalytic process and the specific
reactions involved. Here are some types of S-L-L tri-phase transfer catalysis:
1. Hydrogenation/Dehydrogenation:
- These reactions involve the transfer of hydrogen between two liquid phases facilitated by
a solid catalyst. For example, the hydrogenation of unsaturated compounds (e.g., alkenes,
alkynes) or the dehydrogenation of alcohols or hydrocarbons.
2. Oxidation/Reduction:
- Oxidation or reduction reactions involve the transfer of oxygen or electrons between two
liquid phases with the help of a solid catalyst. Examples include the oxidation of organic
compounds using oxygen or the reduction of organic compounds using hydrogen.
3. Esterification/Transesterification:
- Esterification reactions involve the transfer of an alcohol between two liquid phases in the
presence of a solid acid catalyst. Transesterification reactions involve the exchange of ester
moieties between two liquid phases. These reactions are important in the synthesis of esters
and biodiesel.
4. Acid/Base Catalysis:
- Acid-base catalysis involves the transfer of protons or hydroxide ions between two liquid
phases facilitated by a solid acid or base catalyst. Examples include aldol condensation
reactions, Knoevenagel condensation reactions, or Claisen-Schmidt condensation reactions.
5. Metal-Catalysed Reactions:
- Various metal-catalysed reactions occur in tri-phase transfer catalysis, where metal
catalysts supported on solid surfaces facilitate the transfer of reactants between two liquid
phases. Examples include hydroformylation, hydrogenation, and oxidation reactions
catalysed by metals like palladium, platinum, rhodium, or ruthenium.
6. Organometallic Catalysis:
- Some tri-phase transfer catalytic reactions involve organometallic catalysts, where
organometallic compounds facilitate the transfer of organic groups between two liquid
phases. These reactions are commonly used in organic synthesis for carbon-carbon bond
formation, such as Suzuki-Miyara cross-coupling reactions or Heck reactions.
These types of tri-phase transfer catalytic reactions encompass a wide range of chemical
transformations and are employed in various industries, including fine chemicals,
pharmaceuticals, petrochemicals, and environmental applications.

10
Examples of tri phase S-L-L transfer catalysis
Tri-phase (solid-liquid-liquid) transfer catalysis involves reactions where a solid catalyst
facilitates the transfer of reactants between two liquid phases. Here are a few examples of
such reactions:
1. Liquid-Liquid Hydrogenation:
- In this reaction, a solid catalyst such as palladium or platinum is used to facilitate the
transfer of hydrogen gas from one liquid phase (organic solvent) to another liquid phase
(substrate solution). This process is commonly used in organic synthesis to hydrogenate
unsaturated compounds.
2. Liquid-Liquid Oxidation:
- Certain oxidation reactions involve the transfer of oxygen from one liquid phase (oxidant
solution) to another liquid phase (substrate solution) with the help of a solid catalyst. For
example, the oxidation of organic compounds using oxygen gas facilitated by a solid catalyst
like palladium on activated carbon.
3. Liquid-Liquid Esterification:
- Esterification reactions involve the transfer of an alcohol from one liquid phase (alcohol
phase) to another liquid phase (acid phase) in the presence of a solid acid catalyst. This
process is commonly used in the production of esters, which are important chemicals in
various industries including Flavors, fragrances, and pharmaceuticals.
4. Liquid-Liquid Hydroformylation:
- Hydroformylation is a process in which an aldehyde is formed by the addition of carbon
monoxide and hydrogen to an olefin. In some cases, the reaction occurs between two liquid
phases, where a solid catalyst facilitates the transfer of reactants. For example, the use of
rhodium catalysts supported on solid surfaces for hydroformylation reactions.
5. Liquid-Liquid Aldol Condensation:
- Aldol condensation reactions involve the transfer of an enolate ion from one liquid phase
(base phase) to another liquid phase (carbonyl compound phase) in the presence of a solid
catalyst. This reaction is widely used in organic synthesis to form carbon-carbon bonds and
create complex molecules.
These examples illustrate the diverse range of reactions that can occur in tri-phase transfer
catalysis, where a solid catalyst facilitates the transfer of reactants between two liquid phases,
enabling the synthesis of various important chemicals and compounds.

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Advantages and Disadvantages
Process intensification in S-L-L (solid-liquid-liquid) tri-phase transfer catalysis offers both
advantages and disadvantages:
Advantages:
1. Enhanced Mass Transfer: Process intensification techniques can significantly enhance
mass transfer rates between the solid catalyst, liquid reactants, and liquid products. This leads
to higher reaction rates and improved overall efficiency.
2. Reduced Residence Time: With intensified processes, the residence time required for the
reaction can be reduced, leading to higher productivity and throughput.
3. Improved Selectivity: Intensified processes often offer better control over reaction
conditions, leading to improved selectivity towards the desired products and minimizing
unwanted by-products.
4. Compact Equipment: Process intensification often involves the design of more compact
and efficient equipment, which can lead to reduced footprint and lower capital costs for
industrial-scale applications.
5. Reduced Energy Consumption: By optimizing reaction conditions and improving mass
transfer rates, process intensification can often lead to reduced energy consumption per unit
of product.
Disadvantages:
1.Complexity: S-L-L tri-phase transfer catalysis can introduce complexity into the process
design and operation due to the need for specialized equipment and control systems to
manage multiple phases effectively.
2. Potential Catalyst Deactivation: The presence of multiple phases and interactions with the
catalyst can potentially lead to catalyst deactivation over time, requiring periodic regeneration
or replacement.
3. Difficult Scale-up: Scaling up intensified processes from laboratory-scale to industrial-
scale can be challenging due to the intricacies involved in maintaining optimal conditions
across larger volumes.
4. Higher Operating Costs: Initial capital costs for intensified processes may be higher due to
the need for specialized equipment. Additionally, operating costs may be higher due to the
complexity of the process and potential maintenance requirements.
5. Safety Concerns: Intensified processes may introduce new safety concerns, particularly
when dealing with high-pressure or reactive systems. Proper safety measures and protocols
must be implemented to mitigate risks effectively.

12
Overall, while S-L-L tri-phase transfer catalysis offers potential benefits in terms of improved
efficiency and selectivity, careful consideration must be given to the challenges and
complexities associated with process intensification to ensure successful implementation.

Literature Review : -
ABSTRACT:
The development of reactive-separation processes, in which Products are separated from the reaction
media (i.e., reactants and catalysts) in A single reaction unit, is of great interest in industry as energy-
intensive separation Processes can be obviated. One promising alternative to accomplish this process
Intensification is the utilization of biphasic emulsion systems, where products and Reactants can be
separated based on differences in solubility. Additionally, when Solid nanoparticles with amphiphilic
character and catalytic activity are employed In biphasic systems, it is possible to simultaneously
stabilize the liquid−liquid Interface and catalyse chemical reactions. This new technology leads to (a)
Increased interfacial area, (b) enhanced mass transfer of molecules between the Two phases, (c)
simplified reaction/separation processes by using a recoverable Solid catalyst instead of surfactants,
and (d) effective separation of products from The reaction mixture by differences in their water/oil
solubility and thus avoiding Distillation that leads to product decomposition. To this end, the present
tutorial Review explores the fundamentals of Pickering interfacial catalysis (PIC) and its application
in biomass upgrading (upgrading of Sugars and pyrolysis oil), biogas to liquid products via
Fischer−Tropsch synthesis, and biodiesel production in the context of the United Nations sustainable
development goals

In principle, the transportation of oil in particle-stabilized


Emulsions should be mechanistically different from that in the
Surfactant-stabilized emulsions because of the difference in the
Emulsion stabilization principle and unique behavior of
Interfacial active particles in emulsions.

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1. INTRODUCTION

The use of solid nanoparticles as both stabilizers and catalysts of liquid−liquid interfaces combines
the advantages of solid catalysts and phase transfer catalysis. In conventional

homogeneous catalysis, to have the substrate molecules and the catalytic active center in intimate
contact, it is necessary to carry out the reaction in solvents that are able to dissolve, at

least partially, the reacting species and the catalyst. Therefore, the solvent has to perform several
functions, such as stabilizing the catalyst and reactants, assisting the desirable reaction

pathway by changing either the electronic configuration or the stereoselectivity of the catalyst, and
acting as an acid or base media.1 In many cases, these functional requirements severely

restrict the selection of the organic solvents that are often toxic, environmentally hazardous, and
expensive.2 One alternative to overcome these problems is using simultaneously organic and aqueous
phases, which decouples the functional requirements of the solvent. Furthermore, if the homogeneous
catalyst is replaced by a surface-sensitive complex, like tetraalkylammonium (TAA) cations, a
significant improvement is observed in the reaction process. These cations naturally segregate to the
liquid−liquid interface and continuously draw reactive anions from the aqueous phase to the organic
phase as lipophilic ion pairs (see Figure 1). This system is widely known as phase transfer catalysis
(PTC) and has been extensively studied for decades.3−9 Moreover, the addition of surfactant
molecules to the biphasic reaction media promotes the formation of emulsion droplets that increase
the interfacial surface area

14
and enhance the mass transfer of molecules between phases. The resulting catalytic system retains the
chemoselectivity, Regioselectivity, and/or enantioselectivity of the catalyst,

Observed in homogeneous catalysis, but reduces the environMental impact of the solvent as well as
enhances the reactivity, Catalyst recovery, and product separation.

Practical information :-
Some of the difficulties associated with phase transfer catalysis could be overcome by replacing the
homogeneous catalyst with recoverable and recyclable solid nanoparticles that

simultaneously stabilize emulsions and catalyze reactions at the water−oil interface. A demonstration
of this concept was initially reported by Crossley et al.11 using solid nanohybrids composed of carbon
nanotubes (CNTs) supported on metal

oxide particles, doped with transition or basic metals (see Figure 2). These nanoparticles are capable
of stabilizing Pickering emulsions of water and oil successfully. Also, it was

possible to modify the wettability of the nanohybrid particles by tuning their composition, in order to
produce systematically and reproducibly water-in-oil or oil-in-water emulsions.12 This

approach results in several advantages, which include (1) a simplification of the process scheme (it is
easy to separate the solid catalyst and there is no need of using a surfactant), (2) an enhancement in
the rate of mass transfer between the two phases, (3) an increment of the interfacial surface area, (4)
an easier separation of the products from the reaction mixture due

to differences in the water−oil solubility, which minimizes further decomposition, (5) stabilization of
the catalyst in hot aqueous environments, and (6), depending on the system, faster kinetics due to
solvation effects on the surface reactive species. This so-called Pickering interfacial catalysis (PIC)
wasextended to other systems in which a solid-stabilized emulsion

served as the reaction media for homogeneous catalyzed reactions. This variation of the approached
was named Pickering assisted catalysis (PAC).

STABILIZATION OF WATER−OIL EMULSIONS WITH PARTICLES

The first observation of emulsions stabilized by solid particles Was reported by Pickering in 1907,17
who noticed that colloidal Particles in mixture with water and petroleum can act as

Emulsifying agents to produce oil-in-water emulsions. In this Process, the emulsion formed is a
kinetically stable system Characterized by (1) the formation of a rigid film of particles at

The liquid−liquid interface that suppresses the coalescence of The droplets by steric repulsion18−21
and (2) the modification Of the rheological properties (viscosity) of the liquid at the Droplet−droplet

15
interface (Figure 3), delaying the liquid Drainage between coalescing droplets.21,22 Additionally,
other Studies suggested that, to observe the coalescence of emulsion Droplets, it is necessary to
displace the particles from the Interfacial region to either the organic or aqueous phases. This Means
that additional energy is required to break the emulsion, Providing an energetic barrier for
coalescence.23 Furthermore,

Another possible mechanism by which colloidal particles Stabilize emulsions is related to the
capillary pressure of the Droplet−droplet liquid film, which arises by the deformation of

The liquid interface around the adsorbed particles when the Liquid is squeezed out of the thin film.
Phase Selective Catalysis in PICs. Inspired in the Shape-selectivity of zeolites in gas phase reactions,
in which Confinement is used to control the product selectivity,81 mass Transport limitations in PIC
can be leveraged to control the Catalyst selectivity based on the solubility or polarity of the
Molecules. Essentially, if two reactants are present with distinct

Solubility (i.e., one exclusively soluble in water and the other soluble in oil), then one could convert
the aqueous- or oil- soluble reactant by placing the active sites on either the Hydrophilic or
hydrophobic side of the catalyst in PIC (Figure 13). This can allow the so-called phase selective
catalysts Similarly, if two orthogonal reactions must be conducted (e.g.,

Base and acid catalysis), then one could potentially confine the Antagonistic catalysts to the liquid
phase in which the desired Reaction is required, allowing simultaneous reaction in both Phases.
Soluble reactant by placing the active sites on either the Hydrophilic or hydrophobic side of the
catalyst in PIC (Figure 13). This can allow the so-called phase selective catalysts

To investigate the concept of phase selectivity in emulsion Systems, two aldehydes with different
solubilities were chosen, Benzaldehyde (oil-soluble) and glutaraldehyde (water-soluble). The
contrasting solubilities allowed one to follow the evolution Of the hydrogenation activity for each
molecule, simultaneously And independently, in the organic and aqueous phases. The Results from
this experiment showed that the total turnover Number (TON) of the hydrogenation of benzaldehyde
was 2800 for the catalyst with Pd on both sides and 1488 for the Catalyst with Pd on the hydrophobic
side. The resulting Turnover frequencies (TOFs) are 0.99 and 0.49 s −1 Respectively, calculated based
on HR-TEM of the catalysts Cluster size. When the catalyst contained Pd on both sides of The Janus
particles, high conversion levels were obtained for Both reactants, about 80% for glutaraldehyde in
the water Phase and 100% for benzaldehyde in the oil phase. However, When the catalyst had Pd
selectively deposited on the Hydrophobic side, the conversion of benzaldehyde was kept At 100%
while the conversion of glutaraldehyde decreased to 2%, demonstrating high phase-selectivity.

Conclusion: -

16
The utilization of solid catalysts for the simultaneous stabilization of Pickering emulsions and
activation of chemical reactions holds a great potential in the development of reaction- paration
systems. Since the first report of this concept in 2011 by Resasco et al,143 the so-called PIC system
has been demonstrated using numerous chemistries, often inaccessible using conventional single or
even biphasic reactor concepts, due to the compartmentalization of the liquid phases and
catalysts chemistries.

Further development of a fundamental understanding of the liquid−liquid−solid transfer,


particle−particle and particle− liquid interactions, and catalytic reactions is essential to bring forward
this technology. While it is true that there has been significant progress in our understanding of these
systems, there are still key scientific questions that must be addressed in these systems regarding the
impact of solvation effects on catalytic activity in PIC and the interplay of dynamic changes in the
chemical composition of the liquid−liquid phases and the emulsion stability. Furthermore, the
application of PIC has been often associated with proof-of-concept reactions with very simple
reaction mixtures using highly diluted reaction mixtures, which has limited their
application in industry.

Difference between Process Intensification of Tri Phase Transfer Catalysis


of L-L-L and S-L-L.

Process intensification in tri-phase transfer catalysis (TPTC) involves enhancing the


efficiency and productivity of the reaction while minimizing resource consumption, waste
generation, and operating costs. In TPTC, three phases are involved: solid (S), liquid (L), and
liquid (L), where the reaction occurs at the interface between the liquid phases. The
difference between S-L-L and L-L-L configurations lies in the nature of the solid phase and
its role in the catalytic process:

1. S-L-L (Solid-Liquid-Liquid):

- In this configuration, a solid catalyst is employed to facilitate the transfer of reactants


between two immiscible liquid phases.

- The solid catalyst may act as a support for one of the liquid phases or as an interface
where the reaction occurs.

- Commonly, the solid catalyst enhances mass transfer and provides a surface for catalytic
reactions to take place, improving reaction rates and selectivity.

- Examples include catalytic membrane reactors and supported liquid-phase catalysts.

17
2. L-L-L (Liquid-Liquid-Liquid):

- In this configuration, the catalytic activity is inherent in one or both of the liquid phases,
and no solid catalyst is involved.

- The reaction takes place at the interface between two immiscible liquid phases, where one
phase acts as the catalyst and the other as the reaction medium.

- This configuration often simplifies catalyst recovery and recycling compared to S-L-L
systems, as there is no solid phase to separate.

- Liquid-liquid biphasic systems are commonly used in various organic synthesis reactions,
such as phase-transfer catalysis and liquid-liquid extraction processes.

In both configurations, process intensification aims to improve reaction efficiency, yield, and
selectivity by optimizing various parameters such as mixing, phase contact, temperature,
pressure, and catalyst concentration. However, the choice between S-L-L and L-L-L
configurations depends on factors such as the nature of the reaction, catalyst characteristics,
desired product purity, ease of operation, and economic considerations.

18
References : -

https://www.sciencedirect.com/science/article/abs/pii/S2468823119300100

https://www.sciencedirect.com/topics/chemistry/phase-transfer-catalyst#:~:text=Phase%20transfer
%20catalyst%20(PTC)%20is%20one%20of%20the%20promising%20and,special%20application
%20in%20heterogeneous%20catalysis.

https://en.wikipedia.org/wiki/Phase-transfer_catalyst#:~:text=PTC%20is%20widely%20exploited
%20industrially,PTC%2Dcatalyzed%20alkylation%20of%20phosphothioates.

https://annamalaiuniversity.ac.in/studport/download/sci/chemistry/resources/phasetransfercatalyst,
%20microwave,%20sonochemistry-%20II%20MSc%20Chemistry%20(CBCS)%20&%20V
%20Integrated.pdf

ruiz-faria-2022-catalysis-at-the-solid-liquid-liquid-interface-of-water-oil-pickering-emulsions-a-
tutorial-review

19

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