PROCESS INTENSIFICATION: MICROREACTORS

SEMINAR REPORT

Submitted in partial fulfilment of the requirements for the degree of

MASTER OF TECHNOLOGY in
INDUSTRIAL POLLUTION CONTROL

by
CHINTALAPATI SUSHMA SUSMITA
(14PC06F)

DEPARTMENT OF CHEMICAL ENGINEERING

NATIONAL INSTITUTE OF TECHNOLOGY KARNATAKA
SURATHKAL, MANGLORE 575025
January, 2015

We are what our thoughts have made us; so take care about what you think. Words are secondary.
Thoughts live; they travel far.

INDEX
Chapter
Page number
1. Role of process industries.............................................1
2. Process Intensification...................................................................................1
2.1 Process intensifying equipments..................................................2
2.1.1 Rotating devices.............................................................2
2.1.2 Monolithic catalysts.......................................................3
2.1.3 Microreactors.................................................................3
2.2 Process intensifiying methods......................................................4
2.2.1 Multifunctional reactors.................................................4
2.2.2 Membrane reactors.........................................................4
2.2.3 Hybrid separations..........................................................5
3. Process intensification through microreactor application .............................5
3.1 Impact on research and development ...........................................5
3.2 Heat transfer improvements .........................................................5
3.3 High surface to volume ratio ........................................................6
3.4 Larger interfacial area for multi-phase systems ...........................6
3.5 Efficient mixing ............................................................................7
3.6 Integrated microchemical systems ................................................8
4. Conclusions.........8
5. References...................8

1. Role of Process Indutries

Industries convert raw materials into marketable end-products. This convesion takes place in a
series of well-engineered and tested operations and processes. The production of process goods
usually requires inputs for thermal or chemical conversion, such as heat, time and pressure.
The product typically cannot be disassembled to its constituent parts.
Industrial processes are procedures involving chemical, physical, electrical or mechanical steps
to aid in the manufacturing of an item or items, usually carried out on a very large scale.
Industrial processes are the key components of heavy industry. Process industries supply
materials that form products, provide energy, feed and cure people, in short. They also play a
significant part of the economy in terms of contribution to GDP and employment. In addition
to these, process industries are a major consumer of energy and resources. Modification of the
processes or equipments in such a way that the consumption of these components is effective
both in terms of economy and conservation. Process intensification is one such approach that
improves efficiency of a process.
2. Process Intensification
Process intensification consists of the development of novel apparatuses and techniques that,
compared to those commonly used today, are expected to bring dramatic improvements in
manufacturing and processing, substantially decreasing equipment-size/production-capacity
ratio, energy consumption, or waste production, and ultimately resulting in cheaper, sustainable
technologies.
Any chemical engineering development that leads to a substantially smaller, cleaner, and more
energy efficient technology is process intensification , in short. Major cost savings, short time
to the market, safer processes, high product purity, high selectivity, operational excellence, less
waste and less byproducts, quality by design are the other attractive features of Process
Intensification.
Process intensification concerns only engineering methods and equipment. So, for instance,
development of a new chemical route or a change in composition of a catalyst, no matter how
dramatic the improvements they bring to existing technology, do not qualify as process
intensification. Process intensification, being driven by the need for breakthrough changes in
operations, focuses mainly on novel methods and equipment. But, it also encompasses certain
established technologies and hardware.
The whole field of Process Intensification generally can be divided into two areas:

process-intensifying equipment, such as novel reactors, and intensive mixing, heattransfer and mass-transfer devices. This is again classified as equipment that carry out
chemical reactions and equipment that do not concern chemical reactions;

process-intensifying methods, such as new or hybrid separations, integration of reaction

and separation, heat exchange, or phase transition (in so-called multifunctional reactors),
techniques using alternative energy sources (light, ultrasound, etc.), and new process-control
methods (like intentional unsteady-state operation).
There can be some overlap between these two areas. New methods may require novel types of
equipment to be developed and vice versa, while novel apparatuses already developed
sometimes make use of new, unconventional processing methods. These two methods are
presented in Fig. 1.

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Figure 1: Process intensification modes

2.1 Process-intensifying equipment Relevant examples of process-intensifying equipment are

discussed.
2.1.1
Rotating devices: High heat-transfer coefficients are achievable in the spinning disk
reactor (SDR) . In SDRs, a very thin (typically 100 m) layer of liquid moves on the surface of
a disk spinning at up to approximately 1,000 rpm. At very short residence times (typically 0.1
s), heat is efficiently removed from the reacting liquid at heat-transfer rates reaching 10,000
W/m2K. SDRs currently are being commercialized .
Other reactors especially dedicated to fast and very fast processes worth mentioning include:
the supersonic gas/liquid reactor which employs a supersonic shockwave to disperse gas into
very tiny bubbles in a supersonic in-line mixing device . The other one is the jet-impingement
reactor of NORAM Engineering and Constructors which uses a system of specially configured
jets and baffles to divide and remix liquid streams with high intensity.
Rotor/stator mixers, which are aimed at processes requiring very fast mixing on a micro scale,
contain a high-speed rotor spinning close to a motionless stator. Fluid passes through the
region where rotor and stator interact and experiences highly pulsating flow and shear. In-line
rotor/stator mixers resemble centrifugal pumps and, therefore, may simultaneously contribute
to pumping the liquids.

Figure 2: Spinning Disk Reactor

2.1.2
Monolithic catalysts: Monolithic substrates used today for catalytic applications are
metallic or nonmetallic bodies providing a multitude of straight narrow channels of defined
uniform cross-sectional shapes. To ensure sufficient porosity and enhance the catalytically
active surface, the inner walls of the monolith channels usually are covered with a thin layer of
washcoat, which acts as the support for the catalytically active species.
The most important features of the monoliths are:
very low pressure drop in single- and two-phase flow, one to two orders of magnitude
lower than that of conventional packed-bed systems;
high geometrical areas per reactor volume, typically 1.5 - 4 times more than in the
reactors with particulate catalysts;
high catalytic efficiency, practically 100%, due to very short diffusion paths in the thin
washcoat layer; and
exceptionally good performance in processes in which selectivity is hampered by masstransfer resistances.
One of the problems in monolith reactors, especially for gas-phase catalytic processes, is
difficult heat removal due to the absence of radial dispersion. Monolith channels are fully
separated from each other and, therefore, the only heat transport mechanism is the conductivity
through the monolith material. Monolithic catalysts also can be installed in-line, like static
mixing elements, using the latter as gas/liquid dispersing devices. Compared to conventional
fixed-bed reactors, such reactors offer much better heat-transfer conditions namely, heattransfer coefficients typically of 3,5007,500 W/m 2 K, and heat-transfer areas of up to 2,200
m2.

Figure 3: Monolithic catalysts

2.1.3
Microreactors: Microreactors are chemical reactors of extremely small dimensions
that usually have a sandwich-like structure consisting of a number of slices (layers) with
micromachined channels (10100 m in dia.). The layers perform various functions, from
mixing to catalytic reaction, heat exchange, or separation. Integration of these various
functions within a single unit is one of the most important advantages of microreactors. The
very high heat- transfer rates of upto 20,000 W/m 2K achievable in microreactors allow for
operating highly exothermic processes isothermally, which is particularly important in carrying
out kinetic studies.
Very low reaction-volume/surface-area ratios make microreactors potentially attractive for

processes involving toxic or explosive reactants. The scale at which processes using batteries
of multiple microreactors become economically and technically feasible still needs to be
determined, though.
The channels in the plates of microchannel heat exchangers are usually around 1 mm or less
wide, and are fabricated via silicon micromachining, deep X- ray lithography, or
nonlithographic micromachining.

Figure 4: Microreactor

2.2 Process-intensifying methods Most process-intensifying methods fall into three welldefined areas: integration of reaction and one or more unit operations into so-called
multifunctional reactors, development of new hybrid separations, and use of alternative forms
and sources of energy for processing.
2.2.1
Multifunctional reactors: These can be described as reactors that, to enhance the
chemical conversion taking place and to achieve a higher degree of integration, combine at
least one more function (usually a unit operation) that conventionally would be performed in a
separate piece of equipment. A widely known example of integrating reaction and heat transfer
in a multifunctional unit is the reverse-flow reactor . For exothermic processes, the periodic
flow reversal in such units allows for almost perfect utilization of the heat of reaction by
keeping it within the catalyst bed and, after reversion of the flow direction, using it for
preheating the cold reactant gases.
Reactive (catalytic) distillation is one of the better known examples of integrating reaction and
separation, and is used commercially. In this case, the multifunctional reactor is a distillation
column filled with catalytically active packing. In the column, chemicals are converted on the
catalyst while reaction products are continuously separated by fractionation (thus overcoming
equilibrium limitations). The catalyst used for reactive distillation usually is incorporated into a
fiberglass and wire-mesh supporting structure, which also provides liquid redistribution and
disengagement of vapor.
The advantages of catalytic distillation units, besides the continuous removal of reaction products and higher yields due to the equilibrium shift, consist mainly of reduced energy
requirements and lower capital investment . Also, a reverse process to the one described above,
that is, combination of reaction and condensation, has been studied for benzene oxidation to
cyclohexane and for methanol synthesis. The number of processes in which reactive distillation
has been implemented on a commercial scale is still quite limited but the potential of this
technique definitely goes far beyond todays applications.
2.2.2
Membrane reactor: The membrane can play various functions in such reactor
systems. It, for instance, can be used for selective in-situ separation of the reaction products,

thus providing an advantageous equilibrium shift. It also can be applied for a controlled
distributed feed of some of the reacting species, either to increase overall yield or selectivity of
a process (e.g., in fixed-bed or fluidized-bed membrane reactors or to facilitate mass transfer
(e.g., direct bubble-free oxygen supply or dissolution in the liquid phase via hollow-fiber
membranes). In addition, the membrane can enable in-situ separation of catalyst particles from
reaction products). Finally, the membrane can incorporate catalytic material, thus itself
becoming a highly selective reaction-separation system.
The disadvantage of these systems is the relatively high price of membrane units, although
other factors, such as low permeability as well as mechanical and thermal fragileness, also play
an important role.
2.2.3
Hybrid separations : Many of the developments in this area involve integration of
membranes with another separation technique. In membrane absorption and stripping, the
membrane serves as a permeable barrier between the gas and liquid phases. By using hollowfiber membrane modules, large mass-transfer areas can be created, resulting in compact
equipment.
Membrane distillation is probably the best known hybrid system. The four basic advanatges of
this are:
100% rejection of ions, macromolecules, colloids, cells, and other nonvolatiles;
lower operating pressure across the membrane than in the pressure- driven processes;
less membrane fouling, due to larger pore size; and
potentially lower operating temperatures than in conventional evaporation or
distillation, which may enable processing of temperature-sensitive materials.
3. Process Intensification through Microreactor Application
Process intensification based on micro-devices is a new concept in chemical engineering which
aims at reducing capital and energy costs along with the environmental impact by reducing the
size of the chemical plant. With the decrease of equipment size by several orders of magnitude,
substantial economical benefits, improvement of intrinsic safety, and reduction of
environmental impact can be achieved. In addition, the small scales used reduce exposure to
toxic or hazardous materials, and the enclosed nature of the microreactors means greater ease
of containment in the event of a run-away reaction.
Because of the small amounts of chemicals needed and the high rate of heat and mass transfer,
microscale systems are especially suitable for reactions with highly flammable, toxic and
explosive reactants, for the elimination of by-products, for achieving maximum conversion and
energy utilization. One of the main motivations for the use of microreactor technology are the
gain in yield and safety.
3.1 Impact on research and development Microreactors have been recognized as versatile
tools for rapid optimization of reaction parameters, as reliable instruments for kinetic research
and have been found particularly useful in combination with high-throughput methods. With
the ability to fine-tune the mass transfer contributions, impose temperature profiles, monitor
the progress of extraction and reaction, together with the excellent accessibility for process
modeling, they are becoming indispensable in research and development laboratories from
scaling up.
3.2 Heat transfer improvements Most synthetic transformations performed in microreactors
have involved ambient or low-temperature conditions in order to safely conduct highly

exothermic reactions.
Razzaq et al. developed a high temperature/high-pressure microtubular flow unit for
processing homogeneous reaction mixtures. Stainless steel coils were used that could be
directly heated across their full length by electric resistance heating to temperatures up to 350
C. The pressure could be set and stabilized in the range of 50200 bar, while standard batch
micro wave systems operate at 20 bar. Rapid heating and cooling of the reaction mixture was
possible because of efficient heat transfer through the thin steel reactor coil. They showed how
the long reaction times for Diels-Alder reaction of 2,3-dimethylbutadiene and acrylonitrile to
provide the cyclohexene adduct could be reduced to merely 20 minutes.
The strongly exothermic alkylation could be thermally controlled even at elevated
temperatures leading to high reaction rates and product purity above 99 %. A more than
twentyfold increase of the volumetric production rate compared to a conventional batch
process was the result of process intensification.
For the case of the Grignard reaction, a reduction of the operation time from 5 hours to less
than 10 seconds was demonstrated. The use of five reactors in paral lel was proposed in order
to reach industrial productivity of the stirred tank reactor.
3.3 High surface to volume ratio In a review by van Gerven et al. on the intensification of
photocatalytic processes, microreactors have been investigated in performing photochemical
and photocatalytic reactions. The main advantage described is the high surface to volume ratio,
which in the case of photochemical reactions leads to efficient illumination. This permits
efficient catalytic exposure to radiation, and in addition also leads to maximized reagent
catalyst contact. A much better control over variables such as temperature and flow rates was
possible due to the fast heat and mass transfer.
Biodiesel was produced at a rate of 61 kg m 3 min1 by Kraai et al. This result compares well
with the 42 kg m3 min1 reported for typical batch processes. The process in the microreactor is
much more efficient, since there is no distinct separation step, and cleaning of the reactor
between batches can be omitted. They also showed that it is advantageous to perform chemoand biocatalytic conversions continuously .
Microreactors offer a convenient and highly efficient means to optimize reaction conditions
and the performance of catalysts. In the case of the reaction of 3-bromobenzaldehyde with 4fluorophenylboronic acid, 90 % yields were reported for the microreactors, compared with 50
% in stirred flasks.
A first continuous production process of Baylis-Hillman adducts was developed and optimized
for use under microreactor conditions. After optimization, the reaction could be performed
continuously and approximately 30 % faster compared to batch conditions.
3.4 Larger interfacial area for multi-phase systems It is known that miniaturization could
greatly increase mass and heat transfer efficiency and minimize amount of fluids resulting in
shorter reaction times and reducing the cost of research and development. However, in order to
optimize the design and the operation of multiphase processes in the microreactor, we have to
predict and accurately control the existing flow patterns to achieve optimal conditions for a
specific chemical process.
Slug flow, monodispersed droplets flow, droplets populations flow, parallel flow and annular
flow are the most common flow patterns of two-phase microfluidics. Two mechanisms govern
mass transport, convection through internal circulation and diffusion between the two phases.
The thickness of the interfacial boundary layer is reduced, which augments diffusive
penetration. Internal circulation, which is stimulated within the slugs by their passage along the

channel, is responsible for a large enhancement in the interfacial mass transfer and the reaction
rate.
Liquid-liquid microextractor-reactors were shown to offer superior performance and greater
efficiency in comparison to conventional equipment, with very large specific interfacial areas
in comparison with other contactors, which enhances the mass-transfer and heat-transfer rates.
Moreover, the internal circulation in the slugs also improves the mass-transfer rate by surface
renewal at the phase interface.

Figure 5: Flow patterns for two phase flow in a microreactor

3.5 Efficient mixing By improving the mixing quality in the microreactor, the macroscopic
reaction rate was increased compared to the lab-scale batch process in the case of catalyzed
oxidation of 2-butoxy- ethanol to 2-butoxyacetaldehyde .
The installation of a StarLam 3000 microreactor in an existing production plant was reported
by Kirschneck and Tekautz. The StarLam 3000 is a large-capacity microstructured mixer (with
a throughput of about 3 m3 h1), which creates a finely-dispersed injection of two fluid streams.

The aim was to double the capacity of a running two step batch process and was achieved by
installing a microreactor for the first reaction step. A higher reaction rate made it possible to
reach overall throughputs of 3.6 tons per hour. In addition, energy savings were achieved.
3.6 Integrated microchemical systems Techniques for integrating micro-unit operations
(MUOs) in a multiphase flow network are being developed for constructing microsystems
where a sequence of consecutive operations will be fabricated on one chip. This microintegration methodology is termed continuous-flow chemical processing (CFCP) and will
simplify downstream operations and accelerate sample analysis time. The integration of
fundamental MUOs, such as mixing and reaction, two- and three-phase formations, solvent
extraction, solid-phase extraction, heating, and cell culture has been successfully integrated a
chemical system on a microchip .

Figure 6: Integrated microchemical system

4. Conclusions
Emerging equipment, processing techniques, and operational methods promise spectacular
improvements in process plants, markedly shrinking their size and dramatically boosting their
efficiency. These developments may result in the extinction of some traditional types of
equipment, if not whole unit operations.
Microstructured reactors represent a highly effective means for process intensification for
specific processes. The benefits of employing microreactor technology include enhanced heat
and mass transfer, safety, environmental impact, distributed production, high portability,
remote (on-site) applications and flexible nature of the technology. Reactions in microreactors
are performed under precisely controlled conditions providing improved yields and product
quality compared to the batch procedures. Novel techniques are deployed in order to improve
the technology to a cleaner, smaller and more energy efficient technology. Miniaturization of
chemical processes means that only small quantities of reagents are required and allows for
high-throughput screening of reaction conditions in a highly controlled manner. They are an
ideal tool for high throughput experimentation, and can speed up process research and
development with the ability to maintain the high level of control and selectivity. One set-back
which still has to be overcome for translating the potential of the novel techniques into an
economical advantage is finding numbering-up solutions for increasing production capacities.
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