Process Industries:

Industries convert raw materials into marketable end-products. This conversion 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.

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.

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,
and operational excellence, less waste and less byproduct, 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.

‘Any chemical engineering development that leads to a substantially

smaller, cleaner, safer and more energy efficient technology is
process intensification ’
Key themes of process intensification:

 Capital investment reduction

 Energy use reduction
 Raw material cost reduction
 Increased process flexibility and inventory reduction
  Ever greater emphasis on process safety
 Increased attention to quality
 Better environmental performance

Size reduction for its own sake, however, is not the be-all and end-all of PI. There are
intensified processes which offer us the opportunity to create new or better products
with properties which are better controlled. Pharmaceutical products, which cannot be
made to such a tight specification in any other way, are a case in point.

Increasing the speed of some processes (compatible with knowledge of reaction

kinetics, where appropriate) can also be a strong incentive.

The most impressive examples of PI:

1) HiGee distillation unit of Colin Ramshaw (1983) – This unit operation shows a
remarkable reduction in visual impact of a PI technology, while concepts such as the
‘desktop process plant’, the ‘pocket nitric acid plant ’ the ‘ lab-on-a-chip ’ stimulate.

2) A Toshiba (Anon, 2005a ) mobile phone – a home for the adjacent micro-reactor fuel cell
- This shows the direct methanol fuel cell (DMFC) with an output of 100 mW – awarded
in February 2005 the title of ‘ the world’s smallest DMFC ’ by Guinness World Records.
Areas of Process Intensification:

The whole field of Process Intensification generally can be divided into two areas:

i) Process-intensifying equipment, such as novel reactors, and intensive mixing, heat

transfer and mass-transfer devices. This is again classified as equipment that carry out
chemical reactions and equipment that do not concern chemical reactions.
ii) 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.
Process-intensifying equipment relevant examples of process-intensifying equipment
are discussed.

Rotating devices: High heat-transfer coefficients are achievable in the spinning disk
reactor (SDR) . In SDRs, a very thin (typically 100 μm) 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 theregion 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.
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 (10–100 μm 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/m2K 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 3. Microreactor
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 is the gain in yield and safety.
Intensified Mixing

Mixing is one of the less exciting areas of process engineering, but its importance
in a range of sectors cannot be underestimated. Without effective mixing, many
food products would not be possible and chemical processes would, at best, consume
much additional time and energy. Some years ago it was observed by John
Middleton, then BHR Solutions Mixing Consultant (see Appendix 4), that attention
to the mixing process typically yielded increases in plant productivity of 10–20%,
in some cases reaching 40%.

The stirred tank, of course, uses the stirrer for mixing, but the performance, even
with modern designs of paddles, does little to ensure highly uniform reactions – the
main point of stirring (or mixing) the fluid(s) within the ‘ pot ’ . The most common
types of mixers are in-line units and rotor stator mixers. Other mixer types considered
below include variants based upon ejectors, fluidics, types using venturi aeration and
ideas based upon spinning discs.

Static mixers:

There are many types of static mixers available commercially, all with similar operating
principles. Most units have a number of mixing elements, the ‘ mix ’ of element
configurations depending upon the mixer type. These are inserted into the
pipe work at the point where mixing is needed. Their main advantage is the lack of
moving parts, keeping operating and capital costs relatively low. Cleaning is, of course,
required where product or feedstock changes may be involved.

Static mixers are used to achieve good homogeneity between two or more streams,
which can help in achieving good conditions upstream of, for example, a catalyst where
reactions between the two are taking place. The intensification process using these
mixers allows the components of the stream to be highly mixed within a distance of a
few pipe diameters, with no external energy input apart from the modest additional
pressure drop.

Static mixers are perhaps the simplest and most versatile of process intensification
equipment, with application in reactions where at least one phase is a liquid. They are
tube inserts that use the pumping energy/pressure drop to induce mixing
and can be roughly divided into three categories:

1. Turbulent flow mixers that rely on the vortices shed from tabs positioned on the
walls of the device. They promote mixing in an axial direction and so approximate well
to plug flow devices.

2. Laminar flow mixers that physically redistribute, stretch and fold the fluid.
3. Those used for both regimes.

Figure: Static Mixer

Gravitational Mixer:
 Figure: Gravitational Mixer

HEX-reactors
Heat exchanger reactors (often referred to as a ‘ HEX-reactors ’ ) are essentially
compact heat exchangers used as reactors. The advantage conferred is, as in their heat
transfer duties, their large heat transfer surface areas per unit volume, which when
used as reactors can accommodate highly exothermic reactions.
Candidate process reactions for HEX-reactors should have the potential to be
fast, produce or absorb heat (i.e. exothermic or endothermic) and form byproducts.
Industrial examples include nitrations, polymerisations, hydrogenations, halogenations
and aminations. Typically, such processes have byproduct outputs of rates
between 1–5 kg/kg of desired products (in bulk chemicals), and 5–50 kg/kg of product
for fine chemicals. These processes provide the greatest opportunity for realising the
benefits of HEX-reactors compared to stirred tank reactors. HEX-reactors
of this type are usually derived from existing compact heat exchanger variants, e.g.
the printed circuit reactor (PCR) and Chart-kote units.
Process-intensifying methods: Most process-intensifying methods fall into three well-
defined 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.

Multifunctional reactors: These can be described as reactors that, to enhance the

chemical conversion taking place and to achieve a higher degree of integration combines
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 fiber glass 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 today’s applications.

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.

Figure: WGS reaction using Membrane reactor

Reaction/Separation Coupled Technologies:

Reactive distillation

Using distillation to remove volatile products from reactions is an effective

method of increasing conversion, and consequently there are currently over 150
reactive distillation-based processes at industrial scale (range 100–3000 kte/yr).
Conventionally, the arrangement is essentially a distillation column in which the
packing is either coated with a catalyst or has catalysed particles located within
a supporting structure. The catalyst may also be in the same phase as the reacting
species. The aim of the distillation column is to separate the products of the
reaction by fractionation. Another reason for performing reaction and distillation
simultaneously is to remove impurities or undesired species. ‘ Reactive entrainers ’ may
be added, to react with difficult to remove substances or to convert them to
more volatile species. Advantages of reactive distillation (RD) include:
● Process simplification: the potential for capital cost reduction is clear in that RD
can remove the need for separate reaction and separation steps. Prior to use of
RD, for example, the methyl acetate process required two reactors and eight distillation
columns. It has been succeeded by systems containing one RD column and two
separating columns, with a significant reduction in overall capital cost.

● Improved conversion: by pushing the reaction to the product side by removing

one of the product species.

● Improved selectivity: an example is the production of ethyl benzene from benzene and
ethene. The ethyl benzene produced is more reactive with the ethane than the benzene,
so removing it in situ using RD represents a simple way of preventing byproduct
formation.

● Reduced catalyst requirement per unit product.

● Increased reliability, simply due to the smaller amount of equipment and particularly to
no longer having equipment with moving parts.

● Reduced energy requirement.

● Removal of azeotropes.

● Multifunctionality: RD can encompass more than just these two processes.

● Reduction of byproducts.

● Heat integration: operation at temperatures where heat is more useful.

● Control of highly exothermic reactions: due to operation at a species’ boiling point,

meaning that heat transfer coefficients are high.

● Reduced problems with hot spots and thermal runaway

The main industrial applications of RD are esterification, etherification and alkylations.

Certain hydrogenerations and hydrodesulpurisations are also performed in this way. RD
is most often used for esterification reactions, the most famous example of which (and
indeed the most famous example of RD), is the ‘ Eastman process ’ for methyl acetate,
initiated in 1980.

Other prospective applications of RD include liquid–liquid hydrolyses; saponification;

nitration; oxidation; fermentations; hydrolysis of aqueous methyl formate and
dehydrogenation of cyclohexane to benzene.
Drawbacks:

Not easy to find applications where the separation and the reaction conditions match;
volatility constraints
Reactive extraction

Reactive extraction (RE) is the integration of reaction and solvent extraction

extract process
steps. This results in fewer process steps overall, thereby reducing capital cost. Other
possible advantages that can be realised by performing extraction in this way include
enhanced selectivity and efficiency. RE can be an effective way of removing a desired
product from the reaction zone, preventing any side reactions.
reactions

One mode of RE is the addition of a second liquid phase

phase in the reactor, containing a
selective solvent that removes the product.

Advantages of Reactive Extraction

Reactive adsorption

Adsorption is basic separation techniques that can be used in parallel with a reaction to,
for example, increase conversion by removing a product. Reactive adsorption combines
the separation role of, for example, a solid adsorbent with the
reaction taking place on a different surface. The ability to remove the adsorbent
or to desorbs one or more of the products of the reaction can be convenient and
‘intensive’, although adsorbents do not necessarily respond rapidly. There could well be,
for instance, synergy between the fluidized-bed reactors and such adsorption
processes.