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Process Intensification:
Transforming
Chemical Engineering
Emerging equipment, processing techniques,
and operational methods promise spectacular
improvements in process plants, markedly shrinking
Andrzej I. Stankiewicz, their size and dramatically boosting their efficiency.
DSM Research/Delft University
of Technology These developments may result in the extinction
Jacob A. Moulijn,
Delft University of Technology
of some traditional types of equipment, if not
whole unit operations.
Process Intensification
Equipment Methods
Equipment for
Equipment for
Operations Multifunctional Hybrid Alternative Other
Carrying Out
not Involving Reactors Separations Energy Sources Methods
Chemical Reactions
Chemical Reactions
Examples
Spinning Disk Reactor Static Mixers Reverse-Flow Membrane Absorption Centrifugal Fields Supercritical Fluids
Static Mixer Reactor Compact Heat Reactors Membrane Distillation Ultrasound Dynamic (Periodic)
(SMR) Exchangers Reactive Distillation Adsorptive Distillation Solar Energy Reactor Operation
Static Mixing Catalysts Microchannel Heat Reactive Extraction Microwaves
(KATAPAKs) Exchangers Reactive Crystallization Electric Fields
Monolithic Reactors Rotor/Stator Mixers Chromatographic Plasma Technology
Microreactors Rotating Packed Beds Reactors
Heat Exchange (HEX) Centrifugal Adsorber Periodic Separating
Reactors Reactors
Supersonic Gas/Liquid Membrane Reactors
Reactor Reactive Extrusion Figure 2. Process intensification and
Jet-Impingement Reactive Comminution its components.
Reactor Fuel Cells
Rotating Packed-Bed
Reactor
Side-Stream (Optional)
Monolithic Catalyst
gives a spectacular example of an ap- microreactors. The very high heat- years, Pacific Northwest National
proximately 100-fold reduction in re- transfer rates achievable in microre- Laboratory (Richland, WA) has
actor size from replacing a conven- actors allow for operating highly demonstrated microchannel heat ex-
tional system with an in-line mono- exothermic processes isothermally, changers in a planar sheet architec-
lithic unit. which is particularly important in car- ture that exhibit high heat fluxes and
One of the problems in monolith rying out kinetic studies. Very low re- convective-heat-transfer coefficients.
reactors, especially for gas-phase cat- action-volume/surface-area ratios make The reported values of heat-transfer
alytic processes, is difficult heat re- microreactors potentially attractive for coefficients in microchannel heat ex-
moval due to the absence of radial processes involving toxic or explo- changers range from 10,000 to
dispersion. Monolith channels are sive reactants. The scale at which 35,000 W/m2K (4, 12).
fully separated from each other and, processes using batteries of multiple
therefore, the only heat transport microreactors become economically Rotating devices
mechanism is the conductivity and technically feasible still needs to Almost as high heat-transfer coef-
through the monolith material. For be determined, though. ficients are achievable in the spinning
highly exothermic gas-phase reac- The geometrical configuration of disk reactor (SDR) (13). This unit
tions, so-called HEX reactors devel- microchannel heat exchangers (stacked (see Figure 7) developed by
oped by BHR Group, Ltd. (Cranfield, cross-flow structures) resembles that Ramshaws group at Newcastle Uni-
U.K.) (9) present a promising option. of the cross-flow monoliths in Figure versity (Newcastle, U.K.) primarily is
In these reactors, one side of a com- 6, although the materials and fabrica- aimed at fast and very fast liquid/liq-
pact heat exchanger is made catalyti- tion methods used differ. The chan- uid reactions with large heat effect,
cally active, either by washcoating or nels in the plates of microchannel such as nitrations, sulfonations, and
by introducing catalytically active el- heat exchangers are usually around 1 polymerizations (e.g., styrene poly-
ements (such as pellets or structured mm or less wide, and are fabricated merization (14)). In SDRs, a very thin
packings). A ceramic cross-flow via silicon micromachining, deep X- (typically 100 m) layer of liquid
monolith structure developed by ray lithography, or nonlithographic moves on the surface of a disk spin-
Corning Inc. (Corning, NY) (10) micromachining. Over the past few ning at up to approximately 1,000
(Figure 6) also potentially can be rpm. At very short residence times
used as a catalytic reactor/heat ex- (typically 0.1 s), heat is efficiently re-
changer, e.g., for carrying out two moved from the reacting liquid at
chemical processes (exo- and en- heat-transfer rates reaching 10,000
dothermic) within one unit. Com- W/m2K. SDRs currently are being
pared to conventional fixed-bed reac- commercialized.
tors, such reactors offer much better Other reactors especially dedicated
heat-transfer conditions namely, to fast and very fast processes worth
heat-transfer coefficients typically of mentioning include: the supersonic
3,5007,500 W/m2K, and heat-trans- gas/liquid reactor developed at Prax-
fer areas of up to 2,200 m2. air Inc. (Danbury, CT) (15) for
gas/liquid systems and the jet-im-
Microreactors pingement reactor of NORAM Engi-
Even higher values of heat-trans- Figure 6. Concept of an in-line catalytic neering and Constructors (Vancouver,
fer coefficients than those in the HEX reactor (8). BC) (16,17) for liquid/liquid systems.
reactors can be achieved in microre-
actors. Here, values of up to 20,000 Figure 7.
W/m2K are reported (11). Microreac- Feed Schematic of the
tors are chemical reactors of extreme- spinning-disk
reactor.
ly small dimensions that usually have
a sandwich-like structure consisting Products
of a number of slices (layers) with
micromachined channels (10100 m
in dia.). The layers perform various Heat Exchange
functions, from mixing to catalytic
reaction, heat exchange, or separa-
tion. Integration of these various
functions within a single unit is one
of the most important advantages of
unit operation) that conventionally lower capital investment (30). Also, a membrane unit). Yet, practically no
would be performed in a separate reverse process to the one described large-scale industrial applications have
piece of equipment. A widely known above, that is, combination of reac- been reported so far. The primary rea-
example of integrating reaction and tion and condensation, has been stud- son for this most definitely is the rela-
heat transfer in a multifunctional unit ied for benzene oxidation to cyclo- tively high price of membrane units,
is the reverse-flow reactor (24). For hexane and for methanol synthesis although other factors, such as low
exothermic processes, the periodic (31,32). The number of processes in permeability as well as mechanical
flow reversal in such units allows for which reactive distillation has been and thermal fragileness, also play an
almost perfect utilization of the heat implemented on a commercial scale important role. Further developments
of reaction by keeping it within the is still quite limited but the poten- in the field of material engineering
catalyst bed and, after reversion of the tial of this technique definitely goes surely will change this picture.
flow direction, using it for preheating far beyond todays applications. Multifunctional reactors may inte-
the cold reactant gases. To date, re- Numerous research groups are in- grate not only reaction and heat trans-
verse-flow reactors have been used in vestigating other types of combined re- fer or reaction and separation but also
three industrial processes (24): SO2 actions and separations, such as reac- combine reaction and phase transi-
oxidation, total oxidation of hydrocar- tive extraction (33,34), reactive crystal- tion. A well-known example of such a
bons in off-gases, and NOx reduction. lization (35), and integration of reac- combination is reactive extrusion.
The recent introduction of inert pack- tion and sorption operations, for in- Reactive extruders are being increas-
ing for heat exchange (25) has lead to stance, in chromatographic reactors ingly used in the polymer industries.
a sandwich reactor; it consists of (36,37,38) and periodic separating re- They enable reactive processing of
three zones a catalyst bed between actors, which are a combination of a highly viscous materials without re-
two beds of packing of heat-accumu- pressure swing adsorber with a period- quiring the large amounts of solvents
lating material. The reverse-flow prin- ic flow-forced packed-bed reactor (39). that stirred-tank reactors do. Particu-
ciple also has been applied in rotating larly popular are twin-screw extrud-
monolith reactors, which are used in- Membrane reactors ers, which offer effective mixing, the
dustrially for removal of undesired Today, a huge research effort is de- possibility of operation at high pres-
components from gas streams and voted to membrane reactors (40). The sures and temperatures, plug-flow
continuous heat regeneration (26). membrane can play various functions characteristics, and capability of mul-
Studies also have been carried out on in such reactor systems. It, for in- tistaging. Most of the reactions car-
employing reversed-flow reactors for stance, can be used for selective in- ried out in extruders are single- or
endothermic processes (27). situ separation of the reaction prod- two-phase reactions. New types of
Reactive (catalytic) distillation is ucts, thus providing an advantageous extruders with catalyst immobilized
one of the better known examples of equilibrium shift. It also can be ap- on the surface of the screws, howev-
integrating reaction and separation, plied for a controlled distributed feed er, may allow carrying out three-
and is used commercially (28). In this of some of the reacting species, either phase catalytic reactions (47).
case, the multifunctional reactor is a to increase overall yield or selectivity Fuel cells present another example
distillation column filled with catalyt- of a process (e.g., in fixed-bed or of multifunctional reactor systems.
ically active packing. In the column, fluidized-bed membrane reactors Here, integration of chemical reaction
chemicals are converted on the cata- (41,42)) or to facilitate mass transfer and electric power generation takes
lyst while reaction products are con- (e.g., direct bubble-free oxygen sup- place (see, for instance, Ref. 48). Si-
tinuously separated by fractionation ply or dissolution in the liquid phase multaneous gas/solid reaction and
(thus overcoming equilibrium limita- via hollow-fiber membranes (43,44)). comminution in a multifunctional re-
tions). The catalyst used for reactive In addition, the membrane can enable actor also has been investigated (49).
distillation usually is incorporated in-situ separation of catalyst particles
into a fiberglass and wire-mesh sup- from reaction products (45)). Finally, Hybrid separations
porting structure, which also provides the membrane can incorporate catalyt- Many of the developments in this
liquid redistribution and disengage- ic material, thus itself becoming a area involve integration of mem-
ment of vapor. Structured catalysts, highly selective reaction-separation branes with another separation tech-
such as Sulzers KATAPAK, also are system. The scientific literature on cat- nique. In membrane absorption and
employed (29). The advantages of alytic membrane reactors is exception- stripping, the membrane serves as a
catalytic distillation units, besides the ally rich (see, for instance, Ref. 46) permeable barrier between the gas and
continuous removal of reaction prod- and includes many very interesting liquid phases. By using hollow-fiber
ucts and higher yields due to the ideas (such as heat- and mass-integrat- membrane modules, large mass-trans-
equilibrium shift, consist mainly of ed combination of hydrogenation and fer areas can be created, resulting in
reduced energy requirements and dehydrogenation processes in a single compact equipment. Besides, absorp-
Methyl
Acetate
Solvent Acetic
Distillation Methyl
Acid
Acetate
Extractive
Catalyst Distillation
Water Reactive
Distillation
Azeo Reaction
Reactive
Methanol Distillation
Distillation
Solvent
Entrainer
Water
Heavies
Conventional Task-Integrated
Water
Figure 9. Task-integrated methyl acetate column is much simpler than conventional plant. (Drawing courtesy of Eastman Chemical (76).
tion membranes offer operation inde- the membrane than in the pressure- some fine-chemical processes from
pendent of gas- and liquid flow rates, driven processes; batchwise to continuous operation.
without entrainment, flooding, chan- less membrane fouling, due to
neling, or foaming (50,51). larger pore size; and Use of alternative forms
Membrane distillation is probably potentially lower operating tem- and sources of energy
the best known hybrid, and is being peratures than in conventional evapo- Several unconventional processing
investigated worldwide (52,53). The ration or distillation, which may en- techniques that rely on alternative
technique is widely considered as an able processing of temperature-sensi- forms and sources of energy are of im-
alternative to reverse osmosis and tive materials. portance for process intensification.
evaporation. Membrane distillation Among hybrid separations not in- For instance, we already have dis-
basically consists of bringing a volving membranes, adsorptive dis- cussed the potential benefits of using
volatile component of a liquid feed tillation (55) offers interesting ad- centrifugal fields instead of gravitation-
stream through a porous membrane vantages over conventional methods. al ones in reactions and separations.
as a vapor and condensing it on the In this technique, a selective adsor- Among other techniques, research
other side into a permeate liquid. bent is added to a distillation mix- on sonochemistry (the use of ultra-
Temperature difference is the driving ture. This increases separation abili- sound as a source of energy for
force of the process. Foster et al. ty and may present an attractive op- chemical processing) appears to be
(54) name four basic advantages of tion in the separation of azeotropes the most advanced. Formation of mi-
membrane distillation: or close-boiling components. Ad- crobubbles (cavities) in the liquid re-
100% rejection of ions, macro- sorptive distillation can be used, for action medium via the action of ul-
molecules, colloids, cells, and other instance, for the removal of trace im- trasound waves has opened new pos-
nonvolatiles; purities in the manufacturing of fine sibilities for chemical syntheses.
lower operating pressure across chemicals; it may allow switching These cavities can be thought of as
14. Boodhoo, K. V. K., R. J. Jachuck, and C. 27. Kolios, G., and G. Eigenberger, Styrene
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Chem. Ind., Rotterdam, Netherlands Agen- and Installation of Efficient Energy Systems, tional Perspective, I. & E. C. Res., 38 (10),
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will disappear from plants because The role of education tion of three different processing tasks
of process intensification. They will To make these society-driven takes place via the water-wheel A that
give way to new task-integrated de- changes come true, the teaching of simultaneously supplies power to
vices. A spectacular example of such chemical engineering also will have crush ore in the crusher C, grind it in
task integration already applied on to undergo some essential revision. grinder K, and recover gold by mixing
commercial scale is the new methyl First, future chemical engineers will the ore with mercury in the three-
acetate process of Eastman Chemical have to be taught an integrated, task- stage system of stirred vessels O.
Co.; seven tasks have been integrat- oriented approach to plant design, And, perhaps only now at the
ed into a single piece of equipment not todays sequential, operation-ori- very end of our article, can we say
(77) as illustrated in Figure 9. A sin- ented one. (Eastmans process in Fig- what process intensification really
gle-unit hydrogen-peroxide distilla- ure 9 clearly illustrates the difference is. It is thinking progressively about
tion plant (Figure 10) developed by between these two approaches.) To processes and viewing them inte-
Sulzer (78) is another example of achieve this goal, the education of grally through the tasks they have to
such changes already taking place in future engineers must place much fulfill and the results they have to
industry. more stress on creative, nonschemat- deliver. CEP