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Documente Profesional
Documente Cultură
Process Intensification:
Transforming Chemical
Engineering
Emerging equipment, processing techniques, and
operational methods promise spectacular
improvements in process plants, markedly
Andrzej I. Stankiewicz, shrinking their size and dramatically boosting their
DSM Research/Delft University
of Technology efficiency. These developments may result in the
Jacob A. Moulijn, extinction of some traditional types of equipment,
Delft University of Technology
if not whole unit operations.
Process Intensification
Equipment Methods
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, Pacifi c 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 fl uxes 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-sive changers range from Å10,000 to
dispersion. Monolith channels are fully reactants. The scale at which processes Å35,000 W/m2K (4, 12).
separated from each other and, using batteries of multiple
therefore, the only heat transport microreactors become economically Rotating devices
mechanism is the conductivity through and technically feasible still needs to be Almost as high heat-transfer coef-
the monolith material. For highly determined, though. fi cients are achievable in the
exothermic gas-phase reac-tions, so- The geometrical confi guration of spinning disk reactor (SDR) (13).
called HEX reactors devel-oped by microchannel heat exchangers (stacked This unit (see Figure 7) developed by
BHR Group, Ltd. (Cranfi eld, U.K.) (9) cross-fl ow structures) resembles that of Ramshaw’s group at Newcastle Uni-
present a promising option. In these the cross-fl ow monoliths in Figure 6, versity (Newcastle, U.K.) primarily is
reactors, one side of a com-pact heat although the materials and fabrica-tion aimed at fast and very fast liquid/liq-
exchanger is made catalyti-cally active, methods used differ. The chan-nels in uid reactions with large heat effect,
either by washcoating or by introducing the plates of microchannel heat such as nitrations, sulfonations, and
catalytically active el-ements (such as exchangers are usually around 1 polymerizations (e.g., styrene poly-
pellets or structured packings). A mm or less wide, and are fabricated merization (14)). In SDRs, a very
ceramic cross-fl ow monolith structure via silicon micromachining, deep X- thin (typically 100 µ m) layer of
developed by Corning Inc. (Corning, ray lithography, or nonlithographic liquid moves on the surface of a disk
NY) (10) (Figure 6) also potentially can micromachining. Over the past few spin-ning at up to approximately
be used as a catalytic reactor/heat ex- 1,000 rpm. At very short residence
changer, e.g., for carrying out two times (typically 0.1 s), heat is
chemical processes (exo- and en- efficiently re-moved from the
dothermic) within one unit. Com-pared reacting liquid at heat-transfer rates
to conventional fi xed-bed reac-tors, reaching 10,000 W/m2K. SDRs
such reactors offer much better heat- currently are being commercialized.
transfer conditions — namely , heat- Other reactors especially dedicated
transfer coefficients typically of 3,500– to fast and very fast processes worth
7,500W/m2K, and heat-trans-fer areas mentioning include: the supersonic
of up to 2,200 m2. gas/liquid reactor developed at Prax-air
Inc. (Danbury, CT) (15) for gas/liquid
systems and the jet-im-pingement
Microreactors reactor of NORAM Engi-neering and
Even higher values of heat-trans- ■ Figure 6. Concept of an in-line Constructors (Vancouver, BC) (16,17)
fer coefficients than those in the HEX catalytic reactor (8). for liquid/liquid systems.
reactors can be achieved in microre-
actors. Here, values of up to 20,000 ■ Figure 7.
Feed
W/m2K are reported (11). Microreac- Schematic of
the spinning-
tors are chemical reactors of extreme- disk reactor.
ly small dimensions that usually have
a sandwich-like structure consisting Products
of a number of slices (layers) with
micromachined channels (10–100µ 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 defi nitely is the rela-
heat transfer in a multifunctional unit ied for benzene oxidation to cyclo- tively high price of membrane units,
is the reverse-fl ow 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 and
fl ow reversal in such units allows for which reactive distillation has been thermal fragileness, also play an
almost perfect utilization of the heat of implemented on a commercial scale is important role. Further developments in
reaction by keeping it within the still quite limited — but the poten - the fi eld of material engineering surely
catalyst bed and, after reversion of the tial of this technique defi nitely goes will change this picture.
fl ow direction, using it for preheating far beyond today’s 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-fl ow 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
bons in off-gases, and NOx reduction. lization (35), and integration of reac- a 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 a stance, in chromatographic reactors ingly used in the polymer industries.
“sandwich” reactor; it consists of three (36,37,38) and periodic separating re- They enable reactive processing of
zones — a catalyst bed between two actors, which are a combination of a highly viscous materials without re-
beds of packing of heat-accumu-lating pressure swing adsorber with a period- quiring the large amounts of solvents
material. The reverse-fl ow prin-ciple ic fl ow-forced packed-bed reactor (39). that stirred-tank reactors do. Particu-
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-fl ow
continuous heat regeneration (26). membrane can play various functions in characteristics, and capability of mul-
Studies also have been carried out on such reactor systems. It, for in-stance, tistaging. Most of the reactions car-
employing reversed-fl ow reactors for can be used for selective in-situ ried out in extruders are single- or
endothermic processes (27). separation of the reaction prod-ucts, two-phase reactions. New types of
Reactive (catalytic) distillation is thus providing an advantageous extruders with catalyst immobilized
one of the better known examples of equilibrium shift. It also can be ap-plied on the surface of the screws, howev-
integrating reaction and separation, and for a controlled distributed feed of er, may allow carrying out three-
is used commercially (28). In this case, some of the reacting species, either to phase catalytic reactions (47).
the multifunctional reactor is a increase overall yield or selectivity of a Fuel cells present another example
distillation column fi lled with catalyt- process (e.g., in fi xed-bed or fluidized- of multifunctional reactor systems.
ically active packing. In the column, bed membrane reactors (41,42)) or to Here, integration of chemical reaction
chemicals are converted on the cata- facilitate mass transfer (e.g., direct and electric power generation takes
lyst while reaction products are con- bubble-free oxygen sup-ply or place (see, for instance, Ref. 48). Si-
tinuously separated by fractionation dissolution in the liquid phase via multaneous gas/solid reaction and
(thus overcoming equilibrium limita- hollow-fi ber membranes (43,44)). In comminution in a multifunctional re-
tions). The catalyst used for reactive addition, the membrane can enable in- actor also has been investigated (49).
distillation usually is incorporated into situ separation of catalyst particles from
a fi berglass and wire-mesh sup-porting reaction products (45)). Finally, the Hybrid separations
structure, which also provides liquid membrane can incorporate catalyt-ic Many of the developments in this
redistribution and disengage-ment of material, thus itself becoming a highly area involve integration of mem-branes
vapor. Structured catalysts, such as selective reaction-separation system. with another separation tech-nique. In
Sulzer’s KATAPAK, also are The scientifi c literature on cat-alytic membrane absorption and stripping, the
employed (29). The advantages of membrane reactors is exception-ally membrane serves as a permeable
catalytic distillation units, besides the rich (see, for instance, Ref. 46) and barrier between the gas and liquid
continuous removal of reaction prod- includes many very interesting ideas phases. By using hollow-fi ber
ucts and higher yields due to the (such as heat- and mass-integrat-ed membrane modules, large mass-trans-
equilibrium shift, consist mainly of 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
Acid Distillation Methyl
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 fl ow rates, driven processes; batchwise to continuous operation.
without entrainment, fl ooding, 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 forms
technique is widely considered as an able processing of temperature-sensi- and sources of energy are of im-portance
alternative to reverse osmosis and tive materials. for process intensifi cation. For instance,
evaporation. Membrane distillation Among hybrid separations not in- we already have dis-cussed the potential
basically consists of bringing a volving membranes, adsorptive dis- benefi ts of using centrifugal fi elds
volatile component of a liquid feed tillation (55) offers interesting ad- instead of gravitation-al ones in reactions
stream through a porous membrane vantages over conventional methods. 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-ty sound as a source of energy for
force of the process. Foster et al. and may present an attractive op-tion chemical processing) appears to be
(54) name four basic advantages of in the separation of azeotropes or the most advanced. Formation of mi-
membrane distillation: 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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cy for Energy and the Env., Sittard, The Leafl et 2016/3.0/8.90/Br, Kraftanlagen Hei- pp. 3,715–3,737 (1999).
Netherlands (May 1998). delberg, Heidelberg, Germany (1990).
will disappear from plants because of The role of education tion of three different processing tasks
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 crush
vices. A spectacular example of such chemical engineering also will have ore in the crusher C, grind it in grinder
task integration already applied on to undergo some essential revision. K, and recover gold by mixing the ore
commercial scale is the new methyl First, future chemical engineers will with mercury in the three-stage system
acetate process of Eastman Chemical have to be taught an integrated, task- of stirred vessels O.
Co.; seven tasks have been integrat- oriented approach to plant design, not And, perhaps only now at the very
ed into a single piece of equipment today’s sequential, operation-ori- end of our article, can we say what
(77) as illustrated in Figure 9. A sin- ented one. (Eastman’s process in Fig- process intensification really is. It is
gle-unit hydrogen-peroxide distilla- ure 9 clearly illustrates the difference 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
CEP
industry. more stress on creative, nonschemat- deliver.
The CPI skyline also is likely to ic thinking, not confi ned to known
change. New, highly efficient devices types of equipment and methods. A. I. STANKIEWICZ is a senior researcher with
may replace tens-of-meters tall reactors Second, future chemical engineers DSM Research in Geleen, The Netherlands
and separation columns. And, plants in must gain a much deeper knowledge (31 46 4760820; Fax: 31 46 4760809; E-
mail: Andrzej.Stankiewicz@dsm-group.com)
which reactions take place underground and understanding of process chem-
and associate professor in the Industrial
in pipeline reactors and products are istry (and chemists must become Catalysis Section of Delft University of
separated in 1–2 m dia. rotating devices much more familiar with the related Technology, Delft,
are certainly conceivable. engineering issues) — because, in the The Netherlands (31 15 2785006,
Fax: 31 15 2784452, E-mail:
Will further developments in the highly efficient chemical process-es
A.Stankiewicz@stm.tudelft.nl).
CPI resemble those in the electronics of the coming decade, chemistry and He is author or co-author of over 60
industry and will process plants and engineering will be meeting each papers on chemical reaction engineering
equipment become increasingly other at the molecular level, not at the and industrial catalysis, and holds several
apparatus level as they do today. patents in the field. He received a PhD in
miniaturized as has happened in the fi
chemical engineering from the Industrial
elds of information and communi- Third, material engineering will play Chemistry Research Inst., Warsaw. He is
cation? The answer very much will an essential role in the development a member of AIChE.
depend upon the existence of suffi- of new chemical processes at the J. A. MOULIJN is professor of industrial
catalysis at Delft University of Technology,
ciently strong drivers to stimulate or molecular level (e.g., engineering of
Delft, The Netherlands (31 15 2785008; Fax:
force such changes. In case of infor- catalysts) and, therefore, will become 31 15 2784452; E-mail:
mation and communication, a signifi a much more important part of the J.A.Moulijn@stm.tudelft.nl). The editor
- cant number of such drivers existed chemical engineering curriculum. of five books, the author or co-author of
over 400 professional papers,
in the past, the cold war and the space Meeting these demands will re- and the holder of several international
race of the super powers to mention quire concerted effort and some patents in reactor design, zeolithic
only two. This led to revolu-tionary crucial cultural changes from uni- membranes, and catalysis development,
changes, particularly in mate-rials versities to find the new ways of he is a chief technical advisor to
technologies, that eventually brought the U. N. Devel. Org., and serves as
teaching chemical engineering and
European editor of Fuel Processing
to our desks computers much faster chemistry. But, these steps are es- Technology. He holds a PhD in
and more powerful than their sential if the CPI are to prosper and chemical engineering from the Univ. of
multistory-building-size ances-tors. realize industrial visions of com-pact, Amsterdam, and is a member of AIChE.
In the case of the CPI, the most efficient, sustainable technolo-gies
probable scenario is that society it- like the one recently presented by
self will spur radical changes. With DSM (79) (Figure 11) come true. Related Web Site
ever-increasing population density www.ncl.ac.uk/pin/ administered by the Dept.
of Chemical and Process Engineering of the
and growing environmental con- Epilogue: the
Univ. of Newcastle started up in April. This
sciousness in society, there will be no legacy of Agricola site, under the guidance of Colin Ramshaw,
room (literally and fi guratively) for Now, looking again at Figure 1, professor of intensive processing, will contain
the huge, inefficient chemical facto- we have a different perspective. What research and industry news, technical infor-
ries producing tons of wastes per ton Agricola showed in his woodcut is a mation, articles on new technologies, a direc-
of useful product. Miniaturization highly task-integrated and energy-ef- tory of equipment makers, plus links to other
and process intensifi cation in general fi cient continuous plant for gold re- resources for process intensification.
will become inevitable. covery! The energy-efficient integra-