Review

Received: 30 July 2013 Revised: 31 October 2013 Accepted article published: 6 November 2013 Published online in Wiley Online Library: 3 December 2013

(wileyonlinelibrary.com) DOI 10.1002/jctb.4262

Distillation technology – still young and full

of breakthrough opportunities
Anton A. Kiss∗

Abstract
Throughout history, distillation has been the most widespread separation method. However, despite its simplicity and
flexibility, distillation still remains very energy inefficient. Novel distillation concepts based on process intensification, can
deliver major benefits, not just in terms of significantly lower energy use, but also in reducing capital investment and improving
eco-efficiency. While very likely to remain the separation technology of choice for the next decades, there is no doubt that
distillation technology needs to make radical changes in order to meet the demands of the energy-conscious modern society.
This article aims to show that in spite of its long age, distillation technology is still young and full of breakthrough opportunities.
Moreover, it provides a broad overview of the recent developments in distillation based on process intensification principles,
for example heat pump assisted distillation (e.g. vapor compression or compression–resorption), heat-integrated distillation
column, membrane distillation, HiGee distillation, cyclic distillation, thermally coupled distillation systems (Petlyuk), dividing-
wall column, and reactive distillation. These developments as well as the future perspectives of distillation are discussed in
the context of changes towards a more energy efficient and sustainable chemical process industry. Several key examples are
also included to illustrate the astonishing potential of these new distillation concepts to significantly reduce the capital and
operating cost at industrial scale.

c 2013 Society of Chemical Industry

Keywords: heat pumps; HIDiC; dividing-wall column; membrane distillation; HiGee distillation; cyclic distillation; reactive distillation;
case studies; industrial examples

INTRODUCTION (exergy) losses related to the pressure drop, mass transfer (e.g.
Distillation is a physical process for the separation of liquid re-mixing in separations) and heat transfer (at
T > 0):7 – 10
mixtures, based on differences in the boiling points or relative
volatility of the constituent components. The art of distillation
Sdist = (SD + SB ) − SF < 0 (1)
is believed to have originated in China (∼800 BC) with early
dS = dQ/dt > 0 (2)
applications in the production of alcoholic beverages and the
concentration of essential oils from natural products.1 Over the
η =
Sdist / (
Sdist +
Sirrev ) (3)
centuries, the distillation technique was widely used, and the first
books on this topic appeared in Europe – Liber de arte distillandi Currently, distillation is the most widely used separation method
simplicia et composite (Das kleine Distillierbuch) by Hieronymus at industrial scale with over 40 000 columns in operation
Brunschwig in 1500, The Art of Distillation by John French in 1651, worldwide. Remarkable, almost every product on the market
and La rectification de l’alcool by Ernest Sorel in 1850.2 contains chemicals that went through a distillation column. Along
Originally, distillation was carried out batchwise by heating a with the conventional distillation of binary and multi-component
liquid mixture in a still/pot and condensing the vapor that boiled mixtures, several additional methods were developed for breaking
off, by air cooling or water-cooled condensers (Fig. 1, left). Actually, azeotropes or close boiling mixtures: pressure swing distillation
distillation comes from the Latin word destillare that means ‘drip- (PSD), azeotropic and extractive distillation – topics covered in
ping down’ (condense), referring to the dripping of the condensed several books and reviews.3 – 6,11 – 18
vapor product from the condenser. In the past century, distillation Nowadays, the chemical process industry is undergoing a
became the dominant separation process at industrial scale follow- radical transformation towards higher energy efficiency, creation
ing the development of the petroleum and chemical industries. of value from waste, efficient valorization of water and materials,
Presently, distillation is carried out mainly continuously (Fig. 1, and eventually a truly sustainable bio-based economy. Process
right) in vertical hollow columns/towers, with associated piping,
heat exchangers, pumps, storage vessels, support structures.3 – 6
Considering the product and feed streams, the separation by ∗
Correspondence to: A. A. Kiss, AkzoNobel Research, Development and
distillation requires a decrease of the entropy (
Sdist < 0) so it can Innovation, Process Technology ECG, Zutphenseweg 10, 7418 AJ Deventer,
The Netherlands. E-mail: Tony.Kiss@gmail.com
not happen spontaneously. Consequently, addition of heat is used
in practice to make this process thermodynamically possible. Still, AkzoNobel Research, Development and Innovation, Process Technology ECG,
479

the overall efficiency of distillation is rather low due to irreversible Zutphenseweg 10, 7418 AJ Deventer, The Netherlands

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c 2013 Society of Chemical Industry
 www.soci.org AA Kiss

Condenser
Overhead
vapor Reflux drum
Condenser

Reflux drum NT
Distillate
Reflux
Rectifying D, xD
R, xD
Distillate section LR
Reflux VR
Feed NF Stages

Column F, z, q
LS
Stripping
Receivers 3 VS
section
2 Reboiler
1
Steam
Thermal energy
Condensate
Bottoms
Pot / Still / Reboiler B, xB

Figure 1. Schematics of batch distillation (left) and continuous distillation column (right).

intensification (PI) technologies can drastically reduce the overall In the quest for a bio-based economy that poses new separation
costs and improve the sustainability of many industrial processes, challenges (e.g. diluted aqueous solutions with azeotropes), hybrid
including distillation based separations. Process intensification is PI technologies can lead the way to more efficient integrated
a process design philosophy that improves the process flexibility, distillation processes.6,23,24 Therefore, we believe that in spite
product quality, speed to market and inherent safety, with the of its long age, distillation technology is still young and full of
added benefit of reduced environmental footprint.19 The main breakthrough opportunities, with many exciting developments
principles of process intensification were well described in the going on. Note that this overview primarily cites key review papers
recent research paper of van Gerven and Stankiewicz,20 as follows: and reference books – mainly for brevity reasons, but also to give
1 Maximize the effectiveness of intra- and inter-molecular events. the reader a good starting point for further reading on the topics
2 Give each molecule the same processing experience. 3 Optimize presented here.
the driving forces at every scale and maximize the specific surface
area to which these forces apply. 4 Maximize the synergistic
effects from partial processes. These principles are not entirely PROBLEM STATEMENT
new to chemical engineering, but in process intensification, they In spite of its wide use, distillation has also key drawbacks in
are seen as explicit goals aimed to be reached by intensified terms of high capital costs, due to the large equipment used, and
processes. Moreover, the PI interpretation of these principles often significant operating costs due to the low energy efficiency. In
goes beyond the boundaries of the classical chemical engineering fact, distillation accounts for over 40% of the energy used in the
approach. A completely intensified process is successful in realizing chemical process industry and over 95% of the energy used in
all these process intensification principles, by making use of separation processes.10,25 The main problem is the use of costly
one or more fundamental approaches in four domains: spatial high quality energy (typically steam) that is rejected at a low
(structure), thermodynamic (energy), functional (synergy), and temperature in the condenser. Practically, the thermodynamic
temporal (time).20 In addition, it is worth noting that the PI efficiency of distillation is quite low: from 18% in air separation
technologies also adhere to the guiding principles for conceptual units, to 12% in crude units and only 5% for ethylene and
design of safe chemical processes, thus providing inherent safety propylene production.26 Therefore, higher energy efficiency and
or safety-by-design. lower costs are a must win battle for the players in the chemical
Freund and Sundmacher21 claimed that knowledge of the process industry. Note that when discussing efficiency there are no
existing apparatuses that perform unit operations immediately unique answers, as the required minimum energy and the possible
narrows our creativity in search for new solutions, and they energy saving depends on operating pressures and temperature
proposed to shift from unit apparatuses to functions. A function span. Moreover, the available heat and cooling sources within a
(or a fundamental task) describes what should happen, and not particular chemical plant may also have an impact on the selection
how it should happen. Some examples of functions include: of the most suitable distillation technology.
mass movement, chemical reaction, mixing, separation, heat Several developments of distillation aim to solve the problems
transfer, phase change, temperature change, pressure change, related to the high investment and operating costs, by tackling
form change, etc. An essential function is a function that is needed various aspects: use of other energy sources (e.g. solar energy),27
and unavoidable – e.g. if the feedstock is component A and the upgrade the discharged energy to use it for driving the reboiler (by
product is B, then chemical reaction is an essential function that heat pumps), use of high gravity forces to reduce the equipment
is required. Notably, the functional based design of chemical size, combine distillation with reaction or other separations
processes consists of fewer steps, allows the efficient integration (membrane separation or distillation), use a different operating
of more functions into one piece of equipment, and provides mode based on separate phase movement to increase the
more freedom of equipment design – thus paving the way to separation efficiency, or integrate more functions into a single
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engineering for sustainability.22 operating unit.6 This paper gives an overview of the recent

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Distillation technology www.soci.org

developments and the future perspectives of distillation, in the imply using more theoretical stages – practically possible within
context of changes towards a more energy efficient and sustainable the same space by using more efficient internals – in order to
chemical process industry. reduce the energy usage by about 10–15%.28
• Internal design optimization. The physical and transport
properties of column internals (e.g. packing and trays) have
ADVANCED DISTILLATION TECHNOLOGIES a strong effect on the column efficiency. The essence of a
The efficiency of distillation processes can be improved by using smart design is to take effective steps in order to maximize
‘green’ and ‘smart’ column designs. In addition to applying the the efficiency of column internals and to get the most out
principles of green design (e.g. efficient use of materials, energy of what is available.28 Packing designs have fewer degrees
and water conservation, safe and healthy surroundings), the of freedom than tray designs. After choosing the appropriate
smart designs consider approaches that use minimal resources liquid distributor and packing type that is best for a particular
(materials, feedstocks, energy, effort) over the process lifetime and process, one must determine the packing size that optimizes
that are also safe and environmentally sound.28 The design of a the bed height vs. column diameter. In the case of trays, the
distillation column and its internals typically involves a trade-off large number of variables that can be changed allows more
between capacity and efficiency. The smart design of distillation flexibility in design. Often each set of operating conditions has
columns involves an approach on three levels: a different optimal tray design.

• Construction materials and resources. Great care is taken The following sections describe the advanced distillation
to minimize the quantity of construction materials used, technologies that were able to, or have the potential to
considering the cradle-to-grave resources consumed by the make a strong industrial impact. Moreover, all these distillation
system, from the column construction through its lifespan. technologies still undergo further developments in terms of
The columns are now constructed with the smallest diameter process design, control and applications.
and lowest practical height. Moreover, the internals (trays and
packing) are made as thin as possible, while meeting mechanical Heat pump assisted distillation
needs. Considering the long life of distillation columns (typically In order to perform the separation task, distillation requires the
over 20 years), nowadays the equipment manufacturers and input of high quality energy in the reboiler while also rejecting
engineering companies strive to use as little material as possible a similar amount of heat at lower temperature, in the condenser.
over a lifespan that is as long as possible.28 Several heat pump concepts have been proposed to upgrade
• Process design and configuration. The focus of distillation is to the level of the energy discharged and re-use it in order to
obtain the highest yield with the least amount of energy. This reduce the consumption of valuable utilities.29,30 The temperature
can be achieved by sequencing of multiple columns, modifying lift can be related to the temperature difference between the
the process configuration (e.g. heat integration, heat pumps, heat source (condenser) and heat sink (reboiler), which in turn is
new heat-transfer media, other internals, optimized design determined by the product cuts that are separated. In practice, the
and advanced control strategies). A review of stages vs energy decision to use heat pumps for distillation should follow a careful
(Fig. 2) – or column height vs diameter – is an integral part of the investigation of heat integration opportunities based on Pinch
column design and configuration process.6 The classic designs analysis. Figure 3 illustrates the main configurations of heat-pump
are located to maximize flexibility in design and operation, while assisted distillation technologies, described hereafter.6
reducing sensitivity to process changes. Smarter column designs Vapor compression (VC) is a classical heat pump design proven
already at industrial scale. It uses a specific fluid as heat transfer
Iso-purity curves
medium that runs between the heat source and sink through a
Locus of points for a given separation pipeline.31 A compressor is installed in between to provide the
required work input, while a flash valve closes the cycle. Since
all these elements are external to the separation process, the
distillation column does not require major modifications, except
Number of theoretical stages

Smart designs for the adjustments in heat exchangers for the change in utilities.
VC is particularly beneficial when dealing with corrosive or fouling
Conventional designs compounds. However, the design is dependent on the ability of
the heat transfer fluid to meet the operational, environmental and
safety requirements. For most applications, there is no adequate
alternative – and even when an acceptable working fluid is found,
the energy savings are not always translated into overall economic
savings.32 Moreover, the compressors are quite expensive and
hard-to-maintain equipment, and the inefficiencies in obtaining
Nmin mechanical energy (work) impact heavily the total energy costs.29
Mechanical vapor recompression (MVR) is a state-of-the-art
Minimum number of stages
industrial system for binary distillation, being widely applied in
separation of close boiling components.33 In such a system, the
Minimum reflux ratio
top vapor is used as heat transfer medium, being fed directly
low RRmin Reflux ratio high to the compressor. Accordingly, the heat pump also performs
the function of the condenser, thus saving one heat exchanger
Figure 2. Trade-off between capital (stages) and operating (reflux ratio, compared with the classic alternative. Moreover, it avoids the
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energy) costs. need to cool the heat transfer fluid below the boiling point of the

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 www.soci.org AA Kiss

Top Top
Steam
Top Top
Steam
Feed Feed Feed
Feed DC DC DC
DC

Bottom Bottom Bottom Bottom

Vapor Compression (VC) Mechanical Vapor Thermal Vapor Absorption Heat Pump (AHP)
Recompression (MVR) Recompression (TVR)

Top
Driver
Top
Feed
Feed DC
DC

Bottom
Bottom
Compression-Resorption Thermo-Acoustic Heat Integrated Distillation
Heat Pump (CRHP) Heat Pump (TAHP) Column (HIDiC)

Figure 3. Heat pump assisted distillation (HPAD) – main configurations.

top product – an issue of importance in the VC scheme for heat implementations of AHP suitable for distillation or multi-stage
transfer purposes. Notably, MVR features slightly higher efficiency evaporation processes.29 The key unit of AHP is the steam
and lower investment costs than VC. But MVR does not tackle driven desorber that separates the absorption pair. One of the
directly the main drawback of VC: the economic penalty of using components condenses in the reboiler of the distillation column,
a compressor. Similarly, the distillate still has to meet at least and then it is flashed to cool down the condenser. Afterward, it is
the operational requirements for the heat transfer medium, not to mixed with the other component from the regenerator, to deliver
mention the criteria for safe and economic compressor operations. heat in the reboiler through exothermic absorption. The resulting
Consequently, all these constraints severely limit the application liquid is then pressurized and heated to displace the equilibrium
window of MVR technology. and the whole cycle is repeated. AHP is preferred as it avoids the
Thermal vapor recompression (TVR) is a variant of the MVR, drawbacks of using a compressor as driver for the heat pump.
in which the compressor is replaced by a steam ejector as work However, the use of five heat exchangers gives AHP a very pricy
input mechanism. The steam ejector uses the Venturi effect to installation cost and therefore long payback times.35
obtain mechanical energy from steam injection into a special Compression–resorption heat pump (CRHP) – also called
variable diameter pipeline.34 This makes TVR a robust design with hybrid heat pump – is a recent approach used to take advantage
reduced capital and maintenance expenditures, as there are no of thermo-chemical sorption processes. CHRP can achieve high
rotating pieces involved – hence it comes as no surprise that TVR temperature levels and lifts, with relatively high coefficient of
has been widely implemented in industry. However, the steam performance (COP). Note that the COP is defined as the ratio
ejector has a relatively low efficiency in converting mechanical between the amount of heat upgraded (Qb ) and the HP energy
energy. Moreover, the design of the steam ejector is crucial in requirements (W): COP = (Qb /W) ≤ (Treb /
Tb ). CHRP uses the VC
achieving economical operation. There are large changes in steam scheme in which the working fluid is replaced by an absorption
consumption even at small deviations from the optimal operating pair.29 When the vapor zeotropic mixture approaches the reboiler,
point. Notably, the steam input is mixed with the distillate to gen- the condensation and absorption process run at the same time,
erate the required pressure. As steam is being added to the vapor thus enhancing the heat transfer. This gives CRHP enhanced
distillate, it is clear that the applications of TVR are mostly used overall efficiency and reduced energy requirements – a critical
for systems producing water as top product. In theory, the motive issue for economic operations over wider temperature ranges.
fluid for the ejector can be (part of) the distillate flow, which could After the reboiler, the rich mixture is then flashed to take heat
be boiled and used to pressurize the vapor to the pressure level from the condenser, evaporating both components from the
required in the reboiler. Nevertheless, such applications are rarely working pair. The evaporation in the desorber is incomplete so
encountered due to the potential heat transfer losses. An alterna- that solution recirculation between the desorber and the resorber
tive to MVR and TVR is the self-heat recuperation technology, but and/or wet compression is possible. The hybrid wet compression
adding two compressors leads to very long payback times.29 (HWC) term is used for the cycles where all the solution is sent to
Absorption heat pump (AHP) considers thermo-chemical con- the compressor avoiding the use of a solution pump. Nonetheless,
version to enhance operational efficiency. In this case, absorption solving the issue of wet compression is of crucial importance for
pairs are used as heat transfer fluids (e.g ammonia and water, or the wider implementation of CRHP. At the moment, the issue is
lithium bromide and water). AHP is a known cycle, widely applied still under research at TU Delft (NL), with already successful pilot
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in refrigeration – but there are also standalone (pilot plant) scale implementations of standalone CRHP in place.29,30

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The advantages of CHRP are related to the use of thermo-acoustic device that uses high-amplitude sound waves to
environmentally-friendly refrigerants – such as water, ammonia pump heat from one place to another.38,39 The TA device consists
and CO2 – that can significantly contribute to the improvement of heat exchangers, a resonator, and a regenerator (on traveling
of the performance of heating processes. Specifically for industrial wave devices) or stack (on standing wave devices). Depending
heating processes CHRP allows energy performance gains of on the type of engine, a driver or loudspeaker might be used
more than 20% as compared with VC. The use of a mixture as well to generate sound waves. To limit the space used, an
allows lower pressure levels, and condensation and evaporation at electric driver (linear motor) generates the acoustic power cased
gliding temperatures – which can result in higher efficiency. Wet inside a resonator, the temperature lifts being determined by the
compression has the effect of suppressing vapor superheating, size of resonator, as well as the properties and pressure of the
and it can also improve the heat pump efficiency. Ammonia–water acoustic medium. The resonator – housing the TA engine and the
mixtures can be used as efficient working fluids in CHRP, showing TA heat pump – determines the operating frequency, acts as a
a number of advantages: higher COP because of the use of non- pressure vessel and it transports the acoustic power between the
isothermal phase transition of the mixture in the heat exchangers components.37 The noise levels are similar to the current industrial
at constant pressure; the mixture allows the achievement of high standards (e.g. below 85 db), and since the medium used is a gas
temperature operation at relatively low operating pressures; the (air, noble gas – e.g. helium), the system complies with the safety
cycle can be designed to show a temperature glide in the resorber and environmental regulations, while having no limitations in its
that corresponds to the temperature glide of the industrial flow applications – it can be applied down to cryogenic temperatures,
that has to be heated; and for specific operating conditions the with temperature lifts of up to 100 ◦ C or even more.36,40,41
performance is significantly better than for the vapor compression The most important applications of heat pumps at pilot and
cycle.29,30 industrial scale are listed in Table 1,6 while many others are
Thermo-acoustic heat pump (TAHP) is the frontrunner in reported in the literature. Major benefits are possible in terms of
using a different mechanism for the work input. Although it is a primary energy savings, and total annual costs – in the range of
relatively new technology, the proof-of-principle stage has been 20–80%.29 Recently, a comparison of heat pumps and a technology
successfully completed – with scaling up currently undergoing selection scheme were reported, taking into account not only
intense efforts at ECN.29,36,37 TAHP features a wide applicability heat pump assisted technologies but also other energy efficient
range, much larger than other heat pumps. Basically, TAHP is a distillation technologies.29,30

Table 1. Efficiency indicators of heat pump assisted technologies29

Technology Separation task
Tb [K]
Tlift [K] COP PES [%]
TAC [%] Remarks

AHP Butane-Isobutane 15 25 1.9 47 −42 PBT = 0.9

AHP Water-Acetic acid 55 65 1.7 40 −12 PBT = 7.1
CHRP Steam production 10 30 9.1 78 – –
CRHP Benzene-Toluene 30 <30 8.3 76 – –
HIDIC n-pentane-cyclo-pentane 9 20 10.3 71 – –
HIDIC Cyclohexane-n-heptane 17 33 9.6 75 −62 PBT = 1.8
HIDIC Propane-Propylene 7.7 10.9 10.0 80 −72 PBT = 1.2
HIDIC Methanol–water 35 55 12.9 41 –
HIDIC Benzene-Toluene 30 4.0 46 −46 PBT = 0.9
HIDIC Acetic acid dehydration 35 55 3.2 27 – –
MVR 1butene-nbutane 10 5.5 63 −60 PBT = 0.6
MVR Propane-Propylene 7.6 11.8 – −60% CO2
MVR Benzene-Toluene 30 35 6.7 70 – –
MVR Butane-Isobutane 15 20 6.4 69 −63 PBT = 1.1
MVR Butane-Isobutane 12.9 35.8 7.2 72 −64 PBT = 0.3
MVR Propane-Propylene 7.7 24.9 7.5 73 −65 PBT = 1.4
MVR Acetic acid dehydration 35 55 8.4 50 – –
MVR Methanol–water 35 40 6.6 69 −67 PBT = 0.7
TAHP Methanol–water 35 45 2.0 0 – –
TAHP Methanol–water 35 55 2.3 14 – –
TVR Methanol–water 35 40 1.1 23 −19 PBT = 1.5
VC Methanol–water 35 45 3.0 33 −29 PBT = 2.5
VC 1butene-nbutane 10 20 6.2 67 −57 PBT = 1.6
VC Methanol–water 35 45 4.1 50 – –
VC Methanol–water 35 55 3.1 34 – –
VC Methanol–water 35 43 5.0 60 −57 PBT = 0.9

Primary energy savings (PES) are the yearly savings of primary energy compared with the primary energy requirements of a conventional column;
PBT is the simple payback time (assuming a plant lifetime of 10 years; primary energy cost = ¤30 MWh-1 ; electrical energy cost = ¤65 MWh-1 ; boiler
efficiency = 0.85; efficiency of electricity conversion = 0.42; investments as proposed in papers). Negative
TAC means savings;
Tb is given at the
pressure reported in the reference.
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Downcomer
Parallel columns
Top Top (Haselden, 1977 –US Patent) Heat

distillation columns
Heat exchanging
panel
Feed
Partitioning wall column
Stripper

Heat

Rectifier
(Seader, 1980 –US Patent) Rectifying

Rectifier
Feed

Stripper

Heat
Stripping
Concentric column
Bottom (Govind, 1987 –US Patent)
Downcomer
Bottom

heat exchangers
Plate-fin column

Fractionating
(Tung, 1986)
Rectifying Heat
Top
panel
Feed Feed Shell & tube column

Rectifier
(Aso, 1998 –US Patent) Stripping

Heat
Top

Stripper
Stripper

Figure 5. Proposed configurations for HIDiC (left). Placement of heat

Rectifier

transfer panels inthe rectifying or stripping section of a HIDiC (right).

Heat

Bottom Bottom affect the performance of a HIDiC. Consequently, an important

research task during recent years was the development of more
Figure 4. Heat integrated distillation column (HIDiC) – alternative appropriate configurations, such as: multi-tube and multi-shell,
configurations. plate-type or even structured-packing HIDiC. 45,47,48 The current
directions of development are illustrated in Fig. 5:6 fractionating
heat exchangers (shell-and-tube, plate-fin), or heat exchanging
Heat integrated distillation column
distillation columns (e.g. concentric columns, parallel columns,
The heat integrated distillation column (HIDiC) is the most radical
partitioning-wall columns). Moreover, research and development
approach to heat pump design, making use of internal heat
on HIDiC configurations has so far primarily been confined to the
integration.42 – 47 Instead of using a single point heat source and separation of binary mixtures. Considering that multi-component
sink, the whole rectifying section of a distillation column becomes mixture separations represent a major application of distillation
the heat source, while the stripping part of the distillation column columns, the development of a corresponding HIDiC technol-
acts as a heat sink – thus providing greater potential for energy ogy is an important and extremely challenging topic for future
savings.29 Moreover, the problem of different sizes for rectifying work – especially if HIDiC becomes associated with other tech-
and stripping sections can be conveniently tackled by using one nologies – such as dividing-wall column or reactive distillation.6
of the alternative HIDiC configurations – as illustrated in Fig. 4.6
The internal heat integration enhances the reachable coefficient
of performance, because the required temperature difference for Membrane distillation
heat transfer is kept low with gliding temperatures across both Membrane distillation (MD) is an emerging technology for sep-
parts. The work input is provided by a compressor installed at the arations typically performed by conventional processes such as
top outlet of the stripper section, while the heat pump cycle is distillation or reverse osmosis (RO). Compared with other mem-
closed by the valve flashing the liquid bottom outlet of the rectifier brane technologies, in the case of MD the driving force is the
section. The practical success of HIDiC technology relies on good difference in vapor pressure across the hydrophobic membrane,
hardware performance for both heat and mass transfer tasks, at rather than the total pressure.50 Even though other membrane sep-
the same time.8,48 arations are applied in the petrochemical industry,51 membrane
Although HIDiC claims among the highest energy savings pos- distillation is especially useful for applications involving bulk water
sible in distillation, the capital investment costs are higher than for removal, such as seawater and brackish water desalination, process
conventional distillation – mainly due to the use of an additional water treatment and water purification.52 – 55 Similar hybrid separa-
compressor and a more complex configuration required for the tion methods based on membrane technology are pervaporation
enhanced heat transfer.45 Both thermodynamics and bench-scale (also known as pervaporative separation) which is used for the
experimental evaluations proved that HIDiC has much higher separation of mixtures of liquids by partial vaporization through a
energy efficiency than conventional distillation columns for close- (non-)porous membrane, and vapor permeation (also called imbu-
boiling components separations. Several simulation studies and ing) which is the penetration of a vapor permeate through a solid.56
experimental evaluations have further confirmed that the process Membrane distillation is a thermally-driven separation process
can be operated very smoothly, with no control difficulties.48,49 possible due to phase change. The liquid feed is in direct
A number of important issues must be considered during the contact with one of the membrane sides and does not penetrate
HIDiC design, for example, flexibility to changes in the operating inside the dry pores. Basically, the hydrophobic nature of the
conditions, influence of an impurity or a third component, and pro- membrane prevents the hydrophilic liquid from entering the
cess dynamics and operation. These impose strict constraints on pores due to the presence of surface tension forces. Consequently,
the energy efficiency that can be potentially achieved by a HIDiC liquid–vapor interfaces are formed at the entrance of the
system. Therefore, trade-off between process design economics membrane pores. The driving force of membrane distillation is
and process operation appears to be very important and it has to the trans-membrane vapor pressure difference (which relates to a
be carried out with great caution. It is worth noting that among the temperature difference) between the porous hydrophobic surfaces
design and the operating variables, the compression ratio and the of the membrane. Membrane distillation is actually claimed to be
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heat transfer coefficient and area (U and A) are the ones that most a rather cost effective separation process when alternative sources

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Feed in Permeate out Feed in Coolant out typically lower than for other membrane distillation configurations.
Air gap In addition, AGMD is more versatile than DCMD because permeate
is condensed on a chilled surface, and not directly by the ‘cold’
Condensing
plate permeate. While in the DCMD configuration the permeate must
Membrane
Membrane be diluted to prevent membrane wetting, in the case of AGMD the
concentration of the condensed permeate is not a concern since
it does not come into contact with the membrane.50,62
Feed out Permeate in Feed out Coolant in
Product
Direct Contact Permeate-gap membrane distillation (PGMD)
Membrane Distillation (DCMD) Air Gap Membrane
Distillation (AGMD) This membrane distillation configuration is an enhancement of
DCMD, in which a third channel is introduced by an additional
Feed in
Sweep gas out
Feed in non-permeable foil.62 A key benefit of PGMD is separation of the
Vacuum
distillate (permeate) from coolant, as the permeate channel is sep-
arated from the condenser channel by a condensation surface. As a
Condenser Condenser
Permeate
consequence, the coolant can be any other liquid, such as cold feed
Permeate
Membrane Membrane water. Practically, this offers the opportunity to integrate PGMD
with an efficient heat recovery system. Compared with DCMD, the
Feed out PGMD configuration uses the feed water directly as cooling liquid
Sweep gas in Feed out inside the module, thus it requires only one heat exchanger to
Sweeping Gas Membrane Vacuum Membrane heat the feed before entering the evaporator.62 Still, a drawback
Distillation (SGMD) Distillation (VMD)
of PGMD is the low flow velocity of the distillate in the permeate
Figure 6. Membrane distillation configurations. gap, as it leads to poor heat conduction from the membrane
surface to the condenser wall. Compared with AGMD, a higher
surface related permeate output is achieved as the mass flow is not
of energy (geothermal and solar) or waste water are used.57,58 The
additionally inhibited by the diffusion resistance of an air layer.63
most common technologies are shown in Fig. 6 and described
hereafter.55,59,60 Note that the components that pass through the
membrane are known as permeate, while the components that do Sweeping gas membrane distillation (SGMD)
not pass through are known as retentate. Also known as air stripping, SGMD uses a channel configuration
with an empty gap on the permeate side (same as in AGMD). An
inert gas is used to sweep the vapor at the permeate membrane
Direct contact membrane distillation (DCMD)
side to condense outside the membrane module. Just as for
The hot solution (feed) is in direct contact with the hot membrane AGMD, there is a gas barrier to reduce the heat loss, but this
side surface, so evaporation takes place at the feed membrane is not stationary – this enhances the mass transfer coefficient.
surface. The vapor is transported to the permeate side due The SGMD configuration is very useful for removing volatile
to the vapor pressure difference across the membrane, and compounds from aqueous solutions, but the main drawback
condenses inside the membrane module. Since the membrane is that a small volume of permeate diffuses in a large sweep
is hydrophobic, the feed cannot penetrate the membrane (only gas volume, thus requiring a large condenser.55,60 The SGMD
gas phase exists inside the membrane pores). DCMD is the process combines the low conductive heat loss of AGMD with
simplest and most studied configuration. However, the heat lost the reduced mass transfer resistance of DCMD. In addition, AGMD
by conduction through the membrane is higher than in other and SGMD can be combined in a process called thermostatic
configurations. Practically, DCMD is best suited for applications in sweeping gas membrane distillation (TSGMD). The increase of
which water is the major permeate component, and where the the gas temperature can be minimized by using a cold wall in
aqueous solution does not contain non-volatile components.61 the permeate side. The inert gas circulates at almost constant
Among all the membrane distillation configurations, characterized temperature in the cold chamber and collects the vapor that
by the mode of vapor recovery in the permeate side, DCMD is the permeates through the membrane.62 Vapor is partly condensed
simplest to operate and the distillation process can be carried over the condensation surface (AGMD), the rest being condensed
out in any desired membrane configuration, e.g. flat sheet, spiral outside the cell by an external condenser (SGMD).
wound, capillaries or even hollow fibers.55,60
Vacuum membrane distillation (VMD)
Air gap membrane distillation (AGMD) VMD is based on an air gap channel configuration. The vapor
The evaporator channel is similar to that in DCMD, whereas the per- passes through the membrane, and then it is sucked out of the
meate gap lies between the membrane and a cooled walling and is permeate channel (using a vacuum pump) and condenses outside
filled with air. The feed solution is in direct contact with the hot side the module, just as in the SGMD. The heat lost by conduction
of the membrane surface only. Stagnant air is introduced between is negligible, and this is considered a great advantage.50,55,64
the membrane and the condensation surface. The vapor crosses Note that the VMD process is similar to and often confused with
the air gap to condense over the cold surface inside the mem- pervaporation.65 The key difference between these technologies
brane cell. Since the permeate fluids are not in direct contact with is the role played by the membrane in the separation. For VMD
the membrane surface, AGMD can be applied to remove volatile membrane wetting is avoided, whereas for pervaporation the
components from aqueous solutions. Also, by placing an air gap transport is based on a solution-diffusion mechanism and the
between permeate side and condensing surface, the conductive membrane is thus preferentially wetted by one of the components.
heat transfer resistance is increased, so less heat is lost. The trade- VMD can be applied to remove organic components from aqueous
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off is the increase of mass transfer resistance, thus AGMD fluxes are solutions.50,55

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Liquid
inlet Condenser

Casing Distillate
Liquid Reflux
distributor Vapor
outlet Rectification

Vapor
inlet Feed Liquid Vapor

Stripping
Packed rotor Vapor

Dynamic seal
Reboiler
Liquid
Liquid
outlet Bottoms
Rotor shaft
Figure 7. Rotating packed-bed (left) and HiGee distillation using RPB (right).

Vacuum multi-effect membrane distillation (V-MEMD) HiGee distillation uses the rotating packed bed (RPB) concept
This is a more integrated membrane distillation configuration in a high-gravity field (100–1000 g) technology – claiming HETP
that can provide similar energy savings as multi-effect distillation values as low as 1–2 cm, about 3–6 times higher throughput and
(MED) at lower investment costs, while being applicable also at an equipment volume reduction of 2–3 orders of magnitude lower
smaller scales.64 A typical module (e.g. the memsys brand V-MEMD) compared with that of conventional packed columns.19,67 – 70
consists of a steam raiser, evaporation–condensation stages, Figure 7 shows a schematic diagram of a typical rotating packed
and a condenser. Each stage recovers the heat of condensation, bed with a vertical axis,71 usable in a distillation setup.70 The rotor
providing a multiple-effect design. Distillate is produced in each is an annular, cylindrical packed bed housed in a casing and driven
evaporation–condensation stage and in the condenser.64 by a motor. The rotor is made up of diverse porous media, such as
The selection of a certain type of membrane distillation wound wire mesh, foam metal, and corrugated sheet metal. The
configuration depends upon the flux, volatility and the permeate liquid is fed onto the packing at the inner periphery, through a
composition. SGMD and VMD configurations are usually used stationary distributor located at the eye of the rotor, and it flows
to remove volatile organics or dissolved gases from aqueous over the packing radially outward by virtue of the centrifugal force
solutions, while AGMD (most versatile MD configuration) and as thin films, rivulets and droplets, or films covering the pores of the
DCMD (least equipment and simplest to operate) are best suited packing – depending on the type of packing, the gas/liquid flow
for applications where water is the permeating flux.55,60 In all rates, and the angular velocity. The liquid leaves the packing as a
membrane distillation configurations, water and the volatile solute shower of droplets, which is collected by the casing wall and runs
evaporate from the liquid–vapor interface on the feed side of the downwards along the walls by the action of gravity, leaving the
membrane, then diffuse and/or convect across the membrane, casing. The gas/vapor is tangentially introduced into the casing,
being afterwards condensed or removed from the membrane entering the packing at the outer periphery, and is forced to flow
module as vapor on the permeate side. Note that in all membrane radially inward countercurrent to the liquid by pressure driving
distillation configurations, there are several membrane parameters force. The gas leaves the packing at the eye of the rotor through
affecting the processes: membrane material (e.g. polypropylene, the outlet pipe.70
polyvinylidene fluoride and polytetrafluoroethylene), liquid entry
The main component of HiGee devices is the rotor, the structure
pressure (wetting pressure), membrane thickness, membrane
of which determines the characteristics of different devices. A brief
porosity, pore size and pore tortuosity, as well as thermal
description of the types of rotating beds is given hereafter:19,67,68
conductivity – see also the recent reviews.54,55,59,60,62 Moreover,
membrane distillation may also result in a dramatic increase of • Waveform disks – The rotor contains a series of concentric
the contact area between the two phases, usually exceeding waveform disks that were developed to reduce the gas flow
an order of magnitude compared with conventional distillation resistance. Besides the surface area of the disk, this type of
contactors. rotating bed can utilize the extended interfacial area generated
by atomization.
HiGee distillation • Helical rotating bed – A helical rotating bed features four spiral
The essence of HiGee technology is replacing the gravitational field blades installed on a rotating disk. Due to its small contact area,
by a high centrifugal field achieved by rotating a specially shaped the mass transfer efficiency is still lower as than a RPB, in spite
rigid bed, typically a disk with an eye in the center. The higher of longer flow channel and residence time of gas and liquid.
mass-transfer coefficients and higher flooding limits allow the use • Multistage spraying rotating bed – A multistage spraying
of high surface-area packing. In this way, the momentum, heat rotating bed is similar to the cross-flow RPB, with the rotor
486

and mass transfer can be tremendously intensified.66 Practically, comprising multiple concentric packing rings. In the spraying

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zone, the liquid is sprayed into fine droplets with a large

interfacial area. Despite lower gas frictional resistance, its
drawback is potential liquid entrained by gas flow.
• Rotating packed bed with blade packing – A reported packing D
consists of 12 blades arranged within the RPB, spaced 30◦ apart D
where the gas and liquid were contacted counter currently.72
The mass transfer coefficients obtained (K L a) were in the range d
Capacity h
0.02–0.11 s−1 .72 F
d
• Rotating zig-zag bed (RZB) – The RZB design is characterized Separation
by a unique rotor that combines coaxially a rotating disc F
efficiency
with a stationary disc. Compared with RPB, the RZB can
function without liquid distributors, eliminate one dynamic seal, h
and easily accommodate an intermediate feed in continuous
distillation processes. RZB also effectively increases the contact
B B
time for gas and liquid phases thereby significantly increasing
the mass transfer coefficients.70
Figure 8. Design analogy between conventional and HiGee distillation.
• Rotating split packing bed – In a HiGee contactor, the gas
phase velocity is not much improved compared with the liquid
velocity. In fact, the tangential gas velocity in the rotor is nearly • The thinner liquid film and small inventories favor processing of
the same as that in the packing. Consequently, there is not valuable materials.
much enhancement in the gas side mass transfer coefficient.67 • The RPB unit is unaffected by moderate disturbance in
To overcome this, a radically different rotor design can be orientation, which practically relaxes a major limitation of
used. The rotor is composed of two sets of alternate annular using conventional columns in ship-mounted or portable units
rings: one set fixed to the top plate, and the other set to the where only very small deviations from the vertical are normally
bottom plate. The two sets of rings are rotated in the counter acceptable.
direction or co-direction driven by two motors to promote the
tangential slip velocity between the gas and the packing.73 This Nonetheless, HiGee distillation has also some disadvantages,
dramatically increases the inter-phase velocities and hence the such as additional energy requirements (electricity), problems
gas phase mass transfer coefficient (∼300 L s-1 ) with metal foam related to the reliability and longevity due to the moving parts,
packing – specific surface area of 2500 m2 m-3 .74 mechanical stability issues, as well as complicated hydrodynamics,
sealing and bearings.67,70
The vapor–liquid counter-current flow is horizontal in case of
HiGee distillation and not vertical, as is typical for conventional Cyclic distillation
operation. Basically, this means that the capacity depends on the
Cyclic distillation (CyDist) emerged as another important trend
height of the rotor, while the separation efficiency is determined
for improving distillation performance, enhancing the separation
by the diameter of the rotor – in contrast to classic distillation
efficiency through pseudo-steady-state operation based on
where the diameter gives the rate, while the height of the column
separate phase movement (SPM) and providing up to 50%
gives the separation efficiency (Fig. 8). Moreover, in the case of
energy savings.75 – 77 Basically, cyclic operation can be achieved by
HiGee the separation efficiency varies with the rotational speed,
controlled cycling, stepwise periodic operation, a combination of
having a maximum at the optimal rpm value. Replacing the vertical
these two, or by stage switching. Controlled cycling appears to be
gravitational force by the centrifugal force has many important
the simplest scheme and it is therefore the preferred option. The
benefits for HiGee distillation:19,69
cyclic operation was demonstrated on columns equipped with
• Very high volumetric mass transfer coefficients, leading to various types of internals: plates (brass, mesh-screen, bubble cap,
reduced equipment size. Compact equipment is also convenient sieve, packed-plate) and trays with sluice chambers. Essentially, a
for installation, troubleshooting, and maintenance. cyclic distillation column has an operating cycle consisting of two
• Gas flow velocity can be dramatically increased and the key operations: 1 a vapor flow period, when vapor flows upwards
tendency to flood is reduced, thus higher hydraulic capacity through the column and liquid remains stationary on each plate,
is possible. and 2 a liquid flow period, when vapor flow is stopped, reflux and
• The rotor is practically self-cleaning and it does not suffer from feed liquid are supplied, and liquid is dropped from each tray to
plugging, which is especially beneficial to treatments of fouling the one below – as shown in Fig. 9.6 As a result, the throughput
and solid-containing systems. of such a column using the controlled cycle mode of operation is
• Larger driving force of liquid flow due to high rotational speed typically over two times higher than the conventional throughput.
allows the use of non-Newtonian or very viscous Newtonian A precise analogy exists between the cyclic and conventional
fluids (e.g. stripping monomers, polymer solvents). distillation with liquid-phase concentration gradients across the
• Micro-mixing at molecular scale is extremely intensified, and this plates of the column. This analogy reduces to the substitution of
is particularly beneficial to the preparation of nano-particles. time as independent variable (cyclic distillation), for distance in
• The gas-liquid contact in a RPB is characterized by low the case of conventional distillation.
liquid holdup, thus the time required to reach steady state Nonetheless, the practical limitations of cyclic operation must
operation is drastically reduced. Moreover, the short liquid also be taken into account. The application of cyclic operation to
residence time – due to small equipment size and high flow vacuum distillation seems rather difficult, and the performance
rates – contributes to avoiding the decomposition of heat- enhancement critically depends on complete separation between
487

sensitive materials (e.g. thermally unstable). the liquid and vapor flow periods. However, the more recently

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to condenser to condenser to condenser

Liquid Liquid Liquid

Feed Feed Feed

Vapor Vapor Vapor

to reboiler to reboiler to reboiler

Figure 9. Working principle of cyclic distillation: vapor period (left and right) alternating with liquid period (centre).

proposed sluice-chamber trays seem to avoid the limitations of Dividing-wall column

simple trays.77 Cyclic distillation was carried out at pilot scale, The separation of multi-component mixtures requires typically a
for the separation of methanol–water or methyl-cyclohexane direct or indirect sequence of at least two distillation columns.
and n-heptane (5 plates, 100 mm diameter). At production A more energetically favorable alternative configuration that
scale, cyclic distillation is already used in the food industry avoids the remixing of internal streams is the so-called Petlyuk
(in Ukraine) for concentrating alcohol, from about 8 %wt to distillation.10 Basically, one condenser and reboiler are effectively
27–45 %wt ethanol. MaletaCD (maletacd.com) implemented replaced by thermal (heat) coupling of the pre-fractionator with
several cyclic distillation columns of 15 stages, 0.5 m diameter the main column, while the required condenser and reboiler
and 20 m3 day-1 capacity.77 Other potential applications include are attached to the main column. Dividing-wall column (DWC)
biofuels (bioethanol, biodiesel, biobutanol), organic synthesis, is a practical implementation that allows further equipment
specialty chemicals, gas processing, and petrochemicals. integration and cost savings by integrating the two distillation
The literature review indicates several benefits of cyclic columns of a Petlyuk configuration into a single shell – as shown in
operation over the conventional operating mode: Fig. 10.78 – 82
• High tray efficiencies (140–300% Murphree efficiency), meaning In a typical DWC, the feed is introduced into the prefractionator
that at the same vapor flow rate a required purity can be side facing the partition wall. Deflected by the wall, the lightest
obtained using fewer trays – hence lower CapEx. component flows upward and exits the column as top distillate,
• Reduced energy requirements, meaning that a required purity while the heaviest component drops down and is withdrawn as
can be achieved with lower vapor flow rates, at the same number bottom product. The mid-boiling component is initially entrained
of trays – thus high savings in OpEx (30–50%). up and down with both streams. However, the fluid that goes
• Higher throughput and equipment productivity compared with upward subsequently separates in the upper part and then it falls
conventional distillation. down on the opposite side of the wall. Similarly, the amount of
• The columns can be operated for either maximum capacity mid-boiling component that goes toward the bottom separates
(liquid period longer than the vapor period) or for maximum in the lower part, and then flows up to the back side of the wall,
efficiency (vapor period longer than the liquid period). where the entire mid-boiling product is recovered by a side draw
• For a fixed vapor flow period, the flood rate is different for every stream. At the top of the dividing-wall section, the liquid coming
liquid flow period selected – increasing with the liquid period, down from the rectifying section is split between the two sides, a
until it reaches a constant maximum. part of the total liquid being sent to the prefractionator side and
• Increased quality of the products, due to the higher separation the rest to the side stream section of the column. Assuming similar
efficiency. hydrodynamic conditions on both sides of DWC, the vapor flow is
• Smaller pressure drops on trays compared with conventional split proportionally to the cross-sectional area of each side. Unlike
steady-state operation. classic columns with a side draw, a DWC is capable of delivering
• The cyclic distillation configuration and operation allows larger high purity side product, thus being able to produce several pure
liquid holdups that can be beneficial for reactive distillation components in one unit.81
concepts, such as catalytic cyclic distillation (CCD) – a novel DWC technology found great appeal in the chemical indus-
setup that combines the benefits of RD with those of cyclic try – with Montz and BASF as the leading companies – because
488

operation mode. it offers some major benefits compared with classic distillation

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Liquid split
A A

Dividing wall

ABC ABC
1 2 B B

Prefractionation
section
Main column

Vapour split
C C
Figure 10. Petlyuk configuration (left) and dividing-wall column (right).

ABCD
I II II
I
C

Figure 11. Alternative configurations: bottom and top split column, Kaibel column and multi-partitioned DWC (Sargent and Agrawal arrangements).

design: high thermodynamic efficiency due to reduced remixing column technology is not limited to ternary separations alone,
effects, 25–40% lower energy requirements, high purity for all but it could be used also in azeotropic separations, extractive
product streams, reduced maintenance costs, small footprint and distillation and reactive distillation – DWC configurations shown in
up to 30% lower investment costs due to the reduced number Fig. 12.6,82,90 – 95
of equipment units.83 – 86 Nonetheless, despite its many bene- Although the DWC concept has been already patented in the
fits, one should keep in mind that DWC has some limitations early 1940s, the first theoretical work by Petlyuk was published
as well: operation at a single pressure, larger size (diameter and only in 1965, and it took another 20 years until a company (BASF)
height) compared with any single column of a conventional sepa- implemented it at industrial scale.78,81 Since its first industrial
ration sequence, and larger temperature span across the column application in 1985, DWC has moved from a conceptual to a proven
which requires more expensive utilities and limits the potential technology, steadily growing in number and size of applications.82
application of heat pumps.6 In principle, DWC units are built as both tray and packed columns
The design and control of dividing-wall columns are nowadays although the majority of them have been constructed by Montz
quite well established,81,87,88 and the original DWC concept (and used by BASF) as packed columns. Most of the industrial
was further extended to other useful configurations – such as DWC units are exploited by BASF SE (over 70 units) although other
split-column, Kaibel column or even multi-partitioned dividing- companies – such as Bayer AG, Dow Chemical Co, Lonza, LG Chem
wall column, as illustrated in Fig. 11.82,89 Several short-cut Ltd – have also started employing DWC technology, with over 125
and detailed methods are described in the literature for the applications in total by 2010.6,82 Table 2 conveniently summarizes
design of dividing-wall columns, and rigorous DWC simulations the current DWC applications available at applied research and
can be performed with commercial process simulators such as industrial scale.6,82
Aspen Plus, ChemCAD, HYSYS, ProSim, etc. Additional dynamic Initially, the DWC technology found application mainly for sys-
simulations can provide insight into the behavior of the DWC tems with low fractions of light and heavy boiling components, but
system, and valuable guidance for choosing the appropriate currently DWC technology is exploited for the separation of a broad
control strategy. Although more complex to control, recent spectrum of chemicals, such as hydrocarbons, alcohols, aldehydes,
studies and industrial experience indicate that the control of ketones, acetals, amines and others. DWC can also be used to con-
DWC units is in fact satisfactory, provided that an appropriate duct azeotropic, extractive and reactive distillation without major
489

control structure is implemented.88 Moreover, the dividing-wall changes to the types of internals used, while showing a remarkable

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A, B, E

A,E A B

B S

A,B
A,B

S
A B

R-DWC A-DWC E-DWC

Figure 12. Dividing-wall column used for reactive distillation (R-DWC), azeotropic. distillation (A-DWC) and extractive distillation (E-DWC).

Table 2. Industrial applications of dividing-wall columns6,82

Applied research and industrial applications Additional information/remarks

Ternary separations
Benzene-toluene-xylene fractionation ExxonMobil
Separation of hydrocarbons from Fischer-Tropsch synthesis unit Linde AG, Tray column,
H = 107 m, D = 5 m
Separation of benzene from pyrolysis gasoline Uhde, 170 000 mt yr-1 feed capacity
Separation of C7+ aromatics from C7+ olefin /paraffin UOP, five DWC, Trap tray
Mostly undisclosed systems BASF / Montz, over 70 columns,
D = 0.6–4 m, P = 2 mbar to 10 bar
Undisclosed systems Sumitomo Heavy Ind., Kyowa Yuka,
Sulzer Chemtech Ltd. (20 DWC), Koch Glitsch (10 DWC)
Multi-component separations
Recovery of four component mixtures of fine chemical intermediates BASF/Montz, Single wall column,
H = 34 m, D = 3.6 m, deep vacuum
Integration of a product separator and an HPNA stripper UOP, 5 product streams
Retrofit of conventional columns to DWC
Recovers mixed xylenes from reformate motor gasoline Koch-Glitsch, D = 3.8–4.3 m, tray column, over 50% energy savings
Separation of (iso)paraffins. Production of isohexane Koch-Glitsch
Separation and purification of 2-ethylhexanol (2-EH) Dual operation possible
Undisclosed systems MW Kellogg
Reactive DWC
MeOH + BuOH + AcOH ↔ AcOMe + AcOBu + H2 O Rate-based model/AspenTech ACM
DMC + EtOH ↔ DEC + MeOH Aspen Plus or PRO/II
Methyl Acetate + Water ↔ Methanol + Acetic Acid
Isoamylenes + Ethanol ↔ Tertiary Amyl Ethyl Ether Aspen DISTIL and HYSYS, CSTR
Ethanol + Acetic Acid ↔ Ethyl Acetate + Water Aspen Plus and Aspen Dynamics
Reactive distillation with 10 chemical species Aspen Plus (RADFRAC)
Isobutane + Ethanol ↔ Ethyl Tertiary Butyl Ether Aspen HYSYS
Ethanol + Acetic Acid ↔ Ethyl Acetate + Water Aspen Plus
Methanol + Isobutylene ↔ Methyl Tertiary Butyl Ether Aspen Plus
Ethanol + Ethylene ↔ Ethoxyethanol
Methanol ↔ Dimethyl Ether + Water Aspen Plus (RADFRAC)
Azeotropic DWC
Ethanol dehydration Entrainer: cyclohexane, n-pentane
Extractive DWC
Separation of toluene and non-aromatics with N-formyl-morpholine Uhde, 28000 mt yr-1 feed capacity
Crude butadiene from a crude C4 using N-methyl-pyrrolidone (NMP) as BASF, Both trays and packing
solvent
Bioethanol dehydration Ethylene glycol used as solvent
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reduction in investment and operating costs. The current research

on dividing-wall column technology is aimed at acquiring
Operating
theoretical and experimental knowledge that supports further window
development and implementation of these highly integrated reaction
applications. For example, the reactive dividing-wall column

Temperature
(R-DWC) can be considered an ultimate efficiency approach RD
due to the integration of reactive distillation with dividing-wall
column technology. Relevant research is still required to provide
the required evidence to further develop and validate the Operating Equipment
proposed models.6,81,82 window range
separation

Reactive distillation
In traditional chemical processes, reaction and separation are Pressure
usually carried out in different sections of the plant, using separate
equipment often being operated under different conditions. 5.5% 7.6%
Recycle streams are frequently needed to improve conversion and
14.0% Reaction types
selectivity, minimize the production of undesired by-products,
reduce the energy requirements, and improve process control- aA ↔ bB
lability. The recent economic and environmental considerations 25.4% aA + bB ↔ cC
have encouraged industry to focus on technologies that are more aA ↔ bB + cC
efficient and require less energy, at further reduced investment aA + bB ↔ cC + dD
costs. In reactive distillation (RD), benefits can be realized by using 2-stage reactions
the reaction to improve separation (e.g. overcoming azeotropes, 3-stage reactions
reacting away contaminants, avoiding difficult separations) or 38.6% 8.9%
by using separation to improve reactions (e.g. enhancing overall
rates, overcoming reaction equilibrium limitations, improving Figure 13. Overlapping windows of operating conditions and reaction
selectivity) – the maximum effect being achieved when both types for RD.
aspects apply.6,96 – 99
In a RD process, reaction and distillation take place in the Note that a small number of industrial applications of RD have
same piece of equipment, the reactants being converted with been around for several decades, but even today the RD crown
the simultaneous separation of the products and recycling of is still carried by the Eastman process that reportedly replaced
unused reactants. This implies that the boiling points of the a methyl acetate production plant with a single RD column
products must be different from those of the reactants. Since using 80% less energy at only 20% of the investment costs.99
both operations occur simultaneously in the same unit, there Nowadays, the application with the largest number of installations
must be a proper match between the conditions required for remains the methyl tertiary butyl ether (MTBE) that is used in
reaction and separation – as shown in Fig. 13.100 RD setups may gasoline blending. CDTECH, the major commercial RD technology
consist of multiple catalyst systems, gas and liquid traffic over provider, has licensed until now more than 200 commercial scale
the catalyst, separation, mass flow, and enthalpy exchange – all processes operated worldwide at capacities of 100–3000 kt yr-1
of them being optimally integrated in a single processing unit, for the production of ethers (MTBE, TAME, ETBE), hydrogenation
a key feature of process intensification.101 – 103 By continuously of aromatics and light sulfur hydro-desulfurization, ethyl benzene
removing the products, reactive distillation makes it possible and isobutylene production.106 Sulzer ChemTech also reports
to use only the stoichiometric reactants ratio (neat operation) several industrial scale applications such as synthesis of ethyl,
and to pull the equilibrium to high conversions.99 This is in butyl and methyl acetates, hydrolysis of methyl acetate, synthesis
contrast to the typical practice of using an excess of one of the of methylal, methanol removal from formaldehyde and fatty acid
reactants to push the equilibrium toward the desired products, esters production.24,106
at the penalty of having to recover and recycle the unreacted raw Reactive distillation can be further integrated with membrane
materials.6 separation thus combining the benefits of reactive and hybrid
Remarkably, over 1100 articles and 800 US patents on RD were separation processes in a highly intensified process unit.56,107
published during the past 40 years, covering in total over 235 Although reactive distillation and membrane separations are
reaction systems.99 Figure 13 provides a convenient overview established technologies, the combination of them is relatively
of these systems classified into various chemical reaction types, new with only a few publications reported so far.107 – 110 More
while Table 3 lists the most important applications so far: recently, the use of microwaves to enhance a reactive distillation
(trans-)esterification, hydrolysis, polyesterification, etherification, process was also reported as a remarkable process intensification
hydration and dehydratino, (trans-)alkylation, isomerization, improvement. 111,112
(de-)hydrogenation, amination, condensation, chlorination,
nitration – all these reactions being limited by the chemical
equilibrium.6,98,100,104,105,106 Figure 14 illustrates some reactive CASE STUDIES
distillation configuration alternatives, ranging from a conventional This section presents a number of selected case studies that
reactive distillation column to reactive DWC, and RD columns illustrate some of the most promising advanced distillation
combined with a pre-reactor, side reactors or even membrane concepts (e.g. dividing-wall column and reactive distillation) and
491

separation units.6 their applications in various important industrial processes.

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Polyesters synthesis
Table 3. Main industrial applications of reactive distillation6 Polyester (unsaturated) resins are important chemicals, used in
Reaction type Catalyst/internals
key applications such as sheet or bulk moulding compound,
printer toners, and fiberglass reinforced plastics (FRP). These
Alkylation unsaturated polyesters are formed by the reaction of polyols
Alkyl benzene from ethylene/propylene Zeolite β , molecular sieves (e.g. ethylene glycol) with saturated or unsaturated dibasic acids
and benzene (e.g. maleic or phthalic acid). The reaction scheme is rather
Amination complex and includes several types of reactions: ring opening,
Amines from ammonia and alcohols H2 and hydrogenation catalyst poly-esterification, isomerisation and saturation. At industrial scale,
Carbonylation the unsaturated polyesters are still produced using batch reactors
Acetic acid from CO and methanol / Homogeneous and distillation columns, with a total production time of about
dimethyl ether
12 h, in a process plagued by batch-to-batch inconsistencies and
Condensation
high capital and operating costs.
Diacetone alcohol from acetone Heterogeneous
In a series of papers by Shah et al.,113 – 116 a novel reactive
Bisphenol-A from phenol and acetone N/A
distillation process was proposed as an enhanced process
Trioxane from formaldehyde Strong acid catalyst, zeolite ZSM-5
alternative able to reduce the production time and to achieve
Esterification
a better quality of the product at lower costs. With reactive
Methyl acetate from methanol and acetic H2 SO4 , Dowex 50, Amberlyst-15
acid
distillation, complete conversion can be achieved in a short
Ethyl acetate from ethanol and acetic N/A
time, as the water by-product is continuously removed from
acid the system. Reliable kinetic and thermodynamic models were
2-methyl propyl acetate from 2-methyl Katapak-S developed, and subsequently used in rigorous simulations testing
propanol and acid various process alternatives – as shown in Fig. 15.115,116 Moreover,
Butyl acetate from butanol and acetic Cation exchange resin various internals configurations (packing and trays) were evaluated
acid
and the experimental validation of the process was successfully
Fatty acid methyl esters from fatty acids H2 SO4 , Amberlyst-15, Metal oxides
and methanol
carried out at pilot scale using two configurations: a reactive
distillation column alone, and a RD column coupled with a pre-
Fatty acid alkyl esters from fatty acids H2 SO4 , Amberlyst-15, Metal oxides
and alkyl alcohols reactor.115 The product specification of the polyester produced in
Cyclohexyl carboxylate from Ion exchange resin bags the continuous reactive distillation column was compared with the
cyclohexene and acids polyester product manufactured at industrial scale. Remarkably,
Etherification it was found that the product specifications of the polyester
MTBE from isobutene and methanol Amberlyst-15 produced in the reactive distillation column was comparable with
ETBE from isobutene and ethanol Amberlyst-15/pellets, structured that of the polyester produced in industry, in a classic batch
TAME from isoamylene and methanol Ion exchange resin process.
DIPE from isopropanol and propylene ZSM 12, Amberlyst-36, zeolite The reported results show that the total production time in a
Hydration / Dehydration reactive distillation system is only 1.8–2 h, which is actually 6–8
Mono ethylene glycol from ethylene Homogeneous times lower than the batch process of 12 h.115,116 Remarkably,
oxide and water for the reactive distillation column coupled with a pre-reactor
Hydrogenation / Dehydrogenation the improvements were very promising: 90% lower reaction
Cyclohexane from benzene Alumina supported Ni catalyst volume, 93% shorter production time, and 66% energy savings
MIBK from benzene Cation exchange resin with Pd/Ni compared with the traditional batch process. Overall, using
Hydrolysis reactive distillation clearly improves the polyester process in
Acetic acid and methanol from methyl Ion exchange resin bags all domains of structure, energy and time compared with the
acetate + water
traditional batch process used at industrial scale.
Acrylamide from acrylonitrile Cation exchanger, copper oxide
Isomerization
Iso-parafins from n-parafins Chlorinated alumina and H2 Bioethanol dehydration
Nitration Bioethanol is a very promising alternative fuel, produced in
4-Nitrochlorobenzene from Azeotropic removal of water large amounts as it can be easily used in existing fuel systems
chlorobenzene + nitric acid and engines. Bioethanol production relies on several processes:
Transesterification corn-to-ethanol, sugarcane-to-ethanol, basic and integrated
Ethyl acetate from ethanol and butyl Homogeneous lignocellulosic biomass-to-ethanol. The raw materials undergo
acetate
several pre-treatment steps and then enter the fermentation
Diethyl carbonate from ethanol and Heterogeneous
dimethyl carbonate
stage where bioethanol is produced. A common feature is
the production of diluted bioethanol (typically in the range of
Vinyl acetate from vinyl stearate and N/A
acetic acid 5–12%wt ethanol) that needs to be further concentrated beyond
Unclassified reactions the azeotropic composition, to purities exceeding 99–99.8%wt
Monosilane from trichlorsilane Heterogeneous ethanol.93,94
Methanol from syngas Cu/Zn/Al2 O3 and inert solvent Several energy demanding separation steps are required to
DEA from monoethanolamine and N/A reach the purity target, mainly due to the presence of the
ethylene oxide well known binary azeotrope ethanol–water (95.63%wt ethanol).
Polyesterification Autocatalytic The first step is carried out in a pre-concentration distillation
492

column (PDC) that concentrates bioethanol from 5–12% up

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Rectifying zone
Distillate
Feed Dividing-wall EQ
heavy
RX
RX
Reactive zone
(catalyst)
Prefractionator
Feed Main column RX
RX
light
RDC R-DWC RDC

Stripping zone
Bottoms
Reactive Reactive RD with
distillation column dividing wall column pre-reactor & side reactors
Figure 14. Reactive distillation configurations.

Water Water

Rectifying section
Packed column Rectifying section
Packed column

Monoesters
MAD RDC MAD RDC
PG
Reactor

Stripping section Stripping section

Packed / tray Packed bubble column
(bubble) column

PG Polyester PG Polyester

Figure 15. Reactive distillation configurations for synthesis of unsaturated polyesters – e.g. from maleic anhydride (MAD) and propylene glycol (PG).

to 92.4–94%wt. The second step is ethanol dehydration up of the prefractionator side, thus serving as a reflux to the PDC
to concentrations above the azeotropic composition. This is section. The vapor leaving the feed side of the E-DWC has a near
typically carried out in an extractive distillation column (EDC) azeotropic composition. Solvent is added at the top of the E-DWC,
followed by a solvent recovery column (SRC). Although extractive this section acting in fact as the EDC unit of the conventional
distillation presents relatively high energy costs, it is still the option sequence. Ethanol is separated here as high purity top distillate,
of choice in the case of large-scale production of bioethanol and removed as main product. The liquid flowing down the top
fuel – being preferred over pervaporation, adsorption, pressure- section (EDC) is collected and distributed only to the (SRC) side
swing distillation, azeotropic distillation, or hybrid methods opposite to the feed side (pre-fractionator) and further down the
combining these options.95,117 – 120 bottom of the E-DWC. This complete redistribution of the liquid
In a series of studies by Kiss et al.,93,94 E-DWC systems were flow is required to avoid the presence and loss of solvent on the
proposed for extractive distillation, including or not the pre- feed side (PDC section). In the SRC section of the column, the
concentration distillation column (PDC). The feed considered was solvent is separated as bottom product and then recycled in the
the diluted stream (10%wt) obtained by fermentation. This is separation process.
distilled to near-azeotropic composition of 93.5%wt ethanol, and High purity and recovery is obtained for all three products of
then dehydrated to a purity of over 99.8%wt ethanol in order to the extractive dividing-wall column: ethanol as top distillate, water
comply with all standards. as side product and EG solvent as recovered bottom product. In
Figure 16 shows the conventional extractive distillation (ED) contrast to the well-known DWC configuration, the side stream is
process used for bioethanol dehydration, as well as the novel collected here from the same (feed) side of the column, not the
E-DWC that combines three towers into just one column.94 In opposite. The single-step E-DWC alternative is the most efficient
this column, the feed side (prefractionator) acts as the PDC unit. in terms of energy requirements allowing energy savings of 17%
Water is removed as liquid side stream, but an additional side (specific energy use of 2070 kWh ton-1 ethanol) while being the
reboiler is required in order to return the required amount of least expensive in terms of capital investment and operating costs
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water vapors to the column. The liquid feed stream is fed on top (about 17% lower total annual costs).94

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 www.soci.org AA Kiss

1
Ethanol 1
Solvent
Ethanol
>99.9% Solvent
4
(Ethylene glycol) 4
(Ethylene glycol) EDC
EDC
rL
1
1 Water Feed
PDC-TOP 17
11 1 18
92-94%

PDC
PDC SRC

SRC
17
Feed EDC-BTM 8
21
5-12% 17 34
Water 35
PDC – pre-concentration distillation column
EDC – extractive distillation column rV
SRC – solvent recovery column
16 42
30
Solvent Solvent
Water E-DWC
(recycle) (recycle)

Figure 16. Bioethanol dehydration by extractive distillation: conventional process vs DWC.

Dimethyl ether production

Dimethyl ether (DME) is of great interest due to its use as clean fuel
DME Methanol
for diesel engines or in combustion cells, as a precursor to organic
(recycle)
compounds, as well as a green aerosol propellant. Currently, DME
is produced by conversion of various feedstock such as natural gas, RX DC1 DC2
coal, oil residues and bio-mass into syngas (CO and H2 ), followed
by a two-step process: methanol synthesis and then methanol
dehydration. Methanol is produced first from syngas over a
copper-based catalyst (Cu/Zn, Cu/Zn/Al, Cu/Zn/Co), and then it Methanol Water
is dehydrated over a solid catalyst in order to produce dimethyl
ether. The methanol dehydration step takes place at temperatures METHANOL (136.81 C)
of 250–400◦ C and pressures up to 20 bars. Different types of solid
acid catalysts can be used, but γ -alumina is the preferred one
0.8

due to its thermal stability, mechanical resistance, high surface

area and catalytic properties.121 The current industrial process
0.6

RX
involves a gas-phase reactor (70–80% conversion of methanol),
followed by a direct sequence of two distillation columns that
0.4

deliver high-purity DME (over 99.99%wt). DC1

DC2
Figure 17 illustrates the simplified conventional flowsheet for
0.2

methanol dehydration, along with the ternary diagram of the

process. The equilibrium limited dehydration reaction of vaporized WATER DME
(179.98 C) 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 (44.40 C)
methanol is carried out in a fixed-bed catalytic reactor:
Figure 17. DME production: simplified process flowsheet and ternary
2 CH3 OH ↔ CH3 OCH3 + H2 O (4) diagram.

The outlet of the reactor – consisting of DME, water and

unreacted methanol – is cooled and subsequently distilled in the 28% savings in energy and total annual costs (TAC = $1,138,984
first tower to yield pure dimethyl ether. The unreacted methanol is for a 100 kt yr-1 plant), compared with the conventional distillation
separated from water in a second distillation column and recycled sequence.122
back to the reactor. A major problem of this process is the high Reactive distillation (RD) could be also used a process alternative,
investments costs for several units that require a large overall plant since it can successfully combine the functions of the reactor and
footprint, as well as the associated energy requirements. the DME purification column into one unit, as shown in Fig. 18.
One approach to reduce the capital and operating costs However, a further improved alternative combining all functions
is to integrate the two distillation columns used for DME into one unit is based on a reactive DWC (Fig. 18). Methanol
purification and methanol recovery into only one dividing-wall is fed on top of the reactive zone where the solid catalyst is
column – as shown in Fig. 18.122 DME and water are separated located, while DME is produced as top distillate, water as bottom
as top and bottom end high purity products (>99.99%wt), product, and the unreacted methanol as side stream product
while methanol accumulates towards the middle of the column, that is recycled. The reactive DWC unit has 35 stages in total,
being withdrawn as a side stream (>99%wt) and then recycled with the reactive zone located on stages 8–31 on the feed side,
in the process. The reported process alternative requires less and a common stripping section (stages 32–35) as well as a
494

equipment and 20% lower capital costs (TIC = $1,412,490), with common rectifying zone (stages 1–7). The methanol stream is

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Distillation technology www.soci.org

DME
DME Methanol R-DWC
DME
(recycle) Feed
Feed Methanol Feed
RDC DC Methanol
(recycle)
Steam

Water
Water Water

Figure 18. Process alternatives based on single-step separation in a DWC, reactive distillation process, and all-in-one reactive DWC.

fed into stage 8, at the top of the reactive zone – the feed side few commercial applications in distillation have been reported
of the DWC acting as the RD zone where the solid acid catalyst so far.67,70 A key reason is that several problems such as the
is present. High purity (99.99%wt) DME is delivered as distillate, dynamic seal, middle feed, liquid distributor and the multi-rotor
while similar high-purity water is obtained as bottom product. The configuration have not been properly addressed. In order to
unreacted methanol is collected as side product, and then recycled successfully solve these problems, a novel kind of HiGee device
back to the process. The results reported show that the process was recently proposed and developed – the so called rotating
using a reactive dividing-wall column has superior performance zigzag bed (RZB) that contains a unique rotor. The RZB fills the gap
compared with the conventional or reactive distillation process: in HiGee distillation and it has the potential for a bright future in
high energy savings of up to 60%, as well as around 30% lower process intensification.70
capital investment costs. The methanol conversion in the reactive Cyclic distillation uses a cyclic operating mode that can bring
dividing-wall column is 50%, and the specific energy requirements new life to old distillation columns, providing several key benefits,
are only 0.56 kWh kg-1 DME.92,95 such as increased column throughput, low energy requirements
and high separation performance. Moreover, the separate phase
movement has more degrees of freedom that contribute to a
CONCLUDING REMARKS good process control.77 The main obstacle for the widespread
Although considered a mature technology, distillation is still implementation of cyclic distillation is the pseudo-steady-state
young and full of breakthrough opportunities, as significant operation that requires special operator training and additional
cost reductions and high energy efficiency can be achieved by safety measurements.
employing various approaches based on process intensification Dividing-wall column is one of the best examples of a
principles (e.g. maximized effectiveness, driving forces, and proven process intensification technology in distillation, as
synergy). For example, several heat pump concepts have been it allows significantly lower investment and operating costs
proposed to upgrade the level of the energy discharged and re- (typically 25–40%) while also reducing the equipment and
use it in order to reduce the consumption of valuable utilities. carbon footprint. Considering the number and variety of
These heat pumps have no intrinsic (temperature) limitations and industrial applications, dividing-wall column technology can
therefore, their application range is quite large within the chemical already be considered a success story of process intensification
process industry. Temperature lifts of up to 30–100◦ C are feasible, in distillation and it will certainly develop into a standard type
leading to significant savings of up to 80% in the primary energy of equipment in the near future. Many applications are known
requirements for distillation.29 today, mainly concerning separations of ternary mixtures. The
Membrane distillation is a promising technology for separation development and implementation efforts focus nowadays on the
and purification processes, but it still needs further exploration separation of more than three components or applications of
and optimization to become a mature technology applicable extractive, azeotropic and reactive distillation in a dividing-wall
at industrial scale. Compared with other membrane separation column.6,82
processes, the main advantages of using membrane distillation Reactive distillation brings tremendous benefits to equilibrium
are low operating temperatures (which means that low-grade limited chemical systems, resulting in significantly lower
heat such as solar energy, waste heat and geothermal can be investment and operating costs, as well as reduced plant footprint.
used), high rates of rejection for non-volatile components (salts, The industrial applications of reactive distillation are flourishing as
colloids), possibility to work with high solute concentrations in the the scientific community and the technology providers remove the
feed or even with near saturated solutions, and lower hydrostatic barriers for implementation, develop heuristic process synthesis
pressure than used in pressure driven membrane processes. rules and expert software to identify the attractiveness and
However, the practical application of MD is limited by permeate flux technical feasibility of reactive distillation.24,113
decay (due to concentration and temperature polarization effects,
membrane fouling and total or partial pore wetting), uncertain
energy and economic costs for each membrane distillation
configuration and application, membrane distillation modules ACKNOWLEDGEMENT
not yet commercially available for large-scale applications, and Financial support from the Stichting Hoogewerff-Fonds is
risk of pore wetting – since only vapor and gases must be present gratefully acknowledged by the author – winner of the
inside the pores.55,60 Hoogewerff Jongerenprijs 2013. This review paper is based
Although many commercial applications of HiGee are known on the award lecture given on 23 April 2013, in The Hague,
495

in absorption, stripping, and reactive precipitation only very at the joint conference including the 9th European Congress

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 www.soci.org AA Kiss

of Chemical Engineering (ECCE-9), 2nd European Congress of 30 van de Bor DM and Infante Ferreira CA, Quick selection of industrial
Applied Biotechnology (ECAB-2), European Process Intensification heat pump types including the impact of thermodynamic losses.
Energy 53:312–322 (2013).
Conference (EPIC2013) and the 12th Netherlands Process 31 Annakou O and Mizsey P, Rigorous investigation of heat
Technology Symposium (NPS-12). pump assisted distillation. Heat Recov Syst CHP 15:241–247
(1995).
32 Omideyi TO, Parande MG, Supranto S, Kasprzycki J and Devotta S,
REFERENCES The economics of heat pump assisted distillation systems. Heat
Recov Syst CHP 5:511–518 (1985).
1 Resetarits MR and Lockett MJ, Distillation, in EncPhys Sci Technol, 3rd
33 Fonyo Z and Mizsey P, Economic applications of heat pumps in
edn. 547–559 (2003). DOI: 10.1016/B0-12-227410-5/00182-4
integrated distillation systems. Heat Recov Syst CHP 14:249–263
2 Forbes RJ, A Short History of the Art of Distillation. Brill, Leiden, The
(1994).
Netherlands (1970).
34 Fonyo Z and Benko N, Comparison of various heat pump assisted
3 Kister HZ, Distillation - Design. McGraw-Hill, USA (1992).
distillation configurations. I Chem E Trans 76A:348–360 (1998).
4 Kister HZ, Distillation - Operation. McGraw-Hill, USA (1992).
35 Dı́ez E, Langston P, Ovejero G and Dolores Romero M, Economic
5 Kister HZ, Distillation Troubleshooting. John Wiley & Sons, Hoboken,
feasibility of heat pumps in distillation to reduce energy use. Appl
New Jersey (2006).
Therm Eng 29:1216–1223 (2009).
6 Kiss AA, Advanced Distillation Technologies - Design, Control and
36 Spoelstra S, Saving energy in distillation with thermoacoustic heat
Applications. Wiley, Chichester (2013).
pumps. ECN Brochure B-07-008, Petten, The Netherlands (2008).
7 Freshwater DC, Thermal economy in distillation. Trans Inst Chem Eng 37 Tijani MEH and Spoelstra S, A high performance thermoacoustic
29:149–160 (1951). engine. J Appl Phys 110, Article Number: 093519: 1–6 (2011). DOI :
8 Taylor R and Krishna R, Multi-Component Mass Transfer. Wiley, New 10.1063/1.3658872
York (1993). 38 Xiao JH, Thermoacoustic theory for cyclic flow regenerators. 1.
9 de Koeijer GM and Kjelstrup S, Application of irreversible Fundamentals. Cryogenics 32:895–901 (1992).
thermodynamics to distillation. Int J Thermodynam 7:107–114 39 Herman C and Travnicek Z, Cool sound: the future of refrigeration?
(2004). Thermodynamic and heat transfer issues in thermoacoustic
10 Petlyuk FB, Distillation Theory and its Application to Optimal Design of refrigeration. Heat Mass Transfer 42:492–500 (2006).
Separation Units. Cambridge University Press, New York (2004). 40 Vanapalli S, Tijani MEH and Spoelstra S, Thermoacoustic-stirling heat
11 Holland CD, Fundamentals of Multi-Component Distillation. McGraw pump for domestic applications. Proc ASME Fluids Eng Div Summer
Hill, New York (1981). Conf 2:111–116 (2010).
12 Stichlmair JG and Fair JR, Distillation - Principles and Practice. Wiley- 41 Bassem MM, Ueda Y and Akisawa A, Thermoacoustic stirling heat
VCH, New York (1998). pump working as a heater. Appl Phys Express 4, Article Number:
13 Doherty MF and Malone MF, Conceptual Design of Distillation Systems. 107301: 1–3 (2011). DOI: 10.1143/APEX.4.107301
McGraw-Hill, New York (2001). 42 Nakaiwa M, Huang K, Owa M, Akiya T, Nakane T, Sato M and Takamatsu
14 Lee FM and Wytcherley RW, Azeotropic Distillation. In Encyclopedia T, Energy savings in heat-integrated distillation columns. Energy
of Separation Science 990–995 (2000). DOI: 10.1016/B0-12-226770- 22:621–625 (1997).
2/00681-5 43 Olujić Ž, Fakhri F, de Rijke A, de Graauw J and Jansens PJ, Internal heat
15 Lee FM, Extractive Distillation. In Encyclopedia of Separation Science integration – the key to an energy-conserving distillation column.
1013–1022 (2000). DOI: 10.1016/B0-12-226770-2/04801-8 J Chem Technol Biotechnol 78:241–248 (2003).
16 Mujtaba IM, Batch Distillation - Design and Operation. Imperial College 44 Gadalla M, Olujic Z, de Rijke A and Jansens PJ, Reducing CO2 emissions
Press, London (2004). of internally heat-integrated distillation columns for separation of
17 Lei Z, Chen B and Ding Z, Special Distillation Processes. Elsevier, close boiling mixtures. Energy 31:2409–2417 (2006).
Amsterdam (2005). 45 de Rijke A, Development of a concentric internally heat integrated
18 Luyben WL, Distillation Design and Control using Aspen Simulation. distillation column (HIDiC). PhD thesis, TU Delft, The Netherlands
John Wiley & Sons, Hoboken, New Jersey (2006). (2007).
19 Reay D, Ramshaw C and Harvey A, Process Intensification - Engineering 46 Gadalla MA, Internal heat integrated distillation columns (iHIDiCs)
for Efficiency, Sustainability and Flexibility, 2nd edn. Butterworth- - new systematic design methodology. Chem Eng Res Des
Heinemann, Oxford (2013). 87:1658–1666 (2009).
20 van Gerven T and Stankiewicz A, Structure, energy, synergy, time 47 Bruinsma OSL, Krikken T, Cot J, Sarić M, Tromp SA, Olujić Ž and
- the fundamentals of process intensification. Ind Eng Chem Res Stankiewicz AI, The structured heat integrated distillation column.
48:2465–2474 (2009). Chem Eng Res Des 90:458–470 (2012).
21 Freund H and Sundmacher K, Towards a methodology for the 48 Nakaiwa M, Huang K, Endo A, Ohmori T, Akiya T and Takamatsu T,
systematic analysis and design of efficient chemical processes Internally heat-integrated distillation columns: a review. Chem Eng
- Part 1: from unit operations to elementary process functions. Res Des 81:162–177 (2003).
Chem Eng Process 47:2051–2060 (2008). 49 Fukushima T, Kano M and Hasebe S, Dynamics and control of
22 Jonker G and Harmsen J, Engineering for Sustainability: A Practical heat integrated distillation column (HIDiC). J Chem Eng Japan
Guide for Sustainable Design. Elsevier, Amsterdam (2012). 39:1096–1103 (2006).
23 Sundmacher K, Kienle A and Seidel-Morgenstern A (eds), Integrated 50 Khayet M, Membranes and theoretical modeling of membrane
Chemical Processes: Synthesis, Operation, Analysis, and Control. distillation - a review. Adv Colloid Interface Sci 164:56–88 (2011).
Wiley-VCH, Weinheim (2005). 51 Ravanchi MT, Kaghazchi T and Kargari A, Application of membrane
24 Harmsen GJ, Process intensification in the petrochemicals industry: separation processes in petrochemical industry - a review.
drivers and hurdles for commercial implementation. Chem Eng Desalination 235:199–244 (2009).
Process 49:70–73 (2010). 52 Curcio E and Drioli E, Membrane distillation and related operations -
25 Felder R and Roussea W, Elementary Principles of Chemical Processes. a review. Sep Purif Rev 34:35–86 (2005).
John Wiley & Sons, Hoboken, New Jersey (2005). 53 Suk DE and Matsuura T, Membrane based hybrid processes - a review.
26 Haselden G, Approach to minimum power consumption in low- Sep Sci Technol 41:595–626 (2006).
temperature gas separation. Trans Inst Chem Eng 36:123–132 54 Susanto H, Towards practical implementations of membrane
(1958). distillation. Chem Eng Process 50:139–150 (2011).
27 Sampathkumar K, Arjunan TV, Pitchandi P and Senthilkumar P, Active 55 Alkhudhiri A, Darwish N and Hilal N, Membrane distillation - a
solar distillation - a detailed review. Renew Sustain Energy Rev comprehensive review. Desalination 287:2–18 (2012).
14:1503–1526 (2010). 56 Lipnizki F, Field RF and Ten PK, Pervaporation-based hybrid process:
28 Summers DR and Pilling M, Be smart about column design. Chem Eng a review of process design, applications and economics. J Membr
Prog Nov:32–38 (2012). Sci 153:183–210 (1999).
29 Kiss AA, Flores Landaeta SJ and Infante Ferreira CA, Towards energy 57 Mericq J-P, Laborie S and Cabassud C, Evaluation of systems coupling
efficient distillation technologies - making the right choice. Energy vacuum membrane distillation and solar energy for seawater
496

47:531–542 (2012). desalination. Chem Eng J 166:596–606 (2011).

wileyonlinelibrary.com/jctb

c 2013 Society of Chemical Industry J Chem Technol Biotechnol 2014; 89: 479–498
Distillation technology www.soci.org

58 Hausmann A, Sanciolo P, Vasiljevic T, Weeks M and Duke M, 87 Kim YH, Structural design and operation of a fully thermally coupled
Integration of membrane distillation into heat paths of industrial distillation column. Chem Eng J 85:289–301 (2002).
processes. Chem Eng J 211:378–387 (2012). 88 Kiss AA and Bildea CS, A control perspective on process intensification
59 El-Bourawi MS, Ding Z, Ma R and Khayet M, A framework for better in dividing-wall columns. Chem Eng Process 50:281–292
understanding membrane distillation separation process. J Membr (2011).
Sci 285:4–29 (2006). 89 Ghadrdan M, Halvorsen IJ and Skogestadad S, Optimal operation
60 Hassan AS and Fath HES, Review and assessment of the newly of Kaibel distillation columns. Chem Eng Res Des 89:1382–1391
developed MD for desalination processes. Desal Water Treatment (2011).
51:574–585 (2013). 90 Kiss AA, Pragt H and van Strien C, Reactive dividing-wall columns
61 Burgoyne A, and Vahdati MM, Direct contact membrane distillation. - how to get more with less resources? Chem Eng Commun
Sep Sci Technol 35:1257–1284 (2000). 196:1366–1374 (2009).
62 Camacho LM, Dumee L, Zhang JH, Li JD, Duke M, Gomez J and Gray 91 Kiss AA, Segovia-Hernandez JG, Bildea CS, Miranda-Galindo EY and
S, Advances in membrane distillation for water desalination and Hernandez S, Reactive DWC leading the way to FAME and fortune.
purification applications. Water 5:94–196 (2013). Fuel 95:352–359 (2012).
63 Koschikowski J, Entwicklung von energieautark arbeitenden 92 Kiss AA and Suszwalak DJ-PC, Innovative dimethyl ether synthesis
Wasserentsalzungsanlagen auf Basis der Membrandestillation. in a reactive dividing-wall column. Comput Chem Eng 38:74–81
Fraunhofer Verlag, Germany (2011). (2012).
64 Jiao B, Cassano A and Drioli E, Recent advances on membrane 93 Kiss AA and Suszwalak DJ-PC, Enhanced bioethanol dehydration by
processes for the concentration of fruit juices: a review. J Food Eng extractive and azeotropic distillation in dividing-wall columns. Sep
63:303–324 (2004). Purif Technol 86:70–78 (2012).
65 Vane LM, A review of pervaporation for product recovery from 94 Kiss AA and Ignat RM, Innovative single step bioethanol dehydration
biomass fermentation processes. J Chem Technol Biotechnol in an extractive dividing-wall column. SepPurifTechnol 98:290–297
80:603–629 (2005). (2012).
66 Ramshaw C, HiGee distillation - an example of process intensification. 95 Kiss AA, Novel applications of dividing-wall column technology
Chem Eng 389:13–14 (1983). to biofuel production processes. J Chem Technol Biotechnol
67 Rao DP, Bhowal A and Goswami PS, Process intensification in rotating 88:1387–1404 (2013).
packed beds (HiGee): an appraisal. Ind Eng Chem Res 43:1150–1162 96 Baur R, Higler AP, Taylor R and Krishna R, Comparison of equilibrium
(2004). stage and nonequilibrium stage models for reactive distillation.
68 Trent DL, Chemical processing in high-gravity fields, in Re-Engineering Chem Eng J 76:33–47 (2000).
the Chemical Processing Plant: Process Intensification, ed by 97 Taylor R and Krishna R, Modelling reactive distillation. Chem Eng Sci
Stankiewicz A and Moulijn JA. Marcel Dekker, New York (2004). 55:5183–5229 (2000).
69 Zhao H, Shao L and Chen JF, High-gravity process intensification 98 Sundmacher K and Kienle A (eds), Reactive Distillation: Status and
technology and application. Chem Eng J 156:588–593 (2010). Future Directions. Wiley-VCH, Weinheim (2003).
70 Wang GQ, Xu ZC and Ji JB, Progress on HiGee distillation - introduction
99 Luyben WL and Yu CC, Reactive Distillation Design and Control. John
to a new device and its industrial applications. Chem Eng Res Des
Wiley & Sons, Hoboken, New Jersey (2008).
89:1434–1442 (2011).
100 Kiss AA and Bildea CS, A review on biodiesel production by integrated
71 TU Dormund website: www.fvt.bci.tu-dortmund.de/cms/en/
reactive separation technologies. J Chem Technol Biotechnol
research/research_topics/ Process_intensification_by_unit_opera
87:861–879 (2012).
tion_design/index.html (last accessed on 20 October 2013).
101 Stankiewicz A, Reactive separations for process intensification:
72 Lin CC, Ho TJ and Liu WT, Distillation in a rotating packed bed. J Chem
an industrial perspective. Chem Eng Process 42:137–144
Eng Japan 35:1298–1304 (2002).
(2003).
73 Chandra A, Goswami PS and Rao DP, Characteristics of flow in a
rotating packed bed (HIGEE) with split packing. Ind Eng Chem Res 102 Noeres C, Kenig EY and Gorak A, Modelling of reactive separation
44:4051–4060 (2005). processes: reactive absorption and reactive distillation. Chem Eng
74 Reddy KJ, Gupta A and Rao DP, Process intensification in a HIGEE with Process 42:157–178 (2003).
split packing. Ind Eng Chem Res 45:4270–4277 (2006). 103 Gorak A and Stankiewicz A, Intensified reaction and separation
75 Gaska RA and Cannon MR, Controlled cycling improves various systems. Ann Rev Chem Eng Biomol Eng 2:431–451 (2011).
processes. Ind Eng Chem 53:630–631 (1961). 104 Dimian AC, Bildea CS, Omota F and Kiss AA, Innovative process for
76 McWhirter JR and Cannon MR, Controlled cycling distillation in a fatty acid esters by dual reactive distillation. Comput Chem Eng
packed-plate column. Inst Eng Chem 53:632–634 (1961). 33:743–750 (2009).
77 Maleta VN, Kiss AA, Taran VM and Maleta BV, Understanding process 105 Kiss AA, Heat-integrated reactive distillation process for synthesis of
intensification in cyclic distillation systems. Chem Eng Process fatty esters. Fuel Process Technol 92:1288–1296 (2011).
50:655–664 (2011). 106 Harmsen GJ, Reactive distillation: the front-runner of industrial
78 Kaibel G, Distillation columns with vertical partitions. Chem Eng process intensification: a full review of commercial applications,
Technol 10:92–98 (1987). research, scale-up, design and operation. Chem Eng Process
79 Kolbe B and Wenzel S, Novel distillation concepts using one-shell 46:774–780 (2007).
columns. Chem Eng Process 43:339–346 (2003). 107 Buchaly C, Kreis P and Górak A, Hybrid separation processes -
80 Asprion N and Kaibel G, Dividing wall columns: fundamentals and combination of reactive distillation with membrane separation.
recent advances. Chem Eng Process 49:139–146 (2010). Chem Eng Process 46:790–799 (2007).
81 Dejanović I, Matijašević L and Olujić Ž, Dividing wall column - a 108 Aiouache F and Goto S, Reactive distillation-pervaporation hybrid
breakthrough towards sustainable distilling. Chem Eng Process column for tert-amyl alcohol etherification with ethanol. Chem
49:559–580 (2010). Eng Sci 58:2465–2477 (2003).
82 Yildirim O, Kiss AA and Kenig EY, Dividing wall columns in chemical 109 Steinigeweg S and Gmehling J, Transesterification processes by
process industry: a review on current activities. Sep Purif Technol combination of reactive distillation and pervaporation. Chem Eng
80:403–417 (2011). Process 43:447–456 (2004).
83 Schultz MA, Stewart DG, Harris JM, Rosenblum SP, Shakur MS and 110 Rewagad RR and Kiss AA, Modeling and simulation of a pervaporation
O’Brien DE, Reduce costs with dividing-wall columns. Chem Eng process for fatty ester synthesis. Chem Eng Comm 199:1357–1374
Prog 98:64–71 (2002). (2012).
84 Parkinson G, Dividing-wall columns find greater appeal. Chem Eng 111 Nuchter M, Ondruschka B, Bonrath W and Gum A, Microwave assisted
Prog 103:8–11 (2007). synthesis - a critical technology overview. Green Chem 6:128–141
85 Pendergast JG, Vickery D, Au-Yeung P and Anderson J, Consider divid- (2004).
ing wall columns. Chem Process, 19 Dec 2008, Article 245 (2008). 112 Altman E, Stefanidis GD, van Gerven T and Stankiewicz AI,
URL: http://www.chemicalprocessing.com/articles/2008/245/ Process intensification of reactive distillation for the synthesis
86 Olujić Ž, Jödecke M, Shilkin A, Schuch G and Kaibel B, of n-propyl propionate: the effects of microwave radiation on
Equipment improvement trends in distillation. Chem Eng Process molecular separation and esterification reaction. Ind Eng Chem Res
497

48:1089–1104 (2009). 49:10287–10296 (2010).

J Chem Technol Biotechnol 2014; 89: 479–498

c 2013 Society of Chemical Industry wileyonlinelibrary.com/jctb
 www.soci.org AA Kiss

113 Shah M, Kiss AA, Zondervan E and de Haan AB, A systematic 118 Vane LM and Alvarez FR, Membrane-assisted vapor stripping: energy
framework for the feasibility and technical evaluation of reactive efficient hybrid distillation-vapor permeation process for alcohol-
distillation processes. Chem Eng Process 60:55–64 (2012). water separation. J Chem Technol Biotechnol 83:1275–1287
114 Shah M, Kiss AA, Zondervan E and de Haan AB, Influence of liquid (2008).
back mixing on a kinetically controlled reactive distillation process. 119 Frolkova AK and Raeva VM, Bioethanol dehydration: state of the art.
Chem Eng Sci 68:184–191 (2012). Theoret Found Chem Eng 44:545–556 (2010).
115 Shah M, Kiss AA, Zondervan E and de Haan AB, Pilot-scale 120 Kiss AA and Ignat RM, Optimal economic design of a bioethanol
experimental validation of unsaturated polyesters synthesis by dehydration process by extractive distillation. Energy Technol
reactive distillation. Chem Eng J 213:175–185 (2012). 1:166–170 (2013).
116 Shah M, Kiss AA, Zondervan E and de Haan AB, Evaluation of 121 Muller M and Hubsch U, Dimethyl ether, in Ullmann’s Encyclopedia
configuration alternatives for multi-product polyester synthesis Industrial Chemistry, 7th edn. Wiley-VCH, Weinheim (2005).
by reactive distillation. Comput Chem Eng 52:193–203 (2013). 122 Kiss AA and Ignat RM, Revamping dimethyl ether separation to a
117 Meirelles A, Weiss S and Herfurth H, Ethanol dehydration by extractive single-step process. Chem Eng Technol 36:1261–1267 (2013).
distillation. J Chem Technol Biotechnol 53:181–188 (1992).
498

wileyonlinelibrary.com/jctb

c 2013 Society of Chemical Industry J Chem Technol Biotechnol 2014; 89: 479–498