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Recent Advances in Distillation Intensification

The document reviews recent developments in intensified distillation-based separation processes, emphasizing the importance of process intensification (PI) for improving energy efficiency, reducing costs, and enhancing sustainability in chemical engineering. It discusses various PI technologies, particularly focusing on distillation methods such as dividing-wall columns (DWC), heat-integrated distillation columns (HIDiC), and reactive separation processes. The paper highlights challenges and future prospects for implementing these technologies in industrial applications.

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0% found this document useful (0 votes)
11 views13 pages

Recent Advances in Distillation Intensification

The document reviews recent developments in intensified distillation-based separation processes, emphasizing the importance of process intensification (PI) for improving energy efficiency, reducing costs, and enhancing sustainability in chemical engineering. It discusses various PI technologies, particularly focusing on distillation methods such as dividing-wall columns (DWC), heat-integrated distillation columns (HIDiC), and reactive separation processes. The paper highlights challenges and future prospects for implementing these technologies in industrial applications.

Uploaded by

mcalkane39
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© All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
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Review 2183

Nguyen Van Duc Long1,2


Intensified Distillation-Based Separation
Le Quang Minh1
Faizan Ahmad3 Processes: Recent Developments and
Patricia Luis4
Perspectives
Moonyong Lee1

1
School of Chemical Greater sustainability can be achieved by decreasing the production costs, energy
Engineering, Yeungnam consumption, equipment size, and environmental impact as well as improvement
University, Gyeongsan, South of the raw material yields, remote control, and process flexibility. Process intensifi-
Korea. cation (PI) as the main route for improving the process performance is used
2 widely in heat transfer, reactions, separation, and mixing, which results in plant
Department for Management
compactness, cleanliness, and energy efficiency. Some of the main intensified sep-
of Science and Technology
aration processes and improvement mechanisms are reviewed briefly with the
Development & Faculty of
Applied Sciences, Ton Duc
main focus on the PI of distillation processes, which are the most important sepa-
Thang University, Ho Chi Minh ration methods. In addition to these technologies, the potential and reliability of
City, Vietnam. reactive separation processes are addressed briefly, which will enable higher effi-
3
ciency and capacity.
School of Science and
Engineering, Teesside Keywords: Energy efficiency, Innovative systems, Process intensification,
University, Middlesbrough, Reactive separation processes
United Kingdom.
Received: October 26, 2015; revised: March 13, 2016; accepted: September 09, 2016
4
Materials & Process
Engineering (iMMC-IMAP), DOI: 10.1002/ceat.201500635
Université Catholique de
Louvain, Louvain-la-Neuve,
Belgium.

1 Introduction sumes less energy has the potential to replace conventional


energy-intensive technologies. However, many challenges need
The development of industrial systems for the year 2050 has to be overcome before the membranes can be scaled up using
been well defined in the recent Research Agenda with many PI technologies.
strategic sectors, such as water, energy, food, and health, Considerable efforts have been made in the past to make new
expected to take place consistently based on process intensifica- developments that go beyond traditional separation processes
tion (PI) principles [1]. They require innovative methods for [6]. Materials and process-development strategies for improving
the design of equipment and processes that are expected to the separation energy efficiency include replacing high-energy
achieve significant improvements, such as higher energy effi- technologies, such as distillation, drying, and evaporation, with
ciency, capital reduction, safety, environmental impact, and low-energy technologies, such as extraction, absorption, ad-
improved raw-material yields [2, 3]. However, there are several sorption, membrane separations, crystallization, and physical-
hurdles preventing the rapid implementation of PI technolo- property-based operations or adopting PI strategies [7]. In par-
gies in the process industry, such as the higher failure risk to ticular, to intensify the separation process, there are two areas
the process industry, higher scale-up knowledge uncertainty, [6]: process-intensifying equipment, such as Higee (high grav-
higher equipment unreliability, and increased safety, health, ity) referring to rotating packed bed (RPB) [8], and process-in-
and environmental risks [4]. tensifying methods, such as hybrid processes [9], dividing-wall
Separations, which currently account for 60 to 80 % of the column (DWC) [10], integration of reaction and separation
process cost in most mature chemical processes, can be [11], and techniques using alternative energy sources, including
improved by using PI technologies [5]. Among these separa- microwave, centrifugal field, and electric fields [3] (Fig. 1).
tion processes, distillation, which comprises the largest share of Reactive separations, which are formed through the combi-
the industrial energy use for separations, has attracted consid- nation of a selected separation process with a chemical reaction
erable attention to improve efficiency. A membrane that con- within a single unit, have attracted considerable attention in
industry and academia. This technology can improve the reac-
– tion conversion and selectivity by removing the products from
Correspondence: Prof. Moonyong Lee (mynlee@[Link]), School of the reactive section and circumventing/overcoming the separa-
Chemical Engineering, Yeungnam University, Gyeongsan 712-749, tion boundaries, such as azeotropes in the distillation process
South Korea. [12]. However, reactive separation processes have some limita-

Chem. Eng. Technol. 2016, 39, No. 12, 2183–2195 ª 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim [Link]
2184 Review

Figure 1. Separation pro-


cess intensification toolbox.

tions, such as complex modeling needs, increased operational 2.1.1 Dividing-Wall Column
complexity, limited applications, significant development costs,
and extensive equipment design efforts [3]. The thermal coupling technique is a good mechanism for
This paper reviews some of the intensified separation pro- improving the conventional distillation sequence [21]. Among
cesses and improvement mechanisms. In particular, this study the configurations that employ the thermal coupling technique,
focuses mainly on the PI of distillation, which has attracted a DWC is one of the best PI technologies and the most widely
significant interest from industry and academia. In addition applied in industry, as shown in Fig. 2. This industrially proven
to these technologies, the potential and reliability of reactive technology results in a reduction of the quantity of heat
separation processes are addressed briefly, which would ena- exchangers, enhanced separation efficiency, and energy and
ble the intensification of various production processes. This capital-cost savings. Recently, the application of DWCs was
paper proposes and evaluates new efforts for the membrane- extended to azeotropic [22], extractive [23], and reactive distil-
assisted reactive dividing-wall column (MRDWC), which is lations [24]. Several excellent review papers about DWCs have
an innovative configuration combining reactive distillation been published. In particular, a recent review by Dejanovic et
used to overcome the chemical equilibrium and the dividing- al. [25] gave a comprehensive overview of DWCs, which cov-
wall column employed to reduce the energy requirement, with ered both theoretical descriptions and the patent area, while
a membrane to overcome the azeotrope in azeotropic distilla- another review by Yildirim et al. [26] focused on current indus-
tion systems. The most important and interesting recent devel- trial applications of DWCs and related research activities,
opments in the current main research areas are summarized to including the column configuration, design, modeling, and
highlight the importance as well as the effects, challenges, and control issues. Long and Lee [27] reviewed the retrofitting of
future prospects of PI for distillation-based processes. distillation columns using a thermally coupled distillation
sequence (TCDS) and DWC to improve energy efficiency.
The design, control, and application of DWCs of the three-
2 Intensification of Separation Processes component mixtures are well established [25]. Recently, the
extension of DWCs to the separation of more than three com-
2.1 Distillation ponents including the Kaibel, Sargent, and Agrawal arrange-
ments have attracted attention (Fig. 3) [28]. The Agrawal
Distillation is a highly energy-demanding unit operation and arrangement, which showed better results in this study, was
numerous modes of energy, or process-intensification alterna- applied to improve the natural-gas recovery process [29]. The
tives, which are based either on the application of additional and Kaibel arrangement is an interesting alternative considering its
alternative energy forms or on the manipulation of various simplicity by withdrawing a second side stream of a DWC. The
structural parameters [13, 14], have been proposed and imple- design of this column was almost solved, but the operation and
mented over the years. Several reports considered intensified control still remain open issues [30]. The Kaibel arrangement
distillation, such as DWC [15], internal heat-integrated distilla- is difficult to handle when minimizing the vapor flow rate at a
tion columns (HIDiCs) [16], Higee distillation [17], and even cy- given product purity, whereas it appears to be easier to operate
clic distillation [18], as well as innovative reactive distillation when the product purities are free. This arrangement can be
[19] and reactive DWC [20], which will be discussed in Sect. 3. used in refinery plants where the product purities do not play a
High-performance trays/packings are not reported in this paper. vital role or when a bottleneck problem occurs in the process

[Link] ª 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim Chem. Eng. Technol. 2016, 39, No. 12, 2183–2195
Review 2185

Figure 2. Schematic diagram of the (a) DWC, (b) TDWC, and (c) BDWC.

[30]. Recently, the Kaibel arrange-


ment was investigated further by
means of an examination of the
effects of vapor split manipulation
[31].
Because DWCs can enhance the
energy efficiency in the distillation
sequences, considerable efforts
have been made to retrofit existing
distillation columns to reduce the
energy requirements and/or in-
crease the capacity while maintain-
ing the main product purity and
recovery (Fig. 4) [27, 32–34]. In any
case, a successful retrofit project is
normally based on the maximum
employment of existing equipment
to reduce the investment cost [35].
Therefore, a dividing wall can be
added to the existing distillation to
form a DWC for improving energy
efficiency. In addition, one of the
key ideas in de-bottlenecking is to
have the DWC manage the in-
creased load [36].
Most reports on the column
internals of DWC use the packing
type [26]. Recent efforts on the
design of DWCs with trays, which
is important for systems operating
at high vapor loads, using compu-
tational fluid dynamics were re-
ported [37]. This study pioneers
the studies on the design of trays or
packing type, hydraulic and operat-
ing conditions analysis for a range
Figure 3. Schematic diagram of the (a) Kaibel, (b) Sargent, and (c) Agrawal arrangement. of DWC systems, particularly for

Chem. Eng. Technol. 2016, 39, No. 12, 2183–2195 ª 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim [Link]
2186 Review

a) b) applications to floating, production, storage, and off-loading


facilities (FPSO) and floating liquefied natural gas (FLNG),
which have significant motion. DWC applications are expected
to increase and become a standard distillation piece of equip-
ment over the next 50 years [38].

2.1.2 Internally Heat-Integrated Distillation Column


c)
The heat-integrated distillation column (HIDiC) is the most
revolutionary approach to heat pump design [39]. Remarkably,
up to 70 % energy savings can be achieved using a HIDiC sys-
tem compared to the conventional distillation columns; this is
achieved by utilizing the heat from the rectifying section to boil
the stripping part of the column. However, many challenges,
d) e) such as high investment costs, complex design, and control
problems, need to be overcome before HIDiC can be con-
ducted on a commercial scale [14].
Recently, an excellent review [39] provided a comprehensive
overview of the latest developments of HIDiC, covering all the
major aspects related to the working principle, thermodynamic
analysis, potential energy savings, various design configura-
f) g) tions, and construction options, design optimization, process
control, and operation issues, as well as pilot scale and poten-
tial industrial applications. Remarkably, a development in this
area was reported with a trade name, SuperHIDiC (Fig. 5),
which was developed by Toyo Engineering Corp. [40]. How-
ever, the separation of multicomponent mixtures using this
technology is still an extremely challenging research issue [39].
h) i)
2.1.3 Higee Distillation

Higee, which is a synonym for high-gravity technology, and


utilizes centrifugal fields to form a rotating packed bed (RPB),
provides another mechanism to improve the separation effi-
ciency [8, 41, 42]. The fundamentals of mass transfer in RPBs
need to be explored and understood fully. The flow patterns
inside a rotating packed bed are difficult to observe inside a
rotating packing [13]. Recently, a novel high-gravity device, the
rotating zigzag bed (RZB) shown in Fig. 6, which has a unique
rotor combining the rotational part with a stationary one, was
j) k)
developed to overcome the disadvantages of the rotating bed
[43].
The application of Higee distillation is rather new [44], and
it has not yet been established in industry. Nevertheless, in
China, approximately 200 units of a RZB have been commer-
cialized [42]. Offshore applications of distillation might also
become feasible because the Higee unit is easier to operate
when there is movement [13, 45].

2.1.4 Cyclic Distillation

Cyclic distillation is another intensified unit that has attracted


Figure 4. Schematic diagram of promising configurations for increasing attention. This enhances the separation efficiency
retrofit using DWC.
based on separate phase movement, which can save energy
requirements substantially [46, 47]. The cyclic operating mode

[Link] ª 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim Chem. Eng. Technol. 2016, 39, No. 12, 2183–2195
Review 2187

ing and design of cyclic distillation col-


umns is rather limited. Recently, a cyclic
distillation column on the industrial scale
was modeled with significantly improved
separation efficiency compared to the con-
ventional bubble-cap trays column, exceed-
ing 200–300 % [47]. Sluice-champer trays
were proposed to prevent the limitations
associated with the number of trays (Fig. 7)
[47, 49]. The performance of a pilot-scale
cyclic distillation column was first reported
for ethanol/water separation [49].

2.2 Other Separation Processes

Considerable attention has been paid to the


development and application of PI on sepa-
ration, which requires substantial energy in
many chemical industries. Tab. 1 lists the
other selected separation-process-intensifi-
cation technologies. In recent years, among
the various separation processes available,
membranes have attracted substantial in-
terest from industrial and academic per-
spectives. Membrane engineering has the
potential to contribute towards process in-
tensification by replacing the conventional
energy-intensive separation techniques,
such as distillation and evaporation, to
achieve the selective and efficient transport
of specific components, to improve the per-
formance of the reactive processes, and to
Figure 5. Schematic diagram of a SuperHIDiC configuration [38]. provide reliable choices for environmen-

Figure 6. Simplified sketch of the RZB and its rotor [40]. (1) Ro-
tational disc, (2) rotational baffle, (3) gas inlet, (4) stationary baf-
fle, (5) stationary disc, (6) gas outlet, (7) liquid inlet, (8), middle
feed, (9) liquid outlet, (10) casing, (11) shaft

consisting of a vapor flow period and a liquid flow period can


achieve higher separation efficiency and higher product quality,
as well as reduce the energy requirement and number of trays Figure 7. Cross section of a cyclic distillation and specific inter-
as compared to conventional distillation [18, 47]. nals [47].
However, cyclic distillation has several limitations [47–49].
The application to vacuum distillation is difficult. The perfor- tally friendly industrial growth [70, 71]. Over the last fifteen
mance improvement is difficult to achieve when the column years, some membrane-based processes have been commercial-
has more than ten simple trays [48]. Furthermore, the model- ized, such as membrane distillation, membrane absorbers,

Chem. Eng. Technol. 2016, 39, No. 12, 2183–2195 ª 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim [Link]
2188 Review

Table 1. Summary of other selected separation-process-intensification technologies.

Process type Equipment type Intensification technique Main remarks Ref.


(or name) (or mechanism)
Absorption Higee Rotating packed bed Significant volume reduction can be achieved using Higee over [50]
conventional packed beds.
Reactive absorption (RA) Integrating of reaction and The most common use of RA is for the separation of gas mixtures [51]
absorption in one single piece (e.g., CO2, H2S, NOx, and SOx) in a solvent. The extensive efforts
of equipment in CO2 capture and storage mainly stimulate the current growth
of RA processes. Owing to the large chance for enhancing the
regeneration of the solvent, which is responsible for up to 70–80 %
of the operating costs, most current research had focused on the
development of new solvents.
Adsorption Temperature swing The molecules are strongly The CO2 capture from flue gases can consider TSA as an [52]
adsorption (TSA) adsorbed at low temperatures, interesting option. A gap between the emerging works aimed
and the molecular sieves are at determining quantitative structure-property relationships
regenerated at high of adsorbents and the actual process performance still remains.
temperatures.
Pressure swing The molecules are strongly PSA is normally preferred over TSA because of its lower [53]
adsorption (PSA) adsorbed at high pressures, operating cost.
and the molecular sieves are
regenerated at low pressures.
Electrothermal swing Passing electricity through the This technology proposed for CO2 capture can potentially be [54]
adsorption (ESA) saturated adsorbent and the more energy effective than conventional TSA and PSA, thus
heat generated by the Joule reducing the CO2-capture cost.
effect facilitates the release of
gas.
Centrifugal adsorption Centrifugal force CAT can lead to very good separation efficiencies but it requires [55]
technology (CAT) very compact adsorption equipment with high capacity.
Reactive adsorption Integrating the mechanism This technology still needs to be applied commercially even [56]
of reaction and adsorption though it is well proven on the laboratory scale.
in one single unit
Extraction Podbielniak extractor Centrifugal force Intense contact between the two liquids and generation of an [57, 58]
interfacial surface area for mass transfer.
Electric field A 2- to 6–10-fold increase in the transfer rate can be achieved [59]
relative to the no-field case.
Ultrasound The yield and mass transfer in many solid-liquid extraction [60]
processes can be enhanced.
Microwave The extraction time was reduced, less solvent was used, and the [61]
amount of compound extracted was increased.
Reactive extraction (RE) Integration of reaction and Most studies in the literature are focused on equilibrium, kinetics, [62, 63]
extraction in one single piece and application of RE. The supercritical reactive extraction (SRE)
of equipment process was also suggested for biodiesel production to achieve a
faster rate. However, more fundamental research and development
are needed before this relatively new technology can be used on a
commercial scale.
Membrane Membrane distillation Vapor pressure difference A ‘‘research boom’’ and commercialization efforts for MD have [64]
between membrane surfaces been observed and realized. However, new and better membranes,
improved design of the membranes and of modules, and better
engineering overall are necessary for further industrial exploitation
of this technology.
Membrane absorption/ Selective transportation of the Most of the literature deals with a variety of membranes and [65, 66]
stripping gaseous component through membrane materials at different pressures and temperatures
a membrane while the of operation using different classes of absorbents. The most
component is dissolved in the important industrial application area is the capture of CO2
absorbing liquid. In membrane from flue gas with significant reductions of up to 70–75 and 65 %
stripping, selected components in terms of the weight and size of the equipment, respectively.
are separated from the liquid This can be advanced for offshore technology.
phase using a stripping gas.

[Link] ª 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim Chem. Eng. Technol. 2016, 39, No. 12, 2183–2195
Review 2189

Table 1. Continued.

Process type Equipment type Intensification technique Main remarks Ref.


(or name) (or mechanism)
Membrane This is characterized by the Membrane chromatography offers a process-intensive choice for [67, 68]
chromatography absence of pore diffusion, different chemical processes, such as ion exchange, metal affinity,
which is the main transport and protein and reverse-phase chromatography. Until now, the
resistance in conventional literature mostly discusses the approximate solutions neglecting the
column chromatography dispersion and kinetic aspects. In the future, the complex modeling,
using porous particles. membrane support materials, surface chemistry, and device design
needs to be assessed.
Membrane extraction The treated solution and the On the commercial scale, hollow-fiber membrane solvent- [69]
solvent are separated from extraction units are mostly used. Hydrophobic hollow fibers with
each other using a solid or higher solvent resistance are required for most industrial
liquid membrane. applications. Hydrophilic hollow fibers with an aqueous phase
in the pores are needed for processes that involve organic solvent
extraction.
Membrane A modified form of membrane The study of a membrane crystallizer is a response to the [66]
crystallization distillation that combines the high-market demand of high-value-added products. Moreover, it
principles of membrane and also allows control of the crystal shape, enhances crystal growth,
crystallization to achieve and achieves selective crystallization. These advantages over
separation conventional separation techniques make it an interesting process
in the field of process intensification.
Membrane reactors Integration of the reaction The recent development of catalytic membranes and membrane [56]
(MRs) and membrane in a single unit reactors, together with the membrane contactors units, might
present crucial opportunities for the redesign of industrial
processes based on integrated membrane systems. However, the
implementation of commercial-scale membrane reactors is quite
limited. Therefore, the development of very thin, flawless
membranes that can withstand high-pressure and high-
temperature conditions is needed.

membrane extractors, membrane strippers, and membrane bi- a match between the temperature favorable for the reaction
oreactors [69]. and the temperature favorable for separation [75].
The thermal coupling concept, which improves the thermo-
dynamic efficiency, can be used to improve RD. In particular,
3 Intensification Using Reactive TCDS and DWC, which are the best examples of proven PI
Separations technology, are proposed to form a thermally coupled reactive
distillation sequence (TCRDS) (Fig. 8) [76] and reactive divid-
The development and application of reactive separation pro- ing-wall column (RDWC) (Fig. 9), respectively, as an attempt
cesses integrating reaction and separation in a single set of to improve the energy efficiency and/or increase the capacity.
equipment has attracted significant interest that has resulted in Up to now, only a few industrial applications of RDWC have
equipment-size reduction, improved separation, a cheaper pro- been reported [26].
cess, and improved reaction efficiency [9]. The integration of a In addition, because membrane separation, such as pervapo-
reaction with separation has been investigated extensively for ration and vapor permeation, is not limited by vapor-liquid
reactive distillation but it has received less attention for reactive equilibrium, they can be considered to separate several non-
absorption, reactive adsorption, reactive extraction, and reac- ideal aqueous-organic mixtures, which form azeotropes [9].
tive membranes or membrane reactors. Therefore, a hybrid configuration comprised of membrane-as-
Reactive distillation (RD) has been the most extensively sisted RD is attractive for improving many chemical processes
researched PI method over the last two decades [72]. Com- sustainably. The separation process can be intensified further
pared to conventional reaction-distillation sequences, these by using a novel configuration of a MRDWC (Fig. 10), which
so-called RD processes have enabled higher reactant conver- integrates the RD used to overcome chemical equilibrium and
sion, product selectivity, as well as lower energy, water, and sol- the DWC employed to save energy with a membrane to over-
vent consumption, thereby leading to reduced investment and come the azeotrope. Note that the unreacted reactant separated
operating costs [73]. Normally, RD is applied to etherification, by the membrane can be withdrawn or recycled in the
esterification, and alkylation on an industrial scale [74]. How- MRDWC. This intensified configuration can also be considered
ever, compared to the design of a conventional distillation col- in a retrofit design. More detailed research will be needed to
umn, it is much more sensitive to pressure due to the need for better understand this process as well as to quantify the syner-
gistic effects between the three unit operations. Insight analysis

Chem. Eng. Technol. 2016, 39, No. 12, 2183–2195 ª 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim [Link]
2190 Review

a) b)

Figure 8. Schematic diagram of the TCRDC with (a) side rectifier and (b) side stripper.

a) b) c)

Figure 9. Schematic diagram of the (a) conventional reactive dividing-wall column, (b) top reactive dividing-wall
column, and (c) bottom reactive dividing-wall column.

should be studied and analyzed, which can be used to define


the operating range of this novel process.
Microwave-assisted RD has attracted considerable research
attention with its theoretical potential for enhanced separation
efficiency and reaction rates [12]. However, there is a conflict
in the obtained results. Werth et al. [77] examined the impact
of microwave irradiation on the separation and reaction in a
RD column, but observed no apparent enhancement either in
the separation efficiency on the macroscopic scale or in the
reaction rate. In contrast, the recent result from the application
for acetic acid and ethanol esterification [78] showed the
instantaneous improvement of ethyl acetate content up to
6.9 % under the same reflux ratio, and 6.7 % under the same
acetic acid feed-flow rate compared with the RD process. Fur-
ther study will be needed to prove the potential and feasibility
of the concept of microwave-assisted RD.
A novel PI approach integrating a cyclic operation and RD
Figure 10. Schematic diagram of the hybrid membrane-RDWC in a single unit that outperforms classic RD was proposed
systems. recently [79]. This study developed a rigorous mathematical
model and tested it with the synthesis
of dimethyl ether to reveal the key ben-
efits of a RD with cyclic operation
mode.
Tab. 1 summarizes the brief mecha-
nisms, the main applications, and re-
cent status of other selected reactive
separation processes. Up to now, RD
and RA have been commercialized,
Figure 11. Membrane reactor scheme [2]. whereas some processes, such as reac-

[Link] ª 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim Chem. Eng. Technol. 2016, 39, No. 12, 2183–2195
Review 2191

tive adsorption, reactive extraction, and membrane reactors a commonly used technique for pharmaceutical applications,
(Fig. 11), still require significant fundamental research and has been intensified by using ultrasound, microwave, and elec-
development before becoming viable on a commercial scale. tromagnetic techniques, etc. [87, 88].

4 Industrial Separation Process 4.3 Intensified Separation Systems in Renewable


Applications Energies (Biofuel)

Because PI can reduce the investment cost and inventory, and The production of biofuels already takes advantage of advanced
improve the heat management/energy utilization, it is expected PI technologies, such as reactive separation processes [89].
to have wide-ranging applicability, ranging from petrochemi- Most studies on reactive separation processes for biodiesel pro-
cals and bulk chemicals [4], fine chemical and pharmaceuticals duction were based solely on conventional reactive distillation
industries [3] to biofuels [80], carbon capture [81], and off- [90, 91], or alternatives, such as entrainer-based [92] or dual
shore processing [82]. Owing to the large volume production reactive distillation [93] or reactive absorption [94, 95]. In par-
of petrochemicals and bulk chemicals, reducing the energy ticular, a novel reactive-absorption-based biodiesel process was
consumption and environmental impact are significant moti- proposed, which is a simple and robust process, achieving high
vations of technology innovation. However, achieving improve- conversion and selectivity, with no thermal degradation of the
ments in the selectivity, yield, and processing time are more products, and no waste streams, as well as reducing the capital
important for fine chemicals and pharmaceuticals because the investment and operating costs [94]. Pervaporation, which is
energy cost comprises a smaller fraction of the production cost also described as a PI technology, can be applied to biodiesel
[7]. production [89].
The application of advanced or intensified distillation sys-
tems is expected to be promising when continuing to develop
4.1 Intensified Separation Systems the concept of biorefineries away from single-product systems
in Petrochemicals and Bulk Chemicals to multiple-product systems [96, 97]. In addition, the integra-
tion of bio-based raw materials into existing conventional
Numerous applications of PI technologies have been applied in plants will further push those intensified systems or hybrid
petrochemicals and bulk chemicals. Among them, reactive dis- processing [96]. However, the challenges to the implementation
tillations and DWCs are the most popular technologies with a of distillation systems to biotechnological processes remain
range of applications. In particular, reactive distillations and with respect to the operating conditions, such as handling solid
DWCs have been implemented on a commercial scale in the systems (e.g., enzymes, cells) and highly viscous systems, which
petrochemical industry more than 150 times [83] and more will require the development of new distillation systems, such
than 100 times [4, 84], respectively. as Higee distillation, which could fill this gap in specific cases
Eleven chemicals have been identified to have significant [12].
opportunity for energy savings through the implementation of
PI technologies: ethylene, ethanol, chlorine/sodium hydroxide,
ammonia, nitrogen/oxygen, ethylene chloride, propylene, ben- 4.4 Intensified Separation Systems
zene, ethylene oxide, methanol, and acetone [85]. Future appli- in Carbon Capture
cations in these industries can consider many types of innova-
tive multifunctional processes, such as RDWC, extractive An area of chemical engineering technology that has possibly
DWC, and hybrid configurations. grown most rapidly within the past few years is carbon capture,
the main aim of which is to reduce CO2 emissions from all
plants that burn fossil fuels, such as steel works, offshore facili-
4.2 Intensified Separation Systems in Fine ties, chemical plants, and possibly the largest challenge, power
Chemical and Pharmaceutical Industries generation plants on shore, in particular, but not limited to,
coal-fired power stations [3]. Normally, a packed column is
Fine chemicals, which are normally used as starting materials designed to remove CO2 by chemical absorption [98, 99]. To
for specialty chemicals, such as pharmaceuticals or agrochemi- improve the mass transfer rate in a conventional packed bed, a
cals, are produced in limited volumes with most operations rotating doughnut-shaped packing device, which refers to
being batch based. Besides the trend of changing to continuous Higee or RPB, was suggested [100]. This technology promotes
processes, many applications of PI technologies in these areas size and weight reduction, enhances the inherent safety with
have been realized. The potential benefits of PI that have been lower inventories, improves energy consumption, lowers the
identified are significant with overall cost reduction expected capital cost, and addresses environmental concerns [81, 101].
to be up to 20 % (5–10 years) and 50 % (10–15 years) [86]. The associated centrifugal acceleration leads to droplet flow
In particular, membrane chromatography has been applied and film flow of liquids in the unit. This will increase the inter-
to a wide range of compounds, particularly for purification of facial area and consequently mass transfer. Based on this, the
proteins [68]. Electrostatic fields have been employed to vessel size will be reduced significantly compared to conven-
improve the penicillin extraction process [3]. Drying, which is tional absorbers [101, 102].

Chem. Eng. Technol. 2016, 39, No. 12, 2183–2195 ª 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim [Link]
2192 Review

Furthermore, membrane technology can be considered a capability of each unit. The MRDWC, which combines RD,
promising separation method that overcomes the disadvan- DWC, and membranes for azeotropic-mixture separation, is an
tages of a gas absorption tower [103]. Considerable efforts have interesting and challenging example in this category. Further-
been made to increase the membrane performance with two more, different PI methods and different driving forces, such as
main approaches: gas permeation and membrane contactor. microwaves, magnetism, gravity, and others, need to be consid-
However, there is still a significant gap between the laboratory ered for integration in a unique system to achieve synergy
and commercial scales in the industry [104]. This is particular- effects in PI research and development. To achieve the smooth
ly important for intensifying the desorption process in the development of separation processes, other issues, such as new
stripper. In particular, agitation, ultrasound, and microwaves catalysts, membrane materials, new solvents, better rotary
can be used to improve the release of CO2 [3, 105]. machines, cheaper equipment fabrication, and reliable control
systems, also need to be considered.

4.5 Intensified Separation Systems in Offshore


Processing Acknowledgment
Normally, trays are preferred in the distillation of hydrocar- This study was supported by the Basic Science Research
bons. However, trays should not be applied to the distillation Program through the National Research Foundation of Korea
and separation columns of an offshore plant, such as FPSO and (NRF) funded by the Ministry of Education
FLNG, which must have the ability to withstand waves [106]. (2015R1D1A3A01015621), and by the Priority Research
Therefore, packed-type column designs are suitable because Centers Program through the National Research Foundation of
the columns can withstand motion [82]. The walls formed by Korea (NRF) funded by the Ministry of Education
the corrugated sheets reduce the impact of motion and make (2014R1A6A1031189).
structured packing a better choice than random packing [107].
Furthermore, the use of a DWC for offshore FLNG plants, The authors have declared no conflict of interest.
forming an energy-efficient and compact NGL recovery pro-
cess, has been suggested [82].
In seawater deaeration or deoxygenation, contact plays an Abbreviations
important role in the process with the most popular techniques
for contacting being packed, tray, or bubble columns, or agi- DWC dividing-wall column
tated vessels [3]. Significant intensification can be obtained by FLNG floating liquefied natural gas
using either Higee technology or the tangential injection of FPSO floating, production, storage, and off-loading
liquid into static vessels [108]. Kvarner recently evaluated a facilities
membrane absorption technology for removing CO2 from tur- HIDiC heat-integrated distillation column
bine exhaust gases in offshore applications [65]. Substantial MRDWC membrane-assisted reactive dividing-wall column
decreases in investment and operating costs relative to the con- PI process intensification
ventional amine separation process are expected [109]. RA reactive absorption
RD reactive distillation
RDWC reactive dividing-wall column
5 Conclusion RPB rotating packed bed
RZB rotating zigzag bed
Economic and environmental considerations have encouraged TCDS thermally coupled distillation sequence
many separation processes in the chemical industry to be TCRDS thermally-coupled reactive distillation sequence
focused on PI-based innovative engineering solutions. The use
of alternative energy sources, such as microwaves, centrifugal
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