Front. Chem. Sci. Eng.
https://doi.org/10.1007/s11705-020-2018-6
RESEARCH ARTICLE
Separation of n-heptane/isobutanol via eco-efficient vapor
recompression-assisted distillation: process optimization and
control strategy
Wei Hou1*, Qingjun Zhang1*, Aiwu Zeng (✉)1,2
1 State Key Laboratory of Chemical Engineering, School of Chemical Engineering and Technology, Tianjin University, Tianjin 300350, China
2 Chemical Engineering Research Center, Collaborative Innovative Center of Chemical Science and Engineering, Tianjin 300072, China
© Higher Education Press 2021
Abstract In this study, vapor recompression and heat
integration assisted distillation arrangements with either
the low or high pressure in the reflux drum are proposed to
reduce and/or eliminate the application of the costly
refrigerant for the separation of n-heptane and isobutanol
mixture. The high-pressure arrangement with vapor
recompression and heat integration is the most attractive
among these four intensified configurations since it can
reduce total annual cost by 18.10%, CO2 emissions by
75.01% based on natural gas (78.78% based on heavy oil
fuel), and second-law efficiency by 61.20% compared to a
conventional refrigerated distillation system. Furthermore,
exergy destruction in each component is calculated for the
heat integration configurations and is shown in pie
diagrams. The results demonstrate that the high-pressure
configuration presents unique advantages in terms of
thermodynamic efficiency compared to the low-pressure
case. In addition, dynamic control investigation is
performed for the economically efficient arrangement
and good product compositions are well controlled through
a dual-point temperature control strategy with almost
negligible product offsets and quick process responses
when addressing 20% step changes in production rate and
feed composition. Note that there are no composition
measurement loops in our developed control schemes.
Keywords n-heptane/isobutanol, vapor recompression,
heat integration, low and/or high-pressure options
Received August 6, 2020; accepted September 20, 2020
E-mail: awzeng@tju.edu.cn
*These authors contributed equally to this work.
1 Introduction
n-Heptane can be used as a substitute for diesel oil since its
cetane number and combustion characteristics are similar
[1,2]. Isobutanol, a vital industrial raw material, is widely
used for coatings, paints, medicine, cosmetics, and rubber
[3]. A large amount of n-heptane and isobutanol solution
can be produced during the methyldiethanolamine synth-
esis process [4]. Recycling these components is important
and essential for economic and environment at benefit.
Figure S1 (cf. Electronic Supplementary Material, ESM)
shows the T-xy curves for this binary mixture at different
pressures. Differing pressures can change the azeotropic
composition as well as the azeotropic behaviour, forming a
maximum-boiling azeotrope in the high-pressure range
and a minimum-boiling azeotrope in the low-pressure
range. This azeotropic phenomenon does not exist when
the pressure is sufficiently low [5]. Therefore, numerous
alternatives, such as extractive distillation (ED), pressure-
swing distillation (PSD), and single-column distillation,
can achieve n-heptane and isobutanol mixture separation
as observed from these special azeotropic characteristics.
ED increases the relative volatility of the components
and breaks the original azeotropic composition by
introducing a third component entrainer. In view of the
significant advantages of high separation efficiency, this
process has been widely used in the chemical industry
[6,7]. Wang et al. [8] developed a novel ED process using
N-methyl pyrrolidone as the entrainer to separate
n-heptane and isobutanol. In subsequent research, they
found that the dynamic control performance (the shorter
settling time and smaller transient deviations) could be
enhanced by increasing the solvent flow rate, although this
approach slightly increased the total annual cost (TAC).
However, the authors overlooked the fact that operating
pressure has a significant effect on this process. For the
2 Front. Chem. Sci. Eng.
purpose of utilizing inexpensive cooling water in the
condenser, both the extractive and solvent recovery
columns were arbitrarily set as 1.013
105 Pa. Regardless
whether 1.013
105 Pa was an appropriate pressure value,
the decision was not based on any theoretical foundation
that justifies this choice. In fact, pressure has an important
influence on phase equilibrium behaviour in terms of
relative volatility, column temperature or azeotropic
characteristics, and further affects the capital costs and
operating costs [9,10]. Randomly specifying the operating
pressure will usually cause the final result to deviate from
the global optimal solution [11]. In response to the
deficiencies of the above process, Luyben [12] reduced
the pressures of the extractive and solvent recovery
columns to 2.026
104 and 1.013
104 Pa, respectively.
The results showed that vacuum operation can reduce the
TAC by 27%, compared with the ED process which fixed
the pressures at 1.013
105 Pa. However, this work only
optimized the column pressure rather than all the
parameters, leaving possibility of elevated levels. Cui
and Sun [13] used a genetic algorithm to further optimize
the above process to obtain the global optimal solution. By
simultaneously optimizing all the independent decision
variables, the economy of the process was further
improved. It is worth noting that there are some significant
shortcomings in the ED process that limit its application
under some conditions. First, the third component entrainer
may reduce product purity since it cannot be completely
removed. In addition, entrainer recovery is an energy-
intensive process that generates costs.
Considering the peculiar boiling behaviour of the
n-heptane/isobutanol mixture under different pressures,
PSD can be adopted. Because it is necessary to add an
additional component, the PSD process has the advantages
of high separation efficiency and a simple operating
process. At the same time, there is a large temperature
difference between the bottom of the low-pressure column
and the top of the high-pressure column, which means that
the PSD process has a natural advantage in heat
integration. Wang et al. [5] designed a PSD process for
the separation of the n-heptane/isobutanol mixture. The
results of these schemes indicated that PSD is a feasible
option for the separation of azeotropes. In subsequent
work, Wang et al. [14] studied the steady-state economics
and dynamic controllability of a heat-integrated PSD
process with varied diameters for n-heptane/isobutanol
mixture separation. In this study, the novel process showed
a significant reduction in TAC compared to the conven-
tional PSD process.
In most cases, the relative volatility of n-heptane/
isobutanol mixture increases with decreasing pressure.
Theoretically, the pressure should be as low as possible to
enable a more straightforward separation process. Luyben
[15] designed a single-column separation method for this
mixture. This work set the operating pressure of the
column to 5.065
103 Pa, at which pressure there is no
azeotrope between n-heptane and isobutanol. The boiling
point of the component distilled in the overhead stream is
lower (295 K), so inexpensive cooling water cannot be
used, which makes this process uneconomical. In most
distillation processes, especially azeotropic distillation, it is
customary to avoid the use of vacuum distillation. The
reason is mainly to enable the use of inexpensive cooling
water in the condenser. However, there are some limita-
tions that restrict high-pressure operation. First, thermally
unstable components can constrain the maximum tem-
perature of the bottom. Second, when the pressure of the
light component is close to the critical pressure of the
separated component, hydraulic factors prevent distillation
because the density difference between the vapor and fluid
phases is very small. Low pressure must be used under
such circumstances. Third, in addition to increased
operating costs, vacuum distillation also increases equip-
ment costs because the reduction in pressure has a fatal
effect on the strength requirements of the column. These
limitations make the single-column process less econom-
ical than other distillation configurations. To obtain a more
effective reduction in the TAC, it is necessary to improve
the refrigerated distillation option and intensify the
separation process.
With improvements in energy conservation and social
environmental awareness, conventional refrigerated dis-
tillation can no longer meet the needs of energy savings.
Therefore, heat pump-assisted distillation [16] and heat-
integrated distillation [17] have been frequent topics of
research for reducing TAC and CO2 emissions. Leo et al.
[18] investigated several mechanical vapor recompression
configurations for the separation of ethane/ethylene
mixture via refrigerated distillation. Compared with the
conventional process, the novel system consumed less
energy and achieved a reduction of 35.44% in TAC. In
further research, Luyben [19] operated a condenser at a
higher pressure so that a high-temperature inexpensive
refrigerant could be used. In the case of high-pressure
operation, an unsaturated reflux will provide a larger
overhead vapor flow rate, which means a higher
compressor cost in terms of capital costs and electricity.
However, an inexpensive refrigerant can considerably
reduce energy costs and can sufficiently compensate for the
increase in compressor costs. The results showed that the
high-pressure case achieved a reduction of 7.44% in TAC
compared to the low-pressure case.
Although the refrigerated distillation process for
n-heptane/isobutanol separation has many advantages
over other processes, such as a simple structure and easy
control, the sequence is characteristic of expensive
refrigerant costs, so the economic performance of this
process is worse than that of the ED process. Inspired by
the above studies, the objective of this paper is to propose
two novel separation processes to improve the energy-
savings and economic performance of the benchmark by
combining an intensified vapor recompression and heat
 Wei Hou et al. Separation of n-heptane/isobutanol via vapor recompression distillation 3

integration strategy. First, steady-state simulations for the vapor recompression-assisted distillation option is
processes mentioned above are performed with the adopted. Conversely, the economics of the process will
simulation software Aspen Plus. The parameters for each not be improved when the COP value is less than 5. When
process are determined with the minimum TAC as the the value is between 5-10, the feasibility of this option
objective function. Finally, the economic benefits, second- should be determined through careful calculations.
law efficiency, exergy analysis and CO2 emissions of the
proposed configurations are compared. In addition, a 2.1.2 TAC and return on investment (ROI)
dynamic control investigation is performed for the
economically efficient arrangements. The TAC, including the total capital cost (TCC) and total
operating cost (TOC), is an essential evaluation indicator
for assessing the economic benefits of distillation pro-
2 Case study cesses. According to Douglas [21], the formula for the
TAC is as follows:
The feed conditions and product specifications are main-
tained at the same levels in all cases for a fair comparison. TCC
TAC ¼ TOC þ , (2)
All steady-state designs and simulations are performed Payback period
using the UNIQUAC physical properties in Aspen Plus
where the TOC mainly corresponds to the cooling water,
(V8.8) software. According to the American Society of
steam, and electricity costs. The TCC includes heat
Mechanical Engineers, the polytropic efficiency of 0.8 is
exchanger equipment costs (condenser, reboiler, other
used in the compressor calculations. Details of the feed
heat exchangers), compressor costs, vessel capitals costs
state and column operating conditions are shown in Table 1,
and plate costs. Remarkably, the cost of ambient
in which the parameters are taken from Luyben [15].
temperature cooling water (305 K) is 0.354 $$GJ–1, and
Table 1 Feed and column operating conditions in this work the cost of the refrigerant (253 K) is 7.89 $$GJ–1, which is a
Parameter Value notable difference. The payback period used in this article
is 5 years, with an operating time of 8000 h per year. The
n-Heptane 50 mol-% detailed calculation formulas or parameters are enumerated
Isobutanol 50 mol-% in Table S1 (cf. ESM) of the Supporting Information.
Feed flowrate 100 kmol$h–1 The ROI is a terminology used to evaluate the efficiency
Feed pressure 1.013 ´ 105 Pa
of an investment. It usually refers to the economic return
from the transformation of the original process. In other
Feed temperature 323 K
words, the larger the ROI value, the better the return and
Total stages of column 31 the more profitable the investment. The definition of ROI is
Feeding stage 13 shown in the following equation:
Base temperature 331.36 K
ROI ¼ utility savings=incremental capital costs, (3)
Purity of isobutanol in distillate 99.90 mol-%
Purity of n-heptane in bottoms 99.90 mol-%
where utility savings refer to the profits gained through the
transformation of the basic process and the reduction in
operating costs, and the incremental capital costs refer to
2.1 Evaluation criteria the additional capital costs compared to the basic process.

2.1.1 Heat pump performance 2.1.3 CO2 emissions

Coefficient of performance (COP) is an important Gadalla [22] proposed an accurate model for the calcula-
terminology used to evaluate the feasibility of the vapor tion of CO2 emissions for chemical production processes.
recompression-assisted option, and it is calculated by the The model for calculating CO2 emissions is as follows,
following equation [20]: based on the assumption that no carbon monoxide is
formed during combustion since the air is regarded as in
1 Q TC excess. The carbon footprint for electrical power consumed
COP ¼ ¼ ¼ , (1)
ηCarnot W TR – TC in the compressor is taken as CO2 of 51.1 kg$GJ–1 [23].
where Q (kW) and W (kW) refer to the reboiler duty and
α  C% 
compressor work, respectively, and TR (K) and TC (K) are ½CO2 emiss ¼ Qf uel , (4)
NHV 100
the temperatures of the reboiler and condenser, respec-
tively. Normally, when the COP value exceeds 10, the where Qfuel (kW) is the amount of fuel burnted, α (3.67) is
4 Front. Chem. Sci. Eng.
the molar mass content of carbon in CO2, and the net
heating value (NHV, kJ$kg–1) indicates the net heating
value of the fuel with a carbon content of C% (kg$kg–1).
For heavy oil fuel, C% and NHV are 86.5 and 39771,
respectively; for natural gas, 75.4 and 51600. In the
distillation system, Qfuel can be calculated from the
following equation:
Qproc T – T0
Qfuel ¼ ðh – 419Þ FEB , (5)
lproc proc T FTB – T stack
where the Qproc (kW) is the total energy required, and hproc
(kJ$kg–1) and lproc (kJ$kg–1) represent the enthalpy and
latent heat of utility steam delivered to this system. The
flame temperature and stack temperature are denoted as
TFTB (2073.15 K) and Tstack (433.15 K), respectively.
2.1.4 Exergy analysis and second-law efficiency (h)
The distillation process usually includes chemical potential
transfer, heat transfer and momentum transfer, and exergy
is the driving force of this process. Because of the
irreversibility of the abovementioned transfer process, it
will inevitably lead to losses of exergy. Energy saving
means reducing unnecessary and unreasonable exergy
losses. Therefore, it is of great practical significance to
correctly calculate the exergy losses caused by irreversible
processes and to analye and understand the exergy losses
in detail. The formula of exergy rise in the system is
illustrated in Eq. (6):
X 0.230
106 $$y–1 and a TOC of 0.535
106 $$y–1. The
Exrise-system ¼ Exinput – Exloss-component , (6)
where Exinput includes the exergy input of the process
streams, compressor, and steam, and Exloss-component
represents the exergy destruction in each component,
which is formulated as Eq. (7):
X
Exloss-component ¼ Exinput – Exoutput , (7)
The second-law efficiency determines process efficiency
from the perspective of energy utilization. During the
distillation process, this logical index is used to quantify
the economy of different configurations. The second-law
efficiency can be calculated from the following equation
[24]:
W min
η¼ , (8)
LW þ W min
where Wmin (kJ$h–1) and LW (kJ$h–1) represent the
minimum work required and lost work, respectively and
their definitions are shown in Eqs. (9) and (10),
respectively:
X X
W min ¼ out
nb – in
nb, (9)
X  
T0
 
LW ¼ nb þ Q 1 – þ WS
in TS
X  
T0
 
– nb þ Q 1 – þ WS , (10)
out TS
where Q is the heat requirement in the distillation system,
Ws is the input work required by the compressor,
b (kJ$mol–1) represents the exergy (its expression is
b = h – T0s, where h (kJ$kmol–1) is the enthalpy of the
stream and s (kJ$kmol–1$K–1) refers to the molar entropy of
the stream), n (kmol$h–1) is the molar flow rate, and T0 (K)
represents the ambient temperature (its value is 305 K).
2.2 Conventional single-column arrangement
The conventional distillation (CD) process is operated at a
low pressure (5.065
103 Pa) where no azeotrope is
formed. Figure 1 shows the flowsheet for this configura-
tion. Products (99.9 mol-%) n-heptane and isobutanol are
obtained at the top and bottom of the column, respectively.
Note that the overhead temperature is just 295 K at the
operating pressure of 5.065
103 Pa. Commonly used
cooling water, with a typical temperature of 305 K, is in
adequate for condensing the stream under these circum-
stances, so the expensive low-temperature refrigerant is
used in the condenser. Luyben [15] selected a refrigerant at
253 K with a cost of 7.89 $$GJ–1 (contrasted with cooling
water at a cost of 0.354 $$GJ–1). The TAC for this process
is 0.765
106 $$y–1 including an annual TCC of
refrigerant cost accounts for 47.29% of the operating costs,
which is a very large proportion in the distillation process.
2.3 Vapor recompression-assisted distillation
configurations
In the CD process, the energy supplied by the low-pressure
steam in the reboiler to boilup the bottoms is mostly wasted
during the condensation process, resulting in extremely
low thermodynamic efficiency. In addition, the process
uses expensive refrigerant as a cold utility, which promotes
a very high operating cost. Vapor recompression, as a
representative waste heat recovery technology, can
improve the efficiency of this process and reduce the
application of a cold utility. The COP is 8.194 in the CD
process, so the feasibility and effectiveness of vapor
recompression technology as an intensified option is worth
considering. Note that the introduction of a compressor
will inevitably bring additional equipment costs and a
resulting increase in electricity cost. Whether the economic
benefits of waste heat recovery will offset the increase in
costs needs to be determined by additional rigorous
calculations.
Figure 2 shows a schematic superstructure diagram for
the vapor recompression-assisted options with all possible
Wei Hou et al. Separation of n-heptane/isobutanol via vapor recompression distillation 5

Fig. 1 CD process for separating n-heptane and isobutanol.

Fig. 2 Schematic diagram of the vapor recompression-assisted option.

6 Front. Chem. Sci. Eng.
paths. There are two possible scenarios according to the
pressure in the reflux drum. One is that the pressure of the
stream leaving the reboiler is reduced by a throttle valve to
the same level as that of at top of the column before
entering the reflux drum. In this scenario, a portion of the
overhead stream flow should be directly bypassed through
the compressor, which is called a splitting arrangement, to
reduce the uneconomical outcome caused by the full
compression of the compressor when the heat supplied
(Qs) by the high-grade heat source produced by the
discharged stream from the compressor is greater than the
heat required (Qr) by the reboiler. A non-splitting option is
feasible if the energy required by the heat sink cannot be
neatly paired, and a trim steam-driven exchanger, denoted
as a utility exchanger, should be installed. It is well known
that if more heat is supplied by the high-grade vapor stream
discharging from the compressor, a higher rate of electrical
work consumption (or compression ratio) will result at a
certain vapor flow rate. It is possible to improve the energy
quality of the discharged stream without significantly
increasing the power consumption of the compressor when
a steam-driven preheater is used. In a high-pressure
scenario, the stream (saturated liquid) leaving the reboiler
directly enter the reflux drum with the same pressure as the
discharged stream of the compressor, and is then reduced
to the same level as the top of the column through the
throttle valve. In this case, after the overhead stream passes
through the compressor, it can choose whether to adopt the
split option according to the specific situation. If Qs is
larger than Qr, a portion of the stream flow should be split
and cooled by an auxiliary condenser. It is worth noting
that after being elevated by the compressor, the tempera-
ture of the stream has risen to be able to the point where
cooling water can be used as the cooling medium, which is
one of the advantages of the high-pressure case. Unlike the
saturated liquid reflux in the low-pressure case, although
expensive refrigerant can be avoided, the high-pressure
stream will be flashed before it enters the column, which
will increase the flow rate of the overhead vapor and
generate more compressor costs at the same pressure ratio
(PR). To satisfy the trade-off between the refrigerant cost
and compressor cost, it is necessary to make a global
decision by calculating the TAC of the entire system. The
PR, preheater duty (Qpre), and splitting ratio need to be
simultaneously optimized by taking the minimum TAC as
the objective function, and the detailed optimization
procedure for these possible routes is shown in Fig. 3.
In the vapor recompression configuration with a low-
pressure reflux drum (LPVRC) process, the heat released
from the high-grade discharged stream does not meet the
needs of the reboiler. Therefore, the non-splitting alter-
native option is adopted, and the utility exchanger is used
to offset the deficiency. The optimal operation parameters
are shown in Fig. 4. Undoubtedly, as the PR increases, the
TAC increases more quickly. The TAC decreases when the
preheater load increases from 0 to 150 kW, while the TAC
rapidly increases when the preheater load increases from
150 to 300 kW. The minimum TAC is obtained when the
PR and the Qpre are 6.25 and 150 kW. Figure 5 shows the
LPVRC configuration flowsheet with the optimal operat-
ing parameters. The TAC for the optimal LPVRC process
is 0.738
106 $$y–1, including a TOC of 0.323
106 $$y–1
and an annual TCC of 0.415
106 $$y–1. This process is
prevailed over the CD process slightly since it can achieve
a 3.45% savings in TAC. It is worth noting that the use of
vapor recompression technology enhances to the process
of refrigerated distillation, which requires more expensive
refrigerant; it can reduce not only the heat duty of the
reboiler but also the cold utility requirements of the
condenser.
Figure 4(b) shows the optimal operation parameters for
the HPVRC arrangement, and the optimization procedure
for this process is the same as that in the LPVRC
arrangement. The minimum TAC is obtained when PR and
Qpre are 6.26 and 160.97 kW, respectively. Figure 5(b)
shows the HPVRC configuration flowsheet with the
optimal operating parameters.
A comparison of Figs. 5(a) and 5(b) shows that the
influences of the higher pressure in the reflux drum are as
follows: 1) The vapor fraction of the reflux stream is
changed from 0 to 0.27. 2) The overhead vapor flow rate is
increased from 106.67 to 122.11 kmol$h–1. 3) The power in
the compressor is increased from 196.19 to 219.93 kW.
4) Qpre is increased from 150 to 160.97 kW. 5) The
condenser duty is reduced from 298.50 to 0 kW. 6) The
recovery exchanger duty is increased from 1160.22 to
1296.45 kW. 7) The utility exchanger duty (auxiliary
reboiler) is reduced from 195.89 to 0 kW.
The reflux stream from the high-pressure reflux drum
flashes as it is fed into the column at lower pressure,
resulting in an increase in the flow rate of the overhead
vapor. Correspondingly, the optimal Qpre and the work of
the compressor also increase. However, the increased
overhead vapor flow rate brings unexpected benefits to the
system. This critical fundamental difference means that the
upgraded stream could provide enough energy to gasify the
liquid at the bottom of the column without using a utility
exchanger. Moreover, the heat can be removed entirely by
the recovery exchanger, which means that extra refrigerant
is not required to cool the overhead vapor from the column.
In summary, the high-pressure scenario can save heat and
cold utilities at the same time. Compared with the LPVRC
process, this process is more economically favorable,
which is reflected by the small TAC value (0.651
106
$$y–1) with the summation of the TOC (0.239
106 $$y–1)
and the annual TCC (0.412
106 $$y–1). The comparisons
of economic data and thermodynamic properties for the
alternatives are shown in Section 3.1.
The thermodynamic characteristics of the stream in
different processes can be expressed by a temperature-
enthalpy (T–H) diagram, which is shown in Fig. 6. The
overlap region (shaded zone) between the hot composite
Wei Hou et al. Separation of n-heptane/isobutanol via vapor recompression distillation 7

Fig. 3 Sequential iterative optimization procedure.

8 Front. Chem. Sci. Eng.

Fig. 4 Effect of parameters on TAC for different processes: (a) LPVRC; (b) vapor recompression configuration with a high-pressure
reflux drum (HPVRC); (c) intensified HPVRC process by the combined use of heat integration (HPVRC-HI).

curve and the cold composite curve illustrates the heat
recovery within the process. The implications of these two
composite curves are demonstrated in Zhang et al.’s works
[25–28]. The hot utility is 160.97 kW in the HPVRC
process and is reduced by 84.92 kW in comparison with
that of the LPVRC process. Of particular importance is that
the cold utility is no longer required in HPVRC process,
which is a surprising improvement in refrigerated distilla-
tion.
A helpful graphical method of visualization, which
includes the pressure – temperature (P – T) curves shown in
Fig. S2 (cf. ESM), is used to show the steps of the feed
state change for the overhead vapor. For the LPVRC
alternative, as shown in Fig. S2(a), State 1 indicates that
the initial state of the overhead vapor is 294.6 K and 5.065

104 Pa. After being preheated to 323.9 K (State 2), its
temperature and pressure are further increased by the
compressor to 359.1 K and 3.171
104 Pa (State 3). Then,
the stream exchanges energy with the reboiler through the
recovery exchanger. Its pressure remains unchanged, but
the temperature drops to 336.4 K, as shown in State 4.
State 5 represents the temperature and pressure of the
reboiler. The shaded zone represents that the differential
temperature driving force of the hot-end in the recovery
exchanger is 5 K. The state transforming steps for the
overhead vapor stream for the HPVRC process are shown
in Fig. S2(b).
2.4 Intensified processes by the combined use of heat
integration
Compared with the CD process, the vapor recompression-
assisted distillation processes show superior economic and
environmental performances. However, the pressurized
overhead vapor is condensed immediately after heat is
released in the reboiler in the LPVRC configuration, while
the possible available energy is also lost through the
throttle valve after the reflux in the HPVRC configuration,
resulting in improper heat utilization. Therefore, the
application of the intensified heat integration strategy is
 Wei Hou et al. Separation of n-heptane/isobutanol via vapor recompression distillation 9

Fig. 5 Flowsheets of vapor recompression processes with details: (a) LPVRC; (b) HPVRC; (c) intensified LPVRC process by the
combined use of heat integration (LPVRC-HI); (d) HPVRC-HI.

economically feasible since some energy from the hot
stream could be recovered within the process before further
cooling. Figures 5(c) and 5(d) show the flowsheets of these
two intensified novel configurations, which we label
LPVRC-HI and HPVRC-HI.
In the LPVRC-HI process, the heat requirement in the
preheater is conveniently provided by the hot stream
coming out of the reboiler. All the operating parameters in
the LPVRC-HI arrangement remain the same as the
basically intensified LPVRC configuration owing to the
unchanged operating conditions. This arrangement can
reduce external hot utility consumption (150 kW) and save
a portion of cold utility consumption (150 kW). More
intuitive information can be obtained from the T – H
diagrams shown in Fig. 6(c). With the application of heat
integration, the shaded zone (1310.22 kW) is larger than in
the LPVRC process (1160.22 kW). Additionally, the
requirements of hot utilities (195.90 versus 245.90 kW)
and cold utilities (148.50 versus 298.50 kW) have
significantly reduced, which means that the energy savings
and work reductions are further improved. Different from
the process of using water as a cooling medium, in view of
the tremendous cost of low-temperature refrigerant, any
reduction in cold utility will bring considerable benefits.
The TAC for this process is 0.685
106 $$y–1 including a
TOC of 0.258
106 $$y–1 and an annual TCC of 0.427

10 Front. Chem. Sci. Eng.
Fig. 6 The T-H diagram for different process: (a) LPVRC; (b) HPVRC; (c) LPVRC-HI; (d) HPVRC-HI.
106 $$y–1. This is much more prevalent over the LPVRC
process since it can achieve a 7.26% reduction in the TAC.
For the HPVRC-HI process, the situation becomes more
complicated. Different from the HPVRC process, the feed
state of the hot reflux stream changes after heat exchange,
and the vaporization fraction in the reflux stream will
change accordingly when it enters the column. In the
analysis in Section 2.3, the results show that the change in
the vaporization fraction of the reflux stream will cause a
change in the flow rate of the overhead vapor stream. Thus,
the optimal parameters in the vapor recompression option
should be reoptimized owing to the change in the
vaporization fraction of the reflux stream. Note that the
heat exchange load of the economizer and the vaporization
fraction are in one-to-one correspondence, so the vapor-
ization fraction is selected as the optimization variable.
Figure 4(c) shows the optimal conditions for each
vaporization fraction, which indicates that the optimal
parameters represent appropriate Qpre and PR in a given
vaporization fraction. The appropriate vaporization frac-
tion is 0.07. Relatively, the heat duty of the economizer
corresponding to the vaporization fraction is 115.75 kW. In
addition, we need an additional preheater to provide 75 kW
of heat to meet the optimal situation. At this point, the
optimal PR is 6.26. The heat released from the discharging
stream from the compressor (1188.08 kW) is less than the
reboiler heat requirement (1296.45 kW), so an auxiliary
low-pressure steam-driven reboiler is installed to provide
additional energy (108.37 kW). The T – H diagram of this
process is shown in Fig. 6(d). The amount of heat recovery
within the process is 1368.52 kW, which is far greater than
that of the HPVRC process. The TAC of this process is
0.626
106 $$y–1, which is superior to all the processes
mentioned above. Thus, the heat integration method
applied to this process is superior to the initial configura-
tions in terms of economics and energy savings. More
detailed data related to the economic and environmental
evaluation are shown in Section 3.1.
2.5 Dynamic control
It is well known that it is an indispensable agent for
performing the process dynamic control analysis in
constructing newly intensified or retrofitted processes
since there are many trade-offs between process steady-
state designs and process dynamic characteristics. Accord-
ingly, the dynamic control characteristics and effectiveness
are investigated via Aspen Plus Dynamics in this section
for the above economically optimal HPVRC-HI arrange-
ment.
Luyben [29] gives the corresponding detailed exporting
procedures from the Aspen Plus steady-state flowsheet file
to Aspen Dynamics. The default tuning parameters (gain
and integral time) of the controllers in the inventory control
loops (pressure and level controllers) are also presented in
the work of Luyben [29]. Only the temperature control
 Wei Hou et al. Separation of n-heptane/isobutanol via vapor recompression distillation 11

loops with the 1-min dead-time blocks (dual-point
temperature control scheme) are applied in the regulatory
control loops to regulate both product qualities in our
constructed control strategy that can well address the large
step changes in throughput and feed composition, and the
gains and integral times of these two temperature
controllers are obtained by the relay-feedback testing
procedure with Tyreus–Luyben tuning rules [29].
Figure 7 shows the robust and efficient dynamic control
structure, and the detailed paired sensor-valve control
loops are enumerated below. 1) The fresh feed is flow
controlled, and throughputs are adjusted by manipulating
the setpoint. 2) The bottoms flow rate is adjusted to control
the column base level. 3) The distillate flow rate is adjusted
to control the reflux drum level. 4) The power in the
compressor is regulated to control the column operation
pressure. 5) The heat input in the trim preheater is adjusted
to control the suction temperature of compressor. 6) The
heat input of the trim reboiler is manipulated to control the
Stage 26 temperature. Note that the feedforward action,
i.e., the total reboiler heat duty-to-fresh feed flowrate ratio
(QR/F), is used to weaken product transient peaks and
enhance the process response. Zhang et al. [6] provided the
detailed information for these control loops, and Figure S3
(cf. ESM) shows the detailed Aspen Dynamics implemen-
tation procedures. This stage is selected, shown in Fig. S4

Fig. 7 Dynamic control structure for HPVRC-HI arrangement.

12 Front. Chem. Sci. Eng.

(cf. ESM), because of the large temperature change from
tray to tray at this location. 7) The reflux flow rate is
adjusted to control the Stage 6 temperature. Note that the
feedforward action, i.e., molar the reflux to fresh feed
flowrate ratio (R/F), is also used to weaken product
transient peaks and enhance the process response. This
stage is selected, shown in Fig. S4, because of the large
temperature change from tray to tray at this location.
Note that in this paper, the discharging stream leaving
compressor is fed into the fictitious heat exchanger block
that is the Aspen Heater model labelled “REB1”, and the
heat requirement in the reboiler is provided by the
combination of the heat released in the fictitious heat
exchanger and the heat input in the trim low-pressure
steam-driven utility exchanger. Their detailed heat transfer
relationships are handled in Aspen Dynamics by using
Flowsheet Equations, as illustrated in Fig. S5 (cf. ESM).
3 Results and discussion
3.1 Performance comparison of different arrangements
As presented in Table 2, different configurations of this
separation process are compared in terms of economic,
thermodynamic, and environmental performance. To
obtain more detailed information about different config-
urations, two other feasible separation configurations (ED
and PSD) proposed by Luyben [15] are also given.
Figure 8 shows the TAC for each process. The red part
indicates the annual TCC and the blue part indicates the
TOC. It can be intuitively observed that the annual TCC of
the CD process is much lower than that of the PSD and ED
processes, but due to the high TOC caused by the use of
expensive refrigeration, the CD process exceeds that of the
ED process. Compared with the CD process, the annual
TCC of LPVRC, HPVRC, LPVRC-HI and HPVRC-HI
cases increases by 0.186
106, 0.182
106, 0.197
106,
and 0.174
106 $$y–1, respectively. However, the TOC of
these processes decreases by 0.212
106, 0.296
106,
0.277
106, and 0.312
106 $$y–1, respectively.
Although the annual TCC increases due to the integration
of vapor recompression and heat integration, the TOC of
the models decreases markedly, where the reduction of the
energy consumption plays a leading role; thus, the
decrement of the TOC can compensate for the increment
of the annual TCC. In general, the integration of vapor
recompression and heat integration can further reduce the
TAC and ultimately improve performance ultimately better
than the ED process.
Thermodynamic analysis also provided similar results
for the TAC. LPVRC, LPVRC-HI, HPVRC and HPVRC-
HI configurations improve the thermodynamic efficiency
of the CD process by 35.70%, 51.77%, 59.66%, 61.19%,
respectively. These novel configurations also show good
environmental performance. The CO2 emissions in the
LPVRC, LPVRC-HI, HPVRC and HPVRC-HI are
reduced by 63.11%, 74.17%, 76.74% and 75.01%
respectively (based on natural gas). Among all processes,
the HPVRC-HI process provides the best performance
regardless of the point of view. The ROI in this process is
0.28, which indicates that this project is competitive under
the current industry background. Compared with LPVRC,
a higher pressure is more beneficial for this refrigerated
distillation system.
3.2 Exergy analysis of different arrangements
The exergy losses of heat pump-assisted distillation
processes under different pressures are analyzed in this
section, as shown in Fig. 9. In the visualization process of
exergy analysis, the thermal exergy input is mainly divided
into two parts, including the exergy of the compressor and
the exergy input of the external process stream or hot
utility. The useful exergy in this system is used for
purifying the feed stream, while exergy losses are
generated in different devices. Both processes have the
largest percent of exergy destruction in the column
(approximately 51.05% and 57.25%) due to the most
energy input in the column. The exergy increase in the

Table 2 Comparisons of key performance evaluation indicators for different configurations

Items PSD ED CD LPVRC HPVRC LPVRC-HI HPVRC-HI
Cold utility cost/(106 $$y–1) 0.019 0.016 0.253 0.068 0.000 0.034 0.000
6 –1
Hot utility cost/(10 $$y ) 0.479 0.396 0.282 0.072 0.033 0.041 0.038
6
Electricity cost/(10 $$y ) –1
– – – 0.183 0.205 0.183 0.184
Operation cost/(106 $$y–1) 0.498 0.412 0.535 0.323 0.239 0.258 0.222
Capital costs/(106 $$y–1) 0.311 0.322 0.230 0.416 0.412 0.427 0.404
6 –1
TAC/(10 $$y ) 0.809 0.734 0.765 0.738 0.651 0.685 0.626
ROI – – – 0.226 0.273 0.245 0.280
–1
CO2 emissions/(kg$h )(natural gas) 555.147 453.260 316.938 116.930 73.712 81.874 79.193
CO2 emissions/(kg$h–1)(heavy oil fuel) 826.296 674.646 471.740 156.415 92.087 104.235 100.125
Second-law efficiency/% 10.597 10.696 14.775 20.050 22.425 23.591 23.817
 Wei Hou et al. Separation of n-heptane/isobutanol via vapor recompression distillation
Fig. 8 Comparisons of different alternatives in terms of key
indicators: (a) second-law efficiency and CO2 emissions; (b) TAC.
HPVRC-HI system (25.71%) is larger than that of
LPVRC-HI (22.31%), which indicates that the HPVRC-
HI sequence presents unique advantages in terms of
thermodynamic efficiency. Almost identical consequences
for the processes can be obtained when a second-law
efficiency analysis or exergy analysis is adopted in the
system.
3.3 Control performance of HPVRC-HI arrangement
Figure 10 shows the dynamic control response behavior
when addressing the positive (solid lines) and negative
Fig. 9 Results of exergy analysis in the different processes: (a) LPVRC-HI; (b) HPVRC-HI.
13
(dashed lines) 20% step changes in the production rate.
Robust regulatory control is obtained because both product
compositions are closely and quickly (3 h) restored to their
specifications with almost negligible product offsets.
Figure 10(b) shows the dynamic control response results
when confronting the positive (solid lines) and negative
(dashed lines) 20% step changes in feed isobutanol
composition. Good product composition controls are
well obtained and the transient maximum product
composition peaks are quite small (do not exceed
0.0005). The dynamic control system quickly responds
within approximately 2 h to the new steady-state when
inserting disturbances at 1 h. Therefore, this control
structure can efficiently handle these feed disturbances.
Table 3 enumerates the corresponding tuning parameters
for these two temperature controllers.
4 Conclusions
In this study, two novel alternative vapor recompression-
assisted distillation configurations for separating an
azeotropic mixture of n-heptane and isobutanol were
proposed, optimized, and compared in terms of economic,
thermodynamic and environmental indicators before and
after the addition of heat integration. The high-pressure
case avoided the use of expensive refrigerant, but as it
entered the column, the flashing of the reflux produced a
higher flowrate of overhead vapor through the compressor,
which meant higher compressor costs. The results showed
that the performance of the HPVRC was better than that of
the LPVRC. After the integration of the VRC and HI, TAC
and CO2 emissions could be further reduced. The HPVRC-
HI provided best performance which could reduce the TAC
by 18.10% and enhance the second-law efficiency by
61.20%, compared to the CD configuration. The config-
uration was also preferable from an environmental
perspective, which could reduce the CO2 emissions by
75.01% based on natural gas (78.78% savings in CO2
emissions based on heavy oil fuel). In addition, the exergy
14 Front. Chem. Sci. Eng.

Fig. 10 Dynamic response results of this intensified control structure: (a) 20% throughput disturbances; (b) 20% feed composition
disturbances.
 Wei Hou et al. Separation of n-heptane/isobutanol via vapor recompression distillation 15

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