Article

pubs.acs.org/IECR

Simulation and Optimization of Distillation Processes for Separating

a Close-Boiling Mixture of n‑Butanol and Isobutanol
Xiaoxin Gao,†,‡,* Jun Chen,† Zhengfei Ma,‡ and Limin Yang†
†
School of Petrochemical Engineering, Changzhou University, Changzhou 213164, P. R. China
‡
College of Chemistry and Chemical Engineering, Nanjing Technology University, Nanjing 210009, P. R. China
*
S Supporting Information

ABSTRACT: Separation of close-boiling mixtures by conventional distillation consumes a large amount of energy because of the
very high reflux ratio required. Mechanical vapor recompression heat pumps (MVRHPs) can recycle the energy of the vapor and
can thus be used in such distillation processes to save energy. Three different distillation schemes, namely, conventional
distillation, top MVRHP distillation, and bottom-flashing MVRHP distillation, were simulated for the separation of the close-
boiling mixture of n-butanol and isobutanol using Aspen Plus to determine the economically best option. The research results
indicate that, compared to conventional distillation, the energy savings for bottom-flashing MVRHP distillation and top MVRHP
distillation can reach 67.92% and 72.92%, respectively, and the TACs correspondingly decrease by 71.74% and 75.57%.

1. INTRODUCTION
Distillation is the most important separation technology for
separating mixtures and is extensively used in the chemical
industry because it can separate mixtures effectively. However,
it also consumes a large amount of energy. It is estimated that,
among the process technologies in the chemical industry that
utilize energy as the separating agent, 40−70% of the energy is
consumed in separation units.1 Of this energy, 95% is
consumed by distillation processes.2 Currently, with the sharp
increase in global energy consumption and rapid growth in
energy prices, technologies that can significantly save energy
have been sought. Therefore, great research efforts have been
devoted to energy savings on distillation.
To reduce energy consumption and improve the thermal
efficiency of distillation, various improved technologies have
been suggested, such as use of a new transport facility, namely,
high-gravity rotating bed, and the application of energy-saving
technologies, namely, dividing-wall columns (DWCs), multiple-
effect distillation, heat-pump distillation, and composite heat
integration.3−5 Among energy-saving technologies, mechanical Figure 1. MVRHP system flowchart.
vapor recompression heat pumps (MVRHPs) are the most
efficient technique for minimizing energy consumption, pressure and temperature. The compressed vapor becomes
especially for vapor-involving systems.6−9 As the vapor superheated vapor S2, and its saturation temperature is
compression technique has been fully perfected, it is widely correspondingly increased to TH. Subsequently, vapor S2 as a
applied in the chemical industry and other industries mainly heating agent enters the condenser to release its heat Qo and
related to vapor fields, such as evaporation, the desalination of turn back into saturated liquid S3 under a higher pressure. The
seawater, and the drying of solids.10−15 However, the saturated liquid then goes through the expansion valve as an
application of MVRHPs in distillation has rarely been reported isenthalpic process to reduce its temperature and pressure. The
in the literature. working fluid after the expansion valve becomes moist vapor
A flowchart of an MVRHP system is shown in Figure 1. The S4, which enters into the evaporator to vaporize fully. These
entire cycle includes an evaporator, a compressor, a condenser, steps form a full working cycle. In such a cycle, the heat Qi is
and an expansion valve or their equivalent parts. The absorbed at the low temperature TL, and the heat Qo is released
evaporator operates under low pressure, and the corresponding
saturation temperature of the cycling fluid under this pressure is Received: April 21, 2014
TL. Qi is the heat absorbed at the low-temperature end by the Revised: August 7, 2014
working fluid. The fluid completely vaporizes to saturated vapor Accepted: August 24, 2014
S1, which then enters into the compressor to increase its Published: August 25, 2014

© 2014 American Chemical Society 14440 dx.doi.org/10.1021/ie502695x | Ind. Eng. Chem. Res. 2014, 53, 14440−14445
Industrial & Engineering Chemistry Research Article

at the high temperature TH. Theoretically, Qo = Qi + W;

therefore, the heat released must be greater than the work
imposed by the compressor.
For an evaporation process using the above principles of
MVRHPs, a dilute solution at low temperature is preheated by
a heat exchanger and then concentrated by an evaporator. The
secondary vapor thus produced is compressed by a compressor,
resulting in a stream with a higher pressure, temperature, and
enthalpy. The compressed vapor of high quality is sent back to
the heating chamber of the evaporator and acts as the heating
agent to heat the feed solution. The solution absorbs the latent
heat of the vapor and continues to generate the secondary
vapor. Within the cycle, the latent heat of the secondary vapor
is recycled with the small addition of electrical energy or
mechanical work of the compressor. Therefore, reusing the
latent heat of the secondary vapor saves a large amount of
steam or energy compared to conventional evaporation and
reduces the operating costs. Such a cycle provides huge benefits
for energy savings.
To the authors’ knowledge, the separation of an n-butanol/
isobutanol mixture by these improved distillation techniques
has not yet been reported. In the present study, the distillation
separation of n-butanol/isobutanol mixtures was performed by Figure 2. T−x(y) phase equilibrium diagram for the n-butanol/
conventional distillation, top MVRHP distillation, and bottom- isobutanol system.
flashing MVRHP distillation. The energy consumptions and
operating costs for these three schemes were investigated. The 3. SIMULATION OF THE DISTILLATION PROCESS
results showed that the top MVRHP distillation process can 3.1. Conventional Distillation Process. A representative
save more energy with a much lower total annual cost (TAC) binary distillation process for finishing the separation task is
than for conventional distillation and bottom-flashing MVRHP shown Figure 3. The task of the distillation column is to
distillation. Thus, the optimal operating conditions, including
operating pressure, reflux ratio, and compression ratio, were
determined.

2. PROCESS DESIGN AND OBJECTIVE

For the conventional distillation process, a binary mixture with
55 wt % n-butanol and 45 wt % isobutanol was fed to the
distillation column as a saturated liquid at a rate of 5000 kg/h.
The required purities for the isobutanol product at the column
top and the n-butanol product at the column bottom were not
less than 99 wt %. A plate distillation column with sieve trays
was employed. The top condenser was cooled with cooling
water, and the bottom reboiler was heated with steam.
The phase equilibrium data for the n-butanol/isobutanol
mixture were calculated by Wilson’s equation-of-state model,
which was previously demonstrated to suit the case of this
work.16 Figure 2 shows the resulting phase diagram in terms of
the pseudobinary temperature versus composition [T−x(y)]
(i.e., the equilibrium relationship between temperature and
compositions of liquid and vapor) for the n-butanol/isobutanol
system at 100 kPa.
For the system selected, the boiling points for isobutanol and
n-butanol at 100 kPa are 107.3 and 117.3 °C, respectively, and
the relative volatility is 1.39. Using conventional distillation to
separate this system requires a very high reflux ratio and, thus, a
large amount of energy. For energy savings, the present study
aimed to simulate the separation of the n-butanol/isobutanol
mixture using three different distillation schemes, namely,
conventional, top MVRHP, and bottom-flashing MVRHP
distillations, and to optimize the processes with the goal of
the lowest TAC. All three of these distillation schemes were
simulated with Aspen Plus computer software.
14441
Figure 3. Aspen process flow diagram for conventional distillation.
separate the feed into a liquid distillate with 99 wt % isobutanol
and a liquid bottom product with 99 wt % n-butanol. The
number of theoretical stages and the reflux ratio required for
the column was estimated by using the “DSTWU” block in
Aspen Plus. Then, the column was simulated with the “Radfrac”
block design to fulfill the separation task for varying reflux
ratios. To obtain the best conditions, the operating pressure
was varied from 100 to 50 kPa. A plate distillation column with
sieve trays was employed.
The minimum values of TAC for the different operating
pressures were examined. Here, the TAC includes the operating
costs and annual capital investment, according to the expression
capital cost
TAC = + operating cost
payback period (1)
The costs of fixed capital investment and utility consumption
were estimated by the equations listed in the Appendix. The
energy consumption (QCons) is mainly attributed to the reboiler
duty (QR) and the compressor duty (QC)
dx.doi.org/10.1021/ie502695x | Ind. Eng. Chem. Res. 2014, 53, 14440−14445
Industrial & Engineering Chemistry Research Article

Table 1. Simulated Results for Conventional Distillation at Different Pressures

operating pressure (kPa)
parameter 100 90 80 70 60 50
number of stages 61 61 61 61 62 62
feed stage 34 35 36 38 40 42
reflux ratio 6.55 6.25 5.83 5.99 6.02 6.17
diameter (m) 1.74 1.73 1.71 1.77 1.83 1.90
height (m) 43.18 43.18 43.18 43.18 43.18 43.18
column-shell cost (×103$) 652.36 636.38 64.037 664.35 688.67 728.56
reboiler duty (kW) 2604.25 2509.55 2396.97 2439.74 2463.71 2531.58
condenser duty (kW) 2665.27 2582.83 2457.47 2540.35 2579.82 2664.85
reboiler heat-transfer area (m2) 2127.65 1115.36 710.21 553.22 430.42 359.24
condenser heat-transfer area (m2) 147.34 148.66 147.92 161.36 174.58 194.85
total heat-exchanger cost (×103$) 1,249.51 886.45 708.33 641.24 585.05 558.85
operating cost (×103$) 151.37 1,458.86 1,391.81 1,423.26 1,439.70 1,481.65
capital investment (×103$) 1,901.87 1,534.81 1,348.71 1,305.6 1,273.44 1,275.35
total energy consumption (kW) 2604.25 2509.55 2396.97 2439.74 2463.71 2531.58
TAC (×103$/year) 1,701.56 1,612.34 1,526.68 1,553.82 1,567.04 1,609.18

Q Cons = Q R + 3.29Q C (2) compressed in compressor C-100 to a higher pressure and a

For comparison, we assumed that the compressor work was
completely converted into the equivalent thermal energy. The
factor of 3.29 in eq 2 was used as the ratio of energy costs to
electricity costs in China.
The relationship between the TAC and the operating
pressure for conventional distillation is presented in Table 1.
It is noted that, as the operating pressure decreases, the capital
investment decreases on the whole, and the operating cost
increases. The optimal operating pressure was determined from
the minimum TAC. According to Table 1, the optimal pressure
for this case is 80 kPa. With this value, the reboiler duty is
2396.97 kW, and the reflux ratio is 5.83. The main parameters
for the distillation column are listed in Table S1 (Supporting
Information), and the mass and heat balances are provided in
Table S2 (Supporting Information).
3.2. Top MVRHP Distillation. Figure 4 shows the process
for the top MVRHP distillation scheme. The bottom outlet
stream is divided into two parts: one for the bottom product
and the other for generating the vapor boilup. The top vapor is
Figure 4. Aspen process flow diagram for top MVRHP distillation.
14442
higher temperature. When the pressure at the column top is at
100 kPa and the compression ratio is 2.7, the pressure of the
compressed vapor increases from 100 to 270 kPa, and its
temperature increases from 107.4 to 132 °C. The latent heat of
the top vapor is used to generate the vapor boilup in heat
exchanger H-100, and the vapor is condensed to saturated
liquid.
The temperature difference across the heat-exchanger wall is
about 10 °C. This is an efficient value for a heat-transfer
process, and it is a compromise between capital and operating
costs. The heat balances for the bottom and top equipment are
as follows
Q C ≈ Q R ≈ Q H‐100
where QC is the duty for the conventional column condenser
and QR is the duty of the conventional column reboiler.
The saturated liquid then passes through valve VLV-100 to
reduce its temperature to 107.4 °C and pressure to 100 kPa,
which are the same as the conditions at the reflux position. The
saturated liquid is divided in SPLIT-100 into the top product
and the reflux stream back to the column.
For top MVRHP distillation, the pressure at the column top
was varied from 100 to 60 kPa. A plate distillation column with
sieve trays was again employed. A maximum thermal efficiency
can be obtained by direct heat exchange between the top and
bottom streams. Table 2 reports the simulated results for the
top MVRHP case under different operating pressures.
According to Table 2, the optimal operating pressure at the
minimum TAC is 90 kPa. At this pressure , the compression
ratio is 2.7, and the compressor work is 198.57 kW. The mass
and heat balances for this case are reported in Table S3
(Supporting Information).
3.3. Bottom-Flashing MVRHP Distillation. Figure 5
shows the process of the bottom-flashing MVRHP distillation
scheme. The outlet from the column bottom is divided into
two streams: One is for the bottom product, and the remainder
enters valve VLV-110 to reduce its temperature and pressure as
the recycled stream. This stream gains latent heat from the top
vapor through heat exchanger H-110 and vaporizes fully into
the recycled vapor. When the pressure at the column top is 100
kPa, the temperature of the recycled stream after VLV-110 is
reduced from 127.1 to 97.4 °C, and the corresponding pressure
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Industrial & Engineering Chemistry Research Article

Table 2. Simulated Results for Top MVRHP Distillation at Different Pressures

operating pressure (kPa)
parameter 100 90 80 70 60
T-100 top temperature (°C) 107.4 104.6 101.5 98 94.2
compressor outlet temperature (°C) 132 129.1 126.8 125.9 123.5
column-shell cost (×103$) 652.36 636.38 640.37 664.35 622.42
reboiler duty (kW) 2482.52 2390.05 2336.3 2310.5 2404
reboiler area (m2) 551.67 531.12 535.23 513.45 688.67
compressor inlet steam (kg/h) 14372.8 15609.7 15577 15348.4 15600.9
compression ratio 2.7 2.7 2.8 3.1 3.3
compressor work (kW) 208.12 198.57 199.33 214.56 228.26
compressor cost (×103$) 179.3 172.7 173.2 179.1 193
total heat-exchanger cost (×103$) 511.67 431.24 433.15 421.61 427.80
electricity cost (×103$) 262.55 250.50 251.46 270.68 287.96
capital investment (×103$) 1,273.41 1,240.06 1,246.72 1,265.06 1,309.47
total energy consumption (kW) 684.71 653.3 655.80 705.90 750.98
TAC (×103$/year) 389.89 374.54 376.13 397.18 418.91

Figure 5. Aspen process flow diagram for bottom-flashing MVRHP distillation.

Table 3. Simulated Results for Bottom-Flashing MVRHP Distillation at Different Pressures

operating pressure (kPa)
parameter 100 90 80 70 60 50
T-110 top temperature (°C) 107.4 104.5 101.4 98 94.2 89.7
compressor outlet temperature (°C) 128.2 125.1 122.5 120.6 117 114.7
column-shell cost (×103$) 652.36 636.38 640.37 664.35 688.67 728.56
condenser duty (kW) 2673.12 2583.2 2421 2607.93 2550.71 2729.82
compressor inlet steam (kg/h) 16594.9 15883.6 15072.6 15217.4 15244.7 15531.3
relief-valve outlet pressure (kPa) 47 41.5 36 31.5 27 21.7
relief-valve outlet temperature (°C) 97.4 94.4 91.1 88 84.5 79.7
compression ratio 3.5 3.5 3.6 3.8 3.8 4.2
compressor work (kW) 257.42 244.45 235.29 245.98 244.12 264.77
heat-transfer area (m2) 1069.25 1023.05 940.19 1043.17 990.57 1091.93
compressor cost (×103$) 212.5 203.9 197.8 204.9 203.7 217.3
total heat-exchanger cost (×103$) 679.18 659.96 624.71 668.37 646.26 688.51
electricity cost (×103$) 324.75 308.38 293.83 310.31 307.97 334.02
capital investment (×103$) 1,544.94 1,500.24 1,462.88 1,537.62 1,538.63 1,634.37
total energy consumption (kW) 846.91 804.24 774.10 809.27 803.15 871.09
TAC (×103$/year) 479.15 458.41 443.12 464.08 461.83 497.45

14443 dx.doi.org/10.1021/ie502695x | Ind. Eng. Chem. Res. 2014, 53, 14440−14445

Industrial & Engineering Chemistry Research Article

is reduced from 140 to 47 kPa. The recycled vapor then goes MVRHP distillation scheme provides advantages in terms of
through compressor C-110 to increase its temperature to 127.1 higher energy savings and a lower TAC.
°C as the vapor boilup.
For the bottom-flashing MVRHP case, the pressure at the
column top was varied from 100 to 50 kPa, and a plate column
■ APPENDIX
Sizing and Economic Basis of the Various Process Schemes
with sieve trays was again employed. Table 3 reports the
The height of a distillation column was calculated by the
simulated results under different pressures. It can be seen that
equation
the optimal pressure for this case is 80 kPa. At this pressure, the
compression ratio is 3.6, and the compressor work is 235.29 1.2
H = 2(N − 2)
kW. The mass and heat balances for this case are listed in Table 3.281
S4 (Supporting Information).
3.4. Simulation Results. The simulated results for the The heat-transfer areas of the condenser (SC) and reboiler
three different distillation schemes are reported in Table 4. It (SR) were calculated according to the equations
QC
Table 4. Simulation Results of Three Different Optimal SC =
UCΔTC
Schemes
conventional top MVRHP bottom-flashing QR
distillation distillation MVRHP distillation SR =
UR ΔTR
operating pressure 80 90 80
(kPa) Finally, in terms of the above size estimations, the capital and
total energy 2412.99 653.3 774.1 energy costs of a distillation column were estimated as follows
consumption
(kW)
column‐shell cost = 17640D1.066H 0.802
operating cost 1,397.34 250.5 293.83
(×103$)
total heat‐exchanger cost = 7296SC 0.65 + 7296SR 0.65
capital investment 1,361.7 1,240.06 1,464.55
(×103$)
TAC (×103$/year) 1,533.51 374.54 443.28 Nomenclature
D = diameter (m)
can be seen that the capital investment for the conventional H = height (m)
distillation scheme is not the lowest, even though it does not MVRHP = mechanical vapor recompression heat pump
require a compressor. In comparison with that for conventional N = number of stages
distillation, the capital investment for top MVRHP distillation QC = heat duty of the condenser (kW)
is decreased by 8.05%, whereas that for bottom-flashing QR = heat duty of the reboiler (kW)
MVRHP distillation is increased by 8.61%. Regarding operating SC = heat-transfer area of the condenser (m2)
aspects, conventional distillation requires both a bottom SR = heat-transfer area of the reboiler (m2)
reboiler and a top condenser, whereas top MVRHP distillation ΔT = temperature difference (°C)
omits the top condenser and bottom-flashing MVRHP TAC = total annual cost (103$/year)
U = overall heat-transfer coefficient (kW K−1 m−2)

■
distillation omits the bottom reboiler. Hence, the operating
costs for the last two cases are relatively low. From high to low,
the operating costs fall in the order conventional distillation > ASSOCIATED CONTENT
bottom-flashing MVRHP distillation > top MVRHP distillation. *
S Supporting Information
Correspondingly, compared to the conventional distillation, the Additional information as noted in text. This material is
TAC for top MVRHP distillation is decreased by 75.57%, and available free of charge via the Internet at http://pubs.acs.org.
the TAC for bottom-flashing MVRHP distillation is decreased
by 71.74%. According to the above analysis, it is obvious that
top MVRHP distillation is economically the best option and
■ AUTHOR INFORMATION
Corresponding Author
can save the most energy among these three cases for *E-mail: gaoxiaoxin@163.com. Tel.: +86-519-86330255.
separating a mixture of n-butanol and isobutanol. Notes
The authors declare no competing financial interest.

■
4. CONCLUSIONS
The present study investigated the simulation of three different ACKNOWLEDGMENTS
distillation alternatives for separating an n-butanol/isobutanol We are thankful for support from a project funded by the
mixture, including conventional distillation, top MVRHP Priority Academic Program Development of the Jiangsu Higher
distillation, and bottom-flashing MVRHP distillation. The Education Institution.

simulation results obtained using Aspen Plus were used to
evaluate the energy savings and TACs. The results show that
substantial energy savings can be achieved by using MVRHPs
for separating close-boiling mixtures.
For the cases studied, based on conventional distillation, the
energy savings for the top MVRHP distillation scheme reach
72.92%, and the TAC is decreased by 75.57%. The energy
savings for bottom-flashing MVRHP distillation reach 67.92%,
and its TAC is decreased by 71.74%. Obviously, the top
■
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