Professional Documents
Culture Documents
Reactive Distillation For Producing N-Butyl Acetate: Experiment and Simulation
Reactive Distillation For Producing N-Butyl Acetate: Experiment and Simulation
net/publication/257445661
CITATIONS READS
21 2,872
5 authors, including:
8 PUBLICATIONS 127 CITATIONS
Fujian
21 PUBLICATIONS 160 CITATIONS
SEE PROFILE
SEE PROFILE
Some of the authors of this publication are also working on these related projects:
All content following this page was uploaded by Xiaoda Wang on 02 February 2018.
TIAN Hui (ජ)1, HUANG Zhixian (ܻᄦບ)2, QIU Ting (භ)2, WANG Xiaoda (ฆ໋Ӓ)2
and WU Yanxiang (๑ཀྵີ)2,*
1
College of Chemistry and Chemical Engineering, Yantai University, Yantai 264005, China
2
College of Chemistry and Chemical Engineering, Fuzhou University, Fuzhou 350002, China
Abstract In this paper, a reactive distillation (RD) column was applied for synthesis n-butyl acetate from
n-butanol and acetic acid. The Langmuir-Hinshelwood-Hougen-Watson (LHHW) kinetic model and an equilibrium
stage model for separation were employed to study the RD process. The results obtained from the equilibrium stage
model agreed well with the experiments. The effects of operating variables on the n-butanol conversion and n-butyl
acetate purity were further investigated. The optimal column configuration for the production of n-butyl acetate was
designed with 5 rectifying stages, 8 reaction stages and 13 stripping stages by the simulation study. According to the
simulation results, n-butanol conversion and n-butyl acetate purity all reached greater than 96%.
Keywords reactive distillation, esterification, n-butyl acetate, simulation
Shenbo Chemical CO., and n-BuOH (>99.8%) was ters K are expressed as
supplied by Merck. The catalyst used in the present K a exp(b / RT ) (3)
experiment was cation exchange resin Amberlyst 36
Wet, produced by Rohm and Haas, and the parameters All the parameters of the LHHW kinetic model
were given in Table 1. were taken from the Ref. [11] for the esterification
catalyzed by Amberlyst 36 Wet ion-exchange resin.
The average relative error was less than 2%, and the
Table 1 Physical properties of Amberlyst 36 Wet
kinetic parameters were given in Table 2.
physical form opaque beads
ionic form as shipped hydrogen Table 2 Parameters of the LHHW kinetic model
concentration of acid sites ı1.95 mol·L 1 for n-BuAc reaction system [11]
ı5.4 mol·kg1 Parameter a/kmol·kg1·s1 b/J·mol1
moisture holding capacity 51% to 57% (H+ form) ka 1.23×103 1.96×103
shipping mass 800 g·L1 (50 lbs·ft3) kf 1.45×10 4
6.45×103
fines content <0.425 mm: 0.5% max Ks,HAc 6.44×101 5.41×103
coarse beads >1.180 mm: 4.0% max Ks,BuOH 2.84×10 7
4.80×104
2 1
surface area 33 m ·g Ks,BuAc 2.86×103 2.47×104
average pore diameter 24 nm K s,H2O 3.88×10 4
2.92×104
maximum operating temperature 150°C (300 °F)
Table 3 The relationship of sampling and thermometers stage model is often applied with great success for the
location with number of theoretical stage simulation of RD column [14]. Therefore, the RADFRAC
Sampling Number of module, based on the rigorous equilibrium stage model
Thermometers location containing the mass balance, phase equilibrium, summa-
point theoretical stage
a T2 3
tion and energy balance (MESH) equations, was used to
describe the multistage vapor-liquid separation in the
b T3 5 RD. To simplify the calculation, the low pressure drop
c T4 10 along the column (about 2 kPa) was neglected accord-
d T5 12 ing to some researches [15, 16], for the whole equip-
ment was supposed to operate at atmospheric pressure.
e T6 18
The selection of the physical property method
f T7 22 was very important due to the highly non-ideal nature
of the quaternary system, and the phase equilibrium of
this system was complex because of the existence of
358.15K. The effluent from the fixed-bed reactor, azeotropes. Because of the non-ideal vapor-liquid
which almost achieves the chemical equilibrium, en- equilibrium (VLE) and possible vapor-liquid-liquid
tered the RD column above the reactive zone. n-BuAc, equilibrium (VLLE) for the quaternary system, the
whose boiling point was the highest in this system, UNIQUAC activity coefficient model was adopted [9],
was withdrawn from the bottom of the column. The and the model equation came from the Aspen Plus
overhead distillate was mainly n-BuOH, HAc, water, user manual 11.1. The Hayden-O’Conell model with
and a small amount of n-BuAc. The overhead vapor association parameters was used to account for the
was condensed and cooled to liquid at room tempera- dimerization and trimerization of HAc in the vapor
ture at first and then introduced to a decanter for phase phase [17]. The Aspen Plus built-in association parame-
separation. While the organic phase was completely ters were used to compute the fugacity coefficients.
refluxed back to the column, the aqueous phase which The binary interaction parameters of the UNIQUAC
might still contain small amount of the organic com- model came from the built-in Aspen Plus Databanks
pounds (i.e., n-BuAc, unreacted n-BuOH and HAc) and Ref. [17]. The azeotropes for the four components
was withdrawn from the system. system [HAc-(n-BuOH)-(n-BuAc)-H2O] calculated at
the atmospheric pressure were listed in Table 3. From
Table 4, the calculated azeotropic composition and
4.2 Modeling and simulation
temperature were compared with the literature values,
and the maximal error was less than 1%, showing the
The RD was a complex process, which contains selection of the thermodynamic model was reliable.
not only the mass transfer process but also the separa- Since the available built-in reaction kinetic model
tion and reaction processes. In this paper, simulation in Aspen Plus 11.1 was power law and defined on the
of the synthesis of n-BuAc in a RD column was car- basis of mass or mole fraction, the reaction kinetics
ried out by using Aspen Plus 11.1. The equilibrium model for n-BuAc system based on LHHW [Eq. (2)]
Chin. J. Chem. Eng., Vol. 20, No. 5, October 2012 983
(a) Space velocity: 0.2348 m3·h1·m3 (b) Space velocity: 0.4375 m3·h1·m3
Figure 2 Temperature profile in the RD column
simulation;Ƶexperimental
was incorporated into the process simulator using an for simulating the RD column, the model was used to
additional subroutine written in FORTRAN, and the predict the temperature distribution and vapor composi-
different catalyst concentrations and the efficiency of tion along the RD column, and the predictions were
the catalyst-bundle [18] in the RD column were con- compared with the experimental data obtained in the
sidered. The simulation was run and fitted to the present study. The temperature and concentration profiles
available experimental data by adjusting the Murphree obtained from the experiment and simulation results
stage efficiency (from 0.5 to 0.8), and the value of were shown in Figs. 2 and 3. The experimental values
which is reasonable [15]. were all came from the average value of three experi-
According to the experimental setup, the theo- ments and the relative errors were all less than 2.0%.
retical stages were numbered from the column to the Figure 2 demonstrated the calculated temperature
column bottom (reboiler). The process parameters of profile was similar to the experimental values and the
the experiment and the specification of the RD column maximum relative error was 1.1%, which was accept-
for process simulation were listed in Table 5. able. From Fig. 3, it can be seen that the vapor com-
positions in 6 sampling points were in good agreement
with the simulation results. The errors mainly came
4.3 Model validation
from the equilibrium stage model not accounting for
transport phenomena. The conversion of n-BuOH as
In order to check whether the model was suitable defined as
984 Chin. J. Chem. Eng., Vol. 20, No. 5, October 2012
(a) Space velocity: 0.2348 m3·h1·m3 (b) Space velocity: 0.4375 m3·h1·m3
Figure 3 Experimental and predicted concentration profiles in the sampling location
Ʒ BuOH experimental; BuOH simulation; ƹ BuAc experimental; Ƶ H2O experimental; H2O simulation; BuAc
simulation; HAc experimental
n-BuOH conversion
(4)
Figure 4 Experimental and simulation results at different Increasing the number of reaction stages was not
space velocity always a better option because that will affect the
ƹexperimental; simulation column separation performance, thereby changing
Chin. J. Chem. Eng., Vol. 20, No. 5, October 2012 985
Table 6 Compare of the experiment and simulation value of n-BuOH conversion and n-BuAc purity
n-BuOH conversion Relative n-BuAc purity/mass fraction Relative
Number
Experiment Simulation error/% Experiment Simulation error/%
cascaded with separation units, while the reactive zone was capable of modeling the n-BuAc synthesis rela-
of a RD column could be viewed as a cascade-type tively accurately. The simulation results shown that
two-phase reactor with the reaction temperature deter- the experimental data agreed with the simulation results
mined from the bubble-point temperature of the tray well. The equilibrium stage model could describe the
liquid phase composition. The composition and tem- column profiles quantitatively. The effects of some
perature profiles could affect the performance of the important process parameters were investigated with
reactive zone, and the feed tray location appear to be the aid of simulation studies and the optimal parameters
one of the most important variables for these profiles were obtained: the optimal design variables for the RD
redistribution [21, 22]. The right choice for feed location were 5 rectifying stages, 8 reaction stages and 13
ensured high concentrations of reactants in the reactive stripping stages, and the best feed location was the 6th
zone. Fig. 9 presented the effects of the feed location theoretical stages. According to the simulation results,
on n-BuOH conversion, n-BuAc purity and the heat the RD column was changed to 5 rectifying stages, 8
duty of the reboiler. It was found that feeding equilib- reaction stages and 13 stripping stages based on the
rium reaction mixture at the 5th TS offered the highest experimental setup. n-BuOH conversion and n-BuAc
conversion of n-BuOH (96.83%) and the highest purity purity were all greater than 96% at this condition.
of n-BuAc (96.71%).
REFERENCES
n-butyl acetate over cation-exchange resin catalyst”, Chemical Reaction 17 Zeng, G.B., Li, S.J., Qian, F., “Dynamic simulation and control of
Engineering and Technology, 25 (4), 355359 (2009). (in Chinese) acetic acid dehydration system”, Computers and Applied Chemistry,
12 Klöker, M., Kenig, E.Y., Górak, A., Markusse, A.P., Kwant, G., 25 (5), 533537 (2008). (in Chinese)
Moritz, P., “Investigation of different column configurations for the 18 Li, C.S., Daisuke, H., Suzuki, K., “n-Butyl acetate synthesis via re-
ethyl acetate synthesis via reactive distillation”, Chem. Eng. Process., active distillation: Thermodynamic, process design”, Computers and
43 (6), 791801 (2004). Applied Chemistry, 24 (12), 15851589 (2009). (in Chinese)
13 Du, Y.C., Guo, J.B., Hu, R.T., “Synthesis of n-butyl acetate by cata- 19 Wu, Y.X., Wang, L.E., Zhao, Z.S., “Mass transfer model for catalyst
lytic rectification”, Petrochemical Technology, 36 (4), 349354 capsule in catalytic distillation (II) Mensuration and calculation of
(2007). (in Chinese) effectiveness factor”, Journal of Chemical Industry and Engineering
14 Lee, H.Y., Huang, H.P., Chen, I.L., “Control of reactive distillation (China), 53 (5), 508512 (2002). (in Chinese)
process for production of ethyl acetate”, Journal of Process Control, 20 Subawalla, H., Fair, J.R., “Design guidelines for solid-catalyzed reac-
17 (4), 363377 (2004). tive distillation systems”, Ind. Eng. Chem. Res., 38 (10), 36963709
15 Zheng, Y.X., Flora, T.T.N., Garry, L.R., “Catalytic distillation: A (1999).
three-phase none quilibrium model for the simulation of the aldol 21 Bhatia, S., Mohamed, A.R., Ahmad, A.L., Chin, S.Y., “Production of
condensation of acetone”, Ind. Eng. Chem. Res., 40 (23), 53425349 isopropyl palmitate in a catalytic distillation column: Comparison
(2001). between experimental and simulation studies”, Comput. Chem. Eng.,
16 Almeida-Rivera, C.P., Swinkels, P.L.J., Grievink, J., “Designing re- 31 (10), 11871198 (2007).
active distillation processes: Present and future”, Computers. Chem. 22 Doherty, M.F., Malone, M.F., Conceptual Design of Distillation
Eng., 28 (10), 19972020 (2004). System, McGraw-Hill, New York (2001).