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Liu Mo, Jiang Shao-Tong ∗ , Pan Li-Jun, Zheng Zhi, Luo Shui-Zhong
School of Biotechnology and Food Engineering, The Key Laboratory for Agricultural Products Processing of Anhui Province, Hefei
University of Technology, Hefei 230009, China
a b s t r a c t
Esterification of raw lactic acid from fermentation broth and then hydrolysis of lactate ester in reactive distillation
column is an effective process for purification of lactic acid. Reactive distillation for hydrolysis of methyl lactate is
studied. First, the thermodynamic properties and reaction kinetics are analyzed; then the reactive distillation column
is designed based on the objective function total annual cost. The effects of tray number of rectifying section, tray
number of reactive section, and feed location on the total annual cost are investigated. And a dual-temperature
control structure is proposed for the optimal reactive distillation column, and the results show that it works quite
well for this hydrolysis system.
© 2011 The Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
∗
Corresponding author. Tel.: +86 0551 2901505/8224; fax: +86 0551 2901507.
E-mail addresses: liumo1985@gmail.com (L. Mo), jiangshotong@yahoo.com.cn (J. Shao-Tong).
Received 27 September 2010; Received in revised form 23 February 2011; Accepted 1 March 2011
0263-8762/$ – see front matter © 2011 The Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
doi:10.1016/j.cherd.2011.03.001
2200 chemical engineering research and design 8 9 ( 2 0 1 1 ) 2199–2206
a 1.0 b 1.0
Nomenclature
0.8
Molefrac water
Subscripts 0.6 0.6
Rectifying
Methyl lactate, 3. Process flow sheet and steady-state
section design
water,
methanol, 3.1. Process flow sheet
lactic acid Reactive
Several previous researches focused on continuous process
section for the recovery of lactic acid by reaction distillation have
been reported, a two-phase CSTR and RD column was involved
in this process. The stream containing LA and methanol is
Lactic acid,
continuously fed into the CSTR for esterification, the high
water boiling-point impurities in the broth are separated as a purge
through the bottom stream of the CSTR. The vapor stream of
Fig. 2 – Schematic drawing for methyl lactate hydrolysis the CSTR that contains methyl lactate, water and methanol is
using reactive distillation. fed into the RD column and methyl lactate is hydrolyzed to LA
and methanol in the presence of catalyst in the reactive zone
of the column. The distillate consists of volatile components
E
CHL · CMeOH
r = (k0 + kw · w) · exp − · CML · CH2 O − (2) (methanol and water) and the bottom product contains LA as
RT Ke aqueous solution.
However, in this process, the volatile components (lactate
ester, alcohol, and water) are evaporated under atmospheric
E = 45.84 kJ mol−1
pressure, these make the energy consumption huge; the
k0 = 600.52 mol−1 L min−1 hydrolysis of lactate ester is a slow reaction and it needs
kw = 44.34 g−1 mol−1 L2 min−1 long reaction zone for complete hydrolysis, this reduces col-
umn efficiency; in the purge stream, large amounts of LA and
where r is the reaction rate (mol L−1 min−1 ), C represents the
methyl lactate exist that need further recovery treatment to
mole concentration of the corresponding component (mol L−1 )
improve the process economics. So, we intend to propose a
and W is the catalyst loading (g L−1 ).
new process based on catalysis in fixed bed, vacuum distilla-
From the kinetics, it is observed that this is a slightly
tion and reactive distillation. (1) Esterification of lactic acid
endothermic reaction with an almost negligible heat
with methanol catalyzed by fixed bed; (2) vacuum distilla-
effect. This indicates that an increase in the reac-
tion of esterification products, and the residue is collected
and esterified with methanol again; (3) hydrolysis of methyl
Table 1 – Results of steady state design of reactive lactate catalyzed by fixed bed; and (4) the hydrolysis prod-
distillation for hydrolysis of methyl lactate. ucts are fed into reactive distillation column to hydrolyze
Item Results completely.
The schematic drawing of the methyl lactate hydrolysis in
Total number of trays 44
Number of trays in rectifying section 4
RD column is showed as Fig. 2, a prereactor (plug flow reactor)
Number of trays in reactive section 40 that handles a substantial part of the reaction duty is used
Reactive section 5–44 upstream of the RD column that consists of a rectifier and a
Feed tray 8 reactive section. The optimization of a RD column has a large
Catalyst in each tray/sum (kg) 12.15/473.85 number of design variables, in order to reduce the number
Catalyst in reboiler (kg) 50
of design optimization variables, the following specification
Mass reflux ratio 4.65
and assumption are made: (1) the feed flowrate is fixed at
Condenser duty (W) −784265.4
Reboiler duty (W) 733806.9 1 kg s−1 and it contains 90% water and 10% methyl lactate in
Column diameter (m) 0.59 mole fraction; (2) the product purity of the distillate stream
Column height (m) 21.12 is xD,MeOH = 0.95 (W/W); (3) the product purity of the bottom
Condenser heat transfer area (m2 ) 36.91 stream is xB,ML = 0.001 (W/W); (4) 70% conversion is obtained
Reboiler heat transfer area (m2 ) 20.67 after the prereactor; (5) the liquid that feed into the RD column
Distillate flow rate (kg/h) 427.1
is at saturation state.
Bottom product flow rate (kg/h) 3172.9
Mass fraction of the distillate product
Water 0.0539 3.2. Design procedure
Methanol 0.9461
Methyl lactate 6.3567e−07
Based on this flowsheet, a procedure is used to achieve an
Lactic acid 4.8067e−16
Mass fraction of the bottom product
improved design to reduce the TAC. The design variables
Water 0.6401 are: number of trays of the rectifying section (Nrec ), num-
Lactic acid 0.3587 ber of trays of the reactive section (Nrea ), feed tray location
Methanol 0.0002 in the reactive zone. Two manipulating variables consid-
Methyl lactate 0.0010 ered here including reflux ratio of RD column and reboiler
TAC (¥10,000/year) 234.8
duty.
2202 chemical engineering research and design 8 9 ( 2 0 1 1 ) 2199–2206
Fig. 3 – The effects of stages on the TAC. Nrec : number of trays in rectifying section; Nrea : number of trays in reactive section;
(a) feed on the first stage of reactive section, Nrec = 6; (b) feed on the first stage of reactive section; (c) feed on the second stage
of reactive section; (d) feed on the third stage of reactive section; (e) feed on the fourth stage of reactive section; and (f) feed
on the fifth stage of reactive section.
In this research, all simulations are carried out using RAD- the payback period is assumed to be 3 years and the catalyst
FRAC of Aspen Plus, the steps as follows are adopted to life is 3 months.
obtain a near optimal design: (1) place the reactants feed The details for the TAC computing are the same as Cheng
on the top of the reactive zone; (2) fix the number of reac- et al. (2009) with some changes as follows: M&S index of 1446.5
tive trays (Nrea ); (3) guess the tray numbers in the rectifying (2009, 4th Q) is applied in the calculation; the energy cost for
section (Nrec ); (4) change the reflux flow (R) and reboiler steam is ¥32.00/106 kJ; the price for cooling water is ¥2.00/cum;
heat duty until the products specification is met; (5) go back the price for resin is ¥25.00/kg.
to (3) and change Nrec until the TAC is minimized; (6) go For a RD column, one important issue is the tray holdup in
back to (2) and vary Nrea until the TAC is minimized; (7) go the reactive section, which is calculated by the column diame-
back to (1) and change the feed location until the TAC is ter, the active area of the bubble cap tray, and the liquid depth
minimized. on the tray. The active area of the bubble cap tray is usually
The estimation of the equipment follows the procedure 90% of the total cross-sectional area. The liquid depth is lim-
of Douglas (1988) and specific equation of Elliott and Luyben ited to about 0.1 m by the hydraulic limitation. The diameter of
(1996), Chiang et al. (2002) and Seider et al. (2003) were used. the column is unknown initially because it depends on vapor
The TAC is defined as: velocity that is not known until the column is converged to
the given specifications. So column sizing in RD column is
TACcap
TAC = TACope + (3) an iterative procedure, a diameter is estimated, tray holdups
3
calculated, and the column is converged, then the diameter
where the operating cost (TACope ) includes the costs of steam, calculated in “Tray Sizing” is compared with the estimated
cooling water, and catalyst, and the capital cost (TACcap ) covers diameter and the calculations repeated until the error can be
the cost of column, trays, and heat exchangers. In this work ignored.
chemical engineering research and design 8 9 ( 2 0 1 1 ) 2199–2206 2203
ΔT/ΔQR (%/%)
0.24 0.06
lactic acid 0.1
water
0.4 methanol 0.16 0.04 0
methyl lactate
-0.1
0.2 0.08 0.02
-0.2
Stage
b
390.0
0.3
Temperature K
0.2
Reflux ratio -0.01%
ΔT/ΔRR (%/%)
0.1
0
345.0
-0.1
1.0 5.0 9.0 13.0 17.0 21.0 25.0 29.0 33.0 37.0 41.0 45.0
Stage -0.2
of the design value) are made in the reboiler heat duty and 4.3. Control performance
the reflux ration. Dividing the change of the tray temperature
by the change of the manipulated variable gives the openloop The disturbances of feed flow rate changes (flow rate ±20%)
steady-state gain between temperature on that tray and each and feed composition variations (mass fraction of methyl lac-
manipulated variable. The tray temperatures of the RD col- tate ±5%, mass fraction of methanol ∓5 %) are used to evaluate
umn increase with the reboiler heat duty and an increase of the control performance of this hydrolysis RD system. The
the reflux ration leads to a decrease of the tray temperatures dual temperature control actually works very well for this sys-
of the column. For the disturbance of reboiler heat duty, there tem as shown in Figs. 7 and 8. For these two disturbances, the
are two peaks of temperature change on the fourth and nine- responses are quite symmetrical, the product compositions
teenth tray; for the disturbance of the reflux ratio, there is only settle in less than 5 h, and the steady state offsets are rather
one peak of the temperature change on the fourth tray. So, the small, 1 wt% for methanol in the distillate stream and 0.1 wt%
temperature of fourth tray is chosen to be controlled by the for methyl lactate in the bottom stream.
Fig. 7 – Test results for disturbances of feed flowrate under single temperature control — feed flowrate +20%; . . .. . . feed
flowrate −20%. (a) Temperature of the forth tray; (b) temperature of the nineteenth tray; (c) mass fraction of methanol in the
distillate; (d) mass fraction of methyl lactate in the reboiler; (e) actual duty of condenser; and (f) heat duty of reboiler.
chemical engineering research and design 8 9 ( 2 0 1 1 ) 2199–2206 2205
Fig. 8 – Test results for disturbances of feed composition under single temperature control — mass fraction of methyl lactate
+5%; . . .. . . mass fraction of methyl lactate −5%. (a) Temperature of the forth tray; (b) temperature of the nineteenth tray; (c)
mass fraction of methanol in the distillate; (d) mass fraction of methyl lactate in the reboiler; (e) actual duty of condenser;
and (f) heat duty of reboiler.
5. Conclusion Asthana, N., Kolah, A., Vu, D.T., Lira, C.T., Miller, D.J., 2005. A
continuous reactive separation process for ethyl lactate
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Chiang, S.-F., Kuo, C.-L., Yu, C.-C., Wong, D.S.H., 2002. Design
dure is used to optimize the quantitative design based on total alternatives for the amyl acetate process: coupled
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