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Abstract
A computational platform for the simulation, design and analysis of the Polylactic
(PLA) acid production process using different lignocellulosic raw materials has been
developed. The computational platform considers three main reactive-separation
processes: 1) the bio-conversion process, where an hydrolysis-saccharification-culture
process to produce the inoculated hydrolysate is coupled with a fermentation-separation
process producing the broth with crude lactic acid; 2) the purification process, where a
sequence of conventional and reactive distillation columns to perform the esterification
and hydrolysis reactions, respectively, are used to produce a polymer grade lactic acid;
and 3) the polymerization process, where a ring-opening polymerization reaction
scheme to produce high molecular weight PLA is carried out. The platform was
constructed on the Aspen Plus Environment. The implementation of the platform in a
systematic manner allowed the evaluation of various mono and disaccharide materials
to produce PLA. The results show that with a higher concentration of glucose the
molecular weight of the PLA produced increased. However, the operation of the
purification section, that is, the reactive distillation columns should be carried out
carefully in order to obtain a purified lactic acid near to 88% mass fraction.
1. Introduction
Polylactic acid (PLA), a biodegradable poly hydroxy alkanoate (PHA), it is a promising
replacement for synthetic polymers. The advantages of Polylactic acid are its high tensile
strength, high modulus, thermoplastic property, biodegradability and bioenvironmental
compatibility/absorbability. It is used in making of biodegradable sutures, clamps, bone
plates and biologically active controlled release devices (Jamshidian et al., 2010).
1188 E. S. Pérez-Cisneros et al.
The production of PLA can be divided into two main steps: production of lactic acid and its
polymerization to PLA. The production of lactic acid follows a fermentation process to
produce a broth containing crude lactic acid and a downstream processing of the
fermentation broth to obtain polymer grade lactic acid. Most frequently used procedures for
lactic acid production are batch, repeated batch and continuous fermentation. For the
separation and purification different procedure are used for example: electrodialysis, liquid
extraction and reactive distillation. Various mono and disaccharide materials are generally
used for its production i.e., glucose (dextrose) and glucose syrup as end product of starch
conversion; maltose as a product from barley malt or other source; sucrose as end product of
beet and cane sugar production. The amount of these cheap raw materials in México is
significant all along the country. Therefore, the requirement of a computational tool to
evaluate the economical and environmental feasibility of a PLA production plant is highly
required. The present work proposes a computational platform based on three different
reaction-separation sections: 1) Bio-conversion process: a hydrolysis-saccharification-
culture process to produce the inoculated hydrolysate is coupled with a fermentation-
separation process producing the broth with crude lactic acid; 2) Purification process: a
sequence of conventional and reactive distillation columns to perform the esterification and
hydrolysis reactions, respectively, are used to produce a polymer grade lactic acid, and 3)
Polymerization process: a ring-opening process to produce high molecular weight PLA. The
platform was constructed on the Aspen Plus Environment. Figure 1 shows a simplified
flowsheet of the computational platform to produce PLA.
for large raw material capacity. Adsorption and reactive extraction have particle
selectivity, capacity, and regeneration problems. Most importantly, all of these methods
suffer from low lactic acid recovery.
H2SO4-WATER
(15:85 wt/wt)
Ca(OH)2-WATER FE5
(15:85 wt/wt) FE7 VAPOR
FE3
FILTER 1 FILTER 2 FE9
FE10
BIOMASS RECYCLED
FE4
CaSO4
LA-FEED PUR-2
PUR-8A
PUR-6A
PRECONCEN
ESTERIFICATION HYDROLISIS
COLUMN
REACTIVE REACTIVE METHANOL
DISTILLATION DISTILLATION RECOVERY
CRUDE LACTIC ACID FEED COLUMN
F=2010 (kmol/hr) COLUMN DISTILLATION
X(Lactic)=0.064 COLUMN
T=375 K; P= 2 atm WATER
PUR-3
PUR-4 PUR-9
PUR-5
FRESH METHANOL FEED
52 (kmol/hr)
T=303 K; P= 2 atm
PUR-10
212 (kmol/hr)
POLYMER GRADE X(Lactic)=0.593
LACTIC ACID FEED T=419 K; P= 1.77 atm
TO-EVAP TO-D50
DISTILLATION
COLUMN C-200 RECYCLE
D-50
LIQUID-2 P-500
LIQUID-1 POLYMERIZATION
REACTOR
PLA
DISTILLATION PURG-CAT
CATALYST COLUMN C-300
POLY-LACTIC ACID
POLY-CAT
RECY-2
Figure 1. Simplified flowsheet of the computational platform for polylactic acid production
1190 E. S. Pérez-Cisneros et al.
In view of these limitations, the most attractive method for purification of lactic acid
from fermentation broth is a two-step reactive-distillation process in which the acid is
first reacted with an alcohol to form a more volatile ester which can be purified by
distillation. Then, pure lactic acid is recovered by hydrolysis of the ester. This
purification method not only can handle large raw material capacity but also can
achieve high lactic acid recovery. In the present work, the vDSRUíOLTXLG DQG
YDSRUíOLTXLGíOLTXLG HTXLOLEULD ZHUH HVWLPDWHG IRU HDFK SURFHVV XVLQJ 157/ DFWLYLW\
model for the liquid phase and Hayden-O´Conell second virial coefficient model for the
nonideality of the vapor phase. The alcohol considered for the esterification reaction is
methanol and the corresponding ester is methyl lactate (METHY-01). Also, solid-
catalyzed reaction kinetics are used for each reaction and the reactive zones can be
located in different sections of the reactive distillation columns. Kinetic data on solid-
catalyzed lactic acid esterification and hydrolysis reactions have been reported by Su et
al. (2013). Table 2 shows the simulation results of the purification section for selected
streams of the reference study case.
Table 2. Simulation Results for the Purification Section (reference study case)
Stream LA-FEED PUR-3 PUR-4 PUR-5 PUR-6A PUR-7 PUR-8A PUR-9
Total Flow
(kmol/hr) 2009.89 259.89 530.00 1.63 788.26 500.00 1075.89 212.37
Total Flow (kg/hr) 45394.96 13867.12 16982.34 169.31 30680.15 9007.64 26793.82 12893.97
Temperature K 374.68 348.84 303.15 383.32 312.80 303.15 350.25 419.39
Pressure atm 2.00 0.20 2.00 0.35 1.30 2.00 1.20 1.76
Mass Frac
LACTIC 0.253 0.828 0.000 0.000 0.000 0.000 0.000 0.879
WATER 0.746 0.172 0.000 0.000 0.153 1.000 0.368 0.121
METHANOL 0.000 0.000 1.000 0.002 0.420 0.000 0.632 0.000
METHY-01 0.000 0.000 0.000 0.000 0.427 0.000 0.000 0.000
SUCCI-01 0.001 0.000 0.000 0.998 0.000 0.000 0.000 0.000
A Computational Platform for Simulation, Design and Analysis of a Poly(Lactic) 1191
Acid Production Process From Different Lignocellulosic Raw Materials
Mass Frac
WATER 0.121 0.007 0.000 0.000 0.005 0.000 0.000
LA 0.879 0.125 0.000 0.000 0.002 0.001 0.000
LACTIDE 0.000 0.000 0.000 0.014 0.119 0.999 0.011
PLA 0.000 0.867 0.000 0.986 0.874 0.000 0.989
CATALYST 0.000 0.000 1.000 0.000 0.000 0.000 0.000
Total Flow
(kmol/hr) 212.29 133.49 0.04 1338.00 1416.90 67.25 122.50
Total Flow
(kg/hr) 12892.79 9647.80 5.00 97093.41 106746.21 9685.04 8876.36
Temp. C 25.00 170.00 24.85 209.96 220.00 145.00 187.00
Pressure torr 760.00 400.00 760.00 10.00 10.03 10.00 2.00
DPN 7.55 59.71 62.24 865.13
MWN 561.94 4321.00 4503.57 62362.29
b) beets with 18 and 53%; c) pineapple with 19.4 and 22.4 % and d) banana with 9.6 and
9.4%. Table 4 shows the different composition scenarios of the lignocellulosic raw
materials, the lactic acid broth composition produced and the lactic acid polymer grade
purified. Also, it can be noted the final PLA flow produced and its molecular weight
respectively. It can be observed from the results that the reduction in the lactic acid
composition in the broth from the fermentation step affects significatively the purified
polymer grade lactic acid flow. However, it has small influence on the flow of the PLA
produced. Nevertheless, the molecular weight of the PLA, which is the key property
indicating the biodegradability of the biopolymer, is strongly affected. It should be pointed
out that these differences in the PLA weights are a consequence that the lactic acid exit
purity required of the purification section is not achieved (88% mass fraction).
6. Conclusions
A computational platform for the simulation, design and analysis of the Polylactic
(PLA) acid production process using different lignocellulosic raw materials has been
developed. The implementation of the platform in a systematic manner allowed the
evaluation of various mono and disaccharide materials to produce PLA. The results
show that with a higher concentration of glucose the molecular weight of the PLA
produced increased. However, the operation of the purification section, that is, the
reactive distillation columns should be carried out carefully in order to obtain a purified
lactic acid near to 88% mass fraction.
References
Abdel-Rahman Mohamed Ali, Yukihiro Tashiro , Kenji Sonomoto, Recent advances in lactic acid
production by microbial fermentation processes, Biotechnology Advances 31 (2013) 877–902
Chien-Yuan Su, Cheng-Ching Yu, I-Lung Chien and Jeffrey D. Ward, Plant-Wide Economic
Comparison of Lactic Acid Recovery Processes by Reactive Distillation with Different
Alcohols, Ind. Eng. Chem. Res. 52 (2013) 11070-11083
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Design, John Wiley & Sons, Inc., Hoboken, New Yersey (2008).
Majid Jamshidian, Elmira Arab Tehrany, Muhammad Imran, Muriel Jacquot and Stéphane
Desobry, Poly-Lactic Acid: Production, Applications, Nanocomposites, and Release Studies.
Comprehensive REVIEWS in Food Science and Food Safety, Vol. 9 (2010) 552-571
Wooley R.J., Putsche V., 1996, Development of an ASPEN PLUS Physical Property Database for
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Colorado, USA.