Abstract

Lactic acid is a commonly occurring substance in nature, ranging from existence in

micro-organisms to the human body. Traditionally, lactic acid has applications in
industries such as food, chemicals, pharmaceuticals and textiles. In this work, a
sustainable process for the production of polymer grade lactic acid (99 wt. % on dry
basis) from crude lactic acid was simulated. The simulation was performed using Aspen
Plus® version 8.2. The thermodynamic model used for the process was NRTL – Hayden
O’Connell due to the polar nature and non-ideal behavior of the species involved. The
process was carried out in three stages. First, crude lactic acid was obtained by reacting
calcium lactate with sulfuric acid. The second stage consisted of esterification of lactic
acid by reactive distillation. A RadFrac column was used for this purpose which also
facilitated easy separation of methyl lactate from methanol and water. Pure methyl
lactate obtained from the second stage was then hydrolyzed in the third stage using
pure lactic acid as an auto-catalyst to obtain the desired product. Use of pure lactic acid
as an auto-catalyst helped to achieve the required purity as it minimized contamination.
The process was optimized using sensitivity analysis in Aspen Plus ®.

Keywords

Lactic acid Process simulation Reactive distillation Auto-catalyst RadFrac Sensitivity

analysis

Introduction
Lactic acid was first isolated in 1780 by Swedish scientist Carl Wilhelm Scheele by
crystallizing its calcium salt [1]. It is a weak organic acid with a hydroxyl group and a
carboxylic group present on adjacent carbon atoms in the carbon chain. This duality in
structure allows it to react either as an acid or as an alcohol.

Traditionally, lactic acid has applications in the food, chemical, and pharmaceutical
industries. In the food industry, lactic acid with a purity of about 85 wt. % is used to
induce a sour taste in food products, for example in pickles and sauerkraut. It is also
used as an acidulant in the food industry [2]. In addition, it is also used in the textile
industry as a caustic [3, 4]. Around 80–85 wt. % of lactic acid is manufactured for use in
the food industry. More recently however, there has been an increased focus on
manufacturing lactic acid of high purity (99 wt. % on dry basis) which can be used as
the monomer for producing poly-lactic acid (PLA). PLA can be obtained from lactic acid
via two different mechanisms – 1) direct polymerization of lactic acid by poly-
condensation or 2) condensation to form lactide (intermediate) and corresponding
ring-opening polymerization to obtain PLA [3].

PLA is a biocompatible and biodegradable material that has numerous applications in

sustainable plastic products [5]. Along with ease of disposal, lactic acid polymers also
possess high tensile strength and can be used in the packaging industry and for medical
and biological applications [6]. Table 1 summarizes the applications of PLA in various
industries [2, 7].
 Table 1
Summary of polymer grade lactic acid applications

Industry Property Application

Non-toxic, relatively
Medical strong, bio-compatible, Medical Implants; clinical applications – sutures; meshes, bo
sterilizable

High tensile strength,

thermal resistance,
Packaging Flexible Films, thermoforming, lamination
impact resistance,
transparency

bacteriostatic, flame-
Textile retardant, and Geo-textiles, Industrial Fabrics, Fibers, Home Furnishings
weathering resistance

Environme
Bio-compatible As sorbent in wastewater treatment; As a substrate for nitro
ntal

Biodegradability, flame-
To manufacture sandbags, weed prevention nets, vegetation
Other retardant, thermal
use in the agriculture industry
resistance
PLA competes with traditional plastics like poly-ethylene terephthalate (PET) and poly
propylene (PP) in terms of sustainability [8] and applications. PLA is a biodegradable
polymer and decomposes at composting conditions and temperatures above 60°C. PLA
production requires less energy per kg as compared to PET and PP (42 MJ/kg for PLA as
compared to 73 MJ/kg for PP and 80 MJ/kg for PET) [8]. Recycling PLA, however, is
difficult using traditional mechanical or melt-recycling methods because of its
temperature and water sensitivity. To accomplish this, chemical processes which can
hydrolyze PLA to lactic acid are being developed.

According to a comparison study performed by Tabone, Cregg et. al., PLA is the top
ranked polymer in terms of rankings based on green design principles and ranks sixth
according to Life Cycle Assessment principles [9]. It is therefore considered as one of
the more sustainable alternatives to plastics being used currently.

To obtain high quality PLA, polymer grade lactic acid (~99 wt. % purity) is the starting
point. Several efforts have been made previously to obtain high purity lactic acid [10–
12]. Those methods generally have the following limitations.

1. 1.

High pressure and temperature required to achieve the intended purity which increases
cost.
2. 2.

High pressure and temperature also lead to formation of by-products (unwanted methyl
esters) during the esterification reaction which are difficult to separate.

3. 3.

Use of acid catalyst in the hydrolysis reaction hampers lactic acid purity.

4. 4.

Limited conversion for the esterification reaction due to product build-up.

Process description
The present simulation work is based on a patented process by the National Chemical
Laboratory (Pune) to manufacture polymer grade lactic acid [13]. The process can be
roughly divided into three stages. The first stage consists of reacting 10 wt. % calcium
lactate (obtained as a fermentation product) with concentrated H 2SO4 to yield dilute
crude lactic acid and calcium sulfate as shown in Figure 1. The sulfate is separated out
by means of a centrifuge and the crude lactic acid is concentrated to 60 wt. % by passing
it through a falling film evaporator.

Figure 1
Basic process flow diagram for the first stage of polymer grade lactic acid
production.

In the second stage, the dilute lactic acid is sent to the counter-current reactive
distillation column or the bubble column where it reacts with rising methanol vapors in
the presence of concentrated H2SO4 to produce methyl lactate and water via the
esterification reaction as depicted in Figure 2. Liquid methyl lactate flows to the bottom
of the column while water and unreacted methanol vapors move up the column to the
distillation section where they are separated. Liquid methyl lactate is then isolated by
means of fractional distillation to separate out the methyl lactate by-products of
fermentation impurity carboxylic acids to give highly pure methyl lactate (~98 wt.%).

Figure 2
Basic process flow diagram for the second stage of polymer grade lactic acid
production.

In this process, reactive distillation is the most crucial operation on which the entire
process is dependent. A reactive distillation operation consists of simultaneous reaction
and separation processes [14, 15]. In this case, methanol reacts with crude lactic acid to
produce methyl lactate. As per the patented process, water and methanol are being
simultaneously separated in the same column. However, while simulating this process it
was observed that an additional separation column (Separat 4) was more effective for
carrying out the separation of methanol and water than having a side-draw from the
RadFrac column. It can therefore be said that the Bubble Column Reactor and Separat 4
together represent the Reactive Distillation Column. However, it should be noted that
the more significant separation of methyl lactate and water + methanol is still occurring
in the Bubble Column Reactor.

As the product (i.e. methyl lactate) is being continuously removed from the reactor the
reaction equilibrium shifts towards the product side, thereby increasing maximum
conversion according to Le-Chatelier’s principle.
This is followed by the third stage which involves hydrolysis of pure methyl lactate to
high purity lactic acid (Figure 3). The ingenuity of this stage lies in the fact that pure
lactic acid is used as an auto-catalyst to avoid impurities. The use of an auto-catalyst
facilitates achieving high lactic acid purity (99 wt. % on dry basis) and also increases the
reaction rate. Also, methanol which is a by-product of the hydrolysis reaction is recycled
back to the bubble column, thereby reducing the inventory cost and energy. The design
objective for this simulation is to obtain a high yield of polymer grade (99 wt. % on dry
basis) lactic acid as the final product. The process is optimized by varying the stream
flow rates and design conditions to come up with the most energy efficient alternative
for a given lactic acid output. The process model is created and simulated using Aspen
Plus® version 8.2.

Figure 3
Basic process flow diagram for the third stage of polymer grade lactic acid
production.

It should be noted that the process flow diagrams depicted in Figures 1, 2 and 3 have
been retained as per the process described in the patent and should be used for
reference purpose only. While performing the simulations certain changes have been
made to the process for either simplicity or improved productivity. The final simulated
process flow diagram is as per shown in Figure 4.
Figure 4
Process flow diagram in Aspen Plus for production of polymer grade lactic acid.

Design basis
The design basis was setup based on Example 6 (Control Example) and Example 10
(hydrolysis of methyl lactate to get pure lactic acid) from the patent [13]. The design
specifications are listed in Table 2.
Table 2
Design basis obtained from patented process

Equipment Parameter

Crude lactic acid + Impurities

Lactic acid feed temperature

Bubble column reactor Methanol + water

Methanol feed temperature

Bottom section temp of bubble column

Separator Highly pure methyl lactate

Hydrolysis reactor Distilled water to reactor

Pure lactic acid to reactor

 Equipment Parameter

Reactor temperature
Model development
The following step-wise methodology was adopted while simulating the process.

1. 1.

Thermodynamic model selection

The majority of the process deals with highly polar components like lactic acid and
methyl lactate, so the model must be based on the activity coefficient. In addition, lactic
acid and methyl lactate both display non-ideal behavior which again indicates the
requirement of an activity coefficient model. Therefore, initially the NRTL
thermodynamic model was used as the thermodynamic property model for this process.
But, the NRTL property model works well only for the vapor phase predictions of VLE.
Hence, the Wilson-Hayden O’Connell property model was selected which provides
accurate predictions for both phases in VLE.

2. 2.Unit Operation Model selection

The first step in model development was to select the appropriate unit operation model
based on the information available and the required output. For simulating the reactive
distillation, RadFrac unit operation model is used. The RadFrac model can be used for
rigorous fractionation, mainly for two or three phase vapor–liquid fractionation.
Another advantage of RadFrac is the fact that it can handle chemical reactions, which is
the case for reactive distillation column and also RadFrac can deal with strong liquid
phase non-ideality. The hydrolysis reactor is modeled using the RStoich reactor. The
main reason for selecting RStoich is that both conversion as well as stoichiometry was
known for the reaction. Finally, Distl and Sep 2 model was used to simulate the two
separators; the one used for isolating pure methyl lactate in stage 2 and the other used
for separating pure lactic acid in stage 3.

3. 3.PFD generation
Based on the unit operation model selection, a basic process flow diagram (PFD) is
generated in Aspen Plus® (Figure 4).

4. 4.Sensitivity Analysis
Sensitivity Analysis is a technique available in the Aspen Plus software which can be
used to ascertain the effects of certain parameters on significant process variables. It
can therefore be used to obtain optimum process conditions. In this technique different
process parameters can be varied independently or simultaneously to study their effect
on process variables like mass/mole fraction of desired product (mass/mole purity). In
this work, sensitivity analyses has been performed for several objective variables
including bubble column reactor and separator parameters- number of stages, distillate
to feed ratio, reflux ratio, feed stage; hydrolysis reactor parameters – temperature, pure
lactic acid flow, distilled water flow; methanol recycle split ratio.

Results and discussion

Sensitivity analyses were carried out for several objective variables as shown in Table 3.
As can be observed from the table, methyl lactate and lactic acid purity (mass fraction)
are the main objective variables. The sensitivity analyses were performed in a
systematic manner for each of the major equipment – Bubble Column Reactor,
Hydrolysis Reactor, Lactic Acid Separator (Separator 3), Methyl Lactate Separator
(Separator 1), Methanol Recycle Splitter, Heater 1, and Heater 2. The process variables
were varied to study their effect on objective variables. A summary of the sensitivity
analyses conducted and their results is illustrated in Table 3. The detailed tabulated
results of the sensitivity analyses are provided in Additional file 1: Table S1-S6.
Table 3
Summary of sensitivity analyses performed

Objective Base case Process

Process
No. Equipment variables process variable
variables
(Sensitivity) variable variation r

1 No. of stages 9 9 - 11

2 Lactic acid Distillate to feed 0.5 0.5 - 0.7

separator
3 (Separator 3) Reflux ratio 1 1 - 1.3

4 Feed location 5 4-5

Lactic acid purity
5 Temperature (K) (Mass fraction) 373 313 - 41

Pure lactic acid

6 0.015 0.01 – 0.
Hydrolysis reactor flow (kg/hr)

Distilled water
7 2 1.8 – 2.
flow (kg/hr)

8 No. of stages Methyl lactate 17 5 - 17

purity (Mass
9 Distillate to feed 0.7 0.4 – 0.8
Bubble column fraction)
10 reactor Reflux ratio 2 1-4

Methanol feed
11 15 13 - 17
stage

12 Heater 1 Temperature (K) 376 323 - 41

13 Heater 2 Temperature (K) 392 343 - 43

Methanol recycle
14 Splitter 1 0.15 - 1
split fraction

15 Methyl lactate No. of stages 10 10 - 12

separator
16 Distillate to feed 0.6 0.1 – 0.
 Objective Base case Process
Process
No. Equipment variables process variable
variables
(Sensitivity) variable variation r

17 Reflux ratio 1.5 1-3

18 (Separator 1) Feed location 5 3-8

Note: Italicized numbers depict variables with significant variations over the range.

Using the data from sensitivity studies, optimum process conditions were determined
for each major unit. The optimum was based on achieving the maximum purity for
methyl lactate and lactic acid with minimum chemical inventory. In case of
temperatures, if no significant change in purity was observed, the base case values from
the patent have been used. In all other cases where no significant change in purity was
observed, process conditions understandably leading to least costs (capital and
operating) and energy consumption, were used.

It can be noted from Table 3 that the distillate to feed ratio has a significant effect on
purity in the bubble column reactor as well as both the separators (Separator 1 and
Separator 3). On the other hand, the reflux ratio and number of stages do not have any
significant change on purity in any of the three units. Purity is sensitive towards
methanol feed location in the bubble column reactor but is not affected by the feed
location in either of the two separators.

It was observed that methyl lactate purity increases with an increase in methanol feed
stage till stage no. 15 after which it marginally decreases (Figure 5). This observation
was expected because as the methanol feed stage increases (column stage number
increases from top to bottom), the contact time for methanol and lactic acid increases,
thereby increasing mass transfer, subsequently resulting in higher purity of methyl
lactate. Along with the sensitivity analysis, the bubble column temperature profile was
obtained. The study of profile variations helped in determining the optimum feed stage
for the methanol feed stream (Figure 6).
Figure 5
Sensitivity analysis results illustrating the effect of methanol feed stage variance
in the bubble column reactor.

Figure 6
Temperature profile for the bubble column reactor (base case).

Stream results tables listing important streams with their process parameters for both
the base case and optimized case have been illustrated in Tables 4 and 5. Comparing the
two tables the improvements in product purity in the optimum case becomes evident.
Note that the stream names used are as specified in the process flow diagram.
Table 4
Stream results table (Base case)

Parameter/stream → ↓ LA-FEED METHFEED PURELACT DISTBOT SEP2BOT

Temperature (K) 298.1 298.1 379 393.4 393.4

Pressure (atm.) 1 1 1 1 1

Mass Fflow (kg/hr) 10.5 7.5 11.29 8.171 6.921

Mass fraction (Mass purity)

Lactic acid 0.571 0.001 0.001

Methyl lactate 0.613 0.845 0.997

Methanol 0.996 0.003 62 PPB

Water 0.381 0.004 0.339 0.093 0.003

Others 0.05 0.045 0.059

Note: 1) Italicized numbers depict variables with significant variations over the range.
2) Listed row headers depict streams and column headers depict parameters (As shown
by arrows).
Table 5
Stream results table (Optimized case)

Parameter/stream → ↓ LA-FEED METHFEED PURELACT DISTBOT SEP2BOT

Temperature (K) 298.1 298.1 382.4 414.6 414.6

Pressure (atm) 1 1 1 1 1

Mass flow (kg/hr) 10.5 7.5 11.056 8.625 8.072

Mass fraction (Mass purity)

Lactic acid 0.571 730 PPM 935 PPM

Methyl lactate 0.733 0.933 0.997

Methanol 0.996 0.005 302 PPB

Water 0.381 0.004 0.216 0.009 0.003

Others 0.05 0.045 0.059

Note: 1) Italicized numbers depict variables with significant variations over the range.
2) Listed row headers depict streams and column headers depict parameters (As shown
by arrows).
Conclusion
A process flow diagram for the production of polymer grade lactic acid was developed
using Aspen Plus®. The process was successfully simulated and converged results were
obtained. An extensive sensitivity analysis was conducted on each of the key pieces of
equipment to obtain high purity methyl lactate and subsequently pure lactic acid. The
process conditions were subsequently optimized based on these results. The desired
purity of polymer grade lactic acid (99 wt. %, dry basis) was obtained. Also, the purity of
methyl lactate was above the desired percentage of 98.5 wt. %.