Chemical Engineering Science: X 2 (2019) 100021

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Chemical Engineering Science: X

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Design and optimization of Kemira-Leonard process for formic acid

production
W.X. Chua, S. da Cunha, G.P. Rangaiah ⇑, K. Hidajat
Department of Chemical and Biomolecular Engineering, National University of Singapore, Singapore 117585, Singapore

a r t i c l e i n f o a b s t r a c t

Article history: Formic acid (FA) is a chemical with numerous industrial applications. Available literature including
Received 27 July 2018 patents on FA processes are limited and do not provide sufficient information for process simulation.
Received in revised form 26 March 2019 In the present study, a conventional FA process, known as the Kemira-Leonard (KL) process, for producing
Accepted 28 March 2019
98 wt% FA is developed and simulated using Aspen Plus V9. Then, heat integration and optimization of
the process for two objectives (namely, minimization of total capital cost and annual utility cost) are per-
formed. Finally, further improvement of the optimized process via vapor recompression (VR) is investi-
Keywords:
gated. Bi-objective optimization provides many Pareto-optimal solutions for selection. Total annual
Formic acid
Kemira-Leonard process
cost (TAC) of the chosen optimized KL process without VR is found to be $19,887,834 (=0.724 USD/kg
Process simulation of FA produced), with total capital cost of $18,476,733. Addition of VR brings savings of $1,560,427 in
Process design annual utility cost, with an additional investment of $2,517,191 for the compressor and new heat
Heat integration exchangers; overall, this leads to TAC reduction of $1,035,748 (by 5.2%). Unit TAC after VR addition is
Multi-objective optimization 0.686 $/kg of FA produced.
Vapor recompression Ó 2019 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/by-nc-nd/4.0/).

1. Introduction FA synthesis based on MF hydrolysis are known as the BASF and

Formic acid (FA) is an important chemical with numerous
industrial applications. It is used mainly as a preservative and
antibacterial agent in livestock feed, and to treat textiles and
leather (Hietala et al., 2016). As FA is the simplest carboxylic acid,
it is also used for the production of several other chemical products
(Andrushkevich et al., 2014). There is significant demand globally
for FA, totaling 950,000 tonnes/year in 2014 (Hietala et al., 2016).
This represents a ten-fold increase from FA capacity in 1980, which
was
100,000 tonnes/year (Hoch and Scheeline, 1983). The
demand for FA is expected to continue increasing, particularly with
recent technological advancements in fuel cells and renewable
energy (Aslam et al., 2012). Market analysts project FA demand
HCOOCH3 ð2Þ
to increase at a compound annual growth rate of 4.94% till 2027
(Market Research Future, 2017).
The two main routes of FA synthesis practiced today are:
methyl formate (MF) hydrolysis and preparation of free FA from
formates (Hietala et al., 2016). The current market is dominated
by the first route, whereby 90% of the world’s FA is synthesized.
HCOOH þ CH3 OH ð3Þ
This study focuses on the production of FA through MF hydrolysis
via the Kemira-Leonard (KL) process. Other industrial processes of
⇑ Corresponding author.
E-mail address: chegpr@nus.edu.sg (G.P. Rangaiah).
USSR processes. Among these 3 FA processes, the BASF and KL pro-
cesses are the most common (Hietala et al., 2016).
In principle, the production of FA via MF can be reduced to the
following overall reaction:
CO þ H2 O ! HCOOH ð1Þ
The above is the result of two main reactions, the first being the
carbonylation of methanol (methyl alcohol, MA) to form MF and
the second being the hydrolysis of MF to obtain FA (Hietala et al.,
2016). The carbonylation of MA to produce MF is given by:
CH3 OH þ CO
In the KL process, this reaction occurs in a continuously-stirred
tank reactor (CSTR) in the presence of sodium methoxide catalyst.
After separation, MF undergoes hydrolysis reaction to produce FA
and MA.
HCOOCH3 þ H2 O
The KL process involves two separate hydrolysis reactors, one
as a preliminary reactor to first produce a small amount of FA
while the next serves as the main reactor, where the hydrolysis
reaction is catalyzed by the FA produced (Hietala et al., 2016).

https://doi.org/10.1016/j.cesx.2019.100021
2590-1400/Ó 2019 The Authors. Published by Elsevier Ltd.
This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
2 W.X. Chua et al. / Chemical Engineering Science: X 2 (2019) 100021
Nomenclature
Acronyms
ACCR Annual Capital Charge Ratio
AUC Annual Utility Cost ($/y)
CEPCI Chemical Engineering Plant Cost Index
CSTR Continuous Stirred-tank Reactor
DV Decision Variable
DWC Dividing-Wall Column
FA Formic Acid
HI Heat Integration
KL Kemira-Leonard
MA Methanol
The hydrolysis reactors are both plug flow reactors (PFR) (Leonard,
1981). Finally, FA will be recovered and purified to 98 wt% through
a series of distillation columns.
Despite its current industrial applications and the potential
increase in demand, information on the FA manufacturing
processes is very limited until recently. For the KL process, a patent
by Leonard (1981) describes features and some operating condi-
tions for MF hydrolysis and subsequent separation steps. Kashani
et al. (2014) attempted to simulate this process in Aspen HYSYS,
based on available literature. While this paper provides some
insight into FA process simulation, they modelled hydrolysis reac-
tors using equilibrium reactors without considering reaction kinet-
ics, which could compromise the validity of simulation results.
Further, Kashani et al. (2014) do not cover equipment sizing, cost-
ing, heat integration and optimization, all of which are important
aspects of a comprehensive process design.
For the BASF process, a patent by Wolf et al. (1982) gives pro-
cess configuration and operating conditions. This process employs
one CSTR to perform MF hydrolysis, and uses liquid-liquid extrac-
tion to separate FA from water beyond the azeotropic composition.
More recently, a patent by Huang et al. (2012) discloses a process
for 85 wt% and 99 wt% FA production via reactive distillation (RD).
In this, the RD column is packed with a strong ion-exchange resin,
which catalyzes MF hydrolysis. Novita et al. (2015) compared the
process in Huang et al. (2012) with a new process employing a
reactive dividing-wall column (RDWC), and found that the latter
process (without and with a side-reboiler) requires lower energy.
da Cunha et al. (2018) simulated a conventional FA process and
investigated its retrofitting with a DWC unit. Recently, Sharma
et al. (2018) improved the RDWC process without side-reboiler,
described in Novita et al. (2015), by adding vapor recompression
(VR) heat pump. Novita et al. (2018) investigated many process
configurations involving dividing-wall column (DWC), RDWC
and/or heat integration (HI), for producing 99 wt% FA, and found
the process with non-reactive upper DWC and HI had the lowest
energy requirement.
As reviewed above, reported studies and patents on industrial
FA processes are very limited until recently. Moreover, there is only
one recent study on KL process (Kashani et al., 2014). Hence, the
broad objective of the present paper is to develop and provide
complete design of the KL process for FA, along with relevant cost
estimation, HI and optimization. This, coupled with the growing
worldwide demand for FA, makes this paper useful to both acade-
mia and industry. In this work, the KL process was first simulated
in Aspen Plus V9.0, HI was performed, and effects of design vari-
ables on capital/operating costs were assessed via sensitivity anal-
ysis. Thereafter, the process was optimized using the Improved
Multi-Objective Optimization Differential Evolution (I-MODE) pro-
gram of Sharma et al. (2017), for minimizing capital and utility
costs simultaneously. One of the Pareto-optimal solutions was
MF Methyl Formate
MOC Material of Construction
MOO Multi-Objective Optimization
PFR Plug Flow Reactor
RD Reactive Distillation
RDWC Reactive Dividing-Wall Column
TAC Total Annual Cost ($/y)
TCC Total Capital Cost ($)
UUC Unit Utility Cost ($/kg)
VR Vapor recompression
chosen, and potential of VR was studied for further improving
energy efficiency of the chosen optimal process.
2. Process development
2.1. Kemira-Leonard process description (Hietala et al., 2016)
The KL process outlined by Hietala et al. (2016) and shown in
Fig. 1, served as the primary reference for the process development
and simulation. In this process, carbonlyation reaction is carried
out in a CSTR (R1) at high temperature and pressure. The products
are sent to the MF column (C1), which separates MA into the bot-
toms and MF product into the liquid distillate. This column utilizes
a partial condenser in order to purge non-condensable components
(mainly CO). Recovered MA is recycled back to R1, while the distil-
late stream is sent to the preliminary hydrolysis reactor (R2). A
water feed stream is also introduced into R2 for the hydrolysis
reaction between MF and water to occur.
The product stream from R2 contains small amount of FA from
the autocatalytic hydrolysis reaction. This stream and recycle
streams from the downstream process containing water, MF and
some MA are fed into the main hydrolysis reactor (R3), where
the reaction proceeds as per FA-catalyzed hydrolysis reaction.
The preliminary and main hydrolysis reactors (R2 and R3) operate
at high temperature and pressure. The product of R3 is immedi-
ately flashed in F1 at atmospheric pressure. MF leaves F1 as the
vapor outlet, and the liquid mixture partially depleted of MF leaves
from the bottom. Vaporization of the reactor discharge, caused by
the pressure drop, results in a significant temperature drop from
122.8 °C to 40.9 °C. This low-temperature condition prevents re-
esterification of FA in the liquid outlet.
The vapor product from F1 is recycled to R3, while the liquid
product is sent to the acid separation column (C2). This column
separates MF and MA (in the distillate) from FA and water (in
the bottoms). The distillate is sent to the recycle column (C3). Here,
MF is obtained in the distillate and recycled back to the main
hydrolysis reactor (R3), while methanol is obtained in the bottoms
and returned to the CSTR (R1). The bottoms stream from C2 col-
umn is sent to the first product column (C4) to concentrate FA in
C4 bottoms. As FA and water form a negative azeotrope (i.e., its
boiling temperature is more than that of pure components
involved), column C4 is operated at higher pressure, while the sec-
ond product column (C5) is operated at atmospheric pressure.
Assuming C4 is operated above atmospheric pressure, composition
of C4 bottoms will be
80 wt% of FA compared to azeotropic com-
position of 78 wt% FA at atmospheric pressure (Aguilo and
Horlenko, 1985). This allows for pressure swing distillation
(Luyben, 2012) to produce FA of 98 wt% as the distillate of
column C5. Bottoms of column C5 is recycled to the previous col-
umn (C4).
 W.X. Chua et al. / Chemical Engineering Science: X 2 (2019) 100021
Fig. 1. Kemira-Leonard process for formic acid production.
2.2. Thermodynamic model
Selecting the appropriate fluid package is a crucial step before
process simulation in a simulator. According to the ‘Methods Assis-
tant’ in Aspen Plus, activity coefficient models (for example, NRTL,
UNIQUAC or Wilson) should be used for non-ideal systems like
methanol-water and FA-water. Novita et al. (2015) used UNIQUAC
with Hayden O’Connell equation of state for vapor phase (UNIQ-
HOC) as the fluid package for the simulation in their study on RD
based FA process. This model copes with the dimerization in the
vapor phase of mixtures containing carboxylic acids like FA. Hence,
the present study chose UNIQ-HOC model for the KL process sim-
ulation and optimization. Henry’s law was used to account for CO
dissolution in the liquid phase, which is appropriate at tempera-
tures well above the compound’s critical temperature (Koretsky,
2013). The binary interaction parameters for the UNIQ-HOC model
were obtained by Novita et al. (2015) via thermodynamic model
regression taken from various literature sources. These binary
parameters and the Henry parameters used for CO can be found
in Appendix A.
2.3. Modeling of reactors
The carbonylation and hydrolysis reactors in FA process were
simulated using the kinetic data in the literature. Bai et al. (1996)
and Chen et al. (2004) conducted experiments on methanol car-
bonylation to MF and reported rate equation for this carbonylation
reaction. Bai et al. (1996) presented the following rate expression:
r ¼ 1:414  109 eð Þ ½cat  ½CH OH ½CO
70748
RT
L 3 L L
ð92059Þ
 2:507  1012 e RT ½catL ½HCOOCH3 L
3
Here, r is the reaction rate in mol/(L.min), ½cat L is the liquid
phase concentration of sodium methoxide catalyst in mol/L,
½CH3 OHL is the liquid phase concentration of MA in mol/L, ½COL
is the liquid phase concentration of CO in mol/L, ½HCOOCH3 L is
the liquid phase concentration of MF in mol/L, T is the temperature
in K and R is the gas constant in J/(mol.K). Thus, reaction kinetics
proposed by Bai et al. (1996) gives both forward and reverse reac-
tion rates as functions of concentrations of reactants, product and
sodium methoxide catalyst in the liquid phase. Sodium methoxide
catalyst is solid powder, which dissolves in methanol to participate
in the liquid phase reaction. Eq. (4) is valid for temperature range
of 60 to 110 °C and pressure range of 2 to 4 MPa.
Chen et al. (2004) also used sodium methoxide catalyst, and
they reported the following kinetic expression:
r ¼ 9:96  106 eð Þ pðCOÞ½CH OH
67630
RT
3 L ð5Þ
Here, significance and dimensions of ½CH3 OHL , T and R are as
above, and pðCOÞ is the partial pressure of CO in MPa. The reaction
rate, r is given in units of MPa/min. The reaction kinetics in Eq. (5)
is noticeably different from that reported by Bai et al. (1996). The
former assumes irreversible reaction, the reaction rate is a function
of only reactants in the carbonylation reaction, namely, CO and
MA, and uses partial pressure of CO in the rate expression instead
of its liquid concentration. Eq. (5) of Chen et al. (2004) does not
involve catalyst concentration, and is valid for temperatures 60
to 90 °C and pressures 2 to 4.5 MPa.
Both Bai et al. (1996) and Chen et al. (2004) employed similar
reaction conditions (i.e., temperature, pressure and catalyst) for
the carbonylation kinetics. Sodium methoxide catalyst is a solid
powder soluble in methanol, and will dissolve and remain in the
ð4Þ
liquid phase for carbonylation reaction. As such, liquid concentra-
4 W.X. Chua et al. / Chemical Engineering Science: X 2 (2019) 100021
tion of sodium methoxide catalyst was included in the reaction
kinetics proposed by Bai et al. (1996). Catalyst concentration was
neither stated nor part of the kinetics proposed by Chen et al.
(2004). It may have already been accounted for in the pre-
exponential factor.
For the carbonylation of methanol in the KL process, CO is in the
liquid phase due to high pressure and excess methanol. The kinet-
ics of Bai et al. (1996) seem to be more appropriate. Also, they
include reverse reaction rate, which is appropriate since MF is
formed in significant amount in the carbonylation step. The rate
expression of Bai et al. (1996) was selected for use in FA process
simulation, for the following reasons: (i) both forward and back-
ward reactions are accounted for, (ii) CO is expressed in liquid-
phase concentration instead of partial pressure in gas phase, and
(iii) catalyst concentration is explicitly included. The catalyst con-
centration was assumed to be 0.408 mol/L, which is the highest
concentration used in the experiments conducted by Bai et al.
(1996). Preliminary design of CSTR for carbonylation is based on
the work of da Cunha et al. (2018); accordingly, temperature of
102 °C, pressure of 2.4 MPa and residence of 0.72 h were used for
the KL process simulation before optimization.
Two different hydrolysis reaction kinetics were used in the sim-
ulation. The hydrolysis reaction kinetics proposed by Jogunola
et al. (2010) is used in the simulation of the autocatalytic hydroly-
sis reaction of the preliminary PFR, which occurs when FA concen-
tration is low (e.g., initially). These kinetics are given by:
8

  9
>
<
0
0  ERa EEaa 1 ð1T 1TÞ >
= 
 ð ð Ea 1 1
 k
ÞÞ 1 þ e 1
r ¼ ke R T T
 C C  C A C B 
>
: k >
; KC
Here, r is the reaction rate in mol/(kg.min), T is the reference
temperature (=368.15 K), T is the reaction temperature in K, k is
the rate constant for the un-catalyzed reaction in kg/(mol.min), k
is the rate constant for the autocatalyzed reaction in
kg2/(mol2.min), Ea is the activation energy of the un-catalyzed
0
reaction in kJ/mol, Ea is the activation energy for the autocatalyzed
reaction in kJ/mol, R is the Gas constant in kJ/(mol.K), K C is the
equilibrium constant (dimensionless), C A is MF concentration in
mol/kg, C B is water concentration in mol/kg, C C is FA concentration
in mol/kg, and C D is MA concentration in mol/kg.
The second kinetic expression used is that proposed by Jogunola
et al. (2012) for modeling the FA-catalyzed hydrolysis reaction,
which occurs when FA concentration is sufficient. Jogunola et al.
(2012) have shown that the FA-catalyzed reaction could be mod-
elled using Eq. (7) below when a minimum FA to MF ratio of
0.05 is satisfied. The hydrolysis reaction kinetics of Jogunola et al.
(2012) is used in the simulation of the main hydrolysis PFR. The
kinetic equation is given by:
 0
 larly interested in the design of the PFRs for MF hydrolysis can

0  Ea
ð1T T1Þ 1 recalculate their geometry (length to diameter ratio) using a more
r ¼ k ðK d C C Þ0:5 e R
ðC A C B  CC CD Þ
KC

0
Here, k is the reaction rate constant in kg2/(mol2.min), K d is the
0 2.4. Designed Kemira-Leonard process
acid dissociation constant (mol/kg), Ea is the activation energy in

kJ/mol and T is the reference temperature (=368.15 K). The signif-
icances and units of r, T, R, C A , C B , C C , C D and K c are identical to
those in Eq. (6). Values of parameters in Eq. (7) are taken from
Jogunola et al. (2012) except for K d not given in this reference.
Hence, value of K d is taken to be 1.8  10-4 mol/kg, from Skoog
et al. (2000) after conversion from mol/L to mol/kg assuming liquid
density of 1.0 kg/L. Note that the value of 1.0 kg/L was used only to
convert K d from mol/L to mol/kg. This value is reasonable since
reaction experiments conducted by Jogunola et al. (2012) were
with excess water.
For the rate expressions in Eqs. (6) and (7), two sets of reaction
kinetics are suggested: (i) for auto-catalyzed reaction and (ii) for FA
catalyzed reaction. The auto-catalysed kinetics is applicable when
there is no or little FA in reaction mixture. On the other hand, the
FA-catalysed kinetics should be used when FA concentration in the
reaction mixture is significant. Table 1 shows the parameter values
 
0 0
used for both these reaction conditions; k, k , Ea and Ea for the
auto-catalysed reaction were used with Eq. (6) for simulating the

0 0
preliminary PFR whereas k and Ea for the FA-catalysed reaction
were used with Eq. (7) for the main PFR.
Owing to the concentration units (mol/kg) employed in the
kinetic expressions, hydrolysis reaction kinetics could not be mod-
elled using Aspen Plus V9 alone. As such, a user subroutine had to
be included in the simulation. This can be done by selecting the
option USER as the reaction type, under the item Reactions. This
subroutine needs to be written in FORTRAN and compiled using
the aspcomp command (Microsoft Visual Studio and a FORTRAN
compiler are required for this). The name of this subroutine is
required by Aspen Plus as the reaction input, under the Subroutine
tab. Further, it is necessary to create an OPT file containing the path
to the subroutine. In the Run Settings window, we select this OPT
file under Linker options. For more information on user-defined
subroutines, see Aspen Technology (2008).
The patent by Leonard (1981) gives the temperature and pres-
sure of the two PFRs to be 90 to 140 °C and 5 to 18 atm. Accordingly,
C C C D temperature of 120 °C and pressure of 18 atm were used for both
PFRs as preliminary results showed that they give satisfactory yield
ð6Þ of FA. The length and diameter of the PFRs were manually adjusted
to ensure simulation convergence and MF conversions close to the

ones reported in Leonard (1981). In the optimal solution presented
 in this manuscript, MF conversion in the preliminary and main

reactors are respectively 0.18 and 0.13 compared to 0.19 and 0.13
0
in Leonard (1981). The two PFRs were designed to operate adiabat-
ically, which eliminated the need for heating/cooling utility. The
preliminary PFR was designed to be 8.96 m in length and 0.30 m
in diameter, whereas the main PFR was determined to be 20.08 m
long with a diameter of 0.67 m. Both reactors have a length to diam-
eter ratio of 30, corresponding to the lower limit in Sauer et al.
(2013) for homogeneously operated tubular reactor.
Note that the plug-flow reactor in Aspen Plus uses the simplify-
ing assumption of perfect radial mixing. Therefore, yield of the
hydrolysis reaction in the simulation does not depend on the
geometry of the PFR, but only on its volume. Further, costing
methodology in Turton et al. (2013) uses the reactor volume
instead of its diameter and length to calculate the reactor capital
cost. In other words, any PFR geometry with the same volume
would amount to the same yield and capital cost in this work. Con-
sequently, considering other geometries (with the same reactor
volume) will not affect the results in this paper. Readers particu-
ð7Þ
rigorous approach.
Fig. 2 shows the process flowsheet of the KL process developed
and simulated in the present work. In this figure, heat exchanger
network (HEN) for HI is omitted to keep the process flowsheet easy
to follow; details of HEN are given in Appendix B. The KL process
was designed to produce 98 wt% FA at 3,310 kg/h, which translates
to plant capacity of 27,476 t/y. This capacity was set based on the
FA production rate of 27,100 t/y in da Cunha et al. (2018). The
 W.X. Chua et al. / Chemical Engineering Science: X 2 (2019) 100021 5

Table 1
Parameters of auto-catalysed and FA-catalysed reactions.
 
MF hydrolysis 0
0
Ea (kJ mol-1) Ea (kJ mol-1) KC
k (kg2 mol-2 min-1) k(kg2 mol-2 min-1)
Auto-catalysed 0.12 66.4 0.026 88.2 0.17
(Jogunola et al., 2010)
FA-catalysed 0.39 67.8 – – 0.18
(Jogunola et al., 2012)

Fig. 2. Designed Kemira-Leonard Process.

small difference between these capacities is due to the small loss of
CO in three distillation columns in the BASF process.
Since the description of the process in Fig. 2 is similar to that in
Fig. 1, it is not repeated. Instead, Table 2 describes the purpose of
the major equipment shown in the designed KL process in Fig. 2,
and stream data corresponding to the chosen optimal solution
are given in Appendix C. T-100 was designed for operation at
4 atm as suggested in Novita et al. (2015). T-101, T-102 and
T-104 were designed to operate at atmospheric pressure as it is
the most economic option while still allowing for the desired
separation. As mentioned previously, T-103 was designed to
operate at 3 atm for the purpose of pressure swing distillation.
The KL process outlined in Hietala et al. (2016) and simulated in
Kashani et al. (2014) have a few purge streams, probably to avoid
accumulation of CO in the R1-F1 recycle loop in Fig. 1. Indeed, for
low methanol-to-CO molar ratios (<2 at 4.5 MPa and 80 °C accord-
ing to Kashani et al., 2014), part of CO in the CSTR (R1 in Fig. 1) will
not be dissolved in the liquid phase, resulting in a vent outlet
stream with undissolved CO (shown in Fig. 1). Therefore, without
purge streams, this CO in the gas phase would continue in the pro-
cess and eventually be ‘‘trapped” in the R3-F1 loop. Nevertheless,
the process developed and simulated in the present study (Fig. 2)
uses high methanol-to-CO ratio in the CSTR and does not require
any purge stream. Flash separators F2 and F3 are added to extract
all CO from the downstream process prior to the series of four col-
umns. The recovered CO is then recycled to the CSTR for carbony-
lation reaction. The vapor stream from T-100 is also recycled to the
CSTR as it has a large CO mass fraction. Elimination of purge
streams in the developed process (Fig. 2) resulted in the production
of more FA without the loss of any CO reactant.
6 W.X. Chua et al. / Chemical Engineering Science: X 2 (2019) 100021

Table 2
Main equipment in KL process (Fig. 2) and their purpose.
Equipment Purpose
CSTR Carbonylation reaction of MA to produce MF
F1 Flash separation of CO for recycling back to CSTR
T-100 Recover MA in the bottoms for recycling back to CSTR, recover
CO gas using partial condenser for recycling back to CSTR, and
recover MF in the distillate for the downstream hydrolysis
reaction
PRELIM Preliminary PFR to produce initial amount of FA by auto-
catalyzed hydrolysis reaction
MAIN Main PFR to produce bulk of FA by FA-catalyzed hydrolysis
reaction
F2 Flash drum to reduce the temperature of MAIN reactor outlet
stream to prevent re-esterification of FA to MF
F3 Remove any CO to prevent accumulation of CO in downstream
units
T-101 Recover MF and MA in the distillate, and recover FA and Water
in the bottoms
T-102 Recover MF in the distillate for recycling back to MAIN reactor
and recover MA in the bottoms for recycling to CSTR
T-103 1st column of the FA purification by pressure swing distillation;
operates at higher pressure (3 atm) to obtain 85 wt% FA in the
bottoms. Distillate stream contains pure water to be recycled to
MAIN reactor.
T-104 2nd column of the FA purification by pressure swing
distillation; operates at atmospheric pressure to obtain 98 wt%
FA in the distillate. Bottoms stream contains FA and Water, and
is recycled to T-103.
In short, there are no purge or vent streams in the developed
process because CO is a reactant and there are no inert components
entering the process. Hence, methanol makeup is expected to be
very small, as it should account only for trace quantities of MA
and MF lost in the product stream (namely, FA stream in Fig. 2).
In the present simulation, flowrate of MA makeup is zero because
MA is absent in the product FA stream (mass fraction of 0). How-
ever, in the actual process, FA stream may have trace amounts of
MA and MF, thus requiring tiny amount of MA makeup.
2.5. Sizing and cost estimation
After process simulation, all equipment in the process were
sized. The duties of pumps and compressors were obtained from
Aspen Plus simulation, and then their sizes were calculated by fac-
toring in efficiencies given in Branan (2005) and Boyce et al.
(2008). The compressors COM1 and COM2 were sized as rotary
compressors based on the range and cost correlations given in
Turton et al. (2013). Similarly, their drivers were taken to be inter-
nal combustion engines owing to their small shaft powers. All heat
exchangers were sized based on methods outlined in Branan
(2005). The Blackwell correlation referenced from Wankat (2007)
was used to size the flash drums. Column diameters and reactor
volumes were obtained using Aspen Plus V9. Since Aspen Plus
assumes that all distillation columns have tray efficiency of 100%
by default, tray efficiency of each column was calculated using
the O’Connell correlation in Wankat (2007) and factored into the
height calculation, to find a realistic capital cost estimate. O’Con-
nell correlation gives tray efficiency as a function of relative volatil-
ity between the light and heavy keys, and the viscosity of liquid.
Table 3 summarizes the calculated tray efficiencies for the five dis-
tillation columns in the KL process. The tray spacing and top and
bottom column allowances for the distillation columns were
obtained using heuristics in Branan (2005).
The material of construction (MOC) for each of the unit opera-
tions was obtained based on guidelines in Branan (2005) and
Turton et al. (2013). In short, unit operations involving or process-
ing FA were designed using titanium, as FA can be very corrosive,
particularly at high concentration and elevated conditions. MOC
for all other unit operations were assumed to be carbon steel
(CS) due to its lower cost.
Cost estimation procedures comprised of two main parts: capi-
tal and utility cost calculations. The module costing method in
Turton et al. (2013) was used to estimate the capital cost of all
equipment. The accuracy range for this methodology is within
25% to 40%. Total capital cost (TCC) was obtained by taking the
sum of grassroots cost of all equipment in the designed process.
Chemical Engineering Plant Cost Index (CEPCI) of 600 was assumed
for updating capital cost to the present time.
Annual utility cost (AUC) was calculated by using unit utility
costs in Table 4. Cost of steam contributes to more than 75% of
the total utility cost, and therefore the accuracy of the utility cost
calculations depends mainly on the accuracy of the unit price of
steam in Table 4. Unit cost of steam in 4 papers recently published
in Chemical Engineering Science from volume 175 to date (volume
197, in progress) is in the range of 7.72 $/GJ to 13.28 $/GJ (besides
one other paper using a relatively low value of 4.71 $/GJ). Based on
this, accuracy range of the unit cost of steam used in the present
study is 42% to +0%. Consequently, accuracy range of 42% to
+0% can be assumed for the utility cost calculations in this paper.
2.6. Heat integration
HI assisted by pinch analysis was carried out before optimiza-
tion to minimize utility consumption. The HEN arrangement
obtained for the preliminary design may or may not be optimal
for alternative designs. Indeed, by changing some of the design
parameters in the process, stream temperatures and heating/cool-
ing duties may change, altering pinch analysis results and conse-
quently the optimal HEN. Therefore, the HEN arrangement needs
to be updated for some trial solutions during the optimization. In
the simulation of these trial solutions, extra heat exchangers were
necessary to achieve the target temperatures of certain streams.

Table 3
Tray Efficiencies for the five distillation columns in the KL process.

Distillation Column T-100 T-101 T-102 T-103 T-104

Light Key MF Methanol MF Water FA
Heavy Key Methanol Water Methanol FA Water
Tray Efficiency (%) 49 46 40 57 65

Table 4
Unit utility costs taken from Turton et al. (2013).

Low pressure steam Fuel oil Cooling water Chilled water Electricity
Specifications 5 barg, 160 °C – 30 to 45 °C 5 to 15 °C –
Cost ($/GJ) 13.28 14.2 0.244 4.43 16.8
 W.X. Chua et al. / Chemical Engineering Science: X 2 (2019) 100021
Fig. 3. Heat Exchanger Network for the optimized KL Process; each line corresponds to a stream labelled on the left side, and values above the line are stream temperatures in
o
C. Lines with arrow towards the right and left are respectively hot and cold streams.
For these cases, they were sized considering cooling and heating by
utility. Other cases arose where some heat exchangers were no
longer necessary or feasible due to the temperature approach con-
straint. Then, capital cost of such exchangers was taken as zero.
Fig. 3 shows the HEN for the optimized KL process; this HEN is
assuming minimum temperature driving force of 10 °C. Numbers
in circles correspond to heat exchanger numbers and pairings
given in Appendix B, while stream labels correspond to the streams
in Fig. 2. Note that T-100 condenser in Fig. 3 has two exchangers:
no. 14 uses cooling water and no. 5 uses chilled water, for reducing
AUC by using cheaper cooling water as much as possible. Data for
streams in the HEN for the optimized KL process are also given in
Appendix B.
3. Multi-objective optimization
Practical applications require the simultaneous optimization of
more than one objective function, as can be seen in many chemical
engineering applications, where multiple and often conflicting
objectives are part of the optimization problem (Rangaiah, 2017;
Rangaiah et al., 2015). Multi-Objective Optimization (MOO) is par-
ticularly useful in this regard, allowing for multiple objectives to be
optimized simultaneously with respect to decision variables sub-
ject to bounds and constraints, if any. Rangaiah et al. (2015) sum-
marize similarities and differences between single and multi-
objective optimization. The chosen objective functions, decision
variables (DVs) and their ranges as well as the method and pro-
gram used for FA process optimization are outlined in this section.
7
3.1. Objective functions
Economics and feasibility analysis are key aspects that should
be carefully considered before deciding on the investment in new
process facilities. As such, aim of the MOO problem is to minimize
overall costs associated with the FA process. TCC and AUC were
therefore chosen as the objective functions for the MOO of the KL
process. TCC was calculated assuming undeveloped site for the
plant, which meant the calculation of total grassroots cost
(Turton et al., 2013). AUC, on the other hand, considers the annual
cost of utilities like steam, cooling water, electricity and fuel oil for
the plant (Turton et al., 2013). Like in most applications, TCC and
AUC are conflicting objectives. This leads to many Pareto-optimal
solutions (also known as non-dominated solutions), which can be
clearly observed in the results presented later in Section 4.1. These
optimal solutions provide quantitative trade-off between the
objectives employed, which will be useful for choosing one of
them.
3.2. Decision variables & constraints
For FA process optimization, DVs were chosen considering the
main units (i.e., reactors and distillation columns) and their design
variables that were not fixed based on preliminary analysis. These
are consolidated in Table 5. A sensitivity analysis was conducted to
determine the lower and upper bounds of DVs. For this, each DV
was varied one at a time (with all others at the initial design values
in Table 5), and the corresponding TCC and AUC were recorded for
8 W.X. Chua et al. / Chemical Engineering Science: X 2 (2019) 100021

Table 5
Decision Variables and their respective ranges used for FA process optimization, and also values of DVs at the chosen optimal solution.

Decision variable Initial value (base case) Lower bound Upper bound Optimal value
T-100 Number of Stages 16 15 17 16
T-101 Number of Stages 40 20 40 20
T-102 Number of Stages 38 14 40 14
T-103 Number of Stages 40 37 46 37
T-104 Number of Stages 32 29 37 37
T-100 Feed Stage Fraction* 0.375 0.310 0.400 0.310
T-101 Feed Stage Fraction* 0.700 0.625 0.800 0.791
T-102 Feed Stage Fraction* 0.815 0.250 0.920 0.850
T-103 Feed Stage Fraction* 0.263 0.184 0.579 0.319
T-103 Recycle Feed Stage Fraction* 0.895 0.658 0.921 0.855
T-104 Feed Stage Fraction* 0.187 0.156 0.470 0.353
CSTR Residence Time (h) 0.717 0.490 0.780 0.505
CSTR Temperature (oC) 101.74 70.00 120.00 100.30
Main PFR volume (m3) 7.07 6.83 7.46 7.15
*
Feed stage is expressed as a fraction of the total number of stages. For process simulation, integer value of feed stage is calculated by rounding off the product of this
fraction and total number of stages.

comparison. Each DV was decreased (or increased) from the initial
design value until the process simulation failed to converge or the
converged process has larger capital and utility costs. This point
gave the lower (or upper bound) for each DV. These bounds are
also presented in Table 5. In this table, T-100/101/102/103/104
Stages refer to the number of theoretical plates in the column,
including condenser and reboiler.
All governing equations for the FA process including product
purities are satisfied as part of the process simulation within Aspen
Plus for each set of DV values given by the MOO algorithm. A min-
imum temperature approach of 10 °C was used for all heat
exchangers.
3.3. Optimization program and implementation
A program implemented in MS Excel, namely, Improved Multi-
Objective Differential Evolution (I-MODE) (Sharma et al., 2017)
was utilized for MOO of the KL process for FA. It is based on differ-
ential evolution (DE) for multiple objectives, and incorporates tabu
list, self-adaptation of DE parameters and termination criteria
based on search progress. More details on I-MODE and its applica-
tion can be found in Sharma et al. (2017).
I-MODE was interfaced with Aspen Plus V9 using Visual Basic
for Applications (VBA). This allows for DVs to be transferred from
MS Excel to Aspen Plus simulation file, and simulation results back
to MS Excel for calculating objectives and constraints, if any. The
population size was set to 50 and the maximum number of gener-
ations (MNG) was set to 80. MNG was selected as the termination
criterion for the MOO. Initial values for both mutation and cross-
over probability were set as 0.5. I-MODE program gives Pareto-
optimal solutions along with corresponding values of DVs after
every user-chosen interval number of generations and also upon
termination. These are presented and discussed in the next section.
4. Results and discussion
4.1. The Pareto-Optimal front
To confirm the convergence of the Pareto fronts for FA process
optimization, MOO results are plotted at intervals of 10 genera-
tions (Fig. 4). Each Pareto front shows the set of all non-
dominated solutions after certain number of generations. Fig. 4
shows that the Pareto fronts had converged by 50th generation,
showing the sufficiency of MNG of 80 generations for KL process
optimization. Results after 80th generation are thus taken as the
Pareto-optimal front (shown as an insert within Fig. 4 for clarity)
for discussion and for the selection of an optimal solution.
The tradeoff between capital and utility cost is clear from the
results in Fig. 4. It is interesting to study the effect of each DV on
the objective functions, at the Pareto-optimal front. No clear trend
was observed for the following DVs and their optimal ranges are
stated within brackets: T-100 number of stages (16 or 17), T-102
feed stage fraction (0.64 to 0.89), T-103 feed stage fraction (0.22
to 0.39), T-103 recycle feed stage fraction (0.67 to 0.88), CSTR res-
idence time (0.49 to 0.77), CSTR temperature (85 to 109) and Main
PFR volume (6.83 to 7.46). This implies that these DVs have minor
effect on the objectives.
The following five variables were observed to be constant in the
set of optimal solutions: T-103 number of stages (at 37), T-104
number of stages (at 37), T-100 feed stage fraction (around 0.33),
T-101 feed stage fraction (around 0.79) and T-104 feed stage frac-
tion (around 0.34). This indicates that these variables affect objec-
tives similarly (i.e., increase or decrease). The remaining two
variables (number of stages of columns T-101 and T-102) show a
clear trend when plotted against the objective functions, as in
Fig. 5.
Fig. 5(a) shows that TCC increases with the number of stages of
column T-101. This is expected, as a greater number of stages
would lead to an increase in both the number of real trays and col-
umn height, which results in a higher TCC. Fig. 5(b) shows the
opposite trend where AUC decreases as T-101 stages increase.
Increasing the number of stages makes separation easier, thus
reducing reboiler duty and consequently the utility costs associ-
ated with steam for heating. Fig. 5(c) and (d) on the effect of T-
102 number stages show trends similar to those in Fig. 5(a) and
(b) respectively, albeit a less pronounced relationship. In Fig. 5,
multiple optimal solutions can be seen for the same DV value,
which is clearer in Fig. 5c and d. Such behavior is due to the pres-
ence of discrete DVs in this MOO problem.
The more pronounced trends in Fig. 5(a) and (b) imply that the
number of stages of T-101 has a more significant impact on both
capital and utility costs. Changes in TCC can be attributed to the
costly titanium MOC used for T-101 and a relatively larger column
diameter than all other columns except T-104. These factors mean
that each additional stage in T-101 would contribute significantly
to an increase in TCC. T-101 also has a high reboiler duty that is
not integrated with any other streams in the HEN owing to its high
temperature, which means costly low pressure stream is required
to provide heating. Therefore, increasing the number of stages of
T-101 would reduce reboiler duty and thus decrease AUC. On the
other hand, T-102 was made of cheaper carbon steel MOC, which
explains the less pronounced trend between number of stages
 W.X. Chua et al. / Chemical Engineering Science: X 2 (2019) 100021 9

Fig. 4. Progression of Pareto fronts from Generations 10 to 80.

Fig. 5. DV values corresponding to the Pareto-Optimal solutions.

and TCC (Fig. 5(c)). Also, reboiler of T-102 has a smaller duty,
reducing the impact of T-102 number of stages on AUC.
4.2. Selection and economic aspects of the optimal solution
For choosing one of the optimal solutions, total annual cost
(TAC) is used. TAC is the sum of annual operating cost excluding
depreciation (COMd ) and annualized capital cost (ACC), which is
the product of total grassroots cost (C GR ) and annual capital charge
ratio (ACCR):
TAC ¼ TCC  ACCR þ COMd ð8Þ
ACCR is a factor that annualizes TCC (total grassroots cost here)
to give ACC. It considers rate of return required on invested capital
and plant lifetime (Turton et al., 2013). Here, ACCR is 0.171 based
on the assumed plant lifetime of 15 years (Brennan, 2007) and
annual interest rate of 15%.
According to Turton et al. (2013), COMd can be calculated using
the following expression:
COMd ¼ 0:18  C GR þ 2:73  C OL þ 1:23  ðAUC þ C WT þ C RM Þ ð9Þ
10 W.X. Chua et al. / Chemical Engineering Science: X 2 (2019) 100021
Here, COL, CWT and CRM are cost of operating labor, waste treat-
ment and raw materials, respectively. AUC represents the annual
cost of all heating and cooling utilities, along with electricity and
fuel oil for compressor drives. For the designed FA process, there
are no waste streams and so CWT = 0. Raw materials required in
the KL process are CO and water. Cost of CO was taken to be
$70/ton (Sengupta and Pike, 2013), while cost of (deionized) water
was taken as $1/ton (Turton et al., 2013). Flow rates of the CO
and water feed streams for FA process were fixed at 1969 and
1332 kg/h respectively. The plant is assumed to operate for a total
of 8322 h per year, resulting in CRM = $1,158,187.
COL is calculated based on number of operators required per
shift,N OL (Turton et al., 2013):
0:5
NOL ¼ ð6:29 þ 31:7P2 þ 0:23Nnp Þ
Here, P is the number of processing steps involving particulate
solids and N np is the number of non-particulate processing steps,
inclusive of compressors, towers, reactors and heat exchangers.
For the KL process, P and N np are 0 and 30 respectively, which give
NOL = 4 (rounded up). As recommended in Turton et al. (2013),
4.5  NOL operators are required for 24-hour operation of a chem-
ical plant throughout the year (i.e., 3 shifts and 365 days) and
assuming each operator works for five 8-hour shifts a week for
49 weeks/year. This number of operators at an annual salary of
$59,589 for one operator (Turton et al., 2013) results in COL =
$1,072,602.
Note that C OL ; C WT and C RM are not affected by the DVs, and only
TCC and AUC are affected by values of DVs. As such, TCC and AUC
can be used as the objective functions for MOO to obtain the
Pareto-optimal front, before calculating TAC by Eq. (8) to choose
the best (trade-off) solution. The Pareto-optimal solution that has
the lowest TAC was chosen as the optimal solution. This solution,
shown in the insert in Fig. 4 as ▲, will be hereafter referred as
the proposed process design, and the corresponding optimal values
of DVs can be found in the last column of Table 5. The economics of
the proposed/optimized KL process design are summarized in
Table 6.
As shown in Fig. 4, the proposed process design is at the end of
the Pareto-optimal front, where the capital cost is the lowest. Rea-
sons for this are as follows.
(1) Referring to Fig. 5, the DV having the greatest impact on TAC
was the number of stages of T-101. This column was
designed with titanium as MOC, and so its capital cost was
significant and also increased substantially with the number
of stages. Therefore, the reduction in capital cost for this
variable had a big impact in lowering overall TAC. This
reduction overcomes the additional utility cost for the range
of number of stages given in Table 5.
Table 6
Economics of the proposed/optimized KL process design
for FA.
Quantity Value
TCC 18,476,733 $
COL 1,072,602 $/y
AUC 7,357,246 $/y
CWT Nil
CRM 1,158,187 $/y
COMd 16,727,997 $/y
TAC 19,887,834 $/y
FA production 27,476,222 kg/y
Unit TAC 0.724 $/kg
(2) Referring to Table 5, the optimal DV values for T-101 and
T-102 were at their respective lower bound. One may want
to know whether lower TAC values are achievable by
widening the range of DV values for T-101 and T-102
number of stages. Sensitivity analysis prior to optimization
showed that decreasing the number of stages of columns
T-101 and T-102 below their lower bounds (20 and 14 stages
respectively) increases considerably the reboiler duty of
these columns. As a result, capital cost increases instead of
decreasing (due to the increase in column diameter and con-
denser/reboiler areas). After optimization, further savings in
capital cost can be obtained by reducing the number of
stages of T-101 and T-102 up to 19 and 12, respectively
but corresponding AUC increases. Therefore, minimum TAC
ð10Þ still corresponds to the configuration with 20 and 14 stages
for columns T-101 and T-102, respectively. In other words,
lowering the lower bound of T-101 and T-102 number of
stages will not decrease TAC.
4.3. Comparison with the FA process in da Cunha et al. (2018)
The KL process designed here is slightly less profitable than that
designed by da Cunha et al. (2018) based on BASF process, which
has unit TAC = 0.686 $/kg. From now on, the base case process
designed by da Cunha et al. will be referred to as BASF process.
The higher TAC of 0.724 $/kg found for the KL process is due to
the differences in MF hydrolysis and subsequent separation steps.
In the BASF process, excess water is used for the hydrolysis reac-
tion (2.4:1), and the downstream separation is performed via sim-
ple distillation and liquid-liquid extraction. The hydrolysis reaction
in the KL process is driven with excess MF (2.0:1 in the main PFR),
and the downstream separation steps employ pressure-swing
distillation.
In order to better understand why the KL process is less prof-
itable than the BASF process, we divide each of the processes into
sections with each section corresponding to certain processing
step. For the KL process, the processing steps are: carbonylation
(units CSTR, F1, T-100, COM1 and COM2 in Fig. 2), hydrolysis reac-
tion (reactors PRELIM and MAIN), MF and methanol separation
from aqueous FA (units F2 and T-101), MF + methanol separation
(column T-102), FA + water separation (columns T-103 and T-
104) and CO + MF separation (flash unit F3). All these include cap-
ital cost and utility cost of associated heat exchangers and pumps.
The BASF process discussed in da Cunha et al. (2018) is illus-
trated in Fig. 6. In this process, units for each processing step are
as follows. CSTR1, DC1, F and COMP are responsible for the car-
bonylation, CSTR2 is for MF hydrolysis, DC2 performs MF and
methanol separation from aqueous FA, DC3 separates the MF
+ MA mixture, and DC4, DC5, EXT and DEC together carry out the
FA dehydration step. As for KL process, all these include capital cost
and utility cost of associated heat exchangers and pumps. Note
that CO + MF separation is not considered in the BASF process, as
the CO present in the downstream of CSTR2 is purged from the
process.
Table 7 shows the comparison of KL and BASF processes accord-
ing to each processing step. In this table, UUC refers to unit utility
cost in $/(kg of FA 98 wt%). For the carbonylation step, TCC of both
processes is comparable. However, cost of utility in the BASF pro-
cess is slightly lower because the feed stream to column T-100 in
the KL process (Fig. 2) has a significantly higher methanol flowrate
than the feed stream to DC1 in the BASF process (Fig. 6). Therefore,
the utility consumption in T-100 is higher than that in DC1.
TCC for MF hydrolysis is much higher in the BASF process,
despite the KL process requiring two reactors. This is because the
KL process uses PFRs whereas the BASF process uses a CSTR for
the MF hydrolysis. It was found that the PFR (costed as a jacketed
 W.X. Chua et al. / Chemical Engineering Science: X 2 (2019) 100021 11

Fig. 6. The BASF process designed. Reprinted with permission from da Cunha et al. (2018). Copyright 2018 American Chemical Society.

Table 7
KL and BASF process comparison.

Processing Step TCC ($) UCC ($/kg)

KL BASF KL BASF
Carbonylation 1,539,088 1,624,586 0.0446 0.0384
Hydrolysis reaction 937,896 1,661,089 0.0126 0.0065
MF/methanol separation from aqueous FA 3,708,960 2,658,003 0.0657 0.0684
MF+methanol separation 930,379 1,194,616 0.0137 0.0141
FA+water separation 10,917,722 9,401,256 0.1205 0.0907
CO separation from MF 442,688 – 0.0107 –
Total 18,476,733 16,275,503 0.2678 0.2181

non-agitated reactor) is much cheaper than a CSTR of same vol-
ume, according to the cost correlations in Turton et al. (2013). This
is the reason for the large difference in capital cost. The higher cost
of utility observed for MF hydrolysis in the KL process is due to the
preheating of stream 16 with steam before entering the main reac-
tor (HX 7 in Fig. 3). This preheating is done partially via HI and par-
tially via low-pressure steam, as seen in Fig. 3. Approximately 33
ton/h of the reactant mixture is heated in HX7 from 93.1 °C to
120 °C. In the BASF process (Fig. 6), CSTR2 is a jacketed reactor at
100.0 °C. The preheating of stream 14 to 100 °C is entirely by HI.
However, stream 18 (flow rate of 8 ton/h of water) in the BASF pro-
cess is fed to the reactor at 90.4 °C. Further, the heat of reaction in
the CSTR is negligible (-290 cal/mol). Therefore, steam consump-
tion in CSTR2 is mostly due to the temperature difference between
stream 18 and CSTR2. On the other hand, in KL process, stream 16
has larger flow rate (33 ton/h versus 8 ton/h in the BASF process)
and is heated to a higher temperature (120 °C versus 100 °C in
the BASF process) using low pressure stream prior to sending to
the main hydrolysis reactor. Hence, utility consumption in the
hydrolysis step is more in the KL process.
The utility cost for MF/methanol separation from aqueous FA in
both processes is comparable. Nonetheless, TCC for this step is
higher in the KL process by about 33% (or one million). Column
T-101 in the KL process separates MF and methanol from aqueous
FA, and it is operated at atmospheric pressure. Column DC2 has the
same task in the BASF process, and its operating pressure is 3.8 bar.
Due to this difference in pressure, the average density of the vapor
flow in T-101 is about one third of the vapor density in column
DC2. Therefore, the vapor volumetric flow in column T-101 is
higher, and consequently its diameter is larger than DC2. This is
the main reason for TCC difference for MF/methanol separation
from aqueous FA.
In the fourth step (MF + methanol separation), UUC of both
processes is comparable. In the BASF process (Fig. 6), DC2 and
DC3 operate in a double-effect configuration; DC2 is at a higher
pressure and DC3 is at atmospheric pressure, which allows HI
between DC2 condenser and DC3 reboiler, thus completely avoid-
ing steam use in DC3 reboiler. In the KL process (Fig. 2), all the
heat required for T-102 reboiler is provided by the top vapor
stream in column T-104 (see the HI diagram in Fig. 3). For these
reasons, utility cost for the MF + methanol separation step in both
processes is small. TCC is slightly higher for the BASF process.
This is because the distillation column performing MF + methanol
separation in the BASF process (DC3 in Fig. 6) is taller than the
column performing the same task in the KL process (T-102 in
Fig. 2).
12 W.X. Chua et al. / Chemical Engineering Science: X 2 (2019) 100021
For FA + water separation, TCC and UCC are considerably
higher in the KL process compared to the BASF process (Table 7).
However, the difference in UCC is actually offset by the cost of
make-up solvent (diisopropyl ether) used in the BASF process
(
0.0400 $/kg). The unit cost of utility and solvent together is
0.1307 $/kg in the BASF process, which is slightly more than
the UCC for the same step in the KL process. The difference in
TCC comes from the total cost of the towers involved in this
task. Two towers in the KL process (T-103 and T-104) and two
towers in the BASF process (DC4 and EXT) use expensive MOC,
as they need to withstand FA corrosion. While DC4 and T-104
have comparable grassroots cost (with less than $40,000
difference), EXT in the BASF process is considerably cheaper than
T-103 in the KL process. This is because EXT height is only
10.0 m, whereas T-103 height is 30.5 m. Due to this reason,
TCC for FA + water separation is higher in the KL process
by
15% (
1.5 million).
Finally, CO separation from MF in F3 (Fig. 2) and recycle back to
the carbonylation reactor represents an extra cost not accounted in
the BASF process. However, this separation is essential to avoid
accumulation of CO in the recycle loop from stream 16 to column
T-102 in Fig. 2.
Overall, TCC is more (by about 2.2 million or 13%) and UUC is
more (by about 0.05 $/kg or 20%) in the KL process designed in
the present paper compared to the BASF process designed in da
Cunha et al. (2018). However, the cost of makeup solvent (diiso-
propyl ether) in the BASF process is 0.04 $/kg, almost equal to
the difference in utility cost of these two processes. To improve
the KL process, an effort is made to reduce utility cost by includ-
ing VR heat pump. This is described in the next section.
4.4. Improvement of the optimized FA process via vapor recompression
In the proposed/optimized design of KL process, T-101 reboiler
accounts for 24% of AUC. Hence, VR heat pump was implemented
for the chosen design to integrate T-104 condenser with T-101
reboiler in an attempt to further reduce utility cost. This is possible
as they have comparable temperatures (condenser outlet temper-
ature of 102.1 °C and reboiler outlet temperature of 102.6 °C), mak-
ing VR very suitable for the optimized KL process.
Fig. 7. Schematic of VR heat pump configuration at T-104.
Fig. 7 illustrates the layout of VR heat pump for T-104. In this
configuration, the vapor stream leaving at the top of T-104 is split
into two streams: s1 and s2. This is to ensure that stream s1 after
compression provides the exact amount of heat required to the
reboiler of T-101, which is shown as HX15 in Fig. 7. The heat
exchanger HEX1 preheats stream s1 before compression, in order
to avoid condensation in the compressor COM3. This stream com-
prises 49% of total vapor flow leaving stage 1 at the top of T-104.
The remaining vapor flow, denoted as stream s2, is passed through
the heat exchangers as previously paired in the HEN for the origi-
nal process design (HX1, HX2, HX3 and HX9 in Fig. 7). The cooled
stream s1 exiting from HX15 is brought to saturated liquid at
atmospheric pressure using valve V4. Outlet stream of V4 is later
mixed with the liquid stream leaving HX9; part of the mixed
stream is sent as reflux to T-104 and the rest is recovered as stream
39 in the proposed design (Fig. 2).
The HEN for the proposed KL process with VR heat pump is
shown in Fig. 8. The heat exchanger HEX1 is omitted in this
HEN; its purpose is to preheat stream s1, using low pressure
stream, from 103.2 °C to 110 °C prior to compression in order to
prevent 2-phase flow in the compressor (COM3). Stream s1 at
131.5 °C after compression is represented in Fig. 8 as T104 con-
denser (VR) whereas stream s2 is represented as T104 condenser.
The implementation of the VR compressor and the changes in
the HEN design resulted in additional capital investment of
$2,517,191. The cost of VR compressor and its electrical motor is
$2,244,605, considering a centrifugal compressor made of nickel
alloy, and extrapolating the purchase cost correlation in Turton
et al. (2013) for a fluid power of 241 kW. The remaining capital
investment is for the new heat exchanger HEX1 ($58,346), the
increase in the cost of HX15 (by $347,950) and the decrease in
the cost of HX9 (by $133,710). The heat pump technology brought
about AUC savings of $1,560,427 (by 21.2%), which is due to lower
steam consumption. With the addition of VR, low pressure steam is
reduced from 17.45 to 12.76 MJ/kg of FA produced (by 27%) but
requires electricity for compressor drive at the rate of 0.38 MJ/kg
of FA produced. Overall, VR addition led to TAC reduction of
$1,035,748 (by 5.2%) or unit TAC reduction from 0.724 to 0.686
$/kg of FA produced. The unit TAC after VR addition is the same
as the unit TAC reported for the BASF process in da Cunha et al.
(2018).
 W.X. Chua et al. / Chemical Engineering Science: X 2 (2019) 100021 13

Fig. 8. Heat Exchanger Network for the optimized KL Process with VR heat pump; each line corresponds to a stream labelled on the left side, and values above the line are
stream temperatures in oC.

5. Conclusions mentation of VR heat pump led to savings of $1,560,427 (by

This paper reports the design, simulation, optimization and eco-
nomic evaluation of the KL process for FA production. The process
was successfully developed and simulated using Aspen Plus V9
with the UNIQ-HOC as the thermodynamic model and appropriate
kinetics for carbonylation and hydrolysis reactions. HI using pinch
analysis was applied to the process to reduce external utilities
required. The equipment sizing and cost estimation were con-
ducted to estimate the TCC of the plant, and AUC was also esti-
mated. The KL process was optimized for TCC and AUC using the
I-MODE program. MOO results show that the chosen optimized
process had TCC of $18,476,733 and annual operating cost exclud-
ing depreciation of $16,727,997, which resulted in TAC of
$19,887,834 or unit TAC of 0.724 $/kg. These costs are more than
those for the BASF process designed by da Cunha et al. (2018),
and the process differences for this are discussed. Finally, imple-
21.2%) in AUC due to reduced low pressure steam consumption.
Overall, VR lowered TAC by $1,035,748 or 5.2% to 0.686 $/kg. The
KL process designed in this paper is useful for further research
on its plant-wide control and improvement using process intensi-
fication technologies such as reactive distillation (RD).
Declaration of Interest
None.
Appendix A. Fluid package & thermodynamic model
parameters
In the chosen UNIQUAC model, the parameter sij is calculated
using:

Table A1
Binary parameters used in UNIQUAC model.

Component i MF MF MF Water Methanol Water

Component j Water Methanol FA Methanol FA FA
aij 0 0 1.46 2.06 0 2.5846
aji 0 0 1.86 3.15 0 1.9779
bij 434.24 15.20 471.54 219.04 366.61 920.795
bji 99.35 301.76 132.65 575.68 615.90 539.679
dij 0 0 0 0.007 0 0
dji 0 0 0 0.006 0 0
14 W.X. Chua et al. / Chemical Engineering Science: X 2 (2019) 100021

Table A2 from the APV90 VLE-HOC database accurately replicate this azeo-
Predicted Azeotropic Composition by UNIQUAC model. tropic composition shift (Table A2). Therefore, using this set of bin-
Pressure Azeotropic composition (mass fraction of FA) predicted ary parameters allowed for 85 wt% FA (slightly lower than the
using FA-water parameters taken from azeotropic point of 88 wt% FA) to be obtained in the bottoms of
Novita et al. (2015) APV90 VLE-HOC database T-103.
1.0 atm 0.77 0.78
The Henry’s law for a binary liquid + gas mixture used by Aspen
1.5 atm 0.77 0.80 Plus is given by:
2.0 atm 0.77 0.83

Hi;j
2.5 atm 0.78 0.86
Uvi yi P ¼ xi ci ðA2Þ
3.0 atm 0.78 0.88 c1
i


bij
sij ¼ exp aij þ þ dij ln ðT Þ
T
Here, aij , bij and dij are the binary interaction parameters and T is
the temperature in oC. The help forms in Aspen Plus V9 contain
more details on the UNIQUAC model equations, should readers
require additional information. Values of binary parameters in
Equation (A1) are summarized in Table A1; these are taken from
Novita et al. (2015), to maintain consistency with recent works
on FA production (Novita et al., 2015, 2018; da Cunha et al.,
2017, 2018).
Note that the parameters for FA-water pair in Table A1 are
taken from the APV90 VLE-HOC database within Aspen Plus V9.
This is because the parameters for FA-water in Novita et al.
(2015) did not predict the expected change in azeotropic composi-
tion of 77.5 wt% FA at 1 atm to 88 wt% FA at 3 atm (Aguilo and
Horlenko, 1985). On the other hand, FA-water parameters taken
where the subscript ‘i’ refers to the Henry component. The Henry
parameter Hi;j for the solution of gas i in liquid component j is cal-
culated using the following equation:
ðA1Þ
  Bhi;j
ln Hi;j ¼ Ahi;j þ þ C hi;j ln ðT Þ ðA3Þ
T
For more information on the Henry’s law implemented in Aspen
Plus, see the help form provided in the simulator. Table A3 pro-
vides parameters Ah, Bh and Ch in Henry’s law for CO.
Appendix B. Heat exchangers
The heat exchangers for the optimized Aspen Plus simulation
are listed in Tables B1 and B2. These tables also contain informa-
tion on the paired streams in the HEN shown in Fig. 3. The shell-
and tube-side stream conditions, MOC, utility type and size of all
heat exchangers are also provided in Tables B1 and B2. In these
tables, CS = Carbon Steel, SS = Stainless Steel and Ti = Titanium.

Table A3
Henry parameters used for CO.

Mixture Ahij Bhij Chij P units (Eq. A(2)) Source

CO+MA 4.21187 1144.4 bar APV90 HENRY-AP databank
CO+Water 171.775 8296.75 –23.3372 bar APV90 BINARY databank
CO+MF 2.92 1721 atm Liu (1988)

Table B1
Data on Heat Exchangers, HX1 to HX9 and their Streams.

Name HX1 HX2 HX3 HX4 HX5 HX6 HX7 HX8 HX9
Exchanger pairing HE1 HE2 T-102 Bot T-104 Bot Utilities HE1 HE2 T-103 Bot Utilities
T-104 Top T-104 Top T-104 Top T-103 Top T-100 Top Utilities Utilities Utilities T-104 Top
Duty (kW) 234 803 420 4780 1309 156 683 5296 6619
Shell in (oC) 49.3 59.1 56.0 133.7 5.0 160.0 160.0 160.0 102.9
Shell out (oC) 93.2 93.1 61.4 130.1 15.0 160.0 160.0 160.0 102.1
Tube in (oC) 103.2 103.1 103.0 107.196 40.0 93.2 93.1 144.6 30.0
Tube out (oC) 103.1 103.0 102.9 107.1968 16.9 120.0 120.0 144.7 45.0
Area (m2) 13.64 53.08 16.73 341.13 82.46 3.27 14.27 462.78 113.40
Utility None None None None Chilled water LP steam LP steam LP steam Cooling water
Tube material Ti Ti Ti Ti CS CS CS Ti Ti
Shell material CS CS SS CS CS CS CS CS CS

Table B2
Data on Heat Exchangers, HX10 to HX17 and their Streams.

Name HX10 HX11 HX12 HX13 HX14 HX15 HX16 HX17

Exchanger pairing Utilities Utilities Utilities Utilities Utilities T-101 Bot T-100 Bot T-104 Bot
T-102 Top T-101 Top HE4 HE3 T-100 Top Utilities Utilities Utilities
Duty (kW) 2833 1810 80 2214 391 4506 2459 1309
Shell in (oC) 5.0 30.0 30.0 5.0 30.0 160.0 160.0 160.0
Shell out (oC) 15.0 45.0 45.0 15.0 45.0 160.0 160.0 160.0
Tube in (oC) 32.1 53.1 102.1 40.9 78.9 95.7 104.0 107.1968
Tube out (oC) 32.0 46.3 40.0 15.0 40.0 102.6 104.6 107.197
Area (m2) 191.12 225.61 3.57 147.09 22.18 100.87 59.07 73.48
Utility Chilled Water Cooling Water Cooling Water Chilled Water Cooling Water LP Steam LP Steam LP Steam
Tube material CS CS Ti CS CS Ti CS Ti
Shell material CS CS CS CS CS CS CS CS
 W.X. Chua et al. / Chemical Engineering Science: X 2 (2019) 100021 15

Appendix C. Stream Data for the proposed design

Tables C1 to C4 show the stream data for the proposed design

according to the PFD shown in Fig. 2.

Table C1
Stream Data for Proposed Design – Part 1.

Stream CO Feed H2O Feed 1 2 3 4 5 6 7 8 9

Temperature (oC) 30.1 120.0 100.3 86.0 50.0 50.0 16.9 104.6 98.4 16.9 49.2
Pressure (atm) 40.0 18.0 23.3 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0
Mass Density (g/cm3) 0.045 0.897 0.716 0.063 0.005 0.792 0.949 0.691 0.700 0.005 0.005
Mole Flow (kmol/h) 70.3 74.0 695.6 695.6 11.8 683.8 105.0 577.9 682.6 0.9 13.0
Mass Flow (kg/h) 1969.1 1332.5 24337.4 24337.4 390.7 23946.7 5379.5 18537.2 21938.6 30.0 429.6
Mass fraction
CO 1.000 0.000 0.011 0.011 0.620 0.001 0.001 0.000 0.000 0.762 0.624
MF 0.000 0.000 0.185 0.185 0.255 0.184 0.804 0.004 0.008 0.222 0.260
MA 0.000 0.000 0.799 0.799 0.125 0.810 0.196 0.990 0.987 0.017 0.116
Water 0.000 1.000 0.002 0.002 0.000 0.002 0.000 0.002 0.002 0.000 0.000
FA 0.000 0.000 0.003 0.003 0.000 0.003 0.000 0.003 0.003 0.000 0.000

Table C2
Stream Data for Proposed Design – Part 2.

Stream 10 11 12 13 14 15 16 17 18 19 20
Temperature (oC) 317.2 99.2 17.5 49.3 120.0 123.1 59.1 120.0 122.8 40.9 40.9
Pressure (atm) 40.0 23.3 18.0 18.0 18.0 18.0 18.0 18.0 18.0 1.0 1.0
Mass density (g/cm3) 0.027 0.699 0.948 0.924 0.811 0.792 0.919 0.815 0.802 0.005 0.002
Mole flow (kmol/h) 13.0 682.6 105.0 178.9 178.9 178.9 749.5 749.5 749.5 749.5 251.8
Mass flow (kg/h) 429.6 21938.6 5379.5 6712.0 6712.0 6712.0 33388.1 33388.1 33388.1 33388.1 13963.8
Mass fraction
CO 0.624 0.000 0.001 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000
MF 0.260 0.008 0.804 0.644 0.644 0.526 0.779 0.779 0.676 0.676 0.924
MA 0.116 0.987 0.196 0.157 0.157 0.220 0.083 0.083 0.138 0.138 0.060
Water 0.000 0.002 0.000 0.199 0.199 0.163 0.115 0.115 0.084 0.084 0.013
FA 0.000 0.003 0.000 0.000 0.000 0.091 0.023 0.023 0.101 0.101 0.003

Table C3
Stream Data for Proposed Design – Part 3.

Stream 21 22 23 24 25 26 27 28 29 30 31
Temperature (oC) 15.0 15.0 15.7 15.0 120.2 40.9 46.3 32.0 32.8 61.4 61.4
Pressure (atm) 1.1 1.0 18.0 1.0 4.0 1.0 1.0 1.0 18.0 1.0 1.0
Mass density (g/cm3) 0.767 0.978 0.977 0.002 0.005 0.926 0.002 0.954 0.953 0.752 0.752
Mole flow (kmol/h) 251.8 251.6 251.6 0.2 0.2 497.7 275.8 171.0 171.0 104.8 104.8
Mass flow (kg/h) 13963.8 13954.8 13954.8 8.9 8.9 19424.3 13349.8 9948.3 9948.3 3401.5 3401.5
Mass Fraction
CO 0.000 0.000 0.000 0.332 0.332 0.000 0.000 0.000 0.000 0.000 0.000
MF 0.924 0.924 0.924 0.646 0.646 0.498 0.725 0.963 0.963 0.028 0.028
MA 0.060 0.060 0.060 0.020 0.020 0.194 0.275 0.037 0.037 0.971 0.971
Water 0.013 0.013 0.013 0.002 0.002 0.136 0.000 0.000 0.000 0.000 0.000
FA 0.003 0.003 0.003 0.000 0.000 0.172 0.000 0.000 0.000 0.000 0.000

Table C4
Stream Data for Proposed Design – Part 4.

Stream 32 33 34 35 36 37 38 39 40 41 FA
Temperature (oC) 61.5 102.6 102.6 130.1 130.4 144.7 107.0 102.1 107.2 107.4 40.0
Pressure (atm) 4.0 1.0 3.0 3.0 18.0 3.0 1.0 1.0 1.0 3.0 1.0
Mass density (g/cm3) 0.752 0.864 0.864 0.868 0.867 0.881 0.014 1.054 0.921 0.921 1.160
Mole flow (kmol/h) 104.8 222.0 222.0 148.0 148.0 407.9 407.9 74.0 334.0 334.0 74.0
Mass flow (kg/h) 3401.5 6074.6 6074.6 2772.9 2772.9 15224.2 15224.2 3301.6 11922.6 11922.6 3301.6
Mass fraction
CO 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000
MF 0.028 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000
MA 0.971 0.016 0.016 0.035 0.035 0.000 0.000 0.000 0.000 0.000 0.000
Water 0.000 0.434 0.434 0.927 0.927 0.150 0.150 0.020 0.186 0.186 0.020
FA 0.000 0.550 0.550 0.038 0.038 0.850 0.850 0.980 0.814 0.814 0.980
16 W.X. Chua et al. / Chemical Engineering Science: X 2 (2019) 100021

References Kashani, S.Y., Farhadi, F., Baghalha, M., 2014. Simulation of Leonard-Kemira’s formic
acid production process from CO. 3rd Conference on Process Engineering
Conference (Oil, Gas, Refining and Petrochemicals).
Aguilo, A., Horlenko, T., 1985. Formic Acid. In: McKetta, J. (Ed.), Encyclopedia of
Koretsky, M.D., 2013. Engineering and Chemical Thermodynamics. Wiley, Hoboken.
Chemical Processing and Design: Volume 23 - Fluid Flow: Two-Phase Design to
Leonard, J.D., 1981. Preparation of Formic Acid by Hydrolysis of Methyl Formate.
Froth Flotation. Marcel Dekker, INC., New York.
4,299,981.
Andrushkevich, T.V., Popova, G.Y., Danilevich, E.V., Zolotarskii, I.A., Nakrokhin, V.B.,
Liu, Z., 1988. Methanol synthesis via methyl formate in the liquid phase. University
Nikoro, T.A., Stompel, S.I., Parmon, V.N., 2014. A new gas-phase method for
of Pittsburgh.
formic acid production: tests on a pilot plant. Catal. Ind. 6, 17–24.
Luyben, W.L., 2012. Pressure-swing distillation for minimum- and maximum-
Aslam, N.M., Masdar, M.S., Kamarudin, S.K., Daud, W.R.W., 2012. Overview on Direct
boiling homogeneous azeotropes. Ind. Eng. Chem. Res. 51, 10881–10886.
Formic Acid Fuel Cells (DFAFCs) as an energy sources. APCBEE Procedia 3, 33–
Market Research Future, 2017. Formic Acid Market Research Report- Forecast to
39.
2027.
Aspen Technology, 2008. Aspen Plus User Models. Burlington.
Novita, F.J., Lee, H.Y., Lee, M., 2018. Plantwide design for high-purity formic acid
Bai, L., Zhao, Y.L., Hu, Y.Q., Zhong, B., Peng, S.Y., 1996. Kinetics of the carbonylation
reactive distillation process with dividing wall column and external heat
of methanol in a mechanically agitated reactor. J. Nat. Gas Chem. 5, 229–236.
integration arrangements. Korean J. Chem. Eng. 35, 1–15.
Boyce, M.P., Edwards, V.H., Cowley, T.W., Fan, T., Kaiser, H.D., Geyer, W.B., Nadel, D.,
Novita, F.J., Lee, H.Y., Lee, M., 2015. Self-heat recuperative dividing wall column for
Skoda, L., Testone, S., Walter, K.L., 2008. Transport and Storage of Fluids. In:
enhancing the energy efficiency of the reactive distillation process in the formic
Green, D.W., Perry, R.H. (Eds.), Perry’s Chemical Engineers’ Handbook. McGraw-
acid production process. Chem. Eng. Process. Process Intensif. 97, 144–152.
Hill, New York.
Rangaiah, G.P. (Ed.), 2017. Multi-Objective Optimization: Techniques and
Branan, C., 2005. Rules of Thumb for Chemical Engineers. GPP, Burlington.
Applications in Chemical Engineering. second ed. World Scientific, Singapore.
Brennan, D., 2007. Life-Cycle Evaluation of Chemical Processing Plants. In: Kutz, M.
Rangaiah, G.P., Sharma, S., Sreepathi, B.K., 2015. Multi-objective optimization for
(Ed.), Environmentally Conscious Materials and Chemicals Processing. Wiley.
the design and operation of energy efficient chemical processes and power
Chen, L., Zhang, J., Ning, P., Chen, Y., Wu, W., 2004. Kinetics of methanol
generation. Curr. Opin. Chem. Eng. 10, 49–62.
carbonylation to methyl formate catalyzed by sodium methoxide. J. Nat. Gas
Sauer, J., Dahmen, N., Henrich, E., 2013. Tubular Plug Flow Reactors. Ullmann’s
Chem. 13, 225–230.
Encycl. Ind. Chem. Wiley-VCH.
da Cunha, S., Rangaiah, G.P., Hidajat, K., 2017. Retrofitting via Intensification:
Sengupta, D., Pike, R.W., 2013. Chemicals from biomass : integrating bioprocesses
application to formic acid process. In: Espuña, A., Graells, M., Puigjaner, L. (Eds.),
into chemical production complexes for sustainable development. Green Chem.
Proceedings of the 27th European Symposium on Computer Aided Process
Chem. Eng., 471
Engineering. Elsevier, pp. 1093–1098. https://doi.org/10.1016/B978-0-444-
Sharma, S., Patle, D.S., Gadhamsetti, A.P., Pandit, S., Manca, D., Nirmala, G.S., 2018.
63965-3.50184-7.
Intensification and performance assessment of the formic acid production
da Cunha, S., Rangaiah, G.P., Hidajat, K., 2018. Design, optimization and retrofit of
process through a dividing wall reactive distillation column with vapor
the formic acid process I: base case design and dividing-wall column retrofit.
recompression. Chem. Eng. Process. Process Intensif. 123, 204–213.
Ind. Eng. Chem. Res. 57, 9554–9570.
Sharma, S., Rangaiah, G.P., Marechal, F., 2017. Integrated Multi-Objective
Hietala, J., Vuori, A., Johnsson, P., Pollari, I., Reutemann, W., Kieczka, H., 2016. Formic
Differential Evolution and its Application to Amine Absorption Process for
acid. Ullmann’s Encyclopedia of Industrial Chemistry. Wiley, Weinheim.
Natural Gas Sweetening. In: Rangaiah, G.P., Sharma, S. (Eds.), Differential
Hoch, R., Scheeline, H.W., 1983. Process Economics Program: Formic. Acid. Menlo
Evolution in Chemical Engineering. World Scientific, Singapore.
Park.
Skoog, D.A., West, D.M., Holler, F.J., Crouch, S.R., 2000. Analytical Chemistry: an
Huang, H.P., Lee, M.J., Lee, H.Y., Chen, J.H., 2012. Formic Acid Manufacturing System
Introduction. Brooks/Cole.
and Method of Manufacturing Formic Acid. U.S. Patent 0123157 A1.
Turton, R., Bailie, R.C., Whiting, W.B., Shaeiwitz, J.A., Bhattacharyya, D., 2013.
Jogunola, O., Salmi, T., Eränen, K., Wärnå, J., Kangas, M., Mikkola, J.P., 2010.
Analysis, Synthesis, and Design of Chemical Processes. Pearson, Upper Sadle
Reversible autocatalytic hydrolysis of alkyl formate: Kinetic and reactor
River.
modeling. Ind. Eng. Chem. Res. 49, 4099–4106. https://doi.org/10.1021/
Wankat, P.C., 2007. Separation Process Engineering. Pearson, Westford.
ie902031d.
Wolf, D., Schmidt, R., Block, U., Schoenmakers, H., Bott, K., Kaibel, G., 1982.
Jogunola, O., Salmi, T., Wärnå, J., Mikkola, J.P., 2012. Kinetic studies of alkyl formate
Production of Anhydrous or Substantially Anhydrous Formic Acid. U.S. Patent
hydrolysis using formic acid as a catalyst. J. Chem. Technol. Biotechnol. 87, 286–
4,326,073.
293.