Chemical Engineering Research and Design 1 5 9 ( 2 0 2 0 ) 1–12

Contents lists available at ScienceDirect

Chemical Engineering Research and Design

journal homepage: www.elsevier.com/locate/cherd

Novel energy efficient process for acetic acid

production by methanol carbonylation

Alexandre C. Dimian a,∗ , Anton A. Kiss b

aUniversity P̈olitehnicaöf Bucharest, Polizu 1-7, 011061 Bucharest, Romania
bDepartment of Chemical Engineering and Analytical Science, The University of Manchester, Sackville Street,
Manchester M13 9PL, United Kingdom

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

Article history: Acetic acid is an essential chemical product. The need for ‘green’ acetic acid has spurred
Received 16 January 2020 new research in developing more sustainable processes. This paper presents an original
Received in revised form 26 conceptual design of a low-energy and low-emissions sustainable process for acetic acid
February 2020 manufacturing by methanol carbonylation. The emphasis is set on energy efficiency, as the
Accepted 14 April 2020 exothermic reaction releases a large amount of energy that may be more effectively used.
Available online 27 April 2020 Two processes are investigated by rigorous simulation, based on homo- and heterogeneous
catalysis. The latter reveals as innovative feature the full valorization of the energy released
Keywords: in the reaction section, along with reducing the separation sequence to only two distillation
Acetic acid columns. The first dewatering column is driven by low-pressure steam generated by the
Process design reactor cooling. The second purification column uses heat pumping, in which the energy
Process simulation rejected in condenser is upgraded for reboiler heating by vapor compression (VC), using
Sustainable process water as working fluid. The electricity for the vapor compression is ensured by applying
Energy efficiency an Organic Rankine Cycle (ORC) for waste heat recovery by the reactor cooling. In this way,
the new green process needs very little energy (below 1 MJ/kg product). This eco-efficient
process shows also superior sustainability metrics (e.g. low emissions of 40 gCO2 e/kg) as
compared to the homogeneous catalyst process.
© 2020 Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.

1. Introduction Amidst growing environmental awareness and more strin-

Acetic acid is a major essential chemical product, being an
important chemical reagent used primarily in the produc-
tion of cellulose acetate, vinyl acetate monomer and polyvinyl
acetate, acetic anhydride, monochloroacetic acid, acetate
esters, terephthalic acid, and synthetic fibres and fabrics (Le
Berre et al., 2014). It is often used in descaling agents, or as
food additive. The global market size was 16.3 million tonnes
in 2018, and it is further expected to reach a volume of about
20.3 million tonnes by 2024 (Marketwatch, 2019). Asia-Pacific
has currently the highest market share, followed by North
America, Europe, Middle East and Africa.
∗ iridium-catalyzed systems that operate with high activity at
Corresponding author.
E-mail address: ac dimian@chim.upb.ro (A.C. Dimian).
https://doi.org/10.1016/j.cherd.2020.04.013
0263-8762/© 2020 Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
gent regulations worldwide, there is an imminent shift of
acetic acid production strategy in favour of greener processes
(Pal and Nayak, 2017). The development and advances in acetic
acid processes and catalysts aim primarily to reduce the raw
material consumption, energy requirements, and investment
costs (Yoneda et al., 2001). The most important processes
for acetic acid production are the carbonylation of methanol,
vapor phase-oxidation (ethane and ethene), liquid-phase
oxidation (n-butane and naphta), acetaldehyde oxidation,
oxidative and anaerobic fermentation (Yoneda et al., 2001;
Le Berre et al., 2014). Among them, the manufacturing of
acetic acid by methanol carbonylation takes the largest market
share (about 75%), in continuous growth. Research strategies
to improve the catalyst performance and process economics
of methanol carbonylation resulted in both rhodium- and
reduced water concentration (Haynes, 2010). More sustainable
2 Chemical Engineering Research and Design 1 5 9 ( 2 0 2 0 ) 1–12
catalysts have been explored, such as immobilized rhodium
and iodide species on cross-linked copolymers (Li et al., 2013),
heterogeneous rhodium-incorporated graphitic carbon nitride
(Nam et al., 2017), a halide-free and noble metal-free cata-
lyst based on pyridine-modified H-mordenite zeolite (Ni et al.,
2017). The trend of using methanol carbonylation is favourable
from a sustainability viewpoint, as both raw materials can be
obtained from any feedstock leading to syngas, such as biogas
and biomass. For this reason, acetic acid can be a 100% green
product, and on this basis promotes the synthesis of other
bio-based chemicals. For example, the vinyl acetate monomer
(VAM) manufactured from acetic acid and ethylene (Dimian
and Bildea, 2008) becomes a bio-based product, as well as the
valuable vinyl paints. In this way traditional petrochemicals
can be replaced by green products obtained from a syngas
bio-refinery platform (Dimian, 2007; Dimian et al., 2019).
Other processes based on renewable materials include
hydrothermal processing of biomass waste (Jin et al., 2007),
integrated production in a pyrolysis oil-based biorefinery
(Vitasari et al., 2015), and the fermentation of sugar residue
solutions driven by suitable bacteria (Vidra and Németh, 2018).
Despite the ecological interest, the economic efficiency is
penalized by high energy use in the separation and purifi-
cation operations (Kiss et al., 2016). The result is that the
fermentation process is limited nowadays to only 10% of the
market.
A novel route reported recently involves the hydro-
carboxylation of methanol with CO2 and H2 (Qian et al., 2016).
The reaction can be efficiently catalyzed by Ru–Rh bimetal-
lic catalyst using imidazole as ligand and LiI as promoter in
1,3-dimethyl-2-imidazolidinone (DMI) solvent with outstand-
ing reaction results. This method could open a road to fix CO2
into bulk chemicals, but it is questionable whether the hydro-
gen manufacturing price could be competitive enough. This
might be the case if hydrogen is produced by electrolysis using
renewable energy, while methanol is used for energy storage.
This study focuses on the conceptual design of a novel
low-energy sustainable process for acetic acid manufactur-
ing by methanol carbonylation, using heterogeneous catalysis.
This key feature is obtained by full valorization of the energy
released by the exothermal reaction. The energy efficiency is
improved by steam generation (by reactor cooling), as well as
using vapour compression (VC) coupled with an Organic Rank-
ine Cycle (ORC) that recovers the reactor’s effluent enthalpy.
The plant capacity considered in this work is 200 ktpy acetic
acid with a target purity of 99.7 wt%. The analysis and design is
performed by employing the rigorous process simulator Aspen
Plus v9.0.
2. Production processes and technologies
The methanol carbonylation can be described by the follow-
ing stoichiometric equation, with a theoretical carbon yield of
100%:
CH3 -OH + CO → CH3 -COOH Hr,298 = −135.6 kJ/mol (1)
The reaction is moderately exothermic and thermodynam-
ically favoured by lower temperature. The industrial operation
range is usually 15–200 ◦ C and pressures of 30–60 bar (Le Berre
et al., 2014). Although the overall stoichiometry is simple, the
chemistry is complex considering the catalytic reaction mech-
anism.
2.1. Catalysis and technology issues
Methanol carbonylation may involve rhodium catalyst (Mon-
santo process) or iridium-base catalyst (CativaTM process) as
homogeneous catalysts (Jones, 2000; Le Berre et al., 2014).
The reaction takes place in liquid phase at 150–200 ◦ C and
30–60 bar. Methyl acetate is used as solvent for the catalytic
complex. The elementary reactions are (Moulijn et al., 2013):
CH3 -OH + HI ↔ CH3 I + H2 O Hr,298 = −53.1 kJ/mol (2)
CH3 I + CO → CH3 COI Hr,298 = −66.9 kJ/mol (3)
CH3 COI + H2 O → CH3 COOH + HI Hr,298
= −15.6 kJ/mol (4)
Details about the reaction mechanism and implications on
kinetics may be found in Jones (2000). The key stage reac-
tion (3) involves a metallic complex, with Rh or Ir. In the
first case, the metallic complex [Rh(CO)2 I2 ] reacts initially
with CH3 I giving [Rh(CO)2 MeI3 ]. This intermediate under-
goes a molecular rearrangement leading to the formation of
an acyl group [Rh(CO)(CO-Me)I3 ]. Further, the addition of a
CO molecule leads to an unstable intermediate [Rh(CO)2 (CO-
Me)I3 ]. It follows the expulsion of the acyl iodide CH3 COI and
the hydrolysis reaction (4) that produces the acetic acid and
HI. The initial catalytic complex is rebuilt, as well as HI that
re-joins the cycle. CH3 I, HI and H2 O implied in the catalytic
cycle are recovered and recycled.
Controlling the amount of water is a key factor in process
design. Water is formed directly by the esterification of the
acetic acid with methanol, but it comes mainly by recycling
from the separation section. When the water content is higher
than 8 wt% the rate determining step in is the addition of CH3 I
to the Rh centre:
RCH3COOH = k × [Rh] × [CH3 I] (5)
The reaction rate is essentially first order in both cata-
lyst and methyl iodide concentrations, but independent of
the reactants concentrations, CH3 OH and CO. Therefore, high
conversions can be obtained even in a CSTR of small volume
(Moulijn et al., 2013). If the water content is less than 8 wt%,
the rate determining step is the reductive elimination of the
acyl species.
Keeping the integrity of the catalyst is essential. The
main cause of catalyst loss by precipitation is the reaction of
rhodium-acyl species with HI that leads to acetaldehyde and
the complex [Rh(CO)I4 ]− . The latter may cause a catalyst loss
by precipitation of the inactive and insoluble RhI3 , when the
CO concentration is insufficient.
[Rh(CO)(CO-CH3 )I3 ]− + HI → CH3 -CHO
+ [Rh(CO)I4 ]− → RhI3 + I− + CO (6)
Although rhodium-catalyzed carbonylation of methanol is
highly selective, it suffers from some disadvantageous side
 Chemical Engineering Research and Design 1 5 9 ( 2 0 2 0 ) 1–12
reactions, as for example the water-gas shift reaction. Further
methane appears by reaction of hydrogen with methanol:
CO + H2 O → CO2 + H2 (7)
CH3 OH + H2 → CH4 + H2 O (8)
These side reactions may reduce the amount CO avail-
able for reaction down to a point where the catalyst integrity
is threatened. Another unwanted reaction is the formation
of acetaldehyde. The reaction with hydrogen gives ethanol,
which by carbonylation forms propionic acid as the main
heavy impurity. High boilers can be formed by aldol conden-
sation reactions.
H2 CO
CH3 -CHO→CH3 -CH2 -OH→CH3 -CH2 -COOH (9)
The alternative of using iridium as coordinating metal is
justified by its price, 17 times lower than that for rhodium
(Jones, 2000). Moreover, this brings a significant modification
in the reaction mechanism with strong impact on the process
performance. The oxidative addition of methyl iodide to the
iridium centre is about 150 times faster compared to rhodium,
and thus does not determine the reaction rate. The slowest
step becomes the methyl migration to form the acyl complex.
This step involves substitution of iodide centre with CO. Thus,
the reaction rate dependence is totally different from that for
the Rh catalyzed process:
RCH3COOH = k × [Ir][CO]/[I− ] (10)
The inverse dependence on the ionic iodide concentra-
tion implies that removing it increases the reaction rate. This
operation is done by promoters, such as iodide complexes
of zinc, cadmium, mercury, gallium and indium, as well as
carbonyl-iodide complexes of tungsten, rhenium, ruthenium
and osmium. The use of promoters can increase considerably
the reaction rate, up to 20 times by a molar ratio Ir/Ru of 5.
The Japanese company Chiyoda (www.chiyodacorp.com)
developed the CT-ACETICATM process that uses a heteroge-
neous catalyst in which the rhodium complex is immobilized
on a vinyl-pyridine resin. In this way the catalyst remains in
the reaction space and its integrity is preserved. Since the
amount of water drops under 2%, the energy for dehydrating
the acetic acid is drastically reduced. The same type of reac-
tion system is used in the new integrated process proposed
here, which has the additional advantages of improved overall
efficiency due to effective energy integration and waste heat
recovery by vapor compression and ORC.
2.2. Reactor technology
Fig. 1 depicts the type of industrial reactors employed by
methanol carbonylation. Processes based on homogeneous
catalyst makes use of CSTR-type reactor with mechani-
cally stirring or gas injection device, working at pressures
of 30–40 bar and temperatures of 180–250 ◦ C (Jones, 2000), as
depicted in Fig. 1 left-hand. The reactor is provided with exter-
nal heat exchanger for cooling by steam generation (SG). A
slurry gas–liquid tower reactor was developed for using het-
erogeneous catalyst (Yoneda et al., 2001), as illustrated by
Fig. 1 right-hand. The gas is injected at the bottom through
an efficient distribution device to saturate the liquid phase
in CO. An external loop for liquid-phase circulation is cre-
3
ated by the density difference caused by the CO consumption.
The reaction takes place in the riser, while the downcomer
ensures catalyst recycle and heat transfer through an external
exchanger.
2.3. Process design
A generic flowsheet is available regarding the technology
employed by the Monsanto process (Le Berre et al., 2014). This
employs a three columns separation sequence: the first two
handle the removal of light-ends and water, while the third the
acetic acid purification. By this approach the species involved
in the catalyst complex, as described before, are fully recycled
to reactor. The same conceptual flowsheet is used by Cativa
and CT-ACETICA processes. However, no details about the pro-
cess design were given in terms of design and performance of
reactor and separators, as well as energy integration of units.
This paper presents the first approach of analysis and
design of such process, which is based on computer simu-
lation. The energy released by reaction, considering kinetic
industrial data, reveals substantial capabilities for sustaining
the energetic needs of the separation section. Two flowsheet
alternatives are proposed, based on homogeneous and het-
erogeneous catalysis. The first is close to the actual industrial
flowsheet, but proposes a quantitative assessment of the reac-
tion section, the evaluation of the separations, as well as a first
energy integration level. This is also the reference case in the
sustainability analysis. The second alternative employs only
two distillation columns and incorporates advanced energy
integration methods, as heat pumping and on-site electricity
production by Organic Ranking Cycle (ORC). The comparison
of alternatives by sustainability analysis reveals that the sec-
ond one demonstrates very low energy consumption, CO2
emissions and process water usage. To put it in a nutshell, this
work reports the best process design performance to date, to
the best of our knowledge.
3. Process design and simulation based on
homogeneous catalyst
The plant capacity corresponds to a production rate of
25,000 kg/h or 416.3 kmol/h. The stoichiometric amounts of
raw materials are both 416.3 kmol/h methanol and CO, or
13,339 and 11,661 kg/h, respectively. A preliminary plant mate-
rial balance based on industrial data for Rhodium catalyst (Le
Berre et al., 2014), the yield estimates the yield as 98% for
methanol, and 95% for CO. The lower value for CO may be
explained by secondary reactions leading to impurities and
gases as CO2 , H2 and CH4 .
The analysis and simulation work was done by employing
the process simulator Aspen Plus v9.0. The thermodynamic
modelling involves highly non-ideal mixtures, namely acetic
acid/water, and polar supercritical gases, for which suitable
models are given in Appendix A.
3.1. Reaction section
Since the reaction is fast it achieves practically full CO conver-
sion with excellent yield. In the workable regime, the reaction
rate can be mastered by keeping constant the composition of
the catalytic complex, including co-catalyst and promoters,
since the reaction is zero-order with respect to the concen-
tration of reactive species. For the purpose of this paper a
4 Chemical Engineering Research and Design 1 5 9 ( 2 0 2 0 ) 1–12
Fig. 1 – Chemical reactors for methanol carbonylation (left: homogeneous process, right: heterogeneous process).
practical kinetic approach is assumed by considering indus-
trial reaction rate data. As indicated in Table A-1 (see Appendix
A) by experiments 5–7, a reaction rate R of about 20 kmol/m3 /h
is assumed as achievable for a mixture composition with
methyl iodide as 6–10 wt%, methyl acetate 16–20 wt%, and
water 4–5 wt%. This requirement is solved by a separate input
stream that considers the above species recovered by recycles.
In addition, this approach offer a realistic description of the
reaction mixture involved further in separations (Sunley and
Watson, 2000).
A first design issue is recovery and recycling all the com-
ponents of the catalyst recipe carried out to the separation
section, namely the volatile methyl iodide and methyl acetate,
as well as controlling the amount of water in reactor. The use
of on-line FTIR spectrometry allows monitoring the amounts
of species mentioned before, as well as quantifying the pro-
duction rate (Keit Company, 2019). A second issue is keeping
constant the temperature in reactor and managing the large
amount of heat released by reaction. This requirement is
achieved by building efficient cooling and energy recovery pro-
cedures, as presented in this paper.
Fig. 2 presents the flowsheet of the reaction section. This
comprises the reactor RSTOIC modelling the reaction, fol-
lowed by a flash unit FL-1 introduced for describing the
vapour–liquid equilibrium. The gas stream is condensed at
5 ◦ C, the liquid being recycled to the reactor, while the gas
leaves as vent stream. The liquid reaction mixture is split
further in a process stream and a liquid recycle stream that
enters the cooling loop. The reactor effluent is depressurized
and vaporized in the FLASHER unit in view of separating the
catalyst, recycled as bottom stream to the reactor.
The reactor modelling is based on stoichiometry. The main
reaction has a fractional conversion of 0.98. Secondary reac-
tions describe the formation of by-products and impurities:
(11) Formation of gaseous impurities (relations (7) and (8)),
lumped in the reaction:
CO + CH3 OH = CO2 + CH4
(molarextentofreaction2 kmol/h) (11)
(12) Esterification of acetic acid with methanol:
CH3 -COOH + CH3 -OH = CH3 -COOCH3
+ H2 O (molarextentofreaction2 kmol/h) (12)
(13) Formation of propionic acid:
CH3 -COOH + CH3 -OH = CH3 -CH2 -COOH
+ H2 O (molarextentofreaction4 kmol/h) (13)
The reactant inputs are methanol (424.8 kmol/h
= 13,612 kg/h) and CO (438.2 kmol/h = 12,274 kg/h), accord-
ing to the preliminary material balance formulated before.
Methanol is preheated at 100 ◦ C, while the CO stream is
compressed at 35 bar in a four-stage compressor with inter-
mediate cooling at 50 ◦ C except the last adiabatic stage
where the temperature rises at 152 ◦ C. In addition, a recycle
stream from separations is considered containing acetic
acid (1000 kg/h), methyl acetate (2000 kg/h), methyl iodide
(2000 kg/h), and water (1500 kg/h). The metal catalyst is not
introduced explicitly in simulation due to obvious modelling
constraints.
Effective reactor cooling is an important feature of the pro-
cess design since a significant amount of reaction heat can
be recovered as useful energy for separations. Fig. 2 presents
a flowsheet that includes steam generator and cooler. This
solution is used in industry, as described in a recent patent
(Zinobile, 2014). In view of maximizing the steam amount, the
reaction temperature is set at 220 ◦ C, as indicated in the same
patent. The reactor pressure should be over 35 bar to ensure
liquid phase reaction.
The goal in designing the reaction system is achieving
constant temperature inside the reactor by manipulating the
cooling capabilities. The parameters of the cooling loop were
tuned by an iterative procedure, split fraction of the SPLIT unit
and return temperature of the COOLER unit, such to bring
the duty of the RSTOIC reactor close to zero. In addition, a
 Chemical Engineering Research and Design 1 5 9 ( 2 0 2 0 ) 1–12
Fig. 2 – Simulation flowsheet of the reaction section.
temperature of 150 ◦ C is assumed for generating LP steam of
3.5 bar. The results are split fraction of 0.242 and return CW
temperature of 56 ◦ C that delivers 6.2 MW LP steam for the
separation section. In addition, 6.2 MW duty of the COOLER
remains available for reactant preheating and/or for energy
saving by other means, as electricity generation by Organic
Rankine Cycle (ORC) developed in this study.
The key stream leaving the reaction section is PROCESS,
obtained as vapor from the unit FLASHER after pressure reduc-
tion from 35 to 1.5 bar. This operation allows recovery most of
the Rh/Ir catalyst as bottom stream and recycling it to reactor.
The stream PROCESS sent further to the separation section
has a flowrate of 32,046 kg/h (25,622 acetic acid, 2296 methyl
acetate, 1608 water, 1999 methyl iodide, 148 propionic acid,
235 CO, 78 CO2 and 22 CH4 ). Supercritical components as CO,
CO2 and CH4 , leave in the stream VENT, while the light species
are recycled to the reactor, after absorption in methanol and
deep cooling.
The reactor effluent flowrate from simulation
is 132,760 kg/h (density of 655 kg/m3 ) with a volu-
metric flow Qv = 202 m3 /h. From the mass balance
the amount of acetic acid formed by reaction is:
NA = NMeOH × conversion = 424.8 × 0.99 = 420.55 kmol/h. The
reaction volume is VR = NA /R = 21.03 m3 . Hence the reaction
time is tR = VR /Qv = 373 s. Taking a volume factor of 0.75 gives
a reactor of 28 m3 . For a cylindrical vessel with ellipsoidal
heads, the reactor volume is VR = /4 × D3 × (H/D + 0.166),
leading to a vessel of 2.3 m diameter and 3.2 m height.
3.2. Separation section
The strategy of separations starts by examining the state and
composition of the reactor-outlet mixture (Dimian et al., 2014).
The stream PROCESS (which leaves the flasher as vapor at
1.6 bar and 125 ◦ C) contains acetic acid in large quantity, and
much lower amounts of methyl acetate, methyl iodide and
water (there are also small amounts of dissolved gases and
entrained Rh/Ir catalyst). Vapor pressure is the characteristic
property for determining the separation sequence of compo-
nents. Methyl iodide is the most volatile (nbp 42.4 ◦ C), followed
by methyl acetate (56.9 ◦ C), methanol (64.7 ◦ C), water (100.0 ◦ C),
5
acetic acid (117.9 ◦ C) and propionic acid (141.2 ◦ C). A direct
sequence of three columns is appropriate, as shown in Fig. 3.
The first column C-1 removes lights (methyl iodide, methyl
acetate, methanol) and gaseous species as top distillate
(vapor and liquid), while the bottom recovers completely the
entrained catalyst as acetic acid solution. The acetic acid is
taken over as vapor side-stream and fed to the column C-2.
Here the dehydration of acetic acid takes place, the distil-
late recovering completely the remaining light species and
most of the water amount. The top vapor from C-1 and C-
2 enters the column C-4 where the lights are recovered by
absorption in methanol. A final cooling at 5 ◦ C recovers the
entrained methanol too. As mentioned, the condensate and
the top distillates are recycled to the chemical reactor to pre-
serve the composition of the catalyst complex. A makeup of
methyl iodide might be necessary to compensate losses in exit
gaseous streams. The water inventory should also be balanced
such to ensure the prescribed water concentration in the reac-
tor by means of on-line process monitoring. Finally, the bottom
stream of C-2 is sent to purification in the column C-3, where
high purity acetic acid is obtained as top product, while the
heavy impurities are removed as bottom stream.
The sizing of internals for all columns has been performed
interactively in Aspen Plus by selecting different internals,
trays or packing. Column C-1 has 17 theoretical stages with the
vapor feed stream close to the reboiler, equipped with FLEX-
S trays. The diameter is varied in three steps (1.3/1.8/2.2 m)
to accommodate large variations in vapor and liquid flows,
while aiming an efficient hydraulic regime between 70% and
80% from flooding. The top condenser works at 35 ◦ C and may
be cooled by air or water or a combination.
The column C-2 deals with water removal. This is a dif-
ficult separation as the equilibrium curve shows a tangent
pinch in the region of water distillation. The column needs 35
theoretical stages to ensure water recovery in top over 97.5%.
Simple sieve trays are suitable. Changing the tower diameter
is necessary, this time larger in the middle (1.9 m for the stages
2–20, 2.3 m for 21–26 and 1.9 m for 27–34), with the maximum
flooding approach of 75%, 79%, and 78% respectively. The feed
is located above the stage 27. The column partition in three
regions corresponds to different operation characteristics. The
6 Chemical Engineering Research and Design 1 5 9 ( 2 0 2 0 ) 1–12
Fig. 3 – Flowsheet of the acetic separation section by homogeneous catalyst.
water removal increases continuously from bottom to the top,
while opposite happens for the acetic acid. In the middle sec-
tion a larger vapor flowrate due to the feed needs a larger cross
section to avoid flooding.
Finally, in the column C-3 the acetic acid is obtained as top
product of purity over 99.7 wt%. The bottom stream removes
the heavies, simulated here as propionic acid. The separa-
tion is difficult (30 trays), the relative volatility of acetic acid
to propionic acid being around 1.20. Accordingly, for acetic
acid recovery of 98.5% the separation needs a very large reflux
flowrate, about the same as the top product flowrate. Higher
recovery can be obtained by stripping the bottom product, not
considered here.
3.3. Integration of reaction and separation sections
The exothermic reaction develops an important amount of
energy, equivalent to 15.7 MW. The reactor cooling creates
opportunities for supplying energy to the other units. The unit
ST-GEN can ensure 6.2 MW as steam at 3.6 bar and 140 ◦ C. In
this way the heating requirements of the separation section
(13.5 MW) can be reduced by 45%. Pinch Analysis indicates
that supplementary energy saving is possible for methanol
and recycle preheating (units H-1 and H-2), as well as for
sustaining the vaporization in the unit FLASHER, with a cumu-
lated duty of 2.69 MW. A H-curve plot of the unit COOLER
(duty 6.24 MW) shows that 2.75 MW is available on the inter-
val 150–110 ◦ C, enough for driving the above units ensuring
a Tmin of at least 10 ◦ C. Accordingly, the duty of COOLER
diminishes with 2.69 MW from 6.24 to 3.5 MW. The saving
with respect to enthalpy of the liquid recycle is 72%. This
is substantial, but can be further increased to full recov-
ery.
4. Eco-efficient process based on
heterogeneous catalyst
If heterogeneous catalyst and advanced process integration
methods are applied, an eco-efficient process with superior
sustainability features can be designed, as shown in Fig. 4.
4.1. Reaction system
The CSTR reactor is replaced by a gas-liquid tower reactor
(Fig. 1, right hand) in which the heterogeneous catalyst is recy-
cled. The FLASHER unit is no longer necessary. The PRODUCT
stream is cooled from 210 to 120 ◦ C in the exchanger COOL-P
and sent to the distillation column D-1 after pressure reduc-
tion. The parameters of the recycle loop are slightly modified
in view of optimal heat integration. Thus, the exit temperature
from ST-GEN unit increases to 160 ◦ C. The effect is reducing the
duty of ST-GEN to 5.4 MW (correlated with the reboiler of D-
1) but increasing the duty of the unit COOL-R to 7 MW. Thus,
the units COOL-P and COOL-R cumulate a considerable duty of
9 MW, which raises the question of valorization. The tempera-
ture level well above 100 ◦ C suggests that an Organic Rankine
Cycle (ORC) can be applied for producing electricity from the
residual heat. Then the process/process heat exchange in the
reaction section is limited only to reactants’ preheating in the
units H-1 and H-2, with a cumulated duty of 1.23 MW.
4.2. Separation system
As the heterogeneous catalyst remains in the reactor (hence
not removed with the effluent as in the case for homogeneous
catalysts), the separation system presented in Fig. 4 consist of
only two columns. The first one D-1 handles the removal in
 Chemical Engineering Research and Design 1 5 9 ( 2 0 2 0 ) 1–12 7

Fig. 4 – Eco-efficient process for acetic acid manufacturing.

stage, so that the total column’s height is 17.5 m. A notable

Table 1 – Sizing characteristic of the distillation columns
for acetic acid separation. effect is the pressure drop reduction from 0.32 bar with trays
to less than 0.1 bar with packing. Lower column diameter gives
Item Unit D-1 D-2
lower capital cost too.
Feed kg/h 29,800 25,400 The column D-2 performs the final purification of the raw
Distillate V/L kg/h 400/4000 25,000 acetic acid to 99.7 wt%. It has 35 plates (feed on 17) and works
Bottom 25,400 400 at high boilup ratio (over 100). Mellapack structured pack-
Stages/feed/ss – 35/17 35/17
ing is employed, which leads to a diameter of 1.5 m. A very
Top pressure bar 1.3 1.1
Pressure drop bar <0.1 <0.1
low pressure drop (below 0.1 bar) is convenient for heat pump
Top temp. ◦
C 35 121 implementation, as discussed next.
◦
Bottom temp. C 128 127
Reflux kg/h 15,000 2500 4.3. Heat pump assisted distillation
Internals Mellapak Mellapak
Stages/diameter –/m 2–8/1.4 2–34/1.5
9–17/1.6
The reboiler duty of 5.4 MW of the column D-1 is covered by
Total height m 18–34/1.8 17.5 the steam generated in the reaction section. A simple criterion
17.5 based on Carnot efficiency can be effectively used to decide
Condenser duty MW −5.5 −4.9 whether a heat pump is worth exploring (Kiss and Infante
Reboiler duty MW 5.10 4.8 Ferreira, 2016): Q/W = Tc /(Tr − Tc ) > 10, where Q is the reboiler
duty, W the work provided, Tr the reboiler temperature and
top of water together with light species, while in the second Tc the condenser temperature. When the Q/W ratio exceeds
D-2 the purification of acetic acid takes place. Table 1 presents 10 then a heat pump should be considered. Referring to the
the sizing characteristics of the columns. purification column D-2, after implementing structured pack-
The design of D-1 aims high recovery of water to ensure ing, the temperature difference top-bottom is about 12 ◦ C and
delivering high-purity acetic acid from D-2. The condenser of consequently Q/W is above 30, which is clearly favourable.
D-1 is partial vapor-liquid. The liquid distillate contains the The condenser temperature (121 ◦ C at 1.1 bar) suggests that
water and most of the methyl acetate and methyl iodide, while water may be used as thermal agent for vapor compression.
the vapor distillate takes over the supercritical gases together Compressing LP steam is a widespread technique in industry.
with some methyl acetate and methyl iodide. A mass reflux In this case a heat pump can be installed around the col-
rate of 15,000 kg/h, combined with a tall column of 35 stages umn D-2 driving a steam Rankine cycle (Fig. 6, left-hand).
(feed on 17) results in recovery of 99% of water and 100% of Steam is generated at top by taking over the condensation
lighter components. Fig. 5 shows the composition profiles. The heat. Considering the vapor pressures of acetic water and
dewatering process is particularly difficult in the lower part of water, a mean temperature difference (MTD) of 20 ◦ C is cre-
the stripping region. ated between the hot and cold sides, while high heat transfer
In view of heat integration, the column pressure drop, and coefficients are reached. Then the steam is compressed to a
as consequence the bottom temperature should be at the low- pressure level enough for driving the reboiler. Implementing
est. This goal can be achieved by switching from trays to structured packing leads to a very low pressure drop of maxi-
structured packing. By implementing Mellapak from Sulzer mum 0.1 bar, and a bottom temperature of 126 ◦ C. Considering
the tower diameter drops significantly. The hydraulic calcu- a MTD of 24 ◦ C gives a target steam temperature of 150 ◦ C,
lations in Aspen Plus indicate that a shape of three diameters which corresponds to a pressure of 4.8 bar. The thermal bal-
is suitable: 1.4 m stages 1–8, 1.6 m 9–17, and 1.8 m 18–34, at ance indicates that a steam amount of 9500 kg/h is necessary
flooding of about 80%. A HETP of 0.5 m is selected for a real for running the heat pumping.
8 Chemical Engineering Research and Design 1 5 9 ( 2 0 2 0 ) 1–12

Fig. 5 – Concentration profiles (as vapor and liquid molar fractions) along the acetic acid dehydration column.

Fig. 6 – Heat pumping by vapor compression (left) and power generation using an Organic Rankine Cycle (right).

Table 2 – Organic Rankine Cycles for waste heat recovery in the reaction section.
Fluid R-ORC recycle stream P-ORC product stream Expandera

Flowrate (G) Duty (Q) Power (W) Efficiency (Eff) G Q W Eff T-in T-out
◦ ◦
kg/s MW kW – kg/s MW kW – C C

R-600a 17 7.0 1360 0.194 4.8 2.0 386 0.193 125 35

R-1233ze 18.5 4.92 786 0.160 7.5 2.0 314 0.157 142 44
R-365fa 18.5 4.76 704 0.148 8 2.0 301 0.151 145 60

a
Note: Inlet pressure 30 bar, outlet pressure 2 bar.

The pressure ratio of 4.8 may be achieved by a three-stage
compressor each with a compression ratio of 1.667, which lim-
its the outlet temperature below 200 ◦ C. For the first two stages
intermediate vapor de-superheating is necessary, at 120 and
130 ◦ C respectively. This may be obtained by air cooling, or bet-
ter by spraying liquid water. Assuming an overall efficiency of
0.72 the simulation in Aspen Plus gives a compressor power of
1080 kW. Hence, a good coefficient of performance is obtained,
COP = Qr /Wc = 5.93/1.078 = 5.5.
The practical implementation of the heat pump might raise
controllability problems because of coupling the dynamics of
two units. A significant simplification comes from the fact that
the duties of the hot and cold sources are practically identical,
the column working at a very large reflux rate. The bottom
stream is very small compared with the distillate. As con-
sequence, the effect of disturbances is reduced. A practical
solution is using the heat pumping for covering 90–95% of
the boiling duty by implementing an external heat exchanger,
while a small reboiler handles disturbances (Kiss and Infante
Ferreira, 2016). Direct injection of LP steam from grid can be
used for start-up.
The design of the heat exchangers was done rigorously
by using the EDR tool in Aspen Plus. The evaporator is of
horizontal BEM-TEMA type with organic vapor condensation
in tubes (2 passes) and water evaporation in shell. The heat
transfer coefficient (HTC) reaches a high value of 1800 W/m2 K
 Chemical Engineering Research and Design 1 5 9 ( 2 0 2 0 ) 1–12
because condensation and boiling, respectively, and combined
with MTD of 18 ◦ C allows the exchange of 6 MW for an area of
195 m2 . The condenser that plays the role of column’s reboiler,
is BKM-TEMA kettle type. HTC of 1500 W/m2 K and MTD of
22 ◦ C gives an exchange area of 268 m2 .
A quick economic assessment can be done in term of credit
of saving thermal energy against compressor investment and
operation costs. The evaluation depends on local conditions.
Considering a nominal reboiler duty is 6 MW and assuming 10
$/GJ for LP steam and 8000 h annual operation time gives the
steam cost of (10 × 6 × 8000 × 3600/1000) = 1.73 M$.
On the other hand, an estimation of the compressor cost
can be obtained by means of the correlation C = a + bSn , (Towler
and Sinnott, 2012) in which a = 580,000, b = 20,000, n = 0.6, S
being the power in kW and the resulting cost in USD. The
power of 1080 kW gives a compressor purchased cost of
1.92 M$. An installation factor of 2 leads to a total installed cost
of 3.84 M$. By assuming an electricity price of 0.07 $/kwh gives
a compressor operating cost of (1080 × 8000 × 0.07) = 0.605 M$,
only 35% from the cost of thermal energy.
The estimation of profitability can be done based on Total
Annual Cost (TAC). This considers that the capital of installed
compressor is paid back within 3 years, while the operating
cost each year. As result the TAC is (3.84/3 + 0.605) = 1.89 M$,
to be compared with the annual cost of thermal energy of
1.73 M$. This alternative has the minimum utility require-
ments. The only energy necessary for separations is required
only by the VC system. The implementation is profitable if an
advantageous price is obtained for the compression system,
which is the case since steam compression is widespread in
process industries. In addition, electricity can be generated in
situ, as shown in the next section.
4.4. Organic Rankin Cycle (ORC) for waste heat
recovery
Heat curve calculation in Aspen Plus reveals that 7.5 MW waste
heat is available over the interval 160/49 ◦ C from COOL-R, as
well as 2 MW over 210/120 ◦ C from COOL-P. Waste heat can be
advantageously recovered as electrical power by employing
an ORC system (Dimian et al., 2014). The principle is shown
in Fig. 6 right-hand. The selection of working fluid may fol-
low the recommendations of international agencies (IAE, 2014,
www.iea.org) or experts (Quoilin et al., 2013).
Since the hot source is available as sensible heat spread
over a temperature interval, the feasibility of the ORC method
require the top source temperature above the Tc of the work-
ing fluid. In addition, the TQ profiles inside the evaporator
must avoid temperature crossing and respect a Tmin of 5 ◦ C.
The fluid pressure in evaporator and at expander inlet is set
at 30 bar, located inside the optimal range of 0.8–0.9 from Pc
(Castelli et al., 2019). The outlet expander pressure is set at
2 bar. The feasibility was checked by simulation in Aspen Plus.
Isentropic expansion is 0.85 and mechanical efficiencies 0.9.
The evaporator specification is supplying superheated vapor
with 2 ◦ C. The objective of ORC is getting the highest work
delivered.
Table 2 presents the results: fluid flowrate (G), source duty
(Q), generated power (W) and thermal efficiency (Eff), as well
as the inlet/outlet temperatures of expander for inlet/outlet
pressures of 30 and 2 bar. When using hydrocarbon fluids,
i-butane gives the best results. The i-pentane fluid failed in R-
ORC since it has a higher Tc than the source inlet-temperature.
The whole duty of 7 MW in the Recycle-ORC is converted in
9
Table 3 – Sustainability metrics for acetic acid
manufacturing.
Metrics Material Energy Water CO2e
kg/kg MJ/kg kg/kg kg/kg
Homogeneous 0.0354 2.16 0.82 0.17
Eco-efficient process 0.0248 0.78 0.38 0.038
Improvement, % 29.94 63.90 53.85 77.6
1360 kW (for G = 16.7 kg/s), while 2 MW in the Product-ORC in
386 kW (for G = 4.8 kg/s). Hence, 9 MW waste heat may be con-
verted in 1746 kW electricity with an overall thermal efficiency
W/Q of 19.4%.
The simulation shows that using safer hydrofluorocarbon
(HFC) fluids gives lower thermal efficiency, the operational
duty of the R-ORC dropping to about 5 MW. The reason is that
a temperature-crossing of TQ profiles takes place due to a
steeper slope of the liquid saturation (bubble points) curve
in the T-S plot. However, a total heat of about 7 MW is con-
verted in 1100 kW by R-1233ze (16% efficiency) and 1005 kW by
R-365fa (15% efficiency).
The conclusion of this section is that by steam genera-
tion, heat pumping and waste heat recovery by ORC the large
amount of heat available from the exothermic reaction can be
fully used for driving the separation section. The reboiler of the
dewatering column C-1 is covered by steam generation, while
the purification column C-2 driven by heat pumping with
electricity generated by applying ORC on wasted heat, oth-
erwise rejected in the environment. The reduction in energy
requirements has a strong impact on eco-efficiency that will
be quantified by evaluating the sustainability measures.
5. Sustainability analysis
A simple but efficient approach capturing the key feature of
sustainability in process design proposed by industrial experts
(Schwartz et al., 2002) is based on six metrics: material inten-
sity, energy intensity, water consumption, toxic emissions,
pollutant emissions, and greenhouse gas (GHG) emissions.
These reference output may be the unit of product, the rev-
enues (sales), or the value-added (VA). Note that lower values
mean better performance. Table 3 presents a comparative per-
formance of homogeneous catalyst process vs. eco-efficient
heterogeneous process.
(A) Material intensity expresses the mass of wasted materials
per unit of output.
For the base-case process (homogeneous catalyst) the raw
materials input is methanol 13,612 kg/h + CO 12,273 kg/h,
for an acetic acid production of 25,000 kg/h. The mate-
rial intensity is: wasted materials = 0.0354 kg/kg. In the
eco-efficient process (heterogeneous catalyst) the yield of
methanol rises from 0.98 to 0.99 and the yield of CO from
0.95 to 0.96. Therefore, the material intensity drops to
0.0248 kg/kg, which is 30% reduction.
(B) Energy intensity represents the primary energy consumed
per unit of output.
A difference should be observed between the energy devel-
oped by utility and the primary energy spent for produce
it. An efficiency of 80% can be assumed for steam genera-
tion by fuel combustion and 40% for electricity production
by modern power plants. Here is assumed that an electri-
cal kWh needs three times primary (thermal) energy. Key
elements of the energy balance are given in Figs. 3 and 4.
10 Chemical Engineering Research and Design 1 5 9 ( 2 0 2 0 ) 1–12
In the base case, the separation section requires 13.5 MW
steam from which 6.2 MW available as LP generated steam,
hence only 7.3 MW must be supplied as LP and MP steam.
The electricity consumption regards 1450 kW power for
the CO compression, plus 150 MW for pumping, mixing
and process control, hence a total of 1600 kW or 4.8 MW
thermal energy. To this one may add 0.26 MW required by
cooling-water conditioning via cooling towers (≈2% from
13 MW of C-1 and C-2 condensers) and 0.2 MW for refriger-
ation. The total used energy is then 12.6 MW. Taking an
uncertainty factor of 20%, the total load is 15 MW. The
energy intensity is then 2.16 MJ/kg.
For the eco-efficient process, the reaction section gener-
ates 5.4 MW as LP steam, which covers the reboiler of D-1,
while 9 MW of waste heat is converted into 1746 KW elec-
tricity. Column D-2 is fully driven by a heat pump that
needs 1160 kW electricity. In addition, 1450 kW is used
for CO compression and 150 kW for pumping and pro-
cess control. Hence the electricity consumption is 2760 kW,
but only 2760–1746 = 1014 kW should be imported, which
is equivalent to 3.1 MW of primary energy. The process
needs also 1 MW for feed preheating (units H-1 and H-2).
The cooling water conditioning referring to D-1 con-
denser is 0.02 × 10 = 0.2 MW, while for refrigeration 0.2 MW
is assumed. The total load for the reaction and separation
sections is 4.5 MW, which rises to 5.4 MW after apply-
ing 20% uncertainty. It results that energy intensity is
0.78 MJ/kg, or 64% reduction compared with the base-case.
(C) Water consumption expresses the amount of water used
per unit of output.
Water consumption should include process water that
should be treated because chemical contamination, losses
in vent and purge streams, as well as make-up water for
the cooling system. In this case we consider negligible the
first two sources. For the cooling water (CW) conditioning
via cooling tower is assumed. Turton et al. (2013) estimates
the water loss by evaporation as 1.83% from inflow for
10 ◦ C temperature range. For the base-case water cooling
is needed for the condensers of C-1 and C-2 since top tem-
peratures of 35 ◦ C. The cumulated duty of 13 MW results
in 1118 m3 /h CW, and water make-up of 20.5 m3 /h. Then
the water consumption is 0.82 kg/kg product.
In the eco-efficient process, water cooling is used only for
the condenser D-1 with a duty of 6 kW. Similarly, one gets
CW flow rate of 516 m3 /h and water make-up 9.4 m3 /h.
The freshwater consumption drops to 0.38 kg/kg, or 54%
reduction.
However, the freshwater consumption may be brought to
zero if air-cooling is adopted for taking out most of the
condenser duty (temperature range 94.7–35 ◦ C) but limit-
ing water-cooling in closed circuit (dry cooling) only at the
cold end.
(D) Greenhouse gas (GHG) emissions expresses the total GHG
emitted per unit of output.
GHG emissions cumulate the amounts of CO2 and equiv-
alent GHG gases released, as well as involved in the
production of heat and power, electricity, and cooling
water. The GHG estimations depend on the conversion
factors, in turn depending on the mix used for energy
production. Here we adopt the USA average value of
0.707 kg/h CO2 e per kwh (US Energy Information Agency,
2019). The CO2 conversion factor for steam is also variable.
A reasonable assumption is considering a primary energy
ratio electricity/steam of 3 that leads to 65 kg/h CO2 e
per GJ. With respect to water make-up the EPA GHG cal-
culator (www.epa.gov/p2) estimates 3300 kWh consumed
for 1 million gallons for treatment and distribution, or
0.951 kWh/m3 , which corresponds to 0.672 kg CO2 e/m3 .
For the base-case process the contributions are electricity
(16,000 × 0.707 = 1311), steam (12.6 × 3.6 × 65 = 2948), and
CW (20.5 × 0.672 = 13.8), leading to 4273 kg/h CO2 e in total
or 0.17 kg CO2 e/kg. For the eco-efficient process, the GHG
contributions are: electricity (1014 × 0.707 = 717), steam
(1 × 3.6 × 65 = 234), water (9.4 × 0.672 = 6.4), hence 958 kg/h
CO2 e in total or 0.038 kg CO2 e/kg (78% reduction in GHG
emissions mainly due to less steam).
(E) Toxic emissions include toxics and hazardous materials for
the operating personnel.
The toxicity metrics characterize the threats on health
of species leaving in the process outputs. The main exit
points of in gas streams in the process are VENT (Fig. 2)
and GAS (Fig. 3). Methyl iodide is the most toxic species,
very volatile and difficult to separate from large amount
of gas components, such as CO and CH4 . The absorption
in methanol can ensure over 99.8% recovery. However, the
exit gas stream may carry some methanol, which should
be recovered by deep cooling.
(F) Pollutant emissions express the amount of pollutants pro-
duced per unit of output.
The process requires paying attention to Health, Safety
and Environment aspects. These are well known in the
industrial practice and not treated here. According to
material balance got by simulation, the gaseous effluents
contain small amounts of unreacted CO, as well as CO2
and CH4 with traces of CH3 I, methyl acetate methanol and
other light organics. These are submitted to VOC treat-
ment by combustion. About 1000 kg/h CO2 leaves as plant
emissions. For the eco-efficient process utility this amount
is comparable with the CO2 emissions due to utilities.
Thus, the overall CO2e emissions may be estimated to
2000 kg/h or 0.08 kg/kg product, which is a very low value.
Table 3 shows a summary of the sustainability metrics.
The eco-efficient heterogeneous process shows superior sus-
tainability metrics compared to the homogeneous catalyst
process. A better yield leads to notable reduction in material
intensity. The complete use of the reaction heat for steam gen-
eration, heat pumping and ORC power generation, gives very
low energy intensity below 1 MJ/kg. The new process shows
low CO2 emissions as well (below 50 g/kg), and the consump-
tion of cooling water is also very low.
6. Conclusions
Acetic acid can be efficiently produced by a sustainable pro-
cess based on methanol carbonylation using a heterogeneous
rhodium/iridium catalyst. As the raw materials are available
from renewable feedstock (biogas or biomass) the acetic acid
produced by this method is a bio-based product.
This study proposed innovative process designs in which
the reaction and separation sections are highly integrated.
Since the highly exothermic reaction delivers a large amount
of energy, the focus is achieving low-energy consumption, as
well as superior sustainability metrics for material and energy
intensity, water consumption and GHG emissions.
A first innovative feature in this study is getting zero steam
consumption for driving the separation section. In the het-
 Chemical Engineering Research and Design 1 5 9 ( 2 0 2 0 ) 1–12
erogeneous process this reduces to two columns: dewatering
and acetic acid purification. Since from VLE viewpoint the sep-
aration of acetic acid/water is difficult, both columns need
considerable energy. The LP steam generated in the reaction
section covers the reboiler duty of the dewatering column.
Furthermore, no steam is needed for the purification column
by applying heat pumping by vapor compression using water
as thermal agent. The principle is that the energy available
in condenser at about 120 ◦ C can be upgraded as steam for
reboiler heating at 150 ◦ C and 4.8 bar by using vapor compres-
sion.
A second innovative feature is that the power for heat
pumping is ensured by an Organic Rankine Cycle engine that
upgrades waste heat available in the reaction section from
the recycle and product coolers. Among several candidates
the isobutane appears as the most suitable ORC fluid, as it
gives full waste heat recovery. Additionally, a large part for
the energy for CO compression is covered too.
The overall result is a sustainable eco-efficient process with
very low energy intensity (below 1 MJ/kg) and low GHG emis-
sions (40 g CO2e/kg), as well as nearly zero water consumption.
Conflict of interest
None declared.
Acknowledgement
Financial support of the European Commission through the
European Regional Development Fund and of the Roma-
nian state budget, under the grant agreement POC P-37-449
(acronym ASPiRE) is gratefully acknowledged. AAK thank-
fully acknowledges the Royal Society Wolfson Research Merit
Award (No. WM170003).
Appendix A. Supplementary data
Supplementary material related to this article can be
found, in the online version, at https://doi.org/10.1016/
j.cherd.2020.04.013.
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