Clean Technologies and Environmental Policy

https://doi.org/10.1007/s10098-019-01693-1

ORIGINAL PAPER

Eco‑efficiency and techno‑economic analysis for maleic anhydride

manufacturing processes
Patrick V. Mangili1 · Pedro G. Junqueira1 · Lizandro S. Santos1 · Diego M. Prata1

Received: 27 October 2018 / Accepted: 4 April 2019

© Springer-Verlag GmbH Germany, part of Springer Nature 2019

Abstract
Maleic anhydride may be obtained from different technological routes, being the selective oxidation of benzene and oxida-
tion of butane the only ones that are currently in operation and, hence, represent competitive alternatives. In this paper, the
said technologies are compared with regard to their economics and ecological performances in order to assert which one
corresponds to the cleanest technology. The economics of each process was estimated on the basis of their respective cash
flows, while the environmental comparison was carried out through the Eco-efficiency Comparison Index method by estimat-
ing six different categories of eco-indicators and seven life cycle metrics. To the best of our knowledge, such technologies
have not been compared in terms of a joint evaluation of life cycle and eco-efficiency metrics, let alone considering the
design of their respective utility plants. Finally, a sensitivity analysis was performed in order to analyze how the heuristic
parameters for the utility plants considered in this work affect the estimation of the said indicators. The butane technology
was shown to be more sustainable than the benzene process, since it was approximately 72% more profitable and 38% more
eco-efficient than the latter.
Graphical abstract

Keywords  Cash flow · Eco-efficiency · Maleic anhydride · Process simulation · Utility plants · Waste reduction

Extended author information available on the last page of the article

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Vol.:(0123456789)
 P. V. Mangili et al.

List of symbols V3 Vessel 3

A Heat transfer area 𝜈̇ bfw Boiler feed water volumetric flow rate
C1 Column 1 𝜈̇ cw Cooling water volumetric flow rate
C2 Column 2 𝜈̇ hps High-pressure steam volumetric flow rate
Cbenzene Benzene composition 𝜈̇ lps Low-pressure steam volumetric flow rate
Cbutene n-Butane composition 𝜈̇ mps Medium-pressure steam volumetric flow rate
CMAN Maleic anhydride composition xbenzene Benzene molar fraction
Coxygen Oxygen composition xcumene Cumene molar fraction
Di Inner diameter xDIPB p-Diisopropyl benzene molar fraction
E1 Cooler 1
Greek symbols
E2 Cooler 2
α Cooling water loss factor (process)
E3 Cooler 3
ß Cooling water loss factor (cooling tower)
E4 Cooler 4
γ Cooling water loss factor (blowdown)
EC CO2 emissions eco-indicator
δ Cooling water make-up
Ecomb Total thermal energy from combustion
ε Steam loss factor (condensate losses)
consumption
ζ Steam loss factor (boiler blowdown)
EE Energy use eco-indicator
η Steam loss factor (feed water treatment)
EF Fuel consumption eco-indicator
θ Feed water make-up
Eind Total electricity consumption
Emcomb Total ­CO2 emissions due to thermal energy Abbreviations
consumption ATP Aquatic toxicity potential
Emfug Total ­CO2 emissions due burning off-gases in bfw Boiler feed water
the flare cw Cooling water
Emind Total ­CO2 emissions due to electricity ECI Eco-efficiency Comparison Index
consumption EPA US Environmental Protection Agency
ERM Raw material consumption eco-indicator GWP Global warming potential
EW Water consumption eco-indicator hps High-pressure steam
EWW Wastewater generation eco-indicator HTPI Human toxicity potential by ingestion
f Temperature difference factor HTPE Human toxicity potential by inhalation
F1 Fired heater IPCC Intergovernmental Panel on Climate Change
H Pump head LCA Lice cycle assessment
H1 Heater 1 lps Low-pressure steam
H2 Heater 2 MAN Maleic anhydride
H3 Heater 3 MOC Material of construction
K1 Compressor mps Medium-pressure steam
L Vessel length ng Natural gas
ṁMAN Maleic anhydride mass flow rate NPV Net present value
ṁNG Natural gas mass flow rate NRTL Non-random two liquid
ṁRM Raw material mass flow rate PCOP Photochemical oxidation potential
P1 Pump 1 PEI Potential environmental impact
P2 Pump 2 TTP Terrestrial toxicity potential
P3 Pump 3 UNCTAD United Nations Conference on Trade and
P4 Pump 4 Development
P5 Pump 5 WAR​ Waste reduction
P6 Pump 6
pB Partial pressure of butane
Pc Compressor power Introduction
pM Partial pressure of MAN
Q Energy requirement Maleic anhydride (MAN) is a chemical product associated
R1 Tubular reactor with a broad market due to its application as an intermediate
V̇ Volumetric flow rate for the production of unsaturated polyester resins, polymers,
V1 Vessel 1 vernices and paints, among several other commodities. The
V2 Vessel 2 global MAN market was estimated at approximately 1.8

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Eco‑efficiency and techno‑economic analysis for maleic anhydride manufacturing processes
million tons in 2017 and is expected to reach 2.2 million
tons by 2023, at an estimated compound annual growth rate
of 3.69%, being the region of Asia–Pacific accountable for
the largest market (Mordor Intelligence 2018). MAN can be
manufactured from different technological routes, namely
the selective conversion of furfural (Alonso-Fagúndez et al.
2017), catalytic oxidation of butenes (Matar and Hacth
2000), as side product from phthalic anhydride production
(Matar and Hacth 2000), oxidation of levulinic acid (Chatzi-
dimitriou and Bond 2015), selective oxidation of benzene
(Turton et al. 2010) and oxidation of n-butane (Sharma et al.
1991). The furfural and levulinic acid routes are still under
development and have not yet been established as competi-
tive process alternatives. The phthalic anhydride-recovered
MAN technology, in turn, has very low expressiveness in
the global production demand, whereas there is no butene-
based process currently in operation (Felthouse et al. 2001).
Although old-fashioned, the benzene route is still used by
some companies in Asia and the Far East, while the butane
route corresponds to a most recent alternative since it not
only has lower costs but also is less aggressive to the envi-
ronment (Rase 2010).
This paper aims to compare the economics and environ-
mental performances of both technologies for MAN manu-
facture. As far as we know, a detailed comparison of both
processes with regard to their eco-efficiency, combined with
life cycle burdens, has not been made, let alone considering
their respective utility plants. Eco-efficiency relates the pro-
cess’ environmental impacts to its economic performance.
Such an analysis is generally performed on the basis of the
quantitative evaluation of the process eco-indicators, which
are represented by a relationship between an environmen-
tal variable (e.g., air emissions) and an economic variable
(e.g., production rate or net profit) (Mangili et al. 2018a). In
this regard, raw material consumption, fuel consumption,
energy use, C­ O2 emissions, water consumption and waste-
water generation were chosen as eco-indicators. Other envi-
ronmental metrics considered in the ecological performance
assessment could be calculated through the waste reduction
(WAR) algorithm, namely photochemical oxidation potential
(PCOP), acidification potential (AP), ozone depletion poten-
tial (ODP), human toxicity potential by ingestion (HTPI),
human toxicity potential by exposure (HTPE), aquatic toxic-
ity potential (ATP) and terrestrial toxicity potential (TTP).
The aforementioned indicators were then normalized and
grouped through the Eco-efficiency Comparison Index (ECI)
method (Pereira et al. 2018). On the other hand, the eco-
nomic analysis was performed by evaluating cash flows of
the respective technologies in order to provide the scientific
community with a more complete comparison.
In the next section, a brief revision regarding the maleic
anhydride manufacturing processes is presented. In “Envi-
ronmental analysis” section, we describe the method for
calculating the environmental indicators, whereas the
assumptions to estimate the economics are provided in
“Economic analysis” section. In “Results and discussion”
section, we discuss the methodology required to establish
the comparison between both technologies, while in “Sen-
sitivity analysis” section a sensitivity analysis is carried out
to demonstrate the relevance of design parameters and utility
plant heuristics in estimating the economics and environ-
mental impacts of both processes. Finally, in “Conclusion”
section, we summarize the main results and provide some
suggestions for future works.
Maleic anhydride production
As previously mentioned, maleic anhydride may be obtained
from different technological routes, being the benzene-based
and butane-based designs the only ones that are currently
in operation and, hence, represent competitive alternatives.
The selective oxidation of benzene induces the loss of two
carbon atoms, thus decreasing mass yield and resulting in
the formation of heavy by-products such as phthalic anhy-
dride and benzoquinone. In the oxidation of n-butane, in
turn, lighter by-products such as acetic and formic acids are
obtained (Centi et al. 2001).
Both technologies also differ from each other in terms of
operating conditions that depend on several factors such as
feedstock conditions, process design. The reactor type may
be of fixed, fluidized or moving bed. MAN recovery can be
performed in either aqueous or organic phase, whereas its
purification may be carried out through either azeotropic
distillation or thin-film evaporation (Baerns 2004).
The benzene and butane technologies for MAN manu-
facture studied in this paper were originally proposed by
Turton et al. (2010) and Frank (1975), respectively. Both
processes were simulated in ­UniSim® Design Suite R390.1,
so we could obtain the required data to estimate the costs and
determine their eco-indicators. For the benzene technology,
the same inlet feed conditions and equipment parameters
used by Turton et al. (2010) were considered. The butane
technology design provided by Frank (1975) was scaled up
in order to match both plant capacities and thus allow a fair
comparison regarding the processes’ economics. Both tech-
nologies were simulated under steady-state conditions by
using the non-random two liquid (NRTL) thermodynamic
model (enthalpy, phase equilibrium, etc.).
Benzene technology
According to Turton et  al. (2010), MAN production
from oxidation of benzene is achieved by using a vana-
dium–molybdenum catalyst and may not exceed 650 °C in
order to prevent sintering, as described by Eq. 1.
13

C6 H6 + 4.5O2 → C4 H2 O3 + 2CO2 + 2H2 O
(1)
benzene MAN
Since the reaction is highly exothermic, an increase in the
temperature may result in the total oxidation of the feedstock
and further oxidation of MAN, as described by Eqs. 2 and
3, respectively.
C6 H6 + 7.5O2 → 6CO2 + 3H2 O (2)
C4 H2 O3 + 3O2 → 4CO2 + H2 O (3)
If lower temperatures are achieved, benzene may be oxi-
dized to quinone, as in Eq. 4.
C6 H6 + 1.5O2 → C6 H4 O2 + 2H2 O
(4)
quinone
The process flow diagram for the MAN production tech-
nology via benzene oxidation is illustrated in Fig. 1, which
shows the results obtained by simulation. In the schematic,
cw, bfw, lps, hps and ng stand for cooling water, boiler feed
water, low-pressure steam, high-pressure steam and natural
gas, respectively.
Fresh benzene at 42.3 kmol/h is pressurized and mixed
with compressed air from compressor K1 at 2790.0 kmol/h.
The resulting mixture is heated to 460.0 °C prior to being fed
to a tubular reactor R1, composed of 12,100 catalyst-filled
tubes with 6 m length and 2.5 cm diameter (reaction vol-
ume of 37.7 m3), in which the reactions described by Eqs. 1
Fig. 1  MAN production process via oxidation of benzene
13
P. V. Mangili et al.
to 4 take place, whose kinetics are presented in Table 1.
Assuming a catalyst bulk density of 900 kg/m3 (Westerink
and Westerterp 1988), the catalyst load is 33,930 kg. One
should note that R1 is cooled through a molten salt-cool-
ing system, which is integrated to distillation column C2’s
reboiler and generates hps to be interpreted as credit in the
economic assessment. Such a system was not simulated due
to the software limitations regarding the simulation of solids.
However, since Turton et al. (2010) provided the informa-
tion on Pump P2 and cooler E1, such equipment was taken
into account in both economic and environmental analyses.
The reactor product (containing MAN, side products
and unreacted reagents), at 608.0 °C and 2825.3 kmol/h,
is cooled down to 260.0 °C and fed to the bottom of an
absorption column C1 having 14 sieve plates plus full-reflux
condenser and reboiler. A dibutyl phthalate make-up stream,
Table 1  Reaction kinetics for the benzene technology
Reaction Rate expression (Turton et al. 2010)
Reaction 1—Eq. 1 r1= 7.70 × 106 exp(− 105,198/RT) Cbenzene
Reaction 2—Eq. 2 r2= 2.33 × 104 exp(− 89,659/RT) Cbenzene
Reaction 3—Eq. 3 r3= 7.20 × 105 exp(− 113,591RT) CMAN
Reaction 4—Eq. 4 r4= 6.31 × 107 exp(− 124,892/RT) Cbenzene
Cbenzene: benzene composition. CMAN: MAN composition. Composi-
tion units: kmol  m−3. Reaction rate units: kmol  m−3  s−1. Activation
energy units: kJ kmol−1. R: 8.314 kJ kmol−1 K
Eco‑efficiency and techno‑economic analysis for maleic anhydride manufacturing processes

used as solvent for recovering MAN, is fed at 0.1 kmol/h
to the top of C1. The absorber’s top product consisting of
unreacted components and combustion gases is obtained at
260.0 °C and sent to the flare at 2797.6 kmol/h. C1’s bot-
tom product containing solvent and recovered MAN are fed
to the 27th plate of a 42 plate distillation column C2, from
which MAN is obtained as distillate at 27.6 kmol/h with a
purity of 94.7 mol%. C2’s bottom product, comprised of
dibutyl phthalate, is recycled at 500.0 kmol/h to the top of
the absorption column.
The NRTL model parameters for the pairs predicted by the
software are given in Table 2, while Fig. 2 shows the ternary
diagram and residue curve map of the MAN–water–dibutyl
phthalate mixture at 0.8 bar. Dibutyl phthalate (DB-PHTH)
is used as solvent to extract MAN from water, forming a two-
phase liquid region which, through distillation, separates water
at the top section (raffinate) from MAN/solvent at the bottom
section (extract). In fact, we note from Fig. 2a that, at 0.8 bar,
all mixtures of MAN and DB-PHTH are single phase and,
therefore, only water–DB-PHTH mixtures present two-phase
behavior. From Fig. 2b, in turn, we see that water has the high-
est boiling rate, whereas DH-PHTH has the lowest boiling
rate. Hence, during distillation, the liquid is depleted of water
and becomes richer in dibutyl phthalate, carrying MAN along
with it.
Butane technology
The n-butane route is carried out using a vanadium phosphorus
oxide catalyst, according to Eq. 5, at temperatures kept below
500 °C in order to prevent catalyst deactivation (Ebner et al.
1999). The butane/oxygen concentration ratio must be kept
between 1.4 and 1.6% for safety purposes, since the butane’s
flammability limit may increase rapidly when the temperature
increases. Moreover, in order to avoid excessive loss of unre-
acted butane, a 99.5% purity oxygen feed is recommended
(Baerns 2004).
C4 H10 + 3.5O2 → C4 H2 O3 + 4H2 O
(5)
butane MAN
Similarly to the benzene route, an increase in the tempera-
ture may also result in further oxidation of MAN (as shown
in Eq. 3) and total oxidation of the feedstock, as described by
Eq. 6.
C4 H10 + 6.5O2 → 4CO2 + 5H2 O (6)

Table 2  NRTL model Benzene Oxygen MAN Water CO2 DB-PHTH

parameters for the benzene
route Benzene – − 12.163 762.556 4005.180 69.676 − 444.421
Oxygen 1480.016 – 2886.061 1863.905 0.000 1282.441
MAN 387.981 − 12.163 – 0.000 69.676 0.000
Water 3088.443 − 12.163 0.000 – 69.676 0.000
CO2 − 3918.325 0.000 − 2805.650 − 2941.997 – − 3986.726
DB-PHTH 1248.170 0.000 − 12.163 0.000 69.676 –

Fig. 2  Ternary equilibrium for the benzene process

13
 P. V. Mangili et al.

The process flow diagram for the MAN production tech- Table 3  Reaction kinetics for the butane technology
nology via n-butane oxidation is illustrated in Fig. 3, which Reaction Rate expression (Sharma et al. 1991)
shows the results obtained by simulation. In the schematic,
mps stands for medium-pressure steam. Reaction 3—Eq. 3
( ( ))
−155000 1 1
2.9×10−6 exp R T
− 673 ×pM
r3 =
Fresh n-butane at 70.0 kmol/h is heated to 25.0 °C and
2
(1+310pM )
mixed with air at 820.2 kmol/h and a compressed gas recy- Reaction 4—Eq. 5
( ( ))
−93100 1 1
9.6×10−7 exp R T
− 673 ×p0.54
B
r4 =
cle stream from the absorption section, at 78.3 kmol/h. The 1+310pM

resulting mixture is heated to 420.0 °C prior to being fed Reaction 5—Eq. 6 r5 = 1.5 × 10−7 exp
(
−93100
(
1
− 1
))
× p0.54
to a tubular reactor R1 having 15,000 catalyst-filled tubes R T 673 B

of 2.5 cm diameter and 4.9 m length (reaction volume of
37.0 m3), in which the reactions described by Eqs. 3, 5 and
6 take place, whose kinetics were retrieved from Sharma
et al. (1991)’s work and are presented in Table 3. Assum-
ing a catalyst bulk density of 1000 kg/m3 (Musa 2016), the
catalyst load is 37,000 kg. Here again we can observe that
R1 is cooled through a salt-cooling system, which was not
simulated. However, since the simulation provided the value
of the required energy to cool down the reactor, we used the
said value to estimate the amount of bfw used to cool the
molten salt and consequently generate hps which, similarly
to the benzene technology, was considered as credit in the
economic analysis. In a matter of operational importance,
pM: partial pressure of MAN. pB: partial pressure of butane. Partial
pressure units: atm. Reaction rate units: kmol  m−3  s−1. Activation
energy units: kJ kmol−1. R: 8.314 kJ kmol−1 K
the temperature difference between the salt bath and the
reaction system may not exceed 80 °C in order to prevent
catalyst degradation (Ebner et al. 1999).
The reactor product (containing MAN and unreacted
reagents), at 470.0 °C and 998.7 kmol/h, is cooled down
to 65.3 °C after passing through a series of three coolers
prior to being sent to a flash vessel V1. MAN is obtained
as V1’s bottom product at 98.6 kmol/h with a purity of

Fig. 3  MAN production process via oxidation of n-butane

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Eco‑efficiency and techno‑economic analysis for maleic anhydride manufacturing processes

70.0 mol% MAN and sent to a distillation column C2. In Utilities plant

this paper, we used UniSim’s shortcut method to perform
a preliminary design of the said column and obtain the
required number of stages, optimal feed section and reflux
ratio. Such results were subsequently used in the simula-
tion of a rigorous distillation model, from which water is
retrieved as distillate and recycled to the absorption col-
umn at 68.6 kmol/h and MAN is obtained at 30.0 kmol/h at
the bottom with a purity of 99.9 mol%. The C2’s composi-
tion profiles are shown in Fig. 4.
V1’s top product, containing unreacted components and
combustion gases, is fed at 900.1 kmol/h to the bottom of
an absorption column C1, whose top section is fed by a
water make-up stream at 76.6 kmol/h. C1’s bottom product
is then divided into a water recycle stream, which is sent
back at 100.0 kmol/h to the seventh stage of the absorber,
and a maleic acid waste stream, which is obtained at
172.2  kmol/h containing about 99.5  mol% water. C1’s
top product, in turn, is divided into a gas recycle stream,
which is pressurized in compressor K1 and sent back at
78.3 kmol/h to the feed section, and an off-gas stream,
obtained at 725.3 kmol/h and sent to the flare.
The NRTL model parameters for the pairs predicted by
the software are given in Table 4. As shown in Fig. 5, all
separations may be deemed fairly easy to be performed
by distillation since the curves are quite fat, which thus
require low number of trays and reflux ratios.
The utilities plant was designed to allow a more realistic esti-
mation of the water consumption and wastewater generation
from both technologies. Its flow sheet is illustrated in Fig. 6,
in which 𝜈̇ cw, 𝜈̇ bfw, 𝜈̇ lps, 𝜈̇ mps and 𝜈̇ hps correspond to the total
volumetric flow rate of cooling water, boiler feed water, low-
pressure steam, medium-pressure steam and high-pressure
steam, respectively, whereas α, ß and γ are the cooling water
loss factors due to the process, cooling tower and blowdown,
respectively; and ε, ζ and η are the steam loss factors associ-
ated with the process (condensate losses), boiler blowdown
and feed water treatment, respectively. One should note that
δ and θ represent the cooling water and steam generation
systems’ make-up, respectively. Therefore, δ corresponds
to α + ß + γ, while θ corresponds to ε + ζ + η.
Environmental analysis
Numerous studies related to the evaluation of the environ-
mental impacts from maleic anhydride production processes
are available in the literature. The US Environmental Pro-
tection Agency (EPA 1980) analyzed the benzene emis-
sions from process vents of MAN plants and established a
National Emission Standard for such an air pollutant. Chen
and Shonnard (2004), in turn, estimated the C­ O2 emission
rates for both processes on the basis of the EPA emission

Fig. 4  Distillation column C2’s

mol composition profile

Table 4  NRTL model n-Butane Oxygen MAN Water CO2 Nitrogen

parameters for the butane route
n-Butane – − 12.163 2707.386 3525.34 69.676 21.508
Oxygen 1200.414 – 2886.061 1863.905 0.000 0.000
MAN 1862.748 − 12.163 – 0.000 69.676 20.032
Water 3796.107 − 12.163 0.000 – − 183.691 20.032
CO2 − 3986.46 0.000 − 2805.65 676.278 – 0.000
Nitrogen 3.468 0.000 2003.572 602.209 0.000 –

13
 P. V. Mangili et al.

Fig. 5  Phase equilibrium for the butane process

Fig. 6  Utilities plant flow sheet

13
Eco‑efficiency and techno‑economic analysis for maleic anhydride manufacturing processes
factors. Fermeglia et al. (2009) applied the waste reduction
(WAR) algorithm to compare the benzene and butane tech-
nologies in terms of six life cycle assessment (LCA) indica-
tors, namely global warming potential (GWP), photochemi-
cal oxidation potential (PCOP), acidification potential (AP),
ozone depletion potential (ODP), human toxicity potential
by ingestion (HTPI), human toxicity potential by exposure
(HTPE), aquatic toxicity potential (ATP) and terrestrial tox-
icity potential (TTP). Mangili et al. (2018b) calculated the
­CO2 emissions eco-indicators of both technologies on the
basis of the United Nations Conference on Trade and Devel-
opment (UNCTAD 2004) and Intergovernmental Panel on
Climate Change’s guidelines (IPCC 2006).
Nevertheless, to the best of our knowledge, MAN manu-
facturing technologies have only been studied in terms of
either single environmental indicators or LCA indicators.
The determination of a single indicator is not sufficient to
assert which technology has the highest environmental per-
formance, since most indicators are calculated independently
of one another. In addition, LCA indicators do not take the
product value into consideration, which may represent a
tricky evaluation when the process economics differ sig-
nificantly from each other. In this paper, we compared the
ecological efficiencies of the benzene and butane technolo-
gies not only in terms of the aforementioned LCA indices
(i.e., HTPI, HTPE, TTP, ATP, ODP, PCOP and AP) but also
with regard to eco-efficiency indicators (i.e., raw materials
and fuel consumption, energy use, ­CO2 emissions, water
consumption and wastewater generation). The LCA metrics
are expressed in terms of potential environmental impact
(PEI) per kg of MAN and were calculated with the aid of
the WAR tool, whereas the eco-indicators were determined
through their respective formulae presented in Table 5. One
should note that the GWP index has not been considered in
this study since we have already estimated the ­CO2 release
Table 5  Eco-indicators equations
Indicator Formula Unit
Raw material consumption ṁ RM tRM/tMAN
ERM = ṁ MAN
Fuel consumption EF =
ṁ NG tNG/tMAN
ṁ MAN
Energy use EE =
Eind +Ecomb GJ/tMAN
ṁ MAN
CO2 emissions EC =
Emind +Emcomb +Emfug tCO2/tMAN
ṁ MAN
Water consumption EW = 𝛿+𝜃 m3w/tMAN
ṁ MAN
Wastewater generation EWW = 𝛾+𝜁 +𝜀 m3ef/tMAN
ṁ MAN
ṁ RM: total mass flow rate of raw materials. ṁ MAN: total mass flow rate
of MAN product. ṁ NG: total mass flow rate of natural gas consumed
by fuel consumers. Eind: total electricity consumed by pumps and
compressors. Ecomb: total thermal energy consumed by heaters and
reboilers. ­Emind: total ­CO2 emissions due to electricity consumption.
­Emcomb: total ­CO2 emissions due to thermal energy consumption.
­Emfug: total ­CO2 emissions due to burning gases in the flare
on the basis of the emission factors for Brazil (considering
utility plants, electricity, flare emissions, etc.), which repre-
sents a more complete analysis.
The calculation of the fuel consumption was performed
by assuming that only the hypothetical utility plant’s boiler
and the fired heaters are fuel (natural gas) consumers oper-
ating with 80% thermal efficiency (EPA 2008; Trinks et al.
2004). The energy use and ­CO2 emission indicators were
determined through the guidelines provided by Mangili
et al. (2018a) by assuming that pumps and compressors
operate with electricity at 75% efficiency, whereas heaters
and reboilers were interpreted to operate with steam gener-
ated in the utility plant’s boiler. The same conversion fac-
tors for electricity (0.0227 tCO2 ∕GJ ) and natural gas thermal
energy (0.0561 tCO2 ∕GJ ) to carbon dioxide emissions were
used. The fugitive emissions (flare) were estimated by con-
sidering total combustion of gases. The water consumption
eco-indicators were also determined according to Mangili
et al. (2018a)’s work. Cooling water supply and return tem-
peratures were assumed to be 30 °C and 45 °C, respectively
(Turton et al. 2010). Boiler feed water supply temperature
was considered to be 130 °C (Tvedt and Holloway 1997). α
and ß together were interpreted as 3% (Seider et al. 2008)
of v̇cw, whereas γ was assumed to be 0.3% (Smith 2005) of
𝜈̇ cw. ζ and η were together interpreted as 3% of 𝜈̇ bfw, while
ε was assumed to be 20% (Seider et al. 2008) of the total
steam flow rate ( 𝜈̇ lps + 𝜈̇ mps + 𝜈̇ ̇hps). The low-, medium- and
high-pressure steams conditions used here were taken from
Seider et al. (2008)’s book and are shown in Table 6. Steam
used as heating source was assumed to exit the heat exchang-
ers as saturated liquid.
The ecological performances of the MAN production
technologies were then quantitatively compared by means of
the Eco-efficiency Comparison Index (ECI) method, origi-
nally proposed by Pereira et al. (2018). The ECI method is
intended to jointly evaluate process indicators in order to
define the most eco-efficient. Such a methodology was used
by Mangili et al. (2018a) to compare three acetone–metha-
nol separation technologies in terms of their environmental
performance and proved to be functional for such a purpose.
Junqueira et al. (2018) also applied the ECI approach for
comparing six cumene manufacturing processes in terms
of both environmental and economic aspects. Mangili and
Prata (2019), in turn, based their study on such a method in
Table 6  Steam parameters
Steam Supply temperature Pressure (bar)
(°C)
Low pressure 135.0 3.10
Medium pressure 185.5 11.35
High pressure 254.0 42.38
13
 P. V. Mangili et al.

order to improve different butyl acetate production plants Table 8. A Plant Cost Index of 616.4 was assumed (Access
with regard to ecological, economic and safety indices. The Intelligence LLC 2019).
same procedure applied by the said references was used in It is worth mentioning that both reactors were interpreted
this study. as heat exchangers and that flash/reflux drums were consid-
ered to be horizontal pressure vessels (Seider et al. 2008).
Furthermore, we assumed that the catalyst purchase is a
Economic analysis one-time investment (capital cost) having a price of $30/kg
(Godefroy et al. 2009). The depreciable capital costs were
The economics of both technologies was determined by then estimated by taking into account the general site expen-
estimating their fixed capital investment (FCI) and produc- ditures disclosed in Table 9.
tion expenditures and subsequently carrying out a cash flow Regarding the production costs, benzene and n-butane
analysis. The capital costs for each process were calculated were priced at 3.45 $/gal (ICIS—Independent Chemical
on the basis of the equipment cost equations given by Seider Information System 2018) and 0.65 $/kg (The Chemical
et al. (2008)’s book and are presented in Table 7 by taking Company 2016), respectively, while MAN was priced at
into consideration the equipment specifications provided 0.75 $/lb (ICIS 2018) and maleic acid was priced at 2.165
by the reference authors and simulation results, as given in $/ton (ICIS 2013). Labor costs were assumed to be 50,000
$/operator/year, with 3 shifts and 5 operators per shift. High-
pressure steam credit was 12.33 $/GJ. Electricity and cool-
Table 7  Equipment cost basis ing water were assumed to be 16.80 $/GJ and 1.04 $/GJ,
Equipment Cost equation respectively. Medium- and low-pressure steams were priced
at 14.83 $/GJ and 7.78 $/GJ, respectively, while natural gas
Pumps exp{9.7171 − 0.6019[ln( was assumed to be priced at 4.24 $/GJ. All utility costs were
V̇(H)0.5)] + 0.0519[ln(V̇
(H)0.5)]2} retrieved from Turton et al. (2010), with the exception of the
Compressors exp{7.5800 + 0.8000[ln(Pc)]} natural gas price, which was given by The Chemical Com-
Heat exchangers exp{11.667 − 0.8709[ln(A)]  pany (2016). Other escalation parameters used to estimate
+ 0.09005[ln(A)]2} the production costs are shown in Table 10.
Columns/vessels 361.8(Di)0.7396(L)0.70684 The cash flow analysis was performed by considering that
Fired heaters exp{7.5800 + 0.8000[ln(Q)]} both processes were redesigned, since MAN production pro-
Cooling tower 164fQ0.61 cesses have already been implemented, with a digital control
Boiler 0.36Q0.77 structure and installed on grass-root sites in Brazil. Their
economic life was assumed to be of 13 years with 1 year
V̇  ̇: volumetric flow rate (gal/min). H: pump head (ft). Pc: power con- period of design and 2 years of construction. A 10% straight
sumed (HP). A: heat transfer area (­ft2). Di: inner diameter (in). L:
length (in). Q: energy requirement (Btu/h), f: temperature difference line depreciation method (PwC—PricewaterhouseCoop-
factor ers 2018) was considered along with a 6.90% interest rate

Table 8  Equipment design parameters

Equipment Parameters

Pumps Centrifugal, MOC stainless steel, 75% efficiency

Compressors Centrifugal, MOC carbon steel, 75% efficiency
Coolers/condensers Shell and tube, floating head, MOC stainless steel
Heaters/reboilers Kettle type, MOC stainless steel
Reactor R1 (benzene) Tubular, 12,100 tubes with 2.5 cm diameter and 6 m length, 900 kg/m3 catalyst bulk density, MOC stainless steel
Reactor R1 (butane) Tubular, 15,000 tubes with 2.5- cm diameter and 4.9 m length, 1000 kg/m3 catalyst bulk density, MOC stainless steel
Absorber C1 (benzene) 14 sieve trays with 4.1 m diameter, 0.61-m tray spacing, 0.21 reflux ratio, MOC nickel-based alloy
Column C2 (benzene) 42 sieve trays with 1.0 m diameter, 0.40-m tray spacing, 1.2 reflux ratio, MOC nickel-based alloy
Absorber C1 (butane) 43 sieve trays with 1.83 m diameter, 0.5-m tray spacing, 0.67 reflux ratio, MOC nickel-based alloy
Column C2 (butane) 8 sieve trays with 0.61 m diameter, 0.55-m tray spacing, 0.07 reflux ratio, MOC nickel-based alloy
Fired heaters 80% thermal efficiency, MOC low alloy
Cooling towers 15 °C temperature range, MOC carbon steel
Boilers 80% thermal efficiency, MOC carbon steel

MOC: material of construction

13
Eco‑efficiency and techno‑economic analysis for maleic anhydride manufacturing processes

Table 9  Site expenditures
Basis Parameter Value References

Inside battery limits (ISBL) Process equipment costs 30% of FCI Peters et al. (2003)
Bulk items (piping, instruments, etc.) 25% of FCI
Outside battery limits (OSBL) Utility plant equipment costs 20% of FCI Towler and Sinnott (2008)
Warehouse, lighting, waste handling, etc. 40% of ISBL
Other Land development costs 1% of FCI Silla (2003)
Site development Civil works (roads, buildings, ditches, etc.) 5% of FCI Sinnott (2005)
Field expenses (canteens, overtime, etc.)
Miscellaneous Agent fees, import duties, etc. 5% of FCI Sinnott (2005)
Design and engineering Administration, inspection, etc. 7% of FCI Peters et al. (2003)
General Contingency 7% of FCI Peters et al. (2003)
Working capital 5% of FCI Towler and Sinnott (2008)
Location factor Brazil 1.14 Towler and Sinnott (2008)

Table 10  General production expenses

Basis Parameter Value References

Fixed costs (FC) Maintenance 5% of FCI Sinnott (2005)

Overheads 5% of labor
Insurance, license fees and royalties 2% of FCI
Variable costs (VC) Personal protective equipment, cleaning materials, 1% of maintenance Sinnott (2005)
charts and accessories, etc.
Other Research and development 1% of revenue Towler and Sinnott (2008)
Sales and marketing 2% of FC + VC
Human resources, accounting, finance, etc. 35% of labor

(Banco Central do Brasil 2018) and 34% tax rate (Deloitte
2017).
Results and discussion
Environmental analysis
Table 11 shows the results for the LCA indices obtained
through the WAR tool and the eco-indicators calculated with
the formulae from Table 5. We can verify that the butane
technology has the lowest eco-indicators for all categories
evaluated, except for the raw material consumption, water
consumption and PCOP indices. The higher water consump-
tion is mainly due to the feed water requirement in the first
column, whereas, as in accordance with Fermeglia et al.
(2009)’s work, the highest photochemical oxidation potential
of the butane route may be associated with the PCOP of such
a feedstock (0.8425), which is higher than the benzene’s
(0.3884). On the other hand, disregarding the presence of
the acrylic acid considered by the said reference, the sum
of all other LCA impact categories of the former is lower
than the latter’s.
With regard to C ­ O 2 emissions, Chen and Shonnard
(2004) found that, in fact, the benzene alternative has
a higher emission rate (2.06 tCO2/t MAN) than the butane
technology’s (1.21 tCO2/tMAN). One should note, however,
that the results found by the said reference differ from our
results since the authors considered different parameters
for estimating the C ­ O2 emissions (e.g., emission factors,
waste management, etc.). In spite of this, we note that the
benzene process emits almost twice as much ­CO2 as the
n-butane route.
The contributions of each equipment to the respective
eco-indicators of both processes are shown in Fig. 7. We
can note that the fired heaters F1 and the utility boilers have
the higher energy requirements when compared to other
equipment in both technologies. Also, it is evident that the
­CO2 emissions are mainly due to the off-gases burned in the
flare, which corresponds to approximately 65% and 49% of
the total emissions in the benzene and butane processes,
respectively. In terms of water consumption, we see that
column C1’s condenser has the highest water demand in
both scenarios.
The indicators shown in Table 11 were normalized by
dividing them by the highest value present in the same

13
 P. V. Mangili et al.

Table 11  Environmental Process Benzene technology Butane technology

indicator results
Production rate, t­MAN/h 2.44 2.20
Raw materials eco-indicator, ­tRM/tMAN 1.36 1.41
Fuel consumption eco-indicator, t­fuel/tMAN 0.53 0.32
Energy use eco-indicator, GJ/tMAN 34.78 29.69
CO2 emissions eco-indicator, tCO2/tMAN 4.12 2.68
Water use eco-indicator, m3W/tMAN 11.13 11.34
Wastewater eco-indicator, m3ef /tMAN 19.12 12.42
Human toxicity by ingestion, PEI/kgMAN 0.54 0.43
Human toxicity by exposure, PEI/kgMAN 0.25 0.24
Terrestrial toxicity potential, PEI/kgMAN 0.54 0.43
Aquatic toxicity potential, PEI/kgMAN 0.52 0.01
Ozone depletion potential, PEI/kgMAN 9.74E−09 5.56E−09
Photochemical oxidation potential, PEI/kgMAN 7.06E−04 0.11
Acidification potential, PEI/kgMAN 0.03 0.02

Fig. 7  Equipment contributions to eco-indicators

category, as suggested by Pereira et al. (2018), and are pre-
sented in Table 12.
We should note that the results are between 0 and 1,
thus corresponding to a quantitative range that varies from
the most eco-efficient to the least eco-efficient, respec-
tively. The qualitative analysis was then performed by
plotting the normalized values in an irregular tridecagon-
shaped radar-type chart, as shown in Fig. 8.
The quantitative evaluation was carried out by sum-
ming up the area of each minor triangle calculated with
the law of sines, as shown in Table 13, from which we

13
Eco‑efficiency and techno‑economic analysis for maleic anhydride manufacturing processes

Table 12  Normalized indicators Table 13  Quantitative ECI

Process Benzene Butane Eco-indicator × eco- Benzene technol- Butane technology
technology tech- indicator ogy
nology
ERM × EF 0.96 0.60
Raw materials eco-indicator, t­RM/tMAN 0.96 1.00 EF × EE 1.00 0.52
Fuel consumption eco-indicator, t­fuel/tMAN 1.00 0.60 EE × EC 1.00 0.56
Energy use eco-indicator, GJ/tMAN 1.00 0.85 EC × EW 0.98 0.65
CO2 emissions eco-indicator, tCO2/tMAN 1.00 0.65 EW × EWW 0.98 0.65
Water use eco-indicator, m3W/tMAN 0.98 1.00 EWW × HTPI 1.00 0.52
Wastewater eco-indicator, m3ef /tMAN 1.00 0.65 HTPI × HTPE 1.00 0.75
Human toxicity by ingestion, PEI/kgMAN 1.00 0.80 HTPE × TTP 1.00 0.75
Human toxicity by exposure, PEI/kgMAN 1.00 0.94 TTP × ATP 1.00 0.01
Terrestrial toxicity potential, PEI/kgMAN 1.00 0.80 ATP × ODP 1.00 0.01
Aquatic toxicity potential, PEI/kgMAN 1.00 0.01 ODP × PCOP 0.01 0.57
Ozone depletion potential, PEI/kgMAN 1.00 0.57 PCOP × AP 0.01 0.57
Photochemical oxidation potential, PEI/kgMAN 0.01 1.00 AP × ERM 0.96 0.57
Acidification potential, PEI/kgMAN 1.00 0.57 Sum 10.90 6.73
Tridecagon area 2.53 1.56
Highest values by indicator group
ECI – 38.29%

Table 14  Economic analysis results

Parameters Benzene Butane
technology technol-
ogy

ISBL investment, M$ 12.20 8.01

OSBL investment, M$ 5.00 3.28
Indirect costs (site development, design 3.98 2.67
and engineering, general), M$
Fixed operating costs, M$/year 4.28 4.06
Variable operating costs, M$/year 29.32 28.51
Other operating costs, M$/year 1.46 1.44
Depreciable capital cost, M$ 26.41 23.60
Total production cost, M$/year 35.05 34.00
Revenue (product + credits), M$/year 41.00 40.70
Gross profit, M$/year 5.95 6.70
Net present value (NPV), M$ 8.40 14.42
Internal rate of return, % 13.54 19.23
Return on investment, % 13.18 16.11
Payback period, years 6.82 5.27
Fig. 8  Qualitative ECI
Minimum MAN selling price, $/kg 0.71 0.69

note that the butane process is approximately 38% more
ecologically efficient than the benzene process.
In light of such results, future studies can be performed
with regard to the use of high-pressure steam generated
in the benzene technology. For instance, carbon-free hps
generated in coolers E1 and E2 could be used to heat the
column C1’s reboiler in order to reduce the process oper-
ating costs and ­CO2 emissions.
Economic analysis
Table 14 presents a summary of the economic evaluation
results of both technologies, whereas Fig. 9 illustrates the
net present value (NPV) variation during the project lives.
It can be verified that the butane route proved to be the most
economically attractive since it is approximately 72% more
profitable than the benzene process and achieves positive
NPV values earlier than the latter. This is in accordance with

13

Fig. 9  NPV variation
Rase (2010)’s statement regarding that the butane alterna-
tive is not only more environmentally friendly but also more
economically attractive. These results also corroborate Chen
and Shonnard (2004)’s study, which showed that the butane
process has a higher NPV.
The minimum MAN selling prices for both technologies,
in turn, were estimated by means of the cash flow model
itself by varying the product revenue in order to set the
respective NPVs equal to zero, given the specified discount
rate, and were found to be 0.711 $/lb and 0.685 $/lb for the
benzene-based and butane-based routes, respectively. This
clearly evidences the competitiveness of the latter over the
former.
Fig. 10  Effects of design parameters on the sustainability: a benzene route. b Butane route
13
P. V. Mangili et al.
Sensitivity analysis
The results obtained in this work are based on the original
designs of both technologies described in “Maleic anhydride
production” section. However, one should note that different
equipment sizes and/or process configurations may be alter-
natively considered. Although the flow sheet optimization of
the processes under evaluation lies beyond the scope of this
paper, a sensitivity assessment can be performed in order to
understand how specific design parameters affect the envi-
ronmental and economic results. Since several design con-
straints could be evaluated, only the main parameters were
considered in the analysis. For instance, Fig. 10 shows the
Eco‑efficiency and techno‑economic analysis for maleic anhydride manufacturing processes

effects of varying the number of C1 plates and reactor tubes
in both technological routes with regard to their respective
energy use indicator, water consumption indicator and capi-
tal cost. We note that although not particularly expressive,
increasing the number of stages in the distillation columns
renders the separation easier and, consequently, reduces
the reboiler duties, thus resulting in a decrease in the steam
requirements. On the other hand, increasing the number of
reactor tubes results in an increase in both the capital costs
and boiler feed water demand.
Moreover, the energy use, ­CO2 emissions and water
consumption indicators were calculated in this work on the
basis of the heuristic parameters present in the literature.
Table 15  Parameters evaluated in the sensitivity analysis
Parameters
Fired heater efficiency
Boiler efficiency
ζ (boiler blowdown factor)
γ (cooling tower blowdown factor)
ε (steam condensate loss)
The energy consumption and carbon emissions were esti-
mated by considering that the fired heaters and utility plant’s
boiler operate with a thermal efficiency of 80%, which corre-
sponds to the worst-case scenario according to EPA (2008).
The water consumption of both technologies, in turn, was
estimated by considering the worst-case scenario; that is,
the utility plant’s water blowdown from the boiler and cool-
ing tower was 0.3% each and the condensate loss from the
process to the steam plant was 20%. Therefore, a sensitivity
analysis was performed by varying the said parameters in
order to analyze how they affect such indicators, as shown
in Table 15. The results for the energy and C ­ O2 indicators
are shown in Fig. 11 and Table 16, while the results for the
water and wastewater indicators are presented in Fig. 12 and
Table 17.
From Fig. 11, we verify that, for the Benzene technol-
Range (%) ogy, the energy and C ­ O2 indicators are more sensitive to the
fired heater efficiency than to the boiler efficiency, which is
80–90
due to the former’s higher-energy requirements (accounting
80–90
for 57.3% of the total energy use, as shown in Fig. 7). For
0.1–0.3
the Butane technology, however, since the boiler thermal
0.1–0.3
requirement is the highest (53.8% of the total) as given in
10–20
Fig. 7, the energy and C ­ O2 indicators are more sensitive to

Fig. 11  Influence of thermal efficiencies on the energy and ­CO2 indicators: a benzene process. b Butane process

13
 P. V. Mangili et al.

Table 16  Sensitivity analysis—EE and EC eco-indicators of the total in the benzene technology) and E4 (71.1% of the
Indicators Benzene technology Butane technology
total in the butane technology), since the blowdown heu-
ristics are based on the total water circulating flow rate of
Worst case Best case Worst case Best case
both production plants. Varying the cooling tower and boiler
EE 34.78 31.2 29.69 26.33 blowdowns from 0.3 to 0.1% and the condensate loss from
EC 4.12 3.66 2.68 2.34 20 to 10% resulted in decreases of higher than 60% in the
water and wastewater indicators for both processes.
The worst-case scenario: efficiencies = 80%. The best-scale scenario: The results obtained in the sensitivity analysis could be
efficiencies = 90%
used to recalculate the processes’ eco-efficiencies. Figure 13

its efficiency. In fact, varying the boiler and fired heater effi-
ciencies from 80 to 90% in the benzene technology resulted
Table 17  Sensitivity analysis—EW and EWW eco-indicators
in a decrease of 10.3% in the energy indicator and 11.2% in
the ­CO2 indicator. For the butane process, such values were Indicator Benzene technology Butane technology
of 11.3% and 12.7%, respectively. Worst case Best case Worst case Best case
From Fig. 12, we can note that, for both processes, the
water consumption and wastewater generation indicators EW 11.13 4.01 11.34 4.50
depend much more on the cooling tower and boiler’s blow- EWW 19.12 7.53 12.42 4.82
down than on the percentage of condensate loss. This is due The worst-case scenario: ζ = 0.3%, γ = 0.3%, ε = 20%. The best-case
to the higher water requirements on condensers E3 (87.3% scenario: ζ = 0.1%, γ = 0.1%, ε = 10%

Fig. 12  Influence of blowdown and condensate loss on the water consumption and wastewater generation indicators: a benzene process. b
Butane process

13
Eco‑efficiency and techno‑economic analysis for maleic anhydride manufacturing processes
Fig. 13  Qualitative ECI considering the best-case scenarios
illustrates an ECI result considering the best-case scenario
for both technologies, from which we can observe a slight
difference on the tridecagon areas when compared to Fig. 8.
In fact, if we considered the best-case scenario, the butane
route would be approximately 35% more eco-efficient than
the benzene technology, instead of 38% as previously calcu-
lated for the worst scenario.
Conclusion
This study compared two maleic anhydride production pro-
cesses with regard to their respective economics and ecologi-
cal performance. The environmental analysis was performed
by means of the Eco-efficiency Comparison Index method
based on six categories of eco-indicators and seven LCA
metrics. The processes’ economics, in turn, was evaluated on
the basis of the equipment specifications provided by the ref-
erence authors and utility requirements provided by simula-
tion. The comparison demonstrated that the butane technol-
ogy has higher environmental performance (approximately
38% more eco-efficient) and profitability (approximately
72%) when compared to the benzene technology, which is
mainly due to the former’s lower-energy requirements and
raw material costs. Therefore, the butane oxidation technol-
ogy was shown to be the best alternative for MAN produc-
tion in terms of both economics and sustainability.
In this regard, process simulation proved to be a conveni-
ent technique for estimating the economics and environmen-
tal footprint of industrial processes. In addition, based on
the results provided in this paper, future studies on MAN
production may be developed in order to perform thermal
integration and design new MAN purification methodologies
for reducing costs and mitigating ecological impacts.
Acknowledgements  This study was financed in part by the Coorde-
nação de Aperfeiçoamento de Pessoal de Nível Superior —Brasil
(CAPES)—Finance Code 001.
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* Patrick V. Mangili
patrickmangili@gmail.com
Pedro G. Junqueira
pedrojunqueira@id.uff.br
Lizandro S. Santos
lizandrossantos@gmail.com
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Diego M. Prata
pratadiego@gmail.com
1
Department of Chemical and Petroleum Engineering,
Universidade Federal Fluminense, Niterói, RJ 24210‑240,
Brazil