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Preliminary Design of Sustainable Industrial Process Alternatives Based on

Eco-efficiency Approaches: The Maleic Anhydride Case Study

Patrick V. Mangili, Diego M. Prata

PII: S0009-2509(19)30803-6
DOI: https://doi.org/10.1016/j.ces.2019.115313
Reference: CES 115313

To appear in: Chemical Engineering Science

Received Date: 8 April 2019

Revised Date: 20 October 2019
Accepted Date: 22 October 2019

Please cite this article as: P.V. Mangili, D.M. Prata, Preliminary Design of Sustainable Industrial Process
Alternatives Based on Eco-efficiency Approaches: The Maleic Anhydride Case Study, Chemical Engineering
Science (2019), doi: https://doi.org/10.1016/j.ces.2019.115313

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 Preliminary Design of Sustainable Industrial Process
Alternatives Based on Eco-efficiency Approaches: The
Maleic Anhydride Case Study
Patrick V. Mangili1 *, Diego M. Prata1
1Department of Chemical and Petroleum Engineering, Universidade Federal Fluminense,

24210-240, Niterói, RJ – Brazil.

*Corresponding author: Patrick V. Mangili (E-mail: pmangili@id.uff.br)

Abstract

The increasing need for mitigating environmental impacts has led the industries to develop

more sustainable processes, which may represent an arduous task since economic, safety, social

and environmental factors must be considered. Hence, this paper demonstrates the relevance

of using sustainability indicators in developing cleaner industrial processes. Such metrics were

used to design a more sustainable butane-based maleic anhydride manufacturing technology,

which was compared to the benzene-based route in terms of economic, safety and

environmental indicators. The analysis showed that, although the latter consumes

approximately 2.8% less water, generates about 3.1% less wastewater and is 70 times less

hazardous in terms of fire/explosion risks, the former is not only 33.8% more profitable but

also consumes 28% less energy and, consequently, emits approximately 42.9% less CO2. After

grouping the fifteen sustainability metrics in a composite evaluation index, the butane-based

process proved to be about 34% more eco-efficient than the benzene-based technology.

Keywords: Computational Simulation, Maleic Anhydride, Process Design, Process

Economics, Safety Metrics, Sustainability Indicators.

1. Introduction

Due to the increasing concerns regarding ecological impacts resulting from industrial activities,

environment-related concepts such as “sustainable development” have been attaining more and

more relevance in the last decades. Although installing an industrial facility is necessary for

providing the community with the required products and fostering economic progress, it may

be related to several social and environmental effects. In this regard, the industries realized

that, in order to improve the ecological performance of their processes, new design techniques

should be developed.

Numerous methodologies are available for evaluating the viability of strategies to enhance

process sustainability, among which the concept of eco-efficiency stands out. Eco-efficiency

relates the environmental impacts and economic performance of a process by quantitatively

evaluating its sustainability indicators, which are represented by a relationship between an

environmental variable (e.g. emissions, waste generation, etc.) and an economic variable (e.g.

profit, production rate, etc.) (Mangili et al., 2018). Said analysis is particularly convenient when

different manufacturing technologies can be used to obtain the same product, since it

encompasses the environmental, safety and economic aspects of the processes.

This paper aims to demonstrate the significance of applying the eco-efficiency concept in the

preliminary design and comparison of different industrial processes in terms of environmental,

safety and economic aspects. The maleic anhydride (MAN) production was used as case study

due to its commercial relevance and since sufficient data for estimating the required parameters

are widely available in the open literature. Nevertheless, to the best of our knowledge, MAN

manufacturing technologies have only been studied in terms of either reaction modeling/design

or environmental impacts. No studies concerning safety and economics evaluated together with

2
ecological effects are available in the literature. In addition, such a comparison has not been

reported considering either emission or cost factors for Brazil.

For these particular reasons, we took this opportunity to propose a new design configuration of

the benzene-based process on the basis of not only economic parameters but also sustainability

aspects (e.g. water consumption, CO2 emissions, etc.) and develop a preliminary flowsheet of

the butane-based scheme, which has never been performed on the basis of sustainability

indicators (e.g. water consumption, wastewater generation, irritation factors, fire/explosion

hazards, etc.). Furthermore, the novelty of the present manuscript lies not only on the

aforementioned reasons but also on the fact that we took the utility plants into consideration,

which is usually not performed by most authors (and has never been considered by any study

related to MAN production). This represents a significant breakthrough since we provide

information on the respective flowsheets and heuristics to be considered when estimating water

losses. Thus, we provide the community not only with an assessment of the overall

performance of the maleic anhydride process but also with practical methods for determining

the environmental, safety and economic aspects of industrial processes during the design stage.

It is therefore worth pointing out that we focused on disclosing the importance of assessing

such aspects rather than developing optimal process configurations.

2. Sustainability of Industrial Processes

Although essential for the social and economic development of communities, the industries

play a major role in terms of environmental impacts, especially with regard to atmospheric

emissions and waste generation. Such a contrasting characteristic has led the companies to seek

more sustainable alternatives to their processes and develop new techniques to improve their

already existing technologies. In this context, life cycle assessment (LCA) approaches have

3
been more and more implemented in the evaluation of the environmental burdens of industrial

activities.

Several studies related to the life cycle evaluation of different processes are available in the

literature. Azapagic and Perdan (2011) demonstrated how LCA criteria are useful when

developing more sustainable processes by performing a preliminary and detailed design of a

vinyl chloride monomer manufacturing process. Various economic, environmental and social

characteristics were taken into account in order to provide brainstorming strategies for selecting

the best design alternatives. Morales-Mora et al. (2012) compared two alternatives of

acrylonitrile production plants (old and re-designed configurations) in terms of 18 impact

categories, along with a marginal prevention cost method. The authors aimed at not only

demonstrating the relevance of LCA indicators to the environmental assessment of product

systems but also identifying critical aspects of process design that may be further improved.

Patel and co-workers (2012), in turn, performed a study on the techno-economic aspects and

“cradle to gate” life cycle impacts of solid recovered fuel plants for energy generation in order

to identify the most sustainable process and reveal possible developments for such activities.

Kralisch et al. (2015) carried out a review on LCA approaches applied to several chemical-

related processes and product designs, namely pharmaceutical, manufacturing,

nanotechnology, waste treatment and renewable resources, among others. Through the analysis

of different case studies, the authors compare different life cycle assessment tools and provide

some suggestions regarding their specific applications and limitations. Daful and Görgens

(2017) applied LCA techniques to quantify the environmental impacts associated with

lignocellulosic lactic acid production. Six process scenarios were compared in terms of nine

environmental impact categories and four economic aspects. More recently, Yao and Masanet

(2018) developed a framework to generate energy and life cycle inventories of chemical

4
processes. They designed a logic approach based on chemical technologies’ parameters and

heuristics to estimate the respective environmental burdens.

LCA is in fact a widely applied tool for assessing the sustainability of products and processes

since it provides information on their resulting environmental impacts during all stages of their

life cycle, such as raw materials extraction, production, distribution, consumption and disposal

(Kralisch et al., 2015). However, such frameworks present some drawbacks that might render

it laborious. For example, life cycle assessment methodologies depend highly on the

availability of quality data. According to Bicalho and coworkers (2017), a substantial amount

of data is required in order to establish a life cycle inventory, which is essential for assembling

LCA studies. Nevertheless, such data may not be readily accessible and, thus, gathering

sufficient information can represent a time-intensive task (Zamagni, 2012). Such methods are

also not convenient when used for the comparison between studies, especially because most of

them rely on narrow frameworks that are based on specific territories – which may lead the

calculations to imprecise results – and do not always assert which alternative is the best one

(Bare et al., 2000). Furthermore, LCA indicators do not take the process’ economic aspects

into consideration and therefore do not provide an accurate evaluation of the overall

performance of the process (Goedkoop and Spriensma, 2001).

The need for establishing sustainability evaluation metrics that could overcome the above-

mentioned limitations has led to the development of the concept of eco-efficiency. Differently

from LCA metrics, Eco-efficiency indicators can be estimated through process design and

simulation in a relatively cheap, quick basis without requiring intensive, time-consuming

search for specific data. Such metrics can relate different aspects of the process (e.g.

environmental, safety, corporative, etc.) to its economic performance and provide an overall

assessment of its sustainability, thus being quite relevant in declaring the best alternative.

5
Eco-indicators have been used for the evaluation of numerous technologies and showed to be

conveniently useful in evaluating the sustainability of industrial processes. For instance, Patel

et al. (2012) proposed a methodology for evaluating novel chemical processes in terms of

environmental, economic and safety indices. The authors based their assessment on two but-

1,3-diene production routes (via catalysis of bioethanol and via steam cracking of naphtha) in

order to demonstrate the usefulness of their methodology in aiding practitioners to perform a

quick preliminary evaluation of the processes’ sustainability. Ruiz-Mercado et al. (2012)

presented a set of numerous environmental, economic, energy, efficiency and safety indicators

to be used when assessing the sustainability of chemical processes. The metrics were

systematically defined according to the Gauging Reaction Effectiveness for the ENvironmental

Sustainability of Chemistries with a multi-Objective Process Evaluator (GREENSCOPE)

methodology with regard to data needs and calculation procedures. Valenzuela-Venegas et al.

(2016) provided 249 metrics useful in analyzing social, economic and environmental aspects

of eco-industrial parks. They also established some criteria to select the most suitable indicators

and aid the assessor in evaluating the sustainable performance of a certain product system.

More recently, Pereira et al. (2018) developed an assessment approach based on eco-indicators

that may be applied to any industrial process. The authors performed their work based on five

environmental metrics – calculated through real operating data (retrieved with the aid of

operators and engineers) – that were used to evaluate a petrochemical facility during different

periods. Such data were used for the daily monitoring of the process in order to assist the

planning of corrective actions. The same approach, although based on a few more metrics, was

applied by Junqueira et al. (2018), who compared the eco-efficiency of six cumene

manufacturing technologies, and Mangili and Prata (2019), who evaluated the sustainability

performance of butyl acetate production processes. Both references based their analysis on

computational simulation data.

6
 2.1 Methodology

In this paper, a systematic methodology is carried out in order to better illustrate the relevance

of applying eco-efficiency metrics in the design and assessment of industrial processes with

the aid of computational simulation. The step-by-step procedure is given in Figure 1 and further

detailed in the following sections.

[Figure 1 near here]

3.1. Selection of process routes: Maleic anhydride production

MAN is a relevant chemical good to nowadays society since it is generally used as an

intermediate for the production of unsaturated polyester resins, polymers, vernices and paints,

among other products. It is commonly manufactured by the partial oxidation of n-butane, which

has gained more relevance over the old-fashioned benzene oxidation technology due to the

latter’s hazard potential and higher costs (Lesser et al., 2017; Maußner and Freund, 2018). Said

technologies differ from each other with regard to the operating conditions, which depend

mainly on the feedstock conditions, reactor configuration and purification design.

In order to demonstrate the applicability of sustainability metrics in the preliminary design of

cleaner industrial processes, we compared two different technological routes for the

manufacture of maleic anhydride, which have been mainly studied with regard to reaction

modeling and environmental burdens. For instance, Uraz and Atalay (2007) evaluated the

effects of temperature, benzene flow rate and catalyst type on the MAN selectivity via benzene

oxidation. They performed their experiment in a laboratory scale fluidized bed reactor and

compared six different catalyst compositions to found that the silica gel catalyst having higher

contents of molybdenum and nickel oxides achieves the highest MAN conversion. Dong et al.

(2016) used a two-dimensional pseudoheterogeneous model to analyze the effect of catalyst

pore structure on n-butane oxidation in fixed-bed reactors by solving diffusion–reaction

7
balances inside the catalyst pellets. Lesser et al. (2017), in turn, investigated the dynamics

associated with the phosphorus content of catalysts for the oxidation of butane in a fixed-bed

pilot reactor. The authors could then evaluate several reaction parameters and develop a

detailed reactor model. Maußner and Freund (2018) proposed an improved algorithm for

optimization under uncertainty, which was applied to a fixed bed reactor model for the

conversion of butane to MAN in order to design a high-performance reactor system presenting

less temperature constraint violations and runaway conditions.

In terms of environmental analysis, Schwarz et al. (2001) determined the practical minimum

energy levels for the manufacture of MAN via oxidation of n-butane, from which material,

water and emission indicators could be estimated. Chen and Shonnard (2004) estimated the

economic performance and the CO2 emissions of both processes on the basis of the U.S.

Environmental Protection Agency (EPA) emission factors, whereas Althaus and coworkers

(2007) presented life cycle inventories for maleic anhydride in terms of reaction yield, raw

material consumption, energy use, air emissions and wastewater generation. Laínez et al.

(2008) applied the IMPACT2002+ methodology to assess the environmental impact of the

maleic anhydride supply chain. Fermeglia et al. (2009), in turn, applied the Waste Reduction

Algorithm to compare the benzene and butane technologies in terms of six LCA indicators.

However, it is worth pointing out that Schwarz et al. (2001), Althaus et al. (2007) and Laínez

et al. (2008) presented only their findings without providing information on process

configurations and conditions. On the other hand, Chen and Shonnard (2004) and Fermeglia et

al. (2009) presented the process schemes and most of the parameters used for the design and

simulation of both technologies. Nevertheless, some critical design considerations were not

disclosed, thus rendering the reproduction of their studies impracticable. The main results

obtained by said references will be later discussed and compared to our findings.

8
A more detailed description of both technological routes is presented in the following sections.

Both processes were simulated in Aspen Plus® under steady-state conditions by using the Non-

Random Two Liquid thermodynamic property package.

3.2. Data collection

The first step is one of the most important stages since it will provide crucial information to

assist the practitioner in designing and simulating the processes at issue. All parameters

required for process synthesis and flowsheeting – including the identification of feedstocks,

reaction kinetics, thermodynamics, unit operations, equipment specifications, etc. – may be

retrieved from the literature, open-access databases and, if available, industrial data and/or

restricted-access sources.

3.3. Design and simulation: Benzene technology

As discussed, the benzene-based route is viewed today as obsolete for having higher feedstock

prices, lower carbon yield, more air emissions and higher toxicity risks than the butane-based

configuration. Hence, using a clearly outdated technology may conveniently serve the purpose

of this work with regard to demonstrating the efficacy of eco-efficiency metrics in disclosing

sustainability aspects of industrial processes. The sustainability evaluation of the benzene

process is therefore expected to show its inferiority when compared to the butane design.

The benzene technology studied in this paper was originally proposed by Turton et al. (2018)

and further improved in order to improve its sustainability and allow a more fair comparison.

Such flowsheet was chosen as case study since sufficient data was provided by said reference

author.

3.3.1. Reaction kinetics

9
The selective oxidation of benzene (C6H6) for MAN (C4H2O3) manufacture takes place in the

gas phase over a vanadium-molybdenum catalyst, as shown in Equation 1. Due to the highly

exothermic characteristic of the reaction, the temperature of the system must be strictly

controlled to prevent both the risk of thermal runaways and the formation of undesired side

products. While higher temperatures may result in the total oxidation of the feedstock

(Equation 2) and further oxidation of MAN (Equation 3), lower temperatures favor oxidation

of benzene to quinone (C6H4O2), as shown in Equation 4 (Turton et al., 2018).

C6 H6  4.5O2 C4 H2O3  2CO2  2H2O (1)

C6 H6  7.5O2 6CO2  3H2O (2)

C4 H2O3  3O2  4CO2  H2O (3)

C6 H6 1.5O2 C6 H4O2  2H2O (4)

Table 1 discloses the reaction kinetics used by Turton et al. (2018). All reaction rates are in

kmol.s-1.m-3, whereas CBZ and CMAN stand for benzene and MAN compositions, respectively,

and have units of kmol.m-3. R is 8.314 kJ.kmol-1.K-1 and T denotes the reaction temperature

(K). The catalyst was assumed to have a 0.4 void fraction and a 1250 kg.m-3 density.

[Table 1 near here]

3.3.2. Flowsheet

The flowsheet of the benzene oxidation technology for MAN manufacture, as well as the results

obtained through simulation, are illustrated in Figure 2, in which cw, bfw, lps and hps stand for

cooling water, boiler feed water, low-pressure steam and high-pressure steam, respectively.

[Figure 2 near here]

10
In the process, 42.3 kmol/h of fresh benzene is pressurized in pump P1, heated by lps in heater

HX1 and mixed with 2790.0 kmol/h of compressed air from compressor K1. The mixture is

heated to 460° C in fired heater FH1 prior to being fed to a reactor R1 comprised of 6 m length,

2.5-cm diameter 12,100 catalyst-filled tubes, in which the reactions described by Equations 1

to 4 take place. The reactor effluent, at 608.0° C, is cooled down to 270.0° C by bfw in after-

cooler HE2 and fed at 2825.3 kmol/h to the bottom of an absorption column C1 having 14 sieve

plates plus full-reflux condenser and reboiler. Such a column is fed at the top by a mixture of

a 0.1 kmol/h dibutyl phthalate make-up stream, used as solvent for recovering MAN, and 500.0

kmol/h of a solvent recycle stream. C1’s top product consisting of unreacted components and

combustion gases is retrieved at 260.0° C and burned off in the flare at 2797.6 kmol/h. MAN

and dibutyl phthalate are obtained at the bottom at 526.2 kmol/h and fed to the 27th plate of a

42-plate distillation column C2. MAN is obtained as C2’s distillate at 27.6 kmol/h with a purity

of 99.5 mol %, while dibutyl phthalate is recycled at 500.0 kmol/h to the top of the absorption

column.

3.3.3. Design improvement

Turton et al. (2018) provided only a general description of the maleic anhydride production via

oxidation of benzene without considering any design improvement strategies or sustainability

aspects. In this paper, however, some design trade-offs were examined in order to enhance the

technology’s ecological performance:

(a) The reactor size is of particular importance since it is directly related to conversion and

selectivity. Using larger reactors increase capital costs but allows lower reaction temperatures,

thus reducing operating expenses. Also, it may contribute to reduce the required amount of

feedstock and improve selectivity for a fixed conversion. The effect of the reactor size on the

process parameters is shown in Figure 3.

11
(b) The off-gas stream containing non-reacted components and undesired products could

be recycled in order to reduce the amount of CO2 emitted. However, since such a stream has a

negligible amount of benzene, recycling it would significantly reduce the overall conversion

and increase the plant’s energy demand, as also given in Figure 3.

[Figure 3 near here]

(c) Most energy efficiency issues of industrial processes can be solved through detailed

engineering-related techniques such as, for instance, Pinch Analysis, combined heat and power

system models, etc. However, since we are focused on performing a preliminary assessment,

simple strategies may be deemed more convenient. For example, the use of a fired heater is

necessary to increase the reactor feed’s temperature to the ideal conditions, but it results in both

high operating expenses and CO2 emissions due to the consumption of natural gas. A simple –

yet efficient – strategy to overcome such drawbacks and reduce the amount of bfw used in after-

cooler HE2 may refer to heat-integrating both the reactor feed and product streams.

Nevertheless, reducing the latter results in a decrease of hps generated to be exported and thus

affects the profit. Figure 4 demonstrates the effects of such an integration.

[Figure 4 near here]

From Figure 3 we note that increasing the number of reactor tubes up to approximately 13,000

results not only in a decrease in the off-gas flow rate but also in the increase of the profit, since

energy and water consumptions are reduced. Furthermore, recycling the off-gas stream does

not affect greatly the MAN production rate, but results in a significant increase in both the

process’ energy requirements and costs. The higher recycle flow rate the higher the CO2

emissions, which is mainly due to the higher energy required by the compressor (CO2 generated

due to electricity) and reboilers/fired heater (CO2 from the flue gases of the utility plant’s

boiler) to process larger gas volumes.

12
From Figure 4, in turn, we note that the production expenses decrease, but the gross profit also

decreases. This is mainly due to the lower flow rate of hps exported, which is a significant

factor for the revenues of such a technology. Nevertheless, we also observe that heat-

integrating the reactor’s feed and effluent (FEHE) can reduce significantly the process’

environmental burdens and consequently improve its sustainability. This is mainly associated

with the lower overall fuel consumption since, in the new configuration, no fired heater is

present and, therefore, only the utilities plant boiler consumes natural gas.

The re-designed flowsheet of the benzene technology for MAN production is given in Figure

5, where the differences from the original design are highlighted in red.

[Figure 5 near here]

3.4. Design and simulation: Butane technology

The n-butane-based technology is currently used by several companies using different process

designs, having Sasol-Huntsman GmbH & Co. KG, Polynt S.p.A., DSM Fine Chemicals BV

and Technobell Technology LTD the world’s biggest production capacities. Although the

process designed in this paper may present some similarities to the above-mentioned

companies’, all physical properties, kinetic data and flowsheet information were retrieved from

sources available in the open literature, as cited accordingly throughout the paper. There is no

relation, therefore, between this study and the known commercial processes.

3.4.1. Reaction kinetics

The n-butane (C4H10) partial oxidation usually occurs in the vapor phase using a vanadium-

phosphorus oxide catalyst according to Equation 5. Similarly to the benzene route, an increase

in the temperature may result not only in risks of thermal runaways but also in further oxidation

of MAN (as previously shown in Equation 3) and total oxidation of the feedstock, as described

by Equation 6.

13
 C4 H10  3.5O2 C4 H2O3  4H2O (5)

C4H10  6.5O2 4CO2 5H2O (6)

Table 2 presents the reaction kinetics used in this study, which were retrieved from Sharma et

al. (1991)’s work. All reaction rates are kmol.s-1.m-3, whereas pB and pM stand for butane and

MAN partial pressures, respectively, and have units of atm. R is 8.314 kJ.kmol-1.K-1 and T

denotes the reaction temperature (K). The catalyst was assumed to have a 0.5 void fraction and

a 2000 kg.m-3 density.

[Table 2 near here]

One may note that although reaction 3 occurs in both processes, the kinetics used in this article

are different. This is due to three main reasons. First, the catalysts are different (vanadium-

molybdenum for the benzene alternative and vanadium-phosphorus oxide for the butane

technology), thus resulting in different selectivities and activation energies due to different

temperature dependences. Second, the rate equations are expressed by different basis, i.e. in

Table 1 it is based on the MAN composition (CMAN), whereas in Table 2 its based on the partial

pressures of butane (pB) and MAN (pM). Furthermore, in the butane-based design, the presence

of an adsorption term shows that such a phenomenon is relevant in this case. Third, we based

our study on different scientific references. Evidently, several other kinetic studies have been

performed so as to propose different reaction rates (which we leave here as a suggestion for

future researches).

3.4.2. Flowsheet

The process flow diagram for the MAN production technology via n-butane oxidation is

illustrated in Figure 6, which shows the results obtained by simulation. Here, mps stands for

medium-pressure steam. Fresh n-butane at 67.7 kmol/h is pressurized in pump P1 to 2.8 bar

14
and vaporized in vaporizer V1 prior to being mixed with compressed air at 1488.5 kmol/h and

a compressed gas recycle stream from the absorption section, at 1107.3 kmol/h. The resulting

mixture has a butane concentration of 2.7 mol %, which must be kept low due to the

hydrocarbon’s flammability. Feedstock loss is overcome by recycling part of the absorber’s

top product.

[Figure 6 near here]

The mixture is pre-heated in the feed-salt heat exchanger (FSHE) to 420.0° C and subsequently

fed to a multitubular reactor R1 having 6,876 25-mm diameter, 4.2-m length catalyst-filled

tubes. The reactor is cooled by a molten salt system (consisting in a mixture of sodium nitrite

and sodium nitrate), which is also used to heat the reactor feed. Such dimensions were assumed

according to the analysis shown in Figure 7, which present the effects of the reactor size on the

economic and environmental performances of the process.

[Figure 7 near here]

Figure 8 shows the reactor’s composition profile, from which we note that although using 6,876

reactor tubes may result in an increase in the energy and water requirements, both the MAN

production rate and gross profit increase. Therefore, the relative indicators are not expected to

change significantly.

[Figure 8 near here]

The reactor product is then cooled down firstly to 151.3° C in cooler HE2 and subsequently to

65.0° C in cooler HE3 prior to being sent to a pre-degasser V2, which pre-separates MAN and

water from other components and thus reduces both absorption and distillation’s energy

requirements. V2’s temperature effect on the outlet flows is shown in Figure 9.

[Figure 9 near here]

15
MAN present in V2’s top product may be separated from the other components by employing

two methods, namely solvent-based or water-based. We considered the latter for performing

the separation since it is commonly applied to butane-based maleic anhydride manufacturing

technologies (Technobell Technology, 2018; Trivedi and Culbertson, 1982). Also, we assumed

that the amount of maleic acid formed due to MAN hydrolysis is negligible, which excludes

the necessity of implementing an additional dehydration step in order to recover the anhydride

from the acid. V2’s top product, containing mainly nitrogen and combustion gases, is fed at

2599.8 kmol/h to the bottom of the absorption column C1, whose top section is fed by 112.7

kmol/h of a mixture between a water make-up stream and a C2’s water recycle stream. The

absorber’s top product is split into a gas recycle stream and an off-gas stream. The former is

sent back to the reactor stream at 1107.3 kmol/h, whereas the latter is sent at 1573.4 kmol/h to

the flare. The effect of the gas recycle molar flow rate on some process parameters is also

shown in Figure 7. We can observe that recycling off-gases at a rate of 1107.3 kmol/h refers to

the optimal design since it results in the lowest energy requirements and operating costs of the

process.

C1’s bottom product, along with V2’s bottom product, is fed at 134.9 kmol/h to the distillation

column C2, from which MAN is retrieved at 28.3 kmol/h as bottom product, whereas water is

retrieved at the top. C2’s top product is recycled at 107.5 kmol/h to the C1’s top feed stream.

Figure 10 shows the C2’s temperature and composition profiles.

[Figure 10 near here]

3.5. Utilities plant

Most industrial plants are designed together with their respective utilities plant, which are

required to provide the process with heating and cooling sources. Most authors usually do not

consider such systems in their works, which may result in misleading results since such systems

16
represent approximately 40% of the capital costs (Towler and Sinnot, 2013). The utilities plant

considered in this paper was designed on the basis of Smith (2016)’s description and intended

to allow a more reasonable estimation of the processes’ cost, water consumption and

wastewater generation. The flowsheet is given in Figure 11.

Steam, bfw and cw flow rates are calculated through simulation. All other variables are obtained

from heuristics disclosed in Table 3. The flow rate of effluent is determined from the sum of

condensate losses, boiler blowdown, bfw losses, cw losses and cooling tower blowdown,

whereas the flow rate of make-up water is calculated by summing up the amount of effluent

with treatment and cooling tower losses.

[Figure 11 nere here]

[Table 3 nere here]

3.6. Definition and calculation of metrics

The eco-efficiency analysis is usually performed by means of eco-indicators which, according

to the United Nations Conference on Trade and Development (UNCTAD, 2004), are metrics

that relate the process’ environmental burdens (e.g. air emissions, waste production, etc.) to its

economic features (e.g. net profit, production rate, etc.).

The eco-efficiency of a process must be determined on the basis of an overall assessment of all

aspects of sustainability. The environmental impacts clearly represent a major concern when

designing new processes, but it cannot be solely considered in decision-making tasks.

Economic, safety, corporative and social aspects should also be taken into account so the

process’ performance is evaluated in its entirety. However, corporative and social data may not

be readily available during the planning/design phase since they depend highly on already

existing data and, therefore, are not usually considered.

17
In addition, some evaluation metrics might not be strictly essential when performing a

preliminary assessment. For instance, assessing two process alternatives having the same

feedstock and product specifications that differ only with regard to purification strategies

would not be precisely compared in terms of raw material consumption (Junqueira et al., 2018).

The same apply to comparing process plants that are considered to be installed in a particular

location – and that will occupy the same area – in terms of land use.

In spite of the above, the decision-maker may choose to account for as many indicators as

desired once they comply with a “the lower-the better” premise, that is, the lower the result the

lower the impact.

3.6.1. Environmental metrics

In this paper we considered six eco-indicators to compare the benzene and butane routes,

namely, raw material consumption (RMC), fuel consumption (FC), energy consumption (EC),

CO2 emissions (COE), water consumption (WC) and wastewater generation (WWG). Such

metrics were selected since, according to Pereira and coworkers (2018), they correspond to the

most relevant when it comes to sustainability assessment of industrial processes during the

early stage design. Their respective equations are given in Table 4.

The total mass flow rate of natural gas (ṁng) consumed in the utility plant’s boiler and benzene

plant’s fired heater was calculated from to Equation 7, in which NCVng refers to the natural gas

net calorific value (assumed to be 0.048 GJ/kg according to the International Energy Agency,

2005) and Ei and ηi correspond to the required energy and thermal efficiency of equipment i,

respectively. Both the boiler and fired heater were conservatively interpreted to operate with

80% efficiency (Junqueira et al., 2018).

[Table 4 nere here]

18
 1 E
m ng   i (7)
NCVng i

The total energy consumption was determined through simulation by considering that pumps

and compressors operate with electricity at 75% efficiency, whereas heaters and reboilers

operate with steam generated in the utility plant’s boiler. The CO2 emission indicators were

calculated in accordance with Mangili and co-workers (2018)’s guidelines by using a value of

0.0381 t/GJ for the electricity conversion factor (annual average for 2018 according to MCTIC,

2019) and 0.0561 t/GJ for the natural gas conversion factor (SEEG, 2018) to carbon dioxide

emissions. The amount of CO2 resulting from burning off-gases in the flare was estimated by

considering total combustion. The electricity-to-CO2 factor is considerably low since the

processes were assumed to be implemented in Brazil whose energy mix consists primarily of

hydroelectric power plants. Although such a factor may vary greatly depending on location,

the carbon dioxide indicators would not change significantly since the emissions due to

electricity consumed by compressors and pumps account for only 2% of the total CO2

generated.

The water consumption and wastewater generation were determined from the simulation results

and heuristics shown in Table 3. Cooling water was assumed to be supplied to the process at

30° C and return at 45° C, while boiler feed water was considered to be supplied at 90° C

(Turton et al., 2018). Low-pressure steam was interpreted to be supplied at 135.0° C and 3.0

bar, whereas medium-pressure steam is supplied at 185.5° C and 11.4 bar. For high-pressure

steam, such conditions are 254.0° C and 42.4 bar, respectively (Seider et al., 2017).

3.6.2. Economic metrics

In this work, the economics of both technologies was determined by estimating their respective

cash flows. Since MAN manufacturing technologies have already been studied, the analysis

19
was carried out assuming that both processes were redesigned with a digital control structure

and implemented in grass-root sites in Brazil. The project life was assumed to be of 10 years

plus 1 year of design and 2 years of construction (Towler and Sinnot, 2013; Turton et al., 2018).

A 10% straight-line depreciation method (PwC, 2018) was considered along with a 6.90%

interest rate (Banco Central do Brasil, 2018) and a 34% tax rate (Deloitte, 2017).

The equipment costs were calculated through Aspen Process Economic Analyzer® on the basis

simulation data. A Plant Cost Index of 600 was used (Junqueira et al., 2018). We interpreted

pumps and compressors to be of centrifugal type, whereas columns and flash tanks were

assumed to be vertical pressure vessels. Reactors were costed as shell and tube heat exchangers,

which were all assumed to be of floating head type, with the exception of reboilers, which were

of kettle type. The material of construction for columns and vessels was considered to be carbon

steel, being stainless steel 304 assumed for pumps, compressors and reactors (Seider et al.,

2017). Table 5 presents other site expenses used to estimate the fixed capital investment (FCI).

[Table 5 near here]

The operating expenditures were estimated by considering that benzene and n-butane are priced

at 3.45 $/gal (Independent Chemical Information System, 2018) and 0.65 $/kg (The Chemical

Company, 2016), respectively, while MAN is worth 0.75 $/lb (Independent Chemical

Information System, 2018). We assumed an operator salary of 50,000 $/year, considering that

the plants are operated by 3 shifts having 5 operators each. High-pressure steam credit was

interpreted to be worth 12.33 $/GJ, while electricity and cooling water were priced at 16.80

$/GJ and 1.04 $/GJ, respectively. Medium and low-pressure steams were assumed to be 14.83

$/GJ and 7.78 $/GJ, respectively (Turton et al., 2018). Natural gas was costed at 4.24 $/GJ (The

Chemical Company, 2016). Table 6 gives other cost variables used to estimate the operating

expenses.

20
 [Table 6 near here]

From the cash flow analysis, we could determine the main economic aspects of each process,

namely net present value (NPV), return on investment (ROI), payback period (PP), internal

rate of return (IRR) and net future worth (NFW). However, one should note that the

sustainability analysis performed in this paper is based on a “the lower-the better” premise. In

this regard, with the exception of the payback period, all economic metrics were calculated as

the inverse ratio of the respective parameters, as shown in Table 7. Here, the letter “F” denotes

“Factor” in order to differentiate the indicators from the respective economic terms.

[Table 7 near here]

3.6.3. Safety metrics

The safety of a process depends predominantly on the company’s commitment to providing

sufficient information and training regarding the hazards associated to its activities so as to

identify potential hazards and develop mitigation strategies. According to Warnasooriya and

Gunasekera (2016), such strategies must be taken into consideration, along with health,

environmental and economic aspects, during the early stage design in order to develop

inherently safer and more environmentally friendly processes. However, most of the action

plans to prevent incidents derive from the so-called “lessons learned” and, hence, depend on

data of past events. For this reason, evaluating safety aspects of processes during the

preliminary design phase may correspond to a complicated task.

In this paper, to overcome such a hurdle, it is necessary to utilize metrics that can be determined

from initial design information. We considered that using EPA’s GREENSCOPE metrics

would be a suitable strategy since, according to Smith et al. (2015), said tool is intended to

assess the sustainability of chemical processes by means of relatively simple performance

indicators and computer-aided techniques. Four safety indicators were used in our comparison,

21
namely health hazard irritation factor (HHIF), safety hazard fire/explosion (SHFE), chronic

toxicity factor (CTF) and chemical exposure index (CEI). Their respective equations as given

in Table 8.

[Table 8 near here]

These safety metrics were determined in accordance with Ruiz-Mercado and coworkers

(2012)’s guidelines. For HHIF and CTF, Vi,irr.subst and Vi,air polluted refer to the total volumetric

flow rate of substances whose contact must be avoided and of air polluted to a workplace

threshold value, respectively. Such variables are calculated through Equations 8 and 9,

respectively, where ṁi is the mass flow rate of substance i. PhysVal corresponds to a

hypothetical volume of substance (HHIF) and air polluted (CTF) per mass of material and is

determined from information about the substance’s hazard classification code (e.g. ECclass,

MAK-CH, Rcode, etc.) (The European Parliament and Council, 2008).

k
Vt ,irr.subst   PhysVali  m i (8)
i 1

k
Vt ,air polluted   PhysVali  m i (9)
i 1

The numerator of SHFE, in turn, relates to the probable energy potential of the substance i for

reaction with oxygen, where ΔHc,i is the heat of combustion and IndVali depends on the

substance’s flammability hazard class. It is worth mentioning that we did not account for

reaction runaway in such a metric. Thermal runaway could have been considered if we had

assumed that, at some point during operation, the rate of heat production exceeded the rate of

heat removal. Nevertheless, we believe that such a problem is more related to controllability

issues and depend strongly on technical, industrial data. Hence, since we are aimed at allowing

practitioners to compare the sustainability of processes during the early stages of design, the

SHFE is deemed suitable for providing sufficient information of fire/explosion risks.

22
Finally, for the CEI, AQ refers to the maximum amount of a substance that became airborne

following its release and is estimated from several parameters such as equipment and pipes

size, process conditions and fluid properties. ERPG-2 corresponds to the emergency response

planning guidelines value (American Industrial Hygiene Association Guideline Foundation,

2011). The detailed procedure for determining the variables discussed above is provided by

Ruiz-Mercado et al. (2012).

3.6.4. Indicator results

Table 9 discloses the indicators results of both technologies. We note that only RMC, WC,

WWG and SHFE indicators for the butane process are higher. The higher raw material

consumption (about 48%) is due to the off-gas recycle to the reactor inlet, which decreases the

overall conversion, thus requiring a larger amount of feedstock. In fact, Chen and Shonnard

(2004) stated that the conversion of benzene is typically higher (95%) than the butane’s (85%).

This result is expected since using vanadium-phosphorous oxide catalysts allow reducing direct

use of oxygen, which is refilled in the catalyst matrix during regeneration, and thus increases

dramatically both the butane throughput load and MAN selectivity.

[Table 9 near here]

In terms of water consumption and wastewater generation, the lower indicators for the benzene

process (2.8% and 3.1% lower, respectively) are mainly due to the heat integration between

the reactor’s feed and effluent. The WC value of 1.7467 m3/kmol for the n-butane route is close

to the one disclosed by Schwarz and coworkers (2001), who obtained a result of 1.3743

m3/kmol (1.68 gal/kmol), which is slightly lower since the authors did not consider all

heuristics for the utility plants presented in this paper.

Another similar result corresponds to the COE indicator for the butane route (approximately

43% lower), which Schwarz et al. (2001) determined to be 0.1500 tCO2-eq/kmol (1.53 kgCO2-

23
eq/kg), fairly similar to the one obtained in this study (0.1615 tCO2/kmol). In addition, the

carbon dioxide emission rates for both processes were also estimated by Chen and Shonnard

(2004), being 0.2020 tCO2/kmol (4.59 molCO2/mol) and 0.1184 tCO2/kmol (2.69

molCO2/mol) for the benzene and n-butane technologies, respectively. Such data may differ

from the results of this work (0.2830 tCO2/kmol and 0.1615 tCO2/kmol, respectively) not only

due to the different process configurations but also to the fact that said authors took into

consideration several other parameters for estimating the CO2 emissions. In spite of this, we

note that, in either case, the benzene process emits approximately twice as much CO2 as the n-

butane route.

For the benzene technology, the fuel consumption is approximately 30% higher due to the

higher energy requirements, which is reflected by the EC indicator (28% higher). However, the

CO2 emissions are about two times higher than the butane process’ due to the off-gas stream,

which is completely burned in the former but partially recycled in the latter. It is evident that

the energy consumption indicators – and therefore de fuel, CO2 emissions and water-related

indices – could be reduced in both processes if a more detailed energy-efficiency analysis was

carried out. As discussed earlier in Section 3.1.3, several techniques such as Pinch Analysis

and combined heat and power building models could be used to achieve maximum energy

recovery. The practitioner would therefore be required to analyze not only the general design

criteria to place the matches (e.g. number of exchangers, capital cost, etc.) but also consider

the energy-related indicators to develop the optimal heat exchanger network configuration and

minimize both the process costs and environmental impacts. However, one should note that, in

this paper, we are only aimed at demonstrating how such sustainability metrics can be useful

in assisting practitioners in selecting the most appropriate design schemes according to their

decision criteria, instead of designing the optimal flowsheet that provides the best possible

performance.

24
Regarding process economics, the n-butane route showed to be approximately 34% more

profitable than the benzene process, which is mainly due to both the former’s lower energy

requirements and lower feedstock price. This corroborates Malow (1985)’s work, which

compared the transfer prices for both technologies. According to the authors, for a plant annual

capacity of 20 MMlb of MAN, the transfer price for the butane alternative is approximately

5% lower than for the benzene, despite the former’s higher production costs. The results are

also in accordance with Chen and Shonnard (2004)’s analysis, which showed that the butane

process has a higher NPV. Although said references are not up to date, the butane technology

is still expected to be more economically attractive since the feedstock price is lower than the

benzene-based technology’s, which is reflected in the lowest values of PP, ROIF and IRRF.

Attention must be drawn to the fact that the NPV and NFW are methods defined in absolute

terms that ignore the project size and lifetime. In fact, they could be used in the comparison of

the different MAN manufacture technologies since both processes have nearly the same

production capacities and operate during the same period.

Finally, with respect to safety aspects, attention should be drawn to the higher HHIF of the

benzene-based route when compared to the butane’s technology, since benzene is much more

hazardous in case of either eye/skin contact or ingestion. On the other hand, the fire/explosion

hazards of the butane-based scheme are indeed expected to be much more significant (70 times

higher) due to the feedstock’s flammability characteristics. According to the National Fire

Protection Association regarding flammability categories, n-butane is identified as a class 4,

whereas benzene is classified in category 3. This highlights the significance of considering all

aspects of sustainability when comparing different technologies.

3.7. Sustainability comparison

25
The sustainability performances of the MAN production technologies were compared by means

of the Eco-efficiency Comparison Index (ECI) method, originally proposed by Pereira et al.

(2018). Such a methodology was applied by Mangili et al. (2018) to compare three acetone-

methanol separation technologies in terms of energy consumption, CO2 emissions and water

consumption. Neither economic nor safety aspects were taken into consideration. Junqueira et

al. (2018), compared six cumene production processes on the basis of environmental burdens

and economics without considering safety characteristics. More recently, economic, safety and

environmental metrics were used by Mangili and Prata (2019), who evaluated the sustainability

performance of butyl acetate production processes, and Mangili et al. (2019), who compared

four tetrahydrofuran-ethanol separation schemes. However, since the process configurations

studied by Mangili and Prata (2019) and Mangili et al. (2019) were based on the same

feedstocks and nearly the same conditions, the safety aspects did not represent an opportune

choice.

The ECI is intended to jointly evaluate process indicators in order to define the most sustainable

technology. Such a tool represents a particular advantage when compared to LCA frameworks

since an overall analysis of the environmental, economic and safety aspects is achieved. This

is recommended by ISO 14045:2012, which affirmed that only by considering all attributes

within the assessment is it possible to identify potential trade-offs. Said document also stated

that eco-efficiency is a relative concept and, therefore, it cannot be quantified for just one

process. Instead, the product system may only be deemed “more-or-less eco-efficient in

relation to another product system”. In fact, this represents another advantage of the ECI tool

when processes having different production capacities are being assessed – as in the case of

this paper – since it is based on relative metrics.

In the ECI method, the indicators are divided by the highest value of their respective group and

plotted in a radar chart, thus forming a polygon area having n sides, where n corresponds to the

26
number of metrics evaluated. Each process is represented by a polygon whose area ST is

calculated by summing up the areas (Sa) of the n minor triangles. Sa is determined through the

Law of Sines shown in Equation 10, where lA and lB refer to the adjacent sides A and B

separated by an angle θ that corresponds to 2π/n (since all axis are equidistant from one another

and set apart in a 360° circle). The ECI is then calculated as shown in Equation 11, where ST*

refers to the area of the largest polygon (i.e. the least sustainable process). It is worth

mentioning that the indicators calculated in this paper were assumed to have the same weights.

l A  lB (10)
Sa  sin 
2

 S  (11)
ECI  1  T*  100%
 ST 

3.7.1. Sustainability results

The indicators were subsequently divided by the highest value in the respective group, as

shown in Table 10. The normalized values were then displayed in a range from 0 (most

sustainable) and 1 (least sustainable) and plotted in a radar chart to form pentadecagon-shaped

forms, as illustrated in Figure 12.

[Table 10 near here]

The shape area ST of each polygon was calculated by summing up the area Sa of each minor

triangle, which were determined through Equation 10. Sides lA and lB correspond to the values

of adjacent indicators, while θ corresponds to 24° (i.e. 360° divided by 15 metrics). The

respective areas of the benzene process (ST* = 2.498) and butane process (ST = 1.647) could

then be calculated through Equation 10, as shown in Table 11. In this regard, by using Equation

11, the ECI showed that the benzene-based scheme is approximately 34% more sustainable

than the butane-based alternative. In spite of that, the latter could still be deemed the best

alternative depending on the practitioner’s criteria regarding the weights of the safety metrics.

27
 [Figure 12 near here]

[Table 11 near here]

As previously discussed, jointly evaluating process indicators is particularly convenient for the

comparison of the sustainability of industrial technologies, since single indicators do not

provide sufficient information regarding which process has the highest performance (ISO

14045:2012). Nevertheless, some of the metrics considered in this paper are correlated and may

be deemed nonessential when a quick, rough comparison is required. For instance, calculating

RMC would be unavailing for technologies where no reactions take place and/or only

improvements in the energy consumption were performed. On the other hand, the FC and COE

indicators could be neglected for processes where neither fuel consumers are present nor off-

gases are burned/vented, since the EC indicator itself would be satisfactory. The same applies

to the WWG metric, which is calculated through heuristics from the water consumption results.

In this regard, care should be taken when calculating the WC indicator for industrial processes,

since most authors do not take the utilities plant into consideration when proposing process

flowsheets. Although assuming that the utilities are acquired from external sources – as usually

exercised by most researchers – may be convenient when only techno-economic assessments

are carried out, this might lead the assessor to misjudge the ecological impact potential resulting

from the process under analysis. Depending on the concept employed by the practitioner (e.g.

LCA or eco-efficiency), different utilities can be associated with different impact categories.

For instance, heating steam to be exported may be interpreted as an energy-related aspect

instead of a water-related burden, which should then be deducted from the water consumption

calculation. This deduction, however, will have a different impact if the steam is generated in

a utility plant dedicated to the main plant, since the system boundary would also include the

outside battery limits and therefore receive water (that will be partially used to generate steam)

instead of utility steam.

28
In terms of economics, the NFWF could be neglected since it is related to the value that the

original investment will have over the project life depending on a specific interest rate, which

is the same for the technologies evaluated. Finally, with regard to safety aspects, determining

said indicators would be futile if similar processes were to be compared. For example, the

original and improved benzene technologies have nearly the same HHIF, SHFE, CTF and CEI

indicators, since the same substances at the fairly same conditions are being processed.

Due to the above reasons, most studies in the literature are performed by comparing industrial

processes by means of energy consumption and economics. However, it is recommended to

carry out a systematic overview that encompasses all aspects of sustainability – and as many

metrics as possible – when different technologies are being compared in order to provide a

more transparent and accurate assessment.

3. Conclusion

This study consisted in applying an indicator-based assessment to improve the sustainability

of an existing MAN production technology via oxidation of benzene and design a cleaner

technology via n-butane oxidation. Both processes were compared in terms of six

environmental burdens, five economic metrics and four safety indicators, which were

calculated with the aid of computational simulation. The analysis was performed by means of

the Eco-efficiency Comparison Index, which consisted in normalizing the indicators and

plotting them in a pentadecagon-shaped radar chart.

The comparison showed that the benzene technology has a lower raw material consumption

indicator (about 48%) – due to its higher conversion when compared to n-butane feedstock –

and consumes approximately 2.8% less water and generates 3.1% less wastewater – due to the

heat integration between the reactor feed and effluent. Other advantage associated with the

benzene-based route refers to fire/explosion hazards, which are 70 times lower due to n-

29
butane’s flammability aspects. On the other hand, the butane process proved not only to be

about 34% more profitable but also to consume approximately 28% less energy and,

consequently, emit 43% less CO2 per kmol of MAN. As a result, after carrying out the ECI

methodology, the butane-based technology was deemed the most sustainable alternative,

having an eco-efficient performance 34% higher than the benzene route.

It was demonstrated that sustainability indicators, together with process simulation, are

singularly convenient for designing greener industrial processes. In light of this, future studies

should seek for actual factory data in order to encompass social data and then allow a more

complete assessment. Furthermore, since the ECI framework presumes that all indicators have

the same weight, future researches may be targeted at developing and testing new techniques

for assigning weights to the assessment indicators.

Acknowledgements

This study was financed in part by the Coordenação de Aperfeiçoamento de Pessoal de Nível

Superior - Brasil (CAPES) - Finance Code 001.

Symbols

C1 Column 1
C2 Column 2
CBZ Benzene composition
CMAN MAN composition
E Required energy
FEHE Feed-effluent heat exchanger
FH1 Fired heater
FSHE Feed-salt heat exchanger
H Heat
HE1 Cooler 1
HE2 Cooler 2

30
HE3 Cooler 3
HE4 Cooler 4
HE5 Cooler 5
HE6 Cooler 6
HX1 Heater 1
HX2 Heater 2
HX3 Heater 3
HX4 Heater 4
K1 Compressor 1
K2 Compressor 2
lA Side A of minor triangle
lB Side B of minor triangle
ṁng Mass flow rate of natural gas
n Number of metrics
ng Natural gas
NCVng Natural gas net calorific value
P1 Pump 1
P2 Pump 2
P3 Pump 3
PB Partial pressure of butane
PM Partial pressure of MAN
R Gas constant
R1 Tubular reactor
Sa Area of minor triangle
ST Polygon area
ST* Area of the largest polygon
T Temperature
V Volumetric flow rate
V1 Vessel 1
V2 Vessel 2
xDib Dibutyl phthalate molar fraction
xC4 Butane molar fraction
xC6 Benzene molar fraction
xCO2 Carbon dioxide molar fraction
xH2O Water molar fraction

31
xMAN MAN molar fraction
xN2 Nitrogen molar fraction
xnitrate Sodium nitrate molar fraction
xnitrite Sodium nitrite molar fraction
xO2 Oxygen molar fraction
xQuin Quinone molar fraction

Greek symbols

Δ Differential
η Thermal efficiency
θ Angle between adjacent sides

Subscripts

air polluted Air polluted to a workplace threshold value

c Combustion
i Equipment (fuel consumer) or substance
irr.subst Substances whose contact must be avoided

Abbreviations

bfw Boiler Feed Water

CEI Chemical Exposure Index
COE CO2 Emissions
CTF Chronic Toxicity Factor
cw Cooling Water
EC Energy Consumption
ECI Eco-efficiency Comparison Index
EPA Environmental Protection Agency
ERPG Emergency Response Planning Guidelines
Fc Fixed costs
FC Fuel Consumption
FCI Fixed Capital Investment
Gauging Reaction Effectiveness for the ENvironmental
GREENSCOPE Sustainability of Chemistries with a multi-Objective Process
Evaluator
HHIF Health Hazard Irritation Factor

32
 hps High-Pressure Steam
IRR Internal Rate of Return
IRRF Internal Rate of Return Factor
ISBL Inside Battery Limits
LCA Lice Cycle Assessment
lps Low-Pressure Steam
MAN Maleic Anhydride
MCTIC Ministério da Ciência, Tecnologia, Inovações e Comunicações
mps Medium-Pressure Steam
NPV Net Present Value
NPVF Net Present Value Factor
NFW Net Future Worth
NFWF Net Future Worth Factor
PP Payback Period
RMC Raw Material Consumption
ROI Return On Investment
ROIF Return On Investment Factor
SEEG Sistema de Estimativa de Emissão de Gases do Efeito Estufa
SHFE Safety Hazard Fire/Explosion
UNCTAD United Nations Conference on Trade and Development
Vc Variable costs
WC Water Consumption
WWG Wastewater Generation

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Figure Captions

Figure 1. Sistematic flowchart.

Figure 2. Turton et al. (2018)’s original MAN flowsheet (our results).

Figure 3. Effect of the number of reactor tubes and gas recycle flow rate in the benzene

technology: (a) MAN flow rate; (b) Energy use; (c) CO2 emissions; (d) Water consumption;

(e) Capital costs; (f) Gross profit.

Figure 4. Effects of heat-integrating reactor feed and effluent (benzene process).

Figure 5. Improved sustainability-based design of Turton et al. (2018)’s MAN process.

Figure 6. Preliminary flowsheet of the MAN production process via oxidation of n-butane.

Figure 7. Effect of the number of reactor tubes gas recycle flow rate in the butane technology:

(a) C1 top flow rate; (b) MAN flow rate; (c) Energy use; (c) Water consumption; (e) Capital

costs; (f) Gross profit.

Figure 8. Reactor composition profile.

Figure 9. Flash feed temperature effect on outlet flows.

Figure 10. C2 profiles: (a) temperature; (b) composition.

Figure 11. General schematic of a utility plant.

Figure 12. ECI radar chart.

41
 Table 1. Reaction kinetics for the selective oxidation of benzene.

Reaction Rate expression

 105198 
Equation 1 r1  7.70 106 exp    CBZ
 RT 
 89659 
Equation 2 r2  2.33104 exp    CBZ
 RT 
 113591 
Equation 3 r3  7.20 105 exp    CMAN
 RT 
 124892 
Equation 4 r4  6.31107 exp    CBZ
 RT 

Table 2. Reaction kinetics for the oxidation of n-butane.

Reaction Rate expression

  93100  1 1 
9.6  10 7 exp       pB
0.54

Equation 3  R  T 673  
r3 
1  310 p M
 93100  1 1 
Equation 5 r5  1.5 107 exp       pB
0.54

 R  T 673  
 155000  1 1 
2.9 106 exp       pM
Equation 6  R  T 673  
r6 
1  310 pM 
2

42
 Table 3. Heuristics for utility plant losses.

Variable Value Reference

Treatment losses 1% of make-up water flow rate Smith (2016)

Condensate return 80% of steam flow rate Smith (2016)

Condensate losses 20% of steam flow rate Smith (2016)

Boiler blowdown 2% of bfw flow rate Smith (2016)

bfw losses 1% of cw flow rate Seider et al. (2017)

cw losses 1% of cw flow rate Seider et al. (2017)

Cooling tower losses 1% of cw flow rate Couper et al. (2012)

Cooling tower blowdown 3% of cw flow rate Turton et al. (2018)

Table 4. Environmental indicators.

Indicator Equation Unit

Total molar flow rate of raw materials

RMC kmol/kmol
Total molar flow rate of MAN

Total mass flow rate of natural gas

FC kg/kmol
Total molar flow rate of MAN

Total energy demand

EC GJ/kmol
Total molar flow rate of MAN

Total mass flow rate of CO 2 emitted

COE t/kmol
Total molar flow rate of MAN

Total volumetric flow rate of make-up water

WC m3/kmol
Total molar flow rate of MAN

Total volumetric flow rate of effluent

WWG m3/kmol
Total molar flow rate of MAN

43
 Table 5. General site expenses.

Basis Parameter Value Reference

Process equipment costs 30% of FCI

Inside Battery Seider et al.
Limits (ISBL) (2017)
Bulk items (piping, instruments, etc.) 25% of FCI

Utility plant equipment costs 20% of FCI

Towler and
Outside
Sinnott
Battery Limits Warehouse, lighting, waste handling, 40% of
etc. ISBL (2013)

Turton et al.
Other Land development costs 1% of FCI
(2018)
Civil works (roads, buildings, ditches,
etc.)
Site Turton et al.
5% of FCI
development (2018)
Field expenses (canteens, overtime,
etc.)

Seider et al.
Miscellaneous Agent fees, import duties, etc. 5% of FCI
(2017)

Design and Turton et al.

Administration, inspection, etc. 7% of FCI
Engineering (2018)

Seider et al.
Contingency 7% of FCI
(2017)
General Towler and
Working capital 5% of FCI Sinnott
(2013)
Towler and
Location
Brazil 1.14 Sinnott
factor
(2013)

44
 Table 6. General production costs.

Basis Parameter Value Reference

Maintenance 5% of FCI
Fixed costs Seider et
Overheads 5% of labor
(Fc) al. (2017)
Insurance, license fees and royalties 2% of FCI

Variable Personal protective equipment, cleaning 1% of Seider et

costs (Vc) materials, charts and accessories, etc. maintenance al. (2017)

Research and development 1% of revenue

Towler
Sales and marketing 2% of Fc + Vc and
Other
Sinnott
Human resources, accounting, finance, (2013)
35% of labor
etc.

Table 7. Economic indicators.

Indicator Equation Unit

1
NPVF M$-1
Net Present Value

1
ROIF year/%
Return On Investment

PP Payback Period years

1
IRRF %-1
Internal Rate of Return

1
NFWF M$-1
Net Future Worth

45
 Table 8. Safety and hazard indicators.

Indicator Equation Unit

Vt ,irr . subst
HHIF m3/g
Total mass flow rate of MAN
k

SHFE   H
i 1
c ,i 
104 IndVali  4  m i
MJ/kg
Total mass flow rate of MAN
Vt ,air polluted
CTF m3/g
Total mass flow rate of M AN

AQ
CEI 0.655  Dimensionless
ERPG-2

Table 9. Indicators results.

Indicator Benzene technology Butane technology

RMC 1.6142 2.3922a
FC 15.4150a 11.8006
EC 4.0489a 3.1638
COE 0.2887a 0.1651
WC 1.6985 1.7467a
WWG 1.1639 1.2014a
NPVF 0.0978a 0.0324
ROIF 0.0772a 0.0510
PP 6.0000a 3.5000
IRRF 0.0581a 0.0316
NFWF 0.0377a 0.0125
HHIF 155.9873a 49.7687
SHFE 1.6737 70.1948a
CTF 865.4082a 826.9052
CEI 779.1423a 758.3040
a Highest value in each group.

46
 Table 10. Normalized indicators.

Indicator Benzene technology Butane technology

RMC 0.675 1.000
FC 1.000 0.766
EC 1.000 0.781
COE 1.000 0.572
WC 0.972 1.000
WWG 0.969 1.000
NPVF 1.000 0.331
ROIF 1.000 0.662
PP 1.000 0.583
IRRF 1.000 0.543
NFWF 1.000 0.331
HHIF 1.000 0.319
SHFE 0.024 1.000
CTF 1.000 0.956
CEI 1.000 0.973

Table 11. Quantitative ECI results.

Indicator x indicator Benzene technology Butane technology
RMC x FC 0.675 0.766
FC x EC 1.000 0.598
EC x COE 1.000 0.447
COE x WC 0.972 0.572
WC x WWG 0.942 1.000
WWG x NPVF 0.969 0.331
NPVF x ROIF 1.000 0.219
ROIF x PP 1.000 0.386
PP x IRRF 1.000 0.317
IRRF x NFWF 1.000 0.180
NFWF x HHIF 1.000 0.106
HHIF x SHFE 0.024 0.319
SHFE x CTF 0.024 0.956
CTF x CEI 1.000 0.930
CEI x RMC 0.675 0.973
Sum 12.281 8.100
Pentadecagon area (ST) 2.498 1.647
ECI ______ 34.04%

47
Graphical abstract

48
Highlights

 Preliminary design of MAN manufacturing processes based on sustainability metrics.

 Design and simulation of utility plants through heuristic approaches.

 Calculation of fifteen categories of sustainability indicators.

 Comparison of MAN technologies through a composite sustainability index.

Declaration of Interest Statement

The authors state that there are no interests to declare.

49