Accepted Manuscript

Biodiesel production by the methylic-alkaline and ethylic-enzymatic routes:

discussion of some environmental aspects

Marcia de Mello, André Young, Hugo Villardi, Fernando Pessoa, Andrea Salgado

PII: S0959-6526(17)30039-2

DOI: 10.1016/j.jclepro.2017.01.032

Reference: JCLP 8779

To appear in: Journal of Cleaner Production

Received Date: 15 August 2016

Revised Date: 04 January 2017

Accepted Date: 06 January 2017

Please cite this article as: Marcia de Mello, André Young, Hugo Villardi, Fernando Pessoa, Andrea
Salgado, Biodiesel production by the methylic-alkaline and ethylic-enzymatic routes: discussion of
some environmental aspects, Journal of Cleaner Production (2017), doi: 10.1016/j.jclepro.
2017.01.032

This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to
our customers we are providing this early version of the manuscript. The manuscript will undergo
copyediting, typesetting, and review of the resulting proof before it is published in its final form.
Please note that during the production process errors may be discovered which could affect the
content, and all legal disclaimers that apply to the journal pertain.
 ACCEPTED MANUSCRIPT

Highlights

 Soybean biodiesel production by methylic-alkaline catalysis is simulated in Aspen

HYSYS.
 Soybean biodiesel production by ethylic-enzymatic catalysis is simulated in Aspen
HYSYS.
 Environmental impacts are assessed by means of the 12 Principles of Green Chemistry
 Environmental impacts are assessed by means of sustainability metrics
 The ethylic-enzymatic catalysis is a more environmentally friendly route.
 ACCEPTED MANUSCRIPT

Biodiesel production by the methylic-alkaline and ethylic-enzymatic routes:

discussion of some environmental aspects

Marcia de Mello, André Young *1, Hugo Villardi, Fernando Pessoa and Andrea Salgado

Escola de Química, Universidade Federal do Rio de Janeiro, Av. Athos da Silveira

Ramos, 149, Ilha do Fundão, Rio de Janeiro 21941-909, Brazil.

Abstract. A comparative environmental impact analysis of the soybean biodiesel

production by two different technologies is run in this study. The production routes

evaluated were the alkali-catalyzed (catalyst: sodium hydroxide) methylic

transesterification and enzyme-catalyzed (catalyst: lipase) ethylic transesterification.

The study includes the simulation of the biodiesel production process with the software

Aspen HYSYS, from AspenTech Inc., and a subsequent comparative analysis of the

main environmental impacts observed in each case, based on the application of two

approaches: analysis of the Principles of Green Chemistry and calculation of some

sustainability metrics. Results indicated a better environmental performance for the

enzymatic route, in almost all the analyzed issues, what proves that this route is an

excellent option for future industrial applications, regarding safety and sustainability.

Keywords: Biodiesel, Alkaline catalysis, Enzymatic catalysis, Green chemistry,

Sustainability metrics

1- Introduction

1 Corresponding author. E-mail address: young@eq.ufrj.br

1
 ACCEPTED MANUSCRIPT

Biodiesel is a biodegradable fuel, constituted by a mixture of fatty acid alkyl

esters, which could be produced from several raw materials like vegetable oils, animal

fats, residual cooking oils, residual oils from the vegetable oil refinement and even

sanitary sewage. This alternative fuel can also be produced by means of several

processes, such as the hydrolysis followed by esterification (hydro esterification), the

esterification followed by transesterification and others (Knothe et al., 2005; Young et

al., 2015a). The different production routes could be based on homogeneous catalytic

reactions with acid or alkaline catalysts (Young et al., 2015b, 2015c), heterogeneous

catalytic reactions with chemical (Farooq et al., 2013) or biochemical (Magalhães et al.,

2015) catalysts, or even in the absence of catalysts, under supercritical conditions

(Marulanda, 2012).

The main production route used in industry around the world nowadays is the

homogeneous alkaline transesterification of the alkyl esters with a short chain alcohol,

generally methanol (Young et al., 2015b, 2015c; Zhang et al., 2003). In Brazil, about 75

% of the feedstocks used for biodiesel production is soybean. Soybean is also the most

used feedstock for biodiesel production in the world and, because of that, many authors

have published life cycle assessments regarding the whole soybean biodiesel production

chain (Castanheira et al., 2015; Cavalett and Ortega, 2010; Reijnders and Huijbregts,

2008). However, in a continuous search for more economical and sustainable solutions,

alternative feedstocks, such as microalgae (Monari et al., 2014) and waste cooking oil

(Eguchi et al., 2015), and alternative technologies (Morais et al., 2010) have emerged

and their economic and environmental benefits are being extensively studied.

There is an evident tendency in the scientific literature to the study of processes

that use heterogeneous catalysts (Farooq et al., 2013; Islam et al., 2014). Specially, and

already with industrial application, stands out the enzymatic catalysis, where lipases are

2
 ACCEPTED MANUSCRIPT

used as catalysts in transesterification (Magalhães et al., 2015; Young et al., 2015a).

This process seems to have certain economic (Young et al., 2015a) and environmental

(Harding et al., 2008) advantages over other emerging technologies, such as the

supercritical route (Kiwjaroun et al., 2009).

Among the advantages of the biodiesel production with lipases, the milder

reaction conditions, the lower capital cost involved and the lower generation of effluents

could be mentioned. Environmental benefits of the enzymatic catalysis over the

conventional alkaline catalysis were demonstrated by Harding and co-workers through a

life cycle assessment (Harding et al., 2008). The greatest obstacle to the definitive

implementation of the enzymatic technology at industrial level is probably the high

catalyst cost (Young et al., 2015a).

Another interesting aspect from the environmental point of view would be the

substitution of methanol, normally generated from fossil sources, by ethanol, which

normally comes from renewable sources. This is a particularly interesting alternative to

ethanol producing countries, like Brazil (Hall et al., 2009) or the United States.

The objective of this work is to evaluate the environmental impact of the

soybean biodiesel production by the methylic-alkaline route, which is the most common

technology, and by the ethylic-enzymatic route, which is an emergent and promising

technology. Yet, differently from what has been done in great part of the studies so far,

this article does not aim at a life cycle assessment of the whole biodiesel production

chain. This type of analysis is more complex and generally limited by data availability

and generalizations (Holma et al., 2013; Macombe et al., 2013). The focus is only on

simulation data of the vegetable oil conversion step. This evaluation was done by means

of two different approaches: the analysis of the 12 Principles of Green Chemistry, by

3
 ACCEPTED MANUSCRIPT

Anastas and Warner (1998), and the use of the sustainability metrics proposed by

Jensen et al. (2003).

2 - Biodiesel Production Simulation

Biodiesel production was simulated in the software Aspen HYSYS version 8.4,

from AspenTech Inc. The methods used for soybean oil modeling, as well as for the

simulations of the two routes are described in this section.

2.1 - Soybean Oil Modeling

As an input, an important aspect to be considered is the composition of the

soybean oil load. Many authors have used loads constituted by pure triolein (West et al.,

2008, 2007; Zhang et al., 2003), pure trilinolein (Carneiro Junior et al., 2011), or even

mixtures containing these and other triacylglycerols (TAGs) with three identical fatty

acid chains (Garcia et al., 2010). In this study, the oil inlet was considered a mixture of

the five TAGs that were present in a chromatography analysis of refined soybean oil

given by Castro et al. (2011): POLi (13.21 %), PLiLi (19.44 %), OOLi (14.29 %),

OLiLi (25.40 %) and LiLiLi (27.66 %), being P the representative chain of the palmitic

ester, O the representative chain of the oleic ester and Li the representative chain of the

linoleic ester.

Compounds not included in the software library, like the TAGs (main

components of the soybean oil) and the esters ethyl palmitate, ethyl linoleate and ethyl

oleate (present in the product), were considered in the simulations by means of the

Hypo Manager tool, which allows the construction of hypothetical substances.

Therefore, the compound structures were used as input and the important properties

4
 ACCEPTED MANUSCRIPT

were estimated through standard methods. Critical properties were estimated with the

Constantinou-Gani method (Constantinou and Gani, 1994).

The most used thermodynamic packages to simulate biodiesel production in

literature are NRTL and UNIQUAC (Zhang et al., 2003). In this study, as a function of

each equipment and their systems, either one or the other of these methods was used.

No change was performed in the parameter matrixes presented by the simulator. The

UNIQUAC package of Aspen HYSYS was applied only when the NRTL method was

not able to correctly predict the expected liquid-liquid equilibrium, according to

previous literature information.

2.2 - Biodiesel production by the methylic-alkaline route

Biodiesel production from soybean oil and methanol was simulated in Aspen

HYSYS with the flowsheet proposed in Fig. 1. Properties of the streams can be viewed

in Table A.1 in the Appendix.

Refined soybean oil (stream 101) is heated in the heat exchanger E-101. The

preheated oil at 69.30 ºC (stream 102) is mixed with stream 106, composed by

anhydrous methanol, recycled methanol and catalyst, at mixer M-103. Methanol is

mixed with the oil at a molar to molar ratio of 6:1. Heat provided by the preheated oil is

sufficient to put the reactants mixture at 60 ºC, which is the desired reaction

temperature.

Soybean oil transesterification with methanol occurs in the presence of the

alkaline catalyst NaOH, at 1 % m/m, 60 ºC and 1 atm (Zhang et al., 2003). Conversion

of 98 % was considered under these conditions. A conversion reactor (R-101) was

chosen due to lack of information about the reaction kinetics. The reaction was

5
 ACCEPTED MANUSCRIPT

performed with excess of alcohol, to assure the equilibrium displacement in the

products direction as it is a reversible reaction (Freedman et al., 1986, 1984).

The outlet stream of the reactor is sent to decanter D-101, operating at 60 ºC and

atmospheric pressure. The lightest phase, biodiesel rich, stream 111, presents 8.2 % of

methanol. The heaviest phase, stream 110, has a concentration of 79.4 % of glycerol.

Such compositions indicate the necessity of additional treatment for both streams.

Both streams are sent, separately, to methanol separation in the Flash vessels F-

101 and F-201, respectively. The recovered alcohol in stream 117 is recycled and added

to the methanol stream and the catalyst in mixer M-102, from which the resultant

mixture is added to the preheated oil stream to form the reactor’s load. Both Flash

vessels operate at atmospheric pressure and temperature of 140 ºC, to assure the alcohol

separation and avoid degradation of glycerol or biodiesel at 150 ºC and 250 ºC,

respectively (Goodrum, 2002; Zhang et al., 2003). The obtained glycerin (stream 204)

has a concentration of 93.8 %.

The light phase from decanter D-101, after distillation in the Flash vessel F-101,

goes to a serial countercurrent system of decanters (D-102, D-103, D-104 and D-105),

in order to remove catalyst and traces of glycerol. This system operates at atmospheric

pressure. The biodiesel stream (133) is directed to vessel F-102, for drying at 70.93 kPa

and 210 ºC. After that, biodiesel is pumped by P-101 and goes to a serial countercurrent

system of heat exchangers (E-105 and E-106), with the objective to produce biodiesel

(stream 138) at atmospheric conditions, 25 ºC and 1 atm.

Fig. 2 shows a schematic representation of the global balance involved in the

methylic-alkaline process. Mass and energy balances are showed in Table A.2 in the

Appendix.

6
 ACCEPTED MANUSCRIPT

2.3 - Biodiesel production by the ethylic-enzymatic route

Biodiesel production from soybean oil and ethanol by enzymatic catalysis was

simulated in Aspen HYSYS with the flowsheet exposed in Fig. 3. Properties of the

streams can be viewed in Table A.3 in the Appendix.

Refined oil (stream 101) is heated in heat exchanger E-101. Anhydrous ethanol

(stream 103) is mixed with the preheated oil (stream 102) at 31.58 ºC, at a molar to

molar ratio of 3:1 and 4 % of the vegetable oil mass of water (stream 104) is added in

mixer M-101. Heat supplied by the preheated oil is sufficient to put the reactants

mixture at 30 ºC, which is the desired reaction temperature.

Reaction was conducted in two packed bed reactors, to assure the reduction of

the number of downstream purification steps, besides the possibility of catalyst (lipases)

reuse, favoring the process both economically and environmentally. The catalyst

quantity adopted in each bed consists of 15 % of the processed oil mass. Reaction was

conducted with a stoichiometric quantity of alcohol, which avoided the need for one

more purification step (ethanol recovering). In both reactors the reaction proceeded at

30 ºC and 1 atm. Some references have pointed out excellent results under these

conditions (Magalhães et al., 2015; Watanabe et al., 2000).

The division of the reaction step in two reactors assure not only that the alcohol

does not deactivate the enzymes, but also that higher conversions are reached. The first

reactor receives 4 % of water, 15 % of enzymes (both over the mass of vegetable oil)

and ethanol in a molar to molar ratio of 2:1. The second one has the same quantities of

water and enzymes, but ethanol is added in a proportion of 1:1. Conversions obtained

under these conditions were 64 % and 98 % in the first (R-101) and second (R-102)

reactors, respectively.

7
 ACCEPTED MANUSCRIPT

Between the reactors, there is a decanter (D-101) to avoid the flow of glycerol in

an excessive quantity to the second reactor, what would favor the occurrence of reverse

reaction and contribute to catalyst deactivation (Young et al., 2015a).

Due to the separation step between the reactors, there is an improvement in the

quantity of water present in the biodiesel stream (109). Because of that, a Flash vessel

(F-101) was used before the second reactor, to assure the entrance of just 4 % of water.

The outlet stream from reactor R-102 is sent to a decanter (D-102), operating at 30 ºC

and 1 atm. Two streams are obtained from this equipment: the top stream (120),

biodiesel rich, and the bottom stream (119), glycerol rich. Glycerin generated in this

step has a purity equivalent to 92.43 %, containing 6.93 % of water and traces of

ethanol and biodiesel.

Stream 108A, from decanter D-101, has 82.16 % of glycerol and 16.77 % of

water. Before adding this stream to stream 119, with the objective of commercialization,

it is necessary to use a Flash vessel (F-201) at 142 ºC and 1 atm to reduce its water

content. The outlet stream (202) is then directed to mixer M-201, where it is added to

stream 199. The final glycerin stream (205), after cooling, presents a purity equivalent

to 91.01 %, with 8.62 % of water and traces of ethanol and biodiesel.

The produced biodiesel (stream 102), due to its high content of water, glycerol,

alcohol and unreacted TAG, must be submitted to a purification step, aiming to achieve

the specifications of the regulatory agency (Young et al., 2015b, 2015c). In Brazil,

biodiesel specifications are determined by the National Agency of Petroleum, Natural

Gas and Biofuels (ANP, in Portuguese). Biodiesel is initially sent to a washing step and,

after that, to a Flash vessel (F-102) for water removal. The washing step is performed in

a countercurrent process, divided in two serial stages (D-103 and D-104). In the

proposed system, impure biodiesel (stream 120), interacts in the first stage with the

8
 ACCEPTED MANUSCRIPT

recycle stream 127, the extract phase from the second stage. Preheated fresh water

(stream 126) is added in sequence. It is preheated in heat exchanger E-105, the first of a

series of two exchangers used to cool the purified biodiesel (stream 134).

After washing, the outlet stream from decanter D-104 goes to drying in a Flash

vessel (F-102) operating with vacuum application (70.93 kPa). Vacuum operation is

necessary because of the degradation temperatures of biodiesel and glycerol, as

mentioned earlier (Goodrum, 2002; Zhang et al., 2003). The purified biodiesel stream

(133) is then pumped by P-101 until the heat exchangers E-105 and E-106, from which

it comes out at atmospheric conditions.

Fig. 4 shows a schematic representation of the global balance involved in the

ethylic-enzymatic process. Mass and energy balances are showed in Table A.4 in the

Appendix.

Based on the data showed as simulation results, it is possible to see that the

enzymatic catalysis favors effluent minimization, as well as generates them in less

aggressive compositions. There is also the possibility of catalyst reuse and the use of

alcohol in stoichiometric quantities, what reduces the number of stages required for

purification and could lead to economic advantages (Young et al., 2015a). Besides that,

the presence of milder conditions makes the process safer.

With the intention of making the plants more competitive, an energy integration

procedure was tested in the drying step of the two routes, as the simulations have shown

that this is the point of greatest energy loss. In this sense, the top streams from vessels

F-101 and F-201 (methanol recovery and glycerin purification, respectively), which

compose the methanol recycle, could be cooled by E-103 to liquefy methanol, avoiding

the circulation of this toxic compound in the gas phase. Partial heating of vessel F-101’s

load with the energy stream E-103 could also reduce thermal energy consumption in E-

9
 ACCEPTED MANUSCRIPT

102. These modifications would allow the reduction of the total thermal energy

consumption of the process from 939.83 to 723.13 MJ/h (from 977.70 to 752.26 kJ/kg

of biodiesel produced), a saving of 23 %.

In the enzymatic route, the bottom products from vessels F-101 and F-102 could

be used to partially heat theirs loads. This new configuration would reduce energy loss

in exchangers E-103 and E-106, as well as allow the total thermal energy consumed by

the plant to be reduced from 984.74 to 510.12 MJ/h (from 1038.28 to 537.86 kJ/kg of

biodiesel produced), a saving of 48 %.

By using the proposed energy integration strategies, the enzymatic route

becomes more energetically efficient than the alkaline route, as its energy consumption

would be about 28.5 % lower. These results can be better seen in Tables A.2 and A.4,

which show the energy rates before and after energy integration implementation.

3 - Environmental Impact Evaluation

The environmental impact analysis was performed by means of two different

approaches: the analysis of the 12 Principles of Green Chemistry, by Anastas and

Warner (1998), and the use of the sustainability metrics proposed by Jensen et al.

(2003). Both approaches are discussed next.

3.1 - Application of the Principles of Green Chemistry

The 12 Principles, as exposed by Anastas and Warner (1998), outline an early

conception of what would make a chemical process or product “greener”, i.e. more

environmentally-friendly. These principles are still in accordance with the more recent

12 Principles of Green Engineering (Anastas and Zimmerman, 2003) and the Sandestin

Principles of Green Engineering (Abraham and Nguyen, 2003), but more focused on the

10
 ACCEPTED MANUSCRIPT

chemical aspects involved in the production process. The decision to use these criteria

lies on our intention to restrict our analysis to the biodiesel production process and we

consider it to be more in accordance with the differences we see between these two

routes.

The two production routes were compared in the basis of each one of the 12

Principles. Aiming at giving a more quantitative character to this evaluation, grades

from 0 to 2 were attributed as a function of the lesser or greater attendance of each

principle. The final result was obtained as a sum of the results in each principle. It is a

very simple methodology, based on a more robust one proposed by other researchers

(Jensen et al., 2003). With the observations made at each point, it was possible to

determine what “bottlenecks” could be present in each technology and which route

causes the biggest impact on the environment.

3.1.1 - Principle 1: Prevention

“It is better to prevent waste than to treat or clean up waste after it has been

created” (Anastas and Warner, 1998).

Controlling and treating residues after its generation are environmentally correct

solutions. Nowadays, however, with increasing environmental concerns and application

of green chemistry concepts, a new philosophy stands out: avoiding residues generation

is less expensive than treating them. This principle shows the importance of considering

reductions in effluent generation already in the project phase, aiming at direct

investment application in cleaner and efficient technologies, since the starting point.

According to this principle, the greater the quantity of generated residues and the

more pollutant they are, the greater are the volumes to be treated, more complex the

treatment will be and lower must be the grade attributed to the process.

11
 ACCEPTED MANUSCRIPT

Despite the greater number of effluents, the enzymatic route generates a smaller

quantity of residues per kilogram of biodiesel produced than the alkaline route. It is also

possible to notice that the effluent streams from the alkaline route are more diluted,

while the effluents from the enzymatic route are more concentrated in terms of

contaminants. It occurs because of the greater amount of water in the effluents of the

alkaline route, which have 94.6 % of water, against 61.4 % in the effluents of the

enzymatic route.

Another point to highlight is the fact that, in the alkaline route, the catalyst

(NaOH) is continually eliminated as part of the effluents, while, in the enzymatic route,

the application of the heterogeneous catalyst in a packed bed allows its reuse (Watanabe

et al., 2000).

Due to the given arguments, the enzymatic route, despite providing residues in a

lower quantity, received grade 1, because it is also an effluent generator that would

demand investments for correct treatment and disposal. The alkaline route, due to the

greater quantity and the lower quality of its residual streams, received grade 0.

3.1.2 - Principle 2: Atom Economy

“Synthetic methods should be designed to maximize the incorporation of all

materials used in the process into the final product” (Anastas and Warner, 1998).

An useful parameter to evaluate atom economy is the E-Factor, calculated as the

ratio between the sum of the mass flowrates of all the secondary substances, like

unconverted reactants and solvents, except water, and the mass flowrate of the main

product. The process can be considered more efficient the greater is the incorporation of

the reactants in the final product and, consequently, the lesser is the quantity of effluents

generated, what would lead to lower E-Factor values.

12
 ACCEPTED MANUSCRIPT

Table 1 shows the details in the calculation of the E-Factor for the alkaline and

enzymatic routes. The alkaline route obtained the higher E-Factor value, consequently

being the less “greener” route based on this principle. It was attributed grade 1 to the

enzymatic route as it also presents unreacted compounds, and grade 0 to the alkaline

route, because of the higher E-Factor value.

3.1.3 - Principle 3: Less Hazardous Chemical Syntheses

“Wherever practicable, synthetic methods should be designed to use and

generate substances that possess little or no toxicity to human health and the

environment” (Anastas and Warner, 1998).

The enzymatic route uses soybean oil and anhydrous ethanol as reactants,

besides water and lipases. Reaction products are biodiesel and glycerol. All these

substances are nonhazardous and have high biodegradability potential (Demirbaş, 2009;

Durkee, 2006; Viana et al., 2012). On its side, the alkaline route uses methanol as

reactant and sodium hydroxide as catalyst. Both substances are toxic (Malcolm Pirnie,

1999). Due to this fact, the alkaline route received grade 1, while the enzymatic route

received grade 2.

3.1.4 - Principle 4: Designing Safer Chemicals

“Chemical products should be designed to affect their desired function while

minimizing their toxicity” (Anastas and Warner, 1998).

This principle is complementary to Principle 3, however here the focus is on the

nature of the generated product. As the products obtained in both routes (i.e., biodiesel

and glycerol) are the same and both are nontoxic and biodegradable (Demirbaş, 2009;

Viana et al., 2012), grade 2 was attributed to both routes.

13
 ACCEPTED MANUSCRIPT

3.1.5 - Principle 5: Safer Solvents and Auxiliaries

“The use of auxiliary substances (e.g., solvents, separation agents, etc.) should

be made unnecessary wherever possible and innocuous when used” (Anastas and

Warner, 1998).

There are reactions that require a big quantity of solvents, many times toxic,

which in the end are usually disposed as residues, causing pollution. Higher quantities

of solvent also complicate and make the treatment and disposal steps more expensive.

Based on this principle, the use of solvents should be avoided.

Both the enzymatic and the alkaline routes use water as solvent in the washing

step. Although water is a non-toxic substance, it would be interesting to minimize the

use of this valuable resource in industrial processes. The alkaline route requires much

more water in the washing step (1.56 kg/kg biodiesel) than the enzymatic route (0.25

kg/kg biodiesel), therefore it received grade 1, while the second received grade 2.

3.1.6 - Principle 6: Design for Energy Efficiency

“Energy requirements of chemical processes should be recognized for their

environmental and economic impacts and should be minimized. If possible, synthetic

methods should be conducted at ambient temperature and pressure” (Anastas and

Warner, 1998).

According to this principle, transformations at atmospheric conditions must be

preferred over more severe applications of temperature and pressure. This concept is

based on the fact that milder conditions provide higher operational safety, as well as

lower energy consumption in pumps, compressors, furnaces, refrigeration towers and so

on.

14
 ACCEPTED MANUSCRIPT

In the two routes, it was considered that all the process occurs in atmospheric

conditions, except in the final drying stage, in which vacuum operation is required. It

should be noted that some authors indicate a little pressure increment in the reaction

stage of the alkaline process, to keep the alcohol in the liquid phase and improve the

reaction rate (Young et al., 2015b, 2015c; Zhang et al., 2003), but this approach was not

considered in this study. Regarding the temperatures, however, enzymatic

transesterification occurs in a milder temperature than the alkaline (30 ºC against 60 ºC,

respectively). For this reason, grade 2 was attributed to the enzymatic process and grade

1 was attributed to the alkaline process.

3.1.7 - Principle 7: Use of Renewable Feedstocks

“A raw material or feedstock should be renewable rather than depleting

whenever technically and economically practicable” (Anastas and Warner, 1998).

Soybean oil, the main raw material used in both routes, is an agricultural and

renewable input. The difference between the routes comes from the chosen alcohol.

While the enzymatic route uses ethanol, which comes majorly from renewable sources

like sugar cane, the alkaline route uses methanol, whose origin is majorly fossil. Being

so, grade 2 was attributed to the enzymatic route and grade 1 was attributed to the

alkaline route, which is just partially green according to this principle.

3.1.8 - Principle 8: Reduce Derivatives

“Unnecessary derivatization (use of blocking groups, protection/deprotection,

temporary modification of physical/chemical processes) should be minimized or

avoided if possible, because such steps require additional reagents and can generate

waste” (Anastas and Warner, 1998).

15
 ACCEPTED MANUSCRIPT

The substances cited in this definition tend to originate residual streams or

improve the volume of the streams that would already be formed. It could create the

necessity of additional purification and treatment steps. Because there is not any

contaminant of such group neither in one nor in the other route, both received grade 2.

3.1.9 - Principle 9: Catalysis

“Catalytic reagents (as selective as possible) are superior to stoichiometric

reagents” (Anastas and Warner, 1998).

Catalyst using is environmentally positive because it allows faster and

energetically less expensive reactions. The more developed the technology behind the

catalyst is, the more selective it is expected to be, what favors less residues generation.

Besides that, heterogeneous catalysts could be easily separated after reaction and even

reused.

Both routes use catalysts in their reactors. However, the enzymatic route uses

immobilized lipases, a biochemical, more specific, heterogeneous and reusable catalyst,

while the alkaline route uses sodium hydroxide, a chemical, little specific,

homogeneous catalyst, which implies higher reaction temperatures. Due to this fact, the

enzymatic route received grade 2, while the alkaline route received grade 1.

3.1.10 - Principle 10: Design for Degradation

“Chemical products should be designed so that at the end of their function they

break down into innocuous degradation products and do not persist in the environment”

(Anastas and Warner, 1998).

Biodiesel and glycerol, the two main products of both routes, are substances

with lower toxicity and great biodegradability potential (Demirbaş, 2009; Viana et al.,

16
 ACCEPTED MANUSCRIPT

2012). It is important to mention that even the residual streams from both analyzed

systems are biodegradable. Even methanol, despite its toxicity, is biodegradable

(Malcolm Pirnie, 1999).

However, as a fuel, biodiesel generates in its combustion the same products as

an ordinary fossil fuel, although in different quantities. Among these products, CO2,

CO, NOX and volatile organic compounds (VOCs) could be cited. Being so, both routes

received grade 1. Biodiesel itself should not be understood as the ultimate green energy

source, but as a promptly available option to a world excessively dependent on fossil

fuels.

3.1.11 - Principle 11: Real-time analysis for Pollution Prevention

“Analytical methodologies need to be further developed to allow for real-time,

in-process monitoring and control prior to the formation of hazardous substances”

(Anastas and Warner, 1998).

With process control, it is possible to detect contaminant substances as soon as it

appears, as well as it is possible to study the operational conditions necessary to avoid

degradation.

In the alkaline route, due to the catalyst, acidity control of the vegetable oil load

would be very welcome. It is important because acidity excess could lead to

saponification reactions. The formed soap is not only a contaminant, but it acts as

emulsifier and complicates product separation. Besides that, presence of soap improves

catalyst consumption and viscosity of the medium, factors that cause yield decrease and

production cost increase.

Another point that must be considered is control on the water inlet after the

separation step. Water in the medium promotes hydrolysis of the produced esters,

17
 ACCEPTED MANUSCRIPT

generating fatty acids and alcohols, reducing overall process yield and increasing

product acidity.

Methanol levels can be monitored in the effluent streams from the washing and

drying steps. Methanol has high toxicity, so these streams would have to be treated and

adequately disposed. It is also very important to perform leakage control in proximity of

the methanol tank and along this entire pathway throughout the plant.

Since the enzymatic route requires water addition, in a minimal level, to promote

enzymatic activity, it would be opportune to consider control on the water flow to the

reactor. In the enzymatic medium, there is no risk of soap formation. However, due to

the biochemical nature of the catalyst, the acidity index, as well as the alcoholic level of

the medium, should be monitored, because excessive concentrations could cause loss of

enzymatic activity (Young et al., 2015a).

Therefore, both routes demand control to assure operational efficiency and

occupational or environmental security. Because of the presence of methanol in the

alkaline route, which requires additional and most rigorous control, this route received

grade 0, while the enzymatic route received grade 1.

3.1.12 - Principle 12: Inherently Safer Chemistry for Accident Prevention

“Substances and the form of a substance used in a chemical process should be

chosen to minimize the potential for chemical accidents, including releases, explosions,

and fires” (Anastas and Warner, 1998).

Regarding all the substances involved in biodiesel production by the two

analyzed routes, methanol presents the higher toxicity grade (Malcolm Pirnie, 1999).

Additionally, although biodiesel presents a variable flash point, as a function of its

vegetable oil origin, those values are usually high. The same occurs with vegetable oils

18
 ACCEPTED MANUSCRIPT

and glycerol. So, these compounds do not imply considerable problems in the

attendance of this principle.

The alcohols, however, present much lower flash points and can be considered

inflammable compounds. Because of that, both routes present great explosive and fire

potentials. The risk associated with the alkaline route could be considered higher,

because it requires more alcohol, the drying process is more rigorous and methanol, as

chosen for this route in this study, is more toxic and flammable than ethanol. Because of

that, grade 0 was attributed to the alkaline process, while the enzymatic process

received grade 1.

3.2 - Application of the sustainability metrics.

The sustainability metrics are useful parameters to point out how much of the

energy consumption of a chemical process comes from renewable sources. Additionally,

it serves to verify how much of the materials involved is hazardous and how much

could be better utilized throughout the process, with recycles or correct disposals. In this

study, metrics related to raw material, energy and water consumption were analyzed.

These metrics were proposed by the Institution of Chemical Engineers (IChemE)

(Tallis, 2002) and have been used by other authors as a guide to sustainability (Jensen et

al., 2003). Results are summarized in Table 3.

3.2.1 - Metric E.1 – Total net primary energy usage rate = imports-exports

The objective of this metric is to evaluate energy imports and exports in a

process plant. The imports are the energy acquired from external sources, like liquid,

solid or gas fuels utilized for vapor generation or in furnaces, as well as electricity.

Exports means the total energy that leaves the process, like the electricity that could be

19
 ACCEPTED MANUSCRIPT

commercialized with the local concessionary, vapor or heated water that could be

redirected to another plant and so on.

There are no energy exports in the processes. Without energy integration, total

energy imports are 939.89 MJ/h in the alkaline process and 984.79 MJ/h in the

enzymatic process. When energy integration is applied, total energy imports become

723.18 MJ/h for the alkaline process and 510.17 MJ/h for the enzymatic process,

corresponding to an improvement of 29 %.

The point with bigger demand of imported energy is the entrance of Flash vessel

F-102. This occurs in both routes. It is also observed that, in both of them, the

participation of the imported electricity is little significant against the thermal energy

inputs. According to these data, Metric E.1 demonstrated a higher sustainability level of

the enzymatic route, which presents the lowest energy consumption if energy

integration is adopted.

3.2.2 - Metric E.2 – Percentage total net primary energy sourced from renewables

With this metric, it is possible to analyze, in each route, the quantity of the

consumed energy that comes from renewable sources. According to the Brazilian

Ministry of Mines and Energy (MME, in Portuguese), the electricity generated from

renewable sources in 2015 constituted 84 % of the national matrix (Portal Brasil, 2015).

Regarding the thermal energy, considering that it is obtained only from furnaces

working with diesel, fuel oil or natural gas, as all of these fuels are non-renewable, the

renewable energy fraction of the imported energy content was considered 0 %.

Applying these considerations to the values reported in Tables A.2 and A.4, it is

observed that the renewable fraction of the energy consumed in the alkaline route

corresponds to 0.0061 %, while in the enzymatic route it corresponds to 0.0088 %. It is

20
 ACCEPTED MANUSCRIPT

an improvement of 44 % but, because differences in terms of consumed electricity are

insignificant, differences in Metric E.2 will also be insignificant, with the enzymatic

route having a little advantage.

3.2.3 - Metric E.3 – Total net primary energy usage per kilogram of product

The objective of this metric is to evaluate the relation between the total energy

consumed by the plant and the quantity of product generated. It is calculated by the ratio

between these two variables. These values can be obtained from Tables A.2 and A.4.

For the alkaline route it corresponds to 752.26 kJ/kg of biodiesel and for the enzymatic

route it is equal to 537.86 kJ/kg of biodiesel, corresponding to an improvement of 28 %.

The enzymatic route presents with this metric the best environmental performance.

3.2.4 - Metric M.1 – Net water consumed per unit mass of product

The simulations showed that in the alkaline route total water consumption

corresponds to 1.56 kg/kg of biodiesel produced, while in the enzymatic route this value

falls out to 0.25 kg/kg of biodiesel produced. There is a saving of 84 % of water.

Therefore, the enzymatic route presents the best environmental performance in this

sense.

3.2.5 - Metric M.2 – Quantity of residues generated per kilogram of product

It is not listed among the metrics from IChemE, but it is an adaption of some

metrics related to emissions, effluents and waste disposal (Tallis, 2002).

According to the simulations, in the methylic alkaline route, about 1.65 kg of

residues are generated per kilogram of biodiesel produced. In the enzymatic route, this

21
 ACCEPTED MANUSCRIPT

value falls out to 0.40 kg/kg of biodiesel produced, a reduction of 76 %. Once more, the

enzymatic route is that with the best environmental performance.

3.2.6 - Metric M.3 – Total raw materials used per kilogram of product

In the alkaline process, to produce 961.27 kg/h of biodiesel, 117.34 kg/h of

methanol, 1000 kg/h of TAG and 10 kg/h of catalyst are necessary, totaling 1.17 kg of

raw material consumed per kilogram of biodiesel produced. In the enzymatic route, to

produce 948.43 kg/h of biodiesel, 163.16 kg/h of ethanol, 1000 kg/h of TAG and 40

kg/h of water are necessary, totaling 1.27 kg of raw material consumed per kilogram of

biodiesel produced.

It is observed that the enzymatic route, independently of the presence of water,

requires a bigger quantity (mass) of raw material to produce the same quantity of

biodiesel. The difference is related to the mass of alcohol required.

4 - Results and Discussion

Quantitative results for the application of the 12 Principles of Green Chemistry

are shown in Table 2. The enzymatic route obtained, as a sum of all the grades, a much

higher result than the alkaline route. The alkaline route, as discussed before, presents

some bottlenecks that significantly contributed to this result. Among them, it is possible

to emphasize: the use of a less green catalyst (NaOH); a bigger consumption of thermal

energy; a bigger consumption of water as washing solvent; the use of methanol rather

than ethanol; and the greater quantity of alcohol required.

These aspects, regarding mass and energy balances, can be better analyzed by

the application of sustainability metrics. Once more, the enzymatic route got better

22
 ACCEPTED MANUSCRIPT

results than the alkaline route, presenting better results for every metric, except Metric

M.3. But, in this case, two factors must be considered.

Firstly, the differences in the molar mass of the alcohols (methanol: 32 kg/kmol

and ethanol: 46 kg/kmol). Even if both routes required stoichiometric concentrations of

alcohol for transesterification, a higher value for this metric, applied just to the reactor,

would be found for the ethylic process. A molar comparison would demonstrate that the

ethylic enzymatic route requires less alcohol than the methylic alkaline route.

Besides that, the presence of a recycle stream in the alkaline route is important.

It must be considered that this route requires an excess of alcohol (6:1) to improve

reaction kinetics, while stoichiometric conditions can be present in the enzymatic

process. Without methanol recycle the alkaline route would require an input of alcohol

superior, in mass, than the required by the enzymatic route.

The sustainability metrics were applied only in the process simulated in Aspen

HYSYS. For a more complete analysis, involving the entire biodiesel production chain,

a life cycle assessment (LCA) would be more appropriate. It will be the topic of future

study that will be offered by our research group, evaluating the two routes analyzed in

this article and production decentralization, that would be a very interesting strategy for

big countries like Brazil (Iglesias et al., 2012).

5 - Conclusions

The application of the 12 Principles of Green Chemistry and the sustainability

metrics turned evident how the enzymatic route presents much better environmental

performance than the alkaline route, in many aspects. Quantitatively, with the

application of the 12 Principles, the enzymatic route received 79 % of the possible

points, against only 42 % of the alkaline route. The adoption of the enzymatic route

23
 ACCEPTED MANUSCRIPT

could represent savings of 29 % in the total energy imports, 84 % of water, a reduction

of 76 % in residues generation and an increase of 44 % in energy obtainment from

renewable sources. It can be also stated that the utilization of ethanol is environmentally

better than the choice for methanol and that the adoption of energy integration can make

a big difference regarding energy savings (48 % in the proposed enzymatic route).

This study contributes to a better understanding of the environmental aspects

related to the industrial biodiesel production. A life cycle assessment, involving the

entire biodiesel production chain, will be presented in a subsequent study.

This research did not receive any specific grant from funding agencies in the public,

commercial, or not-for-profit sectors.

6 - References

Abraham, M.A., Nguyen, N., 2003. “Green engineering: Defining the principles”-

results from the Sandestin Conference. Environ. Prog. 22, 233–236.

Anastas, P.T., Warner, J.C., 1998. Green Chemistry: Theory and Practice. Oxford

University Press, New York, USA.

Anastas, P.T., Zimmerman, J.B., 2003. Design through the Twelve Principles of Green

Engineering. Env. Sci. Tech. 37, 94A–101A.

Carneiro Junior, J.A.M., Rodrigues, M.L., Andrade, S.S.L., Costa, T.S.M., Sacramento,

V.J., Lobato, A.K.C.L., Santos, L.C.L., 2011. Simulation of processes of biodiesel

production in PFR reactors, in: 6o Congresso Brasileiro de Pesquisa e

Desenvolvimento em Petróleo e Gás. ABPG – Associação Brasileira de P&D em

Petróleo e Gás, Florianópolis, Brazil (in Portuguese).

Castanheira, É.G., Grisoli, R., Coelho, S., Anderi Da Silva, G., Freire, F., 2015. Life-

24
 ACCEPTED MANUSCRIPT

cycle assessment of soybean-based biodiesel in Europe: Comparing grain, oil and

biodiesel import from Brazil. J. Clean. Prod. 102, 188–201.

Cavalett, O., Ortega, E., 2010. Integrated environmental assessment of biodiesel

production from soybean in Brazil. J. Clean. Prod. 18, 55–70.

Constantinou, L., Gani, R., 1994. New Group Contribution Method for Estimating

Properties of Pure Compounds. AIChE J. 1697 – 1710.

Demirbaş, A., 2009. Biodegradability of Biodiesel and Petrodiesel Fuels. Energy

Sources, Part A 31, 169–174.

Durkee, J., 2006. Management of Industrial Cleaning Technology and Processes, 1st ed.

Elsevier, Amsterdam, The Netherlands.

Eguchi, S., Kagawa, S., Okamoto, S., 2015. Environmental and Economic Performance

of a Biodiesel Plant Using Waste Cooking Oil. J. Clean. Prod. 101, 245–250.

Farooq, M., Ramli, A., Subbarao, D., 2013. Biodiesel production from waste cooking

oil using bifunctional heterogeneous solid catalysts. J. Clean. Prod. 59, 131–140.

Freedman, B., Butterfield, R.O., Pryde, E.H., 1986. Transesterification Kinetics of

Soybean Oil. J. Am. Oil Chem. Soc. 63, 1375–1380.

Freedman, B., Pryde, E.H., Mounts, T.L., 1984. Variables Affecting the Yields of Fatty

Esters from Transesterified Vegetable Oils. J. Am. Oil Chem. Soc. 61, 1638–1643.

Garcia, M., Gonzalo, A., Sanchez, J.L., Arauzo, J., Peña, J.A., 2010. Prediction of

normalized biodiesel properties by simulation of multiple feedstock blends.

Bioresour. Technol. 101, 4431–4439.

Goodrum, J.W., 2002. Volatility and boiling points of biodiesel from vegetables oils

and tallow. Biomass Bioenergy 22, 205–211.

Hall, J., Matos, S., Severino, L., Beltrão, N., 2009. Brazilian biofuels and social

exclusion: established and concentrated ethanol versus emerging and dispersed

25
 ACCEPTED MANUSCRIPT

biodiesel. J. Clean. Prod. 17, S77–S85.

Harding, K.G., Dennis, J.S., von Blottnitz, H., Harrison, S.T.L., 2008. A life-cycle

comparison between inorganic and biological catalysis for the production of

biodiesel. J. Clean. Prod. 16, 1368–1378.

Holma, A., Koponen, K., Antikainen, R., Lardon, L., Leskinen, P., Roux, P., 2013.

Current limits of life cycle assessment framework in evaluating environmental

sustainability - Case of two evolving biofuel technologies. J. Clean. Prod. 54, 215–

228.

Iglesias, L., Laca, A., Herrero, M., Díaz, M., 2012. A life cycle assessment comparison

between centralized and decentralized biodiesel production from raw sunflower oil

and waste cooking oils. J. Clean. Prod. 37, 162–171.

Islam, A., Taufiq-Yap, Y.H., Chan, E.S., Moniruzzaman, M., Islam, S., Nabi, M.N.,

2014. Advances in solid-catalytic and non-catalytic technologies for biodiesel

production. Energy Convers. Manag. 88, 1200–1218.

Jensen, N., Coll, N., Gani, R., 2003. An Integrated Computer Aided System for

Generation and Evaluation of Sustainable Process Alternatives. Clean Technol.

Environ. Policies 5, 209–225.

Kiwjaroun, C., Tubtimdee, C., Piumsomboon, P., 2009. LCA studies comparing

biodiesel synthesized by conventional and supercritical methanol methods. J.

Clean. Prod. 17, 143–153.

Knothe, G., Gerpen, J. Van, Krahl, J., 2005. The Biodiesel Handbook. AOCS Press,

Champaign, Illinois.

Macombe, C., Leskinen, P., Feschet, P., Antikainen, R., 2013. Social life cycle

assessment of biodiesel production at three levels: A literature review and

development needs. J. Clean. Prod. 52, 205–216.

26
 ACCEPTED MANUSCRIPT

Magalhães, S.P., Pessoa, F.L.P., Alves, T.L.M., 2015. Production of Biodiesel via

Enzymatic Palm Oil Ethanolysis: Kinetic Study. Comput. Aided Chem. Eng. 37,

539–544.

Malcolm Pirnie, Inc., 1999. Evaluation of the Fate and Transport of Methanol in the

Environment. Oakland, CA.

Marulanda, V.F., 2012. Biodiesel production by supercritical methanol

transesterification: Process simulation and potential environmental impact

assessment. J. Clean. Prod. 33, 109–116.

Monari, C., Righi, S., Olsen, S.I., 2014. Greenhouse gas emissions and energy balance

of biodiesel production from microalgae cultivated in photobioreactors in

Denmark: A life-cycle modeling. J. Clean. Prod. 112, 4084–4092.

Morais, S., Mata, T.M., Martins, A. a., Pinto, G. a., Costa, C. a. V., 2010. Simulation

and life cycle assessment of process design alternatives for biodiesel production

from waste vegetable oils. J. Clean. Prod. 18, 1251–1259.

Portal Brasil, 2015. Renewable energy represents more than 42 % of the Brazilian

energy matrix. < http://www.brasil.gov.br/meio-ambiente/2015/11/energia-

renovavel-representa-mais-de-42-da-matriz-energetica-brasileira > (accessed

6.28.16, in Portuguese).

Reijnders, L., Huijbregts, M.A.J., 2008. Biogenic greenhouse gas emissions linked to

the life cycles of biodiesel derived from European rapeseed and Brazilian

soybeans. J. Clean. Prod. 16, 1943–1948.

Tallis, B., 2002. The Sustainability Metrics: Sustainable Development Progress Metrics

Recommended for use in the Process Industry. IChemE, Rugby, UK.

Viana, M.B., Freitas, A. V., Leitão, R.C., Santaella, S.T., 2012. Biodegradability and

methane production potential of glycerol generated by biodiesel industry. Water

27
 ACCEPTED MANUSCRIPT

Sci Technol. 66, 2217–22.

Watanabe, Y., Shimaka, Y., Sugihara, A., Noda, H., Fukuda, H., Tominaga, Y., 2000.

Continuous production of biodiesel fuel from vegetal oil using immobilized

Candida antarctica Lipase. J. Am. Oil Chem. Soc. 77, 355–360.

West, A.H., Posarac, D., Ellis, N., 2008. Assessment of four biodiesel production

processes using HYSYS.Plant. Bioresour. Technol. 99, 6587–6601.

West, A.H., Posarac, D., Ellis, N., 2007. Simulation, case studies and optimization of a

biodiesel process with a solid acid catalyst. Int. J. Chem. React. Eng. 5, 1–8.

Young, A.F., Pessoa, F.L.P., Queiroz, E.M., 2015a. Biodiesel Production Technologies:

Production in Supercritical and Enzymatic Environments. Novas Edições

Acadêmicas (in Portuguese).

Young, A.F., Pessoa, F.L.P., Queiroz, E.M., 2015b. Comparison Between Biodiesel

Production from Soybean Oil and Palm Oil with Ethanol: Design and Economic

Evaluation. Chem. Eng. Trans. 43, 325–330.

Young, A.F., Pessoa, F.L.P., Queiroz, E.M., 2015c. Design and Economic Evaluation of

Alternatives to Effluents Treatment on Biodiesel Production from Soybean Oil and

Palm Oil. Comput. Aided Chem. Eng. 37, 1067–1072.

Zhang, Y., Dubé, M.A., McLean, D.D., Kates, M., 2003. Biodiesel production from

waste cooking oil: 1. Process design and technological assessment. Bioresour.

Technol. 89, 1–16.

28
 ACCEPTED MANUSCRIPT

Appendix

Table A.1

Streams of the methylic-alkaline route.

Stream 101 102 103 104 105 106 107 108 110
Temperature (°C) 25.0 69.3 25.0 41.4 25.0 40.6 60.0 60.0 60.0
Pressure (kPa) 101.3 101.3 101.3 101.3 101.3 101.3 101.3 101.3 101.3
Molar Flow (kmol/h) 1.15 1.15 3.66 6.84 0.25 7.09 8.24 8.24 1.42
Mass Flow (kg/h) 1000.00 1000.00 117.34 220.00 10.00 230.00 1230.00 1230.00 95.14
Composition (Mass Fractions)
LiLiLi 0.2770 0.2770 0.0000 0.0000 0.0000 0.0000 0.2250 0.0045 0.0000
LiLiO 0.2540 0.2540 0.0000 0.0000 0.0000 0.0000 0.2070 0.0041 0.0000
LiOP 0.1320 0.1320 0.0000 0.0000 0.0000 0.0000 0.1070 0.0022 0.0000
LiOO 0.1430 0.1430 0.0000 0.0000 0.0000 0.0000 0.1160 0.0023 0.0000
LiLiP 0.1940 0.1940 0.0000 0.0000 0.0000 0.0000 0.1580 0.0032 0.0000
Methanol 0.0000 0.0000 1.0000 0.9950 0.0000 0.9520 0.1780 0.0903 0.1930
Glycerol 0.0000 0.0000 0.0000 0.0035 0.0000 0.0034 0.0006 0.0847 0.7940
Methyl Linoleate 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.5370 0.0006
Methyl Oleate 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.1810 0.0008
Methyl Palmitate 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0823 0.0010
Water 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
NaOH 0.0000 0.0000 0.0000 0.0000 1.0000 0.0435 0.0081 0.0081 0.0108
Stream 111 113 114 115 116 117 118 119 121
Temperature (°C) 60.0 140.0 140.0 140.0 140.0 60.0 94.9 94.9 77.6
Pressure (kPa) 101.3 101.3 101.3 101.3 101.3 101.3 101.3 101.3 101.3
Molar Flow (kmol/h) 6.82 6.82 4.10 2.72 3.18 3.18 78.84 3.46 78.21
Mass Flow (kg/h) 1134.86 1134.86 1047.06 87.80 102.58 102.66 1451.13 1005.80 1409.88
Composition (Mass Fractions)
LiLiLi 0.0049 0.0049 0.0053 0.0000 0.0000 0.0000 0.0000 0.0055 0.0000
LiLiO 0.0045 0.0045 0.0049 0.0000 0.0000 0.0000 0.0000 0.0051 0.0000
LiOP 0.0023 0.0023 0.0025 0.0000 0.0000 0.0000 0.0002 0.0026 0.0001
LiOO 0.0025 0.0025 0.0027 0.0000 0.0000 0.0000 0.0002 0.0028 0.0001
LiLiP 0.0034 0.0034 0.0037 0.0000 0.0000 0.0000 0.0002 0.0038 0.0002
Methanol 0.0817 0.0817 0.0055 0.9900 0.9900 0.9900 0.0040 0.0002 0.0001
Glycerol 0.0253 0.0253 0.0267 0.0075 0.0076 0.0076 0.0193 0.0000 0.0000
Methyl Linoleate 0.5820 0.5820 0.6310 0.0004 0.0004 0.0004 0.0000 0.6570 0.0000
Methyl Oleate 0.1960 0.1960 0.2120 0.0009 0.0008 0.0008 0.0000 0.2210 0.0000
Methyl Palmitate 0.0891 0.0891 0.0965 0.0013 0.0012 0.0012 0.0000 0.1000 0.0000
Water 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.9700 0.0010 0.9990
NaOH 0.0079 0.0079 0.0086 0.0000 0.0000 0.0000 0.0062 0.0004 0.0003

29
 ACCEPTED MANUSCRIPT

Table A.1

Streams of the methylic-alkaline route (continuation).

Stream 122 124 125 127 128 129 130 132 133
Temperature (°C) 77.7 71.9 71.8 25.0 69.3 70.0 70.0 211.0 210.0
Pressure (kPa) 101.3 101.3 101.3 101.3 101.3 101.3 101.3 101.3 70.9
Molar Flow (kmol/h) 3.44 78.18 7.78 83.26 83.26 82.54 8.37 8.37 8.37
Mass Flow (kg/h) 1005.63 1409.70 1083.77 1500.00 1500.00 1488.10 1093.19 1093.19 1093.19
Composition (Mass Fractions)
LiLiLi 0.0055 0.0000 0.0051 0.0000 0.0000 0.0000 0.0051 0.0051 0.0051
LiLiO 0.0051 0.0000 0.0047 0.0000 0.0000 0.0000 0.0047 0.0047 0.0047
LiOP 0.0027 0.0002 0.0025 0.0000 0.0000 0.0002 0.0022 0.0022 0.0022
LiOO 0.0030 0.0003 0.0027 0.0000 0.0000 0.0002 0.0024 0.0024 0.0024
LiLiP 0.0041 0.0004 0.0037 0.0000 0.0000 0.0003 0.0033 0.0033 0.0033
Methanol 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
Glycerol 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
Methyl Linoleate 0.6570 0.0000 0.6100 0.0000 0.0000 0.0000 0.6050 0.6050 0.6050
Methyl Oleate 0.2210 0.0000 0.2050 0.0000 0.0000 0.0000 0.2030 0.2030 0.2030
Methyl Palmitate 0.1000 0.0000 0.0932 0.0000 0.0000 0.0000 0.0924 0.0924 0.0924
Water 0.0008 0.9990 0.0730 1.0000 1.0000 1.0000 0.0821 0.0821 0.0821
NaOH 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
Stream 135 136 137 138 201 202 203 204
Temperature (°C) 210.0 210.0 76.0 25.0 140.0 140.0 140.0 25.0
Pressure (kPa) 70.9 101.3 101.3 101.3 101.3 101.3 101.3 101.3
Molar Flow (kmol/h) 5.12 3.25 3.25 3.25 1.42 0.96 0.46 0.96
Mass Flow (kg/h) 131.92 961.27 961.27 961.27 95.14 80.37 14.77 80.37
Composition (Mass Fractions)
LiLiLi 0.0002 0.0057 0.0057 0.0057 0.0000 0.0000 0.0000 0.0000
LiLiO 0.0001 0.0053 0.0053 0.0053 0.0000 0.0000 0.0000 0.0000
LiOP 0.0001 0.0025 0.0025 0.0025 0.0000 0.0000 0.0000 0.0000
LiOO 0.0000 0.0027 0.0027 0.0027 0.0000 0.0000 0.0000 0.0000
LiLiP 0.0001 0.0037 0.0037 0.0037 0.0000 0.0000 0.0000 0.0000
Methanol 0.0000 0.0000 0.0000 0.0000 0.1930 0.0463 0.9910 0.0463
Glycerol 0.0000 0.0000 0.0000 0.0000 0.7940 0.9380 0.0078 0.9380
Methyl Linoleate 0.1990 0.6600 0.6600 0.6600 0.0006 0.0007 0.0000 0.0007
Methyl Oleate 0.0631 0.2230 0.2230 0.2230 0.0008 0.0009 0.0002 0.0009
Methyl Palmitate 0.0585 0.0971 0.0971 0.0971 0.0010 0.0011 0.0007 0.0011
Water 0.6790 0.0002 0.0002 0.0002 0.0000 0.0000 0.0000 0.0000
NaOH 0.0000 0.0000 0.0000 0.0000 0.0108 0.0128 0.0000 0.0128

30
 ACCEPTED MANUSCRIPT

Table A.2

Mass and energy balances for the methylic-alkaline route.

Input Material Streams kg/h kg/kg biodiesel

Water 127 1500 1.56
Methanol 103 117.34 0.12
Refined Soybean Oil 101 1000 1.04
Output Material Streams kg/h kg/kg biodiesel
Glycerine 204 80.37 0.08
Biodiesel 138 961.27 1.00
TAG 0.82
Water 1407.95
Methanol 5.78
Effluent 1 Biodiesel 0.00
NaOH 8.97
Glycerol 28.00
Total 1451.13 1.51
TAG 0.06
Water 89.55
Methanol 0.00
Effluent 2 Biodiesel 42.34
NaOH 0.00
Glycerol 0.00
Total 131.92 0.14
Energy Streams kJ/h kJ/kg biodiesel
Q-R101 - 93408.61
Q-E101 75673.33
Q-E102 281914.85 (155467.93)
Thermal Energy Q-E103 - 126446.93 (0.00)
(energy integration) Q-E104 546011.29 (455749.57)
(MJ/h) Q-E106 - 90261.72 (0.00)
Q-E201 36234.93
Q-E202 - 25509.54
Total 604207.60 628.55
Electricity (kJ/h) We-P101 52.88 0.0550

31
 ACCEPTED MANUSCRIPT

Table A.3

Streams of the ethylic-enzymatic route.

Stream 101 102 103 104 105 106 108 109

Temperature (°C) 25.0 31.6 25.0 25.0 30.0 30.0 30.0 30.0
Pressure (kPa) 101.3 101.3 101.3 101.3 101.3 101.3 101.3 101.3
Molar Flow (kmol/h) 1.15 1.15 2.29 2.22 5.66 5.66 1.04 4.62
Mass Flow (kg/h) 1000.00 1000.00 105.57 40.00 1145.57 1145.57 56.24 1089.33
Composition (Mass Fractions)
LiLiLi 0.2770 0.2770 0.0000 0.0000 0.2410 0.0869 0.0000 0.0914
LiLiO 0.2540 0.2540 0.0000 0.0000 0.2220 0.0798 0.0000 0.0840
LiOP 0.1320 0.1320 0.0000 0.0000 0.1150 0.0415 0.0000 0.0436
LiOO 0.1430 0.1430 0.0000 0.0000 0.1250 0.0449 0.0000 0.0472
LiLiP 0.1940 0.1940 0.0000 0.0000 0.1700 0.0611 0.0000 0.0642
Ethanol 0.0000 0.0000 1.0000 0.0000 0.0922 0.0037 0.0106 0.0033
Glycerol 0.0000 0.0000 0.0000 0.0000 0.0000 0.0589 0.8220 0.0196
Ethyl Linoleate 0.0000 0.0000 0.0000 0.0000 0.0000 0.3950 0.0000 0.4150
Ethyl Oleate 0.0000 0.0000 0.0000 0.0000 0.0000 0.1330 0.0000 0.1400
Ethyl Palmitate 0.0000 0.0000 0.0000 0.0000 0.0000 0.0606 0.0000 0.0637
Water 0.0000 0.0000 0.0000 1.0000 0.0349 0.0349 0.1680 0.0281
Stream 111 113 114 115 116 117 119 120
Temperature (°C) 117.5 117.5 30.5 25.0 30.0 30.0 30.0 30.0
Pressure (kPa) 101.3 101.3 101.3 101.3 101.3 101.3 101.3 101.3
Molar Flow (kmol/h) 4.62 0.94 3.68 1.25 4.93 4.93 0.33 4.60
Mass Flow (kg/h) 1089.33 18.64 1070.69 57.59 1128.28 1128.28 23.41 1104.87
Composition (Mass Fractions)
LiLiLi 0.0914 0.0001 0.0930 0.0000 0.0883 0.0018 0.0000 0.0018
LiLiO 0.0840 0.0001 0.0854 0.0000 0.0811 0.0016 0.0000 0.0017
LiOP 0.0436 0.0000 0.0444 0.0000 0.0421 0.0008 0.0000 0.0009
LiOO 0.0472 0.0000 0.0480 0.0000 0.0456 0.0009 0.0000 0.0009
LiLiP 0.0642 0.0001 0.0654 0.0000 0.0620 0.0012 0.0000 0.0013
Ethanol 0.0033 0.1310 0.0011 1.0000 0.0521 0.0026 0.0065 0.0025
Glycerol 0.0196 0.0006 0.0199 0.0000 0.0189 0.0519 0.9240 0.0334
Ethyl Linoleate 0.4150 0.0091 0.4220 0.0000 0.4010 0.6220 0.0000 0.6350
Ethyl Oleate 0.1400 0.0025 0.1420 0.0000 0.1350 0.2090 0.0000 0.2140
Ethyl Palmitate 0.0637 0.0014 0.0648 0.0000 0.0615 0.0954 0.0000 0.0974
Water 0.0281 0.8550 0.0137 0.0000 0.0130 0.0130 0.0693 0.0118

32
 ACCEPTED MANUSCRIPT

Table A.3

Streams of the ethylic-enzymatic route (continuation).

Stream 122 123 125 126 127 129 130 131

Temperature (°C) 35.5 35.5 25.0 91.8 49.9 49.9 202.0 200.0
Pressure (kPa) 101.3 101.3 101.3 101.3 101.3 101.3 101.3 70.9
Molar Flow (kmol/h) 4.83 9.95 11.10 11.10 10.18 10.88 10.88 10.88
Mass Flow (kg/h) 116.88 1174.68 200.00 200.00 186.68 1188.04 1188.04 1188.04
Composition (Mass Fractions)
LiLiLi 0.0000 0.0017 0.0000 0.0000 0.0000 0.0017 0.0017 0.0017
LiLiO 0.0000 0.0016 0.0000 0.0000 0.0000 0.0015 0.0015 0.0015
LiOP 0.0000 0.0008 0.0000 0.0000 0.0000 0.0008 0.0008 0.0008
LiOO 0.0000 0.0009 0.0000 0.0000 0.0000 0.0009 0.0009 0.0009
LiLiP 0.0000 0.0012 0.0000 0.0000 0.0000 0.0012 0.0012 0.0012
Ethanol 0.0048 0.0024 0.0000 0.0000 0.0035 0.0019 0.0019 0.0019
Glycerol 0.3140 0.0033 0.0000 0.0000 0.0197 0.0001 0.0001 0.0001
Ethyl Linoleate 0.0000 0.5970 0.0000 0.0000 0.0000 0.5900 0.5900 0.5900
Ethyl Oleate 0.0000 0.2010 0.0000 0.0000 0.0000 0.1990 0.1990 0.1990
Ethyl Palmitate 0.0000 0.0916 0.0000 0.0000 0.0000 0.0906 0.0906 0.0906
Water 0.6810 0.0986 1.0000 1.0000 0.9770 0.1120 0.1120 0.1120

Stream 132 134 136 201 202 203 204 205

Temperature (°C) 200.0 200.0 25.0 142.0 142.0 142.0 108.1 25.0
Pressure (kPa) 70.9 101.3 101.3 101.3 101.3 101.3 101.3 101.3
Molar Flow (kmol/h) 7.80 3.10 3.10 1.00 0.80 0.30 1.10 1.10
Mass Flow (kg/h) 239.60 948.40 948.43 56.20 51.10 5.20 74.50 74.50
Composition (Mass Fractions)
LiLiLi 0.0000 0.0021 0.0021 0.0000 0.0000 0.0000 0.0000 0.0000
LiLiO 0.0000 0.0019 0.0019 0.0000 0.0000 0.0000 0.0000 0.0000
LiOP 0.0000 0.0010 0.0010 0.0000 0.0000 0.0000 0.0000 0.0000
LiOO 0.0000 0.0011 0.0011 0.0000 0.0000 0.0000 0.0000 0.0000
LiLiP 0.0000 0.0015 0.0015 0.0000 0.0000 0.0000 0.0000 0.0000
Ethanol 0.0092 0.0000 0.0000 0.0106 0.0025 0.0911 0.0038 0.0038
Glycerol 0.0007 0.0000 0.0000 0.8220 0.9040 0.0094 0.9100 0.9100
Ethyl Linoleate 0.2950 0.6650 0.6650 0.0000 0.0000 0.0000 0.0000 0.0000
Ethyl Oleate 0.0871 0.2270 0.2270 0.0000 0.0000 0.0000 0.0000 0.0000
Ethyl Palmitate 0.0517 0.1000 0.1000 0.0000 0.0000 0.0000 0.0000 0.0000
Water 0.5560 0.0002 0.0002 0.1680 0.0939 0.9000 0.0862 0.0862

33
 ACCEPTED MANUSCRIPT

Table A.4

Mass and energy balances for the ethylic-enzymatic route.

Input Material Streams kg/h kg/kg biodiesel

104 40
Water 125 200
Total 240 0.25
103 105.57
Ethanol 115 57.59
Total 163.16 0.17
Refined Soybean Oil 101 1000 1.05
Output Material Streams kg/h kg/kg biodiesel
Glycerine 205 74.50 0.08
Biodiesel 136 948.43 1.00
TAG 0.00
Water 15.94
Effluent 1 Ethanol 2.45
(Stream 113) Biodiesel 0.24
Glycerol 0.01
Total 18.64 0.02
TAG 0.00
Water 4.64
Effluent 2 Ethanol 0.47
(Stream 203) Biodiesel 0.00
Glycerol 0.05
Total 5.16 0.01
TAG 0.00
Water 796.00
Effluent 3 Ethanol 56.30
(Stream 122) Biodiesel 0.00
Glycerol 367.00
Total 116.88 0.12
TAG 0.03
Water 133.33
Effluent 4 Ethanol 2.20
(Stream 132) Biodiesel 103.94
Glycerol 0.16
Total 239.61 0.25
Energy Streams kJ/h kJ/kg biodiesel
Q-R101 - 41584.63
Q-R102 - 22923.22
Q-E101 10757.13
Q-E102 227200.20 (44912.95)
Thermal Energy
Q-E103 - 182287.25 (0.00)
(energy integration)
Q-E104 717704.89 (425374.61)
(MJ/h)
Q-E106 - 292330.29 (0.00)
Q-E201 29075.11
Q-E202 - 17268.74
Total 428343.20 451.63
Electricity (kJ/h) We-P101 53.29 0.0562

34
 ACCEPTED MANUSCRIPT

Table 1

E-Factor calculation.

E-Factor Calculation Alkaline Route Enzymatic Route

Considered Streams 108 108 B, 113, 117
Residues output, except water (kg/h) 245.25 117.97
Methylic/ethylic esters output (kg/h) 984.37 1045.48
E-Factor 0.25 0.11

35
 ACCEPTED MANUSCRIPT

Table 2

The 12 Principles of Green Chemistry, results.

Principles Alkaline Route Enzymatic Route

P1 0 1
P2 0 1
P3 1 2
P4 2 2
P5 1 2
P6 1 2
P7 1 2
P8 2 2
P9 1 2
P10 1 1
P11 0 1
P12 0 1
Total 10/24 (42 %) 19/24 (79 %)

36
 ACCEPTED MANUSCRIPT

Table 3

Sustainability metrics, results.

Comments
Metric Alkaline Route Enzymatic Route
(Relative to the Enzymatic Route)
E.1 723.18 MJ/h 510.17 MJ/h Economy of 29 % of energy imports.
Improvement of 44 % in the participation of
E.2 0.0061 % 0.0088 %
renewable sources in the energy inputs.
Economy of 28 % of energy imports per kilogram
E.3 752.26 kJ/kg 537.86 kJ/kg
of biodiesel produced.
Economy of 84 % of water per kilogram of
M.1 1.56 kg/kg 0.25 kg/kg
biodiesel produced.
Reduction of 76 % in the quantity of residues
M.2 1.65 kg/kg 0.40 kg/kg
generated per kilogram of biodiesel produced.
Increase of 8.5 % in the quantity of raw material
M.3 1.17 kg/kg 1.27 kg/kg
consumed per kilogram of biodiesel produced.a
a See discussion.

37
 ACCEPTED MANUSCRIPT

Fig. 1. Flowsheet of the methylic-alkaline route, in Aspen HYSYS.

38
 ACCEPTED MANUSCRIPT

Fig. 2. Schematic representation of the global mass and energy balances, methylic-

alkaline route.

39
 ACCEPTED MANUSCRIPT

Fig. 3. Flowsheet of the ethylic-enzymatic route, in Aspen HYSYS.

40
 ACCEPTED MANUSCRIPT

Fig. 4. Schematic representation of the global mass and energy balances, ethylic-

enzymatic route.

41