Renewable and Sustainable Energy Reviews 163 (2022) 112532

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Renewable and Sustainable Energy Reviews

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

Simulation and economic evaluation of process alternatives for biogas

production and purification from sugarcane vinasse
L.C. Moreira a, P.O. Borges a, R.M. Cavalcante a, A.F. Young b, *
a
Escola de Química, Universidade Federal do Rio de Janeiro, Av. Athos da Silveira Ramos, 149, Rio de Janeiro, Brazil
b
Departamento de Engenharia Química e de Petróleo, Universidade Federal Fluminense, Rua Passo da Pátria, 156, Niterói, Brazil

A R T I C L E I N F O A B S T R A C T

Keywords: Vinasse, which is the main residue of ethanol production, is a promising alternative for the generation of biogas,
Vinasse due to its high generation rate and limited application. The objective of the present work is to simulate and
Biogas economically compare alternative processes for the production and treatment of biogas from the anaerobic
Purification
digestion of vinasse. Different water, H2S and CO2 removal technologies were evaluated: condensation, mem­
Biomethane
Process simulation
brane separation, washing, Pressure Swing Adsorption (PSA), adsorptions with silica gel, activated carbon and
Economic analysis metallic oxides, absorptions with triethylene glycol (TEG), ethylenediaminetetraacetic acid iron (III) (Fe/EDTA)
and diethylamine (DEA). It was shown that an anaerobic lagoon is preferable over a set of Upflow Anaerobic
Sludge Blanket (UASB) reactors due to the large processing scale, reducing the capital costs. Among the 12
evaluated routes, the best process alternative for biogas treatment was water removal through silica gel
adsorption, followed by simultaneous H2S and CO2 absorption in a Fe/EDTA solution. In the best scenario, the
entire biomethane production plant would require an investment of US$ 3.6 million, resulting in an annual net
profit of US$ 1.99 million, with payback in the first year of operation.

1. Introduction
The use of bioenergy has grown at an accelerated pace in recent
decades. In this direction, the production and use of biogas has also
increased significantly. Global biogas production increased from 0.28 EJ
in 2000 to 1.28 EJ in 2014, with a volume of 59 billion cubic meters of
biogas (equivalent to 35 billion cubic meters of methane) [1]. According
to Reis [2], biogas entered the Brazilian green energy agenda in the early
2000s, motivated by the carbon credits market. Around 1000 bio­
digesters were installed in the country between 2005 and 2013, mainly
for processing animal waste. Since then, specific projects have been
proposed by the Federal Government and the private sector, and be­
tween 2014 and 2019 there was an increase of more than 600% in biogas
production from animal waste. Biogas is a fuel, composed mainly of
methane (CH4) and carbon dioxide (CO2), resulting from the anaerobic
biodigestion of organic waste. Its composition varies according to the
substrate to be degraded and the physicochemical conditions at which it
happens [3].
Vinasse, the main residue from ethanol production, contains an
average concentration of 10% organic matter and 90% water. Each liter
of ethanol produced generates 10 up to 15 L of vinasse, depending on the
types of equipment used in the distillation step [4]. Currently, the main
use of vinasse is for fertigation of the sugarcane crop itself. This is due to
its high load of nutrients such as potassium, for example, that is
important for sugarcane growth, and water, reducing its consumption in
the field. This application has the great advantage of not requiring any
treatment of this effluent [5]. One of the main disadvantages of this
technique, however, is the limited application in the field due to the
possibility of groundwater contamination, soil salinization and bad
odors. Another limiting factor is the transport cost. According to the
Brazilian Society of Sugar and Alcohol Technicians (STAB, in Portu­
guese), the average radius of vinasse application in natura is 11 km,
which can be expanded to 29 km through the use of vinasse concen­
trators [6].
The high organic load, low pH and high corrosivity make vinasse a
high polluting effluent, about a hundred times more noxious than do­
mestic sewage [7]. There is also the emission of greenhouse gases, since
the degradation of the organic load occurs naturally and spontaneously
in the soil, as sugarcane does not use it as a source of nutrients. Besides,
during its transport in the conduit channel, an average of 1.83 kg of CO2
is produced for each cubic meter of vinasse [8].
In summary, vinasse is an effluent generated in large quantities in the

* Corresponding author.
E-mail address: ayoung@id.uff.br (A.F. Young).

https://doi.org/10.1016/j.rser.2022.112532
Received 7 January 2022; Received in revised form 13 April 2022; Accepted 1 May 2022
Available online 8 May 2022
1364-0321/© 2022 Elsevier Ltd. All rights reserved.
L.C. Moreira et al. Renewable and Sustainable Energy Reviews 163 (2022) 112532

sugar-alcohol industry, whose treatment is complex and its use by Table 1

conventional means is limited. For this reason, vinasse is presented as a Biogas/biomethane specifications and effects of its impurities.
promising alternative for the generation of biogas and has already been Compounds Biogas Biomethane Effects on Biomethane
explored in this regard. For example, Raízen, an important energy Composition Specification
company in Brazil, inaugurated a biogas plant in October 2020 associ­ CH4 55–65 (% Min 90 (%mol) –
ated with an ethanol plant. Due to its milling capacity of more than 5 mol)
million tons of sugarcane per year, it generates a volume of vinasse that CO2 35–45 (% Max 3 (%mol) Reduction of calorific value,
meets the demand for a full-year commercial scale biogas project. In mol) corrosion.
H2O <5 (% mol) Reduction of calorific value,
other words, the plant has the capacity to produce 138,000 MWh per
–
corrosion (reaction with H2S,
year, enough to supply with energy a city with 238,000 inhabitants [9]. NH3 and CO2) and possible
However, for the consumption or resale of this biofuel - biomethane - condensation at high
to be possible within the standard specifications defined by the Brazilian pressures.
H2S 20–20,000 Max 10 (mg/ Corrosion, toxicity (>5 cm3/
National Agency of Petroleum, Natural Gas and Biofuels (ANP, in Por­
(ppmv) m3) m3) and possible formation of
tuguese), it is necessary to purify the biogas, which can be done through SO2 and SO3.
several process alternatives already available for natural gas purifica­ N2 <2 (% mol) – –
tion, after pertinent adaptations. NH3 <500 (ppmv) – Corrosion.
Therefore, the main objective of the present work is the evaluation of H2 0–0.02 (% – –
mol)
different process alternatives applied in the production and treatment of Total Sulfur – Max 70 (mg/ –
biogas generated from the anaerobic digestion of vinasse. For this, a m3)
process superstructure was elaborated, mass and energy balances were CO2 + O2 + – Max 10 (%mol) –
rigorously solved in the Aspen Plus® v8.8 software, and the results were N2
used in a comparative economic feasibility analysis.
2.2. Biodigestion
2. Biogas production from vinasse
Biodigestion is the natural biological degradation of organic mate­
As explained, vinasse is the main effluent from the sugar-ethanol rial, resulting in the production of biogas by microorganisms under
industry. Bernal et al. [10] carried out a study on the energy potential anaerobic conditions and mineral-rich waste. In recent years, the
of biogas from vinasse and compared it to that of biogas from other anaerobic digestion of agricultural and agro-industry waste, municipal
sources in Brazil, and concluded that vinasse biogas has an economically organic waste and sewage sludge has become one of the most attractive
feasible energy potential of 2.24 TWh per year, second only to landfill avenues for renewable energy production [1]. In livestock, anaerobic
biogas, with a potential of 4 TWh. In the next sections, we describe how digestion helps to mitigate odors associated with the storage and
biogas can be industrially produced through biodigestion of sugarcane decomposition of manure and removes pathogens that can pose a sig­
vinasse. nificant risk to human and animal health. The digestate from biogas
production can still be used as a fertilizer with the same nutrient content
as the original organic matter. This brings additional economic benefits,
2.1. Vinasse reducing the use of chemical fertilizers on farms, nutrient run-off and
avoiding methane emissions [1].
Vinasse is the name given to the effluent as a whole that comes from In the anaerobic digestion of vinasse, 0.30 L of biogas - at NTP - can
the production of ethanol from sugarcane after the fermentation of the be obtained per gram of chemical oxygen demand (COD). The biogas
must and the distillation of the wine [7]. It’s composition is variable and produced is composed of 55%–65% of CH4 and 30%–35% of CO2,
depends on different factors, such as: soil characteristics, type of fertil­ containing O2, N2, H2O and H2S to a lesser extent [13–15].
ization in sugarcane cultivation, rainfall, alcohol content of the wine, the Biodigesters are large compartments sized to degrade different types
nature and composition of the must, and even the applied distillation of biomass and are classified according to their design, type of gas
system [11]. storage, operating mechanism, temperature, agitation, and with or
Vinasse is made up almost entirely of organic matter and a small without accumulation of bacterial mass [16]. The main reactors used are
fraction corresponds to minerals such as potassium (K), calcium (Ca), tubular reactors, covered anaerobic lagoons and the so called Upflow
nitrogen (N) and sulfur (S) [4,11]. Table 1 presents the possible ranges Anaerobic Sludge Blanket (UASB) reactor [15].
of chemical composition of vinasse according to its origin. According to The tubular reactor and the covered anaerobic lagoon have similar
Lamônica [12], there are three categories of vinasse, which are: running and are commonly used in rural areas to treat animal waste due
to their low installation cost and easy operation. The second type con­
- vinasse from molasses must: must prepared with molasses, a by- sists of large ditch with a malleable plastic cover in a dark color, which
product of sugar production, normally in adjacent distilleries; favors an increase in operating environment temperature, which the
- vinasse from juice must: produced from sugarcane juice exclusively effluent pass through in a horizontal flow. Its coverage expands as biogas
intended for alcoholic fermentation, normally in autonomous is produced, functioning as a gasometer. On the side, there are tubes for
distilleries; sampling the effluent and checking the concentration of organic matter.
- vinasse from mixed must: must prepared with sugarcane juice and The retention time is long, as all the conversion of organic matter occurs
molasses, usually in adjacent distilleries. naturally with the organisms that already exist in the environment,
which is the main disadvantage of this type of reactor [17].
Vinasse is generated at an average rate of 11 m3 per 1 m3 of alcohol The UASB reactor was developed in the 1970s derived from Indian
[12]. According to the Brazilian National Agency of Petroleum, Natural and Chinese bioreactors, and has been extensively used since its incep­
Gas and Biofuels (ANP), total ethanol production in Brazil in 2019 was tion for wastewater treatment [17]. This type of reactor can be used to
35,306,997 m3, which would have generated around 388,376,967 m3 of treat effluents with high organic loads in short retention times due to the
vinasse. Considering the high generation of effluent and the impossi­ possibility of recirculation in a concentrated region of active biomass.
bility of its total application to nourish the sugarcane soil, biodigestion They can have different configurations, either as cylindrical, square and
appears as an interesting option from an environmental and economic even rectangular tanks. In all these possibilities, this reactor consists of
point of view for the sugar-alcohol sector [3].

2
L.C. Moreira et al.
three fundamental parts arranged in the form of an ascending column:
the sludge bed, sedimentation zone and a three-phase separator. This
three-phase separator has the function of dividing the digestion zone -
where the sludge blanket is located - and the sedimentation zone [18].
The effluent to be treated is uniformly pumped through the bottom side
of the reactor and flows through the active biological sludge (sludge
bed), where the reactions necessary for its treatment occur. The treated
effluent is collected at the top of the reactor, in spillways or perforated
pipes. The gas produced in the reaction compartment in the form of
bubbles is collected in the central part of the three-phase separator at the
top of the reactor [19]. Digestion takes place in its lower part, and its
upper part consists of a decanter, where the gas is separated [14].
2.3. Biogas
Biogas is a mixture of methane and carbon dioxide, which may
contain impurities depending on their nature, such as H2S and moisture
[3,20,21]. It is colorless, odorless and highly combustible, and the res­
idue from its production can be used as biofertilizer. The formed H2S is
highly corrosive and therefore must be removed [14]. On the other
hand, excess CO2, as well as moisture, reduces the fuel’s energy poten­
tial. Because carbon dioxide is a light gas, difficult to liquefy and volu­
minous, its transport and storage become costly, and its use in the place
of origin is more economically advantageous [3]. The main compounds
present in biogas besides methane are CO2, H2S and moisture. The other
undesirable compounds are present in low concentrations, such as, for
example, NH3, siloxanes, O2, metals, VOCs (volatile organic com­
pounds), among others [3]. Table 1 shows the main components of
biogas and its fractions.
According to ANP, biomethane is a combustible gas arising from the
biogas treatment process. Biogas is produced from agroforestry organic
residues and commercial residues. In the present work, the treated
biogas is classified as an agroforestry residue, since vinasse is a residue
from the production of ethanol, which comes from sugarcane. Therefore,
the existing specification for the generated biomethane can be found in
ANP Resolution No. August 2015. To be used for energy purposes, such
as a substitute/supplement of vehicular fuels and in natural gas distri­
bution networks, it must meet the specifications of the regulatory
agency, in this case ANP, presented in Table 1 [3]. The purification of
biogas to biomethane is important, as it prevents corrosion of pipelines
and mechanical wear of downstream equipment, and increases the
calorific value of the gas.
Traditional purification technologies consist of two main steps:
cleaning the gas and adjusting the calorific value. Gas cleaning is the
removal of polluting components, such as H2S, which is corrosive,
harming the equipment and affecting its performance. The calorific
value adjustment step consists of increasing the concentration of
methane from the removal of CO2 and water, which act to absorb part of
the energy generated in the combustion [22].
3. Process alternatives for biogas treatment
Some well-established technologies for natural gas treatment can be
adapted for biogas treatment, because biomethane is a drop-in fuel, i.e. a
completely interchangeable substitute, analogous to natural gas - which
is essentially methane. Therefore, in the next sections we briefly explain
the 10 treatment technologies that were analyzed in this work.
3.1. Condensation for partial moisture removal
The condensation technique is based on cooling and compression of
biogas, aiming to change the thermodynamic state of the water, which is
subsequently collected [23]. First, the gas is pressurized using a
compressor and then a heat exchanger is used in order to condense the
water vapor. Typically, chilled water exchangers or electric chillers are
used [3].
3
Renewable and Sustainable Energy Reviews 163 (2022) 112532
3.2. Absorption with triethylene glycol (TEG) for moisture removal
This process consists of using a hygroscopic liquid solvent that usu­
ally flows in countercurrent with the biogas to dehydrate it in an ab­
sorption tower. The gas containing H2O rises in the column in
countercurrent with the solvent solution coming from the regeneration
system, where the H2O particles present in the gas will be absorbed by
the solvent by affinity and the solvent will leave the column rich in
moisture at the bottom. The dry gas exits through the top of the column,
which contains a mist eliminator to remove possible entrained droplets
of the solvent [24].
Solvent recovery for reuse occurs with the moisture-rich solvent
being directed to the regeneration column, where it is heated to a
temperature close to 100 ◦ C for water evaporation without loss of sol­
vent, while a coil (cooling to 40 ◦ C) at the top of the column condenses
the rising solvent vapors. The solvent stream is heated again by a heat
exchanger and is directed to a three-phase separator, which separates
the dissolved gas from the solution, the liquid phase and the solvent. At
the bottom of the separator, there is a filtration in order to remove solid
particles and contaminants. The solvent passes again through a heat
exchanger and is directed to the bottom of the column, which contains
an electrical heater. This, in turn, operates at a temperature close to
200 ◦ C and cannot exceed 206 ◦ C, as it is the temperature of thermal
degradation of TEG. The rest of the water is removed at this stage. The
poor solvent passes through heat exchangers for cooling and returns to
the process [24].
When choosing a solvent, consideration should be given to its ease of
regeneration, its affinity with water, possible losses due to evaporation
(low vapor pressure), besides investment and operating costs. Among
the most common solvents, which are mono-alcohols and dial-alcohols
(glycols), triethylene glycol (TEG) stands out due to its high affinity
with water and 98% regeneration capacity [24–26].
3.3. Adsorption on silica gel for moisture removal
Fixed bed adsorption is a physicochemical process used to further
adjust the moisture content of the gas, aiming to reach the levels
established in the regulations, and can reach dew points of up to − 90 ◦ C
depending on the material used for adsorption [3]. The most used
adsorbent elements are silica gel, activated alumina and molecular
sieve. Silica gel is an amorphous form of hard, porous silica similar to
glass, and is obtained by heating the gel to 360 ◦ C, resulting from
acidifying a sodium silicate solution. It is widely used in hydrocarbon
recovery and drying of liquids and gases [27]. Currently, there are three
types of silica gel that differ in their particle size, which are: desiccant,
micronized and precipitated. The IUPAC (International Union of Pure
and Applied Chemistry) classifies the pore size according to their
average diameter and they can be: micropores, mesopores and macro­
pores [28].
Adsorption with silica gel is generally carried out at room tempera­
ture with pressure ranging between 6 and 10 bar. After a certain time,
the bed material becomes saturated, losing efficiency, requiring its
regeneration with hot air (120–150 ◦ C) and low pressures or vacuum. It
is ideal to use two columns operating in parallel so that the process can
be operated continuously. With silica gel, it is possible to obtain a dew
point temperature (- 90 ◦ C) lower than the temperature required by the
biomethane specification (− 45 ◦ C) [3].
3.4. Adsorption on activated carbon for H2S and CO2 removal
The adsorption principle in general is based on the retention of a
substance in a solid matrix with a large surface area. Usually, the
adsorbent has a porous surface, which makes its contact area with the
adsorbate even larger [29]. Activated carbon is a solid commonly
impregnated with potassium compounds that increase the efficiency of
CO2 and H2S removal, the second undergoing catalytic reduction to
L.C. Moreira et al.
elemental sulfur [3].
In this process, it is necessary to work with two columns so that the
operation is continuous: one column operates with the removal of the
compounds - which is the actual adsorption step in which the gas to be
treated passes through the adsorbent bed at room temperature and
pressure close to atmospheric - while the other column is regenerating
[22,29]. Activated carbon, or any other material used as an adsorbent,
has its adsorption capacity reduced after a certain period, that is, it
begins to retain less substances. At this stage, when the material is
saturated, the adsorbent needs regeneration. The regeneration process
occurs through the desorption of the adsorbed compound using heat or
pressure reduction [3,22]. Direct injection of steam with a temperature
above 200 ◦ C is the most used process to provide heat for regeneration
[22,23].
3.5. Absorption with Fe/EDTA for H2S and CO2 removal
This method has as principle the use of chelated metals to simulta­
neously remove H2S through a chemical absorption process and CO2
through a physical absorption process. The first one needs to be solu­
bilized in the liquid phase to oxidize to colloidal sulfur through the re­
action with iron chelate [30]. This is a widely used method when one
wants to reduce H2S concentrations to very low levels, considering its
high efficiency of approximately 99.9%. In addition, the Fe/EDTA so­
lution is easy to regenerate, has good selectivity and produces colloidal
sulfur, that is stable, with easy commercialization and final disposal [3].
As for adsorption, the process can be divided into two steps: ab­
sorption step and Fe/EDTA solution regeneration step. In the absorption
step, the mass transfer of the component to be removed (H2S) from the
gas to the liquid phase occurs first, and then occurs its reaction with the
Fe/EDTA (iron/ethylenediaminetetraacetic acid) solution and the con­
version to colloidal sulfur, insoluble [30]. In turn, iron, that is initially
charged with a +3 charge, is reduced to +2 and thereby becomes
inactive. Equations (1) and (2) represent this first step of the absorption
process [30]:
H2S(g)→H 2S(aq) (1)
H2S (aq) + 2Fe3 + /EDTA→S↓ + 2H + + 2Fe2 + /EDTA (2)
The regeneration of the Fe /EDTA compound to the ferric form
+2
occurs by the oxidation reaction of the solution with aqueous oxygen,
according to Equations (3) and (4) [31]:
O2(g)→O 2(aq) (3)
O2(aq) + 4Fe + 2/EDTA + 2H2O→4Fe + 3/EDTA + 4OH− (4)
Simultaneously with the chemical absorption process of H2S, the
physical absorption of CO2 occurs due to the presence of H2O in the
solution. Equation (5) is the global reaction that represents the biogas
purification process via absorption in Fe/EDTA solution.
H2S(g) + ½O2(g)→S(s) + H2O(l) (5)
Lenzi et al. [31] evaluated the use of this technique in the removal of
H2S and CO2 from biogas. It was verified that the H2S removal efficiency
is significantly influenced by the Fe/EDTA concentration in the solution
and the ratio between the liquid and gas flow (L/G), while the CO2
removal depends only on the L/G ratio.
3.6. Absorption with amines for H2S and CO2 removal
Chemical absorption using amines is a process that involves the
chemical reaction of the amine with both contaminants (CO2 and H2S).
The most used solvents are monoethanolamine (MEA), diethylamine
(DEA) and methyldiethanolamine (MDEA) [3]. Amines can be classified
as primary, secondary and tertiary: this classification is based on the
degree of substitution of the central nitrogen by organic groups. Primary
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Renewable and Sustainable Energy Reviews 163 (2022) 112532
amines, such as MEA, and secondary amines, such as DEA, react directly
with H2S and CO2. Tertiary amines, such as MDEA, react directly with
H2S and indirectly with CO2 [32].
MEA and DEA are very reactive and therefore have a high rate of acid
gas removal. However, there is a stoichiometric limitation of about 0.5
mol of CO2 removed per mol of amine, due to the formation of stable
carbamates with CO2 [32,33]. The absorption process is a reversible
chemical balance. The global stoichiometry of the process is shown in
Equations (6) and (7):
R − NH2 + H2O + CO2 ↔ R − NH3 + +HCO3− (6)
R − NH2 + H2S ↔ R − NH3 + +HS− (7)
where R is an organic radical.
The process is carried out in two parallel columns for absorption and
solvent regeneration. The absorption of H2S and CO2 is done at a
reduced temperature, while the regeneration of the amine solution is
done at a higher temperature, so that there can be energy integration,
thus removing the acid gases. The entire process takes place with pres­
sure close to atmospheric. Due to the higher bond strength, the amine
solution regeneration process takes place at temperatures from 110 to
160 ◦ C and then, for absorption to occur again, it needs to be cooled
down to 40 ◦ C [3].
3.7. Adsorption on metal oxides for H2S removal
The adsorption of H2S using metal oxides such as Fe2O3, ZnO, Cu2O
and MnO is commonly used in gas cleaning plants, with Fe2O3 being the
oxide with the highest efficiency (>99%) [34]. Compared with other
techniques, this one allows the treatment of gas with high concentra­
tions of H2S - up to 6000 ppmv - and can result in very low concentra­
tions - up to 1 ppmv. In addition, iron oxide has strength and good
regeneration capacity where, as seen in Equation (9), elemental sulfur is
formed. This method is known as “iron sponge”, as the fixed matrix is
made of very porous materials, such as steel wool and filings, facilitating
the contact between the solid and gas phases. However, due to the high
risk of ignition and difficulties related to the disposal of chemical resi­
dues, the iron sponges have been replaced by materials developed with
oxide, as these do not undergo combustion and are less toxic [34].
The continuous operation of the desulfurization process takes place
with two columns in parallel. H2S is removed in one of the columns,
while the other undergoes regeneration. The gas with the presence of
H2S passes through the column containing the iron (III) oxide, which
will react by retaining it according to the reaction scheme shown in
Equation (8) [34]. Regeneration occurs by injecting a flow of air/­
oxygen, which reacts with iron (III) sulfide to form elemental sulfur,
according to Equation (9) [3]. Regeneration can only be done twice as
elemental sulfur accumulates in the solid matrix and the iron sponge
activity is reduced by approximately one third [34]. After complete
saturation of the column - called “break-through point” -, there is a need
to change the matrix [3].
Fe2O3 + 3H2S→Fe2S3 + 3H2O (8)
Fe2S3 + 3/2O2→Fe2O3 + 3S (9)
3.8. Water scrubbing for CO2 removal
Water scrubbers are efficient in removing CO2 for biomethane pu­
rification, reaching the established standards [35]. A methane concen­
tration in the purified gas can be reached between 90 and 99% [3].
Scrubbing is based on the difference in solubility of CH4 and CO2 in
water, without chemical reaction, which will be affected by factors such
as temperature, pressure and the L/G ratio [35].
Biogas is cooled, pressurized and injected at the bottom of the col­
umn, while water is sprayed at the top, providing a countercurrent flow
L.C. Moreira et al.
of gas and liquid [36]. This column has a packed bed to maximize the
contact area between the gas and the liquid, interfering with the mass
transfer between the phases. CO2 and a small portion of CH4 are
absorbed by water. The solubility of CO2 in water is approximately 25
times greater than that of CH4 and determines the selectivity of the
process. The treated gas exits the top of the column, and the water
containing dissolved impurities exits the bottom and is directed to a
depletion column for its regeneration [35].
The regeneration column, in turn, operates at high temperature and
low pressure, shifting the balance and releasing CO2. To separate the
residual CH4 present in the contaminants, there can be a flash step,
recycling it to the entrance of the absorption column [3]. Water regen­
eration can also be achieved by agitation, which is a less efficient
alternative [23].
The process also absorbs acidic and alkaline gases, such as H2S and
NH3 present in biogas. The H2S in contact with water is highly corrosive.
In addition, H2S has a high solubility in water and its removal from the
wash water is laborious, allowing its accumulation in the exhaust col­
umn or in the flash tanks. The consequence of these factors is the
decrease in the efficiency of the process. Therefore, the biogas must be
previously desulfurized [3].
Despite their high efficiency, scrubbers have some disadvantages.
The main one is the high demand for water, followed by the high water
vapor content in the purified gas, making it necessary to pass it through
a new drying stage. There is also a large energy consumption for the
absorption and depletion stages [3].
3.9. Pressure swing adsorption (PSA) for CO2 removal
According to Coelho et al. [3], the Pressure Swing Adsorption (PSA)
method is based on the adsorption of gas in solid media such as activated
carbon, zeolites and molecular sieves, with pressure variation. Above
all, the process is based on the ability of CO2 to be adsorbed at high
pressures and desorbed at low pressures [3]. This method allows
removing different gases, however H2O and H2S are irreversibly
adsorbed, and this makes the bed lose efficiency after adsorption.
Therefore, when the intention is to purify biogas, for example, it is
necessary to use other methods of removal of these two compounds
before using a PSA unit, where only the CO2 will be removed [3].
The process consists of forwarding the first dry, H2S-free biogas to a
compressor, so that its pressure is raised from 4 to 7 bar, then going to an
adsorption unit in which the unwanted components are retained and the
biomethane almost completely crosses the column [3]. According to
Monteiro [37], more than 95% of the biomethane passes through the
adsorption column. For the regeneration of the adsorbent, the column is
depressurized and purged with a fraction of the purified gas. Therefore,
one of the disadvantages of this process is the loss of 1–5% of bio­
methane [37]. For the process to be continuous, it is important to
foreseen multiple adsorption beds, usually 4 to 8 [3,37].
3.10. Membrane separation for CO2 removal
Membranes are semipermeable barriers of physical separation
among two phases used in processes of selective separation of the
components in the chemical or physical mixtures. Membrane separation
processes are mainly based on the diffusivity difference between the gas
molecules [36]. The separation process can be carried out in more than
one stage, in order to remove the larger/most interactive molecules first
and then the smaller/less interactive molecules. Factors that interfere
with the purity of the gas obtained are the flow velocity and the surface
area of the membrane [3,36]. The biggest advantages of membrane
separation processes for CO2 removal are the high energy efficiency, low
capital cost, ease of operation and maintenance, high packing density
and ease of scaling [23].
The membrane removal process is able to remove all contaminating
molecules with good efficiency and in a single step [38]. However, the
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Renewable and Sustainable Energy Reviews 163 (2022) 112532
main objective of this treatment when applied to the purification of
biogas is the removal of CO2, since H2S, despite having a high selectivity
ratio in relation to methane, causes corrosion, which would imply higher
maintenance or pre-treatment costs. There is also a need for a filter
applied upstream to remove condensed water, oil and aerosols, avoiding
impairing the performance of the membrane [3]. Due to these impedi­
ments, membranes are usually only used after the other treatment steps,
completely removing the CO2 and remaining traces of contaminants
[38].
For biogas purification, the most used materials for making mem­
branes are polyamide and cellulose acetate. According to Coelho et al.
[3], both have high permeability to CO2, H2O, NH3 and, to some extent,
to H2S and O2, but have low permeability to CH4. It also has low
permeability to N2, but, when compared to methane, it has a CH4/N2
selectivity ratio equal to 5 [3]. CH4/CO2 selectivity in polyamide
membrane is approximately 40 for natural gas [39].
The purity obtained by membrane separation processes will vary
with the number of filtration stages. It is possible to obtain in just a
single stage a degree of purity of 80% and, if necessary, carry out mul­
tiple stages to obtain a high degree of purity. Membrane operating plants
achieve, on average, 90.3% purity. With operating pressure between 8
and 10 bar, the loss of methane is between 1% and 4% [3].
4. Methodology
The biomethane production process from vinasse can be divided in
two stages: anaerobic digestion and biogas purification. The purification
process alternatives were presented in the last sections and they are all
grouped in a single superstructure for better visualization of the plant
possibilities in Fig. 1. This superstructure encompasses 12 possible
routes, that are summarized in Table 2. Each process alternative was
simulated individually, respecting the superstructure nodes. The simu­
lations were performed in Aspen Plus® v8.8.
As the simulations are mathematical representations of the real
processes, whose solely objective is the rigorous solution of the mass and
energy balances to support the economic analysis, not all the blocks
represent real equipment units, and some simplifications are always
required. Therefore, to allow the better understanding of the simula­
tions, the real and simulation flowsheets are presented “side-by-side” in
Figs. 3–13 for each process alternative evaluated, so that the reader
could easily infer if the simulations are actual representations of the real
processes and propose adequate solutions if it seems necessary.
The raw material used for the generation of biogas is sugarcane
vinasse. To insert a raw material that is not part of the database in the
simulation environment, it is necessary to define an average composi­
tion. As already discussed, the composition of vinasse is strongly
dependent on its origin [12]. Therefore, in order to more reliably
reproduce the vinasse found in conventional ethanol production pro­
cesses in Brazil, the vinasse selected was that of juice must. According to
Lamônica [12], vinasse with this specification has an average chemical
composition of: pH 4.15, BOD (biochemical oxygen demand) 16,950
mg/L, COD (chemical oxygen demand) 28,450 mg/L, nitrogen (N) 357
mg/L, potassium (P) 2035 mg/L, calcium (Ca) 515 mg/L, magnesium
(Mg) 226 mg/L, chloride 1219 mg/L and sulfate 1538 mg/L.
However, for the simulation environment the inputs need to be
defined in terms of chemical components. COD and BOD are parameters
that represent the organic portion present in the vinasse, which in turn
consists of a series of compounds that will be converted into the product.
COD is more embracing than BOD, as it deals with all matter susceptible
to oxidation, while BOD deals only with its biodegradable portion [40].
As the COD amount encompasses BOD, it is unnecessary to represent the
second in the simulation environment.
In order to reproduce, as faithfully as possible, the mass balances
related to the fermenter, COD was considered as a pseudo-component
with structure and properties similar to those of glucose. This is a
simplifying hypothesis, but it is necessary, since COD is a parameter that
L.C. Moreira et al. Renewable and Sustainable Energy Reviews 163 (2022) 112532

Fig. 1. Process superstructure.

we chose the NRTL model, in its default configuration, and estimated its
Table 2
binary interaction parameters for liquid-liquid equilibrium.
Alternative routes for biogas purification, according to Fig. 1.
Routes Process Alternatives (Base Scenario)

1 1b 2a 3a – 4.1. Biogas production process simulation

2 1b 2a 3b –
3 1b 2a 3d 4c For the anaerobic biodigestion step of sugarcane vinasse from the
4 1b 2a 3c – juice must, it is necessary to choose the type of bioreactor that will be
5 1b 2b 3a –
6 1b 2b 3b –
evaluated. However, this choice is made more for the purpose of the
7 1b 2b 3d 4c economic analysis and not for simulation, because, as reported by Tunes
8 1b 2b 3c – [43], the choice of the bioreactor does not interfere in the stages of
9 1b 2a 3d 4a treatment and purification of the biogas, which is properly the object of
10 1b 2a 3d 4b
study of this work, because the biogas generation will happen in a
11 1b 2b 3d 4a
12 1b 2b 3d 4b similar way in each of the possible reactor types and the product will
have similar compositions. Also according to Tunes [43], the factors that
will actually interfere in the reaction are temperature, pH, alkalinity,
measures the amount of organic matter, through dissolved oxygen, macronutrients, micronutrients, residence time and the carbon source,
which is not known in the simulator. Glucose was chosen as the repre­ and for high efficiency it is necessary to find the optimal values of each
sentative molecule of organic matter because it has well-defined prop­ of these parameters.
erties. Such approach is also found in the work by Carniato et al. [41], in The type of bioreactor chosen for the Base Scenario was the UASB.
which simple organic molecules such as ethanol, sucrose and water were Tunes [43] carried out experiments on this type of reactor in a bench
chosen for the representative composition of the vinasse, aiming at scale and found a removal efficiency of 71% of COD, working with the
modeling the biogas production system. The other components are those mesophilic band. In the simulation environment, this reactor is repre­
that make up the mineral fraction of vinasse and, therefore, were sented by a RYield (yield reactor) block. This block was chosen because,
considered inert components in the simulation. in order to work with it, it is not necessary to be tied to stoichiometries,
According to ANP [42], the total production of ethanol in Brazil is which is essential since the COD is being simplified as glucose molecules.
currently of 127,616 m3 per day, with 349 (authorized) plants oper­ However, it is necessary to have the inlet and outlet composition well
ating, which corresponds to an average production of 366 m3 per day in defined. The inlet molar composition values can be estimated from the
one plant. As a result, an average ethanol plant in Brazil generates average values of vinasse composition from juice must that was given by
around 4000 m3 of vinasse per day [12]. In this work, it was assumed Lamônica [12]. The outlet values of the yield reactor were set from the
that 75% of the vinasse would be destined to biogas production, conversion conditions and the fractions of the biogas components as
considering that the remaining 25% would be used for fertigation. This found in the literature. Table A1 in the Appendix presents the simulation
results in a flowrate of 3000 m3 of vinasse per day or 125 m3 per hour. conditions and the inlet and outlet streams’ compositions.
It is essential to choose a suitable thermodynamic model to carry out Fig. 2 illustrates the biogas production step. The vinasse inlet stream
the simulations so that they correspond to what is actually found in the (001) enters the process at ambient temperature of 25 ◦ C and goes
industrial environment. For this, it is necessary to consider the condi­ directly to the reactors, represented by a RYield (R001) followed by flash
tions of the process and the species present. Various thermodynamic block (F001). It operates at a mesophilic temperature of 35 ◦ C and a
models are available in Aspen Plus®, such as equations of state and pressure of 1 atm. From the definition of specific yields, COD was 71%
excess Gibbs energy models, which predict the physicochemical prop­ converted into biogas components, in accordance with the work of
erties of the substances and mixtures involved in the simulation, but Tunes [43], and the other elements corresponding to the mineral part
there is no universal model that can be applied to any situation [16]. Due were considered inert. The flash block is needed in order to separate the
to the great non-ideality found in the systems, especially in the liquid liquid waste from the biogas in the reaction product (002). Then, the
phase, the use of excess energy Gibbs methods such as NRTL and UNI­ biogas stream to be treated (003) and the waste stream to be disposed of
QUAC is recommended [17]. To carry out the simulations of this work, (004) come out of the separator. This waste stream is composed of the

6
L.C. Moreira et al. Renewable and Sustainable Energy Reviews 163 (2022) 112532

Fig. 2. Reaction step’s flowsheet.

Fig. 3. Condensation (1b) step’s flowsheet.

unreacted part of COD and the other inert components.
4.2. Moisture removal process simulation
The treatment to remove moisture is extremely important when it is
desired to produce biomethane within the ANP specifications, suitable
for commercialization or prompt application. This is because the pres­
ence of water reduces the calorific value of the fuel. In addition, the
presence of condensed water in pipes combined with other acid con­
taminants can cause corrosion and clogging [16].
4.2.1. Condensation (1b)
The cooling and compression process to condense water and remove
it is one of the simplest but least efficient methods, as it only partially
removes moisture, which is sufficient for direct gas burning, but insuf­
ficient for other applications. To achieve superior quality standards, it is

7
L.C. Moreira et al. Renewable and Sustainable Energy Reviews 163 (2022) 112532

Fig. 4. Absorption with triethylene glycol (2a) step’s flowsheet.

Fig. 5. Adsorption on silica gel (2b) step’s flowsheet.

8
L.C. Moreira et al. Renewable and Sustainable Energy Reviews 163 (2022) 112532

Fig. 6. Adsorption on activated carbon (3a) step’s flowsheet.

Fig. 7. Absorption with Fe/EDTA (3b) step’s flowsheet.

necessary to use it in conjunction with other drying technologies [16]. necessary to raise pressure to values above 12 bar or decrease temper­
The proposed flowsheet for this process is shown in Fig. 3. The ature down to a dew point of 5 ◦ C, or to make a combination of the two
operating conditions and the inlet and outlet stream properties can be effects. In the simulator, the biogas stream (101) was pressurized by a
seen in Table A2 in the Appendix. According to Monteiro [37], it is compressor (P101) up to 5 bar. Then, this stream was taken to a cooler

9
L.C. Moreira et al. Renewable and Sustainable Energy Reviews 163 (2022) 112532

Fig. 8. Absorption with amines (3c) step’s flowsheet.

Fig. 9. Adsorption on metal oxides (3d) step’s flowsheet.

10
L.C. Moreira et al. Renewable and Sustainable Energy Reviews 163 (2022) 112532

Fig. 10. Water scrubbing (4a) step’s flowsheet.

Fig. 11. PSA (4b) step’s flowsheet.

(C101) to reduce the temperature to 5 ◦ C and force the water to values specified by Monteiro [37] were tested in order to find greater
condense. It is important to note that these pressure and temperature water removal efficiency. Then, stream (103) is conducted to a flash
values were found after a series of attempts, that is, values close to the vessel (F101), whose configuration was determined in order to

11
L.C. Moreira et al.
Fig. 12. Membrane separation (4c) step’s flowsheet.
Fig. 13. Equipment cost distribution in the Base Scenario.
maximize the separation of biogas and water, generating the partially
dry biogas stream (104).
4.2.2. Absorption with triethylene glycol (TEG) (2a)
The proposed flowsheet for simulation of the absorption process with
a TEG solution can be seen in Fig. 4 and the streams with their conditions
and compositions from the simulation are shown in Table A3 in the
Appendix. The biogas stream (201) from the reaction stage at a tem­
perature of 35 ◦ C and a pressure of 1 bar is routed to the bottom of the
absorption column (T201). According to Severiano [24], the tempera­
ture of the TEG must be 3–8 ◦ C above the temperature of the biogas, as
values above this range can cause the evaporation of the TEG by
increasing the dew point of the gas, and values below it can lead to
foaming. So, the TEG stream was routed to the column at 40 ◦ C.
The T201 column was configured with 5 stages, without condenser
and reboiler. Due to the lack of information on the number of stages in
the literature, this value was chosen based on efficiency tests in the
simulator itself. The top product stream (203) contains the dry biogas
that will be directed to the other treatments. The underflow (204)
12
Renewable and Sustainable Energy Reviews 163 (2022) 112532
containing rich TEG is directed to the regeneration system, where it
undergoes gradual heating steps in order to reduce solvent loss. The first
heat exchanger (E201) represents the top of the regenerating column in
the process, where heating occurs with heat exchange with the steam
coming from the bottom of the same column (213), reaching a tem­
perature of 101 ◦ C in stream 215. Water evaporated in this step (206) is
removed by a flash vessel F201. The TEG stream goes to the E202 heat
exchanger and then to the F202 flash vessel for evaporation of another
portion of the water (209). The TEG stream is again passed through a
heat exchanger (E203) for heating. Finally, the regenerator column,
equipped with electrical heating, was represented in the simulator by a
heater (H202) and a flash vessel (F203), which separates the liquid
phase (215) from the vapor phase (213). The operating temperature was
190 ◦ C, obtained after some tests in the simulator. All regeneration step
is thermally integrated in order to reduce energy consumption.
4.2.3. Adsorption on silica gel (2b)
For a matter of simplicity - because the objective of this work is the
economic analysis and not a rigorous evaluation of the process systems -,
L.C. Moreira et al.
the adsorption columns were represented in the simulator by mathe­
matical separators. This is because there is no basis for modeling mass
transfer processes in the simulator without further implementation. The
industrial and simulation flowsheets proposed for the silica gel adsorp­
tion process is shown in Fig. 5 and its operating conditions in Table A4 in
the Appendix.
In the simulator, the two columns were represented by a mathe­
matical separator that consists of a separation model so that the mass
and energy balances are solved after specification of the outlet streams’
compositions. It is followed by a mixer and a flash vessel. The mathe­
matical separator (S301) represents the water adsorption operation with
silica gel. The mixing block (M301) aims to represent the regeneration
process of the adsorption column when it reaches its saturation stage.
Regeneration consists of a passage of hot air at low pressure, and this
is done in the simulator using an air stream (306), with a flowrate close
to the flowrate of the waste stream. It is heated in H301, reaching a
temperature of 150 ◦ C then goes to the mixer together with the waste
stream that leaves the mathematical separator. After mixing, there is a
flash vessel (F301) operating at a temperature of 130 ◦ C and 1 bar. The
purpose of this block is to simulate the vaporization of water (309) from
the porous matrix.
According to Coelho et al. [3], adsorption using silica gel has an
efficiency above 98%. Therefore, this was the value used in the simu­
lation of this dewatering unit.
4.3. CO2 and H2S removal process simulation
As already discussed, some treatment alternatives are available for
joint removal of CO2 and H2S. It is necessary to remove them, as these
gases are pollutants. In addition, both are corrosive, H2S is toxic and CO2
- in greater quantities - reduces the calorific value of biomethane [16].
4.3.1. Adsorption on activated carbon (3a)
The adsorption process with activated carbon, according to Bonatto
[29], is used for the total removal of H2S and an increase in the calorific
value of the gas, that is, a partial removal of CO2. It is necessary to add
another CO2 removal step after this treatment to reach the levels
required by ANP. The flowsheet of this process alternative is shown in
Fig. 6 and the stream properties and compositions are shown in Table A5
in the Appendix.
For the simulation of this unit, the dry biogas stream (401) from a
water removal process enters the mathematical separator S401, where
the outlet compositions are defined. In this case, following the results
reported by Martiello [22], the operating conditions were adjusted to
achieve 45% CO2 removal and 100% H2S removal.
However, after a certain time, the adsorption column is saturated
and, for the process to continue, activated carbon must be regenerated.
In the simulator, to represent the activated carbon recovery step, which
occurs with a countercurrent injection of water vapor into the adsorp­
tion column at 200 ◦ C, the stream of gases (403), containing CO2 and
H2S, that is, the contaminants, is forwarded to a mixer (M401) together
with the stream of water (404) previously heated to 200 ◦ C by H401,
changing from liquid to the vapor state.
This mixer has the function of representing the water vapor stream
joining the activated carbon rich in contaminants inside the adsorption
column. Then, this mixture is sent to the F401 separator, where the
removal of contaminants from the fixed carbon matrix takes place. This
M401 - F401 set simulates what happens when a column is regenerating,
that is, the passage of water vapor through the activated carbon bed rich
in CO2 and H2S.
4.3.2. Absorption with Fe/EDTA (3b)
Absorption with Fe/EDTA solution could not be rigorously simulated
due to unavailability of equilibrium information and kinetic data in the
literature. Therefore, to represent this treatment unit - which was
simulated in a simplified way using experimental data of removal
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Renewable and Sustainable Energy Reviews 163 (2022) 112532
efficiency available in the adopted references -, a mathematical sepa­
rator (S501) was used. According to the experiments carried out by Frare
et al. [30], a biogas treatment unit by absorption in Fe/EDTA solution
has a removal efficiency of 99.9% of H2S and approximately 62% of CO2.
The proposed flowsheet for this process is shown in Fig. 7 and the
streams with their conditions and compositions are displayed in
Table A6 in the Appendix. In the simulation environment, separator
S501 receives the dry biogas stream (501) and a Fe/EDTA stream (502),
and the outlet streams’ compositions are defined as explained. The
solvent stream with contaminants is routed to a mixer (M501), which
simultaneously receives a stream of oxygen (505) under normal condi­
tions of pressure and temperature. The air stream with contaminants is
then sent to a RYield reactor (R501), where the reaction of oxidation of
hydrogen sulfide to solid sulfur occurs. It can be commercialized, adding
revenue to the plant. The block containing R501 and S502 represents the
entire Fe/EDTA solvent recovery unit. Stream 508 contains O2 and CO2
-removed through physical absorption with water -, stream 509 contains
the fully regenerated Fe/EDTA solution that will return to the process,
and stream 510 is solid sulfur.
4.3.3. Absorption with amines (3c)
Absorption with amines solutions is one of the best-known technol­
ogies for removing acid gases from gaseous streams. However, rigorous
simulation of this process is not trivial. In this work, as the objective is
the rigorous solution of mass and energy balances to carry out an eco­
nomic analysis and the effects of variations in procedural conditions on
the performance of this step are not being evaluated, it was simulated in
a simplified way. The flowsheet proposed in the simulator for absorption
with amines can be seen in Fig. 8 and the streams with their conditions
and compositions are displayed in Table A7 in Appendix. A DEA solution
was chosen as absorption solvent.
The biogas stream (601) at ambient conditions is compressed (P601)
up to 10.5 bar. Then, it is sent to a cooler in order to reach a temperature
of 40 ◦ C and is directed to a separator (S601), which aims to represent
the absorption column. Stream 605, containing DEA at ambient condi­
tions, passes through a pump (P602) and a heater (H001) to raise its
pressure to 3 bar and its temperature to 44.85 ◦ C, and goes to the S601
separator.
According to Mendieta [32], an absorption column with DEA has an
efficiency of 99% for removing CO2 and 100% for H2S. Secondary
amines are less reactive with impurities and intermediates than primary
amines, and the reaction products are not particularly corrosive.
Therefore, diethanolamine and other secondary amines are the best
choice for gas treatment. The DEA stream enters from the top of the
absorption column and the biogas from the bottom of it. Absorption
takes place in countercurrent. The 608 stream, which is the CO2-rich
DEA solution, goes through a heat exchanger to heat it up to 86.6 ◦ C,
which, according to Mendieta [32], is enough for solvent regeneration.
Then it is directed to a new separator (S602), which represents the
regeneration column. Also according to Mendieta [32], this one has an
efficiency of 80% and gives rise to streams 610, containing the removed
contaminants, and 611, with DEA, that will be reused.
4.4. H2S removal process simulation
As already mentioned, H2S is an acid, polluting and potentially
corrosive gas. In order to have a biomethane suitable for commerciali­
zation, it is necessary to follow ANP regulations, so that the total or
almost total removal of this gas is required. Some techniques are used
today exclusively for this purpose, including adsorption on metal oxides.
4.4.1. Adsorption on metal oxides (3d)
Metal oxides beds can have an efficiency above 99% for H2S
adsorption, according to Cristiano [34], and it is not relevant for other
contaminants - high selectivity. Therefore, it is necessary that this
treatment is coupled with others for the removal of H2O and CO2 in
L.C. Moreira et al.
order to reach the ANP specifications. The flowsheet for the H2S
adsorption unit on metal oxides is shown in Fig. 9 and the streams with
their conditions and compositions are shown in Table A.8 in the
Appendix.
The biogas stream, after going through a process to remove water,
can be optionally directed to an adsorption column that contains a fixed
bed composed of Fe2O3. This column is represented in the simulator by a
mathematical separator (S701), where the outlet streams’ compositions
are based on literature data [34]. Iron oxide was chosen due to its re­
ported better performance when compared to other metal oxides [34].
The column needs regeneration after a certain time, which takes
place through the injection of an air flow that will react with the matrix
forming elemental sulfur. In the simulator, the stream containing H2S
(703) from the adsorption column is directed to a mixer together with an
excess air stream (704). The output stream (705), now containing H2S
and O2, goes to a RYield reactor (R701), used to represent the regen­
eration column, where the elemental sulfur formation reaction and the
separation of streams take place. The entire process is kept at a tem­
perature of 25 ◦ C, in accordance with the range suggested by Cristiano
[34].
4.5. CO2 removal process simulation
As mentioned, CO2 is a contaminant that considerably reduces the
calorific value of biomethane. In order to have a biomethane suitable for
commercialization, it is necessary to follow the ANP specifications,
which demand a gas with high calorific value. This is achieved by
removing as much of the present CO2 as possible. Separation water
scrubbers, PSA and membranes are three of the processes indicated in
the literature for this type of treatment.
4.5.1. Water scrubbing (4a)
The water scrubbing process with water presents efficiency in gen­
eral between 90 and 99% to remove CO2, according to Freddo [35], and
can also absorb H2S. However, this process is not recommended for H2S
removal because it is highly corrosive and because this acid has high
solubility in water, making it difficult to recover. The flowsheet for this
unit is defined in Fig. 10 and the streams with their conditions and
compositions are shown in Table A.9 in the Appendix.
The biogas stream (801), previously treated to remove H2O and H2S,
must be pressurized and cooled to insolubilize the CO2. For this, it goes
through a compressor (P801), reaching a pressure of 8 bar, and later
through a cooler (C801), reaching a temperature of 5 ◦ C. The cooled
stream is then directed to the bottom of the absorption column (T801).
The water stream (804) passes through a pump (P802) to be pressurized
to 10 bar and a cooler (C802), reaching an operating temperature of
5 ◦ C, and enters the top of the T801 column. Coelho et al. [3] worked
with 2 stages for the operation of T801, however, in this work, 5 stages
were used to increase the performance of the process. The top product
stream (807) contains the treated biogas, and the bottom stream (808)
contains the water and absorbed impurities. The maximum efficiency
reached in this simulation was 92.5%.
For the regeneration of process water, an air stream (811), previously
heated (H903) to a temperature of 40 ◦ C, is routed to the separator
(S801), which is intended to represent the regeneration column. The
CO2 rich stream (808) passes through a pump and is depressurized down
to 2 bar, aiming to release the CO2 from the H2O stream, and also goes to
S801. The S801 separator, with 100% efficiency, separates CO2 and CH4
(stream 813) from the process water (810).
4.5.2. Pressure swing adsorption (PSA) (4b)
The four alternate adsorption columns of the PSA unit were repre­
sented by a mathematical separator, followed by a mixing block and a
second separator whose objective is to release the adsorbed CO2, rep­
resenting the adsorbent regeneration. The flowsheet is shown in Fig. 11
and the streams are arranged in Table A.10 of the Appendix with their
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Renewable and Sustainable Energy Reviews 163 (2022) 112532
conditions and compositions.
In this process, it is essential that all the water and H2S have been
previously removed. Therefore, the dry and previously desulfurized
biogas stream (901) is routed to a compressor (P901), so that the pres­
sure is raised to 7 bar. The stream is then directed to a cooler (C901), to
reach a temperature between 50 and 70 ◦ C. The stream leaving the
cooler (903) is then sent to the mathematical separator S901, which
simulates the adsorption process. According to Monteiro [37], the
fraction of contaminants in the product is around 4.1%.
The treated gas stream (904) is taken to a stream divider (D901) and
a purge stream (906), with a flowrate of 4% of the treated gas stream,
goes to the mixer M1001, where it meets the stream of contaminants
(907) coming out of S901. At the mixer outlet, there is a depressuriza­
tion (P902) step, which reduces the pressure to 2 bar and then stream
909 is taken to the second mathematical separator (S902), where CO2
and the CH4 purge are released.
4.5.3. Membrane separation (4c)
The biogas, after undergoing a treatment to remove water and H2S in
order to avoid corrosion, can pass through a series of membranes to
remove CO2 and H2S residues until the desired purity. In the simulation,
it was considered the mean removal values reported in the work by
Cerveira [38] the values obtained for a flat cellulose acetate membrane
filled with carbon nanotubes were considered. According to the author,
after passing through the membranes, the biogas reaches an average
purity of 90.3% at a pressure of 9 bar, with 2.5% loss of methane. The
temperature in the membrane separator is the same as in the inlet
stream. Based on the selectivity ratios of methane with the components
to be removed reported by the authors, a removal of 98.4% of H2S and
97.6% of CO2 is reached. The real and simulation process flowsheets are
shown in Fig. 12 and, in this case, there is only one mathematical
separator (S1001) to represent the membrane module in a simplified
way. The stream properties are shown in Table A.11 in the Appendix.
4.6. Economic evaluation
The equipment units were sized according to recommendations from
the traditional process systems engineering literature and the di­
mensions of the main units can be in seen Table 3 [44,45].
The UASB reactors must be sized based on the plant’s operating ca­
pacity and the residence time recommended in the literature. With this
information in hand, the reactor volume can be calculated by Equation
(10) [8]:
Q⋅HRT
Vreactor = (10)
Nreactor
where Q is the average effluent flowrate (m3/day), HRT is the hydraulic
retention time (days) and Nreactor is the number of reactors.
HRT is a parameter that expresses the time that the effluent must
remain inside the reactor and has a direct relationship with the tem­
perature. According to Barros et al. [16], the ideal HRT for converting
vinasse into biogas at mesophilic conditions as those used in this work is
between 2.8 and 1.8 days. Based on this information, a mean time of 2.3
days was determined. Multiplying this value by the flowrate of 3000
m3/day already defined in Section 3.3, a total volume of 6900 m3 is
obtained for the reactors set. To determine the dimensions and number
of reactors, the proportion suggested by Versiani [46] for a UASB reactor
was adopted, and the reactor height was limited to 15 m for transport
and installation reasons.
In the scenarios where the anaerobic lagoon was assumed, literature
data was used for the design and economic evaluation of this reactor.
According to von Sperling [19], the vinasse conversion at a temperature
of approximately 30 ◦ C, with a retention time of 3.5 days, is around 70%,
which does not significantly interfere with the generated biogas since a
conversion of 71% was assumed for the UASB reactor. Following the
L.C. Moreira et al. Renewable and Sustainable Energy Reviews 163 (2022) 112532

Table 3
Main equipment design.
UASB Reactors

Diameter (m) 7.7

Height (m) 15.0
Number of reactors 10
Volume per reactor (m3) 698.5

Anaerobic Lagoon

Top length - a (m) 96.0

Top width - b (m) 66.0
Height - c (m) 2.0
Bottom length - d (m) 81.0
Bottom width - e (m) 50.6

Heat Exchangers

C101 E201 E202 E203 H201 C301 H301

U (J/s.K.m2) 850.03 433.08 162.85 684.57 – 850.00 79.21

Area (m2) 1.05 0.35 17.06 0.77 – 1.43 0.07
Utility R134a – – – Electricity R134a MP Steam
Utility’s inlet temperature (◦ C) − 25 – – – – − 25 175

H401 C601 E601 H601 C801 C802 H801

U (J/s.K.m2) 849.97 333.37 850.00 426.89 849.98 849.98 850.00

Area (m2) 0.06 1.61 15.56 0.28 1.06 2.23 0.42
Utility HP Steam R134a – LP Steam R134a R134a LP Steam
Utility’s inlet temperature (◦ C) 250 − 25 – 125 − 25 − 25 125

C901

U (J/s.K.m2) 849.97
Area (m2) 0.54
Utility R134a
Utility’s inlet temperature (◦ C) − 25

Absorption/Recovery Columns

T201 S501 S502 S601 S602 T801 S801

Column height (m) 4.57 5.73 5.03 0.91 0.91 4.57 4.57
Column diameter (m) 0.27 0.29 0.16 0.61 0.61 0.25 0.57
HETP (m) 0.92 0.46 0.46 0.46 0.46 0.92 0.92
Number of stages 5 11 11 2 2 5 5
Operational (top) pressure (kPa) 101.3 1000.3 1000.0 100.0 100.0 1000.0 200.0

Adsorption Columns

S301 S401 S701 S901/S902

Column height (m) 4.06 9.58 3.94 0.71

Column diameter (m) 1.35 3.19 1.31 0.24
Bed porosity (%) 0.5 0.6 0.5 0.6
Bed volume (m3) 5.8 76.7 5.3 0.03
Adsorbent densitya (kg/L) 0.72 0.50 5.24 0.5
a
Takes porosity into account.

construction criteria and carrying out a cost estimate through a linear
extrapolation of the data from the Agricultural Research and Rural
Extension Company of the state of Santa Catarina (EPAGRI), south
Brazil, the dimensions described in Fig. 2 were obtained and the final
value of US$ 126,000 for the anaerobic lagoon was estimated [47].
The economic analysis of the present work was performed upon the
mass and energy balance results obtained from the simulation of each
process alternative and the equipment sizes. As presented in Table 2,
there are 10 biogas treatment alternatives presented in this work, which
may be arranged in 12 process routes for biomethane production. Each
of these routes consists of a certain combination of the treatment steps
distributed in the superstructure of Fig. 1 and described in the last
sections.
The purpose of this section is to deduct the necessary investment and
production costs for each route, as well as to perform a cash flow
analysis, so that it is possible to compare the different treatment tech­
nologies and to evaluate which are the most interesting for a biogas
production and purification plant from sugarcane vinasse. The meth­
odology followed in this work is classified as a Study Estimate [44], with
a margin of error of 35%, so that the values presented here should not be
assumed in absolute terms without further development, but it is
perfectly applicable for the comparison of different technologies.
With an availability of 125 m3/h of vinasse, corresponding to an
average Brazilian ethanol plant, approximately 4440 kg/h of biogas are
generated at NTP. For calculation purposes, an operating factor of 7920
h/year was considered, corresponding to 330 days worked, approxi­
mately 90% of the days of the year. The prices of all involved compo­
nents - raw material, solvents, adsorbents, final product and utilities -
are shown in Table 4. The sale price of biomethane was estimated based
on data obtained from the Monthly Monitoring Bulletin for the Natural
Gas Industry of the Brazilian Ministry of Mines and Energy [48]. Vinasse
was supposed zero-cost because it is an effluent and should be processed
in situ.
The Lang method was used to estimate the total investment required
for the process plant. In order to calculate the fixed investment, it is
necessary to calculate the F⋅O⋅B purchase price of each equipment unit,
which can be done through empirical formulas available in the litera­
ture. This cost must be updated for the year the work is performed using

15
L.C. Moreira et al. Renewable and Sustainable Energy Reviews 163 (2022) 112532

Table 4 Table 5
Component prices. Economic results for Routes 1 to 6 in the Base Scenario.
Price (USD/kg) Reference Routes 1 2 3 4 5 6
6
Raw Material Capital Costs (10 US$)
Vinasse 0.00 - Total Equipment Cost 3.16 4.92 3.01 3.06 2.92 4.67
Utilities Fixed Investment (IFixed) 12.77 11.67 12.15 12.35 11.78 10.68
LP steam 0.0042 Aspen Plus® v8.8 Working Capital 2.99 2.73 2.84 2.89 2.76 2.50
MP steam 0.0043 Aspen Plus® v8.8
HP steam 0.0043 Aspen Plus® v8.8 Total Investment (106 18.92 19.32 17.99 18.30 17.46 17.86
Refrigerant 1 (R134a) 0.00001 Aspen Plus® v8.8 US$)
Electricity 0.089 [49]
Solvents Direct Costs (106 US$/year)
Fe/EDTA solution 0.41 [50] Raw Material
TEG solution 1.58 [51] Vinasse 0.00 0.00 0.00 0.00 0.00 0.00
DEA solution 0.60 [52] Solvent
Adsorbents TEG 0.89 0.89 0.89 0.89
Silica Gel 1.80 [53] DEA 0.10
Actived Carbon 0.35 [54] Process Utilities
Metal Oxides 0.40 [55] Refrigerant 1 0.04 0.04 0.04 0.07 0.04 0.04
Products Saturated Steam 0.01 0.01 0.01 0.01 0.00 0.00
Elemental sulfur 2.55 [56] Electricity 0.05 0.05 0.05 0.12 0.05 0.05
Biomethane 0.5714 [48] Operating Labor (COL) 0.07 0.10 0.13 0.10 0.10 0.10
Supervisory and Clerical 0.01 0.01 0.02 0.02 0.01 0.01
Labor (CSC = 0.15 COL)
the Chemical Engineering Plant Cost Index [57]. To the updated cost, it Maintenance and 0.16 0.26 0.42 0.31 0.27 0.19
is necessary to add a factor related to the transport of this equipment to Repairs (CMR = 0.06
IFixed)
the plant site, multiplying it by 1.05, and then to apply the respective Operating Supplies (COS 0.02 0.04 0.06 0.05 0.04 0.03
Lang factor, according to the process type [44]. This procedure is = 0.15 CMR)
summarized in Equation (11): Laboratory Charges (CLC 0.03 0.01 0.02 0.02 0.01 0.01
= 0.15 COL)
∑ (PCI) Patents and Royalties 0.36 0.07 0.08 0.08 0.03 0.03
IFixed = 1.05fL Ci (11)
(PCIb ) (CPR = 0.03 CTP)
i
Subtotal 1.65 1.48 1.72 1.76 0.56 0.46

where IFixed is the fixed investment; fL is the Lang factor; PCI is the Plant Indirect Costs (106 US$/year)
Cost Index for the project year; PCIb is the Plant Cost Index for the base Overhead, Packaging 0.18 0.22 0.34 0.26 0.23 0.18
year; and Ci is the f. o.b. equipment acquisition i. and Storage (COPS =
The Lang factor for a process involving solids and fluids is equal to 0.60 (COL + CSC +
CMR))
4.38 [44] and this was the value used in this work. PCI equal to 603.1
Local Taxes (LT = 0.015 0.05 0.07 0.10 0.08 0.07 0.05
was adopted, referring to the period immediately before the COVID-19 IFixed)
pandemic, so avoiding ocasional inconsistencies. Insurance (IN = 0.005 0.23 0.02 0.03 0.03 0.02 0.02
The total investment is estimated considering the allocation of 15% IFixed)
Subtotal 0.46 0.31 0.48 0.36 0.32 0.24
as working capital [44]. The cost of equipments was completed using
empirical formulas available in the book by Seider et al. [44] and pro­ 6
General Expenses (10 US$/year)
duction costs were estimated according to the methodology of Turton Administrative Costs 0.10 0.06 0.08 0.06 0.06 0.04
et al. [58]. (CAD = 0.25 COPS)
Distribution and Selling 0.21 0.22 0.27 0.26 0.11 0.09
Costs (CDS = 0.10 CTP)
5. Results and discussion Research and 0.22 0.11 0.14 0.13 0.06 0.04
Development (CRD =
Different scenarios were analyzed. In the Base Scenario, biogas is 0.05 CTP)
generated in UASB reactors and a preliminary treatment is considered Subtotal 0.53 0.38 0.49 0.45 0.22 0.18

for partial water removal (condensation - 1b), although it is not Total Production Cost 2.25 2.18 2.69 2.57 1.10 0.87
mandatory in an industrial plant [3]. The results obtained for the Base (CTP) (106 US$/year)
Scenario were used to justify the modifications made in the next sce­
nario, and so on, as described in the next sections. Revenues (106 US$/year)
Methane 2.83 2.83 2.83 2.83 2.83 2.83
Elemental Sulfur 0.20 0.19
5.1. Base Scenario Subtotal 2.83 3.03 3.02 2.83 2.83 2.83

Tables 5 and 6 contain the economic results for the 12 routes in the
Base Scenario. There it is possible to observe the capital and production
costs (direct, indirect and general expenses), as well as the expected
revenues and annual net profit for each route. It is noteworthy that the
cost related to solvents accounted for the respective regeneration effi­
ciencies, which were 98% for TEG and 80% for DEA. In the case of Fe/
EDTA, its recovery is not accounted in the production costs due to its
high regeneration capacity, which in the present work was considered
100%, requiring its acquisition only at plant startup. Therefore, the Fe/
EDTA price was added to the capital cost only.
Fig. 13 shows the equipment costs distribution by process step for
each route. In all the routes, the highest cost is related to the reaction
Annual Net Profit (106 0.58 0.85 0.33 0.26 1.73 2.16
US$/year)
stage. This is due to the high volume flowrate and high HRT required in
the reaction stage, which resulted in a battery of 10 reactors, of
considerable size. It is an indicative that it would not be the best alter­
native for the reaction stage in an industrial vinasse processing plant.
Among the treatment steps, the one that stands out in Routes 1 to 4, 9
and 10 is water removal. In these routes, moisture is removed by ab­
sorption with TEG (2a), where the cost of acquiring this solvent is high,
mainly due to the large volume needed. In fact, comparing the routes,
the initial investment in the dewatering process with TEG is much higher

16
L.C. Moreira et al. Renewable and Sustainable Energy Reviews 163 (2022) 112532

Table 6 Route 4 has a small 10% share of DEA. Even requiring lower initial in­
Economic results for Routes 7 to 12 in the Base Scenario. vestments, in the other routes the other direct costs, indirect costs and
Routes 7 8 9 10 11 12 general expenses account for almost all the production costs. Utilities do
6 not account for more than 16% in the worst cases.
Capital Costs (10 US$)
Total Equipment Cost 2.76 2.81 3.09 3.07 2.85 2.83 In Tables 5 and 6, it is observed that all routes have positive annual
Fixed Investment (IFixed) 11.16 11.36 12.49 12.40 11.50 11.41 net profit, but this does not ensure that all plants are economically
Working Capital 2.61 2.66 2.92 2.90 2.69 2.67 viable, as the investment compensation has not yet been analyzed. This
can be done through a cash flow analysis, where the economic feasibility
Total Investment (106 15.53 16.83 18.50 18.37 17.04 16.91
US$)
can be evaluated based on the calculation of the net present value (NPV)
and the amount of time required for the return of the investment
Direct Costs (106 US$/year) (payback period). It was considered an operational horizon of 20 years
Raw Material and a minimum attractive rate of return of 10% to calculate NPV and
Vinasse 0.00 0.00 0.00 0.00 0.00 0.00
payback. The results are shown in Table 7. In this work, a route is
Solvent
TEG 0.89 0.89 considered economically interesting if it presents payback equal or
DEA 0.10 lower than 3 years.
Process Utilities Routes 5 to 7 were the only ones that presented positive NPV, being
Refrigerant 1 0.04 0.07 0.16 0.05 0.16 0.05 economically viable, but still not interesting, since they all have a long
Saturated Steam 0.00 0.00 0.01 0.01 0.00 0.00
Electricity 0.05 0.12 0.11 0.10 0.11 0.10
payback time. Route 6 presents full return in the 11th year of operation,
Operating Labor (COL) 0.13 0.10 0.13 0.13 0.13 0.13 Routes 5 and 7 in the 20th year, and the others do not have the in­
Supervisory and Clerical 0.02 0.01 0.02 0.02 0.02 0.02 vestment compensated within the operational horizon, which indicates
Labor (CSC = 0.15 COL) the practical unfeasibility of these plants.
Maintenance and 0.35 0.24 0.45 0.44 0.37 0.36
From the Base Scenario, it can be concluded that, in the economic
Repairs (CMR = 0.06
IFixed) context evaluated, the best process alternatives for the biogas treatment
Operating Supplies (COS 0.05 0.04 0.07 0.07 0.06 0.05 would be adsorption with silica gel (2b; for water removal) and ab­
= 0.15 CMR) sorption with Fe/EDTA solution (3b; for joint removal of H2S and CO2).
Laboratory Charges (CLC 0.02 0.01 0.02 0.02 0.02 0.02 Thus, the route that presented the best economic result was Route 6,
= 0.15 COL)
which combines these technologies.
Patents and Royalties 0.04 0.04 0.09 0.09 0.05 0.05
(CPR = 0.03 CTP)
Subtotal 0.69 0.73 1.94 1.81 0.91 0.79 5.2. Alternative Scenario 1

Indirect Costs (106 US$/year)

This scenario aims to reduce the impractical total investments shown
Overhead, Packaging 0.29 0.21 0.36 0.35 0.31 0.31
and Storage (COPS = in Tables 5 and 6, which averaged US$ 18,600,000. As shown in Fig. 13,
0.60 (COL + CSC + the UASB reactors are the main responsible for it. As exposed in Section
CMR)) 2.2, a low-cost and operationally simpler option is an anaerobic lagoon.
Local Taxes (LT = 0.015 0.09 0.06 0.11 0.11 0.09 0.08 With this design change, the cost of the reaction stage, which initially
IFixed)
was more than US$ 2,400,000, is now US$ 126,000, representing a
Insurance (IN = 0.005 0.03 0.02 0.04 0.04 0.03 0.03
IFixed) decrease of 94.80% in the reactor cost and 76.85% on average in the
Subtotal 0.41 0.29 0.51 0.50 0.44 0.43 capital costs of the routes, as can be seen in Fig. 15.
With the cost of the reactor in the Base Scenario being so much
6
General Expenses (10 US$/year)
higher than those of the other equipment units, it masked the compar­
Administrative Costs 0.07 0.05 0.09 0.09 0.08 0.08
(CAD = 0.25 COPS)
ison between the purification processes alternatives in the Base Sce­
Distribution and Selling 0.14 0.13 0.30 0.29 0.17 0.16 nario. Because of that, the equipment cost analysis was remade for
Costs (CDS = 0.10 CTP) Alternative Scenario 1 - now in terms of equipment units - and the results
Research and 0.07 0.06 0.15 0.14 0.09 0.08 are presented in Fig. 16. So, it is possible to identify the contribution of
Development (CRD =
each equipment type to the total equipment cost. It is possible to observe
0.05 CTP)
Subtotal 0.29 0.25 0.54 0.52 0.34 0.31 that vessels, pumps and compressors stand out.
In all Routes, the adsorption and flash vessels stand out, not because
Total Production Cost 1.38 1.27 2.98 2.82 1.68 1.52 they are expensive, but because they are numerous. In Routes 4 and 8 to
(CTP) (106 US$/year)
12, pumps and compressors are also important. In Routes 4 and 8, it is
Revenues (106 US$/year)
justified due to the presence of the absorption process with DEA (3c), in
Methane 2.83 2.83 2.83 2.83 2.83 2.83 which the column must receive the streams at high pressure. On Routes
Elemental Sulfur 0.19 0.19 0.19 0.19 0.19 9 and 11, there are water scrubbers which also requires high pressures.
Subtotal 3.02 2.83 3.02 3.02 3.02 3.02 And, finally, in Routes 10 and 12 it is due to the presence of the PSA
process (4b), where there is a cycle with pressure alternation.
Annual Net Profit (106 1.64 1.56 0.04 0.20 1.34 1.50
US$/year) A new cash flow analysis was performed for Alternative Scenario 1,
with the same parameters used in the Base Scenario. The NPV and
payback results are shown in Table 7.
than the initial investment in other water removal alternatives. It is In this new scenario, 6 routes present full return of the investment
noteworthy that at this stage there are two treatment steps: one is within 3 years, reaffirming a significant improvement in the plants when
condensation (1b), which performs partial drying in all routes. replacing the UASB reactor with the anaerobic lagoon. This scenario
Fig. 13 also indicates that, regardless of the technologies used (3a, 3b indicates that 50% of the proposed routes are economically attractive,
or 3c), joint removal of H2S and CO2 is always less costly than separate and the need to adopt anaerobic lagoons in large industrial applications
removal in terms of capital cost. This is due to the lower cost of equip­ is demonstrated. The number of unfeasible plants (negative NPV) is also
ment that a single step requires compared to two steps added together. significantly reduced, these being Routes 3, 4, 9 and 10.
Fig. 14 shows the distribution of the production costs for the different
routes. Routes 1 to 3, 9, and 10 have a 100% TEG-related expense, while

17
L.C. Moreira et al.
Fig. 14. Production cost distribution in the Base Scenario.
5.3. Alternative Scenario 2
Since in the Alternative Scenario 1 the capital cost is more viable
than in the Base Scenario, the analyzes for Alternative Scenario 2
considered an anaerobic lagoon instead of a set of UASB reactors.
In order to reduce the production cost, Alternative Scenario 2 pre­
sents the same 12 routes, but with the exclusion of the partial water
removal step by condensation (1b). In general, this partial removal is an
optional preliminary treatment intended to facilitate the subsequent
drying steps. For this study, it is not necessary to re-analyze the capital
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Renewable and Sustainable Energy Reviews 163 (2022) 112532
cost, as it varies little with this change. The exclusion of the Conden­
sation step (1b) may impact the costs of the second stage of dewatering,
as one less step means more rigor required later. But this effect has not
been investigated.
Fig. 17 shows a comparison of the annual net profits observed for
Alternative Scenarios 1 and 2, showing that removing the preliminary
drying tep can be a good option to reduce the production costs, if it, in
fact, does not significantly influence the subsequent purification steps.
For comparative purposes, NPV and payback calculations were
performed in the same manner as presented in Base Scenario and
L.C. Moreira et al. Renewable and Sustainable Energy Reviews 163 (2022) 112532

Table 7
Results of the cash flow analysis.
Routes Base Sc. Alternative Sc. 1 Alternative Sc. 2 Alternative Sc. 3

NPV (US$) Payback (years) NPV (US$) Payback (years) NPV (US$) Payback (years) NPV (US$) Payback (years)

1 − 11,001,593.06 >20 584,417.34 15 3,298,602.25 7 9,648,292.17 3

2 − 7,306,766.49 >20 4,279,243.92 5 9,326,344.49 1
3 − 12,328,891.76 >20 − 742,881.36 >20 4,452,134.51 2
4 − 13,228,575.18 >20 − 1,642,564.77 >20 1,071,620.13 11 7,421,310.05 4
5 29,955.87 20 11,615,966.28 3 14,330,151.18 2
6 5,031,567.86 11 16,617,577.97 1 19,331,762.87 1
7 9442.29 20 11,595,452.69 2 14,309,637.60 2
8 − 890,241.13 >20 10,695,769.28 2 13,409,954.18 2
9 − 13,957,647.87 >20 − 3,686,450.50 >20 − 972,265.59 >20 4,325,646.16 5
10 − 3,090,779.06 >20 − 2,224,001.67 >20 490,183.24 15 6,839,873.16 4
11 − 2,934,126.85 >20 8,651,883.55 3 11,366,068.46 2
12 − 3,090,779.06 >20 10,114,332.38 3 12,828,517.29 2

Fig. 15. Capital cost comparison between the Base Scenario and Alternative Scenario 1.

Alternative Scenario 1. These results are presented in Table 7.
As can be seen, there are 8 routes with payback period of less than 3
years. In addition, there are 3 routes that are still not interesting, as their
annual income is not enough to return the amount invested within 3
years of operation. In this new scenario, 92% of the routes proposed in
this work are feasible, with the exception of Route 9.
5.4. Alternative Scenario 3
This scenario aims to solve what makes Route 9 unfeasible and
Routes 1, 4 and 10 unattractive in Scenario 2, which is dehydration with
TEG (2a), already identified as the most expensive process alternative
after the UASB reactors. So, in order to make these routes competitive, it
is necessary to search for ways to improve this step.
An alternative is to replace the solvent. Despite having a water
removal efficiency of 99.9% [24], TEG has the highest value among
glycols, being 1.58 US$/kg in the national market in current data [51].
MEG (monoethylene glycol) is a promising substitute, as it is already
widely used in industry, according to Telles [59]. Its price is approxi­
mately 0.5 US$/kg in the Brazilian national market [51]. When
comparing their efficiencies, 99.9% for TEG and 93.13% for MEG [60],
this difference does not significantly imply the purity of the final product
obtained, keeping it within the ANP specifications.
Therefore, based on this information from the literature and
considering that the difference in efficiency does not impact the final
product, an economic evaluation was made considering the cost of the
new solvent, ethylene glycol (MEG), with a flowrate similar to that of
TEG for comparison purposes.
Fig. 18 shows the annual net profit values for the evaluated routes. It
is noteworthy that Routes 2 and 3, despite having absorption with TEG
in the drying step, were already attractive because they foreseen a
compensatory sale of elemental sulfur as a by-product and because they
make use of less costly processes in the other biogas treatment steps. All
routes showed a significant improvement in the final income value and it
directly impacts their viability. In order to better understand the impact
of this replacement, Table 7 brings the NPV and payback.
It is clear that changing the solvent is a very efficient solution since,
as mentioned, MEG is a solvent commonly used in the natural gas in­
dustry to perform dehydration, and it has much more attractive values.
All routes are now viable, although only Route 1 can actually be
considered economically interesting (payback of less than 3 years).
6. Future Outlook and challenges
The energy sector is responsible for 2/3 of world greenhouse gas
(GHG) emissions [61], then there is a consensus that this sector requires
special attention. In this direction, the UN Climate Conference COP26
increased the perspective of investments in Brazil due to its commitment
to reduce methane gas emissions by 30%. One of the recommendations
is the substitution of fossil fuels for renewable energy [62]. In the case of
Brazil, it involves ethanol and biogas production. So, the future is very
promising for projects in this sector and there is still much room for
development.
As discussed, raw material availability is not a challenge for large-
scale biogas production, since it is abundant, diverse and residual (low
cost) [10,63]. Technology is not such limiting also, because, as we show

19
L.C. Moreira et al.
Fig. 16. Equipment cost distribution in Alternative Scenario 1.
in this article, biogas purification can be performed by means of the
same technologies used for natural gas treatment, with some adaptions.
The only difficulty in this sense is the variability between different raw
materials, and for a certain raw material, regarding composition and
availability throughout the year: it occurs for vinasse as well [64].
Therefore, the main barrier for biogas consolidation is political/­
economic: there is still a lack of public policies aimed at large-scale
initiatives [63], and biogas production remains restricted to the pri­
vate sector - as occurs in the ethanol industry. In addition, there are
logistical issues: in Brazil, for example, the gas pipeline network is
concentrated in the coast and nearby regions. Its expansion would be
20
Renewable and Sustainable Energy Reviews 163 (2022) 112532
necessary for interstate or national distribution [62].
7. Conclusion
In this work, biogas production from sugarcane vinasse was simu­
lated and several process alternatives for anaerobic digestion and biogas
purification were evaluated. The comparative analysis showed that, for
the reaction stage, the most attractive alternative for an average Bra­
zilian ethanol plant is the covered anaerobic lagoon, with a cost of US$
126,000, while for the biogas purification steps, silica gel adsorption
appears as the best alternative for water removal, without a preliminary
L.C. Moreira et al.
Fig. 17. Annual net profits for Alternative Scenarios 1 and 2.
Fig. 18. Annual net profits for Alternative Scenario 3, changing TEG by MEG.
drying step, and CO2 and H2S removal must be done simultaneously,
preferably through Fe/EDTA absorption. In the considered economic
context, among the evaluated process routes, Route 6, which concate­
nate these technologies, would require an investment of US$ 3.6 million,
which would be returned in the first year of operation, with an annual
net profit of U$S 1.99 million.
This work presents the necessary data for its completely reproduc­
tion. Its main contribution is the process superstructure and the basis for
a comparative economic evaluation of the different biogas treatment
technologies. The authors indicate in the text where the simulations
could be improved if the reader demands more rigorous results at some
point. Other technologies can also be included, if available. The eco­
nomic analysis can be easily updated and must be adapted to other
economic contexts - time, place -, for which the conclusions may vary.
The next step is the evaluation of these technologies on a pilot plant,
to validate the assumptions made for equipment modeling in this article
and to elucidate other operational aspects not covered by a theoretical
21
Renewable and Sustainable Energy Reviews 163 (2022) 112532
work. These are our recommendations for future research.
Credit author statement
Moreira, L.C.: Methodology, Investigation, Writing – original draft,
Writing – review & editing. Borges, P.O.: Methodology, Investigation,
Writing – original draft, Writing – review & editing. Cavalcante, R.M.:
Methodology, Writing – original draft, Resources, Supervision. Young,
A.F.: Conceptualization, Methodology, Writing – original draft, Writing
– review & editing, Visualization, Supervision.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
L.C. Moreira et al. Renewable and Sustainable Energy Reviews 163 (2022) 112532

Appendix
Table A.1
Process streams for the reaction stage.

Stream 001 003 004

Molar Flow (kmol/h) 6292.067 35.307 6256.760

Temperature (◦ C) 25 35 35
Pressure (atm) 1.000 1.000 1.000
Molar Fractions
DQO 34.844 – 1.766
N2 0.437 0.278 –
K 2.494 – 1.976
Ca 0.631 – 0.488
Mg 0.277 – 0.354
NaCl 1.493 – 0.791
MgSO4 1.888 – 0.486
CH4 – 27.669 0.014
H2O 6250.000 0.431 6250.866
CO2 – 6.533 0.017
H2S – 0.295 0.002
NH3 – 0.022 –
H2 – 0.078 –

Table A.2
Process streams for the condensation step (1b).

Stream 101 104 105

Molar Flow (kmol/h) 35.307 34.913 0.394

Temperature (◦ C) 35 5 5
Pressure (atm) 1.000 4.935 4.935
Molar Fractions
N2 0.278 0.278 –
CH4 27.669 27.664 0.005
H2O 0.431 0.061 0.371
CO2 6.533 6.525 0.008
H2S 0.295 0.294 0.001
NH3 0.022 0.014 0.008
H2 0.078 0.077 0.005

Table A.3
Process streams for the absorption with triethylene glycol (TEG) step (2a).

Stream 201 202 203 206 209 214 217

Molar Flow (kmol/h) 35.306 11.600 34.797 0.064 0.033 1.445 10.561
Temperature (◦ C) 35 40 40.418 97.638 158.339 90 108
Pressure (atm) 1.000 1.000 1.000 1.000 1.000 1.000 1.000
Molar Fractions
N2 0.278 – 0.278 – – – –
CH4 27.669 – 27.628 0.033 – 0.002 –
H2O 0.431 – 0.000 0.002 0.008 0.265 0.157
CO2 6.533 – 6.489 0.025 0.012 0.007 –
H2S 0.295 – 0.289 0.002 0.002 0.003 –
NH3 0.022 – 0.021 – – 0.001 –
H2 0.078 – 0.077 – – – –
TEG – 11.600 0.015 0.001 0.011 1.169 10.404

Table A.4
Process streams for the adsorption on silica gel step (2b).

Stream 301 304 306 309

Molar Flow (kmol/h) 35.306 34.884 0.345 0.768

Temperature (◦ C) 35 36.600 25 130
Pressure (atm) 1.000 1.000 1.000 1.000
Molar Fractions
N2 0.278 0.278 – –
CH4 27.669 27.669 – –
H2O 0.431 0.009 – 0.422
(continued on next page)

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L.C. Moreira et al. Renewable and Sustainable Energy Reviews 163 (2022) 112532

Table A.4 (continued )

Stream 301 304 306 309

CO2 6.533 6.533 – –

H2S 0.295 0.295 – –
NH3 0.022 0.022 – –
H2 0.078 0.078 – –
Air – – 0.345 0.345

Table A.5
Process streams for the adsorption on activated carbon step (3a).

Stream 401 402 404 407

Molar Flow (kmol/h) 34.876 31.969 0.555 3.463

Temperature (◦ C) 35 35 25 130
Pressure (atm) 1.000 1.000 1.000 1.000
Molar Fractions
N2 0.208 0.279 – –
CH4 27.669 27.669 – –
H2O – – 0.555 0.555
CO2 6.534 3.921 – 2.613
H2S 0.295 – – 0.295
NH3 0.022 0.022 – –
H2 0.077 0.077 – –

Table A.6
Process streams for the absorption with Fe/EDTA step (3b).

Stream 501 502 503 505 508 509 510

Molar Flow (kmol/h) 34.852 26.800 30.507 20.000 24.051 26.800 0.295
Temperature (◦ C) 35 25 25.743 25 25 25 25
Pressure (atm) 1.000 1.000 1.000 1.000 1.000 1.000 1.000
Molar Fractions
N2 0.278 – 2.781 – – – –
CH4 27.669 – 27.669 – – – –
H2O – – – – 0.147 – –
CO2 6.533 – 24.826 – 4.051 – –
H2S 0.295 – 0.003 – – –
S – – – – – – 0.295
H2 0.077 – 0.773 – – – –
Fe/EDTA – 26.800 – – – 26.800 –
O2 – – – 20.000 19.853 – –

Table A.7
Process streams for the absorption with amines step (3c).

Stream 601 604 605 610 611 612 613

Molar Flow (kmol/h) 34.875 27.734 17.382 7.158 17.382 34.875 34.875
Temperature (◦ C) 35 25.990 25 75.997 75.997 230 87.019
Pressure (atm) 1.000 1.974 1.974 1.974 1.974 1.000 1.000
Molar Fractions
N2 0.278 – – 0.278 – 0.278 0.278
CH4 27.669 27.669 – – – 27.669 27.669
H2O – – 16.386 – 16.386 – –
CO2 6.533 0.065 – 6.486 – 6.533 6.533
H2S 0.295 – – 0.295 – 0.295 0.295
NH3 0.022 – – 0.022 – 0.022 0.022
H2 0.077 – – 0.077 – 0.077 0.077
DEA – – 0.996 – 0.996 – –

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L.C. Moreira et al. Renewable and Sustainable Energy Reviews 163 (2022) 112532

Table A.8
Process streams for the adsorption on metals oxides step (3d).

Stream 701 702 704 706 707

Molar Flow (kmol/h) 34.876 34.584 0.150 0.295 0.294

Temperature (◦ C) 36 36 25 31.700 31
Pressure (atm) 1.000 1.000 1.000 1.000 1.000
Molar Fractions
N2 0.278 0.278 – – –
CH4 27.669 27.669 – – –
H2O – – – 0.295 –
CO2 6.534 6.534 – – –
H2S 0.295 0.003 – – –
S – – – – 0.294
NH3 0.022 0.022 – – –
H2 0.077 0.077 – – –
O2 0.278 – 0.150 – –

Table A.9
Process streams for the water scrubbing step (4a).

Stream 801 804 807 810 811 813

Molar Flow (kmol/h) 34.580 175.000 23.427 174.856 200.000 211.297

Temperature (◦ C) 35 25 5.619 14 25 14
Pressure (atm) 1.000 1.000 9.869 2.960 1.000 2.960
Molar Fractions
N2 0.278 – 0.260 – – 0.018
CH4 27.669 – 22.578 0.039 – –
H2O – 175.000 0.023 173.827 – 1.150
CO2 6.533 – 0.488 0.284 – 5.761
NH3 0.022 – – 0.021 – 0.002
H2 0.077 – 0.077 – – 5.052
Air – – – 0.685 200.000 199.315

Table A.10
Process streams for the PSA step (4b).

Stream 901 905 910

Molar Flow (kmol/h) 34.580 26.900 7.682

Temperature (◦ C) 35 62 128
Pressure (atm) 1.000 6.908 1.974
Molar Fractions
N2 0.278 0.264 0.014
CH4 27.669 26.286 1.384
CO2 6.533 0.255 6.280
NH3 0.022 0.021 0.001
H2 0.077 0.073 0.004

Table A.11
Process streams for the membrane separation step (4c).

Stream 1001 1003 1004

Molar Flow (kmol/h) 34.581 27.190 7.392

Temperature (◦ C) 35 35 35
Pressure (atm) 1.000 9.000 9.000
Molar Fractions
N2 0.278 0.056 0.223
CH4 27.669 26.977 0.692
CO2 6.534 0.156 6.378
NH3 0.022 0.001 0.022
H2 0.077 – 0.077

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