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Biomass and Bioenergy 122 (2019) 117–125

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Biomass and Bioenergy


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

Review

A review of biogas production from sugarcane vinasse T


a a,∗ b
Mostafa Parsaee , Mostafa Kiani Deh Kiani , Keikhosro Karimi
a
Biosystem Engineering Department, Shahid Chamran University of Ahvaz, Ahvaz, Iran
b
Department of Chemical Engineering, Isfahan University of Technology, Isfahan, Iran

A R T I C LE I N FO A B S T R A C T

Keywords: Vinasse is considered as the largest source of contamination in the ethanol production industry from sugarcane.
Anaerobic digestion Vinasse can be used to produce suitable fertilizer; however, it contains low macronutrients and micronutrients.
Biogas On the other hand, it is one of the resources with a high potential for biogas production. The biogas production
Vinasse from vinasse has both economical and environmental benefits. Nevertheless, vinasse has a low carbon-to-ni-
Sugarcane
trogen ratio; thus, complementary substances, e.g., animal manure, organic industrial waste, and lime fertilizers,
Methane
should be added to improve the biogas yield. Currently, 22.4 gigalitres of vinasse are produced throughout the
world, which have the potential for producing 407.68 gigalitres of biogas. This potential can be considered as a
significant source of renewable energy. This paper gives a general summary of the properties of vinasse and the
production of biogas from vinasse. Furthermore, a review of the optimal conditions for biogas production, the
potential of biogas production, and the advantages of biogas production from vinasse are provided.

1. Introduction different genera, including Acetobacterium, Syntrophomonas, Clostridium,


Sporomusa, Syntrophospora, Thermosyntropha, and Eubacterium, are in-
In recent years, there are two major crises due to the growing global volved. A number of archeobacteria, including Methanococcus, Metha-
energy consumption of fossil fuels (80% of the required energy) [1]: the nosarcina, and Methanolobus, are in charge of methanogenesis [9–11].
environmental pollution and a growing acceleration in the reduction of This microbial consortium needs specific conditions for optimal biogas
energy resources. Therefore, seeking for clean and renewable energies production, i.e., pH in the range of 6–7.5 and temperature in the range
is at the top of the world's agenda [2,3]. Biomass is a major renewable of 35–55 °C [3].
resource in the world that can replace fossil fuels [4,5]. One of the The three primary resources for producing biogas include lig-
important advantages of energy production from biomass, e.g., by nocellulosic wastes, domestic and urban wastewater, and industrial
conversion to biogas, is less capital investment requirement, compared wastewater [12]. Considering their volume worldwide, the agro-in-
to other renewable energies such as hydro, solar, and wind [1]. dustrial wastes have a high potential to contaminate the environment
In this line, biogas production from organic waste has several ad- [13]. If these residues are discharged to the environment without
vantages compared to other alternatives, e.g., incineration, bio-oil, and proper disposal method that may lead to environmental pollution and
other biological products (such as bioethanol, biobutanol, biohy- harmful impacts. These untreated wastes create different problems with
drogen), electricity, and biodiesel [1,6]. Higher energy-yielding, less climate change by increasing a number of greenhouse gases [14]. Also
environmental impacts, and less capital investment requirements are the high chemical oxygen demand (COD) of these untreated wastes is
among the advantages [1,7]. Biogas is a flammable mixture when the suitable conditions for growth of different pathogenic fungi and bac-
concertation of biomethane is higher than 40%. It is produced through teria [15].
a process involving four stages, i.e., hydrolysis, acetogenesis, acet- The abandonment of industrial wastewater in nature results in
ogenesis, and methanogenesis, using a microbial consortium containing various negative effects on the environment due to the content of the
different types of bacteria. The hydrolysis of organic matter is per- suspended solids, ionic matter, color, and odor. Aerobic or anaerobic
formed by different bacteria, including Clostridium, Cellulomonas, Ba- treatment of this wastewater can greatly reduce their organic load [16].
cillus, Thermomonospora, Ruminococcus, Baceriodes, Acetovibrio, and Most industrial wastewater treatment plants use the anaerobic diges-
Microbispora genera. Lactobacillus, Streptococcus, Bacillus, and Escher- tion to decompose soluble organic waste [17].
ichia are mainly responsible for acidogenesis [8]. In acetogenesis, One of the best alternatives to replace fossil fuels is the production


Corresponding author. Tel.: +986133360016; fax: +986133330079.
E-mail address: m.kiani@scu.ac.ir (M. Kiani Deh Kiani).

https://doi.org/10.1016/j.biombioe.2019.01.034
Received 12 May 2018; Received in revised form 14 December 2018; Accepted 23 January 2019
0961-9534/ © 2019 Elsevier Ltd. All rights reserved.
M. Parsaee et al. Biomass and Bioenergy 122 (2019) 117–125

of bioethanol from sugarcane [18]. Still, one of the problems resulting


from the production of bioethanol is the treatment of vinasse waste-
water [19]. The production of biogas from sugarcane wastes has a great
potential for energy production [20]. Biogas production is the simple
methods for controlling environmental pollution, providing bio-
fertilizer, and producing clean and cheap fuel [21].
Bioethanol can be produced from several resources, including sugar
crops (e.g., sugar beet, sugarcane, molasses, sweet sorghum, and
grapes), starch crops (e.g., corn, wheat, rice, cassava, and barley), tuber
crops (e.g., potato and cassava), dairy products and cellulose materials
(e.g., rice straw, bagasse, wood, and municipal solid waste), agave plant
[22–27] in mesophilic fermentation using Saccharomyces cerevisiae
[28]. The two main types of waste which result from the production of
sugar and bioethanol from sugarcane are the agricultural residues and
the industrial byproducts. The former consists of burned or crushed Fig. 2. The produced bioethanol from sugarcane [47].
sugarcane in the harvesting process. The latter consists of five types of
waste as well as the main product: ash, bagasse, filter cake, molasses, It is a liquid produced in the unit of rectification and distillation in
and vinasse [29]. Among these wastes, vinasse is the largest source of bioethanol production, for which the production process is shown in
contamination in bioethanol production [30]. It is estimated that 88% Fig. 1 [35]. Vinasse accounts for 80 mass percent of the raw materials
of molasses is excreted after alcohol production [19]. A lot of water is used in producing alcohol [38]. The production of vinasse in a tradi-
used to dilute alcohol due to the sensitivity of alcohol-producing yeasts tional alcohol factory is in the range of 8–20 L per liter of ethanol
to concentrations of more than 9–11% of alcohol, which, in turn, results [33,39–44]. Brazil produces 50 percent of the total sugarcane-based
in producing large amounts of wastewater. The large amount of was- bioethanol in the world [45]. The leading sugarcane producers in the
tewater can be reduced via a fermentation process at the highest con- world are Brazil, India, China, Thailand, Pakistan, Mexico, Colombia,
centration of the initial sugar. This is possible by using yeasts resisting Indonesia, the Philippines, and the United States with the contribution
high alcohol concentrations. To achieve this aim, some of the output of 739.000, 341.200, 124.500, 100.100, 63.800, 61.200, 34.900,
effluents are returned to dilute the molasses. This operation is possible 33.700, 31.900, and 27.900 Mt per year, respectively. The corre-
up to 20% of the return flow, but its excessive increase leads to a de- sponding share is 38.1, 17.3, 6.1, 4.3, 3.2, 2.8, 1.8, 1.3, 1.1, and 1.4%
crease in the quality of molasses [31]. [46]. Most sugarcane-based bioethanol is produced in Asia and South
A review of the related literature reveals that vinasse is the largest America (Fig. 2) [47]. The annual production of bioethanol is about
source of contamination in producing bioethanol and its conversion to 0.23, 0.82, 0.18, and 0.37 gigaliters in Africa, Asia, Central America,
biogas can reduce the contamination and produce clean and in- and South America, respectively. A total of 1.6 gigaliters bioethanol is
expensive biofuel. This paper reviews the production of vinasse, its produced annually throughout the world, which will produce 22.4
properties, the production of biogas process from vinasse and its ad- gigaliters of vinasse [47]. In 2009, Brazil produced 325 billion liters of
vantages. vinasse from 25 billion liters of bioethanol [48]. It is estimated that 588
billion liters of vinasse will be produced in Brazil in 2019 [49].
2. Vinasse production from sugarcane

Vinasse is obtained from soluble solids of beet, sugarcane, sweet 2.1. Properties of vinasse
sorghum, grape, and agave. The properties of vinasse are mainly de-
pendent on the raw materials and the operating conditions in the al- Vinasse is a severe and recalcitrant wastewater [24] which is de-
cohol production plant. The specificity of sugarcane-based vinasse de- rived from the ethanolic distillation at a temperature of 65–107 °C and a
pends on the molasses used, the type of fermentation and distillation pH of 3–5 [50–52]. The distillation column temperature is highly de-
used, and the variety and maturity of sugarcane [22,23,27,29,32–35]. pendent on the technology used, which is dominantly Barbet and
Sugarcane vinasse has a higher COD compared with vinasse obtained Othmer systems. These industrial processes can be conducted under
from other materials such as sugar beet, sweet sorghum, grape, and vacuum pressure where the temperature is low, i.e., 65 °C, while for
agave [22]. It is sometimes named as mosto, stillage, thin stillage, atmospheric distillation the temperature is high, e.g., 107 °C. The pH is
distillery wastewater, distillery spentwash, and distillery slope [36,37]. also highly dependent on the cane cultivation conditions and its

Fig. 1. The process of producing vinasse from sugarcane [35].

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M. Parsaee et al. Biomass and Bioenergy 122 (2019) 117–125

Table 1 Table 2
Characteristics of sugarcane vinasse. Organic matter in vinasse [26].
Parameters Abbreviation Units Values Ref. Compound Concentration Compound Concentration

−1
Power of Hydrogen pH – 3.25–4.97 [32] Alcohols %w w Sugars %w w−1
Chemical oxygen COD kg/m3 27.5–299.250 [32,38,60,61]
demand 2,3-Butanediol 0.01 Glucose + fructose 1.30
Biochemical oxygen BOD kg/m3 5.046–47.636 [60,61] 2-Methyl-1,3- 0.20 b-Fructofuranose 0.50
demand butanediol
Total organic TOC kg/m3 20.16 [28] Glycerol 2.70 a-Glucopyranose 0.30
carbon 3-Methoxy-4- 5.4 Trehalose 0.30
Carbon/nitrogen C/N – 11-15/1 [62] hydroxyphenyl
Mineral Solid MS kg/m3 31 [28] glycerol
Volatile Solid VS kg/m3 46.39 [28] Sorbitol 1.40 Saccharose 0.2
Total solids TS kg/m3 27–81.5 [23,40]
Mineral Suspended MSS kg/m3 5.3 [28] Amino acids g kg−1 Organic acids %w w−1
Solid
Volatile Suspended VSS kg/m3 1.62–15.86 [28,60] Aspartic acid 76.9–88.5 Pyroglutamic acid 16.5
Solid Threonine 56.6–73.1 Itaconic acid 9.3
Volatile Solid VA Mg 1.5 [28] Serine 46.4–8.1 Fumaric acid 9.3
acetic acid/L Glutamic acid 121.1–132.3 p-Hydroxybenzoic 4.8
3
Phenols Phenols kg/m 0.45–0.469 [28,32] acid
Volatile Matter VM kg/m3 60 [40] Proline 49.8–60.2 Lactic acid 1.30
Fixed matter kg/m3 21.5 [40] Glycine 40.8–36.1 Succinic acid 0.07
Volatile fatty acids VFA kgCOD/m3 1.31 [43,60] Alanine 25–37.4 Malic acid 0.23
Total fixed solids TFS kgCOD/m3 8–10 [23,60] Cysteine 18.1 Aspartic acid 0.05
Volatile Suspended VSS kgCOD/m3 0.890–1.62 [38] Valine 56.6–71.3 Citric acid 0.80
solids Methionine 45.3 2,4- 0.71
Total volatile solids TVS kgCOD/m3 19–22 [23,60] Dihydroxypentanoic
Suspended solids SS Kg/m3 1.25 [38] acid
Electrical ES μS/cm 8294–15110 [61,63] Isoleucine 57.6–67.9 Quinic acid 0.70
conductivity Leucine 31–45.3 Aconitic acid 1.80
Bicarbonate Ba Mg 295–276 [23,60,63] Tyrosine 49.9–62.3
alkalinity CaCO3/L Phenylalanine 47.3–50.9
Total lipids TL mg/L 250–6894 [32,38] Histidine 47.2–50.9
Total proteins TP mg/L 2750–6894 [32,38] Lysine 9.28–9.96
Dissolved sugars DS mg/L 80 [38] Arginine 7.47–10.57
Betaine mg/L 22530 [32]
Glycerol mg/L 3333 [32]
Carbohydrates mg/L 9117 [32] calcium and sulfate ions, dead yeast cells, minerals from the metabolic
process of microorganisms, alcohol and residual sugar, insoluble mi-
neral compounds, and mineral volatile compounds [26]. Propionic acid
processing. The contamination of ethanolic fermentation by acid
is one of the volatile fatty acids found in vinasse, which is severely
forming bacteria could also be responsible for lowering the vinasse pH.
decomposed by microorganisms [64]. Among the vinasse macro-
Vinasse also contains phytotoxic, antibacterial, and recalcitrant com-
nutrients, potassium (due to potassium in molasses [33]) has the
pounds such as phenols, polyphenols, and heavy metals [51,53,54].
highest concentration, followed by sulfur, magnesium, nitrogen, cal-
Vinasse has 93–97% water [2,5,16,32,33,36,55,56], 5% organic matter
cium, and phosphorus. The macronutrients are mainly added during the
(sugars and carbohydrates), and 2% inorganic insoluble solids [36]. It is
process of sugar production, for example, magnesium for clarification
strongly soluble in water [57]. Sugarcane molasses contain 2% dark
and calcium for carbonation [33]. Among the vinasse micronutrients,
brown pigments called melanoidins, phenolic compounds (tannic and
iron has the highest concentration, followed by manganese, zinc, and
humic acids), caramels, and furfurals, which make vinasse stained
copper at lower concentrations [26]. Due to the addition of sulfuric acid
[16,19,22,28] and negatively affect the growth of microorganisms
to reduce pH in fermentation and yeast production, vinasse contains
[23,58]. About 75% solids of vinasse are organic matter [5]. The
considerable amounts of sulfate [2,33]. Sulfur content in vinasse is
amount of volatile solids in vinasse can be reduced by using calcium
4–10 times higher than the optimum concentration for biogas produc-
hydroxide [59]. Vinasse has density, viscosity, conductivity, boiling
tion [65]. Such high sulfur accompanied with digestion cessation be-
point, specific heat capacity, and thermal value of 1.031 kg/L,
cause of formation of H2S. High concertation of H2S negatively affects
0.00138 Pa s, 16.4 dS/m, 100.25 °C, 0.934 Cal/g.C, and 3.39 Cal/g,
the biogas formation by disturbing the methanogenic microorganisms
respectively [26]. Other characteristics of sugarcane vinasse are given
and competition of sulfate-reduction with methanogenesis, and in-
in Table 1.
hibiting the bioavailability of trace elements [66,67]. Thus, reduction
of H2S production should be considered to improve the biogas pro-
2.2. Chemical compounds in vinasse duction yield [20]. Vinasse also contains heavy metals, chromium,
copper, nickel, and zinc, which are formed in the molasses processing
Vinasse is a suspension of organic matter and solid minerals re- [22]. Vinasse from sugarcane molasses has higher sulfate, potassium,
sulting from distillation of alcohol, containing some residual sugars, and iron than other sources of vinasse [64]. The chemical compounds of
alcohol, and non-volatile compounds. The major components in vinasse vinasse from sugarcane produced in different countries are presented in
are organic matter, which include non-fermentable substances in mo- Table 3.
lasses, such as sugars (glucose and fructose), fermented products that The bacteria found in vinasse are Coccus, Curve rod, Filament,
cannot be separated during distillation (glycerol and organic acids), and Methanosate, Methanosarcina, Fluorescent rods, and S. cerevisiae [41],
the yeast residue that cannot be separated through the industrial pro- among which the two last ones are methanogenic microorganisms [64].
cess [5,29]. A wide range of organic compounds known in vinasse in- Based on the experiment conducted by Gamboa et al. [64] on geno-
cludes alcohols, aldehydes, ketones, esters, acids, and sugars (Table 2). typing vinasse, it was concluded that Methanobacteriales and Metha-
In general, the main componential mineral compounds are potassium, nosarcinales are the best methanogenic microorganisms to produce

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Table 3
Chemical compounds of sugarcane vinasse in different countries.
Parameters Brazil Australia India Iran Louisiana USA Colombia Miscellaneous (mean)

K 0.04–7.83 0.86–1.05 0.4–9.7 0.881 0.89 9.073 3.52 0.04–11.00 (5.52)


P 0.001–0.190 0.002–0.012 0.5–1.5 0.038 0.0001 0.001 0.01 0.0001–1.5 (0.750)
N 0.04–4.004 0.18–0.31 0.1–1.8 0.690 0.015 0.153 1.28 0.015–4.004 (2.0095)
Ca 0.008–5.18 0.11–0.20 0.75–0.82 0.211 0.014 0.143 0.88 0.008–5.18 (2.594)
Mg 0.016–1.529 0.13–0.15 – 0.478 0.006 0.061 0.60 0.0042–1.529 (0.7666)
Ash 1.95–50.972 3.2 – – 5.0 50.97 – 1.95–50.972 (26.461)
SO4−2 0.014–6.4 – – 3.56 – – 1.12 0.014–9.5 (4.757)
Na 0.050–3.82 – – 0.690 – – – 0.050–3.82 (1.935)
Cl 1.62–4.95 – – 1.58 – – – 1.62–4.95 (3.285)
Ba 0.00041 – – – – – – 0.00041
Cr 0.00004–0.00356 – – – – – – 0.00004–0.00356 (0.0018)
Cu 0.00006–0.00035 – – – – – 0.00518 0.00005–0.00518 (0.0026)
Hg 0.0000019 – – – – – – 0.0000019
Mo 0.000008 – – – – – – 0.000008
Ni 0.00003 – – – – – – 0.00003
Zn 0.00027–0.00166 – – – – – 0.00272 0.00027–0.012 (0.0061)
PO4 0.16192 – – – – – – 0.16192
NO3 0.64836 – – – – – – 0.64836
NH4 0.02418 – – – – – – 0.02418
Fe 0.002792 – – – – – 0.0169 0.002792–0.1575 (0.08014)
Mn 0.00118 – – – – – 0.00853 0.00118–0.00853 (0.004855)
BO3 0.00194 – – – – – 0.00275 0.00194–0.00275 (0.002345)
Ref. [23,30,32,33,40,60,61,63,68] [68] [68] [69] [68] [56] [48]

methane from vinasse at the optimum conditions in modified UASB many fish [63]. Vinasse is also toxic because of its low pH and the
reactor. They are more active and adaptable to the media containing presence of metals [61]. It is about 100 times more polluted than
vinasse. Methanothrix, as a methanogenic microorganisms, is suscep- household sewage [26]. To reduce the microbial activity of vinasse, it
tible to toxic substances existing in vinasse compared to Methano- can be stored at below 4 °C [45,61,79,80]. Allium cepa test on vinasse
sarcina. The presence of magnesium and calcium ions in vinasse results showed no germination ability. The cytotoxic activity of 50% was also
in the Methanosarcina growth. Generally, magnesium and calcium are observed in vinasse [45,61].
two chemicals needs for all microbial growth. In the case of methano- Regarding the storage of vinasse, the methane release rate in open
sarcina, the morphology is controlled by magnesium, calcium, and channels is equal to 1.36 kg CO2eq m−3, which is 620 times greater than
substrate concentrations. These factors allowed manipulation of the that in closed reservoirs or environments [74]. This is due to the fact
morphology and interconversions between pseudosarcinal aggregates that it cannot be easily fermented at the closed reservoirs [81]. Vinasse
and individual, coccoid cells. Boone and Robert [70] investigated the disposal should be carried out outside the populated areas due to the
effect of calcium and magnesium on growth of methanosarcina. The contamination and severe odor resulting from vinasse decomposition
results showed that adding 0.5 g of CaCl2.2H2O and MgCl2.6H2O per [26]. The blackness of vinasse makes dirty and immature environment
liter resulted in three times increase in the methanosarcina concentra- [32]. Vinasse has an unpleasant smell for humans, and its influence on
tion. drinking water leads to an outbreak of malaria, amebiasis, and schis-
tosomiasis. It is a medium for worm eggs of Meloidogyne javanica, M.
2.3. The environmental aspects of vinasse incognita, and Drosophila melanogaster to grow [23]. The pollution of
each liter of vinasse is equal to the amount of contamination produced
Bioethanol production plants are one of the 17 industries with se- by 1.43 humans [5].
vere pollution [71]. Vinasse causes emissions of greenhouse gases such
as CH4, N2O, and CO2, of which 99.8% belong to methane. These gases,
in addition to global warming due to changes in the chemical and 2.4. Applications of vinasse
physicochemical properties of the environment, cause several problems
[18,23,26,28,72–74]. Moreover, addition of heavy metals such as lead, Vinasse is used in chemical industries to produce chemical com-
zinc, and copper to the soil [24,26,28,64,73], increased electrical pounds such as organic acids, surfactants with Bacillus subtilis, and
conductivity and total dissolved solids [44], and decreased germination amino acids [13,26]. The use of 150 m3/ha vinasse as fertilizer in fields
of plants (negative effect on microbial activity) [24,27,45,64,76] are is equal to 61 kg/ha of nitrogen, 40 kg/ha of phosphorus, 343 kg/ha of
among the problems. Moreover, toxicity of surface and underground potassium, 108 kg/ha of calcium, and 80 kg/ha of sulfur [82]. Other
water due to high concentrations of solids and hard constituents such as applications of vinasse include production of hydroponic culture [30],
phenols and polyphenols (8000-10,000 mg/L), corrosive organic matter protein, and material compost [24,82] as fuel with a thermal value of
content of indole (3-methylindole) [4,16,24,26,55,77], and increased 12560–15070 kJ/kg [68]. Vinasse is used in civil construction and li-
eutrophication (due to the high content of nitrogen and phosphorus) vestock and poultry food (due to the high content of nutrients) [23],
make a number of problems when vinasse is released to environment. raw materials for lipid production by bacteria and fungi [49], and road
Colored compounds of vinasse reduce the permeability of sunlight in folding and mulching [48]. It can also be used to produce single-cell
rivers and lakes, thereby reducing the photosynthetic activity and the protein and calcium-magnesium acetate for the production of various
concentration of dissolved oxygen (due to high temperature of vinasse) bio-products (including enzymes, chitosan, astaxanthin, planthor-
in water leads to the creation of hazardous conditions for aquatic life mones, biopolymers, alternan, pullulan), algal production (e.g., Chlor-
[24,26,44,78] and the disturbance of life of plants and aquatic animals ella vulgaris and Neochloris oleoabundans [35]), and yeast production
due to reduced photosynthesis [23,32]. “Cowshed-fly” (Stomoxys cal- (requiring high energy and the addition of ammonium and magnesium)
citrans) resulting from the proliferation [76] of the use of vinasse in [23,26]. Vinasse does not have proper standards for direct use in soil
fields and its penetration into groundwater bring about the death of [73].

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2.5. Vinasse treatment methods lagoons, recovering up to 46% of the exergy removed from the natural
environment during the process, which shows the importance of this
Chemical and physical separation, drying, and separation of shells treatment option for vinasse [94].
are among the most widely used methods [35]. The ozone pre-process Vinasse anaerobic digestion can be used to stabilize organic matter
(high cost [83]) and UV ray can also increase 20% of produced methane and produce biogas and energy needed for drying the yeast at the plant
[24,27,84,85], and decrease phenolic compounds and color in addition or ethanol distillation [55]. Following the anaerobic digestion of vi-
to decreasing COD and total organic carbon (TOC) [24]. The ozone pre- nasse, sulfate [2] and the major fraction of organic matter are removed,
process can reduce phenolic compounds by 65% and color combina- while many organic volatile compounds and nutrients (potassium, ni-
tions by 80%, increase methane gas from 250 to 284 ml/gCOD at trogen, and phosphorus) are separated [16,29,73]. Using this method,
standard conditions and reduce COD removal from 79 to 81% [28]. the amount of vinasse sulfur can be reduced to less than 1% [95] be-
According to the test performed by Cabrera et al. [44] at mesophilic cause sulfate is converted into sulfide by sulfate-reducing bacteria
temperature to evaluate the efficacy of treating vinasse using anaerobic (SRB). A tiny amount of sulfur is a required nutrient for methanogens
digestion (AD) followed by ozonation, the methane production in AD microorganisms. The sulfur content of methanogens is higher than in
treatment was 0.315 m3CH4/kgCOD, where the COD removal efficiency other groups of microorganisms commonly find in anaerobic systems
was 75.1%. The anaerobically digested effluent was further treated [64]. The amount of potassium in vinasse does not decrease, so it can be
using ozone in a bubbling column. Using 100 mgO3/L, the COD re- used as a fertilizer after anaerobic digestion [52, [60]. Up to
moval efficiency was 99.2%, where the color removal efficiency was 300 m3.ha−1 vinasse, containing 3–4 kg m−3 potassium, can be used as
99.3%. AD process was done using a laboratory-scale upflow anaerobic a suitable fertilizer in field [96]. Anaerobic digestion does not reduce
filter reactor (UAFR) under continuous operation at 29 °C. Stable con- the amount and value of vinasse fertilizer [48]. The amount of methane
ditions were reached at 10 kgCOD/m3.day and HRT of 5 days. Vinasse and nitrous oxide (NOx) emissions from anaerobically digested vinasse
can be concentrated with evaporation, then its energy can be used by were decreased by 78% and 100%, respectively, compared to when
burning in boilers [23,48]. This method is being employed in Iran, but directly applied to soil [72]. Depending on the vinasse output tem-
it is not used to produce energy. Moreover, several methods have been perature, its anaerobic digestion can be conducted at thermophilic
used to treat vinasse including coagulation-flocculation, electro- temperature (55 °C) [55,73,76,97], which is more profitable and ad-
coagulation, and ultrasonication, which require a lot of energy [44]. vantageous over the mesophilic temperature [55]. The activity of me-
Therefore, vinasse treatment methods include bio-processing, advanced thanogenic microorganisms in vinasse at thermophilic temperature is
oxidative processes, AD, and chemical-based processes. Among of these 2.3 mg CH4/g VS acetate, while it is 1.32 3 mg CH4/g VS acetate at
methods, oxidation and chemical processes, AD, and microbial fer- mesophilic temperature [98]. Carbohydrate, protein, and lipid con-
mentation are effective to reduce its organic and mineral load [35]. centrations are 1560, 250, and 2750 mg/L in vinasse, respectively [38].
The water from vinasse contained in fermented lagoons are evapo- Therefore, the process of anaerobic digestion is similar to Fig. 4. This
rated by wind and solar radiation, and its sludge is released, causing process, like the processes for other materials, consists of the four stages
greenhouse gas emissions as well as environmental contaminations of hydrolysis, acidogenesis, acetogenesis, and methanogenesis, respec-
[86,87]. In contrast with some countries like Brazil, there is no direct tively. Vinasse is rapidly hydrolyzed due to its lack of lignin.
use of vinasse in farms as a fertilizer in some others countries like Iran Treatment methods such as anaerobic digestion are preferred, be-
because of the soil salinity [57]. cause of the transportation costs and the environmental impacts re-
garding vinasse [26]. The anaerobic treatment method can reduce vi-
3. Anaerobic digestion nasse COD and BOD by over 67% and 90%, respectively [51,91,99],
while aerobic systems reduce the maximum vinasse COD up to 67%
Anaerobic digestion has been considered as a biodegradation [43]. Electrolysis can reduce vinasse COD by 89%, but it costs more
method for large-scale treating organic wastes. The purpose of the than anaerobic digestion; thus, it is not economically feasible at com-
anaerobic digestion of the waste is to convert it into two groups of mercial scale [100]. Anaerobic digestion of vinasse is a low-cost and
valuable and needed materials, namely biogas and high-quality agri- low-energy method that produces the lowest amount of sludge and
cultural fertilizer [88]. This process is carried out by a consortium of produces useful byproducts such as biogas [24,79]. One of the problems
microorganisms living symbiotically. Complex organic compounds are with vinasse anaerobic digestion is that melanoidins cannot be elimi-
converted biologically to a wide number of chemicals, including me- nated. Melanoidins are high molecular weight polymers, formed when
thane, carbon dioxide, ammonia, water, and bacterial cells [89]. It sugars and amino acids combined through the Maillard reactions at
produces 10% less sludge compared to aerobic digestion [38]. Vinasse high temperatures and low water activity. They can, however, be re-
has a high potential for anaerobic digestion [2]. duced via the aerobic method of physical-chemical treatment [27].
Vinasse contamination can be further reduced by integrating biological
3.1. Sugarcane vinasse anaerobic digestion treatment with physicochemical treatment [44]. UB2 microorganisms
extracted from the soil, which were exposed to the sewage, can be used
Because of its characteristics, vinasse can be used as a feedstock for to reduce the intensity of the vinasse color with the reduction efficiency
fermentation [13]. The most effective and promising way to reduce of 81% [78].
vinasse contamination is anaerobic digestion [4,29,48,79,90–92],
whose commercial result is the production of methane as an energy 4. Production of biogas from sugarcane vinasse
resource [83,84]. Like most vinasse processing methods, e.g., fertirri-
gation, concentration, and combustion, anaerobic digestion reduces the Vinasse has a great potential for biogas production due to its high
environmental effects of vinasse. As depicted in Fig. 3, this method is organic content [79,91,97]. The production of biogas from vinasse is an
the best way for vinasse treatment, because it is more efficient in re- economically feasible process [5,22,29,49]. The first biogas production
ducing environmental effects compared with other methods. The en- from bagasse occurred in the '80s [26,97]. Due to the lack of lignin, the
vironmental effect of the process on carcinogens, respiratory organics, production of biogas from vinasse is simpler [32] and faster than other
respiratory inorganics, climate change, radiation, ozone layer, eco- materials [101]. Fig. 4 shows the process of producing methane from
toxicity, acidification/eutrophication, land use, minerals, and fossil vinasse and its production stages using anaerobic bacteria. Vinasse is a
fuels is 100, 87, 43, 68, 120, 100, 100, 79, 100, 100, and −100, re- suitable waste for energy extraction [64]. The production of biogas
spectively [93]. The anaerobic digestion of vinasse for energy produc- from vinasse and the use of solids produced as potash fertilizer are
tion is considerably environmentally better than its treatment in evident in Brazil, Argentina, and India [48]. The concentration of H2S

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M. Parsaee et al. Biomass and Bioenergy 122 (2019) 117–125

Fig. 3. Environmental impacts characterization [93].

produced from vinasse fermentation due to the high content of sulfate is Sulfur content in vinasse is one of the challenges in biogas pro-
about one percent; therefore, reduction of sulfide is required after duction, as sulfur content is around four, up to 10, times higher than
biogas production. In this regard, a solution of iron chloride (2% w/v) what is considered as an optimum concentration for the anaerobic di-
can be added to the vinasse solution before entering the reactor [38]. At gestion [65]. Such high sulfur content can cause undesirable effects on
present, 22.4 gigalitres of vinasse are produced throughout the world, biogas formation. This is due to the competition of sulfate-reduction
from which a total of 407.68 gigalitres biogas can be produced via di- with methanogenesis, reducing the conversion of organic acids into
gestion [47]. The efficiency of biogas generated from vinasse in a single biogas. Besides, it negatively influences the bioavailability of trace
sugarcane biorefinery is 38% for electricity generation in stationary elements inside the bioreactors [66,67]. For lignocellulosic waste,
engines and 30% in boilers, where it is 45% in cogeneration and steam sulfur content is rather low. Therefore, the co-digestion of vinasse with
generators and 33% for electrical energy [33]. lignocellulosic waste can reduce the adverse effects of H2S production

Fig. 4. Simultaneous production of biogas from the activity of anaerobic bacteria [102].

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M. Parsaee et al. Biomass and Bioenergy 122 (2019) 117–125

that required costly biogas desulfurization [20]. 1 m3 of vinasse [5]. From 4000 tons of sugarcane, 500 m3 of bioethanol,
720 tons of bagasse, and 4000 tons of vinasse are typically produced
4.1. Optimal conditions for biogas production from sugarcane vinasse [5,48,106]. From 1 g COD at standard conditions (0 °C and 1 atm),
0.35 L of methane gas can be produced; therefore, 1 g COD can produce
Besides nutrients, vinasse contains high level of inhibitors; thus, it 0.395 L of methane gas at 35 °C and 1 atm [32]. Therefore, 10–26.4 m3
should be diluted before anaerobic digestion. It was shown that the of biogas (containing 60% methane) can be produced from 1 m3 of
vinasse to water ratio of 1:3 produced the highest total biogas vinasse. The amount of 1.5–10 kW energy is generated from 1 m3 of the
(37.409 mL/g COD) [83,91,103]. The production of acetic acid, butyric produced biogas in the system of engine-generator with a thermal
acid, and removal of sulfate increases in the pH range of 2.8–8.6, power of 6.5 kWh/m3 [2,5,29]. From the vinasse produced from 1 m3
leading to more methane production [59]. The carbon-to-nitrogen ratio bioethanol, about 115–312 m3 of biogas can be produced, from which
is lower than the optimum carbon-to-nitrogen yield in biogas produc- 169 kW of energy can be generated [48]. The energy efficiency of the
tion because vinasse has a low carbon content [104]. Thus, for ad- biogas produced from the vinasse in reciprocating combustion engines
justing carbon-to-nitrogen ratio, the materials with high carbon-to-ni- is 29%, while it is 32% in the gas turbines and microturbines [82]. The
trogen ratio such as bagasse, straw, and filter cake may be added. total energy in vinasse is about 18% of the energy produced by bioe-
Depending on the feedstock co-digested with vinasse, the HRT needed thanol produced in the plant [48]. The energy produced from the vi-
to achieve 80% of the vinasse degradation should be considerably nasse biogas with a 25% efficiency (in the cycle of Otto, Brayton) is 22,
changed in the range of 10–40 days [20]. Hydraulic residence time 22, 31, and 34 kWh/t sugarcane for the condensing/extraction steam
required to reach 80% of the vinasse destruction is 10–40 days [20]. turbine, the biomass integrated gasification/gas turbine, the biochem-
Acidic pH of vinasse is not suitable for the growth of methanogenic ical, and the thermochemical, respectively [107].
microorganisms [42]. The energy generated from the anaerobic digestion of vinasse is
Organic fertilizers and industrial wastes (cellulose) can be added to calculated via Equation (1) [73,76]:
vinasse for its macronutrient and micronutrient deficiencies since the
fertilizer has a large amount of micronutrients and macronutrients. In a ( v )
P = LHVb f . (ECOD. Q v . CCODV ). ΩCH4
(1)
study by Moraes et al. [27], it was concluded that the addition of cow −3
manure could increase methane production efficiency by 15% [104]. where LHVb is the low thermal value of the biogas (kg Nm ), fv is the
The addition of calcium and phosphorus directly leads to a negative volume percentage of methane in the biogas, ECOD is the removal effi-
effect on the efficiency of the reactor. The amount of nitrogen and ciency of COD, QV is the vinasse volumetric discharge (m3h−1), CCODV is
phosphorus in vinasse is not sufficient for anaerobic digestion, and the vinasse COD (kg m−3), and ΩCH4 is the amount of methane gas
phosphorus cannot be directly injected to compensate it [23,80]. produced from COD (m3kg−1).
Therefore, urea, (CO(NH2)2,) and sodium phosphate, (NaH2PO4), are The biodegradability of vinasse ( ABDV ) is calculated based on
added as soluble to optimize nitrogen phosphorus, respectively [60] Equation (2) [76]:
(Table 4). In an experiment conducted by Boncz et al. [42], the best MYe ⎞
urea value was obtained to be 0.215 g/gCOD for the highest amount of ABDV (%) = ⎛ ⎜ × 100

⎝ MYt ⎠ (2)
produced biogas (10 L/g COD). As a co-substrate, the waste from Coca-
Cola plant [42], the sludge from domestic wastewater treatment in the where MYe is the methane production efficiency of the vinasse COD
UASB reactor [43,60], pig manure, the sludge from sugar beet vinasse value and MYt is the theoretical yield of methane production from vi-
with a specific methanogenic activity rate of 0.25 mg CH4/g VS, the nasse COD, which is equal to 350 mLCH4/gCOD [64,76].
sludge from sugar beet vinasse with a specific methanogen activity rate The amount of the reduction of carbon dioxide emission from vi-
of 0.3 mg CH4/g VS [55], the slurry sludge [105], and the banana nasse anaerobic digestion is calculated by Equation (3) [101,102]:
sludge [64] can be used. ERy = BIOPROD × CH4% × CH4HHV × NGEF (3)
where ERy is the reduction of carbon dioxide emission (tCO2/year),
4.2. Potential of producing biogas from sugarcane vinasse
BIOPROD is the produced biogas value (m3/year), CH4% is the methane
gas content in biogas, CH4HHV is the methane thermal value (55.5 MJ/
Eighty-five liters of bioethanol is typically produced from each ton
kg), and NGEF is CO2 emission coefficient (56.1 tCO2/TJ).
of sugarcane. The average production of vinasse is 12 m3 per m3 of
The efficiency of methane gas theory is obtained from Equation (4)
bioethanol and 14.23 m3 of methane produces from the digestion of
[108]:
Table 4 0.415Carbohydrates + 0.496Proteins + 1.014Lipids
Optimal conditions for the production of biogas from vinasse.
+ 0.373Acetate + 0.530Propionate
Parameter Dose Materials Ref. B0. th =
(Carbohydrate + Proteins + Lipids + Acetate + Propionate )
pH 6.8–8.2 50m/v NaOH & [59] (4)
1g of NaHCO3 per 1 g/L of COD
Tmesophile 35 [32,91,104]
Tthermophile 55 [31,73,76,98] 5. Advantages of producing biogas from vinasse
Eh −150mv [74]
TS 7.15–9.31 Water [32,76] The advantages of biogas production from vinasse can be summar-
COD:P 100:1 NaH2PO4 [64]
ized as follows:
C:N 20-40:1 CO(NH2)2 [62]
FeCl3.6H2O
Ni 1 Contributing to the energy sector and reducing the disadvantages of
Zn fossil fuels [99], in which the toxic gases (mainly sulfur dioxide and
COD:N 600:7 [32,43,83] nitrogen oxides) generated in burning biogas are less than 90% [1];
K 0.15–0.74 [34]
2 Complete burning of biogas in boilers and producing the steam
CO 10 [31]
Fe 0.5 [31] needed for the operation in sugarcane industry (7–9%). In this case,
Ni 0.1 [31] bagasse can be used for other purposes with higher values
N-NH3 200 [64] [29,64,73];

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M. Parsaee et al. Biomass and Bioenergy 122 (2019) 117–125

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