Battista 2020

Renewable and Sustainable Energy Reviews 131 (2020) 110007
Contents lists available at ScienceDirect
Renewable and Sustainable Energy Reviews

journal homepage: http://www.elsevier.com/locate/rser
Added-value molecules recovery and biofuels production from spent

coffee grounds
Federico Battista a, *, Elli Maria Barampouti b, Sofia Mai b, David Bolzonella a, Dimitris Malamis b,
Konstantinos Moustakas b, Maria Loizidou b
a
University of Verona, Department of Biotechnology, Via Strada le Grazie 15, 37134, Verona, Italy
b
National Technical University of Athens, School of Chemical Engineering, Unit of Environmental Science & Technology, 9 Iroon Polytechniou Str., Zographou Campus,
GR-15780, Athens, Greece
A R T I C L E I N F O A B S T R A C T
Keywords: Spent Coffee Grounds worldwide production is estimated at around 6 M tons only at industrial level. The
Biogas abundance and the heterogeneity of this substrate make it an ideal substrate for a biorefinery approach based on
Bioethanol the “cascade biorefinery hierarchy”. Currently, the major part of spent coffee grounds is sent to incineration and
Biorefinery
landfill disposal, options which should be avoided. Instead, they could be valorised through biofuels production.
Coffee oil extraction
All the operational parameters leading to the highest biogas (350-400LCH4/kgTVS), bioethanol (3–4%v/v) and
Polyhydroxyalkanoates
Pyrolysis biodiesel (over 90% of Fatty Acid Methyl Esters concentration) yields from spent coffee grounds have been
discussed in this review paper. They are rich in an oil phase containing different added-value molecules (to
copherols, cafestol, kahweol along with linoleic and palmitic acids), which can be extracted and used as additives
for food, cosmetic and pharmaceutical applications. Solid/liquid extraction techniques of coffee oil from spent
coffee grounds such as the most common Soxhlet technique and the more innovative fluids in supercritical
conditions have been discussed, with coffee oil recovery of around 5–15%w/w and 15–20%w/w, respectively.
The most recent applications of the extracted coffee oil have been also presented: the added-value molecules
recovery and purification after micro/ultra and nano filtrations processes and the polyhydroxyalkanoates (0.84
g/g) and biosurfactants (3.5 g/L) production. Considering the whole information, an integrated biorefinery
scheme, along with the respective mass balances were proposed. The novelty of this paper lies in the integration
of the state-of-the-art data, in a biorefinery concept that would allow the production of both biofuels and value-
added products.
fiscal system of taxation for the less green friendly waste management’s
practises and incentives for the most virtuous recovery and recycling of
1. Introduction
the materials. With references to organic wastes, it promotes the
“cascade pyramidal biorefinery hierarchy”, where the recovery of
The increasing attention drawn upon the catastrophic effects of
valuable biomolecules for pharmaceutical, chemical, cosmetic, agro
climate change is leading European Union (EU). In particular, EU has
nomic applications and the production of added-value compounds are
recently approved a second "circular economy package" which expressly
prioritised. The European Commission, therefore, specifies that bio
sets out the transition from a linear economic system to a circular one.
energy production should be approached only after these processes,
This latter is characterized by a three «r» principle: reduce, reuse and
while waste disposal in landfills should be avoided.
recycle (Com (2015) 614 final) [1]. This Circular Economy package
In Directive 2008/98 EC, in fact, the waste hierarchy is functional
includes the EU Directive 2018/851 [2], which contains some amend
not only to protect the environment and human health, but also to
ments to the waste Directive 2008/98 EC [3] and has introduced rele
achieve a further goal, namely the strengthening of the competitiveness
vant changes regarding the waste management, and mainly their
of EU. More precisely, it aims to ensure an efficient supply of raw ma
collection and valorisation. Compared to the previous Directive EU
terials, thus reducing EU dependence on their import. In this
2008/98, the most recent EU 2018/851 encourages the adoption of a
* Corresponding author.
E-mail addresses: [email protected] (F. Battista), [email protected] (E.M. Barampouti), [email protected] (S. Mai), [email protected]
(D. Bolzonella), [email protected] (D. Malamis), [email protected] (K. Moustakas), [email protected] (M. Loizidou).
https://doi.org/10.1016/j.rser.2020.110007
Received 19 March 2020; Received in revised form 25 May 2020; Accepted 13 June 2020
Available online 9 July 2020
1364-0321/© 2020 Elsevier Ltd. All rights reserved.
F. Battista et al. Renewable and Sustainable Energy Reviews 131 (2020) 110007
Therefore, SCG may not be valorised through composting or incinera

List of abbreviations tion and are mainly dumped in landfill sites, inducing severe environ
mental issues. Hence, alternative ways of treating, or even better
Al: Aluminum, valorising SCG are sought [10], since SCG should be managed in a more
COD: Chemical oxygen demand, sustainable way [9]. Scopus data (Fig. 1) revealed that the interest for
EU: European union, SCG had an exponential growth only since 2013.
FAME: Fatty acid methyl esters, In particular, in 2010 only 5 works investigated the exploitation of
FFA: Free fatty acids, SCG, while this number increased to 83, 97 and 150 in the last three
GCO: Green coffee oil, years (2017–2019). Going deep into the analysis of the topics of these
Fe: Iron, works, it emerged that almost 50% of the papers published in 2017
PHA: Polyhydroxyalkanoates, involved biofuels production, essentially biogas and bioethanol, while
PHB: Polyhydroxybutyrate, the extraction of added-value compounds was considered by only 14%.
SCG: Spent coffee grounds, Nevertheless, the entrance in force of the EU Directive 2018/851 had a
scCO2: Supercritical CO2, double effect: it increased the SCG publications by 33% in just one year,
VFA: Volatile fatty acids, promoting the investigation on the extraction and the synthesis of
VS: Volatile solids valuable molecules instead of SCG biofuels production. Specifically,
reference related to biogas production dropped by 30% of the papers
published in 2019.
In this context, a thorough literature review of SCG characterisation
perspective, waste is not considered a negative output but becomes a will be presented along with all the parameters that influence their
resource to be re-inserted in the economic cycle, creating new valuable composition. Following, the conventional valorisation techniques will
final products. be completed by the newly established and the techniques that are still
This review paper aims to guide through the possible processes in their infancy concluding at integrating all the knowledge by setting up
which can be integrated into the "cascade pyramidal biorefinery hier a SCG biorefinery. Thus, different techniques will be presented along
archy" approach, using one of the most abundant organic wastes in the this review, analysing their performances, their advantages and weak
world, the SCG. nesses. To the authors’ knowledge, there exist no comprehensive
Processing of coffee bean involves many steps such as wet or dry research work that have studied and made a comparison of the various
process, milling, roasting, grinding and brewing, in which solid residues SCG valorisation pathways and management practices. Hence, this work
such as SCG are obtained [4,5]. During wet technique, pulp is removed evaluates the implications of using SCG as a resource for biofuels and
mechanically and dried, while during dry technique entire coffee cher value-added products. In addition, this study paper aspires to identify
ries are dried without removing the pulp. This work focuses on the SCG the most beneficial SCG valorisation hierarchy in an effort to enhance
that constitute the main residue after the brewing of coffee [6–9]. SCG the consistency across the diverse methods.
are massively generated during coffee brewing where just a few com
ponents of the coffee beans are extracted [10]. 65% of coffee beans ends 2. SCG production and physical characterization
up as SCG [7]. Moreover, for each kg of soluble coffee, the amount of
SCG produced is 2 kg [11]. Thus, the total amount of SCG produced 2.1. Data on SCG international and European production
globally is immense. Almost half of this amount is produced from coffee
shops and industrial plants, while the remaining amount is produced Coffee is high-ranked in the consumers’ preferences all over the
domestically [12,13]. At an industrial level, SCG produced are estimated world as far as beverages are concerned. It is of paramount importance
to reach 6*106 tonnes, presenting fluctuations among countries given to the economy given that it is ranked 2nd among commodities
the dispersity of the coffee production plants. following crude oil [6,7]. According to the International Coffee Orga
In contrast to most part of other organic substrates, coffee contains nization, worldwide the production of coffee is around 168.7*106 bags
certain components with adverse effects to the environment given its (60kg/bag) marking a 0.9% decrease, while its consumption will reach
tannin, polyphenol and caffeine contents rendering it toxic [7,9,10,12]. 169.3*106 bags in 2020 [8]. The geographical distribution of coffee
Fig. 1. Number of documents relevant to the exploitation of SCG on scopus.com. For 2020 the first two months of the year are considered.
2
production along with its consumption is presented in Fig. 2. It is evident aluminum (22–280 mg/kg), iron (52–119 mg/kg), manganese (29–40
that there is not a uniform geographical distribution either to production mg/kg) and copper (18–32 mg/kg) [6,11,16]. In general, the ash con
or consumption of coffee. Ten countries are the larger coffee producers tent of SCG (1.3–2.2% w/w) is lower than the combustion residue of
counting for more than 80% of the global coffee production. Brazil, as a other biomass feedstocks, such as mango wood and stems (3.0–4.5%),
major coffee producer and exporter, contributes annually 2.9*106 chestnut (3.9%), almond pruning (3.6%), olive prunings (7.9%), cherry
tonnes coffee to the global market. Europe, on the other hand, although leaves (6.6%) [19].
it does not produce any coffee it consumes 1/3 of the global consump SCG also present interesting functional properties such as good oil
tion, necessitating 62% of total coffee imports [8]. and water holding capacity, stability as well as emulsion activity and
very low porosity [19].
2.2. SCG composition 3. Biofuels production
In view of evaluating different SCG valorisation pathways, it is 3.1. Bioethanol

important to study in depth their composition. As an organic, agricul
tural feedstock, SCG composition is strongly dependent on a wide va SCG is a propitious substrate to be utilised as a sustainable and low-
riety of factors such as type of coffee, origin of coffee beans, cultivation cost feedstock for bioethanol production given its high carbohydrates
conditions, processing methodology and brewing method. However, the content and its abundance as waste.
variations in the SCG composition are within a narrow range [10,14]. SCG bioethanol valorisation pathway includes all or some of the
Fig. 3 summarizes the range of the basic biochemical characteristics stages presented in the flow chart of Fig. 4. The saccharification of SCG
along with the ultimate/proximate analysis of SCG as reported in liter carbohydrates into fermentable sugars is the crucial step in the bio
ature [6,10,11,14–17]. The mean estimated chemical formula of a SCG ethanol approach. In general, the hydrolysis of SCG by chemicals or
sample is also presented. enzymes (Table 1) leads to the production of sugars. Yet, prior to hy
SCG can be considered as carbohydrate material, since poly drolysis, there exist several alternative pretreatment schemes aiming to
saccharides, cellulose and hemicellulose are over half of its mass on dry boost sugar yield.
basis. Mannose, arabinose and galactose are the main monomeric sugars In many studies, defatted SCG are used for ethanol production
of hemicellulose, while glucose is the monomer of cellulose. The poly [20–30] since free fatty acids (FFA) and triglycerides have been reported
saccharide content is followed by lignin and protein, which count for to decrease the sugars hydrolysis rate [24]. Nevertheless, Go et al. [30]
25% and 15% respectively. SCG also contain lipids ranging from 7% to carried out the hydrolysis step prior to oil recovery, and observed
21% and the predominant fatty acids are linoleic and palmitic [11]. elevated sugars and oil yields. In such an approach, the amount of wet
Caffeine, remaining in SCG after brewing, ranges from 0.734 to 41.3 biomass to be dried is lower, leading to energy savings of 1034.21 kJ/kg
mg/mg SCG [16]. of dry SCG [27]. In other approach, Burniol-Figols et al. [28] extracted
Other compounds reported in SCG in lower percentages include phenolic chlorogenic acid of high purity prior to the production of
phenolic compounds and tannins [5]. Volatile organic compounds, such bioethanol. This pretreatment step resulted in elevated sugar yields.
as terpenes and terpenoids with antimicrobial activity, have also been Acidic hydrolysis is commonly applied on SCG. As presented in
reported in SCG composition [14,18]. Table 1, dilute sulfuric acid disrupts SCG structure at elevated temper
Apart from the organic compounds, SCG contain various minerals atures (95–163 � C) leading to saccharification yields of 62–98% [20,21,
such as potassium (3550–11700 mg/kg), magnesium (1293–1900 mg/ 26–32]. SCG sugars may also be recovered by microwave superheated
kg), phosphorous (1475–1800 mg/kg), calcium (777–1200 mg/kg),
Fig. 2. Geographical distribution of coffee production and consumption.
3
Fig. 3. Biochemical and elemental analysis of SCG (% w/w dry base).
Fig. 4. Possible process steps of the SCG bioethanol valorisation pathway.
water [31]. Extraction yields as high as 69%, similar to other techniques, pretreatment (0.17–0.20g sugars/g SCG) [32,33]. The maximum sugar
were observed after several cycles [8,29]. recovery yield was 0.55g sugars/g SCG obtained after alkaline pre
Alternatively, enzymes can be used instead of acid to break down the treatment (4%w/v NaOH, autoclave,121 � C,25min) and enzymatic hy
polysaccharides. Mannanases, cellulases and hemicellulases are some of drolysis (Celluclast 1.5L 0.29 mL/g,7%w/v,50 � C,72h, pH 4.8) [34].
the conventional types of enzymes applied (Table 1) [24,32–35]. A crucial parameter that should be taken into consideration is the
When enzymatic hydrolysis follows a pretreatment scheme, elevated concentration of compounds that can act as potential inhibitory factors
sugar recoveries (0.26–0.55g sugars/g SCG) are observed [24,32,33, for the fermentation such as 5-hydroxymethyl furfural, furfural, acetic,
36–38] in contrast to enzymatically hydrolysed SCG without any lactic, succinic, propionic and oxalic acids.
4
Table 1
SCG saccharification yields when chemical or enzymatic hydrolysis is applied.
SCG Pretreatment Pretreatment conditions Hydrolysis conditions SG Yield Reference
(%)
(g/g)
Acid Hydrolysis
Dried H2SO4 10%w/w 87 0.34 [29]
L/S:10:1163 � C,45min
Defatted H2SO4 2.1%v/v 0.19 [21]
L/S:4 g/g
Autoclave,121 � C,15min
Defatted H2SO4 4%v/v 81–98 0.2–0.29 [20]
L/S:8 mL/g,96 � C,3–4h
Wet H2SO4 5%v/v 62 0.29 [27]
L/S:8 mL/g,95 � C,3h
Wet H2SO4 4%v/v 78 0.31 [30]
L/S:10 mL/g,95 � C,120min
Wet Phenolic extraction C2H5OH 60%v/v H2SO4 3.5%w/w 64 0.38 [28]
L/S:10:1 L/S:3.5 g/g
70 � C,40min Autoclave,140 � C,20min
Alkaline hydrolysis
Defatted NaOH 4 M 76 0.39 [26]
L/S:6.4 g/g,25 � C overnight
0.02 M NaBH4
Subcritical water
Dried 150 � C, 30 MPa 13 0.09 [23]
water flow 10 mL/min
Defatted 175 � C,30 MPa 32 0.172 [23]
water flow 10 mL/min
Enzymatic
Dried Cellulase:3%v/v 0.2 [32,33]
Hemicellulase:0.74%v/v
Loading:1%w/v
50 � C,24h,pH ¼ 6.8
Dried Recombinant mannanase: 0.5 mg/g 0.17 [34]
30%w/v
60 � C,18h,pH ¼ 5
Dried Acid H2SO4 1%v/v CellicCTec2: 2%v/v 70 0.33 [24]
15%w/v 50 � C,24h,pH ¼ 5
121 � C,60min
Defatted Acid H2SO4 1%v/v CellicCTec2:2%v/v 0.39 [24]
15%w/v 50 � C,24h,pH ¼ 5
121 � C,60min
Dried Acid H2SO4 1% Cellulase:3%v/v 0.27 [32]
1.6%w/v Hemicellulase: 0.74%v/v
autoclave 121 � C,10–30min Loading:1%w/v
50 � C,24h,pH ¼ 6.8
Dried Alkaline NaOH 4%w/v,L/S:5:1 Celluclast 1.5L:0.29 mL/g 60 0.55 [36]
autoclave 121 � C,25min 7%w/v,50 � C,72h,pH ¼ 4.8
Dried Popping 1.47 MPa,10min Celluclast 1.5L:18.3 mg/g 74 0.34 [38]
1%w/v,37 � C,48h,pH ¼ 4.8
Defatted Delignification NaClO2 1%w/w/h CH3COOH 1%v/ Cell T. longibrachiatum: 4.1 mg/g,45 � C,12h 78 [37]
Defatted w/h Cell T. reesei: 26921 4.1 mg/g 44 [37]
10% w/v,80 � C,3h 45 � C,12h
Defatted Pec in-house:4.1 mg/g 74 [37]
45 � C,12h
Defatted Cell in-house:4.1 mg/g 59 [37]
45 � C,12h
Defatted Celluclast:4.1 mg/g 59 [37]
45 � C,12h
Defatted 1st step: Pec in-house: 4.1 mg/g 46 1st [37]
step:0.16
45 � C,6h 2nd
step:0.19
2nd step:Pec in-house:8.2 mg/g,
β-glucosidase:2.1 mg/g 45 � C,24h
50% moisture Steam explosion Autoclave 121 � C Cellulase: 3% v/v 0.26 [32]
SCG 30min Hemicellulase: 0.74% v/v
1% w/v
50 � C, 24h, pH ¼ 6.8
Dried Ammonia fibre explosion NH4OH 10 mL/g Cellulase:3%v/v 0.29 [32]
H2O:0.2–2.0 mL/g Autoclave, 120 � C Hemicellulase:0.74%v/v
1–30min 1%w/v
50 � C,24h,pH ¼ 6.8
Dried Phosphoric acid- acetone 1st step H3PO4 85% Cellulase:3%v/v 0.33 [32]
L/S:10:1v/w, 50 � C,1h Hemicellulase:0.74%v/v
2nd step pre-cold acetone Loading:1%w/v
L/S:24:1v/w 50 � C,24h,pH ¼ 6.8h
(continued on next page)
5
Table 1 (continued )
SCG Pretreatment Pretreatment conditions Hydrolysis conditions SG Yield Reference
(%)
(g/g)
Dried Non-thermal plasma 2–6min, 60–80 kV stored 24h,10 � C Cellulase:3%v/v 0.28 [32]
Hemicellulase:0.74%v/v
Loading:1%w/v
50 � C,24h,pH ¼ 6.8
Dried Ferric chloride FeCl3 0.1 M Cellulase:3%v/v 0.27 [32]
1%w/v Hemicellulase:0.74%v/v
Autoclave, 120 � C Loading:1%w/v
30min,15psi 50 � C,24h,pH ¼ 6.8
Dried Organosolv C2H5OH 50–70% Cellulase:3%v/v 0.28 [32]
H2SO4 1%w/w Loading:1%w/v
120 � C, 30 min 50 � C,24h,pH ¼ 6.8, pretreated SCG,pH ¼
6.8,50 � C,24h
Dried Microwave assisted alkali NaOH 1%w/v Cellulase:3%v/v 0.27 [32]
microwave 240–800W, 30–120s Loading:1%w/v
50 � C,24h,pH ¼ 6.8
Dried Phosphoric acid- acetone þ 1st step: H3PO4 85%, L/S:10:1v/w, Cellulase:3%v/v 0.35 [32]
ammonia 50 � C,1h
pre-cold acetone Hemicellulase:0.74%v/v
L/S:24:1v/w Loading:1%w/v
2nd step: solid residue NH3 autoclave 50 � C,24h,pH ¼ 6.8
120 � C,30min
Dried Ultrasound-assisted kmno4 4% KMnO4 Cellulase:3%v/v 0.34 [33]
L/S:10:1 Hemicellulase:0.74%v/v
ultrasound (47 kHz, 310W) 20min Loading:1%w/v
50 � C,24h,pH ¼ 6.8
Dried Alkali assisted NaOH 1–5%w/v Cellulase:3%v/v 0.31 [33]
ultrasonication L/S:10:1 Hemicellulase:0.74%v/v
sonication (25 kHz, 150W) 30min Loading:1%w/v
50 � C,24h,pH ¼ 6.8
The results of the most recent literature reports on bioethanol pro rendering the coffee production process a closed-loop one [45]. Some
duction from SCG are presented in Table 2. In general, yeasts, fungi and studies proposed apart from the valorisation of biogas, the utilization of
bacteria are employed for the conversion of fermentable sugars to bio digestate as a growth medium for agriculture [9].
ethanol. Among them, the most frequently applied yeast is baker’s yeast, Both thermophilic and mesophilic conditions have been investigated
also known as S. cerevisiae [18,21,25,33,35,36]. Bonilla-Hermosa et al. for the anaerobic digestion of SCG at lab scale [38,46–50], resulting that
[36] assessed the bioethanol production yield and studied the produc lipids and carbohydrates may be degraded, whereas lignin remains
tion of volatile substances for 8 different yeast strains: Pichia guillier almost unaffected [43]. The use of SCG as substrate in anaerobic
mondi, Haseniaspora uvarum, Kluyveromyces marxianus, Saccharomyces digestion is beneficial given their elemental and chemical composition
cerevisiae, Pichia stipites, Pichia anomala, Torulaspora delbruekii and and specifically their protein, carbohydrate and mineral contents [40].
Candida tropicalis. The highest ethanol yeast (0.48g ethanol/g sugar) The C/N ratio ranges from 15 to 29 and thus it is on the threshold of the
was obtained by Hanseniaspora uvarum (Table 2) [36]. optimum respective ratio for anaerobic digestion (20–30). Thus, in some
The ethanol distillation cost reduces in an exponential way when the cases adding nutrients such as nitrogen, phosphorous or calcium and
ethanol concentration increases. An ethanol content of 4%v/v is trace elements may result in an increase in the methane content
accepted as the minimum concentration of an economically viable (65–70%) and a substantial efficiency (by 60%) in chemical oxygen
practice. The latter signifies a major challenge since in literature the demand (COD) and volatile solids (VS) biodegradation [43,51].
ethanol content of the fermentation broth is within the range of Anaerobic digestion and co-digestion of SCG has been studied
1.76–3.75%v/v [21,23,27,36,38] (Table 2). Just a few studies report [46–52]. However, most studies conclude that SCG present an excellent
values over 4% [28]. Therefore, economic issues must be taken into potential towards the production of biogas [11,44,46,47].
consideration at the very first stages of process development in order to Lane [49] studied the SCG potential as feedstock for mesophilic
result in viable solutions [39]. anaerobic digestion observing an elevated biogas yield (0.54 m3/kg)
After distillation, purification of bioethanol via membrane-based with 56–63% methane content [43,45,55]. Girotto et al. [45] examined
technologies should be employed in order to meet fuel standards [40]. the influence of substrate to inoculum ratio (0.5–2) on the biogas yield
A life cycle analysis resulted that SCG bioethanol production is under mesophilic conditions. The highest methane yield
economically feasible presenting a total net energy value of 6.8 MJ/L (0.36m3CH4/kgVS) was observed when the ratio was equal to 2. This
bioethanol. Additionally, this scheme presented CO2 savings equal to yield is noteworthy in comparison with other biomass substrates (e.g.
5.107 kg/L bioethanol in comparison with conventional bioethanol 0.25m3CH4/kgVS for wheat straw, 0.05m3CH4/kgVS for rice husk,
production from corn [41,42]. 0.34m3CH4/kgVS for mixed fruit and vegetable waste,
0.24m3CH4/kgVS for corn stover [56,57]), indicating that anaerobic
3.2. Biogas digestion of SCG is a viable alternative.
However, the lignocellulosic content of SCG may prove inhibitory to
The production of biogas from SCG constitutes an alternative “green” the progress of mesophilic digestion [58]. During the one and two-step
technological scheme aiming to produce renewable energy while bio thermophilic anaerobic treatment of SCG, the latter gave more repro
logically treating SCG [11,43,44]. Its composition mainly depends on ducible results [59]. Vitez et al. [47] reported a methane yield ranging
the feedstock and the operating conditions [43]. The produced biogas from 0.271 to 0.325 m3/kg accompanied by an elevated methane con
may be utilised in several applications, coffee roasting among others, tent (~60%) while applying thermophilic anaerobic digestion on SCG.
6
Table 2
Ethanol yields of treatment schemes for SCG valorisation.
SCG Pre treatment Hydrolysis Fermentation Fermentation conditions Ethanol Ethanol yield Ethanol (% Reference
Yield (g (L/kg SCG) w/v)
ethanol/g
sugar)
H.uvarum UFLA CAF76:0.3 g/L 0.48 0.222 2.1 [36]

loading:12%
27 � C
S. cerevisiae:3% 0.104 [39]
Loading:16%w/v
72h,30 � C
Dried Thermal S. cerevisiae:3% 0.220 [40]
Loading:16%w/v
72h,30 � C
Defatted Acid Liquid fraction of S. cerevisiae:10 g/L inoculated 0.50 0.106 1.89 [21]
hydrolysate 10h,30 � C
Dried Acid Enzymatic Hydrolysate liquid S. cerevisiae:10% 0.46 0.186 2.2 [23]
separated 40h,30 � C
Defatted Acid Enzymatic Hydrolysate liquid S. cerevisiae:10% 0.43 0.186 2.2 [24]
separated 40h,30 � C
Wet Phenolic Acid Hydrolysate liquid Autoclaved,121 � C, 20 min, 30 � C, 0.50 0.280 1.74 [27]
extraction separated S. cerevisiae:1 g/L inoculated
Wet Phenolic Acid Hydrolysate liquid Autoclaved,121 � C, 20 min, 30 � C, 0.46 0.130 3.92 [28]
extraction separated S. cerevisiae, 1 g/L of pre-grown
culture
Wet Phenolic Acid Hydrolysate liquid and Autoclaved,121 � C,20min, 30 � C, 0.50 0.280 2.96 [28]
extraction solids fermented S. cerevisiae,1 g/L of pre-grown culture
Enzymatic S. cerevisiae CAT1, 10%v/v 0.40 0.195 1.36 [36]
48h,30 � C
Simultaneous S. Cerevisiae KCTC 7906 0.44 0.194 1.53 [38]
Saccharification Loading:10%w/v
Fermentation 96h,37 � C.
No inhibition on biogas yield was observed despite the presence of (25%) which was 13.1% higher than SCG alone [48]. A detrimental
tannins, caffeine and polyphenols in coffee grounds [43]. impact on methane yield and production flow rate was observed when
Qiao et al. [48] also investigated SCG thermophilic anaerobic excess activated sludge was used in co-digestion [46,55]. Qiao et al. [48]
digestion and observed elevated methane content (60%) along with also performed co-digestion of SCG and excess activated sludge under
biogas productivity (1.5L/L/d). However, the overall yield of anaerobic thermophilic conditions. Nevertheless, in this case, by applying an
process was reduced due to the low nitrogen content, the inefficiency of organic loading rate of 11.1 kg-COD/m3/d and 20 days hydraulic
trace metals and VFA accumulation [43]. retention time, 67.4%COD conversion efficiency achieved [9]. Similar
Recently, Battista et al. [58] studied the impact of chemical pre improvement results were reported by Kim et al. [51] when co-digesting
treatment (either alkaline or acid) of SCG on biogas yield. It was SCG with Ulva biomass (25% on a COD basis) achieving 52%COD
observed that the alkaline pretreatment proved beneficial on cellulose removal [40]. In the study of Abouelenien et al. [60], the efficiency of
and lignin hydrolysis, providing an elevated methane content (80%) co-digestion of SCG, coconut and cassava wastes and chicken manure
[41]. Kourmentza et al. [43] also reported that SCG pretreatment with 2 was assessed under mesophilic and thermophilic conditions. The
M NaOH enhanced the biogas yield. Alkaline pretreatment was also ammonia content was reduced in the co-digestion mixture. As a result,
applied by Girotto et al. [50] aiming to increase the methane yield of the methane yield was doubled in comparison with the control experi
SCG. The optimum NaOH concentration was 8%w/w leading to a BMP ments (manure). In addition, although volatile fatty acids (VFA) were
of 392mLCH4/gVS. In this case, the lignin degradation was 24% higher accumulated, their concentration was not inhibitory [43].
in comparison with the untreated SCG. The simultaneous effect of NaOH Most commercial anaerobic configurations may use several different
addition (0–0.2 M) and temperature applied (60–90 � C) was also studied substrates of various compositions. Thus, these systems may also be
by Kim et al. [52]. The high alkaline concentrations accompanied by utilised for the anaerobic digestion or co-digestion of SCG for industrial
high temperatures resulted in extended SCG solubilization. Yet, the scale biogas production [11].
NaOH addition over a threshold induced the opposite results; that is
reduced methane yields. 3.3. Pyrolysis
The co-digestion of SCG with several substrates has also been tested
by some researchers. Neves et al. [53] used sewage sludge as a The physico-chemical characteristics of SCG render it a suitable
co-substrate with SCG under mesophilic conditions batchwise [38]. The feedstock for pyrolysis in line with the EU strategy of converting waste
methane yields observed were 0.24–0.28m3CH4/kg VS achieving to biofuels [61–63]. The SCG thermal decomposition involves three
elevated efficiencies (75–89% of the theoretical methane yield) [11,43, distinct steps. Initially, the adsorbed water is evaporated. The second
44,53]. VS removal exceeded in most cases 80%. Nevertheless, the long step (150–600 � C) includes the decomposition of hemicellulose, cellu
duration of the anaerobic digestion process (over 4 months) constituted lose (335–360 � C) and lignin (390–425 � C), leading to 75%w/w mass
the rate-limiting step [53]. loss. During the third step (600–1000 � C), the residual solids continue to
The co-digestion of SCG with wastes such as excess activated sludge, decompose very slowly [64].
food waste, whey and Ulva biomass presented in most cases comparable The pyrolysis technique applied as well as the reaction conditions
or higher methane yields than SCG indicating that the composition and (heating rate and temperature) determine the fractionation among the
specific characteristics of each feedstock mixture significantly affect end-products: bio-liquids (bio-oil/organic phase and aqueous phase),
anaerobic digestion [10,11,46,55]. The highest methane yield (0.355L biochar and syngas (hydrocarbon gases and others) [63]. In Table 3 the
CH4/gVS) was observed for a mixture of SCG (75%) and food waste experimental configurations and conditions along with the main
7
Table 3
SCG pyrolysis operational conditions and products’ yields.
Process description Reactor Temperature Heating rate Gas flow Residence Gas Bio-oil Aqueous phase Biochar Reference
configuration �
C ◦C/min mL/min time min yield yield yield % yield
% % %
Fast Fixed bed reactor 400–600 100 150 15 22–31 17–30 19.75–25.4 22–35.0 [62]
Fast Fixed bed reactor 600 100 100 45.4 6.08 25.1 25.1 [74]
with vertical furnace
Fast Fluidized bed reactor 400 0.083 17.6 38 35.2 [72]
Fast Fluidized bed reactor 500 0.083 23 43.8 23 [72]
Fast Fluidized bed reactor 600 0.083 32.1 31 19.6 [72]
Fast Screw-conveyor 500 500 56 [63]
reactor
Fast Screw-conveyor 429 10 500 32 22.3 59.6 20.6 [61]
reactor
reactor
reactor
reactor
reactor
reactor
reactor
reactor
Fast Screw-conveyor 571 10 500 32 24.3 57.8 17.3 []
reactor
Low temperature 380 10 500 180 15 50 29 [71]
conversion LTC
– TGA 500 10 20 12.2 65.2 22.6 [64]
– TGA 500 60 20 12 63 25 [64]
– Tubular reactor 500 50 30 28.2 [68]
– Tubular reactor 800 50 30 10.1 [68]
findings of reports studying SCG pyrolysis are presented in a uniform mainly composed of CO2, CO, CH4 and higher hydrocarbons [71,72].
way, in order to facilitate direct comparisons. It is evident that several Generally, bioliquids consist of a two-phase system; an aqueous (high
reactor configurations have been applied, with the fluidized bed and polarity) and an organic, oily phase (low polarity). The water phase
screw reactors being the most predominant. derives from the SCG water content and as a dehydration reaction
Temperature is a critical parameter during SCG pyrolysis, affecting product [62]. In the SCG bio-oil water phase, the quantitative contri
severely the product yield. For SCG fast pyrolysis at temperatures below bution of each group is 4% phenols, 2% ketones, 1.4% aldehydes, 0.6%
400 � C, lipid clusters are formed and create clogging issues to the alcohols and 1.6% nitrogen compounds. The nitrogen compounds pre
condenser. Thus, for high quality SCG bio-oil, temperatures over 400 � C sent in bio-oil are probably due to the high caffeine content (16%) of
are suggested [61]. Nevertheless, further temperature increase leads to SCG [73].
bio-oil yield decrease because of pyrolysis vapours secondary reactions The oily phase contains mainly 30% acids, 4% esters, 7% hydro
and thus more gaseous products [62]. carbons, 10% nitrogen compounds and 13% phenolic compounds [53,
The very high fuel-to-feed efficiency of pyrolysis is one of its main 71]. Palmitic, oleic and stearic acids are the predominant compounds
advantages. Regarding SCG, Li et al. [64] reported that the pyrolysis identified [62,64]. Aromatic organic compounds, such as catechol, hy
yield was estimated equal to 77–85%, depending on the moisture con droquinone and phenol were also identified in high concentrations [64].
tent of the feedstock. The overall efficiency of the biocrude oil produc The fatty acid and ester content of bio-oil indicates that coffee tri
tion from SCG was estimated 97.4% as the ratio of energy production glycerides are not thermally degraded, but just the ester bond with
(54791 kcal/h) to consumption [65,66]. The latter included the electric glycerol is broken [62]. Nevertheless, it should also be taken into
needs (5845 kcal/h) of supplementary equipment such as heaters, consideration that even during the roasting and coffee extraction pro
pumps, fans etc. as well as the thermal needs of burner (50436 kcal/h). cess, a partial decomposition of coffee grounds glycerides to fatty acids
Nevertheless, the relatively high temperature regimes (400–600 � C) occurs [74]. SCG bio-oils present elevated high heating value (12–34
applied during pyrolysis and the prerequisite of dried feedstock have a MJ/kg) [55,65,71,75] and thus may be burnt diesel engines, gas tur
strong impact on energy needs and overall cost, especially for SCG given bines and burners. Sulphur is not detected in the pyrolysis oil fraction
their high moisture content (50–60%w/w) [67]. Another issue that must [65]. The SCG pyrolysis oil, in general, meets the specifications of ASTM
be taken into account is that coffee is roasted; and, thus biochar yield is D7544-09 (solid residue 0.07–0.25%w/w, ash 0.06–0.19%w/w, pH
significantly higher in comparison with woody biomass or other agri 2.9–3.5). The viscosity (15–266 mm2/s), water content (24–33%w/w)
cultural feedstocks [68]. and density (0.96–1.15 kg/L) have been reported to be over the speci
The bio-oil resulting from pyrolysis may be used as a biofuel and also fications [65,71,75]. However, these parameters can be decreased after
as resins, lubricants, greases and in chemical industry. Biochar, apart mixing with suitable additives [71].
from being used as fuel (~13.3 MJ/m3) [69], it may be used in soil SCG bio-oils contain more carbon and nitrogen but less hydrogen and
remediation, ceramics, as a component of building blocks, as an absor oxygen than agricultural feedstocks bio-oil, according to their elemental
bent, and as active char after appropriate activation [70,71]. The syngas analysis (C:45–74%, H:7.5–12%, O:2.6–42%, N:0.8–16%) [65,75].
may also be utilised as a biofuel (576–3,446J/g biomass) since it is Additionally, since bio-oil presents a high acid value, its use may corrode
8
Table 4
Chemical and enzymatic transesterification: Conditions and yields.
Solvent (solvent:oil molar Catalyst Temperature (oC) Time FAME yield Reference
ratio) (h) (%)
Two-step Methanol 6:1 H2SO4 1%v/v 60 4 99.0 [83]

esterification KOH 1.5% 6
Methanol 7:1 H2SO4 1% 60 2 60.5 [97]
NaOH 1% 60 2
Methanol 20:1 methanol H2SO4 10%w/w 60 2 73.4 [95]
6:1 NaOH 1%w/w 60 2
Methanol 6:1 H2SO4 1%v/v 60 4 96.0 [88]
CH3NaO 0.5%w/w 1
Methanol 0,2:1/hexane 1:1 H2SO4 1%v/v 63 2 89.2 [89]
methanol 3:1 NaOH 1%w/v 2
Methanol 6:1 methanol 6:1 H2SO4 0.9% 70 92.1 [91]
NaOH 1%w/v 60
Methanol 40:1 methanol HCl 5%v/v 55 2 90.0 [87]
6:1 KOH 1%w/w 55 1
Methanol 20:1 methanol HCl 10%w/w 54 1.5 82.0 [99]
9:1 KOH 1%w/w 54 1.5
Alkaline conversion Methanol 9:1 KOH 2.5% 65 4 85.5 [79,83]
Methanol 5:1 KOH 2.5% 65 2.5 55.5 [79,83]
Methanol 5:1 KOH 2.5% 65 4 68.8 [79,83]
Methanol 5:1 KOH 2.5% 85 2.5 63.5 [79,83]
Methanol 5:1 KOH 2.5% 85 1 59.3 [79,83]
Methanol 9:1 KOH 2.5% 85 1 79.6 [79,83]
Methanol 7:1 KOH 1.5%w/w 70 100.0 [81]
Methanol 30:1 KOH 4%w/w 30% ultrasonic 3 97.1 [87]
amplitude
Methanol 9:1 NaOH 1% 65 2 92.0 [96]
Enzymatic conversio Ethanol 4:1 Novozym 435 10%w/w 40 4 60.0 [90]
Ethanol 4:1 Novozym 435 10%w/w 40 8 88.0 [90]
Ethanol 4:1 1.3-specific lipase RMIM (from Mucor miehei) 10% 40 24 70.0 [91]
Ethanol 4:1 combi protein coated 40 48 80.0 [90]
microcrystals Combi-PCMCs
Ethanol 4:1 Novozym 435 þ 1.3-specific lipase RMIM 1:1 40 24 86.0 [90]
Methanol 3:1 5% Novozym 435 and 5% TL-IM (Thermomyces 35 72 98.5 [86]
lanuginose) w/w
common construction materials [76,77]. Its direct use in diesel engines performance of pyrolysis resulting in a higher syngas yield and thus a
is problematic since clogging and misfiring issues may arise [75]. lower bio-oil yield [72].
Blending with diesel, biodiesel, alcohol fuels and cetane improvers could
ameliorate its properties [50,54]. Lee et al. [75] investigated the per 3.4. Biodiesel
formance in a diesel engine of a fuel mixture consisting of SCG pyrolysis
oil, butanol and cetane improvers. Under a stable operation of the en SCG are a promising substrate for biodiesel production, since they
gine, CO and NOx were increased, while hydrocarbons and particulate have a high oil content, comparable with the respective content of the
matters emissions were reduced in comparison with the respective of conventional 1st generation feedstocks [79–82]. The conventional and
diesel. This was attributed to the elevated oxygen content of SCG py the more innovative and promising techniques for coffee oil extraction,
rolysis oil and butanol [75]. Hydrothermal processing of SCG bio-oil is required process before the biodiesel extraction, has been discussed in
another technological alternative able to decrease the oxygen content the next paragraph.
and acid value of bio-oil upgrading its quality to meet marketable fuel In comparison with other waste, coffee oil is a high quality and
chemicals standards [64]. economical substrate for biofuel production. It is cheaper and has a
The removal of oil (with conventional methods such as Soxhlet pleasant smell [83]. As it is presented in Table 4, the biodiesel yields
extraction or solid/liquid extraction or more sophisticated methods such reported are over 56%; similar to the respective efficiencies of other
as supercritical extraction) prior to pyrolysis leads to lower bio-oil yield, vegetable oil substrates [75]. In several cases, the conversion of oil into
aliphatic functionality and energy density and thus upgrading may be biodiesel is nearly complete [81,83–86].
necessary. Lipids removal results in a bio-oil with higher nitrogen and The conversion of SCG oil to biodiesel may be categorized into acid
oxygen but lower carbon and hydrogen contents. The resulting carbo and alkaline catalytic conversion, enzymatic conversion and other
hydrates’ higher content leads to an elevated yield of water phase since technological approaches. In situ-transesterification has also been
carbohydrates decompose in water soluble organic compounds. reported.
Apart from typical pyrolysis in N2, CO2-assisted pyrolysis of SCG has Acid and alkaline chemicals have been extensively applied as
also been studied [76–78]. More gaseous CO was generated, while less chemical catalysts for the production of biodiesel (Table 4). The appli
aromatics were formed in the liquid pyrolytic products. Changes in cation of alkaline catalysts for the oil transesterification is possible when
biochar morphology were also observed [76]. The acceleration of the FFA content is below 1% in order to prevent any saponification
thermal cracking of volatile organic compounds and their secondary phenomena [87].
reactions with CO2 were the main effects of CO2 use [77]. Furthermore, A two-step catalytic procedure, firstly an acid step and then an
Cho et al. [78] proposed a pretreatment step of SCG with FeCl3 prior to alkaline one, is implemented when the acid value of coffee lipids is high
CO2 assisted pyrolysis. This resulted to a higher syngas yield and a [88]. Thus, the acid catalyzed esterification reduces the acid value of oil
reduction in the bio-oil. Similarly, CO2-assisted co-pyrolysis of paper and then an alkaline transesterification step is efficiently applied [89].
mill sludge with SCG improved the end-products’ characteristics. The Nevertheless, in some cases the efficiency achieved even after a two-step
iron and calcium content of paper mill sludge acted catalytically in the transesterification was not that high. This may be the case when
9
unsaponifiable substances are present in the SCG oil affecting the in maintaining its activity. In energetical terms, this technique could
teractions among reactants. It is likely that the formation of soap yielded reduce the energy needs significantly (up to 99%) in comparison with
a larger loss to the glycerin phase [87]. the conventional techniques [92].
The molar ratio of alcohol to oil, the reaction temperature and time The biodiesel quality was assessed according to the existing stan
and the catalyst’s concentration are the principal operational parame dards (ASTM D6751 or EN 14214:2009). SCG biodiesel presented a
ters that control the Fatty Acid Methyl Esters (FAME) yield [83,87]. density of 820–911 g/m3 [66–68,74–76] and a viscosity of 4.16–12.88
Acid-catalyzed esterification is mainly positively affected by the ratio of mm2/s [81,87–89,95–98]. A viscosity over the specification limits may
alcohol to oil [86]. Molar ratios of solvent to coffee oil between 4.5:1 be attributable to the incomplete transesterification reaction [96], to
and 18:1 have been reported (Table 4). As far as alkaline-catalyzed large percentage of saturated methyl ester chains [84] or to ineffective
transesterification is concerned, an increment of the alcohol to oil purification with high residual glycerin in the biodiesel [96].
ratio presents similar effects (Table 4) [83]. Theoretically, the increase The water content of SCG biodiesel falls within the range of 100–632
of solvent to oil ratio affects transesterification in a two-fold manner: a) ppm [84,91,92,94], which in most cases is below the specification limits
increase the efficiency since higher solvent concentrations favour bio [96]. Nevertheless, in the cases where high moisture content was
diesel production (forward reaction) and 2) decrease the efficiency since observed, this may be attributed to the water washing step [88].
low oil concentration favours the triglycerides production (reverse re Most studies present a sulphur content below the specification limit
action) [79]. Furthermore, it has been reported that as the reaction [81,96,98], although high sulphur content (35.9 ppm) has been reported
temperature and/or the solvent to oil ratio increase, the reaction time attributable to the presence of polar compounds [88].
decreases [83]. SCG biodiesel presented oxidative stability of 3.05–8 h [81,87,96]. It
The use of enzymes as catalysts for transesterification leads to more is favorable since it consists of natural antioxidant compounds that may
moderate reaction temperatures and facilitates downstream processing. prevent the oxidative phenomena that usually occur during storage and
Enzymatic transesterification is suggested in cases where SCG oil has an transportation [83,87,97]. Nevertheless, during FAME production, these
elevated FFA content [90]. Lipases have been employed for SCG oil compounds could be lost, reducing the biodiesel’s oxidative properties
transesterification [91] with varying degree of success (60–98%) [98]. Yet, the challenging issue that still has to be dealt with is to find the
(Table 4). Low water content is usually necessary during enzymatic most suitable antioxidant for each fuel blend [96].
transesterification via lipases [91]. SCG biodiesel consists of both saturated (42.3–51.4%) and unsatu
Slight stoichiometric excess of alcohol (3:1–4:1) is recommended in rated (30.4–57.3%) [37,60,74,75,78–80] methyl esters. The fatty acid
order to obtain high transesterification yields, given that an excess may profile of biodiesel revealed that it is mainly comprised of palmitic acid
lead to enzyme inactivation [90]. (33.99–51.4%w/w) and linoleic acid (23.27–40.3%w/w). The other
Although enzyme catalysts are costlier than the conventional principal fatty acids are stearic (8.3–10.91%w/w) and oleic
chemical catalysts (e.g. NaOH, KOH), they may be recycled several times (7.16–11.7%w/w) acids [81,82,95,96,99].
without any purification process, resulting in an overall cost reduction Given the elevated content in saturated fatty acids, the cloud points
[87]. and pour points of SCG biodiesel are high (8–13.1 � C) [81,88,95,96,98]
Other methods, e.g. mechanical stirring, hydrode-oxygenation and and 2–13.0 � C [81,98], respectively) in comparison with biodiesel
ultrasound-assisted transesterification, that are not so commonly deriving from soy-oil (0 � C and 3 � C, respectively), pointing out poor
applied are recently drawing attention for biodiesel production [87]. cold weather properties [88].
Ultrasonication may not only reduce the reaction time but it may also SCG biodiesel acid values reported (0.11–2.14 mg KOH/g) [79,81,
enhance the FAME yield. Through ultrasonication, cavitations are pro 87–89,95–98] are in most cases beyond the acceptable limit range. A
duced causing local temperature increases and compensating heating suitable blend with other biodiesel products may overcome this issue
needs [87]. A non-catalytic biodiesel production process at ambient [87].
pressure, tolerant to FFA and water via a real continuous flow system has Since SCG biodiesel has a high calorific value around 40 MJ/kg
been reported, recognizing temperature as the principal driving force. [100], it could be blended with biodiesel from other biomass sources of
This way, the crude SCG oil was transesterified at 380 � C. lower calorific value.
In a system of in-situ transesterification, in a single reacting vessel Even though in most literature reports, the majority of the properties
both SCG oil extraction and oil transesterification take place simulta are within the permissible range, there are still some that are out of the
neously [79,91–93]. This process usually applies a solution of sodium ASTM D6751 or EN14214 specifications. Thus, corrective measures and
methoxide both as a reactant solution and as an oil extraction solvent. actions should be made so as to increase the biodiesel yield and improve
This way the biodiesel production system is less complex and of smaller the final product’s quality. These may be, inter alia: oil drying, moisture
size. In situ transesterification presents considerable cost savings, thus, it removal between esterification steps, neutralization of remaining acid
may stand as an alternative industrial solution for biofuel production prior to biodiesel production, selection of the optimum ethanol to oil
from SCG [79]. ratio, etc. [101]. Furthermore, treatment of recovered oil (e.g. bleach
Najdanovic-Visak et al. [79] reported a maximal achieved yield of ing, refining, deodorizing) prior to transesterification may also prove
96% when the methanol to oil ratio applied was 400 with 0.2 mol/L beneficial to the end-product’s quality [102].
NaOH concentration, at 60 � C, for 90min [79]. Similarly, Park et al. [93] To sum up, given the oil content of SCG, the valorisation of this
reported a 16.75%w/w maximum biodiesel yield (dry basis) at 95 � C stream may lead to the production of around 1 million tonnes of bio
using methanol 3.33 mL/g SCG, chloroform 3.33 mL/g SCG and H2SO4 diesel, which is almost 4% of the global market [6,103].
as catalyst 0.5 mL/g SCG [93]. The use of supercritical methanol at 30
MPa and 330 � C resulted in a biodiesel yield of 84.9%. In order to reduce 4. Coffee oil extraction
the operating pressure and temperature, CO2 was added to the solvent.
So, at 300 � C, 10 MPa and 0.11 as CO2 to methanol molar ratio, a bio 4.1. Characteristics and the benefits of the coffee oil
diesel yield of 93.4% was observed [94]. Another approach of in-situ
transesterification in a soxhlet apparatus was proposed for the bio Coffee oil is composed by a great amount of lipids (Fig. 3) where fatty
diesel production from wet spent coffee grains. The use of alkaline acids represent the major fraction [104]. Generally, extracts derived
catalyst (0.75 M NaOH) resulted in higher SCG oil recoveries and bio from one-step extractions contained about 59% and 41% of unsaturated
diesel yields than acid catalysts. The optimum results (97%) were ob and saturated fatty acids. This value is also very similar with the un
tained for 1:2 methanol to hexane after 30 min of reaction. Furthermore, saturated fatty acids content of 56% in the commercial green coffee oil
it was reported that the catalyst may be recycled at least 5 times while (GCO) produced by cold pressing. The three major fatty acids in coffee
10
oil were linoleic, palmitic and oleic acids which sum over 82% [105, beans. For this reason, coffee oil from green beans represents one of the
106], while stearic and arachidonic acids are in lower amounts: 8.5% cases where cultivations are used for no-food production, plumping the
and less than 1%, respectively [106]. Linoleic and palmitic acids are controversial debate regarding the correctness on subtracting cultiva
known to be added-value compounds. Linoleic acid is an 18-carbon tions’ products to human nutrition in favour of other applications. Thus,
chain with two double bonds in cis configuration, belonging to the coffee oil extraction from SCG will have a double advantage: the val
polyunsaturated omega-6 fatty acids family. Linolenic acid prevents skin orisation of this waste and the avoidance of any social debate. Purifi
cancer and diseases of the heart and blood vessels [107,108]. Palmitic cation processes of coffee oil would allow the fractionation and the
acid, on the other hand, which was considered as a cancer promoter for a separation of the different added-value molecules. By this way, it will be
long time, has been recently re-evaluated. It was found that palmitic acid possible to allow the possibility to further increase the economic income
exerts multiple fundamental biological functions at cellular and tissue as these compounds are commercialized at very high prices (Table 5)
levels. It represents a fundamental constituent for soap and cosmetics [118].
synthesis and for the production of high performant biodiesel, as it af
fects positively the dynamic viscosity of the biodiesel and the cold filter 4.2. Solid/liquid extraction
clogging point [109].
Coffee oil from SCG also contains other valuable molecules having Oil extraction of SCG results in a color change of the solid matrix
several applications when used as additives. Among them, tocopherols from dark to pale brown [119–121]. In solvent extraction process, SCG
are very precious substances being the basic compounds of vitamin E, are mixed and vigorously stirred with suitable organic solvents, the
useful for the prevention of several diseases, from heart and nervous resulting organic phase is decanted and oil is recovered via vacuum
systems to infertility. Tocopherols are also considered antioxidants, able evaporation. The extraction process can be carried out at ambient
to improve the biofuels oxidation stability. Loyalo et al. [110] adopted temperature or with the aid of heat [9]. N-hexane is the most commonly
different solvents to recover tocopherols finding a maximum tocopherol used solvent [5,6], but the use of other solvents such as ethanol,
extraction of about 20 mg/100g of dry SCG using ethyl acetate and methanol, heptane etc. has also been reported [121].
n-propanol. Other studies reported tocopherols extractions yield in the The oil yields via solvent extraction are in the range of 7–21%
range of 6.5–45.0 mg/100g dry SCG. The difference depends essentially (Table 6). From these studies, it was also made obvious that conven
on the sample origin, the roasting procedure, storage and processing, but tional solvent extraction may demand long time periods for extraction
also on coffee particle sizes during tocopherol extraction [111,112]. (Table 6). In addition, SCG to solvent ratio and oil yield were found to be
Two interesting coffee-specific diterpenes, cafestol and kahweol, are inversely proportional, implying that increased solvent quantities
also included in coffee oil. They are important for health, being anti enhance oil diffusion [80]. Other critical parameters that influence the
carcinogenic substances. Due to the peculiar taste and flavouring, they kinetics of extraction are: process temperature, SCG particles size as well
are also used as additives in the production of many food products, such as the diffusion characteristics of solutes and solvents [79].
as candies, cakes and beverages [113]. Lastly, coffee oil is usually rich in SCG oil yield depends on several parameters such as the extraction
polyphenolic compounds, known to be antioxidants and thus appreci conditions [20,83], the coffee origin (climate, cultivation, collection
ated by pharmaceutical and cosmetic industries [114]. The total time), the variety of the coffee blend along with the downstream pro
phenolic compounds content in coffee oil extracted by SCG, expressed as cesses involved (dry or wet processing, roasting) [6,80,83,95,122]. In
caffeic acid equivalent, reached 587.7 mg/g of oil in the research work general, the amount of lipids in SCG is not a function of the coffee
of Andrade et al. [115]. Among polyphenols, one of the most valuable is brewing method [123].
chlorogenic acid which, with its isomers and derivatives, are known to As far as the extraction conditions are concerned, the most important
be antioxidants and to prevent inflammation, cardiovascular and liver parameters are the solvent and the extraction time [18,83,95]. However,
diseases. Pettinato et al. [116] found a chlorogenic acid concentration of oil extraction yield is also influenced by moisture content, particle size,
about 1.5–2.0%w/w of the total coffee oil composition, representing shape and internal structure and coffee to solvent ratio [83,124].
almost half of the total phenolic compounds. Even though lipids and Among solvents, non-polar ones present better performance during
fatty amounts in coffee oil extracted from SCG are almost constant oil extraction than polar, since the almost neutral nature of non-polar
independently of the operational variables and the extraction tech solvents facilitates their penetration in the low-polarity SCG structure
niques; the concentration of the added-value molecules are extremally [80,83]. On the other hand, with polar solvents, during extraction
depending on the roasting degree of coffee seeds and on the operational competing reactions forming fatty acids and degradation products from
parameters used for the coffee oil extraction from SCG, in particular the carbohydrates may take place [13,15,22,23]. As it is evident from
chemical nature of the solvents and the temperature. Some of these Table 6, hexane is the solvent that in general allows high coffee oil re
valuable molecules, such as tocopherols, cafestol and kahweol are covery, with long extraction time. But, it is also one of the solvents with
known to be thermolabile [117]. higher recovery rate [97].
The presence of several added-value molecules in coffee oil make its A 50:50 mixture of isopropanol (polar) with n-hexane (non-polar) in
commercial value higher than coffee itself. Coffee oil is commercialized Soxhlet extraction presented high extraction oil yields [16,95].
at prices in the range of 20 and 60€ for 100 mL [117], while 1 kg of Considering the cost of solvents, the energy consumption and the sol
coffee oil is sold at 320€ on Sigma Aldrich. Currently, the commercial vents recovery by distillation, this mixture may stand as a suitable
ized coffee oil derives from the mechanical extraction of green coffee choice [21].
Najdanovic-Visak et al. [79] observed that even 10 min could be an
Table 5 effective duration for oil extraction in a Soxhlet apparatus. Al-Hamamre
Commercial prices of the considered molecules from Sigma Aldrich website et al. [83] also studied Soxhlet extractions for short durations
[118]. In the following paragraphs the main extraction techniques are presented (15–30min). Nevertheless, extraction time and oil yield could not be
reporting the relative yields analysing their advantages and weaknesses. mathematically correlated [80]. Although the maximum SCG oil yield
Added-value products Prices (Euro) Amount was observed after an 8-h Soxhlet extraction [80], 4h of extraction seem
as a good compromise to get a high oil yield, preventing technical errors
Coffee Oil 320.00 1 kg
Tocopherols 208.00 1 kg occurring during long heating periods [122].
Linoleic acid 44.80 1g Decreasing the SCG to solvent ratio during Soxhlet extraction
Palmitic Acid 50.70 1 kg significantly improved the extraction yields (Table 6) since the diffusion
Cafestol 33.10 1 mg of solvent into SCG increases and the transport of the solvent is also
Kahweol 11.45 1 mg
improved [124]. This trend fades out when the ratio is extremely
11
Table 6
Oil yields recovered from SCG with different solvents.
Technique Solvent Time (h) Oven drying SCG to Solvent (w/v) Oil yield (%) Reference
Time (h) Temperature (oC)
Solvent extraction Ethanol 0.425–2 (1) 24 105 1:7–1:22.8 (1:16.7) 11.8–21.0 (15.3) [16,121]
Heptane 3 1:14.62 7–14.0 [146123]
N-hexane 0.33–5 (1.61) 24 35–105 1:4–1:24.90 (1:15.57) 10.76–14.98 (13.10) [124–126]
Methanol 19.6 24 105 1:23.8 7.5 [6,121]
Soxhlet extraction Acetone 0.33–0.66 5 102 1:4.16 12.30–12.53 [83]
Butanol 8 5.5 100 1:9 14.78 [80]
Chloroform 0.5–0.83 5 102 1:4.16 8.60–10.98 [83]
Dichloromethane 1-8 (5) 5.5 100 1:9–1:30 (1:19.5) 10.8–15.2 (13.75) [80,97,126]
Ethanol 0.33–8 (3) 5–5.5 100 1:4.16–1:30 (14.03) 11.10–21.00 (14.65) [80,97,115,127]
Ether 1-6 (3.67) 105 1:4 9.3–17.5 (14.4) [12,122]
Ethyl acetate 6 1:30 11.8 [115]
Hexanol 8 5.5 100 1:9 19.28 [80]
Isopropanol 0.5–8 (5.1) 5–5.5 100 1:4.16–1:20 (1:11.05) 10.68–21 (15.08) [80,83,97]
N-heptane 8 5.5 100 1:9–1:20 13.69–19.00 [80,97]
N-hexane 0.25–16 (5.69) 5–120 35–105 1:3–1:125 (1:18) 6–26.85 (15.08) [119,122,123]
N-hexane þ isopropanol (50:50) 3–8 105 1:20 20.6–21.5 [95,97]
N-octane 1:20 25.5 [97]
Pentane 0.25–8 5–5.5 100 1:4.16–1:9 11.94–15.18 [80,83]
Pentanol 8 5.5 100 1:9 15.09 [80]
Toluene 0.25–8 5–5.5 100 1:4.16–1:9 11.25–14.47 [80,83]
decreased implying that there is an optimum ratio for maximum oil yield 4.3. Coffee oil extraction by fluids in supercritical conditions
[8,11,20].
Generally, an increase in the solvent’s boiling point, and conse Supercritical CO2 (scCO2) extraction is ranked among the evolving
quently the extraction temperature increases the lipids solubility since clean technologies adopted by food, pharmaceutical and cosmetics in
higher temperatures disrupt the interactions among oil and oil-matrix dustry. The advantages of CO2 extraction over conventional processes
molecules and increase the lipids rate of diffusion. Nevertheless, oil are established, given that CO2 is a non-toxic and non-flammable com
yield and solvent’s molecular weight could not be correlated [80]. pound with low-critical constants values (Tc ¼ 31.8 � C and Pc ¼ 7.3
Regarding particle size, it has been highlighted that the smaller the MPa), allowing extraction to take place at moderate conditions. In
particle size, the greater the surface area and thus the higher the oil contrary, conventional extraction processes use organic solvents with
yield. Nevertheless, it has been suggested that mixtures of various par high toxicity and difficulties in handling under severe conditions [130].
ticle size SCG facilitate the rheological behaviour of both oil and solvent In a conventional scCO2 extraction system, CO2 is fed to an extraction
resulting in elevated oil yields [80]. vessel (1st vessel) that already contains the SCG. High pressure converts
The moisture content of SCG is another critical aspect. Increasing the CO2 into a liquid, which acts as solvent, passing through the SCG and
moisture content results in a lower oil yield. This is the reason why in extracting the coffee oil. The derived liquid mixture of coffee oil and CO2
almost all studies a drying step is included (Table 6). It is evident that the is transferred to the separator vessel (2nd vessel) where CO2 is released
latter differentiates in literature reports from low to high temperatures as gas and oil is recovered from the vessel’s bottom. Continuous recir
and from short to long residence time. The existence of water molecules culation of CO2 flow is included in the system. Multi-extraction cycles
in the SCG matrix inhibits the oil solubilization in hydrophobic solvents. are performed for the same material upon completion of extraction. It is
Furthermore, SCG intended for subsequent biodiesel production, should estimated that nearly 90% of CO2 could be recycled in a closed loop CO2
be dried in order to prevent the hydrolysis of oil which would lead to extractor.
lower transesterification yield [121]. Nevertheless, when upscaling is Couto et al. [120] applied scCO2 at various temperatures (40,50,55
the ultimate target, energy needs and SCG drying expenses should be �
C) and pressures (15,20,25,30 MPa) and observed the highest oil yield
“weighted” against oil extraction yield [8]. In general, a residual water (15.4%) at 50 � C, 25 MPa for 3h extraction time. Lower oil yield (10.5 �
content below 2% w/w does not have a negative impact on the oil yield 0.2%) was observed by Andrade et al. [115] during SCG scCO2 oil
and may even prove favorable [80]. extraction at temperatures 40, 50 and 60 � C and pressure range 10–30
Extraction conditions are strongly related oil’s FFA concentration MPa for 2.5h extraction time [120]. Ramos-Andres et al. [131] achieved
and its subsequent utilization. The smaller molecular size of FFA in 14.04% coffee oil yield from SCG by scCO2 before transesterification for
comparison with glycerides favors their early extraction via organic biodiesel production. The operational parameters adopted for oil
solvents and thus when short extraction times are applied, FFA content extraction were 45 � C, 300 bar and 5 kg/h scCO2 in recirculation for 2 h.
is greater. On the contrary, when longer extraction times are selected, This oil yield corresponded to a 70.2% of the extraction yield obtained
more glycerides are delivered and thus the FFA content is reduced [80]. by Soxhlet hexane extraction.
The higher the solvent polarity, the greater the FFA concentration [81, All these researches demonstrated that, even if the coffee oil
83]. Moreover, lipids thermal decomposition producing FFA may occur extraction was environmentally more sustainable for the chemical na
due to elevated extraction temperatures that are dictated by the sol ture of CO2 and the lower temperatures, the yields were mostly lower
vents’ boiling points. Hence, the high FFA oil content may be accredited than solid/liquid Soxhlet extraction. Aiming at increasing the coffee oil
to the synergies between high temperatures and solvents’ polarities yield, the use of a liquid solvent which may increase the solubility of the
[127]. SCG was investigated [127]. Couto et al. [120] also performed coffee oil
Although high efficiencies may be achieved by Soxhlet extraction, extraction by using ethanol as co-solvent at mass ratio C2H5OH:CO2 of
the main bottlenecks of the process are: the toxicity, the high cost of 6.5:93.5 (w/w) at 20.0 MPa and 50 � C. The results were encouraging,
some solvents and the high solvent: substrate ratio which decreases the obtaining a decrease of 60% on the extraction time and the solvent
economic sustainability of the extraction [128,129]. amount requirement in order to obtain 12.9% oil yield compared to pure
scCO2 extraction under the same operational conditions.
12
5. Coffee oil valorisation oil conversion in PHA, adding also a step for the SCG conversion in
sugars to be adopted for the same scope. After a first stage of coffee oil
Since coffee oil from SCG is rich in different antioxidant molecules extraction from SCG (~15% w/w), Cupriavidus necator H16 fed to the
and added-value compounds, it represents a high economic product, oil, obtaining a very high yield of 0.86 g PHA/g coffee oil. Additionally,
which can be purified in order to remove the main impurities and then fermentable sugars were produced by applying chemical and enzymatic
commercialized at high price (Table 5). hydrolysis of the solid residues after oil extraction. The produced sugars
This topic has not been extensively investigated and just few research could be further utilised as a substrate for PHA production by employing
works are present within the scientific database. Somnuk et al. [121] Bacillus megaterium (YP/S ¼ 0.04 g/g) or Burkholderia cepacia (YP/S ¼
described the main process for the upgrade of the extracted coffee oil 0.24 g/g). Two bacterial strains, namely Bacillus megaterium and Bur
which consists of two sequential filtration steps at 25 and 10 μm, holderia cepacia have been investigated to be capable of producing PHA
respectively, in order to remove the smaller particles. Then, distillation from SCG hydrolysate. Obruca et al. [138] observed that detoxification
is used for the complete or partial removal of the solvent used for the of SCG by 30% ethanol prior to hydrolysis enhances the yield of PHA by
extraction. At this point, the purified coffee oil can be used as it is and 25%. Combination of both these methods produced approximately 20%
commercialized or adopted as secondary raw material for the produc conversion of SCG to PHA. They recovered a copolymer: poly
tion of new products, such polyhydroxyalkanoates (PHA) and (3-hydroxybutyrate-co-3-hydroxyvalerate) from Bacillus megaterium
biosurfactants. and polyhydroxybutyrate (PHB) homopolymer by the bacteria Burhol
A very recent alternative is the isolation and the recovery of specific deria cepacia.
added-value molecules from SCG with the aim to use them as additives Some researchers investigated the effect of engineered microorgan
for the preparation of pharmaceutical, food and cosmetic products. isms aiming at obtaining biopolymers with better mechanical features.
For instance, Bathia et al. [139] used the engineered strain Ralstonia
5.1. Recovery of added-value compounds eutropha Re2133 for polymers production from coffee oil obtained from
SCG. In particular, they obtained the 3-hydroxybutyrate-co-3-hydroxy
The isolation of added-value molecules from SCG coffee oil has been hexanoate, which has superior properties in terms of biodegradability,
recently performed by sequential operations of ultrafiltration (UF) after biocompatibility, and mechanical strength with a yield of 69%w/w of
a pre-filtration step using a high-pressure filter with 10 μm pore size. SCG. Besides the good performance of coffee oil for the bio-polymers
Multi-step UF is considered appropriate for separation and concentra production, attention should also be drawn on the presence of some
tion of tocopherols (having a molecular weight of 430 g/mol, corre inhibitory compounds in coffee oil which can reduce the PHA yield. This
sponding to about 14 kDa) [132], cafestol and kahweol (316 and 314 problem was faced recently by Kovalcik et al. [140], who observed that
g/mol, respectively) [133,134] and palmitic and linoleic acids (280 and the growth of Halomonas halophila was inhibited by phenolic compounds
256 g/mol, respectively) [135]. This technique has been already with a consequent reduction of the conversion of the fermentable sugars
employed for the hemicellulose extraction from SCG, previously defat in coffee oil in PHA [141]. The authors tested diluted acid hydrolysis
ted by scCO2. A hemicellulose extraction yield of 3.50 g/g dry SCG (4.0%v/v sulfuric acid,120min,100 � C) in order to degrade phenolic
achieved by using three Pellicon XL Biomax polymeric membranes with compounds. This pretreatment allowed poly(3-hydroxybutyrate) pro
50 cm2 filtration area and 30, 10 and 5 kDa molecular weight cut-off duction in high concentration of 0.95 g/L with PHB content in bacteria
[127]. cell dry mass 27%w/w [140].
In the study of Marto et al. [136], the lipid fraction of SCG coffee oil An alternative to PHA production in the coffee oil exploitation is
was used in a concentration of 35% with GCO and zink ozyde in order to represented by the biosurfactants synthesis. Biosurfactants can be
obtain a novel sunscreen formulation with high UVB/A protection, described as surface active biomolecules produced by microorganisms
better tolerability and biological activity. This new formulation led to an with numerous applications. They have both hydrophobic and hydro
increase in the Solar Protection Factor by 20%. philic zones, offering them unique characteristics like low toxicity,
Although the possibility to isolate single valuable molecules from specificity and relative simplicity of preparation. By attracting wide
SCG is receiving attention, few tests have been still conducted and their interest, biosurfactants are used in various industrial sectors such as
economic sustainability has not been extensively investigated. petroleum, petrochemicals, organic chemicals, mining, metallurgy,
fertilizers, agrochemicals, foods, beverages, pharmaceuticals, cosmetics.
5.2. PHA and biosurfactants production Other applications that can be met by biosurfactants are demulsifiers as
well as emulsifiers, wetting agents, spreading agents, foaming agents,
PHA is a class of polyesters which are primarily synthesized by detergents and functional food ingredients [142]. The valorisation of
several species of Gram-negative and/or Gram-positive microorganisms, coffee oil for biosurfactant production has just begun to be investigated
anaerobic photosynthetic bacteria and archaea as intracellular carbon and very few works are present in literature. The most relevant research
and energy sources. They are completely biodegradable, with a wide work in this field is represented by Yaneez-Ocampo et al. [143]. They
range of properties, mostly associated their monomer composition and investigated biosurfactant-producing bacterial isolates in a liquid me
their subsequent behaviour as thermoplastic material [137]. PHA can be dium with 2%v/v composed by cooking oil waste and SCG still con
synthetized by pure or mixed cultures, using simple carbon sources taining the coffee oil, as the carbon source. The experimental trial was
which are stored inside the cellular body of the microorganisms in the performed in 300 mL aliquots of mineral salt media and oils at 100 rpm,
form of PHA granules. Coffee oil, rich in simple organic molecules, can 25 � C for 96 h. An interesting yield of 3.7 g/L of biosurfactants was
be easily adopted as feedstock and converted in PHA by different obtained.
microorganisms.
One of the first attempts in PHA production from coffee oil was 6. Integrated biorefinery scenario and future perspectives
conducted by Cruz et al. [129]. SCG oil, derived from scCO2 extraction
in a pilot plant, was used as substrate for Cupriavidus necator DSM 428. It The versatility of one of the most abundant food wastes, SCG, for the
is reported that 16.7 g/L cell dry weight was achieved with a 78.4%w/w production of different typologies of bio-based products and biofuels has
polymer content. The produced polymer was identified as a homopol been discussed in the previous paragraphs. Besides the great potential,
ymer of 3-hydroxybutyrate with 2.34*105 average molecular weight SCG have been mostly exploited for bioethanol and biogas production at
and presented interesting mechanical properties: 1 GPa Young’s laboratory level, and just few researches have conducted a more “so
Modulus, 16 MP tensile strength at break and a very low elongation at phisticated” valorisation. It is essentially due by the lack of an urban
break (1.3%). Obruca et al. [85] adopted a similar strategy for the coffee separate collection system for the SCG, which at the moment are
13
Fig. 5. A cascade pyramidal biorefinery proposal for the valorisation of SCG.
generally collected and treated with the Organic Fraction of Municipal operational temperature of 50–55 � C allows the release of about
Solid Wastes. 0.35–0.40g glucose/g SCG, which are usually fermented by S. Cerevisiae.
Thus, the ambitious objective of this review paper is represented by The final bioethanol yield is usually around on 3–4%v/v. These con
the proposal of different sequential unit operations in order to build a centrations are very close to the minimal level required for an economic
coherent “cascade pyramidal biorefinery hierarchy” for the SCG, sche valuable distillation process, which separates ethanol from biomass and
matized in Fig. 5. the organic residues of the fermentation. Lastly, anaerobic digestion for
From the previous discussion, it emerged that the most economic biogas production constitutes the last process of the biorefinery
valuable fraction of SCG is coffee oil, rich in added-value molecules. approach for the SCG valorisation. This stage can treat the solid residues
Consequently, the extraction of the coffee oil from SCG has to be the first of SCG from all the previous unit operations. The performance may vary
process of the proposed SCG biorefinery. As seen, coffee oil can be in the range of 200-250LCH4/kgVS, depending on the efficiency of the
recovered both by a solid/liquid extraction through the use of polar and previous SCG valorisation steps. To increase the specific methane yield,
no polar solvents, or by the adoption of gaseous fluids in supercritical two main approaches are usually adopted: i) the co-digestion of SCG
conditions, especially CO2. This last option is preferred as it presents with other organic substrates, such as manure and the organic fraction of
higher performance in the coffee oil recovered with a yield ranging from municipal solid waste, and ii) the conduction of an alkaline pretreatment
15 to 20% against the 6–27%, in respect to the different solvent typol to favour the lignocellulosic matter’s solubilization. These techniques
ogies. Moreover, this technique is also more environmentally friendly lead to a significant improvement of the anaerobic performance allow
and is not toxic. The extracted coffee oil has a high commercial price. ing yields as high as 355 and 400LCH4/kgVS, respectively.
Coffee oil can also be purified by sequential operations of micro/ultra
and nano filtrations in order to extract tocopherols, cafestol and kahweol 7. Conclusions and recommendations for future work
which have high commercial prices to be used as additives for phar
maceutical, cosmetic and food applications. 7.1. Techno-economic analysis and practical implications
Innovative applications of the coffee oil are presented by PHA and
biosurfactants production, innovative bio-based products which have Generally, in industrial processing a crucial issue that needs to be
been receiving great attention lately from the scientific and technical addressed is the availability and continual supply of the raw material-
community. In particular, PHA production reached the highest perfor feedstock. Thus, in setting up a biorefinery with SCG as feedstock,
mance with the Cupriavidus necator H16, which made possible a yield of their up-stream supply should be ensured. SCG have to be collected and
0.86gPHA/g coffee oil. Regarding biosurfactants, a performance of 3.5 transported from the instant coffee industries and the coffee shops. This
g/L was obtained when coffee oil was co-fermented with cooking oil. research area has not been studied in depth and points such as quantity
Anyway, more research is necessary in order to optimize the choice of to be collected, points of collection, transportation means and cost,
the operational parameters and consequentially the yields of PHA and seasonality etc. have not been thoroughly addressed.
biosurfactants production. Lastly, coffee oil can be also adopted as As far as seasonality is concerned, this constitutes a major asset, since
substrate for the biodiesel synthesis by transesterification reactions. In SCG are readily available throughout the year. Nevertheless, the number
particular, a methanol-coffee oil ratio of 6:1 and the adoption of 1%w/w of coffee shops has increased tremendously due to the increased coffee
of NaOH or KOH as catalyst may allow a very high FAME yield of about consumption, mainly in large cities. Therefore, this constitutes a major
95–99%. challenge to a SCG biorefinery since the points of collection are too
After the coffee oil extraction, the solid fraction of SCG can be many and scattered in the city structure. Little information is also
valorised for the production of different biofuels. Pyrolysis represents a available on the SCG transportation cost, although rough estimations
first possibility where the bio-oil produced may be valorised through can be made based on other biomasses of similar densities. Certainly, in
biodiesel production. Another alternative for the extracted SCG is order to determine the optimum design of the whole biorefinery, farther
constituted by bioethanol production, optimized firstly by an acidic or research is needed.
enzymatic hydrolysis stage in order to degrade the complex and long Just a few literature studies [144–146] have been published on the
polymer chains and to convert cellulose into glucose. The adoption of an up-stream supply and the techno-economical aspects of the biorefinery
enzyme concentration of 2%w/w, of slightly acid pH (5.5) and processes, mainly concluding that there is lack of literature and that this
14
gap needs to be filled urgently. Considering these results and market SCG. Finally, after compiling the state-of-the-art information, a SCG
prices, decentralized processing is not a viable solution, since the small integrated biorefinery was presented incorporating the studied unit
dispersed treatment plants cannot serve the economies of scale. The operations in line with the new EU legislation, proving that SCG may
bioprocess economic feasibility is ensured only at elevated production stand as a technically viable solution towards the implementation of
capacities at centralised plants. However, centralised collection still circular economy. Nevertheless, in order to render this biorefinery a
constitutes a critical barrier to profit margins and bioprocess efficiency sustainable option in environmental and economic terms, there are still
[147]. An economically viable SCG biorefinery will be hard to operate some issues that need to be resolved.
efficiently even in large cities [148]. That is the reason why sufficient
and “pure” feedstock supply and sufficient collection points should be
Declaration of competing interest
ensured [149]. The recovery of bioactive compounds from SCG may
contribute to the viability of the scheme, since their elevated market
The authors declare that they have no known competing financial
value stand as an economic driver that dictates their extraction.
interests or personal relationships that could have appeared to influence
the work reported in this paper.
7.2. Policy aspects
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Renewable and Sustainable Energy Reviews 131 (2020) 110007

Contents lists available at ScienceDirect

Renewable and Sustainable Energy Reviews

Added-value molecules recovery and biofuels production from spent

Therefore, SCG may not be valorised through composting or incinera

2.2. SCG composition 3. Biofuels production

In view of evaluating different SCG valorisation pathways, it is 3.1. Bioethanol

Fig. 2. Geographical distribution of coffee production and consumption.

Fig. 3. Biochemical and elemental analysis of SCG (% w/w dry base).

Fig. 4. Possible process steps of the SCG bioethanol valorisation pathway.

H.uvarum UFLA CAF76:0.3 g/L 0.48 0.222 2.1 [36]

Two-step Methanol 6:1 H2SO4 1%v/v 60 4 99.0 [83]

Time (h) Temperature (oC)

Fig. 5. A cascade pyramidal biorefinery proposal for the valorisation of SCG.

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Battista 2020

Uploaded by

Copyright:

Available Formats

Battista 2020

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Battista 2020

Uploaded by

Copyright:

Available Formats

Renewable and Sustainable Energy Reviews 131 (2020) 110007

Contents lists available at ScienceDirect

Renewable and Sustainable Energy Reviews

Added-value molecules recovery and biofuels production from spent

Therefore, SCG may not be valorised through composting or incinera­

2.2. SCG composition 3. Biofuels production

In view of evaluating different SCG valorisation pathways, it is 3.1. Bioethanol

Fig. 2. Geographical distribution of coffee production and consumption.

Fig. 3. Biochemical and elemental analysis of SCG (% w/w dry base).

Fig. 4. Possible process steps of the SCG bioethanol valorisation pathway.

H.uvarum UFLA CAF76:0.3 g/L 0.48 0.222 2.1 [36]

Two-step Methanol 6:1 H2SO4 1%v/v 60 4 99.0 [83]

Time (h) Temperature (oC)

Fig. 5. A cascade pyramidal biorefinery proposal for the valorisation of SCG.

You might also like

Therefore, SCG may not be valorised through composting or incinera