Bioresource Technology 200 (2016) 884890

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Bioresource Technology
journal homepage: www.elsevier.com/locate/biortech

Optimization of biogas production from coffee production waste

Federico Battista a,, Debora Fino a, Giuseppe Mancini b
a
Department of Applied Science and Technology, Politecnico di Torino, Corso Duca degli Abruzzi 24, Torino 10129, Italy
b
Department of Industrial Engineering, University of Catania, Viale A. Doria 6, Catania 95125, Italy

h i g h l i g h t s

The ligno-cellulosic materials in coffee wastes inhibits the biogas production.

NaOH permits the hydrolysis of coffee wastes and a high biogas production.

A scaled-up of the basic pretreatment in continuous mode was realized.

The continuous test reached a good yield of the process: 82%.

The daily biogas production was of 1.14 NL/L d with a methane content of 65%.

a r t i c l e i n f o a b s t r a c t

Article history: This study was conducted to investigate the effects of chemical pretreatments on biogas production from
Received 24 September 2015 coffee waste. After the preparation of a mixture of coffee waste with a TS concentration of 10% w/w, basic
Received in revised form 7 November 2015 and acid pretreatments were conducted in batch mode and their performances were compared with the
Accepted 9 November 2015
biogas produced from a mixture without any pretreatment stage. The basic pretreatment demonstrated a
Available online 14 November 2015
very good action on the hydrolysis of the lignin and cellulose, and permitted a biogas production of about
18 NL/L with a methane content of almost 80% v/v. Thus, the basic pretreatment has been used to scale-
Keywords:
up the process. The coffee refuse was has been carried out in a 45 L anaerobic reactor working in contin-
Coffee production residues
Anaerobic Digestion
uous mode and in a mesophilic condition (35 C) with a Hydraulic Retention Time (HRT) of about 40 days.
Pretreatments A high biogas production of 1.14 NL/L d, with a methane percentage of 65% v/v was obtained, thus per-
Volatile Fatty Acids influence mitting a process yield of about 83% to be obtained.
Batch and continuous mode 2015 Elsevier Ltd. All rights reserved.

1. Introduction (www.aitaer.com), which have a high Lower Heat Value

With an average annual production of 5.9 Mtons, coffee is one
of the most commonly marketed beverages in the world. It is
mainly farmed in tropical areas, in particular in Brazil, and is con-
sumed mainly in Europe and in the United States. Arabica (Coffee
Arabica) and Robusta (Coffee Canephora) are the two varieties
which are traded the most at an international level. Arabica fetches
higher prices, due to its more favorable taste characteristics, and it
makes up 61% of the worlds production (Enden and Calvert, 2003).
Italy yearly imports more than 300,000 tons of coffee seeds, of
which 52% is represented by the Arabica variety. The coffee beans
have to undergo several processing steps in order to remove the
outer parts of the seed, i.e. skin (exopart), pulp (mesocarp), the
mucilage layer and the endocarpal parchment. These residues from
the coffee extraction process are usually converted into pellets
Corresponding author. Tel.: +39 0110904671.
E-mail address: federico.battista@polito.it (F. Battista).
(LHV = 18,000 kJ/Kg TS) and consequentially represent a very inter-
esting source of renewable energy. The most important character-
istics of coffee pellets are their Total Solid (TS) amount of about
90% w/w and high content of organic matter. These features make
the pellets generated from coffee production suitable for Anaerobic
Digestion (AD) (Selvamurugan et al., 2010). In spite of these con-
siderations, coffee waste production AD has not received much
attention by the scientific and engineering communities. It is only
recently that coffee refuse has been considered for biogas produc-
tion and consequently for energy valorisation. Selvamurugan et al.
(2010) developed an integrated system to treat coffee wastewater
through a combination of biomethanation followed by aeration.
The biomethanation was carried out at different HRTs, using an
Up-flow Anaerobic Hybrid Reactor (UAHR), and adopting 18 h as
an optimum value of HRT. A biogas production of 1.335 L/L d was
achieved with a methane content of 61% v/v, which corresponds
to 490 L biogas/kgDVS. The reduction in the polluting load of the
wastewater by means of microbial action augmented by aeration

http://dx.doi.org/10.1016/j.biortech.2015.11.020
0960-8524/ 2015 Elsevier Ltd. All rights reserved.
 F. Battista et al. / Bioresource Technology 200 (2016) 884890
resulted in the reduction of the Electrical Conductivity (EC), Bio-
chemical Oxygen Demand (BOD), Chemical Oxygen Demand
(COD) and TS. In a subsequent research by Jung et al. (2012), the
AD of coffee production refuse was studied using a continuous
two-stage up-flow anaerobic sludge blanket (UASB) reactor sys-
tem, in which thermophilic (55 C) dark fermentative H2 produc-
tion was adopted as the first step, and this was followed by a
second step in mesophilic conditions (35 C) to produce CH4. A
maximum CH4 yield of 325 L CH4/kgDVS was achieved with an
abatement of 93% of the COD under an Organic Load Rate (OLR)
of 3.5 g COD/L d. The developed two-stage UASB reactor system
achieved a biogas conversion of 88.2% of inlet TS with H2 15.2%
and CH4 73%. Another UASB research was conducted by Bruno
and De Oliveira (2008). In this work, the efficiency of two-stage
UASB reactors was evaluated, at a bench scale, by treating a liquid
effluent from coffee pulping, submitted to an HRT of 4.0; 5.2 and
6.2 days, which resulted in an Organic Loading Rate (OLR) of 5.8;
3.6 and 3.0 g COD/L d, respectively, in the first reactor (R1) and in
an HRT of 2.0; 2.6 and 3.1 days with OLR of 5.8; 0.5 and
0.4 g COD/L d in the second reactor (R2). The mean values of the
removal efficiencies of the total COD and TS varied from 66% to
98% and from 93% to 97%, respectively, in the two-stage treatment
system with the UASB reactors. The methane content in the biogas
varied from 69% to 89% in R1 and from 52% to 73% in R2. The max-
imum volumetric methane production of 0.708 L CH4/L d was
obtained with OLR of 3.6 g COD/L d. and an HRT of 6.2 days in R1.
Fia et al. (2012) tried to improve the performances conversion per-
formance using an up-flow anaerobic fixed bed reactor for the
treatment of coffee wastewater. A new inert support material of
polyurethane foam mixed with crushed stone was used for a
microorganism consortium. They demonstrated that the character-
istics of the support materials have an effect on the degradation of
the organic material. The porous structure of the polyurethane
showed a better performance than the traditional support materi-
als (cinders from steel mill blast furnaces, porous ceramics) used
for fixed bed reactors. A continuous stirred tank reactor (CSTR) sys-
tem was used by Houbron et al. (2003) to evaluate the Biochemical
Methane Production (BMP) of coffee production effluents, that is,
both solid refuse and liquid wastewater. The refuse was pretreated
at pH = 3 for 48 h before the fermentation test was carried out in a
4 L CSTR reactor. The test, conducted in mesophilic conditions,
resulted in a biogas production of about 252 LCH4/kgDVS.
Recently, Qiao et al. (2013) have tried to ferment coffee residues
in thermophilic conditions (55 C) and in continuous mode. First,
the biogas production was high, with an average value of 1.5 L/
L d and a methane content of about 60% v/v. Then, the process per-
formances dropped because of the accumulation of VFA in the
reaction medium and the lack of nitrogen in the coffee substrates.
Some researchers have solved these problems by working on the
coffee residue AD in codigestion mode with other substrates. For
example, Henandez et al. (2014) improved the stability of AD for
hydrogen production by mixing the coffee waste with swine man-
ure. In this way, an optimum C/N ratio of about 60 was reached,
which in turn led to a high hydrogen generation of about 3.8 L
H2/L d. Abouelenien et al. (2014) also conducted a codigestion pro-
cess of coffee wastes with chicken manure and other agricultural
residues (cassava and coconut wastes). The methane fermentation
resulted to be improved two-fold compared to the case of chicken
manure fermentation on its own.
The aim of this work has been to estimate the biogas production
from a mixture composed of Coffee Seed Skin (CSS), Seed Refuse
(SR) and Coffee Product Refuse (CPR) previously crushed and dis-
persed in tap water. A first test was conducted to determine the
BMP of the mixture. After two chemical pretreatments, the mixture
was tested in batch mode in order to improve the fermentation of
the ligno-cellulosic materials and consequentially to increase the
885
biogas production. A basic Pretreatment was selected for the con-
tinuous test. which lasted 120 days (3 HRT). The continuous test
was conducted in a 45 L reactor working in mesophilic conditions
at 35 C. During this test, two mixtures with different OLR con-
tents, were supplied to the reactor. First, a mixture with a high
OLR content of 10.28 g COD/L d and with a TS content of about
10% w/w was fed, then the OLR and the TS content were reduced
to 1.95 g COD/L d and 6.5% w/w, respectively.
2. Methods
2.1. The batch tests
The batch tests included the No Pretreatment test (NP) con-
ducted on a mixture of CSS, SR and CPR dispersed in water to deter-
mine the BMP of the coffee refuse, and two chemical
pretreatments: the Basic pretreatment (BP) and the Acid Pretreat-
ment, which are generally known to improve the hydrolysis of
ligno-cellulosic materials (Deublein and Steinhauser, 2008).
2.1.1. The equipment
Batch tests have been conducted in an SGI reactor. The reactor
has a working volume of 2 L and is equipped with pH, rH and tem-
perature controls. The exit valve for the produced biogas is in the
upper part where a condenser is located to remove water from
the biogas flow. Mixing is guaranteed by a Rushton impeller, which
is able to work at different speeds. The biogas flow is measured by
means of the water replacement method. The gas line is composed
of a the gasholder, which is initially filled with water at pH 2 to
prevent CO2 dissolution in water; when the biogas production
starts, the gas moves from the reactor to the gasholder, where it
replaces the water in the plastic vessel. The gasholders are substi-
tuted when the water inside is almost finished. Batch tests has
been conducted in triplicate, in mesophilic conditions (T = 35 C)
under a gentle agitation of 100 rpm.
2.1.2. Substrates, inoculum characteristics and preparation of the tests
Three waste typologies derived from coffee production have
been considered for the AD tests: Coffee Seed Skin (CSS), Seed
Refuse (SR), obtained after the sorting and before the production
operations and Coffee Product Refuse (CPR), which is constituted
by material considered unsuitable for commerce; the three waste
materials were dispersed in tap water. The chemical compositions
of these substrates, which are characterized by high contents of
lingo-cellulosic materials, are reported in Table 1.
The reaction medium of the NP, BP and AP tests were prepared
in order to have a TS concentration of about 10% w/w and accord-
ing to the availability of the three types of waste derived from the
production lines of coffee. The ratio between the CPR, CSS and SR
was about 1:3:1. Therefore, the reaction medium included 22.5 g
of SR, 22.5 g of CPR and 67.5 g of CSS, which were crushed and dis-
persed in 1012 g of tap water. The BP test also included the addi-
tion of NaOH (2 M) till a pH of 12 was reached. This pH was
maintained for 24 h in order to permit the hydrolysis of the
ligno-cellulosic compounds. The AP test included the addition of
H2SO4 (2 M) till a pH of 3 was reached, and this pH was maintained
for 24 h. Before the beginning of each test, the inoculum was added
Table 1
Lignin, hemicellulose and cellulose concentrations in coffee wastes.
Wastes Lignin (% w/w) Hemicelluloses (% w/w) Cellulose (% w/w)
CSS 23.4 11.2 31.3
CPR 12.0 25.0 20.6
SR 10.8 25.6 18.2
886 F. Battista et al. / Bioresource Technology 200 (2016) 884890
to the reactor at a concentration of 10% v/v of the total reaction
medium in order to guarantee the presence of the methanogenic
microorganisms. The inoculum consisted in a mixture of cow and
chicken manure and an anaerobic sludge taken off from a domestic
wastewater treatment system. The most important characteristics
of the inoculum-water mixture were: pH = 7.28, 5.40% w/w TS,
54.8% w/w VS per TS, COD content of 51.94 g/L, Total Nitrogen
(TN), Phosphorous (TP) and Ammonia (NH4N) contents of
1.200 mg/L, 330 mg/L and 412.5 mg/L, respectively. Finally, the
pH was brought to 7 and nitrogen was flushed for 5 min in order
to create an anaerobic environment inside the reactor. All the tests
were conducted in triplicate.
2.1.3. Analytical methods
The cumulative gas production during the fermentation tests
was measured by means of the water-replacement method, as pre-
viously described in the above Section. This is one of the most fre-
quently used methods at a laboratory scale to quantify a low
quantity of biogas because of its low experimental uncertainty,
due to the fact that the volume of biogas is measured by the weight
of the water replaced. The composition of the gas produced in each
test (H2, O2, CH4, CO2, CO and N2) was determined as the mean
value of the gas in each gasholder by means of an off-line gas chro-
matographic analysis device (Varian, CP 4900) equipped with two
columns: a Poraplot U column for CO2 determination (85 C injec-
tion temperature, 200 kPa, and Argon as the carrier) and a Molec-
ular Sieve type for H2, CH4, CO, O2 and N2 determination (95 C
injection temperature, 200 kPa, and Helium as the carrier). As far
as the other parameter measurements are concerned, the following
methods were used: pH was measured by means of a pH meter
CRISON (model micropH 2001), while TS, VS and density were
determined according to the Standard method (APHA/AWWA/
WEF, 1998). The Low Heat Value (LHV) of the reaction medium
was experimentally determined using a PARR 1261 calorimetric
bomb produced by Parr-Instruments, USA; also in this case, the
measurements were repeated three times in order to establish sta-
tistical significance and to be able to evaluate an appropriate
uncertainty of the experimental results.
2.1.4. Energy conversion parameters
In order to evaluate the efficacy of the pretreatments on the cof-
fee production wastes, the energy produced from each test was
compared with that obtained from the un-pretreated test. Addi-
tional information on this approach can be found in Ruggeri et al.
(2013); in short, two energy parameters were used to score the
pretreatments. The first parameter was the energy conversion effi-
ciency (n), which takes into account the quantity of energy pro-
duced as methane that the pretreatment plus bioreaction is able
to extract from the available amount of energy embedded in the
substrate present in the medium; n is defined as follows:
n Ep =E0  100
where Ep is the total energy produced as methane (kJ/L) and E0 is
the initial energy embedded in the substrates i.e. the SR, CSS and
CPR at the concentrations present in the broth (kJ/L). The produced
energy (Ep) was calculated through the following expression:
Ep G0max =22:4  LHVCH4
where G0 max is the total volume of methane referred at normal con-
ditions (NL/L), considering the mean methane concentration of bio-
gas in the test; 22.4 is the equivalent volume of mol (L/mol) and
LHVCH4 is the Low Heat Value of the methane per mol unit
(800.32 kJ/mol). As far as the value of E0 is concerned, it is necessary
to consider only the energy present in the residues, which can be
utilized by microorganisms for cellular activity (Nelson and Cox,
2008) i.e. the edible one. The evaluation of the edible energy is a dif-
ficult task. Bearing in mind that the purpose of this calculation was
to score different pretreatment processes on the same substrates, it
was decided that a good approximation of E0 could be reached using
the LHV of the substrates. Eq. (3) permits E0 to be evaluated:
E0 LHVCM  TS0  103 3
where LHVCM (kJ/kg) is the Low Heat Value of the reaction medium
and it includes CSS, SR and CPR. It resulted to be 18,363 63 kJ/kg
TS. TS is the initial concentration present in the reaction medium
in g/L. It is necessary to underline that not all the energy included
in the substrates is available for methane production. In fact, not
all the CC and CH bonds are of the same type: only the simpler
molecule bonds are easily degraded by microorganisms, while the
complex ones basically remain un-altered. In addition, only a part
of this energy can be harvested as methane by the AD technology,
because part of the energy is consumed in a biological metabolism,
part is developed as heat, part is stored inside the new cells and part
is embedded in the produced metabolites. The aim of this work was
to evaluate if a pretreatment is able to increases the portions of
energy convertible into methane. The second parameter used is
the efficacy (g), which takes into account the efficiency of the actual
test with a pretreatment, compared to that obtained without a pre-
treatment. g was calculated as follows:
g nP =nNP 4
where, nP is the efficiency obtained from the pretreated broth and
nNP is the efficiency obtained from the broth without a pretreat-
ment. In other words, g is the ratio of the energy obtained with a
pretreatment to the energy obtained without a pretreatment. In this
way, it is easy to evaluate the effectiveness of the applied pretreat-
ment: if g is less than 1, it means that the pretreatment has lowered
the efficiency, and has probably produced some inhibitory sub-
stance, whereas if g is about 1, the pretreatment has had no effect
on the bioreaction, and finally if g is greater than 1, the pretreat-
ment is able to increase the energy produced as methane compared
to the un-treated one. Obviously, g permits different pretreatment
options to be scored.
2.2. Continuous test
2.2.1. The equipment
Considered the good performance of BP, it was selected for a
scaled-up test conducted in continuous mode. The test was carried
out in a 45 L CSTR, thermostated at 35 C, by means of an external
jacket, and equipped with a 100 rpm stirrer which was able to
guarantee a homogenous biomass dispersion. Two sampling ports,
devoted to digestate and biogas withdrawal, were located/posi-
tioned at the two reactor outlets. The Hydraulic Retention Time
(HRT) was about 40 days. The test lasted 3 HRT in order to permit
1 the system to reach a quasi-steady-state condition.
2.2.2. Substrates and the inoculum characteristics
The substrates (CPR, CSS and SR) and the inoculum used for the
continuous test had the same characteristics to those previously
described for the batch tests.
2
2.2.3. Experimental procedure
The 45 L reactor feeding procedure is reported in Table 2. After
the inoculum stage (day 1), a start-up period was introduced in
order to guarantee the presence of methanogenic bacteria in the
reaction medium. This period lasted until a working volume of
45 L was reached. A mixture of CSS, SR and CPR was dispersed in
tap water and fed to the bioreactor in the ratios reported in Table 2.
The mixture was prepared to ensure an Organic Load Rate of
 F. Battista et al. / Bioresource Technology 200 (2016) 884890 887

Table 2 test. Its formulation was adapted for the continuous mode as
Feeding plan of the continuous 45 L reactor. follows:
Start up period Continuous mode
n Ep =E0  100 5
Day 1 Days 211 Days 12120
The mean values of n in the two test intervals (start-up and con-
Inoculum (kg) 1  
SR (kg/d)  0.09 0.017 tinuous periods) were calculated.
CSS (kg/d)  0.27 0.051 Ep was expressed by means of the following expression:
CPR (kg/d)  0.09 0.017
Water (kg/d)  4.05 1.035 Ep GCH4 =22:4  LHVCH4 6
Total (kg/d) 1 4.50 1.120
OLR (g COD/L d) nd 10.28 1.950 where GCH4 is the daily volume of methane referred to the normal
conditions (NL/L d); 22.4 is the equivalent volume (L/mol), LHVCH4
is the low heat value of the methane (800.32 kJ/mol). The following
10.28 g COD/L d (Table 2), a TS concentration of about 10% w/w and value of E0 was adopted:
optimum COD/TN and COD/TP ratios of 70 e 350, respectively.
Therefore, the three substrates had similar chemical and physical E0 LHVmixture  TS0  103 =HRT 7
features. The inlet broth was prepared taking in account the avail-
where LHVmixture is the low heat value of the refuse mixture
ability of three types of wastes derived from the production lines.
expressed in kJ/kg, TS0 is the initial concentration of the reaction
The CRR, CSS and SR ratio was about 1:3:1. Because of an increase
medium in g/L and HRT is the Hydraulic Retention Time (d).
in the Volatile Fatty Acids (VFA) content in the reaction medium, a
new inlet mixture, with lower TS and OLR concentrations, was
adopted on the 12th day, with the beginning of the continuous 3. Results and discussions
feeding mode. The TS concentration and the OLR were decreased
to 6.5% w/w and 1.95 g COD/L d, respectively, while the ratio 3.1. The batch tests
between three refuses and COD/TN and COD/TP were not altered.
This new feeding plan program was maintained till the end of The experimental results of the biogas production during the
the experiment. At the end of every working day, except during NP, BP and AP tests are reported in Table 3 (NL/L). In all the tests,
the start up period (days 111), approximately 1 L of digestate the coffee refuses were first diluted with tap water in order to
was fed and 1 L was discharged from the tank to keep the volume reach a TS concentration of about 100 g/L (Table 3). The BP and
of the fermenting broth constant. AP tests were then subjected to basic and acid pretreatments,
respectively, as described in the previous sections. The NP test
2.2.4. Analytical methods was not pretreated. As summarized in Table 3, the lowest amount
Several parameters were measured daily: pH, total Chemical of biogas was produced by NP (about 1.5 NL/L), and the production
Oxygen Demand (COD), Total Solids (TS), Volatile Solids (VS), the took place over the first 10 days. The percentage of methane in the
concentrations of Total Nitrogen compounds (TN) and phosphorus biogas was approximately 60% v/v. The values of the TS and VS
(TP). TS, VS, COD, TN and TP were determined through the standard reductions as well as that of n were very low: 19.76%, 24.92% and
methods described in the scientific literature http://www. 1.72% (Table 3), respectively, thus indicating that, at the end of
aitaer.com/ftp/bioenergy_2013/fava.pdf, 2015. TS and VS are the the test, the reaction mixture was still rich in organic matter which
most commonly used parameters in AD processes. TS represents could be converted into methane. It is likely that the nature of the
the content of solids present in the substrates, including the inert lignocelluloses, reported in Table 1, of the largest organic struc-
materials and the degradable compounds. VS is a way to quantify tures contributed to the low biodegradability of the coffee refuses.
the organic matter that can be degraded by means of a biological The BP test resulted in a robust production of biogas (17.81 NL/
process. For this reason, VS is the fraction of TS that is not included L) with a high methane content (79% v/v; Table 3). These results
in the inert compounds. Another important parameter is the ratio can be explained by the fact that the two most abundant chemical
between the concentration of Volatile Fatty Acids and alkalinity, components in coffee refuse are cellulose, a biopolymer that con-
because this parameter gives information on the stability of the sists of thousands of glucose units, and lignin, an insoluble polymer
system, controlling the Volatile Fatty Acids amount, which, in high of high molecular weight that is composed of complex carbohy-
concentrations, could inhibit the methane producing bacteria. The
methods used to measure volatile acidity and the alkalinity are
Table 3
reported in Chen et al. (2008). The concentration of methane in Results of the NP, BP and AP batch tests.
the produced biogas was measured on-line using a DREGER X
NP BP AP
AM 7000 by Drger (Germany), a hydrocarbon gas analyzer that
is able to evaluate the CO2, O2, H2S, H2 and CO concentrations using TS0 (g/L) 101.32 4.73 101.32 4.73 101.32 4.73
TSf (g/L) 81.06 1.31 51.34 3.11 70.98 2.47
infrared, electrochemical and catalytic sensors. The analyzer is
TS reduction (%) 19.76 5.04 49.07 5.44 29.67 5.72
equipped with a pump, which is continuously controlled by means VS0 (g/L) 91.19 2.17 91.19 2.17 91.19 2.17
of diagnostic software. This pump withdraws the biogas from the VSf (g/L) 68.39 1.57 43.21 0.97 61.36 1.54
collection line through a sampling port. The quantity of produced VS reduction (%) 24.92 3.51 52.93 2.17 32.63 3.29
biogas was measured by means of a TG1PP gas meter (RITTER, Ger- Biogas production (NL/L) 1.49 0.19 17.81 1.28 8.96 1.35

many). The Low Heat Value (LHV) of the broths were experimen- Biogas composition
tally determined using the PARR 1261 calorimetric bomb CH4 (% v/v) 60.18 1.35 79.27 0.98 71.81 0.81
CO2 (% v/v) 36.92 1.92 18.52 2.10 25.81 1.57
produced by Parr-Instrument USA; again in this case, the measure- H2 (% v/v) 2.05 0.51 1.51 0.71 1.83 0.94
ment was repeated three times in order to obtain statistical N2 (% v/v) 0.60 0.01 0.60 0.02 0.04 0.01
significance. O2 (% v/v) 0.25 0.01 0.10 0.01 0.15 0.01
Y (L CH4/kg TS0) 9.98 0.69 157.91 19.28 71.63 4.15
2.2.5. Energy conversion parameter Y (L CH4/kgDVS) 45.63 8.48 327.50 25.13 246.81 33.43
The efficiency parameter, already introduced in the previous n (%) 1.72 0.08 27.12 0.99 12.36 0.44
g () 1.00 0.00 15.80 1.32 7.20 0.59
sections for the batch tests, was also considered for the continuous
888
drate chains. The alkaline hydrolysis mechanism that occurs as a
consequence of the NaOH treatment is believed to involve a
saponification reaction of intermolecular ester bonds (Ruggeri
et al., 2012; Uma Rani et al., 2012). A pretreatment of lignocellu-
losic materials with diluted NaOH leads to swelling and provokes
different effects: an increase in the internal surface area; a
decrease in the degree of polymerization and crystallinity; separa-
tion of the structural links between lignin and carbohydrates; and
the disruption of the lignin structure. Thus, the basic pretreatment
exploits the lignocellulose structures present in the reaction mix-
ture, as evidenced by the efficiency and efficacy values of the BP
test (n = 27.12 and g = 15.80, respectively; Table 3).
The AP test reached good performances, but not as good as the
BP test. The biogas production, the methane content and the effi-
cacy were 8.96 NL/L, 71.81% v/v and 7.20, respectively. The acid
pretreatment favors hemicellulose hydrolysis with the formation
of monomers, such as furfural, and other volatile products. An acid
pretreatment is also indicated in the presence of lignin, a complex
amorphous organic polymer with a crystallinity degree which
gives vegetables the property of resistance and protection against
pathogens and microorganism attack. Lignin is not soluble in
water, does not photo- react and, for these reasons, results to be
very difficult to degrade. The acid pretreatment favors lignin
hydrolysis, but presents a crucial limit: in fact, it is possible that
a part of lignin can recondense immediately in an acid environ-
ment (Vismara et al., 2011). This phenomenon should be avoided
because it reduces the degradation of the organic matter and con-
sequentially its conversion into biogas. The aforementioned phe-
nomenon could explain the lower performances of AP
(n = 12.36%, g = 7.20; Table 3) than BP.
Considering the results obtained from the two tested pretreat-
ments, BP was chosen to scale up the process in a 45 L reactor oper-
ating in continuous mode.
3.2. The continuous test
Fig. 1 reports the quantity of biogas produced daily and the
methane concentration in the biogas. Throughout the start-up per-
iod, when the substrates were fed to the reactor in order to reach a
working volume of 45 L, the biogas production increased con-
stantly. A mean productivity of 0.10 NL/L d was obtained during
the first 11 days of the test, when hydrolysis and acidogenesis of
the substrates governed the bioreaction. In fact, when the first
phase of carbohydrate Anaerobic Digestion begins within a few
hours, the degradation of lipids and proteins occurs in just a few
days. Cellulose and lignin, which are the most important compo-
nents of coffee wastes, as it is possible to see from Table 1, are
1.4
1.2
Biogas Producon (NL/L d)
1
0.8
0.6
0.4
0.2
0 0
0 20
Fig. 1. Biogas production and methane content vs time for the continuous test.
F. Battista et al. / Bioresource Technology 200 (2016) 884890
not degraded completely, and their degradation takes longer Li
et al. (2015a).
An examination of the acidityalkalinity ratio vs. time, reported
in Fig. 2, shows a quick increase in the VFA/ALK ratio between days
9 and 15, in correspondence to a growth in the biogas production.
During the first step, the substrates are mainly degraded into VFA
and hydrogen by facultative anaerobic microorganisms, such as
Clostridium, which has a faster reaction kinetics than strictly anaer-
obic bacteria, such as methanogens, which use the VFA and H2,
produced in the first stage to produce methane and CO2 (Nathao
et al., 2013). The high OLR value of 10.28 g COD/L d obtained dur-
ing the start-up period (Table 2) contributes to further accelerate
the acidogenic bacteria kinetics. Consequently, the VFA/ALK ratio
exceeded the limit value of 0.3 that corresponds to the inhibition
of methanogenic microorganism activity (Deublein and
Steinhauser, 2008). VFAs exist in un-dissociated form and partly
in dissociated form, depending on the pH value. Un-dissociated
acids have a greater inhibiting effect, because they penetrate cells
as lipophilics, where they denaturize cell proteins. The alkalinity
needed to balance this effect reduces the amount of un-
dissociated VFA (Deublein and Steinhauser, 2008). The inhibition,
due to the VFA accumulation in the reaction medium, was also
confirmed by Qiao et al. (2013) whose reactor, which was treating
only coffee grounds, failed after 82 days because of a lack of nitro-
gen and micronutrients. The reactor was inhibited by an accumu-
lation of VFA to 7.2 g/L and a drop in pH to 6.85 (data not shown).
With the beginning of the continuous mode, the feeding plan
was changed too with another having a lower OLR (1.95 g COD/
L d), as it is possible to see from Table 1. The reduction of the
OLR was possible feeding a mixture with a lower TS concentration
(64.50 g/L against the previous 100 g/L). This permits the formed
VFA to be consumed, an equilibrium to be created between the aci-
dogenic and methanogenic bacteria and the VFA/ALK ratio, which
was stabilized in the 0.10.2 range for the remaining part of the
Anaerobic Digestion test, to be reduced progressively, as reported
in Fig. 2. The biogas production, as shown in Fig. 1, started to grow
again, until it reached an average value of 1.14 NL/L d with a
methane concentration of around 65% v/v during the continuous
feeding of the bioreactor when the OLR and TS concentrations were
reduced.
The efficiency and the specific methane production, with refer-
ence to the initial concentration of TS and to the degraded VS, are
82%, 531 L CH4/kgTS0 and 732 L CH4/kgDVS. These data confirm the
efficacy of the basic pretreatment for the hydrolysis of the ligno-
cellulosic materials, whose effects were discussed in the previous
sections.
80
70
60
Methane content (% v/v)
50
Biogas Producon (NL/L d) 40
Methane content (% v/v) 30
20
10
40 60 80 100 120
Time (d)
 F. Battista et al. / Bioresource Technology 200 (2016) 884890
1
0.9
0.8
0.7
VFA /ALK (--)
0.6
0.5
0.4
0.3
0.2
0.1
0
0 20
Fig. 2. VFA/ALK trend over time for the continuous test.
The better performances of the continuous mode clearly emerge
from a comparison of the specific methane production for the basic
pretreatment conducted in batch mode (Table 3) with the one con-
ducted in continuous mode (Specific methane production for batch
test: 158 L CH4/KgTS0 and 327 L CH4/KgDVS; specific methane pro-
duction for continuous test: 531 L CH4/kgTS0 and 732 L CH4/kgDVS).
These results are in line with other studies in which agro-food
wastes have been degraded by means of Anaerobic Digestion
(Battista et al., 2013) (Wang et al., 2005) (Mohan and Bindhu,
2008). Anaerobic Digestion usually produces higher methane
yields when run in continuous mode rather than in a batch process,
due to adaptation and population changes within the microbial
population (Jard et al., 2012).
To the best of the authors knowledge, not many researches
have been conducted on the AD of coffee wastes. For this reason,
has not been easy to conduct a comparison with the present work.
However, the good performances of the present study have been
confirmed considering some previous works. Sophie et al. (2015)
failed in their attempt to degrade coffee grounds by means of AD
because of the recalcitrant ligno-cellulosic composition of the sub-
strates. The authors solved the problem by conducting their test in
thermophilic conditions (55 C), that is, they considered a codiges-
tion of coffee refuses with milk wastes and municipal sludge. They
obtained a good biogas production of 1.5 L/L d and a methane con-
tent of about 60% v/v. Li et al. (2015) conducted two researches on
this topic. In the first study (Li et al., 2015a), coffee grounds were
pretreated with SO2 on the basis of the concentration of COD:
4
SO2
4 = 200:1. The use of sulfate led to the hydrolysis of lignin
and cellulose, which were mainly converted into propionic acid,
which then degraded? into biogas. In this way, biogas was pro-
duced. Lastly Li et al. (2015b) demonstrated that thermophilic con-
ditions (T = 55 C) improved biogas production 1.5-fold more than
mesophilic conditions (T = 35 C). However, the energy required to
heat the reaction medium in order to reach the operative temper-
ature was very high, thus canceling the beneficial effects of a larger
methane production. Therefore, the decision to operate in meso-
philic conditions with a basic pretreatment, as described in the
present research, has been shown to be the optimal operative
choice for high methane production by means of AD.
4. Conclusions
Anaerobic Digestion has been used to valorize coffee refuses. A
first test was conducted to determinate the BMP, and a low biogas
production was obtained because of the high content of ligno-
cellulosic materials. A basic pretreatment favoured the hydrolysis
of lignin and cellulose and as a consequence their conversion into
biogas. A notable biogas production, with a high methane percent-
age, was obtained (18 NL/L, 80% v/v respectively). The basic pre-
treatment was scaled up using a 45 L reactor, operating at
889
40 60 80 100 120
Time (days)
continuous mode for 120 days. An average daily biogas of
1.14 NL/L d was obtained (65% v/v of methane), thus permitting a
robust yield of the process to be reached (n = 83%).
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