Biomass and Bioenergy 123 (2019) 89–103

Contents lists available at ScienceDirect

Biomass and Bioenergy

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

Research paper

A chemical equilibrium model for biomass gasification. Application to Costa T

Rican coffee pulp transformation unit
Cindy Torresa,b, Luis Urvinaa, Hugo de Lasac,d,∗
a
Department of Chemical Engineering, University of Costa Rica, Costa Rica
b
Electrochemistry and Chemical Energy Research Center, University of Costa Rica, Costa Rica
c
Chemical Reactor Engineering Center, Faculty of Engineering, Canada
d
Western University, London, On, N6A5B9, Canada

ARTICLE INFO ABSTRACT

Keywords: The present study considers the establishment of a biomass gasification model using for its validation, experi-
Coffee pulp mental data obtained in a 15–20 kg/h coffee pulp downdraft gasifier unit, operated at ICAFE-Costa Rica. The
Biomass gasification gasification model proposed considers a heterogeneous “downflow” central section and a homogeneous “up-
Synthesis gas flow” exit section, both operating at chemical equilibrium. Each of the sections includes a number of relevant
Gasification modeling
independent chemical reactions. Biomass is incorporated into the model using its elemental composition as well
as its water content. Different reaction paths are examined in order to analyze the applicability of the various
assumptions considered. The established model accounts for biochar thermodynamic properties as well as ga-
sifier operating temperatures in the homogenous “upflow” section, using a numerical fitting method. With this
approach, the proposed model successfully predicts the molar fractions of various syngas components, most
notably, the CH4 and H2 fractions via the CO2 hydrogenation reaction, as well as the carbon converted. It is
anticipated that the developed model will provide a valuable simulation and design tool for scaled-up downdraft
biomass gasifiers.

1. Introduction pulp is considered as a negative value by-product, given its significant

According to energy technology perspectives as reported by the
International Energy Agency in 2017, the energy sector remains key to
sustainable economic growth. The availability of sustainable bioenergy
is a critical factor to achieve climate targets. Thus, research and de-
velopment of integrated systems to support highly efficient production
and use of biomass are essential [1].
The use of agricultural residues opens the opportunity for small
power generation projects in developing countries [2,4]. Costa Rica's
coffee plantations cover an area of more than 90,000 ha [5]. This sector
provides employment to 8% of the Costa Rican workforce. For instance,
the coffee cherry production in the harvest of 2016–2017 was 465,605
tonnes, as reported by the National Coffee Institute of Costa Rica [6]. To
obtain the coffee grain, different layers of the coffee cherry fruit must
be removed. In fact, the wet-processing of the coffee cherry fruit pro-
duces an estimated 43,5% w/w residue from the coffee cherry fruit
composed by the skin and pulp (epicarp and mesocarp, respectively) in
one residue fraction [7,10]. This coffee residue is designated also as
“broza” or “borra”, depending on the producer country. This coffee
disposability issues.
Approximately more than 200,000 tonnes of coffee pulp are pro-
duced every year in Costa Rica [6]. Similar issues are being en-
countered by other coffee producer countries [11]. In accordance to
Costa Rica's environmental policy targets [12–14], GHG emissions from
the coffee pulp natural decomposition are estimated to be close to
60,000 tonnes of CO2e (carbon dioxide GHG emission equivalent) for
2013–2014, with this including the significant impact of emitted me-
thane [5].
Currently, several investigations have been launched to develop
alternatives to valorize this coffee residue by using it to produce biogas
[10,15–17]. In this respect, caffeine and tannin contents, and other
functional compounds, can provide high value products [8,18]. These
by-products represent a small fraction of the coffee waste. As well, its
use as animal feed is limited given its recommended diet limit levels
[19].
Coffee harvesting is a seasonal operation. As a result, coffee pulp
residue offers processing challenges [20]. In this respect, suitable par-
tial drying treatments have to compensate for the coffee harvesting

∗
Corresponding author. Chemical Reactor Engineering Centre, Faculty of Engineering, London, Ontario, N6A 5B9, Canada.
E-mail address: hdelasa@eng.uwo.ca (H. de Lasa).

https://doi.org/10.1016/j.biombioe.2019.01.025
Received 8 August 2018; Received in revised form 17 December 2018; Accepted 21 January 2019
Available online 02 March 2019
0961-9534/ © 2019 Elsevier Ltd. All rights reserved.
C. Torres, et al.
Nomenclature
F Molar flow, (kmol/h)
Go Gibbs free energy of reaction at reference temperature,
(kJ/mol)
Gof Standard Gibbs free energy of formation, (kJ/mol)
H Enthalpy of reaction, (kJ/mol)
H0 Enthalpy of reaction at reference temperature, (kJ/mol)
H fo Standard enthalpy of formation, (kJ/mol)
KP, k Gas phase equilibrium constant for reaction k based on
partial pressures in atm, units of KP, k are function of the
reaction stoichiometry
P Pressure, (Pa).}
Q Volumetric flow, (m3/h.}
R Ideal gas constant, (J/mol K)
Rk Reaction k
T Temperature, (K)
T0 Reference temperature, (T)
a Specific heat capacity correlation coefficient
b Specific heat capacity correlation coefficient
c Specific heat capacity correlation coefficient
cP Specific heat capacity at constant pressure, (kJ/mol K)
d Specific heat capacity correlation coefficient
e Specific heat capacity correlation coefficient, number of
elements
i Elements index
cycle [6].
Some of the broza components are toxic in nature, resulting in
serious disposal issues [7,21]. Broza natural biodegradation is a slow
process taking over several months [22]. As an alternative, broza bio-
degradation in specially designed units, is a possibility. This offers
however, important drawbacks given the intermediate chemical species
produced or the required process scale [9,23–25].
All of the above described issues can be mitigated using an in-
tegrated conversion process for coffee pulp. Among the different tech-
nologies that can be used for biomass transformation, gasification is a
reliable one. This process can produce thermal energy or decentralized
power generation [26–30]. Gasification also adds value to coffee pulp,
since it can be converted into synthesis gas, a marketable fuel for en-
ergy production. Furthermore, biochar is a solid residue with valuable
properties as a soil solid additive.
It is thus anticipated that coffee pulp gasification modeling as at-
tempted in this study, can be used to develop and establish an in-
tegrated industrialized process of the coffee fruit processing.
2. Biomass gasification in downdraft gasifiers
Biomass gasification locally based power generation, is considered
as a suitable technology for developing countries [3]. A frequent
technology proposed is the downdraft gasifier. In these units, the bio-
mass bed is held in a quasi-stationary state while the circulating gases
exit the unit as synthesis gas [28]. The application, design and con-
struction of downdraft gasifiers offer significant technical challenges
[4,31–33]. In this respect, it is important to develop a predictive and
generic model that takes into account the critical operating variables
that impact its performance [34].
The technical literature records chemical equilibrium models for
biomass gasification [30,35–49]. By using thermodynamic models,
authors have tried to minimize model errors using different approaches
and assumptions. This involved empirical coefficients [39,43,49] or
correction factors [41], to accurately predict producer gas composi-
tions. Furthermore, a number of questionable hypotheses were also
included in these models such as: a) Transient behavior [50], b)
90
Biomass and Bioenergy 123 (2019) 89–103
j Chemical species index
k Reactions index
m Number of H atoms in the tar chemical formula
n Number of C atoms in the tar chemical formula
o Number of H atoms in the tar chemical formula
r Number of independent reactions
s Number of independent species
w Number of H atoms in the biochar chemical formula
x Number of H atoms in the biomass chemical formula
y Number of O atoms in the biomass chemical formula
z Number of O atoms in the biochar chemical formula
Stoichiometric coefficient of H2 O in the global reaction
Stoichiometric coefficient of CO in the global reaction
Stoichiometric coefficient of CO2 in the global reaction
Stoichiometric coefficient of CH4 in the global reaction
Stoichiometric coefficient of biochar in the global reaction
Error
Stoichiometric coefficient of H2 in the global reaction
Stoichiometric coefficients matrix
Elemental composition matrix
Stoichiometric coefficient of tar in the global reaction
GHG Greenhouse Gases
ICAFE Coffee Institute of Costa Rica by its acronym in spanish
i. g. Ideal gas
Adiabatic reactor operation [40,51] and c) Total biomass conversion
into a gaseous phase [47,48].
Given that unavoidable errors were observed in syngas composition
[39,52–55], kinetic, or combined kinetic and equilibrium based models
were proposed as alternatives to the classical equilibrium models.
However, these models were hindered by the significant uncertainty of
primary biomass thermolysis reactions [56–58]. Postulated models re-
quire modifications or calibrations to reduce H2 overestimation and CO
or methane underestimation. Correlation coefficients or correction
factors are required to account for tars formed. Overall chemical pro-
duct species model deviations remained significant, near or above 20%,
[39,55,59,60].
Another major issue in biomass gasification is the solid residue,
designated as biochar. Biochar is the product of the breakdown of large
biopolymers (20,000 to 400,000 a.m.u.) into smaller molecules (less
than 200 a.m.u.) [61]. This yields a solid residue with its properties
linked to the original biomass [62,63]. When reviewing methodologies
for thermodynamic property calculations, one can consider char from
coal gasification [64] using pure carbon. As well, Duman et al. [65],
Mitsuoka et al. [66], 2011) showed that biomass alkali/earth and alkali
metals contents may influence gasification. It can thus, be foreseen that
biochar thermodynamic properties may depend both on biomass pro-
cessing and biomass origin. Given all of the above described un-
certainties, chemical equilibrium models are recommended to be re-
visited [26,38,45,67–69]. In this regard, the present study attempts to
review key assumptions and takes into account essential issues for the
thermodynamic modeling as follows: a) It uses biochar (CHwOz) instead
of carbon (C), as the gasification solid residue in the calculation, b) It
considers all the sections in the downdraft gasifier contributing to
chemical changes, such as a “downflow heterogeneous equilibrium
section” followed by an “upflow homogeneous equilibrium section. As
shown in the present study, this can lead to a novel and reliable
downdraft gasifier model. This equilibrium model is validated as re-
ported here, using comprehensive experimental data from a 20 kW-
downdraft coffee pulp pellet gasifier, which was operated at ICAFE-
Costa Rica.
C. Torres, et al.
3. Experimental
3.1. Biomass feedstock
Broza or coffee pulp is a by-product of the coffee wet process. This
coffee pulp results from Coffee Arabica beans processing. Coffee pulp
was pelletized in an Anyang Gemco Energy Machinery Co. Ltd, model
ZLSP-300. The pellets dimensions obtained were approximately 4 cm
long and 8 mm in diameter. To adjust their moisture content, a solar
drying was applied during 4.5 h. Drying conditions were: a)
771.2 ± 183.2 W/m2 of solar radiation, b) 9.3 ± 3.1 km/h of wind
speed, c) 25.08 ± 0.91 °C of dry-bulb temperature and d)
56.6 ± 5.8% of relative humidity. Biomass moisture content were as-
sessed by using the ASTM E−1757 method. The pellets moisture was
controlled by storing them in silage bags. Biomass and biochar
Elemental composition was determined following the standard
methods: ASTM E871, ASTM D1102, ASTM D4239A and ASTM D5373.
Regarding biochar, the ΔH0 enthalpy of formation was established
using calorimetry measurements following the ASTM 5865.
3.2. Instrumentation
The several operating variables required for the mass and energy
balance calculations were monitored in the present study using: a)
Temperatures: Reotemp AM37K1 Thermocouples and K type
Thermocouples b) Humidity: a Vaisala HMP110 thermometer/hygro-
meter, c) Heat losses: a Thermographic Infrared Camera Fluke Ti27.
Furthermore, the synthesis gas composition was measured continuously
using a Syngas Portable Analyzer ETG MCA 100 Syn-P and an Agilent
CG equipped with FID and TCI detectors. A certified syngas mixture was
employed to calibrate the portable analyzer. The data acquisition
system used was a DAQ-9174, NI9207, NI9213 models from National
Instruments, with sampling rates in the 0.2 to 1 samples/s range. To
manage the data, test, measurement, and control, a LabVIEW platform
was used for quick data management. Finally, a Shimatzu Total Organic
Carbon Analyzer SSM-5000A was employed to measure the carbon
Fig. 1. Schematic Description of the Imbert 4-Section Downdraft Gasifier in Operation at ICAFE-Costa Rica. Note: T1, T2 T3 and T4 show temperature measurement
locations.
91
Biomass and Bioenergy 123 (2019) 89–103
content (TOC) from the solid outlet stream. This parameter is needed to
establish the carbon conversion in solid outlet streams including ash
and biochar.
3.3. Downdraft gasifier and experimental Runs Developed
Fig. 1 describes the 15–20 kg/h (20 kW) Imbert moving bed gasifi-
cation system developed by All Power Labs Inc with adaptations [20].
The gasifier has a 55 cm total height with this including all of the four
gasifier zones, designated as “heterogenous section”: biomass drying,
biomass pyrolysis, oxidation and later reduction of the partially con-
verted biomass. Both the air and the syngas formed circulate by
“downflow” in the combustion and reduction zones. The cylindrical
gasifier has an internal diameter which varies from 28 cm down to
11 cm in the upper gasifier section. This controls the superficial gas
velocity, solid residence time and it forces the tars to flow through the
oxidation zone. In the reduction zone, the diameter expands from 11 cm
to 16 cm. The Imbert moving bed gasification system thus, incorporates
an energy integrated system where the syngas separated from the bio-
char and ash moves “upflow” through a “homogenous section” ex-
changing heat with the incoming air flow before leaving the gasifier.
A significant number of demonstration runs were developed in the
ICAFE-Costa Rica downdraft gasifier located in ICAFE facilities. Runs
were developed changing consistently various operating gasifier para-
meters such as feeding rate, temperature, moisture content and
equivalence ratio. To accomplish this, the downflow gasifier conditions
were changed as attested in Table 1: a) biomass flow: 17.1 to 27.3 kg/h
or a difference of 10.2 kg/h, b) air flow range: 12.4–15.9 kg/h or a
difference of 3.5 kg/h, c) Equivalence Ratio: 5.3 to 7.7 or a difference of
2 units. This led to reduction temperatures varying in between 556 °C
and 605 °C with this being a temperature difference of 49 °C.
For typical runs lasting up to 8 h, the steady state gasifier operation
was established using 3 temperatures (T1, T2 and T3) measured at
strategic locations in the downdraft gasifier. Steady state was then
considered achieved when these three temperatures stabilized, as
shown in Appendix B. Therefore, start-up data was discarded and a
C. Torres, et al. Biomass and Bioenergy 123 (2019) 89–103

Table 1
Typical operating conditions of the downdraft gasifier operated at ICAFE-Costa Rica.
RUN NUMBER 1 2 3 4 5 6 7

OPERATING TIME (H) 5.90 1.11 5.64 7.09 7.52 3.04 8.15
BIOMASS FLOW (KG/H) 18.56 17.79 20.56 17.10 23.23 27.30 20.74
STANDARD DEVIATION, BIOMASS FLOW (KG/H) 0.01 0.04 0.02 0.01 0.01 0.03 0.01
BIOMASS MOISTURE CONTENT (%) 15.63 7.60 18.35 16.69 15.18 16.66 16.05
STANDARD DEVIATION, BIOMASS MOISTURE (%) 0.31 0.02 0.09 0.09 0.02 0.02 0.09
AIR FLOW (KG/H) 12.86 14.72 14.35 14.98 14.38 15.97 12.43
STANDARD DEVIATION, AIR FLOW (KG/H) 1.75 0.85 1.43 1.98 1.68 2.26 1.33
AIR RELATIVE HUMIDITY (%) 29.67 30.43 53.54 40.15 50.80 28.66 41.78
STANDARD DEVIATION, AIR RELATIVE HUMIDITY (%) 2.15 1.18 12.92 5.19 2.95 1.00 9.63
CARBON CONVERSION (%) (*) 91.0 83.0 76.7 85.2 79.7 88.3 91.6
TEMPERATURES
T2: REDUCTION TEMPERATURE (°C) (**) 583.8 645.3 605.2 569.3 556.2 565.6 598.4
STANDARD DEVIATION, REDUCTION TEMPERATURE (°C) 6.2 18.0 20.7 16.7 18.8 17.7 27.4
T3: SYNGAS OUTLET TEMPERATURE (°C) (**) 513.9 428.5 421.3 375.5 431.8 465.8 454.3
STANDARD DEVIATION, SYNGAS OUTLET TEMPERATURE (°C) 9.8 11.2 14.5 44.1 16.1 39.1 14.7
AIR INLET TEMPERATURE (°C) 40.5 39.0 31.6 34.4 32.2 38.3 34.6
STANDARD DEVIATION, AIR INLET TEMPERATURE (°C) 0.8 0.3 4.7 1.0 0.6 0.4 2.6
PRESSURES
OXIDATION SECTION PRESSURE (KPA) −3.29 −2.35 −2.28 −2.15 −2.29 −2.32 −1.95
STANDARD DEVIATION, OXIDATION SECTION PRESSURE (KPA) 0.56 0.39 0.54 0.84 0.48 0.99 0.45
GASIFIER OUTLET PRESSURE (KPA) −5.66 −2.84 −4.26 −5.00 −5.40 −6.33 −6.46
STANDARD DEVIATION, GASIFIER OUTLET PRESSURE (KPA) 1.28 0.44 1.34 1.52 1.10 0.80 0.84
SYNGAS COMPOSITION (†)
CO (% Molar FRACTION) 22.14 29.90 24.57 21.26 22.09 20.28 23.86
STANDARD DEVIATION, CO (% MOLAR FRACTION) 1.33 1.15 1.22 1.19 1.41 1.71 1.30
CH4 (% MOLAR FRACTION) 13.61 11.47 14.33 11.46 19.90 17.36 17.21
STANDARD DEVIATION, CH4 (% MOLAR FRACTION) 1.98 1.28 3.09 2.43 3.31 3.42 1.94
H2 (% MOLAR FRACTION) 16.36 15.57 17.31 18.67 17.89 17.80 16.69
STANDARD DEVIATION, H2 (% MOLAR FRACTION) 1.10 1.12 1.46 0.75 1.42 1.10 1.21
CO2 (% MOLAR FRACTION) 17.12 11.58 15.51 17.84 18.39 19.81 16.07
STANDARD DEVIATION, CO2 (% MOLAR FRACTION) 1.29 1.04 2.87 2.26 2.11 2.11 1.22
N2 (% MOLAR FRACTION) 30.76 31.48 28.28 30.77 21.73 24.75 26.16
STANDARD DEVIATION, N2 (% MOLAR FRACTION) 2.93 2.30 4.63 3.60 4.40 4.50 2.89
SYNGAS CALORIFIC VALUE (MJ/NM3) 8.4 8.4 8.9 7.8 9.3 9.6 9.4
STANDARD DEVIATION, SYNGAS CALORIFIC VALUE (MJ/NM3) 0.7 0.6 1.3 0.8 1.6 0.9 0.6
6.7 6.2 6.5 5.3 7.6 7.9 7.7
EQUIVALENCE RATIO (‡) ER =
( Fuel O2 ) (ADIM.)
( O2 )stoic
Fuel

STANDARD DEVIATION, EQUIVALENCE RATIO (ADIM.) 0.9 0.4 0.6 0.7 0.9 1.1 0.8

Notes: (*) Carbon conversion defined as carbon leaving in gaseous species over carbon fed as biomass. (**) T2 reduction temperature and T3 syngas outlet tem-
perature measurement locations as shown in Fig. 1. (†) Dry gas, free of tar and free of oxygen. Tars and oxygen in minor amounts. (‡) Fuel/Oxygen equivalence ratio
(ER) is the ratio between the actual Fuel/Oxygen ratio and the Fuel/Oxygen ratio under stoichiometric requirements, with the fuel defined on a dry and ash free
basis.

steady state period of operation was defined for the model validation gasifier, four zones have been identified: a) An upper drying zone where
analysis. Seven of these runs are considered in the present study to the biomass is fed, b) An upper-middle zone where the biomass is fed,
validate the developed thermodynamic model and the experimental devolatilized and hydrocarbon species are reformed, c) A lower-middle
conditions as shown in Table 1. Mass balances for these runs closed in zone where hydrocarbons are combusted at an estimated 800–1000 °C
the 90% range as reported by Torres & Urvina [20]. range, d) A lower reaction zone where unconverted biomass is con-
The Ultimate Analysis of coffee pulp and biochar elemental analysis verted into biochar, enriching the produced gas with H2 and CO.
are reported in Table 2. On this basis one can observe coffee pulp pellets Furthermore, and to improve the overall biomass conversion to desir-
contain a high level of mineral matter as determined by the 9.8 wt% ash able products, an energy integration section is included. Here, the
content. As well one can notice in Table 2 that the ash content in bio- thermal exchange between the syngas produced and the incoming
char is significantly augmented up to 24.0 wt% and this while com- biomass fed is promoted.
pared with the ash in coffee pulp.
3.3.1.1. Reactions. The specific selected chemical reactions for
3.3.1. Chemical equilibrium model considerations gasification have been a subject of controversy. Some authors
There is a diversity of possible designs for biomass gasification. consider a set chemical reaction that governs gasification, while
More specifically, and as mentioned above, for an Imbert downdraft others propose empirical overall reactions with adjustable
stoichiometric coefficients [70,71].
Table 2 Regarding gasification kinetics, one can consider a “primary reac-
Ultimate Analysis of Coffee Pulp and Biochar characterization in dry basis. tion” leading to intermediate species (light hydrocarbons, tars and
SPECIES C (%) H (%) O (%) S (%) N (%) ASH(%) biochar) formed during biomass thermolysis [72,73], as shown in
Equation (1) where, CHxOy, CHwOz and CnHmOo represent the unit
Coffee Pulp Pellets 45.8 5.2 36.6 0.1 2.5 9.8 chemical formula for biomass, biochar and tar, respectively, with x and
Biochar 63.1 1.0 10.7 0.0 1.2 24.0
y being the elemental hydrogen and oxygen biomass content and w and
Biochar Calorific Value (MJ/kg) 2,075 × 1010
z the elemental hydrogen and oxygen biochar content, both with
carbon having the basis of 1.

92
C. Torres, et al. Biomass and Bioenergy 123 (2019) 89–103

Table 3
CHxOy + α H2O → β CO +γ CO2 + λ H2+ δ CH4 +ε CHwOz + Ω Reactions Used to Describe the Different Paths Analyzed in this Work.
CnHmOo (1)
Reaction Chemical equation
These primary reactions may be followed by several secondary re-
actions which convert these intermediate species into synthesis gas, R1 CH4 + 2H2 O CO2 + 4H2
R2 CHw Oz + (1 z + w /2 ) CO2 (2 z + w /2 ) CO + w /2 H2 O
establishing the final producer gas composition.
R3 CO + H2 O CO2 + H2
Thermodynamics involve non-path dependent state functions, with R4 C + CO2 2CO
exact details of the primary gasification reactions becoming less im- R5 C + O2 CO2
portant. Thus, in the case of chemical equilibrium, one can calculate the R6 CHw Oz + ( z /2 + w /4 ) O2 CO2 + w /2 H2 O
composition of the producer gas and biochar at the gasifier conditions
using an independent set of secondary reactions.
To address the issue of modeling a chemical reaction system, Aris grouped into the elemental and species flows, as F i ´ and F j´ vectors, as
et al. [74] suggested the use of a set of independent stoichiometric shown in Eqs. (4) and (5), respectively.
equations (reactions). Determining this set of equations is accomplished
via a linear Gaussian Elimination matrix reduction procedure, with the
F i = [FC FH FO FN FAsh] (4)
matrix entries being the stoichiometric gasification reaction coefficients
F j = [FCHW OZ FCO FCO2 FH2 FH2 O FCH4 FN2 FO2 FAsh FC ] (5)
[75]. This approach is an advantageous one, given that it reduces the
number of gasification reactions to be considered at chemical equili- Thus, the elemental flow can be calculated as described in Eq. (6).
brium.
To accomplish this, several model gasification reactions have to be Fj = Fi (6)
considered, as shown in Table 3, in order to define the secondary ga-
Since this present study relies on a chemical equilibrium thermo-
sification reactions involved in a selected reaction Path.
dynamic approach, the chemical equilibrium constant of each reaction
can be represented using the vector form as shown in Eq. (7) as follows:
3.3.1.2. Numerical solution technique. A mathematical algorithm was
developed to solve the system of equations for: a) the elemental K P, k = [KP , R1 KP, R2 KP, R3 KP, R 4 KP, R5 KP, R6] (7)
balances, b) the equilibrium conditions and c) the equation of state.
The KP,Ri equilibrium for a specific reaction, at a given gasification
Its solution can be found by using a MathLab® Optimization Tool Box. In
temperature can be calculated using the van't Hoff equation [76], which
addition, the solution involves the minimization of the experimental
includes both the standard Gibbs Energy and the Reaction Enthalpy.
error in order to find either the biochar Gibbs Energy of Formation or
the temperatures of selected reaction paths. This leads to a nested T
Hk (T ) G0, k
optimization problem which involves the use of a FMINCON function. In (KP, k ) = dT
RT 2 RT0 (8)
Table 4 reports the various arrays of matrix elements including the To

biomass constitutive elements, the gasification product species, and the As well, the reaction enthalpy at a set temperature can be calculated
secondary chemical reactions considered. with Eq. (9), using the species heat capacity and the Standard Reaction
Equation (2) reports the ɸ matrix, with the “i” rows representing the Enthalpy.
chemical elements and the “j” columns denoting the chemical species. T
Hk (T ) = cp . k (T ) dT + H0, k
CHw Oz CO CO2 H2 H2 O CH4 N2 O2 Ash C (9)
To
1 1 1 0 0 1 0 0 0 1 C Furthermore, for the thermodynamic properties required for Eq (9),
= w 0 0 2 2 4 0 0 0 0 H
z 1 2 0 1 0 0 2 0 0 O such as H0, k and G0, k were calculated using the corresponding
0 0 0 0 0 0 2 0 0 0 N stoichiometric matrix given by eq (3) and their Standard Enthalpy of
0 0 0 0 0 0 0 0 1 0 Ash Formation or Gibbs Energy of Formation, respectively, as per Eqs. (10)
and (11).
(2) Regarding the biochar, the Standard Enthalpy of Formation was
Furthermore, Equation (3) describes the stoichiometric matrix, determined experimentally and the Gibbs energy of formation was es-
with the “k” rows representing the stoichiometric coefficients asso- tablished using the FMINCON feature mentioned previously.
ciated to the chemical reactions (Refer to Table 3) and the “j” columns o
indicating the chemical species. H0. k = H f ,j (10)

CHw Oz CO CO2 H2 H2 O CH4 N2 O2 Ash C

0 0 1 4 2 1 0 0 0 0
1 (2 z + w/2) (1 z + w/2) 0 w /2 0 0 0 0 0
v= 0 1 1 1 1 0 0 0 0 0
0 2 1 0 0 0 0 0 0 1
0 0 1 0 0 0 0 1 0 1
1 0 1 0 w /2 0 0 (1 z /2 + w/4) 0 0 (3)

The above described matrix notations simplify the numerical solu- o

tions for the various paths to be analyzed. One can notice that in Eq. G0. k = G f ,j (11)
(3), stoichiometric coefficients are required for each one of the postu-
lated reactions. Thus, in the case of biochar, an elemental analysis is As well, the chemical species heat capacities were calculated using
needed to establish these reactions, as was in fact determined for the the product of the stoichiometric matrix entries and the following Eq.
coffee pulp biochar considered in this study. (12).
Furthermore, the various flows in the gasification system can be

93
C. Torres, et al. Biomass and Bioenergy 123 (2019) 89–103

Table 4 state error as per Eq. (20).

Arrays of the Elemental and Stoichiometric Matrices used in the Solution
Algorithm Developed. Fi, in Fi, out = (17)
Array direction Index Array elements
Fi, in Fj, out = (18)
Elements i C , H , O, N , Ash
Species j CHw Oz , CO, CO2, H2, H2 O, CH4 , N2, O2, Ash , C
Reactions k R1, R2, R3, R 4 , R5, R6
ln (KP , k (T )) ln (Pj (Fj, out ,Q)) = (19)

cP , k = cP, j
Thus, for every value of cP , j , the following two equations were used
[85], with the selected expressions being a function of having a che-
mical species either in the gas phase or solid phase (13):
c/T 2 e/T 2
a+b +d if j corresponds to a gas .
CP , J (T ) = sinh(c / T ) cosh(e / t )
a + bT c/T 2 if j corresponds to a solid.
In the case of other variables, such as the total pressure Pj , Eq. (14)
was used to compute them as functions of Fj and a known temperature,
in the absolute temperature scale and this in accordance with Eq. (15).
P j = [PCHw Oz Pco PCO2 PH2 PH2 O PCH4 PN2 PO2 PAsh PC PCOnr ]
RT
Q j
F if j corresponds to a gas.
Pj =
1 if j corresponds to a solid.
One should note that when Eq. (15) was considered for the com-
ponents in the gas phase, since under the gasification process conditions
(total pressures slight below atmospheric), the ideal gas model can be
used without a noticeable error.
As well and on the basis of the equilibrium path considered, Eq. (16)
was used to relate the equilibrium constants with the species partial
pressures and stoichiometric coefficients as follows:
ln (Pj ) = ln (KP, k )
Given all of the above described equations (from Eqs. (4) to 16)), the
degree-of-freedom of the required set is zero and the numerical calcu-
lations involves the minimization of the combined errors of: a) The
elemental balance error given by Eqs. (17) and (18), b) The chemical
equilibrium condition error given by Eq. (19) and c) The equation of
Fj, out RT PQ = i, g .
j (20)
(12)
4. Validation of the proposed numerical solution
The numerical methodology of the present study involves the vali-
dation of a number of relevant assumptions and numerical methods. In
order to address these issues, a number of possible Paths are considered
as described in the following sections.
(13)
4.1. Path I
In a biomass gasifier operating at chemical equilibrium, there is a
possible Path I to be considered as described in Fig. 2 [86]. In Path I,
there is a Unit I where biomass is converted into several chemical
(14) species such as C, O2, H2, N2, H2O and ash. The gasifying agent used is
air (21 v%O2 and 79 v%N2). All product species of Unit I are fed to Unit
II. Here, chemical species reach chemical equilibrium, with the re-
(15) sulting molar fractions being calculated solving simultaneously a set of
4 independent reactions.
One should note that all chemical species involved in Path I, in-
cluding the biomass solid residue modeled with C, are available in
thermodynamic databases such as Aspen Hysys. Thus, the Aspen-Hysys
software allows a comparison and validation of the proposed numerical
methodologies of Path I.
4.2. Path II
(16)
Fig. 3 reports the various details involved in Path II. Path II is a
variation of Path I with the biomass and air being fed to the gasifier and
yielding C, H, O, N elemental components and ash when disassembled.
Once this is accomplished, the atomic flows are fed to Unit II, reaching
chemical equilibrium conditions. Once again, in this case, the resulting
molar fractions are calculated by simultaneously solving 4 independent

Fig. 2. Path I Thermodynamic Biomass Gasification Model Based on: a) Unit I: Biomass Disassembler yielding C, O2, H2, H2O and ash. b) Unit II: Chemical
equilibrium unit involving a selected set of 4 independent reactions.

94
C. Torres, et al. Biomass and Bioenergy 123 (2019) 89–103

Fig. 3. Path II Thermodynamic Biomass Gasification Model Based on: a) Unit1: Biomass and Air Disassembler yielding C,O,H,N elements and ash, b) Unit II: Chemical
Equilibrium Unit involving a selected set of 4 independent reactions.

reactions as described in Fig. 3. Path II are essentially identical.

Fig. 4 reports chemical species fractions for both Path I and Path II
and compares them with Hysys-Aspen simulations. Conditions selected
for this consider, as shown in Table 1, typical runs in the downdraft
gasifier operated at ICAFE, Costa Rica.
Thus, Fig. 4 provides a validation of the numerical method used and
shows that the gasification steps selected in Unit I for both Path I and II,
do not affect the calculated results. Observed differences for chemical
species molar fractions and carbon solid flow are less than 1%, with this
being in line with the state function character of the equilibrium
thermodynamics.
The comparison of Path I and Path II results allows establishing that
the exact knowledge of intermediate species formed following primary
gasification reactions, is not very relevant. This is the case given that
5. Experimental results and validation of the proposed
equilibrium model
Once the proposed numerical method was developed and validated,
the next step was to compare it with the species molar fractions of the
producer gas and char, obtained in the downdraft gasifier which pro-
cesses the coffee pulp in Costa Rica.
For this comparison, a Relative Error was calculated, as in Eq. (21).
|(Xexpi Xmodi)|
i (Xexpi + Xmodi )

equilibrium product compositions determined in Unit II for Path I and

2
Relative Error = × 100
N (21)

Fig. 4. (a) Comparison of predicted gas compositions between Path I and Aspen-Hysys simulations; (b) Comparison of predicted results between Path I and Path II; (c)
Comparison of predicted carbon obtained by Path I and Aspen-Hysys simulations.

95
C. Torres, et al.
Fig. 5. Comparison of Carbon Conversion and Equilibrium Molar Fractions, Experimentally Observed and Calculated using Path II. Note: Relative as per Eq (21),:
50%.
where N represents the 42 data points, including molar fractions syngas
components and carbon conversion.
Fig. 5 evaluates the predicted molar fractions for Path I and Path II
and compares them with the experimental results. In this figure, one
can see the significant molar fraction deviations, with these deviations
being in the same order of magnitude as those reported by others
[39,77]. Furthermore, one can observe that hydrogen deviations are
clustered and consistently overpredicted. As well one, can notice that
both methane and CO are underpredicted. These consistent deviations
in species molar fractions, suggests a deficiency of the Path II proposed
model.
5.1. Path III
Given the above described results, it is required to improve model
Fig. 6. Path III Thermodynamic Biomass Gasification Model Based on: a) Unit I: Biomass Disassembler Unit yielding C,H,O, N elements and ash, b) Unit II: Chemical
Equilibrium Unit involving biochar and a selected set of 4 independent reactions.
96
Biomass and Bioenergy 123 (2019) 89–103
predictability. To address this, a Path III model, as reported in Fig. 6,
was considered. Path III represents, in fact, a chemical equilibrium
model with biochar being included in Unit II. Thus, in Path III, 4 in-
dependent stoichiometric reactions, as shown in Fig. 6, have to be
considered.
Biochar chemical structure is significantly different from that of
graphite. Keilowuet et al. [78] provided a molecular-level assessment of
chemical complexities of biomass-derived chars. These authors mention
specifically, the contribution of aromatic carbons in biochar structures.
Furthermore, for biochar inclusion in thermodynamic equilibrium
models, knowledge of two key ΔH0 and ΔG0 parameters is required.
Given that the ΔH0 for biochar was calculated using calorimetry as
described in Section 3.1, there is only ΔG0 unknown parameter left in
the thermodynamic model. Thus, in the present study, the ΔG0 para-
meter was adjusted, minimizing the combined errors of the following:
C. Torres, et al. Biomass and Bioenergy 123 (2019) 89–103

Fig. 7. Evaluation of Path III, using (22) is calculated using the experimentally measured inlet elemental flows and calculated elemental flows for 7 runs. Notes: a)
Predicted values with limited error are shown in the −45 to −27 kJ/mol, b) Broken lines show the numercial calculation divergent region.

a) Elemental balance error given by Eqs. (17) and (18), b) Chemical
equilibrium condition error given by Eq. (19) and c) Equation of state
error as per Eq. (20).
One should note that the minimization algorithm converges in all
the ranges, except for the Elemental balance error. It is noticeable that
the Equilibrium Model Relative Elemental Error, defined with Eq. (22),
has two distinct zones in which the numerical system converges or
diverges depending on the ΔG0 value. Fig. 7 shows that ΔG0 selection
involves the identification of a −27 and −45 kJ/mol convergence
range. This is the case given that higher than −27 kJ/mol values, leads
to a numerical diverging calculation, with unsuitable ΔG0.

Fig. 8. Path III. The species Molar Fraction error, X exp, i Xmod, i , for individual runs. Notes: a) Predicted X exp, i Xmod, i with limited error for various species are shown
in the highlighted region in “red”, b) Broken lines show lack of convergence region. (For interpretation of the references to colour in this figure legend, the reader is
referred to the Web version of this article.)

97
C. Torres, et al.
i,
,% = 100
i
Fi, in
Furthermore, Fig. 8 shows the syngas molar fraction error,
Xexp, i Xmod, i , for each one of the runs. It can be observed that the re-
gion with error minimization falls consistently and in agreement with
Fig. 7 in a close convergence.
Thus, on the basis of the above observations, and as shown in Fig. 8,
an optimum ΔGo value averaging −28 kJ/mol for the seven runs in the
ICAFE downflow gasifier was identified. Confirmation of this optimum
value, providing minimization of the model residuals, is also described
in Fig. 9. Here, one can see that there is a band of ΔG0 values leading to
a minimum summation of errors in the −27 kJ/mol to −29 kJ/mol
range.
Furthermore, Fig. 9 provides evidence that the value of the ΔGo
obtained for individual runs is close with ΔG0 average being 28,2 kJ/
mol and the standard deviation ± 0,3 kJ/mol.
Fig. 10 a) reports a parity plot comparing the calculated and mea-
sured experimental molar fractions using Path III for both species molar
fractions and carbon converted. One can see a significant improvement
of the Relative Error deviations as defined with Eq. (21) with the pre-
dictions with Path I and II. In this case, Relative Error deviations are
reduced from 50% to 25%. While this is considered significant progress,
there are still model improvements required. In this regard, it is ob-
served that the deviations in the parity plots are strongly related to the
chemical species considered, with methane being significantly model
underestimated and hydrogen being noticeably model overestimated.
Furthermore, Fig. 10 b) additionally shows both models estimated
and experimentally observed carbon conversions. In this regard, it can
be observed that the carbon conversion predictions are in a good
agreement with the experimental results.
5.2. Path IV
Thus, in order to improve the thermodynamic model predictions,
further model modifications are required. To accomplish this, a Path IV
is proposed. Path IV accounts for both biochar and the actual gasifier
Fig. 9. ΔG0 Values Calculated for the 7 Runs Developed in the Downdraft Gasifier using Coffee Pulp Biochar.
Biomass and Bioenergy 123 (2019) 89–103
configuration, including three stages. Thus, the proposed Path IV, still
(22) retains all the details of Path III, leading to a numerical solution in-
volving a set of 10 non-linear equations: a) 4 independent reactions, b)
4 elemental balances for C, H, O, N, c) one ash mass balance and d) one
state equation. However, Path IV considers an extra “upflow” homo-
genous equilibrium reactor where the CO2 hydrogenation reaction is
included.
It can be stated that the proposed Path IV model closely describes
the configuration of the downdraft gasifier where both a “heterogeneous
section” is followed by an “upflow” “homogeneous section” (free of bio-
char) section, as shown in Fig. 1.
A review of the possible homogeneous reactions in the gasifier
“upflow” homogenous section led to the conclusion that “CO2 hydro-
genation” (also designated as CO2 methanation) is likely to be dominant
[79–83]. One should note that reactions involving biochar were not
accounted for, given biochar is separated from syngas flow at the
homogeneous gasifier section entry. Regarding the water-gas-shift re-
action, it was neglected given its anticipated not to contribute [49,84].
This is relevant given the expected 550 °C homogeneous gasifier sec-
tion. Thus, and on this basis, Path IV model was configured with all the
components of Path III plus an extra Gibbs equilibrium involving the
hydrogenation of CO2 at equilibrium.
The numerical solution of Path IV as illustrated in Fig. 11, requires
the numerical regression for Units I and II as previously discussed. In
addition to this, there is a numerical iteration on the exit syngas tem-
perature in Unit III.
Fig. 12 shows the reported converged temperatures with all of them
falling in the 475–520 °C range with 500 °C being an average. One
should notice in this respect, that homogeneous equilibrium section
temperatures were in agreement with the outlet syngas temperature
measured (refer to Table 1), with this confirming hydrogenation CO2
chemical equilibrium is reached before the syngas leaves the homo-
geneous reactor section.
Furthermore, the applicability of Path IV can also be considered
using a parity plot as reported in Fig. 13. This parity plot compares the
deviations of predicted chemical equilibrium with those of experi-
mentally measured molar fractions.
98
C. Torres, et al. Biomass and Bioenergy 123 (2019) 89–103

Fig. 10. Comparison of Experimentally Observed and Calculated Carbon Conversion and Equilibrium Molar Fractions using Path III. Note: Relative Error as per Eq
(21): 25%.

Fig. 11. Path IV Thermodynamic Biomass Gasification Model with: a) Unit I: Biomass Disassembler yielding C,H,O, N elements and ash, b) Unit II: Chemical
Equilibrium Unit Step involving biochar and a selected set of 4 independent reactions, c) Unit III including the CO2 hydrogenation reaction.

In this respect, Fig. 13 shows the very significant improvement in 6. Conclusions

the prediction of molar fractions and carbon conversion at the outlet of
the downdraft gasifier, as established with the Relative Error as per Eq
(21), now reduced to 13%. One can also observe that the deviations of
methane and hydrogen as in Path III, as well as the data clustering are
now significantly reduced, with this demonstrating the validity of the
model developed with Path IV.
a) A chemical equilibrium thermodynamic-based model was success-
fully established for the simulation of a demonstration scale down-
draft biomass gasifier unit, operated at the ICAFE Costa Rica facil-
ities.
b) A minimum set of independent reactions was properly selected via a
Gaussian Elimination Algorithm.

99
C. Torres, et al. Biomass and Bioenergy 123 (2019) 89–103

Fig. 12. Calculated Optimized Temperatures for the 7 gasification Runs at the Exit of the Homogenous “Upflow” Section of the Downflow Gasifier.

Fig. 13. Comparison of Carbon Conversion and Equilibrium Molar Fractions, Experimentally Observed and Calculated using Path IV. Note: Relative Error as per Eq
(21): 13%.

100
C. Torres, et al. Biomass and Bioenergy 123 (2019) 89–103

c) The chemical equilibrium thermodynamic model solution numerical
method was validated by developing an equivalent numerical si-
mulation, which was carried out with an Aspen-Hysys software and
employed graphite as the solid gasification residue.
d) To provide completeness, the chemical equilibrium thermodynamic
model also accounted for the biochar using both elemental compo-
sition and biochar thermodynamic properties.
e) To accomplish this, the biochar Heat of Formation was determined
using a calorimeter, while the Gibbs Free Energy of Formation was
calculated via an iterative non-linear regression method.
f) The established gasifier model was further enhanced by including a
homogeneous “upflow” exit section, following the heterogeneous
“downflow” section.
g) The proposed model was found effective on predicting various
product molar fractions at the outlet of the downdraft gasifier unit.
Acknowledgements
We would gladly like to acknowledge the Inter-American
Development Bank IDB/MIF N° ATN/ME-14064-CR who funded this
study via the NAMA Cafe initiative. We are also grateful to the ICAFE
who supported this research. We would like to express our appreciation
to Ms. Florencia de Lasa who provided valuable support with the
editing of this manuscript as well as with some of the technical
drawing.

Appendix A. The Hysis-Aspen Model

The Hysis-Aspen model of the present study follows closely Path II as described in Fig. 3. Path II is a “convenient” thermodynamic path given it
allowed establishing equilibrium product compositions at the outlet of the “heterogeneous” downdraft gasifier section.
The first step in the Hysis-Aspen model development involved the selection of all relevant chemical species including hydrogen, carbon dioxide,
water, carbon monoxide, methane, carbon, oxygen and nitrogen. In the case of ash, a hypothetical inert solid species was considered with both
density and heat capacity matching the ones of the ICAFE process ash.
Following this, the “Antoine” fluid package was selected and this to have available various fluid and thermodynamic properties available such as
compressibility factors, saturation vapor pressures, Heat of Formation and Gibbs Free Energy of Formation.
Next, Unit I was chosen. This unit converted wet biomass and air in its C, O, H, N elemental components and ash. This is accomplished via a
“Conversion Reactor”. In this unit, exiting elemental components molar flows such H, O and N were represented as ½ H2, ½ O2 and ½ N2. After the
“Conversion Reactor” the calculated stream was fed to a “Gibbs Equilibrium Reactor” or Unit II. This “Gibbs Equilibrium Reactor” accounted for the
simultaneous solution of four independent reaction as follows:

a) C + O2↔CO2, b) C + CO2↔ 2CO, c) CO2+ 4H2↔CH4+ 2H2O, d) CO + H2O↔CO2+ H2

One should note that the Gibbs Free Energy of Reaction, as well as the Heat of Reaction were calculated using the Gibbs Free Energy of Formation
and the Enthalpy of Formation for various species based on the “Antoine” package from Hysis-Aspen thermodynamic property library.
Thus, once the relevant stoichiometries for Units I and II were set, the incoming biomass feed was specified in terms of pressure, temperature and
mass flow. As well, the temperature and pressure conditions for Unit I and Unit II were provided with the outlet reduction temperature T2, being the
temperature for Unit II. Completed these variable specifications numerical calculations were developed for various runs with obtained results
reported In Fig. 4.

Appendix B. Temperature Time Record at the Exit of the Reduction Section (T2) for various Runs

This appendix reports the time record of the reduction temperature (T2) at the outlet of the gasifier. The highlighted areas in “pastel” of Fig. B1
show the time domains where the system was considered at steady state. It was during this time period where the various molar fractions of the
species in syngas produced were considered for model validation.

101
C. Torres, et al.
Fig. B.1. Time record of the reduction temperature (T2) at the exit of the reduction section. The highlighted areas in “pastel” show the time domains where the
system was considered at steady state. Note: temperatures were recorded once every 1 s. 2
References
[1] (IEA) International Energy Agency, Energy Technology RD&D Budgets: Overview,
(2018).
[2] A.A. Bazmi, G. Zahedi, H. Hashim, Design of decentralized biopower generation and
distribution system for developing countries, J. Clean. Prod. 86 (2015) 209–220.
[3] T.K. Patra, P.N. Sheth, Biomass gasification models for downdraft gasifier: a state-
of-the-art review, Renew. Sustain. Energy Rev. 50 (2015) 583–593.
[4] M. Asadullah, Barriers of commercial power generation using biomass gasification
gas: a review, Renew. Sustain. Energy Rev. 24 (2014) 201–215.
[5] A. Nieters, J. Grabs, G. Jimenez, W. Alpizar, NAMA café Costa Rica – a tool for low-
carbon development, NAMA Facil. Tech. Support Unit behalf ger. Ferderal minist.
Environ. Nat. Conserv. Build. Nucl. Saf./UK Dep. Energy Clim. Chang. (2015) 1–6.
[6] ICAFE, Informe Sobre La Actividad Cafetalera De Costa Rica 2017, ” San José, Costa
Rica, 2017.
[7] J.E. Braham, R. Bressani, Coffee Pulp : Composition, Technology, and Utilization,
Canada: International Development Research Centre, 1979.
[8] P. Esquivel, V.M. Jiménez, Functional properties of coffee and coffee by-products,
Food Res. Int. 46 (2) (2012) 488–495.
[9] S. Roussos, et al., Biotechnological management of coffee pulp - isolation,
screening, characterization, selection of caffeine-degrading fungi and natural mi-
croflora present in coffee pulp and husk, Appl. Microbiol. Biotechnol. 42 (5) (1995)
756–762.
[10] C. Galanakis, Handbook of Coffee Processing By-Products: Sustainable Applications,
102
Biomass and Bioenergy 123 (2019) 89–103
Elsevier Inc., United Kingdom, 2017 AP.
[11] B. Janissen, T. Huynh, Chemical composition and value-adding applications of
coffee industry by-products: a review, Resour. Conserv. Recycl. 128 (September
2017) 110–117 2018.
[12] A. Bonilla, Experiencias de aplicación de políticas públicas que fomentan la agri-
cultura sostenible en Costa Rica: Identificación, sistematización y análisis, San José,
Costa Rica, 2016.
[13] Ministry of Agriculture and Livestock, Agro-Environmental Agenda, Climate
Change and Carbon Neutrality in the Agri- Food Sector of Costa Rica, Costa Rica,
2011.
[14] Ministry of Agriculture and Livestock, Política de Estado para el Sector
Agroalimentario y el Desarrollo Rural Costarricense 2010-2021, San José, Costa
Rica, 2011.
[15] A. Heeger, A. Kosińska-Cagnazzo, E. Cantergiani, W. Andlauer, Bioactives of coffee
cherry pulp and its utilisation for production of Cascara beverage, Food Chem. 221
(2017) 969–975.
[16] P.S. Murthy, M. Madhava Naidu, Sustainable management of coffee industry by-
products and value addition - a review, Resour. Conserv. Recycl. 66 (2012) 45–58.
[17] C.E. Hernandez, H.H. Chen, C.I. Chang, T.C. Huang, Direct lipase-catalyzed lipo-
philization of chlorogenic acid from coffee pulp in supercritical carbon dioxide, Ind.
Crop. Prod. 30 (3) (2009) 359–365.
[18] V.A. Bonilla-Hermosa, W.F. Duarte, R.F. Schwan, Utilization of coffee by-products
obtained from semi-washed process for production of value-added compounds,
Bioresour. Technol. 166 (2014) 142–150.
[19] J.B. Ulloa Rojas, J.A.J. Verreth, S. Amato, E.A. Huisman, Biological treatments
C. Torres, et al.
affect the chemical composition of coffee pulp, Bioresour. Technol. 89 (3) (2003)
267–274.
[20] C. Torres, L. Urvina, N. Hernández, D. Molina, Informe Técnico Evaluación de
desempeño de la tecnología comercial de gasificación utilizando residuos de café,
San José, Costa Rica, 2016.
[21] A. Pandey, C.R. Soccol, P. Nigam, D. Brand, R. Mohan, S. Roussos, Biotechnological
potential of coffee pulp and coffee husk for bioprocesses, Biochem. Eng. J. 6 (2)
(2000) 153–162.
[22] G. Corro, U. Pal, F. Bañuelos, M. Rosas, Generation of biogas from coffee-pulp and
cow-dung co-digestion: Infrared studies of postcombustion emissions, Energy
Convers. Manag. 74 (2013) 471–481.
[23] D. Salmones, G. Mata, K.N. Waliszewski, Comparative culturing of Pleurotus spp. on
coffee pulp and wheat straw: biomass production and substrate biodegradation,
Bioresour. Technol. 96 (5) (2005) 537–544.
[24] I. Gaime-Perraud, S. Roussos, D. Martinez-Carrera, Natural Microorganisms of the
Fresh Coffee Pulp vol. 6, (1993), pp. 95–103.
[25] M.G. Godoy, G.M. Amorim, M.S. Barreto, D.M.G. Freire, Agricultural Residues as
Animal Feed, Elsevier B.V., 2018.
[26] S. Heidenreich, P.U. Foscolo, New concepts in biomass gasification, Prog. Energy
Combust. Sci. 46 (2015) 72–95.
[27] S.K. Sansaniwal, K. Pal, M.A. Rosen, S.K. Tyagi, Recent advances in the develop-
ment of biomass gasification technology: a comprehensive review, Renew. Sustain.
Energy Rev. 72 (May 2017) 363–384.
[28] A.A. Ahmad, N.A. Zawawi, F.H. Kasim, A. Inayat, A. Khasri, Assessing the gasifi-
cation performance of biomass: a review on biomass gasification process conditions,
optimization and economic evaluation, Renew. Sustain. Energy Rev. 53 (2016)
1333–1347.
[29] T. Methling, et al., “Bioresource Technology Power generation based on biomass by
combined fermentation and gasification – a new concept derived from experiments
and modelling, Bioresour. Technol. 169 (2014) 510–517.
[30] J.F. Pérez, A. Melgar, P. Nel, “Effect of operating and design parameters on the
gasification/combustion process of waste biomass in fixed bed downdraft reactors :
an experimental study, 96 (2012) 487–496.
[31] M. Simone, F. Barontini, C. Nicolella, L. Tognotti, Gasification of pelletized biomass
in a pilot scale downdraft gasifier, Bioresour. Technol. (2012).
[32] P. McKendry, Energy production from biomass (part 3): gasification technologies,
Bioresour. Technol. 83 (1) (2002) 55–63.
[33] A.A.P. Susastriawan, H. Saptoadi, Purnomo, Small-scale downdraft gasifiers for
biomass gasification: a review, Renew. Sustain. Energy Rev. 76 (May 2016)
989–1003 2017.
[34] M. La Villetta, M. Costa, N. Massarotti, Modelling approaches to biomass gasifica-
tion: a review with emphasis on the stoichiometric method, Renew. Sustain. Energy
Rev. 74 (2017) 71–88 January.
[35] M. Ruggiero, G. Manfrida, An equilibrium model for biomass gasification processes,
Renew. Energy 16 (1–4) (1999) 1106–1109.
[36] N. Couto, A. Rouboa, V. Silva, E. Monteiro, K. Bouziane, Influence of the biomass
gasification processes on the final composition of syngas, Energy Procedia 36
(2013) 596–606.
[37] M. Simone, F. Barontini, C. Nicolella, L. Tognotti, Assessment of syngas composition
variability in a pilot-scale downdraft biomass gasifier by an extended equilibrium
model, Bioresour. Technol. 140 (2013) 43–52.
[38] P.C. Kuo, W. Wu, W.H. Chen, Gasification Performances of Raw and Torrefied
Biomass in a Downdraft Fixed Bed Gasifier Using Thermodynamic Analysis, Fuel,
2014.
[39] G. Mirmoshtaghi, H. Li, E. Thorin, E. Dahlquist, Evaluation of different biomass
gasification modeling approaches for fluidized bed gasifiers, Biomass and Bioenergy
(2016).
[40] A. Melgar, et al., Thermochemical equilibrium modelling of a gasifying process,
Energy Convers. Manag. 48 (1) (2007) 59–67.
[41] A.Z. Mendiburu, J.A. Carvalho, R. Zanzi, C.R.R. Coronado, J.L. Silveira,
Thermochemical equilibrium modeling of a biomass downdraft gasifier: constrained
and unconstrained non-stoichiometric models, Energy 71 (2014) 624–637.
[42] Z.A. Zainal, R. Ali, C.H. Lean, K.N. Seetharamu, Prediction of performance of a
downdraft gasifier using equilibrium modeling for different biomass materials,
Energy Convers. Manag. (2001).
[43] S. Jarungthammachote, A. Dutta, Thermodynamic equilibrium model and second
law analysis of a downdraft waste gasifier, Energy 32 (2007) 1660–1669.
[44] F. Paviet, F. Chazarenc, M. Tazerout, Thermo chemical equilibrium modelling of a
biomass gasifying process using Aspen plus, Int. J. Chem. React. Eng. 7 (2009).
[45] M. Baratieri, P. Baggio, L. Fiori, M. Grigiante, Biomass as an energy source: ther-
modynamic constraints on the performance of the conversion process, Bioresour.
Technol. 99 (15) (2008) 7063–7073.
[46] A.K. Sharma, Modeling and simulation of a downdraft biomass gasifier 1. Model
development and validation, Energy Convers. Manag. 52 (2011) 1386–1396.
[47] D. Castello, L. Fiori, Supercritical water gasification of biomass: a stoichiometric
thermodynamic model, Int. J. Hydrogen Energy 40 (2015) 6771–6781.
[48] I.S. Antonopoulos, A. Karagiannidis, A. Gkouletsos, G. Perkoulidis, Modelling of a
downdraft gasifier fed by agricultural residues, Waste Manag. (2012).
[49] N.S. Barman, S. Ghosh, S. De, Gasification of biomass in a fixed bed downdraft
gasifier - a realistic model including tar, Bioresour. Technol. 107 (2012) 505–511.
[50] O. Yucel, M.A. Hastaoglu, Kinetic modeling and simulation of throated downdraft
gasifier, Fuel Process. Technol. 144 (2016) 145–154.
[51] G. Gautam, S. Adhikari, S. Bhavnani, Estimation of biomass synthesis gas compo-
sition using equilibrium modeling, Energy Fuels 24 (4) (2010) 2692–2698.
[52] L. Gerun, et al., Numerical investigation of the partial oxidation in a two-stage
downdraft gasifier, Fuel 87 (7) (2008) 1383–1393.
[53] M. Simone, C. Nicolella, L. Tognotti, Numerical and experimental investigation of
103
Biomass and Bioenergy 123 (2019) 89–103
downdraft gasification of woody residues, Bioresour. Technol. 133 (2013) 92–101.
[54] M.A. Masmoudi, K. Halouani, M. Sahraoui, Comprehensive experimental in-
vestigation and numerical modeling of the combined partial oxidation-gasification
zone in a pilot downdraft air-blown gasifier, Energy Convers. Manag. 144 (2017)
34–52.
[55] A. Gagliano, F. Nocera, F. Patania, M. Bruno, D.G. Castaldo, A robust numerical
model for characterizing the syngas composition in a downdraft gasification pro-
cess, Compt. Rendus Chem. 19 (2016) 441–449.
[56] A. Demirbaş, Mechanisms of liquefaction and pyrolysis reactions of biomass, Energy
Convers. Manag. 41 (6) (2000) 633–646.
[57] T. Fisher, M. Hajaligol, B. Waymack, D. Kellogg, Pyrolysis behavior and kinetics of
biomass derived materials, J. Anal. Appl. Pyrolysis 62 (2) (2002) 331–349.
[58] T. Xu, F. Xu, Z. Hu, Z. Chen, B. Xiao, Non-isothermal kinetics of biomass-pyrolysis-
derived-tar (BPDT) thermal decomposition via thermogravimetric analysis, Energy
Convers. Manag. 138 (Apr. 2017) 452–460.
[59] S. Sharma, P.N. Sheth, Air-steam biomass gasification: experiments, modeling and
simulation, Energy Convers. Manag. (2016).
[60] M. Formica, S. Frigo, R. Gabbrielli, Development of a new steady state zero-di-
mensional simulation model for woody biomass gasification in a full scale plant,
Energy Convers. Manag. (2016).
[61] M.S. Mettler, S.H. Mushrif, A.D. Paulsen, A.D. Javadekar, D.G. Vlachos,
P.J. Dauenhauer, Revealing pyrolysis chemistry for biofuels production: conversion
of cellulose to furans and small oxygenates, Energy Environ. Sci. 5 (1) (2012)
5414–5424.
[62] A. Mukherjee, A.R. Zimmerman, W. Harris, Surface chemistry variations among a
series of laboratory-produced biochars, Geoderma 163 (3–4) (2011) 247–255.
[63] S. Carter, S. Shackley, S. Sohi, T. Suy, S. Haefele, The impact of biochar application
on soil properties and plant growth of pot grown lettuce (Lactuca sativa) and
cabbage (Brassica chinensis), Agronomy 3 (2) (2013) 404–418.
[64] L. Isaacs, The thermodynamics of coal chars: correlation of free energy of formation
with reactivity, City Coll. City Univ. NY, Dept. (4) (1978) 215–223.
[65] G. Duman, M.A. Uddin, J. Yanik, The effect of char properties on gasification re-
activity, Fuel Process. Technol. 118 (2014) 75–81.
[66] K. Mitsuoka, S. Hayashi, H. Amano, K. Kayahara, E. Sasaoaka, A. Uddin,
“Gasification of woody biomass char with CO 2 : the catalytic effects of K and Ca
species on char gasification reactivity, Fuel Process. Technol. 92 (2010) 26–31.
[67] M.J. Prins, K.J. Ptasinski, F.J.J.G. Janssen, From coal to biomass gasification:
comparison of thermodynamic efficiency, Energy 32 (7) (2007) 1248–1259.
[68] T. Gröbl, H. Walter, M. Haider, Biomass steam gasification for production of SNG-
Process design and sensitivity analysis, Appl. Energy 97 (2012) 451–461.
[69] A. Molino, S. Chianese, D. Musmarra, Biomass gasification technology: the state of
the art overview, J. Energy Chem. 25 (2016) 10–25.
[70] H. de Lasa, E. Salaices, J. Mazumder, R. Lucky, Catalytic steam gasification of
biomass: catalysts, thermodynamics and kinetics, Chem. Rev. 111 (9) (2011)
5404–5433.
[71] S.M. Chern, W.P. Walawender, L.T. Fan, Mass and energy balance analyses of a
downdraft gasifier, Biomass vol. 18, (2) (1989) 127–151.
[72] J.E. White, W.J. Catallo, B.L. Legendre, Biomass pyrolysis kinetics: a comparative
critical review with relevant agricultural residue case studies, J. Anal. Appl.
Pyrolysis 91 (1) (2011) 1–33.
[73] Q.V. Bach, K.Q. Tran, O. Skreiberg, R.A. Khalil, A.N. Phan, Effects of wet torre-
faction on reactivity and kinetics of wood under air combustion conditions, Fuel
(2014).
[74] R. Aris, R.H.S. Mah, Independence of chemical reactions, Ind. Eng. Chem. Fundam.
2 (2) (1963) 90–94.
[75] B.A. Finlayson, L.T. Biegler, I.E. Grossmann, K. Küfer, M. Bortz, Mathematics in
chemical engineering, Ullmann's Encyclopedia of Ind. Chem. (2000) Wiley Online
Library.
[76] J.M. Smith, H.C. Van Ness, M. Abbott, Introduction to Chemical Engineering
Thermodynamics, McGraw-Hill Education, 2005.
[77] A.Z. Mendiburu, J.A. Carvalho, C.J.R. Coronado, Thermochemical equilibrium
modeling of biomass downdraft gasifier: stoichiometric models, Energy 66 (2014)
189–201.
[78] M. Keiluweit, P.S. Nico, M.G. Johnson, Dynamic molecular structure of plant bio-
mass-derived black carbon ( biochar ), Environ. Sci. Technol. 44 (4) (2010)
1247–1253.
[79] J. Gao, et al., A thermodynamic analysis of methanation reactions of carbon oxides
for the production of synthetic natural gas, RSC Adv. 2 (6) (2012) 2358–2368.
[80] G.D. Weatherbee, C.H. Bartholomew, Hydrogenation of CO2 on group VIII metals.
II. Kinetics and mechanism of CO2 hydrogenation on nickel, J. Catal. 77 (2) (1982)
460–472.
[81] S. Medsforth, Promotion of catalytic reactions, J. Chem. Soc. Trans. 123 (1462)
(Jan. 1923) 1452–1469.
[82] E.K. Rideal, R.E. Hugh, S. Taylor, An instrument for the determination of small
quantities of carbon monoxide in hydrogen, Analyst 44 (516) (1918) 89.
[83] S. Rönsch, et al., Review on methanation - from fundamentals to current projects,
Fuel 166 (2016) 276–296.
[84] W.M. Graven, F.J. Long, C.W. Mason, Kinetics and mechanisms of the two opposing
reactions of the equilibrium CO + H20 = C02 + H2, J. Am. Chem. Soc. 76 (1953)
2602–2607.
[85] P.E. Liley, G.H. Thomson, D.G. Friend, T.E. Daubert, E. Buck, Physical and chemical
data*, in: R.H. Perry, D.W. Green, J.O. Maloney (Eds.), Perry's Chemical Engineers'
Handbook, United States of America: McGraw-Hill, 1997, pp. 178–182.
[86] A. Kuhn Bastos, C. Torres, A. Mazumder, H. de Lasa, CO2 biomass fluidized gasi-
fication: thermodynamics and reactivity studies, Can.J.Chem.Engng 96 (2018)
2176–2184.