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9th International Conference on Applied Energy, ICAE2017, 21-24 August 2017, Cardiff, UK

Effect of torrefaction on the high temperature steam gasification of

The 15th International Symposium on District Heating and Cooling
cellulose based upon the Gibbs free energy minimization
Assessing the feasibility Y.W. Huangof a,b using thea,b
, M.Q. Chen heat *, J.J.demand-outdoor
Songc
temperature
a function for a long-term district heat demand forecast
Institute of Thermal Engineering, School of Mechanical, Electronic and Control Engineering, Beijing Jiaotong University, Beijing, China
a
bb
Beijing
Beijing Key Laboratory of Flow and Heat Transfer of Phase Changing in Micro and Small Scale, Beijing, China
a,b,c Electric PoweraBranch, China Shenhua
I. Andrić *, A. Pina , P. Ferrãoa, J. Fournier b Limited, Beijing 100025,
., B. Lacarrièrec, O. Le Correc
cc
Guohua Energy Company China

a
IN+ Center for Innovation, Technology and Policy Research - Instituto Superior Técnico, Av. Rovisco Pais 1, 1049-001 Lisbon, Portugal
Abtract b
Veolia Recherche & Innovation, 291 Avenue Dreyfous Daniel, 78520 Limay, France
c
Département Systèmes Énergétiques et Environnement - IMT Atlantique, 4 rue Alfred Kastler, 44300 Nantes, France
The steam gasification can convert biomass into syngas, which can be conveniently used as fuels or chemical raw materials.
Cellulose, as an important component of biomass, has a significant effect on the gasification behavior. Steam gasification
behaviors of raw and torrefied cellulose at high temperature were investigated using a non-stoichiometric equilibrium model. The
Abstract
effect of torrefaction severity on the high temperature steam gasification of cellulose was evaluated. With increasing of
steam/cellulose molar ratio, the molar numbers of hydrogen and carbon dioxide increased, whereas the molar number of carbon
District heating
monoxide networks
decreased. Less are
thancommonly
1.0 molaraddressed in the literaturewas
ratio of steam/cellulose as one of the mostforeffective
recommended raw andsolutions
torrefiedforcelluloses.
decreasingThethe
greenhouse
methane steamgasreaction
emissionsfor from the building
severely torrefied sector. These
cellulose systems
at low require high
steam/cellulose investments
molar ratio waswhich
found.areThe
returned
molarthrough
numberthe heat
of the
sales. Due
hydrogen to the from
increased changed
1.992climate
to 2.016 conditions andincreasing
mol with the building renovation policies,
of torrefaction heat demand
temperature from 250intothe300future
°C. The could decrease,
influence of
prolonging the investment return period.
steam content on the water-gas reaction was more obvious than that of reaction temperature. This study will promote the
The main scope
development of this
of steam paper is toofassess
gasification biomassthe feasibility of using
for the purpose the heat
of high demand
efficiency – outdoor temperature function for heat demand
utilization.
©forecast.
2017 TheThe districtPublished
Authors. of Alvalade, locatedLtd.
by Elsevier in Lisbon (Portugal), was used as a case study. The district is consisted of 665
©buildings
2017 Thethat
Peer-review Authors.
vary
under Published
in
responsibility by
of Elsevier
both construction Ltd. committee
period
the scientific and typology.
of theThree weather scenarios
9th International (low,onmedium,
Conference Appliedhigh) and three district
Energy.
Peer-review
renovation under responsibility
scenarios of the scientific
were developed (shallow,committee of the
intermediate, 9th International
deep). To estimate Conference on Applied
the error, obtained heatEnergy.
demand values were
comparedCellulose;
Keywords: with results
Steamfrom a dynamic
gasification; heat demand
Torrefaction; model, previously
Thermodynamic developed
equilibrium and validated
model; High temperature;by the authors.
The results showed that when only weather change is considered, the margin of error could be acceptable for some applications
(the error in annual demand was lower than 20% for all weather scenarios considered). However, after introducing renovation
1.scenarios, the error value increased up to 59.5% (depending on the weather and renovation scenarios combination considered).
Introduction
The value of slope coefficient increased on average within the range of 3.8% up to 8% per decade, that corresponds to the
decrease in the number of heating hours of 22-139h during the heating season (depending on the combination of weather and
Gasification is a promising technique for thermochemical conversion of biomass into syngas, which can be
renovation scenarios considered). On the other hand, function intercept increased for 7.8-12.7% per decade (depending on the
conveniently used for fuels or chemical raw materials in many fields [1]. However, raw biomass is characterized by
coupled scenarios). The values suggested could be used to modify the function parameters for the scenarios considered, and
itsimprove
high the
moisture
accuracy content and oxygen
of heat demand content, lower higher heating value (HHV) and energy density levels,
estimations.

© 2017 The Authors. Published by Elsevier Ltd.

Peer-review under responsibility of the Scientific Committee of The 15th International Symposium on District Heating and
* Corresponding author. Tel.: +86 10 51683423; fax: +86 10 51683423.
Cooling.
E-mail address: mqchen@bjtu.edu.cn.
Keywords: Heat demand; Forecast; Climate change
1876-6102 © 2017 The Authors. Published by Elsevier Ltd.
Peer-review under responsibility of the scientific committee of the 9th International Conference on Applied Energy.

1876-6102 © 2017 The Authors. Published by Elsevier Ltd.

Peer-review under responsibility of the Scientific Committee of The 15th International Symposium on District Heating and Cooling.
1876-6102 © 2017 The Authors. Published by Elsevier Ltd.
Peer-review under responsibility of the scientific committee of the 9th International Conference on Applied Energy.
10.1016/j.egypro.2017.12.100
604 Y.W. Huang et al. / Energy Procedia 142 (2017) 603–608
2 Author name / Energy Procedia 00 (2017) 000–000

hygroscopic nature, and low bulk density [2]. These drawbacks will lead to low efficiency for its collection, grinding,
storage and transportation [3], and result in poor quality syngas from biomass gasification [4]. Torrefaction occurs at
a specific temperature range in the absence of oxygen, which can remove all the moisture and a part of oxygen-
containing functional groups [3]. The torrefied biomass has lower oxygen content, higher heating value and energy
density, which can improve the quality of syngas [5]. At present, torrefaction is considered to be a promising
pretreatment technique of biomass before gasification. Lignocellulosic biomass is mainly consisted of cellulose,
hemi-cellulose and lignin. Cellulose is the most abundant component among three components, which accounts for
about 50 wt% of biomass [6]. Some thermally unstable functional groups in the cellulose molecule are largely
decomposed during torrefaction. In addition, biomass gasification is a complicated chemical process, which is
caused by interactions among three components. It is necessary to investigate individually the torrefaction of
cellulose on its gasification behavior.
Gasification agent includes generally steam, air, oxygen, hydrogen and their mixtures. Steam gasification can
generate high-quality syngas with higher heating value. This is because reduction reactions between steam and
carbon, and reforming reactions between steam and the product gas (CH4 and unsaturated hydrocarbons) both occur
in the steam gasification [1]. In addition, the low-temperature gasification will lead to low heating value of the
product gas, as well as the high content of tar [7]. Therefore, the high temperature steam gasification is selected as an
good gasification technique.
Thermodynamic equilibrium analysis is suitable as a simulation tool for gasification processes, which can give a
guide for the design, control, evaluation and improvement of processes. Thermodynamic equilibrium models possess
general applicability for simulating different configurations as they are independent of the design and not limited to a
specified range of operating conditions. At present, stoichiometric and non-stoichiometric equilibrium models are
widely used for predicting the gaseous products at thermodynamic equilibrium state. Shabbar and Janajreh [8]
conducted thermodynamics analysis of gasification process using the Gibbs energy minimization approach,
considering three gasification agents including air, air-steam and solar steam, and found that the cold gasification
efficiency of solar-steam gasification was the highest. Zainal et al. [9] applied equilibrium model to predict the
gasification products of different biomass materials in a downdraft gasifier, and the calorific value and composition
of the gaseous products could be predicted reasonably well. Li et al. [10] developed a non-stoichiometric equilibrium
model based on the Gibbs free energy minimization to predict the product compositions of circulating fluidized bed
coal gasifier. Jarungthammachote and Dutta [11] developed a modified thermodynamic equilibrium model of
gasification in spouted bed and spout-fluid bed gasifiers, considering the carbon conversion in the constraint
equations and the energy balance calculation, the modified model showed improvements. Ghassemiand Shahsavan-
Markadeh [12] built a modified equilibrium model, considering carbon conversion and tar formation, for biomass
gasification at air or mixture of air and oxygen. However, no investigation on the thermodynamic equilibrium
analysis for the effect of torrefaction on high temperature steam of cellulose has been done.
In this study, a non-stoichiometric equilibrium model for cellulose steam gasification is established based on the
Gibbs free energy minimization. The steam gasification behaviors of raw and torrefied celluloses are investigated,
and the effect of torrefaction severity on the gaseous products of cellulose gasification is evaluated at several
steam/cellulose molar ratios.

2. Materials and Methods

2.1. Material

The element components of raw and torrefied celluloses are shown in table 1, which are derived from the work of
Wang et. al [13].

Table 1. H/C and O/C of torrefied cellulose.

Torrefaction temperature (°C) O/C H/C
raw 0.948 1.858
250 0.921 1.825
 Y.W. Huang et al. / Energy Procedia 142 (2017) 603–608 605
Author name / Energy Procedia 00 (2017) 000–000 3

300 0.819 1.670

2.2. Gasification model

The high-temperature steam gasification of cellulose is represented by a global reaction. Given the long residence
time and no formation char, major syngas compositions consist of H 2, CO, CO2, CH4, and H2O. The chemical
formula of cellulose is expressed as CHxOy in order to facilitate the modeling of cellulose gasification. The global
reaction for steam gasification of cellulose can be given by:
CHxOy +mH2O  x co2CO2 +x coCO+x ch4CH4 +x h2H2 +x h2oH2O (1)
where x is the H/C molar ratio, y the O/C molar ratio , xco2 the molar number of CO2, xco the molar number of CO,
xch4 the molar number of CH4, xh2o the molar number of H2O(g), m the steam/cellulose molar ratio.

2.3. Gibbs free energy minimization

The non-stoichiometric thermodynamic equilibrium model of cellulose gasification is established based on the
chemical thermodynamic theory. When all reactions in the system get to the chemical equilibrium, the total Gibbs
free energy of complex system should be mathematically minimum value.
The total Gibbs free energy of system is described by:
N
GT , P   xi i (2)
I 1

where GT,P is the total Gibbs free energy of the system, xi the number of species i. The chemical potential (μi ) of
species i is presented by:
0
i Gi  RT ln( fi / fi 0 ) (3)
0
where G is the standard state of Gibbs free energy of species i, fi the fugacity of species i, f i the standard state
i
0

fugacity of species i.
Eq. (3) can be further expressed as:
0
i Gi  RT ln( Pi / P0 ) (4)
Where φ is the fugacity coefficient, Pi the partial pressure of species i, P the total pressure of all the species. When
0

gases are considered to be ideal gases at standard atmosphere pressure, the fugacity coefficient becomes 1, and the
partial pressure is proportional to the molar fraction. The standard state of Gibbs free energy is equal to the standard
state Gibbs free energy of formation. Therefore, Eq. (4) will be modified as:
0
Gi  RT ln(x i /  xi )
i  (5)
0
where G is the stand state Gibbs free energy of formation.
i

The element conservation must be obeyed during the cellulose gasification, which can be expressed as:
Ak   xi ai ,k (6)
i
where Ak is the total atoms number of the element k, ai,k the atoms number of the k th element in species i.
Due to the constraint of element conservation, the minimum value of Gibbs free energy can be obtained using
Lagrange multiplier method. A new objective function F is established:
0
(7)
 F n ,  
i k i
i i 
x (Gi  RT ln(x / x ))   ( x a  A )
i   k
k
i
i i ,k k

where λk is the Lagrange multiplier corresponding to element k.

The objective function F arrives to minimum value when the partial derivatives for all the variables should be all
zero, which can be written as:
F 0
(8)
 G i  RT ln(x i /  xi )   k ai ,k  0
xi k
606 Y.W. Huang et al. / Energy Procedia 142 (2017) 603–608
4 Author name / Energy Procedia 00 (2017) 000–000

F (9)
  xi ai ,k  Ak 0
i i

The total eight equations from five partial derivatives of gases molar numbers and three partial derivatives of
Lagrange multipliers are written as:
0
G co2  RT ln(x co2 /  xi )  c  2o  0 (10)
0
G  RT ln(x co /  xi )  c  o  0
co (11)
0
G ch4  RT ln(x ch 4 /  xi )  c  4h  0 (12)
0
G  RT ln(x h2 /  xi )  2h  0
h2 (13)
0
G h2o  RT ln(x h2o /  xi )  2h  0  0 (14)
xco2  xco  xch4  1 (15)
4 xch4  2 xh2  2 xh2o 
x  2m (16)
2 xco2  xco  xh2o y  m (17)
The eight undetermined parameters including the five molar numbers of gaseous products and three Lagrange
multipliers can be obtained based on eight independent equations. The non-linear equation set is solved by genetic
algorithm and newton iteration algorithm.

2.4. Thermodynamic properties

0
The standard state Gibbs free energy G i is calculated by:
0 0 0
Gi  H i  T  S i (18)
0 0
where  H is the enthalpy of formation,  S the entropy of formation. The calculation processes of enthalpy and
i i

entropy of formation for carbon dioxide are taken as an example:

0 0 0 0
 H co2  H co2  H c  H o2 (19)
0 0 0 0
S co2  S co2 S S
c o2 (20)
0 0 0
where H co2 is the absolute enthalpy of carbon dioxide, H the absolute enthalpy of solid carbon (graphite), H is the
c o2

0 0
absolute enthalpy of oxygen, S co the absolute entropy of carbon dioxide, S c the absolute entropy of solid carbon
2

0
(graphite), S o is the absolute enthalpy of oxygen. The 298.15 K is selected as the base of enthalpy, where the
2

enthalpy values of reference elements are zero. The absolute enthalpy and entropy are calculated by multi-order
polynomials, which are from NASA technical memorandum 4513 [11].

3. Results and Discussions

3.1. Steam gasification of raw cellulose

The molar numbers of H2, CO, CO2, CH4, and H2O from steam gasification of raw cellulose at high temperature
(1000 K and 1200 K) are calculated, which is shown in Fig. 1.
 Y.W. Huang et al. / Energy Procedia 142 (2017) 603–608 607
Author name / Energy Procedia 00 (2017) 000–000 5

2.0 2.0
1000K-Raw 1200K-Raw
1.981
1.6 1.6
CO2 CO CH4 CO2 CO CH4

Molar number
H2 H2 O
Molar number

H2 H2 O 1.2
1.2

0.8 0.8

0.4 0.4

0.0 0.0
0.0 0.4 0.8 1.2 1.6 0.0 0.4 0.8 1.2 1.6
Steam/cellulose Steam/cellulose
Fig. 1. Molar numbers of gaseous products for raw cellulose against steam/cellulose molar ratio.
From Fig. 1, the syngas from steam gasification of cellulose consists of H2, CO, and CO2, and the molar content
of CH4 is very low. With the increasing of steam/cellulose molar ratio from 0.1 to 1.0, the molar numbers of H2 and
CO2 increase significantly, while the molar content of CO decreases. This is because the water-gas shift reaction
proceeds towards positive direction when the steam content increases. But the molar numbers of all the gaseous
products except H2O are fixed at more than 1.0 of steam/cellulose molar ratio, which corresponds to the point where
the exhausted CO make the water-gas shift reaction stop. This also indicates that water-gas shift reaction plays a
dominant role in the high temperature steam gasification. The similar phenomenon was found in steam gasification
of sawdust char [7]. The molar numbers of all gaseous products change slightly with the increasing gasification
temperature, which also indicates that reaction temperature influences slightly the water-gas shift reaction.

3.2. Effect of torrefaction severity

The values of H/C and O/C in table 1 are equal to the values of x and y in CH xOy. The molar numbers of syngas
components from high-temperature steam gasification of torrefied cellulose are shown in Fig. 2.
2.0 1000K-Torre(250C) 2.0 1200K-Torre(250C)
1.992
1.6 1.6
CO2 CO CH4 CO2 CO CH4
Molar number

Molar number

H2 H2 O H2 H2 O
1.2 1.2

0.8 0.8

0.4 0.4

0.0 0.0
0.0 0.4 0.8 1.2 1.6 0.0 0.4 0.8 1.2 1.6
Steam/cellulose Steam/cellulose
(a) (b)
2.0 2.0
1000K-Torre(300C) 1200K-Torre(300C)
2.016
1.6 1.6
CO2 CO CH4
R CO2 CO CH4
Molar number

Molar number

1.2 H2 H2 O 1.2 H2 H2 O

0.8 0.8

0.4 0.4

0.0 0.0
0.0 0.4 0.8 1.2 1.6 0.0 0.4 0.8 1.2 1.6
Steam/cellulose Steam/cellulose
(c) (d)
Fig. 2. Molar numbers of gaseous products for torrefied cellulose against steam/cellulose molar ratios. (a) and (b) for torrefaction
temperature-250°C; (c) and (d) for torrefaction temperature-300°C;
608 Y.W. Huang et al. / Energy Procedia 142 (2017) 603–608
6 Author name / Energy Procedia 00 (2017) 000–000

From Fig. 2 (a) and (b), it can found that the molar numbers of all the gaseous products of torrefied cellulose from
250 °C torrefaction exhibit the similar trend in comparison with that of raw cellulose. The H/C and O/C of torrefied
cellulose are less than that of raw cellulose, which leads to different molar numbers of gaseous products. For
example, the molar number of H2 changes from 1.981 to 1.992 mol. The torrefied cellulose at 300 °C torrefaction
temperature shows a special region ( R region) in Fig. 2 (c). The molar numbers of H2 and CO increase at the range
from 0.1 to 0.2, whereas these for CH4 and H2O go down. This phenomenon can be attributed to the methane steam
reaction occurs at this region. When the steam content increases further, the CH4 content is exhausted by methane
steam reaction, and the water-gas reaction becomes the main reaction in the steam gasification. The molar numbers
of all the gaseous products for torrefied cellulose at 300 °C torrefaction will have a same trend with raw cellulose
and torrefied celluloses at 250 °C torrefaction. And the molar number of H2 for torrefied cellulose at 300 °C
torrefaction is the highest, which is caused by the high H/O ratio. In addition, the effect of gasification temperature
on the syngas for torrefied celluloses is not significant.

4. Conclusion

A non-stoichiometric equilibrium model is established based on the Gibbs free energy minimization, which is
used to investigate the high temperature steam gasification of cellulose and torrefied cellulose. The syngas is mainly
consisted of hydrogen, carbon monoxide, and carbon dioxide. For raw and moderately torrefied cellulose, the
increasing f molar numbers of hydrogen and carbon dioxide, and the decreasing of molar number of carbon dioxide
are observed at below 1.0 steam/cellulose molar ratio. A special region for severely torrefied cellulose is found, in
which methane steam reaction occurs. The steam content plays more significant role in the steam gasification than
reaction temperature. These findings will provide basic data for high temperature steam gasification of biomass.

Acknowledgements

This work was supported by the National Natural Science Foundation of China under NO 51376017.

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