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Characteristics of low temperature biomass

gasication and syngas release behavior using hot
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Cite this: RSC Adv., 2014, 4, 62105

slag
Yongqi Sun,a Zuotai Zhang,*ab Sridhar Seetharaman,c Lili Liua and Xidong Wangab

Received 12th September 2014
Accepted 31st October 2014
DOI: 10.1039/c4ra10261d
www.rsc.org/advances
This study proposes an emerging method to prepare syngas using integrated low temperature biomass
gasication combined with heat recovery from hot slag. A series of non-isothermal and isothermal
gasication experiments were performed in the temperature range of 250500
C to determine the
eect of the presence of slag on gasication. The results showed that the addition of slag remarkably
increased the production of syngas in the temperature range of 425500
C and during the gasication
at 450
C, with a mass ratio of wheat straw to slag of 1 : 1, syngas with 0.149 L CO, 0.036 L H2 and
0.069 L CH4 can be produced per gram of wheat straw. The kinetic mechanism of biomass gasication
changed from an AvramiErofeev model to a three-dimensional diusion model with the addition of
slag. Although the presence of slag altered the mechanism of gasication, it did not lower the degree of
gasication, and therefore the waste heat from the hot slag can be used to produce syngas. Therefore,
an industrial prototype plant composed of multiple systems was proposed, through which an energy
saving equivalent to 19.1 million tons of standard coal and an emission reduction of 69.9 million tons of
CO2 emission would be achieved in China.

In addition, hot slag is produced periodically resulting in the

1. Introduction
To lower the reliance of energy supplies on fossil fuels and to
reduce greenhouse gas (GHG) emissions and environmental
pollution, it is crucial to recover waste heat and reduce CO2
emissions from traditional industrial sectors.1,2 In the steel
industry, untapped hot slags at temperatures of up to 1550
C
carry a large amount of high quality energy, the recovery of
which represents a potential method for energy reduction.3,4 In
China, the output of crude steel was more than 710 million tons
in 2012 (ref. 5) and accordingly the amount of slag produced
during the blast furnace process was more than 200 million
tons, the total waste heat from which was equivalent to 16
million tons of standard coal. Conventionally, the slag can be
rapidly quenched using water to avoid crystallization and the
slag obtained in this way is in a glassy state with strong
hydraulicity,6 and can therefore be used as a cementitious
material.7 However, the thermal energy of the hot industrial slag
in the steel industry is largely wasted through this water-
quenched method and consequently the recovery rate of waste
heat from the slag is less than 2% in China8 and there is great
potential for energy extraction.
a
Department of Energy and Resources Engineering, College of Engineering, Peking
University, Beijing 100871, P.R. China. E-mail: zuotaizhang@pku.edu.cn
b
Beijing Key Laboratory for Solid Waste Utilization and Management, College of
Engineering, Peking University, Beijing 100871, P.R. China
c
WMG, International Digital Laboratory, University of Warwick, Coventry CV4 7AL, UK
discontinuity of the heat supply,9 and many chemical methods
are therefore exploited that are believed to be a promising way
to transfer the in-continuous waste heat into continuous
chemical energy in syngas.1013 Methane reforming10,11 and coal
gasication have been investigated12,13 and the production of
CO and H2 was achieved. Furthermore, it was found that hot
slag can act not only as a heat carrier, but also as a good catalyst
for some chemical reactions.1113 This catalytic activity could
originate from the crystallization behavior of the slag, which
actually should be avoided from the point of view of material
recycling of the solid slag. Although syngas production was
achieved, the recycling of the material resources of slag has
received only limited discussion in these studies.1113
Biomass is believed to be a promising primary energy
resource for the near future because of its wide availability,
renewability in nature and CO2-neutrality.14,15 In China, the
amount of crop residues was more than 803 million tons in
2009 (ref. 16) and the government attaches great importance to
the usage of biomass energy. Recently biomass gasication
technologies have been extensively investigated and conven-
tionally four reactive agents are widely used, i.e. air,17 oxygen,18
steam19,20 and carbon dioxide,21 or mixture of these.17,18,22 A xed
bed system is widely used to perform the biomass gasica-
tion14,20,22 and generally the content of syngas is detected by a
gas analyzer.14,20 Recently, the co-gasication between biomass
and other energy resources, such as bituminous coal and
petroleum coke have been extensively studied and the

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synergistic eects of dierent gasication materials have been

0.02
value (MJ kg1)
Higher heating

Cl
identied.18,23 The objective of an ongoing investigation by the
current authors is to explore an emerging heat recovery method,
low temperature biomass gasication using hot slag, consid-

16.48

Al2O3
ering both the waste heat recovery and the material recycling of

0.92

0.26
K2O
the slag.
To recover the waste heat of slag, a multi-stage control
method was proposed in our previous work24 and property
changes of slag during the cooling process were studied.25 The

0.11

Fe2O3
whole temperature range of the slag could be divided into a
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MnO
1.07

0.36
liquid region, crystallization region and solid region. Generally,
the temperature for biomass gasication is lower than
1000
C,14 which is located in the solid region and it is therefore

0.81
possible that the hot slag can be used as a heat carrier for

N
biomass gasication. While the advantageous role of the

Na2O

TiO2

0.45
1.11
thermal energy in the slag is obvious, it is not known whether
the presence of slag could hinder biomass gasication or even
exhibit a possible catalytic eect, and therefore the present

49.52
study was motivated. Moreover, there is a great challenge in the

Na2O
steel industry to meet CO2 targets,26 which increases the

0.54
P2O5

1.35
possibility of using biomass gasication to recover waste heat
from hot slag. The produced CO and H2 can potentially be used
directly as a reactive gas to reduce iron in the steel industry.27 In

4.80
Ultimate analysis/%

H
this study, a mixture of oxygen and steam was used to perform

Fe2O3
the gasication, which has been proven as a good medium to

2.12

0.60
perform biomass gasication elsewhere,18,28 and a series of non-

S
isothermal and isothermal experiments were conducted using

41.37
samples with various biomass/slag (B/S) ratios. This may
C
provide a pathway for waste heat recovery from slag and

MgO

0.92
biomass utilization.

2.38

S
2. Materials and methods
Fixed carbon

2.1. Materials analysis

15.93

Al2O3
3.30

8.56
The wheat straw, a typical agricultural residue in Central China,
Cl

was collected from Henan province. The results of ultimate and

proximate analyses are listed in Table 1. Based on the ultimate
analysis, the chemical formula of the raw material is derived as
CH1.39O0.90. This study was mainly focused on the characteris-
9.88
Ash

15.62
CaO

6.14

MgO

tics of the syngas release, including the syngas yield and release
Characteristics of the wheat straw and BF slag

kinetics; however, it should be pointed out that the pressure of

the gases during gasication could remarkably increase due to
release of the high content of volatile components in biomass,
Volatile

which may show some specic utilization for energy generation

74.20

20.09

34.61
K2O

SiO2

and could be the subject of our future work. Before gasication,

Proximate analysis/%

the wheat straw was crushed into particles of sizes less than 200
meshes using a rotary cutting mill and then dried for 24 h at
105
C. Water-quenched blast furnace (BF) slag from Shougang
Corporation, China, was used and the chemical composition
Moisture

53.76

37.88
SiO2

was analyzed using X-ray uoroscopy (XRF, S4-Explorer,

CaO
5.73

Bruker), as shown in Table 1. BF slag alone accounts for more

than 70% of the energy from slags6 and therefore this study
concentrated on BF slag. Before mixing, the slag was crushed
and ground to 200 meshes and characterized by X-ray dirac-
Slag (XRF)
Ash (XRF)

tion (XRD, D/Max 2500, Rigaku) techniques to conrm the

Biomass
Table 1

glassy state. A series of gasication experiments were performed

using 0.1 g, 0.25 g and 0.5 g of biomass and it was found that

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under the present experimental conditions, the syngas
production including CO, H2 and CH4 showed a good linear
relationship versus the biomass amount. In the present work,
0.25 g of wheat straw was used with B/S mass ratios of 1 : 0 (S1),
1 : 1 (S2) and 1 : 3 (S3) for each gasication process.
2.2. Crystallization analysis of BF slag
According to our previous work,24,25 an understanding of the
crystallization behavior of the slag is fundamental to the
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steam generator, a tube furnace reactor, a gas condenser and
purier, and a gas analyzer, as shown in Fig. 1. A quartz tube
reactor, with a length of 110 mm and an inner diameter of 30
mm, was used in this study, and was externally heated by an
electric furnace. Quartz boats were used to hold the reactants.
The ow rate of the gasication agent was 300 ml min1,
with an oxygensteam ratio of 30 : 70. In order to ensure that
the inlet gas composition had an accurate oxygensteam ratio of
30 : 70, the temperature of the humidier (steam generator) was
accurately controlled to be 90
C and then the oxygen owed

exploitation of reasonable waste heat recovery methods.

through the humidier at a ow rate of 90 ml min1 to obtain a
Isothermal experiments were carried out using a Single Hot
gasication agent of 90 ml oxygen and 210 ml steam; mean-
Thermocouple Technique (SHTT) for visualizing the phase
while, to avoid condensation of the steam, the pipe that the
transformation and measuring the crystallization behaviors of
gasication agent ows through was heated to 120
C using
the slag. The procedure is briey introduced here.29 The slag
heating tape. In order to clarify the eect of slag on biomass
was rst melted by heating it to 1550
C, and holding it at this
gasication, both non-isothermal and isothermal experiments
temperature for 120 s to eliminate the bubbles and homogenize
were performed. For the non-isothermal processes, the quartz
the chemical composition; then the liquid slag was rapidly
boat was rst placed in the middle of the tube and the gasi-
quenched to a holding temperature and it then took some time
cation agent was then pumped into the system to fully expel the
to crystallize, dened as the incubation time. All of the
air. The furnace was then heated from room temperature (25
C)
processes were performed in an air atmosphere. Generally, the
to 1000
C at a rate of 10
C s1, during which the gasication
relationship between incubation time and holding temperature
reaction occurred. For the isothermal experiments, the quartz
is presented in a Time Temperature Transformation (TTT)
boat was rst loaded onto the right-hand side of the tube and
curve. Based on the TTT curve, the temperature range for the
the reactive agent was then pumped into the system to fully
slag characteristics could be divided into three regions, which
expel the air. When the temperature reached the holding
are the liquid region, crystallization region and solid region,
temperature, the quartz boat was rapidly pushed into the
respectively. This provided the scientic basis for waste heat
middle of the tube to start the gasication process. Aer puri-
recovery from slag and also favors the selection of reasonable
cation by a gas condenser and purier, the volume and
gasication conditions. It should be pointed out that recrys-
composition of the syngas was detected by the gas analyzer
tallization also occurs as the solid slag is heated to a certain
(Testo pro350, Testo). The morphology and the facial distribu-
temperature, the recrystallization temperature. This tempera-
tion of the elements of the slag/ash aer gasication were
ture represents the stability of the solid slag, which can be
measured using scanning electron microscopy (SEM) along with
measured using thermogravimetric-dierential thermal anal-
energy dispersive X-ray spectroscopy (EDX) (Hitachi S4800,
ysis (TG-DTA, S60/58341, Setaram).
Bruker); simultaneously, the BrunauerEmmettTeller (BET)
surface area of the slag/ash was measured using a surface area
2.3. Gasication apparatus and setup and pore size analyzer (ASAP 2010, Micrometrics).
Gasication processes were carried out in a xed bed system,
which was mainly composed of a reactive gas control part, a

Fig. 1 Schematic of the biomass gasication system.

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3. Results and discussion
3.1. Crystallization behavior of the slag
The TTT curve for the slag presents the crystallization ability of
the slag, which mainly determines the further utilization of the
solid slag. If the cooled slag is to be utilized for applications
such as cementitious materials, then a glassy structure is
required. As can be seen in Fig. 2, the TTT curve shows a double
C shape, which suggests that two dierent crystallization
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recrystallization temperature of the glassy slag was determined
as 790
C using a TG/DTA method, which divided the solid
region into stable region and non-stable regions. To avoid
crystallization and ensure the further recycling of the slag, the
gasication should be performed at temperatures below 790
C.
Therefore, the present gasication temperatures were selected.
3.2. Non-isothermal gasication

events occurred. Additionally, several characteristics relating to During the non-isothermal process, gas release was detected
the crystallization behavior of the slag can be derived based on using a gas analyzer and the transient behavior of the biomass
the TTT curve. First, the highest temperature that a crystal could gasication was recorded. Fig. 3 shows the transient and
form in the slag melt was 1270
C, which was dened as the cumulative syngas production curves, and it can be seen that
crystallization temperature and second, the lowest temperature the syngas was released in a specic temperature region. At
that the crystallization phenomenon could be observed was at 250
C the gas release started and at 500
C the gas release
920
C. It should be pointed out that there is a slight kink at was complete; a peak in the gas release curve can be identied
1160
C, namely the nose position, which signicantly char- at 320
C. The results show that, when comparing S1, S2 and
acterizes the crystallization behavior of the slag. At the
temperature of this position, the incubation time is the shortest
and it is easy for crystals to form in the slag. Based on these
temperature points, the temperature regions of the slag cooling
path can be reasonably dened.24,25 The region at 15501270
C
was dened as the liquid region, in which the slag would be
expected to be in a completely liquid phase. The region between
1270
C and 920
C was dened as the crystallization region, in
which crystals could form in the slag. The region below 920
C
was dened as the glassy region, in which the slag would be
expected to be in a glassy phase, and there was no crystal
precipitation, because of the high resistance to mass transfer of
ions in the slag.
These results derived from the TTT curve are indicative of a
two-step heat recovery process from the hot slag. First, the
liquid slag would be granulated into small particles and rapidly
cooled to a temperature below 920
C, to avoid crystallization;
the waste heat in this region can be extracted through heat
exchange between the hot slag and the air (or steam). Second,
the solid slag would be made to come into contact with ground
biomass and the waste heat could enable gasication to occur.
The temperature region below 920
C covers the temperature
region generally used for biomass gasication.14 Moreover, the

Fig. 3 Non-isothermal syngas release curves for samples (a) S1, (b) S2
Fig. 2 The crystallization behavior and cooling path of BF slag. and (c) S3.

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S3, the onset of the gasication temperature was delayed with

the addition of slag.
Biomass gasication can generally be divided into two
stages, de-volatilization and char reaction,2022 and the former is
especially important because of the high content of volatile
components in biomass. This phenomenon was also observed
in the present work (Fig. 3). It can be seen that the syngas
release curve can be separated into two regions; the former
region of the gas release curve for the three samples was sharp,
whereas the latter region of the gas release curve was at. This
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may suggest that there were two reaction steps in the biomass
gasication even though it was hard to completely separate de-
volatilization and the char reaction.20 From the curves of
cumulative syngas production, it can be seen that the order of
the syngas component amounts was CO > CH4 > H2. It is also
noted that the amount of syngas production slightly increased
with the addition of slag, which is also clearly observed in the
isothermal experiments.

3.3. Isothermal gasication

3.3.1. Kinetics of syngas release. The isothermal experi-
ments were performed at 250500
C. Fig. 4 shows the transient
syngas release and calculated cumulative syngas production
curves obtained at 400
C. Transient curves at the dierent
temperatures showed a similar shape and therefore only the gas
release curve at 400
C is presented here as a typical example. It
can be seen that the produced gases showed an order of CO >
CH4 > H2 for the amount produced and that the gas release
curves showed the characteristic shape composed of a sharp
side in the former stage and a at side in the latter stage. This
indicated that the gas release process was composed of at least
two stages, namely de-volatilization and char reaction.2022 The
de-volatilization process accounted for the main method of gas
release because of the high content of volatile components in Fig. 4 The transient and cumulative syngas production curves
the biomass, and so the transient curve for the gasication obtained at 400
C for samples (a) S1, (b) S2 and (c) S3.
process is mainly composed of one sharp peak. The char reac-
tion occurred at a slow rate and lasted for a long time due to the
x
low gasication temperature, and therefore the latter stage of
dx

F x k T t (2)
the curve showed a at shape. These curve shapes for the 0 f x
transient gas production are similar to those in a previous study
where F(x) is the integral mechanism function. By analyzing the
on the gasication of pine wood chips.20 Additionally, the whole
linear relationship between F(x) and t using dierent mecha-
gas release process was rapidly completed within several
nism functions, the most probable reaction mechanism could
minutes.
be obtained. By plotting F(x) versus t using various mechanism
In this study, the apparent kinetics of biomass gasication
functions, including nucleation growth, chemical reaction and
were interpreted. The common type kinetic equation can
mass diusion, and comparing the correlation coecients (R2)
generally be written as follows:3032
of all of the plots, it was found that the experimental data could
dx

 be reasonably reproduced using an AvramiErofeev model (eqn
k T f x (1)
dt (3)) for sample S1 and a three-dimensional diusion model (eqn
where x is the conversion degree of the syngas which is deduced (4)) for samples S2 and S3 (Fig. 5).
by the division of the total syngas production by the syngas
production at a certain time point, t is time, k is the apparent F(x) ln(1  x) (3)
gasication rate constant, T is the absolute temperature, and
F(x) [1  (1  x)1/3]2 (4)
f(x) is the dierential function of the reaction mechanism.
Alternatively, by rearranging eqn (1) and integrating, the
following equation can be deduced:

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Fig. 5 Mechanistic models for the samples: (a) an AvramiErofeev
model for sample S1, (b) three-dimensional diusion models for
samples S2 and S3.
The AvramiErofeev model is generally applicable to mate-
rials whose porosity changes during the reaction31,32 and the
rate-controlling step is a nucleation process, which is likely to
occur for the biomass gasication because of the high content
of volatile components. As for samples S2 and S3, the presence
of the slag suppressed the contact between the biomass and the
reactive atmosphere, which increased the resistance of mass
transfer; therefore the rate-controlling step would shi towards
gas diusion, and it is reasonable to use a three-dimensional
diusion model to replicate the biomass/slag gasication
process.
3.3.2. Calculation of syngas production. To investigate the
eect of the gasication temperature and B/S ratio on biomass
gasication, the total syngas production was calculated
according to the transient curves as depicted in Fig. 4. Fig. 6
shows the relationship between syngas production per gram of
biomass and gasication temperature. Firstly, it can be seen
that the syngas yield was closely related to the gasication
temperature. For sample S1, without slag, the production of
syngas slightly increased from 250 to 400
C, while it greatly
decreased from 400 to 500
C. Combustion of the biomass was
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Fig. 6 The major gas yields per gram of biomass in terms of the
gasication temperature .
apparently observed at 500
C, indicating that the char reaction
increased and therefore more CO2 was formed. Secondly, the
optimum temperature between 250 and 500
C for biomass
gasication can be obtained, by viewing the maximum
production of syngas on the graph, which was 450
C for these
samples.
Additionally, it can be observed that the B/S ratio did not
signicantly inuence the gas production at low temperatures
(250400
C). However, there was an apparent increase in
syngas production at 425500
C, which could originate from
the eect of the addition of slag on the reaction of the biomass.
The added slag reduced the contact between the atmosphere
and the biomass, suppressed the biomass combustion and CO2
release, and therefore could indirectly improve the production
of syngas.
3.3.3. Characterization of hazardous gas and solid resi-
dues. In this study, the release of pollution gases, namely NOx
and SO2, was also detected by the gas analyzer and the results
showed that the concentrations of NO2 and NO during the
whole process for all samples were less than 2 ppm and 5 ppm,
respectively, which might result from the low gasication
temperature. Furthermore, no SO2 emission was detected in the
experiments. These low emissions of NOx and SO2 would cause
relatively minor environmental pollution and suggests another
advantage of low temperature biomass gasication using hot
slag.
To further explore the track of the S and N elements, their
facial distributions were measured by SEM with EDX. As shown
in Fig. 7, the S, N and Cl elements were uniformly distributed in
the residual slag/ash. These elements were generated from the
biomass ash (Table 1) and are the characteristic elements of
biomass resources.14,16 In contrast, Si and Ca elements were only
distributed in the slag particles, which are the characteristic
elements of hot slag.6,25 Additionally, Fig. 8 shows the
morphology of the original slag and the slag/ash aer gasica-
tion, and it can be noted that the surface of the slag particles
became coarser aer gasication because biomass ash was
produced which adhered to the slag particle surfaces. Further-
more, the BET surface areas of the slag particles were measured
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Fig. 7 Facial distribution of the characteristic elements in the solid residues.

was uniformly distributed on the surface of slag particles. The

change in surface morphology caused by the adherence of
biomass ash and slag might be the reason for the observed
change in the mechanism towards gas phase diusion control
when slag is added to the biomass.
3.3.4. Thermodynamics of biomass gasication by FactS-
age. The syngas composition and production were greatly
inuenced by the reaction medium and the atmosphere, with
an oxygensteam ratio of 30 : 70 adopted to predict the syngas
formation. The exploration of other reaction mediums is also of
great signicance, and constitutes our future work. The exper-
imental results suggest that the presence of slag does not lower
the degree of gasication under the conditions studied. Thus,
syngas production during biomass gasication using hot slag
could be approximated through calculations by FactSage.34
Considering that the optimum gasication temperature for
these samples was 450
C, the equilibrium syngas production
was calculated at 450
C in dierent atmospheres, as an
example. To simplify the calculation process, the amount of C,
H and O atoms were assumed to be 1 mol, 1.39 mol and 0.90
mol, respectively, and the reactive steam and oxygen amounts
were varied from 0.05 mol to 0.5 mol. Then, the lower heating
value (LHV) of the syngas was calculated according to the
following equation:31,35
Fig. 8 Surface morphology of the slag particles: (a) the original slag
and (b) the slag/ash after gasication (using S3 at 450
C). LHV (30[CO] + 25.7[H2] + 85.4[CH4]
+ 151.3[CmHn])  4.2/1000 MJ Nm3 (5)

Fig. 9(a) shows the calculated syngas production at 450
C for

and it was found that the specic surface area increased from
atmospheres of 70% steam/30% oxygen. It can be observed that
1.25 m2 g1 for the original slag to 2.18 m2 g1 and 2.70 m2 g1
the production of H2 and CH4 greatly decreased, while that of
for the produced mixtures of slag and ash aer gasication of
CO slightly increased, with increasing reactive agent and
sample S3 at 425
C and 450
C, respectively. This suggests that
therefore the total syngas production and the LHV decreased.
the produced biomass ash adhered to the slag surface and
Meanwhile, it should be pointed out that the relative content of
therefore increased the specic surface area of the solid resi-
CO and H2 for the calculations and experimental results were
dues. Because the gasication occurred at relatively low
dierent, which could originate from two factors. The reason
temperatures, the produced biomass ash was in the solid
was mainly due to the simplication and assumptions made
state,33 and could not eectively conglomerate and therefore

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Fig. 9 Calculations of the syngas production: (a) syngas production
and LHVs at 450
C (b) contour of the syngas LHVs (MJ Nm3) for
various atmospheres.
Fig. 10 An integrated concept for the proposed prototype.
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during the FactSage calculations. Furthermore, the syngas
production calculated by FactSage was obtained using the
equilibrium conditions; while during the experimental process,
the produced syngas was instantaneously taken away by the
gasication agent. Fig. 9(b) displays the contour of the LHV in
dierent atmospheres and the dashed line shows the results
from the experimental conditions. It can be seen that the LHV
decreased with increasing oxygen content but increased with
increasing steam content. Thus, the key factor for increasing
the LHV of syngas was to reasonably increase the content of
steam in the reactive atmosphere, and actually, pure steam was
one of the most common reactive atmospheres for biomass
gasication.19,20 Additionally, the LHV of the experimentally
detected syngas for samples S1, S2 and S3 reacted at 450
C was
less than 3.79, 5.24 and 4.17 MJ Nm3, respectively, which was
lower than those calculated by FactSage, which could result
from three factors. Firstly, the amount of the reactive agent used
was much more than that of the theoretical values to obtain
complete gasication of the biomass, which diluted the syngas
and therefore reduced the syngas LHV. Secondly, the excess
oxygen promoted the combustion of the biomass and improved
CO2 production, which also result in a decrease of the syngas
LHV. Thirdly, during the calculation process, the breaking of
the chemical bonds in the biomass was ignored, which could
also cause the dierences in the syngas production. Although
the calculated results diered signicantly from the experi-
mentally measured ones, they provided possible ways to
improve the LHV of syngas.
3.4. Prototype of biomass gasication and heat recovery
from slag
According to our study, an integrated prototype including
multiple industrial systems was proposed, the concept of which
is shown in Fig. 10. The whole process can be divided into
several parts. Firstly, the liquid slag would be granulated into
small particles to increase the surface area and the heat transfer
eciency. Secondly, the slag would be rapidly cooled to 790
C,
This journal is The Royal Society of Chemistry 2014

Paper
to form glassy phases and avoid crystallization. The waste heat
in this stage could be transferred into air or steam for further
electricity production. Thirdly, the slag particles would be
mixed with the ground biomass and the gasication process
would be performed. Fourthly, the syngas would be separated
and directly used in the steel industry or exported to other
applications as a fuel; meanwhile the glassy slag would be
applied as a raw material in the cement industry. Thus, a multi-
system industrial prototype plant for the steel industry, chem-
ical industry and cement industry could be conceptually
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designed, which could simultaneously recover energy and
recycle spent materials.
Moreover, the potential energy savings of this prototype
plant based on low temperature biomass gasication using hot
slag can be calculated. The produced CO and H2 are assumed to
be used for DRI (direct reduced iron) production.27 Based on
Fig. 6, the gasication is assumed to be performed at 450
C
with a mass ratio of B/S of 1 : 1, and therefore 0.149 L CO, 0.036
L H2 and 0.069 L CH4 can be produced per gram of wheat straw.
However, an important issue caused by the biomass ash should
be pointed out. According to Table 1, the Cl and alkalis in the
biomass ash may cause contamination of the slag. In order to
eectively avoid this possible contamination, the B/S mass
ratios could be further decreased in an actual industrial process
and the B/S mass ratios should be adjusted for dierent kinds of
biomass with varying ash content. In China, the output of crude
steel in 2012 was 710 million tons5 and therefore more than 210
million tons of slag was produced with a slag production ratio of
0.3 tons of slag per ton of steel. Therefore 3.13  1010 Nm3 CO,
7.56  109 Nm3 H2 and 1.45  1010 Nm3 CH4 would be
produced and this syngas can transform at least 84.7 million
tons of Fe2O3 into 59.3 million tons of Fe. Accordingly, an
energy saving equivalent to 19.1 million tons of standard coal
would be achieved and CO2 emissions would be reduced by 69.9
million tons. The potential value of the energy saving was even
more than the thermal energy untapped in hot slag, which
results from the oxidation of the biomass. Based on the afore-
mentioned analysis, it can be seen that there is great potential
for energy eciency improvement and reduction in CO2 emis-
sions in the steel industry from heat recovery through biomass
gasication, considering the possible higher syngas production
through further optimization of the conditions.
4. Conclusions
This study proposed an important method of heat recovery from
hot slag for syngas production, namely low temperature
biomass gasication. The transient release and cumulative
production of syngas was claried and the results showed that
the hot slag at 250500
C used as a good heat carrier signi-
cantly inuenced the gasication process. The presence of the
slag did not hinder the degree of gasication, while it altered
the mechanism from an AvramiErofeev model to a three-
dimensional diusion model. The produced biomass ash
adhered to the slag particles, which remarkably increased the
surface area of the slag and agreed well with the variation in the
kinetic mechanism. Moreover, the produced syngas can be
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RSC Advances
applied for DRI production, which could remarkably reduce
energy consumption and CO2 emission in the steel industry,
and a prototype plant made up of multi-systems was therefore
proposed, through which the waste energy and spent material
resources were recovered simultaneously.
Acknowledgements
Support by the National High Technology Research and Devel-
opment Program of China (863 Program, 2012AA06A114), the
Key Projects in the National Science & Technology Pillar
Program (2013BAC14B07), the Common Development Fund of
Beijing and the National Natural Science Foundation of China
(51172003, 51272005 and 51172001) is acknowledged.
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