i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 8 ( 2 0 1 3 ) 1 4 5 5 9 e1 4 5 6 7

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Hydrogen and syngas production from glycerol

through microwave plasma gasification

Sang Jun Yoon a,b, Young Min Yun b, Myung Won Seo a, Yong Ku Kim a,
Ho Won Ra a, Jae-Goo Lee a,*
a
Climate Change Research Division, Korea Institute of Energy Research, 71-2 Jang-dong, Yuseong-gu,
Daejeon 305-343, Republic of Korea
b
Advanced Energy Technology Department, University of Science and Technology, 217 Gajungro,
Yuseong-gu, Daejeon, Republic of Korea

article info abstract

Article history: Glycerol which is a byproduct of biodiesel production is considered as a potential feedstock
Received 3 May 2013 for syngas production with the increase of biodiesel demand. In this study, the charac-
Received in revised form teristics of glycerol gasification under a microwave plasma torch with varying oxygen and
20 August 2013 steam supply conditions were investigated. The experimental results demonstrated that
Accepted 1 September 2013 the gasification efficiency and syngas heating value increased with the supplied microwave
Available online 3 October 2013 power while the increase of oxygen and steam led to a lower gasification performance. In
order to achieve high carbon conversion and cold gas efficiency in the microwave plasma
Keywords: gasification of glycerol, the O2/fuel ratio should be maintained at 0e0.4. It was revealed that
Microwave plasma the fuel droplet size and the mixing effect and retention time inside the plasma flames are
Gasification critical factors that influence the product gas yield and gasification efficiency. This study
Hydrogen verified that syngas with a high content of H2 and CO could be effectively produced from
Syngas glycerol through microwave plasma gasification.
Glycerol Copyright ª 2013, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights
reserved.

1. Introduction 2006. The production of biodiesel is expected to grow contin-

There is increasing interest in the use of new and renewable
energy sources due to limited fossil fuel reserves, oil price
fluctuations, and international regulations on CO2 emissions.
Studies on biomass, which is a CO2 neutral source, are being
actively conducted not only regarding its primary use of
obtaining heat and electricity through combustion, but also
regarding its high value-added use through conversion to
transportation fuels such as biodiesel that can replace petro-
leum. The global production of biodiesel has increased
annually by 32.5% on average from 2000 to 2010 [1]. In
particular, biodiesel production has increased sharply since
ually in the United States and the European Union in order to
attain the goal of replacing 20% and 30% of petroleum-based
diesel with biofuels by 2020 and 2030, respectively [2]. The
method of using transesterification reaction to produce bio-
diesel, which is currently the primary method of biodiesel
production, generates crude glycerol of approximately 10 wt%
as a byproduct. As the generation of crude glycerol is also
expected to grow with the increased production of biodiesel,
the effective use of crude glycerol is important from both
economic and environmental perspectives.
For utilization of crude glycerol, many studies are being
conducted on the conversion of glycerol into valuable

* Corresponding author. Tel.: þ82 42 8603353; fax: þ82 42 8603134.

E-mail address: jaegoo@kier.re.kr (J.-G. Lee).
0360-3199/$ e see front matter Copyright ª 2013, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.ijhydene.2013.09.001
14560 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 8 ( 2 0 1 3 ) 1 4 5 5 9 e1 4 5 6 7
components or energy through various techniques, such as
refinement, purification, pyrolysis, reforming, and gasification.
Among these techniques, energy conversion through gasifica-
tion has advantages in that it does not require catalyst or addi-
tional pretreatment of the crude glycerol [3]. Gasification refers
to the technique of generating syngas that contains H2 and CO
through the partial oxidation of hydrocarbon fuels. As a clean
fuel utilization technique, gasification is being applied to the
production of electricity, hydrogen, and chemical materials
using various fuels, such as coals, waste, and biomass. These
days, various studies on gasification using plasma torches are in
progress [4e6]. For plasma gasification, plasma flames are
formed using external electric energy sources and the fuels are
gasified through plasma flames with high temperatures over
several thousand degrees [7]. Thus, it does not require oxygen or
it requires only a small amount of oxygen, which is required in
the conventional gasification process for the partial oxidation of
fuels in order to maintain the reaction temperature. This de-
creases the burden of the installation and operation of highly
expensive air separation units. Unlike the conventional gasifi-
cation method that raises the temperature of the reactor
through preheating, plasma gasification starts simultaneously
with the activation of a high temperature plasma torch. There-
fore, rapid production of syngas is possible. Furthermore, the
high concentration of active species, such as ions and radicals,
in the plasma state accelerates the gasification reaction [8,9]. As
the reaction is activated, a quick reaction can be induced during
the short retention time of fuels in the reactor, and the size of the
total process can be reduced due to the decreased volume of the
reactor. Most previous studies have focused on the plasma
combustion [9], pyrolysis [10], and gasification [11,12] of various
fuels using arc electrodes. The use of arc electrodes, however,
requires periodic replacement due to the loss of electrodes and is
vulnerable to the oxygen and steam that are used as gasification
agents [9,13]. The use of microwaves as the energy source for
Fig. 1 e Schematic diagram of the microwave plasma glycerol gasification system.
plasma generation exhibits a higher power transfer efficiency
than arc plasma and a high durability because electrodes are not
used [14,15]. Therefore, the reforming and gasification of various
hydrocarbons using microwave plasma torches are being
actively investigated [16e18].
In this study, the gasification characteristics of glycerol
under various conditions using a plasma torch equipped with a
2 kW microwave power generator was investigated. For the
uniformity of fuels and convenient interpretation of the gasi-
fication characteristics, pure glycerol was used instead of crude
glycerol. Nitrogen was used as the plasma forming gas, and the
microwave power for plasma formation was adjusted to
1e2 kW. The variations of the gasification characteristics were
studied with the supply amount of oxygen and steam, which
were used as gasification agents. At this time, the O2/fuel ratio
and steam/fuel ratio are varied 0e1.2 and 0e2.4, respectively.
Furthermore, the changes in the product gas composition and
gasification efficiency were examined when the glycerol was
atomized through the reactor using a spray nozzle.
2. Experimental
In this study, 99% pure glycerol (Duksan Chemical) was used
as a substitute for crude glycerol without further purification.
Fig. 1 presents a schematic diagram of the plasma gasification
system with the 2 kW microwave generator (2.45 GHz, SM745,
Richardson Electronics) that was used in this study. This
system consists of a glycerol preheater and feeder, steam
supplier, gasification agent and plasma forming gas feed unit,
microwave generator, gasification reactor, gas purifier and
analyzer, and data collection unit. The glycerol was supplied
to the reactor constantly at a rate of 3 g/min through a gear
pump (Cole-Parmer, 74014-75). In order to supply glycerol to
the plasma reactor, two methods were used and compared:
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 8 ( 2 0 1 3 ) 1 4 5 5 9 e1 4 5 6 7
the use of a stainless steel tube with an outer diameter of
0.32 cm and the use of an external mixing nozzle as shown in
Fig. 2. To improve the fluidity and spray stability of the glyc-
erol, it was preheated to 140  C with a heater before it was
supplied to the nozzle and reactor. When using the nozzle, N2
was used as the spray gas for atomization of the glycerol and
its flow was adjusted to 2.0e3.5 L/min using a mass flow
controller (MFC, Brooks 5850). Nitrogen was used as the
plasma forming gas, which was supplied at 15 L/min through
a MFC. Oxygen was used as the gasification oxidizer, which
was quantitatively supplied at 0e2.6 L/min using a MFC ac-
cording to the experimental conditions. The steam that was
used as the gasification agent was supplied to the reactor at
0e7.2 ml/min using a syringe pump and the feed line was
maintained above 100  C using a band heater so that the
steam would be supplied to the reactor. The plasma forming
gas, oxygen, and steam were supplied to the reactor with a
diameter of 2.54 cm via a swirl-flow in order to increase the
retention time in the reactor and to allow stable formation of
the plasma flames while reducing the thermal shock of the
reactor. The glycerol was supplied in the reactor 2 cm away
from the point where the forming gas and microwave met and
formed plasma flames. To measure the temperature at each
reactor location, two R-type and five K-type thermocouples
with an accuracy of 0.1  C were installed in 5 cm intervals
from the glycerol feeding location. To remove the unburned
carbons, ashes, and moisture from the syngas generated by
the plasma gasification reaction, the syngas was passed
through a cyclone and filter before it was supplied to the gas
chromatograph (GC, HP 6890) for quantitative and qualitative
analyses in real time. A thermal conductivity detector (TCD,
Carbosphere 80/100 Packed column, Alltech) was used to
analyze the product gases, such as H2, CO, CO2, CH4, and N2.
These product gases were quantitatively and qualitatively
calibrated using standard gases with various compositions
and concentrations prior to use in the experiments. Every
experiment was performed at least twice in atmospheric
conditions, and the results were averaged. The relative stan-
dard deviations were less than 5%.
3. Results and discussion
3.1. Glycerol feed using tube
3.1.1. Effect of the O2/fuel ratio
Fig. 3 shows the composition changes of the syngas gener-
ated through the microwave plasma gasification according to
the changing O2/fuel ratio when the glycerol was supplied to
the reactor through a tube. The steam/fuel ratio and micro-
wave power were maintained constant at 0.8 and 1.6 kW,
respectively. When the glycerol was supplied through a tube,
it fell continuously as droplets and reacted in the plasma
flames. The results showed that as the O2/fuel ratio
Mass flow rate of syngas  higher heating value of syngas
h ð%Þ ¼
Mass flow rate of feedstock  higher heating value of feedstock
14561
increased, the H2 content in the syngas linearly decreased.
The CO content remained constant at 35% until an O2/fuel
ratio of 0.6 and then it decreased. The CO2 content increased
with the O2/fuel ratio and began to rapidly increase when the
O2/fuel ratio exceeded 0.6. The CH4 exhibited a low content in
the syngas at 2% or lower and tended to decrease as the O2/
fuel ratio increased. This indicates that as the O2/fuel ratio
increased, the combustion reaction was activated, which
increased the CO2 content. Furthermore, the combustion re-
action following the increase of the O2/fuel ratio increased
the reactor temperature and the CH4 content in the syngas
decreased due to the decomposition. These changes of the
syngas composition can be divided into three categories ac-
cording to the O2/fuel ratio. The O2/fuel ratio range from 0 to
0.3 was where the primary water gas reaction in Eq. (1) and
the secondary water gas reaction in Eq. (2) were most acti-
vated. Therefore, a high content of H2 and CO was exhibited
in the syngas. The O2/fuel ratio range from 0.3 to 0.8 was
where various gasification reactions, such as combustion and
the water gas shift reaction, occurred with the reactions in
Eqs. (1) and (2). Finally, the O2/fuel ratio range above 0.8 was
where the complete combustion reaction was dominant
[19,20]. For this reason, a large CO2 content was detected with
small quantities of H2 and CO in the syngas.
C þ H2O 4 CO þ H2, DH ¼ 131.3 kJ/mol (1)
C þ 2H2O 4 CO2 þ 2H2, DH ¼ 90.2 kJ/mol (2)
These changes in the syngas composition according to the
O2/fuel ratio were similar to those in the conventional gasifi-
cation, which does not use a plasma torch [21e23]. That is, the
reaction mechanism that occurred in the plasma gasification
is similar to that of the conventional gasification. However,
unlike the traditional gasification method that maintains the
reaction temperature by partial oxidation of the fuel, the
plasma gasification that uses high temperature plasma flames
formed by electric energy as the gasification heat source can
be operated without an oxygen supply. When an oxygen
supply was not present and the O2/fuel ratio was 0, the
composition of the plasma gasification product gas of glycerol
was H2 57%, CO 35%, CO2 6%, and CH4 2%. Hence, the plasma
gasification of glycerol could produce syngas with a low CO2
content and a high content of combustible gases.
Fig. 4 shows the variation of the syngas heating value,
carbon conversion, and cold gas efficiency during the micro-
wave plasma gasification of glycerol according to the O2/fuel
ratio. The carbon conversion (Xc) and cold gas efficiency (h),
which is the thermodynamic efficiency indicator of the gasi-
fication process, are defined as follows:
Mass flow of carbon in the syngas
Xc ð%Þ ¼  100 (3)
Mass flow of carbon in the feedstock
 100 (4)
14562 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 8 ( 2 0 1 3 ) 1 4 5 5 9 e1 4 5 6 7

100 4000

Carbon conversion and cold gas efficiency (%)

Syngas heating value (kcal/Nm3)

80
3000

60

2000

40
Carbon conversion
Cold gas efficiency
1000
Syngas heating value
20

0 0
0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4

O2/fuel

Fig. 4 e Effect of the O2/fuel ratio on syngas heating value,

carbon conversion, and cold gas efficiency (feeding of
glycerol using tube).
Fig. 2 e Schematic diagram of the gaseliquid nozzle for
glycerol spray.
the increased product gas yield after the fuel reaction and to
the increased production of CO and CO2. The cold gas effi-
As the O2/fuel ratio increased, the carbon conversion ciency tends to increase with an increased amount of product
increased while the syngas heating value and cold gas effi- gas due to the rising reactor temperature until a certain oxy-
ciency decreased. As shown through the syngas composition gen supply, after which, due to the activated combustion re-
changes in Fig. 3, as the O2/fuel ratio increased, the oxygen action and the decreased content of combustible gases such
supply to the reactor increased and the combustion reaction as H2 and CH4 in the syngas, the syngas heating value and cold
was activated, which in turn increased the CO2 production gas efficiency in turn decreases [22e25]. This suggests that
and carbon conversion. However, the decreased content of with the conventional gasification, the rising reactor temper-
combustible gases in the product gas sharply decreased the ature that results from the oxygen supply has a greater effect
syngas heating value as well as the product gas yield, thereby on the fuel conversion than on the decreased retention time in
rapidly decreasing the cold gas efficiency. the reactor. On the other hand, with the plasma gasification in
The oxygen supply in the gasification reactor activates the this study, the increase of the O2/fuel ratio increased the
combustion reaction of the fuel and simultaneously increases carbon conversion and decreased the cold gas efficiency.
the reactor temperature. Furthermore, the rising reactor Because plasma gasification uses the high temperature of the
temperature decreases the retention time of the fuel and re- plasma flame, unlike the conventional gasification, the reac-
actants in the gasifier due to the increased gas velocity in the tion of feedstock in the plasma flame is very important. An
reactor. In the conventional gasification process, which does increase in the oxygen supply increases the reaction tem-
not use a plasma flame, as the oxygen supply to the reactor perature, but as mentioned above, it also increases the flow
increases, the carbon conversion generally increases due to velocity in the reactor with the same volume, thereby
decreasing the retention time of the reactants in the plasma
flames. Therefore, in plasma gasification, in which the contact
100 and retention time in high temperature plasma flames is
H
90 important, the increase in the oxygen supply decreased the
Syngas composition (vol %, dry, N 2 free)

CO
80 CO cold gas efficiency.
70 CH Compared with the gasification of coals using microwave
plasmas as presented in the literature, the plasma gasification
60
results of glycerol had higher carbon conversion and cold gas
50
efficiency [9,26]. This is because glycerol, which consists of
40 volatile matter with good reactivity even at low temperatures,
30 can be gasified more easily than coals that contain fixed car-
20 bon with lower reactivity, which reacts at high temperatures.
10
When compared with the gasification of crude glycerol in an
entrained flow gasifier that does not use plasma, plasma
0
gasification had a different tendency in gasification efficiency
0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 variation, although there was a difference in the process scale.
O2/fuel For the entrained flow gasification, the carbon conversion
increased as the O2/fuel ratio increased, and the cold gas ef-
Fig. 3 e Effect of the O2/fuel ratio on syngas composition ficiency peaked at an O2/fuel ratio of approximately 0.7 [3].
(feeding of glycerol using tube). However, as shown in Fig. 4, the plasma gasification of the
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 8 ( 2 0 1 3 ) 1 4 5 5 9 e1 4 5 6 7 14563

glycerol had a high carbon conversion and cold gas efficiency by supplying a reactant with a temperature lower than the
at an O2/fuel ratio of 0e0.2. This implies that the plasma reactor temperature [28e31]. Furthermore, it typically in-
gasification process should be undertaken at a lower O2/fuel creases the gas flow rate by increasing the amount of re-
ratio than the conventional gasification process. actants supplied to the reactor. The increase of the gas flow
rate increases the flow velocity and decreases the fuel reten-
3.1.2. Effect of the steam/fuel ratio tion time in the reactor. The reason that there was no change
Fig. 5 shows the variation of the syngas composition produced in the composition of product gas at a steam/fuel ratio of 1.6 or
after the plasma gasification of glycerol according to the higher seems to be that due to the excessive steam supply, the
change in the steam/fuel ratio at an O2/fuel ratio of 0.6 and a decreased fuel retention time was not sufficient for the WGSR
microwave power of 1.6 kW. In the results, as the steam/fuel of the CO that was generated from the reaction of steam and
ratio increased, the H2 and CO2 content in the product gas carbon in the fuel.
increased while the CO content decreased. The CH4 content Fig. 6 presents the changes in the syngas heating value
was less than 1% and it did not change significantly according produced from the plasma gasification of glycerol, carbon
to the steam/fuel ratio. The reactions that can occur in the conversion, and cold gas efficiency according to the steam/
gasifier as a result of the steam injection can be categorized as fuel ratio. When the H2 and CO generation mechanism, which
the reaction of steam and carbon in the fuel and the reaction resulted from the reaction of steam and carbon in the fuel, is
of steam and CO in the gas. The reaction of steam and carbon dominant as the steam supply increased, the carbon conver-
is an endothermic reaction that generates H2 and CO, whereas sion and cold gas efficiency increased. In contrast, the
the reaction of steam and CO is an exothermic reaction that decrease in the reaction temperature and fuel retention time
generates H2 and CO2. When steam is fed with fuel into the in the reactor due to the steam supply decreased the product
reactor, the endothermic reaction of steam and carbon occurs gas yield. Furthermore, the heating value of the syngas
first, and the CO in a gaseous state produced from the fuel decreased when the H2 and CO2 production increased as the
reacts with the residual steam, causing a wateregas shift re- CO content in the syngas decreased due to the WGSR. These
action (WGSR), which is an exothermic reaction. Thus, the decreases in product gas yield and heating value result in a
composition of H2, CO, and CO2 in the product gas changes decrease in the carbon conversion and cold gas efficiency. In
according to the amount of steam supplied to the reactor. For this way, the variation tendencies of the carbon conversion
glycerol, which only consists of volatile matter, because the and cold gas efficiency according to the increase of the steam
WGSR occurs as the steam reacts with the CO produced by the supply differ according to the type and method of the gasifier,
fast reaction of steam and carbon, the H2 and CO2 content in and the fuel characteristics [22,32,33]. The results in Fig. 6
the product gas increased with an increasing supply of steam show that in the plasma gasification of glycerol, the syngas
to the reactor, while the CO content decreased. However, the heating value, carbon conversion, and cold gas efficiency
variable range of gas content decreased as the steam/fuel ratio decreased as the steam/fuel ratio increased. As shown in
increased, and when the steam/fuel ratio increased from 1.6 Fig. 5, the H2 and CO2 content in the syngas increased with the
to 2.4, the composition of the product gas remained almost increase of the steam/fuel ratio, whereas the decrease of the
unchanged. The steam supply to the reactor not only caused CO content and heating value of the syngas resulted in the
two reaction types between steam and carbon and between decrease of the carbon conversion and cold gas efficiency. It
steam and CO, but also changed the reaction temperature. follows that the changes in the gasification efficiency as a
The introduction of a small quantity of steam into the reactor result of the steam supply in the plasma gasification were
increased the gas temperature [27,28]. However, usually, the dominated by the temperature, the length of the plasma
increased steam injection decreases the reaction temperature flames, and the fuel retention time. The results in Fig. 4 also
demonstrate that the increase of the oxygen supply to the
reactor raised the reactor temperature, but the cold gas
50
Syngas composition (vol %, dry, N2 free)

100 2600
Carbon conversion and cold gas efficiency (%)

40

90 2400
Syngas heating value (kcal/Nm )

30

80
2200
20 H Carbon conversion
CO 70 Cold gas efficiency
Syngas heating value 2000
CO
10 CH
60
1800

0
50
1600

40
0.0 0.5 1.0 1.5 2.0 2.5 3.0 0.0 0.5 1.0 1.5 2.0 2.5 3.0

Steam/fuel Steam/fuel

Fig. 5 e Effect of the steam/fuel ratio on syngas Fig. 6 e Effect of the steam/fuel ratio on syngas heating
composition. value, carbon conversion, and cold gas efficiency.
14564 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 8 ( 2 0 1 3 ) 1 4 5 5 9 e1 4 5 6 7

efficiency diminished due to a decrease of the fuel retention 100 2500

Carbon conversion and cold gas efficiency (%)

time in the plasma flames. This shows that for plasma gasi-
90
fication using high temperature plasma flames, the fuel

Syngas heating value (kcal/Nm )

2300

3
retention time has a significant effect on the gasification re- 80
action and efficiency.
2100
70

3.1.3. Effect of the microwave power

60
One of the major parameters that affect the performance of 1900

plasma gasification is the microwave power. Microwave 50

power is closely associated with the gasifier temperature, the Carbon conversion 1700
40 Cold gas efficiency
plasma flames size, and the plasma density. An increase in Syngas heating value
the microwave power increases the plasma flame diameter
30 1500
and length [34], the reactor temperature [35,36], and the 0.8 1.0 1.2 1.4 1.6 1.8 2.0

plasma density, especially the electron density [37]. That is, Power (kW)

the increase in the glycerol retention time in high temperature

Fig. 8 e Effect of the microwave power on syngas heating
plasma flames and the increase of active species, such as
value, carbon conversion, and cold gas efficiency.
electrons and ions, affect the composition of the product gas
and the gasification efficiency.
Fig. 7 shows the effects of the microwave power on the
composition change of the plasma gasification product gas of from 1900 kcal/Nm3 to 2200 kcal/Nm3 because, as shown in
glycerol at constant O2/fuel and steam/fuel ratios of 0.6 and Fig. 7, the content of combustible gases such as H2 and CO in
0.8, respectively. As the microwave power increased from 1 to the product gas increased according to the increase in the
1.8 kW, the H2 and CO content in the syngas increased and the microwave power. In contrast, the carbon conversion and cold
CO2 content decreased. The same tendency can be found in gas efficiency increased almost linearly as the microwave
the gasification of coals and waste using arc plasma [36,38]. power increased because with a microwave power of over
The CH4 content in the product gas was approximately 1% and 1.2 kW, the syngas heating value did not change significantly,
it decreased as the microwave power increased. This shows but the syngas production yield increased continuously.
that, as with general gasification at high temperatures, the When the microwave power was changed from 1 to 1.8 kW,
increase of the gasification temperature and active species the carbon conversion and cold gas efficiency increased by
due to the increase in the microwave power decomposes CH4 more than 20%. At a microwave power of 1.8 kW, almost 100%
into H2 and CO. Furthermore, the water gas reaction as of the carbon conversion and more than 62% of cold gas effi-
described in Eq. (1) was activated, which increases the pro- ciency was achieved. In the literature, the length and diameter
duction of H2 and CO. of the plasma flames were linearly proportional to the mi-
Fig. 8 presents the changes of the syngas heating value, crowave power [34]. Thus, the increased volume of high
carbon conversion, and cold gas efficiency according to vari- temperature flames increased the fuel retention time in the
ations in the microwave power. When the microwave power plasma flames and the reaction temperature, which improved
was increased from 1 to 1.2 kW, the heating value of syngas the gasification efficiency.
sharply increased, and then it increased slowly as the micro- As shown in the results of Figs. 7 and 8, increasing the
wave power increased further. When the microwave power microwave power can improve the combustible gases con-
changed from 1 to 1.8 kW, the syngas heating value increased tent, syngas heating value, gas yield, conversion rate, and
efficiency. However, because it increases the power con-
sumption for the gasification of the same amount of fuel, an
50 appropriate microwave power must be used according to the
feeding amount and heating value of the fuel.
Syngas composition (vol %, dry, N 2 free)

40
3.2. Glycerol feed using nozzle
30
3.2.1. Effect of the nozzle spray gas flow rate
Figs. 3e8 presented the plasma gasification results using a
20
H tube for the glycerol supply to the reactor. Using the tube, the
CO
glycerol falls continuously as droplets into the plasma flames
CO
10
CH and reactions occur. When a smaller glycerol drop size is
supplied to the reactor, a faster reaction can be expected due
0 to the increased reaction surface area. Furthermore,
increasing the reaction surface area through fuel atomization
can improve the gasification efficiency. Thus, the gaseliquid
0.8 1.0 1.2 1.4 1.6 1.8 2.0
nozzle described in Fig. 2 was used to spray the glycerol into
Power (kW)
the plasma flame. Supplying the glycerol as fine particles or
Fig. 7 e Effect of the microwave power on syngas mist can increase not only the contact surface of the glycerol
composition. particles with the high-temperature plasma flames but also
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 8 ( 2 0 1 3 ) 1 4 5 5 9 e1 4 5 6 7 14565

the reaction surface area of the glycerol with the gasification 100 2400

Carbon conversion and cold gas efficiency (%)

agents such as oxygen and steam.
In the plasma gasification of glycerol using a gaseliquid 90

Syngas heating value (kcal/Nm )

3
2300
nozzle, the feed ratio of liquid and spray gas in the nozzle
80 Carbon conversion
determines the size of the sprayed liquid particles, which can Cold gas efficiency
Syngas heating value
affect the gasification reaction and efficiency. Hence, before
70 2200
comparing the results of the plasma gasification using a tube
for the glycerol feed, an experiment to verify the appropriate
60
amount of spray gas for the amount of glycerol injection was
2100
performed. The composition changes of the syngas produced
50
after the plasma gasification when the amount of N2 used as a
spray gas was changed from 2 to 3.5 L/min at a constant
40 2000
glycerol supply of 3 g/min, which is identical to the supply 1.8 2.0 2.2 2.4 2.6 2.8 3.0 3.2 3.4 3.6

through a tube, are shown in Fig. 9. The O2/fuel ratio, steam/ Nozzle spray gas (L/min)

fuel ratio, and microwave power in this case were fixed at 0.6,
Fig. 10 e Effect of the nozzle spray gas flow rate on syngas
0.8, and 1.6 kW, respectively. As the spray gas flow rate
heating value, carbon conversion, and cold gas efficiency.
increased, the H2 and CO content in the syngas increased and
then decreased. In contrast, the CO2 decreased at first and
then increased after a spray gas flow rate of 3 L/min. The CH4 spray gas flow rate increased at a constant glycerol feed rate,
content in the syngas was constant at approximately 0.6%. the glycerol was atomized and sprayed into the plasma
These variations of the syngas composition demonstrate that flames, which increased the reaction surface area and ther-
the size of the glycerol particles supplied to the reactor in- mochemical conversion of glycerol. This indicates that the
fluences the plasma gasification reaction. Furthermore, it amount of conversion to syngas increased. On the other hand,
follows from these results that there is an optimum nozzle an excessive supply of the spray gas (N2) to the reactor lowers
spray condition for the improvement of the gasification the reactor temperature. Hence, a spray gas flow rate of 3.5 L/
efficiency. min lowers the reactor temperature and decreases the heating
Fig. 10 shows the changes in the syngas heating value, value and production yield of syngas, which results in a
carbon conversion, and cold gas efficiency according to vari- decrease of carbon conversion and cold gas efficiency.
ations in the nozzle spray gas flow rate, which were calculated Therefore, with the nozzle used in this study, a spray gas flow
from the results in Fig. 9. The syngas heating value, carbon rate of 3 L/min is appropriate for an efficient spray of glycerol
conversion, and cold gas efficiency increased until a nozzle supplied at 3 g/min.
spray gas flow rate of 3 L/min, after which they decreased. By
increasing the nozzle spray gas flow rate from 2 to 3 L/min, 3.2.2. Effect of the O2/fuel ratio
increases in the syngas heating value, carbon conversion, and At a spray gas flow rate of 3 L/min, which exhibited the opti-
cold gas efficiency by 90 kcal/Nm3, 5%, and 6% were achieved, mum efficiency in the plasma gasification of glycerol using the
respectively. The changes of the carbon conversion and cold nozzle described in Fig. 2, the variation of the syngas
gas efficiency according to the spray gas flow rate were greater composition according to the changing O2/fuel ratio was
than those of syngas as seen in Fig. 9. This results from the investigated. The steam/fuel ratio and microwave power were
difference in the product gas yield according to the spray set to 0.8 and 1.6 kW, respectively, which were identical to
conditions of glycerol to the plasma flames. As the nozzle those used in the glycerol plasma gasification that did not use
the spray nozzle in Fig. 3. When this result is compared with
Fig. 3, similar values and variation trends were exhibited for
the syngas composition according to the O2/fuel ratio. How-
40 ever, using the nozzle resulted in higher H2 and CO content in
Syngas composition (vol %, dry, N 2 free)

the syngas by up to 4% and 6%, respectively. In contrast, a

30 lower CO2 content by up to 8% was shown when the nozzle
was used. The reason for this appeared to be that as the re-
action surface area in the high temperature plasma flames
20
H increased due to the reduced particle size of the glycerol
CO supplied to the reactor, the Boudouard reactions in Eq. (5)
CO
10
CH
occurred more. This implies that the reaction ratio in the
various reactions that occurred in the gasifier changed ac-
cording to the glycerol supply conditions.
0

C þ CO2 4 2CO, DH ¼ 172.5 kJ/mol (5)

1.8 2.0 2.2 2.4 2.6 2.8 3.0 3.2 3.4 3.6
The changes in the syngas heating value, carbon conver-
Nozzle spray gas (L/min)
sion, and cold gas efficiency of the glycerol plasma gasification
Fig. 9 e Effect of the nozzle spray gas flow rate on syngas according to the O2/fuel ratio variation were examined when
composition. the glycerol was supplied to the reactor using a nozzle. In this
14566 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 8 ( 2 0 1 3 ) 1 4 5 5 9 e1 4 5 6 7
case, the carbon conversion and cold gas efficiency increased
by up to 4.5% and 7%, respectively. This resulted from the
increased product gas yield and increased combustible gases
content, such as H2 and CO, in the syngas through using a
nozzle. Therefore, large commercial scale plasma gasification
plants should implement a glycerol supply method that uses a
nozzle for improved efficiency and continuous supply and
uniformity of fuels.
4. Conclusions
In this study, the microwave plasma gasification characteris-
tics of glycerol, which is a byproduct of biodiesel production,
were investigated at various operating conditions. At a zero
O2/fuel ratio condition, it is possible to produce a syngas with
a high H2 and CO content of 57% and 35%, respectively. In
these conditions, the highest cold gas efficiency was achieved,
but the lowest carbon conversion of approximately 80% was
shown. As the O2/fuel ratio increased, the cold gas efficiency
rapidly decreased while the carbon conversion increased.
Therefore, the O2/fuel ratio should be controlled between
0 and 0.4 in order to achieve a high carbon conversion and cold
gas efficiency in the microwave plasma gasification of glyc-
erol. When the steam/fuel ratio was increased, the H2 content
in the syngas increased, whereas the syngas heating value
and gasification efficiency decreased. Increasing the micro-
wave power increases the H2 and CO content in the syngas
and it leads to increased syngas heating value, carbon con-
version, and cold gas efficiency. When the microwave power
was increased from 1.0 to 1.8 kW, the carbon conversion and
cold gas efficiency improved by more than 20%. When glycerol
was supplied to the reactor using a gaseliquid nozzle, the H2
and CO content in the product gas increased while the CO2
content decreased. Furthermore, the carbon conversion and
cold gas efficiency improved by up to 4.5% and 7%, respec-
tively. The experimental results indicate that the reaction
mechanism in the plasma gasification is similar to that in
conventional gasification. However, unlike conventional
gasification, the fuel retention time in the plasma flames is a
critical factor that influences the product gas yield and gasi-
fication efficiency in plasma gasification that uses the high
temperature plasma flames.
Acknowledgments
This research was supported by the Energy Technology
Development project of the Ministry of Knowledge Economy
and was partially conducted under the framework of Research
and Development Program of the Korea Institute of Energy
Research (KIER) (B3-2423-01).
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