The 3rd International Symposium on Engineering, Energy and Environments

Pullman King Power Hotel, Bangkok: 17-20 November 2013

Carrier gas in plasma reforming of glycerol for
hydrogen production
Malee Suntikunaporn*, Chitsanupong Dilokwongwattanan

Department of Chemical Engineering, Faculty of Engineering,
Thammasat University, 99 Paholyothin Rd.,Klong Luang, Patumthani 12120, Thailand

Abstract
Glycerol is a by-product that represents 10 wt.% of the total amount of biodieselproduced.
Therefore when demand for biodiesel increases, the glycerols availability alsoincreased,
which results in a substantial decrease in glycerols market price. In this work,the parameters
used to operate a dielectric barrier discharge jet plasma reactor wereexamined to improve the
conversion of glycerol into renewable hydrogen at lowtemperature and atmospheric pressure.
The discharge voltage was varied from 5.5 to 6.0kV at the frequency range of 280 to 350 Hz,
power input 15 W and glycerol flow rate of0.015 ml/min. Furthermore, effect of carrier gas
on production of hydrogen was alsoobserved using helium, nitrogen and air. Results showed
that glycerols conversion wasas high as 76.9% when helium is used as a carried gas.
Conversion reduces to 57.4% and61.5% when nitrogen and air was used. The gas product
consist of 57.6% H
2
, 0.4% CO,and 42.0% CO
2
(mol%). An increase in the flow rate of helium
has little effect onselectivity, but results in a clear decrease in conversion.

Keywords:Glycerol; Hydrogen; dielectric barrier discharge jet reactor; Plasma
1. Introduction
Due to the rapid decline in the resources of fossil fuel, people are becoming more
interested in using biodiesel, instead of diesel oil. An increased in the production of biodiesel
was observed over the year. Unfortunately, glycerol or glyceride(C
3
H
8
O
3
) is also produced as
a by-product of the tranesterification reaction. Usually glycerol is one of the main ingredients
used to make medicine, cosmetic and toothpaste [1]. However, the glycerols obtained from
this process are highly contaminated. Considering the financial aspect of the production of
biodiesel, it would be better to convert glycerol into hydrogen gas. Hydrogen gas can be
combusted to heat boilers in a steam production plant and it can also be used as a fuel for
vehicles transportation.



CorrespondingAuthor:smalee@engr.tu.ac.th,02-5643001-9ext.3132

Several processes such as steam reforming, partial oxidation andautothermal supercritical
Author name / The 3rd International Symposium on Engineering, Energy and Environments (2013)
water reforming are employed to produced hydrogen gas from glycerol [1,4,6].However,
these processes must be operated at high temperature and pressure. Currently, it was reported
that plasma technology can be applied to convert glycerol to hydrogen gas at lower
temperature and atmospheric pressure.
Plasma gas or ionized gas steam is generated by applying energy to gas molecule. These
excited species usually consisting of ions, electron s and neutral particles. The energy that is
transferred to the gas molecule is in a form of an electrical breakdown which is where an
electric arc is continuously generated to take away electron from gas molecule. At
temperature above 300
o
C, gas molecule loses electron and turn into plasma. Richard G.
Mallinson et. al. reported plasma reforming of glycerol using a modified point-plate
configuration reactor. Their research
In currently, a low temperature plasma (non-thermal plasma) [7] are widely used to
improve the properties of space, the surface film, production of ozone for wastewater
treatment to kill disease risk medical and production of hydrocarbons of the petrochemical
industry, etc. The dielectric barrier discharge jet, which features one of the great plasma at
low temperature and atmospheric pressure. Technical equipment is economical and does not
require a vacuum system [2].
This research presented the conversion of glycerol by non-thermal plasma to hydrogen gas
and the di electric barrier discharge jet which can take at atmospheric pressure. Plasma can
lead to the disintegration of glycerol to synthesis gas equation[8].

C
3
H
8
O
3
4H
2
+ 3CO; H = 350 kJ mol
-1
(1)

That changing glycerol can be donewithoutthe needoxygenation(roll ofwater oroxygen) as the
ratioof oxygento carbonin theglycerolratiowas1: 1[7].
2. Experimental
2.1 Feed
Feed was used in this work is glycerol 93.74% that is by-product of biodiesel, with a feed
flow 0.015 ml/min. In this study, the carrier gas flow rate was 35 ml/min was also observed
using helium, nitrogen and air.
2.2 Activity test

Fittingthelow-temperature plasma(non-thermal plasma), a high-
voltageelectricswitchrunoffincludethe high-voltagetransformer. Drive circuittransformer.
Variablefrequency circuit.Frequencycounter circuit. Lowvoltage powersupply
circuitandcircuitformeasuringvoltage andcurrentof the
load.Theplasmareactorwithadielectricbarrierdischargejet(DBD JET)anda line through
thecenter1 cmwitha cylindricalstructure. Usingquartzasthe material hasa
dielectricelectrodeiscasingringsand rods,the corechallengewithstainless steelthickness2
mmbelowthefirstchallengewasto findtheconditions oftheplasmain the reactorplasmadielectric.
Rickbarrierdischargejet. Whichis the range5.5-6.0 kV, frequency 280 - 350 Hz.



Author name / The 3rd International Symposium on Engineering, Energy and Environments



Fig. 2 Schematic diagram for experimental setup.

3. Results and discussion

3.1 Effect of carrier gas

Carrier gas Glycerol flow Glycerol Selectivities (%) Power
35 ml/min (ml/min) Conversion (%) CO
2
H
2
CO Input (W)
He
0.015
76.89 99.09 99.90 0.81
N
2
57.35 95.44 99.82 4.42 15
Air 61.52 7.42 99.90 92.56


GC - TCD
Plasma
High Voltage
Source

MFC: He
Preheat line
Glycerol

Syringe pump
DBD JET
Reactor
Condenser
Trap
Author name / The 3rd International Symposium on Engineering, Energy and Environments (2013)
0
10
20
30
40
50
60
70
80
90
100
10 30 50 70 90 110
H
2
Y
i
e
l
d

(
m
o
l
%
)
Time (min)
He
N2
Air
0
10
20
30
40
50
60
70
80
90
100
10 30 50 70 90 110
C
O
2
Y
i
e
l
d

(
m
o
l
%
)
Time (min)
He
N2
Air
0
10
20
30
40
50
60
70
80
90
100
10 30 50 70 90 110
C
O

Y
i
e
l
d

(
m
o
l
%
)
Time (min)
He
N2
Air



3.2 Effect of carrier gas flow rate (helium)

Author name / The 3rd International Symposium on Engineering, Energy and Environments
He flow rate Glycerol flow rate
Time(min)
Gas phase composition (mol%)
(ml/min) (ml/min) CO
2
H
2
CO C1 - C2
35 0.01500
120
41.99 57.64 0.35 0.02
45 0.01928 47.81 51.96 0.19 0.04
55 0.02357 34.69 64.82 0.46 0.02


4. Conclusion

The effect of carrier gas on production of hydrogen was also observed using helium,
nitrogen and air. Results showed that glycerols conversion was as high as 76.9% when
helium is used as a carried gas. Conversion reduces to 57.4% and 61.5% when nitrogen and
air was used. The gas product consist of 57.6% H2, 0.4% CO, and 42.0% CO2 (mol%). An
increase in the flow rate of helium has little effect on selectivity, but results in a clear
decrease in conversion.

Acknowledgements

The authors thank The Faculty of Engineering Thammasat University is gratefully
acknowledged.
References
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