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Greenhouse gas treatment and H2 production, by


warm plasma reforming
J. Pacheco a,*, G. Soria b, M. Pacheco a, R. Valdivia a, F. Ramos a, H. Fras a,
 n a, M. Hidalgo a
M. Dura
Instituto Nacional de Investigaciones Nucleares, Km 36.5 Carretera Mexico-Toluca, La Marquesa, Ocoyoacac, CP
52750, Mexico
b
Instituto Tecnol
ogico de Toluca, Av. Instituto Tecnologico, S/N, Ex-Rancho la Virgen, Metepec, Mexico
a

article info

abstract

Article history:

Global warming is a worrying problem that has a direct negative impact on climate change,

Received 4 December 2014

so it is necessary for all countries to reduce emissions of greenhouse gases (GHGs) and

Received in revised form

emergent treatment technologies are developing through worldwide. In this paper, a

17 August 2015

relatively new technique is proposed for the GHGs of gases using a warm plasma reactor.

Accepted 18 August 2015

Carbon dioxide (CO2) and methane (CH4) have been identified as the most significant GHGs

Available online 9 September 2015

arising from anthropogenic activities, affecting the climatic global change. The technique
here used is the so called Dry Reforming, assisted by a warm plasma reactor, including the

Keywords:

reactants treatment, synthesis gas generation, and finally the syngas production (H2 CO).

Plasma reforming

The gases CO2 and CH4 are relatively stable compounds with low potential energies. The

Greenhouse gas

dry reforming is an endothermic reaction and external energy must be provided in order to

Synthesis gas

achieve the targets inquired. More recently, plasma gas reforming is emphasized as
promising technique for energy saving and environment safe purposes with increasing
demand of hydrogen and synthesis gas production. In the case of plasma reforming, high
electron energy provides not only radical species, but also the enthalpy required for
endothermic reaction. The conversion of hydrocarbon in by-products with high added
value is mainly contributed by dissociation and ionization processes. With respect to other
techniques of hydrocarbons reforming by plasma discharges, there are enough references
related to RF plasma discharges operating at reduced pressures, even if these low pressure
plasma could achieve high hydrocarbon conversion and good H2 selectivity; the low H2
production rate and extra energy requirement for vacuum device constrain its practical
use, therefore an alternative procedure and system consisting in a novel plasma reactor is
here proposed. Warm plasma is environment-friendly and auto-sustainable processes,
besides the electric discharge has low specific energy requirement still maintaining enough
high temperature (1000e3000 K) to produce excited species, supporting subsequent
chemical reactions. Such plasma discharges have significant advantages: Do not require
extra cooling systems, since they work with reduced electric current flows and high voltages, avoiding electrodes erosion. Consequently, reactors can be achieved with a simpler
outline and high capacity gas treatment.
Copyright 2015, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights
reserved.

* Corresponding author. Tel.: 52 53297200x12646.


E-mail address: joel.pacheco@inin.gob.mx (J. Pacheco).
http://dx.doi.org/10.1016/j.ijhydene.2015.08.062
0360-3199/Copyright 2015, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.

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Partial Oxidation Reforming POR:

Introduction
Current environmental and energetic problems have influenced researchers to find and develop new processes for
alternative and renewable energy production. Even nowadays
88% of world commercial energy consumption (excluding
photosynthesis and uncontrolled fires) is by combustion processes [1]. Fuel combustion is an exothermic reaction and
usually a slow chemical process, whereby a fuel is oxidized
leading to energy conversion of the chemical species usually
present in the GHG, and delivering toxic exhaust gases, normally composed by NOx, CO and CO2, all of them considered
as greenhouse gases (GHG). In recent decades, different laboratories around the world, have investigated reforming processes assisted by several plasma configurations, from
thermal to non-thermal ones [2e8]. Plasma researchers have
utilized various reforming processes, such as Partial Oxidation
Reforming (POR), Dry Reforming (DR), Steam Reforming (SR),
and Steam-Oxidative Reforming (SOR) to test plasma reactors
capabilities in order to replace traditional combustion process
or metal catalysis-based systems. The catalytic process has
the disadvantages of restricted operating conditions and
problems associated with catalytic converters such as cost,
sulfur poisoning and extended start up time [9e11].
Warm plasma is a transitional discharge, which lies between conventional thermal plasma and non-equilibrium
plasma conditions, working under moderate power density;
but still maintaining enough high gas temperature
(1000e3000 K) to produce excited species, supporting subsequent chemical reactions. Such plasma discharges have significant advantages: they do not require extra cooling
systems, since they work with reduced electric currents and
high voltages, therefore electrode erosion is avoided, and the
reactor has simple construction [12]. Warm plasmas are also
characterized by high chemical selectivity and have found
applications in fuel conversion to syngas production,
hydrogen sulfide dissociation, and carbon dioxide dissociation. Gliding arc plasma discharge or jet atmospheric pressure
plasmas are additional examples of warm plasma discharges.
The ionization process in warm plasma discharges is induced
by a strong electric field, producing relatively high-energy
electrons as well as excited ions, atoms or molecules, leading in selective chemical transitions in a very effective
manner. Because of its high power density, this plasma reactors can be designed for small and large-scale applications,
these types of reactors can also work in portable or on-board
processes [13].
There are numerous methods to generate syngas (H2 CO)
[14]. These methods include steam reforming, dry reforming
(also called CO2 reforming) and partial oxidation, as shown in
the following equations (1)e(3):
Steam Reforming SR:

Dry Reforming DR:

CH4 H2 O /3H2 CO
DH 206 kJ=mol

CH4 CO2 /2H2 2CO


DH 247 kJ=mol

(1)

(2)

1
O/2H2 CO
2
DH 36 kJ=mol

CH4

(3)
Reforming reactions (1e3) are not only a process of substance conversion, but a process of energy conversion. The
merits of dry reforming (2), compared with the others procedures, include the use of carbon dioxide in the reactants
mixture, as is well known, this mixture represents the 94% of
the GHG. The focus of this work comprises the research of the
warm plasma discharge, applied for GHG reforming; in addition the electrical energy cost is optimized to produce higher
GHG conversion and obtaining a high yield and selectivity
rates of H2. However, hydrogen as a fuel has significant
drawbacks, especially those related with its storage. Although
hydrogen's high mass heating value (120 MJ/kg), it has a very
low volumetric heating value (11 kJ/l), compared for instance
to 16,000 kJ/l for methanol. The specific energy (SE) and energy
conversion efficiency (ECE) are concepts treated and evaluated
in section Energy consumption analysis.
Gasification is the thermochemical conversion of organic
matter (i.e. hydrocarbons) into a gaseous product, which could
be used directly for combustion or synthesized into fuel or
chemicals. The main exhaust gas is the syngas composed by
H2 and CO in majority, including lower concentrations of CO2,
H2O, CH4, higher hydrocarbons and N2.
Dry CO2 reforming can be described as a reforming technique whereby the reaction between carbon dioxide and a
hydrocarbon yields a combination of hydrogen and carbon
monoxide as is denoted in (2).
Given the large emissions of CO2 in some industries such as
cement plants, blast furnaces, among others, several authors
[6e11] have proposed alternative uses for CO2 reforming,
using its conversion to synthetic gas and subsequent transformation to useful energy. The ideal scenarios where DR
might be considered, is where the supply of methane is linked
with carbon dioxide and there are no arranged facilities for its
separation. In Energy consumption analysis energy consumption analysis during reactants conversion is considered,
products selectivity and yield rate production are described,
and finally some results are summarized. The general idea
about DR technique consists in using the GHG into plasma
discharge to produce higher energetic synthetic byproducts
(H2 CO). No other gases (neither inert gas) are used during
warm plasma treatment.
In (2) it can be seen that the reaction process of CH4 with
CO2 is highly endothermic, typically [14] this process is
accomplished by introducing the gases in a cylinder containing a fixed volume of catalyst, which is generally
composed by Ni/Al2O3 composite. The process of reforming
catalysts has been investigated since 1988 [11]. Previously
this alloy has received a number of physical chemical and
thermal treatments, such that when a whole energetic balance is considered the overall treatment efficiency is
affected. To improve this type of reforming assisted by
catalysts a combination of plasma technology has been
considered by many authors [11,25e27] as a possible solution, however, this technique has shown several limitations
among which: its scaling to industrial level, a low capacity

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 4 0 ( 2 0 1 5 ) 1 7 1 6 5 e1 7 1 7 1

production and use of metals such as nickel and chromium


for the manufacture of catalysts [28]. The catalysts suffer
various phenomena such as poisoning, saturation and
deactivation of solid carbon deposition, coupled with the
fact that they require ongoing maintenance to exchange the
catalyst once your responsiveness begins to decline.
Another disadvantage of catalysts using is the cost
increasing of the process and furthermore requires large
amounts of energy in the manufacturing process, increasing
the whole energy consumption of the application, thus the
process becomes rather inefficient. Consequently in this
paper is not considered the catalyst use and the GHG are
treated directly in the warm plasma reactor without using
any additional gas or any type of catalyst.
With reference to the additional POR and SR procedures,
which are alternatives to produce syngas from hydrocarbon
fuels, but have some disadvantages, for instance the SR requires an extra energy to crack the H2O molecule, and the POR
process, requires the use of catalyst. The real energy needed
for such process cannot solely be deduced from thermodynamic calculations, since a significant amount of extra energy
will be needed to overcome the reaction energy barrier. This
amount of extra energy is not reflected in the thermodynamic
enthalpy values. Moreover, these enthalpy values are defined
only for a specific reaction, whereas in a plasma conversion
reactor not all energy can be directed into a specific reaction in
a specific place; then an important fraction of energy is lost
due to heat loss, chemical reactions; consequently, there will
always be a large difference between the thermodynamic
ideally required energy and the real required energy for a
process. Besides, the rotationally and vibrationally excited
species are generally considered useless for hydrocarbon
reforming because of the short lifetimes (several ns) and low
threshold energy (<2 eV). It is noted that the bonding energy
for most hydrocarbons are generally between 3 and 6 eV [29].
As a result, the decomposition of hydrocarbons is obtained
from the electron-impact dissociation and ionization. As expected, a higher electric field leads to higher electron energy,
which is more favorable for the electron-impact reactions
responsible for hydrocarbon reforming. In other words, the
energy consumed by the electron-impact reactions would be
reduced while the electric field is increased. It is why; we have
selected the DR technique and warm plasma reactors for this
application in GHG reforming.

Experimental setup
During experimental tests the flux rate of GHG mixture
(CH4 CO2) is previously measured and homogenized and
then introduced to the reactor (See Fig. 1a), which is constructed in double wall stainless steel. The gas mixture enters straight by the bottom side and ascends between the
space formed by a double wall having a dual purpose: to
maintain the reactor wall at low temperature and to preheat
the gas mixture before to be treated by plasma discharge. The
plasma discharge is generated between an external electrode
and a central conical electrode made of tungsten material; at
that point, it moves down to the end of conical electrode and
does not detach from it, formerly, the arc column length

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increases slowly, just rotating by the flow, during a time


represented by (1/uc). The arc discharge continues the spiral
motion descending along the chamber reactor increasing the
column length (during time 1/ud) and a new cycle is recommenced each 25 ms (See Fig. 1b). The plasma jet is expelled
down the reactor chamber and flow in a free space or in a
container. In our case, the post-chamber elongates the
plasma jet (See Fig. 1a), because the atmospheric air surrounding the jet has a shield effect, therefore, the plasma jet
is spread out with a very long volume, as it was reported in
Ref. [12]. Contrary, when the plasma jet blows directly in air,
it has a reduced volume. The residence time tr of the plasma
discharge inside the reactor could be calculated by the
following relation (4):

tr

h
i
pR1  r2 [1 pR2 2 [2 ml
flow rateml=s

(4)

where, R1 the radius of the discharge chamber, R2 the radius of


the post-discharge chamber, r the radius of the internal
electrode, and [1 and [2 the discharge and post discharge
length respectively. As the arc length expands, the heat
dissipation increases. This results in a lowered temperature,
and the plasma tends to be in nonthermal plasma discharge.
The power source consists on a high-frequency series
resonant inverter [15] constituted by one ferrite core setup
transformer to provide up to 15 kV at high frequencies. Four
sequential control pulses (S1 e S4) generated by a microprocessor circuit, trigger the four high-power MOS transistor (M1
e M4) in a specified sequence to command the transformer
primary winding. The power supply handles a wide frequency
range (5e200 kHz). The duty cycle in each phase is adjusted to
50% providing a soft start in the MOS avoiding redundant
power consumption in the plasma discharge. The high frequency transformer transfers the maximum energy towards
the plasma discharge; in addition, it also functions as a stabilizer, because a natural negative feedback controls the
impedance plasma discharge, when the impedance charge
descends, the voltage is automatically adjusted to sustain a
stable plasma discharge, and consequently a lower electrical
field of about 3 kV/mm is applied between electrodes, as a
result, a low-current discharge streaks between the electrodes
closest points and pre-ionizes the gas gap, causing the formation of a stronger current to sustain the warm plasma
discharge in the GHGs. The gliding discharge on the central
electrode is reflected in the electrical signals [12]. The gliding
period (Tg) can be determined from the electrical signals, in
this case, a Tg of 25 ms is obtained, so the gliding frequency
corresponds to 40 Hz. The arc column length is a function of
power applied to the discharge, reactor geometry, and nature
of the gas to be treated.

Energy consumption analysis


Normally in literature, two important parameters are discussed: SE which represents the energy needed to produce a
syngas mol according (5) [14,17], and ECE which represents the
relation of the output energy of products respect the entrance
energy of reactants (6).

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(a)
(b)

Fig. 1 e Schematic of experimental set up system (a) for dry reforming and electrical discharge period (b).

SE

Pdischarge
H2 COproduced

(5)

where Pdischarge represents the plasma discharge energy


applied expressed in (kJ) and the denominator H2 COproduced
denotes the syngas produced in (mol). The process will have a
major performance whereas this rapport stands slight.
h


i
 
hH2 produced LHVH2 hCOproduced LHVCO



 100
ECE
Pdischarge hCH4 converted LHVCH4

(6)

ECE expresses the lower heating value (LHV) of synthesis


gas produced in the reforming process divided by the input
energy. According (6), the desirable ECE value must be equal to
100%. From Refs. [16e19] next values are found: 1)
LHVH2 242.056 kJ*mol1; 2) LHVCO 283.179 kJ*mol1; and 3)
LHVCH4 802.933 kJ*mol1 @ 298.16 K.
Whereas h refers to the moles of the product
(H2 CO)produced (mol); hCH4 the moles of methane converted
(mol); Pdischarge is the input energy of plasma expressed in kJ;
LHV the lower heating value of substance in kJ/mol. SE and
ECE appear to be good indicators for describing DR process
efficiency.
By using the same procedure indicated in Ref. [16], which is
centered on the instantaneous values intensity of voltage and
current waveforms; the root medium square power PRMS can
be deduced, and finally the energy consumption can be obtained which correspond to 175 W at a frequency of 140 kHz,
and flow rates of 3 LPM for CH4 and 3 LPM for CO2. According
these operating conditions, the SE required for CO and H2
(syngas) generation can be calculated from expression 5 and 6.
Considering these two important parameters, plus the
factors listed in Equations (7)e(13), some numerical results
can be obtained and compared with other references [20e22],
as Tables 1 and 2 shown in the Results and discussion.
Equations (7) and (8) correspond to entering GHG conversion; while (9) and (10) relate product selectivity and 11e12
correspond to syngas yield in DR processes. Anywhere hx

refers to the moles of the product x (converter, produced or


feed) in each case.
CH4 conversion %

hCH4 converted
 100
hCH4 feed

(7)

hCO2 converted
 100
hCO2 feed

(8)

CO2 conversion %

In the case of 100% of hydrogen selectivity (9) means that


all hydrogen atoms of the methane molecules are converted
into hydrogen molecules and 100% of CO selectivity (10)
means that all the carbon reactants are converted to CO.
hH2

H2 selectivity %

produced

2  hCH4

CO selectivity %

(9)

converted

hCOproduced
hCH4

converted

hCO2

(10)
converted

The H2 and CO yields (11, 12) are defined as, the relationship of the H2 produced respect the hCH4 entrance; and the CO
produced respect the GHG entrance [21].

H2 yield %

hH2

produced

2  hCH4

(11)

feed

Table 1 e Reactants and products on dry reforming


process.
Substances
CO
CO2
CH4
H2
O2
N2

Before
treatment (% vol.)

After
treatment (% vol.)

0
44
50
0
0
6

24
20
26
24
0
6

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Table 2 e Energy and conversion parameters obtained by


using (5e13).
Parameter

Result

SE
ECE
CH4 conversion
CO2 conversion
H2 selectivity
CO selectivity
H2 yield
CO yield
H2/CO ratio

CO yield %

88.6 kJ/mol
91.4%
48%
54%
100%
100%
48%
51%
1

hCOproduced
hCH4

feed

hCO2

Equation
Ec.
Ec.
Ec.
Ec.
Ec.
Ec.
Ec.
Ec.
Ec.

5
6
7
8
9
10
11
12
13

(12)
feed

Finally a relationship of the principal syngas components


is obtained by (13). All these equations are used to evaluate the
results in next section
Relation H2 =CO

hH2

produced

hCOproduced

(13)

Results and discussion


According the experimental set-up (Fig. 1) the exhaust gases
were evaluated by using the Gas Analyzer GasBoard3100P
and the results are shown in Fig. 2, where three zones are
depicted: The first region (Zone 1) corresponds to the untreated mixture inlet, the Zone 2 relates to the diminution of
gases concentration during DR as a consequence of warm
plasma application, and finally the Zone 3 corresponds to the
recuperation of initial concentration when the plasma is
turned off. The GHG volume distribution before treatment is
50% for CH4 and 44% for CO2 the complementary 6% is due to
the permanent gas inside reactor as N2 (see Table 1). Giving
these results, there is a 24% volume of H2 and 24% volume of
CO generation. A remnant 26% of CH4 and 20% of CO2 appears
without conversion for the power inserted in warm plasma

Fig. 2 e Warm plasma DR analyzed with Gasboard 3100P.

17169

discharge. These results confirm that CH4 and CO2 mixture is


mainly converted into syngas, which is consistent with the
stoichiometry in equation (2).
The gas analyzer used is not able to quantify the N2 part,
remnant in the reforming process as is estimated in Table 1,
where a 6% of the remaining volume is occupied by N2 gas.
Due to these limitations, a supplementary analysis method
was used to determinate the presence of other minor substances. This technique is the well-known mass spectrometry, which experimental results in 630 samples, are shown in
Fig. 3.
In the mass spectra shown in Fig. 3, the horizontal axis
represents the (m/z) index, while the vertical axis corresponds
to the intensity of each of the 630 samples analyzed. The first
pulse (m/z 2) corresponds to the H2 production intensity, at
the same time, the evolution in mass 16, indicates a significant
decrease of CH4 intensity and a growth in the mass 28 (CO or
N2), corresponds to CO generation whose intensity is the difference in magnitude before and after treatment. In 44 mass
indicates a CO2 abatement. These results are consistent with
Gasboard 3100P analyzer. In this mass spectrum, none
important peak in mass 30 and 46 is revealed, therefore there
is no NOX formation.
Agreeing to Tables 1 and 2, a relationship of 1 in syngas
byproducts (H2/CO) is obtained; and an energy yield of 48% for
H2 and 51% for CO is attained. A comparison of these results
respect similar jobs is shown in Table 3, were some key parameters and competitive performance of this process is
attained. The references cited [4,23and24], use a very slow
flows (lower than 1 LPM) of gas treated, whereas [25] employs a
very high flow 73 LPM, but the power used is very significant
(18 kW), giving a SE and ECE of 274 and 57% respectively.
Another significant remark is that [25] uses noble gas (Ar) and
a preheated Catalyst (1000  C during 30 min) to ameliorate the
activation energy during reforming process, but at the same
time, these two factors increase the reforming profitable cost.
In Table 3 the selectivity and yield rates obtained in this work,
are shown in the last raw.

Conclusions
Warm plasma fuel reforming technology has several advantages over traditional catalytic or thermal processes including
fast start time, high productivity by means of a moderately
low electrical energy costs operation.
The results show that warm plasma reactor is talented for
heavy hydrocarbon fuels reforming having high conversion
efficiency.
In this work, a high H2 and CO selectivity is obtained
(reaching 100%) whereas compared with other references
their selectivity is ranging from 30% to 90%, in addition, in this
work there is no generation of NOx.
In this work, the specific energy and energy conversion
efficiency are shown, getting optimal SE and ECE values. With
these results it can be argued that DR technique with warm
plasma is an emerging procedure with competitive results
without the generation of unwanted species.
The high power consumption in the case of thermal
plasma procedure could become higher than the energy

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Fig. 3 e Mass spectra sweep during experimental test.

Table 3 e Some key performance parameters in energy conversion from several authors.
Plasma form
[Reference]
Corona discharge [23]
Microwave discharge [24]
Gliding arc discharge [4]
Thermal plasma jet [25]
Warm plasma This work

Flow
P (W) Conversion Conversion Selectivity Selectivity H2/CO CH4/CO2
SE
ECE
(a.u.)
rate (LPM)
CO2 (%)
CH4 (%)
CO (%)
H2 (%)
(a.u.)
(kJ/mol) (%)
0.043
0.2
1
73.3
6

46.3
60
190
18 k
175

47.8
68.8
31
64.8
54

62.4
70.8
40
78
48

contained in the reformed products, on the other hand, the


use of noble gases raises the cost of the process, moreover the
consumption of N2 in the thermal plasma, causes the production of unwanted species such as NOx.
In this paper, a practical domestic power supply is used,
based in a resonant electronic converter developed by our
group, thus assuring the energy consumption with high
transfer efficiency. Electric analysis was performed to determine the current, voltage, power and energy required for the
GHG treatment and to provide enough energy required to
break GHG gas chemical bonds, under atmospheric pressure
without using supplementary inert gases.
Given his compactness is very adequate for on-board
vehicular reforming systems that should be further developed and optimized.
Reforming conversion of GHG by warm plasmas offers a
promising route to generate higher value products such as
syngas at low energetic cost.

Acknowledgements
The authors would like to thank for the invaluable support of
the LAP laboratory of the ININ. This work was supported
under EAOO2 project from ININ.

66.8
75
62
96.8
100

70
50
50
82.85
100

1.2
1.5
0.9
0.8
1

1
1.5
1
0.66
1

1798
307
608
274
88.6

13
47
28
57
91.4

references

[1] Combustion Charactyeristics, %3cahrefhttp://webserver.


dmt.upm.es/~isidoro/bk3/c15/Combustion%
20characteristics.pdf, by Isidoro Martnez.
[2] Takemura Yuichiro, Kubota Yuusuke,
Yamaguchi Naohiro, Hara Tamio. Development of
atmospheric plasma jet with long flame. IEEE Trans
Plasma Sci 2009;37(8):1604e6.
[3] Lee DH, Kim KT, Suk M, Soong Y. Plasma-controlled
chemistry in plasma reforming of methane. Int J Hydrogen
Energy 2010;35:10967e76.
[4] Indarto A, Wok CJ, Hwaung L, Keun SH. Effect of additive
gases on methane conversion using gliding arc discharge.
Energy Nov. 2006;31(14):2986e95.
[5] Ouni F, Khacef A, Comier JM. Syngas production from
propane using atmospheric non-thermal plasma. Plasma
Chem Plasma Process 2009;29(2):119e30.
[6] Li X, Liao X, Ren X, Carbon dioxide reforming of methane to
syngas by warm plasma: low energy consumption, Power
and Energy Engineering Conference (APPEEC), pp 1e5 AsiaPacific, 28e31 March 2010.
[7] Choudhary TV, Choudhary VR. Energy-efficient syngas
production through catalytic oxy-methane reforming
reactions. Angew Chem Int 2008;47:1828e47.
[8] Lai WH, Lai MP, Horng RF. Study on hydrogen-rich syngas
production by dry autothermal reforming from biomass
derived gas. Int J Hydrogen Energy 2012;37:9619e29.

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 4 0 ( 2 0 1 5 ) 1 7 1 6 5 e1 7 1 7 1

[9] Zhu X, Li K, Liu JL, Li XS, Zhu AM. Effect of CO2/CH4 ratio
on biogas reforming with added O2 through an unique
spark-shade plasma. Int J Hydrogen Energy
2014;39:13902e8.
[10] Ozkara S, Aksoylu AE. CO2 reforming of methane over Pt-Ni/
Al2O3 catalysts: effects of catalyst composition, and water
and oxygen addition to the feed. Int J Hydrogen Energy
2011;36:2950e9.
[11] Zhang AJ, Zhu AM, Guo J, Xu Y, Shi C. Conversion of
greenhouse gases into syngas via combined effects of
discharge activation and catalysis. Chem Eng J
2010;156:601e6.
[12] Pacheco J, Soria G, Valdivia R, Pacheco M, Ramos F, Fras H,
et al. Warm plasma reactor with vortex effect enhanced used
for CH4eCO2 Reforming. IEEE Trans Plasma Sci
2014;42(10):2800e1.
[13] Gallagher MJ, Geiger R, Polevich A, Rabinovich A,
Gutsol A, Fridman A. On-board plasma-assisted
conversion of heavy hydrocarbons into synthesis gas.
Fuel 2010;89:1187e92.
[14] Tao X, Bai M, Li X, Long H, Shang S, Yin Y, et al. CH4-CO2
reforming by plasmadchallenges and opportunities. Prog
Energy Combust Sci Apr. 2011;37(2):113e24.
[15] Pacheco-Sotelo J, Valdivia R, Pacheco-Pacheco M, Ramos J,
 n M, Benitez J, et al. A universal resonant converter for
Dura
equilibrium and nonequilibrium plasma discharges. IEEE
Trans Plasma Sci 2004;32(5):2105e12.
~ ez M,
[16] Pacheco JO, Salazar JA, Valdivia R, Pacheco M, Iban
Soria G, et al. An environmental application in acid gas
cracking with a high frequency pulsed gliding arc. IEEE Trans
Plasma Sci 2014;42(3):767e73.
[17] Tamosiunas A, Valatkevicius P, Valincius V, Grigaitiene V.
Production of synthesis gas from propane using thermal
water vapor plasma. Int J Hydrogen Energy 2014;39.
[18] Waldheim L, Nilsson T. Heating value of gases from biomass
ping,
gasification. May 2001. IEA Bioenergy Agreement, Nyko
China, Tech. Rep. TPS-01/16.

17171

[19] Bossel U. Well to wheel studies, heating values and energy


conservation principle. Proc Eur Fuel Cell Forum Oct.
2003;22:572e7.
[20] Jo S, Lee DH, Song YH. Effect of gas temperature on partial
oxidation of methane in plasma reforming. Int J Hydrogen
Energy 2013;38:13643e8.
[21] Longa Huali, Shanga Shuyong, Taob Xumei, Yinb Yongxiang,
Daib Xiaoyan. CO2 reforming of CH4 by combination of cold
plasma jet and Ni/Al2O3 catalyst. Int J Hydrogen Energy
2008;33. Elsevier.
 n energe
tica de la eliminacio
 n de H2S y
[22] Torres JS. Recuperacio
CO2 con tecnologa de plasma hbrido [PhD Dissertation].
xico; 2014.
Dept. Electron. Eng., Inst. Tecnol., Toluca, Me
[23] Yang Y. Methane conversion and reforming by non-thermal
plasma on pins. Industrial Eng Chem Res 2002;34.
[24] Zhang JQ, Yang YJ, Zhang JS, Liu Q. Study on the conversion
of CH4 and CO2 using a pulsed microwave plasma under
atmospheric pressure. Acta Chim Sin 2002;60(11):1973e80.
[25] Tao X, Bai M, Wu Q , Huang Z, Yin Y, Dai X. CO2 reforming of
CH4 by binode thermal plasma. Int J Hydrogen Energy
2009;34:9373e8.
[26] Schmidt-Szaowski Krzysztof, Krawczyk Krzysztof,
 rska Agnieszka,
Sentek Jan, Ulejczyk Bogdan, Go
Motek Micha. Hybrid plasma-catalytic systems for
converting substances of high stability, greenhouse gases
and VOC. Chem Eng Res And Des 2011;89.
[27] Tao Xumei, Qi F, Yin Y, Dai X. CO2 reforming of CH4 by
combination of thermal plasma and catalyst. Int J Hydrogen
Energy 2008;33(4):1262e5.
[28] Dong Li Xiao, Zhang Hao, Yan Shi Xin, Yan Jian Hua,
Du Chang Ming. Hydrogen production from partial oxidation
of methane using an AC rotating gliding arc reactor. IEEE
Trans Plasma Sci January, 2013;41(1).
[29] Liang Chen H, Ming Lee H, Huei Chen S, Chao Y, Been
Chang M. Review of plasma catalysis on hydrocarbon
reforming for hydrogen productiondinteraction, integration,
and prospects. Appl Catal B Environ 2008;85:1e9.