Documenti di Didattica
Documenti di Professioni
Documenti di Cultura
ScienceDirect
journal homepage: www.elsevier.com/locate/he
article info
abstract
Article history:
Global warming is a worrying problem that has a direct negative impact on climate change,
so it is necessary for all countries to reduce emissions of greenhouse gases (GHGs) and
17 August 2015
relatively new technique is proposed for the GHGs of gases using a warm plasma reactor.
Carbon dioxide (CO2) and methane (CH4) have been identified as the most significant GHGs
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.
17166
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
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:
CH4 H2 O /3H2 CO
DH 206 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
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
17167
tr
h
i
pR1 r2 [1 pR2 2 [2 ml
flow rateml=s
(4)
17168
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
(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)
(6)
hCH4 converted
100
hCH4 feed
(7)
hCO2 converted
100
hCO2 feed
(8)
CO2 conversion %
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
Before
treatment (% vol.)
After
treatment (% vol.)
0
44
50
0
0
6
24
20
26
24
0
6
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
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
hH2
produced
hCOproduced
(13)
17169
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
17170
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
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
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
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