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Kinetic, energetic and exergetic approach to the

methane tri-reforming process

J. Dı́ez-Ramı́rez*, F. Dorado, A. Martı́nez-Valiente, J.M. Garcı́a-Vargas,

P. Sa
nchez
Departamento de Ingenierı́a Quı́mica, Facultad de Ciencias y Tecnologı́as Quı́micas, Avenida Camilo Jos
e Cela 12,
13071 Ciudad Real, Spain

article info abstract

Article history: Energetic and exergetic analyses were applied to the methane tri-reforming process in
Received 23 December 2015 order to assess the suitability of this reaction for the production of syngas with a desirable
Received in revised form H2/CO molar ratio for the FischereTropsch process and methanol production. The kinetic
27 April 2016 equations used in the simulated plug flow reactor were obtained experimentally in a
Accepted 29 April 2016 previous study using typical feed compositions of a landfill gas produced in a landfill site. A
Available online xxx sensitivity analysis was carried out in order to select the best feed composition for the tri-
reforming process. Moreover, the thermodynamic losses were identified and it was found
Keywords: that the exergy destruction occurs mainly in the reactor due to the high irreversibility of
Tri-reforming the chemical reactions. Finally, possible improvements were proposed in an effort to in-
Hysys simulator crease the exergy efficiency.
Exergy analysis © 2016 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
Syngas

reactants used in this process represent a synergetic combi-

Introduction nation of the steam reforming (Eq. (1)), the dry reforming (Eq.
(2)) and the partial oxidation of methane (Eq. (3)). The water-
The shortage of fossil fuels and the increasing rates of egas shift reaction (Eq. (4)) also participates in the tri-
contamination are major concerns for society today. As a reforming process.
consequence, a great deal of effort is made by the scientific
community to identify new sources of energy, to optimize

existing processes from an energetic point of view and to H2O þ CH4 $ CO þ 3H2 (DH ¼ 206.3 kJ mol1) (1)
develop applications for energy streams that are currently not
exploited. One such energy source is represented by landfill

gas streams generated in landfills during the biodegradation CO2 þ CH4 $ 2CO þ 2H2 (DH ¼ 247.3 kJ mol1) (2)
of organic waste by microorganisms [1e3].
The tri-reforming process is one of the most interesting

options for the exploitation of these landfill gas streams, CH4 þ 1/2 O2 $ CO þ 2H2 (DH ¼ 35.6 kJ mol1) (3)
which are usually composed of methane (50e25%), carbon
dioxide (25e7%), water (20e3%) and oxygen (3e0.6%). The

* Corresponding author. Tel.: þ34 926295300; fax: þ34 926295256.

E-mail address: Javier.Diez@uclm.es (J. Dı́ez-Ramı́rez).
http://dx.doi.org/10.1016/j.ijhydene.2016.04.229
0360-3199/© 2016 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.

Please cite this article in press as: Dı́ez-Ramı́rez J, et al., Kinetic, energetic and exergetic approach to the methane tri-reforming process,
International Journal of Hydrogen Energy (2016), http://dx.doi.org/10.1016/j.ijhydene.2016.04.229
2 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 x x x ( 2 0 1 6 ) 1 e1 0


CO þ H2O $ CO2 þ H2 (DH ¼ 41.1 kJ mol1) (4)


mH2 $LHVH2 þ mCO $LHVCO
The advantages of the tri-reforming process compared hThermal ¼
 (5)
mCH4 $LHVCH4 þ Wcompressors þ Wpump
with those of the other well-known reforming processes are:
Where mi and LHVi correspond to the mass flow and lower
 Higher energy efficiency because it combines endothermic heating value of the component ‘i’, respectively, and Wi is the
and exothermic reactions. mechanical work of engine ‘i’.
 The synthesis gas ratio (H2/CO) can be controlled varying As discussed above, the energetic analysis based on the
the feed composition. first law of thermodynamics is not sufficient to carry out a
 The presence of water and oxygen minimizes coke for- performance evaluation of a system. As a result, an exergetic
mation, thus increasing the catalyst stability. analysis was introduced in order to complete the evaluation.
 In the case of the landfill gas, the stream can be used The exergy of a system is defined as the maximum work that
without prior separation of any of its components. can be obtained from a system during a process that brings
this system into thermodynamic equilibrium with its sur-
The above process could be used to obtain synthesis gas roundings using a reference state characterized by a temper-
with an H2/CO molar ratio of 2, which is suitable for the pro- ature T0 and a pressure P0 [17]. In this study, an exergetic
duction of methanol and the FishereTropsch process [4]. analysis was carried out by considering three exergy transfers:
In previous studies by our research group [5e7] the tri- with work (Eq. (6)), with heat interaction (Eq. (7)) and with the
reforming process was extensively investigated and it was mass flow (Eq. (8)) [14,15]. The exergies associated with po-
concluded that a NieMg/SiC catalyst was the most appro- tential and kinetic energy were not considered.
priate due to its excellent catalytic performance. A kinetic
ExW ¼ W (6)
study was carried out [8] with 36 experiments using the typical
feed compositions of landfill gas in order to obtain a kinetic   
T0
model that was statistically meaningful. In the work described ExQ ¼ Q 1  (7)
T
here, a simulation of the tri-reforming process using the ki-
netic expressions was carried out. The performance of the
ExM ¼ Exphys þ Exchem þ Exmix (8)
process is studied by an energetic and exergetic approach.
The performance of a system has been studied by an en- Where Q is the heat transferred, T is the temperature and
ergetic analysis [9] based on the first law of thermodynamics. T0 is the reference temperature. The exergy associated with
The main drawbacks of this kind of analysis are that it does mass flow (ExM) is divided into physical (Exphys), chemical
not provide any information about the degradation (quality) of (Exchem) and mixing exergies (Exmix).
energy that occurs in the process and it cannot identify the The physical exergy (Exphys) is the total amount of work
real thermodynamic inefficiencies associated with irrevers- that can be obtained using a reversible process when the
ible processes in the energy conversion system [10]. Therefore, system is brought from its initial state (temperature T and
an exergetic analysis, based on the first and the second laws of pressure P) to the state determined by the temperature T0 and
thermodynamics, could provide very useful information P0 of the environment. This parameter was calculated as
when evaluating an industrial process for the design, opti- follows:
mization and performance evaluation of a system [11e13]. ( !
The aim of an exergy analysis is to identify where thermo- X
n X
n
Exphys ¼ Dactual stateref state D$ xL $ xi $HIi  T0 $ xi SIi
dynamic losses occur, to identify the equipment in which the i¼1 i¼1
!!)
exergy is destroyed and to pinpoint the area where a process X
n X
n

engineer has to focus their efforts to improve the process, thus þ xv $ yi HVi  T0 $ yi $SVi (9)
i¼1 i¼1
increasing the exergy efficiency and therefore reducing the
operating cost of the industrial plant. Some exergetic analyses Where n is the number of chemical species' in a material
have been applied to different reforming systems [14e16], stream; D is the molar flow rate; xl and xv are the liquid mole
mainly in plants dedicated to the production of hydrogen. In fraction and vapor mole fraction in the material stream,
the work described here the simulation and performance respectively; xi and yi are the mole fraction of species i in the
evaluation of the methane tri-reforming process using real liquid phase and vapor phase, respectively; and Hi and Si are
kinetic expressions was developed. The viability of the pro- the molar enthalpy and molar entropy of pure component i,
cess was analyzed in order to treat landfill gas streams to respectively. The superscripts l and v refer to liquid and vapor
obtain syngas. phase, respectively.
The chemical exergy is defined as the maximum amount of
work obtainable when the substance under consideration is
Energetic and exergetic parameters brought from the environmental state, defined by the pa-
rameters T0 and P0, to the reference state by processes that
One of the main parameters considered in the energetic involve heat transfer and exchange of substances only with
analysis of a system is the thermal efficiency, which is defined the environment. This is given by Eq. (10):
as the ratio of the energy produced (output) to the energy !
X
n
0;i
X
n
supplied (input). In the case of the tri-reforming process this Exchem ¼ D$ x0;i $ x0;i $εchem;i þ x0;v $ y0;i $ε0;v
chem;i (10)
thermal efficiency is given by Eq. (5): i1 i1

Please cite this article in press as: Dı́ez-Ramı́rez J, et al., Kinetic, energetic and exergetic approach to the methane tri-reforming process,
International Journal of Hydrogen Energy (2016), http://dx.doi.org/10.1016/j.ijhydene.2016.04.229
 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 x x x ( 2 0 1 6 ) 1 e1 0
Where ε0;i 0;v
chem;i and εchem;i denote the standard chemical exergy
of any species i in the liquid and vapor phase, respectively.
These parameters are explained in the paper by Hinderink [18]
and were calculated using the reference state model defined
by Szargut [17]. The reference state used in this work was
T0 ¼ 25  C and P0 ¼ 1 atm.
The mixing exergy, which always has a negative value, is
given by Eq. (11).
Exmix ¼ Dmix H  T0 Dmix S atðT; PÞ
With
! !!
X
n X
n
Dmix H ¼ D$ xl $ Hl  xi Hli þ xv $ HV 
i1 i1
! !!
X
n X
n assumed that the partial oxidation was close to full con-
Dmix S ¼ D$ xl $ Sl  xi Sli þ xv $ SV  yi SVi
i1 i1
Hl(v) and Sl(v) denote the enthalpy and the entropy of the
mixture in liquid phase (vapor).
The aim of the exergy analysis is to identify where the
thermodynamic losses are produced by studying where the
exergy is destroyed. The amount of exergy destroyed is
calculated as:
Exdestroyed ¼ Exin  Exout
Where Exin and Exout are the total input and output exergy
flows of the system, respectively.
The unused exergy is defined as the sum of the destroyed
exergy and the exergy wasted in the exhaust stream. In this
study, the exhaust stream is the sum of the stream of the
reactants that did not react in the reactor and the energy
stream of the reactor.
Exunused ¼ Exdestroyed þ Exexhaust
The exergetic efficiency of the system is given by Eq. (16):
 
Exunused
hexergy ¼ 1 
Exin
Tri-reforming process simulation
The tri-reforming process, which is depicted in Fig. 1, was
simulated under steady state conditions using a flowsheet
simulator (Aspen HYSYS V8.4 licensed by Aspen Technology,
Inc.). The description of the different materials and process
energy included in the flow scheme are summarized in Table
1.
The following conditions were selected in order to draw the
flowsheet of the plant:
 The different reactants (methane, carbon dioxide, air and
water) were added to the system at atmospheric pressure
and temperature (1 atm and 25  C).
 The pressure was increased up to 20.52 bar in the case of
gases using compressors (K-01, K-02 and K-03) and up to
21.04 bar in the case of the liquid water using a pump (P-01).
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International Journal of Hydrogen Energy (2016), http://dx.doi.org/10.1016/j.ijhydene.2016.04.229
3
 Liquid water was transformed into steam in the first heat
exchanger (HE-01) with the heat transferred from the
products stream (C-09).
 All of the feed streams were mixed (MIX-01).
 Prior to entering the reactor, the feed stream was heated in
the second heat exchanger (HE-02) with the heat trans-
ferred from the out-reactor stream (C-08).
 The reactor was modeled using a Plug Flow Reactor with
the kinetic expressions and parameters obtained experi-
(11) mentally in a previous study by our group [8]. The kinetic
equations, kinetic expressions and the parameters ob-
tained are listed in Table 2. The reactions that were
considered to make a contribution to the global kinetic of
yi HVi (12)
the tri-reforming process were the steam reforming, the
dry reforming and the water gas-shift reaction. It was
(13) version whenever oxygen was not practically detected in
the effluent gas.
 The final step was the separation of the synthesis gas (CO
and H2) from the rest of the compounds that did not react
(CH4, CO2, H2O, N2, O2 and traces of argon). The process
units used to carry out this separation are not considered
in this work.
The assumptions made are as follows:
(14)
 The thermodynamic data and phase behavior predictions
were calculated using the PengeRobinson equation of
state, which is suitable for hydrocarbons and light gases
and for high temperatures and pressures.
 The reference environmental temperature is 25  C and the
pressure is 1 atm, with these values applied to every inlet
flow.
 The composition of air is summarized in Table 3.
(15)  Heat transfer occurs ideally in reactors and heat
exchangers.
 The minimum temperature difference considered in the
heat exchangers is 15  C.
(16)
 There is a pressure drop of 0.52 atm in every heat
exchanger, while in the rest of the units the pressure drop
was neglected.
 The possible deactivation of the catalyst is not taken into
account.
 The reactor works at 20 atm because the synthesis gas
produced will be used at this pressure.
Sensitivity and energetic analysis
The sensitivity analysis was carried out in order to determine
the best feed composition to carry out the tri-reforming pro-
cess. The methodology applied in the optimization of the feed
stream was to vary the inlet molar flow of one of the reactants
while the rest of the molar flows were kept constant. The in-
fluence of the feed composition with respect to temperature
was analyzed in the range 600  C to 1200  C. The methane
molar flow was the only molar flow that was kept constant
throughout the sensitivity analysis and this was maintained
at 100 kmol h1.
4 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 x x x ( 2 0 1 6 ) 1 e1 0

K-01
Methane C-01

E-01 C-08

K-02 MIX-01
Carbon dioxide C-02
C-06 C-07

E-02 HE-02
E-05
R-01
K-03
Air C-03 C-05

E-03
HE-01
C-09

P-01
C-04
Water
C-11
C-10
E-04 Synthesis Gas

S-01

Fig. 1 e Detailed flowsheet for the methane tri-reforming process.

the most suitable value for methanol synthesis and the

Table 1 e Description of the material and energy streams
FischereTropsch process.
for the tri-reforming process.
- Conversion of methane. The conditions that lead to con-
Material streams Description
versions higher than 90% would be selected.
Methane Methane input (25  C and 1atm) - Thermal efficiency. This parameter was studied in order to
Carbon dioxide Carbon dioxide input (25  C and include the energetic analysis in the study. Thermal effi-
1atm)
ciencies as high as possible would be selected.
Air Air input (25  C and 1atm)
Water Water input (25  C and 1atm)
C-01 Methane pressurized at 20.52 atm The first molar flow studied was that of carbon dioxide
C-02 Carbon dioxide pressurized at (Fig. 2). For this study the methane, water and air molar flows
20.52 atm were kept constant at 100 kmol h1, 50 kmol h1 and
C-03 Air pressurized at 20.52 atm 49.14 kmol h1 (10 kmol h1 O2), respectively.
C-04 Water pressurized at 21.04 atm
The way in which the thermal efficiency increases as the
C-05 Water steam
temperature increases is shown in Fig. 2. A similar trend was
C-06 Feed mixture
C-07 Input reactor stream found for the methane conversion. A significant influence of
C-08 Output reactor stream CO2 on the methane conversion was not observed as all of the
C-09 Hot input and output from heat molar flows showed similar conversions above 900  C.
exchangers Therefore, higher molar flows lead to higher thermal effi-
C-10 All products stream to separator ciencies and conversions. However, the limiting factor in the
C-11 Reactants that do not react stream
case of CO2 is the H2/CO ratio, which is only around 2 at high
Synthesis Gas Mixture of CO and H2 stream
temperatures, where higher conversions and thermal effi-
Energy streams Description ciencies were found for a molar flow of 25 kmol h1. The most
E-01 Compressor (K-01) electrical appropriate temperatures for this molar flow were in the
energy range 850e950  C.
E-02 Compressor (K-02) electrical The water molar flow was studied next (Fig. 3). In this case
energy
the feed composition was kept constant at 100 kmol h1 for
E-03 Compressor (K-03) electrical
energy
methane, 25 kmol h1 for CO2 and 49.14 kmol h1 for air
E-04 Pump (P-01) electrical energy (10 kmol h1 of O2). Increases in thermal efficiency and con-
E-05 Reactor energy stream version were obtained when the temperature was increased
and an appropriate H2/CO molar ratio was also obtained for a
The parameters studied to select the most appropriate molar flow of 100 kmol h1. In order to assess whether molar
molar flows were: flows greater than 100 kmol h1 would lead to higher con-
versions and thermal efficiencies, a molar flow of 150 kmol h1
- H2/CO molar ratio of the synthesis gas produced in the tri- was included in the study. Although the thermal efficiency
reforming process. The target molar ratio was 2, which is and conversion did increase, a value of 2 for the H2/CO molar

Please cite this article in press as: Dı́ez-Ramı́rez J, et al., Kinetic, energetic and exergetic approach to the methane tri-reforming process,
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 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 x x x ( 2 0 1 6 ) 1 e1 0 5

Table 2 e Kinetic expressions and parameters used in the simulated reactor.

Kinetic equations Kinetic expressions Parameters
   
SR ! 26830 Ea1 k01 ¼ 85:77 mol$s1 $kPa1 Ea1 ¼ 74:72 kJ mol1
PCO $P3H
H2O þ CH4 $ CO þ 3H2 rSR ¼ K1 $PCH4 $ 1  PCH 2
KSR ¼ 1; 198E17$e
T
k1 ¼ k01 $e
R$T

4
$PCO2 $KSR
   
DR ! 31230 Ea2 k02 ¼ 70:99 mol$s1 $kPa1 Ea2 ¼ 77:82 kJ mol1
P2CO $P2H
CO2 þ CH4 $ 2CO þ 2H2 rDR ¼ K2 $PCH4 $ 1  PCH 2
KDR ¼ 6; 78E18$e
T
k2 ¼ k02 $e
R$T

4
$PCO2 $KDR
   
WGS   Ea3 k03 ¼ 149:92 mol$s1 $kPa1 Ea3 ¼ 54:26 kJ mol1
T 2;2029
2073
H2O þ CO $ CO2 þ H2 rWGS
P $P PCO2
¼ K3 $ COPH H2 O  keqWGS keqWGS ¼ 10 k3 ¼ k03 $e
R$T

ratio was only obtained at very high temperatures

Table 3 e Air composition.
(1050e1150  C), which are not commonly used in the reform-
Gas Molar fraction ing processes. For this reason, a molar flow of 100 kmol h1
Nitrogen (N2) 0.7567 was selected. The temperatures that gave the best results
Oxygen (O2) 0.2035 (conversion, H2/CO molar ratio and thermal efficiency) were in
Water (H2O) 0.0303 the range 900e1000  C.
Argon (Ar) 0.0091
Finally, the influence of the oxygen molar flow on the
Carbon dioxide (CO2) 0.0003
selected parameters was studied (Fig. 4). Although the values
Hydrogen (H2) 0.0001
that appear in Fig. 4 are related to oxygen, it should be noted
that the molar flow of oxygen depends on the air molar flow.

120 CO2 120 H2O

105 105
Thermal efficiency (%)

Thermal efficiency (%)

0 kmol/h 25 kmol/h
25 kmol/h 50 kmol/h
90 50 kmol/h
90 75 kmol/h
75 75 kmol/h 75 100 kmol/h
60 100 kmol/h 60 150 kmol/h

45 45
30 30
15 15
100 100
90 90
Conversion (%)

Conversion (%)

80 CO2 80 H2O
70
0 kmol/h 70 25 kmol/h
25 kmol/h 50 kmol/h
50 kmol/h 60 75 kmol/h
60
75 kmol/h 50 100 kmol/h
50 100 kmol/h 150 kmol/h
40
40
7 CO2 7 H2O
6 0 kmol/h 25 kmol/h
25 kmol/h 6 50 kmol/h
5
Ratio H2/CO

Ratio H2/CO

50 kmol/h 5 75 kmol/h
4 75 kmol/h 100 kmol/h
100 kmol/h 4 150 kmol/h
3
2 3
1 2
0 1
600 700 800 900 1000 1100 1200 600 700 800 900 1000 1100 1200
Temperature (ºC) Temperature (ºC)
Fig. 2 e CO2 sensitivity analysis: Effect of the CO2 molar Fig. 3 e H2O sensitivity analysis: Effect of the H2O molar
flow on the thermal efficiency, methane conversion and flow on the thermal efficiency, methane conversion and
H2/CO ratio at different temperatures. H2/CO ratio at different temperatures.

Please cite this article in press as: Dı́ez-Ramı́rez J, et al., Kinetic, energetic and exergetic approach to the methane tri-reforming process,
International Journal of Hydrogen Energy (2016), http://dx.doi.org/10.1016/j.ijhydene.2016.04.229
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 x x x ( 2 0 1 6 ) 1 e1 0

120 O2
basis of the temperature ranges that were used in the sensi-
tivity analysis and because they are temperatures that are
105
Thermal efficiency (%)
10 kmol/h
25 kmol/h frequently used in the reforming processes.
90 50 kmol/h The amount of exergy destroyed in each component of the
75 75 kmol/h plant and the unused exergy for each component in the sys-
60 100 kmol/h tem are shown in Table 4 and Fig. 5, respectively. It can be
45 observed that the majority of the exergy destruction occurs in
the reactor, which contributes three-fifths of the exergy
30
destroyed in the entire process. This finding is due to a com-
15
bination of the high irreversibilities of the chemical reactions
100 and the difference in temperature between the reactants and
90 the products in the reformer. The component in which the
80 second highest exergy is destroyed is the heat exchanger (HE-
Conversion (%)

70 O2
01). This is due to the high temperature difference between
60 10 kmol/h the fluids in the exchanger. Finally, the third highest exergy
50 25 kmol/h
loss occurs in the mixer, where the exergy destroyed is un-
40 50 kmol/h
75 kmol/h avoidable and is already minimized in this model because it is
30 100 kmol/h assumed to occur adiabatically and at constant pressure. The
20 amount of exergy destroyed in each component does not
10 show a large dependence on the temperature when the tem-
5 O2 perature of the reactor is above 900  C. However, the same
10 kmol/h behavior is not found for the unused exergy in the exhaust
4 25 kmol/h
stream, which continuously decreases as the reactor tem-
Ratio H2/CO

50 kmol/h
75 kmol/h
3 100 kmol/h
2 was observed that higher reactor temperatures yield a higher
1 smaller proportion of reagents that do not react at higher
600 700 800 900 1000 1100 1200
Temperature (ºC)
Fig. 4 e O2 sensitivity analysis: Effect of the O2 molar flow
on the thermal efficiency, methane conversion and H2/CO
ratio at different temperatures.
For this reason the thermal efficiency decreases when the
oxygen molar flow increases, because when the O2 molar flow
increases the rest of the air gases are also increased. The ni-
trogen included in the air stream decreases the thermal effi-
ciency because it does not participate in the reaction and it
increases the energy required in the compressors and the
energy to heat the streams.
In this case, in order to select the most appropriate oxygen
molar flow, some previously mentioned restrictions were
considered: H2/CO molar ratio of 2, conversion higher than
90% and thermal efficiency higher than 70%. The molar flow
that fulfills these conditions was 50 kmol h1 while the tem-
perature was kept in the range 850e950  C.
Exergetic analysis
Once the best feed composition for the tri-reforming process
had been selected, an exergy analysis was carried out in order
to identify the temperature that gave the best process per-
formance. The different temperatures studied were 850, 900,
950 and 1000  C. These temperatures were selected on the
perature increases. This exhaust stream is the sum of the
exergy of stream C-11, which is composed of the gases that do
not react, and the exergy of the energy stream of the reactor. It
methane conversion (Table 5), which means that there is a
temperatures and, therefore, the exergy of stream C-11 de-
creases, thus decreasing the unused exergy of the exhaust
stream in Fig. 5.
The most important parameters studied are listed in Table
5. The methane conversion was similar at temperatures above
950  C. H2/CO molar ratios with values of 2 ± 0.1 and similar
destroyed exergies were found at temperatures above 900  C.
Finally, the exergy efficiency clearly increases as the temper-
ature increases, albeit more slowly at temperatures around
950  C.
A design engineer could use these results to make design
improvements that could decrease the amount of unused
exergy and increase the exergy efficiency. The unused exergy
(Eq. (15)) is composed of the exergy destroyed and the exergy
exhaust. The former could be reduced by incorporating optimal
designs. In the case of the reactor these optimal designs could
reduce the thermodynamic irreversibility of the chemical re-
actions. Such designs may require a loss of exergy in the sep-
aration and recycling of the reagents but optimal conversions
could be achieved; this means that minimal exergetic losses
per unit of useful reaction products would be obtained [15,19].
In the case of the heat exchangers, where the destroyed exergy
is due to the high temperature difference between the fluids in
the exchangers, one way to minimize the exergy destroyed is to
reduce this difference between the streams. This could be
achieved with larger heat transfer surfaces in the heat ex-
changers. In this respect, there is a tradeoff between the in-
vestment cost (system size) and the operating cost (exergetic
efficiency). These design recommendations based on exergy
analysis would not be identified by first-law analysis alone. The
exhaust exergy could also be reduced. The exergy of the energy

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 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 x x x ( 2 0 1 6 ) 1 e1 0 7

Table 4 e Results of the exergy balance for each reactor temperature.

850  C
Component Exin (kJ/mol) Exout (kJ/mol) Exdestroyed (kJ/mol) Percentage of total exergy destruction (%)
Heat exchangers HE-01 315.72 306.68 9.04 19.65
HE-02 683.26 682.77 0.49 1.07
Reactor R-01 367.4 335.71 31.69 68.89
K-01 319.11 318.44 0.67 1.46
Compressors K-02 3.17 3.01 0.16 0.35
K-03 18.23 17.78 0.45 0.98
Pump P-01 0.358 0.356 0.002 0.00
Mixer MIX-01 351.04 347.54 3.5 7.61

900  C
Component Exin (kJ/mol) Exout (kJ/mol) Exdestroyed (kJ/mol) Percentage of total exergy destruction (%)

Heat exchangers HE-01 299.72 291.35 8.37 22.69

HE-02 644.56 644.11 0.45 1.22
Reactor R-01 344.73 321.11 23.62 64.02
K-01 296.98 296.35 0.63 1.71
Compressors K-02 2.95 2.8 0.15 0.41
K-03 16.96 16.54 0.42 1.14
Pump P-01 0.333 0.331 0.002 0.01
Mixer MIX-01 326.7 323.45 3.25 8.81

950  C
Component Exin (kJ/mol) Exout (kJ/mol) Exdestroyed (kJ/mol) Percentage of total exergy destruction (%)

Heat exchangers HE-01 288.81 280.66 8.15 22.26

HE-02 624.92 624.47 0.45 1.23
Reactor R-01 335.99 312.28 23.71 64.76
K-01 287.05 286.45 0.6 1.64
Compressors K-02 2.86 2.71 0.15 0.41
K-03 16.4 15.99 0.41 1.12
Pump P-01 0.322 0.32 0.002 0.01
Mixer MIX-01 315.78 312.64 3.14 8.58

1000  C
Component Exin (kJ/mol) Exout (kJ/mol) Exdestroyed (kJ/mol) Percentage of total exergy destruction (%)

Heat exchangers HE-01 285.44 278.07 7.37 21.32

HE-02 619.42 618.96 0.46 1.33
Reactor R-01 333.84 311.41 22.43 64.90
K-01 282.86 282.26 0.6 1.74
Compressors K-02 2.81 2.67 0.14 0.41
K-03 16.16 15.76 0.4 1.16
Pump P-01 0.317 0.315 0.002 0.01
Mixer MIX-01 311.17 308.01 3.16 9.14

stream of the reactor could be reduced using this energy temperature. This T-M exergy could be transformed into work
stream in some process in the plant. The exergy of the C-11 by adding a bottoming cycle to the system, as explained below.
stream is separated into two forms: thermo-mechanical (T-M) The chemical exergy of the exhaust stream is the amount of
and chemical. The T-M exergy is due to the fact that the tem- work that could be extracted from the stream if it was brought
perature of the stream is higher than the environmental into chemical equilibrium with the environment. If all the

50 850 ºC
900 ºC
Unused exergy (kJ/kmol syngas)

950 ºC Table 5 e Global parameters and global exergy flows of

40
1000 ºC the tri-reforming process.
30 Reactor temperature ( C) 850 900 950 1000

20 CH4 conversion (%) 90.6 95.58 98.04 99.13

Ratio H2/CO 2.19 2.08 2.01 1.94
10 Synthesis Gas (kmol/h) 265.12 284.88 294.73 299.1
Exin (kJ/mol synthesis gas) 340.8 317.23 306.63 302.15
0 Exdestroyed (kJ/mol synthesis gas) 46.00 36.88 36.60 34.55
HE-01 HE-02 R-01 K-01 K-02 K-03 P-01 MIX-01 Exhaust
Exexhaust (kJ/mol synthesis gas) 49.88 28.28 18.41 14.08
Fig. 5 e Unused exergy per mole of syngas obtained in the h Exergy (%) 71.87 79.46 82.06 83.90
h Exergy (%) (Exexhaust valorization) 86.50 88.37 88.06 88.56
equipment and in the exhaust stream.

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8 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 x x x ( 2 0 1 6 ) 1 e1 0

exhaust exergy were used, the exergy efficiency would be

Table 6 e Description of the material and energy streams
similar for reactor temperatures above 900  C, as can be seen in
for the bottoming cycle.
Table 5. Last, but not least, the total unused exergy in the sys-
Material streams Description
tem could be reduced by using pure oxygen as the reactant or
the inclusion of an air separator. C-11 Output tri-reforming process stream
Based on the results described above, the temperature C-12 Separator S-02 input
C-13 Water output
selected as the most appropriate for the tri-reforming process
C-14 Turbine T-01 input
was 950  C, which combines higher conversions (~98%) with C-15 Turbine T-01 output
the production of synthesis gas with a suitable H2/CO molar C-A01 Liquid isopentane pressurized at 20.52 atm
ratio for many applications and a good exergy efficiency C-A02 Vapor isopentane pressurized at 20 atm
value. C-A03 Vapor isopentane at 1.52 atm
Once the most appropriate reactor temperature was cho- C-A04 Liquid isopentane at 1.52 atm
C-B01 Liquid water at 25  C and 1.52 atm
sen, an example of the valorization of the exhaust stream (C-
C-B02 Hot water at 1 atm
11) was carried out. An organic Rankine cycle was used as a
C-B03 Hot water to cooling tower
bottoming cycle, which is depicted in Fig. 6. The description of
Energy streams Description
the different materials and process energy included in the
flow scheme are summarized in Table 6. E-06 Turbine (T-01) electrical energy
The organic Rankine cycle tries to recover the heat from E-07 Turbine (T-02) electrical energy
E-08 Pump (P-02) electrical energy
the C-11 stream using the heat exchanger (HE-03). The cycle
E-09 Pump (P-03) electrical energy
consists of an expansion turbine (T-02), a heat exchanger
where there is a water cycle to cool down the stream (HE-04), a
pump (P-02) and the mentioned heat exchanger where the
heat is recovered (HE-03). The organic fluid used was iso-
pentane [20], which has a boiling point of 27.8  C. The tem- the turbine of 20 atm, parameters selected taking into account
perature of the C-11 stream is not high enough to use other the higher amount of heat recovered from the C-11 stream.
liquids, as methanol or water, which have higher boiling After the heat exchanger (HE-03), the process stream C-12
points than isopentane (64.7 and 100  C, respectively), as they is separated, and the vapor phase stream (C-14) is used in a
did not evaporate in the heat exchanger, and therefore vapor second turbine (T-02) in order to obtain a high amount of
was not obtained. Other compounds with lower boiling points energy, as shown Table 7. The global energy balance is posi-
needed very low temperatures to be liquefied. The organic tive. If the data of the process before the cycle (Table 5) are
fluid selected was able to be evaporated with the heat of the C- compared, the exergy destroyed has increased and the exergy
11 stream and it could be liquefied using an additional water of the exhaust stream has decreased (See Fig. 7). The exergetic
cycle. In this cycle, water was cooled using a cooling tower, efficiency has increased from 82.06% to 82.62%. This kind of
whose energy was not assumed. The cycle works with an cycles could be more efficient if the exhaust stream was at
isopentane molar flow of 100 kmol h1 and a pressure before high temperature. For our example, if just a turbine was added

C-A01

T-01
HE-03 C-14 C-15
C-11 C-12

C-13
E-06
S-02

C-A02

C-B01
T-02 P-02
HE-04

C-A03 C-A04
E-07
E-08

C-B02
P-03

C-B03 W-01
E-09

Fig. 6 e Detailed flowsheet for the bottoming cycle.

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 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 x x x ( 2 0 1 6 ) 1 e1 0
14
Unused exergy (kJ/kmol syngas)
12
10
8 (grant FPU13/00727) for their financial support.
6
2
0
HE-03 S-02 T-01 T-02 HE-04
Fig. 7 e Unused exergy per mole of syngas obtained in each
equipment and in the exhaust stream in the bottoming
cycle.
Table 7 e Global energy and exergy balances of the
bottoming cycle.
E-06 Turbine T-01 (kW)
E-07 Turbine T-02 (kW)
E-08 Pump P-02 (kW)
E-09 Pump P-03 (kW)
Global Energy Balance
Exin (kJ/mol synthesis gas)
Exdestroyed (kJ/mol synthesis gas)
Exexhaust (kJ/mol synthesis gas)
h Exergy (%)
to the C-11 stream, the energy and the exergetic efficiency
obtained would be higher (584,7 kW and 84.38%, respectively).
Moreover, the investment costs would be lower. This example
clearly shows how an exergy analysis can help to the possible
valorization of a stream.
Conclusion
A thermodynamic analysis was conducted to investigate the
characteristics of the tri-reforming process for methane. The
most important conclusions obtained were:
- The optimal feed composition was identified: 100 kmol h1
methane, 25 kmol h1 CO2, 100 kmol h1 H2O and
50 kmol h1 O2 (245.7 kmol h1 of air). This feed composi-
tion was selected because it combined high thermal effi-
ciency (>70%), methane conversion (>90%) and the
production of synthesis gas with a desirable H2/CO molar
ratio of 2.
- The reactor was the component where most of the exergy
was destroyed. This is mostly due to the high irreversibility
of the chemical reactions that occur.
- A reactor temperature of 950  C combines higher conver-
sions (~98%) with a desirable H2/CO molar ratio and a good
exergy efficiency value.
- Based on the results, research and development efforts
should be focused on reducing the exergy destruction
within the reactor and heat exchangers as well as recov-
ering part of the exhaust stream exergy.
Please cite this article in press as: Dı́ez-Ramı́rez J, et al., Kinetic, energetic and exergetic approach to the methane tri-reforming process,
International Journal of Hydrogen Energy (2016), http://dx.doi.org/10.1016/j.ijhydene.2016.04.229
9
Acknowledgments
The authors would like to thank the Spanish government
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Please cite this article in press as: Dı́ez-Ramı́rez J, et al., Kinetic, energetic and exergetic approach to the methane tri-reforming process,
International Journal of Hydrogen Energy (2016), http://dx.doi.org/10.1016/j.ijhydene.2016.04.229