Fuel 105 (2013) 739–751

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Fuel
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Methanol synthesis from syngas obtained by supercritical

water reforming of glycerol
F.J. Gutiérrez Ortiz ⇑, A. Serrera, S. Galera, P. Ollero
Departamento de Ingeniería Química y Ambiental, Universidad de Sevilla, Camino de los Descubrimientos, s/n, 41092 Sevilla, Spain

h i g h l i g h t s

" A heat-integrated reforming process of glycerol using supercritical water is established.

" The syngas obtained is conditioned and entered in a methanol synthesis loop.
" Power is produced by a turbine and a fuel cell.
" The aim was to maximize the overall process efficiency in terms of total power and methanol production.
" Optimal conditions were systematically identified.

a r t i c l e i n f o a b s t r a c t

Article history: A process for producing methanol from the synthesis gas obtained by reforming of glycerol using super-
Received 9 August 2012 critical water is studied. The process also produces power from the huge pressure energy of product gas
Received in revised form 25 September just at the outlet of the reformer by a turbine. The expanded product gas is conditioned in a PSA system,
2012
which has three sections so as to produce a H2-rich gas stream, a CO-rich gas stream and CO2 for seques-
Accepted 26 September 2012
Available online 11 October 2012
tration. Thus, it can be achieved the feed required for the methanol synthesis. The surplus hydrogen is
sent to a fuel cell to generate power, and the PSA off-gas, purge from the methanol loop and gases sep-
arated from the crude methanol are burnt in a furnace to achieve an energy self-sufficient process. By
Keywords:
Methanol
changing the reforming temperature, the water-to-glycerol mass ratio and the purge from the methanol
Syngas loop, the conditions for optimizing the overall process relative to methanol and power productions were
Reforming achieved. Thus, by reforming at 1000 °C and 240 atm, and performing the methanol synthesis at 250 °C
Supercritical water and 85 atm, the optimal conditions were a water-to-glycerol mass ratio of 1.68 with a purge ratio of 0.2.
Glycerol Under these conditions 0.270 kg MeOH/kg glycerol and overall energy efficiency of 38.0% were obtained.
The separated CO2 for sequestration is 0.38 kg/kg of glycerol.
Ó 2012 Elsevier Ltd. All rights reserved.

1. Introduction The syngas obtained from glycerol reforming using supercritical

water can be used for the synthesis of chemicals such as methanol.
A great deal of research has been carried out following a ther- Methanol is an important industrial chemical, which is used as a
mochemical route to valorize the biodiesel-derived crude glycerol feedstock for further chemicals, such as formaldehyde, methyl ter-
from the transesterification process to obtain synthesis gas (syn- tiary butyl ether (MTBE) and acetic acid [12], apart from as reagent
gas), by different types of reforming [1–6]. As an emerging and in the biodiesel production. Methanol can also serve as a basic
promising media, supercritical water (SCW) may be used to obtain chemical for polymer production [13,14]. In addition, methanol
syngas due to its relevant thermophysical properties such as a high has a high octane number and is considered to play a significant
capability to solubilize gaseous organic molecules and high reac- role as a synthetic fuel [15]; furthermore, hydrocarbon fuels may
tivity, among others [7–9]. Besides, the reactions in SCW are con- also be generated from methanol with the help of the methanol
ducted in a single phase [10]. As a result, it may be possible to to gasoline (MTG) technology [16]. Thus, methanol represents a
perform the process in the absence of a catalyst, although this pre- critical link in synthesis gas based product network structures [17].
mise requires to be experimentally verified [11]. Methanol is produced by the hydrogenation of carbon oxides
over a suitable (copper oxide, zinc oxide, or chromium oxide
based) catalyst:
⇑ Corresponding author. Tel.: +34 95 448 72 68/60.
E-mail address: [email protected] (F.J. Gutiérrez Ortiz).
CO þ 2H2 $ CH3 OH ð1Þ

0016-2361/$ - see front matter Ó 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.fuel.2012.09.073
740 F.J. Gutiérrez Ortiz et al. / Fuel 105 (2013) 739–751

Nomenclature

B_ exergy flow (kW) Subscripts

H_ enthalpy flow (kW) Gly glycerol
LHV Lower Heating Value (kJ/kg) in referred to some entering the control volume consid-
LW _ exergy flow loss (kW) ered (unit, subsystem or system)
m _ mass flow rate (kg/s) MeOH methanol
Q_ heat flow (kW) net referred to the net power of the turbine
S_ entropy flow (kJ/(sK)) out referred to some leaving the control volume considered
T temperature (K) (unit, subsystem or system)
W_ power (kW) SRSG supercritical reforming reactor for syngas production
PEMFC proton exchange membrane fuel cell
Greek DIST distillation column
g efficiency (%) HE heat exchanger

CO2 þ 3H2 $ CH3 OH þ H2 O ð2Þ 99.999 mol% H2) [26]. However, this is not the requirement for
upgrading the syngas before feeding into the methanol synthesis
Methanol synthesis catalysts also have water gas shift activity,
loop, because only the carbon dioxide and other impurities should
which may account for their ability to synthesize methanol from
be retained in the bed, but a mixture of H2 and CO must be ob-
either carbon monoxide or carbon dioxide:
tained, and in the suitable concentrations for reaching the SN re-
CO þ H2 O $ CO2 þ H2 ð3Þ quired at the inlet of the methanol synthesis loop. Several
methods for separating hydrogen and carbon monoxide by PSA
Only two of these three reaction equations are stoichiometrically processes have been patented during the last years. Kumar and
independent. The first reaction is considered as the primary meth- Kratz [27] developed a PSA process (called Gemini-9 and owned
anol synthesis reaction, but a small amount of CO2 in the feed by Air Products and Chemicals) comprising six parallel beds for
(2–10%) acts as a promoter of this primary reaction and helps to CO2 removal, followed by three parallel beds for H2 purification.
maintain catalyst activity. In fact, the lack of carbon dioxide makes Sircar [28] showed how to get the adjustment of the H2/CO ratio
the Boudouard reaction going in its reverse direction, leading to of a stream obtained from steam methane reforming after CO2 re-
catalyst deactivation by carbon deposition: moval, using a rinse step for the recovery of the fraction of the CO
2 COðgÞ $ CO2 ðgÞ þ CðsÞ ð4Þ adsorbed on activated carbon. Krishnamurthy [29] disclosed a
method for separating hydrogen and carbon monoxide using two
For methanol synthesis, the so-called stoichiometric number PSA systems. The first one separates H2 from the feed mixture as
(SN) of inlet syngas is frequently used, which is defined as: a pure non-adsorbed product and CO2, CH4, and CO as an adsorbed
½H2   ½CO2  fraction. The adsorbed fraction is then desorbed and passed to a
SN ¼ ð5Þ second PSA system, which separates CO as an adsorbed fraction
½CO þ ½CO2 
and CO2, CH4, and somewhat of H2, as a non-adsorbed fraction. Re-
where [H2], [CO2] and [CO] express the molar concentrations of H2, cently, Batdorf [30] proposed a method to remove carbon dioxide
CO2 and CO, respectively. The ideal SN is about 2.0–2.1, because the from the effluent gas, while allowing the carbon monoxide and
stoichiometry of reactions 1–3 is satisfied [18]. This SN corresponds hydrogen to pass through the PSA, producing a gas stream amena-
to a H2-to-CO ratio from 2.4 to 3.0 [19], depending on the CO2 ble to the production of methanol and other liquid fuels.
content. This paper proposes an overall process where syngas is obtained
Since the syngas coming from supercritical water reforming of from glycerol reforming using supercritical water, expanded in a
glycerol does not match this SN value, it must be conditioned be- turbine, next upgraded in a PSA system (adjustment of the SN)
fore entering the methanol synthesis loop. Particularly, as carbon and then fed into a methanol synthesis loop, where unreacted syn-
dioxide and hydrogen have relatively high concentrations, they thesis gas from methanol reactor is separated from crude metha-
must be removed by physical or chemical processes [20]. nol, compressed and recycled. A fraction of recycle gas is purged
The most frequently used technologies for CO2 removal from to avoid inerts accumulation. Finally, the crude methanol is puri-
syngas obtained from fossil fuels are absorption systems such as fied by distillation. The off-gases from the different sections are
the Rectisol, Selexol and MEA-based processes [21], specially the burnt to achieve the thermal energy required in the process, mak-
Selexol process, which uses dimethyl ether of polyethylene glycol ing it energy self-sufficient. Fig. 1 depicts the concept in a simple
as solvent and operates at low temperature (5–35 °C) and medium way using a block flow diagram. The main aim is to achieve the
pressure (15–30 atm), making it possible to achieve a CO2 capture optimal operating conditions for maximizing the overall process
efficiency higher than 90% [22]. However, the Selexol process is efficiency in terms of methanol production and power generation
expensive and requires significant utility consumption during by a turbine and a fuel cell, fed with the surplus of the H2-rich
operation, which only escalates with increasing levels of CO2 cap- stream leaving the PSA, as well as obtaining maximum exergy
ture [23]. An adsorption process, and especially pressure swing efficiency.
adsorption (PSA) technology, may be a potentially attractive alter-
native to capture CO2 from stationary sources in the context of Car-
bon Capture and Sequestration (CCS) technologies [24]. 2. Process design and simulation
Traditionally, PSA technology has proven to be economical in
hydrogen purification from steam methane reforming off-gases Fig. 2 shows the overall process flow-sheet, which includes heat
[25], and typically produce a very pure hydrogen stream (up to exchangers suitably located following a strategy based on
 F.J. Gutiérrez Ortiz et al. / Fuel 105 (2013) 739–751 741

POWER

PEM FUEL CELL

Pure H2
Gas

1 atm.,80 ºC METHANOL METHANOL

REFORMER
SYNTHESIS PURIFICATION
EXPANDER
PSA SYSTEM
Product gas CH3OH

CO, H2, CO2 SN

C3H8O3 + H2O

30 atm., 35 ºC
POWER
85 atm., 250 ºC 1 atm

Flue gas
Supercritical water
240 atm
700 –1000 ºC
HEAT REQUIRED PSA off-gas
FOR REFORMING

FURNACE

Fig. 1. Block flow diagram of the process.

minimizing the lost exergy, so small temperature-driving forces gas stream by means of a knock-out drum. The gas stream enters
must be achieved by using countercurrent flow and small temper- the PSA system, which consists of three units, as shown in Fig. 3.
ature approaches at the ends of the exchangers. The PSA produces a H2-rich stream to adjust the stoichiometric ra-
tio of the methanol feed and simultaneously captures CO2 for fu-
2.1. Supercritical water reforming of glycerol section ture sequestration. Within the first unit, the H2 is separated with
a high purity as a non-adsorbed stream and exits the PSA bed at
A glycerol–water mixture is pumped into the supercritical a pressure close to the PSA inlet pressure. The first PSA unit is
water reforming reactor after heating it as much as possible by depressurized to regenerate the adsorbent, so the tail gas leaves
means of three heat exchangers taking heat from hot streams leav- the bed and then is compressed to 30 atm, passing to the second
ing first the reformer-furnace, and then the reforming reactor. In PSA unit, where the CO is separated as the adsorbed component,
the reformer, glycerol is converted at established temperature recovered in the depressurization, and mixed first with a fraction
and pressure. The pressure used in this work was 240 atm [11]. of the CO2-rich stream coming from the third PSA unit. Then, the
The reforming reactor was simulated as a Gibbs reactor, where mixture of CO and CO2 is compressed up to 30 atm and mixed with
the products composition and the heat of overall reaction were cal- the H2-rich stream, so as to adjust the stoichiometric ratio required
culated under conditions that minimize the Gibbs free energy. The for the feed of the methanol synthesis loop to approximately 2.1, so
furnace-combustor, where the off-gas PSA as well as the purge gas the H2-to-CO ratio ranges from 2.4 to 2.5 and the CO2-to-CO ratio is
of the methanol synthesis loop and even the gas separated from about 0.14. As the syngas produced in the reformer has an excess of
the crude methanol are burnt, was simulated by a stoichiometric H2, a fraction of the hydrogen separated in the PSA system is sent
reactor, which transfers the heat released from the combustion to a PEM fuel cell to be converted into power or to the furnace if
reaction to the reforming reactor to operate at the specified tem- necessary. For achieving a CO2-rich gas stream to be led for future
perature. The flue-gas temperature is set at 1000 °C. The flow-rate sequestration, a third PSA unit is necessary (although it could be
of the gas to be burnt is computed as that needed to match the heat also used a membrane-based technology), where CH4 can be sepa-
flow required in the reforming reactor. Every operating condition rated. After depressurization, the CH4-rich stream is available at
leading to have a deficit or surplus of heat flow in the reformer- low pressure as a fuel.
furnace is outside the admissible operation window, as described The three PSA units have been simulated in a simplified way, by
below. The air enters the furnace by a fan with such an excess that ideal separators, but working at realistic pressure and temperature
there is an O2 content of 3 vol% in the flue-gas. The product gas (30 atm and 35 °C, respectively). The depressurization steps are
leaving the reformer is expanded in a turbine up to 30 atm, con- simulated by a valve located at the PSA off-gas stream of the cor-
verting thus the syngas pressure energy into power. responding unit. The PSA system is assumed to give a high purity
H2 (99%) with a hydrogen recovery of 90% (somewhat lower than
2.2. Syngas conditioning section the maximum found in the literature [31]), as well as a CO2 stream
of +95% purity, which is the specification required for transport and
The syngas is cooled down to 35 °C by two serially connected sequestration of CO2 [32]. In addition, it is assumed that the PSA
heat exchangers and the condensed water is separated from the system recovers 98% of the produced CO with a purity of +90%.
 742
F.J. Gutiérrez Ortiz et al. / Fuel 105 (2013) 739–751
Fig. 2. Heat-integrated flow-sheet for producing methanol and power by supercritical water reforming of glycerol.
 F.J. Gutiérrez Ortiz et al. / Fuel 105 (2013) 739–751 743

H2 to PEMFC H2 to furnace

CH4-rich stream
1 atm
H2-rich stream To furnace

PSA unit 3
30 atm
35 ºC

35 ºC PSA unit 1 30 atm

SYNGAS 35 ºC PSA unit 2

30 atm For sequestration Compress to: 85 atm
Heat to: 250 ºC
30 atm
CO2-rich stream
1 atm

Methanol
30 atm
converter
1 atm
H2 − CO 2
≈ 2 .1
CO + CO 2

CO-rich stream
% recovery (PSA system)
PSA-1 (top) PSA-2 (bottom) PSA-3 (top) PSA-3 (bottom) Gas specifications:
H2 95 - 4.5 0.5 • H2/CO = 2.4 – 2.5
CO - 98 1.5 0.5 • CO2/CO = 0.13 – 0.14
CO2 - 1 9 90 • CH4 < 3 vol%
CH4 - 1 90 9
H2-rich stream CO-rich stream CH4-rich stream CO2-rich stream

Fig. 3. PSA system flow-sheet for syngas conditioning.

Also, in this PSA system, CH4 is the second relevant component in specified a CO conversion per pass of 20% as well as a CO2 conversion
the CO2-rich gas stream (Fig. 3). per pass of 3%. If an equilibrium reactor was selected for once-
through operation, the CO conversion and CO2 conversion would
2.3. Methanol synthesis and purification section be 76.8% and 9.6% (thermodynamic limits), respectively, which are
much higher than real conversions per pass in industrial reactors.
The typical operation conditions of the synthesis are in the The reactor effluent is cooled down to 30 °C in order to conden-
ranges of 220 to 280 °C and 50 to 100 atm. Beyond 280–300 °C, sate the crude methanol, and to separate it from the gas phase in a
the catalyst would be subjected to sintering and fusion, which gas–liquid separator. The gas is recompressed and recycled to in-
would result in permanent damage of the catalyst; on the other crease the overall CO conversion into MeOH, and a fraction of the
hand, the decrease in the reaction temperature favors the right recycled gas that is purged to prevent the accumulation of inert
shift in the equilibrium although significantly reduces the reaction gases (mainly, methane) is sent to the furnace for aiding to achieve
rate. Therefore, the operating temperature range is a compromise. the energy self-sufficiency. This has a direct effect on the overall
In addition, higher pressures favor methanol from the equilibrium CO conversion as well as on the performance of the energy-inte-
standpoint but the increase above 80 atm is not very significant. In grated process. Thus, the overall process performance depends on
this work, the upgraded syngas coming from the PSA is first com- the purge ratio or purge-to-recycle ratio, which is one of the
pressed to 85 atm and then heated to 250 °C, which are the oper- parameters to take into account in the global process optimization,
ating conditions to be used in the methanol reactor that operates as below described.
in gas phase and is cooled to remove the heat of reaction. The crude methanol typically contains water and also low con-
The reactor operates with low conversion per pass of syngas centrations of dimethyl ether (about 100 ppm), carbonyl com-
due to the high temperature sensitivity of the catalyst and the pounds (20 ppm) and higher alcohols, C2+, (about 400 ppm). In
thermodynamic equilibrium, which implies a large recycle of fact, high selectivity is a key requirement for methanol catalyst,
unconverted gas. Normally, a gas phase reactor has a CO conver- and it is around 99.8% if a Cu/ZnO/Al2O3 catalyst is used. Usually,
sion per pass lower than 16–20%. A high CO to CO2 ratio increases distillation is normally used to purify the crude methanol product
the reaction rate and the conversion per pass (up to 40% [20]), as to meet specifications [33]. In this paper, minor by-product forma-
well as it lessens the formation of water, reducing the catalyst tion was not considered (a selectivity of 100% is assumed), but a
deactivation rate. subsequent purification of the crude methanol is included in order
Several types of methanol synthesis reactors are used in produc- to separate water and dissolved gases. Thus, the liquid stream leav-
tion plants. They may be adiabatic (e.g., ICI) or quasi-isothermal ing the loop, which contains methanol, water and some dissolved
(e.g., Lurgi). In this paper, the temperature at the reactor outlet gases, is heated and expanded to the atmospheric pressure by a
was specified as constant (250 °C) and the reaction heat is released valve, to separate the dissolved gases in a flash separator, from
to a cooler so saturated steam is produced at 230 °C. The methanol which they are sent to the furnace. Finally, the crude methanol en-
reactor has been simulated as a stoichiometric reactor and it was ters a distillation column where methanol is separated from water
744 F.J. Gutiérrez Ortiz et al. / Fuel 105 (2013) 739–751

Table 1
Specifications of the individual process units for the simulation of the methanol synthesis process from the reforming of glycerol using supercritical water.

Code Equipment Specifications

P1 Pump Efficiency: 0.8
Outlet pressure: 240 atm
HE01 Heat exchanger Hot stream outlet temperature: 200 °C
HE02 Heat exchanger Touthotfluid–Toutcoolfluid = 3 °C
HE03 Heat exchanger Hot stream outlet temperature: 400 °C
SRSG Supercritical Reforming Reactor Operating temperature: variable (700–1000 °C)
TURB Turbine Type: Isentropic; Isentropic Efficiency: 0.72
Outlet pressure: 30 atm
HE04 Heat exchanger Hot stream outlet temperature: 35 °C
PSA1 Pressure swing adsorption unit It removes most the H2 (95%) from the other gases (Fig. 3)
Outlet pressure if valve: 1.1 atm (30 atm in other case)
PSA2 Pressure swing adsorption unit Specified on details given in Fig. 3
Outlet pressure if valve: 1.1 atm (30 atm in other case)
PSA3 Pressure swing adsorption unit Specified on details given in Fig. 3
Outlet pressure if valve: 1.1 atm (30 atm in other case)
COMP1 Train of compression with two intermediate coolers and one final Type: Isentropic; Isentropic Efficiency: 0.72
Three compression stages; intermediate cooling to 35 °C
Outlet pressure: 30 atm
COMP2 Train of compression with two intermediate coolers Type: Isentropic; Isentropic Efficiency: 0.72
Three compression stages; intermediate (and final) cooling to 35 °C
Outlet pressure: 30 atm
COMP3 Compressor Type: Isentropic; Isentropic Efficiency: 0.72
Outlet pressure: 85 atm
HE05 Heat exchanger Cold stream outlet temperature: 250 °C
RMETOH Methanol reactor 250 °C @ 85 atm
Pressure drop: 0.1 atm
CO + 2H2 ? CH3OH; CO conversion per pass: 0.20
CO2 + 3H2 ? CH3OH + H2O; CO2 conversion per pass: 0.03
Surplus heat flow to COOLER2
HE06 Heat exchanger Hot stream outlet temperature: 30 °C
HE07 Heat exchanger Cold stream outlet temperature: 50 °C
HE08 Heat exchanger Hot stream outlet temperature: 120 °C
FURNACE Furnace–combustor Combustion of everything able to be oxidized
1000 °C @ 1 atm
Surplus heat flow to SRSG
FAN1–FAN3 Fans Type: Isentropic; Isentropic Efficiency: 0.72
Outlet pressure: 1.1 atm
HE08 Heat exchanger Hot stream outlet temperature: 140 °C
P2–P5 Pumps Efficiency: 0.8
Outlet pressure: 1.1 atm
HE09 Heat exchanger Cold stream outlet temperature: 80 °C
HE10 Heat exchanger Hot stream outlet temperature: 120 °C
PEMFC PEM fuel cell (stoichiometric reactor) Heat + work to SPLIT5
H2 + 0.5 O2 ? H2O
Isothermal reactor: 80 °C
COOLER1 Heat exchanger Cooling water outlet temperature: 40 °C
COOLER2 Heat exchanger Saturated steam at 230 °C (27.97 atm) – heat flow from RMETOH –
DEST Operating pressure: atmospheric (1 atm)
Total condenser
Reflux ratio: 1.5Rmin
Methanol recovery (distillate stream): 99%
Water recovery (bottom stream): 97%
HEATER1 Heat exchanger Source of heat flow towards the reboiler of the distillation section
COOLER3 Heat exchanger Sink of heat flow coming from the condenser of the distillation section
P6 Pump Efficiency: 0.8
Outlet pressure: 27.97 atm

with a recovery of 99%. This section is also energy-integrated with and the saturated steam were used the NRTL and STEAMNBS
the overall process, so the reboiler duty is provided by the satu- methods, respectively.
rated steam produced in the methanol reactor cooling and the con- The simulation did not predict coke formation in the supercrit-
denser duty is released to the cooling water circuit of the process. ical reformer for any of the experimental conditions used in this
paper, and any other compound apart from those mentioned has
a mole fraction lower than 1012. Likewise, for all operating condi-
2.4. Simulation remarks tions, the calculated glycerol conversion was always 100%, at equi-
librium condition.
Specifications of the main units used in the simulation are
shown in Table 1. The computation has been made with the 3. Method of optimization
aid of AspenPlus™ version 2006.5 (Aspen Technology, Inc.,
USA). The predictive Soave–Redlich–Kwong (PSRK) thermody- The aim was to maximize the overall process efficiency in terms
namic method was used as the most suitable dealing with of total net power and methanol production, for a given mass flow-
supercritical conditions [11], although for the distillation column rate of glycerol fed into the process. As a constraint, the process
 F.J. Gutiérrez Ortiz et al. / Fuel 105 (2013) 739–751 745

Table 2
Main concepts considered in the energy and exergy analysis.

Concept Equation
Lost power for the overall process
X X X   
_ overall ¼ T0 _ 
LW ðB_ in  B_ out Þ  _ out þ
W _ in  1 
W Q cooling 
system
T PEMFC

Overall energy efficiency (for pure

glycerol)
_ net þ m
W _ MeOH LHVMeOH
genergy ¼ _ Gly LHVGly
m
Heat exchangers
X X X X
_ HE ¼ T 0
LW ðS_ out  S_ in Þhotfluid þ T 0 ðS_ out  S_ in Þcoolfluid ¼ T 0 S_ out  T 0 S_ in
Reforming reactor
X
_ SRSG ¼ B_ lost ¼ B_ out þ
LW B_ in ; Q_ SRSG ¼ 0
Furnace
X   
T0 _ 
_ FURNACE ¼ B_ out þ
LW B_ in  1  Q Furnace ; Q_ Furnace ¼ H_ out  H_ in < 0
T Furnace
SRSG and furnace coupled
X X
_ SRSG—Furnace ¼ 
LWS ðB_ out  B_ in ÞFurnace  ðB_ out  B_ in ÞSRSG
Train of compression with intermediate
cooling
X X  
_ COMP ¼ B_ out þ B_ in þ _ i T0
LW W ðH_ out  H_ in Þj 1 
i;8stage j;8int cool
ðT out þ T in Þ=2 j

Methanol reactor
  
_ RMeOH ¼ B_ lost ¼ B_ out þ B_ in  1  T0 _ 
LW Q RMeOH 
T RMeOH
Heater
  
_ Heater ¼ B_ out þ B_ in þ 1  T0 _ 
LW Q heating 
T source
Exergy loss of the PEM fuel cell
subsystem
X   
_ PEMFC ¼ B_ out þ T0 _ 
LW B_ in  1  _ PEMFC
Q cooling   W
T PEMFC
Electric power generated by the fuel cell
()
_ PEMFC ¼ g m
W _
FC H2 LHVH2

Cooler
  
_ Cooler ¼ B_ out þ B_ in  1  T0 _ 
LW Q cooling 
T heatsource
Distillation column
  !
X T0  T0  
_ DIST ¼  _  _ 
LW B_ out þ B_ in þ 1  Q Reboiler   1  Q Condenser 
T saturatedsteam ðT out þ T in Þcoolingwater =2

Note 1: For the analysis, it is assumed that to obtain a power of 1 kW in the PEMFC unit, the required molar flow rate of hydrogen is 33.3 mol/h [34], corresponding to an
efficiency of the fuel cell stack of about 0.45 [35].
Note 2: Lower Heating Value of glycerol: 16 MJ/kg; Lower Heating Value of methanol (19 MJ/kg).

must be energy self-sufficient, so residual gases with chemical en- the outlet pressure of the expander was the minimum required
ergy must be sent to the furnace. The total net power is the PEM to perform the separation of gases in the PSA system (30 atm),
fuel cell power plus the power of the turbine minus the consumed allowing a high power recovery in the turbine. The pressure
power in all the pumps, blowers and compressors. and temperature of the methanol reactor were the usual in these
Among all the possible optimization variables, some of them reactors. Thus, there are still three independent variables for
were fixed in this study. First, the reforming pressure did not optimization: the reforming temperature (RT), the water-to-glyc-
significantly affect the process in the range from 200 to erol mass ratio in the feed (W/G), and the purge ratio in the
300 atm [11] and a fixed value of 240 atm was chosen. Likewise, methanol synthesis loop (PR).
746 F.J. Gutiérrez Ortiz et al. / Fuel 105 (2013) 739–751

Fig. 4. Methanol production versus W/G mass ratio, when reforming using SCW at 800 °C, for the range of purge ratio from 0.1 to 0.5.

Fig. 5. Methanol production versus W/G mass ratio, when reforming using SCW for the two range limits of purge ratio and four reforming temperatures.

Fig. 6. Total net power and PEM fuel cell power versus W/G mass ratio when reforming using SCW at 800 °C for three purge ratios (0.1, 0.3 and 0.5).

The reforming temperature is ranged from 700 to 1000 °C, as higher reforming temperature will provide a higher content of
the best ones for the supercritical reformer performance [11]. A CO and H2 in the syngas and then, the methanol production will in-
 F.J. Gutiérrez Ortiz et al. / Fuel 105 (2013) 739–751 747

Fig. 7. Total net power and PEM fuel cell power versus W/G mass ratio when reforming using SCW for the two range limits of purge ratio and four reforming temperatures.

Fig. 8. Specific production of methanol (kg of produced MeOH per kg of glycerol fed) versus W/G mass ratio.

crease, although a higher hydrogen fraction is needed to reach the Finally, to complete the study, an exergy analysis was also car-
energy self-sufficiency and thus the power obtained in the fuel cell ried out to assess the process performance from this standpoint
will be lower. under the optimal conditions. Table 2 shows some details of this
The range of values for the purge ratio was from 0.1 to 0.5 (re- analysis, so as to compute the exergy loss of all the units and to
cycle-to-purge ratio from 9 to 1), which is somewhat wider than know where the more significant irreversibilities occur. In this ta-
usual [20]. A minimum purge is necessary to avoid accumulation _ represents the energy flow (power)
ble, the term of Lost Work ðLWÞ
of inerts in the methanol loop, but if the purge ratio increases, loss due to the process irreversibilities.
the overall CO conversion and methanol production will decrease
although, at the same time, the higher flow-rate of residual gases 4. Results and discussion
will provide more energy for the reformer-furnace and less hydro-
gen fraction would be needed, leading to generate more power in In this study, a base feed of 1000 kg/h of glycerol was selected.
the fuel cell. The required W/G mass ratio is achieved by adding more or less
Regarding with the W/G mass ratio range, at low glycerol feed water.
concentrations, i.e., a high W/G ratio, the energy demand will greatly As a first result, Fig. 4 illustrates that, for a given RT, the meth-
increase and external fuel will be needed thus violating the energy anol production slightly increases as the W/G mass ratio in-
self-sufficiency constraint. Likewise, at high glycerol feed concentra- creases, and still more for low values of PR. The two gray
tions, there will be a heat surplus in the overall process, even sending dashed lines bound the admissible operation window as they rep-
all the hydrogen not used in the methanol production to the fuel cell. resent points corresponding to fractions of H2 sent to the furnace
The admissible W/G ratio range depends on the RT and the PR used. of 0.0 and 1.0. Likewise, Fig. 5 shows the joint effect of RT and PR
So, for each pair RT–PR the lower and upper limits of W/G correspond on the methanol production, which increases when reducing the
to hydrogen fractions sent to the furnace of 0.0 and 1.0 respectively. PR but also if the RT is increased. It should be noted that when
By this way, an operation window is established. reforming at 1000 °C and the purge ratio is of 0.1 the process does
748 F.J. Gutiérrez Ortiz et al. / Fuel 105 (2013) 739–751

(a)

(b)

(c)

Fig. 9. Indexes of the process performance versus W/G mass ratio: (a) Specific production of methanol production, (b) total net specific power generated, and (c) overall value
of MeOH plus power.

not become energy self-sufficient. When changing the PR, the dif- minimum purge ratio lead to maximum methanol production
ferences in the methanol production are more notorious at high accordingly to higher glycerol feed concentrations (lower W/G
temperatures. Therefore, maximum reforming temperature and mass ratio).
 F.J. Gutiérrez Ortiz et al. / Fuel 105 (2013) 739–751 749

Fig. 10. Overall energy efficiency versus W/G mass ratio.

Distillation column;
2,30 PEM fuel Mixers; 2,86
PSA system; 1,62 cell; 2,29
Pumps; 0,90
Methanol reactor; 0,93 Heat exchangers;
37,40

Furnace; 28,91

Supercritical reformer; Turbine; 2,53 Compressors; 4,33

15,93
Mixers Pumps Heat exchangers
Compressors Turbine Supercritical reformer
Furnace Methanol reactor PSA system
Distillation column PEM fuel cell

Fig. 11. Exergy losses per units or set of units as percentage of the overall lost exergy flow (case study: RT of 1000 °C, all the hydrogen sent to the fuel cell and PR of 0.2).

Fig. 6 depicts that, at a given RT, both the power of the PEM fuel given RT and PR, although it increases as the RT rises at a given PR
cell and the total net power increase as the W/G ratio increases, and as the PR decreases at a given RT.
reaching a maximum just for the W/G in which all the excess of In Fig. 9 the PR is withdrawn from the discussion, so the trends
hydrogen is sent to the fuel cell. If W/G continues to rise, an corresponds to the optimal conditions for the RT and the W/G in
increasing fraction of hydrogen is sent to the furnace, decreasing which all the residual gas is sent to the furnace and all the excess
thus the power of the PEM fuel cell and the total net power. In of hydrogen is sent to the PEM fuel cell, within the admissible
addition, the trends are drawn in an almost parallel way, at a given operation window, which includes a purge ratio range from 0.1
PR, since the power of the turbine barely changes because the flow- to 0.5. In this graph, it seems that there are some W/G values for
rate of the feed is fairly constant due to the narrow allowable W/G which no solution. However, this is only apparent, and indeed
range. As a consequence, the maximum total net power matches these points exist for intermediate temperature between 700 and
the maximum for the power of the PEM fuel cell. Besides, the max- 800 °C. Fig. 9a illustrates an almost linear relationship between
imum shifts to higher W/G ratios as the PR increases. Thus, when the specific production of methanol and the W/G ratio, indepen-
changing the PR, the highest power is obtained at the upper limit dently of the RT, which only would set the allowable W/G ratio.
of the PR. In Fig. 7 the effect of the reforming temperature (RT) Fig. 9b depicts a different behavior of the total net power per kg/h
on the total net power is depicted for the two limits established of glycerol (specific power), which always increases as the W/G ratio
for the PR. It can be observed as there is a maximum for each pair increases for every RT. Fig. 9c is drawn to show how the weighted
of RT and PR, corresponding to the W/G ratio in which all the sur- sum of methanol production and net power varies with W/G and
plus hydrogen is sent to the fuel cell. However, and making a com- RT, within the admissible overall operation window. The weights
parison for a given purge ratio, the highest power is achieved at were calculated according to their current market prices [36,37],
800 °C for a PR of 0.5. and thus it was obtained the following equation:
Fig. 8 shows that the production of methanol per kg of glycerol _ total =m
_ MeOH =m
Overall specific value ¼ 3:5ðm _ Gly Þ þ 1:0ðW _ Gly Þ ð6Þ
(specific production) scarcely varies as the W/G ratio increases, at a
750 F.J. Gutiérrez Ortiz et al. / Fuel 105 (2013) 739–751

since, nowadays, 1 kg/h of MeOH worth 3.5 times more than 1 kW from 0.1 to 0.2. Afterwards, Kordabadi and Jahanmiri [43] achieved
power. a methanol mole fraction of 0.056 in a 7 m length reactor.
The linear relationship shown in Fig. 9c may be explained taking Klier et al. [44] showed the dependence of carbon conversion to
into account the higher weight of the methanol in the computa- methanol using a CO2/CO/H2 synthesis gas containing 70% H2 and a
tion. Therefore, the maximum value of methanol plus power is ob- variable ratio of CO2 and CO. Thus, they obtained a percent carbon
tained for the lower limit of the W/G mass ratio, and the conversion to methanol of about 62% for a composition CO2/CO/H2
corresponding reforming temperature, that is, W/G = 1.68 and of 6/24/70, at 250 °C and 75 atm. In this study, in the case of using a
RT = 1000 °C. The corresponding purge ratio is 0.2. Fig. 10 illus- composition of the syngas entering the methanol synthesis reactor
trates the overall energy efficiency versus the W/G ratio, showing CO2/CO/H2 equal to 5.8/21.6/70.6 (purge ratio of 0.1), it was ob-
similar trends to those of the overall specific value of methanol tained a 64.9% conversion to methanol. Vanden Bussche and Fro-
and power. In addition, an exergy analysis was performed to deter- ment [45] proposed the kinetic model for the methanol synthesis
mine the direction for potential improvements for the system and and verified that their model describes well the experimental data
process units. Thus, Fig. 11 illustrates the contribution of some of obtained by Klier et al. [44].
the units or set of units to the exergy losses expressed as percent- Likewise, Abrol and Hilton [46] obtained a mole fraction of
age of the overall exergy losses, at 1000 °C reforming temperature, methanol at the loop outlet, before entering the purification sec-
and a purge ratio of 0.2. This graph has been obtained for each case tion, of 0.8998 for a syngas composition CO2/CO/H2/CH4 equal to
study (but not shown for simplicity), and the same qualitative re- 3.2/28.5/67.5/0.6 and using a purge ratio of 0.18 (recycle-to-purge
sults arise. It can be seen that 37.4% of the exergy losses are due to ratio of 4.5), operating at 250 °C and 51 atm.. In this study, a mole
the heat exchangers. Furthermore, the contribution of reactors fraction of methanol in crude stream of 0.8969 for a syngas compo-
SRSG and Furnace, as they are coupled, is 44.8% of the total exergy sition CO2/CO/H2/CH4 equal to 3.7/26.9/68.1/0.6, using a purge ra-
losses. For the rest of units or sets of units the exergy losses are tio of 0.20.
lower than 5.0%.
Finally, a comparison of the results obtained in this study with 5. Conclusions
other published results was carried out for the main process units
(supercritical reformer and methanol synthesis reactor). A comprehensive process for methanol and power production
Although the number of publications on the reforming of glyc- from syngas obtained by reforming of glycerol using supercritical
erol using supercritical water is fairly limited, the few experimen- water was proposed and studied. The aim was to maximize the
tal results found in the literature match reasonably well with the overall process efficiency in terms of total net power and methanol
results obtained in this study based on the assumption of reach- production, under the criterion of making the overall process en-
ing chemical equilibrium. Thus, at feed concentration of 30 wt.% ergy self-sufficient. The optimal conditions relative to the reform-
glycerol, Byrd et al. [38] obtained a product gas composition ing temperature and W/G ratio, along with the purge ratio in the
H2/CO/CO2/CH4 of 47.2/3.2/34/15.6, at a temperature of 800 °C methanol synthesis loop, were identified. The results show that
and a pressure of 241 bars, over Ru/Al2O3 catalysts in a tubular the objective is achieved with the use of maximum reforming tem-
fixed-bed flow reactor. In the present study, in the case of sending perature and minimum W/G ratio, corresponding to the admissible
all the excess of hydrogen to the fuel cell, the product gas compo- minimum purge ratio. The overall specific value of methanol pro-
sition H2/CO/CO2/CH4 ranged from 43.9/11.4/25.8/18.9, when duction and power generation was computed using relative
using a glycerol feed concentration of 31.2 wt.% (W/G equal to weights for both variables, as well as the overall energy efficiency.
2.2) corresponding to a purge ratio of 0.1, to 46.9/11.1/25.5/ As a result of this research, the maximum value of these two in-
16.5, when using a feed concentration of 27.3 wt.% (W/G equal dexes were obtained using a reforming temperature of 1000 °C, a
to 2.6) corresponding to a purge ratio of 0.5, at 800 °C and W/G mass ratio of 1.68 and a purge ratio of 0.2, so a specific meth-
240 atm. Experimental yields of CO and CO2 are somewhat differ- anol production of 0.270 kg MeOH/kg glycerol is obtained. The to-
ent from the predicted values at equilibrium, but it should be tal net specific power from the expander and the fuel cell is
noted that the former were obtained in a catalytic reactor with 0.265 kW/kg glycerol. The overall energy efficiency is 38.0%, under
a small residence time (1 s), in which probably equilibrium was these conditions. In addition, the separated CO2 for sequestration is
not attained. 0.38 kg/kg glycerol, which gives added value to the proposed
Regarding with the methanol synthesis reactor and loop, previ- process.
ous experimental or simulated data coincide very well with simu-
lation results illustrated in this study. First, Graaf et al. [39,40]
Acknowledgments
concluded that the chemical equilibria of the reactions involved
could be described very well with the use of thermochemical data
This research is supported by the Science and Technology
based on ideal gas behavior in combination with a correction for
Ministry of Spain under the research Project ENE2009-13755, as
non-ideality of the gas mixture as predicted by the Soave–
a Project of Fundamental Research inside the framework of the
Redlich–Kwong equation of state (SRK EOS). In addition, the results
National Plan of Scientific Research, Development and Technologi-
obtained with the Peng–Robinson equation of state (PR EOS) gave
cal Innovation 2008–2011.
similar results to those of SRK EOS. By this way, it has been con-
firmed that the results of simulation PSRK EOS used in this study
match quite well the results using the SRK or PR equations of state. References
Later, Graaf and Beenackers [41] considered a complete synthesis
[1] Slinn M, Kendall K, Mallon C, Andrews J. Steam reforming of biodiesel by-
loop that included a five-fixed bed reactor. With a CO2/CO/H2/ product to make renewable hydrogen. Bioresource Technol 2008;99:5851–8.
CH4 synthesis gas composition equal to 10.8/17.8/69.7/1.7 [2] Nichele V, Signoretto M, Menegazzo F, Gallo A, Dal Santo V, Cruciani G, et al.
Glycerol steam reforming for hydrogen production: design of Ni supported
(SN = 2.06), they obtained a methanol mole fraction of 0.06 at the
catalysts. Appl Catal B-Environ 2012;111–112:225–32.
reactor outlet, at 242 °C, 85 bar and a recycle ratio of 5, equivalent [3] Wang H, Wang X, Li M, Li S, Wang S, Ma X. Thermodynamic analysis of
to a purge ratio of 0.17 (typical of Haldor Topsøe methanol technol- hydrogen production from glycerol autothermal reforming. Int J Hydrogen
ogy [42]). In the present study, the methanol mole fraction at the Energy 2009;34:5683–90.
[4] Authayanun S, Arpornwichanop A, Paengjuntuek W, Assabumrungrat S.
reactor outlet varied from 0.053 to 0.059 in the purge ratio range Thermodynamic study of hydrogen production from crude glycerol
 F.J. Gutiérrez Ortiz et al. / Fuel 105 (2013) 739–751 751

autothermal reforming for fuel cell applications. Int J Hydrogen Energy [24] Bezerra DP, Oliveira RS, Vieira RS, Cavalcante Jr CL, Azevedo DCS. Adsorption of
2010;35:6617–23. CO2 on nitrogen-enriched activated carbon and zeolite 13X. Adsorption
[5] Davda RR, Shabaker JW, Huber GW, Cortright RD, Dumesic JA. A review of 2011;17:235–46.
catalytic issues and process conditions for renewable hydrogen and alkanes by [25] Sircar S, Golden TC. Purification of hydrogen by pressure swing adsorption.
aqueous phase reforming of oxygenated hydrocarbons over supported metal Separ Sci Technol 2000;35:667–87.
catalysts. Appl Catal B 2005;56:171–86. [26] Sircar S, Golden TC. Pressure swing adsorption for hydrogen production. In: Liu
[6] Menezes AO, Rodrigues MT, Zimmaro A, Borges LEP, Fraga MA. K, Song C, Subramani V, editors. Hydrogen and syngas production and
Production of renewable hydrogen from aqueous-phase reforming of purification technologies. New Jersey: Wiley-AIChE; 2010. p. 414–50.
glycerol over Pt catalysts supported on different oxides. Renew Energy [27] Kumar R, Kratz WC. Separation of multicomponent gas mixtures by selective
2011;36:595–9. adsorption. U.S. Patent 5133,785; 1992.
[7] Savage PE. Organic chemical reactions in supercritical water. Chem Rev [28] Sircar S. Production of mixed gases of controlled composition by pressure
1999;99:603–22. swing adsorption. U.S. Patent 4705,541; 1987.
[8] Matsumura Y, Minowa T, Potic B, Kersten SRA, Prins W, van Swaaij WPM, et al. [29] Krishnamurthy R. Hydrogen and carbon monoxide production by hydrocarbon
Biomass gasification in near – and super-critical water: status and prospects. steam reforming and pressure swing adsorption purification. U.S. Patent
Biomass Bioenergy 2005;29:269–92. 5096,470; 1992.
[9] Guo Y, Wang SZ, Xu DH, Gong YM, Ma HH, Tang XY. Review of catalytic [30] Batdorf JA. Method and apparatus for methanol and other fuel production. U.S.
supercritical water gasification for hydrogen production from biomass. Renew Patent 7655,703; 2010.
Sust Energy Rev 2010;14:334–43. [31] Ribeiro A, Santos JC, Rodrigues AE, Rifflart S. Syngas stoichiometric adjustment
[10] Guo LJ, Lu YJ, Zhang XM, Ji CM, Guan Y, Pei AX. Hydrogen production by for methanol production and co-capture of carbon dioxide by pressure swing
biomass gasification in supercritical water: a systematic experimental and adsorption. Separ Sci Technol 2012;47:850–66.
analytical study. Catal Today 2007;129:275–86. [32] Zhang J, Webley PA. Cycle development and design for CO2 capture from flue
[11] Gutiérrez Ortiz FJ, Ollero P, Serrera A, Sanz A. Thermodynamic study of the gas by vacuum swing adsorption. Environ Sci Technol 2008;42:563–9.
supercritical water reforming of glycerol. Int J Hydrogen Energy [33] Bell DA, Towler BT, Fan M. Methanol and derivatives. In: Coal gasification and
2011;36:8994–9013. its applications; 2011. p. 353–71.
[12] Spath PL, Dayton DC. Preliminary screening-technical and economic [34] Choi Y, Stenger HG. Kinetics, simulation and insights for CO selective oxidation
assessment of synthesis gas to fuels and chemicals with emphasis on the in fuel cell applications. J Power Sources 2004;129:246–54.
potential for biomass-derived syngas. Report no. NREL/TP-510-34929. [35] Hou Y, Zhuang M, Wan G. The analysis for the efficiency properties of the fuel
National Renewable Energy Laboratory; 2003. cell engine. Renew Energy 2007;32:1175–86.
[13] Stocker M. Methanol-to-hydrocarbons: catalytic materials and their behavior. [36] Eurostat. statistical office of the European Union official and leading provider
Micropor Mesopor Mater 1999;29:3–48. of high quality statistics on Europe. http://epp.eurostat.ec.europa.eu>.
[14] Lurgi. Methanol-to-propylene – MTP; 2008. <www.lurgi.com>. [37] Methanex. World’s leading methanol producer website <http://
[15] Feng W, Ji P, Chen B, Zheng D. Analysis of methanol production from biomass www.methanex.com>.
gasification. Chem Eng Technol 2011;34:307–17. [38] Byrd AJ, Gupta RB, Pant KK. Hydrogen production from glycerol by reforming
[16] Tabak SA, Yurchak S. Conversion of methanol over ZSM-5 to fuels and in supercritical water over Ru/Al2O3 catalyst. Fuel 2008;87:2956–60.
chemicals. Catal Today 1990;6:307–27. [39] Graaf GH, Sijtsema PJJM, Stamhuis EJ, Joosten GEH. Chemical equilibria in
[17] Bludowsky T, Agar DW. Thermally integrated bio-syngas-production for methanol synthesis. Chem Eng Sci 1986;41(11):2883–90.
biorefineries. Chem Eng Res Des 2009;87:1328–39. [40] Graaf GH, Sijtsema PJJM, Stamhuis EJ, Joosten GEH. On chemical equilibria in
[18] Katofsky RE. The production of fluid fuels from biomass, center for energy and methanol synthesis. Chem Eng Sci 1990;54(3):769–70.
environmental studies. Princeton University; 1993. [41] Graaf GH, Beenackerts AACM. Comparison of two-phase and three-phase
[19] Supp E. Lurgi’s improvements and developments in methanol production and methanol synthesis Processes. Chem Eng Process 1996;35:413–27.
conversion technologies. AIChE Spring Meeting, Anaheim Ca, USA; May 20–23 [42] Dybkjaer I. Topsøe methanol technology. Chem Econ Eng Rev 1981;13(6)
1984. :17–25.
[20] Hamelinck CN, Faaij APC. Future prospects for production of methanol and [43] Kordabadi H, Jahanmiri A. Optimization of methanol synthesis reactor using
hydrogen from biomass. University of Utrecht; 2001. genetic algorithms. Chem Eng J 2005;108:249–55.
[21] Drage TC, Blackman JM, Pevida C, Snape CE. Evaluation of activated carbon [44] Klier K, Chatikavanij V, Herman RG, Simmons GW. Catalytic synthesis of
adsorbents for CO2 capture in gasification. Energy Fuels 2009;23: methanol from CO/H2: IV. The effects of carbon dioxide. J Catal 1982;74: 343–60.
2790–6. [45] VandenBussche KM, Froment GF. A Steady-state kinetic model for methanol
[22] Metz B, Davidson O, Coninck H, Loos M, Meyer L. Special report on carbon synthesis and the water gas shift reaction on a commercial Cu/ZnO/Al2O3
dioxide capture and storage. Switzerland: IPCC; 2005 [chapter 3]. catalyst. J Catal 1996;161:1–10.
[23] Hufton J, Golden T, Quinn R, Kloosterman J, Wright A, Schaffer C, et al. [46] Abrol S, Hilton CM. Modeling, simulation and advanced control of methanol
Advanced hydrogen and CO2 capture technology for sour syngas. Energy production from variable synthesis gas feed. Comput Chem Eng 2012;40:
Procedia 2011;4:1082–9. 117–31.