synthesis gas by catalytic steam reforming of bio …
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Synthesis gas by catalytic steam Synthesis gas by catalytic steam reforming of bioreforming of bio--oil.oil.
F. Bimbela, J.A. Medrano, L. García, F. Bimbela, J.A. Medrano, L. García, F. Bimbela, J.A. Medrano, L. García, F. Bimbela, J.A. Medrano, L. García, M. Oliva, J. Ruiz, De Chen, J. Arauzo M. Oliva, J. Ruiz, De Chen, J. Arauzo
Thermochemical Processes Group (GPT)Aragón Institute for Engineering Research (I3A)
University of Zaragoza, María de Luna, 3, E-50018, Zaragoza, Spain
Hydrogen economy:
� Increasing interest in Hydrogen economy:
� Several chemical uses.
� Utilization as clean fuel in high energetic efficiencysystems like fuel cells in stationary, mobile or portableapplications that can be used in vehicles.
H2O
THERMOCHEMICAL CONVERSIONTHERMOCHEMICAL CONVERSION
GASIFICATIONGASIFICATION
CHCH44/CO/CO22 HH22/CO/CO
PYROLYSISPYROLYSIS
Supercritical conditionsSupercritical conditions FlashFlash
HH22/CO/CO22
CHCH44/CO/CO22
Reforming Reforming ++ShiftShift
BioBio--oiloil
Reforming Reforming ++ShiftShift
Reforming Reforming ++ShiftShift
ShiftShiftSynthesisSynthesis
CHCH33OH/COOH/CO22
HH22/C/C
SevereSevere
Steam reforming of pyrolysis liquids (Bio-oil):
PyrolysisBio-oil
BTG process (fast pyrolysis)� Complex mixture of organic
compounds and water*.
� Are unstable and suffer fromaging.
* Oasmaa, D. Meier, J. Anal. Appl. Pyr., 73 (2005) 323
Steam reforming:
� Vegetable oils:
� Sunflower� Soya� Rapeseed� Palm� …
� Trap grease � Bioethanol
Introduction
Steam reforming:
� Bioethanol � Biobutanol
Steam reforming:
� Important increasing in biodiesel production
� Glycerol
Glycerol prices decrease, so it isnecessary to find new ways toconvert glycerol into valuableadded products � H2
Introduction
Ligninic fraction
Aqueous fraction
Steam reforming of pyrolysis liquids (Bio-oil):
High valuable coproducts from bio-oil*
Higher stability
* J. Shabtai, W. Zmierczak, E. Chornet, Evironment, Chemicals, Fibers and Materials (Ed. by R.P. Overend, E. Chornet) Vol2 (1997) 1507
OBJECTIVES:OBJECTIVES:
�� ExperimentalExperimental workwork withwith modelmodel compoundscompounds andand withwith thethe aqueousaqueousfractionfraction ofof biobio--oiloil bothboth atat micromicro andand benchbench scalesscales..
�� DevelopmentDevelopment ofof suitablesuitable catalystscatalysts forfor thethe processprocess::
�� AdequateAdequate catalyticcatalytic activityactivity andand selectivityselectivity towardstowards HH22..
�� ResistanceResistance toto deactivationdeactivation byby cokingcoking depositiondeposition..
�� ResistanceResistance toto attritionattrition toto workwork atat fluidizedfluidized bedbed..
�� DevelopmentDevelopment ofof thethe processprocess atat aa benchbench--scalescale fluidizedfluidized--bedbedfacilityfacility andand scalescale upup toto aa demonstrationdemonstration plantplant..
CHARACTERISTICS OF CHARACTERISTICS OF BIOBIO--OOIL*IL*
(*Oasmaa and Meier, (*Oasmaa and Meier, J. Anal. Appl. Pyrol. 73, (2005), 323J. Anal. Appl. Pyrol. 73, (2005), 323))
ORGANICS / WATER
(85/15 w/w)
� Heterogeneous
properties (feedstock)
� Colour: Dark red /
brown
� Odour: smoke like
� Quite viscous at room
temperature
Thermally unstable WATER ADDITION:
� Thermally unstable
(polymerization)
� High oxygen content
(ca. 40 % dry matter)
� pH: 2.3 – 2.8
� Alcohols
� Carboxylic acids
� Sugars
� Aldehydes
� Ketones
� Complex carbohydrates
� Lignin derived materials
WATER ADDITION:
WATER INSOLUBLE
FRACTION
(Pyrolytic lignin)
AQUEOUS
FRACTION
Fine Chemicals(Kelley et al., 1997; Shabtai et al., 1997)
Catalytic Steam
Reforming(Czernik et al., 1997)
Great complexity!
CHARACTERISTICS OF CHARACTERISTICS OF BIOBIO--OOIL*IL*
(*Oasmaa and Meier, (*Oasmaa and Meier, J. Anal. Appl. Pyrol. 73, (2005), 323J. Anal. Appl. Pyrol. 73, (2005), 323))
� Alcohols
� Carboxylic acids
� Sugars
� Aldehydes
� Ketones
� Complex carbohydrates
� Lignin derived materials
↓↓↓↓Experimental work with model
compounds:
• Acetic acid
• Acetol
• 1-Butanol
• D-Fructose
CATALYSTS PREPARED AT INCREASING pH
HYDRATED
PRECURSOR
Ni(NO3)2·6H2O
Al(NO3)3·9H2O
FILTERINGFILTERINGFILTERINGFILTERING
DRYINGDRYINGDRYINGDRYING
3h, 3h, 3h, 3h,
REDUCTIONREDUCTIONREDUCTIONREDUCTION
10 % H10 % H10 % H10 % H2, , , ,
T = 650ºCT = 650ºCT = 650ºCT = 650ºC
1 hour1 hour1 hour1 hour
CALCINED
PRECURSOR
ACTIVATED
CATALYST
NH4OH
pH=7.9pH=7.9pH=7.9pH=7.9
T = T = T = T =
40ºC40ºC40ºC40ºC
COPRECIPITATIONCOPRECIPITATIONCOPRECIPITATIONCOPRECIPITATION
CALCINATIONCALCINATIONCALCINATIONCALCINATION
3h, 3h, 3h, 3h,
T = 750ºCT = 750ºCT = 750ºCT = 750ºC
Characterization: Catalysts prepared at increasing pH
NiONiAl O
23 % NiNiONiAl O
23 % Ni
XRD
XPS
1200 1000 800 600 400 200 0
O 1s
O 2s
Al 2p
Ni 3p
Al 2s
Ni 2p
ab
Ni LMM
C 1s
Binding energy (eV)
28%
33%
23%
O KLL
d
856.0 (2.9)
856.0 (2.8)
856.6 (2.9) −23 %
854.3 (1.8)33 %
−28 %
Ni 2p3/2Sample
856.0 (2.9)
856.0 (2.8)
856.6 (2.9) −23 %
854.3 (1.8)33 %
−28 %
Ni 2p3/2Sample
� BET: – 23 % Ni → Sg = 205 m
2/g
– 28 % Ni → Sg = 205 m2/g
– 33 % Ni → Sg = 180 m2/g
� ICP – OES:
10 20 30 40 50 60 70 80 90
2 θ
c)
Inte
nsit
y (a
.u.)
b)
NiAl2O
4
a)
23 % Ni
28 % Ni
33 % Ni
10 20 30 40 50 60 70 80 90
2 θ
c)
Inte
nsit
y (a
.u.)
b)
NiAl2O
4
a)
23 % Ni
28 % Ni
33 % Ni
22.0 %23 %
32.1 %33 %
26.9 %28 %
RealTheoretical
22.0 %23 %
32.1 %33 %
26.9 %28 %
RealTheoretical
880 870 860 850
Binding energy (eV)
23%
28%
33%
CATALYSTS PREPARED AT CONSTANT pH
HYDRATED
PRECURSOR
FILTERINGFILTERINGFILTERINGFILTERING
DRYINGDRYINGDRYINGDRYING
6h, 6h, 6h, 6h,
REDUCTIONREDUCTIONREDUCTIONREDUCTION
10 % H10 % H10 % H10 % H2, , , ,
T = 650ºCT = 650ºCT = 650ºCT = 650ºC
10 hours10 hours10 hours10 hours
Ni(NO3)2·6H2O
Al(NO3)3·9H2O
Mg(NO3)2·6H2O
CALCINED
PRECURSOR
ACTIVATED
CATALYST
COPRECIPITATIONCOPRECIPITATIONCOPRECIPITATIONCOPRECIPITATION
CALCINATIONCALCINATIONCALCINATIONCALCINATION
6h, 6h, 6h, 6h,
T = 600ºCT = 600ºCT = 600ºCT = 600ºCCu(NO3)2·3H2O
Aging: Aging: Aging: Aging:
T = 80ºC, T = 80ºC, T = 80ºC, T = 80ºC,
15h15h15h15h
pH=8.5pH=8.5pH=8.5pH=8.5NaOH Na2CO3
Study with Microactivity plant*:Study with Microactivity plant*:
�� MicroactivityMicroactivity plantplant::
�� MicroMicro--scalescale fixedfixed bedbed
�� ExperimentsExperiments withwith differentdifferent modelmodelcompoundscompounds::
�� AceticAcetic acidacid�� AcetolAcetol�� AcetolAcetol�� 11--ButanolButanol�� DD--FructoseFructose
�� OptimizedOptimized experimentalexperimental conditionsconditions::
�� 650650ºCºC�� 11 hh previousprevious reductionreduction* Nickel content of the catalyst: 23, 28 and 33 % (Ni/(Ni+Al) * Nickel content of the catalyst: 23, 28 and 33 % (Ni/(Ni+Al)
relative at. %) relative at. %) * Ni/Al modified with Cu and Mg: Collaboration with the Norwegian University of Science and Technology (NTNU, Trondheim (Norway)).
*Results reported by Bimbela, F. et al., J. Anal. Appl. Pyrol., 79 (2007) 112
Fixed bed microactivity setup
Experimental ConditionsExperimental Conditions
�� AtmosphericAtmospheric pressure,pressure, reactionreaction temperaturetemperature setset atat 650650ºCºC..
�� Liquid feeding rate: 0.15 mL/min of acetic acid aqueous solution (23% Liquid feeding rate: 0.15 mL/min of acetic acid aqueous solution (23% w/w)w/w)
0.05 g of catalyst and 0.05 g of catalyst and ca. 1.5 g sand (particle size: 160ca. 1.5 g sand (particle size: 160--320 320 m)m)�� 0.05 g of catalyst and 0.05 g of catalyst and ca. 1.5 g sand (particle size: 160ca. 1.5 g sand (particle size: 160--320 320 µµm)m)
�� W/mW/mHAcHAc ~~ 11..4646 ggcatalystcatalyst·min/g·min/gaceticacetic acidacid,, S/CS/C molarmolar ratioratio == 55..5858
�� GGcc11HSVHSV ~~ 2850028500 hh--11
�� 11 hh reductionreduction timetime
�� 22 hh reactionreaction timetime
Catalytic steam reforming of ACETOL:Catalytic steam reforming of ACETOL:Influence of the nickel content Influence of the nickel content and reaction temperatureand reaction temperature
(W/(W/mmAcAc = 0,88 g cat= 0,88 g cat··min/g Ac)min/g Ac)
0,100,120,140,160,18
Hyd
roge
n yi
eld
(g/g
ace
tol)
Non catalytic
23 % Ni
28 % Ni
33 % Ni
Equilibrium
650 ºC: Better performance: 28 % Ni.650 ºC: Better performance: 28 % Ni.
23 % y 33 % display similar performances.23 % y 33 % display similar performances.
0 20 40 60 80 100 1200,000,020,040,060,08
Hyd
roge
n yi
eld
(g/g
ace
tol)
Time (min)
650 ºC650 ºC
CH4
CO
CO2
C2H4
ACETIC ACID VS ACETOLACETIC ACID VS ACETOL
0 2 0 4 0 6 0 8 0 1 0 0 1 2 00 ,0 00 ,0 20 ,0 40 ,0 60 ,0 80 ,1 00 ,1 20 ,1 40 ,1 60 ,1 80 ,2 00 ,2 2
Gas
yie
lds
(g/g
ace
tic a
cid)
T im e (m in )
Non catalytic reforming, 650 ºC
Catalytic Reforming. W/morg = 1.46 g·min/g, 650 ºC
0 20 40 60 80 100 1200,000,020,040,060,080,100,120,140,160,180,200,22
Gas
yie
lds
(g/g
)
Time (min)
Acetic acid Acetol
��Significant Significant non catalytic non catalytic reforming for reforming for acetol.acetol.
C2H4
C2H6
C2H2
H2
0 20 40 60 80 100 1200,00
0,20
0,40
0,60
0,80
1,00
1,20
1,40
Gas
yie
lds
(g/g
ace
tic a
cid)
Time (min)
Catalytic Reforming. W/morg = 1.46 g·min/g, 650 ºC
0 20 40 60 80 100 1200,00
0,20
0,40
0,60
0,80
1,00
1,20
1,40
Gas
yie
lds
(g/g
ace
tol)
Time (min)
Acetic acid Acetol
��Slower Slower decrease of decrease of the catalytic the catalytic activity for activity for acetol.acetol.
ACETIC ACID VS ACETOLACETIC ACID VS ACETOL
ACETOL:ACETOL:��Better catalytic reforming:Better catalytic reforming:•• Much higher carbon conversion.Much higher carbon conversion.
•• Greater gas yields.Greater gas yields.
��CHCH44, C, C22HH44 and Cand C22HH66 detected.detected.��Product gas compositions:Product gas compositions:��Product gas compositions:Product gas compositions:•• similar Hsimilar H22
•• higher CO higher CO •• lower COlower CO22
Fluidized bed plant:
FLUIDIZED BED PLANT
Experimental methodExperimental method
Experimental conditionsExperimental conditions
�� AtmosphericAtmospheric pressurepressure andand 650650ºCºC temperaturetemperature
�� Liquid flow rate: 0.75Liquid flow rate: 0.75--0.77 ml/min acetic acid aqueous solution0.77 ml/min acetic acid aqueous solution
�� 7 cm height bed: 1,1 g catalyst and 7 cm height bed: 1,1 g catalyst and ~ 38 g sand (particle size of ~ 38 g sand (particle size of 160160--320 320 m)m)7 cm height bed: 1,1 g catalyst and 7 cm height bed: 1,1 g catalyst and ~ 38 g sand (particle size of ~ 38 g sand (particle size of 160160--320 320 µµm)m)
�� W/mW/mHAcHAc ~~ 66 ggcatalystcatalyst·min/g·min/gaceticacetic acidacid,, S/CS/C molarmolar ratioratio == 55..5858
�� u/uu/umfmf == 1010 GGcc11SHVSHV ~~ 68006800 hh--11
�� 22 hh reactionreaction timetime
CatalystCatalyst A*A* A2*A2* BB B2B2 CC C2C2 DD D2D2 EE††
Relative atomic % Relative atomic % (Ni/(Ni+Al)(Ni/(Ni+Al)
1515 1515 2828 2828 2828 2828 2828 2828 3333
Screening of catalysts. Attrition tests.Screening of catalysts. Attrition tests.
Fluidized bed setupFluidized bed setup
�� FluidizationFluidization attritionattrition requirementsrequirements:: %% weightweight loss/hloss/h << 00..55 %% weight/h*weight/h*
�� MaximumMaximum resistanceresistance toto attritionattrition forfor DD catalystcatalyst
Calcination temperature Calcination temperature (ºC)(ºC)
750&750750&750 900&750900&750 750750 850850 750750 900900 750750 900900 850850
Ca/Ni molar ratio Ca/Ni molar ratio 0.320.32 0.320.32 00 00 1.291.29 1.291.29 0.310.31 0.310.31 5.005.00
Ca/Al molar ratioCa/Al molar ratio 0.060.06 0.060.06 00 00 0.500.50 0.500.50 0.120.12 0.120.12 2.502.50
AttritionAttrition
(% weight loss/h)(% weight loss/h)0.620.62 0.460.46 1.161.16 0.990.99 1.471.47 0.690.69 0.220.22 0.160.16 3.253.25
*Prepared*Prepared byby impregnationimpregnation.. SupportSupport calcinedcalcined atat 900900ºCºC andand impregnatedimpregnated precursorprecursor calcinedcalcined atat 750750ºCºC..
††PreparedPrepared byby coprecipitationcoprecipitation methodmethod atat constantconstant pHpH (precipitating(precipitating agentagent:: NaOHNaOH andand NaNONaNO33 solution)solution)..
Catalysts:
FLUIDIZED BED PLANT
Catalyst Preparation methodwt% Ni
Mg/Al molar ratio
Ca/Al molar ratio
Attrition rate (wt%/h)*
Sustainable fluidizable catalyst
NiAl Coprecipitation 28.5 0 0 1.16 No ����
* wt%/h: weight of catalyst lost per hour. Sustainable fluidizable catalyst when attrition rate < 0.5 wt%/h.
NiMgAl0.26 Coprecipitation 29.3 0.26 0 0.27 Yes ����
NiCaAl0.12 Coprecipitation 26.3 0 0.12 0.22 Yes ����
NiCaAl0.03 imp
Impregnation 7.5 0 0.03 0.46 Yes ����
* K.A. Magrini-Bair, S. Czernik, R. French, Y.O. Parent, E. Chornet, D.C. Dayton, C. Feik, R. Bain, Appl. Catal. A, 318 (2007) 199.
Butanol steam reforming:
FLUIDIZED BED PLANT
W/mbutanol
= 6 gcatalyst
·min/gbutanol W/m
butanol= 2 g
catalyst·min/g
butanol
�Complete carbon conversion at GC1HSV of araund 6000 h-1
���� NiAl���� NiMgAl 0.26���� NiCaAl 0.12���� NiCaAl 0.03 imp
0 20 40 60 80 100 1200
20
40
60
80
100
W/mbutanol
= 6 gcatalyst
·min/gbutanol
Car
bon
conv
ersi
on (
%)
Time (min)0 20 40 60 80 100 120
0
20
40
60
80
100
W/mbutanol
= 2 gcatalyst
·min/gbutanol
Car
bon
conv
ersi
on (
%)
Time (min)
GGC1C1HSV ~ 6000 hHSV ~ 6000 h--11
GGC1C1HSV ~ 33800 hHSV ~ 33800 h--11
650ºC, 1 atm, S/C = 14.7, u/u mf = 10
Butanol steam reforming:
FLUIDIZED BED PLANT
W/mbutanol
= 6 gcatalyst
·min/gbutanol W/m
butanol= 2 g
catalyst·min/g
butanol
�Except with the impregnated catalyst CaAl 0.03 imp ����low activity. ��������
Its catalytic activity is lower in butanol steam reformingthan in acetic acid or acetol steam reforming where 99% and
88% carbon conversion were obtained respectively. ☺☺☺☺
���� NiAl���� NiMgAl 0.26���� NiCaAl 0.12���� NiCaAl 0.03 imp
0 20 40 60 80 100 1200
20
40
60
80
100
W/mbutanol
= 6 gcatalyst
·min/gbutanol
Car
bon
conv
ersi
on (
%)
Time (min)0 20 40 60 80 100 120
0
20
40
60
80
100
W/mbutanol
= 2 gcatalyst
·min/gbutanol
Car
bon
conv
ersi
on (
%)
Time (min)
GGC1C1HSV ~ 6000 hHSV ~ 6000 h--11
GGC1C1HSV ~ 33800 hHSV ~ 33800 h--11
650ºC, 1 atm, S/C = 14.7, u/u mf = 10
Butanol steam reforming:
FLUIDIZED BED PLANT
W/mbutanol
= 6 gcatalyst
·min/gbutanol W/m
butanol= 2 g
catalyst·min/g
butanol
�Mg and Ca modified coprecipitated catalysts can perform with a good activity and with a higher resistance to attrition than the non modified Ni/Al catalyst.
���� NiAl���� NiMgAl 0.26���� NiCaAl 0.12���� NiCaAl 0.03 imp
0 20 40 60 80 100 1200
20
40
60
80
100
W/mbutanol
= 6 gcatalyst
·min/gbutanol
Car
bon
conv
ersi
on (
%)
Time (min)0 20 40 60 80 100 120
0
20
40
60
80
100
W/mbutanol
= 2 gcatalyst
·min/gbutanol
Car
bon
conv
ersi
on (
%)
Time (min)
GGC1C1HSV ~ 6000 hHSV ~ 6000 h--11
GGC1C1HSV ~ 33800 hHSV ~ 33800 h--11
650ºC, 1 atm, S/C = 14.7, u/u mf = 10
Butanol steam reforming:
FLUIDIZED BED PLANT
0,30
0,35
0,40
g/g
But
anol
)
0,3
0,4
But
anol
)
—— Equilibrium���� NiAl���� NiMgAl 0.26���� NiCaAl 0.12
650ºC, 1 atm, S/C = 14.7, u/u mf = 10, W/mbutanol = 2 gcatalyst ·min/g butanol
�Mg and Ca modified catalysts showed close hydrogen yields to the non modified
catalysts..
0 20 40 60 80 100 1200,00
0,05
0,10
0,15
0,20
0,25
Hyd
roge
n yi
eld
(g/
g
Time (min)
0 20 40 60 80 100 1200,0
0,1
0,2
CO
yie
ld (
g/g
But
anol
Time (min)
���� NiCaAl 0.12���� NiCaAl 0.03 imp
Butanol steam reforming:
FLUIDIZED BED PLANT
0,3
0,4
But
anol
)
0,30
0,35
0,40
g/g
But
anol
)
—— Equilibrium���� NiAl���� NiMgAl 0.26���� NiCaAl 0.12���� NiCaAl 0.03 imp
650ºC, 1 atm, S/C = 14.7, u/u mf = 10, W/mbutanol = 6 gcatalyst ·min/g butanol
W/mW/mbutanolbutanol from 2 to 6from 2 to 6
�Equilibrium hydrogen yields are reached with all the catalysts.
0 20 40 60 80 100 1200,0
0,1
0,2
CO
yie
ld (
g/g
But
anol
Time (min)
0 20 40 60 80 100 1200,00
0,05
0,10
0,15
0,20
0,25
Hyd
roge
n yi
eld
(g/
g
Time (min)
���� NiCaAl 0.03 imp
Aqueous fraction of bio-oil
� Bio-oil supplied by BTG (technology based on rotating cone reactor)
� Aqueous fraction prepared by dropwise water addition with continuous stirringaddition with continuous stirring
� Elemental analysis: C1.4 H3.4 O1 .
� S/C = 7.64
� pH = 2.52
� Water/organic mass ratio: 85/15
Steam reforming of the aqueous-phase of bio-oil:
FLUIDIZED BED PLANT
� 73.5% carbon conversionNiAl catalyst28.5 wt% Ni
650ºC, 1 atm, S/C = 7.64, u/u mf = 10W/mAqueous Fraction of Bio-Oil ~ 4, GC1SHV ~ 11800 h-1
� 63.3% H2 (%mol, N2 and H2O Free)
0 20 40 60 80 100 1200,00
0,02
0,04
0,06
0,08
0,10
0,12
0,14
0,16
0,18
H2 y
ield
(g/
gA
queo
us F
ract
ion
Bio
-Oil
)
Time (min)0 20 40 60 80 100 120
0
20
40
60
80
100
Car
bon
conv
ersi
on (
%)
Time (min)
Catalytic steam reforming of the aqueous fraction
0.4
0.6
0.8
1.0
1.2
1.4
yiel
d (g
/g o
f org
anic
s)
CH4 CO CO2 C2H4 C2H6 C2H2 H2
� Experimental conditions: 2 h reaction at 650 ºC, GC1HSV = 19000 h-1
� No operational problems detected
� Recovery (liquid+gas) = 97.5 %
� Carbon conversion averages 70 %
0 10 20 30 40 50 60 70 80 90 100 110 1200.0
0.2
time (min)
� Carbon conversion averages 70 % during the first hour of reaction
� 28 % Ni catalyst reduced in diluted H2 (H2:N2 1:10 vol.) at 650 ºC for 1 h
� Other catalysts tested: 23 % and 33 % Ni (increasing pH method) and 0, 1, 3, 5 and 10 % Cu (constant pH method)
� Average gas composition(vol. %):� H2 = 67.4
� CO = 6.3
� CO2 = 25.5
� CH4 = 0.5
Synthesis gas by catalytic steam Synthesis gas by catalytic steam reforming of bioreforming of bio--oil.oil.
F. Bimbela, J.A. Medrano, L. García, F. Bimbela, J.A. Medrano, L. García, F. Bimbela, J.A. Medrano, L. García, F. Bimbela, J.A. Medrano, L. García, M. Oliva, J. Ruiz, De Chen, J. Arauzo M. Oliva, J. Ruiz, De Chen, J. Arauzo
Thermochemical Processes Group (GPT)Aragón Institute for Engineering Research (I3A)
University of Zaragoza, María de Luna, 3, E-50018, Zaragoza, Spain