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DEVELOPMENT OF ADVANCED REACTION SYSTEMS
FOR HYDROGEN GENERATION
June 3rd & 4th, 2010
U. Izquierdo1, V.L. Barrio1, J.F. Cambra1, J.R. Requies1, M.B. Güemez1, P.L. Arias1, J.R. Arraibi2, A.M. Gutiérrez2
1 Faculty of Engineering, Bilbao, [email protected] Naturgas Energía Distribución, Bilbao
INDEX
1. INTRODUCTION1.1. SUPREN group1.2. Hydrogen production
2. OBJECTIVES
3. EXPERIMENTAL METHODOLOGY3.1. Microreactors design3.2. Catalyst preparation 3.3. Process and equipment 3.4. Activity tests analysis
4. RESULTS
5. CONCLUSIONS
6. FUTURE PROSPECTS
1. INTRODUCTION
1.1. SUPREN group1.2. Hydrogen production
2. OBJECTIVES
3. EXPERIMENTAL METHODOLOGY
4. RESULTS
5. CONCLUSIONS
6. FUTURE PROSPECTS
1.1. SUPREN group
Catalytic processes• Advanced systems for syngas and hydrogen production• Development of catalytic hydrotreating processes for clean
fuels production• Bio-refinery processes: bioalcohols valorisation• Catalytic reaction systems integrating membranes• New catalytic systems for VOCs oxidation and for NG
combustion
Recycling and thermal processes• Hydrometallurgical processes for recycling heavy metals• Chemical recycling of organic wastes (tyres, plastics,
MSW…)• Valorisation of liquid organic waste streams
http://www.ehu.es/supren
Sustainable ProcessEngineering
Sustainable ProcessEngineering
1. INTRODUCTION
1.1. SUPREN group1.2. Hydrogen production
2. OBJECTIVES
3. EXPERIMENTAL METHODOLOGY
4. RESULTS
5. CONCLUSIONS
6. FUTURE PROSPECTS
1.2. Hydrogen production
Steam methane reforming (SR)
(1) CH4 + H2O ↔ CO + 3 H2 (∆H0 = +206 kJ/mol)(2) CO + H2O ↔ CO2 + H2 (∆H0 = - 41 kJ/mol)
Catalytic partial oxidation (CPO)
(3) CH4 + ½ O2 → CO + 2 H2 (∆H0 = -36 kJ/mol)
Autothermal reforming
(4) 2 CH4 + O2 + 2 H2O → CO + 2 CO2 + 6 H2
1. INTRODUCTION
1.1. SUPREN group1.2. Hydrogen production
2. OBJECTIVES
3. EXPERIMENTAL METHODOLOGY
4. RESULTS
5. CONCLUSIONS
6. FUTURE PROSPECTS
Biomass gasification
(5) C + O2 → CO2 (6) C + ½ O2 → CO(7) CO + 3 H2 → CH4 + H2O (8) C + 2 H2 → CH4(9) C + CO2 → 2 CO (10) C + H2O → CO + H2(11) 2 H (carbon) → H2 (g) (2) CO + H2O ↔ CO2 + H2
Figure 1: Source: J. Scahill, U.S. DOE
1.2. Hydrogen production
1. INTRODUCTION
1.1. SUPREN group1.2. Hydrogen production
2. OBJECTIVES
3. EXPERIMENTAL METHODOLOGY
4. RESULTS
5. CONCLUSIONS
6. FUTURE PROSPECTS
Electrolysis
(12) 2 OH- → ½ O2 + H2O + 2 e-
(13) 2 H2O + 2 e- → H2 + 2 OH-
Figure 2: Naomi Kreamer and Carol Gross University of Minnesota.
1.2. Hydrogen production
2. Objectives
HYDROGEN PRODUCTION BY STEAM METHANE REFORMING
Resources Requirement
G. Kolb Naturgas Energy
Advanced reaction system Decentralized H2 production
MICROREACTOR
METHOD TO OBTAIN HYDROGEN FROM NATURAL GAS (WO/2006/136632)
1. INTRODUCTION
2. OBJECTIVES
3. EXPERIMENTAL METHODOLOGY
4. RESULTS
5. CONCLUSIONS
6. FUTURE PROSPECTS
3.1. Microreactors design
Design characteristics• Focused on internal and external mass-transfer resistance• Modelled by Aspen Plus software
• Channel width of 500 µm • Channel depth of 250 µm
Advantages• Heat transference optimization • Excellent temperature control• Smaller and more compact systems• Cheaper
1. INTRODUCTION
2. OBJECTIVES
3. EXPERIMENTAL METHODOLOGY
3.1. Microreactors design3.2. Catalyst preparation 3.3. Process and equipment 3.4. Activity tests analysis
4. RESULTS
5. CONCLUSIONS
6. FUTURE PROSPECTS
1. INTRODUCTION
2. OBJECTIVES
3. EXPERIMENTAL METHODOLOGY
3.1. Microreactors design3.2. Catalyst preparation3.3. Process and equipment 3.4. Activity tests analysis
4. RESULTS
5. CONCLUSIONS
6. FUTURE PROSPECTS
3.2. Catalyst preparation
1. INTRODUCTION
2. OBJECTIVES
3. EXPERIMENTAL METHODOLOGY
3.1. Microreactors design3.2. Catalyst preparation3.3. Process and equipment 3.4. Activity tests analysis
4. RESULTS
5. CONCLUSIONS
6. FUTURE PROSPECTS
3.2. Catalyst preparation
SEM analysis
Cat 1: Ni over MgO Cat 2: Katalco, Ni/Ca-Al2O3
Cat 3: Pd over Al2O3 Cat 4: Pt over Al2O3
1. INTRODUCTION
2. OBJECTIVES
3. EXPERIMENTAL METHODOLOGY
3.1. Microreactors design3.2. Catalyst preparation 3.3. Process and equipment3.4. Activity tests analysis
4. RESULTS
5. CONCLUSIONS
6. FUTURE PROSPECTS
Microactivity plant
3.3. Process and equipment
1. INTRODUCTION
2. OBJECTIVES
3. EXPERIMENTAL METHODOLOGY
3.1. Microreactors design3.2. Catalyst preparation 3.3. Process and equipment 3.4. Activity tests analysis
4. RESULTS
5. CONCLUSIONS
6. FUTURE PROSPECTS
Steam Reforming
Methane Temperature: from 973 K to 1073 KAtmospheric pressureCH4:H2O:N2 = 1:1:1,88 (molar ratio)Steam to carbon ratio (S/C): 1,5 and 2
Natural Gas Temperature: 1073 K Atmospheric pressureCH4:H2O:N2 = 1:1:1,88 (molar ratio) S/C: 2 only for CH4
Each catalyst was tested in microreactors and in a fixed bed.
3.4. Activity test
1. INTRODUCTION
2. OBJECTIVES
3. EXPERIMENTAL METHODOLOGY
4. RESULTS
5. CONCLUSIONS
6. FUTURE PROSPECTS
Catalyst 1: Ni over MgO
4. Results
Methane SR at several T: CAT1
0
20
40
60
80
100
0 490 980 1470
Time (min)
%
0,0
0,8
1,6
2,4
Mol
ar r
atio
Conversion CH4 (%)
CO selectivity (%)
H2out / CH4in (Molar ratio)
T = 973 K T = 1023 K T = 1073 K
1. INTRODUCTION
2. OBJECTIVES
3. EXPERIMENTAL METHODOLOGY
4. RESULTS
5. CONCLUSIONS
6. FUTURE PROSPECTS
Catalyst 1: Ni over MgO
4. Results
Methane SR evolution: CAT1
0
20
40
60
80
100
0 200 400 600 800 1000 1200 1400 1600 1800 2000Time (min)
%
0
1
2
3
4
5
Mol
ar r
atio
CH4 conversion (%)
CO Selectivity (%)
H2out/CH4in (Molar ratio)
1. INTRODUCTION
2. OBJECTIVES
3. EXPERIMENTAL METHODOLOGY
4. RESULTS
5. CONCLUSIONS
6. FUTURE PROSPECTS
4. Results
Catalyst 1: Ni over MgO
Table 1: Catalyst activity results for CAT1 at different S/C ratios.
CAT1 CH4 Conversion (%) H2out/CH4in (Molar ratio) CO Selectivity (%)
S/C = 1,0 61,46 1,87 81,63
S/C = 1,5 60,52 2,51 70,68
S/C = 2,0 61,02 2,33 59,68
1. INTRODUCTION
2. OBJECTIVES
3. EXPERIMENTAL METHODOLOGY
4. RESULTS
5. CONCLUSIONS
6. FUTURE PROSPECTS
Catalyst 1: Ni over MgO
4. Results
NG SR at different S/C: CAT1
0
20
40
60
80
100
0 120 240 360 480 600 720Time (min)
%
0,0
0,4
0,8
1,2
1,6
2,0
Conversion CH4 (%) Conversion C2H6 (%) Conversion C3H8 (%)Conversion C4H10 (%) CO Selectivity (%) Ratio H2out/(C1+C2+C3+C4)in
S/C = 1,0 S/C = 2,0
Mol
ar r
atio
1. INTRODUCTION
2. OBJECTIVES
3. EXPERIMENTAL METHODOLOGY
4. RESULTS
5. CONCLUSIONS
6. FUTURE PROSPECTS
4. Results
Table 2: Catalyst activity results for CAT1 in a fixed bed at 1073 K for methane.
CAT 1 CH4 conversion (%) H2out/CH4in (Molar ratio) CO Selectivity (%)
T = 1073 K 1,70 0,06 65,05
CAT 1 CH4Conv. (%)
C2H6Conv. (%)
C3H8Conv. (%)
C4H10Conv. (%)
H2out/CH4in(Molar ratio)
COSelectivity (%)
T = 1073 K 4,35 14,14 27,81 46,31 0,06 65,82
Catalyst 1: Ni over MgO in a fixed bed
Table 3: Catalyst activity results for CAT1 in a fixed bed at 1073 K for natural gas.
1. INTRODUCTION
2. OBJECTIVES
3. EXPERIMENTAL METHODOLOGY
4. RESULTS
5. CONCLUSIONS
6. FUTURE PROSPECTS
4. Results
Catalyst 2: Katalco, Ni/Ca-Al2O3
Table 4: Catalyst activity results for CAT2 at different temperatures.
CAT 2 CH4 conversion (%) H2out/CH4in (Molar ratio) CO Selectivity (%)
T = 973 K 30,73 1,01 59,38
T = 1023 K 46,30 1,58 76,50
T = 1073 K 72,90 2,42 88,82
Table 5: Catalyst activity results for CAT2 at different S/C ratios.
CAT 2 CH4 conversion (%) H2out/CH4in (Molar ratio) CO Selectivity (%)
S/C = 1,0 72,89 2,38 88,82
S/C = 1,5 62,54 2,03 74,34
S/C = 2,0 62,50 2,05 69,63
1. INTRODUCTION
2. OBJECTIVES
3. EXPERIMENTAL METHODOLOGY
4. RESULTS
5. CONCLUSIONS
6. FUTURE PROSPECTS
Catalyst 2: Katalco, Ni/Ca-Al2O3
4. Results
NG SR at different S/C: CAT2
0
20
40
60
80
100
0 495 990Time (min)
%
0,0
0,4
0,8
1,2
1,6
2,0
Conversion CH4 (%) Conversion C2H6 (%) Conversion C3H8 (%)Conversion C4H10 (%) CO Selectivity (%) Ratio H2out/(C1+C2+C3+C4)in
S/C = 1,0 S/C = 2,0
Mol
ar r
atio
1. INTRODUCTION
2. OBJECTIVES
3. EXPERIMENTAL METHODOLOGY
4. RESULTS
5. CONCLUSIONS
6. FUTURE PROSPECTS
Catalyst 2: Katalco, Ni/Ca-Al2O3
4. Results
Methane SR in a fixed bed 1073 K and S/C=1.0: CAT2
0
20
40
60
80
100
0 50 100 150 200Tiempo (min)
%
0,0
0,1
0,2
0,3
0,4
0,5
Mol
ar
ratio
CO Selectivity (%)
CH4 Conversion (%)
H2out/CH4in (Molar ratio)
Methane SR in a fixed bed 1073 K and S/C=1,0: CAT2
0
20
40
60
80
100
0 50 100 150 200Time (min)
%
0,0
0,1
0,2
0,3
0,4
0,5
Mol
ar r
atio
CO Selectivity (%)
CH4 Conversion (%)
H2out/CH4in (Molar ratio)
NG SR in a fixed bed 1073 K and S/C=1,0: CAT2
0
20
40
60
80
100
0 60 120 180Time (min)
%
0,000
0,005
0,010
0,015
0,020
CH4 Conversion CO SelectivityC2H6 Conversion C3H8 ConversionC4H10 Conversion H2out/(C1+C2+C3+C4)in (Molar ratio)
Mol
ar r
atio
1. INTRODUCTION
2. OBJECTIVES
3. EXPERIMENTAL METHODOLOGY
4. RESULTS
5. CONCLUSIONS
6. FUTURE PROSPECTS
Catalyst 2: Katalco, Ni/Ca-Al2O3
4. Results
Methane SR at 1073K: CAT3
0
20
40
60
80
100
0 100 200 300 400Time (min)
%
0,00
0,02
0,04
0,06
CO Selectivity (%)CH4 Conversion (%)H2out/CH4in ratio
Mol
ar r
atio
1. INTRODUCTION
2. OBJECTIVES
3. EXPERIMENTAL METHODOLOGY
4. RESULTS
5. CONCLUSIONS
6. FUTURE PROSPECTS
Catalyst 3: Pd over Al2O3
4. Results
NG SR at S/C= 1,0: CAT3
0
20
40
60
80
100
0 120 240 360Time (min)
%
0,000
0,002
0,004
0,006
0,008
CH4 Conversion (%) CO Selectivity (%)C2H6 Conversion (%) C3H8 Conversion (%)C4H10 Conversion (%) H2out/(C1+C2+C3+C4)in (Molar ratio)
Mol
ar r
atio
1. INTRODUCTION
2. OBJECTIVES
3. EXPERIMENTAL METHODOLOGY
4. RESULTS
5. CONCLUSIONS
6. FUTURE PROSPECTS
Catalyst 3: Pd over Al2O3
4. Results
1. INTRODUCTION
2. OBJECTIVES
3. EXPERIMENTAL METHODOLOGY
4. RESULTS
5. CONCLUSIONS
6. FUTURE PROSPECTS
Catalyst 4: Pt over Al2O3
4. Results
Methane SR at 1073 K: CAT4
0
20
40
60
80
100
0 20 40 60 80Time (min)
%
0,00
0,05
0,10
0,15
0,20
CO Selectivity (%)CH4 Conversion (%)H2out/CH4in (Ratio)
Mol
ar ra
tio
1. INTRODUCTION
2. OBJECTIVES
3. EXPERIMENTAL METHODOLOGY
4. RESULTS
5. CONCLUSIONS
6. FUTURE PROSPECTS
5. Conclusions
• Higher conversion is reached at higher temperatures.
• Conversion does not improve with higher steam to carbon ratio.
• Natural gas activity tests suggest that reaction 1 is much more selective for ethane, propane and butane than for methane.
• For Pd over Al2O3 and Pt over Al2O3 catalyst (Catalyst 3 and 4), bad impregnation and non-uniform particle size distribution is determined.
• Catalyst 1, Ni over MgO, has not suffered apparent deactivation and it has almost reached the conversions of Catalyst 2, Ni/Ca-Al2O3 (Katalco). According to the SEM results, for Catalyst 1 a homogeneous and small particle size is reached.
• Comparing the different catalysts, catalyst 2 obtains higher conversions but suffers quicker deactivation.
• For all the catalysts, lower conversion is reached in a fixed reactor. Thus, higher NG conversions are achieved in the microreactors for SR activity tests.
• A module for decentralized hydrogen production is possible due to the process (heat and mass transfer) intensification.
1. INTRODUCTION
2. OBJECTIVES
3. EXPERIMENTAL METHODOLOGY
4. RESULTS
5. CONCLUSIONS
6. FUTURE PROSPECTS
- SEM analysis for tested microreactors
- New catalyst systems for SR reactions
- CPO / ATR reactions
- Experiments with renewable feeds: biogas and bioalcohols
6. Future Prospects