DEVELOPMENT OF ADVANCED REACTION SYSTEMS · PDF filereaction systems for hydrogen generation...

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


1. INTRODUCTION


2. OBJECTIVES


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


2. OBJECTIVES


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. INTRODUCTION


2. OBJECTIVES


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.


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


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


3.1. 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


3.1. 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


3.1. 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


3.1. 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


3.1. 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


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


4. RESULTS

5. CONCLUSIONS

6. FUTURE PROSPECTS


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


4. RESULTS

5. CONCLUSIONS

6. FUTURE PROSPECTS

4. Results


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


4. RESULTS

5. CONCLUSIONS

6. FUTURE PROSPECTS


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


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


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.


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.


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


4. RESULTS

5. CONCLUSIONS

6. FUTURE PROSPECTS


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


4. RESULTS

5. CONCLUSIONS

6. FUTURE PROSPECTS


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 (%)


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 (%)


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


4. RESULTS

5. CONCLUSIONS

6. FUTURE PROSPECTS


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


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


4. RESULTS

5. CONCLUSIONS

6. FUTURE PROSPECTS

Catalyst 3: Pd over Al2O3

4. Results

1. INTRODUCTION

2. OBJECTIVES


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


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


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

THANK YOU FOR YOUR ATTENTION


Sustainable [email protected]

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