solar hydrogen stellenbosch university, september 2 , 2010 · solar gasification and reforming of...

Stellenbosch University > 2 Sept. 2010

Slide 1

Solar Hydrogen

Stellenbosch University, September 2nd, 2010

Dr. Christian Sattler

DLR – German Aerospace Center - Solar Research

e-mail: [email protected]


Slide 2

Overview

Introduction of DLREnergy

Solar HydrogenFrom Fossil RecoursesThermochemicalCycles

HYDROSOL, HYDROSOL 2, HYDRSOOL 3-DSummary and Outlook


Slide 3

DLRGerman Aerospace Center

Research InstitutionSpace AgencyProject Management Agency


Slide 4

Research Areas

AeronauticsSpaceTransportEnergySpace AgencyProject Management Agency


Slide 5

Locations and employees

6500 employees across 29 research institutes and facilities at

13 sites.

Offices in Brussels, Paris, Washington, and Almería(plus permanent Delegation on the Plataforma Solar de Almería)

Koeln

Oberpfaffenhofen

Braunschweig

Goettingen

Berlin

Bonn

Neustrelitz

Weilheim

Bremen Trauen

Dortmund

Lampoldshausen

Hamburg

Stuttgart


Slide 6

Energy


Slide 7

DLR Energy Research Area

DLR Energy Research concentrates on:

CO2 avoidance through efficiency and renewable energiessynergies within the DLRmajor research specific themes that are relevant to the energy economySecond largest research centre in Germany for non-nuclear energyApprox. 400 employees


Slide 8

Energy Research Program Themes

Efficient and environmentally compatible fossil-fuel power stations(turbo machines, combustion chambers, heat exchangers)Solar thermal power plant technology, solar materials conversionThermal and chemical energy storageHigh and low temperature fuel cellsSystems analysis and technology assessment


Slide 9

Portfolio of Competences – Energy

Simulation/modelling

Fuel cells Power plant technology

Concentratingsolar systems

Combustion

Turbo-machines

Hybrid power plants

Heat storage

Gas turbines with alternativefuels

Fuel cells with alternative fuels

Solar power plants

Solar hydrogen production

Heat exchangers

Heat management

Solar process heat

Manufacturing techniques

Gas turbine systems

Materials

Efficientenergyconversion

Renewableenergies

Solar gas turbines

Syst

ems

anal

ysis

and

tech

nolo

gy a

sses

smen

t

Solar gas turbines


Slide 10

Solar Hydrogen


Slide 11

Vision

Producing hydrogen for mass markets means implementing as efficient processes as possible to convert available energy sources like renewables or nuclear into the chemical energy vector.(De Beni G. 1970; Marchetti 1973; Winter 2000)

Hydrogen should be produced from water to reduce dependencies on fossil fuelsTo reduces environmental impact


Slide 12

Technical and Economic Efficiency

Technical: In which process is the most energy stored in the hydrogenIs the process technical feasible?Are there any knock-out criteria?

Economic: Is the product (hydrogen) cost competitive?Are there any other economic reasons that make the process not competitive?


Slide 13

Hydrogen Production Today

Steam Methane ReformingThermal efficiency 78%1 kg H2 by means of SMR yields to 9.42 kg of CO2The production cost of hydrogen is estimated at 0.04 €/kWh (1.33 €/kg)

Coal GasificationThe Lurgi Process (Fixed-Bed) 500 – 1000 °CThe Winkler Process (Fluidized-Bed) 800 - 1100 °C The Koppers-Totzek/Texaco Process (Entrained-Bed) 1040 – 1540 °C

Thermal efficiency 58 - 63%23 kg CO2 / kg H2

Hydrogen costs from coal gasification are 1.21 to 1.79 €/kg H2(coal price not reported)

Partial Oxidation1300 - 1500 °C 1.45 – 1.67 €/kg


Slide 14

Solar Thermal Processes for Hydrogen Production

Today:Industrial-scaleCheapNot renewable

Future:RenewableExpensive


Slide 15

Production-, Storage- and Infrastructure topics of the European Hydrogen and Fuel Cell JTI


Slide 16

Solar Hydrogen from Hybrid Fossil Processes


Slide 17

Carbon Based Transition ProcessesStarting from applied technologiesReduced risk compared to water splitting technologiesSolar Reforming of Natural Gas

Development by a number of groups since at least 25 yearsCost are estimated to 1.4 €/kg H2

Solar Gasification and Reforming of PetcokeDevelopment by ETH Zurich, CIEMAT, and PDVSA Cost are estimated to about 2.1 €/kg H2

SOLZINC – Carbothermal reduction of ZnOPilot reactor successfully testedZinc is produced not hydrogen!

Solar Cracking of MethaneNo CO2 emission but C, C might be a product toochallenging reactor design: solids and high temperatures


Slide 18

Solar Steam Methane Reforming – Technologies

Reformer heated externally (700 to 850°C)Optional heat storage ( up to 24/7) E.g. DLR Project ASTERIX

Irradiated reformer tubes (up to 850°C), temperature gradient Approx. 70 % Reformer-Development: CSIRO, Australia and in Japan; Research in Germany and IsraelAustralian solar gas plant in preparation

Catalytic active direct irradiated absorberApprox. 90 % Reformer-High solar flux, works only by direct solar radiationDLR coordinated projects: SCR, Solasys, Solref; Research in Israel, Japan

decoupled/allothermal indirect (tube reactor) Integrated, direct, volumetric

Quelle: DLR


Slide 19

Direct heated volumetric receiver:SOLASYS, SOLREF (EU FP4, FP6)

Pressurised solar receiver,Developed by DLRTested at the Weizmann

Institute of Science, IsraelPower coupled into the process gas: 220 kWth and 400 kWth

Reforming temperature: between 765°C and 1000°CPressure: SOLASYS 9 bar, SOLREF 15 barMethane Conversion:

max. 78 % (= theor. balance)DLR (D), WIS (IL), ETH (CH), Johnson Matthey (UK), APTL (GR), HYGEAR (NL), SHAP (I)


Slide 20

Assessment of relevant H2 pathways until 2020including NG Solar-SMR for comparison issues

highhighnegative -neutral

modest -high

neutral -m

odest

Positive impact on GHG emission reduction

highhighhigh

modest -high

modest

Positive impact on security of energy supply

25-33 €/GJ50-67 €/GJ31 €/GJ12*

€/GJ8*

€/GJH2 production cost

BiomassWindelectrolysis

Grid Electricityelectrolysis

NGSolar-SMR

NGSMR

*assuming a NG price of 4€/GJ; NG Solar-SMR: expected costs for large scale, solar-only


Slide 21

Project Perspectives

The consortium forces the realisation of the a prototype reforming plantLink with Australian CSIRO by an ongoing IPHE project Funding was assured in October 2009Development phase of the joint projectSOLREF receiver will run on a second tower at the CSIRO Solar Centre in Newcastle, NSW


Slide 22

Thermochemical Cycles


Slide 23

Thermochemical Water Splitting2500 °C

100 °C0 °C

- 273 °C

H H

O


Slide 24

PROBLEMS!

Hydrogen + Oxygen = explosive gas!DangerousSeparation?

2500 °C MaterialsSpecial ceramics – difficult to handle, expensive

2500 °C TemperatureHow could such high temperatures be achieved?Efficiency?


Slide 25

Sollution

H2O

H2 + O2

2500 °C

H2O

O2

1250 °C

H2

850 °CAre the problems solved now?

•Still high temperatures

•Materials

•Chemical reactions

•Efficiency


Slide 26

Thermochemical Cycle

Firstly developed in the oil crises of the 1970sUse of nuclear energy to produce an energy carrierMainly in the USA (General Atamics, Westinghouse), but also in Europe (FZJ, JRC Ispra) and Japan (JAEA)Up to 900 different cycles are knownMain groups:

Sulphur cyclesVolatile metal oxide cyclesNon-volatile metal oxie cyclesLow temperature cycles

In the 1980s and 1990s the interst went down because of lower oil pricesCome back in the 2000s

Solar thermal more in the focusStudies to identify the most promising cycles (e.g. USA, France)


Slide 27

Thermochemical vs. Electrochemical?

ThermochemicalNo conversion steps necessary = possibly very high efficiency

ElectrochemicalConversion steps necessary for power production = lowerefficiency

No contradiction: use energy forms as efficient as possible


Slide 28

Promising and well researched Cycles

395304Hybrid Copper Chlorine

Low-Temperature Cycles

431100 – 18002Ferrites

6820002Cerium Oxide

4222002Iron Oxide

Non-volatile Metal Oxide Cycles

421600Hybrid Cadmium

4518002Zinc/Zinc Oxide

Volatile Metal Oxide Cycles

38900 (1150 without catalyst)

3Sulphur Iodine (General Atomics, ISPRA Mark 16)

43900 (1150 without catalyst)

2Hybrid Sulphur (Westinghouse, ISPRA Mark 11)

Sulphur Cycles

LHV Efficiency (%)

Maximum Temperature (°C)

Steps


Slide 29

Temperature nuclear

71+%750+(Very) High TemperatureReactor

68%650Advanced Gas CooledReactor

64%550Breeder Reactor, Sodiumcooled

50%320Pressurised Water Reactor

48%300CANDU Reactor (Heavy Water Reactor)

47%285RBMK (Graphite moderated)

47%285Boiling Water Reactor

Carnot-EfficiencyTemperature(°C)Reactor Type


Slide 30

Temperature – Concentrating Solar Power3500 °C

1500 °C

400 °C

150 °C50 °C

Paraboloid: Dish

Solar tower(Central Receiver System)

Parabolic trough


Slide 31

Annual Efficiency of Solar Power TowersPower Tower 100MWth

Optical and thermal efficiency / Receiver-Temperature

0

5

10

15

20

25

30

35

40

45

50

600 700 800 900 1000 1100 1200 1300 1400

Receiver-Temperature [°C]

Opt

ical

effi

cien

cy a

nd th

erm

al a

nnua

l use

ef

ficie

ncy

[%]

R.Buck, A. Pfahl, DLR, 2007


Slide 32

Solar Towers, “Central Receiver Systems”

Solar-TwoPSAPS10+20


Slide 33

Efficiency comparison solar H2 production fromwater, SANDIA 2008

25%62%77%52%RotatingDisc < 1

Future Solar dish

1800Nickel ManganeseFerrit Process

23%83%57%49%MoltenSalt700

Future Solar tower

600Hybrid CopperChlorine-process

22%76%57%51%Particle700

Future Solar tower

850Hybrid Sulphur-process

20%76,2%57%45%Particle700

Future Solar tower

850High temperaturesteam electrolysis

14%83%57%30%MoltenSalt 700

ActualSolar tower

NAElctrolysis (+solar-thermal power)

ηAnnual

EfficiencySolar – H2

ηReceiver

η OpticalηT/C

(HHV)

Solar-receiver+ power [MWth]

Solar plantT[°C]

Process

G.J. Kolb, R.B. Diver SAND 2008-1900


Slide 34

Water based processesLong term necessary for the de-carbonised H2 societyBenchmark: Renewable electricity + electrolysisChallenging technologiesMetal/Metal oxide thermo-chemical Cycles

Zn/ZnO (3,58 – 4,12 €/kg)Mixed Iron Oxides (Ferrites)Already shown in the HYDROSOL project Cost based on the small scale experiments are 7 €/kgCalculated improvements will lead to 3,5 €/kg

Sulphur Cycle Family Developed for use with nuclear heatHybrid Sulfur (ISPRA Mark 11) Cost calculation 0,8 €/kg H2 nuclearSulphur-Iodine Process (ISPRA Mark 16) Cost calculation 1,17 – 1,66 €/kg nuclear, 4,53 €/kg solar


Slide 35

HYDROSOL, HYDROSOL 2, HYDROSOL 3D


Slide 36

Thermochemical Cycle using Mixed Iron Oxides Process Operation

1200°C

800 – 1200 °C

2. Step: Regeneration

1. Step: Water Splitting

O2

H2O O2H2H2O + MOred MOox + H2

MOox MOred + ½ O2

Net reaction: H2O H2 + ½ O2

MOred

MOredMOox

MOox

Redox materials used in theHYDROSOL-2 project:ZnFeO, NiZnFeO


Slide 37

1200° C

1200° C

Reactor for continuous hydrogen production:

Reactor with two modules 15 kW two-chamber system Two different alternating processes:

• Production: 800°C, water steam, nitrogen, exothermic

• Regeneration: 1200°C, nitrogen, endothermic

Transient steps like• Switching between half cycle• Start-up / Shutdown

Closed system: quartz window Four-way-valve

800° C

800° C

H2+N2

O2+N2

O2+N2

H2+N2


Slide 38

HYDROSOL II Pilot Reactor in Operation


Slide 39

Experiments – Process Control Software:

Regeneration

Production

Set parameterSolar Power

Process-Flow-Sheet

N2

N2H2O


Slide 40

Experiments – Process Control Software:

Flux Measurement at test operation FluxMaxboth Modules= 115kW/m2


Slide 41

Results: Thermal cycling


Slide 42

Hydrogen production of 4th day of experimental series

0

1

2

3

4

5

6

7

8

9

10:1

4:25

:00

10:2

3:35

:20

10:3

2:44

:07

10:4

1:52

:96

10:5

1:02

:50

11:0

0:11

:62

11:0

9:20

:68

11:1

8:29

:71

11:2

7:39

:00

11:3

6:48

:32

11:4

6:05

:43

11:5

6:01

:18

12:0

5:54

:21

12:1

5:39

:75

12:2

5:34

:45

12:3

5:25

:87

12:4

5:16

:01

12:5

5:09

:93

13:0

5:27

:85

13:1

5:38

:89

13:2

5:49

:78

13:3

6:25

:34

13:4

6:39

:26

13:5

7:08

:35

14:0

7:44

:28

14:1

7:45

:50

14:2

8:13

:50

14:3

8:43

:34

14:4

8:38

:73

14:5

9:09

:28

15:0

9:48

:46

15:2

0:15

:14

15:3

0:54

:76

15:4

1:34

:09

15:5

2:11

:10

16:0

2:50

:15

16:1

3:29

:14

16:2

3:59

:71

16:3

4:38

:90

16:4

5:13

:87

16:5

4:56

:40

c(H

2) [%

]


Slide 43

Summary and Outlook

• Technologies like solar steam reforming should be short term technologies to introduce solar technology into the chemical industry

• Thermochemical cycles will provide renewable hydrogen with very high efficiency compared to other renewable technologies

• The HYDROSOL reactor concept was scaled up in HYDROSOL 2 from the solar furnace to a 100 kW pilot plant on the tower of the PSA

• Topic of the ongoing HYDROSOL 3-D project is the design of a MW test plant

• Also sulfur cycles should be scaled-up since the development is already on a very advanced level and the temperature level is lower than of other TCCs


Slide 44

Acknowledgement

The Projects HYDROSOL, HYDROSOL II; HYTHEC, HYCYCLES, Hi2H2, INNOHYP-CA, SOLHYCARB und SOLREF are co-funded bythe European CommissionHYDROSOL 3-D is co-funded by the European Joint Technology Initative on Hydrogen and Fuel Cells

HYDROSOL was awardedEco Tech Award Expo 2005, TokyoIPHE Technical Achievement Award2006 Descartes Research Price 2006


Slide 45

Thank you very much for your attention!

solar hydrogen stellenbosch university, september 2 , 2010 · solar gasification and reforming of...

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