Technology Platform Operation Review Days, Brussels 8th-9th December 2005 A. Le Duigou CEA (Commissariat à l’Energie Atomique) / F HYdrogen THErmochemical.

Technology Platform Operation Review Days, Brussels 8th-9th December 2005

A. Le DuigouCEA (Commissariat à l’Energie Atomique) / F

HYdrogen THErmochemical Cycles

Contract N° 502704


MODELS : flow-sheeting, industrial scale-up (components, safety and costs) EXPERIMENTATION for both cycles : SOLAR H2SO4 decomposition step

EXPERIMENTATION on S_I cycle : H2 production step

HYTHEC / the PARTNERS Assessment of two H2 production thermochemical

cycles : the Sulfur-Iodine (S_I) cycle (major effort) and the Hybrid-Sulfur (WH) cycle / Renewable Raw Material

(Water) / Nuclear and RES (solar) / CO2-Free

1/2O2+SO2 + H2O SO2+2H2O+I2 I2 + H2

2HIH2SO4

SO2

H2O2

H2O

I2

H2SO4H2SO4 + 2HI 2HI

Bunsen section not in HYTHEC

120°C

Heat up to 850°C Heat up to

360°C

1/2O2+SO2 + H2O SO2+2H2O

H2SO4

SO2

H2O2

H2O

H2SO4

H2SO4 + H2

Heat up to 850°C

Electrolysis 80°C

Electrolytic section not in HYTHEC

6 PARTNERS : research institutes (DLR, CEA – coordinator), universities (DIMI, USFD), engineering organisation (EA) and SME (ProSim-SA) Duration : 3,5 years - Kick-off : 01/04/2004 - EC funding ~1,9 M€


FLOW-SHEETING AND MODELING / S_I and WH

Importance of T level for H2SO4 section and heat recovery for HIx section

Flash 1bisFlash 3

Flash 1

Flash 2

R1

R2

E1 E2

E3

E4 E5

S205

S206

S201

S204

S202

S203

P E1

E2 E3

E4

C Flash 1

Flash 2

Q1

Q2

Q3

Q4

Q5

Q6

F-VHTR HEAT PUMP

Ec

Eb

Q7

Q8

S_I Hybrid SulfurHIx section

H2SO4 section

Electrolytic section

Flow-Sheets : describe the whole processes / integrate the models from experimentation / are regularly updated


INDUSTRIAL SCALE-UP / S_I and WH

HTR

Power turbine

Generator

I-SCycle

He-HeHeat Exchager

QR

WPT

H2

Compressor

Intermediate loop

WC

HTR

Power turbine

Generator

I-SCycle

He-HeHeat Exchager

QR

WPT

H2

Compressor

Intermediate loop

WC

SP7: Summary of the main achievements

Elaboration of process concepts including the coupling to the energy sources (solar, hybrid, nuclear)

Catalogue of criteria → selection of 2 plants: solar (1200°C) and hybrid (850°C)

Basic flow sheets for solar-only and hybrid have been elaborated

Detailed flow sheet on solar-only operation without storage is completed

Analysis of 50 MWth plant: lay-out and optimisation of solar part of the plant is completed

Steady state analysis of the chemical part at the design point has been carried out: maximum production rate of hydrogen 404 g/s; annual production 3792 t hydrogen

First calculation of mass and energy balances have been completed for that model case: thermal efficiency 39% (LHV)

solar-only operation

Generator Gasturbine

air supply

electrolyser

I

II

H2O

H2SO4H2O

H2O, SO2

O2

O2

H2O, SO2

feed water pump

chimney

H2SO4

reactor nuclear

Decomposition of SO3 Vaporisation of H2SO4

IVSO3,H2O

III

850°C

Concentration of H2SO4

electricity

V

VI

H2

hybrid operation

S_I cycle / first coupling, component sizing and costs performed

WH cycle / elaboration and selection of process concepts (solar / hybrid energy souces)


EXPERIMENTATION / S_I

H2 production step knowledge and improvement

Experimental measurements of the partial pressures above

a mixture of HI, H2O and I2. Use of FTIR, UV-Vis. and RAMAN spectroscopies

Optical selectivity testing

Membrane selectivity test using CARS (Coherent Anti Raman

Spectroscopy)

First significant results obtained at low P and T

Simulations carried to investigate the change in efficiency with different

amounts of dewatering of the process stream


EXPERIMENTATION / H2SO4 decomposition by solar energy

Summary of the main achievements

Comparison and weighting of different reactor concepts for the solar decomposition of sulphuric acid

Selection of the most promising concept of a direct absorbing receiver-reactor

Set-up of FEM and CFD models of the reactor assisting in the optimisation of a final design and in getting a detailed understanding of the solar decomposition process

Performance of test series on H2SO4 evaporation, materials’ corrosion resistance, kinetics, and coupling to a solar furnace to prepare a final design

Final design and manufacture of a dedicated solar receiver-reactor

Installation of the receiver-reactor and all necessary peripheral units and analytics in the solar furnace of Cologne to carry out a test of operability

Success performance of first test campaign proving the general operability of the reactor concept and achieving a homogenous H2SO4 decomposition with conversion rates between 20 and 55 %. receiver-reactor in the solar furnace

foam vaporiser

Comparison and weighting of different receiver-reactor concepts / CFD and FEM

modelling

Success performance of first test campaign

CFD and FEM modelling

Solar input

ConcentratedH2SO4 input

Vaporization

Decomposition

Gas


Major HYTHEC characteristics linked to SRA topics

HYTHEC works in the scope of the following pathway:

S_I cycle: nuclear heat « thermolysis » hydrogen

WH cycle : all the yellow scope, simplier study


Major HYTHEC characteristics linked to SRA topics (1/2)

“The ultimate goal is to produce hydrogen from carbon-dioxide-lean energy sources including nuclear fission”

HYTHEC works on long term processes

• “Long term outlook” (2050) for thermochemical water splitting : Sulfur-Iodine (S_I) and Hybrid-Sulfur (WH) cycles• Hydrogen made from a “variety” (2) of primary energies: Nuclear and Solar heat sources (last one for renewable heat and electricity sources)• Centralised / decentralized production (limits for TC cycles ?): rather large scale plants, 50 to 600 MWth• CO2-Free process: use of water as a raw material, then no need for CO2 sequestration, « technology which still needs to be practically verified and accepted »• « Hydrogen a major transport fuel by 2050”: HYTHEC works on massive hydrogen production plants


Major HYTHEC characteristics linked to SRA topics (2/2)

“Basic research issues: analysis and development of thermochemical processes »

“Recommend basic research areas : analysis and development of thermolysis processes in compliance with available heat sources”:

• VLE model for the HI/I2/H2O system of the S_I cycle;

• Study of thermodynamics and membranes capabilities for enhancement of S_I H2 production section;

• Feasibility, advantages and drawbacks of solar (RES) thermal splitting of H2SO4;

• More generally: flow-sheeting, modelling, large scale assessments with 2 energy sources (Nuclear and Solar)


HYTHEC is a short term R&D activity : 2004 to 2007

Research strategy for hydrogen production for 2005 to 2015

• A constraining level of efficiency seems to be required : be careful about the definition ….HYTHEC will propose very soon its point of view about « efficiency »

• « Thermochemical processes are mostly proposed in the context of advanced nuclear reactors and feature prominently in the Technology Roadmap for Generation IV nuclear reactors. Alternatively, the high temperature heat from solar concentrators may be used »: Nuclear VHTR and Solar heat sources in HYTHEC.

• S_I cycle « generally considered the most promising thermochemical cycle »; HYTHEC considers WH cycle too


How HYTHEC is connected to SRA / DS timetable

HYTHEC2004 2007

« 2020 snapshot »


HYTHEC detailed planned/ongoing activities

Phase 1 Phase 2 Phase 3


Major HYTHEC main expected results/achievements (1/2)

FLOW-SHEETING AND MODELING / S_I and WH – comparative assessments

INDUSTRIAL SCALE-UP / S_I and WH – massive H2 production processes reliability (coupling, components, safety, costs)

EXPERIMENTATION on S_I H2 production step - knowledge and improvement (mainly possible use of membranes)

EXPERIMENTATION on S_I and WH - H2SO4 decomposition by solar energy


HYTHEC main expected results/achievements (2/2)

Phase 1 - April 2004 to March 2005 : acquisition of the input data, flow-sheeting, definition / construction of the devices and measurement techniques, and first steps in the modelisations (membranes, coupling, component sizing)

HYTHEC sent comments on SRA and related topics addressed

(FP6 – HYTHEC – N1 / 01 and FP6 – HYTHEC – N1 / 02 )

Phase 2 - March 2005 to March 2006 : S_I and Westinghouse evaluations on first basic flow-sheets, from theoretical, experimental, industrial scale-up and cost studies

Phase 3 - March 2006 to September 2007 : detailed S_I and Westinghouse evaluations from theoretical, experimental, industrial scale-up and cost studies


Cross-cutting R&D in the SRA : “hydrogen safety with both technical and socio-economical aspects: HYTHEC works on Industrial scale-up, including safety aspects, and costs evaluations for S_I and WH cycles:

-SP2 / S_I cycle

- SP6 / Capability of large-scale H2SO4 decomposition in a solar furnace

- SP7 / WH cycle

Cross-cutting issues (1/3)

Recommend cross-cutting areas:« Hydrogen production is closely linked to hydrogen storage and distribution »: HYTHEC linked to other European projects



A broad Dissemination

• 2 workshops:JRC workshop in Brussels (December 2004)MICANET-WP4 meeting in Brussels (April 6th, 2005)

• 9 communications dedicated to part or all HYTHEC:Hydrogen Energy Congress in Brussels (March 2005), IHEC (Istanbul July 2005), EHEC (Zaragoza November 2005), Cologne Solar Symposium (June 2005, Cologne), 7th WCCE (Glasgow, July 2005), AIChE 2005 (Cincinnatti)

• 3 proposals : German Energy Congress (February 2006), Solar Paces (June 2006), WHEC 2006 (Lyon, June 2006)• HYTHEC mentioned in 8 communications

• 1 paper published in IJHE (HIx separation in S_I cycle), a paper proposed to IJHE (HYTHEC)

A private site, soon a public one



Education

Diploma thesis : 2 finalised at DLR, 6 in progress totally or partially

funded (2 at DLR, 2 at DIMI, 2 at USFD)

3 PHD students at USFD, working on subjects related to HYTHEC background (not directly funded)

Students at CEA, working on subjects related to HYTHEC background (not directly funded)

1 internship at DLR


Enhancing cooperation and future perspectives

A large collaboration with other EU projects

• RAPHAEL (former VHTR – IP)

• 3 interface meetings held (presentations and collaboration possibilities / choice of the boundaries between the 2 projects / exchange of data / choice of a common coupling scheme)

• HYSAFE : first meeting on October 2005 (Karlsruhe) / presentation and collaboration topics to be defined today (DLR attended too)

• EXTREMAT / first contacts ongoing

• HYWAYS (via INNOHYP-CA) (data to be given from HYTHEC industrial scale-up studies)

• INNOHYP-CA (S_I and WH cycles characteristics given, participation to meetings)

HYTHEC Consortium Agreement upgraded


Enhancing cooperation and future perspectives (1/2)

Other collaborations / partners initiatives

CEA : USA (S_I cycle (demonstration loop, R&D), Japan (R&D), Korea (R&D), ENEA, CIEMAT)

USFD : working group with Westinghouse, PBMR (Republic of South Africa), SRNL, ORNL and University of South Carolina

DLR : European Colaboration within the SOLLAB Alliance, and SOLAR PACES

DIMI : participation to a national initiative


Enhancing cooperation and future perspectives (2/2)

Develop the collaborations with other European and national projects : both for the data, knowledge and boundary conditions exchanges, and for an appropriate comparative evaluation with other processes

R&D necessary for high temperature processes (basic knowledge, materials) / need of technological breakthroughs ?

In addition, never forget the large-scale aspects, including component pre-design, coupling to the primary heat source, safety, chemical and materials used, and of course costs (credibility, R&D needs pointed out too),

Demonstration steps


THANK YOU

DANKE

GRAZIE

GRACIAS

MERCI

THE HYTHEC TEAM

Technology Platform Operation Review Days, Brussels 8th-9th December 2005 A. Le Duigou CEA (Commissariat à l’Energie Atomique) / F HYdrogen THErmochemical.

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