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Co-funded by the Horizon 2020
Framework Programme of the
European Union
Sulphur – solar fuel for on demand power generation
> Sulphur – solar fuel for on demand power generation > Thomey et al. • International Workshop on Solar Thermochemistry > Sep. 13, 2017 DLR.de • Chart 1
Int. Workshop on Solar Thermochemistry, Juelich, Germany
Dennis Thomey, Christos Agrafiotis, Nicolas Overbeck, Martin Roeb, Christian Sattler
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• Sulphur as industrial commodity
• Sulphur as thermochemical storage
• Solar sulphur power generation
• Background of DLR on sulphur cycles
• European project PEGASUS
• Conclusions and outlook
Contents
> Sulphur – solar fuel for on demand power generation > Thomey et al. • International Workshop on Solar Thermochemistry > Sep. 13, 2017 DLR.de • Chart 2
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Comparison of energy storage densities
> Sulphur – solar fuel for on demand power generation > Thomey et al. • International Workshop on Solar Thermochemistry > Sep. 13, 2017 DLR.de • Chart 3
Technology Energy density (kJ/kg)
Hydrogen 141,886 1
Gasoline 47,357 1
Sulphur 9,281 2
Molten Salt 282 2
Lithium Ion Battery 580 2
Elevated water Dam (100m) 1 2
1College of the Desert 2General Atomics
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• Sulphur is required for sulphuric acid (SA) production
• SA is world’s most produced chemical
Global annual rate >200 Mio. tons
• SA is measure of industrial development
• SA is mainly needed for fertiliser production
• Sulphur from desulphurisation of hydrocarbons via Claus process
• Sulphur is by-product of metallurgic processes
Sulphur in industrial processes
> Sulphur – solar fuel for on demand power generation > Thomey et al. • International Workshop on Solar Thermochemistry > Sep. 13, 2017 DLR.de • Slide 4
Sulphuric acid plant
Sulphur pile
Claus process
Ore
roasting
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Sulphur world production 2014
Total of 69.1 Mio. tons (avg. world price of US$160 per ton)
> Sulphur – solar fuel for on demand power generation > Thomey et al. • International Workshop on Solar Thermochemistry > Sep. 13, 2017 DLR.de • Slide 5
12,5
40,5
7,8
8,4
Metallurgy (smelting ofsulphide ores)
By-product sulphur fromrefineries etc. (processingnatural gas, petroleum andoil sands)
Mining (pyrite, nativesulphur, undergrounddeposits)
Other
Source: 2014 Minerals Yearbook, SULFUR, U.S. Geological Survey
Mio. tons
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Transportation and storage of sulphur
In solid or liquid form
> Sulphur – solar fuel for on demand power generation > Thomey et al. • International Workshop on Solar Thermochemistry > Sep. 13, 2017 DLR.de • Slide 6
Molten sulphur in heated
pipelines (~140 °C)
Molten sulphur trailer
Molten Sulphur
Rail Car
Pipeline
Ship
Train
Truck
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Thermochemical sulfur storage cycle for
on-demand solar power production
> Sulphur – solar fuel for on demand power generation > Thomey et al. • International Workshop on Solar Thermochemistry > Sep. 13, 2017 DLR.de • Slide 7
SO2 + H2O
Sulphuric Acid
Decomposition
SO2
Disproportionation
SO2
Sulphur
Combustion
S H2SO4
Concentrated
Solar Power
On-demand
Electrical Power
S + O2 SO2
>1000 °C
2 H2SO4
2 H2O + 2 SO2 + O2
>800 °C
2 H2O + 3 SO2
2 H2SO4 + S
<200 °C (liq. phase)
Sulphuric
Acid Sulphur
ΔH = 551 kJ/mol
ΔH = -254 kJ/mol
ΔH = -297 kJ/mol
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SO3
Decomposer
Sulphur
Storage
Sulphuric
Acid
Storage
Absorbers
Disproportionate
Reactor
Sulphur
Burner
Contact
process
SO3, H2O
dilute
H2SO4
SO2
O2
N2
SO3 , O2, N2
S
Air
Electricity
Oxygen
Solar field
Hot particles
storage tank
H2SO4
Evaporator
Cold particles
storage tank
Solar particle
receiver
SO2
900 °C
600 °C
100 °C
Gas
TurbineSteam
Turbine
Steam
O2
N2
Gas
Separation
SO2
O2
H2O
Water
Storage
SO2
Storage
H2O
O2
H2SO4
Concentrator
H2O
> Sulphur – solar fuel for on demand power generation > Thomey et al. • International Workshop on Solar Thermochemistry > Sep. 13, 2017 DLR.de • Slide 8
PEGASUS – Process diagram
Non-solar site
Solar site
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Integration of solar sulphur power generation
> Sulphur – solar fuel for on demand power generation > Thomey et al. • International Workshop on Solar Thermochemistry > Sep. 13, 2017 DLR.de • Slide 9
Sulphuric acid
plant
Refinery Sulphur
gas turbine plant
Sulphuric
acid
Solar particle
plant
Hot
particles
Particle reactor
(sulphuric acid splitting)
Disproportionate reactor
Sulphur
Electrical
power
SO2
SO3
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SO3
Decomposer
Sulphur
Storage
Sulphuric
Acid
Storage
Absorbers
Disproportionate
Reactor
Sulphur
Burner
Contact
process
SO3, H2O
dilute
H2SO4
SO2
O2
N2
SO3 , O2, N2
S
Air
Electricity
Oxygen
Solar field
Hot particles
storage tank
H2SO4
Evaporator
Cold particles
storage tank
Solar particle
receiver
SO2
900 °C
600 °C
100 °C
Gas
TurbineSteam
Turbine
Steam
O2
N2
Gas
Separation
SO2
O2
H2O
Water
Storage
SO2
Storage
H2O
O2
H2SO4
Concentrator
H2O
> Sulphur – solar fuel for on demand power generation > Thomey et al. • International Workshop on Solar Thermochemistry > Sep. 13, 2017 DLR.de • Slide 10
Solar-to-fuel efficiency
Heat recovery
~60%
~90%
~90%
~90%
HRa = -297 J/mol S
HRb = -99 J/mol S
(HRc = -176 J/mol S) solar-to-sulphur~21%
HR1 = 826 J/mol S
solar-to-sulphur=(Hra + HR
b)/ HR1 ∙ ∑
(HR2 = -254 J/mol S)
~600 °C
>1000 °C
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• Experience on solar sulphuric acid cracking since more than 20 years
• Research on Hybrid Sulphur Cycle in European projects
HYTHEC, HycycleS and SOL2HY2 (2004 – 2016)
• Development and on-sun testing of receiver/reactors in solar furnace
• Construction of pilot unit and demo operation on solar tower
• Modelling of reactors
• Testing of catalysts and construction materials
• Flowsheeting and techno-economics of HyS process
• Scale-up concepts
Research of DLR on sulphur cycles
> Sulphur – solar fuel for on demand power generation > Thomey et al. • International Workshop on Solar Thermochemistry > Sep. 13, 2017 DLR.de • Slide 11
Catalyst testing Solar furnace reactor Solar tower demo
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• Funding: United States Department of Energy (DOE)
• 2 project phases from 2010 to 2013
• GO/NO-GO review after phase I
• Phase I completed in Mar. 2012
• GO recommendation for Phase II (May 2012 – Oct. 2013)
• Coordinator: General Atomics (GA), USA
• SO2 disproportionation
• Sulfur combustion
• Experiments, plant design, flowsheeting, economics
• Subcontractor: German Aerospace Center (DLR)
• H2SO4 decomposition
• Experiments, modeling
• Funded work and in-kind contribution
Project Baseload (Sulfur Based Thermochemical Heat Storage for
Baseload Concentrated Solar Power Generation)
> Sulphur – solar fuel for on demand power generation > Thomey et al. • International Workshop on Solar Thermochemistry > Sep. 13, 2017 DLR.de • Slide 12
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• DLR, Germany (Coordinator)
• Solar tower/simulator owner/operator
• Solar receiver/reactor developer
• APTL/CERTH, Greece
• Catalyst materials developer
• KIT, Germany
• Combustion specialist
• Baltic Ceramics, Poland
• Advanced ceramics manufacturer
• Processi Innovativi, Italy
• Power plant designer/contractor
• BrightSource, Israel
• CSP plant designer/contractor
PEGASUS partners
> Sulphur – solar fuel for on demand power generation > Thomey et al. • International Workshop on Solar Thermochemistry > Sep. 13, 2017 DLR.de • Slide 13
Research institute
University
SME
Industry
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• WP1: Catalytic particles development, manufacturing – APTL, Baltic Ceramics
• WP2: Centrifugal particle solar receiver – DLR
• Preparation of existing test receiver
• On-sun test operation with catalytic particles (WP1)
• WP3: Sulphur trioxide decomposer + WP4: Sulphuric acid evaporator – DLR
• Development and construction of moving bed reactors with direct (WP3)
and indirect (WP4) heat transfer
• Off-sun test operation
• WP5: Sulphur Combustor – KIT
• Development, construction and operation of sulphur burner
• WT6.1, 6.5, 6.6:Overall concept evaluation – Processi Innovativi, BrightSource
• System modelling, flowsheeting, techno-economy
• WT6.2-6.4: System integration, test operation – DLR
• Integrated operation of solar receiver (WP2) and sulphuric acid splitting
reactors (WP3, WP4)
PEGASUS – Work plan
> Sulphur – solar fuel for on demand power generation > Thomey et al. • International Workshop on Solar Thermochemistry > Sep. 13, 2017 DLR.de • Slide 14
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• Centrifugal particle receiver was erected on scaffold in
front of Juelich Solar Tower
• Nominal power: 2.5 MWth
• Diameter of aperture: 1.13 m
• Max. particle temperature: 1000 °C
• Commissioning is in progress
• Solar testing of CentRec pilot planned to start
in autumn 2017
Project PEGASUS
• Pre-testing of catalytic particles in CentRec pilot
• Integrated testing together with particle reactors for
sulphuric acid splitting planned in last project year
Centrifugal particle solar receiver optimization
Application of pilot receiver developed in CentRec project
> Sulphur – solar fuel for on demand power generation > Thomey et al. • International Workshop on Solar Thermochemistry > Sep. 13, 2017 DLR.de • Chart 15
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Design options for decomposer and evaporator
SO3 decomposer Sulphuric acid evaporator
• Direct contact • Indirect heat transfer (tube/plate HX)
> Sulphur – solar fuel for on demand power generation > Thomey et al. • International Workshop on Solar Thermochemistry > Sep. 13, 2017 DLR.de • Slide 16
Particles 100 °C
Particles 600 °C
H2SO4
25 °C
SO3, H2O
400 °C
SO3, H2O
400 °C
SO2, O2, H2O
800 °C
Particles 900 °C
Particles 600 °CParticles 750 °C
Particles 750 °C
850 °C
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• Sulphur is one of the most important commodity of chemical industry
• Sulphur has high thermochemical energy density
• Transportation and storage of solid or liquid sulphur is industrial practice
• Solar sulphur cycle for baseload and on-demand power production
• Estimated solar-to-fuel efficiency of ~21%
• Potential for integration of sulphur cycle into existing sulphuric acid plants
• Investigation of solar sulphur cycle in European project PEGASUS
• Development of catalytically active solar particles
• Construction of particle reactor for sulphuric acid splitting
• Prototype development of sulphur burner for SO2 gas turbine
Conclusions and outlook
> Sulphur – solar fuel for on demand power generation > Thomey et al. • International Workshop on Solar Thermochemistry > Sep. 13, 2017 DLR.de • Chart 17
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Thank you for your attention!
> Sulphur – solar fuel for on demand power generation > Thomey et al. • International Workshop on Solar Thermochemistry > Sep. 13, 2017 DLR.de • Chart 18
Co-funded by the Horizon 2020
Framework Programme of the
European Union