the eu horizon 2020 project pegasus and its role in the csp · • dlr institute of solar research...

Co-funded by the Horizon 2020 Framework Programme of the

European Union

The EU Horizon 2020 project PEGASUS and its role in the CSP

> The EU Horizon 2020 project PEGASUS and its role in the CSP > Thomey et al. • CSP Today Sevilla > 22nd Nov. 2017 DLR.de • Slide 1

CSP Today Sevilla 2017 Dennis Thomey, Christos Agrafiotis, Nicolas Overbeck, Martin Roeb, Christian Sattler

• DLR Institute of Solar Research – Solar Chemical Engineering • Potential of solar energy • Sulphur as industrial commodity and thermochemical storage medium • Solar sulphur power generation • Background of DLR on sulphur cycles • European project PEGASUS • Conclusions and outlook

Contents


• Research Institution, Space Agency and Project Management Agency • Research Areas:

• Aeronautics • Space Research and Technology • Transport • Energy • Defence and Security

• 8000 employees across 33 institutes and facilities at 20 sites in Germany • Offices in Brussels, Paris, Tokyo and Washington • Total income 2015: 888 Mio. €

German Aerospace Center (DLR)


Credit: Nonwarit/Fotolia

Institute of Solar Research


Point Focus Systems • Heliostats • High temperature receivers • System technology

Line Focus Systems • Heat transfer media • Collector development • Industrial process heat

New Materials • Absorber materials • High temperature redox

systems • Photocatalysts • Heat transfer fluids

Qualification • Components • Component durability • Systems

Solar Energy Meteorology • Solar radiation measurement

and modelling • Radiation nowcasting • Other meteorological influences

Solar Chemical Engineering • Solar fuels • Solar water treatment

Institute of Solar Research Solar Chemical Engineering


Reactive Systems • Simulation • Synthesis • Chemical characteristics • Physical characteristics

Solar Fuels

Technical development in all dimensions

Solar Plant • Site assessment • Solar field simulation • Environmental impact

Receiver • Design • Simulation • Construction • Testing • Next generation

development

Receiver Components • Materials • Design • Heat and mass transport • Simulation • Testing and

Development

Potential of solar energy


Hydrogen production with solar plants on the area of Lake Nasser is equivalent (energetically) to whole oil production of Middle East.

World EU-25 Germany

M. Schmitz, TSK Flagsol

Comparison of energy storage densities


1College of the Desert 2General Atomics

*at 700 bar

Technology Energy density (kJ/kg)

Volumetric energy density (kJ/l)

Hydrogen 141,886 1 ~6,700 * Gasoline 47,357 1 ~35,000 Sulphur 9,281 2 ~18,000 Lithium Ion Battery 580 2 ~730 Molten Salt 282 2 ~540 Elevated water Dam (100m) 1 2 ~1

• 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


Sulphuric acid plant

Sulphur pile

Claus process

Ore roasting

Sulphur world production 2014 Total of 69.1 Mio. tons (avg. world price of US$160 per ton)


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

Transportation and storage of sulphur In solid or liquid form


Molten sulphur in heated pipelines (~140 °C)

Molten sulphur trailer

Molten Sulphur Rail Car

Pipeline

Ship

Train

Truck

Thermochemical sulfur storage cycle for on-demand solar power production


SO2 + H2O

Sulphuric Acid Decomposition

SO2 Disproportionation

SO2

Sulphur Combustion

S H2SO4

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)

ΔH = 551 kJ/mol

ΔH = -254 kJ/mol

ΔH = -297 kJ/mol

Sulphuric Acid

© Twin Filter B.V.

On-demand Electrical Power

© dpa

Concentrated Solar Power

© DLR

Sulphur

© DLR

• Direct absorption ⇒ high efficiency and energy density • Direct storage • Receiver and storage at ambient pressure • No freezing and no decomposition • Low parasitic • Low security requirements

Solar particle technology Centrifugal receiver


SO3 Decomposer

SulphurStorage

Sulphuric Acid

Storage

Absorbers

DisproportionateReactor

SulphurBurner

Contact process

SO3, H2OdiluteH2SO4

SO2O2N2

SO3 , O2, N2

S

AirElectricity

Oxygen

Solar field

Hot particlesstorage tank

H2SO4Evaporator

Cold particlesstorage tank

Solar particle receiver

SO2

900 °C

600 °C

100 °C

GasTurbine

SteamTurbine

Steam

O2N2

Gas Separation

SO2O2

H2O

WaterStorage

SO2Storage

H2O

O2

H2SO4Concentrator

H2O


PEGASUS – Process diagram

Non-solar site

Solar site

H2SO4 ⇒ SO3 + H2O (400°C)

SO3 ⇒ SO2 + ½ O2 (850°C)

Integration of solar sulphur power generation


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

• Experience on solar sulphuric acid cracking since more than 20 years • Research on Hybrid Sulphur Cycle for Hydrogen production

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


Catalyst testing Solar furnace reactor Solar tower demo

• 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)


• 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


Research institute University SME Industry

• 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


DLR Solar Power Tower in Juelich, Germany Research and demonstration plant

DLR.de • Folie 19 > The EU Horizon 2020 project PEGASUS and its role in the CSP > Thomey et al. • CSP Today Sevilla > 22nd Nov. 2017

• 2153 heliostats (mirrors) à 8 m2 • 60 m tower • 22 m2 solar receiver • 680 °C air outlet temperature of receiver • 1.5 MWel steam turbine • Thermal storage for 1 hour of full load operation

• 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 completed • Solar testing of CentRec started

in autumn 2017

Project PEGASUS • Solar 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


Experimental conditions • Reaction temperature: 850 °C • Pressure: 1 bar • Feed: liquid sulfuric acid 95-98 w% • Catalyst quantity per test: 1 g • On-stream exposure per test: 60 min

Development of catalytic particles


Pump Furnace

TC TC

�

N2

MFC

Sulfuric Acid

vaporization

spectrometer

N2: dilutionfor analysis

Lines heated up to 185oC

Cuvette heated up to 212oC

SO2 analysisvia UV spectrometry

SO2: calibration

vent

H2SO4, SO3, SO2, H2Ocollection

UV-lamp

SO2 0.5%

SO2 1.0%

SO2 1.5%

TC

Results of CuO enriched particles

Setup for catalytic activity measurements

Particle preparation (capacity of 3000 tons/year)

Preparation and qualification of catalytic particles Required quantity for solar testing: 3 tons


Particle characterisation

Crush test Abrasiveness Density Roundness and sphericity

Solubility in acid

Development of particle reactor for sulphuric acid splitting SO3 decomposer Sulphuric acid evaporator

• Direct contact • Indirect heat transfer (tube type)


Particles 100 °C

Particles 600 °C

H2SO425 °C

SO3, H2O400 °C

SO3, H2O400 °C

SO2, O2, H2O800 °C

Particles 900 °C

Particles 600 °CParticles 750 °C

Particles 750 °C

850 °C

H2SO4 ⇒ SO3 + H2O (400 °C) SO3 ⇒ SO2 + ½ O2 (850 °C)

Development of sulphur burner for gas turbines


Test rig for atomization and combustion of sulphur

Development of chemical kinetics and CFD aided burner development

Quantum Mechanics

structure

Kinetics Thermodynamics

Sulphur combustion reaction kinetics mechanism

Transition State Theory

Entropy and Heat Capacities

Heat of Formation

QRRK k(E)-rate const. Needed as input → Mechanism

Input for CFD Model

Flowsheet development

Process simulation and techno-economics


Disproportionation

SO2 AbsorberP= 9 Bar

H2O

H2SO4 25%wt

H2SO4 1,74%wt

H2SO4 15%wt

P=9,4 Bar

340 - 270 °C

H2SO4 94,5%wt

Sulfuric acid concentration

H2SO4 96,96%wtH2SO4 75,69%wt

320 - 80 °CP=1,5 Bar

H2SO4storage

Solar receiver

H2SO4Decomposer

H2SO4 98,3%wt

Hot particles900°C

Cold particles345°C

Hot particles700°C

30-500 °CP=10 Bar

850 - 550 °C 550 - 400 °C 400 - 340 °C

270 - 140 °C 140 - 60 °C

H2SO4 98,3%wt

SO2 - SO3Converter SO3 Absorber

H2SO4 99,99%wt

665 - 400 °CP=1,5 Bar

Gas Turbine

AirC. C.

Sulfur 130°C

Air Dryer

StrongSulfuric acid

Slightly weakenedSulfuric acid

Sulfur Melter

ExhaustDried Air

Tail gas

Dilu

te H

2SO

4

H2SO4 98,3%wt

S1

B1

S2

EVA DEC

S6

S7

S8

HR

SEP1

S10

S11

B6

SEP2

S12

ABS

S13

S14

B9

S16

S18

Techno-economical evaluation

Overall process simulation

https://www.google.it/url?sa=i&rct=j&q=&esrc=s&source=images&cd=&cad=rja&uact=8&ved=0ahUKEwiu7P3eos_XAhUJPhQKHfX5AtUQjRwIBw&url=https://www.freepik.com/free-icon/forward-arrow_749179.htm&psig=AOvVaw3VSDT1MsGmliEVK7jwjTWa&ust=1511340079787243

https://www.google.it/url?sa=i&rct=j&q=&esrc=s&source=images&cd=&cad=rja&uact=8&ved=0ahUKEwjf8Lr3os_XAhVL8RQKHTNRC98QjRwIBw&url=https://dir.indiamart.com/impcat/techno-economic-feasibility-studies.html&psig=AOvVaw2AfkQqLz4S_jm8gEeu5PZ7&ust=1511340140597060

Cosine effect (e.g. 1st Jan.)

Solar field design and modelling Reference site: Ouarzazate, Morocco


8 am

1 pm

5 pm

Blocking & Shadowing (e.g. 21st Mar.)

• 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 allows for baseload and on-demand power production • Potential for integration of sulphur cycle into existing sulphuric acid plants • Investigation of solar sulphur cycle in European project PEGASUS

• Development and on-sun testing of catalytically active solar particles • Construction of particle reactor for sulphuric acid splitting • Prototype development of sulphur burner for gas turbine • Component modelling and solar field design • Process simulation and techno-economic analysis

Conclusions and outlook


Thank you for your attention!


Co-funded by the Horizon 2020 Framework Programme of the

European Union

www.pegasus-project.eu

http://www.pegasus-project.eu/



the eu horizon 2020 project pegasus and its role in the csp · • dlr institute of solar research...

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