Power-to-X Electrolysis and synthetic fuels Jens Oluf Jensen Department of Energy Conversion and Storage Fysikvej, building 310 Technical University of Denmark 2800 Lyngby Denmark jojen@dtu.dk 11 April 2023 DTU Energy Jens Oluf Jensen, 47202 Introduction to Future Energy 1 Outline • Water electrolysis • Types of electrolyzers • Synthetic fuels • Carbon capture and storage or utilization 11 April 2023 DTU Energy Jens Oluf Jensen, 47202 Introduction to Future Energy 2 Learning objectives • Explain the main principles of an electrolyzer • Outline the characteristics of the most common types of electrolyzers (AEC, PEMEC and SOEC) • Explain the function of the components in a stack • Explain the shape of a polarization curve • Calculate the voltage efficiency and the heat evolved at a given cell voltage • Calculate the total current, voltage and electrical power of an electrolyzer stack if given dimensions (electrode area add number of cells) and working point (cell voltage and current density) • Explain the concept of power-to-X • Explain the main synthesis paths to synthetic fuels from hydrogen (Sabatier, Fischer-Tropsch, Methanol and Haber-Bosch) • Explain the advantages and disadvantages of powering vehicles with hydrogen instead of batteries • Explain the advantages and disadvantages of converting hydrogen into carbon based synthetic fuels • Explain CCS and CCU • Discuss the challenges with carbon capture (CCS and CCU) 11 April 2023 DTU Energy Jens Oluf Jensen, 47202 Introduction to Future Energy 3 Renewable and finite reserves Total recoverable reserves for the finite resources. (TWy). Yearly potential for renewables. (TWy/y = TW) Global energy consumption 2016: 17.6 TWy Source: Perez & Perez, 2009 + update 2015 IEA-SHCP-Newsletter Vol. 62, Nov. 2015 – draft 11 April 2023 DTU Energy Jens Oluf Jensen, 47202 Introduction to Future Energy 4 Global energy consumption by sector IEA, World Energy Balances 2017 11 April 2023 DTU Energy Jens Oluf Jensen, 47202 Introduction to Future Energy 5 The transport problem Transport needs 29 % of the 18 TW = 5.2 TW Source TW Fluctuating Electrical Solar 23,000 Yes X Wind 25 - 70 Yes X OTEC* 3 - 11 No X Biomass** 2-6 No Hydro 3-4 No X Geothermal 0.3 - 2 No X Waves 0.2 - 2 Yes X Thermal Chemical X X * OTEC = Ocean thermal energy conversion A need for storage and conversion ** Some biomass will be used for chemicals – return as waste 11 April 2023 DTU Energy Jens Oluf Jensen, 47202 Introduction to Future Energy 6 Power-to-X The raw material: water. - abundant, inexpensive, non-toxic H2O + Energy ⇄ H2 + ½O2 Power “X” Pro - Ingeniøren 11 April 2023 DTU Energy Jens Oluf Jensen, 47202 Introduction to Future Energy 7 The hydrogen cycle Electrolyzer Electrical energy in H2 H 2O Hydrogen cycle Storage O2 H2 + ½O2 ⇄ H2O + Energy H2 Electrical energy out 11 April 2023 DTU Energy Fuel cell Jens Oluf Jensen, 47202 Introduction to Future Energy 8 Hydrogen production 11 April 2023 Class Principle Share Chemical Reforming of carbonaceous fuels. (+cracking of ammonia) Completely dominating (⁓96%) Electrochemical Electrolysis Commercial, but very limited (⁓4%) Thermochemical Combined thermal/chemical Experimental Photochemical Purely light driven Experimental Photoelectrochemical Combined photoand electrochemical Experimental Microbial Anaerobe digestion Experimental DTU Energy Jens Oluf Jensen, 47202 Introduction to Future Energy 9 Electrolysis vs reforming ResearchAndMarkets.com CH4 + 2H2O → 4H2 + CO2 Note: 4 % hydrogen is always quoted. It may vary. It is mostly a by-product from the chlor-alkali process making Chlorine and sodium hydroxide. 11 April 2023 DTU Energy Jens Oluf Jensen, 47202 Introduction to Future Energy 10 Electrolysis 2H2O → 2H2 + O2 Example: system with acidic electrolyte 11 April 2023 DTU Energy Jens Oluf Jensen, 47202 Introduction to Future Energy 11 Electrolysis Int. J. Hydrogen Energy, 44 (20) 9841-9848 (2019) doi.org/10.1016/j.ijhydene.2018.11.007 11 April 2023 DTU Energy Jens Oluf Jensen, 47202 Introduction to Future Energy 12 FC: -ΔG, -ΔH (kJ/mol) EC: ΔG, ΔH (kJ/mol) 300 ΔH 250 200 H2 + ½O2 ⇄ H2O ΔG 150 Voltage 100 50 0 1,4 1,2 1 0,8 0,6 0,4 0,2 0 Cell voltage (V) The available/necessary energy (H2) 0 100 200 300 400 500 600 700 800 900 1000 Temperature (oC) Source: JANAF https://janaf.nist.gov/ 11 April 2023 DTU Energy ∆𝐺𝐺r = ∆𝐻𝐻r − 𝑇𝑇∆𝑆𝑆r Jens Oluf Jensen, 47202 Introduction to Future Energy 13 The maximum electrical efficiency ΔGr is maximum work related to a fuel ΔHr is total energy related to a fuel Maximum fuel cell efficiency: Maximum electrolyzer efficiency: η FC ∆G o (T ) = ∆H o η EC ∆H o = ∆G o (T ) What you get η = What you pay 11 April 2023 DTU Energy Jens Oluf Jensen, 47202 Introduction to Future Energy 14 The available/necessary energy 25°C, 1 bar Fuel cell (→) Electrolyzer (←) H2(g) + ½O2(g) ↔ H2O(l) ΔH (higher heating value) -285.8 kJ/mol 285.8 kJ/mol ΔG -237.1 kJ/mol 237.1 kJ/mol ηmax ΔG/ΔH = 83% ΔH/ΔG = 121% H2(g) + ½O2(g) ↔ H2O(g) ΔH (lower heating value) -241.8 kJ/mol 241.8 kJ/mol ΔG -228.6 kJ/mol 228.6 kJ/mol ηmax ΔG/ΔH = 95% ΔH/ΔG = 106% What you get η = What you pay 11 April 2023 DTU Energy Jens Oluf Jensen, 47202 Introduction to Future Energy 15 The polarization curve H2(g) + ½O2(g) ⇄ H2O(l) Energy 𝐸𝐸 = charge 𝐸𝐸rev = Δ𝐺𝐺(𝑇𝑇) 𝑛𝑛𝐹𝐹 F: faradays constant n: No. of electrons 11 April 2023 DTU Energy Jens Oluf Jensen, 47202 Introduction to Future Energy 16 Schematic overview of losses in electrolyzers 11 April 2023 DTU Energy Jens Oluf Jensen, 47202 Introduction to Future Energy 17 The thermo-neutral voltage H2O(l) → H2(g) + ½O2(g) Etn = ∆H = 1.48V ( HHV , liquid water ) nF Endothermic (heat consuming) H2O(g) → H2(g) + ½O2(g) Etn = ∆H = 1.25V ( LHV , water vapour ) nF At ETN the energy in excess of ΔG produces heat (loss?), which is used (no loss) 11 April 2023 DTU Energy Jens Oluf Jensen, 47202 Introduction to Future Energy 18 The polarization curve Heat demand Heat balanced Heat surplus Arbitrary working point 11 April 2023 DTU Energy Jens Oluf Jensen, 47202 Introduction to Future Energy 19 Minimum energy demand Reference points for commercial electrolyzers (Calculated as perfect gas, 1 bar) 11 April 2023 DTU Energy LHV HHV kJ/mol 241.8 285.8 kWh/kg 33.58 39.69 kWh/m3 2.71 2.81 2.96 kWh/m3 3.20 3.32 3.50 Temperature Molar vol. 25ºC 15ºC 0ºC m3/mol 0.0248 0.0240 0.0227 Jens Oluf Jensen, 47202 Introduction to Future Energy 20 Types of electrolyzers 11 April 2023 DTU Energy Jens Oluf Jensen, 47202 Introduction to Future Energy 21 Types of electrolyzer cells Family Type Low temperature systems High temperature systems 11 April 2023 DTU Energy Electrolyte Abrev. Temperature Alkaline electrolyzer AEC 60-80°C aq. KOH (OH-) Polymer electrolyzer PEMEC 60- 80°C Polymer (H+) Direct methanol electrolyzer DMEC 60- 80°C Polymer (H+) Phosphoric acid electrolyzer PAEC 200°C H3PO4 (H+) Molten carbonate electrolyzer MCEC 650°C Molten salt (CO3-2) Solid oxide electrolyzer SOEC 700-900°C Ceramic (O2-) (charge carrier) Jens Oluf Jensen, 47202 Introduction to Future Energy 22 AEC vs PEM vs SOEC (typical and very schematic) E = 1.85 V (80 % HHV) ETN = 1.48 V (100 % HHV) C. Graves et al. Renewable and Sustainable Energy Reviews 2011, 15, 1–23. 11 April 2023 DTU Energy Jens Oluf Jensen, 47202 Introduction to Future Energy 23 Alkaline electrolyzer (AEC) • Traditional technology • Long time commercial Electrolyte: 25-30 % KOH • MW size, 1-35 bar(a) • Quite inexpensive materials • Proven technology Separator: • Quite bulky Before: asbestos, Today: porous diaphragm (Zirfon) Cathode catalyst (H2): Ni or Ni compounds Anode catalyst (O2): Metal oxides like Ni-Fe oxide Container and bipolar plates: Ni plated Steel IHT 11 April 2023 DTU Energy Jens Oluf Jensen, 47202 Introduction to Future Energy 24 Diaphragm for the alkaline electrolyte Originally: Asbestos. Very stable but phased out for environmental/health reasons Then: NiO fibers Today: porous composites like Zirfon A polysulfone based composite made hydrophilic by particles of ZrO2 The dream: an anion exchange membrane like for PEMEC 11 April 2023 DTU Energy Jens Oluf Jensen, 47202 Introduction to Future Energy 25 Gap or zero gap 11 April 2023 Gap Zero-gap High internal resistance Low internal resistance DTU Energy Jens Oluf Jensen, 47202 Introduction to Future Energy 26 The largest electrolyzers S-556 unit. 760 Nm3/h H2 28 electrolysers Type S-556 21'000 Nm3/h H2 and 10'500 Nm3/h O2 In service since 1973 for Sable Chemical Industries in Zimbabwe 11 April 2023 DTU Energy Jens Oluf Jensen, 47202 Introduction to Future Energy 27 Large scale electrolyzers (Norsk Hydro) Rjukan, Norway; 1927 – 1970’s Glomfjord, Norway; 1953 – 1991 Used for: Hydrogen → ammonia → fertilizers The activity is today with Nel Hydrogen 11 April 2023 DTU Energy Jens Oluf Jensen, 47202 Introduction to Future Energy 28 AEC unit from Green Hydrogen Systems Hyprovide 250 – 450 kW Unknown source (1.1 x 1.8 x 2.3 m) 11 April 2023 DTU Energy Jens Oluf Jensen, 47202 Introduction to Future Energy 29 PEM electrolyzers - PEMEC Anode: Catalyst: IrO2 or (Ir, Ru)O2 Electrode support: Noble metal coated porous Ti • Recent technology • Compact • Efficient • Under further development • Partly commercial 2 MW stack, Giner Cathode: Catalyst: Pt Electrode support: Noble metal coated porous Ti or carbon Electrolyte: PFSA (Nafion) (no problems with wetting) • Medium scale (so far) • Fast transient response Bipolar plates: Noble metal coated Ti • Expensive Unknown origin 11 April 2023 DTU Energy Jens Oluf Jensen, 47202 Introduction to Future Energy 30 PEMEC Selamet, O.F. et al., Int. J. Hydr. Energ., 36, 11480— 11487. 2011 https://doi.org/10.1016/j.ijhydene.2011.01.129 11 April 2023 DTU Energy Jens Oluf Jensen, 47202 Introduction to Future Energy 31 Proton conduction in polymer Hydrophobic backbone Hydrophobic backbone Hydrophilic side chains Sulfonic acid Perfluorosulfonic acid, PFSA 11 April 2023 DTU Energy Jens Oluf Jensen, 47202 Introduction to Future Energy 32 PEM vs alkaline Source: Hydrogenics, 11 April 2023 DTU Energy Jens Oluf Jensen, 47202 Introduction to Future Energy 33 Elemental abundance U.S. Geological Survey Fact Sheet 087-02 11 April 2023 DTU Energy Jens Oluf Jensen, 47202 Introduction to Future Energy 34 Solid oxide electrolyzers - SOEC • Future technology • Early development • Potential for high efficiency (Low ΔG and good kinetics) • Materials like for SOFC • CO2 electrolysis • Not commercial 11 April 2023 DTU Energy 750 - 900 °C SOFC/SOEC from DTU Jens Oluf Jensen, 47202 Introduction to Future Energy 35 Solid oxide electrolyzer cell (SOEC) O2 World record! -3.6 A/cm2 at 1.48 V + 2O2- Electrolysis (SOEC) Fuel cell (SOFC) 2H2O 2H2 ÷ 4 e- SOFC/SOEC from DTU Energy 11 April 2023 DTU Energy Jens Oluf Jensen, 47202 Introduction to Future Energy 36 Ways to the affordable and scalable electrolyzer AEC PEMEC SOEC Poor Excellent Good Acceptable Acceptable Very high Pressurization (moderate) Yes Yes Yes Pressurization (+100 bar) No Yes ? Strategic elements No Yes No Cost Moderate High ? Scalability (materials) Unlimited Limited Unlimited High/Excellent High To be proven High High Low Rate/footprint Conversion efficiency Durability Readiness for roll-out High internal resistance in separator Comments 11 April 2023 DTU Energy Depends on iridium for oxygen catalyst Sizing up challenging. Not ready for first wave Jens Oluf Jensen, 47202 Introduction to Future Energy 37 The simplified electrolyzer system 11 April 2023 DTU Energy Jens Oluf Jensen, 47202 Introduction to Future Energy 38 A PEMEC system 11 April 2023 DTU Energy Jens Oluf Jensen, 47202 Introduction to Future Energy 39 High pressure electrolysis Isothermal compression work, 𝑤𝑤𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐 of n mole gas from P1 to P2 𝑤𝑤𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐 𝑃𝑃2 = 𝑛𝑛𝑛𝑛𝑛𝑛ln 𝑃𝑃1 Same work for any pressure decade 1-10 bar or 10-100 bar PEMEC, 80 bar (ITM) PEMEC, 40 bar (Giner) AEC units, 30 bar (Hydro/Nel) (for a perfect gas only) 11 April 2023 DTU Energy Jens Oluf Jensen, 47202 Introduction to Future Energy 40 Summary on the three electrolyzers AEC: Traditional version: • Well-proven • Robust • Bulky • No strategic materials • Fully commercial. New generations on the way which are expected to resemble PEMEC 11 April 2023 DTU Energy PEMEC: • Compact • Pure water • High rate (several A cm-2) • Costly • Limited scaling due to iridium. • Fully commercial. SOEC: • High conversion efficiency (thermoneutral or better) • No strategic materials. • Possible dual mode (EC/FC) • Not fully commercial yet. • Scaling up pending. Jens Oluf Jensen, 47202 Introduction to Future Energy 41 Electrolysis - IEA, Global Hydrogen Review 2021 Global installed electrolysis capacity by region and technology, 2015-2020 11 April 2023 DTU Energy Jens Oluf Jensen, 47202 Introduction to Future Energy 42 A tremendous need for electrolysis EU Hydrogen strategy 2020 2020-2024 6 GW of electrolysis, 1 million tonnes of hydrogen 2025-2030 40 GW of electrolysis, 10 million tonnes of hydrogen 2030-2050 13-14 % of total energy mix - hydrogen Repower EU 2022 2030 10 million tonnes of hydrogen internally produced + 10 Mt imported hydrogen. 90-100 GWLHV Electrolysis, 140 GW electricity rated (utilization 43 %, eff. 70%) BloombergNEF’s New Energy Outlook (NEO) 2030 Green Scenario: 1.9 TW of electrolyzers to kick-start the hydrogen sector. 2050 Red (nuclear) Scenario 3.572 TW of nuclear capacity to power electrolyzers • Total world average energy flow: 18 TW • Several GW of electrolyzer projects in the European pipeline • European production capacity for electrolyzers is currently in the order of 2 GW per year (currently: 1.75 GWLHV or 2.5 GWLHV electricity rated)* *Joint Declaration. European Electrolyser Summit, Brussels 5 May 2022, Hydrogen Europe. 11 April 2023 DTU Energy Jens Oluf Jensen, 47202 Introduction to Future Energy 43 Power-to-X Power-to-gas Power-to-liquid Power-to-fuel Power-to-chemicals Power-to-whatever … X= Power “X” Pro - Ingeniøren 11 April 2023 DTU Energy • Hydrogen for • Transport • Storage • Industry • Carbonaceous fuels for • Heavy transport • Storage • Industry • Chemicals for industry • Ammonia for • Fertilizers • Fuel Jens Oluf Jensen, 47202 Introduction to Future Energy 44 The hydrogen cycle Electrolyzer Electrical energy in H2 H 2O Hydrogen cycle Storage O2 H2 + ½O2 ⇄ H2O + Energy H2 Electrical energy out 11 April 2023 DTU Energy Fuel cell Jens Oluf Jensen, 47202 Introduction to Future Energy 45 Including the carbon cycle Electrolyzer Reactor H2 Synfuel CxOyHz H2 Hydrogen cycle H2O Storage O2 CO2 Carbon cycle Storage Engine H2 + ½O2 ⇄ H2O + Energy H2 Synfuel H2 CxOyHz Reformer Fuel cell 11 April 2023 DTU Energy Jens Oluf Jensen, 47202 Introduction to Future Energy 46 Hydrogen as an energy carrier Electrolyzer Reactor H2 NH3 H2 Hydrogen cycle H2O Storage N2 Ammonia cycle Storage 3H2 + N2 ⇄ 2NH3 O2 Engine H2 + ½O2 ⇄ H2O + Energy H2 NH3 H2 Cracker Fuel cell 11 April 2023 DTU Energy Jens Oluf Jensen, 47202 Introduction to Future Energy 47 Power-to-X, electrochemical + chemical Electricity Electrolysis X = Methane X = Methanol X = Other hydrocarbons X = Other alcohols X = hydrogen X = Ammonia X = Chemicals X = Fuels and Chemicals 11 April 2023 DTU Energy Jens Oluf Jensen, 47202 Introduction to Future Energy 48 The Sabatier process Synthesis of methane from hydrogen and carbon dioxide CO2 + 4H2 → CH4 + 2H2O ∆H = −165.0 kJ mol-2 Uses: • Production of synthesis natural gas • Upgrading of biogas by conversion of CO2 to more methane. The Sabatier process was discovered by the French chemist Paul Sabatier in the 1910s 11 April 2023 DTU Energy Jens Oluf Jensen, 47202 Introduction to Future Energy 49 Synthetic fuels - hydrocarbons The Sabatier process The Fischer–Tropsch process Synthesis of methane from hydrogen and carbon dioxide Synthesis of liquid hydrocarbons from hydrogen and carbon monoxide CO2 + 4H2 → CH4 + 2H2O ∆H = −165.0 kJ/mol 300-400 ºC with a nickel catalyst Uses: • Production of “synthetic natural gas” • Upgrading of biogas by conversion of CO2 to more methane. The Sabatier process was discovered by the French chemist Paul Sabatier in the 1910s 11 April 2023 DTU Energy Carbon monoxide is formed from carbon dioxide by the reverse water gas shift reaction: ∆H = +41 kJ mol-2 CO2 + H2O → CO + H2 Hydrocarbons by the Fischer–Tropsch process: (2n + 1) H2 + n CO → CnH2n+2 + n H2O ∆H << 0 Developed by Franz Fischer and Hans Tropsch in 1925 Used in Germany during World War II and in South Africa during the embargo in the apartheid days Jens Oluf Jensen, 47202 Introduction to Future Energy 50 Methanol Methanol synthesis from syngas (CO + H2 and some CO2) or just CO2 + H2 at 200-300 ºC and 50–100 bar 1) CO + 2H2 ⇄ CH3OH ΔHr = -89 kJ mol-1 3) CO + H2O ⇄ CO2 + H2 ΔHr = -41 kJ mol-1 2) CO2 + 3H2 ⇄ CH3OH + H2O ΔHr = -48 kJ mol-1 Catalyst: Cu/ZnO/Al2O3 (same as in a methanol reformer) Cu is the catalyst, but both ZnO and the carrier Al2O3 promotes the catalyst 11 April 2023 DTU Energy Jens Oluf Jensen, 47202 Introduction to Future Energy 51 Ammonia, the Haber–Bosch process The Haber-Bosch process is still the state-of-art process for ammonia synthesis Nitrogen isolated from air reacts with hydrogen under pressure after N2 + 3H2 → NH3 ∆H = −91.8 kJ mol-1 100 – 250 bar and 400 - 500 ºC on an iron based catalyst Fritz Haber demonstrated it in 1909 on the lab scale and Carl Bosch (BASF) scaled it up 1910. 11 April 2023 DTU Energy Jens Oluf Jensen, 47202 Introduction to Future Energy 52 Electricity to ”wheel” efficiency Efficiency vs. energy density (schematic) 11 April 2023 DTU Energy Super caps Batteries Hydrogen Synthetic Energy density fuels Jens Oluf Jensen, 47202 Introduction to Future Energy 53 Scaling with power and energy Scaling with power Scaling with energy Batteries Hydrogen Synthetic fuels (Only storage tank) 11 April 2023 DTU Energy Jens Oluf Jensen, 47202 Introduction to Future Energy 54 CCS and CCU 11 April 2023 DTU Energy Jens Oluf Jensen, 47202 Introduction to Future Energy 55 CCS and CCU (and CCUS) Carbon capture and storage (CCS) Concept: collecting CO2 and storing it somehow/somewhere forever Motivation: Continued use of fossil fuels without increasing the atmospheric CO2 concentration. We may even collect and store CO2 from the atmosphere (negative emissions) Carbon capture and utilization (CCU) Concept: collecting CO2 and using it for synthesizing fuels and chemicals Motivation: A central part of power-to-X when hydrogen is not practical Carbon capture, utilization and storage (CCUS) The term covering both concepts 11 April 2023 DTU Energy Jens Oluf Jensen, 47202 Introduction to Future Energy 56 Ways to store CO2 (sequestration) Geological formations • Saline aquifers • Aging oil fields (aiding extended oil recovery) • Reaction with minerals forming carbonate Deep ocean • High pressure liquid/supercritical CO2 pumped to deep waters (potential for a trillion tons of CO2, but concerns for ocean life and long term stability) As solid carbon • Pyrolysis of biomass, deposition of free carbon in soil 11 April 2023 DTU Energy Jens Oluf Jensen, 47202 Introduction to Future Energy 57 All figures in Gt CO2 Annual world CO2 emissions: 33 Gt 11 April 2023 DTU Energy Jens Oluf Jensen, 47202 Introduction to Future Energy 58 www.globalccsinstitute.com/wpcontent/uploads/2019/12/GCC_GLOBAL_STATUS_REPORT_2019.pdf Global status of CCS targeting climate change 2019. The Global CCS Institute. Storage potentials 11 April 2023 DTU Energy Jens Oluf Jensen, 47202 Introduction to Future Energy 59 www.globalccsinstitute.com/wpcontent/uploads/2019/12/GCC_GLOBAL_STATUS_REPORT_2019.pdf Global status of CCS targeting climate change 2019. The Global CCS Institute. Current CCS facilities around the world Pyrolysis and gasification Biomass/waste etc. Gasses (CO2 + CO + H2 + low hydrocarbons + water) Oils + gasses + carbon (char) For distillation and further processing for fuels Can be deposited on fields 11 April 2023 DTU Energy Jens Oluf Jensen, 47202 Introduction to Future Energy 60 Carbon capture 11 April 2023 DTU Energy Jens Oluf Jensen, 47202 Introduction to Future Energy 61 Ways to capture CO2 Absorption (bulk sorption) • Amines (pure liquid or solutions) • Solutions of hydroxides Adsorption on high surface area materials (surface sorption) • Carbon materials • Zeolites • Metal-organic frameworks (MOF) Filtration • Selective membranes 11 April 2023 DTU Energy Jens Oluf Jensen, 47202 Introduction to Future Energy 62 Absorption/desorption Amines (liquids or solutions, state-of-art) • Monoethanolamine, NH2CH2CH2OH (MEA) • Diethanolamine, NH(CH2CH2OH)2 (DEA) • Methyldiethanolamine, CH3N(C2H3OH)2 (MDEA) Hydroxides (solutions) • Ca(OH)2 • NaOH Ca(OH)2 + CO2 ⇄ CaCO3 + H2O Desorption: reverse of process by heat at around 800 ºC or more CaCO3 + heat ⇄ CaO + CO2 Desorption at 85-120 ºC 11 April 2023 DTU Energy CaO + H2O ⇄ Ca(OH)2 Jens Oluf Jensen, 47202 Introduction to Future Energy 63 Adsorption/desorption, zeolites Highly ordered structures of mixed oxides of cations, commonly Na+, K+, Ca2+, Mg2+ and Si4+. 11 April 2023 DTU Energy Jens Oluf Jensen, 47202 Introduction to Future Energy 64 Adsorption/desorption, MOFs 11 April 2023 DTU Energy Jens Oluf Jensen, 47202 Introduction to Future Energy 65 The optimum material for DAC • Strong bonding to make capture effective • Weak bonding to make release energy efficient • Minimum thermodynamic work for bringing CO2 from 400 ppm to 1 bar: 𝑤𝑤𝑚𝑚𝑚𝑚𝑚𝑚 = 𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅 • HHV: • Methanol: • Methane: 11 April 2023 DTU Energy 𝑝𝑝2 𝑝𝑝1 = 𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅 726 kJ mol-1 890 kJ mol-1 1 400�10−6 = 20 kJ mol-1 Jens Oluf Jensen, 47202 Introduction to Future Energy 66 Direct air capture (DAC) First commercial CO2 capturing project in Hinwil, Switzerland in 2017. CarbFix project, Iceland Deposition of CO2 as carbonate in minerals 900 tons CO2 each year (for greenhouses) DAC by Climeworks Mg2SiO4 + 2CO2 → 2MgCO3 + SiO2 With Audi 2020: 4,000 metric tons of CO2 will be stored as rock underground each year 11 April 2023 DTU Energy Jens Oluf Jensen, 47202 Introduction to Future Energy 67 Power-to-X around the world (2019) M.Thema et al. Renewable and Sustainable Energy Reviews. 112 (2019) 775-787 11 April 2023 DTU Energy Jens Oluf Jensen, 47202 Introduction to Future Energy 68 11 April 2023 From https://brintbranchen.dk/en/danish-hydrogen-projects/ https://stateofgreen.com/en/partners/state-ofgreen/news/new-strategy-kick-starts-denmarkproduction-of-green-hydrogen-and-e-fuels/ Power-to-X in Denmark DTU Energy Jens Oluf Jensen, 47202 Introduction to Future Energy 69 GreenHyScale, 100 MW electrolysis plant end of 2024 2022 2024 6 MW 100 MW • 6 MW X-Series electrolyzer pressurized AEC module, demonstrated by the end of 2022 (Green Hydrogen Systems). • 6 MW module to be multiplied to a 100 MW electrolysis plant end of 2024. • 7.5 MW high-pressure electrolyzer for offshore application in operation end of 2025. (with Siemens Gamesa) 11 April 2023 DTU Energy Partners GreenLab Skive A/S (lead) Green Hydrogen Systems A/S Energy Cluster Denmark Lhyfe Siemens Gamesa Equinor Energy AS Technical University of Denmark Imperial College London Everfuel Quantafuel Euroquality Jens Oluf Jensen, 47202 Introduction to Future Energy 70 HySynergy, 1 GW electrolysis plant by 2030 2022 2025 2030 20 MW 300 MW 1 GW • Hydrogen for Shell Fredericia refinery • Hydrogen for heavy duty transportation Partners Everfuel (lead) Shell Aktive Energi Anlæg Trefor Elnet Energinet TVIS EWII 11 April 2023 DTU Energy Jens Oluf Jensen, 47202 Introduction to Future Energy 71 Esbjerg Green Hydrogen and Green ammonia (1 GW) 2024 1 GW • Copenhagen Infrastructure Partners (CIP) plans to build Europe’s largest Power-to-X-facility, • The facility will consist of 1GW electrolysis • Europe’s largest production facility of CO2-free green ammonia. • Power from offshore wind turbines to green ammonia. • CO2-free green fertilizer • CO2-free green fuel for shipping industry • The excess heat will be used to provide heating for around one third of the local households in Esbjerg • Located in Esbjerg on the west coast of Denmark 11 April 2023 DTU Energy Partners Copenhagen Infrastructure Partners H2 Energy Europe (market leaders agriculture/shipping) Arla (agriculture) Danish Crown (agriculture) DLG (agriculture) Maersk (shipping) DFDS (shipping) Jens Oluf Jensen, 47202 Introduction to Future Energy 72 Green Fuels for Denmark (1.3 GW) 2021-23 2023-27 2027-2030+ 10 MW 250 MW 1.3 GW • 1.3 GW electrolysis 2030 • Powered by 2-3 GW offshore wind from the Bornholm energy island • Phase 1 (2021-2023): Electrolyzer module of 10MW producing renewable hydrogen for fuel cell buses and trucks • Phase 2 (2023-2027): Scale-up and commercial operation of a 250MW electrolyser coupled with offshore wind, CO2 capture and e-methanol for maritime transport and renewable e-kerosene for aviation. • Phase 3 (2027-2030+): Further scale-up to reach a combined electrolyser capacity of 1.3 GW, corresponding to 30% of Copenhagen Airport’s fuel consumption, a large proportion of truck and bus operations in Greater Copenhagen and a full-sized container vessel. • Frontrunner for a large industry-coordinated heavy-duty transport sector decarbonization. 11 April 2023 DTU Energy Partners Everfuel Ørsted (lead) Copenhagen Airports NEL hydrogen Molslinjen Maersk Haldor Topsoe DSV Panalpina COWI DFDSSAS Municipality of Copenhagen Denmark’s Capital Region Jens Oluf Jensen, 47202 Introduction to Future Energy 73 Energy islands as hubs for of-shore wind North Sea Bornholm Decided in Danish parliament Question: Energy transport via cable or pipe? 11 April 2023 DTU Energy Jens Oluf Jensen, 47202 Introduction to Future Energy 74
