Tags:

Transcription

The quest for CO2-free hydrogen – methane pyrolysis atscaleWilliam Daloz, Frederik Scheiff, Kai Ehrhardt, Dieter Flick, Andreas BodeReaction Process Engineering, BASFARPA-E Methane Cohort Kickoff, Houston, December 10, 2019

BASF – We create chemistryOur chemistry is used in almostall industriesWe combine economic success,social responsibility and environmentalprotectionSales 2017: 64,457 millionEBIT 2017: 8,522 millionEmployees: 115,490 (as of December 31, 2017)6 Verbund sites and347 other production sites2

Agenda1.Why CO2-free hydrogen via methane pyrolysis?2.Technological routes for methane pyrolysis3.Summary3December 10, 2019 I Dr. William Daloz, BASF

Agenda1.4Why CO2-free hydrogen via methane pyrolysis?December 10, 2019 I Dr. William Daloz, BASF

Methane pyrolysis and CO2 activationBMBF sponsored first project FfPaG (“fluid and solid products from gas”, 2013-2017)CO2 UtilizationH2 CO2 CO H2OSyngasCO2FKZ 033RC1301H2Basic ideas behind FfPaG Activation of CO2 from steel plant (CCU)EnergyNew heatingconcepts Breakthrough technology forsustainable hydrogen with with low carbon footprint and low energy demandMethanePyrolysisCH4 2 H2 C Substitution of coal-based carbonMethane5High PurityCarbonDecember 10, 2019 I Dr. William Daloz, BASF Bode et al., 1. Jahrestagung der GDCh Fachgruppe Chemie Oct. 06, 2016 und Energie, 6.-7.10.2016 in Jena

Our target: CO2-neutral1 growth until 2030Absolute GHG emissionsIndexed (1990 100)160Global GHG emissionsAssumed policy shift140120World36.4 billion t1008060BASF businessas usualBASF40.1 million tCarbon ManagementBASF GHG emissions2030 target:No increaseof F operations excluding the discontinued oil and gas business. The goal includes other greenhousegases according to the Greenhouse Gas Protocol, which are converted into CO2 equivalents.62030

BASF’s C-balance calls for CO2-avoidance and renewable energyCO2-emissionsequivalentsProcess optimization, energy management,N2O decompositionClean hydrogen research, e-furnace research,clean olefins researchPurchase of renewable energy7December 10, 2019 I Dr. William Daloz, BASFDr. Martin Brudermüller, BASF Research Press Conference on January 10, 2019

Agenda1.Why CO2-free hydrogen via methane pyrolysis?2.Technological routes for methane pyrolysis8December 10, 2019 I Dr. William Daloz, BASF

Towards a new clean hydrogen production technologyDirectCO2 emissionsMinimumenergy demandin kg CO2/kg hydrogenin kJ/mol hydrogen*State-of-the-artSteam reformingof natural gasCH4 2H2O 4H2 CO2Option 1Water electrolysis2H2O 2H2 O20Option 2Methane pyrolysisCH4 2H2 C08.85Water electrolysis and methane pyrolysisyield clean - CO2-free – hydrogen,but only in case of non-fossil electric heatingDr. Andreas Bode, BASF Research Press Conference on January 10, 20199December 10, 2019 I Dr. William Daloz, BASF* Standard reaction enthalpy as approximation2728637

Several projects since 190019501960197019801990200020102020FfPaGAlox Chem/etcEsso/ExxonCSIRO – COMBENUniversal - HYPROM.S.* - HY-C* M.S. Meyer SteinbergMuradovHazerScaling up,Pilot/production 2018,commercial demo 20211st industrial scale plant,decommissioned 2001Kvaerner - CB&HMonolithLytenPyrolysis MethodPlasma-arc tube carbon blackGasPlas2-step catalyst bedAHIFluidized/moving bed / thermalLiquid metal bubbler*Feste und fluide Produkte aus Gas195010Early efforts worked on lab scale butcould not compete or were notoptimized to the product marketDecember 10, 2019 I Dr. William Daloz, BASFInstalling full plant, NebraskaM.S. – CARNOLKIT/IASSUCSB - CZeroCO2 emission concerns provideadvantage to CO2-free H2 frommethane pyrolysisRecent works suffer fromunwanted C buildup,unsalable C product, ordifficult scalabilityCurrent commercialprocesses rely heavilyon C sales, reducedfocus on H21. Jahrestagung der GDCh Fachgruppe Chemie und Energie, 6.-7.10.2016 in Jena2020

Methane pyrolysis in thermal plasmas (I):plasma is only the heat source for thermal decomposition Hüls acetylene process: in operation since 1940th Kvaerner: industrial plant operated ca 2000, for carbon black production Monolith: industrial plant to be commissioned 2020, for carbon black productionFincke et al., Plasma thermal conversion of methane to acetylene,Plasma Chemistry and Plasma processing, Vol. 22 (1), 200211December 10, 2019 I Dr. William Daloz, BASFGautier et al., Direct decarbonization of methane by thermal plasmafor the production of hydrogen and value-added carbon black,International journal of hydrogen energy, 42, 2017, 28140 – 28156F. Scheiff KEROGREEN wksp – Plasma catalysis for renewable Fuels and Chemicals, Eindhoven, 11.15.2019

Methane pyrolysis in thermal plasmas (II):plasma is only the heat source for thermal decomposition Opportunities high conversions and selectivities close toequilibrium feasible heating technically proven Challenges and limitations of thermal plasmas narrow carbon black specifications difficultto meet high temperatures impede heat integrationand limit thermal efficiencyBakke et al. Pure & Appl. Chem., Vol. 70, No. 6, pp.1223-1228,1998L; A.N. Wrernes, 0. Raaness, S.Lynum, “Carbon Black and Hydrogen direct fromhydrocarbones”, 4th European Congress onGautier et al., Direct decarbonization of methane by thermal plasmafor the production of hydrogen and value-added carbon black,International journal of hydrogen energy, 42, 2017, 28140 – 2815612December 10, 2019I Dr. William Daloz, BASFF. Scheiff KEROGREEN wksp – Plasma catalysis for renewable Fuels and Chemicals, Eindhoven, 11.15.2019

Non-thermal plasmas for methane pyrolysis:a variety of newly emerging approaches for CO2-free hydrogenNT-plasma sources Microwave (MW) Gliding arc (GA) Dielectric barrier discharge (DBD)From process development point ofview NT-plasma reactors must provide full conversion permit sufficient residence time fordehydrogenation and nucleation allow narrow carbon specificationYang et al. , Direct non-oxidative methane conversion by non-thermal plasma:experimental study, Plasma Chem, Plasma Process, 23, 2003, 283-296Warm microwave and gliding arc plasmas with a thermal decomposition contributionappear promising routes to hydrogen generation13December 10, 2019I Dr. William Daloz, BASFF. Scheiff KEROGREEN wksp – Plasma catalysis for renewable Fuels and Chemicals, Eindhoven, 11.15.2019

Methane pyrolysis is not new:Several projects initiated, but no commercial realization & still broad technological field Thermal non-catalytic (fixed/moving/fluidized bed) no deactivationsince 1960‘s Catalytic (fixed/moving/fluidized bed)since 1990’s, today e.g. Hazer Group (AU)Since 1990’s Plasma (thermal/non-thermal)14December 10, 2019I Dr. William Daloz, BASF lower temperature,material of construction scalability- C product impure- Catalyst deactivation- Catalyst cost, inerting good heat transfer no blocking catalytic function too Liquid metal/saltsince 1990’s, today e.g. Monolith pure C product- high temperature- heat efficiency,inhomogeneity flexible reactors,fast on/off known technology no deactiv.- corrosion- loss of metals/salts- C product impure- low energy efficiency- limited scalability- broad C qualityF. Scheiff KEROGREEN wksp – Plasma catalysis for renewable Fuels and Chemicals, Eindhoven, 11.15.2019

Several projects since 190019501960197019801990200020102020FfPaGAlox Chem/etcEsso/ExxonCSIRO – COMBENUniversal - HYPROM.S.* - HY-C* M.S. Meyer SteinbergMuradovHazerScaling up,Pilot/production 2018,commercial demo 20211st industrial scale plant,decommissioned 2001Kvaerner - CB&HMonolithLytenPyrolysis MethodPlasma-arc tube carbon blackGasPlas2-step catalyst bedAHIFluidized/moving bed / thermalLiquid metal bubbler*Feste und fluide Produkte aus Gas195015Early efforts worked on lab scale butcould not compete or were notoptimized to the product marketDecember 10, 2019 I Dr. William Daloz, BASFInstalling full plant, NebraskaM.S. – CARNOLKIT/IASSUCSB - McFarlandCO2 emission concerns provideadvantage to CO2-free H2 frommethane pyrolysisRecent works suffer fromunwanted C buildup,unsalable C product, ordifficult scalabilityCurrent commercialprocesses rely heavilyon C sales, reducedfocus on H21. Jahrestagung der GDCh Fachgruppe Chemie und Energie, 6.-7.10.2016 in Jena2020

Agenda1.Why CO2-free hydrogen via methane pyrolysis?2.Technological routes for methane pyrolysis3.Summary16December 10, 2019 I Dr. William Daloz, BASF

Summary Methane pyrolysis is attractive for CO2-free hydrogen and high-purity carbon asvaluable by-product. The chemistry is well known, but the process is not – many processes havesignificant differences in efficiency, cost, and product Historical efforts focused on H2 OR C, but couldn’t compete, renewed interest onceCO2 is considered More recent efforts, economics w/o CO2 credit require C sale, removal and carbonvalue is a hurdle. Targeting high value carbon, often H2 is left behind Broad technological field approaching commercial realization, but no clear winner.Challenges are process specific, likely many routes will co-exist17December 10, 2019I Dr. William Daloz, BASF

Project outlook – methane pyrolysis for clean hydrogen1st commercial unitPilot unit*FKZ 03SF0571ATest of reactor design andcarbon outletSecond R&D project*R&D projectProof of concept for reactordesign and carbon outletLab-scale proof of concept andsample productionDuration 3 yearsSecond R&D project with2019* Government funding will be necessary due to high technological and commercial risk18December 10, 2019 I Dr. William Daloz2025

Towards a new clean hydrogen production technology 9 State-of-the-art Steam reforming of natural gas CH 4 2H 2 O 4H 2 CO 2 8.85 0 0 Minimum energy demand in kJ/mol hydrogen* Option 1 Water electrolysis 2H 2 O 2 O 2 Option 2 Methane pyrolysis CH 4 2H 2 C Water elect