® Low-Cost Precursors to Novel Hydrogen Storage Materials S. Linehan, N. Allen, B. Butterick, A. Chin, N. Kendall, L. Klawiter, S. Mancroni, D. Millar, D. Molzahn, S. November The Dow Chemical Company June 10, 2010 Project ID #ST042 This presentation does not contain any proprietary, confidential, or otherwise restricted information Project Overview ® Timeline Barriers Start: March 1, 2005 System cost Regeneration processes End: September 30, 2010 – Cost Percent complete: 90 % – Energy efficiency – Environmental impacts Budget Partners Total FY09 FY10 Funding Actual Budget* DOE $3,473K $945K $1,232K Dow $1,489K $405K $528K Phase 2 DOE:Dow Split 70:30 Does not include DOE funding to INL ($700K) in Phase 2 2 Objectives/Relevance ® Provide engineering support to guide Center’s development of cost effective ammonia borane (AB) processes – Identify key parameters impacting cost and energy usage – Define opportunities for improvement Reduce cost of NaBH4 to enable lower cost ammonia borane DOE Targets (current): Regen AB - Fuel Cost = $2-3/kg H (2010/2015) RMs 2 AB First Fill 1st Fill AB - Storage System Costs = $4/kWh (2010), (NaBH4) $2/kWh (2015) AB Fuel AB H Delivery Forecourt 2 Regeneration Spent AB 3 Approach/Milestones – Low Cost NaBH4 st for 1 Fill AB ® Determine Detail Identify Leading Feasibility of Performance to Develop Single Pathways Leading Select Single Pathway Pathways Pathway . Develop screening . Demonstrate key . Establish complete . Develop single and evaluation criteria chemical and process material balance to NaBH4 process specific to NaBH4 steps in laboratory determine regeneration cycles studies intermediates and . Confirm scalability purification . Review prior technical . Develop flow sheets requirements . Update process and patent literature and preliminary flowsheets and energy requirements . Demonstrate all economics . Select leading NaBH4 and cost estimates for chemical and process regeneration leading systems steps pathways based on theoretical energy Sept 2007: No Go . Investigate scalability efficiencies from decision for July 2009: Current focus reaction energetics NaBH4 as a and relevant metrics storage material. Metal reduction Investigate low selected over st carbothermal for cost NaBH4 for 1 fill AB. development Phase 2 4 Approach/Milestones – Engineering Analysis Methodology ® Methodology developed for determining energy efficiency and delivered costs H2A model used to develop economics Results reviewed with TIAX; feedback incorporated 5 ® Accomplishments: First Fill Ammonia Borane 6 Leading First Fill AB Pathways Being Evaluated ® Metathesis of ammonium salt and MBH4 in organic solvents nNaBH4 + (NH4)nX → nNH3BH3 + NanX + nH2 Purdue: Ramachandran et al, Inorg. Chem, 2007, 46, 7810-7817 THF NaBH4 + ½ (NH4)2SO4 NH3BH3 + ½ Na2SO4 + H2 (>95%) dioxane NaBH4 + (NH4)HCO2 NH3BH3 + NaHCO2 + H2 (>95%) Current analysis PNNL: Heldebrant et al., Energy & Envir. Science, 2008, 1, 156-16 NH3 THF NH4Cl + NaBH4 NH4BH4 NH3BH3 (up to 99% yield) -NaCl -H2 Base displacement of borane complexes with ammonia L-BH3 + NH3 → NH3BH3 + L Shore: WO2007/120511 A2 7 st 1 Fill AB: PNNL Route ® Metathesis – NH4 salt Fresh THF H2 (makeup) NH3 / THF Recycled THF Separator 1 NaBH4 Fresh NH3 Recycled NH3 (makeup) H2 / NH3 / THF Wet Mixer Reactor * NH4BH4 Decomp. Separator Evaporator Product Dryer 2 1 Reactor 2 Byproduct Additional solvent NaCl NH / THF 3 Ammonia recovery/separation Borane steps required Mixer Dryer 1 2 NaCl NH4Cl * 2 Options: Pressurized: 25 C, 20 atm Cryogenic: -70 C, 1 atm 8 PNNL Pressurized Route is Lower Capital than Low Temperature Option ® AB plant capacity = 10,000 MTA 60 $51 $46 50 Raw Material Storage Separations and Reaction solvent recovery dominate capital cost 40 Evaporation / Solvent Recovery Lower refrigeration Product Drying demands favor 30 Solids Conveying moderate pressure option Insolubles Processing 20 Building Utilities Overall Capital Cost, $MM Cost, Capital Overall 10 Other 0 Pressure Cryo 9 PNNL Route Provides Numerous Benefits ® PNNL Purdue Chemistry NH4BH4 decomposition Metathesis Boron source Sodium Borohydride Nitrogen source Ammonium Chloride Ammonium Formate / Sulfate Solvent THF and NH3 Dioxane or THF AB yield 99% 95% AB purity 99% 98% Reactor conditions -70˚C /1 atm or 25˚C /20 atm. 40˚C /1 atm Feed stoichiometry Near-stoichiometric 50% excess NH4 formate Raw material costs NaBH4 principal component of costs Low NH4HCO2 pricing requires high NH4Cl pricing well defined. volume Solvent requirements >2M NaBH4 in solvent 1M NaBH4 in solvent Distillation column required to separate Single solvent – no solvent separation Solvent separation THF and NH3 solvents required. Relatively easy separations via Separation of Na and NH4 salts Na byproduct recovery solubility differences. requires more complex processing Minimal waste – only losses are small Moderate liquid waste generated from Waste generation solvent losses. insolubles processing step. 10 Pressurized PNNL AB Process Provides Best Overall Cost and Performance ® AB plant capacity = 10,000 MTA NaBH4 is dominant st 10 factor on 1 fill AB $9.1 $9.5 $9.1 cost 9 8 $0.41 $1.06 $0.77 Royalty 7 Capital 6 Labor 5 Utilities 4 Other RM $6.79 $6.52 $6.52 3 NaBH4 RM AB 1st Fill Cost, $/kg AB $/kg Cost, Fill 1st AB 2 1 (Based on $5/kg NaBH4 . 0 NH4 formate pricing assumes large scale use ) Purdue-Formate PNNL-Cryo PNNL-Pres 11 Other AB Synthesis Routes ® Base displacement of borane complexes with ammonia L-BH3 + NH3 → NH3BH3 + L – High AB yields (>95%) and purities (>99%) reported for dimethylaniline borane (Shore) – Effective means to produce BH3 adducts needed » NaBH4 conversion to diborane and subsequent condensation in L » NaBH4 reaction with amine hydrochloride avoids diborane L-HCl + NaBH4 → L-BH3 + NaCl + H2 » Multi-step reactions involved - will not offer lower cost than PNNL route 12 Low-Cost NaBH4 May Enable AB to Meet DOE Storage System Cost Targets ® * Current storage system cost targets 200 2 180 2 mol H2 released / mol AB 160 140 * $4/kWh or DOE 2010 Target * $133/kg H 120 2 2.5 mol H2 released / mol AB 100 80 DOE 2015 Target * Storage System Cost, $/kg H $/kg Cost, System Storage * $2/kWh or 2 60 $66/kg H2 40 PNNL @ $5 / kg NaBH4 On-Board H On-Board 20 0 0 3 6 9 12 15 18 21 24 27 30 AB 1st Fill Cost, $ / kg AB $9/kg AB (produced from $5/kg NaBH4) → $60/kg H2 (for 2.5 mol H2 released per mol AB) Current fuel cost projection represents 45% of 2010 storage system cost target Current fuel cost projection represents 90% of 2015 storage system cost target (only 10% remaining for rest of system) 13 ® Accomplishments: st Low Cost NaBH4 for 1 Fill Ammonia Borane 14 Carbothermal Reduction of Borate ® Approach – Reproduce prior INL studies where NaBH4 was produced – Year 1 Go/No Go Milestone: INL experimental results should confirm a consistent plasma carbothermic conversion of borate to NaBH4 of at least 40% – Detail process window, separation / purification needs Experimental - NaBH4 formation remains elusive – NaBH4 has not been produced, but unidentified water- NaBO2 + 2CH4 NaBH4 + 2CO + 2H2 reactive material has – Studies plagued by equipment issues & analytical challenges - exact repetition of prior run conditions has proven difficult – Extensive troubleshooting has failed to identify the same set of conditions under which NaBH4 was produced No Go Decision for Carbothermal Year 1 Go/No Go Criterion Not Met Metal Reduction Selected for Development 15 Metal Reduction of Borate ® Recyclable process identified based on solid-solid reactive milling (high- energy laboratory mill) – Good material balance – Full accountability for all products – No intractable by-products 90+% Mass Balance – Isolation and purification steps identified 99% NaBH4 yield Quantitative recovery of L 99% purity Identification of a scalable, solid-solid reactive milling technology has been met with challenges: low NaBH4 yields – Implications for the Metal Hydrides Center 16 Modeling Defines Reactive Milling Scaleup Challenges ® Discrete-element method modeling applied to obtain fundamental understanding Stress Energy Distribution during Milling of ball motions and particle collisions 1 0.8 Mill 1 Difficult to achieve sufficient Mill 2 milling energy in large scale 0.6 mills (NaBH4 volume to supply 10,000 MTA AB plant) 0.4 0.2 Cumulative Distribution Cumulative 0 Stress Energy per Collision 17 Alternatives to Solid-Solid Reactive Milling ® Slurry milling – Scalable, but insufficient NaBH4 yields Solution-based approach – Scalable with potential use of conventional reactors and unit operations – All steps of reaction scheme demonstrated – Focus on defining chemistry and process window for each reaction step » Identification of byproducts » Separation and purification needs » Establish material balance Results to date very promising… 18 Solution-Based Metal Reduction: Results Point to Scalable Process ® Alane formation step: 99+% yield – Pressure, temperature, Al source, ligand, reaction medium NaBH4 formation step: 94% yield – Pressure, temperature, B source, reaction medium Product isolation and purification – 99% NaBH4 purity – Separation scheme (crystallization, extraction, etc.) – Full impurity profile characterization in progress (ICP, NMR, etc) Recycle streams – 97% ligand recovery, 99+% purity – 99% recovery of aluminum by-product 19 Excellent Alane Formation Kinetics Obtained ® 100 90 80 70 60 50 40 Conversion % Conversion 30 20 10 1000 psi H2 0 1 5 9 13 17 21 25 29 33 37 41 45 49 53 57 61 65 69 73 77 81 Time (min) Aluminum “A” Aluminum “B” Aluminum “C”