Presented at the 2006 DOE Hydrogen, Fuel Cells & Infrastructure Technologies Program Annual Merit Review in Washington, D.C., May 16-19, 2006

Diakov, V.

Fisher, T.

Gore, J.

Kramer, R.

Maness, P.

Patterson, J.

Pelter, L.

Ramachandran, P. V.

Shafirovich, E.

Ting, B. E.

Varma, A.

Zheng, Y.

UNT Digital Library

The Energy Cen te rPurdue Hydrogen Technology ProgramJ. Gore*, P. V. Ramachandran*, Y. Zheng*, R. Kramer**, A. Varma*, T. Fisher*, J. Patterson*, P. Maness*** B. E. Ting**, L. Pelter**, E. Shafirovich*, V. Diakov**Purdue University, West Lafayette, IN**Purdue University, Calumet, IN***National Renewable Energy LaboratoryMay 18, 2006Project ID #STP 40This presentation does not contain any proprietary or confidential informationNREL/PR-560-41727Presented at the 2006 DOE Hydrogen, Fuel Cells & Infrastructure Technologies Program Annual Merit Review in Washington, D.C., May 16-19, 2006.2The Energy Cen te rOverview (storage)• Start – June 2006• End – May 2007• Barriers addressed– Cost of ammonia borane– Formation of harmful compounds in combustion-based methods– Thermal Management• Targets – storage systemTimelineBudgetBarriers2007 2010 2015Specific EnergykgH2/kg(wt%)(4.5%) (6%) (9%)• General Motors• General AtomicsPartners• $825,000– $660,000 (DOE)– $165,000 (Purdue)• Funding for FY06: expected3The Energy Cen te rOverview (bio-production)• Start – June 2006• End – May 2007• Barriers addressed¾ Hydrogen production levels¾ Gas Separation ¾ System Efficiency• TargetsTimelineBudgetBarriers• Cargill• Grifffith Labs• Advanced Power Technologies• InnovenePartners2006 2010 2015Hydrogen Production percentage20 40 45+• $415,500– $330,000 (DOE)– $85,500 (Purdue)• Funding for FY06: expected4The Energy Cen te rObjectives (storage)• Examine the dehydrogenation of ammonia borane at lower temperatures• New synthesis of ammonia borane to decrease the cost • Develop a method for generating hydrogen from boron-hydrogen compounds with hydrogen yield >6 wt%, no catalyst and no harmful byproducts• Design efficient thermal management sub-systems to facilitate dehydrogenation and fast-filling processes5The Energy Cen te rObjectives (bio-production)• Provide a renewable energy source to further DOE goals for development of a hydrogen energy economy • Use biological organisms to produce hydrogen from waste using anaerobic process• Use solar energy to preprocess the feed material• Produce electricity in remote locations with the produced hydrogen used in either a fuel cell or reciprocating engine• Consider ways to produce fertilizer • Possibly separate/sequester carbon dioxide by use of organometallic nano catalysis6The Energy Cen te rApproach (storage)• Mixtures of boron-hydrogen compounds with metal (Al or Mg) and gelled water, upon ignition, exhibit parallel reactions :• The highly exothermic metal-water reaction assists hydrolysis of B-H compound, eliminating the need for catalyst. • Water is an additional H2 source.• Solid byproducts are environmentally friendlymaterials.NaBH4 + 2 H2O → NaBO2 + 4 H2Al + 1.5 H2O → 0.5 Al2O3 + 1.5 H2NaBH4 + 2 H2O → NaBO2 + 4 H2Mg + H2O → MgO + H27The Energy Cen te rApproach (storage)• Reviewed heat transfer issues in on-board hydrogen storage technologies, including compressed_H2, LH2, chemical hydrides and metal hydrides– Zhang et al., J. Heat Transfer, 127, pp1391 (2005).• Studied SBH systems– Heat of reaction measurement– Kinetics measurement– Sub-scale (1-kWe) system design, construction and tests– Sub-scale (1-kWe) system modeling• Investigating high-pressure metal hydride systems– Sub-scale (1/50) system design, construction and tests– Sub-scale (1/50) system modeling8The Energy Cen te rApproach (bio-production)• Preliminary laboratory studies have verified the feasibility to use anaerobic digestion of organic waste for the production of hydrogen• Determine the biological, chemical, and physical parameters that influence hydrogen production levels and develop a scheme to optimize production.– Individual organism– Consortium of organisms• Develop an energy model that integrates design considerations with the research process– Heat flow modeling– Biological processes– Preliminary bio reactor concepts– Overall energy balance9The Energy Cen te rTechnical Accomplishments (storage)• Examined the transition-metal catalyzed dehydrogenation of ammonia borane in solution at lower temperatures• Examined the transition-metal catalyzed alcoholysis and hydrolysis of ammonia borane• Achieved several new syntheses of ammonia borane (and amine boranes) that should decrease the cost of ammonia borane10The Energy Cen te rNew Synthesis of Borane-AmmoniaLiBH4 + NH4ClTHF40 oC7 hBH3NH3  +  LiCl  +  H2B(OMe)3 + LiAlH4 + NH4ClTHF3 hrsBH3NH3  +  Al(OMe)3  +  LiCl  +  H2THFBH3NH3  +  Al(OMe)3  +  4 LiCl  +  H2B(OMe)3  +  4 LiH  +  NH4Cl AlCl3,8 hrsUnpublished results, patent appliedTechnical Accomplishments (storage)11The Energy Cen te rComparison of Procedures for the Synthesis of BH3NH3Existing Methods: B(OMe)3 → NaBH4 → LiBH4 → BH3NH3New Method: One-pot ReactionB(OMe)3    → BH3NH3           Yield: 86%,  Purity: > 95%Unpublished results, patent appliedTechnical Accomplishments (storage)12The Energy Cen te rDehydrogenation of Borane-Ammonia3 NH3-BH3PdCl2B3N3H6 + 6 H2THFrefluxOther transition metal salts used: NiCl2, CoCl2, etc.Similar results were obtained with all other TM salts.Unpublished results, patent appliedTechnical Accomplishments (storage)13The Energy Cen te rOne-pot Synthesis and Dehydrogenation of Borane-Ammonia3 LiBH4 + 3NH4ClPdCl2B3N3H6 + 3 LiCl + 9 H2THF, reflux6 hOther transition metal salts used: NiCl2, CoCl2, etc.Similar results were obtained with all other TM salts.Various other ammonium salts gave similar results.Unpublished results, patent appliedTechnical Accomplishments (storage)14The Energy Cen te rTechnical Accomplishments, (storage)• Mixtures of NaBH4 with water, metal (Al or Mg) and additional minor ingredients (gellant, stabilizer) were developed.• The developed mixtures exhibit stable combustion and 7 wt% H2 yield, with safe solid byproducts. 15The Energy Cen te rCombustion of mixtureExample: NaBH4 : nanoAl : H2O=1:2:3 (mass ratio). Sample diameter: 10 mm• The reaction wave propagates uniformly along the sample.• The gaseous products flow in the reverse direction through the combustion products towards the open top end of the sample.t = 1 s t = 4 s t = 7 s t = 10 sTechnical Accomplishments, (storage)16The Energy Cen te rHydrogen generation0 20 40 60 80 100024681012  Al (theory)   Al (exp)  Hydrogen Yield, wt%Me/(NaBH4+Me), wt% Mg (theory) Mg (exp)The maximum observed H2 yield is ~7 wt%. Evolved gas: H2 (>99%).  Efficiency of H2generation:Al 74-77%Mg 88-92%Technical Accomplishments (storage)17The Energy Cen te rTechnical Accomplishments (storage)• Heat of reaction (SBH) 1mL syringeNaBH4 test sample15cm needleTest Cell Reference Cell4mL VialOMNICAL CRC90100mL gas burette– Widely cited: 75 kJ/molH2– This study: 52.5 kJ/molH2• Kinetics (SBH)commercially available 3% Ruon 2mm carbon extrudeSBHSBHuaSBH KCKCTREAr +⎟⎟⎠⎞⎜⎜⎝⎛ −−=1expy = 32.488x - 178.38R2 = 0.9979y = 86.862x - 71.502R2 = 0.9965y = 172.43x - 15.27R2 = 0.998201002003004005006000 2 4 6 8 10 12 14 16 18Time (min)(CA0-CA)+1/Kln(CA0/CA)Data-25°C, K0=0.22 L/mmolCF data-25°CData-55°C, K0=0.22, E_ads=-35CF data-55°CData-85°C, E_ads=-35 kJ/molCF data-85°CK0=0.05 L/mmolK0=1 L/mmolE_ads=-20 kJ/molE_ads=-60 kJ/molLi (CF d t 25°C)Zhang et al., Int. J.Hydrogen Energy, in press, (2006)18The Energy Cen te r0 0.05 0.1 0.15 0.2 0.25 0.302040608010000.20.40.60.81Axial location, z  [m]Temperature (°C)Conversion, xAPred. TemperatureMeas. TemperatureMeas. ConversionPred. ConversionTechnical Accomplishments (storage)• 1-kWe SBH reactor measurementsfm =64.3g/min, 15%&• 1-kWe SBH reactor modeling10% NaBH420304050607080900 5 10 15 20 25 30Distance (cm)Temperature (°C)10mL/min30mL/min45mL/min60mL/minvmhMWhdxTdkdxdTuC fgfforeffeffp && −−= ωρ 22,19The Energy Cen te rTechnical Accomplishments (storage)• High-pressure metal hydride sub-scale system modelingHeat Transfer Efficiencytime (t), s0 60 120 180 240 300Hydryding progress variable (F)0.00.20.40.60.81.0heat release is dominant at very beginningTtFHtTC effrmp22]H[ ∇+∂∂Δ−=∂∂ λρ( )FktF −=∂∂ 1equaa PPTRECk lnexp ⎟⎟⎠⎞⎜⎜⎝⎛−=⎥⎥⎦⎤⎢⎢⎣⎡⎟⎟⎠⎞⎜⎜⎝⎛ −Δ=ouroeq TTRHPP 11expmxxF = ][]H[Mx =20The Energy Cen te rTechnical Accomplishments (storage)• High pressure metal hydride sub-scale system modeling (3D)Pcharging = 400 bar,Tmax= 82 oC, tss= 6 min, κeff = 1 W/mKt = 30 st = 5 min0  2 4 6 8 1000.10.20.30.40.50.60.70.80.91Time, minProgress (f)Variation of Progress with time  Middle pointFar cornerNear tube21The Energy Cen te rTechnical Accomplishments (bio-production)• Preliminary laboratory studies have verified the feasibility to use anaerobic digestion of organic waste for the production of hydrogen Note:  Inoc = inoculated with anaerobic waste water treatment effluentBoil = boiled for 10 minutes before startUninoc = not inoculatedVial # TreatmentInitial pH Final pH H2(μmol)Digestionfraction25 Inoc 6.8 6.17 933.63 .52926 Inoc 6.8 6.17 1989.67 .51227 Inoc 6.8 6.15 0 .47928 Inoc 6.8 6.07 0 .44437 Inoc, Boil 6.8 6.18 7323.00 .62438 Inoc, Boil 6.8 6.19 5435.99 .46640 Inoc, Boil 6.8 6.19 9144.62 .46943 Inoc, Boil 6.8 6.16 6706.92 .37221 Uninoc 6.8 6.5 0 .25041 Uninoc 5.8 5.74 0 .24522The Energy Cen te rTechnical Accomplishments (bio-production)• An initial computer simulation model of the proposed system has been developed• Model will be used to consider possible design and process alternatives as well as means to optimize the processH bio reactorMethaneBio reactorH feed stockprocessingMethane feedstockSolarcollectorHeat storageGas Conditioner InverterACDCFuel Cellor recipΔ P ?Raw Feedmaterial23The Energy Cen te rFuture Work (storage)• New formulation of ammonia-borane(AB) doped with transition metal salts• Thermolysis of AB in the presence of water vapor• Thermal management for AB systems– Thermo-chemical property measurements– Hydrogen generator and AB regenerator modeling– Sub-scale hydrogen generator and AB regenerator tests24The Energy Cen te rFuture Work (storage)• Insight into combustion mechanisms of B-H compounds mixed with metals and water.• Optimization of mixture compositions and process conditions• Focus on ammonia borane, with the goal to further increase hydrogen yield• Design and construction of power system demonstration unit25The Energy Cen te rFuture Work (bio-production)6/1/2006 6/30/20077/1/2006 8/1/2006 9/1/2006 10/1/2006 11/1/2006 12/1/2006 1/1/2007 2/1/2007 3/1/2007 4/1/2007 5/1/2007 6/1/2007ID Task Name Start Finish Duration2007JanNov Dec MarSep AprAugJun Oct Feb1 11d6/15/20066/1/2006Develop Initial Plan Details3 66d9/29/20066/30/2006Establish Interface With Industry Contacts TimelineMajor MilestonesTask Schedule4 88d11/1/20067/3/2006Construct Test Device7 54d6/29/20074/17/2007Prepare Final ReportJun2006Jul May2 32d7/21/20066/8/2006Conduct Literature Search6/1/2006Start6/15/2006Complete Initial Plan Details6/30/2006Initiate InterfaceWith Industry Contacts7/21/2006Complete LiteratureSearch6/30/2007Submit Final Report6/1/2007Complete TechnicalEvaluation11/1/2006Complete Test Device Development and Construction5 252d6/1/20076/15/2006Conduct Evaluation of Innoculum and Conditions to Maximize H Production6 153d6/1/200711/1/2006Conduct Energy Evaluation 26The Energy Cen te rSummary (storage)• All on-board hydrogen storage technologies involves heat transfer challenges• Unknown thermo-physical properties need to be measured or modeled • Designs of reactors and other components need to be tested and modeled at appropriate sub-scales• Mixtures of boron-hydrogen compounds with metal and water can be used for hydrogen generation by combustion– high specific energy– no catalyst for H2 generation– safe reaction byproducts, which can be recycled27The Energy Cen te rSummary (bio-production)• Anaerobic production of hydrogen holds promise as a viable source of energy• Waste streams provide a low cost source of feed for the energy production process • Initially this approach holds promise to provide an environmentally friendly means to produce electricity in remote or third world applications• As the technology is developed there is the opportunity to scale up the size of the energy production28The Energy Cen te rPublications and PresentationsPatents1. Shafirovich, E., Diakov, V., and Varma, A., “System and Method for Generating Hydrogen,” U.S. Patent application 60/663,238 (March 18, 2005).Archival Journal Articles1. Shafirovich, E., Diakov, V., and Varma, A., “Combustion of Novel Chemical Mixtures for Hydrogen Generation,” Combustion and Flame, Vol. 144, 2006, pp. 415-418.2. Shafirovich, E., Diakov, V., and Varma, A., “Combustion-Assisted Hydrolysis of Sodium Borohydride for Hydrogen Generation,” International Journal of Hydrogen Energy, in review.3. Zhang, J. , Fisher, T. S., Ramachandran, P. V., Gore, J. P., and Mudawar, I., “A Review of Heat Transfer Issues in Hydrogen Storage Technologies,” Journal of Heat Transfer, Vol. 127, 2005, pp. 1391-13994. Zhang, J., Fisher, T. S., Gore, J. P., Hazra, D., and Ramachandran, P. V., “A Review of Heat Transfer Issues in Hydrogen Storage Technologies,” International Journal of Hydrogen Energy, 2006, in press. Conference Presentations1. “Hydrogen Generation via Combustion of Metal Borohydride/Aluminum/Water Mixtures,” Preprints of Symposia - American Chemical Society, Division of Fuel Chemistry, Vol. 50(2), 2005, pp. 450-451. 2. “Novel Chemical Mixtures for Hydrogen Generation by Combustion,” 2005 AIChE Annual Meeting, October 30-November 4, 2005, Cincinnati, OH. 3. “Novel Chemical Mixtures for Hydrogen Generation by Combustion,” 44th AIAA Aerospace Sciences Meeting and Exhibit, January 9-12, 2006, Reno, NV, AIAA Paper 2006-1445.4. “Combustion-Based Methods to Generate Hydrogen for Fuel Cells,” NSF Workshop on Research Frontiers for Combustion in the Hydrogen Economy, March 10, 2006, NSF Headquarters, Arlington, VA. 5. Zhang, J., Zheng, Y. Fisher, T. S., and Gore, J. P., “Modeling of Packed-bed Reactor in a Sodium Borohydride-based Hydrogen Storage System,” SAE paper 06P-612, 2006. 

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Purdue Hydrogen Technology Program

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