ACS Symposium: Finding Alternatives to Critical Materials in Photovoltaics and Catalysis from an Academic and Industrial Perspective
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ACS Symposium: Finding Alternatives to Critical Materials in Photovoltaics and Catalysis from an Academic and Industrial Perspective

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By James Stevens, Dow and Harry Atwater, CalTech

By James Stevens, Dow and Harry Atwater, CalTech

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ACS Symposium: Finding Alternatives to Critical Materials in Photovoltaics and Catalysis from an Academic and Industrial Perspective Presentation Transcript

  • 1. Finding Alternatives to Critical Materials In Photovoltaics and Catalysis Part II: Industrial Perspective Jim Stevens and Harry A. Atwater Corporate Fellow Howard Hughes Professor Core Research & Development Applied Physics The Dow Chemical Company Caltech August 21, 2012
  • 2. Strategic Elements  Strategic material - properties are essential to nation, performs a unique function, and no viable alternative exists.  Critical material – Strategic material with significant risk of supply disruption.  Prediction of future demand is difficult - distribution of metal use changes with time as demands change.  Digital photography - huge reduction in demand for silver for film since 2000.  Silver for PV contacts and thin fibers in socks to counteract odors more than compensated Ag demand. Slide 2
  • 3. Criticality Depend on Timescale Source - DOE “Critical Materials Strategy” report, 2010.  Other sources include Pt-group (Pt,Pd, Rh, Ir, Ru, Os) Slide 3
  • 4. Issues in Finding Alternatives to Critical Materials in Catalysis Slide 4
  • 5. Context – Homogeneous / Heterogeneous Catalysts Heterogeneous Homogeneous  Product/catalyst separation is  More selective / high reaction easy rates.  More stable / high reaction  Can design complex structures temp. possible. for specific jobs.  Challenging to study.  Amenable to study and rational  Poor degree of synthetic design. control.  Limited to lower reaction temperatures. Opportunities Opportunities  Rational design of sophisticated  New reaction mechanisms. Het. cats.  High throughput techniques.  Emissions catalysis. Slide 5
  • 6. Context – Catalysis in Chemical Industry  Catalysts produce many moles of product per mole of catalyst (productivity) ⇒ used in small amounts  Catalysts have very high rates of reaction (turn-over frequency) ⇒ used in small amounts. >2,000,000 t/o; 600,000 h-1 tof1 Largest application of asymmetric catalysis ~10,000,000 Kg/y requires ~5 Kg Ir (assumes no recycle)2 (0.1% of 2010 Ir imports) 1 H.U. Blaser, et al., Chimia 53 (1999), 275. 2 Calculated from data in Blaser, Adv. Synth. Catal. 2002, 344, 17. Slide 6
  • 7. Ligand Cost Can Dominate Catalyst Cost Enantioselective homogeneous hydrogenation catalyst. Ir represents < 30% of catalyst cost.* Generally metal can be recovered but ligands can not.* Calculated from data in Blaser, Adv. Synth. Catal. 2002, 344, 17 and spot market price of Ir on 9/15/2011 Slide 7
  • 8. Ligand Cost Can Dominate Catalyst Cost Ethylene copolymerization, Isotactic polypropylene Enantioselective EPDM catalyst catalyst hydrogenation catalyst Ti ~ 0.05 – 0.5% of total Zr ~ 0.05 – 0.5% of total Rh < 15% of total catalyst catalyst cost1 catalyst cost1 cost2 Metal Spot Market $/Kg • Pt $57,544 • Os $13,404 • Au $54,480 • Pd $23,044 • Co $37 • Ag $1,280 • Rh $59,707 • Ni $22 • Zr $50 • Ir $37,038 • Ti $10 • Ru $5,9971 Calculated from data in Metallocene Monitor and spot market metal price on 9/15/2011. 2 P. Moran, Dow Chemical, personal communication. Slide 8
  • 9. Rhodium Historical Price (Spot market) Rhodium, $/Kg $350,000 $300,000 $250,000 $200,000 $150,000 $100,000 $50,000 $- Jan-00 May-01 Oct-02 Feb-04 Jun-05 Nov-06 Mar-08 Aug-09 Dec-10 Slide 9
  • 10. Issues With Catalysts in Refineries  Refineries use enormous quantities of catalysts – millions of Kg.  FCC units crack ~2x109 L/day of ~C14-C42  Reforming, isomerization reactions – Pt, Pd.  PGM’s can be considered as working capital.  Metals price can swing significantly, affecting earnings.  Limitations on supply of some particularly rare elements for such large volume catalysts.  Potential opportunity for non-PGM catalysts. Slide 10
  • 11. Hydrosilylation Catalysis  4-6 MT of Pt (as metal) per year is consumed in cured silicones and “lost” with the product*- $252M - $377M at 9/15/2011 price.  Additional 0.8 – 1.2 MT Pt used in silane / organofunctional silicone, high % recycled.* Mechanism credit to T. Don Tilley, UC Berkeley * Richard Taylor, Dow Corning Corp., personal communication
  • 12. Potential Opportunities in Hydrosilylation Catalysis  Desirable improvements: Pt $57,000 / Kg*  Lower cost catalysts ($ / Kg product), especially for Pd $23,000 / Kg cured elastomers. Ni $22 / Kg  Need to meet critical performance requirements to be commercially viable (kinetics, “snap cure”, chemo- selectivity, environmentally benign, etc.).  Higher selectivity (regio-, chemo-, enantio-).  Potential approaches:  Identify new silane, olefin activations  Identify new mechanisms for hydrosilylation (e.g., mechanisms that do not require a 2-electron redox process)  High-throughput discovery Slide prepared with T. Don Tilley, UC Berkeley * Spot price, 9/15/2011 Slide 12
  • 13. Acetic Acid  5 million MT y-1 produced by catalytic carbonylation of methanol (2nd largest use of homogeneous catalysis).  1963 – BASF Co2(CO)8 catalyst  1970 – Monsanto [I2Rh(CO)2]- catalyst  1990’s – BP Cativa process [I2Ir(CO)2]- / Ru promoter - ~350 KTPa plant  2000’s – Celanese AO+ process – Rh / better I and H2O management - ~800 – 1,200 KTPa plant, lower capital Slide 13
  • 14. Cativa Acetic Acid Process (BP)  Runs in same plant as Monsanto Rh-based process.  Lower H2O in process – lower capital from fewer drying columns  Higher selectivity  Lower propionic acid  Suppresses water-gas shift reaction Ir – a “non-critical” PGM? Acetic acid synthesis may not be a good opportunity for future research. Slide 14
  • 15. Assemblies AERIFY* Monoliths AERIFY*Advantages of diesel• High performance & High torque • Emissions catalysis consumes 81%• Durability & Reliability At least 500,000 miles life of PGM imports.• Low maintenance • CeO2 also used as oxygen buffer /• Fuel Economy 30% better than gasoline engine NOx reduction.• Low gas emission (HC, CO, NOx) • Some Pt can be substituted with Pd,• Low CO2/mile (GHG) Rh.Disadvantages• PM emission• Difficult to reduce NOx by existing catalyst technology * Registered Trademark of The Dow Chemical Company Slide 15
  • 16. Opportunities for Emissions Catalysis  Non PGM catalysts  Cannot form volatile compounds with CO (i.e., Ni)  Need to meet critical performance requirements / legislated standards.  Cu cannot be used in N.A.  Better NOx catalysts, especially for diesel particulate filters, new filter structures. Slide 16
  • 17. The LP OxoSM Process • 1975 - UCC commercialised Rh-PPh3 catalyst - Low pressure (17 bar) and temperature (90oC) - 200 equivalents of PPh3 required - n:iso ratio = 10 • 1995 - UCC commercialised Rh-bisphosphite catalyst - 50 times more active than PPh3 system - Lower pressure (7 bar) and temperature (75oC) - n:iso ratio = 30 World production levels - 2.5 million mt.p.a. of 2EH - 4.5 million mt.p.a. of butanols - 95% made by Rh catalysed hydroformylation Olefin hydroformylation is the largest volume homogeneous catalytic reaction Page 17
  • 18. Potential Opportunities in Hydroformylation andEnantioselective Catalysis  Desirable improvements:  Higher chemoselectivity and/or functional group tolerance  Need to meet critical performance requirements to be commercially viable (kinetics, overall catalyst cost including ligand, stability, sensitivity, safety, etc.).  Enantioselective catalysts with high rates and TON for addition reactions to C=O bonds  Aldol reaction, Ene reaction, addition of MR to RCHO, Hetero Diels- Alder, addition of CN- to C=O.  Enantioselective catalysts with high rates and TON for cross-coupling and metathesis reactions.  Potential approaches:  Identify new mechanisms.  High-throughput discovery methodologies  New ligand families. Slide 18
  • 19. Issues in Finding Alternatives toCritical Materials in Photovoltaics Slide 19
  • 20. Why Does Chemical Industry Care About PV?  Chemical Industry is a large consumer of electricity/energy  Dow Chemical uses as much electricity as Australia, and ~1x106 barrels of oil equivalent per day.  Huge addressable market.  Worldwide electricity consumption: 20 PWh / $2 Trillion  Low market penetration - Oct 2011 US PV electricity: 169 GWh from total of 309,279 GWh (0.05%) (US EIA)  Technological materials-based solution with rapidly changing & disruptive economics.  At inflection point for economic viability  Plastic, adhesives, encapsulants, wafer processing chemicals, etc. supply. Slide 20
  • 21. 2010 - 2011 Solar Sector Dynamics Enormous capacity build (2H 2010-1H 2011), especially in China. 2 Demand “shocks” from austerity measures and subsidy cuts  Italy Q4 2010-Q3, 2011. 100  Germany Q1-Q2 2011. Module Sales Price, $/W Inventories soared, prices collapsed >50%1 10  $0.80 - $1.00 per Wp module Today Resulting shakeout of non-competitive 1 technologies. Spectacular and highly politicized solar 0.1 module manufacturer bankruptcies. 1980 2000 2020  Solyndra, Evergreen Solar, SpectraWatt, Energy Conversion Devices, Uni-Solar Ovonic, Q-Cells 1. Axiom Capital report, and A. Goodrich, Sr. Analyst NREL, personal communication. Slide 21
  • 22. Two Electricity Delivery Architectures Centralized Grid-Tied Distributed Generation cost Generation cost + Connection fee + Connection fee + Transmission cost + Utility profit = Cost to consumer + Taxes & fees Your view of PV electricity depends on which side of the electric meter you are on (consumer vs. producer) = Cost to Consumer Slide 22
  • 23. US Electricity Consumption Rises Steeply below$0.18/kWh • PV electricity cost is a function of capital ($/W), lifetime, interest rate & average insolation. • Average US insolation is 4.8kWh / m2 * day. (NREL). • PV electricity value at $0.118 / kWh (US residential average) $2/w $3/w $4/w ranges from $0.06 / m2 * day (10% efficient) to $0.59 / m2 * day (100% efficient) at average US insolation. • Current PV market penetration – 0.05% of total US electricity At $2/W total installed cost, >$1.5 trillion of production. demand potentially economically served by .Source - US EIA, Oct 2011 residential PV. Slide 23
  • 24. 4 Key Obstacles to Widespread Residential Solar Adoption 1. Installation complexity 2. Aesthetics 3. Price 4. Warranty concerns The Opportunity: Dow set out to design a cost effective, easy to install, and aesthetically appealing roofing material that both generates electricity and withstands elements for 20+ years Total residential rooftop area available for PV systems in US: 6.4 billion m2 (total area of Delaware) This would provide 7.0 EJ/yr with 20% modules (50% total US demand) Rooftop Area from Navigant Consulting Slide 24
  • 25. POWERHOUSE™ Photovoltaic ShinglesCore R&D/Energy/Dow Dow Plastics /Specialty Films Dow Building SolutionsWire& Cable  PV packaging  BIPV commercial roofing Thin film processing  Back sheet, low-cost injection molding  BIPV residential roofing Mfg. process optimization Materials Science expertise Top layer Wire & Cable business Encapsulant Back sheet
  • 26. Strategic / Critical Materials in PV Price could be the limitation (Rare = expensive) Silver (ECA) Supply & demand are difficult - TCO to predict Indium (ITO) Window Emitter + Absorber Tellurium (CdTe), Indium (CIGS) Barrier Steel Indium Tellurium 1200 $250 1000 In, US$/Kg $200 800 Te, US$/Kg $150 600 $100 400 $50 200 $0 0 1990 1995 2000 2005 2010 2015 1990 1995 2000 2005 2010 2015 Slide 26
  • 27. Caltech/Dow Earth Abundant PV ProjectCombining the R&D strengths of Dow and Caltech to create a powerfulalliance for innovation in the field of PhotovoltaicsFocus on development and commercial implementationof PV materials that are inexpensive and earthabundant such as Zn3P2 and Cu2Ofrom P.H. Stauffer et al Rare Earth Elements – Critical Resourcesfor High Technology, USGS (2002)
  • 28. Summary  Most industrial chemical processes are very efficient users of PGM’s and other critical metals  Emissions catalysis is a significant opportunity & consumes significant amounts of PGM’s.  Hydrosilylation catalysis consumes ~2-4% of annual Pt imports (2010 basis).  Alternatives to critical materials must meet numerous critical performance requirements to avoid significant economic impact.  Extension of thin-film PV technology to the terawatt scale demands abundant materials and high efficiency. Slide 28