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Basic Research Needs in Catalysis for Energy Workshop: August 6-9, 2007. Co-Chairs: Alexis T. Bell (UC-Berkeley) Bruce C. Gates (UC-Davis) Douglas Ray ( PN NL). Breakout Session Panel Leaders: Gand Challenges in Catalysis Mark Barteau, U Delaware Dan Nocera, MIT - PowerPoint PPT Presentation
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Co-Chairs: Alexis T. Bell (UC-Berkeley)Bruce C. Gates (UC-Davis)Douglas Ray (PNNL)
Basic Research Needs in Catalysis for EnergyBasic Research Needs in Catalysis for EnergyWorkshop: August 6-9, 2007Workshop: August 6-9, 2007
Charge: Identify the basic research needs and opportunities in catalytic chemistry and materials that underpin energy conversion or utilization, with a focus on new, emerging and scientifically challenging areas that have the potential to significantly impact science and technology. The workshop ought to uncover the principal technological barriers and the underlying scientific limitations associated with efficient processing of energy resources. Highlighted areas must include the major developments in chemistry, biochemistry, materials and associated disciplines for energy processing and will point to future directions to overcome the long-term grand challenges in catalysis.
Breakout Session Panel Leaders:Gand Challenges in Catalysis
Mark Barteau, U DelawareDan Nocera, MIT
Conversion of Fossil Energy FeedstocksMarvin Johnson, Philips Petrol. – ret.Johannes Lercher, TU-Munich
Conversion of Biologically-Derived FeedstocksHarvey Blanch, UC-BerkeleyGeorge Huber, U Massachusetts
Photo- and Electrochemical Conversion of H2O and CO2
Michael Henderson, PNNLPeter Stair, Northwestern U
Cross-Cutting ThemesJingguang Chen, U DelawareBruce Garrett, PNNL
BES shepherds: John Miller and Raul Miranda
Basic Research Needs to Assure a Secure Energy Future, February 2003: world energy needs will double by 2050; clean, CO2-neutral processes needed; catalysis is 1 of 10 multidisciplinary areas.
Basic Research Needs for the Hydrogen Economy, May 2003: catalysis is 1 of 6 crosscutting research directions that are vital for enabling breakthroughs in reliable and cost-effective production, storage and use of hydrogen.
Basic Research Needs for Solar Energy Utilization, April 2005: catalysts to convert solar energy into chemical fuels is 1 of 5 crosscutting areas.
Catalysis: A Cross-Cutting DisciplineCatalysis: A Cross-Cutting Discipline
The report on BRN in Catalysis for Energy Applications is the first BRN report fully devoted to catalysis and its impact on fuels production
Industry14
Gov't20
National Laboratory
43Academia
53
Workshop Participation and ProgramWorkshop Participation and Program
Distribution of Workshop Participants
Total Number of Participants = 130
Workshop Program:
Plenary Session- Anthony Cugini – NETL- Brian Valentine – EERE- William Banholzer – Dow- Harvey Blanch – UCB- Rutger VanSanten – Eindhoven U
Breakout Sessions- Grand Challenges in Catalysis- Conversion of Fossil Energy Feedstocks- Conversion of Biologically-Derived Feedstocks- Photo- and Electrochemical Conversion of H2O and CO2
- Cross-Cutting Themes
Plenary Midpoint Session
Plenary Closing Session
2 Academic and 1 Industrial participant from Europe
Research Drivers – Energy Security Research Drivers – Energy Security and Environmental Concernsand Environmental Concerns
0
10
20
30
40
50
%
World Fuel Mix 2001oil
gas coal
nucl renew
0.005.00
10.0015.0020.0025.00
1970 1990 2010 2030
TW
World Energy Demand
total
industrialdeveloping
Table 1: Fossil fuel reserves.
FeedstockRecoverable Reserves (Gigaton Carbon)A
Reserve Life At Current Consumption Rate (Years)B
Reserve Life At Projected Gdp Growth (Years)C
Oil 120 35 25
Natural Gas 75 60 45
Coal 925 400 100
a)Source: Energy Information Administration website (www.eia.doe.gov).b)Estimated reserves divided by current consumption.c)Source: Population trends for each geographic sector of the world were taken from the Population Reference Bureau website (www.prb.org) and GDP per Capita for every country were taken from a table at www.photius.com/wfb1999/rankings/gdp_per_capita_0.html. Estimates were made for how fast GDP/Capita (in constant dollars) might grow in each country, and were then multiplied by the expected population growth in each country and summed for the whole world to get a ratio of how energy demand will grow (energy demand grows historically at half the rate of GDP growth). Provided courtesy of Jeffrey Siirola.
Research Drivers – Energy Security Research Drivers – Energy Security and Environmental Concernsand Environmental Concerns
12001000 1400 1600 1800 2000240260280300320340360380
Year AD
Atm
osph
eric
CO2 (
ppm
v) Temperature (°C)
- 1.5
- 1.0
- 0.5
0
0.5
1.0
1.5-- CO2
-- Global Mean Temp
0.00
5.00
10.00
15.00
20.00
25.00
1970 1990 2010 2030
TW
World Energy Demand total
industrial
developing
• Growing demand for energy and finite availability of traditional energy feedstocks (oil and gas) motivates the consideration of alternative fossil feedstocks (tar sands, shale, coal) for the short term
• Biomass conversion offers the possibility of a sustainable source of fuel
• Generation of H2 from H2O and H2/CO from H2O/CO2 should be considered using non-thermal sources of energy (e.g., photons and electrons)
Research Drivers – Energy Security Research Drivers – Energy Security and Environmental Concernsand Environmental Concerns
Conclusions:- Changes in the feedstocks from which fuels are produced are likely to occur in this century
- Future fuel-supply technologies must be sustainable
- Novel catalytic technologies will be required for the production of fuels
Implications:- Research should be directed at developing a fundamental understanding of how future feedstocks (shale oil, tar sands, biomass) can be converted to fuels efficiently
- Basic research aimed at understanding catalyst structure and catalytic phenomena will contribute to the knowledge base used to guide the discovery and development of new catalysts
Grand Challenges in Grand Challenges in CatalysisCatalysis
tappE exp t
OCHRexp
2
+ CH3OH
= 24 kcal/moltheorappE theor
OCHR 2= 0.27 s-1
= 23 kcal/mol = 0.35 s-1
Imaging and simulation of electronic and geometric structures of catalytic materials under reaction conditions
Prediction of catalytic activity and selectivity, and their response to reaction conditions
Determination of reaction mechanisms and understanding of their kinetics
Understanding dynamics of catalytic reaction
A B
1
2
21
1 22
2 1
C
[001]
[110]
t = 0 t = 2 min
1 atom distance displacement
Difference
2 atom distance displacement
Grand Challenges in CatalysisGrand Challenges in Catalysis
Catalysts particles of uniform size and shape can serve as models
Micro- and meso-porous material can be made with controlled pore size and composition
Control of catalyst structures at the atomic and nanometer length scale
Creation of multifunctional catalysts emulating motifs found in biological catalysts
Grand Challenges in CatalysisGrand Challenges in Catalysis
Synthesis of biomimetic catalysts with applicability for energy applications
Advanced Catalysts for Conversion of Advanced Catalysts for Conversion of Fossil Energy FeedstocksFossil Energy Feedstocks
Petroleum feeds are becoming heavier and more S-containing, placing an ever heavier demand for H2 on refiners
Feedstock H/C wt% S wt% N
Petroleum 1.8 1.7 0.1
Residuum 1.0-1.8 1.0-4.0 0.4-1.0
Shale Oil 1.6 0.7 2.2
Tar Sands Oil 1.5 4.7 < 0.5
Coal 0.6-0.9 0.6-4.8 1.1-1.7
Coal Oil 1.4-1.8 < 0.2 <0.5
Alternative fossil feedstocks have lower H/C ratios than petroleum and higher S and N contents, raising the demand for H2
H2 comes from reforming of CH4 or naptha (e.g., CH4 + 2 H2O 4 H2 + CO2)Increasing H2 demand is paralleled by increasing CO2 generation
Challenge: Discover catalysts for the direct transfer of H atoms from light alkanes
Challenge: Discover catalysts for heteroatom removal that minimize product hydrogenation
• Refinery processes are very sensitive to feedstock composition
• Changing feedstock requires an understanding the effects of feedstock composition on individual processes
Advanced Catalysts for Conversion of Fossil Advanced Catalysts for Conversion of Fossil Energy FeedstocksEnergy FeedstocksPetroleum
Oil Shale
Tar Sands
Coal
Challenge: to describe complex feedstocks and processes on a molecular basis taking into account catalyst properties
Advanced Catalysts for Conversion of Fossil Advanced Catalysts for Conversion of Fossil Energy FeedstocksEnergy FeedstocksPetroleum
Oil Shale
Tar Sands
Advanced Catalysts for Conversion of Advanced Catalysts for Conversion of Fossil Energy FeedstocksFossil Energy Feedstocks
Structure-oriented lumping (SOL) permits the description of feeds and products at the molecular level
Asphaltene representation as a set of connected “cores”
Challenge: To represent dynamics of each reaction step in terms of catalyst properties, including dynamics of transport
S. B. Jaffe et al., I&EC Res., 2005, 44, 9840
Advanced Catalysts for Conversion of Advanced Catalysts for Conversion of Biologically-Derived FeedstocksBiologically-Derived Feedstocks
Liquid-phase processing of lignocellulose to begins with deconstruction cellulose and hemicelluose to release sugars
Challenge: To identify catalyst/solvent systems for the efficient deconstruction of biomass
Biomass can be converted to fuels by:
- Pyrolysis – complex liquid products requiring further processing
- Gasification – produces CO/H2 that can be converted further to diesel
- Deconstruction – produces sugars that can be converted to fuels by enzymatic or non-enzymatic catalysts
Gasification of Biomass and Production of Fuels
C Sources
Products
FT and MeOH synthesis
Challenge: Development of catalysts for the elimination of char produced during gasification of biomass
Challenge: Catalysts for control of product distribution obtained from FTS
Advanced Catalysts for Conversion of Advanced Catalysts for Conversion of Biologically-Derived FeedstocksBiologically-Derived Feedstocks
O
OO
nO
HOOH
OH
OH
HO-5kcal/mol
HO
OH
OH
OH
HOOH -20kcal/mol
hydrogenation
+H2
+H2O
HO
OH
HO
-5 kcal/mol
+H2
C-Chydrogenolysis
OH
OH + H2O
C-Ohydrogenolysis
-25 kcal/mol
+ H2
dehydration/hydrogenation
O
OOH- 3 H2O
-5kcal/mol
O
OHOH
+H2
-35kcal/molhydrogenation
O
OHOH
+2H2
-10kcal/molhydrogenation
O
OO
oxidation
+ H2O
-50kcal/mol+1/2O2
O
OH OH
-10 kcal/mol
+ H2O
aldol condensation+Acetone
O
OH OH
+3H2 -60kcal/molhydrogenation
O
+2H2O
+2H2-50kcal/mol
+2H2
-50 kcal/mol
+ H2O
hydrolysis
dehydration
3CO+4H2
Alkanes+CO2+H2O
reforming&FT synthesis
6CO2+12H2
reforming150 kcal/mol
+6H2O
C-Ohydrogenolysisdehydration-
hydrogenation
C-Ohydrogenolysisdehydration-
hydrogenation
a polysaccharide
glucose
HMF
DHMF
DHM-THF
DFF
sorbitolglycerol
BH-HMF
synthesisgas
propanediol
HO
O
HO
glyceraldehyde
HO
Olacticacid
OH
dehydrogenation15 kcal/mol
isomerization-15kcal/mol
reforming80 kcal/mol
-30 kcal/mol
- H2
Challenge: To identify catalysts for the selective formation of targeted fuel components
Challenge: To determine the reaction pathways via which glucose is converted to fuels
Compound Energy density (MJ/L)
Boiling point (oC)
Fraction of C in C6H12O6 Rejected as CO2
pentane 72 36 0.33
hexane 68 69 0.37
gasoline 35 n/a n/a
dimethyl furan 30 93 0.14
butanol 29 117 0.33
1,6-hexane diol 27 216 0.29
ethanol 24 78 0.33
-valerolactone 23 253 0.17
1,5-pentane diol 23 242 0.33
methanol 16 65 0.50
Many fuel components can be made starting from glucose
Fuel targets can be selected on the basis of energy content, volatility, and C rejection as CO2
Advanced Catalysts for Photo- and Electro-Advanced Catalysts for Photo- and Electro-Driven Conversion of HDriven Conversion of H22O and COO and CO22
All fossil energy feed stocks require H2 to increase their H/C content and to remove heteroatoms (S and N)
CHhSsNnOo + [(2-h)/2 + s + 3n/2 + o] H2 -CH2- + s H2S + n NH3 + o H2O
Petroleum
H/C = 1.8Tar Sands
H/C = 1.6
Oil Shale
H/C = 1.5
Coal
H/C = 0.6-0.9
H/C = 2.0; O/C = 1.0
BiomassBiomass conversion to fuels requires the removal of O
C6H12O6 2 C2H5OH + 2 CO2 C6H12O6 4 -CH2- + 2 CO2 + 2 H2O
33% of C in sugar is rejected at CO2
Challenge: To provide an inexpensive, non-carbon source of H2
Challenge: To recover the C-value of CO2 so as to avoid the need for CO2 emission or sequestration
CO2 rejection can be eliminated by using a non-carbon source of H2
Total Carbon Use – HTotal Carbon Use – H22-CAR*-CAR*
• All of US transportation fuel needs could be supplied by a land area equivalent to about half of that used for agriculture today
*R. Agrawal et al., PNAS, 104, 2007, 4828
O2 + “2H2” = NADPH
CO2
Sugar
hh
CO2H2O + energy +
h
et ht
VB
–
+
+
–CB
2H2O+ O
4OH
2H
H2
Pt
Advanced Catalysts for Photo- and Electro-Advanced Catalysts for Photo- and Electro-Driven Conversion of HDriven Conversion of H22O and COO and CO22
Plants use solar energy to convert H2O and CO2 to sugars with an energy efficiency of < 1%
Photo-electrocatalytic systems convert H2O to H2 with an energy efficiency of 1-10%
Electrochemical systems convert H2O/CO2 to H/CO with an energy efficiency of ~50%
Challenge: To understand the relationships of catalyst composition and structure to the elementary processes leading to the generation of H2
Challenge: To identify catalysts that enable the efficient utilization of e-/h+ pairs for the splitting of H2O and the reduction of CO2
Humidified CO2
CO2 + reductionproducts
Liquid water
Diffusion media
Cation-exchange membrane
HCO3-
H+
CO2 + H2O
Catalystlayers
Buffer layer(aqueous KHCO3)
e- e-CO2
O2
H2O
CO + H2 + H2O
Liquid water + O2
Humidified CO2
CO2 + reductionproducts
Liquid water
Diffusion media
Cation-exchange membrane
HCO3-HCO3-
H+H+
CO2 + H2OCO2 + H2O
Catalystlayers
Buffer layer(aqueous KHCO3)
e- e-CO2CO2
O2O2
H2OH2O
CO + H2 + H2O
CO + H2 + H2O
Liquid water + O2
h+ e-
2 H2O
4 H+ + O2
6H+ + CO2
CH3OH + H2O
H+
h
6e-
4h+
semiconductorelectrode
proton channel H2O oxidation catalyst
CO2 reduction catalyst
Advanced Catalysts for Photo- and Electro-Advanced Catalysts for Photo- and Electro-Driven Conversion of HDriven Conversion of H22O and COO and CO22
Challenge: To design efficient catalysts for the photo- or electro-reduction of CO2
Cross-Cutting Themes: Advanced Instrumentation andCross-Cutting Themes: Advanced Instrumentation andTheory, Modeling, and SimulationTheory, Modeling, and Simulation
Reference electrode
Counterelectrode
Electrolyte solution
Prism IR beam
Thin metal film (10-30 nm thick) (working electrode)
Chem. Comm. 1619(1999)Chem. Comm. 1619(1999)
Challenge: To develop advanced instrumentation for in situ observation of catalysts
Neutron
Raman
Synchrotron
TEM
Infrared
Cross-Cutting Themes: Advanced Cross-Cutting Themes: Advanced Instrumentation andInstrumentation and
Theory, Modeling, and SimulationTheory, Modeling, and Simulation
Challenge: To develop reliable theoretical methods for describing the reactions of complex molecules including the effects of transport
Challenge: To develop simulation strategies for describing the complex systems of reactions occurring during the processing of fossil and bio-derived feedstocks
Workshop ProductsWorkshop ProductsGrand Challenges
1. Understanding mechanisms and dynamics of catalytic transformations
2. Design and controlled synthesis of catalytic structures
Priority Research Directions1. Understanding complex transformations of fossil fuel feedstocks
2. Understanding lignocellulosic biomass and the chemistries of deconstruction
3. Understanding the chemistry for conversion of biomass-derived oxygenates to fuels
4. Photo- and electrochemical conversion of H2O and CO2
Cross-Cutting Themes1. Advanced instrumentation for in situ characterization of catalysts
and catalytic processes
2. Advanced theoretical methods for the simulation of catalysts and catalytic processes
Technology Maturation & Deployment
Relationships Between the Science and the Technology Offices in DOE
Applied Research Discovery Research Use-Inspired Basic Research
Basic Research Needs – Catalysis for Energy Applications
Develop catalytic systems that exploit nonequilibrium conditions for fuel production
Demonstrate viability of a catalytic system for converting CO2 to fuels
Develop advanced catalytic systems for H management to use in selective heteroatom removal from feedstocks
Overall efficiency improvements leading to economically viable energy conversions
Robust catalytic systems
Systems for production of HC from biomass, coal, and heavy crude oils
Energy conversion systems that are carbon neutral
Scalable systems to harness solar energy for conversion of CO2 to fuels
Sustainable domestic source of fuel with minimal environ-mental impact
BESBES Technology OfficesTechnology Offices
Understand mecha-nisms and dynamics of catalyzed reactions at the molecular level
Understand and describe the kinetics of complex reactions networks in multiphase systems
Synthesize uniform catalytically active sites
Develop instrumenta-tion with enhanced spatial, temporal, & energy resolution for in situ studies of catalytic systems
Develop theoretical and computational methods for complex catalytic systems
Develop catalysts for tailored biomass deconstruction and conversion to targeted fuels
Develop catalysts for selective removal of heteroatoms
Develop catalysts for CO2 reduction and H2O splitting using solar and electrical energy
Develop catalysts for selective synthesis complex molecules
Synthesize working catalysts with multiple active sites to mimic nature