Reversible Storage of Alternative Fuels in Nanoporous Carbon: Methane and Hydrogen

Transcription

1 Reversible Storage of Alternative Fuels in Nanoporous Carbon: Methane and Hydrogen Peter Pfeifer Department of Physics University of Missouri Columbia, MO Your next car might well run on clean natural gas and be ready for hydrogen when it comes along EMPA Zurich 3/28/07 1

2 Feb. 16, 2007: EMPA Zurich 3/28/07 2

3 Programmatic overview EMPA Zurich 3/28/07 3

4 Why alternative fuels? Reduce dependence on foreign oil Harness domestic renewable energy sources Create new opportunities for domestic agriculture Create clean air in cities Reduce transportation costs by improving energy efficiency Reduce greenhouse gas emissions Develop sustainable transportation in U.S. What are alternative fuels? Ethanol (from corn, wood, ) Natural gas* (NG; from domestic gas fields, deep-sea methane hydrate fields, landfills, biomass); 85% of NG used in U.S. is domestic Biodiesel (from soybeans, vegetable oils, ) Hydrogen* (from NG, water & electricity, coal, ) Electricity (from coal/nuclear/hydroelectric/solar/wind power plants) * ALL-CRAFT At pump: ~$1.25 less than equivalent gallon of gasoline EMPA Zurich 3/28/07 4

5 How do alternative fuels work together? U.S. energy consumption World energy consumption EMPA Zurich 3/28/07 5

6 Who we are Partners MU (lead institution): Physics (Pfeifer, Principal Project Leader; Wexler), Chemistry (Atwood & Hawthorne), Chemical Engineering (Suppes), Civil Engineering (Bowders), Office of Research (Coleman) Lincoln University, Jefferson City Midwest Research Institute (MRI), Kansas City DBHORNE, LLC, Atlanta Renewable Alternatives, LLC, Columbia Missouri Biotechnology Association (MOBIO), Jefferson City Clean Vehicle Education Foundation, Washington, DC Missouri Dept. of Natural Resources (Energy Center), Jefferson City City of Columbia (Municipal Landfill), Columbia Kansas City Office of Environmental Quality/Central Fleet, Kansas City EMPA Zurich 3/28/07 6

7 Who we are People MU, Physics Sarah Barker, Jacob Burress, Sara Carter Carol Faulhaber (Northwest MO State U.) John Flavin, Lacy Hardcastle Cintia Lapilli, Jeff Pobst, Robert Schott Demetrius Taylor, Mikael Wood MU, Chemistry Jerry Atwood Praveen Thallapally,Trevor Wirsig MU, Chemical Engineering Mona-Lisa Banks (Lincoln University) Joshua Bulloc, Sean Crockett Tarek Dannoon, Matt Factor, Mike Gordon Monty Kemiki (Penn State University) Parag Shah, Serean Spellerberg Mustafa Yousif (Alabama A&M U.) Galen Suppes MU, Civil & Environmental Engineering Joshua Bergsten John Bowders MRI Bob Barton, Phil Buckley Tom Breier, David Dolson Jason Downing, Steve Eastman (MU) Phil Freeze, Sam Grinter (MU) Steve Graham, Antonio Howard (Lincoln U.) Greg Jones, Juan Martinez Darren Radke, Todd Vassalli (MU) Kansas City Office of Environmental Quality Dennis Murphy Sam Swearngin Consultants Cindy Carroll, MO Dept. of Natural Resources Anne Dillon, National Renewable Energy Lab., CO Doug Horne, Clean Vehicle Education Foundation Cynthia Mitchell, Columbia Municipal Landfill John Noller, MO Dept. of Natural Resources Phil Parilla, National Renewable Energy Lab., CO David Quinn, Royal Military College of Canada Francisco Rodriguez-Reinoso, U. Alicante, Spain Rusty Sutterlin, Renewable Alternatives LLC Jim Wegrzyn, Brookhaven National Laboratory EMPA Zurich 3/28/07 7

8 What we do Develop low-pressure, high-capacity storage technologies for natural gas (NG, methane, CH 4 ) and hydrogen (H 2 ), based on new adsorbent materials discovered at MU: nanoporous carbon from waste corncob in Missouri ( sponge for NG ) calixarene ( crystalline vacuum pump ) Demonstrate low-pressure, flat-panel NG tank for next-generation clean vehicles (NG internal combustion engines) hydrogen fuel cell cars (no hydrogen infrastructure needed) collection of NG from landfills ( pollutant to renewable energy ) large-scale shipping of NG from Alaska and deep-sea methane hydrate fields (reduction of dependence on foreign oil) Develop low-pressure, flat-panel H 2 tank for hydrogen fuel cell car Funded by: NSF Program Partnerships for Innovation MU, MRI, Advanced Photon Source/DOE, DED/GAANN EMPA Zurich 3/28/07 8

9 Where it all started 1.4 nm Van der Waals attraction in nanopores forces NG into liquid-like dense fluid (170 g/l at 35 bar) EMPA Zurich 3/28/07 9

10 Why are nanopores important? Binding energy: 17 kj/mol In narrow pores, van der Waals potentials overlap; create deep energy well: Max. CH 4 capacity in pores of width 1.1 nm (Nicholson, 1998). Molecules are held in tightpacked configurations. EMPA Zurich 3/28/07 10

11 Why are nanopores important (cont. d)? Width ~6 Å ~3.7 Å Width ~11 Å Width ~22 Å EMPA Zurich 3/28/07 11

12 Current natural-gas vehicles Low emission of hydrocarbons ( ozone, smog), NO x, particulate matter. Up to 40% reduction of CO 2. NG stored as compressed natural gas (CNG) in steel or composite cylinders at 250 atm (3600 psi). Clean Cities Coalitions: / Los Angeles: 1500 CNG buses Kansas City: 200 CNG public utility vehicles U.S.: 130,000 CNG vehicles worldwide: over 5 million CNG vehicles EMPA Zurich 3/28/07 12

13 Why are we not already driving NG-fueled cars? High-pressure cylindrical/spherical tanks take up passenger or trunk space. CNG cylinders in transit bus: Only NG passenger car in U.S.: Honda Civic GX; CNG tank in trunk: Goal: Develop low-pressure (35 atm, 500 psi), flat-panel tank, like gasoline tank. Store NG in nanoporous carbon; pores adsorb NG like a sponge: ANG tank EMPA Zurich 3/28/07 13

14 Best flat-panel tank previously Atlanta Gas Light Adsorbent Research Group (AGLARG), 1997: Adsorbent: monolithic activated carbon ( briquettes ) from peach pit; troublesome maintenance of consistent quality of briquettes; binder blocks pores AGLARG 1997 AGLARG tanks in bed of NG Dodge Dakota ALL-CRAFT: Monolithic carbon, with superior performance, from corncob. Missouri corn can supply raw material for NG tanks of all cars in the U.S. EMPA Zurich 3/28/07 14

15 Performance of ALL-CRAFT tank Target pressure for flat tank: 35 bar (35 atm, 500 psig *); without adsorbent, pressure would have to be 150 bar, much more than what a flat tank can bear DOE target capacity: 118 g/l (volume CH 4 at 25 o C & 1 bar, per volume tank: 180) AGLARG tank: 98 g/l ALL-CRAFT target: >100 g/l achieved! DOE target achieved! DOE target; best ALL-CRAFT carbon AGLARG capacity Adsorbent Filled Tank (ANG) ALL-CRAFT 2007 Empty Tank (CNG) *) 500 psi: pressure in NG pipelines EMPA Zurich 3/28/07 15

16 Recovery of biomethane from landfills and farms Landfills: largest human-made source of methane (CH 4 ) in U.S. Landfill gas (LFG): ~ 50% CH 4, ~ 50% CO 2 CH 4 : 20 times more potent greenhouse gas than CO 2 Capture CH 4 at landfill: pollutant to renewable energy If no power plant: recover CH 4 in 60,000 pound ANG tanks Annual CH 4 emission from landfills in U.S.: Could power 4 million homes: $5 billion/yr Greenhouse equivalent to emission from 90 million cars (~1/2 of cars in U.S.) If captured, equivalent to planting forest 2 x area of MO EMPA Zurich 3/28/07 16

17 ALL-CRAFT accomplishments in the lab and on the road October present EMPA Zurich 3/28/07 17

18 Carbon production & methane storage capacity Produced over 100 different carbons from corncob (variable activation procedures) & over 300 monoliths for test tank Starting material & final product ( Missouri hockey puck ) Searched for maximum storage capacity, with: M/V: gram of NG per liter of carbon V/V: NG, as volume of gas at 25 o C and 1 atm, per volume of carbon M/M: gram of NG per kilogram of carbon ALL-CRAFT, typical monolith (#6, 22, 30, 46, 70) M / V g/liter Av.: 107 g/liter V / V liter/liter Av.: 164 liter/liter M / M g/kg Av.: 188 g/kg ALL-CRAFT, best performance (Sample S-33/k) g/liter 120% of AGLARG 100% of DOE AGLARG, best performance ANG DOE target 98 g/liter 118 g/liter liter/liter 150 liter/liter 180 liter/liter g/kg 140% of AGLARG 170 g/kg N/A EMPA Zurich 3/28/07 18

19 Methane storage capacity, cont. d 100% of DOE target 83% of DOE target Typical monolith, #46 Mass-per-volume storage at 25 o C (volumetric instrument) Best Sample, S-33/k Mass-per-volume storage at 25 o C (gravimetric instrument) Best Sample, S-33/k Mass-per-mass storage at 25 o C (gravimetric instrument) EMPA Zurich 3/28/07 19

20 Methane storage capacity, cont d Gravimetric measurement of CH 4 uptake on small samples: Temperature of monolith during fueling Volumetric measurement of CH 4 uptake, & temperature on 3.5 monoliths (MRI test fixture): MRI 2006 EMPA Zurich 3/28/07 20

21 Absolute adsorbed, excess adsorbed, amount stored EMPA Zurich 3/28/07 21

22 Summary of storage capacities 119 g/l 118 g/l 24.9 g/l EMPA Zurich 3/28/07 22

23 Small-angle x-ray scattering Spatial arrangement of pores from small-angle x-ray scattering (Advanced Photon Source, Argonne National Laboratory): EMPA Zurich 3/28/07 23

24 Computer modeling of pore formation EMPA Zurich 3/28/07 24

25 Scanning & transmission electron microscopy EMPA Zurich 3/28/07 25

26 S-33/k zoomed in EMPA Zurich 3/28/07 26

27 Nitrogen adsorption isotherm EMPA Zurich 3/28/07 27

28 Pore-size distribution from N 2 isotherm (subcritical ads.) EMPA Zurich 3/28/07 28

29 Methane adsorption isotherm: binding energy, EMPA Zurich 3/28/07 29

30 Pore-size distribution from CH 4 isotherm (supercritical ads) EMPA Zurich 3/28/07 30

31 Comparison/validation EMPA Zurich 3/28/07 31

32 Hydrogen storage EMPA Zurich 3/28/07 32

33 Hydrogen excess adsorption isotherm EMPA Zurich 3/28/07 33

34 Hydrogen absolute adsorption isotherm EMPA Zurich 3/28/07 34

35 Hydrogen storage isotherm EMPA Zurich 3/28/07 35

36 Hydrogen storage validation & comparison with other adsorbents EMPA Zurich 3/28/07 36

37 Road test of ALL-CRAFT natural gas prototype tank EMPA Zurich 3/28/07 37

38 ALL-CRAFT ANG tank on Ford F-150: MRI, Kansas City Office of Environmental Quality October 2006 to present Ford F-150 pickup for road test in Kansas City (MRI, 4/06-9/06) MRI 2006 MRI Al tubes holding 300 carbon briquettes MRI 2006 EMPA Zurich 3/28/07 38

39 ALL-CRAFT tank on Ford F-150 EMPA Zurich 3/28/07 39

40 Natural gas vehicles over time First NG vehicle 1910 (USA) with balloon tank on trailer NG vehicle ~1930 (France) with balloon tank on roof Current NG vehicle with high-pressure tank in trunk Future NG vehicle with low-pressure tank under floor EMPA Zurich 3/28/07 40

41 From agricultural waste to high-tech storage tanks

42 Recovery of NG (biomethane) from landfills: Example Columbia, MO EMPA Zurich 3/28/07 42

43 Current recovery of methane from landfills Electricity generation (large sites: STL, KC, ) Direct heat (large/intermediate sites: STL, KC, Columbia, ) Opportunity: During high-flow periods, store in stationary tanks Flare off (small sites) Not captured (abandoned sites) Opportunity: Store in transportable tanks EMPA Zurich 3/28/07 43

44 Columbia landfill EMPA Zurich 3/28/07 44

45 Renewable NG from landfills Methane recovery in transportable tanks Collect & purify methane at landfill 40,000 lb carbon tank, with 24 wt% storage capacity, can store 9,600 lb of methane Ship full tank on tractor trailer to central processing facility; discharge methane Return empty tank to landfill Example: Columbia landfill Flow rate One tank full in Operated as dry 250 cuft/min tomb, ,000 lb/day 0.64 days Operated as 980 cuft/min bioreactor, ,000 lb/day 0.17 days Tanks of interest at small or abandoned landfills EMPA Zurich 3/28/07 45

46 Conclusions & outlook R&D For methane: Achieved DOE target of 118 g CH 4 /liter 35 bar, 298 K Corresponds to 238 g CH 4 /kg 35 bar, 298 K Operational ANG tank on road, with monoliths made from corncob For hydrogen: Achieved 80 g H 2 /kg 47 bar, 77 K Compares favorably with best-performing adsorbents in literature Plan: dope carbon with boron to increase binding energy EMPA Zurich 3/28/07 46

47 Conclusions & outlook economic opportunities National level NG fueled cars = next-generation clean vehicles 1. Reduce smog, respiratory disease, cardio-vascular disease, 2. Reduce greenhouse gas emissions 3. Reduce dependence on foreign oil now 4. Harness domestic NG fields (Alaska), deep-sea methane hydrate fields (Oregon), renewable NG from landfills & biomass (Missouri, ) Recovery of NG from landfills 1. Pollutant to energy 2. Economic growth in rural areas State level Produce NG tanks, from MO corn cob, for 10 million cars/year: $10 billion/yr Produce & operate NG tanks, from MO corn cob, for 2,500 landfills: $10 billion/yr Produce NG tanks, from MO corn cob, for large-scale NG shipping: $5 billion/yr EMPA Zurich 3/28/07 47