Environmentally Benign EnergyEnvironmentally Benign Energy Technologies
Marco J. Castaldi D f E h & E i l E i iDepartment of Earth & Environmental EngineeringHenry Krumb School of Mines, Columbia University
Presentation to Free University of Bolzano
Bolzano, ItalyNovember, 11,2010
FUB – Nov 2010
Marco J Castaldi - IntroductionChemical Engineering Background
Ph.D. UCLA in high temperature chemical kineticsEPA Pollution Prevention Fellowship
M f F l P D l~ 10 Years Industrial Experience
• Manager of Fuel Processor Development• Research Engineer, Catalytic Combustor Development• 8 patents awarded to date
Technology Development with:Technology Development with:
Solar Turbines
C l bi U i i R h & D l I
A Caterpillar Company
FUB – Nov 2010
Columbia University Research & Development Interests• Catalysis and Combustion• Environmentally Benign Energy Technologies
Central Park
FUB – Nov 2010
•Founded 1754 – King’s College (Colony of New York)•Renamed Columbia University after American Revolution•Engineering•Engineering
School of Mines founded in 1864; Origins of Engineering School1964 Renamed Henry Krumb School of Mines (HKSM)1997 Renamed Earth & Environmental Engineering1997 Renamed Earth & Environmental Engineering
First mining and metallurgy school in the U.S. Part of Manhattan Project (WWII)Prominent Researchers: Enrico Fermi, Richard Feynman
FUB – Nov 2010
Environmental Stresses
Phys & Chem
Earth & Environmental Engineer
Ch EMech Eng
Ci il EBio
FUB – Nov 2010
Chem Eng Civil EngGeo Phys&Chem
EAEE Department
Integrated analysis and managementof the Earth System
• Sustainable Energy
• Materials, Mineral Processing & Manufacturing, g g
• Water Quantity/Quality and Climate Risks
• Environmental Health Engineering
FUB – Nov 2010
Enrollment Trends
60
70total
40
50
60
dent
s
totaljuniors&seniors
20
30
40
# of
stu
d
0
10
09-10 junior class size reflects declared SEAS sophomores
2000 2002 2004 2006 2008 2010 2012
year
FUB – Nov 2010
09-10 junior class size reflects declared SEAS sophomoresbut not include incoming 3-2 Combined Plan students
Equipment at Combustion and Catalysis Laboratory (CCL)Catalysis Laboratory (CCL)
Netzch 409 PC Thermo-gravimetric Analyzer
Agilent 6890 GC/ 5973 MS system5973 MS system
•Concentrations•Spatial, Temporal
•Mass changes•Volume change•Fundamental High Temperature Kinetic
FUB – Nov 2010
Portable micro GC(field testing)
Columbia University Working Collaboratively on Fundamental and Applied y g y ppResearch Studies
Advanced, Combustion, Materials and Energy Test Complex
FUB – Nov 2010
Validation Testing
• 3 random grab samples• Results show biomass content
66%, 68% and 66%• Biocarbon emission = 0.19 MTCE/ton MSW• Fossil based emission = 0 08 MTCE/ton MSW
FUB – Nov 2010
• Fossil based emission = 0.08 MTCE/ton MSW• 10% - 36% reduction of CO2 emissions compared to landfill
FUB – Nov 2010
FUB – Nov 2010
Energy
• Two-fold increase in energy consumption (demand)gy p ( )• From 472 exajoules to 791-1107 over next 40 years
• The world is sensitive to energy supply (new paradigm)− Security, Procurement supply chain disruptions
• CO2 atmospheric concentrations are rising (environment)− Prevent carbon dioxide emissions sequester create valuePrevent carbon dioxide emissions sequester, create value
FUB – Nov 2010
Biomass Energy
Source: IEA
Total mass of living matter (including moisture) - 2000 billion ton d i i l biEnergy stored in terrestrial biomass 25 000 EJ
Net ann. Prod. terrestrial biomass - 400 000 million ton
Rate of energy storage by land biomass - 3000 EJ/y (95 TW) i f f f 400 / (12 )
FUB – Nov 2010
Total consumption of all forms of energy - 400 EJ/y (12 TW) Biomass energy consumption - 55 EJ/y ( 1. 7 TW)
BioenergyS i bl b l h d h i l f d k• Sustainable carbon neutral power, heat and chemical feedstocks.
• Potential to provide ~ 15% of energy demand.• Gasification
• Lower PM NO and SO than combustion• Lower PM, NOx, and SO2, than combustion• Steam addition – Increased concentration of H2• CO2 usage – enhanced char conversion and less residue for landfill.• Provides reagents (CO & H2) for synthetic fuel/chemical production
Estimations vary widelyEstimations vary widely due to land availability and crop yields.
One piece of the alternative energy future technologies
FUB – Nov 2010
•Energy sector is inefficient
What is the Problem?Energy sector is inefficient
• ~60% of energy is wasted!
World Energy Consumption 5 1020 J (2008)5x1020 J (2008)
Remaining Fossil Fuel 0.4x1024 J (800x)
Fossil + hydrate 2x1024 J (4000x)
FUB – Nov 2010
Conversion Problem
90
100 Heating Rate = 10oC min-1
90
100 Heating Rate = 10oC min-1
(%) 70
80
90
(%) 70
80
90Determining and Understanding Reaction Mechanisms allows design of more efficient and selective processes and technologies
Res
idua
l Mas
s
40
50
60
Res
idua
l Mas
s (
40
50
60 and technologies.
R
10
20
30
R
10
20
30Unprocessed residual
Reactor Temperature (oC)
0 200 400 600 800 10000
10
Reactor Temperature (oC)
0 200 400 600 800 10000
10
Completely processed to desired outcome
FUB – Nov 2010
p ( )
Atom Economy : Carbon DioxideEnergy production & Environment
CO2 CH4Energy conversion & Efficiency
BiomassCxHy
Fuel (e g C2H OH)
Energy conversion & Efficiency
Biomass + H2O CO + H2 ηatom =100%Biomass + CO2 CO + H2 ηatom =100%
MSWCoal
Fuel (e.g. C2H5OH)
Biomass CO2 CO H2 ηatom 100%• Energy and water savings
20% of 2008 total transportation energy demand incorporates CO2
FUB – Nov 2010
f p gy p 2•Remove 308 million vehicles from the road•Eliminate CO2 emissions from 57 - 1000 MW coal-fired power plants.
Combustion & Catalysis Lab (CCL)Air
H2
CO2 CH4 H2OElec.
H2 + CO2
Air
FuelReforming
Fuel CellOther fuelsFuelCell
This presentation
Alternative CH4/CO2source – Landfill gas
CH4HydratesCO2
This presentation•Hydrates•GHG Reforming•WTE
CO/H2 – engine application
sou ce a d gas
CO2 capture &GHG reforming
To market or community. Stock: plastic furniture
C2H2
plastics or raw materials
Biomas andWaste to Energy
electricity
CO2 household etcWaste to Energy (WTE)
Resources for energy production will continue to be in demand
FUB – Nov 2010
“The nature of environmental issues is changing from a regulatory to a resource focus” R. MacLean, Env. Protec. April 2003, P.12
Resources for energy production will continue to be in demand
Gasification or Combustion
• Sub stoichiometric air • Excess air• Lower total volumetric flow• Lower fly ash carry over• Pollutants in reduced form (H2S,
• Higher volumetric flowrate• Fly ash carry over• Pollutants in oxidized form (SOx,
COS)• Char – Low T• Slag – vitrification – high T
NOx, etc)• Bottom ash
FUB – Nov 2010
Gasification status• 163 commercial gasification projects worldwide consisting of• 163 commercial gasification projects worldwide consisting of
a total of 468 gasifiers. DOE survey reported for 2003• ~ 120 plants began operations between 1960 and 2000p g p
– majority (more than 72 plants) commissioned after 1980. Currently ~34 new plants are at various stages of planning and construction.
h j i f h i i l d i d d• The majority of the existing plants were designed and constructed to produce a synthetic gas, consisting primarily of H2 and COH2 and CO
• Ethanol – EnerChem/City of Edmonton – 2008• Energos (Sweden, UK) building plants @
Chemicals From Waste News
• Military MISER programT h/Bi /S lid h d b t f l– Trash/Biomass/Solid hydrocarbons to fuels
• American Chemical Society (ACS)American Chemical Society (ACS)– Letters to the editor – “chemicals from waste”
• C&EN April 2006
• Discover Magazine –– “DATA” Section : The Ultimate Garbage Disposalg p
• How to turn trash into clean energy – Geoplasma Unit– 160 MW by 2009, St. Lucie County, Florida
FUB – Nov 2010
Attractive features of Gasification
• Produce consistent productgeneration of electricity– generation of electricity
– primary building blocks: chemicals and transportation fuels.• Remove contaminants in the feedstock and to produce a clean
syngas product.• Process range of feedstocks
– coal, heavy oils, petroleum coke, heavy refinery– residuals, refinery wastes, hydrocarbon contaminated– soils, biomass, and agricultural wastes.soils, biomass, and agricultural wastes.
• Convert wastes or low-value products to higher value products.• Minimize the amount of solid waste requiring landfill disposal. • Solid by-products have a market value can be used as fuel or
construction material, and are non-hazardous.
FUB – Nov 2010
FUB – Nov 2010
Fuel + air + steam CO + H O
Fuel + air + steam CO + H CO2 + H2OCO + H2
ΔH > 0 ΔH < 0
If perfectly balanced – reaction should occur at T = 298K (25oC)
∏−
= RTE
CeARact
α
FUB – Nov 2010
∏=i
iCeAR
C ( ) +
• Most HC fuels (CxHyOzNaSb) exist above lines
• Need oxygen source or hydrogen to get below C (s) + gashydrogen to get below
(CO2, O2, air H2O, H2)
Gas only – no C(s)
FUB – Nov 2010M. J. Prins et al. / Chemical Engineering Science 58 (2003) 1003 – 1011
Stiochiometry & Equilibrium
C + O2 CO2 + 2H2ODeep Ox 2H2 + COC + O2
Partial Ox
0.4 2500H2
0.3
0.35
2000
C )
H2
Temperature
0 15
0.2
0.25
ompo
sitio
n
1000
1500
pera
ture
( o C
H2O CO
0 05
0.1
0.15Co
500
1000
Tem
p
CO2
0
0.05
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7
CH4/Air
0
C / Air
FUB – Nov 2010 Ref: STANJAN calculationsNet effect: Temp rise; Reactive partial ox. products (CO, H2)
CH4/AirC / Air
Exergy (Entropy) Analysis
26
27
27
• More oxygen in fuel, more exergy• Higher heating value – more exergyRelated to arrangement of molecules and
h t ti t h i l
24
25
25
26
26 heat generation or capture as chemical energy
23
23
24
24
0 0.5 1 1.5 2 2.5
FUB – Nov 2010 Source: M. J. Prins et al. / Chemical Engineering Science 58 (2003) 1003 – 1011
Total energy is constant
Once all carbon is converted,Once all carbon is converted, more air does not help
Begin combustion reactions regime
Rearrangement (chemical
g
Rearrangement (chemical Exergy)
Heating (physical Exergy)
FUB – Nov 2010
Total energy increases –addition of steam
Once all carbon is converted, only energy from steam
Excess steam -no reaction
Rearrangement (chemicalRearrangement (chemical Exergy)
Heating (physical Exergy)
FUB – Nov 2010
CO & H2 --------- CO2 & H2O
Transitioning from chemical rearrangement to heat generation, thus Carnot cycle comes into play
FUB – Nov 2010
Catalytically Controlled Reaction GasifierCatalytically Controlled Reaction Gasifier (CRG Process)
O2
COsplit
O2
CoalH O2
CO2(optional)
H2H2CO H2
COout
H2
COH O2
AshH2
AshSeparator
H OSep.
2
CO+O to CO2 2CO2
SOFCCO2
Biomass2
COH OAsh
2
H O2 CO
Ashto waste stream H O2 CO2
recycle2
FUB – Nov 2010
H O Make up (optional)2
CRG Aspen™ Simulation
CO PROD
CO-SPLIT
CO-ELECCMBSTOR
O2-COMB
COMBOUT
CO2RECYL
CO2EXHST
CO-PRODCO-COMB
CO2RETRN
C-IN
REF-PROD
H2-SEP
COOLDOWN COOLPRODH2O-PROD
REFORMERWATER-IN
H2-PROD
FUB – Nov 2010
Biomass constituents
• Typical C6H12O6 – S~1.8%, N~2%Typical C6H12O6 S 1.8%, N 2%– Sulfur – likely to bind with hydrogen– Some water – another source of hydrogeny g– Nitrogen – likely to form NH3– Ash is variable depending on biomass
• Spruce – near zero• Alfalfa – significant
FUB – Nov 2010
1.2H2 Production, basis:0.5 kmol/hr C
ate
(kg/
hr)
0.8
1.0s/c:1.0, r:0
Baseline simulation results of energy balance and hydrogen
H2 F
low
ra
0 2
0.4
0.6generation for CCRG process
Conventional Gasifier
0.0
0.2
10
20
Energy Requirements
H2O/C = s/c, CO2 recyc = rConventional Gasifier
H2 0.7 kg/hrCO2 ~ 15%
CCRG
y (M
J/hr
)
0
10Energy req'd by gasifierbalanced by CO combustion
CCRGH2 0.85 kg/hrCO2 ~ 1.5%
e- ~13 kW/kmol C
Ene
rgy
-20
-10s/c:1.0, r:0CO Combustion ~48%
FUB – Nov 2010 CO Split (to combustor)
0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9-30
1.0
1.2H2 Production, basis:0.5 kmol/hr C
s/c:1.0, r:0.25
Flow
rate
(kg/
hr)
0.6
0.8s/c:1.0, r:0
H2 F
0.2
0.4
H2O/C = s/c, CO2 recyc = r
Comparison of baseline and 25% CO2 recycle to the
reformer0.0
10
20
Energy Requirements
Energy req'd by gasifierCCRG
H 0 95 kg/hr
nerg
y (M
J/hr
)
-10
0
s/c:1.0, r:0
balanced by CO combustionH2 0.95 kg/hrCO2 ~ 1.5%
e- ~13 kW/kmol CCO Combustion ~42%
E
-20
s/c:1.0, r:0.25
FUB – Nov 2010
CO Split (to combustor)
0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9-30
1.0
1.2H2 Production, basis:0.5 kmol/hr C
s/c:1.0, r:0.25
owra
te (k
g/hr
)
0.6
0.8s/c:1.0, r:0
s/c: 1.0, r:0.5
H2 F
lo
0.2
0.4
H2O/C = s/c, CO2 recyc = rCO recycle comparison for0.0
10
20
Energy Requirements
H2O/C s/c, CO2 recyc r
Energy req'd by gasifier
CO2 recycle comparison for steam to carbon ratio of 1.0.
Tradeoff: energy neutral vs
nerg
y (M
J/hr
)
-10
0
s/c:1.0, r:0
balanced by CO combustionH2 production
En
-20
10
s/c:1.0, r:0.25s/c:1.0, r:0.5
FUB – Nov 2010
CO Split (to combustor)
0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9-30
s/c:1.0, r:0.5
Comparison of CO Evolution for Woods vs. GrassesComparison of CO Evolution for Woods vs. Grasses
• Steam gasification, (0%CO2)
b i i d0 00090.00120.00150.0018
Frac
tion
Alfalfa
• Carbonization and gaseous CO evolution as a transition between pyrolysis regimes, i e 400oC ( h i f li i
00.00030.00060.0009
0 200 400 600 800 1000
CO
Mol
e F
Oak
i.e. 400oC (mechanisms for lignin decomposition: Kawamoto (2003) and Demirbas (2000))
• Boudouard reactions
0 200 400 600 800 1000
Furnace Temperature (oC)
0.0025
0.003
• Boudouard reactions dominant above 800oC, enhanced CO production
Th id l b l0.001
0.0015
0.002
0.0025
Mol
e Fr
actio
n
Beachgrass
• The residual carbonyl groups in the char are decarboxylated to CO and CO2
0
0.0005
0 200 400 600 800 1000
CO
Pine
FUB – Nov 2010
Furnace Temperature ( o C)
Comparison of H2 Evolution for Woods vs. Grassesp 2•Steam gasification, (0%CO2)
•WGS reaction dominates 500-600oC0.00260.00325
0.0039
on
•Dehydrogenation reactions are
continuously occurring during0 000650.0013
0.00195
H2 M
ole
Frac
tio
Beachgrass
continuously occurring during
decomposition and devolatilization
•H2 consumption ceases sooner for
0
0.00065
400 500 600 700 800 900 1000
Furnace Temperature ( o C)
Spruce
H2 consumption ceases sooner for
cellulosic material that thermally
degrades sooner, resulting in H20.00260.00325
0.0039
actio
n
evolution rise earlier for cellulosic
material (mechanism for cellulose 0.000650.0013
0.00195
H2
Mol
e Fr
a
Pine Needles
Maple
FUB – Nov 2010
decomposition Demirbas (2000))0400 500 600 700 800 900 1000
Furnace Temperature ( o C)
Maple
Comparison of CH4 Evolution for Woods vs. Grasses
•Steam gasification, (0%CO2)
•350 500oC highest rate of lignin0 00030.00040.00050.0006
Frac
tion
•350-500oC highest rate of lignin decomposition
•CO available in reactor combines i h H f WGS i
00.00010.00020.0003
0 200 400 600 800 1000
CH
4 Mol
e Pine Needles
Pine
with H2 from WGS reaction to produce elevated CH4 levels from low To methanation reactions
0 200 400 600 800 1000
Furnace Temperature ( o C)
•Degradation of levoglucosan via hydrogenolysis involves repeated consumption of H2 in several steps,
0 0003
0.0004
0.0005
0.0006
Frac
tion
Beachgrass
thus decreasing competing CH4production near ~300oC (mechanism of cellulose decomposition Demirbas (2000))
0
0.0001
0.0002
0.0003
0 200 400 600 800 1000
CH
4 Mol
e F
Oak
FUB – Nov 2010
(2000)) 0 200 400 600 800 1000Furnace Temperature ( o C)
Waste Gasification 100 Heating Rate = 10
oC min-1
0.12
al M
ass (
%)
50
60
70
80
90
100 Heating Rate = 10 C min
0.08
0.1
ctio
n 20%30%
40%50%
Res
idua
0
10
20
30
40
50
0.04
0.06
O M
ole
Frac 10%
5%
% CO2 injectedReactor Temperature (oC)
0 200 400 600 800 1000
0
0.02
CO
0%
500 600 700 800 900 1000
Furnace Temperature ( oC )
• Enhanced CO production with CO
FUB – Nov 2010
• Enhanced CO production with CO2• Production begins to level off above 20% CO2
Value: CO2 Enhanced Char Burnout
• Identical time on stream, reaction
temperature profile total flow ratetemperature profile, total flow rate
• Physical evidence of more efficient
Walnut Shells: 0% CO2 Walnut Shells: 30% CO2
y f ff
gasification with CO2
Douglas Fir: 0% CO2 Douglas Fir: 30% CO2
~20% biomass
C C i COChar Pore Development- Enhanced Char Burnout With CO2
LigninLigninLignin Lignin
100% CO21oC/min
Lignin
100% CO21oC/min
Lignin
0% CO2 -H2O/N21oC/min,
FUB – Nov 2010
22-930oC 22-860oC 22-860oC
SEM - Douglas Fir Char Fiber Enhanced i d i ifi imicropore structure during steam gasification
Increased porosity following thermalthermal treatment
FUB – Nov 2010
CO2 impact on gasification productsCO2 impact on gasification products
1.00CO2 Variation
0.020CO2 Variation
0-1 ) 0 40
0.60
0.80 0% 5%10%15%20%30%
40%
2
1 )
0.015
0% 5%10%15%20%40%50%
CO2 Variation
Mol
e Fr
actio
n (1
0
0.04
0.20
0.40 40%50%
ole
Frac
tion
(10-
1
0.010
Increasing CO2
Increasing CO2
CO
M
0 01
0.02
0.03
H2 M
o0.005
Increasing CO2
Reactor Temperature (oC)
200 400 800 900 10000.00
0.01
R T (oC)
600 700 800 900 10000.000
FUB – Nov 2010
Reactor Temperature ( C)Fi 1 H d i i h CO ifi i
Reactor Temperature (oC)
CO increases with CO2 H2 decreases with CO2
H2/CO (Syngas) Tuning
4.5
5
5.5• Fuels • Chemicals• Combustion
SOFC operation
3
3.5
4
in g
asifi
er
• Fuel cellsGas Turbine Combustion – Low NOx operation/good stability
2
2.5
3
CO
pro
duce
d
Fisher Tropsch – diesel fuels
Fisher Tropsch – Fe & Co-based
0 5
1
1.5H2/C Catalyst processes
specialty chemicals
0
0.5
0% 10% 20% 30% 40% 50%
% CO dd d t ifi ti i fl t
FUB – Nov 2010
% CO2 added to gasification influent
Major Gasification Reactions
Water Gas Shift Steam GasificationLow Temperature High TemperatureWater Gas Shift
CO + H2O ⇋ CO2 + H2M th ti
C + H2O ⇋ H2 + CO
BoudouardMethanation
C + 2H2 ⇋ CH4C + CO2 ⇋ 2CO
2CO + 2H2 ⇋ CH4 + CO2CO + 3H2 ⇋ CH4 + H2O
Char Burnout: O (Biomass/Steam)C + ½O2 ⇋ CO
Steam GasificationC + H2O ⇋ H2 + CO
Reverse Water Gas ShiftCO + H ⇋ CO + H O
FUB – Nov 2010
C H2O H2 CO CO2 + H2 ⇋ CO + H2O
CO2 Impact on Coal
• Decrease in H2production with COproduction with CO2
• Increase in CO production with CO2
FUB – Nov 2010
MSW DATA
Mass % vs Temp for Varius Amounts of CO2100
80 20
25Area 1: water volatilization
20
25
Area 2: biomass degradation
ass %
605
10
15
5
10
15
Ma
40
20% CO210% CO2
700 750 800 850 900 950 10000
Area 3:
700 750 800 850 900 950 10000
0
20 5% CO22.5% CO2Inert1% CO2
Area 3: petrochemical degradation
Area 4: boudouard reaction (C O2 + C 2C O)
FUB – Nov 2010
Temperature (oC)0 200 400 600 800 1000
0
Gasification and Combustion: Operating facilityp g y
Current conditions found in combustors
Air atmosphere (20% O2, 80% N2)
Gasification/ pyrolysis (100% N2)
p ( 2, 2)
Lean atmosphere (6% O2, 94% N2)
FUB – Nov 2010
Mass Decomposition Curve•Bulk mass loss between 250-400oC
1.00
Bulk mass loss between 250-400 C through devolatilization and pyrolitic decomposition
Li ll l i d iti d
0.60
0.80
actio
n
Grasses
•Ligno-cellulosic decomposition due to gasification between 400-700oC
•High temperature reaction between Grasses
0.40
Mas
s Fra 700-900oC as oxygen in the biomass,
steam and recycle CO2 aid in char burnout
0 00
0.20
Woods•By 950oC nearly all of the biomass samples slowly heated at 10oC/min completed their mass burnout Woods0.00
0 200 400 600 800 1000
Temperature oC•Biomass samples having lower lignin content (alfalfa, maple bark and grasses) yield higher mass percent
FUB – Nov 2010
grasses) yield higher mass percent gasification residues
Combustion Comparisonswaste tires
40
O
30
6.9% - O2Air30% - O2
O
H2C CH2Epoxyethane
Mas
s (%
)
20
M
10
30% O2 Air
350 400 450 500 550 6000
6.9% O2
FUB – Nov 2010
Temperature (oC)
350 400 450 500 550 600
Experiment & Simulation Comparison
Combustion Gasification
Experiment & Simulation Comparison
Combustion Gasification
Model
Model
Model
FUB – Nov 2010
Experiment & Simulation “Scale Up”
TGA (~20 mg)TGA ( 20 mg)
O2/Coal=0.6
Image Source: Tondu Corporation, Houston, Texas 77079Plant Simulation (ASPEN ®)
O2/Coal=0.9O2/Coal=0.9CO2 Recycle
CO2 Recycle
FUB – Nov 2010
O2/Coal=0.6
Drop tube (~ 2 g/min)
Ballistic Heating @ ~700oC min-1
Mass Loss and Temperature continuously measured
Δt for test (~100 seconds)
Temperature (centigrade) achieved for test
FUB – Nov 2010
p g
Online gas analysis capability
Chemical Species with Ballistic Heating @ ~700oC min-1
Online gas analysis capabilityH2: MW = 2 g gmol-1C4’s HC: MW = 58 g gmol-1
Major Species
%) 75
80
Con
cent
ratio
n (%
15
20
70
Minor Species
1
hem
ical
Spe
cies
C
5
10
Con
cent
ratio
n (%
)
0.1
1
Temperature (oC)
200 400 800 825 850 875 900 925 950 975 1000
Ch
0
Che
mic
al S
peci
es C
0.01
Collection T(*C) vs N2 Collection T(*C) vs O2 Collection T(*C) vs CO Collection T(*C) vs CO2 Temperature (oC)
200 300 400 500 800 825 850 875 900 925 950 975 1000
C
0.001
Collection T(*C) vs H2
FUB – Nov 2010
Collection T( C) vs H2 Collection T(*C) vs CH4 Collection T(*C) vs Ethylene Collection T(*C) vs Ethane Collection T(*C) vs Acetylene Collection T(*C) vs Propylene Collection T(*C) vs Propane Collection T(*C) vs Butane
5 2 5
Major Chemical Species Results
3
4
5
ntra
tion
(%)
1000oCH2
1.5
2.0
2.5
entr
atio
n (%
)
800oC
O2
0
1
2
0 200 400 600 800 1000
H2 C
once
800oC
0.0
0.5
1.0
0 200 400 600 800 1000
O2 C
once
1000oC
0 200 400 600 800 1000
Temperature (oC)
0 200 400 600 800 1000
Temperature (oC)
7.5
9.0
(%) 1000
oCCO2.5
3.0
(%) 1000oC
CH4
3.0
4.5
6.0
O C
once
ntra
tion
800oC
1.0
1.5
2.0
4 Con
cent
ratio
n ( 1000 C
800oC
0.0
1.5
0 200 400 600 800 1000
Temperature (oC)
CO
0.0
0.5
0 200 400 600 800 1000
Temperature (oC)
CH
4
FUB – Nov 2010
• Increased H2 & similar CO productions with higher final temperature• Similar or increased O2 consumption
Fuel Synthesis: Aromatic Adjustment
N1 5
Peak Identification
20.7 16.66
15.6020.03
N
CH3
CH
2
36
FUB – Nov 2010
CH3
4 7
Summary• Reaction Mechanism Development Focused on Carbon
– New processes – Better conversion
• Carbon neutral energy production
• CO2 utilization
– New Technologies – Atom Economy
• Modification of renewable fuels with CO2
• Reforming of GHG – (e.g. LFG, stranded NG)
• Nano-dipersed CaO for equilibrium constrained reactionsreactions
• Fundamental understanding enables technology development
FUB – Nov 2010
Acknowledgments• Collaborators
– Tuncel Yegulalp, Columbia Univ.
– Robert Farrauto BASF Catalysts LLC
• Visiting Scholars – John Dooher, Adelphi University
– Zhixiao Zhang, Hangzhou University
• Post-DocsRobert Farrauto, BASF Catalysts, LLC.
• Students– Forrest Zhou
N i Kli h ff
Post Docs – Eilhann Kwon
– Heidi Butterman
– Maik Eichlebaum
Phili G– Naomi Klinghoffer
– Alexander McCurdy
– McKenzie Primerano
– Philipp Gruene
– Brian Wiess (ugrad)
– Kelly Westby (ugrad)
You, the audience for listening
FUB – Nov 2010
Please visit CCLlabs.org
• Industry Award: World’s Best Waste‐to‐Energy facilities:
• 2006 – ASM Brescia, Italy
• Industry Award: World’s Best Waste‐to‐Energy facilities:
• 2006 – ASM Brescia, Italy
http://www.seas.columbia.edu/earth/wtert/index.html
• 2004 – Martin GmbH, Germany
• Education Award: Person who has advanced Integrated Waste Management globally:
• 2004 – Martin GmbH, Germany
• Education Award: Person who has advanced Integrated Waste Management globally:
FUB – Nov 2010
• 2006 – Prof. Paul H. Brunner, Technical University of Vienna
• 2004 – Prof. George Tchobanoglous, University of California‐ Davis
• 2006 – Prof. Paul H. Brunner, Technical University of Vienna
• 2004 – Prof. George Tchobanoglous, University of California‐ Davis
