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June 2013
Klaus S. LacknerColumbia University
Carbon Managementand
The Importance of Thinking
Outside the Box
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World needs affordable andclean energy for all
Energy is central tohuman well-being
Clean energy overcomessustainability limits
Atmospheric CO2 levelmust be stabilized
Fossil carbon is notrunning out
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0
2
4
6
8
10
12
14
16
18
2000 2020 2040 2060 2080 2100
Fractional
Change
Year
Growth Relative to 2000
Constant Growth 1.6% Plus Population Growth to 10 billion Closing the Gap at 2%
Energy intensity drop 1%/yr Energy Intensity drop 1.5%/yr Energy Intensity drop 2% per year
Constant growth
Plus Population Growth
Closing the Gap
1% energy intensity reduction
1.5% energy intensity reduction
2.0% energy intensity reduction
Room for 21st century growth
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Future energy demand: 15 100 TW
15 TW: Current demand is a low-end prediction Extreme increases in efficiency Move away from production of physical goods Economic collapse (?)
50 TW: Business as usual With large drop in energy intensity
High efficiency, world wide transition to a service economy No new big energy drivers Economic stagnation (?)
100 TW: Past performance Energy consumption grew twelve fold between 1900 - 2000
Where do we find 50 - 100 TW?
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Fossil Fuels Are Plentiful
Coal resources alone could be 3000 to 5000 Gt C 400 Gt consumed since 1800 annual production of 8 Gt/yr of fossil carbon
Beware of resource vs. proven reserve
Curve fitting of past production does notmake the known resources go away
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Coal Fields in the US
anthracite bituminous bituminous subbituminous lignite coking coal
Source: wikipedia
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The change in Gas Scenarios
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Fossil fuels are fungible
Refining
Carbon
Diesel
Coal
Shale
Tar
Oil
Natural
Gas
Jet Fuel
Heat
Electricity
Ethanol
Methanol
DMEHydrogen
SynthesisGas
and they are not running out
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200
300
400
500
600
700
800
1900 1950 2000 2050 2100 2150 2200
Continued
ExponentialGrowth
Constant
Emissionsafter 2010
100%
of 2010 rate
33%
10%
0%Preindustrial Level
280 ppm
Hazardous Level
450 ppm
Hazardous Level
450 ppm
Stabilize CO2 concentration not CO2 emissions
CO2
(ppm)
year
Environmental Limits Not Resource Limits
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Fossil carbon sequestration
Carbon inputsand outputsmust match
Fossil carbon
Environment
Sequestration
Total carbon is conserved
Maintain or shrink the size of the carbon pool
7Mobilization of
carbon Fixation ofcarbon
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The personal carbon allowance
Picture from emercedes online blog: http://www.emercedesbenz.com/Aug08/08_001327_Mercedes_Benz_Econic_Semi_Trailer_Tanker_Trucks_Enter_Service_At_London_Farnborough_Airport.html
~ 30 tons for every person will reach 450 ppm
Permanent allotment
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Without Carbon Capture and Storageall fossil fuels will have to be phased out
The allowable CO2
concentrationlimits the effective resource size
Roughly: Emission of 4 Gt C raises atmospheric CO2 by 1 ppm
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The big three energy options
Solar energy Nuclear energy
Fossil energy(not necessarily coal)
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Cost effective, but cannot operate not at full scale
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Dividing The Fossil Carbon Pie
900 Gt C
total
550 ppm
Pastcenturies
1 trillion tons of CO2
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Removing the climate constraint
5000 Gt C
totalPast
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Net Zero Carbon Economy
CO2extraction
from air
Permanent &
safe disposal
CO2 from
concentrated
sourcesCapture from power
plants, cement, steel,
refineries, etc.
Geological Storage
Ocean disposal
Mineral carbonate disposalCCS is in troublewith the public
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NEW FIELDS NEED NEW IDEAS
CCS is still developing
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Challenging Nascent Orthodoxies
Economies of size or economies of numbers? New technologies need to start small
Sequestration is not just geological sequestration Do not put all eggs in one basked
Carbon dioxide capture is not for old coal plants Carbon is fungible
New fields must be givenroom to develop
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FINDING THE RIGHT SCALE
Example I
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Retrofits have to be big and low in cost
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Spot the low costpower plant
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Scaling: Surface to volume ratio
Surface to volume ratios can help or hurt Structurally size tends to hurt
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Separating Scale from Size
Power plants are big, cars are small100s of MW vs. 100 kW
Yet, cars operate on a bigger scaleCars produced in a single year have a power
capacity comparable to the US power grid.
8 million times 100 kW = 800 GW
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Economies of Size vs. Mass Production
Car engines are $10-$20/kW Power plants are $1000/kW or more
Operating life of a car engine is 5000 hours Extends to 20,000 if treated well
Efficiency is comparable to power plant If operating at optimal conditions
Operating large numbers is expensive
Large units require less labor
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Why did the Large Power Plant Win?
Power companies pay their operators Car companies are paid by the car operator Number of operators scales with number of units
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True in many industries
Mining Trucks
Cost of the driver matters
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Massively parallel infrastructures
Trend to smaller units is possible and on its way Nuclear plants are modularizing
Avoid the complexity of siting at large scale Chlorine production is modularizing
Demonstrating full automation
Smaller units pose smaller risks Eliminate transport of dangerous goods
Biomass gasification Distributed resource difficult to transport
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EconomiesofScalevs.
Unitcostdropsbyforeverydoublingofproduc5on
( ) 1,sizeCost
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The autonomous car
http://wot.motortrend.com/google-autonomous-car-testing-fleet-adds-lexus-rx-450h-logs-300000-miles-245621.html
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Economies of scale exact a big price
Individually engineered units Field assembled units High risk in making changes High hurdle to entry into market Slow turnaround Slow learning
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Small, modular, mass produced units
Allow rapid entry into a new market Promote learning and fast improvementsAdapt to changing markets and needs
Necessary ingredients for asuccessful new technology
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Shorter life cycle has advantages
Shorter life cycle reduces risks Smaller unit size lowers piloting costs Shorter development times lead to faster
progress Lower unit cost encourages experimentation
20 Generations from Henry Ford
2 Generations from Thomas Alva Edison
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NOT JUST GEOLOGICAL SEQUESTRATIONALTERNATE CARBON SINKS
Example II
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Ocean Disposal
Dilution as a solution?
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Underground Injection
statoil
Enhanced Oil Recovery
Deep Coal Bed Methane
Saline Aquifers
Storage Time
Safety
CostVOLUMEPerception &
Accounting
Concentrated disposal
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Mineral Sequestration:Accelerating Natural Weatherin
Mg3Si2O5(OH)4 + 3CO2(g) 3MgCO3 + 2SiO2 +2H2O(l)+63kJ/mol CO2
Safe and permanent storage optionHigh storage capacityPermanence on a geological time scaleClosure of the natural carbon cycle
Stable Waste Disposal
Question of cost and size
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Minerals are available
For solids: calcium or magnesium silicates
Molar abundance in the Earths crust
Calcium 2.0%
Magnesium 2.1%
Carbon 0.035%
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Peridotite and Serpentinite Ore Bodies
nn n
n
n
n
n
n
n
nn n
n
n
n
n
nn
n
nn
n
nn
n
n
n nn n
nn
n
nn
n
n
n
nn
nn
nn
n
n
n
n
nn
n nn
n
n
n
n n
n
n
n
n
nn
n
n
nn
n
n
n
nn
nn
nn
n
n
n
n
n n n
n nn n
n nn
nn
nn
n
n
n
n
nn n
n
n
n
n
n
n
nn
n
n
n
n
n
n
n
nn
nn
n nn
n n n
n
n
n
n
nnn
n
n
nn
n n
nn
nn n
n
n
n
nn
n nn
n
n
nnn
n
n
n
nn
n
nn
n
n
nn
nn
nnn
nn
n
n
n
n
nn
n
n
n
n
n
nn
n
nnn
n
n
n
n
nn
n n
n
n
n
n
n
n
n
nn
n
Magnesium resources far exceed world fossil fuel
supplies
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Basalts are far more common
Wikipedia CommonsLIP: Large Igneous Province
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Energy States of Carbon
Carbon
Carbon Dioxide
Carbonate
400 kJ/mole
60...180 kJ/mole
The ground state of carbonis a mineral carbonate
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Challenges for Mineral Carbonation
Cost R&D to speed up the complex chemistry Find by-products, or become the by-product
Carbonate tailings, use carbonic acid for extraction of values Find ways to live with slower speeds
Underground mineralizationAir exposure of minerals
Mining scale Remote locations are preferable Need nearby sources of CO2 (air)
Mining impacts and mined materials Trace elements Mined materials can be hazardous Different outlook because this is environmental remediation
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Belvidere Mountain, Vermont
Serpentine Tailings
Asbestos and Serpentine Spontaneous carbonation (Dipple et al.)
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BEYOND RETROFITS:ADVANCED PLANT DESIGNSNATURAL GAS SCRUBBING
AIR CAPTURE
Example III
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Retrofits wont work
sequestration cost becomes part of coal cost$30/t CO2 > $100t coal
Plus: reduced energy efficiencyEffective coal cost goes from $30/t to > $160/t
Natural gas power cannot be ignoredConventional scrubbing even
more difficult
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Focus on next generation plants
Zero emissions No release to the atmosphere
Ultra-high efficiency Fuel cell technology Hydrogen and/or electricity Synthetic fuels CO2as by-product where possible
Gasification, oxyfuel Entry point for advanced designs NGCC plants are strong competitors
Applies to natural gas as well
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Boudouard Reaction
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Air capture provides options
Maintaining access to fossil fuels Air capture as part of CCS Focus on dispersed and mobile sources Complementing power plant capture
Air capture with non-fossil energy Allowing liquid fuels in the transportation sector Synthetic fuel production from CO2 and H2O Requires cheap non-fossil energy
Air capture for drawing down CO2 First emissions must be stopped or canceled out Provides no excuse for procrastination
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Can bootstrap from small scales
Small existing CO2 markets make it possible to start Without government support for huge pilot plants With a profitable learning phase Learning on a small scale Basic R&D would be helpful
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Separation of emissions and mitigation
Create an industry that wants CO2 reductions Foster competition, on an international scale Drive down costs of alternatives
Create a world wide carbon price
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After initial work at bothLos Alamos and Columbia
GRT* demonstrated aircapture in Tucson in 2007**
Klaus Lackner
Allen WrightGary Comer
Proof of principle
*Now Kilimanjaro Energy, Inc.**KSL is an advisor the company
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Demonstration unit
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55 SOURCE: National Research Council (1987)
Not your run of the mill separation problem
Sherwoods Law for minerals ~ $10/ton of ore
U from seawater
Air capture aspirations
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Artificial kelp to absorb uranium from seawater
Passive, long term exposure to water Braids of sorbent covered buoyant plastic Anchored to the floor Replaced initially active systems
Low energy sorbent Laminar flow over sorbent Uptake is limited by boundary layer transport
Regeneration After harvesting the strings
Gross violation of Sherwoods Law Cost estimates range from $200 to $1200/kg Sherwood $3 million/kg
wikipedia
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Air capture flue gas separation
APS Study (Socolow et al.) Too difficult, too costly, not practical $600 per ton of CO2
House et al. Dilution is too extreme Separation technology cannot be extrapolated Second law efficiency unavoidably deteriorates
Conclusion: Dont try to extrapolate Conventional technologies will have difficulties Too much of an extrapolation Extrapolation raises costs and uncertaintiesNeed non-conventional approach from the start
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Technical challenges of air capture
Move huge volumes of air cheaply This is the term Sherwood warned you about Make good contact at low pressure drops
Like a tree, like a lung, passive designs are favored Avoid water capture
There is far more water than CO2 in the air Avoid emissions of entrained liquid, vapors etc.
Need to clean up the air Avoid expensive energy
Low grade heat, water evaporation, wind energy Find ways of bootstrapping from small niche markets
Start small and grow Take advantage of learning
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Out-of-the-box thinking
No extrapolation
from here
to there
Start from first principlesand
air capture becomes feasible
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CO2
1 m3
of Air40 moles of gas, 1.16 kg
wind speed 6 m/s
0.016 moles of CO2
produced by 10,000 J of
gasoline
0.4 liter/m3 of CO2
2
20 J
2
mv
=
Volumes are drawn to scale
Still plenty of CO2 in air
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Thermodynamics works
Separation Process
involvingSorbents
Membranes
etc.
Air (P0, P1)
CO2 (P0, P0)
CO2
depleted
air
Theoretical minimum free energyrequirement for the regeneration is thefree energy of mixing
Specific irreversible processes havehigher free energy demands
(P0, P2)
Gas pressure P0CO2 partial pressure PxDenoted as (P0, Px)
= &'0 21 2-10 ln
10 '0 11 2-
20 ln20 + '
0 10 - '0 20 -
01 2 ln0 10 2
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Air Capture Free Energy
0
10
20
30
40
50
60
0 10 20 30 40
Fre
eEnergyRequirement(kJ/
mol)
Exit Partial Pressure (Pa)
Thermodynamic Limit
Single Sorbent
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depends logarithmically on CO2 concentration
at collector exit
Sorbent Strength
-30
-25
-20
-15
-10
-5
0
100 1000 10000 100000
CO2 Partial Pressure (ppm)
Fre
eEnergy(kJ/mole)
350K
300KAir Power plant
G = RT log P
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Inspiration comes from nature
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Considered many different options
Contacting Convection towers, fans, passive designs
Liquid and solid sorbents Solutions and slurries Packed beds, packings, and filter boxes
Different sorbents Hydroxides and carbonatesAmines and physisorption
Regeneration High temperature calcination routes Low grade heat, thermal swings Pressure swings, combined with thermal swings Electrochemistry
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Moisture swing: Serendipity
We were in a position to compare and see easier regeneration
just add water, no heat losses, no chemical losses suitability for passive systems
flexible sorbent designs can handle low recovery rates
no emissions that would require processing exit air stream compatibility with pressure and thermal swing
Combined with other swings, moisture lowers the temperatureand/or pressure amplitude
Prevents thermal damage to sorbents (100,000 cycles) water acts as cheap fuel
Direct energy demand is greatly reduced
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Free energy from water evaporation
Separation Process
involvingSorbents
Membranes
etc.
Dry air
Moist air
Liquid
Water
CO2
enriched air
Free energy of water evaporationat a relative humidity RH:G = RTln(P/Psat) = RT ln(RH)
Ball park estimate: 2.5 kJ/mol140 MJ/m3
@ 20/m3 0.5/kWh
Water evaporation can drive CO2 captureEnthalpy is balanced by cooling the large air volume (T 3K)
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Anionic Exchange Resins
Solid carbonate solution
Quaternary ammonium ions form strong-base resin
GRT photo
Positive ions fixed to polymer matrix Negative ions are free to move Negative ions are hydroxides, OH-
Dry resin loads up to bicarbonate OH- + CO2 HCO3- (hydroxide bicarbonate)
Wet resin releases CO2 to carbonate 2HCO3- CO3-- + CO2 + H2O
Moisture driven CO2 swing
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Membrane material
Snowpureelectrochemical membrane(1mm thick)
Polypropylene matrix withembedded fine resinparticles (25m)
Quaternaryammonium cationsCarbonate/bicarbonate
form
1.7 mol/kg chargeequivalent
thin sheets
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The Moisture Swing
Absorption Isotherm Dry
0.9
0.91
0.92
0.93
0.94
0.95
0.96
0.97
0.98
0.99
1
0.8
0.82
0.84
0.86
0.88
0.9
0.92
0.94
0.96
0.98
1
0 200 400 600 800
Saturation
CO2 Concentration(ppm)
CO3 Exp
CO3 Langmuir
OH Exp
OH Langmuir
Tao Wang et al
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The Moisture Swing
Desorption Isotherm - Wet
00.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
0 2 4 6 8
Saturation
EquilibriumCO2 PartialPressure(kPa)
24 Celsius Exp
35 Celsius Exp
45 Celsius Exp
24 Celsius
Langmuir
35 Celsius
Langmuir
45 Celsius
Langmuir
Tao Wang et al
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The moisture swing
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CO2 loading at constant PCO2 = 40Paand varying PH2O
0(, ) = + (1 + ) + ( 0)
K. S. Lackner
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The standard free energy change
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Water vs. carbon dioxide
CO3
2(R+)2
H2
O + C O2(g)
2(HCO3
R+ H2
O) + ( 2 1)H2
O(g)
= 2 1
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CO2 partial pressure vs. resin water loading
T= 25C
First data to show dependence on resins water loading rather than water vapor partial pressure
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The moisture swing design
Boost partial pressure of CO2 from 40 Pa to 5,000 Pa (50 kPa)use water to pay for the compression
Flexible designadd pressure swingadd thermal swing featurespreprocess for moisture removal
First stage in multistep processutilize very cheap chemical potential
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Multiple options to create pure CO2
OptionsSecond stage physisorptionVacuum extractionWashing with carbonate
Combines with other technologies
Optionality complicates analysis, but lowers riskand raises flexibility
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Make the air do your work
Air carries kinetic energy sufficient to move the air
Air carries thermal energy sufficient to evaporate water
Air carries chemical potential out of equilibrium with water sufficient to compress CO2 two
hundredfold
Take advantage of the resource you have
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The energy cost of active fanning
0
2
4
6
8
10
12
14
0 100 200 300 400
GJ/ton
ppm removed
100 Pa
250 Pa
500 Pa
Blower efficiency not included
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Matching air drag to CO2 capture
Balance the FILTER design Capture momentum (viscous drag) and CO2 (diffusion)
Design for a velocity vand a pressure drop P Diffusion (and turbulent transport) is similar for momentum and CO2
Match air-side transport resistance to sorbent side resistance High air-side resistance strong sorbent limit thick diffusion layer
Maximizes CO2 uptake for a given pressure drop Underutilizes sorbent material
Low air-side resistance weak sorbent limits thin diffusion layer Maximizes sorbent utilization Reduced CO2 uptake for a given pressure drop
Optimal pressure drop is O(v2) Free to choose v: Choose a low flow velocity vthrough filter For wind w2 > v2
Novel design strategy for air capture:decouple pressure drop from CO2 uptake
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The air is full of water
The air carries 10 to 100 times as much H2O as CO2You cant just suck the water out and pay for it
Options:Hydrophobic CO
2sorbent: ???
Wet regeneration: water consumption, performanceWater must not compete for adsorption site
Moisture swing: Built-in water managementWater and CO2 are counter-cyclicalWe cool during adsorption and produce heat during release
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Going to Scale
10 million units @ 1/tonne per daycapture 3.6 Gt CO2 per year (12% of emissions)Require annual production of 1 million (10yr life)
Compared to 70 million cars and light trucks 100 million units would lower CO2 in the air
O t d it
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One ton per day unit100 million units wouldeliminate all emissions
world production of cars:70 million per year
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86 Shanghai container port, wikipedia picture
Shanghai harbor process 30 million containers a year
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P di ti i diffi lt
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Prediction is difficult
started at $600/t CO2avoided at the tailpipe
too inefficient
to lift its ownweight
Price dropped fortyfold
Price droppedhundredfold
Cost of lighting dropped7000 fold in the 20thcentury
Wikipedia pictures
Our ingredient costs are small (resin, power, water etc.)
$600
$500
$400
$300
$200
$100
$0
APS (low tech)
GRT (first of a kind)
Current estimates
CO2 enriched air
Per ton CO2
Raw material and energy limit
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Conclusion
Moisture swing is a versatile air capture step Boosts CO2 pressure 100-fold to 0.01 to 0.1 bar (today to 0.05 bar) Interfaces with passive contacting Eliminates water loss as a problem Initial 200-fold pressure amplification without direct energy input Can eliminate concerns over losses to the atmosphere Can completely eliminate heat losses Can interface with any flue-gas like separation process to produce
pure CO2
Moisture swing can improve all othertechnologies
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A NEW IDEA: REMOTE CCS
Looking forward
A h t i l t ti
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A new approach to mineral sequestration
Solve the NIMBY/NUMBY problem by moving to remote sites Air capture can work in the remote locations favored by mines
Start at near zero cost and accelerate a spontaneous process Peridotite mine tailings carbonate spontaneously (G. Dipple) Even a low carbon price can motivate additional effort Air capture can avoid the cost of pressurization and purification of CO2
Mining engineering of in situ carbonation on tailings or mineral heaps CO2 enhanced air flowing through engineered tailing piles Bicarbonate brines flowing through tailing piles or ponds Compensate for mine emissions Improve tailing stability, strengthen environmental remediation
Mineral processing in reactor vessels For improved metallurgical extraction (improved flotation properties etc.) For stabilizing alkaline wastes For freeing alkalinity to neutralize strong acids For enhanced carbonation
Develop processes, monitoring and verification techniques
Eli i t th bi t
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Eliminate the big costs
Avoid compression and pipelining of CO2Air capture to produce CO2 enriched air or bicarbonate brineAt least half the energy goes to compression On site capture avoids the high energy step
Use slow but cheap carbonation reaction Tailing pond or tailing pile processing Slow but possibly cost effective
A little happens for free Thus we can start at a low cost point
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A NEW IDEA: CCU
Looking forward
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Carbon based non fossil fuels
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EnergySource
H2O H2O
O2
O2
Carbon based non-fossil fuels
Power Consumer
Powergenerator
H2 CH2
CO2
Carbon Cycle
Enhancing the biological cycle
Carbon neutral energy systems
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Carbon neutral energy systems
Nuclear and
renewable energy
Coal, tar, shale
Natural Gas
Petroleum
Synthesis GasCO2 and H2O
inputs
Electricity
Liquid Fuel
Stationary energy
demand
Mobile energydemand
electrolysis
Air captureFischer Tropsch
CCS
Energy Sources Conversion Outputs
CarbonStorage
CO2 scrubbing
Carbon neutral energy systems
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Carbon neutral energy systems
Nuclear and
renewable energy
Coal, tar, shale
Natural Gas
Petroleum
Synthesis GasCO2 and H2O
inputs
Electricity
Liquid Fuel
Stationary energy
demand
Mobile energydemand
electrolysis
Air captureFischer Tropsch
CCS
Energy Sources Conversion Outputs
CarbonStorage
CO2 scrubbing
Carbon neutral energy systems
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Carbon neutral energy systems
Nuclear and
renewable energy
Coal, tar, shale
Natural Gas
Petroleum
Synthesis GasCO2 and H2O
inputs
Electricity
Liquid Fuel
Stationary energy
demand
Mobile energydemand
electrolysis
Air captureFischer Tropsch
CCS
Energy Sources Conversion Outputs
CarbonStorage
CO2 scrubbing
energy storage
New ideas change the world
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New ideas change the world
Steam Engine Trains & Ships TelephonesAutomobile TelevisionAirplanes Internet
Unpredicted andunmodeled, theseinventions changed the
course of future societaldevelopments inunexpected ways
It is not all about technology
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Private SectorCarbon
ExtractionCarbon
SequestrationFarming, Manufacturing, Service, etc.
Certified Carbon Accounting
certificates
certification
Public Institutions
and GovernmentCarbon Board
guidance
It is not all about technology
Increased cost favor non-fossil alternatives
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Economy must decarbonize fast
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Stabilization point (ppm of CO2)
450 ppm 7.3% annual reduction550 ppm 5.2% annual reduction650 ppm 4.8% annual reduction750 ppm 4.6% annual reduction
Economy must decarbonize fast
Ca
rbonintensityr
eduction(%)
Annual reduction in the worlds carbon intensity (CO2/GDP)