K. Lackner - Carbon Management and the Importance of Thinking Outside the Box

7/28/2019 K. Lackner - Carbon Management and the Importance of Thinking Outside the Box

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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

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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

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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

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0.8

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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

i l


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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

C l i


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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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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



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Nuclear and

renewable energy

Coal, tar, shale

Natural Gas

Petroleum


inputs

Electricity

Liquid Fuel

Stationary energy

demand

Mobile energydemand

electrolysis


CCS


CarbonStorage

CO2 scrubbing



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Nuclear and

renewable energy

Coal, tar, shale

Natural Gas

Petroleum


inputs

Electricity

Liquid Fuel

Stationary energy

demand

Mobile energydemand

electrolysis


CCS


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)

Documents

K. Lackner - Carbon Management and the Importance of Thinking Outside the Box