Carbon Management and The Importance of Thinking Outside the Box

Klaus S. Lackner Columbia University

June 2013

Energy is central to human well-being World needs affordable and clean energy for all Clean energy overcomes sustainability limits

Atmospheric CO2 level must be stabilized Fossil carbon is not running out

Room for 21st century growth Growth Relative to 2000

18 16 14
Closing the Gap

Fractional Change

12 10 8 6 4 2 0 2000
Plus Population Growth 1% energy intensity reduction Constant growth 1.5% energy intensity reduction 2.0% energy intensity reduction

2020

2040

Year

2060

2080

2100

Constant Growth 1.6% Energy intensity drop 1%/yr

Plus Population Growth to 10 billion Energy Intensity drop 1.5%/yr

Closing the Gap at 2% Energy Intensity drop 2% per year

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?

4

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 not make the known resources go away

Coal Fields in the US

anthracite

bituminous

bituminous

subbituminous
6

lignite

coking coal Source: wikipedia

The change in Gas Scenarios

Fossil fuels are fungible

Coal Shale Tar Oil Natural Gas Refining Synthesis Gas Carbon Diesel Jet Fuel Ethanol Methanol DME Hydrogen Heat Electricity

and they are not running out

8

Environmental Limits Not Resource Limits

Stabilize CO2 concentration not CO2 emissions
800 700
CO2 (ppm)
Continued Exponential Growth Constant Emissions after 2010 100% of 2010 rate

600 500 400 300 200 1900

Hazardous Level 450 ppm

33% 10% 0%

Preindustrial Level 280 ppm

1950

2000
9

2050

year

2100

2150

2200

Fossil carbon sequestration

Fossil carbon Mobilization of carbon

Carbon inputs and outputs must match

Environment

Sequestration Fixation of carbon

Total carbon is conserved Maintain or shrink the size of the carbon pool
10

The personal carbon allowance

~ 30 tons for every person will reach 450 ppm Permanent allotment

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

11

Without Carbon Capture and Storage all fossil fuels will have to be phased out

The allowable CO2 concentration limits the effective resource size

Roughly: Emission of 4 Gt C raises atmospheric CO2 by 1 ppm

12

The big three energy options

Solar energy Nuclear energy

Fossil energy (not necessarily coal)

13

Cost effective, but cannot operate not at full scale

14

Dividing The Fossil Carbon Pie

900 Gt C total
Past centuries

1 trillion tons of CO2

550 ppm
15

Removing the climate constraint

5000 Gt C total

Past

16

Net Zero Carbon Economy

CO2 from concentrated sources
Capture from power plants, cement, steel, refineries, etc.

CO2 extraction from air

Permanent & safe disposal

Geological Storage Ocean disposal Mineral carbonate disposal

CCS is in trouble with the public

CCS is still developing

NEW FIELDS NEED NEW IDEAS

18

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 given room to develop

19

Example I

FINDING THE RIGHT SCALE

20

Retrofits have to be big and low in cost

21

Spot the low cost power plant

22

Scaling: Surface to volume ratio

Surface to volume ratios can help or hurt Structurally size tends to hurt

23

Separating Scale from Size

Power plants are big, cars are small
100s of MW vs. 100 kW

Yet, cars operate on a bigger scale

Cars produced in a single year have a power capacity comparable to the US power grid.
8 million times 100 kW = 800 GW

24

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

25

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

26

True in many industries

Mining Trucks

Cost of the driver matters

27

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

28

Economies of Mass Economies of Scale vs. Manufacturing Cost = C0 (size) , < 1

Monolithic Plant

Unit cost drops by for every doubling of produc5on

Modular Plant

Total cost = C0 N Empirically: 1 + log2 Automa5on can eliminate personnel cost Small scale allows for a modular approach Focus is on tying informa5on networks to machinery
29

1+ log2

Images courtesy of Wikipedia

The autonomous car

http://wot.motortrend.com/google-autonomous-car-testing-fleet-adds-lexus-rx-450h-logs-300000-miles-245621.html

30

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

31

Small, modular, mass produced units Allow rapid entry into a new market Promote learning and fast improvements Adapt to changing markets and needs

Necessary ingredients for a successful new technology

32

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

33

Example II

NOT JUST GEOLOGICAL SEQUESTRATION ALTERNATE CARBON SINKS

34

Ocean Disposal

Dilution as a solution?
35

Underground Injection

Enhanced Oil Recovery Deep Coal Bed Methane Storage Time Saline Aquifers Safety Cost

VOLUME Perception & Accounting

Concentrated disposal
36

statoil

Mineral Sequestration: Accelerating Natural Weathering

Mg3Si2O5(OH)4 + 3CO2(g) 3MgCO3 + 2SiO2 +2H2O(l) +63kJ/mol CO2

Safe and permanent storage option High storage capacity Permanence on a geological time scale Closure of the natural carbon cycle

Stable Waste Disposal Question of cost and size

37

Minerals are available

For solids: calcium or magnesium silicates Molar abundance in the Earths crust Calcium Magnesium Carbon 2.0% 2.1% 0.035%

38

Peridotite and Serpentinite Ore Bodies

n n n n n

n n nn

n n n nn n nn nn n

n nn n n n nn n n nn n n n n nnn n n n n nn n nn n

nn n n n

nn n nn nn n n n n n n nn n n
n n

n n

n n n n n nn n

n n nn n n n n n

nn n n n n n n n nnn n

n nn nn n

n n

n n nn n n n nn nn

n n
n

nn

n nn

nn n

n n n n n n nn n n n

n nn n n

n nn
n n n

n
nn n

n nn n

n nn n n n nn n nn n n n n n
n

n n nn n n n n n n

n n n n n

n n

n n

Magnesium resources far exceed world fossil fuel supplies

39

Basalts are far more common

LIP: Large Igneous Province

40

Wikipedia Commons

Iceland CarbFix Project

CO2 injection and monitoring area

CO2 from condensers

Steam, gases and water from deep and hot (>240 C) geothermal wells

Hellisheii geothermal power plant

41

Energy States of Carbon

Carbon The ground state of carbon is a mineral carbonate

400 kJ/mole

Carbon Dioxide
60...180 kJ/mole

Carbonate

42

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 mineralization Air 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
43

Belvidere Mountain, Vermont Serpentine Tailings Asbestos and Serpentine Spontaneous carbonation (Dipple et al.)

44

Example III

BEYOND RETROFITS: ADVANCED PLANT DESIGNS NATURAL GAS SCRUBBING AIR CAPTURE
45

Retrofits wont work

sequestration cost becomes part of coal cost
$30/t CO2 > $100t coal
Plus: reduced energy efficiency

Effective coal cost goes from $30/t to > $160/t

Natural gas power cannot be ignored Conventional scrubbing even more difficult
46

Focus on next generation plants

Zero emissions
No release to the atmosphere

Ultra-high efficiency
Fuel cell technology Hydrogen and/or electricity Synthetic fuels CO2 as by-product where possible

Gasification, oxyfuel
Entry point for advanced designs NGCC plants are strong competitors

Applies to natural gas as well

47

Boudouard Reaction

48

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

49

Air capture is the capture of last resort

Can handle emissions from any and all sources Sets upper limit on cost of carbon management Assures feasibility of zero carbon scenarios Provides a solution to the risk of leaking storage
50

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

51

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

52

After initial work at both Los Alamos and Columbia GRT* demonstrated air capture in Tucson in 2007** Klaus Lackner Allen Wright Gary Comer

Proof of principle

*Now **KSL

Kilimanjaro Energy, Inc. is an advisor the company

53

Demonstration unit

54

Not your run of the mill separation problem

Sherwoods Law for minerals ~ $10/ton of ore

U from seawater

Air capture aspirations

55

SOURCE: National Research Council (1987)

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

56

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 uncertainties

Need non-conventional approach from the start

57

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

58

Out-of-the-box thinking
No extrapolation

from here to there

Start from first principles and air capture becomes feasible
59

Still plenty of CO2 in air

1 m3of Air
40 moles of gas, 1.16 kg wind speed 6 m/s

mv 2 = 20 J 2
0.016 moles of CO2
CO2

produced by 10,000 J of gasoline 0.4 liter/m3 of CO2

Volumes are drawn to scale

60

Thermodynamics works
Theoretical minimum free energy requirement for the regeneration is the free energy of mixing Gas pressure P0 CO2 partial pressure Px Denoted as (P0, Px)
CO2 (P0, P0)

Separation Process involving

Air (P0, P1)

Sorbents Membranes etc.

CO2 depleted air (P0, P2)

0 2 1 1 0 1 2 2 0 1 0 2 0 0 1 = &' - ln ' - ln + ' -' ln 2 1 2 0 0 1 2 0 0 0 0 1 2 0 2

Specific irreversible processes have higher free energy demands

61

Air Capture Free Energy

60 Free Energy Requirement (kJ/ mol) 50 40 30 20 10 0 0 10 20 30 Exit Partial Pressure (Pa)
62

Thermodynamic Limit Single Sorbent

40

Sorbent Strength
depends logarithmically on CO2 concentration at collector exit G = RT log P
0

Free Energy (kJ/mole)

-5 -10 -15 -20 -25 -30 100

350K Air 300K Power plant

1000
63

10000

100000

CO2 Partial Pressure (ppm)

Inspiration comes from nature

64

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 carbonates Amines and physisorption

Regeneration
High temperature calcination routes Low grade heat, thermal swings Pressure swings, combined with thermal swings Electrochemistry
65

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 temperature and/or pressure amplitude Prevents thermal damage to sorbents (100,000 cycles)

water acts as cheap fuel

Direct energy demand is greatly reduced

66

Free energy from water evaporation

Water evaporation can drive CO2 capture Enthalpy is balanced by cooling the large air volume (T 3K)

Separation Process
Dry air Liquid Water

CO2 enriched air

involving Sorbents Membranes etc.

Moist air

Free energy of water evaporation at a relative humidity RH: G = RT ln(P/Psat) = RT ln(RH)

67

Ball park estimate: 2.5 kJ/mol 140 MJ/m3 @ 20/m3 0.5/kWh

Anionic Exchange Resins

Solid carbonate solution Quaternary ammonium ions form strong-base resin

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

GRT photo

Moisture driven CO2 swing

68

Membrane material thin sheets

Snowpure electrochemical membrane (1mm thick) Polypropylene matrix with embedded fine resin particles (25m) Quaternary ammonium cations Carbonate/bicarbonate form 1.7 mol/kg charge equivalent

69

The Moisture Swing

Absorption Isotherm Dry
1 0.98 0.96 0.94 0.92 0.9 0.88 0.86 0.84 0.82 0.8 1 0.99 0.98 0.97 0.96 0.95 0.94 0.93 0.92 0.91 0.9
CO3 Langmuir
CO3 Exp

Saturation

OH Exp

OH Langmuir

0
Tao Wang et al

200

400

600

800

CO2 Concentration (ppm)

70

The Moisture Swing

Desorption Isotherm - Wet
1 0.9 0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0
0 2 4 6 8
24 Celsius Exp

35 Celsius Exp

Saturation

45 Celsius Exp

24 Celsius Langmuir
35 Celsius Langmuir 45 Celsius Langmuir

Equilibrium CO2 Partial Pressure (kPa)

Tao Wang et al
71

The moisture swing

72

CO2 loading at constant PCO2 = 40Pa and varying PH2O

K. S. Lackner

0 (, ) = + (1 + ) + ( 0 )
73

The standard free energy change

74

Water vs. carbon dioxide

+ + CO2 3 (R )2 H2 O + CO2 (g ) 2(HCO3 R H2 O) + ( 2 1)H2 O(g )

= 2 1

75

CO2 partial pressure vs. resin water loading

T= 25C

First data to show dependence on resins water loading rather than water vapor partial pressure
76

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 design
add pressure swing add thermal swing features preprocess for moisture removal

First stage in multistep process

utilize very cheap chemical potential
77

Multiple options to create pure CO2

Options
Second stage physisorption Vacuum extraction Washing with carbonate

Combines with other technologies

Optionality complicates analysis, but lowers risk and raises flexibility

78

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

79

The energy cost of active fanning

14 12 10 GJ/ton 8 6 4 2 0
0 100 200 300 ppm removed
80

100 Pa 250 Pa 500 Pa

400

Blower efficiency not included

Cost of air capture?

Cost C as function of dilution D = 1/P C = C1 D + C2 + C3 log D Constants depend on technology choice
C1 : contacting the air stream
Passive system sitting in the wind

C2 : handling of sorbent material (transport etc.)

Likely small, can be very much limited

C3 : sorbent regeneration

Not much different from flue gas scrubbing

81

Matching air drag to CO2 capture

Balance the FILTER design
Capture momentum (viscous drag) and CO2 (diffusion)
Design for a velocity v and a pressure drop P Diffusion (and turbulent transport) is similar for momentum and CO2 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

Match air-side transport resistance to sorbent side resistance

Optimal pressure drop is O(v2 )

Free to choose v: Choose a low flow velocity v through filter For wind w2 > v2

Novel design strategy for air capture: decouple pressure drop from CO2 uptake
82

The air is full of water

The air carries 10 to 100 times as much H2O as CO2 You cant just suck the water out and pay for it Options: Hydrophobic CO2 sorbent: ??? Wet regeneration: water consumption, performance Water must not compete for adsorption site Moisture swing: Built-in water management Water and CO2 are counter-cyclical We cool during adsorption and produce heat during release
83

Going to Scale
10 million units @ 1/tonne per day
capture 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

84

One ton per day unit

100 million units would eliminate all emissions
world production of cars: 70 million per year

85

Shanghai harbor process 30 million containers a year

86

Shanghai container port, wikipedia picture

The cost estimation fallacy

1980s: $20 per disk

2011: $0.10 per disk

87

Prediction is difficult
Per ton CO2

$600

APS (low tech)

too inefficient to lift its own weight

$500

Cost of lighting dropped 7000 fold in the 20th century

Price dropped fortyfold

$400
Price dropped hundredfold

$300
GRT (first of a kind)

$200
Current estimates

$100
CO2 enriched air Raw material and energy limit

started at $600/t CO2 avoided at the tailpipe

$0

Our ingredient costs are small (resin, power, water etc.)

88
Wikipedia pictures

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 other technologies

89

Looking forward

A NEW IDEA: REMOTE CCS

90

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 For For For For improved metallurgical extraction (improved flotation properties etc.) stabilizing alkaline wastes freeing alkalinity to neutralize strong acids enhanced carbonation

Mineral processing in reactor vessels

Develop processes, monitoring and verification techniques

91

Eliminate the big costs

Avoid compression and pipelining of CO2
Air capture to produce CO2 enriched air or bicarbonate brine At least half the energy goes to compression On site capture avoids the high energy step 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

Use slow but cheap carbonation reaction

92

Looking forward

A NEW IDEA: CCU

93

All carbon dioxide emitted to the air will need to be recaptured

94

Fuels from electricity: Hydrogen

O2

Hydrogen Cycle
O2 H2
Power Consumer

Power generator

Energy Source

H2O
95

H2O

Carbon based non-fossil fuels

O2 CO2 O2
Energy Source

H2

CH2
Power Consumer

Power generator

Carbon Cycle
H2O
96

H2O
Enhancing the biological cycle

Carbon neutral energy systems

Energy Sources

Conversion

Outputs

Nuclear and renewable energy electrolysis Coal, tar, shale Synthesis Gas Natural Gas

Electricity

Stationary energy demand CO2 scrubbing CO2 and H2O inputs CCS Carbon Storage

Fischer Tropsch

Air capture

Petroleum

Liquid Fuel

Mobile energy demand

97

Carbon neutral energy systems

Energy Sources

Conversion

Outputs

Nuclear and renewable energy electrolysis Coal, tar, shale Synthesis Gas Natural Gas

Electricity

Stationary energy demand CO2 scrubbing CO2 and H2O inputs CCS Carbon Storage

Fischer Tropsch

Air capture

Petroleum

Liquid Fuel

Mobile energy demand

98

Carbon neutral energy systems

Energy Sources

Conversion

Outputs

Nuclear and renewable energy electrolysis Coal, tar, shale Synthesis Gas Natural Gas

Electricity

Stationary energy demand CO2 scrubbing CO2 and H2O inputs CCS Carbon Storage

Fischer Tropsch

Air capture

energy storage
Petroleum Liquid Fuel Mobile energy demand

99

New ideas change the world

Steam Engine Trains & Ships Telephones Automobile Television Airplanes Internet

Unpredicted and unmodeled, these inventions changed the course of future societal developments in unexpected ways
100

It is not all about technology

Public Institutions and Government
guidance

Carbon Board
certification

Private Sector
Carbon Carbon Farming, Manufacturing, Service, etc. Extraction Sequestration

Certified Carbon Accounting

certificates

Increased cost favor non-fossil alternatives

101

102

Economy must decarbonize fast

Annual reduction in the worlds carbon intensity (CO2/GDP) Carbon intensity reduction (%)
450 ppm 7.3% annual reduction 550 ppm 5.2% annual reduction 650 ppm 4.8% annual reduction 750 ppm 4.6% annual reduction

Stabilization point (ppm of CO2) Must overcome 3% economic growth plus 1% population growth
103