Adaptive Utilization of Carbon Dioxide Brent R. Constantz, Ph.D.

Geological & Environmental Sciences

FAILURE IS ONLY A PRELUDE TO SUCCESS

- TOMAS FOGARTY, MD, INVENTOR

Policy Path

Lentz, TM, 2010. Carbon Management 1(1), 145-160

Timothy M. Lenton Carbon Management, 2010, 1(1), 145 - 160

THE ACCEPTED POLICY APPROACH TO ACHIEVING STABILIZATION (OF ATMOSPHERIC CARBON DIOXIDE CONCENTRATION) IS TO RAPIDLY REDUCE CARBON DIOXIDE EMISSIONS TO MATCH NATURAL (LAND AND OCEAN) SINKS, AND THEN SLOWLY REDUCE CARBON DIOXIDE EMISSIONS TO ZERO AT THE SAME RATE THAT NATURAL SINKS DECAY.

Modern global anthropogenic carbon emissions.

Coal Production: Selected Countries

Coal will be the primary source of electricity for the world for the next century

Source: EIA Annual Energy Review 2007

U.S. Electricity By Source

2007 2030
% of Total Electricity

Coal is the primary generator of electricity and will continue to be

% of Total Electricity

49% Coal 2.5% Renewable

Wind = 0.4% Solar = <0.1% Projection

48% Coal 8.6% Renewable

3,000 2,500 2,000

Billion kwh

Coal
(Enough reserves in U.S. for 300 years)

1,500

Natural Gas
1,000 500 0

Nuclear Hydro
1960 1970 1980 1990 2000 2010 2020

Renewable
Petroleum
2030

1950

Source: EIA: Annual Energy Review 2007 & Energy Outlook 2008, Calera Analysis

Emission reduction wedges for California in 2050.

J H Williams et al. Science 2012;335:53-59

Published by AAAS

The three main energy system transformations required to reduce GHG emissions 80% below 1990 levels by 2050 in California.

J H Williams et al. Science 2012;335:53-59

Published by AAAS

Electricity consumption, load profiles, and fuel mix in baseline and mitigation scenarios.

J H Williams et al. Science 2012;335:53-59

Published by AAAS

Mixed-case net cost by mitigation type in 2020, 2035, and 2050.

J H Williams et al. Science 2012;335:53-59

Published by AAAS

Permanent and Large Enough Storage

16 Billion tonnes CO2/year

CO2 Permanent Conversion

CO3

32 Billion tones building materials/year

A Robust Technology
CO2 + criteria pollutants (SO2) Clean Flue Gas

I N P U T S

Fly Ash

Aqueous Precipitation

Brines

Green Building Products

O U T P U T S

Waste Water

Manufactured Alkalinity

Fresh Water

Adaptive Carbon Dioxide Reservoirs

28 billion tons anthropogenic 32 billion tons rock aggregate mined has potential to sequester 16 billion tons 10 billion tons aggregate used in 12.5 billion tons concrete 5 billion tons limestone mined to make 2.5 billion tons Portland cement 20 billion tons aggregate used in roads
2/6/2012 For George Schultz at Hoover

Carbon Negative Building Materials

Amorphous Calcium Carbonate Cement Replacement

Aggregate

Green Concrete

Cement & CO2

Cement is Inherently a Heavy CO2 Emitting Process (since 1824)

Approximately 1 ton CO2 for each ton of cement

(Range 0.7 1.1)

Source: EPA 2004, International Energy Agency July 2008

Cement Production is Growing

Cement Production Emits Over 2.5 Billion tons of CO2 Per Year
2,000

Cement Production
Asia/Pacific

1,500 MMT 1,000

5-8% global CO2

N. America

500

1990 Source: USGS Annual Review 2001, IEA 2008

2004

Global market estimated at $523 B in 2007

Market Value Asia-Pacific Europe Americas 348.8 94.3 80.6 % 66.60% 18.00% 15.40%

Maket Value Brick Cement Crushed stone Sand & Gravel 154.5 145.1 135.6 88.5

% 29.50% 27.70% 25.90% 16.90%

Three large players with 4% each and vertically integrated (Lafarge, Holcim and Cemex) Cement production emits over 2.5 bn tons of CO2 per year (5%-8% of world s emissions)

Option 2: CCS Cost for Cement Plant

To upgrade cement plant Capital Investment: $140 to 200 million Annual cost $40 million, adding $50+ per ton

Bankrupt? Import?

Source: CO2 Capture in the Cement Industry, IEA July 2008, European Concrete Research Academy 2007

Mining Reduction
Limestone Quarry 7.5 tons Limestone Cement Kiln
5 tons Cement

Carbon Dioxide Conversion

2.5 tons CO2

1 ton coal

Aggregate Quarry

5 tons Aggregate

Cement
50% natural alkalinity, 50% manufactured alkalinity

100%OPC

407kgCO2/m3 concrete avoided

100% Cement

Life Cycle Carbon Emissions

Coal Plant

(% of power plant emissions)

Alkalinity: 50% Brines, 50% ABLE Product: 100% cement

Power plant emissions

Net CO2 converted to carbonate

Capture from power

Process

Cement displaced

Dominant Reactions
++ + CO = Ca 3

Ca CO3

++ Ca

+ 2HCO3

Ca CO3 + H2O + CO2

Calera Corporation

Generation I

Permanent Sequestration
Calera CO2 Life Cycle CO2 permanently sequestered

ILLUSTRATIVE
Skyonics CO2 Life Cycle CO2 sequestered released in application

Breakthrough Alkalinity Manufacturing

State-of-the-art: Chlor Alkali Process

2NaCl + 2H2O
Calera ABLE (NaOH)

2NaOH + H2 + Cl2

Ecell = -2.19 V
1,468 kWh/tonne NaOH eq. Calera ABLE-C (NaHCO3)

NaCl + H2O

NaOH + HCl

NaCl + H2O + CO2

NaHCO3 + HCl

Ecell = -0.83 V
556 kWh/tonne NaOH eq. 62% less $/tonne NaOH eq.

Ecell = -0.415 V
278 kWh/tonne NaOH eq. 81% less $/tonne NaOH eq.

Proven at 10MW Scale

Q1-10 Electrochemistry Pilot Plant Q4-09 Continuous 10 MW Demonstration Plant Desalination Pilot Plant Q2-09 Continuous Pilot Plant Q2-08 R&D Center

Moss Landing Power Station >1000 MW Fuel: Natural Gas Operator: Dynegy

Types of Alkalinity
NATURALLY OCCURING NON-CARBONATE
General Characteristics Converted to carbonate alkalinity through CO2 capture Can be used for both CO2 capture and carbonate cement production Characteristics Utilizes basic nature of many naturally occurring minerals Examples Borate lakes/deposits (B[OH]4-) Mined or solution mined ultramafic minerals (e.g. olivine) (OH-) Ophiolite formations (OH-) Characteristics CO2 capture via bicarbonate reinjection Direct reaction with hard brine for cement products Examples Soda lakes (CO32-, HCO3-) Mined or solution mined trona mineral (Na3[CO3][HCO3]2H2O)

PRODUCED
Characteristics Highest CO2 capture efficiency Examples NaOH(aq) (ABLE, ABLE-RB)

CARBONATE
General Characteristics Solutions containing Na2CO3

Characteristics CO2 capture integrated into process Lower energy demand for e-chem operations Examples Na2CO3(aq) (ABLE-C, ABLE-RBC)

Closed System Approach

High-pH solutions with high concentrations of dissolved carbon, in combination with electrochemically produced strong base, to sequester additional CO2 by
Dissolving CO2 to create a bicarbonate-rich solution
2  2Na   CO32  H 2CO3 n p2Na   2HCO3 

Using sodium hydroxide to drive the carbon speciation equilibrium near the CO32--HCO3- equivalence point, in the  presence of Ca2+
   2Na   2HCO3  Na   OH   Ca 2  2Cl n pCaCO3(s)  3Na   HCO3  2Cl

Carbon mass balance Base efficiency with varying contributions (0-30%) from electrochemically produced base CO2 capture rate, relative to other base sources Thermodynamic stability of host rock upon possible reinjection of supernatant fluids

Data Collection and Analyses for Hard Brine Sourcing in Southwest Wyoming:

Site Development Process: Step 1

Ca2+??

Alkalinity

CO2

Power Plants: Wyoming Trona Deposit

Rock Springs Uplift

Trona Distribution in Southwest Wyoming

Trona World s largest deposit (estimated 127 billion tons) Located in the Eocene Green River Formation of the Green River Basin. Characterized by laminated chalky lacustrine shale. Trona is distributed in 22 fields ranging from 50 to 775mi2 Depths range from 650 to 3000 ft below the surface.

Wiig, Stephen V., Grundy, W.D, Dyni, John R. Trona resources in the Green River Basin, Southwest Wyoming. USGS Report 95-476 Textoris, Daniel A. Stratigraphy of the Green River Formation in the Bridger Basin, Wyoming

Trona Mining in Wyoming

US Bureau of Mines, Availability of Federally Owned Minerals for Exploration and Development in the Western United States

Hydrogeologic Feedstocks
Geologic and hydrologic framework Hard water common and abundant Extremely hard water less common, but abundant Shallow, extremely hard water even less common, but abundant Alkaline water less common, but abundant (>500 mEq.) Extremely alkaline water rare and less abundant (>1500 mEq.)

Potential Calcium Sources

Areas of Interest Based on Water Chemistry and Produced Calcium: Water Volumes 10,180-77,360 ppm
Produced Water: 18,880,799 bbls Depth Range: No data Distance Jim Bridger: 70 miles Naughton: 71 miles

Calcium: 31,790 ppm Distance Jim Bridger: 39 miles

114 Sites in 100 mile radius have Calcium concentrations above 10,000 mg/L

Average Calcium: 25,409 Produced Water: 58,191,239 bbls Depth Range: 1570-9645ft measured depth Distance from Jim Bridger: 63 miles

Green River Basin, Wyoming

Hydraulic Head

Pipelines and CO2 Sources

Population Density and Railroad Networks

Cement and Concrete Industries

Railroads and Major Roadways

Sensitivity Analysis: Wy Assumptions

Excel roll-up of Aspen Absorption, Product estimates; external echem and brine field

Approximate ranking of sensitivities in terms of IRR/ (% input) For this base case only Does not reflect different uncertainties for different inputs

CONFIDENTIAL

Inner Mongolia

China 12 MW Overall Mass Balance

Purchased NaOH Metric Units Annual Basis (85% capacity factor)

Flue Gas Return to Stack (14,500 tonne/yr CO2)

12 MW of Flue Gas (71,500 tonne/yr CO2) 115,000 tonne/yr NaOH 4.8 GL/yr Ca-rich brine (52,000 tonne Ca2+/yr)

57,000 tonne/yr CO2 captured (80%) < 8900 MWh (10%) consumed (< 1.2 MW) Total Lifecycle CO2 Mitigated: 155,000 tonne/yr 4.8 GL/yr brine (reinjected)

130,000 tonne/yr Solid Product

Tonne = 1000 kg = metric ton; GL= 109 liters; mass flow of NaOH is dry basis of NaOH

Harold Urey (1893-1981)

The Planets, published in 1952. Carbon dioxide in our atmosphere was governed by an equation: CO2 + CaSiO4 CaCO3 + SiO2

This equation describes chemical weathering

The concentration of carbon dioxide in our atmosphere corresponds to the equilibrium expected for this reaction. The amount of carbon dioxide in the atmosphere is set by the presence of the water on Earth. Equilibrium approach

IPCC Estimate (in GtC)

Process Design Scale

Global Scale
Gigaton Scale Open System

Industrial Scale
Megaton Scale Closed System Ecosystem Level Engineering

Industrial Process Scale-Up IDEA

Bench Top Prototype Pilot Demonstration Plant Commercial Scale

Spatial Components to Reactions

Industrial Closed System

Surface Reactions Angstroms Microns Surface Gradient Microns Millimeters Bulk Solution Centimeters Meters

Pre-Industrial Open System

Open Ecosystem Meters Kilometers

71st Seabees Build an Airfield in the Admiralties Coral surfacing on June 1, 1944

Carbon Dioxide in the Past

2/6/2012

For George Schultz at Hoover

Two Dominant Reactions in Ocean

++ + CO = Ca 3

CaCO3

++ Ca

+ 2HCO3

CaCO3 + H2O + CO2

Comparison of the temporal distribution of mineralogies for nonskeletal marine carbonates and evaporates and of biologically simple carbonate-producing taxa that have functioned as important reef-builders and producers of marine sediment.(1, 20) The large upper diagram shows nonskeletal precipitation of low-Mg calcite, high-Mg calcite, and aragonite as a function of the Mg/Ca molar ratio of seawater.(11, 12) The graph at the upper right illustrates incorporation of Mg in nonskeletal calcite as a function of the ambient Mg/Ca ratio at two temperatures.(9, 10) The uppermost two broad horizontal bars show intervals of aragonite and calcite seas, as indicated by two assessments of the geologic record of nonskeletal carbonate precipitation.(5, 6) The lowermost broad horizontal bar shows temporal oscillations observed in the geologic record between calcitic and aragonitic nonskeletal carbonates and between KCl and MgSO4 marine evaporates.(11) Shown below are temporal distributions of the carbonate-producing taxa.(1, 20, 2)

Published in: Steven M. Stanley; Chem. Rev. 2008, 108, 4483-4498. DOI: 10.1021/cr800233u Copyright 2008 American Chemical Society

Toungue of the Ocean, Great Bahamas Bank

Ooid Shoals

Maastrichtian, Late Cretaceous

Micro-architectural details of the Cretaceous, calcitic skeleton of Coelosmilia sp.

Carbonate Formations
100 Mya

High pCO2 in the Cretaceous led to: -Warm, shallow inland seas -Extensive carbonate formation

Austin Chalk, Texas

2/6/2012 For George Schultz at Hoover

Chalk Group, UK

Sedimentary rocks & marine sediments 70-100 million Gigatons CO2

Dover - England

2/6/2012

For George Schultz at Hoover

A colorized scanning electron micrograph (SEM) of an Emiliania huxleyi coccosphere; diameter is about 5 m.

Published in: K. Henriksen; S. L. S. Stipp; Crystal Growth & Design 2009, 9, 2088-2097. DOI: 10.1021/cg8004272 Copyright 2009 American Chemical Society

SCIENCE, MAY 31,2011

Coccolith volume and CaCO3

Average mass of CaCO3 per coccolith

Halimeda incrassata. This specimen represents the widespread Indo-Pacific population traditionally assigned to this species. Molecular systematics has shown, however, that it belongs to a distinct species from the Atlantic population assigned to H. incrassata although the morphologies of the two populations are nearly identical.(122) Photo from Gerald McCormack (2007) Cook Islands Biodiversity Database, Version 2007.2. Cook Islands Natural Heritage Trust, Rarotonga. Online at http://cookislands.bishopmuseum.org.

Published in: Steven M. Stanley; Chem. Rev. 2008, 108, 4483-4498. DOI: 10.1021/cr800233u Copyright 2008 American Chemical Society

2/6/2012

For George Schultz at Hoover

Superimposition
Calcite (open circles) Aragonite (dots) (001) crystal faces

Realistic Public-Private Partnerships

Successful in Southern California Tax-exempt Municipal Bonds DOE/DOT Development Funding Joint Powers Authorities Regulatory Coordination and Cooperation