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Policy Path
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.
% of Total Electricity
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
Published by AAAS
The three main energy system transformations required to reduce GHG emissions 80% below 1990 levels by 2050 in California.
Published by AAAS
Electricity consumption, load profiles, and fuel mix in baseline and mitigation scenarios.
Published by AAAS
Published by AAAS
CO3
A Robust Technology
CO2 + criteria pollutants (SO2) Clean Flue Gas
I N P U T S
Fly Ash
Aqueous Precipitation
Brines
O U T P U T S
Waste Water
Manufactured Alkalinity
Fresh Water
Aggregate
Green Concrete
Cement Production
Asia/Pacific
N. America
500
2004
Maket Value Brick Cement Crushed stone Sand & Gravel 154.5 145.1 135.6 88.5
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)
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
1 ton coal
Aggregate Quarry
5 tons Aggregate
Cement
50% natural alkalinity, 50% manufactured alkalinity
100%OPC
100% Cement
Process
Cement displaced
Dominant Reactions
++ + CO = Ca 3
Ca CO3
++ Ca
+ 2HCO3
Calera Corporation
Generation I
Permanent Sequestration
Calera CO2 Life Cycle CO2 permanently sequestered
ILLUSTRATIVE
Skyonics CO2 Life Cycle CO2 sequestered released in application
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
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.
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)
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:
Ca2+??
Alkalinity
CO2
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
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.)
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
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
Hydraulic Head
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
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)
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
Global Scale
Gigaton Scale Open System
Industrial Scale
Megaton Scale Closed System Ecosystem Level Engineering
Surface Reactions Angstroms Microns Surface Gradient Microns Millimeters Bulk Solution Centimeters Meters
71st Seabees Build an Airfield in the Admiralties Coral surfacing on June 1, 1944
2/6/2012
CaCO3
++ Ca
+ 2HCO3
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
Carbonate Formations
100 Mya
High pCO2 in the Cretaceous led to: -Warm, shallow inland seas -Extensive carbonate formation
Chalk Group, UK
Dover - England
2/6/2012
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
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
Superimposition
Calcite (open circles) Aragonite (dots) (001) crystal faces