New York State Energy Research and Development Authority Disposing of Greenhouse Gases through Mineralization Using the Wollastonite Deposits of New York State Final Report May 2012 No. 12-14 NYSERDA’s Promise to New Yorkers: New Yorkers can count on NYSERDA for objective, reliable, energy-related solutions delivered by accessible,dedicated professionals. Our Mission: Advance innovative energy solutions in ways that improve New York’s economy and environment. Our Vision: Serve as a catalyst—advancing energy innovation and technology, transforming New York’s economy, and empowering people to choose clean and efficient energy as part of their everyday lives. Our Core Values: Objectivity, integrity, public service, and innovation. Our Portfolios NYSERDA programs are organized into five portfolios, each representing a complementary group of offerings with common areas of energy-related focus and objectives. 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DISPOSING OF GREENHOUSE GASES THROUGH MINERALIZATION USING THE WOLLASTONITE DEPOSITS OF NEW YORK STATE Final Report Prepared for the NEW YORK STATE ENERGY RESEARCH AND DEVELOPMENT AUTHORITY Albany, NY nyserda.ny.gov Amanda D. Stevens Project Manager Prepared by: COLUMBIA UNIVERSITY Department of Earth and Environmental Engineering, Lenfest Center Klaus S. Lackner Ah-Hyung Alissa Park Huangjing Zhao NYSERDA NYSERDA 10114 May 2012 Report 12-14 NOTICE This report was prepared by Klaus S. Lackner and Ah-Hyung Alissa Park, at Columbia University, in the course of performing work contracted for and sponsored by the New York State Energy Research and Development Authority (hereafter NYSERDA). The opinions expressed in this report do not necessarily reflect those of NYSERDA, or the State of New York. Moreover, reference to any specific product, service, process or method does not constitute an implied or expressed recommendation or endorsement of it. Further, NYSERDA, the State of New York, and the contractor make no warranties or representations, expressed or implied, as to the fitness for particular purpose or merchantability of any product, apparatus, or service, or the usefulness, completeness or accuracy of any processes, methods or other information contained, described, disclosed or referred to in this report. NYSERDA, the State of New York and the contractor make no representation that the use of any product, apparatus, process, method or other information will not infringe privately-owned rights and will assume no liability for any loss, injury or damage resulting from, or occurring in connection with, the use of information contained, described, disclosed or referred to in this report. Abstract: Recently, carbon mineralization has received much attention as one of the most promising options for CO2 sequestration. Carbon mineralization has unique advantages, such as the abundance of naturally occurring calcium- and magnesium-bearing minerals and the formation of environmentally benign and stable carbonates via a thermodynamically favored mechanism. However, several challenges need to be overcome to successfully deploy this technology. In particular, acceleration of the extremely slow weathering step, along with process optimization, is essential to ensure economic feasibility. In this study, the effect of various types of chelating agents on the dissolution rate of wollastonite, a calcium-silicate mineral, was explored to accelerate the weathering rate. Wollastonite was chosen because the largest deposits of wollastonite in the U.S. exist in New York State. It was observed that chelating agents, such as acetic acid 2+ and gluconic acid, which bind Ca from the mineral, significantly improved the dissolution kinetics of wollastonite, even at a diluted concentration of 0.006 M. Calcium extracted from wollastonite was then reacted with CO2 to form precipitated calcium carbonate (PCC) that mimics commercially available CaCO3-based filler materials. The particle size distribution and the morphological structures of synthesized PCC were investigated as functions of reaction time, pH, and reaction temperature. Keywords: CO2 mineralization, wollastonite, mineral dissolution, chelating agents, carbonation, precipitated calcium carbonate, sequestration iii Acknowledgments The work presented in this report was funded by New York State Energy Research and Development Authority (Agreement Number: 10114). iv Table of Contents Summary2....................................................................................................................................................S-1 1 Introduction2.....................................................................................................................................21 2 Materials2and2Methods2...................................................................................................................25 2.1 Wollastonite ...................................................................................................................................... 5 2.2 Mineral Dissolution........................................................................................................................... 6 2.3 Formation of Calcium Carbonate...................................................................................................... 8 3 Results2and2Discussion2....................................................................................................................29 3.1 Mineral Dissolution........................................................................................................................... 9 3.2 Formation of Calcium Carbonate....................................................................................................13 3.2.1 Effects on Particle Size ...................................................................................................13 3.2.2 Effects on Morphological Structure................................................................................15 3.2.3 Effects of Different Calcium Sources on Synthesis of Precipitated Calcium Carbonate....... 17 4 Thermodynamic2Modeling2and2Flow2Diagram2of2Industrial2Process2......................................221 4.1 Thermodynamic Modeling..............................................................................................................21 4.2 Flow Diagram of Industrial Process................................................................................................23 References2....................................................................................................................................................225 v Listing of Tables and Figures 2+ Table 1. List of chelating agents and their stability constants (p) with Ca ................................................. 11 2 Figure 1. Examples of commercially available precipitated calcium carbonate morphologies. .................... 3 Figure 2. Particle-size distribution and SEM image of the ground wollastonite particles. ............................ 5 Figure 3. XRD patterns and Rietveld refined fits (Rwp = 14.1%) of wollastonite. Inset illustrates the crystal structure of wollastonite 1A.................................................................................................. 6 Figure 4. Schematic diagram of experimental setup for mineral dissolution................................................. 7 2+ Figure 5. (a) [Catotal] in liquid samples from the differential bed reactor, where [Catotal] = [Ca ] + [CaL] (L=ligand) and (b) Ca extraction as a function of time at 25 °C. ....................................................10 Figure 6. Comparison of Ca extraction from wollastonite using various chelating agents (25 °C, reaction time = 6 min). ....................................................................................................................11 Figure 7. Speciation of various chelating agents, as a function of pH, simulated using Visual MINTEQ: (a) 0.006 M acetic acid, (b) 0.003 M oxalic acid, (c) 0.002 M citric acid, and (d) 0.0015 M EDTA........................................................................................................................12