Carbon dioxide sequestration in cement kiln dust through miner carbonation

The feasibility of carbon sequestration in cement kiln dust (CKD) was investigated in a series of batch and column experiments conducted under ambient temperature and pressure conditions. The significance of this work is the demonstration that alkaline wastes, such as CKD, are highly reactive with carbon dioxide (CO2). In the presence of water, CKD can sequester greater than 80% of its theoretical capacity for carbon without any amendments or modifications to the waste. Other mineral carbonation technologies for carbon sequestration rely on the use of mined mineral feedstocks as the source of oxides. The mining, pre-processing and reaction conditions needed to create favorable carbonation kinetics all require significant additions of energy to the system. Therefore, their actual net reduction in CO2 is uncertain. Many suitable alkaline wastes are produced at sites that also generate significant quantities of CO2. While independently, the reduction in CO2 emissions from mineral carbonation in CKD is small (~13% of process related emissions), when this technology is applied to similar wastes of other industries, the collective net reduction in emissions may be significant. The technical investigations presented in this dissertation progress from proof of feasibility through examination of the extent of sequestration in core samples taken from an aged CKD waste pile, to more fundamental batch and microscopy studies which analyze the rates and mechanisms controlling mineral carbonation reactions in a variety of fresh CKD types. Finally, the scale of the system was increased to assess the sequestration efficiency under more pilot or field-scale conditions and to clarify the importance of particle-scale processes under more dynamic (flowing gas) conditions. A comprehensive set of material characterization methods, including thermal analysis, Xray diffraction, and X-ray fluorescence, were used to confirm extents of carbonation and to better elucidate those compositional factors controlling the reactions. The results of these studies show that the rate of carbonation in CKD is controlled by the extent of carbonation. With increased degrees of conversion, particle-scale processes such as intraparticle diffusion and CaCO3 micropore precipitation patterns begin to limit the rate and possibly the extent of the reactions. Rates may also be influenced by the nature of the oxides participating in the reaction, slowing when the free or unbound oxides are consumed and reaction conditions shift towards the consumption of less reactive Ca species. While microscale processes and composition affects appear to be important at later times, the overall degrees of carbonation observed in the wastes were significant (> 80%), a majority of which occurs within the first 2 days of reaction. Under the operational conditions applied in this study, the degree of carbonation in CKD achieved in column-scale systems was comparable to those observed under ideal batch conditions. In addition, the similarity in sequestration performance among several different CKD waste types indicates that, aside from available oxide content, no compositional factors significantly hinder the ability of the waste to sequester CO2.

Effects of carbonation on the mineral composition of cement kiln dust

Due to their relatively high calcium oxide content, industrial mineral oxide wastes are potential candidates for mineral sequestration of carbon dioxide (CO2). Cement kiln dust (CKD), a byproduct of cement manufacturing contains 20-60% CaO making it a possible candidate for CO2 sequestration. In this study, three types of CKD are characterized, before and after carbonation, using environmental scanning electron microscopy and energy dispersive x-ray microanalysis to determine the mineralogical and morphological changes occurring due to carbonation. The reactants, products, and precipitation mechanisms were investigated to enhance understanding of the governing processes and allow better utilization of CKD for CO2 sequestration. The results of multiple independent analyses confirmed the formation of CaCO3 during carbonation. Examinations of the reaction pathways found that CaO and calcium hydroxide (Ca(OH)2) were the major reactants. Three types of CaCO3 precipitation mechanisms were observed: (1) diffusion of CO2 into Ca(OH)2 particles causing precipitation in the pores of the particle and the growth of a CaCO3 ring from the outside inward, (2) precipitation onto existing particles, and (3) precipitation from aqueous solution. The growth of a CaCO3 ring on the outside of a particle may slow further diffusion of CO2 into a particle slowing iv the overall sequestration rate. Additionally, changes caused by carbonation in the solubility of trace metals were studied by mixing pre- and post-carbonated CKD with water and analyzing the solution using inductively coupled plasma mass spectrometry. Decreases in the leaching of chromium, lead, and copper were observed, and is an incentive for use of CKD for CO2 sequestration. Equilibrium modeling using PHREEQC confirmed that CaO and Ca(OH)2 would carbonate readily and form CaCO3.

Development and improvement of warm-mix asphalt technology

Traditionally, asphalt mixtures were produced at high temperatures (between 150°C to 180°C) and therefore often referred to as Hot Mix Asphalt (HMA). Recently, a new technology named Warm Mix Asphalt (WMA) was developed in Europe that allows HMA to be produced at a lower temperature. Over years of research efforts, a few WMA technologies were introduced including the foaming method using Aspha-min® and Advera® WMA; organic additives such as Sasobit® and Asphaltan B®; and chemical packages such as Evotherm® and Cecabase RT®. Benefits were found when lower temperatures were used to produce asphalt mixtures, especially when it comes to environmental and energy savings. Even though WMA has shown promising results in energy savings and emission reduction, however, only limited studies and laboratory tests have been conducted to date. The objectives of this project are to 1) develop a mix design framework for WMA by evaluating its mechanical properties; 2) evaluate performance of WMA containing high percentages of recycled asphalt material; and 3) evaluate the moisture sensitivity in WMA. The test results show that most of the WMA has higher fatigue life and TSR which indicated WMA has better fatigue cracking and moisture damage resistant; however, the rutting potential of most of the WMA tested were higher than the control HMA. A recommended WMA mix design framework was developed as well. The WMA design framework was presented in this study to provide contractors, and government agencies successfully design WMA. Mixtures containing high RAP and RAS were studied as well and the overall results show that WMA technology allows the mixture containing high RAP content and RAS to be produced at lower temperature (up to 35°C lower) without significantly affect the performance of asphalt mixture in terms of rutting, fatigue and moisture susceptibility. Lastly, the study also found that by introducing the hydrated lime in the WMA, all mixtures modified by the hydrated lime passed the minimum requirement of 0.80. This indicated that, the moisture susceptibility of the WMA can be improved by adding the hydrated lime.

MATURE FINE TAILINGS (MFTs): A STUDY OF COMPRESSIVE STRENGTH AND RHEOLOGICAL PROPERTIES OF ATHABASCA OIL SANDS PETROLEUM MINING WASTE APPLIED IN CONCRETE MIXTURES

This study investigates the compressive properties of concrete incorporating Mature Fine Tailings (MFTs) waste stream from a tar sands mining operation. The objectives of this study are to investigate material properties of the MFT material itself, as well as establish general feasibility of the utilization of MFT material in concrete mixtures through empirical data and visual observations. Investigations undertaken in this study consist of moisture content, materials finer than No. 200 sieve, Atterburg Limits as well as visual observations performed on MFT material as obtained. Control concrete mixtures as well as MFT replacement mixture designs (% by wt. of water) were guided by properties of the MFT material that were experimentally established. The experimental design consists of compression testing of 4”-diameter concrete cylinders of a control mixture, 30% MFT, 50% MFT and 70% MFT replacement mixtures with air-entrainer additive, as well as a control mixture and 30% MFT replacement mixture with no air-entrainer. A total of 6 mixtures (2 control mixtures, 4 replacement mixtures) moist-cured in lime water after 24 hours initial curing were tested for ultimate compressive strength at 7 days and 28 days in accordance to ASTM C39. The test results of fresh concrete material show that the addition of air-entrainer to the control mixture increases slump from 4” to 5.5”. However, the use of MFT material in concrete mixtures significantly decreases slump as compared to controls. All MFT replacement mixtures (30%, 50%, and 70%) with air-entrainer present slumps of 1”. 30% MFT with no air-entrainer presents a slump of 1.5”. It was found that 7-day ultimate compressive stress was not a good predictor of 28-day ultimate compressive stress. 28-day results indicate that the use of MFT material in concrete with air-entrainer decreases ultimate compressive stress for 30%, 50% and 70% MFT replacement amounts by 14.2%, 17.3% and 25.1% respectively.

Improving the sustainability of an appropriate technology solution; bone char defluoridation filters in Arusha, Tanzania

High concentrations of fluoride naturally occurring in the ground water in the Arusha region of Tanzania cause dental, skeletal and non-skeletal fluorosis in up to 90% of the region’s population [1]. Symptoms of this incurable but completely preventable disease include brittle, discolored teeth, malformed bones and stiff and swollen joints. The consumption of high fluoride water has also been proven to cause headaches and insomnia [2] and adversely affect the development of children’s intelligence [3, 4]. Despite the fact that this array of symptoms may significantly impact a society’s development and the citizens’ ability to perform work and enjoy a reasonable quality of life, little is offered in the Arusha region in the form of solutions for the poor, those hardest hit by the problem. Multiple defluoridation technologies do exist, yet none are successfully reaching the Tanzanian public. This report takes a closer look at the efforts of one local organization, the Defluoridation Technology Project (DTP), to address the region’s fluorosis problem through the production and dissemination of bone char defluoridation filters, an appropriate technology solution that is proven to work. The goal of this research is to improve the sustainability of DTP’s operations and help them reach a wider range of clients so that they may reduce the occurrence of fluorosis more effectively. This was done first through laboratory testing of current products. Results of this testing show a wide range in uptake capacity across batches of bone char emphasizing the need to modify kiln design in order to produce a more consistent and high quality product. The issue of filter dissemination was addressed through the development of a multi-level, customerfunded business model promoting the availability of filters to Tanzanians of all socioeconomic levels. Central to this model is the recommendation to focus on community managed, institutional sized filters in order to make fluoride free water available to lower income clients and to increase Tanzanian involvement at the management level.