Monitoring thermal variations in carbon capture by brucite

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MONITORING THERMAL VARIATIONS IN

CARBON CAPTURE BY BRUCITE

Mémoire

Diana Aksenova

Maîtrise en génie chimique

Maître ès sciences (M. Sc.)

Québec, Canada

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MONITORING THERMAL VARIATIONS IN

CARBON CAPTURE BY BRUCITE

Mémoire

Diana Aksenova

Sous la direction de :

Faïçal Larachi, directeur de recherche

Xavier P.V. Maldague, codirecteur de recherche

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Résumé

L'augmentation rapide du niveau de concentration de dioxide de carbone dans l'air ambiant à la suite de diverses activités humaines est l'un des principaux défis environnementaux du XXIe siècle. Par conséquent, la résolution des problèmes d'émissions de carbone est l'une des principales tâches de la société moderne. Diverses technologies ont été développées et testées au cours des dernières décennies pour atténuer ce problème. La carbonatation minérale est reconnue comme l'une des technologies les plus sûres permettant de capturer et de stocker en permanence du carbone sous forme de carbonates thermiquement stables. La minéralisation passive du carbone par les résidus miniers en tant que processus naturel a lieu dans des conditions environnementales, partout où l'accès de l'air et de l'eau au tas de résidus miniers est possible.

Le présent travail explore l'utilisation de la thermographie infrarouge comme méthode non destructive de surveillance du comportement exothermique au cours de la capture passive du carbone par la brucite. La configuration de carbonatation à deux cellules, consolidée avec une caméra infrarouge, a été conçue pour surveiller simultanément les variations thermiques de la surface du matériel dues à l'absorption de CO2 ainsi que le flux de chaleur échangé entre la brucite et son environnement. Les résultats montrent une influence significative de la température ambiante sur le système qui a contribué à l'échange thermique de la couche réactive avec l'environnement. La comparaison des profils de température entre les demi-cellules de référence et réactives montre des différences dans les variations thermiques par rapport à la température adiabatique à cause de l'influence de la température ambiante. L'élévation de température adiabatique par rapport aux profils de température de surface démontre une différence substantielle dans le taux de génération de chaleur de carbonatation en raison de l'échange de flux de chaleur avec l'environnement pendant le processus.

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Abstract

Rapid increment of the level of carbon concentration in ambient air in consequence of various human activities is one of the major environmental challenges of 21st century. Therefore, solving carbon emissions issues is one of the main tasks of the modern society. Variety of technologies have been developed and tested over the past decades to alleviate this concern. Mineral carbonation is recognized as one of the safest technologies that allows to capture and permanently store carbon in the form of thermally stable carbonates. Passive mineral carbonation by mining residues as a naturally occurring process takes place under environmental conditions anywhere where the air and water access to mining residue heap can be obtained.

The present work explores the use of infrared thermography as a non-destructive method of monitoring exothermal behavior of passive carbon capture by brucite. Dual-cell carbonation setup consolidated with an infrared camera was designed in order to provide simultaneous monitoring of thermal variations on the surface of the material due to CO2 uptake as well as exchange of heat fluxes between brucite and its surroundings. The results show a significant influence of room temperature on the system that contributed to heat exchange of the reactive layer with the surrounding. The temperature profiles comparison between reference and reactive half-cells demonstrates striking differences in thermal variations than the adiabatic temperature due to the room temperature influence. Adiabatic temperature rise in comparison with surface temperature profiles demonstrates a substantial difference in carbonation heat generation rate due to heat fluxes exchange with surrounding during the process.

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List of figures

Figure 1.1 Global carbon cycle. Amount of CO2 released and consumed in Gt [17]... 2 Figure 1.2 CCS techniques [23, 24, 25]. ... 3 Figure 1.3 Ex-situ and in-situ carbonation concepts. ... 5 Figure 1.4 Location of ultra(mafic) rocks lying in the immediate vicinity (less than 300 km) from a CO2-emission plant [56]. ... 7 Figure 1.5 IR imaging: (A) ice cube was added to a freshwater (left) and a saltwater (right); (B) in 4 min; (C) in 9 min; (D) in 16 min [118] ... 18 Figure 1.6 Temperature profiles during fast exothermal reaction [121] ... 19 Figure 2.1 Scheme of carbonation reactor setup: (1) gas reservoir; (2) reaction compartment; (3) piston; (4) CO2 probe; (5) airbag; (6) reference cell; (7) reactive half-cell; (8) baffle; (9) infrared camera; (10) TDR probe; (11) four thermocouples ... 37 Figure 2.2 Front view photograph of the carbonation setup (a); reactive (left) and reference (right) half-cells (b); side view of carbonation reactor (c); IR camera field of view, FOV(d). ... 39 Figure 2.3 Structure and layout of the reactive and reference half-cells, positions of thermocouples, and the various heat flux components involved in each stratum during the carbonation reaction: heat losses due to conduction (qc1, qc2), water evaporation (qw,perm) & CO2 leakage (qCO2,perm) across infra read film, heat exchange with external domain at room temperature (qroom). ... 40 Figure 2.4 Instantaneous CO2 mole fraction measured in gas reservoir: Profile#1_brucite carbonation; Profile#2_dilution/permeation in brucite-free blank test; Profile#3_equilibrium baseline mole fraction assuming impermeable film. Initial CO2 fraction in gas reservoir,

y0CO2 = 0.11, water saturation = 50 % (reactive half-cell), reaction time window = 8 h. ... 43 Figure 2.5 Photographs of pristine brucite and of partially reacted brucite after 8 h carbonation. Same reaction conditions as in Figure 2.4. ... 44 Figure 2.6 Instantaneous evolutions of apparent (Profile#1: -Rapp), dilution/permeation (Profile#2: -Rd/p) and intrinsic carbonation (Profile#3: -RCO2) rates, and specific heat generation rate per unit mass of brucite/silica sample during brucite carbonation. Same reaction conditions as in Figure 2.4. ... 45 Figure 2.7 False-color infrared images of reference upper disc (a); reactive lower half-disc (b); ROI to be segmented (c); segmentation applying color-based clustering for an initial number of clusters k = 3 (d,e,f). ... 47

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Figure 2.8 Snapshots of the thermograms captured by the infrared camera during the course of carbonation at t = 0 (a); 50 min (b), 90 min (c). Brucite reactive surface = lower half-disc, silica inert surface = upper half-disc, temperatures at two selected equidistant pixels located mid-height from baffle. ... 48 Figure 2.9 Temperature instantaneous variations: brucite surface, headspace and silica layer in reactive half-cell (a); brucite surface in reactive half-cell and silica surface in reference half-cell (b); silica surface, headspace and silica layer in reactive half-cell (c); temperature contrasts between reactive and reference half-cells, silica layers (TC1-TC3) and headspaces (TC2-TC4). ... 50 Figure 2.10 Evolution with time of the adiabatic temperature rise of brucite layer and of compound brucite-silica layer and their comparison to actual difference between surface temperatures of brucite in reactive half-cell and silica in reference half-cell (a); relative strength of conductive heat fluxes, heat generation rate, accumulation and aggregated heat exchange rate to the surroundings in the energy balance of the reactive brucite layer. ... 52

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List of tables

Table 1.1 Minerals for carbon storage and their occurrence ... 7 Table 1.2 Various carbonates formation ... 10 Table 1.3 Various studies on carbon mineralization by brucite ... 14

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List of abbreviations

GHG Greenhouse Gas

ESRL Earth System Research Laboratory

IPCC Intergovernmental Panel on Climate Change CCS Carbon Capture and Storage

EOR Enhanced Oil Recovery ECBM Enhanced Coal-Bed Methane TEM Transmission Electron Microscopy XRD X-Ray Diffraction

DDW Distilled Deionized Water SEM Scanning Electron Microscopy IRT Infrared Thermography

NDT Non-Destructive Testing R&D Research and Development BET Brunauer–Emmett–Teller TDR Time Domain Reflectometer

MWIR Medium Wavelength Infrared

FOV Field of View ROI Region of Interest

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Twenty years from now you will be more disappointed by the things that you didn’t do than

by the ones you did do. So throw off the bowlines. Catch the trade winds in your sails.

Explore. Dream. Discover.

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Acknowledgments

My master's program has passed so fast, richly and interestingly that I did not even realize that it is time to finish and write the story of my research. First of all, it is the merit of my supervisor and mentor – Prof. Faiçal Larachi, whose knowledge, professionalism and patience helped and guided me through all 2 years of my study. I am infinitely grateful for the opportunity that you gave me by taking to your team. This chance falls once in life and I am happy that it was me who got it.

Next, I would like to express my gratitude to my co-supervisors Prof. Xavier P. V. Maldague who kindly provided infrared camera and Prof. Georges Beaudoin who shared his exceptional knowledge on minerals composition. Thank you for continuous support of my MSc study and research.

Additionally, I would like to express my appreciation to my college and friend Dr. Bardia Yousefi who went with me through hours of scientific discussions, shared his experience, and gave me lots of knowledge related to infrared thermography and data processing. Also, I am thankful to Dr. Clemente Ibarra Castanedo who helped me in many difficulties throughout infrared camera usage and initial data pre-processing.

I would like to thank all the members of Chemical Engineering Department and particularly Jerome Noel who helped to design and build the reactor as well as to perform further modifications, and Marc Lavoie who helped to install an electrical part of my setup. You are literally made my work possible from the technical point of view.

I am grateful to all of those with whom I have had the pleasure to work during my MSc project. My sincere thanks go to my colleagues Ali Entezari Zarandi, Dariush Azizi, Shahab Boroun, Amir Motamed Dashliborun, Olivier Gravel, Muhammad Khalid, and Jian Zhang. Additionally, I would like to thank Denis Ouellet for translation of some parts of this thesis into French.

Family is our greatest treasure and I am not sure that I can express in words how grateful I am to have such a family. All that I am or ever hope to be, I owe to my parents Olga and Renat, who, by their example, have shown that nothing is impossible. Thank you for your love and support.

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Foreword

This MSc thesis is composed of two chapters. Chapter 1 introduces the literature review related to the subject of the project, state of knowledge, and study objectives. Chapter 2 represents the results of current study in form of scientific article which is under submission in Canadian Journal of Chemical Engineering. This research project was supervised by Prof. Faïçal Larachi and co-supervised by Prof. Xavier P.V. Maldague and Prof. Georges Beaudoin.

List of publications:

Larachi, F., Aksenova, D., Yousefi, B., Maldague, X. P. V., Beaudoin, G. Observations of Brucite Thermochemical Carbonation Effects Using Passive Infrared Thermography. Can.

J. Chem. Eng. (under submission).

Some of the research results were presented in the following conference:

Aksenova, D., Yousefi, B., Larachi, F., Maldague, X. P. V., Beaudoin, G. Monitoring thermal phenomena in CO2 capture by brucite. QIRT-Asia, 2017, Daejeon, Korea.

Some of the research results were presented in poster form in the following events:

 Colloque annuel de centre E4m, 2016, Université Laval

 Journée de la Recherche en Sciences et Génie, 2017, Université Laval

 Colloque annuel de centre E4m, 2017, Université Laval

Author contributions:

The experimental work, data post-processing, and participation in drafting the manuscript was done by D. Aksenova. B. Yousefi contributed in developing the mathematical algorithm and its MATLAB implementation. In addition, he assisted in the redaction of the image analysis section of the article. F. Larachi amended the calculations, separately edited the manuscript, guided me and provided expertise in designing experiments, inspected the setup modification and data interpretation. X. Maldague and G. Beaudoin also provided the valuable contributions by editing the manuscript and guided me scientifically throughout the project.

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Chapter I

Introduction and scope of the project

1.1. Global warming and carbon footprint

The innovative way of development of any state, not excluding Canada, depends on the level of development of the science and technology. There is an opinion that all types of crises in the modern world - energy, ecological, protein or food - are consequences of the general technological crisis characterizing the efficiency of the use of raw materials and energy. Natural energy sources are currently the main source of raw materials and energy [1]. At the same time, energy is the driving force of any production. The main task of modern society is to ensure decent living conditions of the existing generation, but at the same time the responsibility to leave a full habitat for future generations as a legacy, which is possible only on the basis of an integrated scientific approach that ensures, on the one hand, maximum efficiency and competitiveness of technologies, and on the other hand, preservation of the environment conditions [2, 3]. Along with local environmental consequences, accompanied by air, water and soil pollution, there is a danger of a significant change in the global climate, including a greenhouse gas emissions influence [4].

In the atmospheric layers of our planet, there are many phenomena directly affecting the climatic conditions of the Earth [5]. The greenhouse effect, being a process influencing the formation of the Earth's climate for millions of years, continues to play a decisive role in the state of the planet [6]. This process is considered one of the global environmental problems of our times, because of which solar radiation is absorbed by Greenhouse Gases (GHGs) and creates the preconditions for global warming [7].

Global warming can lead to unpredictable consequences, possibly, to an ecological catastrophe on Earth [8]. Everyone notices the ongoing changes in the climate of our planet. Change in climatic conditions poses a danger to the existence of the entire population of the globe [9]. In an age of continuous technological progress, it is important not to forget about the resources that are given to us by nature, how we manage them and how we influence the flora and fauna [10]. Nowadays, atmospheric GHG accumulation plays an essential role in climate change. Increasing amount of GHGs causes global warming [11]. According to the Intergovernmental Panel on Climate Change (IPCC), an increase in the global average surface temperature of

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more than 20C contains potential significant damage to the ecosystems upon which we depend directly [12].

The main GHGs, in order of their estimated impact on the heat balance of the Earth, are water vapor, carbon dioxide (CO2), methane and ozone [13]. There are two sources of carbon emissions in the Earth's atmosphere – of natural origin and due to the human activities (Fig.1.1). The former includes an ocean-atmosphere exchange, plant and animal respiration and decomposition, and volcanic eruptions. The main anthropogenic sources are: electricity and heat production, burning biomass, manufacturing and construction, and transportation [14]. Anthropogenic emissions increase the concentration of carbon dioxide in the atmosphere, which is presumably the main factor in the climate change. Moreover, carbon dioxide has a "long live" in the atmosphere – around 96 years [15]. Excessive contribution of human activity to the amount of CO2 emitted to the ambient air is scientifically proven [16].

Figure 1.1 Global carbon cycle. Amount of CO2 released and consumed in Gt [17].

In concordance with the latest data taken from NOAA Earth System Research Laboratory (ESRL), Hawaii present atmospheric CO2 concentration is equal to 403.64 ppm (October, 2017) [17]. If CO2 emissions continue to rise, the enhanced greenhouse effect may permanently change the climate system in the world [18].

Canada and particularly Quebec province has extensive mining plants. However, zero emissions and clean technology concept is getting a primary position in any production line development [19]. Therefore, the significance of Carbon Capture and Storage (CCS) has been rising steadily [20]. To alleviate the negative influence of the human activity, multiple ways of trapping and keeping carbon away from the atmosphere have been investigated over the past several decades and interest in developing new technologies has been growing alongside [21].

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1.2. Carbon capture and storage: the process

In general, CCS is a process composed of several stages: carbon dioxide capture and separation from industrial and energy-related sources, transportation to a storage location and long-term isolation from the ambient air in geological formations, in the oceans, or as carbonate minerals [22]. CO2 capture, separation and storage techniques should be distinguished: pre-, oxy- and post-combustion as uptake methods; absorption (amines, carbonates, ammonia, and limestone), adsorption (metal organic frameworks and zeolites), membranes (fibers and microporous), biological (algae and cyanobacteria) as separation techniques; and geological, ocean and mineral sequestration as storage methods (Fig. 1.2) [23, 24, 25].

Figure 1.2 CCS techniques [23, 24, 25].

More and more companies are choosing the way to “zero” emissions or at least to reduce their carbon footprint by applying various CO2 trapping and separation techniques to optimize the technological process [26]. Following the capture step, gas is compressed and transported to appropriate storage location [27]. Geological storage options include an Enhanced Oil Recovery (EOR), Enhanced Coal-Bed Methane (ECBM) recovery, and saline aquifers injection [28]. But, unfortunately, the abovementioned techniques provide only short-term storage in geological scale and cannot be left unsupervised. Ocean storage seems challenging due to the increasing ocean acidification and marine life depletion as a result of CO2 injection directly into the ocean [29]. CO₂ trapping •Pre-combustion •Post-combustion •Oxy-combustion CO₂ separation •Absorption •Adsorption •Membranes •Biological CO₂ storage •Geological •Ocean •Mineral

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Thus, among the variety of storage options, carbon mineralization appears the most stable and environmentally benign technique that can be successfully applied all over the world. Since the possibility of safe and long-term storage is a crucial issue, mineral sequestration has been receiving an increasing attention as an efficient method of CCS [30].

1.3. Carbon mineralization

Different methods of carbon capture and storage from the ambient air as well as directly from industrial sources have been researched and developed recently [31]. While geologic and ocean sequestrations allow storage of CO2 in large quantities, high operation costs along with a cost of transportation and negative environmental impact emphasizes the need for more mature technologies [32]. As a result, much attention has been recently paid to the mineral carbonation or weathering as well as utilization of captured CO2 in industrial materials production [33]. Numerous technological routes for carbon sequestration by various minerals have been investigated to date [34]. The diversity of methods directly depends on the way of the process performing such as ex-situ which represents aboveground carbonation of naturally occurring Mg-based silicates and industrial wastes via mineral carbonation plant, in-situ where CO2 is injected into rocks formations or residues (Fig. 1.3). There is a third technique of carbon capture which does not require any external help in gas trapping and called a passive carbonation method where CO2 is captured naturally by various mine tailings as well as rocks [35, 36]. Currently, the research in carbon mineralization has largely focused on ex-situ and in-situ carbonation processes which is broadly exposed in the literature [23]. The principal distinction from passive mineralization is the presence of accelerators such as elevated temperature and high pressure (e.g., 185°C, 150 atm) [37]. Unlike aforementioned methods, natural passive carbonation takes place at atmospheric CO2 concentration, pressure, and temperature and has been documented all over the world [38, 39, 40].

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Figure 1.3 Ex-situ and in-situ carbonation concepts.

Mineral carbonation technology first was proposed by Seifritz in 1990 and the initial idea of this method is to simulate a natural phenomenon called weathering which principally represents a thermodynamically favorable reaction between silicate minerals with high magnesium (Mg) content and gaseous CO2 [41, 42]. There are several advantages that make mineral carbonation a viable process and motivate further investigations [43]. Firstly, the process naturally occurs and products of the reaction are a thermodynamically stable carbonates that have benign environmental impact [44]. Secondly, the capacity for large scale sequestration owing to Mg-rich minerals are widely available globally as relatively low-cost feedstock [45]. Finally, the process provides significant heat due to the exothermal behavior (R1.1-1.3) of ongoing reactions and hence it gives the potential for economic viability [20].

Mg2SiO4(s) + 2CO2(g) = 2MgCO3(s) + SiO2(s) + (- 90 kJ/mol CO2) (R1.1) Mg3Si2O5(OH)4(s) + 3CO2(g) = 3MgCO3(s) + 2SiO2(s) + 2H2O(l) + (- 64 kJ/mol CO2) (R1.2) Mg(OH)2(s) + CO2(g) = MgCO3(s) + H2O(l) + (- 81.1 kJ/mol CO2) (R1.3)

Direct gas-solid mineral carbonation has been receiving much less attention after Lackner research work in 1995 that investigated “wet” carbonation and recognized the gas-solid method as unviable due to it too slow carbonation rate and high energy consumption [46]. Direct one-step aqueous carbonation technology produces high–purity carbonates at the expense of high severity conditions such as high temperature and up to supercritical CO2 pressure which adversely affect the method economic viability [47]. Reactivity evolution was examined and has shown the importance of the presence of water in the pores. Since CO2 gas is soluble, it

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dissolves in porous water and provides the acidification required for leaching the material before the reaction develops between the aqueous carbonate ions and the basic metal cations [48, 49, 20, 21].

In the process of developing the idea of mineral sequestration, mining tailings, due to their availability and abundance, low cost, and a larger surface area, very quickly attracted the attention of various researchers [49, 50, 38]. Along with carbon emission mitigation policy emerged a demand to reduce the cost of CCS and, as a result, the use of lower temperatures and pressures close to ambient conditions that would consume less energy [51]. By far, sequestration kinetics, carbonation potential, water saturation of the material, products mineralogy, and temperature impact on the process were examined under environmental conditions by various research groups over the world [38, 48, 52, 53, 54, 55].

However, passive mineral sequestration suffers from a couple of drawbacks such as low intrinsic reaction rates in comparison with active mineral carbonation and the challenge to control the process under ambient conditions [49].

Summing up all aforesaid, the main advantage of mineral sequestration over other methods is the stable carbonates formation that permanently preserves carbon over geological time scale without risk of CO2 leakage back into the atmosphere [56].

1.4. Feedstock

Magnesium is the eighth most abundant element in the Earth's crust by mass. Depending on the 60+ naturally occurring Mg-bearing minerals, it is a more or less reactive when it comes to CO2 capture [57]. Nevertheless, magnesium silicates are favorable for carbon sequestration owing to their high abundance over the globe (Fig. 1.4) [31]. However, Mg-bearing alkaline industrial wastes, particularly mafic and ultramafic mining tailings, are used much more often than alkaline rocks by reason of fine particle size that as a result provides bigger reactive surface and greater reactivity in comparison to other silicate minerals [55].

By virtue of large amounts of mines all over the world and notably in Canada, mining residues became a widely utilized feedstock for permanent CCS [36]. Abundance of the material for CO2 sequestration is sufficient to capture substantial proportions from the carbon already accumulated in current atmosphere for the decades ahead [58].

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Figure 1.4 Location of ultra(mafic) rocks lying in the immediate vicinity (less than 300 km) from a CO2

-emission plant [56].

Mining tailings composition greatly varies and depends on the ore mineralogy and often consists of up to 20 wt. % Mg primarily in form of silicates [59]. In Quebec region mining tailings are represented as by-products after extraction and recovery of nickel as a valuable metal [60]. The mining residues composition can be generally presented by several mineral groups: serpentine ((Mg,Fe)3Si2O5(OH)4) which can be found in nature in form of several polymorphs – lizardite, chrysotile, antigorite; olivine ((Mg, Fe)2SiO4) and its Mg-dominant member forsterite, and brucite (Mg(OH)2) (Table 1.1) [52, 48]. Mg-rich olivine and serpentine are relatively much more common than Fe-bearing [52].

Table 1.1 Minerals for carbon storage and their occurrence

Mineral Formula Location

Serpentine (Mg,Fe)3Si2O5(OH)4 Canada (Quebec), China, Russia, France, Korea, New Zealand, New Caledonia, US (northern California, Rhode Island, Connecticut, Massachusetts, Maryland and southern Pennsylvania), Afghanistan, Britain (the Lizard peninsula), Ireland, Greece (Thessaly) Austria (Styria and Carinthia), India (Assam, and Manipur), Myanmar (Burma), Norway and Italy Olivine (Mg, Fe)2SiO4 Canada (Quebec), Norway, Italy

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The Quebec province is considered to be one of the main regions for the natural carbon mineralization due to the broad amount of feedstock for a passive carbon capture and storage [49, 38]. There are several regional mining sites with different brucite content. Black Lake Mine, Thetford Mines contains mainly lizardite and chrysotile with traces of brucite. Whereas Dumont Project, Royal Nickel Corporation has up to 11% of brucite with lizardite and chrysotile as main components [55, 61].

1.5. Process principles and reaction products

MgCO3 is the most desirable product of sequestration due to the lowest solubility and as a result highest stability over geological time scales [62, 63]. General reaction of CO2 uptake with formation of geologically stable carbonates can be represented as [64]:

MgxSiyOx+2y+ xCO2 = xMgCO3 + ySiO2 (R1.4) Unfortunately, from the chemical standpoint the reaction rate of the naturally occurring gas-solid process is very slow which leads to use of high temperature and pressure as acceleration factors to form MgCO3 as a product [65]. On industrial site, the process of CO2 uptake by mine wastes with precipitation of MgCO3 occurs in one step or as a multi-step process, also known as direct and indirect carbonation, respectively [66]. Simultaneous implementation of magnesium extraction from the mineral matrix and CO2 dissolution and carbonate formation in the same reactor is referred to as direct carbonation [67]. A one-step process takes place in either dry or aqueous medium under high pressure and can be illustrated as single reaction with serpentine or olivine (R1.5, R1.6) [68]:

Mg3Si2O5(OH)4 + 3CO2 → 3MgCO3 + 2SiO2 + 2H2O (R1.5) Mg2SiO4+ 2CO2 → 2MgCO3 + SiO2 (R1.6) From the point of further utilization, the challenge with direct carbonation is that the process cannot provide high purity carbonates and silica due to the different reaction conditions that are required for every step (mineral and CO2 dissolution, carbonate precipitation), limiting their application [69].

In an indirect process, Mg-bearing silicate minerals conversion to carbonates comprises three reactions: (R1.7) represents the magnesium separation from the mineral matrix (serpentine, for example) in the presence of an extracting agent such as hydrochloric acid (HCl); the second

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step is shown as a series of reactions (R1.8-1.11) to obtain Mg in the hydroxide form and dissolved CO2 [68].

Mg3Si2O5(OH)4(s) + 6HCl(l) → 3MgCl2 + 2SiO2(s) + 5H2O(l) (T = 100 °C) (R1.7) MgCl2·6H2O(aq) → MgCl(OH)(aq) + HCl(aq) + 5H2O(l) (T = 250 °C) (R1.8) 2MgCl(OH)(aq) → Mg(OH)2(s) + MgCl2(aq) (T = 80 °C) (R1.9) CO2 dissolution takes place in accordance with following reactions:

CO2(g) + H2O(l) ↔ H2CO3 ↔ H+ + HCO3- (R1.10) HCO3- ↔ CO32- + H+ (R1.11) Eventually, the magnesium hydroxide reacts with dissolved CO2 in pore water (R1.12) to form stable carbonates with low solubility [68].

Mg(OH)2(s) + CO2(aq) → MgCO3(s) + H2O(l) (T = 375 °C; PCO2 = 20 atm) (R1.12) CO2 hydration and mineral dissolution are favored at acidic pH conditions (pH˂5) therefore these steps can be combined in some cases. However, the fact that mineral dissolution requires a higher temperature should be taken to the account, whereas carbonate precipitation is favored at alkaline pH conditions (pH˃8) [70]. This difference in pH for multi-step process is used in a “pH-swing” concept to get purer products [71]. As opposed to single-step processes, indirect carbonation separates individually the reaction steps to be performed under individual conditions. This enables production of high-purity carbonates and silica with potential utilization whether as construction materials and for a use in other fields [72].

In contrast to the most thermodynamically stable MgCO3, various hydrated magnesium carbonates are formed due to the different operating conditions that affect their formation as temperature, partial pressure of CO2, and water content [72]. Table 1.2 shows the carbonates formation as dominant species depending on temperature [54, 73]:

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Table 1.2 Various carbonates formation

Tformation, 0C Mineral name Formula

Less 10 Lansfordite MgCO3·5H2O

20-35 Nesquehonite Mg(HCO3) (OH)·2H2O

35-50 Dypingite 4MgCO3·Mg(OH)2·5H2O

50-70 Hydromagnesite 4MgCO3·Mg (OH)2·4H2O

Above 70 Magnesite MgCO3

Under ambient conditions Mg-rich minerals fixate CO2 in the form of hydrated carbonates such as nesquehonite (Mg(HCO3)(OH)·2H2O), dypingite (4MgCO3·Mg(OH)2·5H2O) and hydromagnesite (4MgCO3·Mg(OH)2·4H2O) while formation of MgCO3 requires elevated temperature and can be only reached during industrial process [74]. Nesquehonite (R1.13, R1.14) is the most frequently observed carbonate product from a reaction with fresh feedstock in the range of 20-350C (Table 1.2) [75]. Based on theoretical calculations, the reactions chemistry is exothermic which contributes to economic benefits of mineral sequestration [76]. The reactions with serpentine and olivine produce ~1.6 and ~2 MJ/kg of CO2 respectively.

2Mg3Si2O5(OH)4(s) + 3CO2(g) + 6H2O(l) →

3(Mg(HCO3)OH · 2H2O)(s) + Mg3Si4O10(OH)2(s) + (-72.4kJ/mol CO2) (R1.13) Mg2SiO4(s) + 2CO2(g) + 6H2O(l) → 2(Mg(HCO3)OH·2H2O)(s) + SiO2(s) + (-91 kJ/mol CO2) (R1.14) Each mineral in Table 1.2 represents less hydrated form of previous one with regard to Mg content, which directly depends on the ambient temperature. Lansfordite is stable for several months at temperature around 10-150C, but can slowly dehydrate, eventually turning into nesquehonite [77]. Dypingite is the higher hydrated analog of hydromagnesite while magnesite remains the most stable form with the lowest solubility and forms at 1200C and a PCO2 of 3 bar [78, 79]. Transformation of hydrated Mg carbonates to anhydrous forms has been widely reported in industry. It remains quite a complicated process that can be implemented via dehydration or dissolution and precipitation in conjunction with elevated temperatures (60-1500C), different CO2 pressures, and pH-swing [72, 80, 81, 82]. The initial formation of less stable hydro carbonates instead of magnesite can be explained by Ostwald empirical rule of stages which implies that thermodynamically less stable hydrous carbonate phases occur first and then transformed to the stable anhydrous form [83, 63].

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1.6. Carbon mineralization by brucite

Considering significant energy consumption of enhanced CCS methods that require stringent process conditions, passive mineralization seems economically more viable and demands no human supervision [38, 50]. However, general carbonation behavior investigation has been conjugated with accelerated conditions such as high temperature and pressure [69].

Permanent capture and storage of CO2 in mineral formations is being seen as a way to reduce the carbon concentration in the atmosphere and thus contributing to the mitigation of global warming [84]. Due to the fact that the reaction takes place at long geological timescale, turning on the chemistry of the process of mineral sequestration into a fast one is challenging. One of the minerals in mining wastes that can enhance the material reactivity and speed up the reaction rate is brucite. In connection with this, brucite employment as a carbon sink is widely studied [85].

Native brucite is commonly formed in association with (ultra)mafic rocks and carbonates. It also can be found in mining residues in considerable amounts (up to 15%wt.) [37]. Brucite presence in mining tailings is a key to faster carbon dioxide capture from the ambient air due to its higher reactivity in comparison with silicate minerals [86]. Brucite as a part of residue composition despite its minor availability in nature is getting an increasing attention for carbon capture. It is known that in the mining site brucite is spontaneously carbonated leading to formation of hydrous magnesium carbonates such as nesquehonite and hydromagnesite during weathering of residue pile [87].

Prior to study of brucite carbon mineralization, several research groups investigated the brucite content in mining wastes and its contribution to the carbonation kinetics. It revealed that brucite content is directly related to the reaction rate and brucite-rich tailings react much faster under various conditions [88, 89, 90]. Current research on mineral sequestration are mainly devoted to the surface chemistry, morphology, dissolution rate and carbonates precipitation (Table 1.3) [22].

In 1996, Butt et al. studied magnesium hydroxide behavior as a function of elevated temperature (275-475°C) and observed the simultaneous dihydroxylation and carbonation processes. The intent of the work was to study the reaction kinetics and after 12 h of experiment at 375°C and 0.76 atm was measured the fastest brucite powder transformation into MgCO3

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(~16.7 wt.%). Magnesium carbonate precipitation on the surface of brucite crystals was observed using TEM (Transmission Electron Microscopy) [91].

Later, in 2002, Bearat et al. used a single crystal peace of natural brucite from Delora, Canada as a sample to monitor the carbonate formation at various high pressure and temperature (375-585°C) in 16 h. During the course of the gas-solid carbonation process several conclusions were made:

- Direct carbonation occurs only at CO2 critical pressure which is needed for MgCO3 formation at 375°C;

- For a CO2 pressure of 25.2 atm, temperature increase has a positive influence on the reactivity until 537°C where MgCO3 becomes thermodynamically unstable;

- The use of low-temperature dehydroxylation prior to carbonation provides the porous intermediates formation with increased reactivity to carbonization at a lower temperature and pressure [92].

Later research was mainly focused on aqueous carbonation due to its milder conditions and better performance. Thus, in 2004, Pokrovsky and Schott monitored Mg(OH)2 crystals dissolution rate in 0.01 mol/L NaCl solutions at room temperature at various pH values (2.5-12) and oxygen presence. It was determined that oxygen positively affects the reaction evolution due to its incorporation into the water molecule which facilitates the reaction rate.

In 2010, Zhao et al. observed nesquehonite formation at room temperature, mild CO2 pressure, and in aqueous environment as confirmed by FT-IR (Fourier Transform Infrared Spectroscopy) and XRD (X-Ray Diffraction) analyzes. Tests were carried out in two different solutions - diluted HCl (0.39 mol/L) and 300 mL Distilled Deionized Water (DDW). Monitoring of the reaction indicated hydrous carbonate formation in both cases. XRD analyses reported 95% brucite conversion in nesquehonite in 2.5 h in DDW whereas in case of HCl only 78% conversion was reached [86].

Schaef et al., 2011 published a study of brucite carbonation at 82 bar pCO2, elevated temperature (50 and 75°C), and various water saturation levels. Supercritical CO2 pressure gave an opportunity to investigate the process under different conditions to find the optimal one. Brucite sample treated by anhydrous CO2 stream showed no reactivity and lesser then 1% carbonates precipitation based on XRD. Once water was added, the performance changed significantly. Wet carbonation due to the carbon dioxide supersaturation gave 100% conversion

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of brucite to nesquehonite at 50°C; magnesite formation was observed at 75°C with complete brucite conversion [93].

Research conducted by Fagerlund et al. (2011) in a gad-solid carbonation at high CO2 pressure using a pressurised fluidised bed. The highest CO2 conversion (38 wt.%) was observed at 60 bar. However, too much elevated (close to supercritical) CO2 pressure led to a reduction of the reactivity of Mg(OH)2 since high H2O pressure prevents its diffusion [94].

Fricker and Park (2012) studied various pathways in order to determine optimal carbonation conditions. Effect of water presence in a slurry phase was compared with a high pressure gas-solid carbonation:

- Gas-solid carbonation suffered from serious restrictions and even high pCO2 tests did not enhance the reactivity sufficiently at a given reaction temperature (260, 280, 300, 320°C);

- At 673 K about 17.6% of brucite was converted to carbonate in the aqueous phase; - Increase in water pressure led to a sharp increase in carbonation conversion at a given

reaction temperature (200, 300, 400°C). Thus, at 5.5 MPa H2O pressure, 400°C and 1.45 MPa pCO2, 70% of brucite was converted to MgCO3.

In 2013, Harrison et al. performed a series of tests to study carbonation kinetics and brucite dissolution employing high pCO2 to enhance the process. Nesquehonite precipitation was observed within 2 h in 100% CO2 gas stream. SEM (Scanning Electron Microscopy) analysis showed nesquehonite morphology as well as formation of more stable hydrous carbonate (dypingite) for 10% and 50% CO2 supply stream, while in case of 100% CO2 the prevailing product was nesquehonite. Brucite dissolution was found to be dependent on the solution pH. Thus, CO2 dissolution promotes the process due to increased HCO3- ions concentration in the solution. In case of 100% pCO2, 223 g of nesquehonite was produced and 71 g of CO2 captured within 10 h, while during an atmospheric pCO2 test 14 g of carbon dioxide was captured in ca. 2800 h of experiment [95].

In the same year, Bharadwaj et al. (2013) examined brucite dissolution at range of pH values (7.6-9.6) and 22-52°C temperature. Decline in pH values led to the acceleration in Mg(OH)2 dissolution rate due to the higher H+ ion production at lower pH. Carbonation temperature also had a distinguishable influence on dissolution rate. Temperature rise from 22 to 52°C enhanced the reaction rate constant by a factor 5 at 8.6 pH value [96].

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Table 1.3 Various studies on carbon mineralization by brucite

Research group Process conditions Best process conditions to enhance the process

Butt et al., 1996 275-475°C 375°C and 0.76 atm

Bearat et al., 2002 High pressure 375-585°C

537°C and 25.2 atm

Pokrovsky and Schott, 2004

25°C 2.5-12 pH

O2

-

Zhao et al., 2010 Room temperature

15 atm DDW or 1%HCl

DDW

Schaef et al., 2011 50 and 75°C

82 bar

Various water content

CO2 supersaturation

Fagerlund et al., 2011 415-545°C

15, 20, 25, 30, 55, 60 bar

525°C and 60 bar

Fricker and Park, 2012 Gas-solid: 1.03-1.45 MPa

pCO2; 260, 280, 300, 320°C Aqueous phase: 1.03-1.45 MPa pCO2; 200, 300, 400°C 400°C and 1.45 MPa (aquatic phase)

Harrison et al., 2013 Range of pCO2 (0.04, 10, 50, 100%) Room temperature 100% pCO2 Bharadwaj et al., 2013 22-52°C 7.6-9.6 pH 52°C and 8.6 pH

Unfortunately, brucite carbonation under ambient conditions has been almost an orphan research subject in comparison to accelerated methods mentioned above. Passive carbon mineralization is a complex process occurring in nature. To investigate and assure effective

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passive carbonation under ambient conditions by mining residues and particularly by brucite several studies have been performed [60, 97].

Aqueous mineralization of brucite (ΔGr = -38.73 kJ/mol) [98] involves the following steps:

1) Gaseous CO2 hydration and dissolution in the aqueous phase:

CO2 (g) → CO2 (aq) (R1.15) CO2 (aq) + H2O (l) → H2CO3 (aq) (R1.16) 2) H2CO3 (aq) dissociation with formation of bicarbonate and carbonate ions:

H2CO3 (aq) → H+ (aq) + HCO3– (aq) (R1.17) HCO3– (aq) → H+ (aq) + CO32– (aq) (R1.18) 3) Dissolution of water saturated brucite into Mg2+ (aq) and OH– (aq) :

Mg (OH)2 (s) + H+ (aq) → Mg2+ (aq) + H2O (l)+ OH– (aq) (R1.19) 4) Mg2+ reacts with bicarbonate ions with precipitation of solid phase in form of

nesquehonite:

Mg2+ (aq) + HCO3– (aq) + OH– (aq) + 2H2O (l) → Mg (HCO3) (OH)∙2H2O (s) (R1.20) In a study investigating passive mineral carbonation, Pronost et al. (2012) reported that several warm vents were discovered on the top of the residue heap. Especially, it was seen in the cold season (November to March), when the ambient air temperature ranged from -13.2 to 0°C, and the temperature of venting zones ranged from 6.6 to 12°C. The presence of such temperature variations is a direct evidence of heat generation during the CO2 capture directly from the atmosphere by mining wastes. Thermal variations were measured by means of an infrared camera FLIR-5i [61, 99].

Significant contribution and discussion on the subject of heat generation was made by Assima et al. (2014). During the course of experiments under ambient conditions on a laboratory scale, Assima used a carbonation reactor where mixture of CO2 and N2 was recirculating through the mining tailings by means of a peristaltic pump. Thus, at 20°C temperature difference between the gas phase and residues bed was 1.1°C within 100 h [100].

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Altogether, these studies provide important insights into the heat generation during the reaction of CO2 sequestration. Although, the exothermic behavior of the process is well known and documented in the literature [101, 102], there have been no controlled studies in the laboratory scale that investigate it in detail.

1.7. Infrared thermography

Historically, temperature measurements were implemented by means of thermometers. However, with technological advancements, other methods began to emerge as thermocouples, thermistors, pyrometers, and infrared cameras. Infrared radiation has a wide range of applications in various fields including Infrared Thermography (IRT). Since infrared radiation is able to non-invasively determine the object's temperature, this served as a starting point for development in the field of Non-Destructive Testing (NDT) [103]. IRT implementation for temperature measurements comprises accurate equipment selection such as suitable camera, lenses, and optical window (polymer IR film) as well as pre-experimental calibration to improve spatial resolution and correct post-processing method application for temperature determinations [104].

IRT can be divided into two schemes, active and passive. While active approach needs an external excitation source (thermal or electromagnetic radiation, mechanical stimulation, electrical, and chemical), passive IRT is based on a temperature difference between the environment and the object of study [105].

Passive infrared thermography is a powerful tool mainly used in medical (to observe blood flow in the skin and to track body temperature), industrial (to detect overheating of electrical and mechanical devices and systems, for building diagnostics), and many other technical/scientific (to track the temperature during the process, in material testing) applications [106, 107, 108].

Human body temperature is a natural indicator of health. Any deviations from normal body temperature (36.1-37.2 C) may indicate inflammation, infection, hypothermia or heat stroke. IRT application can be employed as a remote non-invasive technique instead of traditional clinical thermometers. Moreover, IRT is successfully used in the diagnosis of first signs of breast cancer, neuropathy of diabetes, heart operations, skin diseases, dentistry and dermatology, and vascular disorders [109, 110, 111].

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Recently, researchers have shown an increased interest in industrial application of IR thermal imaging as a real-time, affordable, portable, non-intrusive and reliable measurement tool. IRT as a condition-monitoring instrument contributes in electrical inspections as well as the maintenance of various mechanical equipment (pumps, motors, fans, drives, conveyors, etc.). IR images analysis helps to prevent a costly shutdown and apparatus failure or human injury by preventing a problem before the emergence of a critical situation [112].

Research and development (R&D) sector is constantly going towards process improvement and that is one of the major reasons of IRT utilization in online temperature control to provide instantaneous temperature data throughout the process [113]. Particularly in chemical engineering, IRT is employed in temperature tracking as one of the surface features indicators [114].

In 1995, Greenberg et al. implemented application of Hughes TVS 4500 Probeye thermal video system for polymer solution evaporation representation. This study pointed out the importance of IRT as a remote technique for real-time measurement of the temperature profiles [115]. Later Marengo et al. (1997) conducted a series of catalytic experiments to observe thermal variations by means of Agema Thermovision 900 apparatus. The primary aim of the study was to track thermal effects under real operating conditions on the surface of the material and compare them with data from thermocouples inserted in the material bulk. Temperature profiles from IR camera and thermocouples had similar tendencies but different values due to the temperature gradient [116].

Surface thermal profiles depending on the temperature distribution due to an oscillatory process occurring in solution, was examined by Pekala et al. (2010). A ThermaCAM SC2000 was integrated into an experimental setup to monitor the process and allowed to identify temperature gradients at the surface of the solution apart from bulk techniques to measure bulk temperature [117].

Various temperature tracking tests were performed by Xie (2011) using a FLIR i5 infrared camera. The intent of the work was to provide visualization of different chemical processes as latent heat, evaporation, condensation, heat of solution, and temperature gradient (Fig. 1.5). This work allowed depiction of the basics of thermal phenomena and IR imaging implementation in chemical engineering [118].

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Figure 1.5 IR imaging: (A) ice cube was added to a freshwater (left) and a saltwater (right); (B) in 4 min;

(C) in 9 min; (D) in 16 min [118]

The use of IRT to access to enthalpy of highly exothermic chemical reactions as between a strong base and a strong acid was demonstrated by Hany et al. (2012). IR thermal imaging provided a good sensitivity and a direct measurement of the heat flux. In order to determine the enthalpy of the chemical reaction, temperature profiles were measured and then the total exothermic flux was calculated. Based on the literature, the experimental result had a relative error of less than 3% [119].

Barin et al. (2015) carried out a number of investigations into IR imaging application in analytical chemistry to determine the total acidity of vinegar. Thus, enthalpy of neutralization, precipitation, redox and complexation reactions was determined by means of IR camera FLIR-E60 that tracked the temperature of these reactions by a non-contact method from the surface of the material. Results were compared with those based on traditional technique (mercury thermometer) and no difference was observed [120].

Zhang et al. (2016) used a PI400 infrared camera to determine the reaction enthalpy. Temperature profiles were monitored during the fast exothermal reaction in a coiled capillary (Fig. 1.6). Obtained data was compared with theoretical calculations and conventional calorimeter method and relative experimental error was below 5% [121].

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Figure 1.6 Temperature profiles during fast exothermal reaction [121]

During the last decade, IRT has developed into a powerful instrument of surface temperature distribution analysis. Nevertheless, it is essential to consider all factors that affect the system to provide correct temperature measurements. Most of the new generation IR cameras provide fast and easy to operate systems along with high-quality spatially-resolved pixelated temperature images [112].

1.8. Objectives

Majority of research groups investigated severe conditions to accelerate carbonation reactions. Passive carbon mineralization using ambient air CO2 is believed to diminish carbon footprint naturally and without additional monetary costs and resources [122]. In addition, exothermal behavior of the reaction allows considering its potential use for heat exploitation and/or recovery.

This research project examines the heat release phenomena during carbonation of brucite, the most reactive mineral in the mining residues.

The aim of this research is to explore mineral carbonation and the heat release through tracking the thermal variations during carbon capture at ambient conditions in a fully instrumented laboratory scale carbonation reactor. The specific goals of this research program are as follows: - Passive carbon mineralization simulation in laboratory scale for summer season

conditions;

- Suitable MATLAB code development that is able to represent the experimental data; - Temperature evolution and heat balance assessment based on reactor's configuration.

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Monitoring thermal variations in carbon capture by brucite

MONITORING THERMAL VARIATIONS IN

CARBON CAPTURE BY BRUCITE

Mémoire

Diana Aksenova

Maîtrise en génie chimique

Maître ès sciences (M. Sc.)

Québec, Canada

MONITORING THERMAL VARIATIONS IN

CARBON CAPTURE BY BRUCITE

Mémoire

Diana Aksenova

Sous la direction de :

Faïçal Larachi, directeur de recherche

Xavier P.V. Maldague, codirecteur de recherche

Résumé

Abstract

Table of Contents

List of figures

List of tables

List of abbreviations

Twenty years from now you will be more disappointed by the things that you didn’t do than

by the ones you did do. So throw off the bowlines. Catch the trade winds in your sails.

Explore. Dream. Discover.

Acknowledgments

Foreword

Chapter I

Introduction and scope of the project

1.1.

Global warming and carbon footprint

1.2.

Carbon capture and storage: the process

1.3.

Carbon mineralization

1.4.

Feedstock

1.5.

Process principles and reaction products

1.6.

Carbon mineralization by brucite

1.7.

Infrared thermography

1.8.

Objectives

1.9.

References