Mohammad Ghaddaffi Mohd Noh

Conventional production methods of aragonite production utilize chemical inducers to promote the evolution of the calcite crystalline phase to the aragonite phase of calcium carbonate. The chemical inducers used require a considerable amount of magnesium chloride (MgCl₂) to induce crystallization, which is a major operational cost. Application of such materials in large amounts can be a deterrent to achieving a sustainable and economically feasible end-product derived from carbon dioxide (CO₂) molecules. A number of previous research works focused mainly on optimizing the usage of MgCl₂ or introducing alternative chemical inducers for aragonite production. In this work, we are proposing the usage of natural seawater as it is a naturally available and abundant resource to induce the synthesis and continuous production of aragonite compounds. Due to inconsistent quality and salinity of the natural seawater sampled, harvested, and dried, Red Sea Salt is utilized, blended at 33 g/L throughout the laboratory experiments for better statistical control, and is referred to as blended or artificial seawater. A methodology of utilizing seawater, which has a considerable concentration of MgCl₂ compound, can be utilized as a sustainable, natural, and economically feasible natural inducer to synthesize aragonite has been developed by utilizing artificial seawater for laboratory proof of concept. The main effects identified for the optimization of aragonite synthesis are lime (CaO) feedstock concentration in seawater, reaction temperature, and reaction duration. The experiment results indicated that only by increasing temperature and reaction duration, or both, can the aragonite yield be increased. It is suggested that the range of operation to obtain > 80% aragonite purity has been identified with the reaction temperature at 90 °C, reaction duration of 10 min, and CaO concentration in seawater at 1 g/L. The quality of the aragonite synthesized via seawater is characterized using XRD, ICP, FESEM, and TGA, and compared with aragonite particles synthesized using MgCl₂ inducers. In comparison, seawater aragonite has lower residual alkalinity compared to both calcite and aragonite via MgCl₂ and has a mixture of predominantly needle-shaped crystalline structure and remnants of cubic-shaped particles, presumably calcite, suitable for application in food, beverages, and pharmaceuticals (calcium antacids, nutritional supplements, chewable, lozenges).

The Global Cement and Concrete Association (GCCA) estimated that by 2050, 36% industry-wide sustainable value will be created, which includes sequestering CO₂ into the cement and concrete industry to produce commercially feasible high-value products. Direct utilization of CO₂ in the cement and concrete industry, which utilizes natural and sustainable materials, is gaining momentum. Naturally occurring mixtures of hydro magnesite and huntite are important industrial minerals which, upon endothermic decomposition over a specific temperature range, will release water and CO₂. This unique chemistry has led to such mixtures being successfully utilized as fire retardants, replacing aluminum hydroxide or Alumina Tri-Hydrate (ATH). Despite the developed marketplace for magnesium-based fire-retardant products, there is little mention of CO₂ mineral carbonation methods, which attempt to recover and convert magnesium from natural seawater or industrial waste into oxides or carbonates as part of the carbon sequestration initiative. The hypothesis to be proven in this work states that if the process of seawater mineral carbonation is prematurely quenched, Mg²⁺ ionic species in seawater adsorbed on the calcite lattice formation will be trapped and therefore recovered in various oxidized forms, such as magnesium oxides, magnesium hydro magnesite, and magnesium carbonate precipitates. A novel method to recover magnesium Mg²⁺ ions from seawater was successfully explored and documented; as such, from an initial concentration of 1250 ppm Mg²⁺ in raw seawater, the average concentration of spent Mg²⁺ ions after the reaction was as low as 20 ppm. A very efficient near-total recovery of Mg²⁺ from the seawater into the solid precipitates was recorded. Subsequently, the process for continuous seawater mineral carbonation for the production of magnesium/brucite/huntite products was successfully proven and optimized to operate with a 30 s reaction time, a dynamic feedstock concentration, [CaO] at 1 gpl in seawater and a room temperature reaction temperature (30 °C), where the average yield of the fire-retardant magnesium-based compounds was 26% of the synthesized precipitates. Approximately 5000 g of the hydro magnesite materials was molded into a fire-retardant brick or concrete wall, which was subjected to an accredited fire performance and durability testing procedure BS476-22:1987. There were encouraging results from the fire resistance testing, where the fire-retardant material passed BS476-22:1987, with performance criteria such as physical integrity failure, the maximum allowable face temperature, and a minimum duration before failure, which was up to 104 min, evaluated.

The current state of the art research, and latest engineering technology application in the synthesis of the aragonite crystalline phase of calcium carbonate is presented here. Aragonite crystalline products are highly valuable in selected industries, such as medical and personal care, and in food additives using MgCl₂ as a chemical inducer. The outcome of this literature review provides the outlook of the available research whitespace opportunity in optimizing the current process parameters and in ensuring that sustainable and economically feasible continuous production of aragonite products could be achieved. One of the major improvements proposed in this study is to investigate the methods of synthesizing aragonite crystalline particles using a continuous mineral carbonation reactor system and optimizing the operating parameters. An experimental design was established to identify all the main effects to maximize aragonite production. The three main effects investigated are the effect of feedstock or reactant concentration, the effect of reaction temperature, and the effect of reaction time towards aragonite yield in the final products synthesized. An optimized operating parameter for maximum aragonite yield at 95% purity was proposed at the reaction temperature T of 90 °C, reaction time t of 10 min, and feedstock ratio Mg-to-Ca of 0.4. Subsequently, the continuous reactor system was designed, operated, and tested for at least 50 h operation, where the lime CaO(s) feed was successfully converted into aragonite products with purity between 75 and 81%. The properties and quality of the aragonite produced were analytically characterized from the following laboratory methods which include the thermalgravimetric analysis, TGA; X-Ray Diffraction, XRD; scanning electron microscopy, SEM; and induction coupled plasma, ICP. TGA mass balance after decomposition suggests that 44% of the mass balance represents the weight of CO₂ sequestered in the aragonite crystalline carbonates. Hence, the aragonite crystalline carbonates can be labeled as a green product which sequesters 0.44 kg of CO₂ per 1 kg of precipitated aragonite products synthesized. Interestingly, SEM microscopy characterization results revealed that the aragonite precipitate has a physical morphology of needle-like shape with a good aspect ratio (length/diameter) AR of between 8.67 micron and 11.35 micron. The properties were found to be suitable for paper making fillers, medical, personal care, and food additive applications.