Production of Mg(OH)2 from Mg-silicate rock for CO2 mineral sequestration

Sequestration of carbon dioxide in mineral rocks, also known as CO2 Capture and Mineralization (CCM), is considered to have a huge potential in stabilizing anthropogenic CO2 emissions. One of the CCM routes is the ex situ indirect gas/sold carbonation of reactive materials, such as Mg(OH)2, produced from abundantly available Mg-silicate rocks. The gas/solid carbonation method is intensively researched at Åbo Akademi University (ÅAU ), Finland because it is energetically attractive and utilizes the exothermic chemistry of Mg(OH)2 carbonation. In this thesis, a method for producing Mg(OH)2 from Mg-silicate rocks for CCM was investigated, and the process efficiency, energy and environmental impact assessed. The Mg(OH)2 process studied here was first proposed in 2008 in a Master’s Thesis by the author. At that time the process was applied to only one Mg-silicate rock (Finnish serpentinite from the Hitura nickel mine site of Finn Nickel) and the optimum process conversions, energy and environmental performance were not known. Producing Mg(OH)2 from Mg-silicate rocks involves a two-staged process of Mg extraction and Mg(OH)2 precipitation. The first stage extracts Mg and other cations by reacting pulverized serpentinite or olivine rocks with ammonium sulfate (AS) salt at 400 - 550 oC (preferably < 450 oC). In the second stage, ammonia solution reacts with the cations (extracted from the first stage after they are leached in water) to form mainly FeOOH, high purity Mg(OH)2 and aqueous (dissolved) AS. The Mg(OH)2 process described here is closed loop in nature; gaseous ammonia and water vapour are produced from the extraction stage, recovered and used as reagent for the precipitation stage. The AS reagent is thereafter recovered after the precipitation stage. The Mg extraction stage, being the conversion-determining and the most energy-intensive step of the entire CCM process chain, received a prominent attention in this study. The extraction behavior and reactivity of different rocks types (serpentinite and olivine rocks) from different locations worldwide (Australia, Finland, Lithuania, Norway and Portugal) was tested. Also, parametric evaluation was carried out to determine the optimal reaction temperature, time and chemical reagent (AS). Effects of reactor types and configuration, mixing and scale-up possibilities were also studied. The Mg(OH)2 produced can be used to convert CO2 to thermodynamically stable and environmentally benign magnesium carbonate. Therefore, the process energy and life cycle environmental performance of the ÅAU CCM technique that first produces Mg(OH)2 and the carbonates in a pressurized fluidized bed (FB) were assessed. The life cycle energy and environmental assessment approach applied in this thesis is motivated by the fact that the CCM technology should in itself offer a solution to what is both an energy and environmental problem. Results obtained in this study show that different Mg-silicate rocks react differently; olivine rocks being far less reactive than serpentinite rocks. In summary, the reactivity of Mg-silicate rocks is a function of both the chemical and physical properties of rocks. Reaction temperature and time remain important parameters to consider in process design and operation. Heat transfer properties of the reactor determine the temperature at which maximum Mg extraction is obtained. Also, an increase in reaction temperature leads to an increase in the extent of extraction, reaching a maximum yield at different temperatures depending on the reaction time. Process energy requirement for producing Mg(OH)2 from a hypothetical case of an iron-free serpentine rock is 3.62 GJ/t-CO2. This value can increase by 16 - 68% depending on the type of iron compound (FeO, Fe2O3 or Fe3O4) in the mineral. This suggests that the benefit from the potential use of FeOOH as an iron ore feedstock in iron and steelmaking should be determined by considering the energy, cost and emissions associated with the FeOOH by-product. AS recovery through crystallization is the second most energy intensive unit operation after the extraction reaction. However, the choice of mechanical vapor recompression (MVR) over the “simple evaporation” crystallization method has a potential energy savings of 15.2 GJ/t-CO2 (84 % savings). Integrating the Mg(OH)2 production method and the gas/solid carbonation process could provide up to an 25% energy offset to the CCM process energy requirements. Life cycle inventory assessment (LCIA) results show that for every ton of CO2 mineralized, the ÅAU CCM process avoids 430 - 480 kg CO2. The Mg(OH)2 process studied in this thesis has many promising features. Even at the current high energy and environmental burden, producing Mg(OH)2 from Mg-silicates can play a significant role in advancing CCM processes. However, dedicated future research and development (R&D) have potential to significantly improve the Mg(OH)2 process performance.

DFMA Aspects in the Design of a Transfer Line for Off-line Ion Sources

In this thesis, the DFMA is presented and used for the purpose of having a design for a vertical transfer line that can be easily manufactured and assembled. The design of the transfer line, the major components and drawings are presented. The ease of assembly, the costs of manufacturing and differences between the use of steel structure and aluminum are compared. The ALARA principle is followed to minimize the risk of radiation exposure by the means of locating the test ion sources outside the radioactive area.

Buckling analysis of PVC sheets with RIB

This study has a technical and applied character. A PVC structured wall pipe can be produced by spirally winding a ribbed sheet having a male-female lock, chemically welded by an adhesive. These pipes are "flexible" and are used mainly in underground installations, to convey fluids in free duct regime. Initial studies have indicated that the buckling resistance of the ribs from the sheet coiling to the tube manufacturing is the critical design parameter. This study presents the theoretical analytical development in order to obtain the critical buckling moment of these sheets. This analysis uses concepts initially developed to calculate buckling resistance in monosymmetrical profiles that are very used in the metallic structure industry. Since the material used was PVC, that has different mechanical properties than steel and aluminum, it was necessary to consider the differences in the analytical treatment. It is important to emphasize that the results obtained are product of the co-operative work of engineers from industry and university.

Potential utilization ways of recovered chemical products from digestate

The study evaluates the potential application of chemical substances, obtained from biogas plants` by-products. Through the anaerobic digestion process with biogas the large amount of digestate is produced. This digestate mainly consists on the organic matter with the high concentration of nutrients such as nitrogen and phosphorus. During ammonia stripping and phosphorus precipitation the products- ammonia water, ammonium sulfate, ammonium nitrate, ferrous phosphate, aluminum phosphate, calcium phosphate and struvite can be recovered. These chemicals have potential application in different industrial sectors. According to Finnish market and chemicals properties, the most perspective industrial applications were determined. Based on the data, obtained through the literature review and market study, the ammonia water was recognized as a most perspective recovered substances. According to interview provided among Finnish companies, ammonia water is used for flue gas treatment in SNCR technology. This application has a large scale in the framework of Finnish industrial sectors. As well nitrogen with phosphorous can be used as a source of nutrients in the biological wastewater treatment plants of paper mills.

Unexpected effects of pigeon-peas (Cajanus cajan) in the restoration of rupestrian fields

Several degraded areas can be found along the Highway MG-010 that crosses the Espinhaço Mountain Biosphere Reserve in the Brazilian state of Minas Gerais. Restoration by planting the legume Cajanus cajan was implemented in some of these areas. The present study compares plant species richness, diversity, abundance, equitability, similarity, and soil composition between restored and non-restored areas, in an attempt to evaluate the effectiveness of the use of C. cajan in the restoration process in the mountain environment. Each treatment (restored and non-restored) had four sampling areas, each with three 300 m² plots. We counted and identified every individual plant found within these plots. We also collected soil from the superficial layer (0-10 cm) of each sampling area in both treatments. The areas where C. cajan was planted revealed lower species richness, diversity, and plant abundance. The soil of these areas also contained higher levels of Phosphorus and Magnesium. Plant equitability and similarity between plots and other soil components (pH, Nitrogen, Aluminum, Calcium, Potassium, H+Al, sum of bases - SB, cation exchange capacity - CTC, base saturation - V%, aluminum saturation - M%) did not differ between the two treatments. Contrary to the expectations, soil enhancement in the quartzitic soil poor in nutrients in the rupestrian fields can facilitate the invasion by exotic plants, which are not adapted to the lack of nutrients. As it appears, the use of C. cajan in restoration projects represents a mistake and future restoration plans should avoid the use of exotic species, given that they may cause negative effects on the native plant community, as demonstrated here in the rupestrian fields.

Sorption of oxadiazon in soils cultivated in the brazilian cerrado

The objective of this study was to evaluate oxadiazon sorption in different soils of the Brazilian Cerrado, highlighting the correlations of lethal doses of this herbicide capable of inhibiting 50% of the dry matter accumulation of the bio-indicator (LD50) among the chemical characteristics of the soil and its direct and indirect effects. The experiment was carried out in a greenhouse in a randomized block design and four repetitions. Each experimental unit consisted of a pot with increasing rates of oxadiazon and oat (Avena sativa), as the bio-indicator species. For sorption evaluation, washed sand and 22 soils (substrates) from Cerrado Brazilian's Alliaceae cultivated areas were used. LD50 and sorption ratio (SR) = [(LD50soil - LD50sand)/LD50sand] to the substrates were determined. Pearson correlation analysis was performed between the chemical characteristics of the substrates and the LD50 of oxadiazon. A path analysis was quantified, to deploy only the significant correlations estimated in direct and indirect effects of the characters on LD50, which is a basic variable. A more pronounced LD50 (528.09 g ha-1) for the Cerrado soil sample resulted in higher SR (> 53.00), while in the washed sand substrate, LD50 corresponded only to 9.74 g ha-1 of the oxadiazon (available in soil). It was concluded that oxadiazon sorption is influenced by the chemical characteristics of the soils, highlighting the correlation with pH (CaCl2), magnesium content, aluminum, organic matter, organic carbon, and aluminum saturation.