Characterization Method for Comminution Behavior of Limestone and Fuel Ash in a Circulating Fluidized Bed Boiler

Työn tavoite oli kehittää karakterisointimenetelmät kalkkikiven ja polttoaineen tuhkan jauhautumisen ennustamiselle kiertoleijukattilan tulipesässä. Kiintoainekäyttäytymisen karakterisoinnilla ja mallintamisella voidaan tarkentaa tulipesän lämmönsiirron ja tuhkajaon ennustamista. Osittain kokeelliset karakterisointimenetelmät perustuvat kalkkikiven jauhautumiseen laboratoriokokoluokan leijutetussa kvartsiputkireaktorissa ja tuhkan jauhatumiseen rotaatiomyllyssä. Karakterisointimenetelmät ottavat huomioon eri-laiset toimintaolosuhteet kaupallisen kokoluokan kiertoleijukattiloissa. Menetelmät kelpoistettiin kaupallisen kokoluokan kiertoleijukattiloista mitattujen ja fraktioittaisella kiintoainemallilla mallinnettujen taseiden avulla. Kelpoistamistaseiden vähäisyydestä huolimatta karakterisointimenetelmät arvioitiin virhetarkastelujen perusteella järkeviksi. Karakterisointimenetelmien kehittämistä ja tarkentamista tullaan jatkamaan.

Canopy openness and lai estimates in two seasonally deciduous forests on limestone outcrops in central Brazil using hemispherical photographs

Patches of seasonally dry tropical forests occur on limestone outcrops in Central Brazil surrounded by the dominant savanna vegetation. They contain valuable timber species but are threatened by farming and mining activities. The objective of this study was to describe canopy opening and light relations in two seasonally deciduous dry forests on slopes and limestone outcrops, in the Paranã valley at the northeastern region of the Goiás state, Brazil. The studied forests were in the Fazenda Sabonete in Iaciara-Go and Fazenda Forquilha in Guarani-GO. Woody plants were sampled in 25 (20 x 20 m) plots in each forest. In the Sabonete forest 40 species, 705 ind./ha-1 with a basal area of 15.78 m²/ha-1 were found, while in Forquilha there were 55 species, 956 ind./ha-1 with a basal area of 24.76 m²/ha-1. Using hemispherical photographic techniques, 25 black and white photographs were taken at each site, during the dry season, totaling 50 photographs. These were taken at the beginning of each vegetation-sampling plot. The photographs were scanned in grey tones and saved as 'Bitmap'. The canopy opening and leaf area index (LAI) were calculated using the software Winphot. The mean canopy opening was 54.0% (±9.36) for Fazenda Sabonete and 64.6% (±11.8) in Fazenda Forquilha, with both sites presenting significant differences in the opening estimates (P < 0.05). Their floristic richness and structure also differed with the more open canopy forest, Forquilha, being richer and denser, suggesting the need for further studies on species-environment relationships in these forests.

Modelling of combustion and sorbent reactions in three-dimensional flow environment of a circulating fluidized bed furnace

This thesis presents a three-dimensional, semi-empirical, steady state model for simulating the combustion, gasification, and formation of emissions in circulating fluidized bed (CFB) processes. In a large-scale CFB furnace, the local feeding of fuel, air, and other input materials, as well as the limited mixing rate of different reactants produce inhomogeneous process conditions. To simulate the real conditions, the furnace should be modelled three-dimensionally or the three-dimensional effects should be taken into account. The only available methods for simulating the large CFB furnaces three-dimensionally are semi-empirical models, which apply a relatively coarse calculation mesh and a combination of fundamental conservation equations, theoretical models and empirical correlations. The number of such models is extremely small. The main objective of this work was to achieve a model which can be applied to calculating industrial scale CFB boilers and which can simulate all the essential sub-phenomena: fluid dynamics, reactions, the attrition of particles, and heat transfer. The core of the work was to develop the model frame and the required sub-models for determining the combustion and sorbent reactions. The objective was reached, and the developed model was successfully used for studying various industrial scale CFB boilers combusting different types of fuel. The model for sorbent reactions, which includes the main reactions for calcitic limestones, was applied for studying the new possible phenomena occurring in the oxygen-fired combustion. The presented combustion and sorbent models and principles can be utilized in other model approaches as well, including other empirical and semi-empirical model approaches, and CFD based simulations. The main achievement is the overall model frame which can be utilized for the further development and testing of new sub-models and theories, and for concentrating the knowledge gathered from the experimental work carried out at bench scale, pilot scale and industrial scale apparatus, and from the computational work performed by other modelling methods.

NATURAL REGENERATION STRATUM AS AN INDICATOR OF RESTORATION IN AREA OF ENVIRONMENTAL COMPENSATION FOR MINING LIMESTONE, MUNICIPALITY OF BARROSO, MG, BRAZIL

ABSTRACT This study was conducted in a forest under restoration process, which belongs to the company Holcim Brasil S/A, in the municipality of Barroso, state of Minas Gerais (21º00'to 22º00'S and 43º00' to 44º00'W), where 40 plots (2 x 2 m) were set, spaced at 10 m, forming eight strata parallel to the watercourse present in the area. Floristic composition and natural regeneration stratum were characterized, and the formed strata allowed evaluating whether the riparian vegetation and watercourse influence on the local regeneration. It was found 162 individuals of 13 families, 18 genera and 22 species, and 10,125 individuals/ha were estimated. Successional classes from pioneer and early secondary and zoochory dispersion syndrome prevailed among species and individuals. The watercourse and riparian vegetation did not exercise significant influence (p> 0.05) on the number of species and regenerating individuals among the different strata of the forest. The diversity index of Shannon-Wiener (H') and equability of Pielou (J') were 2.691 and 0.870, respectively. The species Psidium guajava and Myrtaceae families presented the highest VI (value of importance). Natural regeneration analysis showed the low floristic diversity in the area, suggesting that corrective management actions should be adopted.

Modeling study of limestone reactions in fluidized bed conditions

Traditionally limestone has been used for the flue gas desulfurization in fluidized bed combustion. Recently, several studies have been carried out to examine the use of limestone in applications which enable the removal of carbon dioxide from the combustion gases, such as calcium looping technology and oxy-fuel combustion. In these processes interlinked limestone reactions occur but the reaction mechanisms and kinetics are not yet fully understood. To examine these phenomena, analytical and numerical models have been created. In this work, the limestone reactions were studied with aid of one-dimensional numerical particle model. The model describes a single limestone particle in the process as a function of time, the progress of the reactions and the mass and energy transfer in the particle. The model-based results were compared with experimental laboratory scale BFB results. It was observed that by increasing the temperature from 850 °C to 950 °C the calcination was enhanced but the sulfate conversion was no more improved. A higher sulfur dioxide concentration accelerated the sulfation reaction and based on the modeling, the sulfation is first order with respect to SO2. The reaction order of O2 seems to become zero at high oxygen concentrations.

Limestone Reactions in a Fluidized Bed Heat Exchanger of an Oxy-fuel Circulating Fluidized Bed Boiler

Oxy-fuel combustion in a circulating fluidized bed (CFB) boiler appears to be a promising option for capturing CO2 in power plants. Oxy-fuel combustion is based on burning of fuel in the mixture of oxygen and re-circulated flue gas instead of air. Limestone (CaCO3) is typically used for capturing of SO2 in CFB boilers where limestone calcines to calcium oxide (CaO). Because of high CO2 concentration in oxy-fuel combustion, calcination reaction may be hindered or carbonation, the reverse reaction of calcination, may occur. Carbonation of CaO particles can cause problems especially in the circulation loop of a CFB boiler where temperature level is lower than in the furnace. The aim of the thesis was to examine carbonation of CaO in a fluidized bed heat exchanger of a CFB boiler featuring oxy-fuel combustion. The calculations and analyzing were based on measurement data from an oxy-fuel pilot plant and on 0-dimensional (0D) gas balance of a fluidized bed heat exchanger. Additionally, the objective was to develop a 1-dimensional (1D) model of a fluidized bed heat exchanger by searching a suitable pre-exponential factor for a carbonation rate constant. On the basis of gas measurement data and the 0D gas balance, it was found that the amount of fluidization gas decreased as it flew through the fluidized bed heat exchanger. Most likely the reason for this was carbonation of CaO. It was discovered that temperature has a promoting effect on the reaction rate of carbonation. With the 1D model, a suitable pre-exponential factor for the equation of carbonation rate constant was found. However, during measurements there were several uncertainties, and in the calculations plenty of assumptions were made. Besides, the temperature level in the fluidized bed heat exchanger was relatively low during the measurements. Carbonation should be considered when fluidized bed heat exchangers and the capacity of related fans are designed for a CFB boiler with oxy-fuel combustion.

Particle model for simulating limestone reactions in novel fluidised bed energy applications

The development of carbon capture and storage (CCS) has raised interest towards novel fluidised bed (FB) energy applications. In these applications, limestone can be utilized for S02 and/or CO2 capture. The conditions in the new applications differ from the traditional atmospheric and pressurised circulating fluidised bed (CFB) combustion conditions in which the limestone is successfully used for SO2 capture. In this work, a detailed physical single particle model with a description of the mass and energy transfer inside the particle for limestone was developed. The novelty of this model was to take into account the simultaneous reactions, changing conditions, and the effect of advection. Especially, the capability to study the cyclic behaviour of limestone on both sides of the calcination-carbonation equilibrium curve is important in the novel conditions. The significances of including advection or assuming diffusion control were studied in calcination. Especially, the effect of advection in calcination reaction in the novel combustion atmosphere was shown. The model was tested against experimental data; sulphur capture was studied in a laboratory reactor in different fluidised bed conditions. Different Conversion levels and sulphation patterns were examined in different atmospheres for one limestone type. The Conversion curves were well predicted with the model, and the mechanisms leading to the Conversion patterns were explained with the model simulations. In this work, it was also evaluated whether the transient environment has an effect on the limestone behaviour compared to the averaged conditions and in which conditions the effect is the largest. The difference between the averaged and transient conditions was notable only in the conditions which were close to the calcination-carbonation equilibrium curve. The results of this study suggest that the development of a simplified particle model requires a proper understanding of physical and chemical processes taking place in the particle during the reactions. The results of the study will be required when analysing complex limestone reaction phenomena or when developing the description of limestone behaviour in comprehensive 3D process models. In order to transfer the experimental observations to furnace conditions, the relevant mechanisms that take place need to be understood before the important ones can be selected for 3D process model. This study revealed the sulphur capture behaviour under transient oxy-fuel conditions, which is important when the oxy-fuel CFB process and process model are developed.

Floristic composition and community structure of a seasonally deciduous forest on limestone outcrops in Central Brazil

The objective of this study was to analyze the floristic composition and structure of the tree component in a seasonally deciduous forest on limestone outcrops, located in the northeast region of Goiás State, Brazil. A sample composed of 25 randomly sampled plots of 20 x 20 m (400 m²) within a 50 ha forest, was measured. All woody individuals > 5 cm diameter at breast height (DBH) had their diameter and height measured. The tree community was composed of 39 species with a density of 734 individuals ha-1; the richest families were Leguminosae (11 species), Bignoniaceae (4 species) and Apocynaceae (4 species). The forest had a basal area of 16.37 m² ha-1, with the most important species Cavanillesia arborea (3.26 m² ha-1), Pseudobombax tomentosum (2.35 m² ha-1), Dilodendron bipinnatum (1.84 m² ha-1), Tabebuia impetiginosa (1.36 m² ha-1) and Myracrodruon urundeuva (1.26 m² ha-1) occupying 61.5% of the total basal area of the forest. Several species grew on rocks, or in rock fissures or in places with a shallow layer of soil or even in litter over rocky layers. The floristic composition showed links with the "Caatinga" flora, with other patches of seasonal forests in Central Brazil and in the Pantanal, and with the Chiquitano forests of Bolivia too, containing even two species considered as endemic to the "Caatinga".

New aspects in limestone dissolution for wet flue gas desulfurization

Fortsättningsvis tillgodoses största delen av världens energibehov genom förbränning av fossila bränslen, dessutom forsätter världens totala energibehov att öka. Eftersom förbränning av fossila bränslen som t.ex. olja och kol orsakar utsläpp av svaveldioxid som är skadligt för både människa och natur, finns det fortfarande ett akut behov av forskning och utveckling av metoder för svavelrening. De vanligaste teknikerna för svavelrening är våt- och semitorrskrubbning, där svaveldioxiden absorberas av en skrubbervätska. Det är allmänt känt att våtskrubbning är en av de effektivaste teknikerna för svavelrening både ekonomiskt och tekniskt sett samt den mest använda. Våtskrubbningsprocessen har dock flera nackdelar, som dess höga vatten- och energiförbrukning. I större kraftverk går ca 1-3% av dess eleffekt åt till rökgasreningsprocessen, vilket kraftigt motiverar utveckling av nya reningsprocesser samt effektivering av existerande reningsanläggningar. Skrubbervätskan som till huvudsak består av vatten innehåller vanligtvis även kalcium vars syfte är att binda svavlet. Kalciumet kan tillsättas i flera former varav bränd kalk och kalksten är de vanligaste formerna. Kalksten används ofta i svavelreningsprocessen p.g.a. dess låga pris och för att den ger upphov till den användbara biprodukten gips. Kalkstenens upplösningshastighet är en de av faktorer som kraftigast påverkar reningsprocessen. En detaljerad experimentell karakterisering och analys av kalkstenspartiklar i fast form och i vätskeform har utförts i detta arbete. En experimentell metod för att studera kalkstenens upplösningshastighet vid låg till obegränsad massöverföring har även utvecklats i detta arbete. Metoden möjliggör identifieringen av systemoberoende kinetiska parametrar, vilka kan användas för att undersöka reningsprocesser samt för att planera nya reningsanläggningar. Kinetiska modeller utvecklades genom att använda kalkstenpartiklars specifika yta, som mättes genom kväveadsorption. Efter att de kinetiska parametrarna bestämts experimentellt utvecklades en skrubbermodell för att optimera en i driftvarande skrubber. Genom att kombinera experimentellt bestämda modeller med matematisk optimering erhölls en djupare insikt i hur olika råmaterial påverkar processen och hur driftparameterar bör justeras för att minska elförbrukningen.

Performance of lowland rice seeds coated with dolomitic limestone and aluminum silicate

The objective of this study was to evaluate the performance of seeds of two cultivars of lowland rice (Oryza sativa L.), coated with dolomitic limestone and aluminum silicate. It was used a completely randomized experimental design, with the treatments arranged in a 4 X 2 factorial scheme [4 treatments: dolomitic limestone; dolomitic limestone + aluminum silicate; aluminum silicate, at the dosages of 50 g/100 kg of seeds; and control (without the products) X 2 cultivars: IRGA424 and IRGA 422 CL], totaling eight treatments with four replications each. The variables analyzed were: fresh and dry weights of aerial biomass; plant height; leaf area at 10, 20, and 30 days after emergence (DAE). The physiological quality of seeds was also assessed using tests of: seed emergence; first count of germination; emergence speed index; and field emergence. It was concluded that the coating of rice seeds with dolomitic limestone and aluminum silicate does not affect seed germination and field seedling emergence. Aluminum silicate used via seed coating on cultivar IRGA 424 promoted greater leaf area, after 20 DAE. The dolomitic limestone and the aluminum silicate used via seed coating generated plants with larger dry biomass, after 20 DAE, for the cultivar IRGA 422 CL.

Spatangoid-produced ichnofabrics (Bateig Limestone, Miocene, Spain) and the preservation of spatangoid trace fossils

A spatangoid-produced ichnofabric is described from the Miocene Bateig Limestone, SE Spain. This ichnofabric is characterized by the dominant presence of large meniscate burrows (Bichordites) produced by irregular echinoids. This constitutes an unusual mode of occurrence for spatangoid bioturbation, as their traces are most typically preserved in bases and tops of sandstone event beds. In fact, despite their important role as burrowers in modern settings (that can be extended back to the Early Cretaceous based on their body fossil record), spatangoid trace fossils (Scolicia and Bichordites) are comparatively rare. Several factors play an important role in their preservation: mechanism of burrowing, sediment characteristics, early diagenesis and presence/absence of deep-tier burrowers. Spatangoid-produced ichnofabrics, such as those from the Bateig Limestone, characterize depositional settings with intermittent deposition of event beds where there is an absence of deeper-tier bioturbation. (C) 2008 Elsevier B.V. All rights reserved

An ichnofabric approach to the depositional interpretation of the intensely burrowed Bateig Limestone, Miocene, SE Spain

The foraminiferal-rich pelagic Bateig Limestone forms several varieties of the important building stones quarried at Bateig Hill in southeastern Spain. Three principal ichnofabrics (Bichordites, mottled-Palaeophycus and mottled-Ophiomorpha) are recognized, which are present in at least two (possibly up to four) repeated successions (cycles). Each succession begins with an erosional event. The Bichordites ichnofabric represents a new type of facies, formed as thin turbidity/grain flow, stratiform units derived from sediment slips off a fault into deep water. Each slipped unit became almost completely bioturbated by infaunal echinoids, colonizing by lateral migration. Because of the thinness of the units, successive colonizations tended to truncate the underlying burrows giving rise to a pseudo-stratification. As the Bichordites ichnofabric accumulated on the fault apron, thus reducing the effective height of the fault scarp, the substrate gradually came under the influence of currents traversing the shelf. This led to a change in hydraulic regime, and to the mottled-Palaeophycus and mottled-Ophiomorpha ichnofabrics in sediment deposited under bed load transport, and associated with laminar and cross-stratified beds and local muddy intervals. Reactivation of the fault triggered erosion and channeling and a return to grain flow sedimentation, and to the Bichordites ichnofabric of the succeeding cycle. The highest unit of the Bateig Limestone is formed entirely of cross-stratified calcarenites with occasional Ophiomorpha (Ophiomorpha-primary lamination ichnofabric) and is similar to many shallow marine facies but they still bear a significant content of pelagic foraminifera. The sedimentary setting bears resemblance with that described for the Pleistocene Monte Torre Paleostrait and the modem Strait of Messina (Italy), where the narrow morphology of the depositional area enhanced tidal currents and allowed for high-energy sandy deposition in relatively deep areas. More data on the Miocene paleogeography of the Bateig area should provide further testing for this hypothesis. The ichnofacies and stacking of the Bateig Limestone differ from the classic Seilacherian model in that they reflect changes in hydraulic process and are associated with faulting and subsidence and changes in sediment supply. Recognition of the unusual ichnofabrics and their relationships provides a clear indication of the overall dynamic setting. (c) 2006 Elsevier B.V. All rights reserved.

New beetles (Insecta : Coleoptera) from the Berriasian Purbeck Limestone Group, Dorset, UK

Four new beetle species are described from the Lower Cretaceous Purbeck Limestone Group of southern England: Mesogyrus anglicus sp. nov. (Gyrinidae), Coptoclavella purbeckensis sp. nov. (Coptoclavidae), Palaeodytes incompleta sp. nov. (Dytiscidae) and Cretorabus suleatus sp. nov. (Carabidae). The first three taxa were aquatic; the last is terrestrial but may have frequented the margins of water bodies. © 2005 Elsevier Ltd. All rights reserved.