Thesis (Sc. D.)--Massachusetts Institute of Technology, Dept. of Chemical Engineering, 1982. / MICROFICHE COPY AVAILABLE IN ARCHIVES AND SCIENCE / Bibliography: leaves 429-434. / by Richard John Quann. / Sc.D.

A combustão do carvão para a produção de energia elétrica tem como consequência a geração de cinzas, que é um dos maiores resíduos gerados no Brasil, em termos de volume (4.109 dm³/ano). Visando a minimização do impacto ambiental causado pelo mau descarte das cinzas, este trabalho teve como objetivo sintetizar e caracterizar zeólitas obtidas a partir de cinza de carvão e aplicar na agricultura como fertilizante potássico. Para isso a cinza utilizada foi obtida no combustor piloto de leito fluidizado operando com carvão da Mina do Leão/RS e empregada para sintetizar material zeolítico a partir do tratamento hidrotérmico alcalino. Foram realizados ensaios experimentais utilizando razão solução/cinzas constante em 6 L mg-1, variando a concentração de hidróxido de potássio (KOH) entre 3 e 5 M, a temperatura entre 100 e 150 ºC e o tempo de reação entre 24 e 72 h. O material sintetizado e a cinza foram caracterizados quanto a sua composição química, mineralógica, morfologia, área superficial específica e capacidade de troca catiônica. Através da caracterização foi observada a formação de duas fases zeolíticas, a chabazita-K e a merlinoíta. A partir da caracterização do material, foi escolhido um dos produtos zeolíticos obtidos para aplicação em solo, como fertilizante de potássio para o cultivo de trigo (Triticum aestivum L.). A condição experimental escolhida foi de 5 M a concentração da solução de KOH, temperatura de 150 ºC e tempo de reação de 24 h. Nesta condição obteve-se apenas uma fase zeolítica identificada, a zeólita merlinoíta, com uma área superficial de 23,37 m² g e uma capacidade de troca catiônica (CTC) de 2,62 meq g 1. Para fins de comparação foi utilizado o fertilizante comercial, cloreto de potássio (KCl), que contém em torno de 60 % de K2O. Foram realizados 35 ensaios experimentais em casa de vegetação da EMBRAPA, utilizando 7 tratamentos (3 doses diferentes de KCl e zeólita 50, 100 e 150 % da dose máxima recomendada e o solo não tratado (testemunha)) em 5 blocos aleatórios. Os experimentos na casa de vegetação foram concluídos com 59 dias de cultivo de trigo e submetidos às análises como determinação da produção de matéria seca da parte aérea e raízes das plantas e análise química do solo e tecido foliar. Verificou-se que a zeólita merlinoíta obtida a partir da cinza de carvão pode ser utilizada como fertilizante, pois teve um desempenho similar ao KCl no crescimento do trigo, não inibindo seu crescimento. Utilizando o tratamento com zeólita 100 % a produção de matéria seca da parte aérea foi de 1,07 ± 0,09 g e raízes 1,6 ± 0,23 g e na análise do tecido foliar teve uma absorção de 3,39 ± 0,31. / Coal combustion for electricity production results in the generation of ash, which is one of the main waste generated in Brazil in terms of volume. Intending the minimization of the environmental impact caused by poor disposal of ashes, this study aimed to synthesize and characterize zeolites obtained from coal ash and apply in agriculture as potassium fertilizer. For this purpose, coal fly ash was obtained from a fluidized bed pilot combustor operating with coal from Mina do Leão/RS and used to synthesize zeolitic material through the alkaline hydrothermal treatment. Experimental tests were performed using the ratio volume of solution/mass of coal fly ash constant at 6 mL mg -1, varying the concentration of potassium hydroxide (KOH) between 3 and 5 M, temperature between 100 and 150 °C and reaction time between 24 and 72 h. The synthesized and coal fly ash material was characterized by their chemical composition, mineralogy, morphology, specific surface area and cation exchange capacity. With the characterization, it was observed the formation of two phases zeolite K-chabazite and merlinoite. By the characterization of the material, it was chosen one of the zeolitic products obtained for application to soil as a potassium fertilizer for the cultivation of wheat (Triticum aestivum L.). The chosen experimental condition was 5 M KOH solution, temperature of 150 °C and 24 h time of reaction. At this condition, only one zeolitic phase was identified, zeolite merlinoite, with a surface area of 23.37 m² g a cation exchange capacity (CEC) of 2.62 meq g-1. For purposes of comparison, the tests in the soil were performed using also a commercial fertilizer, potassium chloride (KCl), containing about 60 % of K2O. A total of 35 experimental trials were carried out in a greenhouse at EMBRAPA, using 7 treatments in 5 random blocks: 50, 100 and 150 % of the maximum recommended dose for KCl and for zeolite and untreated soil (witness). The experiments in the greenhouse were concluded with 59 days of wheat cultivation. The plants were submitted to analysis for dry matter in aerial parts and roots determination. Likewise, soil and foliar tissue were submitted to chemical analysis. It was found that the zeolite Merlinoite obtained from the coal fly ash can be used as a fertilizer because it had a similar performance to KCl in the wheat growth. The treatment with 100% zeolite presented a dry matter production of 1.07 ± 0.09 g for aerial parts and 1.6 ± 0.23 g for roots. Also, the leaf tissue analysis showed a potassium absorption of 3.39 ± 0.31 % m/m in this treatment.

With the pressure on the construction industry to lower CO2 emissions it has become increasingly important to utilise materials that supplement Portland cement (CEM I) in concrete. These include additions such as ground granulated blast-furnace slag (GGBS) and fly ash, which have found greater use due to the benefits they provide to many properties of the material (in addition to environmental impact). While studies have investigated these materials in binary blends with CEM I, little work has examined the effect of combining materials in ternary blend concretes. A wide-ranging study was, therefore, set up to examine this for the range of more commonly available additions. This thesis reports on research carried out to investigate the effects of cement combinations based on CEM I / GGBS with either fly ash or limestone. The experimental programme investigated these materials in both paste and concrete and covered fresh properties, compressive strength, permeation and durability properties (using standard water curing for the latter three) and considered, for the hardened properties, how these may be balanced with environmental cost. The mixes covered a range of w/c ratios (0.35. 0.50 and 0.65), which was the main basis of comparison, and combinations of CEM I with GGBS (at levels of 35%, 55% and 75%), and fly ash and LS part-replacing this (at levels of 10 to 20 % and 10 to 35% respectively), after consideration of the relevant standards and related research. The initial phase of the study examined the characteristics of the materials, which indicated that they conformed to appropriate standards and were typical of those used in the application. Studies with cement paste (0.35 and 0.50 w/c ratio) indicated that there were reductions in water demand with the use of addition materials (binary and ternary) compared to CEM I. The setting times of the cement pastes were also affected, generally increasing with GGBS level for the binary mixes, although the effect was influenced by w/c ratio. Whilst fly ash and limestone delayed setting at the higher w/c ratio, the opposite occurred as this reduced, compared to the binary mixes. It was also found that the yield stress increased with GGBS level and further with the addition of ternary materials (particularly limestone) compared to CEM I. The superplastiser (SP) dosage requirement in concrete was found to decrease with increasing w/c ratio, and ternary additions reduced this compared to binary and CEM I concrete with the effect most noticeable at low w/c ratio. Early strength development was less than CEM I for binary concretes and differences increased with GGBS level. Improvements with the introduction of fly ash compared to the binary concretes were noted with increasing GGBS levels and w/c ratio. In general, the addition of LS gave reduced early strength for all concretes. Although at the 35% GGBS level binary concretes achieved similar strength to those of CEM I, the others generally gave reductions at all ages to 180 days, with differences increasing with GGBS level. However, with increasing w/c ratio and GGBS level improved strength development of ternary concretes, was noted compared to those of CEM I from 28 days. Permeation (absorption (initial surface absorption and sorptivity) and permeability (water penetration and air permeability)) and durability properties (accelerated carbonation and chloride ingress) of the test concrete were also investigated. At 28 days, for low GGBS levels, the binary concretes gave reduced absorption properties compared to CEM I, while the reverse occurred at high level. The effect of the ternary concretes gave further improvements at the lower GGBS levels and with increasing w/c ratio and curing time compared to CEM I. At the higher GGBS level the effect of the ternary additions was less noticeable but, in the case of limestone, improvements were still seen with increasing w/c ratio compared to CEM I. Similar effects were noted for the sorptivity results. The air permeability results gave higher values at 28 days for the binary and ternary concretes compared to CEM I, but significant improvements in the long-term at the lower GGBS level across the range of w/c ratios compared to CEM I concrete. Similar trends were found with water penetration tests. Accelerated carbonation increased with GGBS level for binary concretes compared to CEM I. These differences increased further with the introduction of fly ash and LS, particularly the former. In contrast rapid chloride tests indicated improvements with increasing GGBS levels compared to CEM I and further benefits with the inclusion of fly ash and limestone. Embodied CO2 (ECO2) was calculated based on published British Cement Association (BCA) values for each component of the mix and was shown to reduce with increasing w/c ratio and addition level in concrete. For concrete of an equal strength of 40N/mm2 the ECO2 could be almost halved (reduced from 343 kg/m3 for the CEM I to 176 kg/m3) for the ternary concretes at higher GGBS levels. These combination concretes also gave enhanced durability with regard to chloride ingress and at the lower w/c ratio comparable properties to CEM I in the case of carbonation. Overall, the results suggest that there is potential for ternary concretes to be used in the concrete industry given their ability to reduce ECO2, without compromising strength, permeation and durability properties of concrete.

Coal fly ash is a by-product of coal combustion that has drawn renewed public scrutiny due to the negative environmental impacts from accidental release of this waste material from storage facilities. Historically, the leaching of toxic elements from coal fly ash into the environment has always been a major environmental concern. Despite extensive efforts into the characterization of coal fly ash, effective models for the fate and transport of toxic fly ash constituents have remained lacking, making it difficult to perform accurate environmental impact assessment for coal fly ash. To close this critical knowledge gap, the overall objective of this study was to develop a predictive model for the leaching of toxic elements from fly ash particles. First, physical properties of coal fly ash were characterized to evaluate their contribution to elemental transport. Unburned carbon was shown to contribute to the sorption of arsenic to fly ash, which slowed the release of arsenic from fly ash. In parallel, leaching properties of various elements were determined to differentiate species of varying leaching capacities, demonstrating that the majority of toxic elements were not mobile under environmentally relevant conditions. Subsequently, a mechanistic model for the dissolution of fly ash elements was developed and validated with batch kinetics studies. Furthermore, elemental dissolution was integrated with hydrodynamic modeling to describe the leaching of toxic elements from fly ash in dry disposal facilities, which was validated by column studies. The mechanistic model developed and validated in this research represents the first such model that successfully characterized the complex processes underlying the release and transport of toxic elements in coal fly ash, providing a valuable tool to predict the environment impact of coal fly ash and develop more effective management practices for both the industry and regulators.

I Sverige ökar förbränningen av avfall som inte är ett helt definierbart bränsle. Detta är i mångt och mycket ekonomiskt och miljömässigt försvarbart genom den höga kvalitén på rökasreningen, som garanterar att en mycket liten del av föroreningar når atmosfären, utan dessa koncentreras i askorna. Avfallsaskor går till stor del till deponier och används där för sluttäckning eller för att deponeras, samt att en stor mängd flygaska transporteras till Langöya. Inom en tioårsperiod kommer deponierna vara sluttäckta och Langöya uppfyllt, samtidigt som mängden avfallsaskor ökar, vilket innebär krav på nya lösningar. Orsaken till att framförallt flygaskan klassas som farligt avfall är koncentrationen av tungmetaller och föroreningar som härrör från bränslet. Det har forskat i åratal om metoder som ger miljöriktig användning och metoder för att minska miljöpåverkan från askor, men ytterligare forskning krävs för att få svar på den långsiktiga miljöpåverkan samt alternativa användningsområden. Är avfallsaskorna farligt avfall eller en framtida resurs, en svår fråga att besvara, eftersom det är mycket arbete som behövs ifrån politiker, myndigheter, branschen, forskningen och gemene mans inställning till sopsortering för att lyckas förvandla ett farligt avfall till en resurs. / The combustion of waste is increasing in Sweden and the waste is not an entirely definable fuel. This is very much economically and environmentally defensible by the high quality of smoke purification, which ensures that a very small percentage of pollutants reaching the atmosphere, but on the other hand they are concentrated in the ash. Ashes from the incineration of waste go largely to landfills and are used to cap or to be deposited, and that a large amount of fly ash is transported to Langöya. Within a decade, the landfill will be completed covered and Langöya fulfilled, while the amount of ashes from the incineration are increasing, which would require new solutions. The reason for the particular fly ash as hazardous waste is the concentration of heavy metals and pollutions emanating from the fuel. It has been researched for years about the methods that provide environmentally sound use and methods to reduce the environmental impact of ashes, but further research is needed to find answer to the long-term environmental impact and alternative uses. Are ashes from waste hazardous waste or a future resource, a difficult question to answer, because there is much work needed from politicians, government agencies, industry, research and the general public attitude towards waste separation to successfully transform a hazardous waste into a resource.

ABSTRACT Key words: PCDD/FS , aromatic precursor compounds , transition metal catalysts , chlorine donor , surface of fly ash particles In the last 20 years , increasing concern has focused on the environmental chemicals that mimic hormone functions , some of them toxic , which producing cancer , suppression of the immune system , and death from undefined causes . These chemicals are not made intentionally , but are formed as contaminants in combustion sources , including PCDD/FS of dioxin-like compounds that emitted from municipal solid waste incinerators (MWSI) and hazardous waste incinerators (HWI) . This study investigated the role that fly-ash plays in the formation of PCDD/FS using a commercial scale fluidized bed waste incinerators (FBWI) , which rated capacity at 3750000 kcal/hr (LHV) . In this design , a lay of sand is placed on the bottom of the combustion chamber. During combustion, the hot gases are channeled through the sand and crushed solid waste at relatively high velocity . This generated about eight times more mass of fly-ash will be produced from combustion zone than the others, and also makes much greater of PCDD/FS through the air pollutants control devices(APCD) to emission stack . The general reaction in this formation pathway is an interaction between an aromatic precursor compound and chlorine promoted by a transition metal catalyst on a reactive fly-ash surface. Since these reactions involve heterogenous chemistry , the rate of emissions is less depended on reactant concentration than conditions that promote formation such as temperature , retention time , transition metal catalysts (e , g,. Cu , Fe , Pb , Zn , Sn) and availability on catalytic surfaces of fly ash particle . These forming conditions will be proceeding a series of well study and experiment on fly-ashes from 4 zones (F1 , F2 ,F3 , F4) of FBWI . PCDD/FS synthesis from combustion of FBWI can potentially be explained by three principal mechanisms that results can be divided into several major parts as follows¡G 1. The fly-ash from zone F3 generated about 47 times more mass of PCDD/FS than zone F1 . 2. The F3 fly-ash proved to be the most active catalytic (Cu , Zn) medium , despite similarities with respect to specific surface area and average pore diameters . In addition , there are up to 75.9 percent by weight of Zn and 97.6 percent of Cu has been found in F3 of overall ashes. 3. In both fly- ash and transition metal catalysts in formation mechanisms are the dominant controlling factor for rates of PCDD/FS.

This research studies the properties of self-compacting concrete by applying bamboo-charcoal to improve the fresh concrete property, physical property and micro-scale property.Conventionally, the Pozzolanic materials used in the self-compacting concrete are fly ash and slag. They are used to replace part of the cement such that the flowing property and compacting property can reach the requirement of the self-compacting concrete. According to previous research the bamboo-charcoal can absorb part of water, and enhance the early strength of concrete. In this study, we use bamboo-charcoal to replace parts of the fine-aggregate in the mixture of self-compacting concrete. The replacement ratio is designed as 0‰,2‰,3‰,3.5‰,4‰ and 5‰. From the experimental test of fresh concrete property, we can evaluate whether the concrete mix design can achieve the requirements of self-compacting concrete. Test for the compressive strength development, water absorption and rapid chloride penetration test are performed to evaluate the physical property of concrete. In addition, the scanning electronic microscope photos are taken to examine the microstructure of the concrete. In our results, it is found that the best proportion of replacement is 3‰. The requirements of self-compacting concrete can be satisfied, and the development of strength is also good.

Concrete structures are often exposed to sulfates, which are typically found in groundwater and soils, in agricultural run-off, in industrial facilities, and in other source points. These sulfates may attack concrete and significantly shorten the service life of concrete due to reactions between sulfate ions and concrete constituents. These reactions form expansive and deleterious compounds that lead to cracking and spalling of the concrete. This reaction is a function of the sulfate solution but also the physical, chemical, and mineralogical properties of the cement and supplemental cementitious materials (SCMs). It is widely understood that the addition of some fly ashes, by-products of coal combustion power plants, improve the sulfate resistance of the concrete but some fly ash additions actually reduce the sulfate resistance. This project aims to understand this relationship between fly ash and sulfate resistance. Using sulfate testing results on mortar previously obtained at The University of Texas at Austin, this research evaluated the mineralogical, chemical, and physical characteristics of fly ash and attempted to link these measured characteristics (or combinations thereof) to sulfate resistance of concrete. / text

Chancey, Ryan / text

Fly ash has been used extensively to control deleterious alkali-silica reaction in concrete. The majority of fly ashes can be used to control ASR induced expansion. Fly ashes with high CaO contents are less effective at reducing expansion and fly ashes with high alkali contents can be counter active. Class C fly ashes are less effective at reducing the pH of the pore solution because they are less pozzolanic. The pozzolanic reaction in Class F fly ashes enhances the ability for the hydration products to bind alkalis. This prevents the availability of these alkalis for ASR. This project aims to characterize fly ash in a way that best predicts how it will perform in concrete with an emphasis on ASR. Fly ashes with a variety of chemical compositions were evaluated using a range of analytical and characterization techniques. Research data from several universities were used to correlate their long term data with this project’s accelerated tests. This research aimed at evaluating the mineralogical, chemical, and physical characteristics that most affect the ability of a given fly ash to prevent ASR-induced expansion and cracking. / text