McDonalds Lime Ltd, situated in Otorohanga, New Zealand, operate two dry process rotary lime kilns producing burnt and hydrated lime for a range of industries including agriculture, roading, water treatment, gold mining and steel making. The following Technology in Industry Fellowship (TIF) funded Masters Project is structured around investigating the combustion characteristics of Kiln Two at McDonald’s Lime Ltd using Computational Fluid Dynamics (CFD). Numerical results obtained using the commercial CFD code FLUENT were first validated against experimental data from the International Flame Research Foundation’s (IFRF) Furnace No.1. The validation study focussed on comparing the finite rate and mixture fraction/PDF approaches to combustion chemistry, as well as different methods for defining coal particle size distributions. Numerical modelling of Kiln Two at McDonald’s Lime Ltd began with full three-dimensional simulations, however due to their complexity and large computational times, two-dimensional axisymmetric models were primarily used for investigations. Comparisons were made between the two approaches. Investigations into the original pulverised coal fired system focussed on how the kiln aerodynamics and heat transfer properties were affected by changes to the coal and air inlet properties. The performance of a recently installed waste oil firing system was also investigated, with results showing that firing the kiln with a 25% thermal substitution of oil is the most efficient mode of operation. As the investigations focussed on the combustion characteristics the effects of the reacting limestone bed were ignored in all simulations. CFD modelling of the combustion characteristics within a large scale rotary kiln proved to be an extremely complex task. The work presented in this thesis has however provided some promising results which will ultimately assist McDonalds Lime Ltd in reducing their operating costs and environmental impact. Futhermore, the project has laid the foundation for further investigations.

Calcined coke is the best material for making carbon anodes for smelting of alumina to aluminum. Calcining is an energy intensive industry and a significant amount of heat is wasted in the calcining process. Efficiently managing this energy resource is tied to the profit margin and survivability of a calcining plant. 3-D computational models are developed using FLUENT to simulate the calcining process inside the long slender kiln. Simplified models are employed to simulate the moving petocke bed with a uniform distribution of moisture evaporation, devolatilization, and coke fines entrainment rate with a conjugate radiation-convection-conduction calculation. The results show the 3-D behavior of the flow, the reaction inside the kiln, heat transfer and the effect of the tertiary air on coke bed heat transfer. The ultimate goals are to reduce energy consumption, recover waste-heat, increase thermal efficiency, and increase the product yield.

Biochar has been heralded as a promising technology for climate change mitigation that can also benefit soils. Biochar is a carbonaceous solid produced by pyrolysis of biomass – the thermal decomposition of plant and plant-derived matter in the absence of oxygen. When added to soils, biochar has the potential to increase crop yields and suppress soil emissions of greenhouse gases, whilst sequestering carbon in a stable form. In addition to biochar, biomass pyrolysis produces liquids and gases that can serve as biofuels. Biochar production systems that generate excess heat or power are particularly environmentally and economically attractive. Rotary kilns are the favoured process reactor in many industries, given their potential to handle a wide range of feedstocks and provide good process control. This thesis investigates the potential to coproduce biochar and excess biofuels by slow pyrolysis in a pilot-scale rotary kiln. The work attempts to progress towards the ultimate aim of scaling up the rotary kiln and optimising its operating conditions to produce biochar of good quality along with an excess of useful biofuels. Experimental work, involving the development and application of new methodologies, was used to gain a better understanding of the process. The data gathered were then used to support preliminary numerical simulation efforts towards the development of a comprehensive process model. Five biomass feedstocks were considered: softwood pellets, miscanthus straw pellets, wheat straw pellets, oilseed rape straw pellets and raw rice husks. The granular flow of biomass feedstocks was observed in a short closed drum faced with acrylic and resting on rollers. All pelletized feedstocks displayed similar angles of repose, validating the use of softwood pellets as a model biomass for these feedstocks. Bed mixing, which can improve product uniformity, was slow under typical operating conditions, requiring 5 min to complete at 4 rpm for softwood pellets. Mixing quickened considerably at higher rotation rates. A digital image analysis method was developed to measure the distribution of solid residence times inside the rotary kiln. The mean residence time of softwood pellets ranged from 19 to 37 min under typical operating conditions, decreasing with increases in kiln rotation rate, but mostly unaffected by feeding rates. These findings show that kiln rotation rates must be selected to balance the residence time of solids inside the kiln with bed mixing levels. Thermogravimetry and differential scanning calorimetry were performed on samples of ground softwood pellets under five different heating profiles to study the kinetics and heat flows of the pyrolysis process. Both exothermic and endothermic regions were identified, with most reactions taking place between 250°C and 500°C. Results suggest that exothermic pyrolysis reactions can be promoted by altering the process heating rate, thereby improving net biofuel yield from the process. The thermogravimetric data collected was used to develop a distributed activation energy model (DAEM) of the kinetics of softwood pellet pyrolysis for integration into a comprehensive model of the process. The applicability of the kinetic model to large-scale processes was confirmed using a simplified process model developed to simulate biomass pyrolysis inside the pilot-scale rotary kiln. Although crude, the simplified process model produced sufficiently accurate estimates of char yield for preliminary design purposes. The simplified model also allowed important process parameters, such as kiln filling degree, solid residence time and heating rate, to be evaluated. A series of pyrolysis experiments was performed on the pilot-scale rotary kiln to evaluate the yields of biochar and biofuels and determine the temperature profile inside the kiln. This work required the design of a suspended thermocouple system that measures temperatures along the kiln, both in the gas phase and inside the solid bed. For most experiments at 550°C, a region of high temperature gas and solids was observed, possibly indicative of exothermic reactions. Biochar yield varied from 18% to 73% over the range of feedstocks and operating conditions tested. A vapour sampling methodology that relies on the use of a tracer gas was developed to determine the yield of pyrolysis liquids and gases. Due to analytical difficulties, it was not possible to obtain accurate mass closure with this method. However, the methodology revealed significant air ingress into the pilot-scale rotary kiln that is responsible for partially combusting biofuels produced by the process, thereby reducing their calorific value. Energy balances on the kiln confirmed that the calorific content of pyrolysis liquids and gases exceeds the energetic demand of the process, yielding between 0.3 and 11 MJ in excess biofuels per kg of biomass feedstock. An attempt was made to develop a multiphase model of the flow of vapours and solids inside the rotary kiln using computational fluid dynamics (CFD), but the continuous modelling approach was found inadequate to simulate the dense bed of biomass inside the kiln. The discrete element method (DEM) was sought as an alternative to model the granular flow of biomass inside the kiln. Extensive parameter calibration was required to reproduce the experimental behaviour of softwood pellets observed in the short closed drum. A model of the pilot-scale rotary kiln was constructed to simulate particle residence times. Further parameter calibration was required to replicate softwood pellet holdup inside the kiln. The calibrated model was able to reproduce the mean residence time of softwood pellets within 10% under different kiln operating conditions. However, simulated residence time distributions could not be established as a result of the long execution times required for this modelling work. Few data are currently available on large-scale continuous biomass pyrolysis processes; the experimental data gathered in this thesis help to fill this gap. Along with the numerical simulation work presented herein, they provide the foundation for the development of a comprehensive model of biomass pyrolysis in rotary kilns. Such a numerical model would prove invaluable in scaling up the process and maximizing its efficiency. Future work should consider the agronomic value and carbon sequestration potential of biochar produced under different operating conditions. In addition, the performance and efficiency of different conversion technologies for generating heat and power from biofuels need to be investigated.

Gotland has a very long tradition of lime burning. Traces of lime burning on Gotland stretch back to the 12th century. An inventory of all the lime kilns in Gotland was made in 1942. Since then the market, the use and the tradition of lime burning have changed significantly. By the start of WW2 a shortage of black coal occurred. This meant that the large, traditional lime kilns could no longer be operated with the same capacity. The small, wood-burning kilns were the only furnaces that survived. With the cement's entry the demand for lime mortar got heavily reduced, which in turn meant the end for the last lime kilns. The cement quickly proved inadequate in many situations, especially in the field of monument care​​, and the demand for traditional lime mortar increased again already in the 1960s. Since then, three lime kilns were taken into use on Gotland; two smaller, traditional lime kilns and one large, industrial kiln. This thesis intends to follow up on the inventory that was made in 1942 in order to create a basis for further discussion of the historical values the lime kilns possesses and how these values can be cared for. In order to ensure the being of cultural heritage of the traditional lime industry, it requires popular demand, care and knowledge of the furnace, its use and production and its product. / Gotland har en mycket lång tradition av kalkbränning. Spår av kalkbränning sträcker sig på ön tillbaks till 1100-talet. En inventering av samtliga kalkugnar och kalkmilor på Gotland gjordes år 1942. Sedan dess har marknaden, användningen och traditionen av kalkbränning förändrats kraftigt. Vid andra världskrigets början uppstod en bristsituation på stenkol. Detta medförde att de stora, traditionella kalkugnarna inte längre kunde drivas med samma kapacitet. De mindre, vedeldade ugnarna var de enda ugnarna som överlevde. Med cementens intåg minskade även efterfrågan på kalkbruk, vilket i sin tur betydde slutet för de sista kalkugnarna. Cementen visade sig snabbt vara bristfällig i flera situationer, särskilt inom kulturvårdens praktik, och efterfrågan på traditionellt kalkbruk ökade igen redan på 1960-talet. Sedan dess har tre kalkugnar tagits i bruk på Gotland; två mindre, traditionella kalkugnar och en stor, industriell ugn. Uppsatsen ämnar följa upp inventeringen som gjordes 1942 för att skapa ett underlag för att vidare resonera kring de kulturhistoriska värden kalkugnarna besitter och hur dessa tas till vara. För att kunna vårda kulturarvet från den traditionella kalkindustrins dagar fordras efterfrågan på kalk, vård och kunskap om ugnarna, dess användning och produktion och dess produkt.

Energy efficiency calculations and an economical analysis has been conducted on two different carbon regeneration kiln types. The purpose was do determine what economical winnings there could be by replacing the carbon regeneration system using propane burner with one heated by electricity. This project was conducted on a carbon regeneration kiln that stands at the G1A processing plant in Boliden. The two different heating solutions were implemented in the multiphysics software Comsol to determine their energy efficiency’s, and then an economical analysis was conducted by comparing the annual consumption of energy per kiln type. The models were built to be as accurate as possible, but some simplifications had to be made to make the simulations possible. The results from the study showed that the electrical heating solution was over four times more energy efficient, which would lead to an annual saving of 745 714 SEK/year. The results of this simulation must however be considered somewhat inconclusive due to implementation difficulties, but it might serve as a good predictor as to why electrical heating panels could be economically feasible.

Numera sker all industriell torkning av virke i sågverken i virkestorkar, som värms upp och därmed torkar virket till den optimala slutfuktkvot som tillönskas. Virkestorkar byggda i betong har länge varit ett stort problem för sågverksindustrin. Problematiken går tillbaka till 80-talet då man tvingades riva ett flertal torkar på grund av att betongtorkarna höll på att vittra sönder. Detta gällde för alla betongtorkar byggda fram till 70-talet. Det genomfördes i slutet på 90-talet en stor rapportundersökningen som behandlade de flesta typer av skador i betongtorkar. Fram tills idag har en närmare undersökning ej gjorts och det har fortfarande inte hittats standarder för reparation och underhåll som förlänger livslängden på betongtorkar. Sågverksindustrin förlorar varje år 10-tals miljoner kronor på reparationer och underhåll som i de flesta fall inte verkar fungera. Därför finns det en stor efterfrågan av tydliga instruktioner för val av material och hur dessa reparationer skall gå till. Rapporten behandlar den allmänna problematiken av skador som uppstår p.g.a. bland annat väldigt högt temperaturbelastade virkestorkar som är konstruerade i betong. Arbetet är uppdelat i två faser den ena fasen består av en teoridel som bland annat förklarar skadorna och dess uppkomst i betongtorkar. Den andra fasen behandlar en fältundersökning som genomfördes under rapportskrivningen samt de förslag till åtgärder som tagits fram. Denna rapport är en liten del av ett stort pågående projekt, där CBI Betonginstitutet och SP trä är projektutförare och samverkar med deltagande sågverk i Sverige och Norge samt leverantörer. Projektet ska mynna ut i en Guideline till sågverksindustrin, för att kunna utföra rätt reparationer med rätt materialval och därmed förlänga betongtorkarnas livslängd. Detta med utgångspunkt från fältundersökningens provtagningar. / Nowadays, all the process of industrial drying of lumber in sawmills are done in kilns, which the wood is heated and dried for the desired optimal moisture content. Timber drying kilns built in concrete has for a long time been a major issues for the sawmill industry. The problems goes as far back to the 80s when several wood kilns was forced to be demolished due to concrete kilns were about to crumble. This was mainly for all the concrete dries built up until the 70s. In the late 90's a report survey was carried out to investigate the damages that were inflicted in concrete dries. No other survey has been done since then and the report didn’t give tangible standards for repairs and maintenance that extends the service life in wood kilns. The sawmill industry loses each year tens of millions on repairs and maintenance that hasn’t shown any results of working. Therefore, there is a great demand of clear instructions for the selection of materials and how these repairs need to be done. The report deals with the general issues of very high temperature-loaded kilns constructed in concrete. The work is divided into two phases; one phase consists of a theoretical part including explaining of the damages and its emergence in the concrete kilns. The second phase deals with a field survey conducted during the report writing as well as the proposed measures have been developed. This report is one small part of a large ongoing project, where CBI and SP wood are the project implementers and interact with participating sawmills in Sweden and Norway and the suppliers. The project will culminate in a Guideline for the sawmill industry, to be able to perform the correct repair with proper materials and thereby extend the life of concrete kilns. This is based on field survey sampling. The project will culminate in a Guideline for the sawmill industry, to be able to perform the correct repair with proper materials and thereby extend the life of concrete drying. This is based on field survey sampling.

This thesis studies Tang sancai, a multi-coloured lead-glaze ceramic decorated ware which emerged in the Tang dynasty (AD 618 - AD 907), attaining mass production in the middle of the Tang era and declining towards its end. It examines the functions of sancai in its different aspects, namely as burial objects, as containers for ritual offerings and as architectural material. I argue that Tang sancai ware as burial objects were employed exclusively by the Tang imperial and elite families. The approach to my argument is made, in a first stage, through the observation of the physical locations of tombs that contained Tang sancai wares to demonstrate that these tombs belonged to the Tang imperial and elite family members. In a further step, I bring up two Tang decrees which laid down regulations for burials, to indicate that there was a strict hierarchical system for the allocation and utilization of burial land. These two Tang texts enable us to establish that the tombs located around the area of the imperial tombs belonged to the Tang officials and elite, and therefore not to ordinary people. In addition, the study I undertake of the structure of the tombs, with layout and organization mirroring palatial environments, reinforces my argument to that end. Lastly, I look at the cost of production of Tang sancai showing that it was higher than that of unglazed ceramics and that, consequently, sancai wares were, from an economical point of view, inaccessible to the common people. This thesis also reflects on the agency of Tang sancai, considering its aesthetic qualities and its suitability in the functions for which it served, as a force in engaging the viewers. The lasting debate on whether Tang sancai utensil-shaped wares were used for everyday eating and drinking is dealt with in this thesis by carefully examining the locations of the shards that were excavated at the sites of imperial palaces. My research enables to point out that this data is not sufficient to ascertain that this type of Tang sancai was used as daily wares. On the contrary, on the grounds that these locations were the places where ritual performances took place, I argue that sancai utensil wares were used as presentation containers for ritual performances. In the absence of records in Tang texts which could have informed about the relationship between Tang sancai and religious practice, I borrow an evidence from Japan, in the form of the hand-brush writing on a couple of Nara sancai dishes, which were copies of Tang sancai made in Japan during the time of Tang, mentioning that these vessels were specifically for use for ritual ceremonies. Furthermore, on the basis of analyses made on lead-glazed ware, some scholars assert that such ware is poisonous and could not have been used to contain food or drink, as much as no evidence exists to show that ancient Chinese had used lead-glazed wares for that purpose. This leads to the clarification that Tang sancai utensil-shaped wares were not produced for everyday use, their purpose having actually been to serve as vessels for offerings in rituals. I further observe that this connection between sancai and ritual-themed objects, initiated by the Tang, has in fact pervaded through the succeeding dynasties affirming its role in religious ceremonials. Finally, this thesis also looks at Tang sancai as an architectural material to show that it was skillfully used in decorating buildings, not only as tiles and tile-ends, but also as large-sized roof ornaments. The research reveals, in the process, the possible dates when sancai architectural material started to be used popularly during the Tang era.

O pó de aciaria elétrica é um importante subproduto da indústria siderúrgica devido ao seu alto teor de zinco. Assim, tecnologias vêm sendo desenvolvidas visando seu aproveitamento, sendo o forno Waelz a mais difundida delas atualmente. No entanto, sua operação, por contar com um forno rotativo de grandes dimensões que abriga uma infinidade de fenômenos físico-químicos, apresenta difícil previsibilidade ab initio. Por essa razão, este trabalho faz uso de uma ferramenta avançada da termodinâmica computacional, destinada à modelagem de processos, chamada SimuSage, a fim de modelar o seu comportamento. Para a criação do modelo utilizou-se também uma base de dados termodinâmicos advinda do software FactSage e a plataforma de desenvolvimento Lazarus. Com base em dados e resultados operacionais da literatura, foi possível realizar simulações nos modos adiabático e isotérmico, comparando os resultados com os da prática industrial. Constatou-se uma grande capacidade do modelo de reproduzir os resultados da literatura, mesmo quando não há muita informação para aferição dos parâmetros, gerando boa concordância com a composição química relatada dos produtos Óxido Waelz e Escória Waelz. / The electric arc furnace dust is an important by-product of the steel industry due to its high content of zinc. Thus, technologies have been developed aiming for its use, and the Waelz Kiln is the most widespread of them today. However, counting on a very large rotary kiln that houses an infinity of physico-chemical phenomena, its operation is difficult to predict ab initio. For this reason, in order to model its behaviour this work uses an advanced tool of computational thermodynamics designed to process modelling, called SimuSage. To create the model, a thermodynamic database, provided by the FactSage software, as well as a development platform, Lazarus IDE, were also used. Based on operational data and results from de literature, it was possible to perform simulations on both adiabatic and isothermal modes comparing its results with the industrial practice. A great capability of the model to reproduce results from the literature was found, even when there is not much information for the parameters calibration, generating good agreement regarding the reported chemical composition for the products, Waelz Oxide and Waelz Slag.

The characteristics of cement kiln dusts (CKDs) and their effects as partial replacement of Portland Cement (PC) were studied in this research program. The materials used in this study were two different types of PC (normal and moderate sulfate resistant) and seven CKDs. The CKDs used in this study were selected to provide a representation of those available in North America from the three major types of cement manufacturing processes: wet, long-dry, and preheater/precalciner. Two fillers (limestone powder and quartz powder) were also used to compare their effects to that of CKDs at an equivalent replacement of PC. It was found that CKDs can contain significant amounts of amorphous material (>30%) and clinker compounds (>20%) and small amounts of slag and/or flyash (<5%) and calcium langbeinite (<5%). The study found that CKDs from preheater/precalciner kilns have different effects on workability and heat evolution than CKDs from wet and long-dry kilns due to the presence of very reactive and high free lime contents (>20%). The blends with the two CKDs from preheater/precalciner plants had higher paste water demand, lower mortar flows, and higher heat generation during initial hydrolysis in comparison to all other CKD-PC blends and control cements. The hardened properties of CKD as a partial substitute of PC appear to be governed by the sulfate content of the CKD-PC blend (the form of the CKD sulfate is not significant). According to analysis of the ASTM expansion in limewater test results, the CKD-PC blend sulfate content should be less than ~0.40% above the optimum sulfate content of the PC. It was also found that the sulfate contribution of CKD behaves similar to gypsum. Therefore, CKD-PC blends could be optimized for sulfate content by using CKD as a partial substitute of gypsum during the grinding process to control the early hydration of C3A. The wet and long-dry kiln CKDs contain significant amounts of calcium carbonate (>20%) which could also be used as partial replacement of limestone filler in PC.

The pulp and paper industry has been struggling to meet the new and stringent TRS (Total Reduced Sulphur) emission compliance standards established in recent years. However, a new approach by some regulatory bodies gives intricate operational parameters a new and important role in achieving environmental compliance. TRS compounds that cause the distinctive pulp mill odour, originate from sodium sulphide in white liquor used in the kraft pulping process. Up to 20% of TRS emissions could originate from the lime kiln and lime mud solids content is one of the operational parameters that could help reduce the TRS emissions from the lime kiln. Residual sodium sulphide in the lime mud that results in TRS gases, is dissolved in the moisture content of the mud. Although efficient lime mud washing can remove most of the residual sodium sulphide, the remaining moisture content of the mud still contains some sodium sulphide. Therefore, improved lime mud dewatering can be effective in reducing the TRS emissions from the lime kiln. Data presented in this study confirms that as the lime mud solids content increases, TRS emissions from the lime kiln decrease. Data analysis demonstrates a negative linear correlation at 5% significance level between TRS emissions and lime mud solids.