Characterisation of waste for combustion : with special reference to the role of zinc

Waste combustion has gone from being a volume reducing discarding-method to an energy recovery process for unwanted material that cannot be reused or recycled. Different fractions of waste are used as fuel today, such as; municipal solid waste, refuse derived fuel, and solid recovered fuel. Furthermore, industrial waste, normally a mixture between commercial waste and building and demolition waste, is common, either as separate fuels or mixed with, for example, municipal solid waste. Compared to fossil or biomass fuels, waste mixtures are extremely heterogeneous, making it a complicated fuel. Differences in calorific values, ash content, moisture content, and changing levels of elements, such as Cl and alkali metals, are common in waste fuel. Moreover, waste contains much higher levels of troublesome trace elements, such as Zn, which is thought to accelerate a corrosion process. Varying fuel quality can be strenuous on the boiler system and may cause fouling and corrosion of heat exchanger surfaces. This thesis examines waste fuels and waste combustion from different angles, with the objective of giving a better understanding of waste as an important fuel in today’s fuel economy. Several chemical characterisation campaigns of waste fuels over longer time periods (10-12 months) was used to determine the fossil content of Swedish waste fuels, to investigate possible seasonal variations, and to study the presence of Zn in waste. Data from the characterisation campaigns were used for thermodynamic equilibrium calculations to follow trends and determine the effect of changing concentrations of various elements. The thesis also includes a study of the thermal behaviour of Zn and a full—scale study of how the bed temperature affects the volatilisation of alkali metals and Zn from the fuel. As mixed waste fuel contains considerable amounts of fresh biomass, such as wood, food waste, paper etc. it would be wrong to classify it as a fossil fuel. When Sweden introduced waste combustion as a part of the European Union emission trading system in the beginning of 2013 there was a need for combustion plants to find a usable and reliable method to determine the fossil content. Four different methods were studied in full-scale of seven combustion plants; 14Canalysis of solid waste, 14C-analysis of flue gas, sorting analysis followed by calculations, and a patented balance method that is using a software program to calculate the fossil content based on parameters from the plant. The study showed that approximately one third of the coal in Swedish waste mixtures has fossil origins and presented the plants with information about the four different methods and their advantages and disadvantages. Characterisation campaigns also showed that industrial waste contain higher levels of trace elements, such as Zn. The content of Zn in Swedish waste fuels was determined to be approximately 800 mg kg-1 on average, based on 42 samples of solid waste from seven different plants with varying mixtures between municipal solid waste and industrial waste. A review study of the occurrence of Zn in fuels confirmed that the highest amounts of Zn are present in waste fuels rather than in fossil or biomass fuels. In tires, Zn is used as a vulcanizing agent and can reach concentration values of 9600-16800 mg kg-1. Waste Electrical and Electronic Equipment is the second Zn-richest fuel and even though on average Zn content is around 4000 mg kg-1, the values of over 19000 mg kg-1 were also reported. The increased amounts of Zn, 3000-4000 mg kg-1, are also found in municipal solid waste, sludge with over 2000 mg kg-1 on average (some exceptions up to 49000 mg kg-1), and other waste derived fuels (over 1000 mg kg-1). Zn is also found in fossil fuels. In coal, the average level of Zn is 100 mg kg-1, the higher amount of Zn was only reported for oil shale with values between 20-2680 mg kg-1. The content of Zn in biomass is basically determined by its natural occurrence and it is typically 10-100 mg kg-1. The thermal behaviour of Zn is of importance to understand the possible reactions taking place in the boiler. By using thermal analysis three common Zn-compounds were studied (ZnCl2, ZnSO4, and ZnO) and compared to phase diagrams produced with thermodynamic equilibrium calculations. The results of the study suggest that ZnCl2(s/l) cannot exist readily in the boiler due to its volatility at high temperatures and its conversion to ZnO in oxidising conditions. Also, ZnSO4 decomposes around 680°C, while ZnO is relatively stable in the temperature range prevailing in the boiler. Furthermore, by exposing ZnO to HCl in a hot environment (240-330°C) it was shown that chlorination of ZnO with HCl gas is possible. Waste fuel containing high levels of elements known to be corrosive, for example, Na and K in combination with Cl, and also significant amounts of trace elements, such as Zn, are demanding on the whole boiler system. A full-scale study of how the volatilisation of Na, K, and Zn is affected by the bed temperature in a fluidised bed boiler was performed parallel with a lab-scale study with the same conditions. The study showed that the fouling rate on deposit probes were decreased by 20 % when the bed temperature was decreased from 870°C to below 720°C. In addition, the lab-scale experiments clearly indicated that the amount of alkali metals and Zn volatilised depends on the reactor temperature.

Blade and rod coating of low solid dispersions

Työn aiheena oli tehdä ohut barrierkalvo terä- tai sauvapäällystys menetelmällä. Erilaisissa elintarvikepakkauksissa käytetään hyviä barrier-ominaisuuksia omaavia ohuita päällysteitä. Elintarvikepakkauksen tehtävä on suojata pakattua tuotetta ympäristöltä, mahdollistaa helppo kuljetus ja säilytys sekä antaa tarvittavat tiedot tuotteesta tuotteen käsittelijöille ja loppukäyttäjille. Diplomityön teoriaosuudessa keskityttiin barrierpäällystykseen, eri päällystysmenetelmiin, niiden erityisvaatimuksiin ja ominaisuuksiin. Teoriaosuudessa käsiteltiin myös vaadittavia barrier-ominaisuuksia ja haasteita niiden saavuttamisessa. Kirjallisuuden perusteella haasteiksi nousivat helposti muodostuvat mikroreiät. Kokeellinen osa jakautui kahteen osakokonaisuuteen: laboratoriokokeisiin ja pilot-koeajoon. Laboratoriokokeita tehtiin ennen pilot-ajoa, jotta pilot-koeajoon voitiin valita parhaat päällystereseptit. Pilot-koeajonäytteiden päällystemäärät osoittautuivat liian pieniksi ja siksi laboratoriossa tehtiin jatkotutkimuksia riittävän päällystemäärän saavuttamiseksi. Tämän työnperusteella pohjakartongin ominaisuuksilla, erityisesti karheudella, on merkittävä vaikutus päällystyksen onnistumisessa ja yksinkertaisilla resepteillä ja päällystysmenetelmillä ei saada tarpeeksi laadukasta kalvoa.

Modeling of Liquid-Solid Flow in Industrial Scale

In the present work, liquid-solid flow in industrial scale is modeled using the commercial software of Computational Fluid Dynamics (CFD) ANSYS Fluent 14.5. In literature, there are few studies on liquid-solid flow in industrial scale, but any information about the particular case with modified geometry cannot be found. The aim of this thesis is to describe the strengths and weaknesses of the multiphase models, when a large-scale application is studied within liquid-solid flow, including the boundary-layer characteristics. The results indicate that the selection of the most appropriate multiphase model depends on the flow regime. Thus, careful estimations of the flow regime are recommended to be done before modeling. The computational tool is developed for this purpose during this thesis. The homogeneous multiphase model is valid only for homogeneous suspension, the discrete phase model (DPM) is recommended for homogeneous and heterogeneous suspension where pipe Froude number is greater than 1.0, while the mixture and Eulerian models are able to predict also flow regimes, where pipe Froude number is smaller than 1.0 and particles tend to settle. With increasing material density ratio and decreasing pipe Froude number, the Eulerian model gives the most accurate results, because it does not include simplifications in Navier-Stokes equations like the other models. In addition, the results indicate that the potential location of erosion in the pipe depends on material density ratio. Possible sedimentation of particles can cause erosion and increase pressure drop as well. In the pipe bend, especially secondary flows, perpendicular to the main flow, affect the location of erosion.

Optimization and validation of the solid-liquid extraction technique for determination of picloram in soils by high performance liquid chromatography

The objective of this study was to optimize and validate the solid-liquid extraction (ESL) technique for determination of picloram residues in soil samples. At the optimization stage, the optimal conditions for extraction of soil samples were determined using univariate analysis. Ratio soil/solution extraction, type and time of agitation, ionic strength and pH of extraction solution were evaluated. Based on the optimized parameters, the following method of extraction and analysis of picloram was developed: weigh 2.00 g of soil dried and sieved through a sieve mesh of 2.0 mm pore, add 20.0 mL of KCl concentration of 0.5 mol L-1, shake the bottle in the vortex for 10 seconds to form suspension and adjust to pH 7.00, with alkaline KOH 0.1 mol L-1. Homogenate the system in a shaker system for 60 minutes and then let it stand for 10 minutes. The bottles are centrifuged for 10 minutes at 3,500 rpm. After the settlement of the soil particles and cleaning of the supernatant extract, an aliquot is withdrawn and analyzed by high performance liquid chromatography. The optimized method was validated by determining the selectivity, linearity, detection and quantification limits, precision and accuracy. The ESL methodology was efficient for analysis of residues of the pesticides studied, with percentages of recovery above 90%. The limits of detection and quantification were 20.0 and 66.0 mg kg-1 soil for the PVA, and 40.0 and 132.0 mg kg-1 soil for the VLA. The coefficients of variation (CV) were equal to 2.32 and 2.69 for PVA and TH soils, respectively. The methodology resulted in low organic solvent consumption and cleaner extracts, as well as no purification steps for chromatographic analysis were required. The parameters evaluated in the validation process indicated that the ESL methodology is efficient for the extraction of picloram residues in soils, with low limits of detection and quantification.

Production of a bioherbicide agent in liquid and solid medium and in a biphasic cultivation system

The use of fungi in weeds control programs depends upon the conidia production in large scale. Therefore, this study aimed to evaluate liquid and solid culture media and the cultivation by biphasic system for the conidia production of Bipolaris euphorbiae Muchovej & Carvalho a specific pathogen of Euphorbia heterophylla. The liquid media were obtained from agro-industrial waste or by-products, and the solid media were prepared with mixtures of grains and grain derivatives. The liquid medium made with sugar cane molasses stood out from the others because it provided great sporulation (23 x 10(4) conidia mL-1 of medium), conidial viability (99.7%), and formation of mycelial fungal biomass (1.26 g 100 mL-1 of medium). On solid media conidial production was markedly higher than in liquid media, especially the medium composed by a blend of sorghum grain (40%) and soybean hulls (60%) where the fungus produced 2.3 x 10(7) conidia g-1 of medium. The cultivation of B. euphorbiae in biphasic system not promoted a significant increase in the production of conidia. The solid media were more effective for the mass production of fungus and mixtures of grains and derivatives were effective for increasing conidia production.

Jätteen kaasutus ja energiakäyttö

Kiinteiden polttoaineiden muuntaminen kaasumaiseen muotoon eli kaasuttaminen herätti jo vuosia sitten tutkijoiden kiinnostusta. Suomessa yleinen mielenkiinto on viimeaikoina keskittynyt edullisempien polttoaineiden kaasuttamiseen ja saatavan tuotekaasun polttamiseen. Lahti Energian uudessa Kymijärvi 2 voimalaitoksessa kaasutetaan puuta ja kierrätyspolttoainetta (REF). Saatava tuotekaasu jäähdytetään ja suodatetaan, jotta epäpuhtaudet saadaan pois tuotekaasusta. Puhdistettu tuotekaasu poltetaan kaasukattilassa korkeilla höyrynarvoilla. Tuotekaasun jäähdyttämistä ei ole paljoa tehty eikä siitä ole juurikaan tieteellistä tutkimusta eikä kokemusta. Tuotekaasun jäähtyessä partikkelit tarttuvat lämpöpinnoille aiheuttaen kerrostumia. Kerrostumat heikentävät lämmönsiirtoa olennaisesti. Tämän työn tarkoitus on tutkia kaasutusprosessia, tuotekaasun jäähdyttimen likaantumista sekä antaa lisätietoja likaantumiseen vaikuttavista tekijöistä.

Container logistic innovations in forest-energy sector: Markets, future service concepts and technical improvements

The report presents the results of the commercialization project called the Container logistic services for forest bioenergy. The project promotes new business that is emerging around overall container logistic services in the bioenergy sector. The results assess the European markets of the container logistics for biomass, enablers for new business creation and required service bundles for the concept. We also demonstrate the customer value of the container logistic services for different market segments. The concept analysis is based on concept mapping, quality function deployment process (QFD) and business network analysis. The business network analysis assesses key shareholders and their mutual connections. The performance of the roadside chipping chain is analysed by the logistic cost simulation, RFID system demonstration and freezing tests. The EU has set the renewable energy target to 20 % in 2020 of which Biomass could account for two-thirds. In the Europe, the production of wood fuels was 132.9 million solid-m3 in 2012 and production of wood chips and particles was 69.0 million solidm3. The wood-based chips and particle flows are suitable for container transportation providing market of 180.6 million loose- m3 which mean 4.5 million container loads per year. The intermodal logistics of trucks and trains are promising for the composite containers because the biomass does not freeze onto the inner surfaces in the unloading situations. The overall service concept includes several packages: container rental, container maintenance, terminal services, RFID-tracking service, and simulation and ERP-integration service. The container rental and maintenance would provide transportation entrepreneurs a way to increase the capacity without high investment costs. The RFID-concept would lead to better work planning improving profitability throughout the logistic chain and simulation supports fuel supply optimization.

Interphase cytogenetics using fluorescence in situ hybridization: an overview of its application to diffuse and solid tissue

Interphase cytogenetics, utilizing fluorescence in situ hybridization (FISH) techniques, has been successfully applied to diffuse and solid tissue specimens. Most studies have been performed on isolated cells, such as blood or bone marrow cells; a few have been performed on cells from body fluids, such as amniotic fluid, urine, sperm, and sputum. Mechanically or chemically disaggregated cells from solid tissues have also been used as single cell suspensions for FISH. Additionally, intact organized tissue samples represented by touch preparations or thin tissue sections have been used, especially in cancer studies. Advantages and pitfalls of application of FISH methodology to each type of specimen and some significant biological findings achieved are illustrated in this overview.

Hydrolysis of xylans by enzyme systems from solid cultures of Trichoderma harzianum strains

Xylanase activity was isolated from crude extracts of Trichoderma harzianum strains C and 4 grown at 28oC in a solid medium containing wheat bran as the carbon source. Enzyme activity was demonstrable in the permeate after ultrafiltration of the crude extracts using an Amicon system. The hydrolysis patterns of different xylans and paper pulps by xylanase activity ranged from xylose, xylobiose and xylotriose to higher xylooligosaccharides. A purified ß-xylosidase from the Trichoderma harzianum strain released xylose, xylobiose and xylotriose from seaweed, deacetylated, oat spelt and birchwood xylans. The purified enzyme was not active against acetylated xylan and catalyzed the hydrolysis of xylooligosaccharides, including xylotriose, xylotetraose and xylopentaose. However, the enzyme was not able to degrade xylohexaose. Xylanase pretreatment was effective for hardwood kraft pulp bleaching. Hardwood kraft pulp bleached in the XEOP sequence had its kappa number reduced from 13.2 to 8.9 and a viscosity of 20.45 cp. The efficiency of delignification was 33%.

Polysiloxane/PVA-glutaraldehyde hybrid composite as solid phase for immunodetections by ELISA

We developed an efficient method to prepare a hybrid inorganic-organic composite based on polyvinyl alcohol (PVA) and polysiloxane using the sol-gel disc technique. Antigen obtained from Yersinia pestis was covalently immobilized onto these discs with glutaraldehyde and used as solid phase in ELISA for antibody detection in serum of rabbits experimentally immunized with plague. Using 1.25 µg antigen per disc, a peroxidase conjugate dilution of 1:4,000 and a serum dilution of 1:200 were adequate for the establishment of the procedure. These values are similar to those used for PVA-glutaraldehyde discs, plasticized filter paper discs and the polyaniline-Dacron composite discs. This procedure is comparable to that which utilizes the adsorption of the antigen to conventional PVC plates, with the amount of antigen being one fourth that employed in conventional PVC plates (5 µg/well). In addition to the performance of the polysiloxane/PVA-glutaraldehyde disc as a matrix for immunodetection, its easy synthesis and low cost are additional advantages for commercial application.

Use of blends of bioabsorbable poly(L-lactic acid)/poly(hydroxybutyrate- co-hydroxyvalerate) as surfaces for Vero cell culture

Vero cells, a cell line established from the kidney of the African green monkey (Cercopithecus aethiops), were cultured in F-10 Ham medium supplemented with 10% fetal calf serum at 37°C on membranes of poly(L-lactic acid) (PLLA), poly(hydroxybutyrate-co-hydroxyvalerate) (PHBV) and their blends in different proportions (100/0, 60/40, 50/50, 40/60, and 0/100). The present study evaluated morphology of cells grown on different polymeric substrates after 24 h of culture by scanning electron microscopy. Cell adhesion was also analyzed after 2 h of inoculation. For cell growth evaluation, the cells were maintained in culture for 48, 120, 240, and 360 h. For cytochemical study, the cells were cultured for 120 or 240 h, fixed, processed for histological analysis, and stained with Toluidine blue, pH 4.0, and Xylidine ponceau, pH 2.5. Our results showed that cell adhesion was better when 60/40 and 50/50 blends were used although cells were able to grow and proliferate on all blends tested. When using PLLA/PHBV (50/50) slightly flattened cells were observed on porous and smooth areas. PLLA/PHBV (40/60) blends presented flattened cells on smooth areas. PLLA/PHBV (0/100), which presented no pores, also supported spreading cells interconnected by thin filaments. Histological sections showed that cells grew as a confluent monolayer on different substrates. Cytochemical analysis showed basophilic cells, indicating a large amount of RNA and proteins. Hence, we detected changes in cell morphology induced by alterations in blend proportions. This suggests that the cells changed their differentiation pattern when on various PLLA/PHBV blend surfaces.

Solid-state reference and ion-selective electrodes : towards portable potentiometric sensing

Potentiometric sensors are very attractive tools for chemical analysis because of their simplicity, low power consumption and low cost. They are extensively used in clinical diagnostics and in environmental monitoring. Modern applications of both fields require improvements in the conventional construction and in the performance of the potentiometric sensors, as the trends are towards portable, on-site diagnostics and autonomous sensing in remote locations. The aim of this PhD work was to improve some of the sensor properties that currently hamper the implementation of the potentiometric sensors in modern applications. The first part of the work was concentrated on the development of a solid-state reference electrode (RE) compatible with already existing solid-contact ion-selective electrodes (ISE), both of which are needed for all-solid-state potentiometric sensing systems. A poly(vinyl chloride) membrane doped with a moderately lipophilic salt, tetrabutylammonium-tetrabutylborate (TBA-TBB), was found to show a satisfactory stability of potential in sample solutions with different concentrations. Its response time was nevertheless slow, as it required several minutes to reach the equilibrium. The TBA-TBB membrane RE worked well together with solid-state ISEs in several different situations and on different substrates enabling a miniature design. Solid contacts (SC) that mediate the ion-to-electron transduction are crucial components of well-functioning potentiometric sensors. This transduction process converting the ionic conduction of an ion-selective membrane to the electronic conduction in the circuit was studied with the help of electrochemical impedance spectroscopy (EIS). The solid contacts studied were (i) the conducting polymer (CP) poly(3,4-ethylienedioxythiophene) (PEDOT) and (ii) a carbon cloth having a high surface area. The PEDOT films were doped with a large immobile anion poly(styrene sulfonate) (PSS-) or with a small mobile anion Cl-. As could be expected, the studied PEDOT solid-contact mediated the ion-toelectron transduction more efficiently than the bare glassy carbon substrate, onto which they were electropolymerized, while the impedance of the PEDOT films depended on the mobility of the doping ion and on the ions in the electrolyte. The carbon cloth was found to be an even more effective ion-to-electron transducer than the PEDOT films and it also proved to work as a combined electrical conductor and solid contact when covered with an ion-selective membrane or with a TBA-TBB-based reference membrane. The last part of the work was focused on improving the reproducibility and the potential stability of the SC-ISEs, a problem that culminates to the stability of the standard potential E°. It was proven that the E° of a SC-ISE with a conducting polymer as a solid contact could be adjusted by reducing or oxidizing the CP solid contact by applying current pulses or a potential to it, as the redox state of the CP solid-contact influences the overall potential of the ISE. The slope and thus the analytical performance of the SC-ISEs were retained despite the adjustment of the E°. The shortcircuiting of the SC-ISE with a conventional large-capacitance RE was found to be a feasible instrument-free method to control the E°. With this method, the driving force for the oxidation/reduction of the CP was the potential difference between the RE and the SC-ISE, and the position of the adjusted potential could be controlled by choosing a suitable concentration for the short-circuiting electrolyte. The piece-to-piece reproducibility of the adjusted potential was promising, and the day-today reproducibility for a specific sensor was excellent. The instrumentfree approach to control the E° is very attractive considering practical applications.

Recombinant E2 glycoprotein of bovine viral diarrhea virus induces a solid humoral neutralizing immune response but fails to confer total protection in cattle

Two recombinant baculoviruses were produced in order to obtain a bovine viral diarrhea virus (BVDV) immunogen: AcNPV/E2 expressing E2 glycoprotein, and AcNPV/E0E1E2 expressing the polyprotein region coding for the three structural proteins of BVDV (E0, E1, and E2). Mice were immunized with Sf9 cells infected with the recombinant baculoviruses in a water in oil formulation and the production of neutralizing antibodies was evaluated. Since E2 elicited higher neutralizing antibody titers than E0-E1-E2 polyprotein, it was selected to immunize cattle. Calves received two doses of recombinant E2 vaccine and were challenged with homologous BVDV 37 days later. The recombinant immunogen induced neutralizing titers which showed a mean value of 1.5 ± 0.27 on the day of challenge and reached a top value of 3.36 ± 0.36, 47 days later (84 days post-vaccination). On the other hand, sera from animals which received mock-infected Sf9 cells did not show neutralizing activity until 25 days post-challenge (62 days post-vaccination), suggesting that these antibodies were produced as a consequence of BVDV challenge. Even when no total protection was observed in cattle, in vitro viral neutralization assays revealed that the recombinant immunogen was able to induce neutralizing antibody synthesis against the homologous strain as well as against heterologous strains in a very efficient way.

Intensive chemotherapy as salvage treatment for solid tumors: focus on germ cell cancer

Germ cell tumors present contrasting biological and molecular features compared to many solid tumors, which may partially explain their unusual sensitivity to chemotherapy. Reduced DNA repair capacity and enhanced induction of apoptosis appear to be key factors in the sensitivity of germ cell tumors to cisplatin. Despite substantial cure rates, some patients relapse and subsequently die of their disease. Intensive doses of chemotherapy are used to counter mechanisms of drug resistance. So far, high-dose chemotherapy with hematopoietic stem cell support for solid tumors is used only in the setting of testicular germ cell tumors. In that indication, high-dose chemotherapy is given as the first or late salvage treatment for patients with either relapsed or progressive tumors after initial conventional salvage chemotherapy. High-dose chemotherapy is usually given as two or three sequential cycles using carboplatin and etoposide with or without ifosfamide. The administration of intensive therapy carries significant side effects and can only be efficiently and safely conducted in specialized referral centers to assure optimum patient care outcomes. In breast and ovarian cancer, most studies have demonstrated improvement in progression-free survival (PFS), but overall survival remained unchanged. Therefore, most of these approaches have been dropped. In germ cell tumors, clinical trials are currently investigating novel therapeutic combinations and active treatments. In particular, the integration of targeted therapies constitutes an important area of research for patients with a poor prognosis.

Microfibers for juice analysis by solid-phase microextraction

In view of the interest in analyzing volatile compounds by SPME, the following five microfibers were tested, polydimethylsiloxane; polyacrylate; polydimethylsiloxane/divinylbenzene; carboxen/polydimethylsiloxane, and carbowax/divinylbenzene, to select the one which presents the best performance for the adsorption of the volatile compounds present in the headspace of acid lime juice samples. Sample stabilization time variations (30 and 60 minutes) were assessed as well the addition of NaCl to the samples. It was verified that the chromatogram with the most adsorbed volatile compounds was obtained with PDMS/DVB microfiber at 30 minutes and the addition of 0.2 g NaCl.