Abstract Gasification is an energy conversion method for the utilisation of biomass for obtaining energy (heat and power). In the gasification process carbon residue is formed as a waste. For improving the cost-effectiveness of the gasification process the utilisation of this waste is important and the present legislation also creates requirements for the utilisation of waste material. Activated carbon is typically used for purification of water, for example, wastewaters as well as gaseous emissions. Consequently, commercial activated carbon is fairly expensive and its preparation is energy consuming. However, this inhibits sometimes its widespread use in wastewater treatment and therefore there is a need to develop cost-effective adsorbents from alternative biomass-based low-cost raw materials to remove harmful substances from aqueous solutions. The first aim of this thesis was to determine physical and chemical properties of carbon residues from wood gasification, and fly ashes from burning processes were used as reference samples. The properties are essential to known when evaluating the potential utilisation applications for unknown carbon residue samples. Properties of carbon residue indicate that it would be suitable adsorbent due to the high carbon content but its activation or modification is needed. The second aim was to modify this industrial carbonaceous by-product by physical and chemical activation and chemical modification methods to maximise the adsorption capacity of material. Based on our results, adsorption properties can be enhanced by using zinc chloride as a chemical activating agent, carbon dioxide as a physical activating agent and ferric chloride in the chemical modification and adsorbents with specific surface areas 285, 590 and 52 m2 g-1 were produced, respectively. The third aim was to test produced adsorbents to anions removal. Chemically activated carbon residue removes phosphate well and physically activated carbon residue removes phosphates and nitrates. Chemically modified carbon residue was observed to be suitable sorbent for sulphate removal. Optimal initial pH and concentration were determined and effect of time was studied and kinetic calculations and isotherm analysis was done for studied adsorbents. / Tiivistelmä Kaasutus on tehokas tapa hyödyntää biomassaa sähkön- ja lämmöntuotannossa. Kaasutuksessa muodostuu jätteenä hiilijäännöstä, jonka hyödyntäminen on tärkeää kaasutusprosessin kustannustehokkuuden parantamiseksi. Myös nykyinen lainsäädäntö asettaa vaatimuksia jätemateriaalien hyödyntämiselle. Aktiivihiiltä on tyypillisesti käytetty mm. jäteveden sekä kaasujen puhdistukseen. Aktiivihiili on kuitenkin kallista ja sen valmistaminen on energiaa kuluttava prosessi, mikä rajoittaa sen käyttöä. Tämän vuoksi tarvitaan uutta tietoa myös kustannustehokkaampien adsorbenttien valmistamiseen soveltuvista vaihtoehtoisista biomassapohjaisista raaka-aineista. Tutkimuksen tavoitteena oli aluksi määrittää puun kaasutuksessa muodostuneen hiilijäännöksen fysikaalisia ja kemiallisia ominaisuuksia, joiden tunteminen on tärkeää arvioitaessa soveltuvia hyödyntämiskohteita kyseiselle tuntemattomalle jätemateriaalille. Referenssinäytteinä käytettiin polttolaitoksilla muodostunutta lentotuhkaa. Hiilijäännöksen ominaisuuksien perusteella se voisi olla soveltuva adsorbentti, mutta aktivointi tai modifiointi on välttämätöntä hiilijäännöksen adsorptiokapasiteetin parantamiseksi. Työn toinen tavoite oli parantaa hiilijäännöksen adsorptio-ominaisuuksia fysikaalisesti ja kemiallisesti aktivoimalla tai kemiallisesti modifioimalla. Tulosten perusteella adsorptio-ominaisuuksia voidaan parantaa parhaiten käyttämällä sinkkikloridia kemiallisessa aktivoinnissa, hiilidioksidia fysikaalisessa aktivoinnissa ja rautakloridia kemiallisessa modifioinnissa, jolloin valmistettujen adsorbenttien ominaispinta-alat olivat 285, 590 ja 52 m2 g-1. Työn kolmas tavoite oli tutkia valmistettujen adsorbenttien adsorptiokykyä anionien poistossa laboratoriomittakaavassa. Kemiallisesti aktivoitu hiilijäännös poistaa tehokkaasti fosfaattia, fysikaalisesti aktivoitu fosfaattia ja nitraattia ja kemiallisesti modifioitu hiilijäännös on hyvä sorbentti sulfaatinpoistossa. Adsorptiokokeissa määritettiin optimaalinen alku pH ja alkukonsentraatio ja lisäksi tutkittiin ajan vaikutusta adsorptioon. Tulosten perusteella tehtiin kinetiikkamallinnusta sekä isotermianalyysi.

The thesis, through experimental and numerical investigations reports on the work related to packed bed reactors in co-current configuration for biomass gasification. This study has extensively focused on the gasification operating regimes and addressing the issues of presence of tar, an undesirable component for engine application. Systematically, the influence of fuel properties on the gasification process has been studied using single particle analysis and also in packed bed reactors. Studies related to the effect of fuel properties - size, surface area volume ratio and density on the reactor performance are addressed. The influence of these parameters on the propagation rate which indirectly influences the residence time, tar generation, gas compositions is explicitly elucidated. Most of the reported work in literature primarily focuses on counter-current configurations and analysis on propagation flame front/ignition mass flux and temperature profiles mostly under the combustion regime. In this work, flame propagation front movement, bed movement and effective movement for a co-current packed bed reactor of different reactor capacities and a generalized approach towards establishing ‘effective propagation rate’ has been proposed. The work also reports on the importance of particle size and sharing of air from the top and through nozzles on tar generation in the open top down draft reactor configuration. Firstly, pyrolysis, an important component of the thermochemical conversion process has been studied using the flaming time for different biomass samples having varying size, shape and density. The elaborate experiments on the single particle study provides an insight into the reasons for high tar generation for wood flakes/coconut shells and also identifies the importance of the fuel particle geometry related to surface area and volume ratio. Effect of density by comparing the flaming rate of wood flakes and coconut shells with the wood sphere for an equivalent diameter is highlighted. It is observed that the tar level in the raw gas is about 80% higher in the case of wood flakes and similar values for coconut shells compared with wood pieces. The analysis suggests that the time for pyrolysis is lower with a higher surface area particle and is subjected to nearly fast pyrolysis process resulting in higher tar fraction with low char yield. Similarly, time for pyrolysis increases with density as observed from the experimental measurements by using coconut shells and wood flakes and concludes the influence on the performance of packed bed reactors. Studies on co-current reactor under various operating conditions from closed top reactor to open top reburn configuration suggests improved residence time reduces tar generation. This study establishes, increased residence time with staged air flow has a better control on residence time and yields lower tar in the raw gas. Studies on the influence of air mass flux on the propagation rate, peak temperature, and gas quality, establishes the need to consider bed movement in the case of co-current packed bed reactor. It is also observed that flame front propagation rate initially increases as the air mass flux is increased, reaches a peak and subsequently decreases. With increase in air mass flux, fuel consumption increases and thereby the bed movement. The importance of bed movement and its effect on the propagation front movement has been established. To account for variation in the fuel density, normalized propagation rate or the ignition mass flux is a better way to present the result. The peak flame front propagation rates are 0.089 mm/s for 10 % moist wood at an air mas flux of 0.130 kg/m2-s and while 0.095 mm/s for bone-dry wood at an air mass flux of 0.134 kg/m2-s. These peak propagation rates occur with the air mass flux in the range of 0.130 to 0.134 kg/m2-s. The present results compare well with those available in the literature on the effective propagation rate with the variation of air mass flux, and deviations are linked to fuel properties. The propagation rate correlates with mass flux as ̇ . during the increasing regime of the front movement. The extinction of flame propagation or the front receding has been established both experimentally supported from the model analysis and is found to be at an air mass flux of 0.235 kg/m2-s. The volume fraction of various gaseous species at the reactor exits obtained from the experiment is 14.89±0.28 % CO2, 15.75±0.43 % CO and 11.09±1.99 % H2 respectively with the balance being CH4 and N2. The model analysis using an in-house program developed for packed bed reactor provide a comprehensive understanding with respect to the performance of packed bed reactor under gasification conditions. The model addresses the dependence on air mass flux on gas composition and propagation rate and is used to validate the experimental results. Based on the energy balance in the reaction front, the analysis clearly identifies the reasons for stable propagation front and receding front in a co-current reactor. From the experiments and modelling studies, it is evident that turn-down ratio of a downdraft gasification system is scientifically established. Both the experimental and the numerical studies presented in the current work establishes that the physical properties of the fuel have an impact on the performance of the co-current reactor and for the first time, the importance of bed movement on the propagation rate is identified.

The diploma thesis deals with the design of nearly zero energy buildings. It focuses primarily on optimizing the thermal insulation thickness at a cost-optimal level. Based on energy consumption analysis, three heat sources are selected and then evaluated using an energy assessment. The building is evaluated in terms of energy, economic and environmental.