Fate of peat utilization

Peat is an organic substance with the maintenance of a mineral part, what shows it as interesting object for studying. Both organic and mineral parts of peat find application in various fields of activity of the people. Antibacterial properties of peat are known since an antiquity. Today people have expanded a spectrum of application of peat to use of by-products of its processing for reception of rather ecologically harmless fuel. The master theses are focused on peat, as on ambiguous raw materials for processing and fuel manufacture. The purpose of theses to show how much widely applied peat, technologies on its processing and its influence on environment at all stages of its working out.

Occurrence and photochemical fate of selected pharmaceutical active ingredients in the aquatic environment

Läkemedel konsumeras årligen i enorma mängder världen över. Efter intag kommer en del av läkemedlets aktiva förening(ar) att utsöndras från kroppen med urin och fekalier för att sedan transporteras till avloppsreningsverk. Till följd av att reningsverken inte fullständigt förmår rena avloppsvattnet från dessa föreningar kommer de att kontinuerligt tillföras vattenmiljön. Således är det viktigt att utveckla analytiska metoder för att kunna studera halterna av de aktiva föreningarna i reningsverkens utloppsvatten och den närliggande vattenmiljön. Ute i naturen kommer föreningarna att utsättas för olika fysikaliska, kemiska och biologiska processer, vilka kan orsaka förändringar i deras kemiska struktur och därigenom deras identitet och biologiska aktivitet. En stor del av de befintliga aktiva föreningarna genomgår kemisk förändring då de i vattenmiljön utsätts för solljus (fototransformation). Genom fototransformation kan nya föreningar (transformationsprodukter) med andra kemiska och biologiska egenskaper bildas. Denna avhandling inriktar sig på de aktiva föreningarnas förekomst och fotokemiska öde i miljön. I avhandlingen presenteras framtagna analytiska metoder för kvantifiering av läkemedelsföreningar i avloppsvatten och ytvatten samt för studier av vissa utvalda föreningars fotokemiska transformationsvägar. Därtill beskrivs några syntetiska metoder för att få tillgång till transformationsprodukter av det antiinflammatoriska ämnet diklofenak.

Fate of fuel-bound nitrogen and sulfur in biomass-fired Industrial boilers

Användning av biomassa som energikälla för produktion av el och värme är ett sätt att minska beroendet av fossila bränslen och höja självförsörjningen av energi. Fossila bränslen är den främsta källan till koldioxid utsläpp förorsakad av människan. Biomassa, å andra sidan, betraktas som en koldioxidneutral energikälla. Svavlet och kvävet i biomassan bildar dock föroreningar såsom kväveoxider (NOX) och svaveldioxid (SO2), som bidrar till försurning av mark och sjöar. Svavlet i bränslet kan även både förorsaka och förhindra korrosion i en förbränningsanläggning, beroende på förbränningen och bränslet. Huvudsyftet med detta arbete var att få en bättre förståelse om hur utsläppen av NOX och SO2 bildas från bränslebundet kväve och svavel vid förbränning av olika biobränslen. Mätkampanjer i fullskaliga förbränningsanläggningar utfördes, där gassammansättningen mättes i eldstaden och rökgasen. Förståelsen om gaskemin i eldstaden är viktig, för att möjliggöra utvecklandet av renare och effektivare förbränningsanläggningar. Ett annat syfte med arbetet var att klargöra om sulfatering av askkomponenter vid förbränning av biobränslen med olika askegenskaper. Alkaliklorider som bildas vid biomassaförbränning kan orsaka korrosion av värmeöverföringsytor. Svavlet i bränslet visade sig ha en viktig roll i att sulfatera alkaliklorider till mindre korrosiva alkalisulfater. Närvaron av gasformig svavelsyra i rökgaskanalen av förbränningsanläggningar studerades även. Kondensering av svavelsyra leder till korrosion av rökgaskanalen och dess delar. Om svavelsyrakoncentrationen i rökgasen är känd, kan daggpunktstemperaturen beräknas och kondensering av svavelsyra förhindras. I arbetet utvecklades en mätmetod för att mäta låga koncentrationer av gasformig svavelsyra i rökgaser. Denna metod användes för att undersöka risken av lågtemperaturkorrosion orsakad av svavelsyra i förbränningsanläggningar. ------------------------------------------------------------------------------------------------------------ Käyttämällä biomassaa energianlähteenä voidaan vähentää sähkön- ja lämmöntuotannon riippuvuutta fossiilisiin polttoaineisiin. Biomassan käytöllä voidaan myös lisätä energiantuotannon omavaraisuutta. Fossiiliset polttoaineet ovat pääasiallinen syy ihmisen aiheuttamiin hiilidioksidipäästöihin. Biomassa sen sijaan luetaan hiilidioksidineutraaleihin energianlähteisiin. Biopolttoaineiden käytössä tosin vapautuu typpi- ja rikkioksideja, jotka edesauttavat maaperän ja merien happamoitumista. Lisäksi biopolttoaineen rikki voi sekä vähentää että aiheuttaa laitteiden korroosiota energiantuotannossa riippuen biopolttoaineesta ja palamisesta. Tämän työn päätavoitteena oli selvittää mitä biopolttoaineeseen sitoutuneelle typelle ja rikille tapahtuu teollisissa polttolaitoksissa. Kyseisten oksidien muodostumista tutkittiin polttamalla eri biomassoja polttolaitoksissa. Tutkimukset toteutettiin mittauskampanjoilla useissa polttolaitoksissa. Kaasujen koostumusta mitattiin sekä tulipesässä, että savukaasuista. Kaasujen koostumus varsinkin tulipesässä on tärkeää, jotta tulevaisuudessa voidaan rakentaa puhtaampia ja tehokkaampia polttolaitoksia. Työn toisena tavoitteena oli selvittää biomassan polton yhteydessä tapahtuvaa tuhkan sulfatoitumista. Alkalikloridit, joita muodostuu biomassan poltossa, voivat aiheuttaa lämmönsiirtopintojen korroosiota. Rikki osoittautui tärkeäksi osaksi prosessia, jossa korroosiota aiheuttavat alkalikloridit sulfatoituivat vähemmän korrosoiviksi alkalisulfaateiksi. Myös kaasumaisen rikkihapon läsnäoloa savukaasuissa tutkittiin. On todettu, että kaasumuotoinen rikkihappo johtaa korroosioon savukaasukanavan kylmässä päässä ja sen eri osissa rikkihapon tiivistyessä lämpötilan laskiessa. Mikäli rikkihapon pitoisuus savukaasussa tiedetään, sen kastepiste voidaan laskea ja tiivistyminen estää. Tässä työssä kehitettiin mittausmenetelmä rikkihapon alhaisten pitoisuuksien mittaamiseen. Menetelmää hyödynnettiin polttolaitoksissa, joissa tutkittiin rikkihapon tiivistymisestä johtuvaa korroosiota.

Corrosion behaviour of boiler tube materials during combustion of fuels containing Zn and Pb

Många förbränningsanläggningar som bränner utmanande bränslen såsom restfraktioner och avfall råkar ut för problem med ökad korrosion på överhettare och/eller vattenväggar pga. komponenter i bränslena som är korrosiva. För att minimera problemen i avfallseldade pannor hålls ångparametrarna på en relativt låg nivå, vilket drastiskt minskar energiproduktionen. Beläggningarna i avfallseldade pannor består till största delen av element som är förknippade med högtemperaturkorrosion: Cl, S, alkalimetaller, främst K och Na, och tungmetaller som Pb och Zn, och det finns också indikationer av Br-förekomst. Det låga ångtrycket i avfallseldade pannor påverkar också stålrörens temperatur i pannväggarna i eldstaden. I dagens läge hålls temperaturen normalt vid 300-400 °C. Alkalikloridorsakad (KCl, NaCl) högtemperaturkorrosion har inte rapporterats vara relevant vid såpass låga temperaturer, men närvaro av Zn- och Pb-komponenter i beläggningarna har påvisats förorsaka ökad korrosion redan vid 300-400 °C. Vid förbränning kan Zn och Pb reagera med S och Cl och bilda klorider och sulfater i rökgaserna. Dessa tungmetallföreningar är speciellt problematiska pga. de bildar lågsmältande saltblandningar. Dessa lågsmältande gasformiga eller fasta föreningar följer rökgasen och kan sedan fastna eller kondensera på kallare ytor på pannväggar eller överhettare för att sedan bilda aggressiva beläggningar. Tungmetallrika (Pb, Zn) klorider och sulfater ökar risken för korrosion, och effekten förstärks ytterligare vid närvaro av smälta. Motivet med den här studien var att få en bättre insikt i högtemperaturkorrosion förorsakad av Zn och Pb, samt att undersöka och prediktera beteendet och motståndskraften hos några stålkvaliteter som används i överhettare och pannväggar i tungmetallrika förhållanden och höga materialtemperaturer. Omfattande laboratorie-, småskale- och fullskaletest utfördes. Resultaten kan direkt utnyttjas i praktiska applikationer, t.ex. vid materialval, eller vid utveckling av korrosionsmotverkande verktyg för att hitta initierande faktorer och förstå deras effekt på högtemperaturkorrosion.

Application of capillary electrophoretic methods for determining carbohydrates and aliphatic carboxylic acids formed during wood processing

Knowledge of the behaviour of cellulose, hemicelluloses, and lignin during wood and pulp processing is essential for understanding and controlling the processes. Determination of monosaccharide composition gives information about the structural polysaccharide composition of wood material and helps when determining the quality of fibrous products. In addition, monitoring of the acidic degradation products gives information of the extent of degradation of lignin and polysaccharides. This work describes two capillary electrophoretic methods developed for the analysis of monosaccharides and for the determination of aliphatic carboxylic acids from alkaline oxidation solutions of lignin and wood. Capillary electrophoresis (CE), in its many variants is an alternative separation technique to chromatographic methods. In capillary zone electrophoresis (CZE) the fused silica capillary is filled with an electrolyte solution. An applied voltage generates a field across the capillary. The movement of the ions under electric field is based on the charge and hydrodynamic radius of ions. Carbohydrates contain hydroxyl groups that are ionised only in strongly alkaline conditions. After ionisation, the structures are suitable for electrophoretic analysis and identification through either indirect UV detection or electrochemical detection. The current work presents a new capillary zone electrophoretic method, relying on in-capillary reaction and direct UV detection at the wavelength of 270 nm. The method has been used for the simultaneous separation of neutral carbohydrates, including mono- and disaccharides and sugar alcohols. The in-capillary reaction produces negatively charged and UV-absorbing compounds. The optimised method was applied to real samples. The methodology is fast since no other sample preparation, except dilution, is required. A new method for aliphatic carboxylic acids in highly alkaline process liquids was developed. The goal was to develop a method for the simultaneous analysis of the dicarboxylic acids, hydroxy acids and volatile acids that are oxidation and degradation products of lignin and wood polysaccharides. The CZE method was applied to three process cases. First, the fate of lignin under alkaline oxidation conditions was monitored by determining the level of carboxylic acids from process solutions. In the second application, the degradation of spruce wood using alkaline and catalysed alkaline oxidation were compared by determining carboxylic acids from the process solutions. In addition, the effectiveness of membrane filtration and preparative liquid chromatography in the enrichment of hydroxy acids from black liquor was evaluated, by analysing the effluents with capillary electrophoresis.

Behavior of black liquor nitrogen in combustion : formation of cyanate

The Kraft pulping process is the dominant chemical pulping process in the world. Roughly 195 million metric tons of black liquor are produced annually as a by-product from the Kraft pulping process. Black liquor consists of spent cooking chemicals and dissolved organics from the wood and can contain up to 0.15 wt% nitrogen on dry solids basis. The cooking chemicals from black liquor are recovered in a chemical recovery cycle. Water is evaporated in the first stage of the chemical recovery cycle, so the black liquor has a dry solids content of 65-85% prior to combustion. During combustion of black liquor, a portion of the black liquor nitrogen is volatilized, finally forming N2 or NO. The rest of the nitrogen remains in the char as char nitrogen. During char conversion, fixed carbon is burned off leaving the pulping chemicals as smelt, and the char nitrogen forms mostly smelt nitrogen (cyanate, OCN-). Smelt exits the recovery boiler and is dissolved in water. The cyanate from smelt decomposes in the presence of water, forming NH3, which causes nitrogen emissions from the rest of the chemical recovery cycle. This thesis had two focuses: firstly, to determine how the nitrogen chemistry in the recovery boiler is affected by modification of black liquor; and secondly, to find out what causes cyanate formation during thermal conversion, and which parameters affect cyanate formation and decomposition during thermal conversion of black liquor. The fate of added biosludge nitrogen in chemical recovery was determined in Paper I. The added biosludge increased the nitrogen content of black liquor. At the pulp mill, the added biosludge did not increase the NO formation in the recovery boiler, but instead increased the amount of cyanate in green liquor. The increased cyanate caused more NH3 formation, which increased the NCG boiler’s NO emissions. Laboratory-scale experiments showed an increase in both NO and cyanate formation after biosludge addition. Black liquor can be modified, for example by addition of a solid biomass to increase the energy density of black liquor, or by separation of lignin from black liquor by precipitation. The precipitated lignin can be utilized in the production of green chemicals or as a fuel. In Papers II and III, laboratory-scale experiments were conducted to determine the impact of black liquor modification on NO and cyanate formation. Removal of lignin from black liquor reduced the nitrogen content of the black liquor. In most cases NO and cyanate formation decreased with increasing lignin removal; the exception was NO formation from lignin lean soda liquors. The addition of biomass to black liquor resulted in a higher nitrogen content fuel mixture, due to the higher nitrogen content of biomass compared to black liquor. More NO and cyanate were formed from the fuel mixtures than from pure black liquor. The increased amount of formed cyanate led to the hypothesis that black liquor is catalytically active and converts a portion of the nitrogen in the mixed fuel to cyanate. The mechanism behind cyanate formation during thermal conversion of black liquor was not clear before this thesis. Paper IV studies the cyanate formation of alkali metal loaded fuels during gasification in a CO2 atmosphere. The salts K2CO3, Na2CO3, and K2SO4 all promoted char nitrogen to cyanate conversion during gasification, while KCl and CaCO3 did not. It is now assumed that cyanate is formed when alkali metal carbonate or an active intermediate of alkali metal carbonate (e.g. -CO2K) reacts with the char nitrogen forming cyanate. By testing different fuels (bark, peat, and coal), each of which had a different form of organic nitrogen, it was concluded that the form of organic nitrogen in char also has an impact on cyanate formation. Cyanate can be formed during pyrolysis of black liquor, but at temperatures 900°C or above, the formed cyanate will decompose. Cyanate formation in gasifying conditions with different levels of CO2 in the atmosphere was also studied. Most of the char nitrogen was converted to cyanate during gasification at 800-900°C in 13-50% CO2 in N2, and only 5% of the initial fuel nitrogen was converted to NO during char conversion. The formed smelt cyanate was stable at 800°C 13% CO2, while it decomposed at 900°C 13% CO2. The cyanate decomposition was faster at higher temperatures and in oxygen-containing atmospheres than in an inert atmosphere. The presence of CO2 in oxygencontaining atmospheres slowed down the decomposition of cyanate. This work will provide new information on how modification of black liquor affects the nitrogen chemistry during thermal conversion of black liquor and what causes cyanate formation during thermal conversion of black liquor. The formation and decomposition of cyanate was studied in order to provide new data, which would be useful in modeling of nitrogen chemistry in the recovery boiler.

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Chemical changes in biomass during torrefaction

Torrefaction is moderate thermal treatment (~200-300 °C) of biomass in an inert atmosphere. The torrefied fuel offers advantages to traditional biomass, such as higher heating value, reduced hydrophilic nature, increased its resistance to biological decay, and improved grindability. These factors could, for instance, lead to better handling and storage of biomass and increased use of biomass in pulverized combustors. In this work, we look at several aspects of changes in the biomass during torrefaction. We investigate the fate of carboxylic groups during torrefaction and its dependency to equilibrium moisture content. The changes in the wood components including carbohydrates, lignin, extractable materials and ashforming matters are also studied. And at last, the effect of K on torrefaction is investigated and then modeled. In biomass, carboxylic sites are partially responsible for its hydrophilic characteristic. These sites are degraded to varying extents during torrefaction. In this work, methylene blue sorption and potentiometric titration were applied to measure the concentration of carboxylic groups in torrefied spruce wood. The results from both methods were applicable and the values agreed well. A decrease in the equilibrium moisture content at different humidity was also measured for the torrefied wood samples, which is in good agreement with the decrease in carboxylic group contents. Thus, both methods offer a means of directly measuring the decomposition of carboxylic groups in biomass during torrefaction as a valuable parameter in evaluating the extent of torrefaction. This provides new information to the chemical changes occurring during torrefaction. The effect of torrefaction temperature on the chemistry of birch wood was investigated. The samples were from a pilot plant at Energy research Center of the Netherlands (ECN). And in that way they were representative of industrially produced samples. Sugar analysis was applied to analyze the hemicellulose and cellulose content during torrefaction. The results show a significant degradation of hemicellulose already at 240 °C, while cellulose degradation becomes significant above 270 °C torrefaction. Several methods including Klason lignin method, solid state NMR and Py-GC-MS analyses were applied to measure the changes in lignin during torrefaction. The changes in the ratio of phenyl, guaiacyl and syringyl units show that lignin degrades already at 240 °C to a small extent. To investigate the changes in the extractives from acetone extraction during torrefaction, gravimetric method, HP-SEC and GC-FID followed by GC-MS analysis were performed. The content of acetone-extractable material increases already at 240 °C torrefaction through the degradation of carbohydrate and lignin. The molecular weight of the acetone-extractable material decreases with increasing the torrefaction temperature. The formation of some valuable materials like syringaresinol or vanillin is also observed which is important from biorefinery perspective. To investigate the change in the chemical association of ash-forming elements in birch wood during torrefaction, chemical fractionation was performed on the original and torrefied birch samples. These results give a first understanding of the changes in the association of ashforming elements during torrefaction. The most significant changes can be seen in the distribution of calcium, magnesium and manganese, with some change in water solubility seen in potassium. These changes may in part be due to the destruction of carboxylic groups. In addition to some changes in water and acid solubility of phosphorous, a clear decrease in the concentration of both chlorine and sulfur was observed. This would be a significant additional benefit for the combustion of torrefied biomass. Another objective of this work is studying the impact of organically bound K, Na, Ca and Mn on mass loss of biomass during torrefaction. These elements were of interest because they have been shown to be catalytically active in solid fuels during pyrolysis and/or gasification. The biomasses were first acid washed to remove the ash-forming matters and then organic sites were doped with K, Na, Ca or Mn. The results show that K and Na bound to organic sites can significantly increase the mass loss during torrefaction. It is also seen that Mn bound to organic sites increases the mass loss and Ca addition does not influence the mass loss rate on torrefaction. This increase in mass loss during torrefaction with alkali addition is unlike what has been found in the case of pyrolysis where alkali addition resulted in a reduced mass loss. These results are important for the future operation of torrefaction plants, which will likely be designed to handle various biomasses with significantly different contents of K. The results imply that shorter retention times are possible for high K-containing biomasses. The mass loss of spruce wood with different content of K was modeled using a two-step reaction model based on four kinetic rate constants. The results show that it is possible to model the mass loss of spruce wood doped with different levels of K using the same activation energies but different pre-exponential factors for the rate constants. Three of the pre-exponential factors increased linearly with increasing K content, while one of the preexponential factors decreased with increasing K content. Therefore, a new torrefaction model was formulated using the hemicellulose and cellulose content and K content. The new torrefaction model was validated against the mass loss during the torrefaction of aspen, miscanthus, straw and bark. There is good agreement between the model and the experimental data for the other biomasses, except bark. For bark, the mass loss of acetone extractable material is also needed to be taken into account. The new model can describe the kinetics of mass loss during torrefaction of different types of biomass. This is important for considering fuel flexibility in torrefaction plants.