Oxidation of terpenes in indoor environments : A study of influencing factors

In this thesis the oxidation of monoterpenes by O3 and NO2 and factors that influenced the oxidation were studied. In the environment both ozone (O3) and nitrogen dioxide (NO2) are present as oxidising gases, which causes sampling artefacts when using Tenax TA as an adsorbent to sample organic compounds in the air. A scrubber was developed to remove O3 and NO2 prior to the sampling tube, and artefacts during sampling were minimised when using the scrubber. The main organic compounds sampled in this thesis were two monoterpenes, alfa-pinene and delta-3-carene, due to their presence in both indoor and outdoor air. The recovery of the monoterpenes through the scrubber varied between 75-97% at relative humidities of 15-75%. The reactions of alfa-pinene and delta-3-carene with O 3, NO2 and nitric oxide (NO) at different relative humidities (RHs) and reaction times were studied in a dark reaction chamber. The experiments were planned and performed according to an experimental design were the factors influencing the reaction (O3, NO2, NO, RH and reaction times) were varied between high and low levels. In the experiments up to 13% of the monoterpenes reacted when O3, NO2, and reaction time were at high levels, and NO, and RH were at low levels. In the evaluation eight and seven factors (including both single and interaction factors) were found to influence the amount of alfa-pinene and delta-3-carene reacted, respectively. The three most influencing factors for both of the monoterpenes were the O 3 level, the reaction time, and the RH. Increased O3 level and reaction time increased the amount of monoterpene reacted, and increased RH decreased the amount reacted. A theoretical model of the reactions occurring in the reaction chamber was created. The amount of monoterpene reacted at different initial settings of O3, NO2, and NO were calculated, as well as the influence of different reaction pathways, and the concentrations of O3 and NO2, and NO at specific reaction times. The results of the theoretical model were that the reactivity of the gas mixture towards alfa-pinene and delta-3-carene was underestimated. But, the calculated concentrations of O3, NO2, and NO in the theoretical model were found to correspond to a high degree with experimental results performed under similar conditions. The possible associations between organic compounds in indoor air, building variables and the presence of sick building syndrome were studied using principal component analysis. The most complex model was able to separate 71% of the “sick” buildings from the “healthy” buildings. The most important variables that separated the “sick” buildings from the “healthy” buildings were a more frequent occurrence or a higher concentration of compounds with shorter retention times in the “sick” buildings. The outcome of this thesis could be summarised as follows; - - -

Evaluation of solvent for pressurized liquid extraction of PCDD, PCDF, PCN, PCBz, PCPh and PAH in torrefied woody biomass

Biomass torrefaction for sustainable energy production has gained an increasing interest. However, there is a lack of information on the thermal formation of persistent organic pollutants such as dioxins in the torrefied solid product. In this paper, we investigated the applicability of pressurized liquid extraction (PLE) for simultaneous extraction of a number of polychlorinated planar aromatic compounds from torrefied wood. The targeted compounds included polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs), naphthalenes (PCNs), benzenes (PCBz), phenols (PCPhs) and PAHs. PLE tests were conducted on torrefied and non-torrefied (i.e. raw) eucalyptus wood chips using 5 single solvents (n-hexane, toluene, dichloromethane, acetone and methanol) and a mixture of n-hexane/toluene (1:1, v/v). The performance of each solvent was evaluated in terms of recoveries of spiked internal standards and the amount of co-extracted sample matrix. High polarity solvents such as methanol and acetone resulted in poor recoveries from torrefied wood for most of the target compounds, probably due to the high co-extraction of thermally degraded lignocellulosic compounds. Raw wood was less solvent-dependent and comparable results were obtained for polar and non-polar solvents. Toluene showed the best performance of the investigated solvents, with average recoveries of 79 +/- 14% and 66 +/- 9% for raw and torrefied wood, respectively. The method was validated using pentachlorophenol-tainted spruce wood chips. The proposed PLE method was compared to the traditional Soxhlet method. Results show that PLE gave equivalent or better extraction for all target compounds

Evaluation of solvent for pressurized liquid extraction of PCDD, PCDF, PCN, PCBz, PCPh and PAH in torrefied woody biomass

Biomass torrefaction for sustainable energy production has gained an increasing interest. However, there is a lack of information on the thermal formation of persistent organic pollutants such as dioxins in the torrefied solid product. In this paper, we investigated the applicability of pressurized liquid extraction (PLE) for simultaneous extraction of a number of polychlorinated planar aromatic compounds from torrefied wood. The targeted compounds included polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs), naphthalenes (PCNs), benzenes (PCBz), phenols (PCPhs) and PAHs. PLE tests were conducted on torrefied and non-torrefied (i.e. raw) eucalyptus wood chips using 5 single solvents (n-hexane, toluene, dichloromethane, acetone and methanol) and a mixture of n-hexane/toluene (1:1, v/v). The performance of each solvent was evaluated in terms of recoveries of spiked internal standards and the amount of co-extracted sample matrix. High polarity solvents such as methanol and acetone resulted in poor recoveries from torrefied wood for most of the target compounds, probably due to the high co-extraction of thermally degraded lignocellulosic compounds. Raw wood was less solvent-dependent and comparable results were obtained for polar and non-polar solvents. Toluene showed the best performance of the investigated solvents, with average recoveries of 79 +/- 14% and 66 +/- 9% for raw and torrefied wood, respectively. The method was validated using pentachlorophenol-tainted spruce wood chips. The proposed PLE method was compared to the traditional Soxhlet method. Results show that PLE gave equivalent or better extraction for all target compounds

NIR provides excellent predictions of properties of biocoal from torrefaction and pyrolysis of biomass

When biomass is exposed to high temperatures in torrefaction, pyrolysis or gasification treatments, the enrichment of carbon in the remaining 'green coal' is correlated with the temperature. Various other properties, currently measured using wet chemical methods, which affect the materials' quality as a fuel, also change. The presented study investigated the possibility of using NIR spectrometry to estimate diverse variables of biomass originating from two sources (above-ground parts of reed canary grass and Norway spruce wood) carbonised at temperatures ranging from 240 to 850 C-circle. The results show that the spectra can provide excellent predictions of its energy, carbon, oxygen, hydrogen, ash, volatile matter and fixed carbon contents. Hence NIR spectrometry combined with multivariate calibration modeling has potential utility as a standardized method for rapidly characterising thermo-treated biomass, thus reducing requirements for more costly, laborious wet chemical analyses and consumables

NIR provides excellent predictions of properties of biocoal from torrefaction and pyrolysis of biomass

When biomass is exposed to high temperatures in torrefaction, pyrolysis or gasification treatments, the enrichment of carbon in the remaining 'green coal' is correlated with the temperature. Various other properties, currently measured using wet chemical methods, which affect the materials' quality as a fuel, also change. The presented study investigated the possibility of using NIR spectrometry to estimate diverse variables of biomass originating from two sources (above-ground parts of reed canary grass and Norway spruce wood) carbonised at temperatures ranging from 240 to 850 C-circle. The results show that the spectra can provide excellent predictions of its energy, carbon, oxygen, hydrogen, ash, volatile matter and fixed carbon contents. Hence NIR spectrometry combined with multivariate calibration modeling has potential utility as a standardized method for rapidly characterising thermo-treated biomass, thus reducing requirements for more costly, laborious wet chemical analyses and consumables

Biochemical Conversion of Torrefied Norway Spruce After Pretreatment with Acid or Ionic Liquid

The chemical effects of torrefaction and the possibility to combine torrefaction with biochemical conversion were explored in experiments with five preparations of wood of Norway spruce that had been torrefied using different degrees of severity. Compositional analysis and analyses using solid-state CP/MAS C-13 NMR, Fourier-transform infrared (FTIR) spectroscopy, and Py-GC/MS showed small gradual changes, such as decreased hemicellulosic content and increased Klason lignin value, for torrefaction conditions in the range from 260 A degrees C and 8 min up to 310 A degrees C and 8 min. The most severe torrefaction conditions (310 A degrees C, 25 min) resulted in substantial loss of glucan and further increase of the Klason lignin value, which was attributed to conversion of carbohydrate to pseudo-lignin. Even mild torrefaction conditions led to decreased susceptibility to enzymatic hydrolysis of cellulose, a state which was not changed by pretreatment with sulfuric acid. Pretreatment with the ionic liquid (IL) 1-butyl-3-methylimidazolium acetate overcame the additional recalcitrance caused by torrefaction, and the glucose yields after 72 h of enzymatic hydrolysis of wood torrefied at 260 A degrees C for 8 min and at 285 A degrees C for 16.5 min were as high as that of IL-pretreated non-torrefied spruce wood. Compared to IL-pretreated non-torrefied reference wood, the glucose production rates after 2 h of enzymatic hydrolysis of IL-pretreated wood torrefied at 260 A degrees C for 8 min and at 285 A degrees C for 16.5 min were 63 and 40 % higher, respectively. The findings offer increased understanding of the effects of torrefaction and indicate that mild torrefaction is compatible with biochemical conversion after pretreatment with alternative solvents that disrupt pseudo-lignin-containing lignocellulose.Bio4Energ

Reduced ash related operational problems(slagging, bed agglomeration, corrosion andfouling) by co-combustion biomass with peat

Projektet behandlar effekter av torvinblandning i problematiska biobränslen (grot, salix, halm) med avseende på uppkomsten av askrelaterade driftsproblem (beläggning, slaggning, högtemperatur-korrosion och bäddagglomerering). Studien visar att inblandning av torv i de problematiska biobränslen som studerats ger tydligt positiva effekter vad avser bäddagglomerering och beläggningsbildning/korrosion i pannans konvektionsdelar redan vid relativt låga inblandningsgrader (15-20 vikts-%) i salix och grot, samt vid inblandningsgrader upp mot 40 vikts-% i halm. Resultaten indikerar dock även att vissa torvslag i vissa bränslesammansättningar ger upphov till ökade slaggningstendenser på brännarrosters. De bakomliggande askkemiska och processmässiga mekanismerna till de observerade effekterna diskuteras i rapporten.Upprättat; 2006; 20070816 (ysko

Combustion characterization of rape seed meal and suggestions for optimal use in combustion appliances

When rape oil is chemically extracted, rape seed meal, a solid residue remains. Currently, it is used as animal feed. Several plants for the production of rape methyl ester (RME, biodiesel) are in operation or under construction. Combustion properties have been studied for rape seed meal produced as a by product to rape-methyl esther (RME, biodiesel). Composition of the material has been measured, using proximate and ultimate analysis. The lower heating value was 18.2 ± 0,3 MJ/kg d.w. and the ash content was 7-8 percent d.w. The material is rich in nitrogen and sulphur. Concentrations of K, P, Ca and Mg are high in the fuel. Rape seed meal was mixed with bark and pelletised. Bark pellets were also used as a reference fuel. Pellets with 10 and 30 percent rape seed meal were produced. Material with 80 percent rape seed meal and 20 percent planer shavings was also pelletised. Wood had to be added to provide enough friction in the pelletising process, with adapted equipment rape seed meal could probably be easily pelletised). The material was studied using Thermo-Gravimetric Analysis (TGA), and compared with data from tests with wood powder. The pyrolysis of the rape seed meal has a characteristic temperature of 320oC. Devolatilisation starts at 150 oC (at a lower temperature than for wood powder), and proceeds within a rather wide temperature range. The probable cause is the difference in organic content, in particular protein content. The result does not suggest that the material will be difficult to ignite. Experiments in a bench-scale fluidised bed (5 kW) showed that pellets containing only bark, and the mixture rape seed meal/wood had a bed agglomeration temperature well over the normal operational bed temperature. For the fuel mixtures rape seed meal and bark, the agglomeration temperature was slightly over the operational temperature. Particle emissions from fluidised bed combustion and grate combustion were, the latter simulated using a commercial pellet burner, were roughly doubled with fuels containing rape seed meal compared to bark. In the powder burner tests, particle emissions increased with a factor 17 with rape seed meal compared to wood powder. The emitted particles were mainly found in the fine (1 µm) and a fine mode fraction. The particles from grate combustion of bark contain mostly K, S, Na and Cl apart from oxygen and carbon. When rape seed meal is present, Cl and Na concentrations decrease considerably and the main contents of the particles are K and S (and O and C). The results from the X-ray Diffraction Spectroscopy (XRD) analyses showed the presence of crystalline K2SO4 och KCl. The fine particles (<1 µm) from powder combustion contain mainly K, P and S. The only identified crystalline phase was K2SO4, suggesting that most phosphorus was in the amorphous phase, i.d. most probably molten. The deposit formation on a cooled probe was studied during the fluidized bed and powder combustion experiments. The fine particles deposited during fluidised bed combustion contained K, Cl and S. When bark was combusted in the fluidised bed, the coarse fraction contained Ca and Si, when rape seed meal in different mixes was combusted this changed to P, K, Ca and Mg. The deposits formed during combustion of rape seed meal in the powder burner were mainly made up of phosphates (Ca-, Mg/K-, Ca/Mg-phosphates) and MgO. Sintered material (slag) from grate combustion of bark contained mainly Si, Ca, K and Al, probably as silicates. Adding rape seed meal tended to increase P, Ca and Mg while Si and Ca content tended to decrease. Through XRD a number o crystalline phases in the sintered material and the rest of the bottom ashes could be identified. NO emissions from the combustions tests increased two to four times with rape seed meal compared to typical wood fuels. For the fluidised bed test, SO2 concentrations were rather high for the rape seed meal pellets (with 20 percent wood), still only about 20 percent of the sulphur in the fuel formed SO2. For the grate combustion and powder burner combustion, 60 percent and 70 percent of the sulphur respectively formed SO2. HCl emissions were low for all tests. The rather high emissions of NOx and SOx mean that the material should be used in large-scale facilities with external SOx and NOx cleaning. In smaller facilities, the material may be used in small amounts mixed with other fuels. The risk of slagging is not very high, and should not rule out grate combustion of pellets with rape seed meal mixed with other fuels. The risk of corrosion of superheater surfaces during combustion is probably low since the smaller-size particles formed at fluidised bed combustion and grate combustion contain K2SO4. However, a large fraction of the particles formed in powder burner combustion probably contains low temperature melting K2PO4, making the risk for deposit formation significant. Rape seed meal for powder burner applications should be used with care. The content of phosphorus in the material may be an advantage when mixes of rape seed meal and other fuels are considered. The high affinity between potassium and phosphorus means that more sulphur in the fuel will be available for sulphatising of any KC. (formed from combustion of many forest and agricultural fuels). Use of rape seed meal as a sulphur containing additive could thus be an option. For grate combustion and fluidised bed combustion, addition of rape seed meal may reduce the risk of slagging and bed agglomeration, respectively. Full scale tests in fluidised beds or grate combustors with problematic biofuels (containing Cl and K) would be useful to test whether ash-reduced operational problems could be reduced through the addition of rape seed meal.Effektiva värmevärdet hos rapsmjöl är 18,2 +/- 0,3 MJ/kg TS och askhalten varierar mellan 7-8 %. Bränslet har högt N- och S-innehåll, och bränslet är rikt på K, P, Ca och Mg. Partikelemissionerna från fluidbäddseldning och rosterförbränning med rapsmjölsblandningar var ungefär dubbelt så höga som från barkförbränning. Vid pulverförbränning av rapsmjöl ökade partikelemissionerna med en faktor 17 jämfört med träpulver. De höga NOx och SOx emissionerna från rapsmjölsförbränning innebär att materialet bör utnyttjas i storskaliga anläggningar med extern svavel.- eller NO-rening, eller i relativt låga inblandningsgrader i andra bränslen. Mindre anläggningar med enbart cyklonrening är olämpliga på grund av de höga stofthalterna. Rapsmjöl torde vara ett intressant sameldningsbränsle vid roster- och fluidbäddseldning med klor- och kaliumrika skogs- och åkerbränslen då rapsmjöl eventuellt skulle kunna användas som svaveladditiv för reduktion av klorinducerad korrosion på t ex överhettare. Slaggningstendensen torde minska vid inblandning av rapsmjöl i båda dessa bränslekategorier och bäddagglomereringstendensen torde minska vid inblandning av rapsmjöl i åkerbränslen.Godkänd; 2007; 20080625 (guerik