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.

The action of red wine and purple grape juice on vascular reactivity is independent of plasma lipids in hypercholesterolemic patients

Although red wine (RW) reduces cardiovascular risk, the mechanisms underlying the effect have not been identified. Correction of endothelial dysfunction by RW flavonoids could be one mechanism. We measured brachial artery reactivity by high-resolution ultrasonography, plasma lipids, glucose, adhesion molecules (ICAM-1 and VCAM), and platelet function in 16 hypercholesterolemic individuals (8 men and 8 women; mean age 51.6 ± 8.1 years) without other risk factors. Twenty-four normal subjects were used as controls for vascular reactivity. Subjects randomly received RW, 250 ml/day, or purple grape juice (GJ), 500 ml/day, for 14 days with an equal wash-out period. At baseline, all 16 subjects were hypercholesterolemic (mean LDL = 181.0 ± 28.7 mg/dl) but HDL, triglycerides, glucose, adhesion molecules, and platelet function were within normal limits. Brachial artery flow-mediated dilation was significantly decreased compared to controls (9.0 ± 7.1 vs 12.1 ± 4.5%; P < 0.05) and increased with both GJ (10.1 ± 7.1 before vs 16.9 ± 6.7% after: P < 0.05) and RW (10.1 ± 6.4 before vs 15.6 ± 4.6% after; P < 0.05). RW, but not GJ, also significantly increased endothelium-independent vasodilation (17.0 ± 8.6 before vs 23.0 ± 12.0% after; P < 0.01). GJ reduced ICAM-1 but not VCAM and RW had no effect on either molecule. No significant alterations were observed in plasma lipids, glucose or platelet aggregability with RW or GJ. Both RW and GJ similarly improved flow-mediated dilation, but RW also enhanced endothelium-independent vasodilation in hypercholesterolemic patients despite the increased plasma cholesterol. Thus, we conclude that GJ may protect against coronary artery disease without the additional negative effects of alcohol despite the gender.

Vascular complications of black patients with type 2 diabetes mellitus in Southern Brazil

Ethnicity has been shown to be associated with micro- and macrovascular complications of diabetes in European and North American populations. We analyzed the contribution of ethnicity to the prevalence of micro- and macrovascular complications in Brazilian subjects with type 2 diabetes attending the national public health system. Data from 1810 subjects with type 2 diabetes (1512 whites and 298 blacks) were analyzed cross-sectionally. The rates of ischemic heart disease, peripheral vascular disease, stroke, distal sensory neuropathy, and diabetic retinopathy were assessed according to self-reported ethnicity using multiple logistic regression models. Compared to whites, black subjects [odds ratio = 1.72 (95%CI = 1.14-2.6)] were more likely to have ischemic heart disease when data were adjusted for age, sex, fasting plasma glucose, HDL cholesterol, hypertension, smoking habit, and serum creatinine. Blacks were also more likely to have end-stage renal disease [3.2 (1.7-6.0)] and proliferative diabetic retinopathy [1.9 (1.1-3.2)] compared to whites when data were adjusted for age, sex, fasting plasma glucose, HDL cholesterol, hypertension, and smoking habit. The rates of peripheral vascular disease, stroke and distal sensory neuropathy did not differ between groups. The higher rates of ischemic heart disease, end-stage renal disease and proliferative diabetic retinopathy in black rather than in white Brazilians were not explained by differences in conventional risk factors. Identifying which aspects of ethnicity confer a higher risk for these complications in black patients is crucial in order to understand why such differences exist and to develop more effective strategies to reduce the onset and progression of these complications.

Comparison of bone quantity by ultrasound measurements of phalanges between white and black children living in Paraná, Brazil, with Europeans

The objective of this study was to determine bone quantity by ultrasound measurements of the proximal finger phalanges (AD-SoS = amplitude-dependent speed of sound) of healthy Brazilian schoolchildren living in Paraná, Brazil and to compare these values with European populations. The sample was composed of 1356 Brazilian schoolchildren of both genders (660 males, 696 females), aged 6 to 11 years, divided into white (840) and black (516) groups and compared to age- and gender-matched Europeans. AD-SoS of the schoolchildren increased significantly with age for both genders. Significantly higher AD-SoS values were observed for the white children (1916 ± 58) compared to their black counterparts (1898 ± 72) and for the female gender (1920 ± 61) compared to the male gender (1898 ± 66). Overall, the AD-SoS outcomes for females were similar to those of European studies. However, the AD-SoS of the Brazilian schoolchildren of both genders and skin colors was lower than that reported for children in Poland. AD-SoS outcomes for Brazilian schoolboys were similar to those obtained in Italian studies and were lower than those of the Spanish children. In conclusion, Brazilian schoolchildren of both genders and skin colors showed lower bone quantities than Polish children and Spanish males, and levels similar to Italian children and Spanish females.

Tangential microfiltration of orange juice in bench pilot

The aim of this study was to introduce the tangential microfiltration (TMF) technique on the production of orange juice (TMFJ), and compare it with pasteurised juice (control) as regards chemical composition and sensorial characteristics. We used a TMF pilot equipped with four monotubular ceramic membranes (0.1, 0.2, 0.8 and 1.4mm) arranged in series with a filtering area of 0.005 m² each. Commercial flash-pasteurised orange juice was used as the initial product. Experiments were divided into three parts: a) the characterisation of the TMF pilot; b) optimisation of operational conditions; c) production of the TMFJ. In the second part, membrane with 0.8-mm pores presented best flux followed by those with 1.4-, 0.1-, and 0.2-mm pores. However, to guarantee permeate sterility, we chose the membrane with 0.1-mm pores for TMFJ production. Initially, the orange juice was sieved in order to separate part of the pulp, being subsequently submitted to TMF. A mixture of retentate and pulp was made, and was subsequently pasteurised. We obtained the TMFJ by adding the permeate to the mixture. TMFJ presented soluble solids content (°Brix), pulp, pH, and titrable acidity similar to the initial pasteurised juice (control). Nevertheless, 28% of vitamin C was lost during the TMFJ production. According to the juice taster panel, the control juice presented best sensorial characteristics (greater aroma intensity and fruity flavour) when compared with the TMJF.

Storage stability of cashew apple juice preserved by hot fill and aseptic processes

Cashew (Anacardium occidentale L.) apples from Pacajus, Ceará State, Brazil, were processed into high pulp content juice. The juice was packed either by hot fill or an aseptic process and evaluated for physical, physical-chemical, and sensorial changes during a 12-month storage period at room temperature. The results indicated that pH, soluble solids, total acidity, total sugar content and color did not change significantly during storage nor were affected by the type of filling. The sensorial analysis showed that juice acceptance remained high throughout the storage period regardless of the filling system. Differences in juice viscosity persisted between both processes.

Market anomalies and tactical asset allocation: Utilising market anomalies in multiple asset class portfolios with the Black−Litterman model

This thesis discusses the basic problem of the modern portfolio theory about how to optimise the perfect allocation for an investment portfolio. The theory provides a solution for an efficient portfolio, which minimises the risk of the portfolio with respect to the expected return. A central feature for all the portfolios on the efficient frontier is that the investor needs to provide the expected return for each asset. Market anomalies are persistent patterns seen in the financial markets, which cannot be explained with the current asset pricing theory. The goal of this thesis is to study whether these anomalies can be observed among different asset classes. Finally, if persistent patterns are found, it is investigated whether the anomalies hold valuable information for determining the expected returns used in the portfolio optimization Market anomalies and investment strategies based on them are studied with a rolling estimation window, where the return for the following period is always based on historical information. This is also crucial when rebalancing the portfolio. The anomalies investigated within this thesis are value, momentum, reversal, and idiosyncratic volatility. The research data includes price series of country level stock indices, government bonds, currencies, and commodities. The modern portfolio theory and the views given by the anomalies are combined by utilising the Black-Litterman model. This makes it possible to optimise the portfolio so that investor’s views are taken into account. When constructing the portfolios, the goal is to maximise the Sharpe ratio. Significance of the results is studied by assessing if the strategy yields excess returns in a relation to those explained by the threefactormodel. The most outstanding finding is that anomaly based factors include valuable information to enhance efficient portfolio diversification. When the highest Sharpe ratios for each asset class are picked from the test factors and applied to the Black−Litterman model, the final portfolio results in superior riskreturn combination. The highest Sharpe ratios are provided by momentum strategy for stocks and long-term reversal for the rest of the asset classes. Additionally, a strategy based on the value effect was highly appealing, and it basically performs as well as the previously mentioned Sharpe strategy. When studying the anomalies, it is found, that 12-month momentum is the strongest effect, especially for stock indices. In addition, a high idiosyncratic volatility seems to be positively correlated with country indices on stocks.

Rheological and thermophysical properties of blackberry juice

Rheological and thermophysical properties were determined for blackberry juice, which was produced from blackberry fruit at 9.1 ± 0.5 °Brix and density of 1.0334 ± 0.0043 g cm-3. The concentration process was performed using a roto evaporator, under vacuum, to obtain concentrated juice at about 60 °Brix. In order to obtain different concentrations, concentrated juice was diluted with distilled water. Rheological measurements were carried out using a Rheotest 2.1 Searle type rheometer. In the tested ranges, the samples behaved as pseudoplastic fluids, and the Power-Law model was satisfactorily fitted to the experimental data. The friction factor was measured for blackberry juice in laminar flow conditions of pseudoplastic behavior. Thermal conductivity, thermal diffusivity and density of blackberry juice at 9.4 to 58.4 °Brix were determined, in triplicate, at 0.5 to 80.8 °C. Polynomial regression was performed to fit experimental data obtaining a good fit. Both temperature and concentration showed a strong influence on thermophysical properties of blackberry juice. Calculated apparent specific heat values varied from 2.416 to 4.300 kJ.kg-1 °C in the studied interval.

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.

Sensory evaluation of black instant coffee beverage with some volatile compounds present in aromatic oil from roasted coffee

The oil obtained from Brazilian roasted coffee by supercritical CO2 extraction shows considerable aromatic properties, mainly composed by five aromatic compounds, 2-methylpyrazine; 2-furfurylalcohol, 2,5-dimethylpyrazine; γ-butyrolactone and 2-furfurylacetate. Sensory analyses were used to verify the influence of a mixture of these important classes of aromatic coffee compounds (pyrazines, furans and lactones) and of the roasted coffee aromatic oil on the coffee aroma and flavour of black instant freeze and spray-dried coffee beverages. In the acceptance evaluation of the aroma, the samples prepared with freeze-dried instant coffee without the mixture of volatile compounds (sample 4) were not significantly different from the freeze-dried instant coffee in which the aromatic coffee oil was added (sample 5) and from the sample prepared with freeze-dried coffee in which the mixture of the five volatile was added (sample 3), coincidentally from the same drying process. Therefore, sample (3) did not differ from samples prepared with spray dried instant coffee without (sample 1) and to which (sample 2) the mixture of volatile was added. Therefore, with respect to this attribute, the addition of this mixture did not interfere in this drink acceptance. Taking into consideration the flavor, samples prepared with freeze-dried instant coffee in which the aromatic coffee oil was added (5) and the samples with (3) and without (4) the mixture of the five volatile was added did not differ significantly, however sample (4) did not differ from samples (1) and (2). Regarding this attribute, the addition of the aromatic oil of roasted coffee or a mixture of volatile in samples of freeze-dried instant coffee had a better acceptance than those dried by spray dryer (1) and (2). Thus, the enrichment of drinks with the aromatic oil of roasted coffee, or even with the mixture of the five components did not influence the consumer acceptance with respect to the aroma, but exerts influence with respect to flavour.

Study of clarification process of sugar cane juice for consumption

Sugar cane juice or garapa darkens quickly after extraction due to the oxidation of some of its constituents harming its commercialization thus requiring rapid consumption. The objective of this study was to develop a mild process for sugar cane clarification, obtaining a cloudy, greenish-yellow beverage. The following parameters were combined to aiming at this objective: heat treatment at 65 ºC/50 minutes; pH change (to 7.0, 7.5, and 8.0); addition of flocculant (0, 30, and 60 ppm Aluminum polychloride or APC - "Panclar P-1010"), and clarifier aid (0, 2, or 4 ppm of positively charged polyelectrolyte - "Magnafloc LT-27"). The decantation time was 45 minutes and the supernatant liquid was removed with a vacuum pump. The treatments were defined using the Response Surface Methodology and were submitted to physicochemical analysis for turbidity (%), total polysaccharide content (µg.mL-1), dextran content (µg.mL-1), and sensory analysis (acceptance test) for the attributes of color, appearance, and turbidity. It was concluded that the addition of 60 ppm APC, pH 8, and 0 ppm polyelectrolyte represented the best treatment to obtain a low polysaccharide content, 90% turbidity, and high scores for color, appearance, and turbidity. The beverage was sensorially well accepted by consumers.