(E)-2-Nonenal determination in brazilian beers using headspace solid-phase microextraction and gas chromatographic coupled mass spectrometry (HS-SPME-GC-MS)

(E)-2-nonenal is considered an important off-flavor of beer, related to the flavor of beer staling. In this study, a new method for determination of (E)-2-nonenal in beer using headspace solid-phase microextraction and gas chromatographic coupled mass spectrometry (HS-SPME-GC-MS) was developed and applied in Brazilian beer samples. The extractions were carried out in CAR-PDMS (carboxen-polydimethylsiloxane) fiber and the best results were found with 15 minutes of equilibrium and 90 minutes of extraction at 50 °C. The method was linear in the range from 0.02 to 4.0 μg.L-1 with correlation coefficient of 0.9994. The limits of detection and quantification were 0.01 and 0.02 μg.L-1, respectively. 96.5% of recovery and 4% precision (RSD) were obtained in the fortification of beer samples with 2.0 μg.L-1 of (E)-2-nonenal. The developed method proved to be simple, efficient and highly sensitive to the determination of this analyte being easily applied in the quality control of the brewery. (E)-2-nonenal was found in all beer samples analyzed with levels between 0.17 and 0.42 μg.L-1.

Dynamics of gas levels inside packages containing minimally processed Pera orange

The purpose of this study was to evaluate the changes in concentrations of O2 and CO2 inside packages of minimally processed Pera orange. Previously selected oranges that were washed, sanitized, and chilled were peeled using hydrothermal treatment (immersion of fruits in water at 50 °C for 8 minutes). The peeled oranges were then packed in five different plastic packages under passive and active modified atmosphere (5% O2 + 10% CO2 + 85% N2). The fruits were stored at 6 °C and 12 °C. The package headspace gas composition was evaluated for twelve days at 6 °C and nine days at 12 °C. The polypropylene film (32 µm) promoted modified atmosphere similar to that initially injected (5% O2 + 10% CO2 + 85% N2) at 6 °C and 12 °C. With regard to the atmosphere modification system, the injection of a gas mixture anticipated achieving an equilibrium atmosphere inside the packages at 12 °C. At 6 °C, the gas composition inside the packages was kept close to that of the injection, but the equilibrium was not verified.

Characterization and classification of pequi trees (Caryocar brasiliense Camb.) based on the profile of volatile constituents using headspace solid-phase microextraction - gas chromatography - mass spectrometry and multivariate analysis

In order to determine the variability of pequi tree (Caryocar brasiliense Camb.) populations, volatile compounds from fruits of eighteen trees representing five populations were extracted by headspace solid-phase microextraction and analyzed by gas chromatography-mass spectrometry. Seventy-seven compounds were identified, including esters, hydrocarbons, terpenoids, ketones, lactones, and alcohols. Several compounds had not been previously reported in the pequi fruit. The amount of total volatile compounds and the individual compound contents varied between plants. The volatile profile enabled the differentiation of all of the eighteen plants, indicating that there is a characteristic profile in terms of their origin. The use of Principal Component Analysis and Cluster Analysis enabled the establishment of markers (dendrolasin, ethyl octanoate, ethyl 2-octenoate and β-cis-ocimene) that discriminated among the pequi trees. According to the Cluster Analysis, the plants were classified into three main clusters, and four other plants showed a tendency to isolation. The results from multivariate analysis did not always group plants from the same population together, indicating that there is greater variability within the populations than between pequi tree populations.

New aspects in limestone dissolution for wet flue gas desulfurization

Fortsättningsvis tillgodoses största delen av världens energibehov genom förbränning av fossila bränslen, dessutom forsätter världens totala energibehov att öka. Eftersom förbränning av fossila bränslen som t.ex. olja och kol orsakar utsläpp av svaveldioxid som är skadligt för både människa och natur, finns det fortfarande ett akut behov av forskning och utveckling av metoder för svavelrening. De vanligaste teknikerna för svavelrening är våt- och semitorrskrubbning, där svaveldioxiden absorberas av en skrubbervätska. Det är allmänt känt att våtskrubbning är en av de effektivaste teknikerna för svavelrening både ekonomiskt och tekniskt sett samt den mest använda. Våtskrubbningsprocessen har dock flera nackdelar, som dess höga vatten- och energiförbrukning. I större kraftverk går ca 1-3% av dess eleffekt åt till rökgasreningsprocessen, vilket kraftigt motiverar utveckling av nya reningsprocesser samt effektivering av existerande reningsanläggningar. Skrubbervätskan som till huvudsak består av vatten innehåller vanligtvis även kalcium vars syfte är att binda svavlet. Kalciumet kan tillsättas i flera former varav bränd kalk och kalksten är de vanligaste formerna. Kalksten används ofta i svavelreningsprocessen p.g.a. dess låga pris och för att den ger upphov till den användbara biprodukten gips. Kalkstenens upplösningshastighet är en de av faktorer som kraftigast påverkar reningsprocessen. En detaljerad experimentell karakterisering och analys av kalkstenspartiklar i fast form och i vätskeform har utförts i detta arbete. En experimentell metod för att studera kalkstenens upplösningshastighet vid låg till obegränsad massöverföring har även utvecklats i detta arbete. Metoden möjliggör identifieringen av systemoberoende kinetiska parametrar, vilka kan användas för att undersöka reningsprocesser samt för att planera nya reningsanläggningar. Kinetiska modeller utvecklades genom att använda kalkstenpartiklars specifika yta, som mättes genom kväveadsorption. Efter att de kinetiska parametrarna bestämts experimentellt utvecklades en skrubbermodell för att optimera en i driftvarande skrubber. Genom att kombinera experimentellt bestämda modeller med matematisk optimering erhölls en djupare insikt i hur olika råmaterial påverkar processen och hur driftparameterar bör justeras för att minska elförbrukningen.

Production of magnesium carbonates from serpentinites for CO2 mineral sequestration : optimisation towards industrial application

Global warming is one of the most alarming problems of this century. Initial scepticism concerning its validity is currently dwarfed by the intensification of extreme weather events whilst the gradual arising level of anthropogenic CO2 is pointed out as its main driver. Most of the greenhouse gas (GHG) emissions come from large point sources (heat and power production and industrial processes) and the continued use of fossil fuels requires quick and effective measures to meet the world’s energy demand whilst (at least) stabilizing CO2 atmospheric levels. The framework known as Carbon Capture and Storage (CCS) – or Carbon Capture Utilization and Storage (CCUS) – comprises a portfolio of technologies applicable to large‐scale GHG sources for preventing CO2 from entering the atmosphere. Amongst them, CO2 capture and mineralisation (CCM) presents the highest potential for CO2 sequestration as the predicted carbon storage capacity (as mineral carbonates) far exceeds the estimated levels of the worldwide identified fossil fuel reserves. The work presented in this thesis aims at taking a step forward to the deployment of an energy/cost effective process for simultaneous capture and storage of CO2 in the form of thermodynamically stable and environmentally friendly solid carbonates. R&D work on the process considered here began in 2007 at Åbo Akademi University in Finland. It involves the processing of magnesium silicate minerals with recyclable ammonium salts for extraction of magnesium at ambient pressure and 400‐440⁰C, followed by aqueous precipitation of magnesium in the form of hydroxide, Mg(OH)2, and finally Mg(OH)2 carbonation in a pressurised fluidized bed reactor at ~510⁰C and ~20 bar PCO2 to produce high purity MgCO3. Rock material taken from the Hitura nickel mine, Finland, and serpentinite collected from Bragança, Portugal, were tested for magnesium extraction with both ammonium sulphate and bisulphate (AS and ABS) for determination of optimal operation parameters, primarily: reaction time, reactor type and presence of moisture. Typical efficiencies range from 50 to 80% of magnesium extraction at 350‐450⁰C. In general ABS performs better than AS showing comparable efficiencies at lower temperature and reaction times. The best experimental results so far obtained include 80% magnesium extraction with ABS at 450⁰C in a laboratory scale rotary kiln and 70% Mg(OH)2 carbonation in the PFB at 500⁰C, 20 bar CO2 pressure for 15 minutes. The extraction reaction with ammonium salts is not at all selective towards magnesium. Other elements like iron, nickel, chromium, copper, etc., are also co‐extracted. Their separation, recovery and valorisation are addressed as well and found to be of great importance. The assessment of the exergetic performance of the process was carried out using Aspen Plus® software and pinch analysis technology. The choice of fluxing agent and its recovery method have a decisive sway in the performance of the process: AS is recovered by crystallisation and in general the whole process requires more exergy (2.48–5.09 GJ/tCO2sequestered) than ABS (2.48–4.47 GJ/tCO2sequestered) when ABS is recovered by thermal decomposition. However, the corrosive nature of molten ABS and operational problems inherent to thermal regeneration of ABS prohibit this route. Regeneration of ABS through addition of H2SO4 to AS (followed by crystallisation) results in an overall negative exergy balance (mainly at the expense of low grade heat) but will flood the system with sulphates. Although the ÅA route is still energy intensive, its performance is comparable to conventional CO2 capture methods using alkanolamine solvents. An energy‐neutral process is dependent on the availability and quality of nearby waste heat and economic viability might be achieved with: magnesium extraction and carbonation levels ≥ 90%, the processing of CO2‐containing flue gases (eliminating the expensive capture step) and production of marketable products.

Drying soybean seed using air ambient temperature at low relative humidity

Under subtropical and tropical environments soybean seed (Glycine max (L.) Merrill) are harvested early to avoid deterioration from weathering. Careful after-harvest drying is required and is an important step in maintaining the physiological quality of the seed. Soybean seed should be harvested when the moisture content is in a range of 16-20%. Traditional drying utilizes a high temperature air stream passed through the seed mass without dehumidification. The drying time is long because the system is inefficient and the high temperature increases the risk of thermal damage to the seed. New technology identified as heat pipe technology (HPT) is available and has the unique feature of removing the moisture from the air stream before it is passed through the seed mass at the same environmental temperature. Two studies were conducted to evaluate the performance of HPT for dry soybean seed. In the first study the seeds were dried from 17.5 to 11.1% in 2 hours and 29 minutes and in the second sudy the seeds were dried from 22.6 to 11.9% in 16 hours and 32 minutes. This drying process caused no reduction in seed quality as measured by the standard germination, tetrazolium-viability, accelerated aging and seedling vigor classification tests. The only parameter that indicated a slight seed quality reduction was tetrazolium vigor in the second study. It was concluded that the HPT system is a promising technology for drying soybean seed when efficiency and maintenance of physiological quality are desired.

Drying peanut seed using air ambient temperature at low relative humidity

The moisture content of peanut kernel (Arachis hypogaea L.) at digging ranges from 30 to 50% on a wet basis (w.b.). The seed moisture content must be reduced to 10.5% or below before seeds can be graded and marketed. After digging, peanuts are cured on a window sill for two to five days then mechanically separated from the vine. Heated air is used to further dry the peanuts from approximately 18 to 10% moisture content w.b. Drying is required to maintain peanut seed and grain quality. Traditional dryers pass a high temperature and high humidity air stream through the seed mass. The drying time is long because the system is inefficient and the high temperature increases the risk of thermal damage to the kernels. New technology identified as heat pipe technology (HPT) is available and has the unique feature of removing the moisture from the air stream before it is heated and passed through the seed. A study was conducted to evaluate the performance of the HPT system in drying peanut seed. The seeds inside the shells were dried from 17.4 to 7.3% in 14 hours and 11 minutes, with a rate of moisture removal of 0.71% mc per hour. This drying process caused no reduction in seed quality as measured by the standard germination, accelerated ageing and field emergence tests. It was concluded that the HPT system is a promising technology for drying peanut seed when efficiency and maintenance of physiological quality are desired.

Hydrogen Sensor Application of Anodic Titanium Oxide Nanostructures

Hydrogen (H2) fuel cells have been considered a promising renewable energy source. The recent growth of H2 economy has required highly sensitive, micro-sized and cost-effective H2 sensor for monitoring concentrations and alerting to leakages due to the flammability and explosiveness of H2 Titanium dioxide (TiO2) made by electrochemical anodic oxidation has shown great potential as a H2 sensing material. The aim of this thesis is to develop highly sensitive H2 sensor using anodized TiO2. The sensor enables mass production and integration with microelectronics by preparing the oxide layer on suitable substrate. Morphology, elemental composition, crystal phase, electrical properties and H2 sensing properties of TiO2 nanostructures prepared on Ti foil, Si and SiO2/Si substrates were characterized. Initially, vertically oriented TiO2 nanotubes as the sensing material were obtained by anodizing Ti foil. The morphological properties of tubes could be tailored by varying the applied voltages of the anodization. The transparent oxide layer creates an interference color phenomena with white light illumination on the oxide surface. This coloration effect can be used to predict the morphological properties of the TiO2 nanostructures. The crystal phase transition from amorphous to anatase or rutile, or the mixture of anatase and rutile was observed with varying heat treatment temperatures. However, the H2 sensing properties of TiO2 nanotubes at room temperature were insufficient. H2 sensors using TiO2 nanostructures formed on Si and SiO2/Si substrates were demonstrated. In both cases, a Ti layer deposited on the substrates by a DC magnetron sputtering method was successfully anodized. A mesoporous TiO2 layer obtained on Si by anodization in an aqueous electrolyte at 5°C showed diode behavior, which was influenced by the work function difference of Pt metal electrodes and the oxide layer. The sensor enabled the detection of H2 (20-1000 ppm) at low operating temperatures (50–140°C) in ambient air. A Pd decorated tubular TiO2 layer was prepared on metal electrodes patterned SiO2/Si wafer by anodization in an organic electrolyte at 5°C. The sensor showed significantly enhanced H2 sensing properties, and detected hydrogen in the range of a few ppm with fast response/recovery time. The metal electrodes placed under the oxide layer also enhanced the mechanical tolerance of the sensor. The concept of TiO2 nanostructures on alternative substrates could be a prospect for microelectronic applications and mass production of gas sensors. The gas sensor properties can be further improved by modifying material morphologies and decorating it with catalytic materials.

Dynamic Modelling of Circulating Fluidized Bed Plant with Gas Turbine Repowering

Increasing amount of renewable energy source based electricity production has set high load control requirements for power grid balance markets. The essential grid balance between electricity consumption and generation is currently hard to achieve economically with new-generation solutions. Therefore conventional combustion power generation will be examined in this thesis as a solution to the foregoing issue. Circulating fluidized bed (CFB) technology is known to have sufficient scale to acts as a large grid balancing unit. Although the load change rate of the CFB unit is known to be moderately high, supplementary repowering solution will be evaluated in this thesis for load change maximization. The repowering heat duty is delivered to the CFB feed water preheating section by smaller gas turbine (GT) unit. Consequently, steam extraction preheating may be decreased and large amount of the gas turbine exhaust heat may be utilized in the CFB process to reach maximum plant electrical efficiency. Earlier study of the repowering has focused on the efficiency improvements and retrofitting to maximize plant electrical output. This study however presents the CFB load change improvement possibilities achieved with supplementary GT heat. The repowering study is prefaced with literature and theory review for both of the processes to maximize accuracy of the research. Both dynamic and steady-state simulations accomplished with APROS simulation tool will be used to evaluate repowering effects to the CFB unit operation. Eventually, a conceptual level analysis is completed to compare repowered plant performance to the state-of-the-art CFB performance. Based on the performed simulations, considerably good improvements to the CFB process parameters are achieved with repowering. Consequently, the results show possibilities to higher ramp rate values achieved with repowered CFB technology. This enables better plant suitability to the grid balance markets.

The relationship between b2b branding and industrial buying in the digital era: evidence from Finnish gas industry

The aim of this study is to understand the importance of b2b brands in different phases of the industrial buying process in the digital era. The research problem is approached by examining a b2b supplier brand in the context of gas supplier selection. The data was collected by interviewing individuals from ten different companies. The findings contribute to previous theory by showing that as industrial buying behaviour is eventually individual behaviour, brands can influence decision making. The relevance of a brand depends on individual’s personality and preferences. Digital media cannot be ignored in managing brand image as buyers are present in the online environment. The results reveal that traditional personal selling is, nevertheless, in a key role in brand image building and is a source of added value. The salesperson influences buyers’ perceived associations of a brand and gives the brand a face.

Screening of power to gas projects

The purpose of this thesis was the screening of power to gas projects worldwide and reviewing the technologies used and applications for the end products. This study focuses solely on technical solutions and feasibility, economical profitability is excluded. With power grids having larger penetrations of intermittent sources such as solar and wind power, the demand and production cannot be balanced in conventional methods. Technologies for storing electric power in times of surplus production are needed, and the concept called power to gas is a solution for this problem. A total of 57 projects mostly located in Europe were reviewed by going through publications, presentations and project web pages. Hydrogen is the more popular end product over methane. Power to gas is a viable concept when power production from intermittent sources needs to be smoothed and time shifted, when carbon free fuels are produced for vehicles and when chemical industry needs carbon neutral raw materials.

Phonon spectra and thermodynamic properties of rare gas solids based on empirical and semi-empirical (ab initio) two-body potentials : a comparative study /

We study the phonon dispersion, cohesive and thermal properties of raxe gas solids Ne, Ar, Kr, and Xe, using a variety of potentials obtained from different approaches; such as, fitting to crystal properties, purely ab initio calculations for molecules and dimers or ab initio calculations for solid crystalline phase, a combination of ab initio calculations and fitting to either gas phase data or sohd state properties. We explore whether potentials derived with a certain approaxih have any obvious benefit over the others in reproducing the solid state properties. In particular, we study phonon dispersion, isothermal ajid adiabatic bulk moduli, thermal expansion, and elastic (shear) constants as a function of temperatiue. Anharmonic effects on thermal expansion, specific heat, and bulk moduli have been studied using A^ perturbation theory in the high temperature limit using the neaxest-neighbor central force (nncf) model as developed by Shukla and MacDonald [4]. In our study, we find that potentials based on fitting to the crystal properties have some advantage, particularly for Kr and Xe, in terms of reproducing the thermodynamic properties over an extended range of temperatiures, but agreement with the phonon frequencies with the measured values is not guaranteed. For the lighter element Ne, the LJ potential which is based on fitting to the gas phase data produces best results for the thermodynamic properties; however, the Eggenberger potential for Ne, where the potential is based on combining ab initio quantum chemical calculations and molecular dynamics simulations, produces results that have better agreement with the measured dispersion, and elastic (shear) values. For At, the Morse-type potential, which is based on M0ller-Plesset perturbation theory to fourth order (MP4) ab initio calculations, yields the best results for the thermodynamic properties, elastic (shear) constants, and the phonon dispersion curves.

An application of cell-cluster theory to a rare gas crystal /|n[by] K. Westera. - 260 St. Catharines [Ont.] : Dept. of Physics, Brock University,

The Lennard-Jones Devonshire 1 (LJD) single particle theory for liquids is extended and applied to the anharmonic solid in a high temperature limit. The exact free energy for the crystal is expressed as a convergent series of terms involving larger and larger sets of contiguous particles called cell-clusters. The motions of all the particles within cell-clusters are correlated to each other and lead to non-trivial integrals of orders 3, 6, 9, ... 3N. For the first time the six dimensional integral has been calculated to high accuracy using a Lennard-Jones (6-12) pair interaction between nearest neighbours only for the f.c.c. lattice. The thermodynamic properties predicted by this model agree well with experimental results for solid Xenon.