Wet oxidation of biomass for chemical production

Tämän kandidaatintyön tarkoituksena oli tutkia märkähapetusprosessia jätevesien käsittely-menetelmänä ja mahdollisena menetelmänä kemikaalien tuottamiseksi jätevesistä. Erityishuomio on kiinnitetty paperiteollisuudessa syntyviin jätevesiin. Teoriaosassa käsitellään vesikiertoja paperitehtaassa, paperitehtaalla syntyvän jäteveden ominaisuuksia sekä itse märkähapetusprosessia. Märkähapetusprosessissa perehdytään tavalliseen happea käyttävään märkähapetukseen sekä vetyperoksidia käyttävään menetelmään sekä näissä prosesseissa syntyviin väli- ja lopputuotteisiin. Märkähapetus (WO) on terminen hapetusmenetelmä, jolla voidaan käsitellä jätevesiä, jotka ovat liian konsentroituja biologisiin käsittelyihin tai jotka ovat huonosti biohajoavia. Märkähapetuksen tarkoituksena on parantaa molekulaarisen hapen ja orgaanisen aineen välistä kontaktia, jolloin orgaaninen aines pilkkoutuu muodostaen pääasiassa karboksyylihappoja, aldehydejä, hiilidioksidia ja vettä. Märkähapetuksessa hapettavana kaasuna voidaan käyttää joko puhdasta happea tai ilmaa. Vetyperoksidia käyttävässä märkähapetuksessa (WPO) hapettava kaasu on korvattu nestemäisellä vetyperoksidilla. Kokeellisessa osassa tutkittiin orgaanisen aineksen hapetusta käyttäen Fentonin reagenssia, jolloin katalyyttina reaktiossa toimii rautaionit (Fe2+ ja Fe3+) ja hapettimena vetyperoksidi. Hapetettavana jätevetenä käytettiin paperitehtaan hiomolta saatua kiertovettä, TMP-vettä. Hapetuskokeita tehtiin eri vetyperoksidin annoksilla ja katalyytin määrillä eri lämpötiloissa. Hapetuksen jälkeen näytteistä mitattiin kemiallinen hapenkulutus (COD), orgaanisen hiilen kokonaismäärä (TOC) sekä pH. Lisäksi näytteistä määritettiin nestekromatografilla (HPLC) tyypillisten välituotteiden, kuten oksaalihapon, muurahaishapon ja etikkahapon, määrät. Tehdyissä kokeissa COD-arvoja saatiin pienennettyä 50-88 % siten, että suodatetuissa näytteissä muutos oli suurempi kuin suodattamattomissa näytteissä. Lisäksi TOC-arvot laskivat 28-58 %. Tehdyissä kokeissa saatiin myös tuotettua välituotteina karboksyylihappoja, joista etikkahappoa ja oksaalihappoa tuotettiin suurimmat määrät. Myös muurahaishappoa ja meripihkahappoa saatiin tuotettua.

Chemical derivatization of galactoglucomannan for functional materials

In the framework of the biorefinery concept researchers aspire to optimize the utilization of plant materials, such as agricultural wastes and wood. For most of the known processes, the first steps in the valorisation of biomass are the extraction and purification of the individual components. The obtained raw products by means of a controlled separation can consecutively be modified to result in biofuels or biogas for energy production, but also in value-added products such as additives and important building blocks for the chemical and material industries. Considerable efforts are undertaken in order to substitute the use of oil-based starting materials or at least minimize their processing for the production of everyday goods. Wood is one of the raw materials, which have gained large attention in the last decades and its composition has been studied in detail. Nowadays, the extraction of water-soluble hemicelluloses from wood is well known and so for example xylan can be obtained from hardwoods and O-acetyl galactoglucomannans (GGMs) from softwoods. The aim of this work was to develop water-soluble amphiphilic materials of GGM and to assess their potential use as additives. Furthermore, GGM was also applied as a crosslinker in the synthesis of functional hydrogels for the removal of toxic metals and metalloid ions from aqueous solutions. The distinguished products were obtained by several chemical approaches and analysed by nuclear magnetic resonance spectroscopy (NMR), Fourier transform infrared spectroscopy (FTIR), size exclusion chromatography (SEC), thermal gravimetric analysis (TGA), scanning electron microscope SEM, among others. Bio-based surfactants were produced by applying GGM and different fatty acids as starting materials. On one hand, GGM-grafted-fatty acids were prepared by esterification and on the other hand, well-defined GGM-block-fatty acid derivatives were obtained by linking amino-functional fatty acids to the reducing end of GGM. The reaction conditions for the syntheses were optimized and the resultant amphiphilic GGM derivatives were evaluated concerning their ability to reduce the surface tension of water as surfactants. Furthermore, the block-structured derivatives were tested in respect to their applicability as additives for the surface modification of cellulosic materials. Besides the GGM surfactants with a bio-based hydrophilic and a bio-based hydrophobic part, also GGM block-structured derivatives with a synthetic hydrophobic tail, consisting of a polydimethylsiloxane chain, were prepared and assessed for the hydrophobization of surface of nanofibrillated cellulose films. In order to generate GGM block-structured derivatives containing a synthetic tail with distinguished physical and chemical properties, as well as a tailored chain length, a controlled polymerization method was used. Therefore, firstly an initiator group was introduced at the reducing end of the GGM and consecutively single electron transfer-living radical polymerization (SET-LRP) was performed by applying three different monomers in individual reactions. For the accomplishment of the synthesis and the analysis of the products, challenges related to the solubility of the reactants had to be overcome. Overall, a synthesis route for the production of GGM block-copolymers bearing different synthetic polymer chains was developed and several derivatives were obtained. Moreover, GGM with different molar masses were, after modification, used as a crosslinker in the synthesis of functional hydrogels. Hereby, a cationic monomer was used during the free radical polymerization and the resultant hydrogels were successfully tested for the removal of chromium and arsenic ions from aqueous solutions. The hydrogel synthesis was tailored and materials with distinguished physical properties, such as the swelling rate, were obtained after purification. The results generated in this work underline the potential of bio-based products and the urge to continue carrying out research in order to be able to use more green chemicals for the manufacturing of biorenewable and biodegradable daily products.

Effects of terpineol on the compound action potential of the rat sciatic nerve

Terpineol, a volatile terpenoid alcohol of low toxicity, is widely used in the perfumery industry. It is an important chemical constituent of the essential oil of many plants with widespread applications in folk medicine and in aromatherapy. The effects of terpineol on the compound action potential (CAP) of rat sciatic nerve were studied. Terpineol induced a dose-dependent blockade of the CAP. At 100 µM, terpineol had no demonstrable effect. At 300 µM terpineol, peak-to-peak amplitude and conduction velocity of CAP were significantly reduced at the end of 180-min exposure of the nerve to the drug, from 3.28 ± 0.22 mV and 33.5 ± 7.05 m/s, respectively, to 1.91 ± 0.51 mV and 26.2 ± 4.55 m/s. At 600 µM, terpineol significantly reduced peak-to-peak amplitude and conduction velocity from 2.97 ± 0.55 mV and 32.8 ± 3.91 m/s to 0.24 ± 0.23 mV and 2.72 ± 2.72 m/s, respectively (N = 5). All these effects developed slowly and were reversible upon 180-min washout.

Potential applications of nanotechnology in the agro-food sector

Nanoscience and nanotechnology are new frontiers of this century. Their application to the agriculture and food sectors is relatively recent compared with their use in drug delivery and pharmaceuticals. Smart delivery of nutrients, bioseparation of proteins, rapid sampling of biological and chemical contaminants, and nanoencapsulation of nutraceuticals are some of the emerging topics of nanotechnology for food and agriculture. In this review, some applications of nanotechnology in agro-food sector are discussed.

Physical-chemical, caloric and sensory characterization of light jambolan (Syzygium cumini Lamarck) jelly

In Brazil, several little economically explored fruits have good potential as raw material for the agro-industry. This study aimed to produce and determine the physical-chemical and sensory characteristics of light jambolan jelly. This fruit has intense purple color, which gave the jellies - both standard and light - a quite attractive visual aspect. The light jellies exhibited similar physical-chemical characteristics to the ones developed through the conventional method and; with the proportion of sweeteners used, the caloric values of the formulations were reduced to the range of 41 to 53%, attending the requirements of the Brazilian legislation for this type of product. The sensory profile obtained for the 4 light formulations developed, clearly showed the tasters' preference for the jelly elaborated with the association of cyclamate and saccharin. Thus, the results revealed good perspectives for the application of this fruit in the food industry.

Chemical sanitizers to control biofilms formed by two Pseudomonas species on stainless steel surface

The biofilm formation of Pseudomonas aeruginosa and Pseudomonas fluorescens on AISI 304 stainless steel in the presence of reconstituted skim milk under different temperatures was conducted, and the potential of three chemical sanitizers in removing the mono-species biofilms formed was compared. Pseudomonas aeruginosa cultivated in skim milk at 28 °C presented better growth rate (10.4 log CFU.mL-1) when compared with 3.7 and 4.2 log CFU.mL-1 for P. aeruginosa and P. fluorescens cultivated at 7 °C, respectively. Pseudomonas aeruginosa formed biofilm when cultivated at 28 °C. However, only the adhesion of P. aeruginosa and P. fluorescens was observed when incubated at 7 °C. The sodium dichloroisocyanurate was the most efficient sanitizer in the reduction of the adhered P. aeruginosa cells at 7 and 28 °C and those on the biofilm, respectively. The hydrogen peroxide was more effective in the reduction of adhered cells of P. fluorescens at 7 °C.

Soymilk plain beverages: correlation between acceptability and physical and chemical characteristics

The objective of the research was to relate the physical and chemical characteristics of soymilk plain beverages to its sensory acceptance. Five commercial products and a new product formulated based on the less accepted sample were used. The overall acceptance was evaluated by 102 assessors using a 10-point hybrid hedonic scale. The hedonic scores ranged from 3.8 (sample E) to 7.0 (A). Most assessors (55%) preferred sample A, which was viscous (26.6 cp), dark (L* = 77.7), and slightly acidic (pH = 6.6). Sample C, which had lower solid content and higher acidity, was preferred by 29% of the assessors. These two beverages showed the greatest commercial potential of the products analyzed. The least-accepted sample (E), preferred by 8% of the assessors, had a lighter color (L* = 96.8), lower viscosity (13.5 cp), higher lipid content (2.2 g/100 g), and less protein (1.68 g/100 g) than the other products evaluated. A reformulation of the least preferred product (E) with the addition of maltodextrin and also vanilla and milk flavors increased its acceptance, yielding an average score of 7.2. Overall, it was observed that a soymilk plain beverage with higher viscosity, darker color, and higher protein content best meets consumer expectations.

Chemical constituents and technological functional properties of acerola (Malpighia emarginata DC.) waste flour

Acerola is a fruit that can be consumed in the form of juice and pulp. However, during its processing, a large amount of waste is generated (seed and bagasse). Adding value to these by-products is of great interest, since their use can enrich foods with nutrients and fiber. In this study, we performed phytochemical screening, determined the proximate and mineral composition, bioactive compounds and the technological functional properties of acerola seed flour and acerola bagasse flour. Seeds were dried in a ventilated oven at ± 45 °C and the bagasse was lyophilized. Samples were ground, stored in flasks protected from light. Phytochemical screening revealed metabolites of nutritional and pharmacological interest and no potentially toxic substances in the flours. Seed flour and bagasse flour showed high levels (g 100 g- 1 of dry matter - DM) of soluble fiber: 4.76 and 8.74; insoluble fiber: 75.76 and 28.58, and phenolic compounds: 4.73 and 10.82, respectively. The flours also showed high absorption of water, oil and emulsion stability, presenting potential for inclusion in meat products and bakery products.

Chemical composition and bioactive compounds of grape pomace (Vitis vinifera L.), Benitaka variety, grown in the semiarid region of Northeast Brazil

Grape pomace (Vitis vinifera L.), Benitaka variety, grown in the semiarid region of Northeast Brazil was evaluated in relation to chemical composition, and content of minerals and functional properties. Its microbiological quality and toxic potential, using Artemia salina sp, were also investigated. The results showed that the flour obtained from these residues had below neutral pH (3.82), moisture (3.33g/100g), acidity of (0.64g of citric acid/100g), and ash (4.65 g/100g). The amount of total dietary fiber (46.17g/100g) stood out quantitatively compared to the content of carbohydrate (29.2g/100 g), protein (8.49g/100g), and lipids (8.16g/100g). The total energy was 224Kcal/100g. With regard to the compounds with functional properties, higher values of insoluble fiber 79% (36.4 g/100 g); vitamin C (26.25 mg of acid ascorbic/100g), and anthocyanins (131mg/100g) were found. The minerals iron, potassium, zinc, manganese, and calcium were present in higher concentrations. There were no significant copper values. The results showed that the grape residues are an important source of nutrients and compounds with functional properties suggesting that they can be incorporated as an ingredient in the diet and/or used as a dietary supplement aiming at health benefits. The residues did not show microbiological contamination and were considered nontoxic.

Prevention of enzymatic browning of yacon flour by the combined use of anti-browning agents and the study of its chemical composition

Yacon roots present functional properties because of the high levels of fructooligosaccharides (FOS), which are considered as prebiotic fibers. In addition, yacon roots are rich in phenolic compounds. During the processing of yacon, the freshly cut surface undergoes rapid enzymatic browning. Control of enzymatic browning during processing is very important to preserve the appearance of yacon flour. In this study, it was evaluated the combined effect of anti-browning agents (ascorbic acid, citric acid and L-cysteine) on the inhibition of enzymatic browning of yacon, using Response Surface Methodology. The yacon pre-treated with anti-browning agents in concentrations of 15.0 mM for ascorbic acid, 7.5 mM for citric acid and 10.0 mM for L-cysteine was used for the processing of flour. Yacon flour presented an attractive color and good sensory properties, without residual aroma. The contents of FOS and phenolic compounds obtained in yacon flour were 28.60 g.100 g- 1 and 1.35 g.100 g- 1. Yacon flour can be considered as a potential functional food, especially due to high levels of FOS, which allows for its use in formulation of various foods.

Chemical composition and antioxidant activity of jatobá-do-cerrado (Hymenaea stigonocarpa Mart.) flour

The Brazilian Savannah, known as "Cerrado," has an extensive biodiversity, but it is under explored. Among the native vegetables is the jatobá-do-cerrado (Hymenaea stigonocarpa Mart.), a legume with great potential for exploration for its content of dietary fiber. Legumes are an important source of nutrient compounds, such as phenolic compounds and vitamins that have antioxidant properties. This study aimed at determining the chemical composition and antioxidant activity of the jatobá flour. The jatobá flour showed high fiber content (insoluble and soluble fiber 47.8 and 12.8 g.100 g- 1, respectively), significant amounts of carotenoids such as beta-carotene and lutein, and some minerals such as calcium: 145 mg.100 g- 1, magnesium: 125 mg.100 g- 1, and potassium: 1352 mg.100 g- 1. The jatobá flour extracted with different solvents (water, methanol, and acetone) exhibited antioxidant activity by the DPPH, FRAP, and ORAC methods. The solvent used in the extraction affected the total phenolic content and antioxidant activity. Acetone extraction produced the best results. Therefore, the jatobá flour is an ingredient that can be used to develop new products with properties that promote health.

Chemical composition and effects of micronized corn bran on iron bioavailability in rats

The degermination of corn grains by dry milling generates 5% of a fibrous residue. After segregation and micronization, corn bran becomes a potential source of dietary fiber consumption. However, its effect on iron bioavailability has not been reported in the literature. The objective of the present study was to determine the nutritional composition of corn bran and its effects on iron bioavailability using the hemoglobin depletion-repletion method in rats. The animals were divided into two groups: cellulose (control) and corn bran (experimental). The bran had high content of total dietary fiber, especially the insoluble fraction, and low phytate content. Hemoglobin uptake did not differ between groups at the end of repletion period, and the iron relative bioavailability value of the corn bran diet was 104% in comparison to that of the control group. The product evaluated proved to be a potential source of dietary fiber and it showed no negative effects on iron bioavailability.

Effect of different stress conditions on the stability of quercetin-loaded lipid microparticles produced with babacu ( Orbignya speciosa ) oil: evaluation of their potential use in food applications

Lipid micro and nanoparticles have been extensively investigated as carriers for hydrophobic bioactives in food systems because they can simultaneously increase the dispersibility of these lipophilic substances and help improve their bioavailability. In this study, lipid microparticles of babacu oil and denatured whey protein isolate were produced, and their ability to protect quercetin against degradation was evaluated over 30 days of storage. Additionally, the lipid microparticles were subjected to the typical stress conditions of food processing (presence of sucrose, salt, and thermal stresses), and their physico-chemical stability was monitored. The data show that the babacu microparticles efficiently avoided the oxidation of quercetin because 85% of the initial amount of the flavonoid was preserved after 30 days. The particles were notably stable up to a temperature of 70 °C for 10 minutes at relatively high concentrations of salt and sucrose. The type of stirring (mechanical or magnetic) also strongly affected the stability of the dispersions.

Chemical, morphological, and thermogravimetric of Terminalia catappa Linn

The objective of this study is to evaluate the chemical composition, morphology, and the thermogravimetric behavior of the pulp of Terminalia catappa, also known as tropical almond. The analytical results show, based mainly on its lipid content, that this fruit has a considerable energy value. Its fiber content contributes to enhance the functional properties of the fruit. Morphological characteristics show a spongy-like structure with dispersion of starch granules and high concentration of fiber bundles, confirming the results of the chemical composition analysis. The thermogravimetric behavior exhibited by this fruit pulp when submitted to progressive temperature increase under dynamic air atmosphere shows that this raw material has great potential for industrial use due to its high absorption rate of water soluble and/or lipid-based compounds, allowing its use as a dietary complement or supplement ingredient in food products.

The feasibility of torrefaction for the co-firing of wood in pulverised-fuel boilers

Torrefaction is the partial pyrolysis of wood characterised by thermal degradation of predominantly hemicellulose under inert atmosphere. Torrefaction can be likened to coffee roasting but with wood in place of beans. This relatively new process concept makes wood more like coal. Torrefaction has attracted interest because it potentially enables higher rates of co-firing in existing pulverised-coal power plants and hence greater net CO2 emission reductions. Academic and entrepreneurial interest in torrefaction has sky rocketed in the last decade. Research output has focused on the many aspects of torrefaction – from detailed chemical changes in feedstock to globally-optimised production and supply scenarios with which to sustain EU emission-cutting directives. However, despite its seemingly simple concept, torrefaction has retained a somewhat mysterious standing. Why hasn’t torrefied pellet production become fully commercialised? The question is one of feasibility. This thesis addresses this question. Herein, the feasibility of torrefaction in co-firing applications is approached from three directions. Firstly, the natural limitations imposed by the structure of wood are assessed. Secondly, the environmental impact of production and use of torrefied fuel is evaluated and thirdly, economic feasibility is assessed based on the state of the art of pellet making. The conclusions reached in these domains are as follows. Modification of wood’s chemical structure is limited by its naturally existing constituents. Consequently, key properties of wood with regards to its potential as a co-firing fuel have a finite range. The most ideal benefits gained from wood torrefaction cannot all be realised simultaneously in a single process or product. Although torrefaction at elevated pressure may enhance some properties of torrefied wood, high-energy torrefaction yields are achieved at the expense of other key properties such as heating value, grindability, equilibrium moisture content and the ability to pelletise torrefied wood. Moreover, pelletisation of even moderately torrefied fuels is challenging and achieving a standard level of pellet durability, as required by international standards, is not trivial. Despite a reduced moisture content, brief exposure of torrefied pellets to water from rainfall or emersion results in a high level of moisture retention. Based on the above findings, torrefied pellets are an optimised product. Assessment of energy and CO2-equivalent emission balance indicates that there is no environmental barrier to production and use of torrefied pellets in co-firing. A long product transport distance, however, is necessary in order for emission benefits to exceed those of conventional pellets. Substantial CO2 emission reductions appear possible with this fuel if laboratory milling results carry over to industrial scales for direct co-firing. From demonstrated state-of-the-art pellet properties, however, the economic feasibility of torrefied pellet production falls short of conventional pellets primarily due to the larger capital investment required for production. If the capital investment for torrefied pellet production can be reduced significantly or if the pellet-making issues can be resolved, the two production processes could be economically comparable. In this scenario, however, transatlantic shipping distances and a dry fuel are likely necessary for production to be viable. Based on demonstrated pellet properties to date, environmental aspects and production economics, it is concluded that torrefied pellets do not warrant investment at this time. However, from the presented results, the course of future research in this field is clear.