Purification of Hydrocarbon Waste Streams

Purification of hydrocarbon waste streams is needed to recycle valuable hydrocarbon products, reduce hazardous impacts on environment, and save energy. To obtain these goals, research must be focused on the search of effective and feasible purification and re-refining technologies. Hydrocarbon waste streams can contain both deliberately added additives to original product and during operation cycle accumulated undesired contaminants. Compounds may have degenerated or cross-reacted. Thus, the presence of unknown species cause additional challenges for the purification process. Adsorption process is most suitable to reduce impurities to very low concentrations. Main advantages are availability of selective commercial adsorbents and the regeneration option to recycle used separation material. Used hydrocarbon fraction was purified with various separation materials in the experimental part. First screening of suitable materials was done. In the second stage, temperature dependence and adsorption kinetics were studied. Finally, one fixed bed experiment was done with the most suitable material. Additionally, FTIR-measurements of hydrocarbon samples were carried out to develop a model to monitor the concentrations of three target impurities based on spectral data. Adsorption capacities of the tested separation materials were observed to be low to achieve high enough removal efficiencies for target impurities. Based on the obtained data, batch process would be more suitable than a fixed bed process and operation at high temperatures is favorable. Additional pretreatment step is recommended to improve removal efficiency. The FTIR-measurement was proven to be a reliable and fast analysis method for challenging hydrocarbon samples.

Study of the effects of ß-myrcene on rat fertility and general reproductive performance

ß-Myrcene (MYR) is a monoterpene found in the oils of a variety of aromatic plants including lemongrass, verbena, hop, bay, and others. MYR and essential oils containing this terpenoid compound are used in cosmetics, household products, and as flavoring food additives. This study was undertaken to investigate the effects of MYR on fertility and general reproductive performance in the rat. MYR (0, 100, 300 and 500 mg/kg) in peanut oil was given by gavage to male Wistar rats (15 per dose group) for 91 days prior to mating and during the mating period, as well as to females (45 per dose group) continuously for 21 days before mating, during mating and pregnancy, and throughout the period of lactation up to postnatal day 21. On day 21 of pregnancy one-third of the females of each group were submitted to cesarean section. Resorption, implantation, as well as dead and live fetuses were counted. All fetuses were examined for external malformations, weighed, and cleared and stained with Alizarin Red S for skeleton evaluation. The remaining dams were allowed to give birth to their offspring. The progeny was examined at birth and subsequently up to postnatal day 21. Mortality, weight gain and physical signs of postnatal development were evaluated. Except for an increase in liver and kidney weights, no other sign of toxicity was noted in male and female rats exposed to MYR. MYR did not affect the mating index (proportion of females impregnated by males) or the pregnancy index (ratio of pregnant to sperm-positive females). No sign of maternal toxicity and no increase in externally visible malformations were observed at any dose level. Only at the highest dose tested (500 mg/kg) did MYR induce an increase in the resorption rate and a higher frequency of fetal skeleton anomalies. No adverse effect of MYR on postnatal weight gain was noted but days of appearance of primary coat, incisor eruption and eye opening were slightly delayed in the exposed offspring. On the basis of the data presented in this paper the no-observed-adverse-effect level (NOAEL) for toxic effects on fertility and general reproductive performance can be set at 300 mg of ß-myrcene/kg body weight by the oral route.

Stability of Natural Colorants of Plant Origin

In recent years, there have been studies that show a correlation between the hyperactivity of children and use of artificial food additives, including colorants. This has, in part, led to preference of natural products over products with artificial additives. Consumers have also become more aware of health issues. Natural food colorants have many bioactive functions, mainly vitamin A activity of carotenoids and antioxidativity, and therefore they could be more easily accepted by the consumers. However, natural colorant compounds are usually unstable, which restricts their usage. Microencapsulation could be one way to enhance the stability of natural colorant compounds and thus enable better usage for them as food colorants. Microencapsulation is a term used for processes in which the active material is totally enveloped in a coating or capsule, and thus it is separated and protected from the surrounding environment. In addition to protection by the capsule, microencapsulation can also be used to modify solubility and other properties of the encapsulated material, for example, to incorporate fat-soluble compounds into aqueous matrices. The aim of this thesis work was to study the stability of two natural pigments, lutein (carotenoid) and betanin (betalain), and to determine possible ways to enhance their stability with different microencapsulation techniques. Another aim was the extraction of pigments without the use of organic solvents and the development of previously used extraction methods. Stability of pigments in microencapsulated pigment preparations and model foods containing these were studied by measuring the pigment content after storage in different conditions. Preliminary studies on the bioavailability of microencapsulated pigments and sensory evaluation for consumer acceptance of model foods containing microencapsulated pigments were also carried out. Enzyme-assisted oil extraction was used to extract lutein from marigold (Tagetes erecta) flower without organic solvents, and the yield was comparable to solvent extraction of lutein from the same flowers. The effects of temperature, extraction time, and beet:water ratio on extraction efficiency of betanin from red beet (Beta vulgaris) were studied and the optimal conditions for maximum yield and maximum betanin concentration were determined. In both cases, extraction at 40 °C was better than extraction at 80 °C and the extraction for five minutes was as efficient as 15 or 30 minutes. For maximum betanin yield, the beet:water ratio of 1:2 was better, with possibly repeated extraction, but for maximum betanin concentration, a ratio of 1:1 was better. Lutein was incorporated into oil-in-water (o/w) emulsions with a polar oil fraction from oat (Avena sativa) as an emulsifier and mixtures of guar gum and xanthan gum or locust bean gum and xanthan gum as stabilizers to retard creaming. The stability of lutein in these emulsions was quite good, with 77 to 91 percent of lutein being left after storage in the dark at 20 to 22°C for 10 weeks whereas in spray dried emulsions the retention of lutein was 67 to 75 percent. The retention of lutein in oil was also good at 85 percent. Betanin was incorporated into the inner w1 water phase of a water1-in-oil-inwater2 (w1/o/w2) double emulsion with primary w1/o emulsion droplet size of 0.34 μm and secondary w1/o/w2 emulsion droplet size of 5.5 μm and encapsulation efficiency of betanin of 89 percent. In vitro intestinal lipid digestion was performed on the double emulsion, and during the first two hours, coalescence of the inner water phase droplets was observed, and the sizes of the double emulsion droplets increased quickly because of aggregation. This period also corresponded to gradual release of betanin, with a final release of 35 percent. The double emulsion structure was retained throughout the three-hour experiment. Betanin was also spray dried and incorporated into model juices with different pH and dry matter content. Model juices were stored in the dark at -20, 4, 20–24 or 60 °C (accelerated test) for several months. Betanin degraded quite rapidly in all of the samples and higher temperature and a lower pH accelerated degradation. Stability of betanin was much better in the spray dried powder, with practically no degradation during six months of storage in the dark at 20 to 24 °C and good stability also for six months in the dark at 60 °C with 60 percent retention. Consumer acceptance of model juices colored with spray dried betanin was compared with similar model juices colored with anthocyanins or beet extract. Consumers preferred beet extract and anthocyanin colored model juices over juices colored with spray dried betanin. However, spray dried betanin did not impart any off-odors or off-flavors into the model juices contrary to the beet extract. In conclusion, this thesis describes novel solvent-free extraction and encapsulation processes for lutein and betanin from plant sources. Lutein showed good stability in oil and in o/w emulsions, but slightly inferior in spray dried emulsions. In vitro intestinal lipid digestion showed a good stability of w1/o/w2 double emulsion and quite high retention of betanin during digestion. Consumer acceptance of model juices colored with spray dried betanin was not as good as model juices colored with anthocyanins, but addition of betanin to real berry juice could produce better results with mixture of added betanin and natural berry anthocyanins could produce a more acceptable color. Overall, further studies are needed to obtain natural colorants with good stability for the use in food products.

Silicon-containing species in used lube oil re-refining

Nowadays, the re-refining of the used lube oils has gained worldwide a lot of attention due to the necessity for added environmental protection and increasingly stringent environmental legislation. One of the parameters determining the quality of the produced base oils is the composition of feedstock. Estimation of the chemical composition of the used oil collected from several European locations showed that the hydrocarbon structure of the motor oil is changed insignificantly during its operation and the major part of the changes is accounted for with depleted oil additives. In the lube oil re-refining industry silicon, coming mainly from antifoaming agents, is recognized to be a contaminant generating undesired solid deposits in various locations in the re-refining units. In this thesis, a particular attention was paid to the mechanism of solid product formation during the alkali treatment process of silicon-containing used lube oils. The transformations of a model siloxane, tetramethyldisiloxane (TMDS), were studied in a batch reactor at industrially relevant alkali treatment conditions (low temperature, short reaction time) using different alkali agents. The reaction mechanism involving solid alkali metal silanolates was proposed. The experimental data obtained demonstrated that the solids were dominant products at low temperature and short reaction time. The liquid products in the low temperature reactions were represented mainly by linear siloxanes. The prolongation of reaction time resulted in reduction of solids, whereas both temperature and time increase led to dominance of cyclic products in the reaction mixture. Experiments with the varied reaction time demonstrated that the concentration of cyclic trimer being the dominant in the beginning of the reaction diminished with time, whereas the cyclic tetramer tended to increase. Experiments with lower sodium hydroxide concentration showed the same effect. In addition, a decrease of alkali agent concentration in the initial reaction mixture accelerated TMDS transformation reactions resulting in solely liquid cyclic siloxanes yields. Comparison of sodium and potassium hydroxides applied as an alkali agent demonstrated that potassium hydroxide was more efficient, since the activation energy in KOH presence was almost 2-fold lower than that for sodium hydroxide containing reaction mixture. Application of potassium hydroxide for TMDS transformation at 100° C with 3 hours reaction time resulted in 20 % decrease of solid yields compared to NaOH-containing mixture. Moreover, TMDS transformations in the presence of sodium silanolate applied as an alkali agent led to formation of only liquid products without formation of the undesired solids. On the basis of experimental data and the proposed reaction mechanism, a kinetic model was developed, which provided a satisfactory description of the experimental results. Suitability of the selected siloxane as a relevant model of industrial silicon-containing compounds was verified by investigation of the commercially available antifoam agent in base-catalyzed conditions.

Improving the fire retardancy of extruded/coextruded wood-plastic composites

The main objective of this thesis is to study the impact of different mineral fillers and fire retardants on the reaction-to-fire properties of extruded/coextruded wood-plastic composites (WPCs). The impact of additives on the flammability properties of WPCs is studied by cone calorimetry. The studied properties are ignition time, peak heat release rate, total heat release, total smoke production, and mass loss rate. The effects of mineral fillers and fire retardants were found to vary with the type of additive, the type of additive combinations, the amount of additives, as well as the production method of the WPCs. The study shows that talc can be used to improve the properties of extruded WPCs. Especially ignition time, peak heat release rate and mass loss rate were found to be improved significantly by talc. The most significant improvement in the fire retardancy of coextruded WPCs was achieved in combinations of natural graphite and melamine. Ignition time, peak heat release rate and total smoke production were improved essentially. High increase in smoke production was found in samples where the amount of ammonium polyphosphate was 10% or higher. Coextrusion as a structural modification was found as a promising way to improve the flammability properties of composite materials in a cost-effective way.

Production of yeast extracts from whey for food use: market and technical considerations

Whey is produced in large amounts by cheese industries. This by-product can be used for biomass production by yeast cultivation, resulting in commercially attractive products. The use of yeast extracts as source of flavour enhancer consists of an expansible market, encouraged by costumer's choice for natural additives. The development of a suitable and economically viable project for the generation of valued-added by-products, may allow the dairy industry to diversify their portfolio and increase their rentability.

Evaluation of antioxidants stability by thermal analysis and its protective effect in heated edible vegetable oil

In this work, through the use of thermal analysis techniques, the thermal stabilities of some antioxidants were investigated, in order to evaluate their resistance to thermal oxidation in oils, by heating canola vegetable oil, and to suggest that antioxidants would be more appropriate to increase the resistance of vegetable oils in the thermal degradation process in frying. The techniques used were: Thermal Gravimetric (TG) and Differential Scanning Calorimetry (DSC) analyses, as well as an allusion to a possible protective action of the vegetable oils, based on the thermal oxidation of canola vegetable oil in the laboratory under constant heating at 180 ºC/8 hours for 10 days. The studied antioxidants were: ascorbic acid, sorbic acid, citric acid, sodium erythorbate, BHT (3,5-di-tert-butyl-4-hydroxytoluene), BHA (2, 3-tert-butyl-4-methoxyphenol), TBHQ (tertiary butyl hydroquinone), PG (propyl gallate) - described as antioxidants by ANVISA and the FDA; and also the phytic acid antioxidant and the SAIB (sucrose acetate isobutyrate) additive, which is used in the food industry, in order to test its behavior as an antioxidant in vegetable oil. The following antioxidants: citric acid, sodium erythorbate, BHA, BHT, TBHQ and sorbic acid decompose at temperatures below 180 ºC, and therefore, have little protective action in vegetable oils undergoing frying processes. The antioxidants below: phytic acid, ascorbic acid and PG, are the most resistant and begin their decomposition processes at temperatures between 180 and 200 ºC. The thermal analytical techniques have also shown that the SAIB antioxidant is the most resistant to oxidative action, and it can be a useful choice in the thermal decomposition prevention of edible oils, improving stability regarding oxidative processes.

Identification of fatty foods with contamination possibilities by plasticizers when stored in PVC film packaging

Poly-(vinyl chloride) (PVC) requires the addition of plasticizers - additives that give flexibility and malleability for its processing into flexible film. The most used ones are: di-(2-ethylhexyl) adipate (DEHA) and di-(2-ethylhexyl) phthalate (DEHP). Toxic effects of DEHP have been observed by several authors. Phthalates are being replaced by alternative substances in PVC flexible products, because of their possible toxicological effects. DEHA is a substitute for phthalates widely used as a plasticizer in PVC materials for involving food. Some authors have shown that the exposure to DEHA also induces toxicity. A cross-sectional study was performed to identify which fatty foods carry the possibility of contamination by DEHP and DEHA. Eighteen different foods with at least 3% (m/m) fat and the possibility of being wrapped in plastic film were determined. This study suggested that all foods were subject to contamination by DEHP and DEHA in those conditions - in decreasing consumption order of 96 to 22% in the convenience sample. New guidelines on the limits of DEHA and DEHP established by the Brazilian legislation, as additives in PVC film for packaging fatty food, are still relevant to ensure human health.

Study of the shelf-life of a mixed araça (Psidium guineensis Sw.) and marolo (Annona crassiflora Mart.) jam

The objective of this study was to add value to araça and marolo fruits by developing jams and verifying changes in their physical, chemical, and microbiological parameters during storage. The analyses were carried out every 2 months. From the results, it was shown that the levels of moisture (35.89 - 26.34%), lipids (0.43 - 0.27%), sucrose (30.62 - 28.98%), total pectin (0.83 - 0.50%), soluble pectin (0.52 - 0.38%), total phenolic compounds (180.31 - 135.52 mg.GAE 100 g-1), and organic acids (401.1 - 68.5 µg.g-1 citric acid) decreased during storage. However, the levels of protein (0.83 - 0.95%), carbohydrate (62.52 - 72.5%, calories (257,11 - 295,931 kcal), fiber (0.72 - 1.4%), total soluble sugar (62.52 - 70.44%), reducing sugar (32.05 - 41.41%), soluble solids (68.4 - 72.18 °Brix), consistency (0.33 - 0.44 N), total antioxidant potential (11.3 - 22.63%), and color (a* 7.56 - 9.49, and b* 8.63 - 10.49) increased during 1-year storage. The quality of the fruit jams studied was in accordance with the microbiological standards established by the Brazilian legislation. It was concluded that the mixed araça and marolo jam can be stored for 1 year without the addition of additives.

Comparison between freeze and spray drying to obtain powder Rubrivivax gelatinosus biomass

The use of colorants in products of animal origin is justified by the improvement in the color of foods since this attribute is considered a quality criterion. These additives can be produced using industrial effluents as substrates and appropriate organisms, such as Rubrivivax gelatinosus. Oxycarotenoids represent a class of carotenes responsible for the pigmentation of animals and vegetables. R. gelatinosus grows in fish industry effluent with the resulting production of a bacterial biomass containing oxycarotenoids. The purpose of this study was to compare the use of two drying processes - spray and freeze drying - to obtain powder biomass in terms of the process parameters (yield, productivity, and product recovery) and the product characteristics (color, proximate composition, and oxycarotenoids). No difference was detected in the yield between these techniques, while productivity was higher using spray drying. Higher product recovery and moisture were achieved with freeze drying, while ash was higher with spray drying. The freeze dried biomass was redder, darker and less saturated than the spray dried biomass. No difference in oxycarotenoids was detected between the biomasses. Although it results in lower recovery rate, spray drying was faster and more productive, and it provided the same yield as freeze drying, which makes it the method of choice for obtaining R. gelatinosus biomass.

Chemical characterization of the flour of peel and seed from two papaya cultivars

Papaya is among the currently most important tropical fruits grown in Brazil and in the world. The fruit is mainly consumed fresh although it offers many industrial products. The processing of this fruit, as well as its fresh consumption, results in large amounts of waste, such as peels and seeds. Papaya consumption is one of the causes of significant loss of food value; therefore, new aspects on the use of its waste as by-products, or in the production of food additives, or even the incorporation of its flour in food have aroused great interest because these are products of high nutritional value, and their use may be economically viable. The objective of this study was to produce and characterize peel and seed flours from two papaya cultivars (Havai and Calimosa) for their chemical constituents focusing on possible use in foods. The proximate and mineral composition, titratable acidity, soluble solids, pH, contents of vitamin C, and phenolic compounds were determined. According to the results obtained, the papaya peel and seed flours had high contents of protein and fiber and therefore can be used as alternative sources of nutrients and can also be added in foods avoiding waste and adding value to the fruit.

Main food sources of carotenoids, according to the purpose and degree of processing, for beneficiaries of the 'Bolsa Família' in Brazil

The intake of carotenoids is associated with antioxidant properties and some of these substances have activity of pro-vitamin A. This study aimed to estimate the intake of carotenoids (average values) by the Brazilian population focusing on beneficiaries of the 'Bolsa Família' Program and identify the dietary sources, according to the purpose and degree of processing and the inclusion of food additives. The database used is the personal food consumption module of the Household Budget Survey of 2008-2009, conducted by the Brazilian Institute of Geography and Statistics. The content of carotenoids in foods was obtained primarily from a National data source. Food products were classified into three categories: 1) fresh and minimally processed foods; 2) processed foods (containing food additives, except for flavoring and coloring agents); and 3) highly processed foods (containing flavoring and coloring agents). Insufficient intakes were identified for the conditional cash transfer program beneficiaries (3,547.1 µg). Fresh and minimally processed foods supplied between 48.6% (for girls) and 65.7% (for male adults) of pro-vitamin carotenoids. Processed foods were sources of between 55.5% and 57.0% of lutein + zeaxanthin for elderly and between 58.0% and 67.8% of lycopene for adults. Highly processed foods contributed to less than 5.0% of total carotenoids.

In vitro antioxidant, antimutagenic and antiproliferative activities of collagen hydrolysates of jumbo squid (Dosidicus gigas) byproducts

AbstractHydrolysates from two different jumbo squid byproducts (fins and arms), produced by trypsin and protease type XIV were compared on the basis of their antioxidant (DPPH and ABTS radical scavenging assays), antimutagenic (Ames test) and antiproliferative (Transformation cell proliferation in M12.C3F6 murine cells) activities. Jumbo squid arms had higher content of collagen than fins, and their hydrolysates had the highest antioxidant activity. Also, jumbo squid arm-derived collagen hydrolyzed with protease XIV showed the highest antimutagenic activity. The four hydrolysates obtained showed low antiproliferative activity, however they are susceptible for further studies to be applied as food additives.

Cytotoxic and genotoxic potential of powdered juices

Abstract Powdered juices are widely consumed by the population especially because of their convenient preparation, availability in various fruit flavors and low cost when compared to other industrialized beverages. They have complex formulation, consisting of several classes of food additives. However, there are no scientific studies on the toxicity of these foods. Thus, this study evaluated the toxicity at the cellular level of industrialized powdered juices of orange and guava flavors of three different food companies. This analysis was made using root meristem cells of Allium cepa L., at the exposure times of 24 and 48 hours, and two concentrations, 30 g/1000 mL, considered ideal for consumption according to the label of the products, and 30 g/500 mL. Both flavors of juices, of the three companies, in both concentrations and the two exposure times promoted significant antiproliferative effect to root meristem cells and caused a statistically significant number of mitotic spindle changes and micronuclei in cells of the test system used. Therefore, under the studied conditions, all the samples of juice powder exhibited cytotoxic and genotoxic potential.

Partikkelikokojakaumamenetelmän testaus INCA Feature

Tässä työssä testattiin partikkelikokojakaumien analysoinnissa käytettävää kuvankäsittelyohjelmaa INCA Feature. Partikkelikokojakaumat määritettiin elektronimikroskooppikuvista INCA Feature ohjelmaa käyttäen partikkeleiden projektiokuvista päällystyspigmenttinä käytettävälle talkille ja kahdelle eri karbonaattilaadulle. Lisäksi määritettiin partikkelikokojakaumat suodatuksessa ja puhdistuksessa apuaineina käytettäville piidioksidi- ja alumiinioksidihiukkasille. Kuvankäsittelyohjelmalla määritettyjä partikkelikokojakaumia verrattiin partikkelin laskeutumisnopeuteen eli sedimentaatioon perustuvalla SediGraph 5100 analysaattorilla ja laserdiffraktioon perustuvalla Coulter LS 230 menetelmällä analysoituihin partikkelikokojakaumiin. SediGraph 5100 ja kuva-analyysiohjelma antoivat talkkipartikkelien kokojakaumalle hyvin samankaltaisen keskiarvon. Sen sijaan Coulter LS 230 laitteen antama kokojakauman keskiarvo poikkesi edellisistä. Kaikki vertailussa olleet partikkelikokojakaumamenetelmät asettivat eri näytteiden partikkelit samaan kokojärjestykseen. Kuitenkaan menetelmien tuloksia ei voida numeerisesti verrata toisiinsa, sillä kaikissa käytetyissä analyysimenetelmissä partikkelikoon mittaus perustuu partikkelin eri ominaisuuteen. Työn perusteella kaikki testatut analyysimenetelmät soveltuvat paperipigmenttien partikkelikokojakaumien määrittämiseen. Tässä työssä selvitettiin myös kuva-analyysiin tarvittava partikkelien lukumäärä, jolla analyysitulos on luotettava. Työssä todettiin, että analysoitavien partikkelien lukumäärän tulee olla vähintään 300 partikkelia. Liian suuri näytemäärä lisää kokojakauman hajontaa ja pidentää analyysiin käytettyä aikaa useaan tuntiin. Näytteenkäsittely vaatii vielä lisää tutkimuksia, sillä se on tärkein ja kriittisin vaihe SEM ja kuva-analyysiohjelmalla tehtävää partikkelikokoanalyysiä. Automaattisten mikroskooppien yleistyminen helpottaa ja nopeuttaa analyysien tekoa, jolloin menetelmän suosio tulee kasvamaan myös paperipigmenttien tutkimuksessa. Laitteiden korkea hinta ja käyttäjältä vaadittava eritysosaaminen tulevat rajaamaan käytön ainakin toistaiseksi tutkimuslaitoksiin.