PRODUÇÃO DE BIODIESEL A PARTIR DE ÁCIDOS GRAXOS PROVENIENTES DO REFINO DE ÓLEOS VEGETAIS VIA CATÁLISE ÁCIDA HETEROGENEA E MICRO-ONDAS

This work presents the biofuel production results of the esterification of fatty acids (C12-C18) and high-acid-content waste vegetable oils from different soap stocks (soybean, palm, and coconut) with methanol, ethanol, and butanol by acid catalysis. We used Amberlyst-35 (A35) sulfonic resin as a heterogeneous acid catalyst and p-toluenesulfonic acid as a homogeneous catalyst for comparison. Both the heterogeneous (A35) and homogeneous (p-toluenesulfonic acid) reactions were performed with 5% w/w of catalyst. The final products were analyzed by proton nuclear magnetic resonance (1H NMR). The homogeneous catalyzed esterification of fatty acids with methanol, ethanol, and butanol produced esters with yields higher than 90%. In the reaction with fatty acids and methanol catalyzed by A35, the best results were achieved with lauric acid and methanol, with a yield of 97%. An increase in the hydrocarbon chain decreased the rate of conversion and yield for stearic acid with methanol, which was 90%. Maximum biodiesel production was achieved from coconut and soybean soap stocks and methanol (96%-98%), which showed conversions very close to those obtained from their respective fatty acids. Microwave irradiation reduced the reaction time from 6 to 1 h in the esterification reaction of fatty acids with butanol.

Val av species och bestämdhetsform i ett test för finska grundskolelever

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Catalytic transformations of fatty acid derivatives for food, oleochemicals and fuels over carbon supported platinum group metals

Växtoljor som utgör en förnybar naturresurs används som sådana eller i modifierade former i många industriella processer, som är av stor betydelse för vårt vardagliga liv. Växtoljor används i livsmedel, i kemiska och farmaceutiska produkter, i textilindustrin, för framställning av färgämnen och beläggningsmaterial samt som miljövänliga bränslekomponenter. Fetter och oljor hör till de äldsta kemiska komponenterna som utnyttjas av människan. De består huvudsakligen av glycerolestrar och fettsyror. Fetter och oljor har typiskt en kolkedja med kol-koldubbelbindningar samt karboxyl- och estergrupper, som kan genom hydrering eller dekarboxylering konverteras till nyttiga och miljövänliga produkter med hjälp av ädelmetallkatalysatorer. Aktivt kol (C) används som bärare på katalysatorerna. Väteaddition, d.v.s. hydrering av växtoljor har varit föremål för omfattande forskning i över hundra års tid. Hydreringen är en viktig process, för den tillämpas på produktion av fetter och margarin. Omättade fettsyror hydreras traditionellt på nickelbaserade heterogena katalysatorer. Samtidigt med en partiell hydrering av fettsyrorna och fettsyraestrarna som har två dubbelbindningar pågår också isomeringsreaktioner, vilka ger cis- och transisomerer av reaktantmolekylerna. Den största nackdelen med nickelkatalysatorerna är deras giftighet samt bildning av ohälsosamma transisomerer i reaktionsprodukterna. Dessutom deaktiveras nickelkatalysatorn snabbt p.g.a. att nickeltvålar bildas i reaktionsblandningen. Platinabaserade katalysatorer lider däremot inte av dessa begränsningar. Metaller i platinagruppen i det periodiska systemet studerades i detalj för att avslöja kinetiska effekter i hydreringen av cis-metyloleat. Palladium, rutenium, rhodium, platina och iridium användes som katalytiska metaller. Metallhalten på aktivkolbärare var 1 vikt-%. De olika platinametallerna undersöktes för att kartlägga konkurrerande hydrerings- och isomeringsrutter på metallerna. Det visade sig att metallerna i andra raden av det periodiska systemet (Ru, Rh, Pd) är aktivare i isomeringsprocesserna, medan metallerna i tredje raden (Ir, Pt) har en lägre aktivitet. Pd/C valdes bland platinametallerna, för att den är attraktiv ur ekonomisk synvinkel och den är mycket aktiv och selektiv, speciellt jämfört med nickel. Tyngdpunkten i arbetet var utvecklingen av en alternativ, palladiumbaserad hydreringsteknologi som skulle ersätta den traditionella teknologin som är baserad på användningen av nickelkatalysatorer. Palladiumbaserade katalysatorer kan återcirkuleras, de är aktivare och mera resistenta mot syror och de bildar mindre mängder av skadliga transisomerer. För att denna teknologi skall bli ekonomiskt hållbar och konkurrenskraftig, måste den basera sig på de bästa möjliga katalysatorerna, vilket innebär att en optimal kombination av hög aktivitet och selektivitet samt en lång livstid för katalysatorn krävs. Därför inkluderades teknologiska aspekter kraftigt i forskningen. Mycket arbete satsades på design av palladium på en mesoporös kolbärare och undersökning av korrelationerna mellan katalysatorns egenskaper och dess aktivitet i isomeriseringsreaktionerna och i hydreringen av kol-koldubbelbindningarna i reaktantmolekylen. Katalysatorerna karakteriserades med många fysikaliska och kemiska metoder (transmissionselektronmikroskopi (TEM), röntgendiffraktion (XRD), röntgenfotoelektronspektroskopi (XPS), temperaturprogrammerad reduktion (TPR), temperaturprogrammerad desorption (TPD) av kolmonoxid, kemisorption av kolmonoxid, fysisorption av kväve). Temperaturens, vätetryckets och katalysatorkoncentrationens inverkan på fettsyra- och isomersammansättningen hos de hydrerade oljorna bestämdes under kinetiska betingelser, i frånvaro av massöverföringseffekter. Syreavspjälkning genom fullständig dekarboxylering av karboxylgruppen i fettsyramolekylen är det hittills bästa sättet att framställa miljövänlig dieselolja, eftersom linjära paraffiner fås som reaktionsprodukter och en tillsats av dyr vätgas undviks. Deoxygeneringen undersöktes systematiskt på en Pd/C-katalysator (Sibunit) genom att använda mättade fettsyror C16-C20 och C22 som råvara. Produktmolekylen blev en dieselliknande kolvätemolekyl, med en kolatom färre än i utgångsmolekylen. Lika stora dekarboxyleringshastigheter observerades för rena, mättade fettsyror. En jämförelse av deoxygenereringshastigheterna för stearin-, olein- och linolsyra som råvara vid 300oC i närvaro av 1-volymprocent väte på mesoporös Pd/C (Sibunit) avslöjade att katalysatorns aktivitet och selektivitet ökade med en ökande mättningsgrad av reaktantmolekylen. Då stearinsyra användes som utgångsmolekyl, bestod huvudprodukterna av önskade C17-kolväten, medan mängden av aromatiska C17-komponenter ökade, då olein- och linolsyra användes som utgångsmolekyler. Katalysatordeaktiveringen var relativt påfallande vid deoxygeneringen av linolsyra så att endast 3% av fettsyrorna omsattes till produkter i 330 min. Deaktiveringen orsakades av aromatiska C17-komponenter samt av fettsyradimerer, som bildades via en Diels-Alderreaktion. Hydreringen av omättade fettsyror kan därför rekommenderas som ett primärt kemiskt steg i framställningen av miljövänliga dieselprodukter. Målet var också att öka förståelsen av palladiummetallernas roll i nanoskala, speciellt effekten av metallpartiklarna i katalytisk hydrering och deoxygenering. Pd/C-katalysatorer med lika stora halter av Pd syntetiserades och metallens dispersion på bärarmaterialet varierades systematiskt genom en kontrollerad uppväxt av palladiumnanopartiklar på aktiv kolbärare. Metalldispersionens effekt på hydrerings-hastigheten och cis-transförhållandet undersöktes i detalj. En optimal metalldispersion som gav den högsta dekarboxyleringshastigheten hittades. Massöverföringens inverkan på reaktionens hastighet studerades experimentellt och temperaturprogrammerad desorption av kolmonoxid från katalysatorytan undersöktes ingående. Hydrering av växtoljor genomfördes under satsvisa och kontinuerliga betingelser. Både finfördelat Pd/C och katalysatorgranulat användes i experimenten. Ett av målen med arbetet var uppskalningen av hydreringsprocesserna. Med tanke på stora produktionsvolymer var det logiskt att undersöka kontinuerliga hydrerings- och dekarboxyleringsteknologier. En kontinuerlig packad bäddreaktor studerades i laboratorieskala, vilket gav viktig information om katalysatorns långtidsstabilitet och deaktivering. Effekten av rena fettsyror och triglycerider som råvara samt metallpartikelstorleken och palladiumhalten studerades med hjälp av den kontinuerliga reaktorn. Produktionskapaciteten som erhölls med satsvis och kontinuerlig drift jämfördes. Dekarboxyleringen av stearinsyra undersöktes också i en kontinuerlig packad bädd. Omsättningsgraden blev 15% för en stabil katalysator.

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In vitro development and acclimatization of dendezeiro (Elaeis guineensis)

Fruits and almond from the dendezeiro, oil palmbelonging to the Elaeis genus,are widely used for the production of cookingoils or for the pharmaceutical and cosmetic industries.In the last decade, this oil palm also emerged as a promising source for commercialbiofuel production. This study evaluated the effect of different culture media, MS (MURASHIGUE AND SKOOG) and Y3 (EEUWENS)and carbohydrates duringin vitro germination of zygotic embryos, the effect of growth regulators GA3, NAA and BA Ponin vitro seedling development, and the survival rate of acclimatized seedlingsof Manicoré hybrid (Elaeis oleifera x E. guineensis). Zygotic embryos were inoculated on MS and modified Y3 media, supplemented with different sucrose concentrations (30, 45, and 60 gL-1) or sorbitol (36 gL-1), and the germination rate was evaluated after 30 days. Subsequently, seedlings were transferred to modified Y3 culture medium supplemented with differentGA3 concentrations (3.5 and 7 mgL-1) or without it, combined or not with 1 mgL-1 of NAA, 5 mgL-1 of BAP.The highest germinationpercentage of germinated embryos (92%) was observed in MS medium supplemented with 36 gL-1 sorbitol. Culture media supplemented with growth regulatorsGA3, NAA and BAP promoted greater shoot lengththan control media. Rooted seedlings showed high survival percentage (85%) during acclimatization.

FRUIT MORPHOLOGY AND PRODUCTIVITY OF BABASSU PALMS IN NORTHERN MINAS GERAIS STATE, BRAZIL1

ABSTRACT The objectives of this study were to morphologically characterize fruits of the babassu palm tree (Attalea vitrivir) and to estimate their productivity in the north of Minas Gerais State, Brazil. Twenty mature fruits were collected from 10 plants in three different areas in Januária, Minas Gerais. Eighteen biometric parameters of the fruits were measured, the oil contents of the seeds was determined, the adherence to normal distribution was evaluated, distribution frequencies were evaluated and the effects of individuals and areas on the variables and the correlations between them were analyzed. The production of fruit bunches per plant and the number of fruits per bunch from 10 plants were quantified in three areas and the potential production under both natural harvesting and cultivation conditions were estimated. Significant differences were found among all of the biometric parameters examined between the different individuals and the different areas, which shows wide morphological variability in the fruits. The average oil content was 45.7%, but with significant differences among individuals. The observed variability favors the selection of productive individuals in genetic improvement programs. The potential productivity of endocarps and oil based on a density of 400/plants per hectare would be respectively 6.4 and 1.2 tons/ha, which indicates the possibility of using A. vitrivir for producing charcoal, bio fuels, and for carbon fixation.

EVALUATION OF THE POTENTIAL OF SEED RAIN AS AN ALTERNATIVE FOR FOREST RESTORATION IN PERMANENT PRESERVATION AREAS1

ABSTRACT The ecological restoration of degraded areas using seeds collected in forest remnants has shown significant results. This study was developed to verify the potential of seed rain to regenerate forest fragments of a Permanent Preservation Area (PPA) in the Apa River Basin which is located in the southwestern portion of the Mato Grosso do Sul state, Brazil. To develop the study, we installed 25 collectors measuring 1 m2 each, which were systematically distributed on an area of 1.5ha. Seed gathering was conducted in a monthly basis throughout the year of 2013. A total of 26.411 propagules were identified and distributed among 50 species, 45 genera and 32 families. In terms of the propagules distribution, 70.51% were identified as trees, 22.8% as lianas, 6.5% as shrubs, 0.1 as herbaceous, 0.05% as palm and 0.05% could not be classified. The value for the Shannon Diversity Index was (H') = 1.67 and the Pielou Evenness index was (J) = 0.42. These results indicate that the seeds rain has low species diversity with the abundance of a few species. The overall results suggest that seed rain can be a potential technique for restoration of the PPAs and other forested areas. However, it is necessary to enhance the diversity of tree species.

EFFECTS OF HARVESTING ON LEAF PRODUCTION AND REPRODUCTIVE PERFORMANCE OF Copernicia prunifera (Mill.) H.E. Moore1

ABSTRACT This work aimed to evaluate the consequences of the monthly extraction of immature leaves in survival, leaf production and reproductive performance ofCopernicia prunifera H. E. Moore palm, popularly known as carnaúba. One hundred sixty reproductive adult palms were monitored for 17 months in four extractive communities located at the coast of the state of Piauí. As a result, it was observed that leaves, flowers, fruits and seeds production were reduced in the palm submitted to 50% or 75% monthly extraction. Higher levels of extraction were followed by smaller levels in seed germination. No deaths were observed even in the group subjected to 75% monthly leaves exploration. In order not to produce damage to palm trees development it is suggested that leaf extraction rate should not exceed 25% monthly as well as pausing of extractive activity preferentially during fruit maturation.

Combustion properties of biomass residues rich in phosphorus

Tillgången på traditionella biobränslen är begränsad och därför behöver man ta fram nya, tidigare outnyttjade biobränslen för att möta de uppställda CO2 emissionsmålen av EU och det ständigt ökande energibehovet. Under de senare åren har intresset riktats mot termisk energiutvinning ur olika restfraktioner och avfall. Vid produktion av fordonsbränsle ur biomassa är den fasta restprodukten ofta den största procesströmmen i produktionsanläggningen. En riktig hantering av restprodukterna skulle göra produktionen mera lönsam och mer ekologiskt hållbar. Ett alternativ är att genom förbränning producera elektricitet och/eller värme eftersom dessa restprodukter anses som CO2-neutrala. Målsättningen med den här avhandlingen var att studera förbränningsegenskaperna hos några fasta restprodukter som uppstår vid framställning av förnybara fordonsbränslen. De fyra undersökta materialen är rapskaka, palmkärnskaka, torkad drank och stabiliserat rötslam. I studien används ett stort urval av undersökningsmetoder, från laboratorieskala till fullskalig förbränning, för att identifiera de huvudsakliga utmaningarna förknippade med förbränning av restprodukterna i pannor med fluidiserad bäddteknik. Med hjälp av detaljerad bränslekarakterisering kunde restprodukterna konstateras vara en värdefull källa för värme- och elproduktion. Den kemiska sammansättningen av restprodukterna varierar stort jämfört med mera traditionellt använda biobränslen. En gemensam faktor för alla de studerade restprodukterna är en hög fosforhalt. På grund av de låga fosforkoncentrationerna i de traditionella biobränslena har grundämnet hittills inte ansetts spela någon större roll i askkemin. Experimenten visade nu att fosfor inte mera kan försummas då man studerar kemin i förbränningsprocesser, då allt flera fosforrika bränslen tränger in på energimarknaden.

Soursop seedlings: emergence and development under different cultivation environments and substrates – Part I

ABSTRACT Seedling quality is crucial to obtain vigorous plants in the field. This study aims to evaluate the emergence and development of soursop seedlings in different substrates in protected environments. The experiment was conducted at the Mato Grosso do Sul State University and carried out using five protected environments: greenhouse, greenhouse with thermo-reflective screen, nursery with monofilament screen, nursery with thermo-reflective screen, and nursery with palm thatch. The substrates (S) consisted of cattle manure (M), humus (H), cassava branches (C), and vermiculite (V) as in the following ratios: S1 = H + V (1:3), S2 = H + V (1:1), S3 = H + V (3:1), S4 = H + C (1:3), S5 = H + C (1:1), S6 = H + C (3:1), S7 = M + V (1:3), S8 = M + V (1:1), S9 = M + V (3:1), S10 = M + C (1:3), S11 = M + C (1:1), S12 = M + C (3:1), S13 = H + M + V (1:1:1), S14 = H + M + C (1:1:1), and S15 = H + M + V + C (1:1:1:1). For the statistical analysis, each of those environments was considered as an experiment in which was used the completely randomized design; subsequently, it was performed a combined analysis of them. In summary, the greenhouse with thermo-reflective screen and combined substrates with “M + V” promote greater development of the seedlings. High concentrations of “V” or “C” cause no beneficial effect on soursop seedlings.

Svenskans ordföljd hos finska universitetsstuderande. Deklarativ och procedural kunskap om ordföljden

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Greenhouse gas emissions from peat and biomass-derived fuels, electricity and heat — Estimation of various production chains by using LCA methodology

More discussion is required on how and which types of biomass should be used to achieve a significant reduction in the carbon load released into the atmosphere in the short term. The energy sector is one of the largest greenhouse gas (GHG) emitters and thus its role in climate change mitigation is important. Replacing fossil fuels with biomass has been a simple way to reduce carbon emissions because the carbon bonded to biomass is considered as carbon neutral. With this in mind, this thesis has the following objectives: (1) to study the significance of the different GHG emission sources related to energy production from peat and biomass, (2) to explore opportunities to develop more climate friendly biomass energy options and (3) to discuss the importance of biogenic emissions of biomass systems. The discussion on biogenic carbon and other GHG emissions comprises four case studies of which two consider peat utilization, one forest biomass and one cultivated biomasses. Various different biomass types (peat, pine logs and forest residues, palm oil, rapeseed oil and jatropha oil) are used as examples to demonstrate the importance of biogenic carbon to life cycle GHG emissions. The biogenic carbon emissions of biomass are defined as the difference in the carbon stock between the utilization and the non-utilization scenarios of biomass. Forestry-drained peatlands were studied by using the high emission values of the peatland types in question to discuss the emission reduction potential of the peatlands. The results are presented in terms of global warming potential (GWP) values. Based on the results, the climate impact of the peat production can be reduced by selecting high-emission-level peatlands for peat production. The comparison of the two different types of forest biomass in integrated ethanol production in pulp mill shows that the type of forest biomass impacts the biogenic carbon emissions of biofuel production. The assessment of cultivated biomasses demonstrates that several selections made in the production chain significantly affect the GHG emissions of biofuels. The emissions caused by biofuel can exceed the emissions from fossil-based fuels in the short term if biomass is in part consumed in the process itself and does not end up in the final product. Including biogenic carbon and other land use carbon emissions into the carbon footprint calculations of biofuel reveals the importance of the time frame and of the efficiency of biomass carbon content utilization. As regards the climate impact of biomass energy use, the net impact on carbon stocks (in organic matter of soils and biomass), compared to the impact of the replaced energy source, is the key issue. Promoting renewable biomass regardless of biogenic GHG emissions can increase GHG emissions in the short term and also possibly in the long term.

Floristic composition and topographic variation in a tidal floodplain forest in the Amazon Estuary

Slight topographic variations appear to exert dramatic effects on the structure of forests subject to inundation. In a late successional tidal floodplain forest near the Amazon port of Belém, Brazil, we examined these effects by studying floristic composition along a topographic gradient. We predicted that, relative to high sites, low sites would be characterized by high representation of life forms and taxa characteristic of inundated sites. We found striking variations in floristic composition along a slight topographic gradient. In comparison with topographically high sites, low sites were characterized by a high representation of Palm trees (Arecaceae), low diversity of trees and lianas, and high plant density. These variations appear to reflect edaphic limitations imposed by periodic flooding. The high spatial variation in floristic composition found in this ecosystem suggest caution in implementing intensive forms of agriculture.

Composição florística de veredas no Município de Uberlândia, MG

Foram estudadas quatro comunidades vegetais de veredas no Municipio de Uberlândia, MG, durante dois anos com o objetivo de conhecer sua composição florística. As veredas foram percorridas por meio de trilhas estabelecidas, ao acaso, passando pela borda (local de solo mais seco), meio (solo medianamente úmido) e fundo (solo saturado com água). A freqüência de visitas à cada vereda foi mensal e o material botânico coletado foi incluído no Herbarium Uberlandense (HUFU). A identificação das espécies foi feita utilizando-se chaves analíticas, consultas a especialistas de várias famílias e/ou comparação com exsicatas devidamente identificadas e depositadas nos herbários HUFU, IBGE e UB. No levantamento florístico foram registradas 526 espécies, 250 gêneros e 89 famílias. As cinco famílias com maior número de espécies foram Poaceae (64), Asteraceae (63), Cyperaceae (54), Melastomataceae (27) e Fabaceae (23). Na zona de borda da vereda foram amostradas 361 espécies sendo 168 exclusivas deste ambiente. Um total de 300 espécies ocorreu na zona de meio, sendo 75 exclusivas. Na zona de fundo ocorreu a menor riqueza específica, compreendendo um total de 136 espécies com 52 exclusivas desta área. A grande riqueza florística encontrada nas veredas amostradas deve-se, possivelmente, às diferenças edáficas, especialmente aquelas relacionadas com a umidade.

Mental rotation of anthropoid hands: a chronometric study

It has been shown that mental rotation of objects and human body parts is processed differently in the human brain. But what about body parts belonging to other primates? Does our brain process this information like any other object or does it instead maximize the structural similarities with our homologous body parts? We tried to answer this question by measuring the manual reaction time (MRT) of human participants discriminating the handedness of drawings representing the hands of four anthropoid primates (orangutan, chimpanzee, gorilla, and human). Twenty-four right-handed volunteers (13 males and 11 females) were instructed to judge the handedness of a hand drawing in palm view by pressing a left/right key. The orientation of hand drawings varied from 0º (fingers upwards) to 90º lateral (fingers pointing away from the midline), 180º (fingers downwards) and 90º medial (finger towards the midline). The results showed an effect of rotation angle (F(3, 69) = 19.57, P < 0.001), but not of hand identity, on MRTs. Moreover, for all hand drawings, a medial rotation elicited shorter MRTs than a lateral rotation (960 and 1169 ms, respectively, P < 0.05). This result has been previously observed for drawings of the human hand and related to biomechanical constraints of movement performance. Our findings indicate that anthropoid hands are essentially equivalent stimuli for handedness recognition. Since the task involves mentally simulating the posture and rotation of the hands, we wondered if "mirror neurons" could be involved in establishing the motor equivalence between the stimuli and the participants' own hands.