Recuperação de metais de catalisadores mássicos e monometálicos

This work presents a study on the dissolution of some commercial monometallic and non-supported deactivated catalysts in HF + H2O2 mixtures (and, eventually, other media) under mild experimental conditions, after a previous oxidation step. The samples were neither crushed nor grinded. The best experimental conditions were dependent on the nature of the support and of the active phase. For example, the Pt/Al2O3 catalyst was dissolved in about 10 minutes, without agitation and heating; however, dissolution of the Pd/Al2O3, Ni/Al2O3, Ni/SiO2, Cu/Al2O3 and V2O5 samples required a temperature of 60 ºC and an agitation of 400 rpm. A careful addition of a NaOH solution allowed a quantitative precipitation of aluminium as criolite (Na3AlF6) or precipitation of Si as Na2SiF6; NaF was obtained as a by-product. As expected, processing of Pd/C, V2O5 and CuO.Cr2O3 samples was relatively simple. Metals recovery from catalysts reached a quantitative level in all samples studied; it is particularly interesting that platinum and palladium could be easily recovered in a single step process, thus separing them from aluminium.

Utilização de zeólitas sintetizadas a partir de xisto retortado na remoção de arsênio em águas contaminadas

The solid by-product of the oil shale processing (PETROBRAS - Brazil) was used as raw material to synthesize zeolites A and faujasite. Alkaline fusion followed by hydrothermal treatment was the synthesis procedure used, and five different starting material compositions were obtained. The more crystalline zeolite-type materials synthesized, the pretreated oil shale ash and commercial zeolites were used as adsorbents in the purification of pollutant solutions with arsenic. The zeolite-type material composed of a mixture of zeolite A (42.6%) and faujasite (52.9%) presented an ion exchange capacity comparable to the pure zeolites A and faujasite, much better than the pretreated ash.

Composição química de um resíduo alcalino da indústria de papel e celulose (DREGS)

Dregs is an alkaline solid by-product generated in the cellulose manufacturing industry that could be used to correct soil acidity. The present study aimed to evaluate the chemical composition of this product and some of its properties. The dregs presented 354 g kg-1 of calcium, neutralization capacity of 80.3%, and pH 10.7, besides low concentration of sodium (10.2 g kg-1), lead (62.9 mg kg-1) and cadmium (5.6 mg kg-1). Thus, it is a product that can safely be used to increase the soil pH.

Sellutehtaan sekundäärilämmön käytön tehostaminen

Energia on olennainen osa nykyaikaisen sellutehtaan prosesseja, joissa kuluu suuria määriä lämpöä ja sähköä. Pyrittäessä entistä kustannustehokkaampaan liiketoimintaan nousee energiatehokkuus usein mielenkiinnon kohteeksi. Pitkälle viety sähkön ja lämmön yhteistuotanto yhdistettynä korkeaan biopolttoaineiden osuuteen energian tuotannossa luovat pohjan tälle pyrkimykselle. Sekundäärilämpöä syntyy prosessien sivutuotteena ja sen mahdollisimman suuri hyödyntäminen on yksi keino päästä kohti parempaa energiatehokkuutta. Joissain tapauksissa sillä voidaan korvata jopa primäärienergian käyttöä ja mahdollisesti pienentää ostopolttoaineiden tarvetta. Diplomityössä tutkitaan sellutehtaan sekundäärilämpöjärjestelmän toimintaa, ohjausta ja energiankulutusta. Sekundäärilämpöjärjestelmästä muodostetaan taseet talvitilanteessa ja samalla etsitään mahdollisia uusia talteenotettavia sekundäärilämpövirtoja tai vastaavasti käyttökohteita. Lisäksi päivitetään sekundäärilämpöjärjestelmän raportoinnin ja ohjauksen työkaluja nykytilannetta vastaavaksi. Työn aikana kiinnitetään myös huomiota järjestelmän toimintaan muutostilanteissa, joissa kaikkia vesijakeita ei välttämättä ole saatavilla prosessin tarvitsemia määriä.

Composição volátil dos defeitos intrínsecos do café por CG/EM-headspace

About 20% of Brazilian raw coffee production is considered inappropriate for exportation. Consequently, these beans are incorporated to good quality beans in the Brazilian market. This by-product of coffee industry is called PVA due to the presence of black (P), green (V) and sour (A) defective beans which are known to contribute considerably for cup quality decrease. Data on the volatile composition of Brazilian defective coffee beans are scarce. In this study, we evaluated the volatile composition of immature, black-immature, black defective beans and PVA compared to good quality beans. Potential defective beans markers were identified.

Caracterização de subproduto da indústria de alumínio e seu uso na retenção de cádmio e chumbo em sistemas monoelementares

The present work aimed to characterize an aluminum industry by-product in natura (L.A. nat) and after phosphate and thermal pretreatments; evaluate the adsorption/desorption capacity of Cd and Pb by this L.A. nat form and after the aforementioned pretreatments, comparing them with an in natura iron mining by-product (L.F. nat). The L.A. nat presented a high pH as well as a high Na concentration and also an oxide-rich mineralogy. Pretreatment of the by-product had no significant effect upon Cd and Pd adsorption/desorption. The L.A. nat performed better than the L.F. nat as an Cd and Pb adsorbent.

Development and validation of a LC-method for the determination of phenols in a pharmaceutical formulation containing extracts from Stryphnodendron adstringens

A sensitive RP-HPLC method with UV detection successfully measured phenol(s) in an ointment containing 3% Stryphnodendron adstringens extract. Chromatography used acetonitrile (0.05% trifluoroacetic acid):water (0.05% trifluoroacetic acid) (v/v), flow rate 0.8 mL min-1. Quantitation was accomplished by the external-standard method. Linearity for 2.00 to 16.00 μg mL-1 (gallic acid) and 1.14 to 18.24 μg mL-1 (gallocatechin) was established. Intra- and inter-day precision levels were under 5%. LOD and LOQ were 0.231 and 0.770 μg mL-1 (gallic acid) and 0.151 and 0.504 μg mL-1 (gallocatechin), respectively. Determination of phenols was unaffected by product excipients.

Aproveitamento da glicerina proveniente da produção de biodiesel na obtenção de híbrido de caulinita para adsorção de Cr3+

The aim of this work was to contribute to the creation of new ways of treating wastewater contaminated with Cr3+, based on solid-liquid adsorption. An adsorbent material was prepared by functionalization of kaolinite with glycerin biodiesel by-product. This material was tested for adsorption performed using a batch method, and results showed that inclusion of glycerin in the structure of kaolinite led to a significant increase in the capacity of Cr3+ adsorption. This contributes to the allocation of by-product of biodiesel and to the treatment of effluents from tanneries.

Vähempiarvoisen kalan käsittelyketjut ja hiilijalanjälki

The condition of Baltic Sea has weakened considerably because of eutrophication which has caused massive increase of devalued fish. The condition of Baltic Sea can be helped by fishing these fish. This study handles three different ways to approach those fish utilizations and counts carbon footprint for those three chains. Environmental point of views are also examined. There are three different fish processing chains. Every processing chain begins with fishing the fish in Baltic Sea. After that the fishes are prepared by crushing and some formic acid is added to ensure preservation. In the first processing chain the fishes are processed as biodiesel. The waste from the biodiesel process is taken to the anaerobic digestion and the forming methane is used as energy. In the second chain the fishes are taken straight to the anaerobic digestion after preparing. In the third chain, the fish will be first prepared and then taken to fur farms as forage. The carbon footprint has been calculated for 1000 kg fish. The carbon footprint in the first chain is 164-178 kg CO2e, in the second chain 313 – 333 kg CO2e and in the third chain 363 kg CO2e. In the processing chains the bioenergy is produced from the biodiesel, anaerobic digestion and from the glycerol, which is by-product of the biodiesel. The energy produced from the biodiesel is so-called emission neutral, which is not taken into account when calculating emissions. The energy is used to compensate the emissions caused by fossil fuels. The PAS 2050 was used to calculate the carbon footprint. Only carbon dioxide and methane were used when calculating the carbon footprint.

Uutto-olosuhteiden vaikutus kasviperäisen indigon saantoon

Indigo on väriaine, jota valmistetaan petrokemianteollisuuden välituotteena syntyvästä aniliinista. Indigolla on kuitenkin pitkä historia. Sitä on valmistettu perinteisesti eri viljelykasveista, joista Euroopassa merkittävin on ollut morsinko. Luonnonmukaisten tuotteiden suosion kasvaessa on ryhdytty selvittämään morsingon viljelyn potentiaalia. Viljelyn kannattavuuden kannalta olennaista on kasvin lehdissä esiintyvien indigon esiasteiden mahdollisimman täydellinen eristäminen. Indigoa tuotetaan uuttamalla indigon esiasteet veteen. Esiasteet hajoavat synnyttäen indoksyyliä, josta hapen vaikutuksella muodostuu indigoa. Syntynyt indigo saostuu ja laskeutuu pohjalle. Samalla kuitenkin tapahtuu epätoivottuja sivureaktioita, jotka vähentävät indigon saantoa. Tutkimuksen tavoitteena oli laboratorio- ja kenttäkokeiden avulla löytää indigon saantoa parantavat uutto-olosuhteet. Kokeiden perusteella havaittiin, että indigon saantoon vaikuttavat positiivisesti pH:n laskeminen, lämpötilan nostaminen, morsingon lehtien pilkkominen ja uuttoliuoksen sekoittaminen. Uuttoliuoksen suolapitoisuuden havaittiin puolestaan vaikuttavan indigon saantoon negatiivisesti. Laboratoriokokeiden perusteella havaittu pH:n laskemisen vaikutus indigon saantoon todistettiin myös kenttäolosuhteissa. Kokeiden havaintojen perusteella esitettiin olosuhteiden indigosaantoa parantavien vaikutusten johtuvan kahdesta tekijästä: indoksyylin stabiloitumisesta happamassa ympäristössä, jolloin sivureaktioiden osuus vähenee, sekä aineensiirron paranemisella sekoituksen, faasien rajapinnan kasvamisen ja etenkin lehtien vahakerroksen rikkoutumisen kuuman veden ja hapon vaikutuksesta.

Humic substances from sediments of Lobos Pond (Argentina). Isolation, characterization and limnological implications

Humic substances (HS) were isolated from the sediments of Lobos Pond (Argentina) using mild conditions to preserve their native structure. The HS (humic and fulvic acids) were characterized by means of elemental analysis and FTIR spectroscopy. Also a by-product obtained during fulvic acids (FA) fractionation (an amorphous white solid residue) was analyzed. Results revealed possible interactions between FA and inorganic-organic substances that may have implications referring to bioavailability. Other limnological implications, such as autochtonous origin of HS linked with the hydrology, and change of pH during stormy weather that affects HS interactions, are discussed.

Sähkön ja lämmön yhteistuotannon mahdollisuudet vaneritehtaan yhteydessä

Tämän diplomityön tarkoituksena oli tehdä sähkön ja lämmöntuotannon kannattavuustarkastelu erään esimerkkitehtaan näkökulmasta. Tarkoitus oli selvittää onko vaneritehtaalla edellytyksiä investoida sähköä ja lämpöä tuottavaan yhteistuotantolaitokseen, vai onko edullisempaa tuottaa itse ainoastaan valmistusprosessin kannalta välttämätön lämpöenergia ja ostaa tarvittava sähköenergia ulkoiselta toimijalta. Johdantona on tarkasteltu ensin vanerin valmistusprosessia ja prosessissa syntyviä sivutuotteita. Toisena osiona on pyritty hahmottamaan vanerinvalmistuksessa syntyvien sivutuotteiden määriä ja ominaisuuksia niiden polttoainekäyttöä silmällä pitäen. Lopuksi johdannossa on perehdytty mahdollisiin tekniikoihin, joilla sähkön ja lämmön yhteistuotanto vaneritehtaan yhteydessä olisi mahdollista. Johdannossa käsiteltävät asiat perustuvat teorialähteisiin. Aineisto ja menetelmät osiossa on tarkasteltu esimerkkitehdasta voimalaitoksen sijoituskohteena. Osiossa on perehdytty prosessin sivutuotteiden määrään ja energian kulutukseen. Näiden seikkojen perusteella on tehtaan yhteyteen mitoitettu sähköä ja lämpöä tuottavia yhteistuotantolaitosesimerkkejä. Lopuksi tuloksissa on tarkasteltu yhteistuotantolaitoksien kannattavuutta vaneritehtaan yhteydessä ja tutkittu kannattavuuteen vaikuttavia tekijöitä.

SPECIES RICHNESS AND ABUNDANCE OF LOW-TRUNK HERB EPIPHYTES IN RELATION TO HOST TREE SIZE AND BARK TYPE, EASTERN AMAZONIA

ABSTRACTThe composition and structure of the low-trunk epiphytic herb assembly as well as its vertical distribution were studied. DBH of host tree and bark type influence species richness and abundance in a nonlooded lowland tropical rainforest in Eastern Amazonia (1º57’36"S 51º36’55"W). A total of 37 epiphytic herb species were identified, among which 60% were Araceae. Species richness and abundance of epiphytic herbs showed tendency of positive correlation with host tree size and no relationships with bark type. Low positive correlation may be a by-product of the predominance of trees with smaller diameter in our sample rather than a reflection of neutral relationship. The absence of relationships with bark type may be partially explained by the large number of secondary, generalist, hemi-epiphytes and also may reflect the absence of suitable substrate in trees with smaller diameter.

Alternative liquid biofuels for lime kilns

Causticizing plant is an important part of kraft pulp mill. It uses green liquor from recovery boiler as a raw material and consumes lime to produce white liquor, which is an important chemical used in pulping. Lime kiln is a part of the causticizing process. It is used to convert lime mud, a by-product obtained from the causticizing back to lime in high temperatures. This conversion requires a lot of energy. The most common fuels used as energy source for lime kiln are heavy fuel oil and natural gas. In a modern pulp mill lime kiln is the only user of significant amount of fossil fuels. Replacing fossil fuels with biofuels can have prominent economical and environmental benefits. Interest in using biofuels as energy source of lime kiln has become a worldwide issue in the recent years. However fuels used for lime kiln have a lot of certain requirements. The purpose of this work is to study the required characteristics from liquid fuels used in pulp mill lime kiln and to map suitable liquid biofuels already available in the markets. Also taxation of liquid biofuels compared to heavy fuel oil in Finland, Sweden and Germany is shortly introduced.

Production of Mg(OH)2 from Mg-silicate rock for CO2 mineral sequestration

Sequestration of carbon dioxide in mineral rocks, also known as CO2 Capture and Mineralization (CCM), is considered to have a huge potential in stabilizing anthropogenic CO2 emissions. One of the CCM routes is the ex situ indirect gas/sold carbonation of reactive materials, such as Mg(OH)2, produced from abundantly available Mg-silicate rocks. The gas/solid carbonation method is intensively researched at Åbo Akademi University (ÅAU ), Finland because it is energetically attractive and utilizes the exothermic chemistry of Mg(OH)2 carbonation. In this thesis, a method for producing Mg(OH)2 from Mg-silicate rocks for CCM was investigated, and the process efficiency, energy and environmental impact assessed. The Mg(OH)2 process studied here was first proposed in 2008 in a Master’s Thesis by the author. At that time the process was applied to only one Mg-silicate rock (Finnish serpentinite from the Hitura nickel mine site of Finn Nickel) and the optimum process conversions, energy and environmental performance were not known. Producing Mg(OH)2 from Mg-silicate rocks involves a two-staged process of Mg extraction and Mg(OH)2 precipitation. The first stage extracts Mg and other cations by reacting pulverized serpentinite or olivine rocks with ammonium sulfate (AS) salt at 400 - 550 oC (preferably < 450 oC). In the second stage, ammonia solution reacts with the cations (extracted from the first stage after they are leached in water) to form mainly FeOOH, high purity Mg(OH)2 and aqueous (dissolved) AS. The Mg(OH)2 process described here is closed loop in nature; gaseous ammonia and water vapour are produced from the extraction stage, recovered and used as reagent for the precipitation stage. The AS reagent is thereafter recovered after the precipitation stage. The Mg extraction stage, being the conversion-determining and the most energy-intensive step of the entire CCM process chain, received a prominent attention in this study. The extraction behavior and reactivity of different rocks types (serpentinite and olivine rocks) from different locations worldwide (Australia, Finland, Lithuania, Norway and Portugal) was tested. Also, parametric evaluation was carried out to determine the optimal reaction temperature, time and chemical reagent (AS). Effects of reactor types and configuration, mixing and scale-up possibilities were also studied. The Mg(OH)2 produced can be used to convert CO2 to thermodynamically stable and environmentally benign magnesium carbonate. Therefore, the process energy and life cycle environmental performance of the ÅAU CCM technique that first produces Mg(OH)2 and the carbonates in a pressurized fluidized bed (FB) were assessed. The life cycle energy and environmental assessment approach applied in this thesis is motivated by the fact that the CCM technology should in itself offer a solution to what is both an energy and environmental problem. Results obtained in this study show that different Mg-silicate rocks react differently; olivine rocks being far less reactive than serpentinite rocks. In summary, the reactivity of Mg-silicate rocks is a function of both the chemical and physical properties of rocks. Reaction temperature and time remain important parameters to consider in process design and operation. Heat transfer properties of the reactor determine the temperature at which maximum Mg extraction is obtained. Also, an increase in reaction temperature leads to an increase in the extent of extraction, reaching a maximum yield at different temperatures depending on the reaction time. Process energy requirement for producing Mg(OH)2 from a hypothetical case of an iron-free serpentine rock is 3.62 GJ/t-CO2. This value can increase by 16 - 68% depending on the type of iron compound (FeO, Fe2O3 or Fe3O4) in the mineral. This suggests that the benefit from the potential use of FeOOH as an iron ore feedstock in iron and steelmaking should be determined by considering the energy, cost and emissions associated with the FeOOH by-product. AS recovery through crystallization is the second most energy intensive unit operation after the extraction reaction. However, the choice of mechanical vapor recompression (MVR) over the “simple evaporation” crystallization method has a potential energy savings of 15.2 GJ/t-CO2 (84 % savings). Integrating the Mg(OH)2 production method and the gas/solid carbonation process could provide up to an 25% energy offset to the CCM process energy requirements. Life cycle inventory assessment (LCIA) results show that for every ton of CO2 mineralized, the ÅAU CCM process avoids 430 - 480 kg CO2. The Mg(OH)2 process studied in this thesis has many promising features. Even at the current high energy and environmental burden, producing Mg(OH)2 from Mg-silicates can play a significant role in advancing CCM processes. However, dedicated future research and development (R&D) have potential to significantly improve the Mg(OH)2 process performance.