Interlamellar modification of smectite clays

Clay minerals, both natural and synthetic, have a wide range of applications. Smectite clays are not true insulators, their slight conductivity has been utilized by the paper industry in the development of mildly conducting paper. In particular, the synthetic hectorite clay, laponite, is employed to produce paper which is used in automated drawing offices where electro graphic printing is common. The primary objective of this thesis was to modify smectite clays, particularly laponite, to achieve enhanced conductivity. The primary objective was more readily achieved if the subsidiary objective of understanding the mechanism of conductivity was defined. The cyclic voltammograms of some cobalt complexes were studied in free solution and as clay modified electrodes to investigate the origin of electroactivity in clay modified electrodes. The electroactivity of clay modified electrodes prepared using our method can be attributed to ion pairs sorbed to the surface of the electrode, in excess of the cationic exchange capacity. However, some new observations were made concerning the co-ordination chemistry of the tri-2-pyridylamine complexes used which needed clarification. The a.c. conductivity of pressed discs of laponite RD was studied over the frequency range 12Hz- 100kHz using three electrode systems namely silver-loaded epoxy resin (paste), stainless-steel and aluminium. The a. c. conductivity of laponite consists of two components, reactive (minor) and ionic (major) which can be observed almost independently by utilizing the different electrode systems. When the temperature is increased the conductivity of laponite increases and the activation energy for conductivity can be calculated. Measurement of the conductivity of thin films of laponite RD in two crystal planes shows a degree of anisotropy in the a.c. conductivity. Powder X-ray diffraction and 119Sn Mossbauer spectroscopy studies have shown that attempts to intercalate some phenyltin compounds into laponite RD under ambient conditions result in the formation of tin(IV) oxide pillars. 119Sn Mossbauer data indicate that the order of effectiveness of conversion to pillars is in the order: Ph3SnCl > (Ph3Sn)2O, Ph2SnCl2 The organic product of the pillaring process was identified by 13C m.a.s.n.m.r. spectroscopy as trapped in the pillared lattice. This pillaring reaction is much more rapid when carried out in Teflon containers in a simple domestic microwave oven. These pillared clays are novel materials since the pillaring is achieved via neutral precursors rather than sacrificial reaction of the exchangeable cation. The pillaring reaction depends on electrophilic attack on the aryl tin bond by Brønsted acid sites within the clay. Two methods of interlamellar modification were identified which lead to enhanced conductivity of laponite, namely ion exchange and tin(IV) oxide pillaring. A monoionic potassium exchanged laponite shows a four fold increase in a.c. conductivity compared to sodium exchanged laponite RD. The increased conductivity is due to the appearence of an ionic component. The conductivity is independent of relative humidity and increases with temperature. Tin(IV) oxide pillared laponite RD samples show a significant increase in conductivity. Samples prepared from Ph2SnCl2 show an increase in excess of an order of magnitude. The conductivity of tin(IV) oxide pillared laponite samples is dominated by an ionic component.

Organometallic precursors for pillared clay synthesis

The synthetic hectorite, laponite has been used within the paper industry to produce mildly conducting paper for use in electrographic printing. The aim of this research was to modify laponite in order to improve the electrical conductivity. In a continuation of a previous investigation involving organotin intercalation of laponite, the organotin precursor (p-CH3,OC6H4)4Sn was synthesised and characterised using Mass Spectroscopy, Infrared Spectroscopy and elemental analysis. Results of intercalation with this compound and a range of organobismuth and organoantimony compounds suggested that a halide content within the precursor was necessary for improvement in conductivity to be observed. Organometallic intercalation of a range of organotellurium compounds with laponite provided evidence that a hydrolysis reaction on the clay surface followed by the release of hydrochloric acid was an important first step if a reaction was to occur with the clay. Atomic Absorption Spectroscopy studies have shown that the acid protons underwent exchange with the interlayer sodium ions in the clay to varying degrees. Gas-liquid Chromatography and Infrared Spectroscopy revealed that the carbon-tellurium bond remained intact. Powder X-ray diffraction revealed that there had been no increase in the basal spacing. The a.c. conductivity of the modified clays in the form of pressed discs was studied over a frequency range of 12Hz - 100kHz using two electrode systems, silver paste and stainless steel. The a.c. conductivity consists of two components, ionic and reactive. The conductivity of laponite was increased by intercalation with organometallic compounds. The most impressive increase was gained using the organotellurium precursor (p-CH3OC6H4)2TeCl2. Conductivity investigations using the stainless steel electrode where measurements are made under pressure showed that in the case of laponite, where poor particle-particle contact exists at ambient pressure, there is a two order of magnitude increase in the measured a.c. conductivity. This significant increase was not seen in modified laponites where the particle-particle contact had already been improved upon. Investigations of the clay surface using Scanning Electron Microscopy suggested that the improvement in particle-particle contact is the largest factor in the determination of the conductivity. The other important factor is the nature and the concentration of the interlayer cations. A range of clays were synthesised in order to increase the concentration of sodium interlayer cations. A sol-gel method was employed to carry out these syntheses. A conductivity evaluation showed that increasing the concentration of the sodium cations within the clay led to an increase in the conductivity.

Waste to power

ABSTRACT: There has been a growing trend towards the use of biomass as a primary energy source, which now contributes over 54% of the European pulp and paper industry energy needs [1]. The remaining part comes from natural gas, which to a large extent serves as the major source of energy for numerous recovered fiber paper mills located in regions with limited available forest resources. The cost of producing electricity to drive paper machinery and generate heat for steam is increasing as world demand for fossil fuels increases. Additionally, recovered fiber paper mills are also significant producers of fibrous sludge and reject waste material that can contain high amounts of useful energy. Currently, a majority of these waste fractions is disposed of by landspreading, incineration, or landfill. Paper mills must also pay a gate fee to process their waste streams in this way and the result of this is a further increase in operating costs. This work has developed methods to utilize the waste fractions produced at recovered fiber paper mills for the onsite production of combined heat and power (CHP) using advanced thermal conversion methods (pyrolysis and gasification) that are well suited to relatively small scales of throughput. The electrical power created would either be used onsite to power the paper making process or alternatively exported to the national grid, and the surplus heat created could also be used onsite or exported to a local customer. The focus of this paper is to give a general overview of the project progress so far and will present the experimental results of the most successful thermal conversion trials carried out by this work to date. Application: The research provides both paper mills and energy providers with methodologies to condition their waste materials for conversion into useful energy. The research also opens up new markets for gasifier and pyrolysis equipment manufacturers and suppliers.

Characterisation of waste derived intermediate pyrolysis oils for use as diesel engine fuels

This paper studies the characteristics of intermediate pyrolysis oils derived from sewage sludge and de-inking sludge (a paper industry residue), with a view to their use as fuels in a diesel engine. The feedstocks were dried and pelletised, then pyrolysed in the Pyroformer intermediate pyrolysis system. The organic fraction of the oils was separated from the aqueous phase and characterised. This included elemental and compositional analysis, heating value, cetane index, density, viscosity, surface tension, flash point, total acid number, lubricity, copper corrosion, water, carbon residue and ash content. Most of these results are compared with commercial diesel and biodiesel. Both pyrolysis oils have high carbon and hydrogen contents and their higher heating values compare well with biodiesel. The water content of the pyrolysis oils is reasonable and the flash point is found to be high. Both pyrolysis oils have good lubricity, but show some corrosiveness. Cetane index is reduced, which may influence ignition. Also viscosity is increased, which may influence atomisation quality. Carbon residue and ash content are both high, indicating potential deposition problems. Compared with de-inking sludge pyrolysis oil (DSPO), sewage sludge pyrolysis oil (SSPO) has a higher heating value, but higher corrosiveness and viscosity. The conclusions are that both intermediate pyrolysis oils will be able to provide sufficient heat when used in diesel engine; however poor combustion and carbon deposition may be encountered. Blending of these pyrolysis oils with diesel or biodiesel could overcome these problems and is recommended for further investigation.

Experimental investigation of the fuel properties of glidfuel, palm oil mill effluent biodiesel and blends

Biofuels derived from industry waste have potential to substitute fossil fuels (Diesel and Gasoline) in internal combustion (IC) engines. Use of waste streams as fuels would help to reduce considerably life-cycle greenhouse gas emissions and minimise waste processing costs. In this study an investigation into the fuel properties of two waste derived biofuels were carried out, they are: (i) Glidfuel (GF) biofuel - a waste stream from paper industry, and (ii) Palm Oil Mill Effluent (POME) biodiesel - biodiesel produced from palm oil industry effluent through various treatment and transesterification process. GF and POME was mixed together at various proportions and separately with fossil diesel (FD) to assess the miscibility and various physical and chemical properties of the blends. Fuel properties such as kinematic viscosity, higher heating value, water content, acid number, density, flash point temperature, CHNO content, sulphur content, ash content, oxidation stability, cetane number and copper corrosion ratings of all the fuels were measured. The properties of GF, POME and various blends were compared with the corresponding properties of the standard FD. Significance of the fuel properties and their expected effects on combustion and exhaust emission characteristics of the IC engine were discussed. Results showed that most properties of both GF and POME biodiesel were comparable to FD. Both GF and POME were miscible with each other, and also separately with the FD. Flash point temperatures of GF and POME biodiesel were 40.7°C and 158.7°C respectively. The flash point temperature of GF was about 36% lower than corresponding FD. The water content in GF and FD were 0.74 (% wt) and 0.01 (% wt) respectively. Acidity values and corrosion ratings of both GF and POME biodiesel were low compared to corresponding value for FD. The study concluded that optimum GF-POME biofuel blends can substitute fossil diesel use in IC engines.

Efeito da disponibilidade de oxigénio na produção de bioetanol por Scheffersomyces stipitis

O bioetanol constitui uma alternativa renovável aos combustíveis fósseis. Contudo, o bioetanol de primeira geração, produzido a partir de matérias-primas alimentares, desencadeou sérios problemas económicos e sociais, pelo que é fundamental encontrar estratégias que permitam a viabilidade comercial do bioetanol de segunda geração, produzido a partir de matérias-primas lenho-celulósicas. O licor de cozimento ao sulfito ácido de árvores folhosas (HSSL) é um subproduto da indústria papeleira que, devido ao seu elevado conteúdo em açúcares, pode ser utilizado como substrato para a produção de bioetanol de segunda geração. No entanto, a maior fração dos açúcares do HSSL é composta por pentoses. Por isso, a fermentação do HSSL é realizada pela levedura Scheffersomyces stipitis, pois esta é capaz de fermentar tanto as hexoses como as pentoses. Todavia, a S. stipitis só produz etanol sob condições microaerófilas, pelo que o maior desafio da produção de bioetanol por S. stipitis reside no estabelecimento das condições ótimas de arejamento. Este trabalho teve assim por objetivo estabelecer uma estratégia de arejamento que permita a eficiente produção de bioetanol a partir de HSSL por S. stipitis C4, a qual é uma estirpe adaptada a este substrato. Deste modo, foram realizados ensaios em Erlenmeyer, de modo a caracterizar o crescimento da S. stipitis C4, e ensaios em biorreator, com vista a estudar a produção de etanol por S. stipitis C4 em duas estratégias de arejamento diferentes. Na primeira estratégia foi usado apenas um único estágio de arejamento, com controlo da tensão de oxigénio dissolvido, DOT (%), e na segunda estratégia foram usados dois estágios de arejamento, com controlo da DOT no primeiro estágio e com restrição de oxigénio no segundo estágio. Nos ensaios em Erlenmeyer com HSSL o crescimento da S. stipitis C4 foi completamente inibido. Por sua vez, nos ensaios em biorreator com um único estágio de arejamento o controlo da DOT não permitiu a produção de etanol. No entanto, nos ensaios com dois estágios de arejamento em meio sintético foi possível produzir etanol de forma eficiente. Nesta estratégia, a utilização de um maior valor de DOT no primeiro estágio de arejamento permitiu aumentar a taxa específica de crescimento máxima e o rendimento em biomassa do primeiro estágio. Para além disso, a utilização de um maior valor de DOT no primeiro estágio também permitiu aumentar a produtividade em etanol durante o segundo estágio de arejamento. Por sua vez, no segundo estágio de arejamento verificou-se que a restrição de oxigénio evitou a reassimilação de etanol pela S. stipitis C4. Deste modo, os melhores resultados para a produção de etanol foram obtidos com controlo da DOT a 50% durante o primeiro estágio e com 0 mLAr.min-1 e 250 rpm durante o segundo estágio de arejamento. A aplicação desta estratégia de arejamento a 60% HSSL/40% meio sintético permitiu obter, no primeiro estágio de arejamento, uma taxa específica de crescimento máxima de 0,17 h-1, o que demonstra que a elevada disponibilidade de oxigénio durante o primeiro estágio aumenta a tolerância da S. stipitis C4 aos inibidores. Para além disso, a taxa volumétrica de produção de etanol e o rendimento em etanol de toda a fermentação foi de respetivamente de 0,03 g.L-1.h-1 e 0,38 g.g-1. Assim, a elevada eficiência de conversão dos açúcares em etanol (74,4%) demostra que a fermentação com dois estágios de arejamento constitui uma estratégia promissora para a produção de bioetanol de segunda geração a partir de HSSL.

Melhoria do processo de lavação das rolhas de cortiça

O presente trabalho, realizado na empresa Amorim & Irmãos, S.A. teve como principal objetivo a avaliação e otimização da lavação de rolhas de cortiça técnicas, designadas por Twin Top®, em termos do perfil de consumo de reagentes químicos e do desenvolvimento da sua brancura. Para tal foi desenvolvida uma metodologia de análise de brancura de rolhas Twin Top® que serviu de base para a determinação de uma gama de brancuras aceitável. Para além disto, efetuou-se a avaliação do processo de lavação atualmente praticado e apartir do qual se realizaram os ensaios de otimização a nível laboratorial e piloto. Foram aplicados diferentes métodos de análise tais como, UV-Vis, FTIR-ATR, RMN e brancura ISO. Tendo como base de análise os espetros de refletância difusa de espetroscopia de UV-Vis foi proposta uma metodologia de determinação da brancura de rolhas Twin Top® a 457nm, adoptando as condições da Norma ISO 3688, aplicada na indústria da pasta e papel. De seguida, aplicando o método anteriormente definido, analisaram-se 1000 rolhas Twin Top® de lavação branca. Sendo que os resultados demonstraram que para rolhas dentro de especificação a brancura ISO deve estar entre os 30 e 35%. Foram ainda analisadas rolhas de diferentes classes visuais e provenientes de várias máquinas de lavação da fábrica para determinar possíveis diferenças. Para proceder à avaliação da lavação existente analisaram-se as colas usadas na produção das rolhas, um grânulo de cortiça e a matéria seca do efluente de lavação por FTIR-ATR e RMN. Desta avaliação resultou a presença de compostos de cortiça e cola degradada no efluente de lavação. Determinou-se a concentração dos reagentes intervenientes no processo que se mostraram de acordo com as especificações indicadas pelos fornecedores. Para a otimização da lavação combinou-se o peróxido de hidrogénio e hidróxido de sódio em diferentes quantidades, concentrações e diferentes tempos de reação o que permitiu identificar a melhor alternativa à lavação convencional. Assim existem duas propostas que devem ser tidas em consideração: uma em que a lavação mantém a mesma sequência da convencional e em que se altera o local de adição dos reagentes, que deve ser o mais próxima e direta possível das rolhas, e a outra em que se reduz o tempo do processo em 29,3 min, que compreende apenas uma oxidação e em que a quantidade de reagentes aplicada corresponde à soma dos volumes de reagentes das três oxidações do processo convencional.

Elintarvikepakkauskartongin vettyminen

Elintarviketeollisuudessa tärkeimpiä pakkausmateriaaleja ovat erilaiset kartonkipakkaukset ja erityisesti niiden kuljetuksessa käytettävät aaltopahvipakkaukset. Aaltopahvilta vaadittavia ominaisuuksia ovat muun muassa puristuslujuus ja kosteudenkestävyys. Elintarvikekäyttöön tarkoitetuilla aaltopahveilla on myös tiettyjä vaatimuksia niissä käytettävistä yhdisteistä. Erilaiset kuitumateriaalit käyttäytyvät vettyessään eri tavalla ja niistä voi liueta yhdisteitä pakattavaan elintarvikkeeseen. Työn tavoitteena oli selvittää vettymiseen vaikuttavia tekijöitä ja veden vaikutus aaltopahvin rakenteeseen. Havaittiin, että ligniiniä tai uuteaineita sisältävä mekaanisesti valmistettu kartonkimateriaali ei sido vettä yhtä paljon kuin kemiallisesti valmistettu tai valkaistu kartonki. Aaltopahvissa tapahtuvan kapillaariabsorptio sai veden nousemaan pääasiassa aallotuskartonkiin. Vesi imeytyi korkeammalle puolikemiallisesti valmistetuissa aaltopahveissa kuin keräyskartonkipahveissa, jotka eivät myöskään turvonneet yhtä voimakkaasti. Työssä kartoitettiin myös elintarvikekäyttöä rajoittavia liukoisia yhdisteitä, jotka löytyivät paperiteollisuudessa yleisesti käytetyistä liimoista. Tällaisia yhdisteitä olivat märkälujaliimojen formaldehydiyhdisteet ja polyamidoamiini-epikloorihydriinihartsi. Keräyskartongin joukossa olevat raskasmetallit rajoittavat myös niiden käyttöä elintarvikepakkauksissa.

Life cycle management of TVO nuclear power plant

Tämä diplomityö tutkii eri elinkaarihallinnan menetelmiä ja vertaa niitä TVO:n menetelmiin. Lisäksi TVO:n prosessin ongelmakohdat tunnistetaan ja niihin esitetään ratkaisuja. Vertailukohteina toimii ydinvoimateollisuuden lisäksi vesivoima, fossiiliset voimalaitokset sekä paperiteollisuus. Sähkön hinnan jatkaessa laskuaan on elinkaariajattelusta tullut ajankohtaista myös ydinvoimayhtiöille. Ydinvoimalaitoksien pitkän suunnitellun käyttöiän ansiosta laitoksen elinkaaren aikana voi tapahtua useita asioita, jotka vaikuttavat laitoksen investointitarpeisiin. Turvallisen sähköntuotannon varmistamiseksi eri laitososia on joko muokattava tai uusittava. Elinkaariajatteluun kuuluu tehokas laitoksen kunnon valvonta, laitoksen ikääntymiseen vaikuttavien ilmiöiden tunnistaminen, sekä ikääntymistä hillitsevien toimenpiteiden pitkän tähtäimen suunnittelu. Hyvällä ennakkosuunnittelulla pyritään varmistamaan se, että laitoksella voidaan tuottaa sähköä koko sen jäljellä olevan käyttöiän aikana. Kun tarpeiden tunnistus ja suunnittelu tehdään hyvissä ajoin mahdollistetaan myös investointien optimointi. Paras hyöty pyritään saamaan ajoittamalla oikeat investoinnit oikeaan aikaan.

Comprehensive economic and financial analysis of the enterprise activity: approaches, methods and implementation

This thesis intends to analyse the performance and the efficiency of companies and to identify the key factors that may explain it. A comprehensive analysis based on a set of economic and financial ratios was studied as an instrument which provides information on enterprise performance and its efficiency. It was selected a sample with 15 enterprises: 7 Portuguese and 8 Ukrainian ones, belonging to several industries. Financial and non-financial data was collected for 6 years, during the period of 2009 to 2014. Research questions that guided this work were: Are the enterprises efficient/profitable? What factors influence enterprises’ efficiency/performance? Is there any difference between Ukrainian and Portuguese enterprises’ efficiency/performance, which factors have more influence? Which industrial sector is represented by more efficient/profitable enterprises? The main results showed that in average enterprises were efficient; comparing by states Ukrainian enterprises are more efficient; industries have similar level of efficiency. Among factors that influence ATR positively are fixed and current assets turnover ratios, ROA; negatively influencing are EBITDA margin and liquidity ratio. There is no significant difference between models by country. Concerning profitability, enterprises have low performance level but in comparison of countries Ukrainian enterprises have better profitability in average. Regarding the industry sector, paper industry is the most profitable. Among factors influencing ROA are profit margin, fixed asset turnover ratio, EBITDA margin, Debt to equity ratio and the country. In case of profitability both countries have different models. For Ukrainian enterprises is suggested to pay attention on factors of Short-term debt to total debt, ROA, Interest coverage ratio in order to be more efficient; Profit margin and EBITDA margin to make their performance better. For Portuguese enterprises for improving efficiency the observation and improvement of fixed assets turnover ratio, current assets turnover ratio, Short-term financial debt to total debt, Leverage Ratio, EBITDA margin is suggested; for improving higher profitability track fixed assets turnover ratio, current assets turnover ratio, Debt to equity ratio, Profit margin and Interest coverage ratio is suggested.

Reporte financiero Burkenroad / Latinoamérica – Colombia / Carvajal Empaques S.A.

De acuerdo con los resultados obtenidos en la valoración, la recomendación es comprar la acción de Carvajal Empaques S.A., ya que se espera que se valorice en un 16.68% a diciembre 31 de 2016, debido a la progresiva recuperación del flujo de caja después de grandes inversiones hechas en años anteriores para la ampliación de su capacidad instalada, permitiéndoles crecer y suplir la demanda ascendente del mercado de food service, dejando ver también el impacto de las eficiencias operacionales buscadas por la compañía -- Además, a nivel mundial se espera un crecimiento del sector empaques por encima de la economía y la empresa ocupa uno de los tres primeros puestos en cada geografía donde tiene presencia, por lo que para seguir supliendo el aumento de la demanda, este año planean construir una nueva planta de producción en Perú y aumentar la diversidad de su portafolio -- Sin embargo, a pesar de lo logrado por la compañía en crecimiento y eficiencias, el panorama regional político-económico de la mayoría de países latinoamericanos es incierto, puesto que atraviesan una fase de decaimiento, por lo que los ingresos podrían verse afectados en cierto grado en años cercanos -- Realizando una prueba de sensibilidad frente a las variables macroeconómicas que pueden afectar el valor de la compañía, se hallaron los comportamientos y distribuciones del PIB y la inflación para cada uno de los países donde la empresa tiene operaciones -- También se tuvieron en cuenta otras variables como: la relación del dólar con el peso colombiano, el costo de capital, la tasa de crecimiento a perpetuidad, el capital de trabajo neto operativo, el crecimiento del activo fijo y el flujo de caja libre operativo -- Como variable de interés se eligió el valor objetivo por acción a diciembre 31 de 2016 -- Luego de 10.000 iteraciones se obtuvo el siguiente rango para el valor de la acción: un mínimo de $2.033,14 y un máximo de $3.538,66, con una media de $2.697,22 a un nivel de confianza del 95%

Uso de resíduos da indústria de papel e celulose em plantios florestais: aspectos técnicos e legais.

Introdução; Principais resíduos sólidos e semi-sólidos gerados em complexos integrados de celulose e papel; Aspectos técnicos e legais voltados à elaboração de projeto agronômico para uso de resíduos em plantios florestais; Caracterização e classificação dos resíduos quanto aos seus riscos potenciais ao meio ambiente e à saúde pública; Caracterização de resíduos sob o aspecto agronômico; Critérios para definição de doses, épocas e formas de aplicação; Avaliação de problemas de ordem ambiental; Avaliação da viabilidade econômica; Seleção e caracterização das áreas de aplicação; Monitoramento agronômico e ambiental da área de aplicação; Manuseio, transporte e armazenamento; Processos adicionais de tratamento.

ACE research briefing paper 007 : Ken Talbot - an entrepreneur's contribution to the growth of the Australian Mining Industry

Ken Talbot was one of Australian mining’s most successful entrepreneurs and rose to the top of his industry to become one of Australia’s wealthiest men. Although the nation’s resources industry is synonymous with global names such as Xstrata, BHP Billiton and Rio Tinto, Ken was an individual who made a big impact on the development and growth of the sector. This case study examines Ken’s achievements, his transition from employee to entrepreneur, and the qualities that enabled him to succeed at such a high level. In particular, it focuses on his Jellinbah and Coppabella mining developments that directly led to the creation of Macarthur Coal and the Talbot Group. By the time of his premature death in an African plane crash in 2010, Ken had amassed a fortune estimated at almost $1 billion and was aged just 59. The last publically available Talbot Group annual report for calendar year 2009 showed that the investment portfolio of the group returned 113 per cent that year. Even throughout the global financial crisis the portfolio made a positive return on investment of no less than 10 per cent. Ken’s sense of mateship and his tremendous people skills were keys to his success in the mining industry and the wider community. In addition to excelling in business, he is also remembered for his philanthropy and leaving 30 per cent of his estate to charity through the Talbot Family Foundation.