Dissertations / Theses on the topic 'Natural Clinoptilolite'

Clinoptilolite is the most abundant zeolite mineral in nature. In this study a reproducible synthesis recipe for clinoptilolite was established and the limits of the crystallization field were developed by changing synthesis parameters such as temperature, composition and the nature of reactants. Clinoptilolite was reproducibly synthesized as a pure phase and in high yield at 140oC using a benchmark batch composition of 2.1 Na2O:Al2O3:10SiO2:110.1 H2O. Clinoptilolite was crystallized from 10wt% or 28wt% seeded systems while it was not formed if no seeds were present. Clinoptilolite was also crystallized as a pure phase when the cation in the benchmark batch composition was Na,K mixture, or when alkali salts such as carbonates or chlorides were used besides alkali hydroxides, or when the SiO2/Al2O3 ratio was in the range of 10-12. Clinoptilolite was still crystallized as a single phase when alkali hydroxides in the batch were reduced by 20%. With the benchmark batch composition, clinoptilolite was crystallized in pure phase form at 100oC, 120oC, 140oC and 160oC while synthesis at 175oC resulted in the formation of pure mordenite. At 140oC clinoptilolite was crystallized together with Linde L when cation in the benchmark composition is only potassium. Phillipsite crystallized together with clinoptilolite at SiO2/Al2O3 ratio of 8 to 9. At SiO2/Al2O3 ratios of 6 or 4, phillipsite or analcime was formed as pure phase respectively. When the alkali hydroxides in the batch was increased by 20%, sanidine was formed. Use of reactive aluminosilicate gels enhanced the formation of clinoptilolite while attempts to use mineral raw materials were unsuccessful. For both Na and (Na,K)-clinoptilolite, Si/Al ratio of products were greater than four. Thermal stability of synthetic clinoptilolites were comparable with natural clinoptilolite and potassium ion increased thermal stability of clinoptilolite.

Thesis (Master)--İzmir Institute Of Technology, İzmir, 2005.
Keywords: Natural zeolite, clinoptilolite, aqueous media, ion exchange, adsorption. Includes bibliographical references (leaves . 70-73).

Ce travail étudie les matériaux composites zéolithes surfactifs, principes actifs pour des applications pharmaceutiques. D'abord sont identifiées les principales propriétés physiques, chimiques et biologiques des matériaux, requises pour des applications en tant que supports médicamenteux ciblant certaines formes de cancer. Par la suite sont décrits les différentes étapes de formulation des supports médicamenteux à base des zéolithes naturelles, les caractéristiques des matériaux intermédiaires ainsi obtenus, ainsi que les mécanismes des phénomènes interfaciaux à l'origine de l'action de ces matériaux. La dernière partie est consacrée à l'étude d'un relargage contrôlé des principes actifs de l'interface jusque dans un milieu aqueux modèle
This work studies the composite zeolites surfactants, active principles for pharmaceutical applications. First identified the main physical, chemical and biological materials, required for applications as drug carriers targeting some cancers. Subsequently described the various stages of formulation of drug carriers based on natural zeolites, the characteristics of intermediate materials obtained, and the mechanisms of interfacial phenomena at the origin of the action of these materials. The last part is devoted to the study of controlled release of active ingredients of the interface into a model aqueous medium

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Universidade Federal de Sao Carlos
Natural zeolites are the most important inorganic cationic exchangers exhibiting high ion exchange capacity, selectivity and environment compatibility. Heavy metals are well known for toxicity and their disposal is a significant industrial waste problem. The goal of this work was directed to evaluate the selectivity of a purified homo-ionic clinoptilolite mineral for aqueous Pb2+, Zn2+, Cu2+ and Na+ ions at 0,005 eq/L and 303 K, interpreted through the application of empirical thermodynamic models to the zeolite phase (Margules, Van Laar, Wilson) coupled with a well established ion-interaction approach for the electrolyte solution (Pitzer). The present study considered the following stages: (1) adsorbent material: preparation and characterization; (2) aqueous solutions: nitrates of sodium, lead, zinc and copper; (3) equilibration of weighed amounts of homo-ionic clinoptilolite with a series of solutions containing the two competing cations; (4) analysis for aqueous cations by AAE; (5) construction of the equilibrium points; isotherm analysis; (6) test for thermodynamic reversibility; (7) empirical models for the zeolite phase (admitted as a solid solution) jointed to the ion-interaction model chosen for the aqueous solution; (8) equilibrium constant and Gibbs free energy for the ion-exchange reactions; phenomenological interpretation of the thermodynamic parameters obtained by means of the application of empirical models to the zeolite phase. The above procedure was, in the same way, followed for the ternary systems. The results obtained in this work shown that the empirical models adopted for the solid phase coupled to Pitzer s model for the activity coefficients in the electrolyte solution describe successfully the binary ion-exchange equilibria. The calculated equilibrium constant and the corresponding Gibbs free energy for each binary-exchange reaction resulted in a selectivity sequence, at the normality and temperature of this study, easily deduced as: 2 2 2 Pb Na Cu Zn + + + + > > . Besides, the parameters estimated applying the Margules , Van Laar s and Wilson s equations for cations in the solid binary mixture resulted in useful values quantifying adequately the cation zeolite framework interactions, thus, an alternative way to interpret the adsorbent selectivity from the charge and cationic radius effect. The ternary parameters obtained applying multi-component empirical models do not explain properly the non-ideality of ions in a solid mixture containing more than two components. This is in accordance with the results encountered in a number of publications on crystal structure of heulandite-group zeolites: these aluminosilicates are found to contain crystallographically distinct set of sites throughout the exchanger framework and that normally each set of sites is partially populated by the exchanging ions. As a consequence, activity coefficients for a multi-component exchange reaction cannot be predicted from appropriate binary data for a heterogeneous exchanger, since the phenomenological binary coefficients are complicated functions of each site set, population and composition, and both these properties will change on introducing other species of ion in the exchanger. In this sense, and from what were obtained here, is believed that multi-component solid phase nonideality must, at least, be interpreted through the application of statistical thermodynamic models considering the energetic heterogeneity of a number of site set and the charge density of the specific zeolite framework.
Obs.: Devido a restrições dos caracteres especias, verifcar resumo em texto completo para download. As zeólitas naturais constituem os trocadores iônicos inorgânicos mais importantes, as quais mostram elevada capacidade de troca iônica, seletividade e compatibilidade com o ambiente natural. Os metais pesados são conhecidos pela sua toxicidade e seus depósitos constituem o maior problema quanto a despejos industriais. Os objetivos básicos deste trabalho foram a interpretação do equilíbrio de adsorção e a avaliação da seletividade de um mineral de clinoptilolita purificado e homo-iônico por Pb2+, Zn2+, Cu2+ e Na+ aquosos à normalidade de 0,005 eq/L e temperatura de 303 K. O estudo proposto foi feito obedecendo as seguintes etapas: (1) preparação e caracterização do material adsorvente; (2) preparação e análise de soluções eletrolíticas; (3) equilíbrio termodinâmico de clinoptilolita homo-iônica com soluções contendo os dois cátions competitivos; (4) análises, no equilíbrio, das soluções mediante EAA; (5) construção dos pontos experimentais e análise das isotermas; (6) testes de reversibilidade termodinâmica; (7) uso de modelos empíricos para a fase zeólita, admitida como uma pseudo-solução, e modelos de interação iônica para a solução eletrolítica; (8) análise da constante de equilíbrio e da energia livre de Gibbs das reações de troca binárias e interpretação fenomenológica dos parâmetros termodinâmicos. Os resultados obtidos mostraram que os modelos adotados para a fase zeólita, considerada como uma mistura, junto com o modelo de Pitzer para os coeficientes de atividade na solução eletrolítica descrevem com sucesso o equilíbrio de troca binária dos sistemas estudados. A constante de equilíbrio calculada e a correspondente energia livre de Gibbs, para cada reação de troca binária à normalidade e temperatura estudadas, resultaram numa seqüência de seletividade dada por: 2 2 2 Pb Na Cu Zn + + + + > > . Paralelamente, os parâmetros estimados através do o uso das equações de Margules, Van Laar e Wilson para os cations na mistura binária resultaram em valores úteis na quantificação das interações cátion estrutura. Desta forma, a avaliação destes parâmetros constituiu uma alternativa na interpretação da seletividade do adsorvente pelos diferentes cátions de troca a partir do efeito do raio e da carga dos cátions. Os parâmetros ternários obtidos através da aplicação de modelos clássicos de estrutura multicomponente resultaram não satisfatórios na interpretação fenomenológica da mistura de mais de dois componentes. Este resultado confirma o encontrado em estudos sobre a estrutura cristalina das zeólitas tipo heulandita: estes aluminosilicatos geralmente contêm grupos de sítios cristalográficos distinguíveis e, por outro lado, que os coeficientes de atividade dos íons em cada tipo de sítios é uma função fortemente dependente da composição e população destes. Desta forma, a inclusão de um terceiro componente torna extremamente complicada a predição e interpretação dos coeficientes de atividade fenomenológicos na mistura sólida multicomponente. Neste sentido e, a partir dos resultados deste estudo, acredita-se que a interpretação da não idealidade da mistura sólida multicomponente deve ser feita através do uso de modelos que considerem a heterogeneidade energética dos diferentes grupos de sítios dentro da zeólita, acoplado a considerações da termodinâmica estatística que têm em conta a população e composição em cada grupo de sítios, além da densidade de carga da rede cristalina do adsorvente.

The current study investigated application of natural adsorbents in brine treatment. Brines are hypersaline waters generated in power stations and mining industries rich in Mg2+, K+, Ca2+, Na+, SO4 2- , Cl- and traces of heavy metals, thus there is a need for these brines to be treated to recover potable water and remove problematic elements. Natural adsorbents have been successfully used in waste water treatment because of their high surface area and high adsorptive properties when they are conditioned with acid or base. The investigation of pH showed that natural adsorbents did not perform well at low pH of 4 and 6. The adsorbents were able to work efficiently at the natural pH of 8.52 of the brine solution. These results show that natural adsorbents hold great potential to remove cationic major components and selected heavy metal species from industrial brine wastewater. Heterogeneity of natural adsorbents samples, even when they have the same origin, could be a problem when wastewater treatment systems utilizing natural clinoptilolite and bentonite are planned to be developed. Therefore, it is very important to characterize the reserves fully in order to make them attractive in developing treatment technologies.

Aflatoxins are metabolites from fungi, that may be injurious to animal health, resulting in reduced production and affecting poultry industry by decrease the growth rate and worsening feed conversion. A study was carried out to evaluate the electrophoresis profile of serum protein in broilers fed with diets containing aflatoxins and natural clinoptilolite clay. A total of 528 male broilers Ross were used, distributed in 6 treatments with 4 replications each: T1 control (without aflatoxins or clinoptilolite), T2 5ppm of aflatoxins, T3 0.25% of clinoptilolite, T4 5ppm of aflatoxins and 0.25% of clinoptilolite, T5 0.5% of clinoptilolite and T6 5ppm of aflatoxins and 0.5% of clinoptilolite. The broilers were placed in 24 boxes and submitted to treatments from 1 to 42 days, when they were slaughtered. Were analyzed the total proteins, albumin fractions, alpha 1, alpha 2, beta and gamma. The aflatoxins decreased (P<0.05) total protein, albumin, and globulins (alpha and beta fractions). However, no effect (P<0.05) of aflatoxins was observed about gamma fraction. The clinoptilolite no modify (P<0.05) the serum proteins. Related to control, broilers fed with diets containing aflatoxins and clinoptilolite presented low (P<0.05) levels of total protein, albumin, and globulins (alpha and beta fractions). In conclusion, aflatoxins change the electrophoresis profile and clinoptilolite is not able to protect against this change
Aflatoxinas são metabólitos de fungos, que podem causar danos à saúde do animal, resultando em redução da produção e afetando à indústria avícola, pela diminuição da taxa de crescimento e péssima conversão alimentar. O objetivo do presente trabalho foi avaliar o perfil eletroforético das proteínas séricas de frangos de corte alimentados com dietas contendo aflatoxinas e/ou argila clinoptilolita natural. Foram utilizados 528 frangos de corte, machos, da linhagem Ross, distribuídos em 6 tratamentos com 4 repetições cada: T1 testemunha (ração sem aflatoxinas ou clinoptilolita), T2 ração com 5ppm de aflatoxinas, T3 ração com 0,25% de clinoptilolita, T4 ração com 5ppm de aflatoxinas e 0,25% de clinoptilolita, T5 ração com 0,5% de clinoptilolita e T6 ração com 5ppm de aflatoxinas e 0,5% de clinoptilolita. Os animais ficaram alojados em 24 boxes, e submetidos aos tratamentos do 1º ao 42º dia, quando foram sacrificados. Foram analisadas as proteínas totais, as frações albumina, alfa 1, alfa 2, beta e gama. Com exceção das médias da fração gama, o teste de Tukey revelou diferenças significativas (P<0,05) nas médias de todas as proteínas totais e frações protéicas nos tratamentos onde as aflatoxinas estavam presentes. A ação das aflatoxinas nas proteínas totais ocorre na síntese de albumina e globulinas (frações alfa e beta). As gamaglobulinas não são afetadas pelas aflatoxinas. Em relação ao controle, as aves alimentadas com dietas com aflatoxinas e clinoptilolita apresentaram baixos (P<0,05) níveis de proteína total, albumina e globulinas (alfa e beta). Conclui-se que as aflatoxinas alteram o perfil eletroforético e a clinoptilolita adicionada na ração, não é capaz de evitar essa alteração

Usage of modified forms of rocks that contain the mixture of zeolites as catalyst of the process of methanol transformation into dimethyl ether and hydrocarbons was considered. Possibility in principal of usage of modified rocks containing mordenite and clinoptilolite as the catalyst of the process of methanol transformation was demonstrated.

Orientador: Meuris Gurgel Carlos da Silva
Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Quimica
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Resumo: Neste trabalho foi estudada a remoção do íon cádmio, chumbo e cobre pela zeólita natural Clinoptilolita. Este estudo foi realizado em coluna de leito fixo construído em acnlico nas dimensões de 13,3 em de altura e 1,4 em de diâmetro interno. O estudo de pH foi feito visando a determinação dos valores no qual não ocorre à precipitação dos metais, sendo adotado o pH de 5,0. Utilizou-se a técnica de planejamento experimental 22 com 3 pontos centrais para o estudo do processo de adsorção de cada metal individualmente, avaliando as variáveis, vazão de operação e concentração de alimentação na resposta capacidade total de metal removida. Foram efetuados vários planejamentos experimentais, o planejamento 1 foi realizado para o cádmio, nas condições de concentração de 200 e 600 ppm e vazão de 10 e 50mL/min, no entanto os resultados não foram satisfatórios. Definiu-se então o planejamento experimental 2, nas condições de 400 e 600 ppm e 15 e 25 rnL/min, para cádmio, chumbo e cobre, encontrando-se a variável concentração como sendo a mais significativa e maior quantidade de metal é removido em maior concentração. Fez-se análise da zona de transferência de massa (ZTM) para o processo de adsorção de chumbo, mantendo a concentração constante e variando a vazão de operação, a vazão com menor valor de ZTM foi de 20mL/rnin. Os dados de equihõrio foram correlacionados utilizando isoterma de Langmuir, encontrou-se para o chumbo: qmax = 200,54 mg de chumbo/g de zeólita, b= 0,00223 mgIL; para o cádmio: qmax = 84 mg de cádmio/g de zeólita, b= 0,0022 mgIL e para o cobre qmax = 70,44 mg de cobre/g de zeólita, b= 0,0021 rng/L. O modelo matemático utilizado para o ajuste dos resultados experimentais foi proposto por Silva, 2001. Para o cádmio, chumbo e cobre, foram realizadas simulações onde os parâmetros de equilíbrio foram obtidos de forma dinâmica e com os dados obtidos por Zambon (2003), obtidos em batelada, para o chumbo. Os resultados das simulações foram satisfatórios para sistema dinâmico com todos os metais. Para o chumbo foi feita também simulações para os dados de equiliDrio obtidos em sistema batelada, no entanto não foram satisfatórias. A transferência de massa no sólido (K) foi influenciada pela concentração inicial de todos os metais nas faixas estudadas. Os ensaios de mistura foram realizados na vazão de 15mL/min e na concentração total de 600 ppm (frações de 1/3 e 2/3). Estes dados foram analisados de duas formas, inicialmente foi avaliado o efeito sinérgico entre os metais e em seguida foi feito um Planejamento Centróide Simplex. Através da análise do efeito sinérgico observou-se que quando o chumbo está influenciando a remoção dos demais metais ocorre uma queda na quantidade de remoção destes metais maior que 60%, enquanto a presença dos outros metais na remoção de cbumbo acarreta uma redução de no máximo 25,24%. O planejamento Centróide Simplex mostrou que a composição de chumbo é a variável mais significativa, maior quantidade total de remoção ocorre em maiores concentrações de chumbo. A variável composição de cádmio e cobre também apresentam um efeito significativo e positivo, assim como a mistura dos três metais, as misturas dois a dois de Cd+Cu e Cd+Pb exercem um efeito significativo e negativo na capacidade de remoção
Abstract: The removal of cadmium., lead and copper using natural zeolite Clinoptilolite was studied in a 13,3 em height and 1,4 em internal diameter fixed bed column. A prelirninary pH study was developed in order to detenninate the range in which ionic metal precipitation does not occur and pH 5 was found to be the adequate value for this purpose. A factorial design 22 with 3 center points was established in order to study the adsorption process of each metal individuaIly with what concerns the influence of the operation flow rate and feed concentration over the total metal removal capacity. The experimental design 1 was conducted to study cadmium removal. The lower values of flow rate and concentration factors were 10 mL/min and 200 ppm whereas the high values were 50 mL/min and 600 ppm respectively. The results were not satisfactOIyand a new design was set. The new experimental design 2 set lower factors to 15 mL/min and 400 ppm and higher values to 25mL/min and 600 ppm for cadnúum, lead and copper removal analysis. Concentration was found to be the most significant factor in the metais removal whilst higher concentrations result in bigher metal removal. The mass transfer zone (MTZ) was analyzed for the lead adsorption process, keeping the concentration constant and varying the flow rate. The lowest MTZ value was obtained with a flow rate of 20mL/min. The equilibrium data were correlated using Langmuir' s isotherm model. The constants obtained were for lead removal: qmax = 200,54 mg of Leadlg of zeolite, b= 0,00223 mg/L; for cadmium removal: qmax = 84 mg of cadmium/g of zeolite, b= 0,0022 mg/L and for copper removal: qmax = 70,44 mg of copper/g of zeolite, b= 0,0021 mg/L. The model used to adjust the experimental results was proposed by Silva, 2001. Simulations were made on cadmium, lead and copper removal breakthrough curves. The equilibrium parameters used were based on experimental data obtained for the dynamic adsorption process of cadmium, lead and copper ofthe present work as well as Zambon's (2003) bateh lead adsorption. The simulation results involving the dynamic parameter data were satisfactory for ali the metais studied. In the case of lead simulations were also done based on the batch parameters and the results were not satisfactory. The mass transfer in the solid (K) was inHuenced by the initial concentration of all the metais in the studied range. The mixture tests were done using 15ml/min flow rate and a total metal concentration of 600ppm (113 and 2/3 ftactions). These data were ana1yzed in two distinct ways: first the metais synergic effects were evaluated, then a simplex-centroid design was developed. Through the analyzes of the synergic effects it was possible to notice that when the lead is present in the mixture with the other metais there is a great drop in their removal quantity up to more than 60%. The presence of the other metais in lead removal results in a removal capacity reduction of in to maximum of 25.24%. The simplex-centroid design indicated the lead is the most significant component in the mixture for total metal removal, the greater the lead concentration the greater the total meta! capacity removal is achieved. Cadmium and copper compositions also showed a significant positive effect over as well as the mixture of the three metais. The mixture of two metais of Cd+Cu and Cd+Pb on the other hand have a negative effect over the capacity removal
Mestrado
Engenharia de Processos
Mestre em Engenharia Química

Biogas is a source of renewable energy and is produced at anaerobic conditions. The gas consists mainly of methane (55-70 %) and carbon dioxide (30-45 %). Biogas can be used as vehicle fuel after the gas has been upgraded to a methane content of approximately 97 %. There are several companies in Sweden producing biogas. Svensk biogas AB in Linköping is one of the largest. The company has two biogas production plants; one in Linköping and one in Norrköping. To meet the surge demand for biogas it is not only important to increase the volumetric capacity of the digesters, but also to optimize the process at the existing production plants in different ways. Zeolites, a clay mineral, have earlier been shown to have a positive effect on anaerobic digestion of certain substrates. The aim of this master’s thesis was to investigate if the organic loading rate could be increased and/or if the hydraulic retention time could be reduced by addition of zeolites to a reactor treating slaughterhouse waste as a substrate. The aim was further to investigate which substance/substances that zeolites possibly could affect. Addition of the zeolite clinoptilolite in a continuously stirred lab tank reactor showed a significantly lower accumulation of volatile fatty acids compared to that in a control reactor without zeolites added, when the hydraulic retention time was kept low (30 days) and the organic loading rate was high (4.8 kg VS/ (m3 × day)). The same results were observed upon zeolite addition in a batch experiment, which also showed a decreased lag phase. Neither the specific gas production nor the methane concentration was significantly affected by addition of zeolites. Furthermore, addition of a possible inhibitor, long-chain fatty acids (LCFA), increased the lag phase further when slaughterhouse waste was used as a substrate. The conclusion from the observed results is that a metabolite or metabolites produced during the anaerobic degradation is/are the reason to inhibition and an increased lag phase.

Urine comprises around 1% of domestic sewage volume but holds 80% of total nitrogen. Source separation is a sustainable way to wastewater management than traditional way due to low energy cost and preventing certain pollutants into wastewater treatment plants. Currently, removing and recovering nitrogen from source-separated urine has attracted more and more interests. Of them, ion exchange was used for removal and recovery of nitrogen in the form of ammonia from synthetic urine for potential application as a fertilizer in agriculture. No previous research studies were conducted to investigate the removal and recovery of nitrogen from hydrolyzed urine by ion exchange using POPs (porous organic polymers). So this study focused on evaluating the performance of POPs and comparing with clinoptilolite in synthetic hydrolyzed urine in terms of adsorption capacity (isotherm), adsorption rate (kinetics), regeneration rate, and cost. The ammonium removal from hydrolyzed urine using POPs was rapid with a high capacity of 68.03 mg/g than clinoptilolite (15.36 mg/g), and the regeneration efficiency of clinoptilolite and POPs can achieve 91% and 95.3%, respectively based single time use result. Although POPs had the better performance at one time use and multiple times use, it also had high materials cost. Additionally, the capacity of POP was estimated using the integrated ion exchange regeneration process model as 30.24 mg/g and 28.65 mg/g on cycle 10 and cycle 24, respectively. The regeneration efficiency of POPs was predicated as 45.4% and 38.4% in cycle 10 and cycle 24, respectively. The predicted capacity decreased with the number of cycles, but remained at about 55% of virgin POPs after 24 cycles, indicating POPs can maintain good performance after multiple reuses than clinoptilolite.

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Ammonia is a colorless gas that has a very strong smell and its presence in high concentrations in swine facilities is associated with health risks to animals and workers. Zeolites are aluminosilicates that have negative charges in their structure, in addition to micropores, increasing its capacity of cation exchange and adsorption of molecules, allowing the adsorption of ions such as ammonium ion and ammonia gas. The aim of this study was to evaluate the effect of inclusion of natural zeolite (clinoptilolite) as feed for growing and finishing pigs on the concentration of ammonia in plants, pH of the waste, animal performance and carcass quality. Treatments consisted of two diets of same nutritional compositions, one without zeolite (control), and another, with the inclusion of 0.5 % zeolite. 240 Immunocastrated males were used, with an initial weight of about 22 kg, for 90 days, spread over two buildings with pens (plots) of 10.88 m², consisting of semi-slatted floor (62.5 % with slatted floor and 37.5 % with compact floor). At each treatment was prepared with 12 repetitions of 10 animals. At the end of the housing, 184 animals were slaughtered to evaluate carcass quality. There was no difference (P>0.05) in ammonia concentration on different floors, compact and slatted floor. There was a reduction (P<0,05) in the concentration of ammonia in the facilities with the inclusion of zeolite in the diet. The inclusion of zeolite in the diet increased (P<0.05) the pH of the waste. The inclusion of zeolite in the diet did not affect (P>0.05) the growth performance and carcass quality of the animals during the growing and finishing phases. The inclusion of 0.5 % of natural zeolite in the diet of growing-finishing pigs decreases the concentration of ammonia in plants, increases the pH of the waste and does not affect the animal production performance and carcass quality
A amônia é um gás incolor que possui odor extremamente forte e sua presença em concentrações elevadas nas instalações para suínos estão associadas a riscos à saúde dos animais e trabalhadores. As zeólitas são aluminossilicatos que possuem em sua estrutura cargas negativas, além de microporos, aumentando sua capacidade de troca de cátions e adsorção de moléculas, permitindo a adsorção de íons, como o íon amônio e o gás amônia. O objetivo desse estudo foi avaliar o efeito da inclusão de zeólitas naturais (clinoptilolita) na alimentação de suínos em crescimento e terminação sobre a concentração de amônia nas instalações, pH dos dejetos, desempenho zootécnico e qualidade de carcaça. Os tratamentos consistiram de duas dietas isonutritivas, sendo uma, isenta de zeólita (controle) e, outra, com inclusão de 0,5 % de zeólita. Foram utilizados 240 machos imunocastrados, com peso inicial de aproximadamente 22 kg, durante 90 dias, distribuídos em duas instalações de alvenaria com baias (parcelas experimentais) de 10,88 m², constituídas de piso semi-ripado (62,5 % da baia com piso ripado e 37,5 % com piso compacto). Em cada instalação foi disposto um tratamento, com 12 repetições de 10 animais. Ao final do período de alojamento, 184 animais foram abatidos para a avaliação da qualidade de carcaça. Não houve diferença (P>0,05) nas concentrações de amônia sobre os diferentes pisos, compacto e ripado. Ocorreu redução (P<0,05) na concentração de amônia nas instalações com inclusão de zeólitas na dieta. A inclusão de zeólitas na dieta aumentou (P<0,05) o pH dos dejetos. A inclusão de zeólitas na dieta de suínos não afetou (P>0,05) o desempenho zootécnico e qualidade de carcaça dos animais nas fases de crescimento e terminação. A inclusão de 0,5 % de zeólitas naturais na dieta de suínos em crescimento e terminação diminui a concentração de amônia nas instalações, aumenta o pH dos dejetos e não afeta o desempenho zootécnico e de qualidade de carcaça dos animais

Orientadores: Telma Teixeira Franco, Meuris Gurgel Carlos da Silva
Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Quimica
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Resumo: Uma das grandes preocupações mundiais atuais é a qualidade das águas, pois o atual nível de avanço populacional e industrial tem causado grande poluição em rios e demais corpos d'água. Neste sentido, várias tecnologias têm sido propostas para descontaminação da água. O processo estudado pelo presente trabalho baseia-se na adsorção de chumbo, um metal pesado altamente tóxico, presente em efluentes industriais, urbanos e de mineração, por meio da troca iônica em materiais adsorventes naturalmente ocorrentes como as zeólitas. A investigação consistiu na avaliação da capacidade de adsorção, Q (mg Pb2+/g zeólita), da zeólita natural c1inoptilolita em sistema de banho finito, utilizando a técnica de planejamento fatorial 23 completo com ponto central. As três variáveis foram: concentração inicial de chumbo de 200 a 600 mg/L, massa de adsorvente de 1,0 a 2,0 g e pH da solução de 3,0 a 5,0. Concentração e massa foram expressas na forma de um único fator chamado R que representou a quantidade potencial de chumbo disponível por massa de zeólita, resultando entre 20 e 120 mg Pb2+/g zeólita. Foram obtidas a cinética e a isoterma de adsorção para estas condições. A metodologia indicou a que a capacidade de adsorção depende da concentração e da massa e independe do pH e que maiores capacidades de remoção são obtidas elevando-se a concentração de. chumbo e diminuindo-se a massa de zeólita, ou seja, com maiores valores de R. Foi estudada também a capacidade de adsorção de chumbo pela zeólita c1inoptilolita em coluna de leito fixo. Neste sistema foi investigado o efeito da vazão da solução de chumbo (10 a 50 rnL/min) em alta concentração (1000 mg/L) e da granulometria do adsorvente (diâmetro médio entre 0,55 e 0,78 mm) sobre a capacidade de adsorção. Com o leito fixo, obteve-se as curvas de ruptura do sistema em diferentes vazões e diâmetro de partícula. A técnica de planejamento fatorial utilizada demonstrou que o diâmetro da zeólita não influencia na capacidade de remoção da mesma, e que vazões baixas propiciam maiores remoções. A operação de dessorção da zeólita também foi possível no leito fixo, mostrando o potencial de reutilização da mesma. Uma modelagem matemática foi feita a fim de obter uma equação empírica que reproduzisse a curva de ruptura para diversas vazões dentro da faixa de dados experimentais disponível, obtendo-se uma equação com alta capacidade de previsão de resultados. Palavras chaves: adsorção, chumbo, zeólita, banho finito, leito fixo
Abstract: The quality of water is a matter of increasing concern as the current population and industrial growth results in pollution of rivers and other water reservoirs. Thus, several technologies have been proposed to perform water decontamination. The process studied in this work is based on the adsorption of lead, which is a highly toxic heavy metal present in industrial, domestic and mining wastewater, by mean of ion exchange in adsorptive materials, such as natural zeolites. The work consists of the evaluation of the clinoptilolite zeolite adsorption capacity, Q (mg Pb2+/g zeolite), in batch equilibrium, utilizing a full experimental design 23 with central point. The three variables studied were: initiallead concentration (200, 400, 600 mg/L), adsorbent mass (1.0, 1.5, 2.0 g) and pH solution (3.0, 4.0, 5.0). Concentration and mass are expressed by a unique factor called R, representing the lead potential quantity available per mass of adsorber, with values between 20 and 120 mg Pb2+/g zeolite. For these conditions, adsorption kinetics and isothermal were obtained. The results suggested that the adsorption capacity depends on concentration and mass and not of the pH, in order that, the higher the removal capacity, the greater the lead initial concentration and the minor zeolite mass, e.g., the greater R-values. The adsorption isotherm was compared with the Langmuir and Freundlich adsorption models, being better adjusted by the former. The capacity of the c1inoptilolite zeolite to remove lead in a fixed bed was also studied. The effects of the high eoneentration lead solution (1000 mg/L) flow rate (10, 30, 50 mL/min), and the zeolite grain size (mean diameters: 0.55, 0.65, 0.78 mm) in the adsorption capacity was examined. The breakthrough eurves for different flow rates and partic1e diameters were obtained. The experimental design technique showed that zeolite removal capacity does not depend on the partic1e diameter and that low flow rates increase its eapaeity. The zeolite desorption in fixed bed was also possible, showing the possibility of reusing this zeolite. Mathematieal modeling provided an empiric function that was able to describe the breakthrough curve for the several flow rates in the range defined by the available experimental data, and this equation showed a high eapaeity to forecast results
Mestrado
Desenvolvimento de Processos Químicos
Mestre em Engenharia Química

Zeolites are porous alumino-silicate materials with properties that result in a wide range of industrial applications. Predictions of zeolite properties can enhance higher performance and economic value for many industries. In this research, the structure and ion exchange behaviour of synthetic zeolite N is modelled using computational chemistry techniques. Modelled outcomes are compared with experimental data that are also obtained on natural zeolites from two Australian deposits. This research shows that a precise understanding and prediction of zeolite chemical and physical properties can be achieved by correlated atomic-scale modelling and high-quality experimental techniques.

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior
Gaseous losses of nitrogen (N) during composting of pig slurry (PS), mainly due to volatilization of ammonia (NH3), have important environmental and economic implications, requiring technological alternatives for their mitigation. The objective of this study was to evaluate the efficiency of natural zeolites clinoptilolite and stilbite at different doses and in different particle sizes and frequency of addition of clinoptilolite, to mitigate the losses of NH3 in the initial phase of PS composting. For this, experiments were conducted in a pilot scale, lasting between 14 and 17 days, wherein each zeolite was added at increasing doses of 5, 10 and 20% (w / v), the PS formed on a substrate by mixing sawdust (70%) and shavings (30%). In each experiment was performed three to four applications of PS, with or without addition of zeolites, followed by simultaneous plowing, plus three or four additional turnings in the compound. All these experiments were divided in two articles that make up this dissertation. NH3 emissions were reduced with Zeolites when compared to the control treatment only with the application of manure, and the efficiency was directly related to the dose and frequency for both zeolites addition to clinoptilolite. The clinoptilolite was more efficient in reducing ammonia emissions than stilbite and showed no differences between the analyzed particle sizes. The average of all experiments, the reduction in NH3 emissions that clinoptilolite and stilbite provided regarding PS without zeolites was between 24-76% and 8-37%, respectively. These results demonstrate the high potential of natural zeolites, mainly clinoptilolite in mitigating NH3 volatilization during composting of PS.
As perdas gasosas de nitrogênio (N) durante a compostagem de dejetos líquidos de suínos (DLS), principalmente por volatilização de amônia (NH3), têm implicações ambientais e econômicas importantes, necessitando de alternativas tecnológicas para sua mitigação. O objetivo do presente trabalho foi avaliar a eficiência das zeólitas naturais clinoptilolita e estilbita utilizadas em diferentes doses, e variação de granulometria e frequência de adição da clinoptilolita, em mitigar as perdas de NH3 na fase inicial da compostagem de DLS. Para isso, foram conduzidos experimentos em escala piloto, com duração entre 14 e 17 dias, em que cada zeólita foi adicionada em doses crescentes, de 5, 10 e 20% (m/v), aos DLS, sobre um substrato constituído pela mistura de serragem (70%) e maravalha (30%). Em cada experimento foram realizadas entre três e quatro aplicações de DLS, com ou sem adição de zeólitas, seguidas de revolvimento simultâneo, além de três ou quatro revolvimentos adicionais no composto. Todos esses experimentos foram alocados nos dois artigos que compõem esta dissertação. Ambas zeólitas testadas reduziram as emissões de NH3 quando comparadas ao tratamento testemunha, somente com a aplicação de dejetos, sendo que a eficiência em mitigar a emissão de amônia esteve diretamente relacionada à dose utilizada para as duas zeólitas e também à frequência de adição para a clinoptilolita. A clinoptilolita apresentou maior eficiência em reduzir a emissão de amônia do que a estilbita e não apresentou diferença entre as granulometrias avaliadas. Na variação média de todos os experimentos, a redução nas emissões de NH3 que a clinoptilolita e a estilbita proporcionaram em relação aos DLS sem zeólitas foi entre 24 a 76% e 8 a 37%, respetivamente. Os resultados deste trabalho evidenciam o alto potencial das zeólitas naturais, principalmente da clinoptilolita, em mitigar a volatilização de NH3 durante a compostagem de DLS.

M.Tech.
Clinoptilolite possesses acid and base properties, and is hydrothermally stable at high temperatures. It can be reactivated by simple oxidation, and is highly selective due to its unique-shape selectivity. It is also not harmful to the environment and it has shown benefits to soil as well (Mumpton,1977). An initial study of the reactions of methanol amination was done using both natural local and synthetic clinoptilolites. Characterization of each was done before and after modification using XRD, TPD and BET analysis. The BET analysis showed an increase in the surface area and pore diameter of both the natural and synthetic types after acid treatment and calcination. Most interesting of all was the large increase in surface area, where the natural type increased from 16 to 36.7 m 2/g after acid treatment and the synthetic type increased almost 13 times, from 2 to 27.7 m2/g after acid treatment. This effect had a strong influence on the selectivity of methylamines by allowing a larger surface area to be in contact with the feed reagents. The XRD of the treated and untreated natural and synthetic clinoptilolite were compared and discussed. The catalytic properties of zeolites depend on the treatment of clinoptilolite, and the characteristic peaks of natural and the acid treated form can be identified in the XRD plots.The TPD analyses showed that there were two acid sites associated with the clinoptilolite; one weak and one strong. The synthetic clinoptilolite weak acid site also showed a much lower ammonia uptake, than the natural clinoptilolite weak acid site. Clinoptilolite was shown to be successful as a catalyst for the production of dimethylamine with high selectivity. This was attributed to a transition state shape selectivity associated with the clinoptilolite channels. The natural clinoptilolite displayed good selectivities at 400°C and a 5:1 ratio of methanol to ammonia, and gave a high conversion of > 90% ammonia to amines. The synthetic clinoptilolite gave better conversions and lower TMA selectivity than the natural clinoptilolite over a large range of feed ratios and temperatures. This included conversions of over 90% for most ratios (at 400 and 450°C). The natural clinoptilolite gave better results than those obtained using the amorphous clinoptilolite, which is currently used in industry. For example, low TMA selectivity was observed when a ratio of 5:1 or greater (methanol to ammonia) was used. The TMA selectivity is still far lower than the thermodynamic equilibrium selectivities obtained without a catalyst (62%). The catalyst lifetime has been shown to deteriorate with time.

Student Number : 9400913V - MSc (Eng) dissertation - School of Chemical and Metallurgical Engineering - Faculty of Engineering and the Built Environment
Natural zeolites are finding applicability in a broad range of industrial processes. This study assesses the potential applications of a South African natural zeolite, Clinoptilolite, and develops a methodology to quickly screen and assess these applications. Zeolites are known to have ion exchange and adsorption properties. Wastewater treatment has been identified as a potentially important opportunity in South Africa, since South Africa - and particularly Gauteng - is a water scarce region. The wastewater treatment industry in this region can be divided into two main categories of effluent: namely chemicals from coal and the metal recovery and finishing related to the mining industry. The focus of this work was to find a method to screen for potential uses of Clinoptilolite in these industries. The major effluent treatment issue in respect of the effluents from coal-based processes was identified to be the removal of oxygenate organics that are highly soluble in water, such as ethanol and acetone. This problem cannot be solved using vapour-liquid equilibrium based processes due to high energy costs, and liquid-liquid equilibrium based processes inherently introduce new contaminants into the wastewater. We therefore screened the zeolite for application in the removal of soluble organics via adsorption. The zeolite was found to be unsuitable for the adsorption of acetone and ethanol due to the preferential adsorption of water. As a result we tested the potential of the zeolite as a drying agent for ethanol and acetone. It was found that this zeolite could find application in the dehydration of ethanol, but not acetone. In effluent from the mining and metals based industries, heavy metals frequently occur and are usually toxic, such as lead, zinc and nickel. Such contaminated water must be disposed of as toxic waste, and this is very costly. Thus being able to selectively remove these metals allows for the possible recovery and recycling of a potentially valuable metal. If no application can be found for the recovered metal, the loaded zeolite would need to be disposed of as toxic waste, but the volume of this waste is significantly smaller than that of the original effluent due to the concentration effect of ion exchange processes. All of the metals were ion exchanged onto the zeolite successfully. The zeolite exhibited exceptional selectivity for the removal of lead, and reduced the concentration of lead in the water to levels below detection by Atomic Adsorption. The selectivity for the uptake of the metals in decreasing order was lead, zinc and lastly nickel. Therefore, provided the zeolite can be regenerated, it could be used for effluent treatment in mining activities that have traces of lead in the ore body, such as zinc and silver deposits, and in the battery industry. As a result of the work presented in this dissertation, a further project was undertaken to investigate the regeneration of the zeolite. Preliminary findings indicate that although it can be regenerated, the zeolite capacity decreases with each successive regeneration cycle. More work is required on regeneration to improve the lifespan of the zeolite.

M.Sc.
The metallurgical industrial losses of base metals with waste solutions are an environmental threat to water sources, hence these metal ions must be removed prior to discharge into receiving bodies. In this study, Southern African clinoptilolite’s capability as an ion-exchanger with respect to Cu2+ and Co2+ was investigated in order to consider its application in metal cation removal from aqueous solutions. The clinoptilolite was characterised with X-ray powder diffraction (XRD), X-ray fluorescence (XRF), FTIR, thermogravimetric analyser (TGA) and SEM-EDS. The clinoptilolite was found to be a thermally stable alumino-silicate with calcite, dolomite and quartz as the main minerals. Investigations of Co2+ and Cu2+ uptake were first performed on non-mixed solutions of these cations. It was found that Cu2+ was removed faster than Co2+ with removal efficiencies of 79% and 63% respectively. The column method was used in the cation-exchange processes with synthetic solutions of 0.0020 M, 0.0698 M and 0.2000 M of Co2+ and Cu2+ concentrations which were measured using atomic absorption spectroscopy (AAS). The effects of Co2+ and Cu2+ ions on one another’s removal efficiency were investigated on Co/Cu mixed synthetic solutions by varying their concentration ratios in solution. The Cu2+ was generally found to be removed at lower rates than the Co2+. Investigations on added impurities in the form of Si4+ and Fe2+ in the mixed Co/Cu synthetic solutions were carried out to determine their effect on the removal efficiencies of the targeted metals. It was found that both Si4+ and Fe2+ greatly reduced the removal efficiency of Cu2+, especially with increased amounts of Si4+ in the Co/Cu solution.

Loss of N via NH₃ volatilization during composting of poultry manure reduces the agronomic value of the end-product and contributes to environmental pollution. The objectives of this study were to evaluate N losses via NH₃ volatilization during aerobic composting of poultry layer manure, examine the potential of natural zeolites to adsorb the volatilized NH₃ during composting, and evaluate the poultry manure-zeolite compost as a controlled-release N fertilizer. Eleven mineral samples were characterized for their physical properties, chemical composition, and NH₄⁺ adsorption capacity. The effectiveness of a clinoptilolite zeolite ZI as an NH₄⁺ adsorbent at pH range 4 to 7 was tested. The kinetics of NH₄⁺ exchange on the zeolite was evaluated at the pH range 4 to 7, initial NH₄⁺ concentrations ranging from 70.1 to 1401 mgN L⁻¹, and a temperature range of 25 to 55 °C. Ammonia emissions were measured during composting of poultry manure with zeolites and other amendments in a laboratory composting simulator. The resulting composts were applied to a sand based medium planted with ryegrass (Lolium multiflorum) where growth, N uptake, and NH₄⁺ and N0₃⁻ leaching were evaluated. The cation exchange capacity (CEC) and purity of the zeolites, with respect to mineralogy and constituent ions, influenced their affinity and adsorptive capacity for NH₄⁺. The amount of NH₄ ⁺ adsorbed increased with increasing pH and NH₄⁺ concentration. The estimated NH₄⁺ adsorption capacity increased linearly with pH (r2 = 0.994), ranging from 9660 mg N L⁻¹ at pH 4 to 13830 mg N L⁻¹ at pH 7. Studies on thermodynamics of NH₄⁺exchange on the zeolite ZI indicated a higher activation energy for desorption (5.65 kJ mol1) than for adsorption (2.32 kJ mol⁻¹). Composting poultry manure with 60% zeolite ZI (weight basis) reduced NH₃ losses by 44.3%. The compost had total N concentration of 17.04 g N kg⁻¹ and a high NH₄ ⁺ concentration (52.8% of the total N). The 60% zeolite Zl-amended compost treatment produced the highest ryegrass dry matter, N accumulation and N use efficiency compared to the other composts evaluated. Nitrogen leaching losses were low. Although composting poultry manure amended with the natural zeolite clinoptilolite can reduce N losses to the atmosphere, recycling it for crop utilization, the cost of the high amount of zeolite required may be prohibitive.

The influence of decationization and dealumination on adsorption of water with rock from Transcarpathian deposit (Lypcha village, Ukraine) containing mordenite and clinoptilolite in the ratio 1:1 was studied. The obtained results can be used for preparation of adsorbents for dehydration of gases and organic liquids.

This work examined the effects of thermal and chemical treatments on zeolite reactivity and determined the zeolite properties governing the development of compressive strengths and pozzolanic reactivity. Zeolites are naturally occurring aluminosilicate minerals found abundantly around the world. Incorporation of zeolites in cement mixtures has been shown by past research to increase concrete’s compressive strength and durability. In addition, use of zeolites as SCMs can decrease the environmental impact and energy demands associated with cement production for reinforced concrete structures. Further, in contrast to man-made SCMs such as fly ash, zeolite minerals provide a reliable and readily available SCM source, not affected by the production limits and regulations of unrelated industries such as the coal power industry. In this work, six sources of naturally occurring clinoptilolite zeolite were examined. The zeolites were first characterized using x-ray fluorescence, quantitative xray diffraction, thermal analysis, particle size analysis, pore size distribution and surface area analysis, and scanning electron microscopy. Cation exchange capacity was also tested for one of the zeolites. Following comprehensive material characterization, the six pozzolanic reactivity of the natural zeolites was determined by measuring the quantity of calcium hydroxide in paste after 28 or 90 days, by measuring calcium hydroxide consumption of the zeolite in solution and by tracking the development of strengths of zeolite-cement mortars. Pretreatments that attempted to increase the reactivity of the zeolites, including calcination, acid treatment, milling and cation exchange, were then tested and evaluated using the same methods of material characterization and testing mentioned previously. Last, the results of the reactivity testing were reanalyzed to determine which properties of natural zeolites, including particle size, nitrogen-available surface area, and composition, govern the development of compressive strengths, pozzolanic reactivity and improved cement hydration parameters of pastes and mortars using natural zeolites as SCMs. Pretreatment testing showed that milling and acid treatment successfully increased the reactivity of zeolites used as SCMs. Additionally, particle size was shown to be the dominant property in determining the development of compressive strengths while particle size and surface area of the zeolites contributed to zeolite pozzolanic reactivity.
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Research Doctorate - Doctor of Philosophy (PhD)
Contamination of groundwater with fluoride has received worldwide attention due to its associated health problems with the prolonged intake of elevated fluoride concentration above 1.5 mg/L. This thesis dealt with the remediation of highly contaminated groundwater with the spent potliner leachate (SPLL) which is characterized by high concentration of fluoride among a cocktail of other chemicals (anions, cations, heavy metals and organics). The viability of natural calcite (limestone) and natural zeolite (clinoptilolite) for fluoride removal associated with SPLL was tested. The purpose was to find the optimal mixture of calcite and zeolite that will maximise fluoride removal and stop/or minimise the inhibitory effect of SPLL chemicals on calcite capacity to remove fluoride. Four calcite-zeolite mixtures were used, that is calcite, zeolite, calcite-zeolite (50:50) and calcite-zeolite (70:30). The removal capacity of these mixtures in batch and column tests was not the same. For a long residence (contact) time (as in batch tests), more fluoride was removed by calcite-zeolite 50:50 and 70:30 mixtures than calcite or zeolite alone. That was true for both synthetic and SPLL solutions. In continuous column tests (where the contact between fluoride and sorbents is spatial and temporal), SPLL tests showed a prevalence of zeolite over calcite or its mixtures (calcite-zeolite 50:50 and 70:30). For synthetic fluoride solution, all columns containing zeolite showed nearly similar fluoride removal which was higher than that obtained using column containing calcite. Overall, in batch tests calcite showed better fluoride removal than zeolite while the inverse was true in column tests. That was attributed to the fact that zeolite has more surface area than calcite and moreover the removal mechanism of fluoride by calcite depends on the slow hydrolysis process. Hence calcite is more effective in batch tests setup where enough time is allowed for calcite dissolution. Fluoride removal by calcite and zeolite was depleted in SPLL by ~40-67% in 1.18 mm and ~12-46% in 150 µm fraction sizes as compared to synthetic fluoride solution. Heavy metals (lead, magnesium and manganese) and organics (3-methylphenol and 4-methylphenol) associated with fluoride in SPLL showed an interfering effect for fluoride removed by calcite. Other major heavy metals (vanadium, copper, barium and cobalt) and organics (aniline, phenol, 2-methyl phenol, 2-methylnaphthalene, acenaphthene, fluorene and carbazole) in SPLL solution have not shown any effect on calcite capacity to remove fluoride.