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Design of nanoporous materials for light alkane transformationSchmidt, Iver January 2001 (has links)
No description available.
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A manifold destiny : advancing the frontiers of the ADOR processFirth, Daniel Sean January 2017 (has links)
This thesis deals with the various attempts to expand the ADOR (Assembly, Disassembly, Organisation and Reassembly) process. This includes the use of the ADOR process to incorporate new elements into a zeolite framework, the expansion of the ADOR process to other germanosilicate frameworks, and the first ever synthesis of a new ADORable germanosilicate and its subsequent daughters. Chapter 4 deals with the expansion of the ADOR process to the already known ADORable zeolite UTL, using the organisation and reassembly steps to incorporate Al and P, resulting in the formation of a zeolite-AlPO hybrid with distinct silicate layers connected by AlPO based s4r linkages. The material was shown to contain Al and P species and was unstable to acidic medium, atypical of the wholly silica zeolite frameworks produced by the ADOR process. MAS NMR studies showed the presence of both tetrahedral P and Al species in the material and that the presence of Si-OH groups was limited. Indicating that the layers had been reconnected with Al and P now present, forming a zeolite-AlPO hybrid. 29 Si-enriched materials were synthesised to confirm the presence of P-O-Si bonds, through 2D MAS NMR correlation experiments; however, results were limited due to the lack of signal strength. Chapter 5 deals with attempts to expand the ADOR process by applying the ADOR process to other already known germanosilicates. It was found that the non-ideal ADORable candidates NUD-1 and ITQ-33 were unable to undergo a controlled disassembly process, primarily due to their high Ge content and distribution of d4r/d3r. The zeolites ITQ-38 and IM-20 showed more promise. Both could undergo disassembly to form a layered material, which could then be organised and reassembled to form new materials. However, these materials were shown to not form perfect daughter zeolites and had a high degree of disorder. This was associated with the complexity of the ADOR process and the many factors that play a role in each step. Chapter 6 deals with the use of a family of SDAs (with the same biphenyl backbone) to synthesise new ADORable zeolites. The synthesis of the SDAs and their use in various zeolite syntheses was discussed. The potential of these SDAs for the synthesis of new zeolites was then evaluated. The investigations were relatively successful with the successful formation of an ADORable zeolite, which was already known, UTL. However, the suitability of such SDAs also put into question, due to their instability under hydrothermal conditions. Chapter 7 discussed the first successful a priori synthesis of a parent germanosilicate and its daughter zeolites by the ADOR process. The successful synthesis of an ADORable zeolite (SAZ-1) was conducted with the use of an imidazolium-naphthalene based SDA. Investigations were first conducted into changing the synthesis condition, exploring the impact of these changes on the resulting products, and optimising the synthesis conditions to favour the formation of the new zeolite SAZ-1. These investigations led to the new zeolite framework SAZ-1, which showed similarities to the zeolites NUD-2 and CIT-13, which were developed simultaneously by other institutions. The properties of the SAZ-1 framework were discussed and were found to be highly suitable for the ADOR process. SAZ-1 was then successfully disassembled, organised, and reassembled to form two new daughter zeolites SAZ-2 and SAZ-3. The alumination of SAZ-1P to form aluminated SAZ-2 and SAZ-3 was also attempted. Both zeolites showed an increase in catalytic activity, compared to the typical pure-silica daughter zeolites. The layers of SAZ- 1P were also able to undergo the same shifting process as seen for the ‘unfeasible' zeolites IPC-9 and IPC-10, but the resultant products were not as ordered as these previous examples. This in addition to the previous work highlighted some of the non-ideal properties of SAZ-1 compared to other ADORable zeolites, like UTL.
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Syntéza, charakterizace a katalytické využití nových typů zeolitů / Synthesis, characterization and catalytic application of novel zeolitesEliášová, Pavla January 2014 (has links)
The PhD thesis concerns the synthesis of novel zeolite materials, investigation of their properties and their possible use in catalytic application. The work was focused on the two- dimensional zeolites. The thesis was worked out at the Department of Synthesis and Catalysis at J. Heyrovský Institute of Physical Chemistry, AS CR. Germanosilicate UTL (Si/Ge molar ratio 4.0-6.5) was found to undergo unique structural changes in the neutral or acid environment leading to transformation of its three-dimensional framework into two-dimensional layered material denoted IPC-1P. The UTL degradation, so called top-down synthesis, was enabled due to a presence of double-four-units (D4Rs), which can be seen as supporting units/pillars between the rigid layers. The preferential location of Ge in D4Rs makes the units an ideal target for their selective degradation. The interlayer space in lamellar IPC-1P was modified by swelling with long-organic chain surfactant (material IPC-1SW). To keep the interlayer space permanently expanded (up to 3.3 nm) the silica amorphous pillars were subsequently introduced (material IPC-1PI). The integrity of the layers and their preserved UTL character was confirmed in all members of IPC-1 family by HRTEM and electron diffraction measuring. The layers of IPC-1P were condensed back...
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Ionothermal synthesis : a new synthesis methodology using ionic liquids and eutectic mixtures as both solvent and template in zeotype synthesisParnham, Emily Ruth January 2006 (has links)
The aim of this thesis was to research the new synthesis methodology of ionothermal synthesis, used for the synthesis of zeolite type materials, mainly aluminophosphates. An ionic liquid or eutectic mixture is to act as both the organic template and the solvent, hence eliminating the space filling effects in the reaction from the water. Initial reactions were carried out using the ionic liquid 1-ethyl-3-methylimidazolium bromide which acted as the solvent and template in the production of four three-dimensional structures and one layered structure. The addition of cobalt into the aluminophosphate framework was investigated and resulted in three different cobalt-aluminophosphates being synthesised, including one new zeolite framework. Experiments were carried out into the effect of altering the imidazolium cation alkyl chain. It appears likely that in the presence of fluoride, some of the imidazolium cations undergo a metathesis reaction forming 1,3-dimethylimidazolium which acts as a template in the formation of an aluminophosphate. Preliminary investigations have also been started into the effects of changing the ionic liquid anion from bromide to phosphorus hexafluoride and bis((trifluoromethyl)sulfonyl)amide. The use of these anions resulted in the production of several different one and two-dimensional structures. The use of eutectic mixtures as solvent and template was also investigated as a cheaper, more easily synthesised solvent than the ionic liquids. The results show a new methodology of eutectic mixtures acting as template delivery agents through the slow, in situ decomposition of the urea derivative of the eutectic mixture. This synthesis method resulted in the formation of nine one and two-dimensional aluminophosphates.
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Synthesis of zeolite (ZSM-5 and Faujasite) and geopolymer from South African coal fly ashNdlovu, Nkululeko Zenzele Neville January 2016 (has links)
Thesis (MTech (Chemical Engineering))--Cape Peninsula University of Technology, 2016. / Population growth in South Africa has led to a direct increase in electricity demand. Due to the
abundance of coal in the country, most of the energy requirement is met through coal combustion.
Although there is a vast coal resource, the natural high grade coal is mainly exported, while the
low grade coal is exploited for electricity generation. The combustion of low grade coal during
electricity production results in huge quantities of coal fly ash (CFA) that require careful
disposal, due to its toxicity. Poor management of this waste constitutes serious human and
environmental problems, such as respiratory diseases, contamination of soil, surface water and
groundwater. This is in part due to the fact that only a small percentage of fly ash is utilised
efficiently in the construction industry. Several studies have recently been conducted into the use
of CFA as a starting material for the synthesis of zeolites and geopolymers, due to its high
silicon and aluminium content. However, the synthesis of zeolites from CFA has been subject to
criticism, because the synthesis of zeolites from the bulk CFA results in zeolite products that are
mixed with non-reacted fly ash and toxic elements. On the other hand, pure phase zeolites can only
be synthesised from CFA extracts, which results in a small yield of the zeolite products and a huge
amount of solid waste. Therefore, this does not facilitate either the use of fly ash-based zeolites
as catalysts in advanced chemical processes or scaling up of the synthesis process. This study seeks to make optimal use of CFA by developing a method for optimal extraction of Si and Al for the synthesis of ZSM-5 and faujasite zeolites, and use the resulting solid waste for the synthesis of geopolymers such that the resultant waste is minimised or completely eliminated. Two distinct processes are employed in this study to synthesise ZSM-5 or faujasite zeolite from CFA extracts, while the solid residue is transformed into a geopolymer. In the first process, an alkaline leaching method is employed for extraction of Si from CFA using 8 M NaOH at 150 0C for 24 h. It was found that the Si extract contained a certain amount of Al, enough for the synthesis of a high silica zeolite such as ZSM-5. However, the Si extract had to be treated with oxalic acid in order to remove the excess Na in the extract, since this could prevent the formation of ZSM-5. The obtained Si extract was then used as a feedstock for the synthesis of Zeolite ZSM-5 with NaOH and tetraethyl ammonium hydroxide (TEAOH) as mineralising and structure directing agents respectively. The obtained gel underwent hydrothermal synthesis at 160 °C for 72 h, while the solid residue obtained after Si extraction was used in the synthesis of geopolymer at 70 °C for 5 days. The obtained ZSM-5 and geopolymer products were characterised using ICP, XRD, SEM, FTIR and NMR techniques.
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Structure direction in the formation of zeolitic materialsWarrender, Stewart James January 2007 (has links)
Structure direction in the formation of zeolitic materials has been investigated through the parallel approaches of structural and synthesis studies. The structures of gallosilicates TNU-6 and TNU-7 have been solved from powder X-ray diffraction. TNU-6 (P6₃, a = b = 10.5078(1)Å, c = 8.5277(1)Å) is found to possess a stuffed tridymite-like structure isostructural with BaFeGaO₄. Evidence from electron diffraction, single crystal and high-resolution powder X-ray diffraction suggests the presence of a √3a superstructure, analogous to the related KAlGeO₄ phase, arising from a subtle variation in tilt of tetrahedral units. The structure of TNU-7 consists of an ordered 1:1 intergrowth of alternating sheets of mazzite and mordenite (Pmmn, a = 7.5721(1)Å, b = 17.0739(2)Å, c = 25.8438(5)Å). The crystallisation field of TNU-7 is found to lie between those of mazzite and mordenite, suggesting that this is an example of a ‘boundary phase’ - phase selectivity being governed strongly by the presence and quantity of Ga in the synthesis gel. The distribution of extra-framework Na⁺ cations in the as-made material, and Cs⁺ and Sr²⁺ in ion-exchanged samples, suggests a higher extra-framework charge per T-site associated with the mazzite region of the structure, indicating the possible existence of compositional zoning, consistent with the preference to form mazzite at high Ga gel-content. The structures and synthesis conditions for both TNU-6 and TNU-7 suggests a cooperative effect between Ga and extra-framework species in directing the formation of these phases. The structure of the novel aluminosilicate TNU-9 has been confirmed by energy minimisation and powder neutron diffraction studies (C2/m, a = 28.177(2)Å, b = 20.030(1)Å, c = 19.464(1)Å, β = 92.311(4)º ). Monte Carlo-Simulated Annealing studies have been employed to investigate the favoured location of the 1,4-bis(N- methylpyrrolidinium)butane template molecule within the complex pore system. Remarkably, three (possibly four) different positions are assumed by the structure-directing agent, forming head-to-middle and head-to-head motifs between constituent framework aluminosilicate sheets. TNU-9 crystallises in a very narrow gel composition window suggesting a strong cooperative effect between organic and inorganic gel components. Structure direction of phosphate-based materials (aluminophosphates, magnesium aluminophosphates and silicoaluminophosphates) has been investigated through co-templating synthesis studies. In particular, the structure-directing activity of Cu²⁺ (and to a lesser extent Ni²⁺) complexes of the azamacrocyles cyclam and cyclen, and related derivatives, is investigated in the presence of additional amines (dipropylamine, diisopropylamine, tetraethylammonium hydroxide, diisopropylethylamine). Complexes of a selection of linear polyamines, and also cobalticinium are studied for comparison. Although added primarily as pH moderators, the additional amines are also found to influence the crystallisation and hence provide effective routes to the synthesis of transition metal-containing materials with potential catalytic application. The ‘strength’ of the structure-directing ability of the additional amines is found to vary depending on the identity of the primary structure-directing agent, with behaviour ranging from passive pH moderator to dominating structure-directing agent. The outcome of syntheses is also highly dependent on inorganic gel composition. Through appropriate combination of structure-directing agent and additional amine, mixed Cu²⁺/Ni²⁺-containing MgAPO and SAPO STA-6 (SAS) and STA-7 (SAV) materials have been synthesised for the first time, as well as a low Si form of SAPO STA-7 (with and without Cu²⁺). Also, the combination of cyclam, tetraethylammonium hydroxide and HF has been found to produce a SAPO analogue of STA-7 possessing silicate islands. In addition, transition metal-containing materials possessing the AEL, AFI, CHA, UT-6 and LEV topologies have also been synthesised via this approach. Elemental analysis, UV-Vis, ESR and NMR spectroscopy are employed to confirm the presence of the desired complex in selected samples, while X-ray diffraction and ESR spectroscopy are employed to investigate the environment of extra-framework transition metal species, post calcination, in MgAPO STA-6, SAPO STA-6 and STA-7, MgAPO-18, and MgAPO-5.
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Performance of zeolite ZSM-5 synthesised from South African fly ash in the conversion of methanol to hydrocarbonsFolifac, Leo January 2018 (has links)
Thesis (Master of Engineering in Chemical Engineering)--Cape Peninsula University of Technology, 2018. / Zeolites have found applications as heterogeneous or solid catalyst in the petrochemical and refining industries. Zeolite ZSM-5 in particular is a highly siliceous solid catalyst with a porous network that consists of medium pore structure (pore openings 5-5.5 A). The solid catalyst (ZSM-5) is well known for its high temperature stability and strong acidity, which makes it an established catalyst used for different petrochemical processes such as Methanol-To-Gasoline (MTG), isomerisation, disproportionation, and cracking. Unlike in the past, the synthesis of zeolite ZSM-5 from other sources that contains silica (Si) and alumina (Al) with the addition of a template (TPBr) as a structure-directing agent is eminent. Its synthesis can be achievable from coal fly ash that is a waste material and a cheap source of Si and Al. Coal fly ash is a waste material that is produced during the combustion of coal to generate electricity. The elemental composition of coal fly ash consists of mostly SiO2 and Al2O3 together with other significant and trace elements. Zeolite ZSM-5 catalyst synthesised from coal fly ash by previous authors required an excessive amount of additional source of silica even though the XRD spectra still show the presence of quartz and mullite phase in the final products. These phases prevented the use of fly ash (solid) as a precursor to synthesise zeolite ZSM-5 products. However, the synthesis of high purity zeolite ZSM-5 products by extracting silica and alumina from South African fly ash and then using it with small amounts of fumed silica was investigated This aim was achieved by fusing fly ash (FA) with sodium hydroxide (NaOH) under hydrothermal condition set at 550 oC for 1 hour 30 minutes. The quartz and mullite phase observed by previous authors was digested by the fusion process. Thereafter, the treatment of fused fly ash filtrate (FFAF) with concentrated H2SO4 (98-99%), precipitated silica and removed Al that therefore increased the Si/Al ratio from 1.97 in fly ash (FA) to 9.5 in the silica extract (named fused fly ash extract). This route was designed to improve the quality of the final products and reduced the amount of fumed silica added to the synthesis mixture prior to hydrothermal synthesis. In this line of investigation, the process of adding fumed silica to the hydrothermal gel was optimised. H-FF1 with a Si/Al ratio of 9.5 was synthesised using the silica extract without the addition of fumed silica. Its XRD, SEM and relative crystallinity results proved that H-FF1 was inactive and hence was not further characterised and utilised in the conversion of methanol to hydrocarbons (MTH). Purer phase zeolite ZSM-5 products (H-FF2 and H-FF3) that were synthesised from silica extract with the addition of small amounts of fumed silica were characterised and successfully used in the methanol to hydrocarbons (MTH) reaction. The synthesised ZSM-5 products had different Si/Al ratio, different morphology, crystal size, BET surface area, and relative crystallinity as well as different trends in the MTH reaction. It was also observed that H-FF2 and H-FF3 (pure phase) solid catalyst deactivated faster than the commercial H-ZSM-5 in the MTH reaction. However, the MTH conversion over H-FF2 competed with that of the commercial H-ZSM-5 within 3 hours of time on stream (TOS) but later deactivated at a faster rate. This was caused by the large crystal size and reduced BET surface area of H-FF2 when compared to the commercial H-ZSM-5. However, H-FF2 performed better than H-FF3 on stream (MTH reaction) due to its smaller crystal size and higher BET. This study has successfully utilised a route that synthesised high purity zeolite ZSM-5 products from the South African fused fly ash extract (FFAE) with the addition of small amounts of fumed silica. The properties of the synthesised zeolite ZSM-5 products (H-FF2 and H-FF3) were similar to that of the commercial H-ZSM-5 as well as active in the MTH reaction. This promoted the utilisation of a waste material (coal fly ash) to synthesise highly siliceous zeolite ZSM-5 products that avoided the presence of mineral phases from fly ash in the final products.
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Hydrothermal synthesis and characterization of high-silica MFI zeolites with Titanium heteroatoms in the matrix and their testing in the catalytic oxidation with hydrogen peroxide as the oxidant.Maanaso, Morule Fortune. January 2014 (has links)
M. Tech. Chemical Engineering. / Discusses the scope of this research study composes of three interactive steps. The first step involves the design of the specific zeolite system (ZSM-5) and the set-up of an autoclave reactor for the hydrothermal synthesis of this and other zeolites and nano materials, then the oxidation catalyst (TS-1) development, i.e. the substitution of aluminium with titanium in the zeolite framework, and finally the formulation and preparation of the isomorphous Silicalite zeolite by omitting the aluminium in the synthesis. And further, set-up of suitable equipments and apparatus for the catalytic testing of the Titanium Silicalite-1 in the oxidation reaction of phenol as the test reaction. Therefore, the overall objectives of this research are: set up an autoclave reactor for the hydrothermal synthesis, formulation of a synthesis recipe for MFI family of catalysts in the laboratory, synthesis of ZSM-5, Silicalite-1, and TS-1 zeolites catalysts in the laboratory, characterization and optimization of the of catalysts listed above, testing the Ti-Silicalite catalyst in the oxidation reaction of phenol with hydrogen peroxide, as the oxidant, set up analytical system (Gas Chromatography, ASS) for analysis of catalyst performance in the oxidation reaction, Evaluate the conversion of the reaction and the selectivity of the individual catalysts reaction Evaluate the conversion of the reaction and the selectivity of the individual catalysts reaction and verify results obtained and compare with systems described in the literature.
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Cristalização da zeólita ferrierita sem direcionador orgânico, variando-se a alcalinidade e o teor de sementesBranco, Monique Peixoto Castelo 28 February 2011 (has links)
Zeolites are crystalline aluminosilicates of natural or synthetic origin, with a structure consisting of an extensive microporous three-dimensional network, routinely used as catalysts, ion exchange and adsorbents. The production of ferrierite and other zeolites are limited due to the high cost of the organic structure-directing agents used in synthesis. Many studies are conducted with the goal of finding a viable and more economical route to the possibility of industrial scale production. The purpose of this study was to obtain a methodology for synthesis of ferrierite without using organic structure-directing agents, by hydrothermal method, inserting seeds during the crystallization gel preparation and varying the alkaline concentration of the mixture in order to achieve shorter times of crystallization and lower cost production at a temperature of 200°C. For the synthesis of materials prepared in this work were used: fumed silica as silicon source, pseudoboehmite as a source of aluminum, sodium and potassium hydroxide as sodium and potassium sources, respectively. As seeds to crystallization, samples of commercial ferrierita were used. The synthesized samples were characterized by X-ray diffraction (XRD), spectroscopy of the Fourier transform infrared (FT-IR) and thermal analysis (TG/DTA). The X-ray diffraction patterns showed characteristic peaks of zeolite desired in all conditions of synthesis. The infrared spectra showed bands characteristic of ferrierite, as a further indication of the formation of zeolite. TG curves showed a mass loss of up to 10% in the temperature range from 23 to 400°C. The results of the analysis confirmed the formation of zeolite ferrierite with good crystallinity and purity, proving the efficiency of the methodology. / As zeólitas são aluminossilicatos cristalinos, de origem natural ou sintética, com estrutura constituída por uma extensa rede tridimensional microporosa, rotineiramente utilizadas como catalisadores, trocadores iônicos e adsorventes. A produção da ferrierita, e outras zeólitas, são limitadas devido ao alto custo do direcionador orgânico utilizado na síntese. Muitos estudos são realizados com o objetivo de encontrar uma rota mais econômica e viável para a possibilidade de produção em escala industrial. O objetivo deste trabalho foi obter uma metodologia para síntese da ferrierita sem utilizar direcionador orgânico, pelo método hidrotérmico, inserindo sementes de cristalização durante o preparo do gel e variando a concentração alcalina da mistura reacional, a fim de alcançar menores tempos de cristalização e menor custo de produção, numa temperatura de 200°C. Para a síntese do material preparado neste trabalho foram utilizados: sílica fumed como fonte de silício, pseudoboehmita como fonte de alumínio, e hidróxido de sódio e potássio como fontes de sódio e potássio, respectivamente. Já para sementes de cristalização, foram utilizadas amostras de ferrierita comercial. As amostras sintetizadas foram caracterizadas por difração de raios X (DRX), espectroscopia na região do infravermelho por transformadas de Fourier (FT-IR) e análises térmicas (TG/DTA). Os difratogramas de raios X mostraram picos característicos da zeólita desejada em todas as condições de síntese. Os espectros de infravermelho apresentaram bandas características da ferrierita, sendo mais um indício da formação da zeólita. As curvas de TG mostraram uma perda de massa de no máximo 10% numa faixa de temperatura de 23 a 400°C. Os resultados das análises realizadas comprovaram a formação da zeólita ferrierita com boa cristalinidade e pureza, comprovando a eficiência da metodologia proposta.
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Investigation of some scale-up conditions on the synthesis of faujasite zeolites from South African coal fly ashBrassell, James Philip January 2017 (has links)
Thesis (MTech (Chemical Engineering))--Cape Peninsula University of Technology, 2017. / Coal fly ash waste produced from the coal combustion process is becoming an ever increasing concern. It is produced in such abundance due to not only South Africa, but the whole of the world relying mainly on coal combustion for the main source of energy production. With the growing rate of the human population this energy production is ever increasing. The current methods of disposal of this fly ash is not sustainable, it is being dumped in ash dumps, and poses a risk to the surrounding environment and human population. Therefore, processes need to be developed to take this waste and turn it into useful materials. This would not only solve the problem of its disposal but also create useful products that can be applied to further protect the environment. It was discovered that one of the useful materials that can be synthesised from fly ash are zeolites. These nano-porous structures have a wide variety of uses. Therefore, many studies have been conducted around optimising the synthesis of various zeolites from coal fly ash. More recently these studies have focused on the scale-up conditions needed to synthesise these zeolites on the large industrial scale, regarding the sheer volume of fly ash produced annually. The most robust and widely used technique for zeolite synthesis involves a pre-synthesis fusion of the fly ash with sodium hydroxide at a temperature of 550 0C. This would not be feasible to scale-up to industrial scale because of the energy intensity. Therefore, alternative pre-synthesis techniques have been proposed. One of those techniques involves using a sonochemical treatment as a pre-synthesis. It can be argued that this technique may not be able to be easily scaled. To solve this problem, another alternative technique was investigated within this study. It involves the use of a jet loop pilot plant mixing system, which can be scaled-up very readily to industrial scale.
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