Hydroisomerization of n-decane over SAPO-11 catalysts synthesized with methylamine as co-template

The present work deals with preliminary studies concerning a new synthesis approach to prepare SAPO materials with AEL structure and evaluate their catalytic behavior in the hydroisomerization of long paraffins. The new SAPO-11 catalysts were synthesized with the help of a small amine (methylamine, MA) added during the preparation of the initial gel. As MA incorporates into the structure of the final materials, it contributes, together with DPA (dipropylamine), to an increase in Si incorporation as isolated species, which results in Bronsted acid sites. Thus, this new and original synthesis strategy allows to obtain materials with enhanced Bronsted acidity when compared with free MA materials. The catalysts were tested in n-decane hydroisomerization (n-decane was used as a model molecule) and confirmed the effect of MA on the acidic properties of the catalysts. The samples synthesized with MA present a higher number of acid sites that increase the catalytic conversion but have a negative effect in the isomerization selectivity, i.e. a more significant amount of cracking products is formed.

Preparação e avaliação das propriedades catalíticas de materiais do tipo SAPO-11 na hidroisomerização de n-decano

Neste trabalho efectuou-se o estudo do comportamento de catalisadores bifuncionais do tipo SAPO-11, contendo 0,5% em massa de platina, em que foram efectuadas alterações durante o processo de síntese, na reacção de hidroisomerização do n-decano. As modificações efectuadas nos catalisadores foram: quantidade de silício; utilização di-propilamina (DPA) como agente estruturante ou a mistura de di-proppilamina (DPA) e metilamina (MA), funcionando esta última como co-estruturante; diferentes tempos de cristalização (24 e 12h); e a introdução de nióbio (Nb). Os catalisadores preparados foram caracterizados recorrendo às técnicas de difracção de raio-X, microscopia electrónica de varrimento, adsorção de N2, adsorção de piridina acompanhada por espectroscopia de infravermelho, reacção de hidrogenação do tolueno e quimissorção de H2. A quantidade de Si afecta a acidez e, ligeiramente, a actividade hidrogenante, levando a uma diminuição da selectividade aos produtos mono-ramificados com o aumento de Si. A utilização de MA aumenta, significativamente, o tamanho dos cristais, reflectindo-se na menor selectividade aos isómeros mono-ramificados. Nos catalisadores preparados com menor tempo de cristalização o crescimento dos cristais não é completo, sendo o seu tamanho inferior aos preparados com 24h com consequente diminuição da cristalinidade dos materiais. A presença de Nb exerce um efeito na acidez dos catalisadores e na não uniformidade do tamanho dos cristais, provocando o aumento da selectividade aos produtos multi-ramificados e reacções de craking.

Incorporation of niobium in SAPO-11 materials: Synthesis and characterization

The present work concerns a new synthesis approach to prepare niobium based SAPO materials with AEL structure and the characterization ofNb species incorporated within the inorganic matrixes. The SAPO-11 materials were synthesized with or without the help of a small amine, methylamine (MA) as co-template, while Nb was added directly during the preparation of the initial gel. Structural, textural and acidic properties of the different supports were evaluated by XRD, TPR, UV-Vis spectroscopy, pyridine adsorption followed by IR spectroscopy and thermal analyses. Pure and well crystalline Nb based SAPO-11 materials were obtained, either with or without MA, using in the initial gel a low Si content of about 0.6. Increasing the Si content of the gel up to 0.9 led to an important decrease of the samples crystallinity. Niobium was found to incorporate the AEL pores support as small Nb2O5 oxide particles and also as extra framework cationic species (Nb5+), compensating the negative charges from the matrix and generating new Lewis acid sites. (C) 2011 Elsevier Inc. All rights reserved.

Effects of oxidante acid treatments on carbon-templated hierarchical SAPO-11 materials: synthesis, characterization and catalytic evaluation in n-decane hydroiosomerization

Hierarchical SAPO-11 was synthesized using a commercial Merck carbon as template. Oxidant acid treatments were performed on the carbon matrix in order to investigate its influence on the properties of SAPO-11. Structural, textural and acidic properties of the different materials were evaluated by XRD, SEM, N-2 adsorption, pyridine adsorption followed by IR spectroscopy and thermal analyses. The catalytic behavior of the materials (with 0.5 wt.% Pt, introduced by mechanic mixture with Pt/Al2O3), were studied in the hydroisomerization of n-decane. The hierarchical samples showed higher yields in monobranched isomers than typical microporous SAPO-11, as a direct consequence of the modification on both porosity and acidity, the later one being the most predominant. (C) 2014 Elsevier B.V. All rights reserved.

Síntese, caracterização e estudo da regeneração do silicoaluminofosfato-11 (SAPO-11)

heterogeneous catalyst such as a silicoaluminophosphate, molecular sieve with AEL (Aluminophosphate eleven) structure such as SAPO-11, was synthesized through the hydrothermal method starting from silica, pseudoboehmite, orthophosphoric acid (85%) and water, in the presence of a di-isopropylamine organic template. For the preparation of SAPO-11 in a dry basis it was used as reactants: DIPA; H3PO4; SiO4; Pseudoboehmite and distilled water. The crystallization process occurred when the reactive hydrogel was charged into a vessel and autoclaved at 200ºC for a period of 72 hours under autogeneous pressure. The obtained material was washed, dried and calcined to remove the molecular sieves of DIPA. The samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), infrared spectroscopy (FT-IR), nitrogen adsorption (BET) and thermal analysis (TG/DTG). The acidic properties were determined using adsorption of nbutylamine followed by programmed thermodessorption. This method revealed that SAPO-11 shows an acidity that ranges from weak to moderate. However, a small quantity of strong acid sites could be detected there. The deactivation of the catalysts was conducted by artificial coking followed by the cracking of the n-hexane in a fixed bed with a continuous flow micro-reactor coupled on line to a gas chromatograph. The main products obtained were: ethane, propane, isobutene, n-butane, n-pentane and isopentane. The Vyazovkin (model-free) kinetics method was used to determine the regeneration and removal of the coke

Síntese, caracterização e avaliação catalítica do silicoaluminofosfato SAPO-11 sulfatado

Due to environmental restrictions around the world, clean catalytic technology are of fundamental importance in the petrochemical industry and refineries. Creating the face of this a great interest in replacing the liquid acids for solid acids, so as molecular sieves have been extensively studied in reactions involving the acid catalysis to produce chemical substances with a high potential of quality. Being the activity of the catalysts involved in the reaction attributed to the acid character of them involved for the Lewis and Brönsted acid sites. Based on this context, this study aimed to prepare catalysts acids using a molecular sieve silicoalumino-phosphate (SAPO-11) synthesized in hidrotermical conditions and sulphated with sulphuric acid at different concentrations, using to it the method of controlled impregnating. The samples resulting from this process were characterized by x-ray difratometry (DRX), scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FT-IR), thermal analysis (TG-DTG) and determination of total acidity (by n-butilamin adsorption). The results show that the synthesis method used was efficient in the formation of AEL structure of SAPO-11 and when being incorporated the sulfate groups in this structure the acidity of the material was increased, pointing out that to very high concentrations of acid there is a trend of decrease the main peaks that form the structure. Finally they were tested catalytictly by the reaction model of conversion of m-xylene which showed favorable results of conversion for this catalyst, showing to be more selective of cracking products than isomerization, as expected, in order that for the o-xylene selectivity there was no positive change when to sulfate a sample of SAPO-11, while for light gases of C1-C4 this selectivity was remarkably observed

Síntese, caracterização e estudo da regeneração do silicoaluminofosfato-11 (SAPO-11)

heterogeneous catalyst such as a silicoaluminophosphate, molecular sieve with AEL (Aluminophosphate eleven) structure such as SAPO-11, was synthesized through the hydrothermal method starting from silica, pseudoboehmite, orthophosphoric acid (85%) and water, in the presence of a di-isopropylamine organic template. For the preparation of SAPO-11 in a dry basis it was used as reactants: DIPA; H3PO4; SiO4; Pseudoboehmite and distilled water. The crystallization process occurred when the reactive hydrogel was charged into a vessel and autoclaved at 200ºC for a period of 72 hours under autogeneous pressure. The obtained material was washed, dried and calcined to remove the molecular sieves of DIPA. The samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), infrared spectroscopy (FT-IR), nitrogen adsorption (BET) and thermal analysis (TG/DTG). The acidic properties were determined using adsorption of nbutylamine followed by programmed thermodessorption. This method revealed that SAPO-11 shows an acidity that ranges from weak to moderate. However, a small quantity of strong acid sites could be detected there. The deactivation of the catalysts was conducted by artificial coking followed by the cracking of the n-hexane in a fixed bed with a continuous flow micro-reactor coupled on line to a gas chromatograph. The main products obtained were: ethane, propane, isobutene, n-butane, n-pentane and isopentane. The Vyazovkin (model-free) kinetics method was used to determine the regeneration and removal of the coke

Estudo da regeneração de aditivos para catalisadores de craqueamento aluminofosfatos (ALPO s)e silicoaluminofosfatos (SAPO s)

Heterogeneous catalysts such as aluminophosphate and silicoaluminophosphate, molecular sieves with AEL of ALPO-11 and SAPO-11, were synthesized by the hydrothermal method with the following molar composition: 2.9 Al +3.2 P + 3.5 DIPA +32.5 H20 (ALPO-11); 2.9 Al +3.2 P + 0.5 Si + 3.5 DIPA +32.5 H20 (SAPO-11) starting from silica (only in the SAPO-11), pseudoboehmite, orthophosphoric acid (85%) and water, in the presence of a di-isopropylamine organic template. The crystallization process occurred when the reactive hydrogel was charged into a vessel and autoclaved at 170ºC for a period of 48 hours under autogeneous pressure. The obtained materials were washed, dried and calcined to remove the molecular sieves of DIPA. The samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), infrared spectroscopy (FT-IR), thermo gravimetric differential thermal analysis (TG/DTA) and nitrogen adsorption (BET). The acidic properties were determined using adsorption of n-butylamine followed by programmed thermodessorption. This method revealed that ALPO-11 has weaker acid sites due to structural defects, while SAPO-11 shows an acidity that ranges from weak to moderate. However, a small quantity of strong acid sites could be detected there. The deactivation of the catalysts was conducted by the cracking of the n-hexane in a fixed bed continuous flow microrreator coupled on line to a gas chromatograph. The main products obtained were: ethane, propane, isobutene, n-butane, n-pentane and isopentane. The Vyazovkin (model-free) kinetics method was used to determine the regeneration and removal of the organic template

Estudos comparativos do ciclo de regeneração de diferentes tipos de silicoaluminofosfatos

Different types of heterogeneous catalysts of the silicoaluminophosphate type, (SAPO-5, SAPO-11, SAPO-31, SAPO-34 and SAPO-41), molecular sieves with a: AFI, AEL, ATO, CHA and AFO structure, respectively, were synthesized through the hydrothermal method. Using sources such as hydrated alumina (pseudobohemita), phosphoric acid, silica gel, water, as well as, different types of organic structural templates, such as: cetyltrimethylammonium bromide (CTMABr), di-isopropylamine (DIPA), di-n- propylamine (DNPA) and tetraethylammonium hydroxide (TEOS), for the respective samples. During the preparation of the silicoaluminophosphates, the crystallization process of the samples occurred at a temperature of approximately 200 ° C, ranging through periods of 18-72 h, when it was possible to obtain pure phases for the SAPOs. The materials were furthermore washed with deionized water, dried and calcined to remove the molecules of the templates. Subsequently the samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), absorption spectroscopy in the infrared region (FT-IR), specific surface area and thermal analysis via TG/DTG. The acidic properties were determined using adsorption of n-butylamine followed by programmed termodessorption. These methods revealed that the SAPO samples showed a typically weak to moderate acidity. However, a small amount of strong acid sites was also detected. The deactivation of the catalysts was conducted by artificially coking the samples, followed by n-hexane cracking reactions in a fixed bed with a continuous flow micro-reactor coupled on line to a gas chromatograph. The main products obtained were: ethane, propane, isobutene, n-butane, n-pentane and isopentane. The Vyazovkin (model-free) kinetics method was used to determine the catalysts regeneration and removal of the coke

Catalisadores bifuncionais à base de silicoaluminofosfato e fosfatos de nióbio para emprego em reações de hidroisomerização e hidrocraqueamento do n-hexadecano

Lubricants and cutting middle distillates typically have large amounts of n-paraffins to increase its freezing point and fluidity. Accordingly, the removal of n-paraffins of long chain lubricants oils and diesel is essential to get a product with good cold flow properties. The development of new catalysts, which exhibit thermal stability and catalytic activity for the hydroisomerization reaction is still a challenge. Thus, silicoaluminophosphates (SAPO) were synthesized by different routes. Have been used also post-synthesis treatment for obtaining hybrid structures and others synthesis have been carried out with mesoporous template (soft and hard-template). Therefore, SAPO have been impregnated with H2PtCl6 solution by the incipient wetness method. Then assessments of catalytic activities in hydroisomerization and hydrocracking reactions of hexadecane have been held. Besides SAPO, niobium phosphate - NbP - were also impregnated with platinum and evaluated in the same reaction. After impregnation, these catalysts have been characterized by X-ray diffraction (XRD), nitrogen adsorption, infrared spectroscopy with adsorbed pyridine (IV-PY), scanning electron microscopy (SEM) and resonance nuclear magnetic 29Si (29Si-NMR). The characterization results by XRD have shown that it has been possible to obtain mesoporous SAPOs. However, for the syntheses with soft template there was collapse of the structure after removal of the organic template. Even so, these catalysts have been actives. It was possible to obtain hybrid materials through the synthesis of SAPO-11 made with hard templates and by means of post-synthesis treatments samples of SAPO-11. Moreover, NbP has shown characteristic XRD of amorphous materials, with high acidity and were active in the conversion of hexadecane.

Catalisadores bifuncionais à base de silicoaluminofosfato e fosfatos de nióbio para emprego em reações de hidroisomerização e hidrocraqueamento do n-hexadecano

Lubricants and cutting middle distillates typically have large amounts of n-paraffins to increase its freezing point and fluidity. Accordingly, the removal of n-paraffins of long chain lubricants oils and diesel is essential to get a product with good cold flow properties. The development of new catalysts, which exhibit thermal stability and catalytic activity for the hydroisomerization reaction is still a challenge. Thus, silicoaluminophosphates (SAPO) were synthesized by different routes. Have been used also post-synthesis treatment for obtaining hybrid structures and others synthesis have been carried out with mesoporous template (soft and hard-template). Therefore, SAPO have been impregnated with H2PtCl6 solution by the incipient wetness method. Then assessments of catalytic activities in hydroisomerization and hydrocracking reactions of hexadecane have been held. Besides SAPO, niobium phosphate - NbP - were also impregnated with platinum and evaluated in the same reaction. After impregnation, these catalysts have been characterized by X-ray diffraction (XRD), nitrogen adsorption, infrared spectroscopy with adsorbed pyridine (IV-PY), scanning electron microscopy (SEM) and resonance nuclear magnetic 29Si (29Si-NMR). The characterization results by XRD have shown that it has been possible to obtain mesoporous SAPOs. However, for the syntheses with soft template there was collapse of the structure after removal of the organic template. Even so, these catalysts have been actives. It was possible to obtain hybrid materials through the synthesis of SAPO-11 made with hard templates and by means of post-synthesis treatments samples of SAPO-11. Moreover, NbP has shown characteristic XRD of amorphous materials, with high acidity and were active in the conversion of hexadecane.

Estudos comparativos do ciclo de regeneração de diferentes tipos de silicoaluminofosfatos

Different types of heterogeneous catalysts of the silicoaluminophosphate type, (SAPO-5, SAPO-11, SAPO-31, SAPO-34 and SAPO-41), molecular sieves with a: AFI, AEL, ATO, CHA and AFO structure, respectively, were synthesized through the hydrothermal method. Using sources such as hydrated alumina (pseudobohemita), phosphoric acid, silica gel, water, as well as, different types of organic structural templates, such as: cetyltrimethylammonium bromide (CTMABr), di-isopropylamine (DIPA), di-n- propylamine (DNPA) and tetraethylammonium hydroxide (TEOS), for the respective samples. During the preparation of the silicoaluminophosphates, the crystallization process of the samples occurred at a temperature of approximately 200 ° C, ranging through periods of 18-72 h, when it was possible to obtain pure phases for the SAPOs. The materials were furthermore washed with deionized water, dried and calcined to remove the molecules of the templates. Subsequently the samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), absorption spectroscopy in the infrared region (FT-IR), specific surface area and thermal analysis via TG/DTG. The acidic properties were determined using adsorption of n-butylamine followed by programmed termodessorption. These methods revealed that the SAPO samples showed a typically weak to moderate acidity. However, a small amount of strong acid sites was also detected. The deactivation of the catalysts was conducted by artificially coking the samples, followed by n-hexane cracking reactions in a fixed bed with a continuous flow micro-reactor coupled on line to a gas chromatograph. The main products obtained were: ethane, propane, isobutene, n-butane, n-pentane and isopentane. The Vyazovkin (model-free) kinetics method was used to determine the catalysts regeneration and removal of the coke

Peixes da Estação Ecológica Serra Geral do Tocantins, bacias dos Rios Tocantins e São Francisco, com observações sobre as implicações biogeográficas das "águas emendadas" dos Rios Sapão e Galheiros

Um levantamento preliminar da ictiofauna que ocorre na Estação Ecológica Serra Geral de Tocantins, situada no Sudeste do Estado do Tocantins e Noroeste do Estado da Bahia, é apresentado. A Estação Ecológica Serra Geral de Tocantins situa-se no divisor de águas entre as bacias do Rio São Francisco (Rio Sapão) e Rio Tocantins (bacias dos Rios Novo, Balsas e Manuel Alves). A cabeceira comum ou "água emendada" do Rio Sapão e Rio Galheiros, este um afluente do Rio Novo, situa-se no interior da estação e é considerada na literatura como uma possível área de intercâmbio ictiofaunístico entre a bacia do Rio São Francisco e a bacia do Rio Tocantins. Trinta e cinco espécies de peixes foram registradas dentro da Estação Ecológica Serra Geral de Tocantins e em seu entorno imediato, algumas delas desconhecidas da ciência e possivelmente endêmicas da região. Um total de 111 espécies de peixes foi registrado regionalmente (incluindo espécies de peixes registrados nos trechos do Rio Sapão e do Rio Novo/do Sono abaixo da estação). O acará Cichlasoma sanctifranciscense é aqui registrado pela primeira vez na bacia do Rio Tocantins. A ocorrência desta espécie, bem como do lambari Astyanax novae, no Rio Sapão e no Rio Novo/do Sono, são considerados os únicos exemplos inequívocos de transposição natural de espécies de peixes entre as bacias do Rio São Francisco e Tocantins efetuado pelas águas emendadas dos rios Sapão e Galheiros.

Craqueamento termocatalítico de óleo de girassol na presença da peneira molecular SAPO-5

The catalytic cracking of triglycerides presents itself as a possible alternative to the production of biofuels with low emission of pollutants. In this work were synthesized the SAPO-5, the catalysts for the cracking reaction of soybean oil is presented. The solids were powder X-ray diffraction (XRD), thermogravimetric analysis (TG/DTG) and infrared spectroscopy (FTIR). The analyses indicated that the synthesis method has employed to obtain materials with high surface area and high acid. The soybean oil thermal and thermal catalytic cracking, realized from the room temperature to 450 ºC in a simple distillation system, has allowed obtaining two liquid fractions, each consisting of two phases, one aqueous and another organic, organic liquid (OL). The OL obtained from first fractions has shown high acid index, even in the thermal catalytic process. The products obtained in the cracking of soybean oil were analyzed by distillation, acid number, infra-red spectroscopy, density, viscosity, carbon residue, cetane number determination and characterization. The analysis of the products obtained in the presence and in the absence of the SAPO-5 permitted to conclude that all the solids tested presented catalytic activity in the deoxygenation of final products only at the second step of the cracking process