Synthesis of ethyl acetate employing celite-immobilized lipase of Bacillus cereus MTCC 8372

A wide range of fatty acid esters can be synthesized by esterification and transesterification reactions catalyzed by lipases in non-aqueous systems. In the present study, immobilization of a purified alkaline extra-cellular lipase of Bacillus cereus MTCC 8372 by adsorption on diatomaceous earth (celite) for synthesis of ethyl acetate via transesterification route was investigated. B. cereus lipase was deposited on celite (77% protein binding efficiency) by direct binding from aqueous solution. Immobilized lipase was used to synthesis of ethyl acetate from vinyl acetate and ethanol in n -nonane. Various reaction conditions, such as biocatalyst concentration, substrates concentration, choices of solvents ( n -alkanes), incubation time, temperature, molecular sieves (3Å × 1.5 mm), and water activity(a _w ), were optimized. The immobilized lipase (25 mg/ml) was used to perform transesterification in n -alkane(s) that resulted in approximately 73.7 mM of ethyl acetate at 55 °C in n -nonane under shaking (160 rpm) after 15 h, when vinyl acetate and ethanol were used in a equimolar ratio (100 mM each). Addition of molecular sieves (3Å × 1.5 mm) as well as effect of water activity of saturated salt solutions (KI, KCl and KNO ₃ ) to the transesterification efficiency has inhibitory effect. Batch operational stability tests indicated that immobilized lipase had retained 50% of its original catalytic activity after four consecutive batches of 15 h each.

Enzymatic synthesis of isopropyl acetate catalysed by immobilized bacillus cereus lipase in organic medium

Selective production of fragrance fatty acid ester from isopropanol and acetic acid has been achieved using silica-immobilizedlipase of Bacillus cereus MTCC 8372. A purified thermoalkalophilic extracellular lipase was immobilized by adsorption onto the silica. The effects of various parameters like molar ratio of substrates (isopropanol and acetic acid; 25 to 100 mM), concentration ofbiocatalyst (25–125 mg/mL), reaction time, reaction temperature, organic solvents,molecular sieves, and initial water activity werestudied for optimal ester synthesis. Under optimized conditions, 66.0mM of isopropyl acetate was produced when isopropanol and acetic acid were used at 100mM: 75mM in 9h at 55◦C in n-heptane under continuous shaking (160 rpm) using bound lipase(25mg). Addition of molecular sieves (3 °A ×1.5mm) resulted in a marked increase in ester synthesis (73.0mM). Ester synthesiswas enhanced by water activity associated with pre-equilibrated saturated salt solution of LiCl. The immobilized lipase retained more than 50% of its activity after the 6th cycle of reuse.

Structure retention in cross-linked poly(ethylene glycol) diacrylate hydrogel templated from a hexagonal lyotropic liquid crystal by controlling the surface tension

Retaining hexagonal lyotropic liquid crystal (LLC) structures in polymers after surfactant removal and drying is particularly challenging, as the surface tension existing during the drying processes tends to change the morphology. In this study, cross-linked poly(ethylene glycol) diacrylate (PEGDA) hydrogels were prepared in LLC hexagonal phases formed from a dodecyltrimethylammonium bromide (DTAB)/water system. The retention of the hexagonal LLC structures was examined by controlling the surface tension. Polarized light microscopy, X-ray diffraction and small angle X-ray scattering results indicate that the hexagonal LLC structure was successfully formed before polymerization and well retained after polymerization and after surfactant removal when the surface tension forces remained neutral. Controlling the surface tension during the drying process can retain the nanostructures templated from lyotropic liquid crystals which will result in the formation of materials with desired nanostructures.

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 e impregnação de peneiras moleculares Fe MCM-41 derivada de sílica da casca do arroz

The mesoporous molecular sieves of the MCM-41 and FeMCM-41 type are considered promissory as support for metals used as catalysts in oil-based materials refine processes and as adsorbents for environmental protection proposes. In this work MCM-41 and FeMCM41 were synthesized using rice husk ash - RHA as alternative to the conventional silica source. Hydrothermal synthesis was the method chosen to prepare the materials. Pre-defined synthesis parameters were 100°C for 168 hours, later the precursor was calcinated at 550°C for 2 hours under nitrogen and air flow. The sieves containing different proportions of iron were produced by two routes: introduction of iron salt direct synthesis; and a modification post synthesis consisting in iron salt 1 % and 5% impregnation in the material followed by thermal decomposition. The molecular sieves were characterized by X ray diffraction XRD, Fourier transform infrared spectroscopy FT-IR, X ray fluorescence spectroscopy XFR, scanning electronic microscopy SEM, specific surface area using the BET method, Termogravimetry TG. The kinetic model of Flynn Wall was used with the aim of determining the apparent activation energy of the surfactant remove (CTMABr) in the MCM- 41 porous. The analysis made possible the morphology characterization, identifying the presence of hexagonal structure typical for mesoporous materials, as well as observation of the MCM41 and iron of characteristic bands.

Síntese e caracterização de peneiras moleculares mesoporosas do tipo MCM-41 e AlMCM-41 a partir de fontes alternativas de sílica e de alumínio

The mesoporous molecular sieves of MCM-41 and AlMCM-41 type are considered as promising support for metal in the refining processes of petroleum-based materials as catalysts and adsorbents for environmental protection. In this work the molecular sieves MCM-41 and AlMCM-41 were synthesized by replacing the source of silica conventionally used, for quartz, an alternative and abundant, and the use of waste from the production of diatomaceous earth, an aluminum-silicate, as a source aluminum, due to abundant reserves of diatomaceous earth in the state of Rio Grande do Norte in the city of Ceará-Mirim, with the objective of producing high-value materials that have similar characteristics to traditional commercial catalysts in the market. These materials were synthesized by the method of hydrothermal synthesis at 100 º C for 7 days and subjected to calcination at 500 º C for 2 hours under flow of nitrogen and air. The molecular sieves were characterized by X-ray diffraction (XRD), differential thermal analysis (DTA) and thermogravimetric analysis (TG), adsorption of N2 (BET and BJH methods), spectroscopy in the infra red (FTIR), microscopy scanning electron (SEM) and transmission electron microscopy (TEM). The analysis indicated that the synthesized materials showed characteristic hexagonal structure of mesopores materials with high specific surface area and sort and narrow distribution of size of pores

Síntese de zeólitas e argilas ácidas pilarizadas a partir de matérias primas naturais

Structural changes in waste for zeolites synthesis are subject of many studies carried out in the synthesis of molecular sieves. These materials are named molecular sieves because they have well defined pore sizes and they have the capacity of select molecules by its size. In this work, it was studied the synthesis processes of two types of molecular sieves: pillared acid clays using as starting material one natural montmorillonite clay and the synthesis of zeolites from a silico-aluminous residue. This residue is a byproduct of the extraction of lithium -spodumene. The preparation of pillared acid clays was performed in two steps: 1° acid treatment of clay samples (time and temperature studies) and 2°pilarization of them with Al13 (Keggin ion). The temperature and acid concentration affect the removal of cations in the structure and porosity of the material obtained. The analysis of X-ray diffraction (XRD) and infrared spectroscopy (IR), showed that increasing the severity of the acid treatment compromises the structural material. Also the pore size distribution is approximately uniform. Despite presenting a structural disorganization, the samples were pillared. As evidenced by XRD increasing the basal spacing, specific area and uniform porosity by adsorption of N2. Regarding the microporous molecular sieves were synthesized zeolites A and NaP1 from a silico-aluminous residue, a byproduct of extracting lithium. The temperature and time of agitation during the synthesis were the most important factors for obtaining zeolite A. The aging of the gel and the highest crystallization time promoted the formation of zeolite NaP1 using a Si / Al ratio = 3.2

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

Reforma a seco de metano com catalisadores Ni/MCM-41 sintetizados a partir de fontes alternativas de sílica

The production of synthesis gas has received renewed attention due to demand for renewable energies to reduce the emissions of gases responsible for enhanced greenhouse effect. This work was carried out in order to synthesize, characterize and evaluate the implementation of nickel catalysts on MCM-41 in dry reforming reactions of methane. The mesoporous molecular sieves were synthesized using as silica sources the tetraethyl orthosilicate (TEOS) and residual glass powder (PV). The sieves were impregnated with 10% nickel to obtain the metallic catalysts (Ni/MCM-41). These materials were calcined and characterized by Thermogravimetric Analysis (TG), Infrared spectroscopy (FTIR), X-ray Diffraction (XRD), Temperature-Programmed Reduction (TPR) and N2 Adsorption/Desorption isotherms (BET/BJH). The catalytic properties of the samples were evaluated in methane dry reforming with CO2 in order to produce synthesis gas to be used in the petrochemical industry. The materials characterized showed hexagonal structure characteristic of mesoporous material MCM-41 type, being maintained after impregnation with nickel. The samples presented variations in the specific surface area, average volume and diameter of pores based on the type of interaction between the nickel and the mesoporous support. The result of the the catalytic tests showed conversions about 91% CO2, 86% CH4, yelds about 85% CO and 81% H2 to Ni/MCM-41_TEOS_C, and conversions about 87% CO2, 82% CH4, yelds about 70% CO and 59% H2 to Ni/MCM-41_PV_C. The similar performance confirms that the TEOS can be replaced by a less noble materials

Germinação de sementes de Caesalpinia leiostachya (benth.) ducke (pau-ferro) classificadas pelo tamanho e pela forma

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Eficiência relativa de diferentes frações granulometricas de calcários na neutralização da acidez dos solos, avaliada em laboratório

As frações granulométricas retidas nas peneiras n°s (ABNT) 5-10, 10-30, 30-50, e 50-60 de quatro calcários, sendo dois sedimentares e dois metamórficos, foram incubadas durante 160 dias com três tipos de solos, em condições de laboratório. A eficiência das frações na neutralização da acidez dos solos foi avaliada pela variação do pH. Os resultados permitiram concluir que a referida eficiência independe da natureza geológica do calcário mas depende do tipo de solo, sendo decrescente na seguinte ordem: LVd, LEd e LEm. Apesar da legislação atual normatizar as características físicas dos calcários, bem como os seus graus de eficiência, a presente pesquisa sugere novos valores para a eficiência relativa das diferentes frações granulometricas de calcários: fração maior do que 10:0%, de 30:35%; de 30-50:75% e menor que 50:100%.

Procedimento para condução do teste de envelhecimento acelerado em sementes de algodão

The evaluation of the effect of seed has been fundamental tool in the program of quality control, and the accelerated aging test, an important part of that process. Some authors report that the germination and vigor are associated with seed size and facing the lack of consensus for the use of this test methodology and the relationship of seed size on the physiological quality, this work aimed to adapt the existing methodology as the temperature and period of conditioning on the performance of two sizes of seed cotton. The seeds were classified into two meshes of sieves, and then subjected to tests of water content, germination and electrical conductivity. The experimental design was completely randomized, analyzed statistically in a factorial threefold. Seeds of different sizes, showed no difference in percentage of germination. Seeds subjected to 40 degrees C for 42h of conditioning showed better percentage of germination.

Tamanho e secagem de sementes de palmeira Jussara sobre a germinação e o vigor

With the objective to determine the influence of the dehydration and of the size and/or weight on germination percentage and the vigor of jussara palm seeds (Euterpe edulis Mart.), 10 individuals' ripe fruits, picked in the Experimental Station of Ubatuba (IAC) they were classified by size in 5 sieves of circular sieve: 26/64" (10,31mm), 28/64" (11,11mm), 30/64" (11,90mm), 32/64" (12,69mm) and 34/64" (13,49mm). It was determined, the medium weight of the classified seeds. The quality of the seeds was evaluated through the following parameters: water content of the seeds; germination and vigor (first germination counting). It was evaluated the drying speed of different seed sizes for 48 hours, in dry chamber. The sizes of 28/64", 30/64" and 32/64" represented 98,7% of the total weight of the harvested seeds and showed similar drying speed, percentage of germination and vigor. With the increase of the drying period, the smaller seeds (28/64") had their germination less affected them the intermediate (30/64") and bigger sized seeds (32/64").

Influência do tamanho na germinação e no vigor de sementes de milheto (Pennisetum americanum (L.) Leeke)

O milheto é uma gramínea anual de sementes pequenas, com grande diversidade de tamanho, e com dificuldade, às vezes, do estabelecimento da população adequada de plantas. Este experimento objetivou verificar a influência do tamanho da semente de milheto sobre sua germinação e vigor. Foram utilizados quatro lotes de sementes (I, II, III e IV), classificados em quatro tamanhos, através de peneiras de malha quadrada, sendo: peneira 1 ≥ 2,00mm, peneira 2: 1,68 a 2,00mm, peneira 3: 1,41 a 1,68mm, peneira 4: 0,71 a 1,41mm e mais uma porção do lote original (testemunha), que constituíram os tamanhos. Foram realizados os testes de: peso de 1000 sementes, germinação inicial e após seis meses de armazenamento (TGI e TGII, respectivamente) e vigor (primeira contagem do teste de germinação e condutividade elétrica das sementes). Utilizou-se o delineamento experimental inteiramente casualizado, com quatro repetições por tratamento. As sementes de peneira 4 apresentaram menores pesos de 1000 sementes para todos os lotes, menores valores de germinação para o TGI, em todos os lotes, e para o TGII nos lotes II e IV. Para o vigor (primeira contagem do teste de germinação) observou-se menor valor para peneira 4, nos lotes I, II e IV; enquanto para a condutividade, a peneira 4 apresentou maior valor para todos os lotes, indicando pior qualidade fisiológica dessas sementes. Concluiu-se que a germinação e o vigor das sementes de milheto são influenciados pelo seu tamanho; sementes maiores são de melhor qualidade do que as menores.

Teste de condutividade elétrica em sementes de amendoim

O teste de condutividade elétrica (CE) tem potencial para ser empregado no controle de qualidade pelas empresas produtoras de sementes, no entanto há fatores que podem afetar os resultados obtidos. Neste sentido, o trabalho teve como objetivo estudar os efeitos do tamanho da semente, do número de sementes da amostra e do período e temperatura de embebição que podem influenciar a interpretação dos resultados do teste de CE, em sementes de amendoim. Utilizou-se o delineamento experimental inteiramente casualizado em esquema fatorial 3 x 3: três lotes de semente, classificados em três tamanhos (peneiras 18, 20 e 22). Avaliou-se a CE em dez tempos de embebição (3, 6, 9, 12, 15, 18, 21, 24, 27 e 30 horas). O trabalho foi composto de quatro ensaios, onde se combinou número de sementes e temperatura de exposição das mesmas à embebição: a) quatro repetições de 25 sementes a 20ºC; b) quatro repetições de 50 sementes a 20ºC; c) quatro repetições de 25 sementes a 25ºC; d) quatro repetições de 50 sementes a 25ºC. A leitura da CE foi realizada por condutivímetro e os resultados expressos em µS.cm-1.g-1. O tamanho da semente afetou os resultados da CE; o tempo de embebição pode ser reduzido para até 3 horas; a temperatura de embebição de 25ºC mostrou-se mais promissora do que 20ºC, assim como a utilização de 50 sementes puras.