The effect of the acid pretreatment temperature of natural diatomaceous earth on the Si/Al ratio of ZSM-5 zeolite

La tierra de diatomea boliviana es una fuente de silicio potencialmente más económica en comparación a los reactivos de alta pureza comúnmente utilizados para la síntesis de zeolitas. Dada su composición compleja es necesario realizarle un pretratamiento ácido con el fin de reducir las impurezas y regular el contenido de aluminio. En este artículo se realizaron múltiples experimentos durante la etapa de pretratamiento ácido. La temperatura del pretratamiento ácido fue modificada en un rango entre 50 y 155 °C esto con el fin de determinar su efecto en la relación Si/Al final. Los resultados mostraron que la relación Si/Al puede ser modulada en un rango entre 6,2 y 38,1. Posteriormente, se obtuvieron zeolitas a partir de la tierra de diatomea modificada. Las zeolitas obtenidas presentaron una relación Si/Al entre 9,6 y 40,2. Se aplicaron distintas técnicas de caracterización para la determinación de las propiedades. El grado de cristalinidad y el área superficial específica están directamente relacionadas con la relación Si/Al. Los sitios ácidos están conformados por ácidos fuertes de tipo Brönsted y ácidos fuertes y débiles de tipo Lewis. Para la zeolita con menor relación Si/Al se determinó una elevada acidez total (>0,51 molNH3/Kgzeolita), mientras que para la zeolita con mayor relación Si/Al la acidez total se redujo considerablemente (<0,38 molNH3/Kgzeolita).

Bolivian diatomaceous earth is a potentially lower cost silica source than conventional high purity reagents used in zeolite synthesis. Due to its complex composition, it is necessary to pre-treat it with sulfuric acid in order to reduce impurities and regulate the aluminum content. In the present work several experiments were carried out with natural Bolivian diatomaceous earth in the pre-treatment stage. In order to determine the effect on the final Si/Al ratio, the temperature of the acid pre-treatment was varied between 50 to 155 °C. The results show that the Si/Al ratio can be modulated from 6.2 up to 38.1. These treated diatomaceous earth samples were used to synthetise ZSM-5 zeolite. The obtained ZSM-5 zeolites have a Si/Al ratio in the following range: 9.6 to 40.2. XRD, NH3-TPD and Nitrogen Physisorption techniques were used to characterise the properties of the obtained zeolites. The degree of crystallisation and the specific surface area are directly related to the Si/Al ratio, resulting in high values at high Si/Al ratios. The acid sites are composed of strong Brönsted acid sites and, strong and weak Lewis acid sites. For the zeolite with a low Si/Al ratio a high total acidity was found (>0.51 molNH3/Kgzeolite), while at high Si/Al ratios the total acidity is reduced (<0.38 molNH3/Kgzeolite).

A terra diatomácea boliviana é uma fonte potencialmente mais barata de silício em comparação com os reagentes de alta pureza comumente usados para a síntese de zeólitas. Dada a sua composição complexa, é necessário realizar um pré-tratamento ácido para reduzir as impurezas e regular o teor de alumínio. No presente trabalho, vários experimentos foram realizados durante a etapa de pré-tratamento ácido. A temperatura do pré-tratamento ácido foi modificada em uma faixa entre 50 e 155 °C para determinar seu efeito na relação Si/Al final. Os resultados mostram que a razão Si/Al pode ser modulada em uma faixa entre 6,2 e 38,1. Posteriormente, as zeólitas foram obtidas a partir de terra diatomácea modificada. As zeólitas obtidas possuem uma razão Si/Al entre 9,6 e 40,2. Diferentes técnicas de caracterização foram aplicadas para determinar as propriedades. O grau de cristalinidade e a área superficial específica estão diretamente relacionados com a razão Si/Al. Os sítios ácidos são compostos por ácidos fortes do tipo Brönsted e ácidos fortes e fracos do tipo Lewis. Para a zeólita com menor relação Si/Al, foi determinada uma alta acidez total (>0,51 molNH3/Kgzeólita), enquanto para a zeólita com maior relação Si/Al, a acidez total foi consideravelmente reduzida (<0,38 molNH3/Kgzeolita).

Brachiaria brizantha Grass as a Feedstock for Ethanol Production

HIGHLIGHTS Brachiaria brizantha proved to be a promising biomass for ethanol production. Fermentation was not impaired by the inhibitors furfural and hydroxymethylfurfural.

Abstract Different lignocellulosic biomasses are found worldwide and each country has its own important industrial crop that can be converted into high-value products, such as ethanol. Therefore, evaluation of new biomasses to be used in biorefineries is important to decrease the dependence on non-renewable resources and to guarantee sustainable development. This work evaluated Brachiaria brizantha, a grass commonly used as animal forage, and the standard biomass for 2G-ethanol, sugarcane bagasse. The chemical compositions of both biomasses were determined and different times and temperature of acid pretreatment were tested. Morphological analysis via scanning electron microscopy showed more deconstructed fibers after harsher biomass pretreatments. Simultaneous saccharification and fermentation of pretreated Brachiaria brizantha presented higher efficiency than when using sugarcane bagasse as the carbon source. A biomass conversion of 46 % was achieved when Brachiaria brizantha grass was pretreated with 2% sulfuric acid for 60 minutes. Moreover, fermentation was not impaired by the inhibitors furfural and hydroxymethylfurfural. It was concluded that Brachiaria brizantha is a promising biomass for ethanol production.

Chemical pretreatment of Arundo donax L. for second-generation ethanol production

Background: Pretreatment of lignocellulosic biomass is essential for using it as a raw material for chemical and biofuel production. This study evaluates the effects of variables in the chemical pretreatment of the Arundo biomass on the glucose and xylose concentrations in the final enzymatic hydrolysate. Three pretreatments were tested: acid pretreatment, acid pretreatment followed by alkaline pretreatment, and alkaline pretreatment. Results: The amounts of glucose and xylose released by the enzymatic hydrolysis of the Arundo biomass obtained from acid pretreatment ranged from 6.2 to 19.1 g/L and 1.8 to 3.1 g/L, respectively. The addition of alkaline pretreatment led to a higher yield from the enzymatic hydrolysis, with the average glucose concentration 3.5 times that obtained after biomass hydrolysis with an acid pretreatment exclusively. The use of an alkaline pretreatment alone resulted in glucose and xylose concentrations similar to those obtained in the two-step pretreatment: acid pretreatment followed by alkaline pretreatment. There was no significant difference in 5-hydroxymethylfurfural, furfural, or acetic acid concentrations among the pretreatments. Conclusion: Alkaline pretreatment was essential for obtaining high concentrations of glucose and xylose. The application of an alkaline pretreatment alone resulted in high glucose and xylose concentrations. This result is very significant as it allows a cost reduction by eliminating one step.