Mariana Busto

Adsorption in Biodiesel Refining - A Review

Biodiesel is a petrodiesel substitute composed of a mixture of fatty acid methyl esters obtained by the transesterification of plant oils or animal fats with short chain alcohols such as methanol or ethanol. Despite its natural origin biodiesel is technically fully compatible with petroleum diesel, requiring virtually no changes in the fuel distribution system or the Diesel motor. Its production and use have increased significantly in many countries and are in nascent status in many others. Other advantages of biodiesel compared to petrodiesel are reduction of most exhaust emissions, biodegradability, higher flash point, inherent lubricity and domestic origin (Chang et al., 1996; Romig & Spataru, 1996; Wang et al., 2000). Literature on the refining of biodiesel is abundant but concentrates almost exclusively on the transesterification steps for transforming fats and oils into esters of short alcohols and fatty acids. In this sense in the last years the most important advances in the reaction technology have been the development of continuous heterogeneous transesterification reactors (Bournay et al., 2005; Portilho et al., 2008) and the design of new robust non-catalytic processes for multifeedstock operation (Saka & Kusdiana, 2001; Saka & Minami, 2009). In the case of the refining operations downstream and upstream the transesterification reactors the biodiesel literature is however scarce. Two are the reasons for this: (i) Feedstock pretreatment in the case of biodiesel is a mature technology developed decades ago for the production of edible oil. (ii) After natural triglycerides are converted into fatty acid methyl esters, the product mixture needs little chemical adjustment since many properties of these esters are ideal for the functioning of Diesel motors. Some reports on post-reactor biodiesel refining have dealt with classical and simple techniques of purification, e.g. water washing (Karaosmanoglu et al., 1996). Others have indicated that adsorption technologies are particularly suited for the refining of biodiesel (Yori et al. 2007; Mazzieri et al., 2008; Manuale et al. 2011). In order to elucidate the role of adsorption processes in the refining of biodiesel, this review studies some theoretical and practical aspects related to the functioning, design and operation of adsorbers and their application to the purification of biodiesel product and feedstocks.

Poisoning and regeneration of Pt-Pd/WO3-ZrO2 short paraffin isomerization catalysts

WO3-ZrO2 catalysts promoted with Pt and Pd were tested as paraffin isomerization catalysts using n-hexane as model compound. Sulfur and amine poisoning and regeneration tests were used to assess the impact of the addition of Pt and Pd on the deactivation resistance and regenerability. Pt and PtPd catalysts were the most active for n-hexane isomerization. The low activity of the Pd catalyst was attributed to poor Pd metal properties when supported over WO3-ZrO2 and to a decrease of the number of BrQnsted acid sites. PtPd was the only catalyst capable of full regeneration after S poisoning. Amine poisoning completely supressed the isomerization activity and the original activity could only be restored by calcination and reduction.

Coupling Solvent Extraction Units to Cyclic Adsorption Units

The possibility of regenerating the solvent of extraction units by cyclic adsorption was analyzed. This combination seems convenient when extraction is performed with a high solvent-to-impurity ratio, making other choices of solvent regeneration, typically distillation, unattractive. To our knowledge, the proposed regeneration scheme has not been considered before in the open literature. Basic relations were developed for continuous and discontinuous extraction/adsorption combinations. One example, deacidification of plant oil with alcohol, was studied in detail using separate experiments for measuring process parameters and simulation for predicting performance at different conditions. An activated carbon adsorbent was regenerated by thermal swing, making cyclic operation possible. When extracting the acid with methanol in a spray column, feed = 4 L min−1, solvent = 80 L min−1, feed impurity level 140 mmol L−1, and extract concentration 7.6 mmol L−1, the raffinate reaches a purity of 1.2 mmol L−1, the solvent being regenerated cyclically in the adsorber (364 kg) to an average of 0.7 mmol L−1. Regeneration of the solvent by cyclic adsorption had a low heat duty. Values of 174 kJ per litre of solvent compared well with the high values for vaporization of the whole extract phase (1011 kJ L−1).

New Strategies for Obtaining Inorganic-Organic Composite Catalysts for Selective Hydrogenation

Pd/composites are catalysts in which the catalytically active metal phase is located in a small layer on the support surface. The metal distribution obtained on these supports corresponds to a structure commonly known as “egg-shell”. This distribution is optimal for reactions that have heat or mass transfer resistances. The small thickness of the metal layer is mainly attributed to the use of support pellets of mixed organic–inorganic composition, the special interaction between the hydrophobic–hydrophillic support surface and the metal species (Pd or Pt) present in the impregnating aqueous solution. Pd/composite catalysts are active and selective for the reactions of selective hydrogenation of styrene, 1-heptyne, 3-hexyne and 2,3-butanone, and enantioselective hydrogenation of ethyl pyruvate. These reactions are of interest in both academic and industrial aspects.