Use of residual soapstock from the refining of edible vegetable oils to make biodiesel.

Se estudia un procedimiento para la obtención de Biodiesel a partir de las “Oleínas”. Biodiesel es un producto capaz de sustituir al combustible Diesel ordinario que se obtiene del petróleo y que consiste en una mezcla de ésteres metílicos de ácidos grasos. Las oleínas son unos residuos que resultan del proceso de refina- do de aceites vegetales para su uso alimentario y se componen de una mezcla de triglicéridos y ácidos grasos libres, con un con- tenido de estos últimos componentes superior al 50% . El merca- do de oleinas es fluctuante, con lo que en ocasiones surge el problema de su eliminación. Como resultado del trabajo efectua- do se define un proceso de obtención que consta de las siguien- tes etapas: 1. Esterificación de los ácidos libres de la Oleína con meta- nol, aplicando catálisis ácida, centrifugando el producto obtenido y separándolo de la fase metanol-ácido. En ésta etapa se obtiene un producto que contiene alrededor de un 70% de metil- esteres. 2. Transesterificación de los triglicéridos presentes en el producto esterificado con metanol, aplicando catálisis alcalina. El producto obtenido, previamente separado de la fase metanol- agua, contiene alrededor de un 90% de metil-esteres. 3. Purificación del producto resultante de las etapas 1 y 2 , por rectificación a vacío. El producto destilado tiene un contenido en metil-esteres superior al 98%.A procedure to obtain Biodiesel from “Oleinas” is studied. Biodiesel is a suitable product to replace diesel oil currently used to power the Diesel engines. It consists of a mixture of methyl esters of the fatty acids presents as triglycerides in vegetables oils (olive, sunflower, soya, rape oils). As a result of the refining of these oils for their use as food, a waste product is formed, the “oleinas” (acidulated soapstock). The oleinas consist of a mixture of triglycerides and free fatty acids, the latter amounting to 50% or more of the mixture and are subject to a fluctuating market, therefore it exist at times a problem for their disposal. In our research work we have tried to obtain biodiesel from oleinas. The process resulting from our experimental work is as follows: 1. Sterification of the free fatty acids with methanol, by acid catalysis, centrifuging the reaction product and removal of the acid-methanol phase. Drying of the latter. At this stage we have a product containing about 70% of methyl esters. 2. Transesterification of the triglycerides present in the sterified product with methanol by alkaline catalysis, washing the reaction product with a water methanol solution. Centrifuging and removal of the water-methanol phase. At this stage a biodiesel product is obtained containing about 90% of methyl esters. 3. Fractional vacuum distillation of the 90% biodiesel gives a final product with a methyl esters content higher than 98%

Production of Oxygenated Fuel Additives from Residual Glycerine Using Biocatalysts Obtained from Heavy-Metal-Contaminated Jatropha curcas L. Roots

This work aims to shed light on the use of two biochars, obtained from the pyrolysis at 550 C of heavy-metal-contaminated Jatropha curcas L. roots, as heterogeneous catalysts for glycerol esterification using residual glycerine. To do this, glycerine from biodiesel production was purified. In a first step, H3PO4 or H2SO4 was used to remove non-glycerol organic matter. The glycerol-rich phase was then extracted with ethanol or propanol, which increased the glycerol content from 43.2% to up to 100%. Subsequently, the esterification of both purified glycerine and commercial USP glycerine was assayed with acetic acid (AA) or with acetic anhydride (AH) at 9:1 molar ratio to glycerol using Amberlyst-15 as catalyst. Different reaction times (from 1.5 to 3 h) and temperatures (100–115 C when using AA and 80–135 C when using AH) were assessed. Results revealed that the most suitable conditions were 80 C and 1.5 h reaction time using AH, achieving 100% yield and selectivity towards triacetylglycerol (TAG) almost with both glycerines. Finally, the performance and reuse of the two heterogeneous biocatalysts was assessed. Under these conditions, one of the biocatalysts also achieved 100% TAG yield.VI Plan Propio de Investigación y Transferencia of University of Seville grant VIPPIT-2019-I.

Biodiesel production from olive-pomace oil of steam-treated alperujo

Recently interest has been revived in the use of plant-derived waste oils as renewable replacements for fossil diesel fuel. Olive–pomace oil (OPO) extracted from alperujo (by-product of processed olives for olive oil extraction), and produced it in considerable quantities throughout the Mediterranean countries, can be used for biodiesel production. A steam treatment of alperujo is being implemented in OPO extraction industry. This steam treatment improves the solid–liquid separation by centrifugation and facilitates the drying for further extraction of OPO. It has been verified that the steam treatment of this by-product also increases the concentration of OPO in the resulting treated solid, a key factor from an economic point of view. In the present work, crude OPO from steam-treated alperujo was found to be good source for producing biodiesel. Oil enrichment, acidity, biodiesel yield and fatty acid methyl ester composition were evaluated and compared with the results of the untreated samples. Yields and some general physicochemical properties of the quality of biodiesel were also compared to those obtained with other oils commonly used in biodiesel production. As for biodiesel yield no differences were observed. A transesterification process which included two steps was used (acid esterification followed by alkali transesterification). The maximum biodiesel yield was obtained using molar ratio methanol/triglycerides 6:1 in presence of sodium hydroxide at a concentration of 1% (w/w), reaction temperature 60 °C and reaction time 80 min. Under these conditions the process gave yields of about 95%, of the same order as other feedstock using similar production conditions.Junta de Andalucía (P06-AGR- 01906)Dr. Guillermo Rodríguez is grateful to the JAE-Doc Programme (CSIC) co-funded by European Social Fund (Operational Programme ESF 2007-2013

Esterification of Free Fatty Acids with Glycerol within the Biodiesel Production Framework

Companies in the field of the collection and treatment of waste cooking oils (WCO) for subsequent biodiesel production usually have to cope with high acidity oils, which cannot be directly transformed into fatty acid methyl esters due to soap production. Since glycerine is the main byproduct of biodiesel production, these high acidity oils could be esterified with the glycerine surplus to transform the free fatty acids (FFA) into triglycerides before performing the transesterification. In this work, commercial glycerol was esterified with commercial fatty acids and commercial fatty acid/lampante olive oil mixtures over tin (II) chloride. In the first set of experiments, the esterification of linoleic acid with glycerol excess from 20 to 80% molar over the stoichiometric was performed. From 20% glycerol excess, there was no improvement in FFA reduction. Using 20% glycerol excess, the performance of a biochar obtained from heavy metal-contaminated plant roots was compared to that of SnCl2. Then, the effect of the initial FFA content was assessed using different oleic acid/lampante olive oil mixtures. The results illustrated that glycerolysis was impeded at initial FFA contents lower than 10%. Finally, the glycerolysis of a WCO with 9.94% FFA was assayed, without success

Metal Accumulation by Jatropha curcas L. Adult Plants Grown on Heavy Metal-Contaminated Soil

Jatropha curcas has the ability to phytoextract high amounts of heavy metals during its first months just after seeding. Notwithstanding, there is scarce information about metal uptake by adult J. curcas plants. To shed light on this issue, 4-year-old J. curcas L. plants were planted in a soil mixture of peat moss and mining soil (high metals content), and the biomass growth and metal absorption during 90 days were compared with those of plants growing in peat moss. The main metal found in the mining soil was Fe (31985 mg kg-1) along with high amounts of As (23717 mg kg-1). After the 90-day phytoremediation, the plant removed 29% of Fe and 44% of As from the soil mixture. Results revealed that J. curcas L. translocated high amounts of metals to its aerial parts, so that translocation factors were much higher than 1. Because of the high translocation and bioaccumulation factors obtained, J. curcas L. can be regarded as a hyperaccumulator plant. Despite the great capacity of J. curcas L. to phytoremediate heavy-metal-contaminated soils, the main drawback is the subsequent handling of the metal-contaminated biomass, although some potential applications have been recently highlighted for this biomass.University of Seville (VIPPIT-2019-I.5

Análisis de residuos orgánicos y posibles contenidos en ánforas púnicas y turdetanas procedentes del valle del Guadalquivir

En este trabajo abordamos el estudio de los principales contenedores anfóricos que circularon en el Bajo Guadalquivir durante la II Edad del Hierro, cuáles eran los más representativos desde el punto de vista cuantitativo y, por tanto, los más elocuentes sobre los productos comercializados en los mercados turdetanos. Para ello se han tenido en cuenta tanto los recipientes de supuesta fabricación local (Pellicer B-C y Pellicer D) como los procedentes del ámbito púnico, especialmente la bahía de Cádiz y su hinterland (T-8.2.1.1 y T-8.1.1.2). Con las muestras obtenidas en las excavaciones en la calle Cilla (Alcalá de Río) y en Vico (Marchena), y exceptuando los envases de salazón de origen gaditano, los análisis de contenidos grasos indican que las ánforas T-8.1.1.2, contenían aceite de oliva, mientras que las ánforas “turdetanas” eran envases polifuncionales que podían transportar diversos productos (aceite de oliva, carnes en conserva, derivados lácteos) y/o ser reutilizadas.This work presents the results of a study of amphorae contents in the Lower Guadalquivir Valley during the Second Iron Age. The questions addressed include which were the most common contents and, therefore, which were, plausibly, the most commonly commercialised products in Turdetanian markets. Both local (Pellicer B-C and Pellicer D) and Punic containers, especially from the Bay of Cadiz and its hinterland (T-8.2.1.1 and T-8.1.1.2), have been taken into consideration. The analysis of the fats in the samples recovered during the excavation of Calle Cilla (Alcalá de Río, Seville) and Vico (Marchena, Seville) reveal that amphorae T-8.1.1.2 manufactured in the rural areas of Cadiz, with the exception those used for the storage and transport of salted products, were used to contain olive oils, as previously claimed, while ‘Turdetanian’ amphorae were multifunctional containers which could be used to store a wide variety of products (olive oil, meat preserves, milk by-products) and/or be reused

Identification of Copper in Stems and Roots of Jatropha curcas L. by Hyperspectral Imaging

The in situ determination of metals in plants used for phytoremediation is still a challenge that must be overcome to control the plant stress over time due to metals uptake as well as to quantify the concentration of these metals in the biomass for further potential applications. In this exploratory study, we acquired hyperspectral images in the visible/near infrared regions of dried and ground stems and roots of Jatropha curcas L. to which different amounts of copper (Cu) were added. The spectral information was extracted from the images to build classification models based on the concentration of Cu. Optimum wavelengths were selected from the peaks and valleys showed in the loadings plots resulting from principal component analysis, thus reducing the number of spectral variables. Linear discriminant analysis was subsequently performed using these optimum wavelengths. It was possible to differentiate samples without addition of copper from samples with low (0.5–1% wt.) and high (5% wt.) amounts of copper (83.93% accuracy, >0.70 sensitivity and specificity). This technique could be used after enhancing prediction models with a higher amount of samples and after determining the potential interference of other compounds present in plants.University of Seville VIPPIT-2019-I.5University of Seville VIPPIT-2019-I.

Energetic Valorisation of Olive Biomass: Olive-Tree Pruning, Olive Stones and Pomaces

Olive oil industry is one of the most important industries in the world. Currently, the land devoted to olive-tree cultivation around the world is ca. 11 106 ha, which produces more than 20 106 t olives per year. Most of these olives are destined to the production of olive oils. The main by-products of the olive oil industry are olive-pruning debris, olive stones and di erent pomaces. In cultures with traditional and intensive typologies, one single ha of olive grove annually generates more than 5 t of these by-products. The disposal of these by-products in the field can led to environmental problems. Notwithstanding, these by-products (biomasses) have a huge potential as source of energy. The objective of this paper is to comprehensively review the latest advances focused on energy production from olive-pruning debris, olive stones and pomaces, including processes such as combustion, gasification and pyrolysis, and the production of biofuels such as bioethanol and biodiesel. Future research e orts required for biofuel production are also discussed. The future of the olive oil industry must move towards a greater interrelation between olive oil production, conservation of the environment and energy generation

Determination of the Composition of Bio-Oils from the Pyrolysis of Orange Waste and Orange Pruning and Use of Biochars for the Removal of Sulphur from Waste Cooking Oils

Waste generated in the agri-food sector is a potential source of biomass and other products of high added value. In this work, the pyrolysis of orange waste and orange pruning was carried out to produce adsorbent biochars and characterise the bio-oils aiming for high-added-value compounds. Pyrolysis was carried out in a vertical tubular furnace on the laboratory scale modifying the temperature (400–600 °C), the heating ramp (5–20 °C·min−1) to reach the previous temperature and the inert gas flow rate (30–300 mL Ar·min−1) throughout the furnace. The most suitable conditions for obtaining biochar were found to be 400 °C, 5 °C·min−1, and 150 mL Ar·min−1 for orange waste, and 400 °C, 10 °C·min−1, and 150 mL Ar·min−1 for orange pruning. Thermogravimetric analysis showed higher thermal stability for orange pruning due to its higher lignin content (20% vs. 5% wt. on a wet basis). The bio-oil composition was determined by GC-MS. Toluene and 5-hydroxymethylfurfural were the main compounds found in orange waste bio-oils, while orange pruning bio-oils were composed mainly of 4-hydroxy-4-methyl-2-pentanone. Finally, the removal of the sulphur content from waste cooking oil was assayed with the biochars from both orange waste and orange pruning, whose BET surface areas were previously determined. Despite their low specific surface areas (≤1 m2·g−1 for orange waste biochars and up to 24.3 m2·g−1 for orange pruning biochars), these biochars achieved a reduction of the initial sulphur content of the waste cooking oil between 66.4% and 78.8%.European Union under the LIFE 13 BIOSEVILLE Programme ENV/ES/1113 (analysis, materials and salaries)European Regional Development Fund (ERDF) through the CARBOENERGY project (materials and salaries) granted by the FEDER INNTERCONECT