M. Joana Neiva Correia

Multivariate near infrared spectroscopy models for predicting the methyl esters content in biodiesel.

Biodiesel is the main alternative to fossil diesel. The key advantages of its use are the fact that it is a non-toxic renewable resource, which leads to lower emissions of polluting gases. European governments are targeting the incorporation of 20% of biofuels in the general fuels until 2020. Chemically, biodiesel is a mixture of fatty acid methyl esters, derived from vegetable oils or animal fats, which is usually produced by a transesterification reaction, where the oils/fats react with an alcohol, in the presence of a catalyst. The European Standard (EN 14214) establishes 25 parameters that have to be analysed to certify biodiesel quality and the analytical methods that should be used to determine those properties. This work reports the use of near infrared (NIR) spectroscopy to determine the esters content in biodiesel as well as the content in linolenic acid methyl esters (C18:3) in industrial and laboratory-scale biodiesel samples. Furthermore, calibration models for myristic (C14:0), palmitic (C16:0), stearic (C18:0), oleic (C18:1), linoleic (C18:2) acid methyl esters were also obtained. Principal component analysis was used for the qualitative analysis of the spectra, while partial least squares regression was used to develop the calibration models between analytical and spectral data. The results confirm that NIR spectroscopy, in combination with multivariate calibration, is a promising technique to assess the biodiesel quality control in both laboratory-scale and industrial scale samples.

Studies on the Use of Ionic Liquids as Potential Extractants of Phenolic Compounds and Metal Ions

Abstract The present work was aimed at investigating the usefulness of 1‐(n‐alkyl)‐3‐methylimidazolium‐derived ionic liquids (ILs) in liquid–liquid separation processes. For this purpose, a series of 1‐(n‐alkyl)‐3‐methylimidazolium tetrafluoroborates and hexafluorophosphates were prepared by standard synthetic methods and characterized by 1H NMR. Experiments were performed to assess the influence of the alkyl group and the anion on the physical properties of the IL. Equilibrium studies on the extraction of heavy metal ions (copper, zinc, and chromium) and some common pollutant aromatic compounds (phenol, tyrosol, and p‐hydroxybenzoic acid) from aqueous media then were performed with some selected ILs. The effects of temperature and the pH on the distribution ratio of solutes between the IL/aqueous phases also were analyzed. The results suggest that some of the ionic liquids tested are adequate to extract metal ions and organic compounds from aqueous solutions, with a high efficiency in some instances.

Multivariate near infrared spectroscopy models for predicting the iodine value, CFPP, kinematic viscosity at 40 °C and density at 15 °C of biodiesel

Biodiesel is one of the main alternatives to fossil diesel. It is a non-toxic renewable resource, which leads to lower emissions of polluting gases. In fact, European governments are targeting the incorporation of 20% of biofuels in the fossil fuels until 2020. Chemically, biodiesel is a mixture of fatty acid methyl esters, derived from vegetable oils or animal fats, which is usually produced by a transesterification reaction, where the oils or fats react with an alcohol, in the presence of a catalyst. The European Standard (EN 14214) establishes 25 parameters that have to be analysed to certify biodiesel quality and the analytical methods that should be used to determine those properties. This work reports the use of near infrared (NIR) spectroscopy to determine some important biodiesel properties: the iodine value, the cold filter plugging point, the kinematic viscosity at 40 degrees C and the density at 15 degrees C. Principal component analysis was used to perform a qualitative analysis of the spectra and partial least squares regression to develop the calibration models between analytical and spectral data. The results support that NIR spectroscopy, in combination with multivariate calibration, is a promising technique applied to biodiesel quality control, in both laboratory and industrial-scale samples.

Monitoring biodiesel fuel quality by near infrared spectroscopy

Biodiesel is produced mainly by a transesterification reaction which involves the reaction of vegetable oils, animal fats or waste oils with an alcohol (such as methanol) in the presence of a catalyst (such as sodium hydroxide or methoxide). Since the presence of contaminants can cause severe engine problems, the assessment of the biodiesel quality is very important. This work reports the use of near infrared (NIR) spectroscopy to determine the content of water and methanol in industrial and laboratory-scale biodiesel samples. A qualitative analysis of the spectra by principal components analysis was carried out and partial least squares regression was used to develop calibration models between spectral and analytical data. The results indicate that the use of NIR spectroscopy, in combination with multivariate calibration, is a promising technique to assess the biodiesel quality in both laboratory-scale and industrial-scale samples.

The leaching of tetrahedrite in ferric chloride solutions

Abstract This paper presents a study of the kinetics of the leaching of tetrahedrite in FeCl3–NaCl–HCl solutions for temperatures between 60°C and 104°C and ferric ion concentrations of 0.001 to 1 M at atmospheric pressure. The shrinking core model was applied to the results. The calculated activation energy is 65±6 kJ/mol; the order of the reaction with respect to ferric ion is 0.35±0.03; and the apparent rate constant is proportional to the inverse of the mean particle size. These results show that, for temperatures below the normal boiling point of the solution, the leaching of tetrahedrite is reaction controlled. From the analyses of the solutions and X-ray and microprobe analyses of the solid residues, it was concluded that the leaching of tetrahedrite involves the complete breakdown of the sulphide structure.

Monitoring the quality of oils for biodiesel production using multivariate near infrared spectroscopy models

Biodiesel is a mixture of fatty acid methyl esters, derived from vegetable oils or animal fats, which is usually produced by a transesterification reaction, where the oils or fats react with an alcohol in the presence of a catalyst. The quality of the oils used for biodiesel production strongly influences the final properties of biodiesel, namely its compliance to the European Standard. This work reports the use of near infrared (NIR) spectroscopy in the quality control of several oil properties, such as the iodine value, the water content and the acid number but, more importantly, the weight–weight percentages (wt%) of soybean, palm and rapeseed oil in mixtures. Principal component analysis was used to perform a qualitative analysis of the spectra, whereas partial least squares regression allowed the development of calibration models between analytical reference data and NIR spectra. The calibration ranges were 60–126 g I2 100 g−1 for the iodine value, 478–2500 mg kg−1 for the water content and 0.13-6.56 mg KOH g−1 for the acid number, whereas the validation errors were around 3.1 g I2 100 g−1, 111 mg kg−1 and 0.22 mg KOH g−1, respectively. The results obtained show that NIR spectroscopy is a promising technique to carry out the quality control of the commonly used vegetable oils for biodiesel production, namely the quality assurance and authenticity. Furthermore, it is of great value to have a simple, fast and reliable method to identify the composition of an oil mixture and/or some of its quality parameters, prior to storage or upon admission of a new lot of oil.

Vanadium phosphate catalysts for biodiesel production from acid industrial by-products

Biodiesel production from high acidity industrial by-products was studied using heterogeneous acid catalysts. These by-products contain 26-39% of free fatty acids, 45-66% of fatty acids methyl esters and 0.6-1.1% of water and are consequently inadequate for direct basic catalyzed transesterification. Macroporous vanadyl phosphate catalysts with V/P=1 (atomic ratio) prepared via sol-gel like technique was used as catalyst and it was possible to produce in one reaction batch a biodiesel contain 87% and 94% of FAME, depending on the by-product used as raw material. The initial FAME content in the by-products had a beneficial effect on the reactions because they act as a co-solvent, thus improving the miscibility of the reaction mixture components. The water formed during esterification process seems to hinder the esters formation, possibly due to competitive adsorption with methanol and to the promotion of the FAME hydrolysis reaction.The observed catalyst deactivation seems to be related to the reduction of vanadium species. However, spent catalysts can be regenerated, even partially, by reoxidation of the reduced vanadium species with air.

Modeling of the Extraction Equilibrium of Copper from Sulfate Solutions with Acorga M5640

The extraction equilibrium of copper from sulfate media with the aldoxime Acorga M5640 in ShellSol D70 has been investigated. The distribution results were interpreted by taking into account the nonideality of the aqueous phase. The activity of copper and hydrogen ions in the target systems CuSO4/H2SO4/Na2SO4 and CuSO4/H2SO4/Fe2(SO4)3/ZnSO4 were calculated through the speciation of the aqueous solutions and by applying the Pitzer model. The experimental pH values were found in good agreement with the predicted pH values. A model considering the dimerization of the aldoxime extractant was proposed to predict the distribution ratio and the copper loading isotherms. The extraction constant at infinite dilution and the apparent dimerization constant were evaluated from the experimental data and were found to be 103.06 ± 0.07 and 51 ± 9 M−1, respectively, at 25°C.

Status of biodiesel production using heterogeneous alkaline catalysts

This paper describes biodiesel production using heterogeneous alkaline catalysts instead of the conventional homogenous alkaline catalysts, such as NaOH, KOH or sodium methoxide, for the methanolysis reaction, in the search for more profitable and sustainable alternatives regarding biodiesel production. The heterogeneous catalytic process has many differences from that currently used in industrial homogeneous processes. The main advantage is that it requires lower investment costs, as there is no need for separation steps such as methanol/catalyst, biodiesel/catalyst and glycerine/catalyst. This paper also describes experimental work towards the development of new heterogeneous alkaline catalysts able to produce biodiesel from vegetable oils. The research has resulted in the selection of CaO and CaO modified with alkaline and alkaline earth metal catalysts. They show very good catalytic performances with high activity and stability. In fact, biodiesel (FAME) yields higher than 94% were observed in several consecutive reaction batches without expensive intermediate reactivation procedures. Therefore, those catalysts appear to be suitable for biodiesel production.

BIOSORPTION OF COPPER, ZINC AND NICKEL BY GRAPE- STALKS AND CORK BIOMASSES

The removal of copper, zinc and nickel from aqueous solutions by biosorption using grapestalks and cork biomasses is reported. The adsorption isotherms were determined and the uptake capacity for copper with grape stalks and cork was, respectively, 19.9 mg/g and 16.5 mg/g, while for zinc was 18.3mg/g with grape stalks and 13.4 mg/g with cork and for nickel was 11.1 mg/g with cork. The kinetics of copper biosorption in both biomasses was studied and a second order model was fitted to the experimental data. Copper biosorption is a fast process and within the first 5 minutes 80% of the maximum capacity was attained. The calculated activation energy for the biosorption reaction of copper was 28±3 KJ/mol for grape stalks and 6±2 KJ/mol for cork biomass. These low values indicate that the metal diffusion inside the particles is the rate controlling step of the reaction.