Visible and NIR Spectroscopy to assess biodiesel quality: Determination of alcohol and glycerol traces

Biodiesel quality control is of relevant importance as biodiesel properties influence diesel engine performance. In the present work, the benefits of the use of visible and near-infrared Spectroscopy (NIRS) as a technique for screening undesirable contaminants, i.e. methanol and glycerol content in biodiesel are presented. Excess of methanol decreases heating value and flash point and increases carbon deposits, while the presence of glycerol may cause injector tip coking and deposits in the combustion chamber. Biodiesel samples contaminated with different amounts of methanol and glycerol were scanned by NIRS. Their NIR spectra were acquired at 2-nm intervals over a wavelength range from 400 to 2500 nm (visible plus near-infrared regions). First derivative of the spectra were calculated and correlated to the raw optical data by means of modified partial least-squares (MPLS) regression. First derivative equation of the optical data, pretreated by standard normal variate (SNV) and De-trending (DT) transformations, showed a coefficient of determination r² in the cross-validation step of 0.99 and 0.81, for the samples contaminated with methanol and glycerol, respectively. Also, the standard deviation to standard error of cross-validation ratio (RPD) was 10.0 and 2.5, respectively. These statistics are indicative of the high capacity of prediction of the equations for methanol content and acceptable for glycerol content. Visible spectra also showed differences related to the samples, thus indicating it could serve to determine the presence of these contaminants. The use of NIRS technology provides a trustworthy and low-cost method to determine the presence of undesirable amounts of methanol and glycerol. It also offers an important saving of time (each analysis requires less than two minutes).     

Sustainable value-added C_3 chemicals from glycerol transformations:A mini review for heterogeneous catalytic processes

It is of importance to convert glycerol, the primary by-product from biodiesel manufacturing, to various valuable C_3 chemicals, such as acrolein via dehydration, lactic acid, 1,3-dihydroxyacetone via oxidation,and 1,3-propanediol, allyl alcohol via hydrogenolysis. As compared to petroleum-based resources, C_3 chemicals from glycerol provide a benign, sustainable and atomically economic feature. Extensive heterogeneous catalysts have been designed, prepared and tested for these transformations. In recent five years,great progress, including high yields to target products over appropriate catalysts, insight into reaction mechanism and network, has been achieved. The present review systematically covers recent research progress on sustainable C_3 chemical production from catalytic glycerol transformations. We hope that it will benefit future research on transformations of glycerol as well as other polyols.     

Treatment of industrial glycerol from biodiesel production by adsorption operation: kinetics and thermodynamics analyses

Abstract

Equilibrium, thermodynamic, and kinetic analyses of the pigments adsorption of the industrial glycerol onto activated charcoal were performed. As the pigments concentration was not known, then, a relative adsorption capacity was defined using absorbance values measured in a spectrophotometer at a wavelength of 265?nm. Kinetic study showed that about 60?s were needed to reach equilibrium conditions. Relative adsorption capacity reached 8?g^?1 for 1% of adsorbent amount (w/w). Adsorption enthalpy was of –17.63?kJ mol^?1, while for isosteric heat values were obtained between –7.39 and –18.46?kJ mol^?1. The mathematical methodology used for the parameters determinations proved to be robust and able to express the relationships of kinetics, equilibrium and thermodynamics. Enthalpy values obtained by Van't Hoff method was confirmed by isosteric heat calculation, evidencing that this methodology can be used for systems whose compositions are unknown, but detectable by indirect form.     

Investigation of terminalia (Terminalia belerica Robx.) seed oil as prospective biodiesel source for North-East India

Terminalia (Terminalia belerica Robx.) is available in the northeastern region of India. The fruit of terminalia has some medicinal value and its kernel contains 43% oil. The prospect of terminalia oil for biodiesel production is investigated with reference to some relevant properties. The fatty acid profile of oil extracted from terminalia is found comparable with similar seed oils attempted for biodiesel production in this region. Terminalia oil contains 32.8% palmitic acid, 31.3% oleic acid, and 28.8% linoleic acid. The calorific value and kinematic viscosity of terminalia oil are 37.50 MJ/kg and 25.60 cSt, respectively. The calorific value and cetane number of terminalia FAME are within the acceptable limit of the EN 14214 standard. However, the flash point of terminalia FAME (90 °C) is relatively lower than the minimum required standard. Overall, the properties of biodiesel obtained from terminalia seed conform to the existing biodiesel standard. In addition to assisting the national biodiesel mission, the extension and regeneration of forest areas through terminalia planting would help us to curb the seemingly irreversible trend of de-forestation in the northeast region of India.     

Revalorization of glycerol: Comestible oil from biodiesel synthesis

High dependence on fossil fuel has caused increase of carbon dioxide concentration in the atmosphere. The actual political trends are towards an increased use of renewable fuels from agricultural origin. One of the main products of the European biorefineries is biodiesel. The main reaction involved in biodiesel synthesis produces a large amount of glycerol as by-product. Two aspects are arising in this respect: the glycerol obtained as residue and the food conversion to fuel. This paper deals with the revalorization of the residual glycerol stream to obtain triacetin (glyceryl triacetate), the lightest comestible oil. The application of glycerol as raw material to produce triacetin is not new. The goal of this paper is to check the feasibility of this transformation in an efficient integrated continuous process which is suitable for processing high quantities of glycerol. A kinetic model was determined experimentally for the production of triacetin from glycerol and acetic acid in the absence of catalyst. The results showed that by process integration of the reaction and distillation in the same unit (reactive distillation), a more sustainable process can be developed. The proposed configuration output is checked by rigorous simulation.     

Influence of diesel particulate filter additives on biodiesel quality

The influence of the diesel particulate filter additives (DPA) SATACEN and EOLYS on biodiesel fuel quality has been evaluated. Both additives significantly affected the oxidation stability of neat biodiesel. The influence on acid values and CFPP was found to be only small. Combination of diesel additives with biodiesel additives like oxidation stability and CFPP improvers led to similar results. Results indicated that DPA also lowered the efficiency of the oxidation stability improver Baynox. Furthermore, the CFPP additives Chimec and Infineum were also prone to have a small influence on biodiesel oxidation stability.     

Kinematic viscosity of biodiesel fuel components and related compounds. Influence of compound structure and comparison to petrodiesel fuel components

Biodiesel, defined as the mono-alkyl esters of vegetable oils and animal fats is an alternative diesel fuel that is steadily gaining attention and significance. One of the most important fuel properties of biodiesel and conventional diesel fuel derived from petroleum is viscosity, which is also an important property of lubricants. Ranges of acceptable kinematic viscosity are specified in various biodiesel and petrodiesel standards. In this work, the kinematic viscosity of numerous fatty compounds as well as components of petrodiesel were determined at 40 °C (ASTM D445) as this is the temperature prescribed in biodiesel and petrodiesel standards. The objective is to obtain a database on kinematic viscosity under identical conditions that can be used to define the influence of compound structure on kinematic viscosity. Kinematic viscosity increases with chain length of either the fatty acid or alcohol moiety in a fatty ester or in an aliphatic hydrocarbon. The increase in kinematic viscosity over a certain number of carbons is smaller in aliphatic hydrocarbons than in fatty compounds. The kinematic viscosity of unsaturated fatty compounds strongly depends on the nature and number of double bonds with double bond position affecting viscosity less. Terminal double bonds in aliphatic hydrocarbons have a comparatively small viscosity-reducing effect. Branching in the alcohol moiety does not significantly affect viscosity compared to straight-chain analogues. Free fatty acids or compounds with hydroxy groups possess significantly higher viscosity. The viscosity range of fatty compounds is greater than that of various hydrocarbons comprising petrodiesel. The effect of dibenzothiophene, a sulfur-containing compound found in petrodiesel fuel, on viscosity of toluene is less than that of fatty esters or long-chain aliphatic hydrocarbons. To further assess the influence of the nature of oxygenated moieties on kinematic viscosity, compounds with 10 carbons and varying oxygenated moieties were investigated. A reversal in the effect on viscosity of the carboxylic acid moiety vs. the alcohol moiety is noted for the C10 compounds compared to unsaturated C18 compounds. Overall, the sequence of influence on kinematic viscosity of oxygenated moieties is COOH≈C-OH>COOCH₃≈CO>C-O-C> no oxygen.     

Enzymatic transesterification for production of biodiesel using yeast lipases: An overview

Biodiesel has provided an eco-friendly solution to fuel crisis, as it is renewable, biodegradable and a non-toxic fuel that can be easily produced through enzymatic transesterification of vegetable oils and animal fats. Enzymatic production of biodiesel has many advantages over the conventional methods as high yields can be obtained at low reaction temperatures with easy recovery of glycerol. Microbial lipases are powerful biocatalysts for industrial applications including biodiesel production at lower costs due to its potential in hydrolyzing waste industrial materials. Among them, lipases from yeasts, Candida antarctica, Candida rugosa, Cryptococcus sp., Trichosporon asahii and Yarrowia lipolytica are known to catalyze such reactions. Moreover, stepwise addition of methanol in a three step, two step and single step reactions have been developed using yeast lipases to minimize the inhibitory effects of methanol. The latest trend in biodiesel production is the use of whole-cell as biocatalysts, since the process requires no downstream processing of the enzyme. Synthesis of value added products from the byproduct glycerol further reduces the production cost of biodiesel. This review aims at compiling the information on various yeast lipase catalyzed transesterification reactions for greener production of biodiesel.     

Solid oxide derived from waste shells of Turbonilla striatula as a renewable catalyst for biodiesel production

Biodiesel production via transesterification of mustard oil with methanol using solid oxide catalyst derived from waste shell of Turbonilla striatula was investigated. The shells were calcined at different temperatures for 4 h and catalyst characterizations were carried out by X-ray diffraction (XRD), scanning electron microscope (SEM), energy dispersive spectrometer (EDS), Fourier transform infrared spectrometer (FT-IR), thermogravimetric analysis (TGA)/differential scanning calorimetry (DSC) and Brunauer-Emmett-Teller (BET) surface area measurements . Formation of solid oxide i.e. CaO was confirmed at calcination temperature of 800 °C. The effect of the molar ratio of methanol to oil, the reaction temperature, catalyst calcination temperature and catalyst amount used for transesterification were studied to optimize the reaction conditions. Biodiesel yield of 93.3% was achieved when transesterification was carried out at 65 ± 5 °C by employing 3.0 wt.% catalyst and 9:1 methanol to oil molar ratio. BET surface area indicated that the shells calcined in the temperature range of 700 °C-900 °C exhibited enhanced surface area and higher pore volume than the shells calcined at 600 °C. Reusability of the catalysts prepared in different temperatures was also investigated.     

In situ production of fatty acid methyl ester from low quality rice bran: An economical route for biodiesel production

Low quality rice bran was used to produce fatty acid methyl ester (FAME) via in situ extraction, esterification and transesterification process. The effects of the acid and alkaline catalysts on the ester yield, esterification and transesterification process were studied. When 75 ml of absolute methanol, 150 ml of petroleum ether, 0.75 g of concentrated sulfuric acid and 0.71 g of sodium hydroxyl were used, 16.69% (w_FAME/w_{rice bran}) of FAME was obtained. The esterification rate and the transesterification rate reached 98.83% and 80.47%. Based on the proposed route, the production process of FAME (biodiesel) could be simplified and the production cost could be reduced.     

An ideal feedstock, kusum (Schleichera triguga) for preparation of biodiesel: Optimization of parameters

Kusum (Schleichera triguga), a non-edible oil bearing plant has been used as an ideal feedstock for biodiesel development in the present study. Various physical and chemical parameters of the raw oil and the fatty acid methyl esters derived have been tested to confirm its suitability as a biodiesel fuel. The fatty acid component of the oil was tested by gas chromatography. The acid value of the oil was determined by titration and was found to 21.30 mg KOH/g which required two step transesterification. Acid value was brought down by esterification using sulfuric acid (H₂SO₄) as a catalyst. Thereafter, alkaline transesterification was carried out using potassium hydroxide (KOH) as catalyst for conversion of kusum oil to its methyl esters. Various parameters such as molar ratio, amount of catalyst and reaction time were optimized and a high yield (95%) of biodiesel was achieved. The high conversion of the feedstock into esters was confirmed by analysis of the product on gas chromatograph-mass spectrometer (GC-MS). Viscosity and acid value of the product biodiesel were determined and found to be within the limits of ASTM D 6751 specifications. Elemental analysis of biodiesel showed presence of carbon, hydrogen, oxygen and absence of nitrogen and sulfur after purification. Molar ratio of methanol to oil was optimized and found to be 10:1 for acid esterification, and 8:1 for alkaline transesterification. The amounts of H₂SO₄ and KOH, 1% (v/v) and 0.7% (w/w), respectively, were found to be optimum for the reactions. The time duration of 1 h for acid esterification followed by another 1 h for alkaline transesterification at 50 ± 0.5 °C was optimum for synthesis of biodiesel.     

Technologies for production of biodiesel focusing on green catalytic techniques: A review

Biodiesel production is undergoing rapid technological reforms in industries and academia. This has become more obvious and relevant since the recent increase in the petroleum prices and the growing awareness relating to the environmental consequences of the fuel overdependency. In this paper, various technological methods to produce biodiesel being used in industries and academia are reviewed. Catalytic transesterification, the most common method in the production of biofuel, is emphasized in the review. The two most common types of catalysts; homogeneous liquids and heterogeneous solids, are discussed at length in the paper. Two types of processes; batch and continuous processes, are also presented. Although batch production of biodiesel is favored over continuous process in many laboratory and larger scale efforts, the latter is expected to gain wider acceptance in the near future, considering its added advantages associated with higher production capacity and lower operating costs to ensure long term supply of biodiesel.     

Cultivation of microalgae for biodiesel production: A review on upstream and downstream processing

Fluctuating market price of fossil fuel and overwhelming emission of greenhouse gases to the atmosphere have resulted in climate change and have been a global concern in this decade.Hence,biodiesel has become an alternative option to fossil diesel as it is renewable and environmentally friendly.Nevertheless,this alternative fuel that is usually derived from terrestrial oil crops will cause shortage in food supply and deforestation if mass production is realized.In recent years,cultivation of aquatic microorganism (particularly microalgae) to produce biodiesel is considered as a practical solution due to their high growth rate and ability to synthesize large quantity of lipid within their cell.However,the development of energy and cost-efficiency of microalgae cultivation system are the main issues in producing renewable microalgae biodiesel.Of late,wastewater or organic compost has been used as the cultivation medium as it can provide sufficient nutrients to sustain microalgae growth.Microalgae cultivation method and system are vitally important as these factors undoubtedly affect the final microalgae biomass and lipid yield.In this review,the cultivation system of microalgae,nutrients demanded for microalgae production,cell harvesting and drying,microalgae oil extraction,and utilization of microalgae biomass for biodiesel production are introduced and discussed.It is anticipated to convey clearer perspectives in upstream and downstream processes in microalgae-derived biodiesel production.     

Development of multifunctional additives based on vegetable oils for high quality diesel and biodiesel

The increasing qualitative requirements of the modern diesel fuels can be satisfied by applying environmental friendly blending components and additive-packages having high performance level.The aim of our experimental work was to produce multifunctional additives based on rapeseed oil methyl ester by applying radical initiation. This process is more environmental friendly and energy economic respect to the widely used thermal synthesis method for the production of polyisobutylene (PIB)-succinimide type additives. Beside, our aim was to use raw materials originated from partly renewable source to meet the biodegradability requirements. These synthesized additives showed same or even better detergent–dispersant properties compared to the traditional PIB-succinimides and also provided corrosion inhibiting and lubricity improving effects when applied in diesel fuel, 5% biodiesel containing diesel fuel and 100% biodiesel.     

Optimal processing pathway for the production of biodiesel from microalgal biomass: A superstructure based approach

In this study, we propose a mixed integer nonlinear programming (MINLP) model for superstructure based optimization of biodiesel production from microalgal biomass. The proposed superstructure includes a number of major processing steps for the production of biodiesel from microalgal biomass, such as the harvesting of microalgal biomass, pretreatments including drying and cell disruption of harvested biomass, lipid extraction, transesterification, and post-transesterfication purification. The proposed model is used to find the optimal processing pathway among the large number of potential pathways that exist for the production of biodiesel from microalgae. The proposed methodology is tested by implementing on a specific case with different choices of objective functions. The MINLP model is implemented and solved in GAMS using a database built in Excel. The results from the optimization are analyzed and their significances are discussed.     

Preparation of magnetic biochar derived from cyclosorus interruptus for the removal of phenolic compounds: Characterization and mechanism

A novel magnetic biochar was prepared via pyrolysis method and modification. The influence factors of contact time, initial concentration, temperature, and pH on the adsorption were investigated. The experimental results exhibited that the adsorption ability of methyl salicylate onto biochar was higher than that of phenol and para-chlorophenol under the same condition, which may be owing to the effect of hydrogen bonding, hydrophobicity, and π–π interaction. The maximum adsorption capacities of phenol, para-chlorophenol and methyl salicylate were 62.6, 131.6, and 169.7 mg/g at 298 K, respectively. This magnetic biochar exhibited high reusability (retained 82.1% after five cycles) and sharply magnetic performance (21.4emu/g).     

从生产角度谈复混肥配方技术

为获得易造粒,产量高,成球率高,颗粒圆整度好的优质产品,根据生产复混肥原料的粘结性不同,吸湿点、溶解度的差异,不同原料间的配伍性,并结合多年的生产经验,介绍在复混肥配方中应如何把握物料的适度粘性,沙性物料的适度比例,提高物料吸湿点的方法,干燥物料的适度用量等.最后介绍15-15-15规格复混肥的配方实例.