1) Ethanol was studied as an alternative solvent to hexane for extracting oil from sunflower collets. Ethanol extracted a similar amount of oil but also extracted more minor components like tocopherols, phospholipids, and sugars compared to hexane.
2) Batch extraction experiments with ethanol were conducted at 50 and 60°C, and extraction kinetics were studied. Oil extraction reached equilibrium, limited by the solubility of extractable material in ethanol.
3) Using ethanol as the solvent extracted about 70% less waxes and at least 38% more tocopherols and phospholipids compared to hexane. It also extracted over 75% of the initial sugar content from the sunflower collets
This document evaluates alternative solvents for improving oil extraction from rapeseeds compared to the commonly used n-hexane solvent. It assesses the extraction kinetics, fatty acid compositions, lipid yields, and micronutrient contents of oils extracted using ethanol, isopropanol, D-limonene, α-pinene, and p-cymene. P-cymene showed the most promise as a substitute for n-hexane with a higher lipid yield and selectivity, though micronutrient contents were relatively low. The Hansen solubility parameter model was also applied to better understand the dissolving mechanisms between alternative solvents and rapeseed oil.
This document reviews the use of supercritical carbon dioxide in food processing applications. It discusses how supercritical CO2 can be used to extract compounds like caffeine, vitamins, oils, and flavors from foods. Specific applications covered include decaffeinating coffee, extracting vitamin E from natural sources, removing alcohol from wine and beer, removing fat from foods, and enriching compounds like tocochromanols from palm and corn oils. The document also discusses how supercritical CO2 extraction is being used for food safety applications like analyzing for pesticide residues and environmental pollutants in foods.
Dry cleaning involves cleaning fabrics with nonaqueous solvents using three steps: washing, spinning to extract solvent, and drying. Two main types of cleaning fluids are used: petroleum solvents and synthetic solvents like perchloroethylene. There are also two types of machines: transfer machines that separate washing and drying, and dry-to-dry machines that integrate all steps. The dry cleaning industry consists of coin-operated facilities, commercial shops, and industrial cleaners. Emissions occur from various sources in the dry cleaning process. Controls include solvent recovery systems using condensers and carbon adsorption to minimize emissions.
This study investigated the kinetics of extracting lycopene and β-carotene from tomato skin using near critical liquid carbon dioxide, with and without oleic acid as a co-solvent. Extractions were performed in a high-pressure autoclave at 299K and 64 bar over various time periods. The presence of oleic acid improved extraction of lycopene but decreased extraction of β-carotene. It also reduced the amount of the cis isomer form of lycopene extracted. Analysis by HPLC showed that maximum lycopene extraction with oleic acid occurred after 20 hours, compared to extraction without the co-solvent. The solubility of oleic, stearic and pal
This document summarizes production processes for phosphoric acid. It describes three main wet processes that use sulphuric acid to decompose phosphate rock: the dihydrate, hemihydrate, and di-hemihydrate (double stage) processes. These processes differ in the form of the resulting calcium sulphate byproduct - dihydrate, hemihydrate, or a combination. The document provides an overview of the raw materials, chemical reactions, production equipment and methods, emissions controls, and byproduct handling for phosphoric acid production.
Solvent free synthesis of malonyl chlorides a green chemistry approacheSAT Journals
This document describes a study on the solvent-free synthesis of methyl malonyl chloride and ethyl malonyl chloride. The synthesis involved a three-step process: 1) selective saponification of dialkyl malonate, 2) hydrolysis of monoalkyl malonic acid, and 3) chlorination of monoalkyl malonic acid. The reaction was studied with and without the solvent methylene chloride. Kinetics analysis found the reaction to be first order. Conversions were higher without solvent at 93.08% for methyl and 98.23% for ethyl, compared to 78.67% and 84.39% with solvent. The solvent-free process is recommended as a greener approach.
Koch Modular Process Systems presented on extractive distillation. Extractive distillation involves adding a high-boiling solvent to a binary mixture to alter the relative volatility of the components and allow separation via distillation. It can be considered for mixtures that form azeotropes or have low relative volatility. Examples were given of mixtures like acetone/methanol and THF/water that can be separated through extractive distillation using appropriate solvents. Attendees were encouraged to evaluate extractive distillation for difficult separation challenges.
En el marco de la jornada Microalgas, ¿una fuente de petróleo verde?, organizada con IMDEA y celebrada el 8 de abril en EOI, Escuela de Organización Industrial, Emilio Molina Grima, de la Universidad de Almería, presenta como han llegado a un proceso eficiente de producción en laboratorio de aceite de algas.
8_04_2010
This document evaluates alternative solvents for improving oil extraction from rapeseeds compared to the commonly used n-hexane solvent. It assesses the extraction kinetics, fatty acid compositions, lipid yields, and micronutrient contents of oils extracted using ethanol, isopropanol, D-limonene, α-pinene, and p-cymene. P-cymene showed the most promise as a substitute for n-hexane with a higher lipid yield and selectivity, though micronutrient contents were relatively low. The Hansen solubility parameter model was also applied to better understand the dissolving mechanisms between alternative solvents and rapeseed oil.
This document reviews the use of supercritical carbon dioxide in food processing applications. It discusses how supercritical CO2 can be used to extract compounds like caffeine, vitamins, oils, and flavors from foods. Specific applications covered include decaffeinating coffee, extracting vitamin E from natural sources, removing alcohol from wine and beer, removing fat from foods, and enriching compounds like tocochromanols from palm and corn oils. The document also discusses how supercritical CO2 extraction is being used for food safety applications like analyzing for pesticide residues and environmental pollutants in foods.
Dry cleaning involves cleaning fabrics with nonaqueous solvents using three steps: washing, spinning to extract solvent, and drying. Two main types of cleaning fluids are used: petroleum solvents and synthetic solvents like perchloroethylene. There are also two types of machines: transfer machines that separate washing and drying, and dry-to-dry machines that integrate all steps. The dry cleaning industry consists of coin-operated facilities, commercial shops, and industrial cleaners. Emissions occur from various sources in the dry cleaning process. Controls include solvent recovery systems using condensers and carbon adsorption to minimize emissions.
This study investigated the kinetics of extracting lycopene and β-carotene from tomato skin using near critical liquid carbon dioxide, with and without oleic acid as a co-solvent. Extractions were performed in a high-pressure autoclave at 299K and 64 bar over various time periods. The presence of oleic acid improved extraction of lycopene but decreased extraction of β-carotene. It also reduced the amount of the cis isomer form of lycopene extracted. Analysis by HPLC showed that maximum lycopene extraction with oleic acid occurred after 20 hours, compared to extraction without the co-solvent. The solubility of oleic, stearic and pal
This document summarizes production processes for phosphoric acid. It describes three main wet processes that use sulphuric acid to decompose phosphate rock: the dihydrate, hemihydrate, and di-hemihydrate (double stage) processes. These processes differ in the form of the resulting calcium sulphate byproduct - dihydrate, hemihydrate, or a combination. The document provides an overview of the raw materials, chemical reactions, production equipment and methods, emissions controls, and byproduct handling for phosphoric acid production.
Solvent free synthesis of malonyl chlorides a green chemistry approacheSAT Journals
This document describes a study on the solvent-free synthesis of methyl malonyl chloride and ethyl malonyl chloride. The synthesis involved a three-step process: 1) selective saponification of dialkyl malonate, 2) hydrolysis of monoalkyl malonic acid, and 3) chlorination of monoalkyl malonic acid. The reaction was studied with and without the solvent methylene chloride. Kinetics analysis found the reaction to be first order. Conversions were higher without solvent at 93.08% for methyl and 98.23% for ethyl, compared to 78.67% and 84.39% with solvent. The solvent-free process is recommended as a greener approach.
Koch Modular Process Systems presented on extractive distillation. Extractive distillation involves adding a high-boiling solvent to a binary mixture to alter the relative volatility of the components and allow separation via distillation. It can be considered for mixtures that form azeotropes or have low relative volatility. Examples were given of mixtures like acetone/methanol and THF/water that can be separated through extractive distillation using appropriate solvents. Attendees were encouraged to evaluate extractive distillation for difficult separation challenges.
En el marco de la jornada Microalgas, ¿una fuente de petróleo verde?, organizada con IMDEA y celebrada el 8 de abril en EOI, Escuela de Organización Industrial, Emilio Molina Grima, de la Universidad de Almería, presenta como han llegado a un proceso eficiente de producción en laboratorio de aceite de algas.
8_04_2010
Treatment of aged transformer oil using dry sludge in lab-scale refining unitPremier Publishers
Experimental analysis of drinking water treatment sludge revealed that it is enriched with aluminum and silicon oxides which are the most metal oxides used in reclamation of transformer insulating oils. The potential use of inexpensive and available water treatment dry sludge as sorbent material for the removal of acidity, water content and some impurities from aged transformer oil by adsorption methodology was investigated using lab-scale refining unit. Dry sludge was found to improve the electrical and physical properties of aged transformer oils.High improvement of breakdown voltage occurs after using dry sludge reclaimed transformer oil and changed from 15 to 72 kV/ cm. Also some improvements have been achieved such as water content changed from 48 to 9 ppm and total acidity changed from 0.37 to 0.01mg KOH/g of oil.Viscosity, specific gravitywere improved. Also, some undesirable gases in aged oil(more than ten years in service) were removed. Furthermore the use of dry sludge as sorbent material renders the treated oil to some extent like new one. Also Dry sludge is available at any water treatment plant with no costs (waste product). Environmentally, after sludge reclamation process for the used transformer oil, the sludge can be recycled by ignition and used in further treatment processes.
Product purification and recovery remains a priority for chemical engineers, today. Designing separations processes to accomplish the above is a challenge, especially as streams get more complex in composition. Though often overlooked, liquid-liquid extraction (LLE) is a powerful separation technique for both organic and aqueous liquids. Whereas distillation technology relies on relative volatility differences among chemicals, LLE exploits the differences in relative solubilities of compounds in two immiscible liquids, to perform the key separation. Distillation may not be feasible when boiling points are nearly identical or for other reasons, economic and technical. When distillation is not a viable solution, LLE is a great alternative to achieve product purification and recovery.
This document provides information on the production of single superphosphate (SSP) fertilizer. It discusses the raw materials used, including rock phosphate and sulfuric acid. The production process involves acidulation of rock phosphate using sulfuric acid in a den, followed by scrubbing, granulation, drying, and screening. Process flow diagrams and material balances are presented. Equipment used is also described. The document evaluates capital costs, production costs, profitability, and provides a HAZOP analysis for the feeder.
Statistical Modeling and Optimization of Biodiesel Production from Azadiracht...IJAEMSJORNAL
This document summarizes a study that used statistical modeling and optimization to produce biodiesel from neem (Azadirachta Indica) oil using a co-solvent transesterification process. Neem oil was extracted and pretreated. A central composite design was used to experimentally vary reaction temperature, catalyst amount, reaction time, and methanol-to-oil ratio. Biodiesel yield and properties were measured. An optimized yield of 84.77% was achieved at 34°C, 1.10% catalyst, 35 minutes, and a 6:1 molar ratio. The produced biodiesel met ASTM specifications for properties like cetane number, viscosity, and flash point.
Desulphur - A new Desulphurisation TechniqueTecnoVeritas
This Presentations intends to present a new technique of Desulphurisation, a revolutionary product to help the environment and the marine/ shore industry.
The document reports on a study of extracting passion fruit seed oil using supercritical CO2. Experimental data was collected for extraction conducted at varying pressures, temperatures, and CO2 flow rates. An increase in pressure, temperature, and flow rate increased the extraction yield, with a maximum yield of 18.5% obtained. Mass transfer coefficients for passion fruit oil were determined to be 8.496 x 10-5 s-1 at specific conditions. Rheological studies observed dilatant fluid behavior in all tests. Bayesian inference was used to model mass transfer and account for parameter uncertainty.
This document summarizes a study on optimizing the extraction of sandalwood oil using subcritical carbon dioxide compared to conventional techniques like steam distillation. Subcritical carbon dioxide extraction at 200 bars and 28°C yielded 4.11% oil in the first hour, higher than other methods and with higher quality as indicated by acid value and santalol content. Analysis found the oil extracted in each hour contained varying amounts of key constituents like α-santalene and β-santalol. The study demonstrates that subcritical carbon dioxide extraction is more efficient and yields higher quality sandalwood oil than conventional techniques like steam distillation.
The seed from the fruit of the Beilschmiedia mannii (Lauraceae) tree provides edible oil. In order to contribute to the valorization of this seed, which is a traditional Vegetable in Côte d’Ivoire; study of its food potential has been carried out, Particular the determination of some physico-chemical characteristics of its oil. The results obtained are as follows: the yield (8.75%); the refractive index (1.41); the acid index (2.62); the Iodine index (83.8); Saponification index (263.14); the peroxide index (8.97).
Wauquier, j. p._-_petroleum_refining_i_crude_oil_-_petroleum_products_-_proce...Khalid Nawaz
This document provides an overview of topics related to petroleum refining, including: the composition of crude oil and petroleum products; fractionation and analysis of crude oils; characterization of crude oils and fractions; methods for calculating hydrocarbon properties; characteristics of petroleum products for energy and non-energy uses; standards and specifications for products; evaluation of crude oils; refining activities for motor fuels and lubricants; and an introduction to refining processes. It includes appendices on pure component characteristics and standard test methods.
This document describes a proposed project to build a methane to acetic acid plant in Bangladesh. The plant would produce 300 tons per day of 99% acetic acid and 450 tons per day of 91.5% methanol using methane from a local natural gas field as the raw material. Several processes for converting methane to methanol and methanol to acetic acid are considered, including catalytic, thermal cracking, photo-catalytic, and biological methods. The document selects the ICI process for methane to methanol conversion and the Cativa process for methanol to acetic acid conversion.
The document describes a process for producing acetic acid from methane using three steps. First, methane is oxidized in a reactor to produce methanol and acetic acid. The products are separated using flash distillation, yielding methanol and acetic acid. The methanol is then converted to additional acetic acid in a carbonylation reactor using a rhodium catalyst. Mass and energy balances were performed on the overall process. The reactors and separation equipment are also described.
Ethylic esterification of free fatty acids content in macauba palm oil (acroc...AcessoMacauba
This study evaluated the use of cationic resin catalysts for the esterification of free fatty acids in macauba palm oil, which has a high acidity of 40.8% that makes it unsuitable for conventional biodiesel production. Esterification experiments using ethanol and methanol as alcohols achieved the greatest acidity reduction of 38.6% using Purolite CT275DR resin at 90°C, 20:1 alcohol:oil ratio, and 8 hours. Temperature had the most significant effect on reducing acidity. The Purolite resin performed better than Mitsubishi PK208 resin due to its higher ion exchange capacity. Cation exchange resins show potential as pretreatment catalysts for high
Performance of KOH as a Catalyst for Trans-esterification of Jatropha Curcas ...ZY8
This document summarizes a study on using potassium hydroxide (KOH) as a catalyst for the trans-esterification of Jatropha curcas oil to produce biodiesel. The authors extracted oil from Jatropha fruits and conducted kinetics experiments to investigate the performance of KOH catalyst. They varied reaction parameters like oil to methanol molar ratio, catalyst concentration, and temperature. The results showed that an oil to methanol ratio of 1:16, KOH concentration of 1.5%, and temperature of 60°C produced the optimal biodiesel yield. An activation energy of 28.8 kJ/mol was calculated using the Arrhenius equation. The biodiesel properties met ASTM standards for
Phase equilibrium feasibility studies of free fatty acids extraction from pal...Alexander Decker
This document summarizes a study that investigated the extraction of free fatty acids from palm oil using supercritical carbon dioxide. The study assessed the feasibility of using a thermodynamic model based on UNIFAC to predict phase equilibrium and activity coefficients for the carbon dioxide/fatty acid system. Experimental results were obtained for extract mole fraction at different pressures from 60-180 bars and temperatures of 313.15K and 353.15K. Mass transfer parameters like diffusion coefficient and solubility were also determined. The model predictions matched reasonably well with experimental data.
These slides are developed for a part of the undergraduate course in Petroleum Refinery Engineering. The slides are also helpful for Masters level introductory course.
The document provides details about various refinery units including:
- Crude Distillation Unit (CDU), Naphtha Hydrotreating Unit (NHT), Isomerization Unit, Continuous Catalytic Reformer (CCR) Unit, Diesel Hydrotreating (DHDT) Unit, Vacuum Gas Oil Hydrotreating (VGO HDT) Unit, Fluidized Catalytic Cracking (FCC) Unit, Hydrogen Generation Unit (HGU), Polypropylene Unit (PPU), Sour Water Stripping (SWS) Unit, and Amine Regeneration Unit.
It describes the objectives, key inputs and outputs of each unit.
1. The document provides an overview of the catalytic reforming process, including feed preparation, the platform process, process variables, and chemistry involved.
2. It discusses catalyst deactivation factors like poisoning, fouling, and thermal degradation. Methods for catalyst regeneration like coke removal through pyrolysis and combustion are also presented.
3. Troubleshooting tips are given for various process issues like low naphthenic feedstock, sulfur contamination, high chlorides, and excess water contamination. The document outlines steps to identify the root cause and remedy such problems.
This document provides an overview of azeotropic distillation. It begins with an introduction that defines azeotropic distillation as a process where an entrainer is added to a feed mixture to form an azeotrope that can be separated. The document then discusses the working principle, provides examples of residue curve maps, and outlines considerations for process design and simulation. Finally, it discusses several industrial applications of azeotropic distillation, including alcohol dehydration, acetic acid dehydration, and ester production, before concluding and listing references.
This document describes a one-pot synthesis of 3,4-dihydropyrimidin-2(1H)-ones and thiones using 4-nitrophthalic acid as a catalyst under solvent-free conditions. Various aldehydes, 1,3-dicarbonyl compounds, and urea or thiourea reacted smoothly in good to excellent yields. The reaction conditions were optimized to use a 2 mol% catalyst loading at 90°C for 30 minutes. 4-Nitrophthalic acid proved to be an effective and inexpensive catalyst for this Biginelli reaction, providing advantages over other reported catalysts such as higher yields, simpler workup, and an environmentally friendly procedure. The products were characterized
Use of Immobilised Lipase from Candida antarctica in Supercritical Fluid Extr...Egidijus Dauksas
This document summarizes an experiment investigating the use of immobilized lipase from Candida antarctica in supercritical fluid extraction (SFE) of borage (Borago officinalis L.) seed oil. In the first series of experiments, borage seed oil extraction yield increased over twice when pressure was increased from 15 to 25 MPa using pure CO2, but further increases to 35 MPa were less effective. Fatty acid composition was similar across pressures. Additional experiments added the lipase enzyme, achieving total yields of 8.8%, 23.6%, and 28.9% at 15, 25, and 35 MPa, respectively. Thin layer chromatography showed higher fatty acid ester content at 15 MPa
Extraction of Essential Oil from Neem Seed by Using Soxhlet Extraction MethodsIJAEMSJORNAL
Extraction of essential neem oil from neem seed was carried by soxhelt extraction method using different organic solvents and parameters. Physico-chemical property of the extracted oil was also determined by using classical wet chemical method. Result revealed that, soxhlet extraction using hexane has 40.35%; using ethanol-hexane mixture of 60:40% volume proportion has 43.71%, using ethanol 42.65% and using methanol 42.89%. For all solvent type particle size has 355μm, extraction time 1hr up to 3hrs and applied constant and varies temperatures .At smaller extraction time, hexane produced oil yield greater than from ethanol and methanol. Actually, ethanol not produced oil at one hour extraction time. Thus, by effective determination of factors like particle sizes, solvent type, temperature, and time it is possible to investigate the result on the quality and quantity of neem oil. Surprisingly, mixtures of Ethanol and Hexane gave admirable results. Predominantly, ethanol-hexane mixtures of 60:40, and 40:60% (volume proportions) gave better oil yields of 44%, and 41.2% respectively than that of hexane (40.35%) at 3 hours of process time.
This document summarizes an experimental study on the kinetics of soybean oil extraction using ethanol as a solvent. The study examined the effects of temperature (40, 50, 60°C) and ethanol hydration level (0%, 5.98% water) on the extraction of soybean oil and free fatty acids (FFA). Experimental data showed that higher temperatures and lower hydration levels favored extraction of both compounds. The data were modeled using two kinetic models, which determined mass transfer coefficients and estimated diffusivity coefficients. The diffusivity of soybean oil increased with temperature and decreasing hydration, ranging from 3.61 to 5.36 × 10−11 m2/s.
Treatment of aged transformer oil using dry sludge in lab-scale refining unitPremier Publishers
Experimental analysis of drinking water treatment sludge revealed that it is enriched with aluminum and silicon oxides which are the most metal oxides used in reclamation of transformer insulating oils. The potential use of inexpensive and available water treatment dry sludge as sorbent material for the removal of acidity, water content and some impurities from aged transformer oil by adsorption methodology was investigated using lab-scale refining unit. Dry sludge was found to improve the electrical and physical properties of aged transformer oils.High improvement of breakdown voltage occurs after using dry sludge reclaimed transformer oil and changed from 15 to 72 kV/ cm. Also some improvements have been achieved such as water content changed from 48 to 9 ppm and total acidity changed from 0.37 to 0.01mg KOH/g of oil.Viscosity, specific gravitywere improved. Also, some undesirable gases in aged oil(more than ten years in service) were removed. Furthermore the use of dry sludge as sorbent material renders the treated oil to some extent like new one. Also Dry sludge is available at any water treatment plant with no costs (waste product). Environmentally, after sludge reclamation process for the used transformer oil, the sludge can be recycled by ignition and used in further treatment processes.
Product purification and recovery remains a priority for chemical engineers, today. Designing separations processes to accomplish the above is a challenge, especially as streams get more complex in composition. Though often overlooked, liquid-liquid extraction (LLE) is a powerful separation technique for both organic and aqueous liquids. Whereas distillation technology relies on relative volatility differences among chemicals, LLE exploits the differences in relative solubilities of compounds in two immiscible liquids, to perform the key separation. Distillation may not be feasible when boiling points are nearly identical or for other reasons, economic and technical. When distillation is not a viable solution, LLE is a great alternative to achieve product purification and recovery.
This document provides information on the production of single superphosphate (SSP) fertilizer. It discusses the raw materials used, including rock phosphate and sulfuric acid. The production process involves acidulation of rock phosphate using sulfuric acid in a den, followed by scrubbing, granulation, drying, and screening. Process flow diagrams and material balances are presented. Equipment used is also described. The document evaluates capital costs, production costs, profitability, and provides a HAZOP analysis for the feeder.
Statistical Modeling and Optimization of Biodiesel Production from Azadiracht...IJAEMSJORNAL
This document summarizes a study that used statistical modeling and optimization to produce biodiesel from neem (Azadirachta Indica) oil using a co-solvent transesterification process. Neem oil was extracted and pretreated. A central composite design was used to experimentally vary reaction temperature, catalyst amount, reaction time, and methanol-to-oil ratio. Biodiesel yield and properties were measured. An optimized yield of 84.77% was achieved at 34°C, 1.10% catalyst, 35 minutes, and a 6:1 molar ratio. The produced biodiesel met ASTM specifications for properties like cetane number, viscosity, and flash point.
Desulphur - A new Desulphurisation TechniqueTecnoVeritas
This Presentations intends to present a new technique of Desulphurisation, a revolutionary product to help the environment and the marine/ shore industry.
The document reports on a study of extracting passion fruit seed oil using supercritical CO2. Experimental data was collected for extraction conducted at varying pressures, temperatures, and CO2 flow rates. An increase in pressure, temperature, and flow rate increased the extraction yield, with a maximum yield of 18.5% obtained. Mass transfer coefficients for passion fruit oil were determined to be 8.496 x 10-5 s-1 at specific conditions. Rheological studies observed dilatant fluid behavior in all tests. Bayesian inference was used to model mass transfer and account for parameter uncertainty.
This document summarizes a study on optimizing the extraction of sandalwood oil using subcritical carbon dioxide compared to conventional techniques like steam distillation. Subcritical carbon dioxide extraction at 200 bars and 28°C yielded 4.11% oil in the first hour, higher than other methods and with higher quality as indicated by acid value and santalol content. Analysis found the oil extracted in each hour contained varying amounts of key constituents like α-santalene and β-santalol. The study demonstrates that subcritical carbon dioxide extraction is more efficient and yields higher quality sandalwood oil than conventional techniques like steam distillation.
The seed from the fruit of the Beilschmiedia mannii (Lauraceae) tree provides edible oil. In order to contribute to the valorization of this seed, which is a traditional Vegetable in Côte d’Ivoire; study of its food potential has been carried out, Particular the determination of some physico-chemical characteristics of its oil. The results obtained are as follows: the yield (8.75%); the refractive index (1.41); the acid index (2.62); the Iodine index (83.8); Saponification index (263.14); the peroxide index (8.97).
Wauquier, j. p._-_petroleum_refining_i_crude_oil_-_petroleum_products_-_proce...Khalid Nawaz
This document provides an overview of topics related to petroleum refining, including: the composition of crude oil and petroleum products; fractionation and analysis of crude oils; characterization of crude oils and fractions; methods for calculating hydrocarbon properties; characteristics of petroleum products for energy and non-energy uses; standards and specifications for products; evaluation of crude oils; refining activities for motor fuels and lubricants; and an introduction to refining processes. It includes appendices on pure component characteristics and standard test methods.
This document describes a proposed project to build a methane to acetic acid plant in Bangladesh. The plant would produce 300 tons per day of 99% acetic acid and 450 tons per day of 91.5% methanol using methane from a local natural gas field as the raw material. Several processes for converting methane to methanol and methanol to acetic acid are considered, including catalytic, thermal cracking, photo-catalytic, and biological methods. The document selects the ICI process for methane to methanol conversion and the Cativa process for methanol to acetic acid conversion.
The document describes a process for producing acetic acid from methane using three steps. First, methane is oxidized in a reactor to produce methanol and acetic acid. The products are separated using flash distillation, yielding methanol and acetic acid. The methanol is then converted to additional acetic acid in a carbonylation reactor using a rhodium catalyst. Mass and energy balances were performed on the overall process. The reactors and separation equipment are also described.
Ethylic esterification of free fatty acids content in macauba palm oil (acroc...AcessoMacauba
This study evaluated the use of cationic resin catalysts for the esterification of free fatty acids in macauba palm oil, which has a high acidity of 40.8% that makes it unsuitable for conventional biodiesel production. Esterification experiments using ethanol and methanol as alcohols achieved the greatest acidity reduction of 38.6% using Purolite CT275DR resin at 90°C, 20:1 alcohol:oil ratio, and 8 hours. Temperature had the most significant effect on reducing acidity. The Purolite resin performed better than Mitsubishi PK208 resin due to its higher ion exchange capacity. Cation exchange resins show potential as pretreatment catalysts for high
Performance of KOH as a Catalyst for Trans-esterification of Jatropha Curcas ...ZY8
This document summarizes a study on using potassium hydroxide (KOH) as a catalyst for the trans-esterification of Jatropha curcas oil to produce biodiesel. The authors extracted oil from Jatropha fruits and conducted kinetics experiments to investigate the performance of KOH catalyst. They varied reaction parameters like oil to methanol molar ratio, catalyst concentration, and temperature. The results showed that an oil to methanol ratio of 1:16, KOH concentration of 1.5%, and temperature of 60°C produced the optimal biodiesel yield. An activation energy of 28.8 kJ/mol was calculated using the Arrhenius equation. The biodiesel properties met ASTM standards for
Phase equilibrium feasibility studies of free fatty acids extraction from pal...Alexander Decker
This document summarizes a study that investigated the extraction of free fatty acids from palm oil using supercritical carbon dioxide. The study assessed the feasibility of using a thermodynamic model based on UNIFAC to predict phase equilibrium and activity coefficients for the carbon dioxide/fatty acid system. Experimental results were obtained for extract mole fraction at different pressures from 60-180 bars and temperatures of 313.15K and 353.15K. Mass transfer parameters like diffusion coefficient and solubility were also determined. The model predictions matched reasonably well with experimental data.
These slides are developed for a part of the undergraduate course in Petroleum Refinery Engineering. The slides are also helpful for Masters level introductory course.
The document provides details about various refinery units including:
- Crude Distillation Unit (CDU), Naphtha Hydrotreating Unit (NHT), Isomerization Unit, Continuous Catalytic Reformer (CCR) Unit, Diesel Hydrotreating (DHDT) Unit, Vacuum Gas Oil Hydrotreating (VGO HDT) Unit, Fluidized Catalytic Cracking (FCC) Unit, Hydrogen Generation Unit (HGU), Polypropylene Unit (PPU), Sour Water Stripping (SWS) Unit, and Amine Regeneration Unit.
It describes the objectives, key inputs and outputs of each unit.
1. The document provides an overview of the catalytic reforming process, including feed preparation, the platform process, process variables, and chemistry involved.
2. It discusses catalyst deactivation factors like poisoning, fouling, and thermal degradation. Methods for catalyst regeneration like coke removal through pyrolysis and combustion are also presented.
3. Troubleshooting tips are given for various process issues like low naphthenic feedstock, sulfur contamination, high chlorides, and excess water contamination. The document outlines steps to identify the root cause and remedy such problems.
This document provides an overview of azeotropic distillation. It begins with an introduction that defines azeotropic distillation as a process where an entrainer is added to a feed mixture to form an azeotrope that can be separated. The document then discusses the working principle, provides examples of residue curve maps, and outlines considerations for process design and simulation. Finally, it discusses several industrial applications of azeotropic distillation, including alcohol dehydration, acetic acid dehydration, and ester production, before concluding and listing references.
This document describes a one-pot synthesis of 3,4-dihydropyrimidin-2(1H)-ones and thiones using 4-nitrophthalic acid as a catalyst under solvent-free conditions. Various aldehydes, 1,3-dicarbonyl compounds, and urea or thiourea reacted smoothly in good to excellent yields. The reaction conditions were optimized to use a 2 mol% catalyst loading at 90°C for 30 minutes. 4-Nitrophthalic acid proved to be an effective and inexpensive catalyst for this Biginelli reaction, providing advantages over other reported catalysts such as higher yields, simpler workup, and an environmentally friendly procedure. The products were characterized
Use of Immobilised Lipase from Candida antarctica in Supercritical Fluid Extr...Egidijus Dauksas
This document summarizes an experiment investigating the use of immobilized lipase from Candida antarctica in supercritical fluid extraction (SFE) of borage (Borago officinalis L.) seed oil. In the first series of experiments, borage seed oil extraction yield increased over twice when pressure was increased from 15 to 25 MPa using pure CO2, but further increases to 35 MPa were less effective. Fatty acid composition was similar across pressures. Additional experiments added the lipase enzyme, achieving total yields of 8.8%, 23.6%, and 28.9% at 15, 25, and 35 MPa, respectively. Thin layer chromatography showed higher fatty acid ester content at 15 MPa
Extraction of Essential Oil from Neem Seed by Using Soxhlet Extraction MethodsIJAEMSJORNAL
Extraction of essential neem oil from neem seed was carried by soxhelt extraction method using different organic solvents and parameters. Physico-chemical property of the extracted oil was also determined by using classical wet chemical method. Result revealed that, soxhlet extraction using hexane has 40.35%; using ethanol-hexane mixture of 60:40% volume proportion has 43.71%, using ethanol 42.65% and using methanol 42.89%. For all solvent type particle size has 355μm, extraction time 1hr up to 3hrs and applied constant and varies temperatures .At smaller extraction time, hexane produced oil yield greater than from ethanol and methanol. Actually, ethanol not produced oil at one hour extraction time. Thus, by effective determination of factors like particle sizes, solvent type, temperature, and time it is possible to investigate the result on the quality and quantity of neem oil. Surprisingly, mixtures of Ethanol and Hexane gave admirable results. Predominantly, ethanol-hexane mixtures of 60:40, and 40:60% (volume proportions) gave better oil yields of 44%, and 41.2% respectively than that of hexane (40.35%) at 3 hours of process time.
This document summarizes an experimental study on the kinetics of soybean oil extraction using ethanol as a solvent. The study examined the effects of temperature (40, 50, 60°C) and ethanol hydration level (0%, 5.98% water) on the extraction of soybean oil and free fatty acids (FFA). Experimental data showed that higher temperatures and lower hydration levels favored extraction of both compounds. The data were modeled using two kinetic models, which determined mass transfer coefficients and estimated diffusivity coefficients. The diffusivity of soybean oil increased with temperature and decreasing hydration, ranging from 3.61 to 5.36 × 10−11 m2/s.
Moringa is a plantfood of high nutritional value, ecologically and economically beneficial and readily available in the countries hardest hit by the food crisis. http://miracletrees.org/ http://moringatrees.org/
A Study On The Performance And Combustion Of A Diesel Engine Fuelled With B...theijes
This paper highlights the performance and combustion of a single cylinder four stroke diesel engine operated on blends of biodiesel produced from waste cooking oil. An additive Diethyl ether (DEE) has been added in three different proportions to B20 blended fuel to study the effect of additive on the performance and combustion of the diesel engine. Our results conclude that the break thermal efficiencies of the diesel engine show an increasing trend with both blended fuels and additive mixed blended fuels, slightly higher than the case of pure diesel fuel.
This document summarizes the formulation, compounding, and assessment of de-emulsifiers for de-emulsifying Nigerian crude oil emulsions. Various resole and polyester-based de-emulsifiers were formulated by varying reaction parameters such as formaldehyde to phenol ratios, reaction temperatures, and blend ratios. The de-emulsifiers' performance was evaluated using a bottle test method, and the most effective sample was found to be an 80% resole (1.8:1 formaldehyde to phenol ratio) and 20% polyester blend produced at 1830°C, with xylene. This de-emulsifier achieved a water separation efficiency of 81.8%, higher than the 73%
Biotechnological applications in agriculture a new source of edibleSiamak Alizade
This document summarizes research on using the Terminalia belerica plant for various biotechnological applications. Key points:
- The plant's seeds can be used to produce a new edible oil, comprising 37% of the dry kernel weight. Analysis found the oil contains fatty acids similar to olive oil.
- Byproducts of oil extraction include an oilcake containing high levels of nitrogen (8.34%) and proteins (60% digestible) suitable for use as biofertilizer.
- Other byproducts include tannins extracted from the fruit pulp, suitable for use in leather/medicine, and antioxidants like gallic acid in the seed coat with potential to preserve vegetable oils.
Lipase-Catalyzed Biodiesel Production From Waste Activated Bleaching Earth as...ZY8
The document describes a pilot plant study of lipase-catalyzed biodiesel production from waste activated bleaching earth (ABE). Waste ABE containing vegetable oils was used as a raw material with lipase and methanol to produce fatty acid methyl esters (FAMEs), which can be used as biodiesel fuel. In a 50-liter pilot plant reactor, the process achieved 97% FAME yield within 12 hours using 1% lipase at 25°C and an agitation rate of 30 rpm. Analysis showed the biodiesel quality of a 45:55 mixture of FAME and diesel oil met European fuel standards. Emissions testing found reduced carbon monoxide and sulfur dioxide from burning the biod
Optimization, kinetic degradation and quality characterization of oil extract...Alexander Decker
This document summarizes a study that optimized oil extraction from Nigeria Hibiscus sabdariffa (sorrel) oilseeds using response surface methodology. The study extracted oil from the seeds using solvent extraction with n-hexane. It investigated 17 experimental runs using a Box-Behnken design to determine the optimal extraction conditions of time, solvent volume, and sample weight. The study also characterized the physicochemical properties of the extracted oil and analyzed its fatty acid composition. Additionally, it examined the kinetics of degradation when heating the oil at temperatures up to 250°C. The results showed that the maximum oil yield of 18.25% could be achieved with an extraction time of 2 hours, solvent volume of 157mL, and
Optimization, kinetic degradation and quality characterization of oil extract...Alexander Decker
This document summarizes an experimental study that aimed to optimize oil extraction from Nigeria Hibiscus sabdariffa (Sorrel) oilseeds using Response Surface Methodology, and characterize the physicochemical properties and kinetics of degradation of the extracted oil. The study conducted 17 experimental runs using a Box-Behnken design to determine the optimal extraction time, solvent volume, and sample weight. The maximum oil yield of 18.25% was predicted at 2 hours, 157 ml solvent, and 22 g sample weight. Analysis showed the oil was highly unsaturated with potential food and industrial uses. Kinetic studies found the degradation rate of peroxide value in the oil increased with temperature, following first order reaction kinetics.
The oil from Moringa oleifera seeds variety Periyakulam 1 from India was extracted using cold press, n-hexane extraction, and chloroform:methanol extraction. The chloroform:methanol extraction yielded the highest oil concentration of 41.4% while cold press yielded the lowest at 25.1%. The oils were characterized and compared to virgin olive oil and Moringa oleifera var. Mbololo seed oil. Moringa oleifera seed oil showed high levels of unsaturated fatty acids like oleic acid and stability to oxidation, though extraction method affected characteristics.
The document discusses the synthesis and characterization of polymeric additives and their effectiveness as pour point depressants and viscosity improvers for waxy crude oils. Polyethylene acrylic acid (PEAA) was esterified with docosanol to produce PEAA-DcA, which was then grafted with vinyl acetate to produce PEAA-DcA-g-VA. The products were characterized using FT-IR and 1H NMR. Rheological measurements and pour point tests were performed on crude oils treated with the polymers. The pour point of crude oils was reduced from 27°C to 6°C depending on polymer composition and concentration. PEAA-DcA-g-VA performed best at reducing pour point, indicating these
Separation techniques in oils & fats scienceSadanand Patel
Novel Separation Techniques in Oil/Fats, Fatty acids and By products viz, sterols, tocopherols etc.
Chromatographic techniques, urea inclusion and exclusion, distillation, fractionation, crystallization etc
Biofuel from Algae for future use (Lipid extraction)Pravin clap
Lipid Extraction from algae Bio fuel production for future use
Submitted by,
Ahamed Nashath A, Pravin C, Vishak P
Research Guide. Dr. Helen sheeba, Department of Microbiology, Scott Christian College, Nagercoil
May 2023 Project thesis submitted to Scott Christian College (Autonomous) In partial fulfillment of the degree of Bachelor of Science in Microbiology
Increasing global demand for fuels and the consequent increases in environmental pollution and human health risks have collectively driven research toward finding sustainable and economically viable alternatives. The third-generation biofuels have been considered as promising strategies for meeting this goal.
Algae are chlorophyll-containing photosynthetic organisms found everywhere on the earth, such as in the sea, rivers, lakes, soil, in animal, and plants. Algae represent a potential biomass to be explored as a source to develop biofuel because algal biomass is abundant, fast-growing, and unexploited resource often left to decompose on the shores posing waste problems. High percentage of lipids and carbohydrates make algae an excellent candidate for the synthesis of biofuel.
Algae are an economical choice for biodiesel production, because of its availability and low cost. Our results prove that biodiesel can be produced from macroalgae. In this way algae can be used as renewable energy. Many researchers reported that microalgae might better for higher biodiesel production.
Biofuels are liquid or gaseous fuels primarily produced from biomass, and can be used to replace or can be used in addition to diesel, petrol or other fossil fuels for transport, stationary, portable and other applications. Crops used to make biofuels are generally either high in sugar (such as sugarcane, sugarbeet, and sweet sorghum), starch (such as maize and tapioca) or oils (such as soybean, rapeseed, coconut, sunflower).
Biodiesel is a clean-burning diesel fuel produced from vegetable oils, animal fats, or grease. Its chemical structure is that of fatty acid alkyl esters (FAAE). Biodiesel as a fuel gives much lower toxic air emissions than fossil diesel. In addition, it gives cleaner burning and has less sulfur content, and thus reducing emissions. Because of its origin from renewable resources, it is more likely that it competes with petroleum products in the future.
The benefits of using biodiesel are as follows,
Algae is a economical choice for Biodiesel
It reduce vehicle emission which makes it eco-friendly.
It is made from renewable sources and can be prepared locally.
It has excellent lubricity.
Increased safety in storage and transport because the fuel is nontoxic and bio degradable (Storage, high flash pt)
Production of bio diesel in India will reduce dependence on foreign suppliers, thus helpful in price stability.
Reduction of greenhouse gases at least by 3.3 kg CO2 equivalent per kg of biodiesel.
Thank you for viewing and reading 😊
Determination of physico chemical properties of castor biodiesel a potentialIAEME Publication
This document summarizes a study that determined the physicochemical properties of castor biodiesel as a potential alternative to conventional diesel. Castor oil was extracted from seeds using solvent extraction. The oil was then transesterified to produce fatty acid methyl esters (biodiesel) using methanol and a base catalyst. Physicochemical properties of the castor oil and biodiesel were analyzed and found to exhibit properties suitable for biodiesel, with improved properties compared to the original oil. Thermal stability tests also showed satisfactory results, indicating castor biodiesel's potential as an alternative fuel.
This document summarizes a study that analyzed the physicochemical characteristics and storage stability of crude palm oils produced traditionally and industrially in Cameroon. The study found that the traditional and industrial crude palm oils had higher levels of moisture content, free fatty acids, and peroxide values compared to a reference oil before storage. When stored at 30°C and 20°C over 3 months, the free fatty acid and peroxide values of both oils increased significantly, indicating deterioration, with the traditional oil deteriorating faster than the industrial oil. The physicochemical properties showed the oils were edible but suggested the traditional oil may not be suitable for long-term storage.
Extraction and characterization of pectin from citric waste aidicphuongchi53
The document discusses the extraction of pectin from citrus waste in Brazil. It examines the optimum extraction conditions for pectin from lime orange waste through a factorial design experiment. Higher acid concentration, temperature, and extraction time resulted in the highest pectin yield of 78% but lowest degree of esterification. Texture and compression profile analysis found the extracted pectins had similar characteristics to commercial pectin. The study aimed to add value to citrus waste through extraction and characterization of pectin.
Production of Biodiesel from Waste Cooking Oil By Co-Solvent Method.IRJESJOURNAL
Abstract:- Biodiesel is a mixture of mono-alkyl esters of long chain fatty acids derived from a renewable lipid feedstock. It can be used as an alternative fuel as the fossil fuels are getting depleted day by day. Moreover the use of biodiesel leads to the substantial reduction in the pollution caused by PM, HC, CO etc. This paper consists of the production of biodiesel from waste cooking oil using alkaline catalysts NAOH and KOH and cosolvent acetone in the presence of methanol. Waste cooking oil is used because of its high oil content and abundant availability. This method used is co-solvent method.
Methanol is the simplest alcohol and can be used as an alternative fuel or chemical feedstock. It is produced via a four step process: feed purification using desulphurization; steam reforming of natural gas over nickel catalysts at high pressures and temperatures; methanol synthesis over copper catalysts in a reactor; and methanol purification through distillation. Methanol production facilities are located globally and the demand for methanol is increasing in countries like India at 7-8% annually.
Supercritical extraction of borage (Borago officinalis L.) seeds with pure CO...Egidijus Dauksas
The document discusses supercritical fluid extraction of borage (Borago officinalis L.) seeds using pure CO2 and mixtures of CO2 with caprylic acid methyl ester. It finds that increasing the CO2 pressure from 100 to 350 bar increased the borage seed extract yield from 0.14% to 24.29% by weight. Adding caprylic acid methyl ester as an entrainer further increased the extract yields, with the highest solubility of the entrainer in CO2 determined to be approximately 1 g of ester in 1 g of CO2 at pressures of 100 and 300 bar. The addition of the entrainer increased extract yields up to 47.8 times at 100 bar and 2
This document describes a process to extract free fatty acids from wet biomass of the microalga Nannochloropsis gaditana for biodiesel production. The process involves five steps: 1) direct saponification of the wet biomass using KOH-ethanol solution to extract fatty acids as potassium salts, 2) separation of unsaponifiable lipids from the solution with hexane, 3) acidification and extraction of purified free fatty acids with hexane, 4) esterification of the free fatty acids into biodiesel using methanol catalyzed by sulfuric acid, and 5) purification of the biodiesel by washing with hot water and adsorption with bentonite. The final biodiesel purity was
Presentation of IEEE Slovenia CIS (Computational Intelligence Society) Chapte...University of Maribor
Slides from talk presenting:
Aleš Zamuda: Presentation of IEEE Slovenia CIS (Computational Intelligence Society) Chapter and Networking.
Presentation at IcETRAN 2024 session:
"Inter-Society Networking Panel GRSS/MTT-S/CIS
Panel Session: Promoting Connection and Cooperation"
IEEE Slovenia GRSS
IEEE Serbia and Montenegro MTT-S
IEEE Slovenia CIS
11TH INTERNATIONAL CONFERENCE ON ELECTRICAL, ELECTRONIC AND COMPUTING ENGINEERING
3-6 June 2024, Niš, Serbia
International Conference on NLP, Artificial Intelligence, Machine Learning an...gerogepatton
International Conference on NLP, Artificial Intelligence, Machine Learning and Applications (NLAIM 2024) offers a premier global platform for exchanging insights and findings in the theory, methodology, and applications of NLP, Artificial Intelligence, Machine Learning, and their applications. The conference seeks substantial contributions across all key domains of NLP, Artificial Intelligence, Machine Learning, and their practical applications, aiming to foster both theoretical advancements and real-world implementations. With a focus on facilitating collaboration between researchers and practitioners from academia and industry, the conference serves as a nexus for sharing the latest developments in the field.
A SYSTEMATIC RISK ASSESSMENT APPROACH FOR SECURING THE SMART IRRIGATION SYSTEMSIJNSA Journal
The smart irrigation system represents an innovative approach to optimize water usage in agricultural and landscaping practices. The integration of cutting-edge technologies, including sensors, actuators, and data analysis, empowers this system to provide accurate monitoring and control of irrigation processes by leveraging real-time environmental conditions. The main objective of a smart irrigation system is to optimize water efficiency, minimize expenses, and foster the adoption of sustainable water management methods. This paper conducts a systematic risk assessment by exploring the key components/assets and their functionalities in the smart irrigation system. The crucial role of sensors in gathering data on soil moisture, weather patterns, and plant well-being is emphasized in this system. These sensors enable intelligent decision-making in irrigation scheduling and water distribution, leading to enhanced water efficiency and sustainable water management practices. Actuators enable automated control of irrigation devices, ensuring precise and targeted water delivery to plants. Additionally, the paper addresses the potential threat and vulnerabilities associated with smart irrigation systems. It discusses limitations of the system, such as power constraints and computational capabilities, and calculates the potential security risks. The paper suggests possible risk treatment methods for effective secure system operation. In conclusion, the paper emphasizes the significant benefits of implementing smart irrigation systems, including improved water conservation, increased crop yield, and reduced environmental impact. Additionally, based on the security analysis conducted, the paper recommends the implementation of countermeasures and security approaches to address vulnerabilities and ensure the integrity and reliability of the system. By incorporating these measures, smart irrigation technology can revolutionize water management practices in agriculture, promoting sustainability, resource efficiency, and safeguarding against potential security threats.
Introduction- e - waste – definition - sources of e-waste– hazardous substances in e-waste - effects of e-waste on environment and human health- need for e-waste management– e-waste handling rules - waste minimization techniques for managing e-waste – recycling of e-waste - disposal treatment methods of e- waste – mechanism of extraction of precious metal from leaching solution-global Scenario of E-waste – E-waste in India- case studies.
Electric vehicle and photovoltaic advanced roles in enhancing the financial p...IJECEIAES
Climate change's impact on the planet forced the United Nations and governments to promote green energies and electric transportation. The deployments of photovoltaic (PV) and electric vehicle (EV) systems gained stronger momentum due to their numerous advantages over fossil fuel types. The advantages go beyond sustainability to reach financial support and stability. The work in this paper introduces the hybrid system between PV and EV to support industrial and commercial plants. This paper covers the theoretical framework of the proposed hybrid system including the required equation to complete the cost analysis when PV and EV are present. In addition, the proposed design diagram which sets the priorities and requirements of the system is presented. The proposed approach allows setup to advance their power stability, especially during power outages. The presented information supports researchers and plant owners to complete the necessary analysis while promoting the deployment of clean energy. The result of a case study that represents a dairy milk farmer supports the theoretical works and highlights its advanced benefits to existing plants. The short return on investment of the proposed approach supports the paper's novelty approach for the sustainable electrical system. In addition, the proposed system allows for an isolated power setup without the need for a transmission line which enhances the safety of the electrical network
We have compiled the most important slides from each speaker's presentation. This year’s compilation, available for free, captures the key insights and contributions shared during the DfMAy 2024 conference.
ACEP Magazine edition 4th launched on 05.06.2024Rahul
This document provides information about the third edition of the magazine "Sthapatya" published by the Association of Civil Engineers (Practicing) Aurangabad. It includes messages from current and past presidents of ACEP, memories and photos from past ACEP events, information on life time achievement awards given by ACEP, and a technical article on concrete maintenance, repairs and strengthening. The document highlights activities of ACEP and provides a technical educational article for members.
Harnessing WebAssembly for Real-time Stateless Streaming PipelinesChristina Lin
Traditionally, dealing with real-time data pipelines has involved significant overhead, even for straightforward tasks like data transformation or masking. However, in this talk, we’ll venture into the dynamic realm of WebAssembly (WASM) and discover how it can revolutionize the creation of stateless streaming pipelines within a Kafka (Redpanda) broker. These pipelines are adept at managing low-latency, high-data-volume scenarios.
2. (Conkerton et al., 1995; Wan et al., 1995a, 1995b) or alcohols
(Abraham et al., 1988; Rittner, 1992; Hron et al., 1994; Sineiro et al.,
1998) as solvents for oil extraction. Isopropanol and ethanol are the
most promising solvents for the oil extraction from cottonseed
(Abraham et al., 1988; Hron et al., 1994), sunflower seed (Sineiro
et al., 1998) and soybean (Baker and Sullivan, 1983; Rittner, 1992).
Ethanol is a worthy candidate to be studied as alternative solvent
because it is cheap and it can be produced by fermentation from a
large variety of biological materials using simple technology, and
therefore labeled as “natural” or “biorenewable”. In addition,
although flammable, this alcohol is recognized as non-toxic and has
less handling risks than hexane (Rittner, 1992). The use of ethanol
as an extraction solvent also avoids eventual toxicity problems of
meals for animal feedstuff (Ferreira-Dias et al., 2003), but it has
been reported that the solubility of lipids in ethanol is drastically
affected by the moisture content of the solvent and the extraction
temperature (Rao and Arnold, 1956, 1957).
Due to the lower selectivity of ethanol towards triglycerides,
during the extraction process other compounds such as phospha-
tides, polyphenols, pigments and soluble sugars are extracted
jointly (Hron et al., 1982, 1994; Sineiro et al., 1996). After the
ethanol extraction, and when the miscella cools down, it can be
expected that part of the extracted material becomes insoluble (in
ethanol) and separates as an emulsion. At about 38 C, the gums
obtained (mucilaginous material consisting of emulsified oil,
phospholipids, pigments and sugars) lose some of their entrained
miscella, agglomerate and sink to the bottom of the oil phase (Hron
and Koltun, 1984). The aim of this work was to determine the
performance of ethanol (extractive power, quantity and quality of
extracted oil, and oil extraction kinetics) when used in the oil
extraction from sunflower collets.
2. Materials and methods
2.1. Sample characterization
All experimental determinations were made with sunflower
expanded material, known as “collets”, which were kindly provided
by a local factory. Collets were stored in polyethylene containers
with screw caps in the dark at 4 C until used in the extraction
experiments. A sample of 20 collets was randomly selected to
determine the average size of the collets. Collet dimensions, namely
length (L) and radius (R), were measured using a gage with an ac-
curacy of 0.01 mm. The initial moisture and oil content were
determined according to IUPAC method 1.121 and 1.122 (IUPAC,
1992), respectively. The oil content of the solid was determined
by an exhaustive extraction with analytical-reagent grade n-hexane
(90%, bp 68e72 C) in a Soxhlet apparatus. Similarly, the maximal
ethanolic extraction yield was determined using analytical-reagent
grade ethanol (95%, bp 78 C). Solvents were removed from the
miscellas firstly by rotary evaporation at 50 C and low pressure,
and then by nitrogen displacement until constant weights were
reached.
The extracted material obtained using ethanol as solvent was
fractionated in hexane-soluble material and other compounds
(hexane-insoluble fraction) by phase separation with n-hexane.
The hexane-soluble material constituted the lipid material that was
used to study oil extraction kinetics.
2.2. Analyses of minor components
For the extracted material obtained using ethanol, contents of
minor components (tocopherols, phospholipids, waxes and sugars)
are expressed on a total extracted material basis and then referred
to as moisture-free sunflower collets mass, in order to allow
comparison with the results obtained using n-hexane as extraction
solvent.
2.2.1. Tocopherol analysis
Tocopherol content was determined using AOCS method Ce
8e89 (AOCS, 2009) with a Waters e2695 HPLC (Waters Associates,
Milford, MA, USA) equipped with a Nucleosil Si-100A column
(250 mm length, 4.6 mm i.d., 5 mm particle size, Phenomenex, USA)
and a fluorescence detector (Waters 2475) with the excitation
wavelength set at 290 nm and the emission wavelength set at
330 nm. The mobile phase used was n-hexane:isopropanol
(99.5:0.5 v/v, HPLC solvent, J.T. Baker, Phillipsburg, USA) at a flow
rate of 1.0 mL/min. Tocopherol content was determined by the
external standard method. Areas were converted to concentrations
using the standard curve of a-tocopherol (Sigma Chemical Co., 95%)
in n-hexane in the relevant concentration range for the sample
concentrations (R2
¼ 0.99). Determinations were performed in
triplicate.
2.2.2. Phospholipid analysis
Quantitative determination of phospholipids (PL) was carried
out by enrichment using a diol solid-phase extraction cartridge (J.T.
Backer Inc., Phillipsburg, NJ, USA) and subsequent analysis by HPLC-
UV (Carelli et al., 1997). A Waters 600E HPLC system (Waters As-
sociates, Milford, MA, USA) and a Lichrosorb SI-60 column
(250 Â 4 mm, 5 mm particle size, Merck, Darmstadt, Germany) were
used. Identification of PL was carried out by comparing the reten-
tion times with pure standards. The following PL reference stan-
dards with purities greater than 98% were supplied by Sigma
Chemical Co. (St. Louis, MO, USA): L-a phosphatidylethanolamine
(PE), L-a phosphatidylcholine (PC), L-a phosphatidylinositol (PI)
and phosphatidic acid (PA). Calibration curves were obtained using
standard solutions prepared by dissolving the standard PL in HPLC
mobile phase at different concentrations. Determinations were
performed in duplicate.
2.2.3. Wax determination
Wax composition was determined by separation on a silica gel
chromatographic column and analysis by GLC (Carelli et al., 2012).
Briefly, column chromatography was performed using a glass col-
umn (i.d. ¼ 15 mm, length ¼ 400 mm) with a double phase of silver
nitrate-impregnated silica gel (3 g) placed at the bottom of the
column and hydrated silica gel 2% (12 g) placed on top as a solid
stationary phase. The waxes were eluted with n-hexane/ethyl ether
(99:1 v/v) at a flow rate of 3 mL/min using Sudan I dye to control the
end of the elution (Carelli et al., 2012). The eluted wax fraction was
evaporated to dryness and diluted with n-heptane, and analyzed by
capillary GLC with an on-column injection system. A Perkin Elmer
AutoSystem XL gas chromatograph equipped with an FID detector,
a temperature programmable on-column injector and a TotalCrom
Workstation data processor version 6.3.1 (Perkin Elmer, MA, USA)
was used. The capillary column was an HP-5 (5% diphenyl and 95%
dimethyl-polysiloxane), fused-silica 15 m length  0.32 mm i.d.,
0.25 mm film thickness (HewlettePackard, Palo Alto, CA). C32 to
C44 wax standards of 99% purity were obtained from Sigma
Chemical Co. (St. Louis, MO, USA).The C32 standard was used as
internal standard, and the purified sunflower wax recovered from a
filter cake following the method proposed by Carelli et al. (2012)
was used as standard for the identification of waxes with more
than 44 carbon atoms. Waxes were categorized as follows: with less
than 40 carbon atoms they were considered the oil soluble fraction,
waxes with 40 and 42 carbon atoms were the partially soluble
fraction, and waxes with more than 44 carbon atoms constituted
the crystallized fraction. Determinations were performed in
duplicate.
E.R. Baümler et al. / Journal of Food Engineering 178 (2016) 190e197 191
3. 2.2.4. Sugar content determination
Sugar content of the solid material was determined by an
exhaustive extraction following AOAC method 925.05 (AOAC, 1990)
with the modification proposed by Liu and Markakis (1987). Sam-
ples of approximately 4 g of sunflower collets were defatted by
soaking the material in hexane for 20 min, and then subjected to
extraction using 80 mL 80% ethanol in an 80 C bath for 4 h with
occasional shaking. The extract was cleaned by adding 2 mL of
saturated lead acetate to precipitate proteins and then centrifuging
down the impurities. The supernatant was diluted with distilled
water and filtered. Enough anhydrous Na2CO3 was added to pre-
cipitate the lead. Finally the purified extract was diluted with
distilled water to a final volume of 250 mL (extract). Four mL of the
extract were lyophilized and then rehydrated with 4 mL of mobile
phase, and then an aliquot was passed through a 0.45 mm MILLI-
PORE filter and injected into an HPLC system, following the method
proposed by Martínez Ruiz (2005) with modifications. A Waters
e2695 HPLC (Waters Associates, Milford, MA, USA) equipped with a
Rezex ROA organic acid column (300 mm length, 7.8 mm i.d.,
Phenomenex, USA) and a refraction index detector (Waters 2414)
was used. The mobile phase used was H2SO4 5 10À3
N at a flow rate
of 0.3 mL/min, the column temperature was maintained at 20 C,
and the injection volume loop was 10 mL. The following reference
sugars were supplied by Anedra (Argentina): glucose, fructose,
arabinose, galactose, raffinose, rhamnose, sucrose, cellobiose,
maltose, xylose, mannitol, starch, pectin and inulin. In order to
obtain calibration curves, standard solutions were prepared by
dissolving the reference sugars in HPLC mobile phase to different
concentrations. The amount of sugar extracted using ethanol was
determined by the difference between the sugar retained in the
solid matrix after ethanol extraction and the initial sugar content.
Determinations were performed in quadruplicate.
2.3. Equilibrium studies
The equilibrium studies were performed using a magnetically
stirred batch system immersed in a temperature-controlled water
bath. Samples of sunflower collets (approximately 10.0 ± 0.1 g)
were subjected to ethanol extraction with different collet-to-
solvent ratios: 1:4, 1:11 and 1:18 (g/mL). Solid and solvent were
brought to extraction temperature (50 C and 60 C) separately
before every experience. The miscella was withdrawn after 16 h
(960 min), which was considered enough time to attain the equi-
librium state. The amount of extracted material in the liquid phase
was measured gravimetrically by solvent evaporation. The residual
extractable material in the moisture-free sunflower collets was
determined as the difference between the maximal extractable
material determined by Soxhlet and the extracted material in the
liquid phase. The partition coefficient was determined as the ratio
of the concentration of the residual extractable material in the
moisture-free sunflower collet to the concentration of the extracted
material in the miscella. Extractions were replicated three times for
each experimental condition. For the sake of comparison, equilib-
rium was also analyzed using n-hexane as extraction solvent.
2.4. Solvent extraction experiments
In order to determine the extraction kinetic parameters, ex-
periments were performed in a similar way to Baümler et al. (2010),
working at 50 and 60 C, with extraction times from 0 to 960 min
(considered as infinite time). The extraction mixture consisted of
approximately 10.0 ± 0.1 g of sunflower collets and 180 mL of
ethanol (95%, bp 78 C), corresponding to a collet-to-solvent ratio of
1:18 (g/mL). The agitation rate was kept constant in all experi-
ments, being sufficient to maintain a well-mixed fluid and the
particles in suspension. At the end of contact time, the contents of
the flasks were immediately filtered, and the miscella was
concentrated using a rotary evaporator, not exceeding 50 C. The
remaining solvent traces were removed under a nitrogen stream to
constant weight. All the extractions were carried out in triplicate.
The extracted material obtained using ethanol as solvent was
fractionated as described in Section 2.1.
2.5. Mathematical modeling
2.5.1. Equilibrium
During solvent extraction, the concentration of the extracted
material in the occluded phase was considered in equilibrium with
the concentration of the extractable material in the moisture-free
sunflower collet matrix, according to a ratio which was experi-
mentally determined by the following expression:
Cs ¼ K* CL (1)
where Cs is the concentration of the extractable material in the
solid phase at the radial position r ¼ R, K is the equilibrium or
partition constant, and CL is the concentration of the extracted
material in the occluded phase at the same radial position R, i.e. at
the interface.
Thus, equilibrium is reached between the solution surrounding
the particles (miscella) and the extractable material contained in
the solid.
2.5.2. Oil extraction kinetics
Modeling of the oil extraction kinetics was made following the
theory proposed by various authors (Meziane et al., 2006; Carrín
and Crapiste, 2008; Meziane and Kadi, 2008; Baümler et al.,
2010; Perez et al., 2011; Saxena et al., 2011), who considered that
the extraction process is accomplished through two main mecha-
nisms: a washing process of the extractable material on the seed
surface, and a diffusion process, which can take place in one or two
phases, depending on the proportion of broken and intact cells that
remain after pre-extraction treatments. The rate of dissolution of
the extractable material into the solution was described by a
modified model of Fick's Law of diffusion in non-stationary state for
cylindrical particle geometry, suspended in a homogeneous me-
dium with a constant concentration without volume restriction
(Perez et al., 2011):
Mt
Minf
¼ 1 À
X∞
n¼1
An expðÀBn tÞ (2)
where Mt and Minf represent the mass of oil that diffuses at time t
and infinite, respectively, and An and Bn are the diffusion model-
fitting parameters which depend on the particle geometry (Crank,
1975). For cylindrical particle geometry their expressions are:
An ¼
4
R2l2
n
(3)
Bn ¼ De l2
n (4)
where De is the effective diffusion coefficient (m2
/s), R is the
average radium (m), and ʎn are roots of J0ðRlnÞ ¼ 0, where J0 is the
Bessel function of the first kind of zero order.
For a sufficiently long time, Eq. (2) can be simplified to:
E.R. Baümler et al. / Journal of Food Engineering 178 (2016) 190e197192
4. Mt
Minf
¼ 1 À A expðÀB tÞ (5)
where the exponential coefficient is given by B ¼ Del2
1 and the pre-
exponential coefficient by A ¼ 1 À M0
Minf
!
A1 expðB t0Þ. Coefficient A
is associated with the average value of the material extracted in the
washing step (M0, kg solute/kg dry defatted meal).
The mathematical model represented by Eq. (5) was applied to
fit the experimental oil extraction data for sunflower collets at
different temperatures using nonlinear regression (Systat Software,
2008).
2.6. Statistical analysis
The statistical analysis was carried out by Analysis of Variance
using the Infostat software (Di Rienzo et al., 2011). Fisher's LSD
method was used to compare the means of pairs of treatments with
a significance level p 0.05. Physical and chemical properties of the
raw material were expressed as the means of n determinations
with 95% confidence intervals. The number of replicates (n) carried
out in each case was stated above.
Fitting regression models for different solvents and tempera-
tures were compared through their parameters using a procedure
based on the principle of “Extra Sum of Squares” (ESS) and “con-
ditional error”, with a significance level of 95% (Fernandez et al.,
2012). The null hypothesis (H0) and the alternative hypothesis
(H1) were proposed: H0, the model parameters A and/or B do not
depend on temperature or solvent (Global model if both are
consistent with temperature or solvent, common A model when
only B varies with temperature or solvent, and common B model
when only A depends on temperature or solvent); H1, model pa-
rameters A and B depend on temperature or solvent (individual
parameter model). In order to test the null and alternative hy-
potheses by parameter comparison, contrast statistics (Fo) was
compared with the corresponding critical value (Fc) obtained by the
following equations (Boche and Lavalle, 2004; Fernandez et al.,
2012):
Fo ¼
Pq
i¼1
ðxmod
i
ÀyiÞ
2
À
Pq
i¼1
ðxdiffAB
i
ÀyiÞ
2
ðqÀbÞÀðqÀdÞ
Pq
i¼1
ðxdiffAB
i
ÀyiÞ
2
ðqÀdÞ
(6)
Fc ¼ F½0:05; d À b; q À dŠ (7)
where xmod
i and x
diffAB
i
are the simulated values of Mt/Minf obtained
with the model being compared (common A, common B or global
model) and the different A and B model, respectively; yi is the mean
value of the three replicated measurements; q is the number of
total measurements; b and d are the number of parameters to be
estimated from the model being compared and the different A and
B model, respectively. For the global model b ¼ 2, for common A
and common B models b ¼ 3, and for the different A and B model
four parameters must be estimated (d ¼ 4).
3. Results and discussion
3.1. Characterization of the raw material
The raw material (sunflower collets) was characterized physi-
cally and chemically, giving the following mean values accompa-
nied by the standard error: L ¼ 49.17 ± 7.57 mm;
R ¼ 9.56 ± 0.34 mm; initial moisture content ¼ 6.0 ± 0.6% d.b.; oil
content ¼ 22.8 ± 0.6% d.b.; total sugar content ¼ 44.56 ± 4.60 mg/
g d b. The sugar profile exhibited a high relative percentage of su-
crose (51.1 ± 1.8%) and raffinose (35.7 ± 0.9%), presenting in minor
amounts glucose (4.1 ± 0.7%), rhamnose (3.2 ± 0.5%), galactose
(2.1 ± 0.7%), fructose (2.1 ± 0.5%) and arabinose (1.7 ± 0.4%).
The extraction yield obtained by Soxhlet, and the chemical
composition of the extracted material using ethanol and n-hexane
are presented in Table 1. It can be observed that the yield of
extracted material when the solvent used was ethanol is higher
than that for n-hexane. The material extracted with ethanol had
69% of soluble hexane components or lipid fraction that represents
22.2 ± 0.5% d.b., this value being similar to that for the material
extracted with hexane (22.8 ± 0.6% d.b.).
Some authors point out the lower selectivity of ethanol towards
oil, with the consequent extraction of other compounds such as
phosphatides, polyphenols, pigments and soluble sugars (Hron
et al., 1982, 1994; Sineiro et al., 1996), which is in agreement with
our results. On the other hand, it was found that ethanol has a
similar capacity to extract lipid material to that of n-hexane.
Therefore, due to the simultaneous extraction of other compounds,
the results obtained in this work when ethanol was used as solvent
are referred to as “extracted material” instead of “extracted oil”.
In Table 1, contents of minor components (tocopherols, phos-
pholipids, waxes and sugars) are expressed on a total extracted
material basis for each solvent. From these results, the content of
extractable minor components in the solid, or moisture-free sun-
flower collets, was estimated as kg of component per kg of
moisture-free sunflower collets in order to demonstrate the dif-
ferences in extractability. As it can be observed, tocopherols and
phospholipids extracted using n-hexane and ethanol did not show
significant differences; but when the results are expressed in g or
mg of extracted compound per kg of moisture-free sunflower col-
lets on d.b., the results show a greater extractability (over 38%) with
ethanol. This result could be partially explained by the difference
between solvent polarities (Li et al., 2014). Ethanol can extract more
polar lipids, such as phospholipids, than n-hexane. Some authors
reported the use of ethanol to fractionate phospholipids from a
solid matrix (Montanari et al., 1999). Among the minor compounds
in oilseeds, tocopherols are intrinsically bound to oil body struc-
tures (Fisk et al., 2006), they are amphipathic molecules, with the
hydrophobic tail associating with membrane lipids and the polar
head groups remaining on the membrane surface (Sattler et al.,
2004). The higher tocopherol yield obtained could be the result of
the breakdown of the collet structure caused by moisture contri-
bution by the use of the ethanol azeotrope.
When waxes are considered, the material extracted using
ethanol had a significantly lower content, being its composition
different from that obtained with n-hexane as solvent (Table 1).
Ethanol extracts 70% less crystallizable waxes than hexane, which
would imply a less rigorous winterization or dewaxing stage in the
refining process.
Sugars are not extracted with n-hexane, but they are with
ethanol. This partially explains the higher yield obtained with the
latter solvent. Sugar composition of the extracted materials is
presented in Table 1. It is possible to observe that ethanol has a
great ability to extract sugars, mainly raffinose and sucrose,
extracting over 75% of the initial sugar content. Thus it could in-
crease the nutritional value of the meal, because consumption of
the indigestible sugars raffinose and stachyose is associated with
flatulence and abdominal discomfort (Rackis, 1975).
3.2. Equilibrium constant
The equilibrium constant or partition constant, defined as the
E.R. Baümler et al. / Journal of Food Engineering 178 (2016) 190e197 193
5. ratio of the residual extractable material in the solid phase to the
extracted material in the bulk miscella (K¼ Cs/CL), varied according
to the nature of the solvent, the collet-to-solvent ratio and tem-
perature considered (Table 2). The statistical analysis was per-
formed separately for each solvent due to their different selectivity.
Interactions between temperature and the collet-to-solvent ratio
were detected; for this reason, temperature was chosen as partition
variable for the ANOVA (Table 2). The equilibrium constant is
related to the level of difficulty to extract solutes from the solid
matrix. When ethanol was used, the equilibrium constant was
strongly influenced by temperature, decreasing with increasing
temperature. Therefore, the extractability of the material increased
with temperature. It was observed that the collet-to-solvent ratio
was also important, the extractability being higher when the sol-
vent proportion was increased.
In contrast, when the extraction solvent was n-hexane, the
equilibrium constant values were lower, making clear the superior
oil extraction capacity of this solvent. In this case, temperature did
not affect this parameter.
The ratio of the concentration of extractable material between
the solid phase and the drained miscella is shown in Fig. 1. For
ethanol, the shape of the curve exhibits a linear region at lower
concentrations and a moderately curved behavior at higher con-
centrations, similar to those reported by Abraham et al. (1988), who
studied oil extraction from cotton seed using ethanol, and by Perez
et al. (2011), who analyzed oil extraction from different ground
sunflower seeds using n-hexane as solvent at 50 C. Experimental
data were adjusted according to the following equation (Perez et al.,
2011):
Table 1
Extraction yield and chemical composition of the material extracted by Soxhlet with ethanol and hexane from sunflower collets.
Analytical determination Extraction solvent
Ethanol Hexane
Yield of extracted material (% d.b.) 32.2 ± 1.3b
22.8 ± 0.6a
hexane-soluble material (%) 69.0 ± 1.3 100
Phospholipids (g/kg e.m.) 2.90 ± 0.01a
2.52 ± 0.29a
(g/kg of solid in d.b.*) 0.93 ± 0.32 10À2a
0.58 ± 6.68 10À2b
PE (%) 9.1 ± 0.8a
13.3 ± 1.6a
PA (%) 16.1 ± 0.8b
24.4 ± 2.2a
PI (%) 35.5 ± 1.2a
30.6 ± 2.7a
PC (%) 39.3 ± 1.1b
31.7 ± 2.1a
Tocopherols (mg/kg e.m.) 499 ± 125a
512 ± 63a
(mg/kg of solid in d.b.*) 160.76 ± 40.21a
116.95 ± 14.50a
Alpha (%) 99.0 ± 0.1a
98.2 ± 0.7a
Beta (%) 1.0 ± 0.2a
1.8 ± 0.9a
Waxes (mg/kg e.m.) 329 ± 8a
670 ± 2b
(mg/kg of solid in d.b.*) 105.78 ± 2.50a
152.93 ± 0.48b
Oil soluble (%) 24.5 ± 0.1b
12.9 ± 0.04a
Partially oil soluble (%) 34.2 ± 0.3b
19.3 ± 0.2a
Crystallizable (%) 41.3 ± 0. 3a
67.8 ± 0.2b
Sugars (g/kg e.m.) 105.66 ± 11.45 e
(g/kg of solid in d.b.*) 34.02 ± 3.69 e
Raffinose (%) 33.3 ± 2.6 e
Sucrose (%) 59.7 ± 3.4 e
Glucose (%) 2.1 ± 0.3 e
Galactose (%) 1.5 ± 0.2 e
Fructose (%) 2.1 ± 0.3 e
Rhamnose (%) 1.3 ± 0.8 e
Data are mean values ± standard errors.
Values in the same row with the same letter are not significantly different (p 0.05) by the LSD Fisher method.
d.b. ¼ dry basis.
e.m. ¼ extracted material.
*solid in d.b. means moisture-free sunflower collets.
Table 2
Equilibrium constant at 50 and 60 C and different collet-to-solvent ratios. Com-
parison between ethanol and hexane as extraction solvents.
Collet-to-solvent ratios (g/mL) Kethanol Khexane
50
C
1:4 17.13 ± 0.22c
0.49 ± 0.01b
1:11 10.51 ± 0.56b
0.34 ± 0.04a
1:18 7.55 ± 0.84a
0.54 ± 0.03b
60
C
1:4 8.17 ± 0.86b
0.55 ± 0.02b
1:11 5.14 ± 0.46a
0.18 ± 0.01a
1:18 3.52 ± 0.40a
0.60 ± 0.09b
In the same column and for each temperature, values with the same letter are not
significantly different (p 0.05) by the LSD Fisher method.
K ¼ ratio of the residual e. m. in the solid*
phase to the e. m. in the bulk miscella.
e.m. ¼ extracted material.
*solid means moisture-free sunflower collets.
Fig. 1. Relationship between the extractable material occluded in the solid matrix and
the extracted material in the miscella at equilibrium (bullets: experimental data; solid
lines: fitting model).
E.R. Baümler et al. / Journal of Food Engineering 178 (2016) 190e197194
6. CS ¼
a CL
1 þ b CL
(8)
where the constant a is the slope of the linear region, and the
constant b represents the curvature that is significant at higher
concentrations. Both constant values were obtained by nonlinear
regression, giving a ¼ 3.43 ± 0.43 and b ¼ À33.16 ± 1.19 at 50 C
(r2
¼ 0.99), and a ¼ 2.34 ± 0.05 and b ¼ À17.57 ± 0.16 at 60 C
(r2
¼ 0.99). For n-hexane, the correlations were linear, CS ¼ a CL,
being a ¼ 0.70 ± 0.09 at 50 C (r2
¼ 0.91) and a ¼ 0.50 ± 0.07 at 60 C
(r2
¼ 0.89). Patricelli et al. (1979) also obtained a linear relation in
their study of sunflower oil distribution between the liquid and
solid phase using crushed and laminated partially-decorticated
sunflower seeds, hexane at 22 C and low solid-to-solvent ratio.
The differences in the fitting curve slopes are associated with the oil
solubility in the solvent used, as well as the raw material used. On a
molecular level, there is a driving force, or potential, that causes the
oil to dissolve in the solvent. If the oil is only partially miscible in
the solvent, as in the case of ethanol, then this force decreases as
the concentration of oil in the solvent increases and goes to zero at
the saturation concentration (Abraham et al., 1988). This could
explain the curvature obtained when ethanol was used as extrac-
tion solvent.
3.3. Oil extraction kinetics using ethanol as solvent
As mentioned above in Material and Methods (Section 2.1), the
material extracted with ethanol was fractionated using n-hexane.
The material soluble in n-hexane was used to study the oil
extraction kinetics. Because the oil is only partially miscible in
ethanol, the driving force decreases as the concentration of oil in
the solvent increases and goes to zero at the saturation concen-
tration; therefore in the oil extraction experiences, a high collet-to-
solvent ratio (1:18) was used to keep the driving force large.
Experimental and predicted oil extraction data of Mt/Minf at
different temperatures using ethanol as solvent are presented in
Fig. 2. The extraction rate increased markedly with temperature;
the change in yield can be attributed to the fact that a rise in
temperature increases the solubility and diffusion of the oil while
decreasing viscosity. Table 3 shows the obtained coefficients of the
model used to represent oil extraction for all the studied cases:
different A and B model, common A model, common B model and
global model (as explained in Section 2.6). For the temperature
analysis, the comparison of the model with different A and B co-
efficients with the common B and global models showed significant
differences (Fo Fc). On the other hand, the comparison of the
model with different A and B coefficients with that using a common
A coefficient did not present significant differences (Fo Fc), indi-
cating that only the B coefficient depends on temperature within
the range studied. Thus, in order to represent the oil extraction
kinetics using ethanol as solvent and to obtain the diffusion co-
efficients, the common A model was selected. De values determined
by Eq. (4) were 9.94 10À10
at 50 C and 3.11 10À9
m2
/s at 60 C,
values that were lower than those reported for n-hexane (1.68
10À8
at 50 C, 2.25 10À8
m2
/s at 60 C) (Baümler et al., 2010).
Experimental oil extraction results obtained using ethanol were
also compared with reported data of sunflower collet oil extraction
using n-hexane as solvent (Baümler et al., 2010). For the solvent
analysis, the comparison of the different A and B model with the
common A, common B and global models showed significant dif-
ferences in all cases (Fo Fc), indicating that both parameters A and
B depend on the solvent used, as it can be easily deduced from the
experimental data (Fig. 3) and the parameters of the kinetic model
(Table 4). Comparing the experimental data, it is worth mentioning
that at the equilibrium condition the oil yields obtained with
hexane were 45% higher than those obtained when ethanol was
used, thus extracting almost the total lipid content determined by
exhaustive extraction (23.5 ± 0.4% d.b.) (Baümler et al., 2010).
Moreover, the equilibrium ethanolic extraction improved by 10%
when temperature was increased by 10 C, whereas the hexane
extraction did not change significantly.
4. Conclusions
This work demonstrated the feasibility of using ethanol as an
alternative solvent to hexane in the oil extraction from sunflower
collets. Oil extraction was described by modified nonlinear
Fig. 2. Experimental (bullets) and predicted (lines) oil extraction kinetics at 50 C and
60 C using ethanol as solvent.
Table 3
Coefficients obtained from the different models proposed for oil extraction yield using ethanol as solvent.
Fitting description Coefficients Temperature (ºC) Fo Fc
50 60
Different A and B A Â 101
8.69 ± 0.19 8.88 ± 0.35 e e
B Â 105
6.42 ± 0.59 20.81 ± 2.51
R2
0.98 0.97
Common A A Â 101
8.62 8.62 0.84 4.49
B Â 105
6.29 ± 0.47 19.66 ± 1.98
R2
0.98 0.97
Common B A Â 101
9.34 ± 0.40 7.90 ± 0.46 53.82 4.49
B Â 105
11.07 11.07
R2
0.89 0.90
Global (Common A and B) A Â 101
8.62 ± 0.42 37.48 3.63
B Â 105
11.07 ± 1.86
R2
0.58
E.R. Baümler et al. / Journal of Food Engineering 178 (2016) 190e197 195
7. diffusion models derived from Fick's second law, which involved
two parameters: A, associated with the portion extracted during
the washing stage, and B, proportional to the effective diffusion
coefficient.
A statistical comparison was carried out in order to evaluate the
temperature dependence of model parameters A and B. In the
comparison, differences between the models could be detected.
Only parameter B depended on temperature, therefore the model
selected was that which considered parameter B depending on
temperature (common A model). The same analysis was performed
to evaluate the solvent dependence of the parameters. As expected,
results demonstrated that both parameters depended on the sol-
vent used.
The extracted material obtained using ethanol consisted of two
phases: a hexane-soluble fraction and a hexane-insoluble fraction
that could be separated by simple fractionation using n-hexane.
Both fractions consisted of partially degummed sunflower oil with
a relatively low crystallizable wax content and a hexane-insoluble
fraction composed of oil, phospholipids, pigments and sugars.
This confers an interesting property to ethanol: that of providing
partially degummed sunflower oil on the one hand, as well as a
higher recovery of PL in the other phase (hexane-insoluble frac-
tion). This hexane-insoluble fraction could be refined and used as
sunflower lecithin. In addition, it was demonstrated that sugars are
extracted when ethanol is used as solvent. Thus the sugar content
in the residual solid material, especially the indigestible raffinose,
was reduced and this increased its nutritional value.
It was observed that other compounds, different from
Fig. 3. Comparison between the oil extraction kinetics using ethanol as solvent and reported data of sunflower oil extraction using n-hexane (Baümler et al., 2010).
Table 4
Comparison of the coefficients obtained from the different models proposed for fitting the oil extraction yield data when ethanol and n-hexane were used as solvent. Results of
the ESS.
Fitting description Coefficients Solvent Fo Fc
Ethanol n-hexane (Baümler et al., 2010)
50
C
Different A and B A Â 101
8.62 4.23 ± 0.08 e e
B Â 105
6.29 ± 0.47 116.00 ± 4.78
R2
0.98 0.99
Common A A Â 101
5.73 5.73 526.6 4.49
B Â 105
2.62 ± 2.05 199.70 ± 18.12
R2
0.40 0.95
Common B A Â 101
9.29 ± 0.38 2.16 ± 0.43 174.90 4.49
B Â 105
10.69 10.69
R2
0.91 0.54
Global (Common A and B) A Â 101
5.73 ± 1.06 902.77 3.63
B Â 105
10.69 ± 6.92
R2
0.32
60
C
Different A and B A Â 101
8.62 4.80 ± 0.11 e e
B Â 105
19.66 ± 1.98 180.20 ± 7.46
R2
0.97 0.99
Common A A Â 101
6.11 6.11 128.50 4.49
B Â 105
10.66 ± 4.58 253.70 ± 16.38
R2
0.74 0.97
Common B A Â 101
9.57 ± 0.46 2.65 ± 0.39 45.50 4.49
B Â 105
32.26 32.26
R2
0.93 0.74
Global (Common A and B) A Â 101
6.11 ± 1.07 250.70 3.63
B Â 105
32.26 ± 16.91
R2
0.49
E.R. Baümler et al. / Journal of Food Engineering 178 (2016) 190e197196
8. triglycerides, were extracted when ethanol was used as solvent.
Knowledge of the extraction of these compounds is a very impor-
tant point to be taken into account to determine the quality of the
extracted oil and the requirements of the subsequent purification
steps. This aspect will be further studied in future work.
Conflict of Interest statement
The authors have declared no conflict of interest
Acknowledgments
The authors acknowledge the financial support from CONICET
(Consejo Nacional de Investigaciones Científicas y Tecnicas), ANP-
CyT (Agencia Nacional de Promocion Científica y Tecnologica) and
Universidad Nacional del Sur, Argentina.
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