Dissertations / Theses on the topic 'Vegetable oil and protein extraction'

Дисертація на здобуття наукового ступеня кандидата технічних наук за спеціальністю 05.18.06 – технологія жирів, ефірних масел і парфумерно-косметичних продуктів. – Національний технічний університет "Харківський політехнічний інститут" Міністерства освіти і науки України, Харків, 2016. Дисертацію присвячено науковому обґрунтуванню технології комплексної переробки соняшникової макухи з безлушпинного ядра. Встановлено залежність ступеню вилучення олії і хлорогенової кислоти з соняшникової макухи безлушпинного ядра від складу розчинника, температури та тривалості екстрагування у кавітаційній установці та отримано математичний опис цього процесу у вигляді регресійного рівняння. Виявлено антиоксидантні властивості сухих речовин екстрактів соняшникової макухи безлушпинного ядра. Показано, що досліджені екстракти інгібують ланцюгові вільно-радикальні реакції окиснення. Розроблено перспективну технологію комплексної переробки соняшникової макухи з безлушпинного ядра, за якою можна отримати: олію екстракційну, шрот (або борошно) та жиророзчинний рослинний антиоксидант. Результати роботи впроваджені на ТОВ "Нові енергозберігаючі технології" (м. Херсон), ПАТ "Харківська бісквітна фабрика" (м. Харків) та в навчальний процес кафедри технології жирів та продуктів бродіння НТУ "ХПІ".
Thesis for a candidate of technical sciences degree. Speciality 05.18.06 − fats, essential oils and perfume-cosmetic products technology − National Technical University "Kharkiv Polytechnic Institute". Ministry of Education and Science of Ukraine, Kharkiv, 2016. The dissertation is devoted to the basis of technology of complex processing of sun-flower cakes obtained from dehulled sunflower kernels. During the work it was ascertained that sunflower oil and chlorogenic acid extraction rates depend on solvent type, temperature, and extraction time in the cavitation facility. The regression equations for the abovementioned processes were derived. Antioxidant properties of solids extracts obtained from dehulled sunflower kernels (SE) were discovered. It was shown that all of the investigated SE terminate the chain reactions during the propagation step. Complex technology of sunflower cakes processing obtained from dehulled sunflow-er kernels was designed. This technology allows obtaining of extracted oil, sunflower meal (or proteinrich flour), and fat-soluble antioxidant. The results of the work are adopted at "New Energy-Efficient Technologies", LLC, "Kharkiv Biscuit Factory", OJSC, and implemented in the educational process at the Department of Technology of Fats and Fermentation Products of NTU "KhPI".

Дисертація на здобуття наукового ступеня кандидата технічних наук за спеціальністю 05.18.06 – технологія жирів, ефірних масел і парфумерно-косметичних продуктів. – Національний технічний університет "Харківський політехнічний інститут" Міністерства освіти і науки України, Харків, 2016. Дисертацію присвячено науковому обґрунтуванню технології комплексної переробки соняшникової макухи з безлушпинного ядра. Встановлено залежність ступеню вилучення олії і хлорогенової кислоти з соняшникової макухи безлушпинного ядра від складу розчинника, температури та тривалості екстрагування у кавітаційній установці та отримано математичний опис цього процесу у вигляді регресійного рівняння. Виявлено антиоксидантні властивості сухих речовин екстрактів соняшникової макухи безлушпинного ядра. Показано, що досліджені екстракти інгібують ланцюгові вільно-радикальні реакції окиснення. Розроблено перспективну технологію комплексної переробки соняшникової макухи з безлушпинного ядра, за якою можна отримати: олію екстракційну, шрот (або борошно) та жиророзчинний рослинний антиоксидант. Результати роботи впроваджені на ТОВ "Нові енергозберігаючі технології" (м. Херсон), ПАТ "Харківська бісквітна фабрика" (м. Харків) та в навчальний процес кафедри технології жирів та продуктів бродіння НТУ "ХПІ".
Thesis for a candidate of technical sciences degree. Speciality 05.18.06 − fats, essential oils and perfume-cosmetic products technology − National Technical University "Kharkiv Polytechnic Institute". Ministry of Education and Science of Ukraine, Kharkiv, 2016. The dissertation is devoted to the basis of technology of complex processing of sun-flower cakes obtained from dehulled sunflower kernels. During the work it was ascertained that sunflower oil and chlorogenic acid extraction rates depend on solvent type, temperature, and extraction time in the cavitation facility. The regression equations for the abovementioned processes were derived. Antioxidant properties of solids extracts obtained from dehulled sunflower kernels (SE) were discovered. It was shown that all of the investigated SE terminate the chain reactions during the propagation step. Complex technology of sunflower cakes processing obtained from dehulled sunflow-er kernels was designed. This technology allows obtaining of extracted oil, sunflower meal (or proteinrich flour), and fat-soluble antioxidant. The results of the work are adopted at "New Energy-Efficient Technologies", LLC, "Kharkiv Biscuit Factory", OJSC, and implemented in the educational process at the Department of Technology of Fats and Fermentation Products of NTU "KhPI"

Apiaceae could be defined as Aroma Tincto Oleo Crops (ATOC), e.g. plants containing both vegetable oil and essential oil. Applying agroreffinery concept to ATOC led to propose a sequential fractionation process coupling co-extraction of vegetal oil and essential oil to a valorization of by-product residues as biosourced active molecules and substrates for designing agromaterials. The aim of this thesis is to determine the biological and technological feasability of application of the ATOC-refinery concept to coriander (Coriandrum sativum L.) Chapter I reports a bibliographic state of the art study on extraction and characterisation of coriander vegetal oil and essential oil while chapter II describes materials and methods setting up during the thesis for sampling, extraction, analysis and data processing. Chapter III focus on the study of major various biological parameters influencing bioaccumulation of vegetal oil and essential oil in coriander (different plant varieties, different plant organs, different biological stages) and their impact on anti-oxidant activity of extracts obtained from extraction residues. In chapter IV, coriander fruits are processed by extrusion technology (mono screw and twin-screw extruder) in order to evaluate the feasability of mechanical pressing for extracting a flavored vegetal oil. Influence of operating parameters on vegetal oil extraction yields (nozzle diameter and nozzle/screw distance (single-screw extruder) or screw configuration, device’s filling coefficient and pressing temperature (twin-screw extruder)) is studied while the feasability of valorization of extraction cake as agromaterial (thermopressing) was stated.

Ces dernières années, l’intérêt croissant porté aux considérations environnementales et à la sécurité des procédés pose la question de l’utilisation de solvants pétrochimiques nocifs non renouvelables tels que l’hexane, mais aussi de la quantité d’énergie investie dans le procédé de trituration des graines oléagineuses. L’objectif de cette thèse a donc consisté en la recherche et le développement de procédés d’éco-extraction d’huile végétale, issue de graines oléagineuses, grâce à des technologies innovantes (ultrasons et micro-ondes) et des solvants alternatifs plus respectueux de la santé et de l’environnement. La première partie de ce manuscrit propose en premier lieu l’optimisation du procédé d’extraction à l’hexane d’huile de colza à partir d’écailles de pression avec des ultrasons. Bien que ceux-ci aient un impact positif sur les rendements, le temps d’extraction et la consommation de solvant, l’utilisation de l’hexane reste problématique. Dans une deuxième partie, la substitution de l’hexane par des solvants alternatifs plus « verts » a donc été considérée. Une première approche expérimentale a été complétée par une approche prédictive grâce à l’utilisation d’outils d’aide à la décision : les paramètres de solubilité de Hansen et le modèle COSMO-RS. Cette démarche a conduit à la sélection d’un solvant, le 2-méthyltétrahydrofurane, pour la réalisation d’une étude complète allant de l’échelle laboratoire à l’échelle pilote. Dans une troisième et dernière partie, la combinaison de solvants alternatifs avec une technique innovante, les micro-ondes, pour l’extraction d’huile colza à partir d’écailles de pression a été envisagée. Cette étude a mis en évidence l’intérêt des micro-ondes dans le cas d’une sélectivité de chauffage entre la biomasse et le solvant
In recent years, the growing interest in environmental considerations and process safety raises the issue of the use of non-renewable petrochemical harmful solvents such as hexane, but also the amount of energy invested in the process of oilseed crushing. The objective of this thesis has consisted in the research and development of green extraction processes of vegetable oil from oil seeds through innovative technologies (ultrasonic and microwave) and alternative solvents more respectful of health and environment. The first part of this manuscript describes the optimization with ultrasound of the extraction process, using hexane, of oil from rapeseed cake. Although ultrasound have a positive impact on extraction yield, extraction time and solvent consumption, the use of hexane remains questionable. In the second part, substituting hexane by "green" alternative solvents has been considered. A first experimental approach was supplemented by a predictive approach through the use of decision tools: Hansen solubility parameters and COSMO-RS model. This led to the selection of a solvent, 2-methyltetrahydrofuran, for conducting a comprehensive study from laboratory to pilot scale. In a third and final part, the combination of alternative solvents with an innovative technology, microwaves, for the extraction of oil from rapeseed cake was investigated. This study highlighted the benefit of microwaves in the case of a selective heating between biomass and solvent

New soybean lines have been developed with significantly higher oil, protein + oil and higher meal protein. These soybeans contain a VgD1 gene (highly active acyl-CoA:diacylglycerol acyltransferase, DGAT from Vernonia galamensis (VgDGAT1A) produces much higher oil synthesis and accumulation activity in soybean. Soybean with active DGAT from Vernonia galamensis (VgDGAT1A) has active TAG biosynthesis relative to other DGATs including from soybeans and Arabidopsis. DGATs catalyze the final step of TAG synthesis: DAG (diacylglycerol) + acyl-CoA → TAG + CoASH (Coenzyme A is notable for its role in the synthesis and oxidation of fatty acids, and the oxidation of pyruvate in the citric acid cycle). A thorough analysis of the major components in VgD1 lines, especially those of nutritional or anti-nutritional value including what else changed (decreased); and what remained at normal levels was conducted. A field study was conducted in Spindletop and Princeton KY, reviled no reduction in yield nor protein, and about 4 % (DW) more oil was obtained in Princeton and 2% (DW) in Spindeltop. No consistent reduction in the other seed composition.VgDGAT1A soybean lines indicated noticeably early maturation compared to the parental line. This is associated with higher expression of the flowering genes FT2 (FLOWERING LOCUS T2) and FT5 (FLOWERING LOCUS T5), for the high oil lines. A single recessive mutation in soybean (MIPS) myo-inositol 1-phosphate synthase, confers a seed phenotype of increase inorganic phosphate (Pi) crossed with high oil lines expressing a DGAT from Vernonia galamensis (VgDGAT1A) (VgD). The oil and protein were maintained compart to VgD. VgD X MIPS (VM), had 21.2, and 22 % oil in 2015, and 23.3 and 24.0 oil in 2016, and protein 46, 49 in 2015, and 37 and 39 % in 2016. Phosphate results suggesting the cross MV is still segregating for MIPS and more selection and planting are needed. Measurement of seed phosphate levels is an established technique for screening for low phytate mutants but to date, it has not been performed non-destructively from single soybean seeds. A protocol was developed greatly reducing the sample size thereby reducing the cost and time and saving a generation in the selection of low phytate mutant seeds based on the high Pi phenotype. Genotyping single seeds are useful in breeding and genetics while maintaining high germination rates. Nondestructive single-seed genomic DNA extraction protocols using 12 mg cotyledon tissue with a modified cetyl trimethyl ammonium bromide (CTAB) technique and a commercial seed DNA extraction kit using 1 mg cotyledon tissue were developed for dry soybean seeds and cross-verified with leaf DNA analysis.

La présente étude a eu pour objectif la comparaison de la fabrication du biodiesel à partir de graines de caméline suivant les procédés conventionnels ou assistés/intensifiés par Détente Instantanée Contrôlée (DIC). La caméline est l'une des matières premières les plus adaptées à la fabrication de biodiesel puisqu’elle ne présente aucune concurrence aux cultures alimentaires et/ou à l’utilisation des terres agricoles. Son intérêt réside en sa teneur élevée en huile, sa courte saison de culture, ainsi que sa grande capacité à enrichir les sols pauvres, arides ou semi-arides. L'insertion de la texturation par DIC permet l'intensification à la fois de 1/ l'extraction de l’huile suivie de transestérification et 2/ du processus de transestérification in-situ en une seule étape. Dans les deux cas, les analyses statistiques ont conduit, à l'aide de la méthode de surface de réponse (RSM), à des modèles mathématiques empiriques adéquats capables de mieux développer les résultats expérimentaux, d'optimiser les paramètres de traitement et de mieux définir le changement d’échelle. Le procédé DIC se distingue par son aptitude à réaliser avec succès l’expansion structurelle des produits naturels sans affecter la qualité des huiles et des carburants produits. L'augmentation de la quantité d'huile extraite après texturation des graines par DIC a été de 38% et 22%, respectivement pour le pressage et l'extraction par solvant. En mode ISTE, la texturation DIC a permis de doubler le rendement en FAMEs. En outre, la technologie DIC est une technique très économique en raison de la grande capacité de traitement due au faible temps d’opération et d’une consommation réduite d'énergie
The objective of this study was to compare the production of biodiesel from Camelina seeds using conventional methods or assisted/intensified by Instant Controlled Pressure-drop DIC. Camelina is one of the most suitable feedstocks for biodiesel production as it does not compete with food crops and/or agricultural land use. Its interest lies in its high oil content, short growing season, and great ability to enrich poor, arid or semi-arid soils. The insertion of texturing by DIC allows the intensification of both 1/ extraction of the oil followed by transesterification and 2/ a single step in-situ transesterification process. In both cases, using the response surface method (RSM), statistical analyzes have led to adequate empirical mathematical models capable of better developing experimental results, optimizing treatment parameters and better define the scaling-up. The DIC process stands out for its ability to successfully achieve the structural expansion of natural products without affecting the quality of sensitive compounds such as oils and fuels produced. The increase in the amount of oil extracted after DIC texturing of seeds was 38% and 22% for pressing and solvent extraction, respectively. In ISTE mode, DIC texturing approximately doubled FAMEs yields (98% increased yields). In addition, DIC technology is a very economical technique due to its high processing capacity, low operating time, and weak energy consumption

Le développement de la chimie verte, l’épuisement des ressources pétrolières et la prise de conscience des risques liée à l’utilisation des solvants pétroliers ont conduit à la recherche de nouvelles alternatives pour réduire l’utilisation des solvants nocifs non renouvelables tels que l’hexane. L’objectif de cette thèse a donc consisté en la recherche de solvants alternatifs plus respectueux de la santé et de l’environnement pour l’éco-extraction des composés phénoliques et des acides gras à partir des graines de Pistacia lentiscus et des arômes à partir de ces feuilles. Pour ce faire, une première approche in silico basée sur des outils de prédictions tels que COSMO-RS a été complétée par une approche expérimentale associée à des traitements chimiométriques. Cette démarche a conduit à la sélection de quatre solvants verts, le MetHF pour l’extraction des acides gras, l’EtOAc pour l’extraction des arômes, l’EtOH/H2O (70/30) pour l’extraction des polyphénols et des flavonoïdes et l’EtOH/H2O (80/20) pour l’extraction des anthocyanes. Par la suite, l’activité anti-inflammatoire de l’extrait lipidique obtenu par le MeTHF et l’activité antioxydante des extraits aromatiques et des extraits phénoliques de P. lentiscus ont été évaluées in vitro. Ces travaux ont montré que l’huile végétale a présenté une activité anti-inflammatoire potentielle, inhibant de 91,9% la libération d’oxyde nitrique (NO.) dans les macrophages RAW 264,7. De plus, les résultats ont permis de mettre en évidence la richesse des fruits en antioxydants. En effet, l’extrait obtenu par l’EtOH/H2O (80/20) a montré une activité antiradicalaire (IC50 = 2,39 μg/ml) comparable à celle de l’antioxydant de synthèse le Trolox (IC50 = 2,56 μg/ml). En outre, l’extrait aromatique de P. lentiscus obtenu avec l’EtOAc a présenté une activité antiradicalaire intéressante contre le DPPH (IC50 = 5,82 μg/ml)
The development of Green chemistry, the depletion of petroleum resources and the awareness of the risks associated to the use of petroleum solvents have led to search a new alternatives to reduce the use of non-renewable petrochemical harmful solvents such as hexane. The objective of this thesis has consisted in the research of alternative solvents more respectful of health and environment for the eco-extraction of fatty acids and phenolic compounds from Pistacia lentiscus fruits and aromas from these leaves. A first in silico approach using the COSMO-RS predictions was supplemented by an experimental approach paired with chemometrics analysis. This led to selection of four alternative solvents, MeTHF for oil extraction, EtOAc for aromas extraction, EtOH/H2O (70/30) for polyphenols and flavonoids extraction and EtOH/H2O (80/20) for anthocyanins extraction. Subsequently, the anti-inflammatory activity of MeTHF lipid extract and the antioxidant activity of aromatic and phenolic extracts of P. lentiscus were evaluated in vitro. Results showed that vegetable oil exhibited a potential anti-inflammatory activity, inhibiting by 91.9% the release of (nitric oxide) NO in RAW 264.7 macrophages. In addition, results highlighted the richness of the fruits in antioxidants. In fact, EtOH/H2O (80/20) extract showed a good antiradical activity (IC50 = 2.39 μg/ml) comparable to that of the synthetic antioxidant Trolox (IC50 = 2.56 μg / ml). In addition, the aromatic extract obtained with EtOAc showed an interesting anti-radical activity against DPPH (IC50 = 5.82 μg/ml)

No presente estudo objetivou-se avaliar o desempenho do etanol e isopropanol, absoluto e azeotrópico, na extração de óleo de macadâmia e milho. Nesse sentido, foram realizados experimentos de extração em batelada para determinar os efeitos do tipo de solvente e temperatura sobre o índice de retenção, rendimento de extração, qualidade do óleo e fração proteica. Assim, torta parcialmente desengordurada de macadâmia sem pré-tratamento prévio à etapa de extração (teor de lipídios 57,4 ± 0,7 % em base seca) foi submetida a extração, nas temperaturas de 60, 75 e 90 °C, enquanto as extrações de óleo do gérmen de milho em pellets (teor de lipídios 12,61 ± 0,05 % em base seca) foram realizadas a 50, 60, 70 e 80 °C. Os experimentos de extração em correntes cruzadas foram realizados a 70 e 75 °C para o gérmen de milho e a macadâmia, respectivamente. Os resultados mostraram que o rendimento de extração de óleo de macadâmia e milho é influenciado pelo tipo solvente, temperatura e pré-tratamento do material, sendo que com isopropanol absoluto, a 90 °C, foi possível extrair 66 % do óleo de macadâmia e a 80 °C, 87 % do óleo de milho. O índice de retenção de solução aderida as fibras (IR) foi impactado pelo tipo de solvente e características da matéria-prima, obtendo-se valores de IR maiores nas fases rafinado de macadâmia. A composição em ácidos graxos dos óleos de gérmen de milho extraídos com os solventes alcoólicos foi típica do óleo de milho, com predominância dos ácidos graxos oleico (34 %) e linoleico (48 %). As fases rafinado dos dois materiais apresentaram teor de proteínas maior que as matérias-primas iniciais, no entanto as condições do processo de extração impactaram negativamente no índice de solubilidade de nitrogênio, tornando inviável a produção de concentrado proteico de gérmen de milho. Para o óleo de milho a extração de tocoferóis e tocotrienóis foi maior com etanol, enquanto que com isopropanol conseguiu-se uma maior extração de carotenoides, o que pode ser decorrente da polaridade destes compostos bioativos. Os óleos de macadâmia extraídos com os solventes alcoólicos apresentaram maior estabilidade oxidativa (mais de 37 horas) quando comparados ao óleo bruto obtido por prensagem industrial (11,7 horas), sendo possível inferir que o uso dos solventes alcoólicos possibilita a extração de compostos que contribuem para o aumento da estabilidade do óleo. Nos experimentos em correntes cruzadas foi observado que para desengordurar a macadâmia com etanol e isopropanol absoluto são necessários mais de quatro estágios de contato, enquanto para o gérmen de milho dois estágios são suficientes. Em relação aos concentrados proteicos de macadâmia, o rendimento foi maior com os rafinados oriundos das extrações com isopropanol absoluto (13 %). Estes concentrados apresentaram boa capacidade de retenção de água e óleo (aproximadamente 2 g/g de concentrado) e estabilidade e atividade de emulsão na faixa de 56 a 59 %, desta forma pode-se sugerir que estes produtos apresentam potencial para seu aproveitamento na indústria de alimentos. A partir dos resultados pode-se inferir que a utilização dos solventes alcoólicos na extração de óleo de milho e macadâmia é tecnicamente viável, no entanto o desempenho dos solventes alcoólicos é influenciado pelas características da matéria-prima e pelo pré-tratamento do material sólido prévio à etapa de extração, obtendo-se maiores rendimentos de extração de óleo com o gérmen de milho em pellets. Também é possível inferir que os solventes em grau absoluto impactam menos na solubilidade das proteínas, permitindo a produção de concentrados proteicos de macadâmia com propriedades funcionais adequadas para seu uso na indústria de alimentos.
The objective of this study was to evaluate the performance of ethanol and isopropanol, absolute and azeotropic, in the extraction of macadamia and corn oil. Accordingly, extraction experiments were performed in batch to determine the effect of solvent type and temperature on retention index, extraction yield, quality indices of oil and protein fraction. Thus, partially defatted macadamia meal without pre-treatment prior to the extraction step (lipid content 57.4 ± 0.7 % on dry basis) was submitted to extraction at temperatures of 60, 75 and 90 °C, while oil extractions of corn germ in pellets (lipid content 12.61 ± 0.05 % on dry basis) were performed at 50, 60, 70 and 80 °C. The crosscurrent extraction experiments were performed at 70 and 75 °C for corn germ and macadamia, respectively. The results showed that the oil extraction yield of macadamia and corn is influenced by the solvent type, temperature and pre-treatment of the material, being that with absolute isopropanol at 90 °C, it was possible to extract 66 % of the macadamia oil and 87 % of the corn oil at 80 °C. The retention index of the solution adhered to the fibers (RI) was affected by the type of solvent and characteristics of the raw material, obtaining higher values of RI in the raffinate phases of macadamia. The fatty acid composition of corn germ oils extracted with alcoholic solvents was typical of corn oil, with predominance of oleic acid (34 %) and linoleic acid (48 %). The raffinate phases of the two materials showed higher protein content than the initial raw materials, however the conditions of the oil extraction process had a negative impact on the nitrogen solubility index, turning the production of protein concentrate from corn germ infeasible. For corn oil the extraction of tocopherols and tocotrienols was higher with ethanol, whereas with isopropanol a greater extraction of carotenoids was obtained, which can be due to the polarity of these bioactive compounds. Macadamia oils extracted with the alcoholic solvents showed higher oxidative stability (more than 37 hours) when compared to crude oil obtained by industrial cold pressing (11.7 hours). It is possible to infer that the use of alcoholic solvents enables to extract compounds that contribute to the increase of oil stability. In the crosscurrent extraction experiments it was observed that to produce defatted macadamia with absolute ethanol and isopropanol more than four stages of contact are required, whereas for the corn germ two stages are sufficient. Regarding protein concentrates of macadamia, the yield was higher with raffinate phases coming from the extractions with absolute isopropanol (13 %). These concentrates showed good water and oil retention capacity (approximately 2 g/g of concentrate) and emulsion stability and activity in the range of 56 to 59 %, therefore it can be suggested that these products have potential for their use in the food industry. From the results it can be inferred that the use of the alcoholic solvents in the extraction of corn and macadamia oil is technically feasible, however the performance of the alcoholic solvents is influenced by the characteristics of the raw material and by pre-treatment of the solid material prior to the extraction step, obtaining the highest oil extraction yields with the corn germ in pellets. Also, it is possible to infer that the solvents in absolute degree impact less on the solubility of the proteins, enabling the production of macadamia protein concentrates with functional properties suitable for use in the food industry.

L’une des préoccupations actuelles majeures des acteurs de la trituration repose sur l’identification d’une alternative au procédé utilisant l’hexane en raison de son impact sur l’environnement, la qualité des produits et la santé humaine. L’utilisation de l’eau comme solvant de substitution présente plusieurs avantages, mais cette piste a été longtemps écartée en raison de la non miscibilité de l’eau et des huiles. La solution proposée suggère d’utiliser une solution aqueuse de tensioactifs permettant la réduction de la tension interfaciale entre l’eau et l’huile sous les 10-2 mN/m (i.e. la formation de microémulsion). Cette thèse vise donc à étudier l’extraction des huiles végétales à partir de graines oléagineuses en milieux aqueux en présence de tensioactifs. L’objectif principal est d’acquérir une meilleure compréhension des mécanismes mis en jeu et notamment des interactions physicochimiques entre les différents composés du système. Différentes questions ont été abordées dans cette thèse de façon à prendre en considération pas à pas le rôle et l’impact de chaque constituant du système. D’abord, la caractérisation physicochimique de différents types de tensioactifs, en particulier les tensioactifs dits rallongés et les tensioactifs biosourcés largement moins étudiés dans la littérature, a permis de sélectionner ceux capables de solubiliser un maximum d’huile végétale dans l’eau. Ensuite, les systèmes étudiés se complexifient par la prise en compte des graines oléagineuses, et donc de l’interface solide-liquide jamais étudiée dans la littérature. Des hypothèses quant aux mécanismes d’action des tensioactifs sur la modification de la mouillabilité des surfaces oléagineuses ont pu être proposées. Finalement, l’étude du procédé d’extraction a été abordée. L’influence des paramètres opératoires sur les rendements d’extraction a été appréhendée. Les résultats obtenus offrent des perspectives de poursuite, dans le but d’envisager l’émergence de cette technologie à l’échelle industrielle
One of the major current concerns in the crushing industry is to identify an alternative to the processthat uses hexane because of its impact on the environment, product quality, and human health. Theuse of water as a substitute solvent has several advantages, but this path has long been set apart dueto the immiscibility of water and oils. The proposed solution suggests using an aqueous solution ofsurfactants allowing the reduction of the interfacial tension between water and oil below 10-2 mN/m(i.e., the formation of microemulsion). This thesis, therefore, aims to study the extraction of vegetable oils from oilseeds in aqueous media in the presence of surfactants. The main objective is to acquire a better understanding of the mechanisms involved, in particular, the physicochemical interactions between the different compounds of the system. Different questions have been addressed in this thesis to consider step by step the role and the impact of each constituent of the system. First, the physicochemical characterization of different types of surfactants, in particular, the so-called extended surfactants and bio-based surfactants that are largely less studied in the literature, which made it possible to select those capable of solubilizing a maximum of vegetable oil in water. Then, the studied systems become more complex by considering the oilseeds, therefore the solid-liquid interface, which has never been studied inthe literature. Hypotheses as to the mechanisms of action of surfactants on the wettabilitymodification of oleaginous surfaces have been proposed. Finally, the study of the extractionprocess was approached. The influence of the operating parameters on the extraction yields hasbeen apprehended. The results obtained offer prospects for further action to consider the emergenceof this technology on an industrial scale

À l’heure où l’intégration des enjeux environnementaux dans le développement de procédés éco-efficients joue un rôle essentiel dans le moteur de l’innovation responsable, la chimie verte est devenue l’un des sujets de préoccupation majeure. Ainsi, le développement de nouveaux procédés éco-respectueux pour la production d’ingrédients naturels issus de matières premières végétales renouvelables est devenu une démarche incontournable dans le modèle de recherche. L’objectif de cette thèse a consisté au développement d’une stratégie d’éco-valorisation innovante employant les fluides sub/supercritiques pour l’extraction, la caractérisation, la production et l’imprégnation sur support cosmétique de produits naturels d’origine végétale. Pour cela, nous avons utilisé comme modèle végétal : les graines oléagineuses de la plante Kniphofia uvaria, sélectionnée pour des applications cosmétiques grâce à ses propriétés bioactives antioxydantes et anti-âge. Dans un premier temps, le développement de méthodes complémentaires en SFC ainsi que le développement du couplage SFC-MS a été réalisé à l’aide de la source APCI afin d’identifier les molécules responsables des activités bioactives des graines de Kniphofia uvaria. Ainsi, le développement d’un système hybride (U)HPLC/SFC-HRMS a été réalisé afin de mettre en place ce couplage. Des optimisations en termes de proportion et nature de solvant make-up ainsi qu’un travail au niveau des paramètres SFC et MS ont été faits afin de d’améliorer la sensibilité et la spécificité des analyses lipidiques. Dans un second temps, nous nous sommes attachés au développement d’une stratégie d’enrichissement en composés bioactifs à l’aide des méthodes : SFE et CPC. Ainsi, en SFE, des optimisations en termes de température, pression, nature/proportions de co-solvant dans le fluide ont été réalisées alors qu’en CPC, des optimisations au niveau de l’injection ont été faites. Des conditions optimales pour le fractionnement sélectif des anthraquinones et des triglycérides ont été déterminées en SFE et CPC. Dans un dernier temps, ce travail a consisté à développer un couplage en-ligne pour extraire et imprégner sélectivement sur silice cosmétique : les anthraquinones. Le développement et l’optimisation de ce procédé en-ligne ont été réalisés à l’échelle du laboratoire et ont démontré la faisabilité de ce couplage ainsi qu’un intérêt certain pour l’obtention de produits naturels sous une première forme galénique, destinée à une future incorporation dans la formulation de cosmétiques
Nowadays, green chemistry is a great challenge. It seeks innovation in the development of eco-efficient processes. The production of natural products from renewable materials by these new environmentally friendly processes is more and more used. The aim of this Ph.D thesis is to develop an eco-valuation strategy to extract, characterize, produce and impregnate natural products onto a cosmetic support using sub/supercritical fluids. Consequently, we used oleaginous plant seeds from Kniphofia uvaria as a plant model, which was selected for its interesting cosmetic properties such as antioxidant or anti-ageing. Firstly, the SFC-MS hyphenation with the APCI as an ionization source was developed to screen bioactive molecules; responsible of cosmetic properties. This coupling was performed by the hybrid combination of (U)HPLC/SFC-HRMS. Various optimizations in terms of the solvent make-up (nature and proportion), modulation with SFC and MS parameters were carried out in order to improve sensitivity and selectivity of lipid analysis. Secondly, an enrichment strategy to concentrate bioactive compounds in the final extract was developed by SFE and CPC. Thus, in SFE, experimental parameters (temperature, pressure, nature/proportion of the modifier in the CO2 fluid) were optimized while in CPC, the injection optimization was realized. Methods for the selective fractionation of anthraquinones and triglycerides were obtained in CPC and SFE. Finally, an on-line sub/supercritical extraction-impregnation process was developed to extract and for simultaneously impregnating anthraquinones onto a cosmetic silica. Development and optimization of this process was realized on a laboratory scale. Consequently, this study demonstrated the feasibility of this concept and it presents a great interest to provide natural products as a galenic form, which could be used in the cosmetic formulation

碩士
國立臺灣大學
生物產業機電工程學研究所
94
Rapeseed oil is one the major feed stocks for biodiesel with great potential. The feasibility and efficiency of various rapeseed oil extraction systems with hexane, ethanol and water as solvents were studied and compared. Mathematical model of multi-stage counter-current-flow extraction was build and verified in this research. Six-stage counter-current-flow extraction experiments were carried with two different solvent to raffinate ratio (E/R) i.e. E/R=4, 8. A better result was found with E/R=4, that gave 90% in oil recovery and 8~9% (w/w) oil concentration in extract. Counter-current-flow ethanol-rapeseed oil extraction with varies stages and E/R ratios were simulated. A nine-stage extraction with E/R=20 shown that the oil concentration in ethanol was 1.5~1.6% (w/w) and oil recovery was 87%. Although extraction-transesterification might be considered for the ethanol - rapeseed oil system, but the oil concentration in extract might obstruct the idea to be practical. In respect of Aqueous Enzymatic Oil Extraction (AEOE), pectinase and proteinase were used for rapeseed and soybean oil extraction. Oil recovery was 69% and 65% respectively as pectinase was used. Oil recovery was 58% and 70% respectively as proteinase was used. AEOE might be a process with less energy consumed, but inefficient in extraction yields and oil recovery from solution would be the main difficulty to be overcome.

Sub-Saharan Africa is a treasure chest of natural materials remaining to be explored for commercial applications and as alternative foods to diversify and improve food sustainability. The Marula tree is available in abundance in South Africa and bears a fruit with a highly nutritious kernel containing high oil and protein content. The oil from the kernels has various applications from food to cosmetics. The accepted oil processing practice is required to be a green technology, producing no effluent or using toxic solvents. Therefore, the oil is extracted using an expeller. However, with average 55 wt. % oil in the kernel the extracted oil yield is far from optimal, typically ranging from as low as 7 wt. % to 47 wt. %. The latter is obtained only with proprietary modified expellers. Therefore, an alternative green technology which retains the native characteristics of the Marula oil is needed. Communication with local producers, South African and Namibian, confirmed the need for investigation of an alternative means of extraction of Marula oil from the seed kernels which can improve the yield and potentially the quality of the oilcake. The latter of which is typically adversely affected by the expelling process. A review of various processing technologies available for oil extraction was completed and supercritical fluid extraction utilizing carbon dioxide as the extraction solvent was identified as a potential solution. An overview on supercritical fluid extraction using carbon dioxide (SFE-CO2) of similar materials to the Marula kernels, such as hazelnuts, walnuts and pine kernels indicates that yields similar to that of solvent extraction and of the quality of the oils obtained by cold pressing can be obtained with the technique. The theory, practical applications, and how one can use the system to improve yield from various natural materials were reviewed. It was determined that the two main parameters one can manipulate on supercritical extraction systems to optimize the yield, were pressure and temperature. Subsequently kernels of the Sclerocarya birrea tree, common name Marula, cultivated in South Africa, were obtained for extraction with supercritical carbon dioxide. The effects of pressure and temperature on extraction yield were investigated. The total maximum yield of Marula kernel oil obtained was found to be 54 wt. %, compared to a solvent extracted yield of 52 wt. %, such that a 100 % oil recovery was obtained with SFE-CO2. The optimal conditions were found to be 450 bar and 60 °C as the yield per kg solvent initially was 41 g kg-1 CO2. Following the extractions, the oils were characterized for fatty acid composition using gas chromatography. Quality parameters of a cold pressed sample and a sample obtained at the optimal extraction conditions were determined and compared; and the results indicate that the two oils are of similar composition and quality. Supercritical fluid extraction using carbon dioxide was successfully verified as a potential processing method for the extraction of Marula oil from the kernels. The SFE-CO2 provided an improved yield compared to cold pressing and a quality of oil similar to cold pressed Marula oil. Additionally, after SFE-CO2 processing, the defatted Marula kernels contain high protein content, 69 wt. %, in the form of a pure white powder. Due to the favourable nutritional content the residue may be used for human consumption to create new products such as meat analogues, porridges, and shakes, or can be sold as a high protein powder.
MSc (Engineering Sciences in Chemical Engineering), North-West University, Potchefstroom Campus, 2015

Fish and fish waste can be used to produce various value added by products such as proteins, oil, omega-3 fatty acids, biodiesel, amino acids, peptides, collagen, gelatin and silage, each of which has various applications in the food industry, renewable energy and medicinal purposes. Fish protein contains amino acids and many bioactive peptides . Fish proteins are found in the flesh, head, frames, fin, tail, skin and guts in varying quantities. After removing the flesh, all other parts are considered waste which is not properly utilized. The aim of this study was to evaluate the enzymatic extraction of amino acids from fish protein for use as substrates in the microbial production of jadomycin, an antimicrobial agent and potential anti-cancer drug. In this study, enzymatic extraction of proteins was carried out using Alcalase enzyme at three enzyme concentrations (0.5, 1 or 2%) and four time intervals (1, 2, 3 and 4 h). The fish protein hydrolysate was dried using spray dryer to obtain protein powder. The highest protein yield (76.30% from whole fish and 74.53% from the frame) was obtained using 2.0% enzyme concentration after 4 h of hydrolysis. The enzymatic extraction of amino acids were carried out using the enzymes Alcalase and Neutrase (individually and in combination) and the effect of reaction time (24 and 48 h) on the hydrolysis of proteins was studied. The profiling of amino acids was carried out using gas chromatography. Fourteen amino acids were extracted from fish proteins of which twelve amino acids have been used by researchers for the production of jadomycins. These are: alanine (7.59%), glycine (5.82%), histidine (3.59%), isoleucine (5.30%), leucine (9%), lysine (7.34%) methionine (2.2%), phenylalanine (4.2%), serine (4.3%), threonine (5.40%), tyrosine (3.17%) and valine (7.2%). Tryptophan which is suitable of producing jadomycin was not present in the fish protein. No reports were found in the literature for jadomycin production from glutamic acid. Therefore, glutamic acid (9.85%), and proline (0.98%) which are present in the fish protein should be investigated for possible production of jadomycins.