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Continuous succinic acid fermentation by Actinobacillus succinogenesVan Heerden, Carel Daniel 01 August 2012 (has links)
Please read the abstract in the section front of this document. / Dissertation (MEng)--University of Pretoria, 2012. / Chemical Engineering / unrestricted
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Continuous succinic acid fermentation using immobilised Actinobacillus succinogenesMaharaj, Karishma January 2013 (has links)
Actinobacillus succinogenes cells were grown on Poraver® support particles in a
packed-bed reactor. Dilution rates (D) of 0.054–0.72 h-1 were investigated. Glucose
was used as substrate. CO2 (g) was bubbled into a complex medium to satisfy the
fixation requirements and maintain anaerobic conditions. At D ≥ 0.31 h-1, an initial glucose concentration of 35 g.L-1 was used; at lower dilution rates, this was
increased to 60 g.L-1 in order to avoid substrate limitations. By-product formation
included acetic and formic acids. A maximum productivity of 10.7 g.L-1 was obtained
at D = 0.7 h-1.
It was found that the system provided repeatable results at a given D. The longest
steady state period was maintained for about 97 h at D = 0.31 h-1. Steady state
stability was maintained for > 72 h at D < 0.31 h-1. For periods longer than 75 h,
however, inhibitory acid titres resulted in a gradual decline in productivity. At higher
dilution rates, long-term stability could not be maintained. The low acid titres
produced significant biofilm sloughing following aggressive biofilm growth, resulting
in oscillatory system behaviour.
For fermentation times < 115 h, the dilution rate was secondary to the attachment
area in determining the total biomass at steady state. Total biomass values were
then used to determine specific rates. A clear trend was observed, with the specific
glucose consumption rate, and specific acid production rates, increasing with
increasing D. This was explained by assuming a maintenance-driven system at all
Ds studied.
A product analysis indicated that at ΔS < 15 g.L-1, pyruvate formate lyase was the
preferred oxidative route. A shift to the pyruvate dehydrogenase pathway occurred at
higher ΔS values, so that the highest YSS values obtained exceeded 0.85 g.g-1.
A decrease in C3 by-product formation resulted in high YSS values being maintained,
indicating an additional, unknown source of nicotinamide adenine dinucleotide
(NADH). It is recommended that any process utilising immobilised A. succinogenes cells
should operate at an intermediate D, in order to maintain long-term reactor stability,
high productivities and good yields. / Dissertation (MEng)--University of Pretoria, 2013. / gm2014 / Chemical Engineering / unrestricted
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Continuous production of succinic acid by Actinobacillus succinogenes : steady state metabolic flux variationBradfield, M.F.A. (Michael Ford Alexander) January 2013 (has links)
Continuous fermentations were performed in a novel external-recycle, biofilm reactor using D-glucose and CO2 as carbon substrates. Corn steep liquor (CSL) and yeast extract (YE) served as nitrogen sources.
In anaerobic fermentations using medium containing CSL and YE, succinic acid (SA) yields were found to be an increasing function of glucose consumption. The ratio of SA to the major by-product, acetic acid (YAASA), increased from 2.4 g g-1 at a glucose consumption of 15 g L-1, to 5.7 g g-1 at a glucose consumption of 46 g L-1. For medium containing no CSL, YAASA remained near 1.97 g g-1, exceeding this for cases where biofilm grown on CSL-containing medium was present.
The ratio of formic acid to acetic acid (YAAFA), for CSL-containing medium, decreased from an equimolar value (0.77 g g-1) at a glucose consumption of 10 g L-1 to zero at 46 g L-1 glucose consumed. In contrast, YAAFA for YE-only medium remained at 0.77 g g-1. Therefore, pyruvate was metabolised solely by pyruvate-formate lyase when no CSL was present.
The highest SA yield obtained on glucose, SA titre and SA productivity were 0.91 g g-1, 48.5 g L-1 and 9.4 g L-1 h-1, respectively, all for medium containing CSL. Medium that included CSL significantly outperformed medium that excluded CSL, achieving 64%, 21% and 203% greater SA titres, yields on glucose and productivities respectively.
Metabolic flux analyses based on the established C3 and C4 metabolic pathways of Actinobacillus succinogenes revealed that the increase in YAASA, for CSL-containing fermentations, could not be attributed to the decrease in formate and biomass formation, and that an additional source of reducing power was present. The fraction of reducing power (NADH) unaccounted for increased with glucose consumption, suggesting that the maintenance or non-growth metabolism encountered at higher SA titres differs from the growth metabolism. It is postulated that the additional reducing power originates from an active pentose phosphate pathway in non-growing cells or from an undetected component(s) in the fermentation medium. No major metabolic flux variations were found in fermentations that excluded CSL. / Dissertation (MEng)--University of Pretoria, 2013. / gm2014 / Chemical Engineering / unrestricted
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Analysis of succinic acid-producing biofilms of Actinobacillus succinogenesMokwatlo, Sekgetho Charles 28 August 2020 (has links)
Biofilms of the bovine rumen bacterium Actinobacillus succinogenes have demonstrated their exceptional capabilities as biocatalysts for high productivity, titre and yield production of succinic acid (SA). Succinic acid is set to become a significant building block chemical in the biobased economy. Although substantial progress has been made towards understanding the productive aspect of this microorganism with regard to its metabolic limits and performance on unrefined biorefinery stream substrates, more research is still required to address other challenges. One aspect is to understand how the biofilm biocatalyst is affected by bioreactor conditions, which would help in developing stable and highly active biofilms. For this reason the aim of this thesis was (i) to characterise how the accumulation of acid metabolites in continuous operation impacts A. succinogenes biofilms with respect to biofilm development, biofilm structure and cell activity within the biofilm, (ii) to show how shear conditions in the fermenter can be used to manipulate the biofilm structure and viable cell content of biofilms, leading to improved cell-based succinic acid productivities, and lastly (iii) to investigate the internal mass transfer effects on biofilm performance, further showing the role played by differences in shear and acid accumulation conditions in this respect.
The first part of the study addressed the interaction between the biofilm and the accumulation of metabolites produced. The results showed that biofilms of A. succinogenes develop rapidly and with high activity when cultivated under low product accumulation (LPA) conditions (< 10 g L-1 SA). High product accumulation (HPA) conditions considerably slowed down biofilm development, and increased cell mortality. Under HPA conditions some cells exhibited severe elongation while maintaining a cross-sectional diameter like the rod/cocci-shaped cells predominantly found in LPA conditions. The elongated cells formed in HPA conditions were found to be more viable and thus more resistant than the clusters of rod-shaped or cocci-shaped cells. The global microscopic structure of the HPA biofilms also differed significantly from that of the LPA biofilms. Although both exhibited shedding after 4 days of growth, the LPA biofilms were more homogenous (less patchy), thicker and had high viability throughout the biofilm depth.
In the second part of the study, two custom-designed bioreactors were used to evaluate the effect of shear on the biofilms. The first bioreactor allowed for in situ removal of small biofilm samples used for microscopic imaging. The second bioreactor allowed for complete removal of all biofilm and was used to analyse biofilm composition and productivity. Results clearly indicated that high shear biofilm cultivation in LPA conditions has beneficial morphological, viability and cell-based productivity characteristics. The smooth, low-porosity biofilms obtained under high shear and LPA conditions had an average cell viability of 79% (over a 3-day cultivation period) compared with the low shear value of 57%, also developed under LPA conditions. The EPS content of the high shear biofilm was 58% compared with 7% of the low shear equivalent. The cell-based (EPS excluded) succinic acid productivity for the high shear biofilm was 2.4 g g-1DCW h-1 compared with the 0.8 g g-1DCW h-1 for the low shear biofilm. This threefold increase in productivity obtained from the second bioreactor corresponded to the cell viability differences obtained from the first bioreactor. Clear evidence was provided for shear-induced shaping of the biofilm which resulted in improved volumetric glucose turnover attributes within the biofilm matrix.
The last section of the study investigated internal mass transfer effects in biofilm fermentations of Actinobacillus succinogenes by performing batch fermentations using attached and resuspended biofilms as biocatalysts. In the latter, the biofilms were resuspended after initial development to simulate mass transfer-free fermentations. Intrinsic kinetics for succinic acid production obtained from resuspended fermentations predicted faster production rates than for the attached biofilm runs (biofilm thicknesses in the range of 120–200 µm), indicating internal mass transfer limitations. A developed biofilm reaction diffusion model gave good prediction of attached biofilm batch operation results by accounting for internal mass transfer in the biofilm. Biofilm effectiveness factors ranged from 75% to 97% for all batches at the inception of batch conditions, but increased with the progression of batch operation due to the increased succinic acid titres which inhibited the production rates. Analysis of pseudo-steady-state continuous fermentation data from the literature, as well as from the second part of the study, using the model developed, showed that active biofilm thickness and effectiveness factors were dependent on the shear conditions and succinic acid titres in the biofilm reactors. A simplified algorithm was developed to estimate the pseudo-steady-state glucose penetration and biofilm effectiveness of A. succinogenes biofilms without the requirement to solve the overall mass transfer model. The results clearly showed that internal mass transfer needs to be considered in biofilm fermentations involving A. succinogenes as high biomass concentrations may not always equate to increased productivities if mass transfer effects dominate. / Thesis (PhD)--University of Pretoria, 2020. / NRF / Chemical Engineering / PhD / Unrestricted
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Study on succinic acid extraction by liquid membranes and aqueous two-phase systems containing ionic liquids / イオン液体を含む液膜および水性2相法によるコハク酸の抽出に関する研究 / イオン エキタイ オ フクム エキマク オヨビ スイセイ 2ソウホウ ニヨル コハクサン ノ チュウシュツ ニカンスル ケンキュウプラティヴィ アウリア インダ, Aulia Indah Pratiwi 22 March 2015 (has links)
近年発酵生産が注目されているコハク酸の抽出分離法についてイオン液体を含む液膜法及び水性2相抽出法を用いて研究した.イオン液体を含む含浸型液膜により,受容相に塩酸水溶液を用いることでコハク酸の上り坂輸送を達成できた.次にイオン液体を含む高分子溶媒膜によるコハク酸の透過を検討した.最適な条件は含浸液膜と異なり,透過にはコハク酸の各化学種が関与していた.最後に水溶性有機溶媒やイオン液体を用いた水性2相抽出法によるコハク酸の抽出を行った.塩および糖を相分離剤とすることで,発酵液で想定されるコハク酸の80%以上の抽出が達成できた. / Succinic acid is widely used in many industrial sectors; pharmacy, textile, food, etc. The bio-production of succinic acid from renewable resource was desired because the petrochemical production of succinic acid became costly. In this study, the extraction and separation techniques of succinic acid by liquid membranes (LMs) and aqueous two-phase system (ATPS) containing ionic liquids (ILs) were exploited. The permeation mechanisms and optical conditions were elucidated. / 博士(工学) / Doctor of Philosophy in Engineering / 同志社大学 / Doshisha University
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Formation and physicochemical properties of crystalline and amorphous salts with different stoichiometries formed between ciprofloxacin and succinic acidPaluch, Krzysztof J., McCabe, T., Müller-Bunz, B., Corrigan, O.I., Healy, A.M., Tajber, L. 15 August 2013 (has links)
Yes / Multi-ionizable compounds, such as dicarboxylic
acids, offer the possibility of forming salts of drugs with
multiple stoichiometries. Attempts to crystallize ciprofloxacin,
a poorly water-soluble, amphoteric molecule with succinic acid
(S) resulted in isolation of ciprofloxacin hemisuccinate (1:1)
trihydrate (CHS-I) and ciprofloxacin succinate (2:1) tetrahydrate
(CS-I). Anhydrous ciprofloxacin hemisuccinate (CHS-II)
and anhydrous ciprofloxacin succinate (CS-II) were also
obtained. It was also possible to obtain stoichiometrically
equivalent amorphous salt forms, CHS-III and CS-III, by spray
drying and milling, respectively, of the drug and acid. Anhydrous CHS and CS had melting points at ∼215 and ∼228 °C, while
the glass transition temperatures of CHS-III and CS-III were ∼101 and ∼79 °C, respectively. Dynamic solubility studies revealed
the metastable nature of CS-I in aqueous media, resulting in a transformation of CS-I to a mix of CHS-I and ciprofloxacin 1:3.7
hydrate, consistent with the phase diagram. CS-III was observed to dissolve noncongruently leading to high and sustainable drug
solution concentrations in water at 25 and 37 °C, with the ciprofloxacin concentration of 58.8 ± 1.18 mg/mL after 1 h of the
experiment at 37 °C. This work shows that crystalline salts with multiple stoichiometries and amorphous salts have diverse
pharmaceutically relevant properties, including molecular, solid state, and solubility characteristics. / Solid State Pharmaceutical Cluster (SSPC), supported by Science Foundation Ireland under grant number 07/SRC/ B1158.
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Succinic acid production by wine yeastsDe Klerk, Jean-Louis 03 1900 (has links)
Thesis (MScAgric (Viticulture and Oenology))--University of Stellenbosch, 2010. / ENGLISH ABSTRACT: One of the most striking qualities of wine is its tart, sour taste. The sensory perception
of sourness is mainly attributed to the presence of hydrogen ions (protons) at high
concentrations. Large amounts of weak carboxylic acids (organic acids) are the main
sources of these ions within wine. Once wine enters a person's mouth, the dissociable
protons of the weak organic acids within wine are partially neutralized or, in other words,
titrated by the saliva secreted inside one's mouth. This explains why the duration and
intensity of a wine's sourness is related to its titratable acidity content. The sour taste of
wine is usually considered refreshing and it helps balance wine flavour. In fact, wines
become watery when its titratable acidity content is too low.
After alcoholic fermentation, the titratable acidity of wine will usually be less than
that of the grape juice from which was made due to ethanol-induced precipitation of
potassium bitartrate crystals and partial consumption of malic acid by fermenting
wine yeasts. Occasionally however, increases in titratable acidity are observed during
alcoholic fermentation. If wine is produced from grape juice with optimum levels of
titratable acidity, unforeseen increases in titratable acidity during alcoholic fermentation
can be detrimental to the quality of the final product.
Although the net production of malic acid by wine yeasts contributes to increases in
titratable acidity seen during grape juice fermentations, the production of succinic acid is
regarded as the primary contributor. In fact, succinic acid accounts for approximately
90% of the non-volatile acids produced during fermentation of grape juice. Between 0.5
and 1.5 g/L succinic acid is normally found in wine, but higher concentrations thereof
(up to 3.0 g/L) have been detected within certain red wines.
Acidity adjustments should preferably be carried out before the onset of alcoholic
fermentation to allow better integration of the added compound(s) and to ensure that
conditions during fermentation favour the quality and microbial stability of the final
product. In doing so unfortunately, winemakers run the risk of ending up with wines that
may taste too sour if they are unable to accurately predict and take into consideration
the amount of succinic acid produced during alcoholic fermentation. Knowledge with
regard to the factors involved in succinic acid's production by fermenting wine yeasts is
therefore required in order to manage the titratable acidity of wines more accurately.
Ever since Louis Pasteur first noticed succinic acid amongst the by-products of
alcoholic fermentation, attempts have been made to determine the metabolic pathways
and factors involved in its production by fermenting wine yeasts. Up until now however,
it remains unclear why wines sometimes end up with exceptionally high levels of
succinic acid.
For these reasons it was decided to investigate the possible causes of very high
succinic acid concentrations within wine. Due to complexity of grape juice's chemical
composition and the problems associated with sterilizing grape juice, fermentation
experiments were conducted within a chemically defined grape juice-like medium. Succinic acid production by nine different industrial wine yeast strains was studied
under various conditions with regard to the nutrient status of the synthetic grape juice,
temperature and availability of molecular oxygen during alcoholic fermentation.
The amount of succinic acid produced during alcoholic fermentation was found to
depend on the yeast strain, fermentation temperature and chemical composition of the
synthetic grape juice. Out of the nine commercial yeast strains selected for this study,
strain WE372 produced the largest amount of succinic acid in synthetic grape juice at
28°C. Strain WE372 produced significantly smaller amounts of acetic acid than the
other yeast strains of this study and very little acetic acid at 28°C, which indicated that
strain WE372 may have less acetaldehyde dehydroganase activity than the other yeast
strains of this study under the conditions tested. The effect this has on NAD: NADH
balance is the probable cause for its ability to form more glycerol, succinic and malic
acid than the other strains.
Results from our study show that succinic acid production is influenced primarily by the
metabolizable fraction of YAN, which we termed metabolically available nitrogen (MAN).
Succinic acid production by fermenting yeasts will be favoured by moderate to high
fermentation temperatures (20°C to 28°C) in grape juice with a nicotinic acid and/ or
nicotinamide deficiency, high sugar content (200 g/L to 240 g/L), moderate amounts of
metabolically available nitrogen (300 ± 50 mg/L MAN), the presence of flavonoids and
large supplies of unsaturated long-chain fatty acids. Even higher concentrations of
succinic acid were produced when oxygen was made available to fermenting yeasts by
aerating the fermenting grape juice. Fermentation temperatures below 18°C, too much
metabolizable nitrogen (> 450 mg/L MAN), very high concentrations of fermentable
sugar (> 240 g/L), lipid deficiencies and a lack of pantothenic acid, thiamine, biotin or
pyridoxine will decrease the amount of succinic acid produced fermenting yeasts. / No Afrikaans summary available.
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Potential study of chemical and pharmacological of secundary metabolites of coast cearense fungi: Aspergillus sp. / Estudo do potencial quÃmico e farmacolÃgico de metabÃlitos secundÃrios de fungos da costa cearense: Aspergillus sp.JoÃo Evangelista de Ãvila dos Santos 25 September 2015 (has links)
CoordenaÃÃo de AperfeiÃoamento de Pessoal de NÃvel Superior / This study aimed to the chemical and pharmacological research of biodiversity of marine fungi associated with sediment from the coastline of northeastern Brazil, especially the state of CearÃ. From the collection of marine sediments at the beach Pecem - SÃo GonÃalo do Amarante-CE, were cultivated various fungi, of which the strain identified as Aspergillus sp. (BRF 087), showed a preliminary cytotoxic activity. The methodology has been directed in finding secondary metabolites with cytotoxic activity using a kinetic fungus study was grown in four different media, BD (potato dextrose), BDL (potato dextrose and yeast), MPD (malt, peptone and dextrose ) and MntPL (mannitol, peptone and yeast) and in different culture periods (7, 14, 21, 28 days). This procedure resulted in the isolation of nine diketopiperazines two tetrapeptides cycle, 3 derivatives of succinic acid and p-hydroxyphenylacetic acid, characterized as cyclo (L-Pro-L-Leu) (A-1), cyclo (L-Pro-L -Phe) (A-2), cyclo (4-OH-Pro-Leu) (A-3), cyclo (4-OH-Pro-Phe) (A-4), cyclo (L-Pro-L-tyr ) (A-5), cyclo (L-Leu-L-Val) (A-6), cyclo (L-Phe-L-Val) (A-7), cyclo (L-Phe-L-Leu) (A-8), cyclo (L-Leu-L-Ile) (A-9), cyclo (L-Ile-L-Pro-L-Leu-L-Pro) (A-10), cyclo (Leu-Ile Leu-Phe) (A-11), 2-metilenosuccinic acid (A-12), 3-Methyl-2-metilenosuccinic (A-13), 4-metoxy-2-methylidene-4-oxobutanoic acid (A-14) and p-hydroxyphenylacetic acid (A-15). The isolation of secondary metabolites was conducted by using usual chromatographic techniques, including chromatography on reverse phase C18 column and high-performance liquid chromatography (HPLC). For structural characterization of the compounds were used customary spectrometric techniques like IR, mass spectrometry and nuclear magnetic resonance (NMR), one and two dimensional, and compared with literature data. / O presente trabalho teve como objetivo principal a investigaÃÃo quÃmico-farmacolÃgica da biodiversidade dos fungos marinhos associados a sedimentos da costa litorÃnea do Nordeste do Brasil, e em especial do estado do CearÃ. A partir da coleta de sedimentos marinhos na praia do PecÃm - SÃo GonÃalo do Amarante-CE, foram cultivados vÃrios fungos, dos quais a cepa identificada como Aspergillus sp. (BRF 087), mostrou uma atividade citotÃxica preliminar. A metodologia empregada foi direcionada na busca de metabÃlitos secundÃrios com atividade citotÃxica, atravÃs de um estudo cinÃtico do fungo que foi cultivado em quatro meios diferentes, BD (batata dextrose), BDL (batata dextrose e levedura), MPD (malte, peptona e dextrose) e MntPL (manitol, peptona e levedura) e em diferentes perÃodos de cultivo (7, 14, 21, 28 dias). Este procedimento resultou no isolamento de nove dicetopiperazinas, dois ciclo tetrapeptÃdeos, 3 derivados do Ãcido succinio e o Ãcido p-hidroxifenilacÃtico, caracterizados como ciclo (L-Pro-L-Leu) (A-1), ciclo (L-Pro-L-Fen) (A-2),ciclo (4-OH-Pro-Leu) (A-3), ciclo (4-OH-Pro-Fen) (A-4), ciclo (L-Pro-L-Tyr) (A-5), ciclo (L-Leu-L-Val) (A-6), ciclo (L-Fen-L-Val) (A-7), ciclo (L-Fen-L-Leu) (A-8), ciclo (L-Leu-L-Ile) (A-9), ciclo (L-Ile-L-Pro-L-Leu-L-Pro) (A-10), ciclo (Leu-Ile-Leu-Fen) (A-11), Ãcido 2-metilenosuccinio (A-12), Ãcido 3-metil-2-metilenosuccinio (A-13), Ãcido 4-metoxi-2-metileno-4-oxobutanÃico (A-14) e o Ãcido p-hidroxifenilacÃtico (A-15). O isolamento dos metabÃlitos secundÃrios foi realizado atravÃs do uso de tÃcnicas cromatogrÃficas usuais, incluindo cromatografia em coluna de fase reversa C18 e cromatografia lÃquida de alta eficiÃncia (CLAE). Para a caracterizaÃÃo estrutural dos compostos foram utilizadas tÃcnicas espectromÃtricas usuais como infravermelho, espectrometria de massa e ressonÃncia magnÃtica nuclear (RMN), uni e bidimensional, alÃm de comparaÃÃo com dados da literatura.
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Hydrogénation de l'acide succinique en phase aqueuse pour l'obtention sélective de 1,4-butanediol / Selective aqueous phase hydrogenation of succinic acid to 1,4-butanediolLy, Bao Khanh 16 April 2013 (has links)
Le but du projet est d’hydrogéner l’acide succinique en phase aqueuse à 160°C, sous 150 bar d’hydrogène pour obtenir sélectivement le 1,4-butanediol (BDO) en utilisant des catalyseurs x%Re-2%Pd/TiO2. Les catalyseurs monométalliques au palladium permettent d’obtenir sélectivement le produit intermédiaire : la γ-butyrolactone et très peu de BDO est obtenu. Leur activité catalytique est fonction de la dispersion de la phase métallique. L’addition de rhénium aux catalyseurs monométalliques au palladium permet de poursuivre la réaction jusqu’à l’obtention du BDO. Nous avons d’abord essayé deux méthodes d’addition ex situ de rhénium : réduction catalytique (RC) et imprégnation successive (IS). La meilleure sélectivité en BDO obtenue jusqu’à maintenant est de 90% en présence du solide 3,4%Re-2%Pd/TiO2 préparé par IS. Quelle que soit la méthode de dépôt (RC ou IS), le rhénium dans ces solides bimétalliques est réoxydé et lixivié dans la phase aqueuse sous l’atmosphère non réductrice. Malgré la lixiviation et le redépôt du rhénium sous hydrogène, le comportement des catalyseurs bimétalliques Re-Pd/TiO2 préparés ces deux méthodes reste différent. Le dépôt in situ de Re conduit à des catalyseurs bimétalliques prometteurs : SBDO = 73% avec 2% de rhénium déposé / The aim of our research project is the hydrogenation of the succinic acid in aqueous phase at 160°C, under 150 bar hydrogen to obtain selectively 1,4-butanediol (BDO) by using x%Re- 2%Pd/TiO2 catalyst. Palladium monometallic catalysts allow us to obtain selectively the intermediate product γ-butyrolactone and very little BDO. Their catalytic activity depends on the dispersion of the metallic phase. The reaction can be extended until obtaining BDO by adding the rhenium to palladium based monometallic catalysts. Firstly, we have tried two ex situ methods to add the rhenium: catalytic reduction (CR) and successive impregnation (SI). The best selectivity to BDO is 90% with the presence of 3,4%Re-2%Pd/TiO2 prepared by IS method. Moreover, for both deposition methods, the rhenium in the bimetallic catalysts is reoxidized with air and then leached into the aqueous phase. Despite leaching and redeposition of rhenium under hydrogen pressure, the behavior of bimetallic catalysts prepared by the two methods (CR and SI) is different. In situ deposition of the rhenium leads to promising bimetallic catalysts: SBDO = 73% with 2% of rhenium
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Hydrogenation of succinic acid and carbon dioxide over molybdenum carbide catalysts / Carbures de molybdène catalyseurs supportés pour hydrogénation de l'acide succinique et du dioxyde de carboneAbou Hamdan, Marwa 28 May 2019 (has links)
Ce travail de thèse porte sur la synthèse de carbures de molybdène sur support afin de tester leurs performances catalytiques dans des réactions d’hydrogénation. Dans ce but, la conversion d'acide succinique en phase aqueuse dans un réacteur discontinu et du dioxyde de carbone en phase gazeuse dans un réacteur à flux continu, ont été effectuées. Les catalyseurs ont été préparés par la méthode de carburation par réduction en température programmée, pendant laquelle des paramètres ont été modifiés conduisant à différents rapports molybdène/carbone. Les différents catalyseurs testés dans cette réaction étaient actifs pour la conversion de l'acide succinique en gamma-butyrolctone et, plus remarquablement, en acide butyrique, ce dernier n'était pas obtenu en quantités significatives avec des catalyseurs à base de métaux précieux. L’augmentation de la conversion d’acide succinique avec une sélectivité plus élevée en acide butyrique a été faite avec les catalyseurs contenant plus de carbone, préparés en augmentant la vitesse spatiale horaire gazeuse. Les intermédiaires ont été ensuite convertis en tétrahydrofurane, butanol, 1,4-butanediol et butane. La désactivation observée lors de recyclage du catalyseur a été principalement attribuée à une diminution de la quantité de molybdène et de carbone carbidique, démontrée par l'analyse XPS. Des essais préliminaires de ces catalyseurs dans l'hydrogénation du dioxyde de carbone ont montré qu'ils fonctionnaient principalement en tant que catalyseurs pour la réaction du gaz à l’eau inverse, et l'excès de carbone entrave l'activité catalytique d'une manière opposée à la réaction en phase aqueuse. Le support semble jouer un rôle dans la réactivité des catalyseurs, la conversion du dioxyde de carbone ainsi que la sélectivité en méthane et méthanol, qui ont augmenté dans l'ordre suivant: carbure de molybdène sur support DT51 TiO2> P25 TiO2 ˜ ZrO2 / This work focuses on the synthesis of supported molybdenum carbides and evaluating their catalytic performance in succinic acid hydrogenation reactions in aqueous phase using batch reactor and carbon dioxide hydrogenation in gas phase using continuous flow reactor. The catalysts were prepared by the temperature programmed reduction carburization method, where the parameters were modified leading to different molybdenum to carbon ratios. The different catalysts tested were active in converting succinic acid to gamma butyrolctone and more remarkably butyric acid which is not reported in significant quantities in this reaction with precious metal based catalysts. The catalysts containing more carbon contents that were prepared by increasing the gas hourly space velocity showed higher activity in converting succinic acid and higher selectivity to butyric acid. The intermediates were then converted to tetrahydrofuran, butanol, 1,4-butanediol and butane gas. The deactivation observed while recycling the catalyst was mainly attributed to a decrease in the amounts of carbidic molybdenum and carbidic carbon, as demonstrated by XPS analysis. Preliminary tests for these catalysts in carbon dioxide hydrogenation showed that they functioned mainly as reverse water gas shift catalysts, and the excess of carbon hinders the catalytic activity in an opposite manner of the reaction in aqueous phase. The support seems playing a role in the reactivity of the catalysts, carbon dioxide conversion as well as methane and methanol selectivity increased in the order: molybdenum carbide supported on DT51 TiO2 > P25 TiO2 ˜ ZrO2
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