Abstract: Lignin is a major constituent of woody biomass, and exists abundantly in nature. It is the major byproducts from the paper industry and bioethanol production processes. The byproducts are mainly used for low-valued applications. Instead, lignin can be converted into higher-valued gaseous fuel, thereby helping to curtail the ever-growing price of oil and to slow down the trend of global warming. Although biochemical treatment is capable of converting cellulose into liquid ethanol fuel, it cannot be applied to the conversion of lignin. Alternatively, it is possible to convert lignin into gaseous fuel thermochemically. In the present work, trans-4-hydroxycinnamic acid, a model compound for lignin, which closely resembles the basic building blocks of lignin, is gasified in an autoclave with ethanol at elevated temperatures and pressures, that are above the critical point of ethanol. Ethanol, instead of water, is chosen, because ethanol dissolves trans-4-hydroxycinnamic acid easily and helps to convert it into lighter gaseous species relatively well. The major operating parameters for the gasification reaction include temperature (673-873 K), reaction pressure (5-25 MPa) and feed concentration (0.05-0.3 M). Generally, more than 80% of the reactant, including trans-4-hydroxycinnamic acid and ethanol, were converted into gaseous products at an operating condition of 873 K and 5 MPa.
Abstract: Carbon dioxide is highly thermochemical stable molecules where it is very difficult to activate the molecule and achieve higher catalytic conversion into alcohols or other hydrocarbon compounds. In this paper, series of the bimetallic Cu/ZnO-based catalyst supported by SBA-15 were systematically prepared via impregnation technique with different Cu: Zn ratio for hydrogenation of CO2 to methanol. The synthesized catalysts were characterized by transmission electron microscopy (TEM), temperature programmed desorption, reduction, oxidation and pulse chemisorption (TPDRO), and surface area determination was also performed. All catalysts were tested with respect to the hydrogenation of CO2 to methanol in microactivity fixed-bed reactor at 250oC, 2.25 MPa, and H2/CO2 ratio of 3. The results demonstrate that the catalytic structure, activity, and methanol selectivity was strongly affected by the ratio between Cu: Zn, Where higher catalytic activity of 14 % and methanol selectivity of 92 % was obtained over Cu/ZnO-SBA-15 catalyst with Cu:Zn ratio of 7:3 wt. %. Comparing with the single catalyst, the synergetic between Cu and Zn provides additional active sites to adsorb more H2 and CO2 and accelerate the CO2 conversion, resulting in higher methanol production under mild reaction conditions.
Abstract: Nowadays, the main biofuels source production as bioethanol is food crops. This means a high competition between foods and energy production. For this reason, it is necessary to take into account the use of new raw materials friendly to the environment. The main objective of this paper is to evaluate the potential of the agro-industrial banana crop residues in the production of bioethanol. A factorial design of 24 was used, the design has variables such as pH, time and concentration of hydrolysis, another variable is the time of fermentation that is of 7 or 15 days. In the hydrolysis phase, the pH is acidic (H2SO4) or basic (NaOH), the time is 30 or 15 minutes and the concentration is 0.1 or 0.5 M. It was observed that basic media, low concentrations, fermentation, and higher pretreatment times produced better performance in terms of biofuel obtained.
Abstract: A systematic study was conducted to explore the photocatalytic reduction of carbon dioxide (CO2) into methanol on TiO2 loaded copper ferrite (CuFe2O4) photocatalyst under visible light irradiation. The phases and crystallite size of the photocatalysts were characterized by X-ray diffraction (XRD) and it indicates CuFe2O4 as tetragonal phase incorporation with anatase TiO2 in CuFe2O4/TiO2 hetero-structure. The XRD results confirmed the formation of spinel type tetragonal CuFe2O4 phases along with predominantly anatase phase of TiO2 in the CuFe2O4/TiO2 hetero-structure. UV-Vis absorption spectrum suggested the formation of the hetero-junction with relatively lower band gap than that of TiO2. Photoluminescence (PL) technique was used to study the electron–hole (e−/h+) recombination process. PL spectra analysis confirmed the slow-down of the recombination of electron–hole (e−/h+) pairs in the CuFe2O4/TiO2 hetero-structure. The photocatalytic performance of CuFe2O4/TiO2 was evaluated based on the methanol yield with varying amount of TiO2 over CuFe2O4 (0.5:1, 1:1, and 2:1) and changing light intensity. The mechanism of the photocatalysis was proposed based on the fact that the predominant species of CO2 in aqueous phase were dissolved CO2 and HCO3- at pH ~5.9. It was evident that the CuFe2O4 could harvest the electrons under visible light irradiation, which could further be injected to the conduction band of TiO2 to increase the life time of the electron and facilitating the reactions of CO2 to methanol. The developed catalyst showed good recycle ability up to four cycles where the loss of activity was ~25%. Methanol was observed as the main product over CuFe2O4, but loading with TiO2 remarkably increased the methanol yield. Methanol yield over CuFe2O4/TiO2 was found to be about three times higher (651 μmol/gcat L) than that of CuFe2O4 photocatalyst. This occurs because the energy of the band excited electrons lies above the redox potentials of the reaction products CO2/CH3OH.
Abstract: Three emerging contaminants (amitriptyline hydrochloride, methyl salicylate and 2-phenoxyethanol) frequently found in waste-waters were selected to be individually degraded in ultra-pure water by the combined advanced oxidation process constituted by UV radiation and chlorine. The influence of pH, initial chlorine concentration and nature of the contaminants was firstly explored. The trend for the reactivity of the selected compounds was deduced: amitriptyline hydrochloride > methyl salicylate > 2-phenoxyethanol. A later kinetic study was carried out and focused on the specific evaluation of the first-order rate constants and the determination of the partial contribution to the global reaction of the direct photochemical pathway and the radical pathway. A comparison between the rate constant values among photochemical experiments without and with the presence of Cl2 reveals a clear increase in the oxidation efficiency of the combined process with respect to the photochemical reaction alone. In a second stage, the simultaneous oxidation of mixtures of the selected contaminants in several types of water (ultrapure water, surface water from a reservoir, and two secondary effluents) was also performed by the same combination UV/Cl2 under more realistic operating conditions. The efficiency of this combined system UV/Cl2 was compared to other oxidants such as the UV/S2O82- and UV/H2O2 AOPs. Results confirmed that the UV/Cl2 system provides higher elimination efficiencies among the AOPs tested.
Abstract: Alumina supported platinum and tin catalysts with different loadings of Pt and Sn were prepared and characterized by low temperature N2 adsorption/desorption, H2-temperature programed reduction and CO pulse chemisorption. Pt and Sn below 1% loading were suitable for acetic acid hydrogenation. The best performance over 0.75Pt1Sn/Al2O3 can reach 87.55% conversion of acetic acid and 47.39% selectivity of ethanol. The operating conditions of acetic acid hydrogenation over 1Pt1Sn/Al2O3 were investigated. High reaction temperature can enhance the conversion of acetic acid, but it decreased total selectivity of ethanol and acetyl acetate. High pressure and low weight hourly space velocity were beneficial to both conversion of acetic acid and selectivity to ethanol.
Abstract: Lactulose is a synthetic disaccharide which has remarkable applications in food and pharmaceutical fields. Lactulose is not found in nature and it is produced by isomerization reaction of lactose in an alkaline environment. It should be noted that this reaction has a very low yield since significant amount of lactose stays un-reacted in the system. Basically, purification of lactulose is difficult and costly. Previous studies have revealed that solubility of lactose and lactulose are significantly different in ethanol. Considering the fact that solubility is also affected by temperature itself, we investigated the effect of ethanol and temperature on separation process of lactose from the syrup containing lactose and lactulose. For this purpose, a saturated solution containing lactulose and lactose was made at three different temperatures; 25⁰C (room temperature), 31⁰C, and 37⁰C first. Five samples containing 2g saturated solution was taken and then 2g, 3g, 4g, 5g, and 6g ethanol separately was added to the sampling tubes. Sampling tubes were kept at respective temperatures afterward. The concentration of lactose and lactulose after separation process measured and analyzed by High Performance Liquid Chromatography (HPLC). Results showed that ethanol has such a greater impact than operating temperature on purification process. Also, it was observed that the maximum rate of separation occurred at initial amount of added ethanol.
Abstract: Zymomonas mobilis is known as an example of the
uncoupled growth phenomenon. This microorganism also has a
unique metabolism that degrades glucose by the Entner–Doudoroff
(ED) pathway. In this paper, a genome-scale metabolic model
including 434 genes, 757 reactions and 691 metabolites was
reconstructed to simulate uncoupled growth and study its effect on
flux distribution in the central metabolism. The model properly
predicted that ATPase was activated in experimental growth yields of
Z. mobilis. Flux distribution obtained from model indicates that the
major carbon flux passed through ED pathway that resulted in the
production of ethanol. Small amounts of carbon source were entered
into pentose phosphate pathway and TCA cycle to produce biomass
precursors. Predicted flux distribution was in good agreement with
experimental data. The model results also indicated that Z. mobilis
metabolism is able to produce biomass with maximum growth yield
of 123.7 g (mol glucose)-1 if ATP synthase is coupled with growth
and produces 82 mmol ATP gDCW-1h-1. Coupling the growth and
energy reduced ethanol secretion and changed the flux distribution to
produce biomass precursors.
Abstract: In Brazil, there is a diverse fauna of social bees, known by Meliponinae or native stingless bees. These bees are important for providing a differentiated product, especially regarding unique sweetness, flavor, and aroma. However, information about the volatile fraction in honey produced by stingless native bees is still lacking. The aim of this work was to characterize the volatile compound profile of monofloral honey produced by jandaíra bees (Melipona subnitida Ducke) which used chanana (Turnera ulmifolia L.), malícia (Mimosa quadrivalvis) and algaroba (Prosopis juliflora (Sw.) DC) as their floral sources; and by uruçu bees (Melipona scutellaris Latrelle), which used chanana (Turnera ulmifolia L.), malícia (Mimosa quadrivalvis) and angico (Anadenanthera colubrina) as their floral sources. The volatiles were extracted using HS-SPME-GC-MS technique. The condition for the extraction was: equilibration time of 15 minutes, extraction time of 45 min and extraction temperature of 45°C. Through the results obtained, it was observed that the floral source had a strong influence on the aroma profile of the honey under evaluation, since the chemical profiles were marked primarily by the classes of terpenes, norisoprenoids, and benzene derivatives. Furthermore, the results obtained suggest the existence of differentiator compounds and potential markers for the botanical sources evaluated, such as linalool, D-sylvestrene, rose oxide and benzenethanol. These reports represent a valuable contribution to certifying the authenticity of those honey and provides for the first time, information intended for the construction of chemical knowledge of the aroma and flavor that characterize these honey produced in Brazil.
Abstract: Power law approximation was used in this study to evaluate the reaction orders of calcium oxide, CaO catalyzed transesterification of refined cottonseed oil and methanol. The kinetics study was carried out at temperatures of 45, 55 and 65 oC. The kinetic parameters such as reaction order 2.02 and rate constant 2.8 hr-1g-1cat, obtained at the temperature of 65 oC best fitted the kinetic model. The activation energy, Ea obtained was 127.744 KJ/mol. The results indicate that the transesterification reaction of the refined cottonseed oil using calcium oxide catalyst is approximately second order reaction.
Abstract: Carbon dioxide (CO2) emission to the environment is inevitable which is responsible for global warming. Photocatalytic reduction of CO2 to fuel, such as methanol, methane etc. is a promising way to reduce greenhouse gas CO2 emission. In the present work, Bi2S3/CdS was synthesized as an effective visible light responsive photocatalyst for CO2 reduction into methanol. The Bi2S3/CdS photocatalyst was prepared by hydrothermal reaction. The catalyst was characterized by X-ray diffraction (XRD) instrument. The photocatalytic activity of the catalyst has been investigated for methanol production as a function of time. Gas chromatograph flame ionization detector (GC-FID) was employed to analyze the product. The yield of methanol was found to increase with higher CdS concentration in Bi2S3/CdS and the maximum yield was obtained for 45 wt% of Bi2S3/CdS under visible light irradiation was 20 μmole/g. The result establishes that Bi2S3/CdS is favorable catalyst to reduce CO2 to methanol.
Abstract: Wetting efficiency of microstructures or nanostructures patterned on Si wafers is a real challenge in integrated circuits manufacturing. In fact, bad or non-uniform wetting during wet processes limits chemical reactions and can lead to non-complete etching or cleaning inside the patterns and device defectivity. This issue is more and more important with the transistors size shrinkage and concerns mainly high aspect ratio structures. Deep Trench Isolation (DTI) structures enabling pixels’ isolation in imaging devices are subject to this phenomenon. While low-frequency acoustic reflectometry principle is a well-known method for Non Destructive Test applications, we have recently shown that it is also well suited for nanostructures wetting characterization in a higher frequency range. In this paper, we present a high-frequency acoustic reflectometry characterization of DTI wetting through a confrontation of both experimental and modeling results. The acoustic method proposed is based on the evaluation of the reflection of a longitudinal acoustic wave generated by a 100 µm diameter ZnO piezoelectric transducer sputtered on the silicon wafer backside using MEMS technologies. The transducers have been fabricated to work at 5 GHz corresponding to a wavelength of 1.7 µm in silicon. The DTI studied structures, manufactured on the wafer frontside, are crossing trenches of 200 nm wide and 4 µm deep (aspect ratio of 20) etched into a Si wafer frontside. In that case, the acoustic signal reflection occurs at the bottom and at the top of the DTI enabling its characterization by monitoring the electrical reflection coefficient of the transducer. A Finite Difference Time Domain (FDTD) model has been developed to predict the behavior of the emitted wave. The model shows that the separation of the reflected echoes (top and bottom of the DTI) from different acoustic modes is possible at 5 Ghz. A good correspondence between experimental and theoretical signals is observed. The model enables the identification of the different acoustic modes. The evaluation of DTI wetting is then performed by focusing on the first reflected echo obtained through the reflection at Si bottom interface, where wetting efficiency is crucial. The reflection coefficient is measured with different water / ethanol mixtures (tunable surface tension) deposited on the wafer frontside. Two cases are studied: with and without PFTS hydrophobic treatment. In the untreated surface case, acoustic reflection coefficient values with water show that liquid imbibition is partial. In the treated surface case, the acoustic reflection is total with water (no liquid in DTI). The impalement of the liquid occurs for a specific surface tension but it is still partial for pure ethanol. DTI bottom shape and local pattern collapse of the trenches can explain these incomplete wetting phenomena. This high-frequency acoustic method sensitivity coupled with a FDTD propagative model thus enables the local determination of the wetting state of a liquid on real structures. Partial wetting states for non-hydrophobic surfaces or low surface tension liquids are then detectable with this method.
Abstract: In Algeria, the conditioning units of dates, generate
significant quantities of waste arising from sorting deviations. This
biomass, until then considered as a waste with high impact on the
environment can be transformed into high value added product. It is
possible to develop common dates of low commercial value, and put
on the local and international market a new generation of products
with high added values such as bio ethanol. Besides its use in
chemical synthesis, bio ethanol can be blended with gasoline to
produce a clean fuel while improving the octane.
Abstract: This work studies the effect of chemical composition
on the activity and selectivity of γ–alumina supported CuO/
MnO2/Cr2O3 catalysts toward deep oxidation of CO, dimethyl ether
(DME) and methanol. The catalysts were prepared by impregnation
of the support with an aqueous solution of copper nitrate, manganese
nitrate and CrO3 under different conditions. Thermal, XRD and TPR
analysis were performed. The catalytic measurements of single
compounds oxidation were carried out on continuous flow equipment
with a four-channel isothermal stainless steel reactor. Flow-line
equipment with an adiabatic reactor for simultaneous oxidation of all
compounds under the conditions that mimic closely the industrial
ones was used. The reactant and product gases were analyzed by
means of on-line gas chromatographs.
On the basis of XRD analysis it can be concluded that the active
component of the mixed Cu-Mn-Cr/γ–alumina catalysts consists of at
least six compounds – CuO, Cr2O3, MnO2, Cu1.5Mn1.5O4,
Cu1.5Cr1.5O4 and CuCr2O4, depending on the Cu/Mn/Cr molar ratio.
Chemical composition strongly influences catalytic properties, this
influence being quite variable with regards to the different processes.
The rate of CO oxidation rapidly decrease with increasing of
chromium content in the active component while for the DME was
observed the reverse trend. It was concluded that the best
compromise are the catalysts with Cu/(Mn + Cr) molar ratio 1:5 and
Mn/Cr molar ratio from 1:3 to 1:4.
Abstract: Strong anion exchange resins with QN+OH-, have the
potential to be developed and employed as heterogeneous catalyst for
transesterification, as they are chemically stable to leaching of the
functional group. Nine different SIERs (SIER1-9) with QN+OH-were
prepared by suspension polymerization of vinylbenzyl chloridedivinylbenzene
(VBC-DVB) copolymers in the presence of n-heptane
(pore-forming agent). The amine group was successfully grafted into
the polymeric resin beads through functionalization with
trimethylamine. These SIERs are then used as a catalyst for the
transesterification of triacetin with methanol. A set of differential
equations that represents the Langmuir-Hinshelwood-Hougen-
Watson (LHHW) and Eley-Rideal (ER) models for the
transesterification reaction were developed. These kinetic models of
LHHW and ER were fitted to the experimental data. Overall, the
synthesized ion exchange resin-catalyzed reaction were welldescribed
by the Eley-Rideal model compared to LHHW models,
with sum of square error (SSE) of 0.742 and 0.996, respectively.
Abstract: Kigelia africana (Lam.) Benth. (Bignoniaceae) is a
reputed traditional remedy for various human ailments such as skin
diseases, microbial infections, melanoma, stomach troubles,
metabolic disorders, malaria and general pains. In spite of the fruit
being widely used for purposes related to its antibacterial and
antifungal properties, the chemical constituents associated with the
activity have not been fully identified. To elucidate the active
principles, we evaluated the antimicrobial activity of fruit extracts
and purified fractions against Staphylococcus aureus, Enterococcus
faecalis, Moraxella catarrhalis, Escherichia coli, Candida albicans
and Candida tropicalis. Shade-dried fruits were powdered and
extracted with hydroalcoholic (1:1) mixture by soaking at room
temperature for 72 h. The crude extract was further fractionated by
column chromatography, with successive elution using hexane,
dichloromethane, ethyl acetate, acetone and methanol. The
dichloromethane and ethyl acetate fractions were combined and
subjected to column chromatography to furnish a wax and oil from
the eluates of 20% and 40% ethyl acetate in hexane, respectively. The
GC-MS and GC×GC-MS results revealed that linoleic acid, linolenic
acid, palmitic acid, arachidic acid and stearic acid were the major
constituents in both oil and wax. The crude hydroalcoholic extract
exhibited the strongest activity with MICs of 0.125-0.5 mg/mL,
followed by the ethyl acetate (MICs = 0.125-1.0 mg/mL),
dichloromethane (MICs = 0.250-2.0 mg/mL), hexane (MICs = 0.25-
2.0 mg/mL), acetone (MICs = 0.5-2.0 mg/mL) and methanol (MICs =
1.0-2.0 mg/mL), whereas the wax (MICs = 2.0-4.0 mg/mL) and oil
(MICs = 4.0-8.0 mg/mL) showed poor activity. The study concludes
that synergistic interactions of chemical constituents could be
responsible for the antimicrobial activity of K. africana fruits, which
needs a more holistic approach to understand the mechanism of its
antimicrobial activity.
Abstract: This experimental study aims at studying the
conversion of macro-algae into bioethanol under several steps of
procedure: preparation, pre-treatment, fermentation, and distillation.
The main objective of this work was to investigate the role of buffer’s
type as a stabiliser of pH level and fermentation time on the yield of
ethanol. For this purpose, experiments were carried out on biomass
macro-algae to de-couple the pre-treatment and fermentation
processes from those associated with distillation process. β-
glucosidase was used as cellulose decomposer during hydrolysis step
and yeast was used during fermentation process. The species of
macro-algae utilised as energy feedstock was Ulva lactuca and it was
harvested from southern coast of Central of Java Island – Indonesia.
Experiments were conducted in a simple fermenter over a different
buffer: citrate buffer and acetic buffer, and over a range of
fermentation times between 5 to 20 days. The ethanol production was
found to be significantly affected by both variables. The optimum
time of fermentation was 10 days with citrate buffer; result in
0.88458% of ethanol, and the ethanol content after distillation
process was shown 0.985015%.
Abstract: The fight against climate change and the replacement
of fossil energies nearing exhaustion gradually emerge as major
societal and economic challenges. It is possible to develop common
dates of low commercial value, and put on the local and international
market a new generation of products with high added values such as
bio ethanol. Besides its use in chemical synthesis, bio ethanol can be
blended with gasoline to produce a clean fuel while improving the
octane.
Abstract: Abundant and cheap agricultural waste of oil palm trunk (OPT) juice was used to produce bioethanol. Two strains of Saccharomyces cerevisiae and a strain of Pichia stipitis were used to produce bioethanol from the OPT juice. Fermentation was conducted at previously optimized condition at 30oC and without shaking. The kinetic parameters were estimated and calculated. Monod equation and Hinshelwood model is used to relate the specific growth to the concentration of the limiting substrate and also to simulate bioethanol production rate. Among the three strains, single S. cerevisiae Kyokai no. 7 produce the highest ethanol yield of 0.477 g/l.h within the shortest time (12 h). This yeast also produces more than 20 g/l ethanol concentration within 10 h of fermentation.
Abstract: Natural dye extracted from Caesalpinia sappan Linn. was applied to a cotton fabric and silk yarn by dyeing process. The dyestuff component of Caesalpinia sappan Linn. was extracted using water and ethanol. Analytical studies such as UV–VIS spectrophotometry and gravimetric analysis were performed on the extracts. Brazilein, the major dyestuff component of Caesalpinia sappan Linn. was confirmed in both aqueous and ethanolic extracts by UV–VIS spectrum. The color of each dyed material was investigated in terms of the CIELAB (L*, a* and b*) and K/S values. Cotton fabric dyed without mordant had a shade of reddish-brown, while those post-mordanted with aluminum potassium sulfate, ferrous sulfate and copper sulfate produced a variety of wine red to dark purple color shades. Cotton fabric and silk yarn dyeing was studied using aluminum potassium sulfate as a mordant. The observed color strength was enhanced with increase in mordant concentration.