Abstract: An ammonium based ionic liquid (methyltrioctylammonium chloride) [N8 8 8 1] [Cl] was investigated as an extraction potential solvent for volatile organic solvents (in this regard, solutes), which includes alkenes, alkanes, ketones, alkynes, aromatic hydrocarbons, tetrahydrofuran (THF), alcohols, thiophene, water and acetonitrile based on the experimental activity coefficients at infinite THF measurements were conducted by the use of gas-liquid chromatography at four different temperatures (313.15 to 343.15) K. Experimental data of activity coefficients obtained across the examined temperatures were used in order to calculate the physicochemical properties at infinite dilution such as partial molar excess enthalpy, Gibbs free energy and entropy term. Capacity and selectivity data for selected petrochemical extraction problems (heptane/thiophene, heptane/benzene, cyclohaxane/cyclohexene, hexane/toluene, hexane/hexene) were computed from activity coefficients data and compared to the literature values with other ionic liquids. Evaluation of activity coefficients at infinite dilution expands the knowledge and provides a good understanding related to the interactions between the ionic liquid and the investigated compounds.
Abstract: Next generation bio-alcohols produced from non-food based sources like cellulosic biomass are promising renewable energy sources. The present study investigates engine performance, combustion characteristics, and emissions of a small single cylinder direct injection diesel engine fueled by four kinds of next generation bio-alcohol isomer and diesel fuel blends with a constant blending ratio of 3:7 (mass). The tested bio-alcohol isomers here are n-butanol and iso-butanol (C4 alcohol), and n-pentanol and iso-pentanol (C5 alcohol). To obtain simultaneous reductions in NOx and smoke emissions, the experiments employed supercharging combined with EGR (Exhaust Gas Recirculation). The boost pressures were fixed at two conditions, 100 kPa (naturally aspirated operation) and 120 kPa (supercharged operation) provided with a roots blower type supercharger. The EGR rates were varied from 0 to 25% using a cooled EGR technique. The results showed that both with and without supercharging, all the bio-alcohol blended diesel fuels improved the trade-off relation between NOx and smoke emissions at all EGR rates while maintaining good engine performance, when compared with diesel fuel operation. It was also found that regardless of boost pressure and EGR rate, the ignition delays of the tested bio-alcohol isomer blends are in the order of iso-butanol > n-butanol > iso-pentanol > n-pentanol. Overall, it was concluded that, except for the changes in the ignition delays the influence of bio-alcohol isomer blends on the engine performance, combustion characteristics, and emissions are relatively small.
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: This study explored the effects of different organic solvents, temperature, and the amount of glycerol on the alcohol dehydrogenase (ADH)-catalysed stereoselective reduction of different ketones. These conversions were then analyzed by gas chromatography. It was found that when the amount of deep eutectic solvents (DES) increases, it can improve the stereoselectivity of the enzyme although reducing its ability to convert the substrate into the corresponding alcohol. Moreover, glycerol was found to have a strong stabilizing effect on the ADH from Ralstonia sp. (E. coli/ RasADH). In the case of organic solvents, it was observed that the best conversions into the alcohols were achieved with DMSO and hexane. It was also observed that temperature decreased the ability of the enzyme to convert the substrates into the products and also affected the selectivity. In addition to that, the recycling of DES up to three times gave good conversions and enantiomeric excess results and glycerol showed a positive effect in the stability of various ADHs. Using RasADH, a good conversion and enantiomeric excess into the S-alcohol were obtained. It was found that an enhancement of the temperature disabled the stabilizing effect of glycerol and decreased the stereoselectivity of the enzyme. However, for other ADHs a temperature increase had an opposite positive effect, especially with ADH-T from Thermoanaerobium sp. One of the objectives of this study was to see the effect of cofactors such as NAD(P) on the biocatlysis activities of ADHs.
Abstract: Ionic liquids are finding a wide range of applications from reaction media to separations and materials processing. In these applications, Vapor–Liquid equilibrium (VLE) is the most important one. VLE for six systems at 353 K and activity coefficients at infinite dilution [(γ)_i^∞] for various solutes (alkanes, alkenes, cycloalkanes, cycloalkenes, aromatics, alcohols, ketones, esters, ethers, and water) in the ionic liquids (1-ethyl-3-methylimidazolium bis (trifluoromethylsulfonyl)imide [EMIM][BTI], 1-hexyl-3-methyl imidazolium bis (trifluoromethylsulfonyl) imide [HMIM][BTI], 1-octyl-3-methylimidazolium bis(trifluoromethylsulfonyl) imide [OMIM][BTI], and 1-butyl-1-methylpyrrolidinium bis (trifluoromethylsulfonyl) imide [BMPYR][BTI]) have been used to train neural networks in the temperature range from (303 to 333) K. Densities of the ionic liquids, Hildebrant constant of substances, and temperature were selected as input of neural networks. The networks with different hidden layers were examined. Networks with seven neurons in one hidden layer have minimum error and good agreement with experimental data.
Abstract: The biomass-based fuels have become great concern in order to replace the petroleum-based fuels. Biofuels are a wide range of fuels referred to liquid, gas and solid fuels produced from biomass. Recently, higher chain alcohols such as 3-methyl-1-butanol and isobutanol have become a better candidate compared to bioethanol in order to replace gasoline as transportation fuel. Therefore, in this study, 3-methyl-1-butanol was produced through a fermentation process by yeast. Several types of yeast involved in this research including Saccharomyces cerevisiae, Kluyveromyces lactis GG799 and Pichia pastoris (KM71H, GS115 and X33). The result obtained showed that K. lactis GG799 gave the highest concentration of 3-methyl-1-butanol at 274 mg/l followed by S. cerevisiae, P. pastoris GS115, P. pastoris KM71H and P. pastoris X33 at 265 mg/l, 190 mg/l, 182 mg/l and 174 mg/l respectively. Based on the result, it proved that yeast have a potential in producing 3-methyl-1-butanol naturally.
Abstract: Jojoba oil-wax is extracted from the seeds of the jojoba (Simmondsia chinensis Link Schneider), a perennial shrub that grows in semi desert areas in Egypt and in some parts of the world. The main uses of jojoba oil-wax are in the cosmetics and pharmaceutical industry, but new uses could arise related to the search of new energetic crops. This paper summarizes a process to convert the jojoba oil-wax to biodiesel by transesterification with ethanol and a series of aliphatic alcohols using a more economic and energy saving method in a domestic microwave. The effect of time and power of the microwave on the extent of the transesterification using ethanol and other aliphatic alcohols has been studied. The separation of the alkyl esters from the fatty alcohols rich fraction has been done in a single crystallization step at low temperature (−18°C) from low boiling point petroleum ether. Gas chromatography has been used to follow up the transesterification process. All products have been characterized by spectral analysis.
Abstract: Steam reforming is industrially important as it is
incorporated in several major chemical processes including the
production of ammonia, methanol, hydrogen and ox alcohols. Due to
the strongly endothermic nature of the process, a large amount of heat
is supplied by fuel burning (commonly natural gas) in the furnace
chamber. Reaction conversions, tube catalyst life, energy
consumption and CO2 emission represent the principal factors
affecting the performance of this unit and are directly influenced by
the high operating temperatures and pressures.
This study presents a simulation of the performance of the
reforming of methane in a primary reformer, through a developed
empirical relation which enables to investigate the effects of
operating parameters such as the pressure, temperature, steam to
carbon ratio on the production of hydrogen, as well as the fraction of
non converted methane.
It appears from this analysis that the exit temperature Te, the
operating pressure as well the steam to carbon ratio has an important
effect on the reforming of methane.
Abstract: This work focused on the interactions which occur between ester solvents and alcohol solutes. The alcohols selected ranged from the simplest alcohol (methanol) to C10-alcohols, and solubility predictions in the form of infinite dilution activity coefficients were made using the Modified UNIFAC Dortmund group contribution model. The model computation was set up on a Microsoft Excel spreadsheet specifically designed for this purpose. It was found that alcohol/ ester interactions yielded an increase in activity coefficients (i.e. became less soluble) with an increase in the size of the ester solvent molecule. Furthermore, activity coefficients decreased with an increase in the size of the alcohol solute. The activity coefficients also decreased with an increase in the degree of unsaturation of the ester hydrocarbon tail. Tertiary alcohols yielded lower activity coefficients than primary alcohols. Finally, cyclic alcohols yielded higher activity coefficients than straight-chain alcohols until a point is reached where the trend is reversed, referred to as the ‘crossover’ point.
Abstract: The studying of enzymatic esterification of carboxylic
acids and higher alcohols was performed by esterase Saccharomyces
cerevisiae in water-organic medium. Investigation of the enzyme
specificity to acetic substrates showed the best result with acetic acid
in esterification reactions with ethanol whereas within other
carboxylic acids the esterification decreased with acids: hexanoic >
pentanoic > butyric > decanoic. In relation to higher alcohols C3-C5,
esterification increased with alcohols propanol < butanol < amylol.
Also it was determined that esterase was more specific to alcohols
with branched chain such as isobutyl alcohol and isoamyl alcohol.
Data obtained may have important practical implications, for
example, for application of yeast esterase in producing various
volatile esters as well as in enzymatic transformation of volatile acids
and toxic fusel alcohols into volatile esters by providing the
production of the high quality alcoholic beverages with redused
content of higher alcohols as well as with improved degustational and
hygienic properties.
Abstract: Commercially available lipases (Candida antarctica lipase B, Novozyme 435, Thermomyces lanuginosus lipase, and Lipozyme TL IM), as well as sol-gel immobilized lipases, have been screened for their ability to acylate regioselectively xylitol, sorbitol, and mannitol with a phenolic ester in a binary mixture of t-butanol and dimethylsulfoxide. HPLC and MALDI-TOF MS analysis revealed the exclusive formation of monoesters for all studied sugar alcohols. The lipases immobilized by the sol-gel entrapment method proved to be efficient catalysts, leading to high conversions (up to 60%) in the investigated acylation reactions. From a sequence of silane precursors with different nonhydrolyzable groups in their structure, the presence of octyl and i-butyl group was most beneficial for the catalytic activity of sol-gel entrapped lipases in the studied process.
Abstract: The influence of copper promoters and reaction
conditions on the formation of alcohols byproducts of a common
Fischer-Tropsch synthesis used iron-based catalysts were investigated.
A good compromise of 28%Cu/FeKLaSiO2 can lead to the
optimization of an improved Fischer-Tropsch catalyst. The product
distribution shifts towards hydrocarbons with increasing the reaction
temperature, while pressure promotes the formation of alcohols. It was
found that the production of either alcohols or hydrocarbons followed
A-S-F distributions, and their α parameters were essentially different
which indicated a competition in the growing chain between the two
species. TPD after acetaldehyde adsorption gave strong evidence of
the insertion of a C1 oxygen-containing species into an alkyl chain.
Abstract: Attempt was made to improve certain characteristics of bio-oil derived from palm kernel pyrolysis by blending it with diesel fuel and alcohols. Two types of alcohol, ethanol or butanol, was used as cosolvent to stabilize the phase of ternary systems. Phase behaviors and basic fuel properties of palm kernel bio-oildiesel- alcohol systems were investigated in this study. Alcohol types showed a significant influence on the phase characteristics with palm kernel bio-oil-diesel-butanol system giving larger soluble area than that of palm kernel bio-oil-diesel-ethanol system. For fuel properties, blended fuels showed superior properties including lower values of density (~860 kg/m3 at 25°C), viscosity (~4.12 mm2/s at 40°C), carbon residue (1.02-2.53 wt%), ash (0.018-0.034 wt%) and pour point (
Abstract: Sol-gel immobilization of enzymes, which can improve considerably their properties, is now one of the most used techniques. By deposition of the entrapped lipase on a solid support, a new and improved biocatalyst was obtained, which can be used with excellent results in acylation reactions. In this paper, lipase B from Candida antarctica was double immobilized on different adsorbents. These biocatalysts were employed in the kinetic resolution of several aliphatic secondary alcohols in organic medium. High total recovery yields of enzymatic activity, up to 560%, were obtained. For all the studied alcohols the enantiomeric ratios E were over 200. The influence of the reaction medium was studied for the kinetic resolution of 2-pentanol.
Abstract: Adsorption of methanol and ethanol over mesoporous
siliceous material are studied in the current paper. The pure
mesoporous silica is prepared using tetraethylorthosilicate (TEOS) as
silica source and dodecylamine as template at low pH. The prepared
material was characterized using nitrogen adsorption,nX-ray
diffraction (XRD) and scanning electron microscopy (SEM). The
adsorption kinetics of methanol and ethanol from aqueous solution
were studied over the prepared mesoporous silica material. The
percent removal of alcohol was calculated per unit mass of adsorbent
used. The 1st order model is found to be in agreement with both
adsorbates while the 2nd order model fit the adsorption of methanol
only.
Abstract: The performance of a sucrose-based H2 production in
a completely stirred tank reactor (CSTR) was modeled by neural
network back-propagation (BP) algorithm. The H2 production was
monitored over a period of 450 days at 35±1 ºC. The proposed model
predicts H2 production rates based on hydraulic retention time
(HRT), recycle ratio, sucrose concentration and degradation, biomass
concentrations, pH, alkalinity, oxidation-reduction potential (ORP),
acids and alcohols concentrations. Artificial neural networks (ANNs)
have an ability to capture non-linear information very efficiently. In
this study, a predictive controller was proposed for management and
operation of large scale H2-fermenting systems. The relevant control
strategies can be activated by this method. BP based ANNs modeling
results was very successful and an excellent match was obtained
between the measured and the predicted rates. The efficient H2
production and system control can be provided by predictive control
method combined with the robust BP based ANN modeling tool.
Abstract: The epoxidation of soybean oil at temperature of 600C
was provided the best result in terms of attaching the –OH
functionality. Temperatures below and above 600C it is likely the
attaching reaction did not proceed sufficiently fast. The considerable
yield below 40%, implies the oil is not completely converted, it is not
possible by conventional methods, because the epoxide decomposes
at the temperature required. The objective of this work was the
development of catalyst toward the conversion of epoxide and polyol
with reaction temperature at 50,60, and 700C. The effect of different
type of catalyst were studied, the effect of alcohols with different
molecular configuration was determined which leads to selective
addition of alcohols to the epoxide oils.
Abstract: Chemical detection is still a continuous challenge when
it comes to designing single-walled carbon nanotube (SWCNT)
sensors with high selectivity, especially in complex chemical
environments. A perfect example of such an environment would be in
thermally oxidized soybean oil. At elevated temperatures, oil oxidizes
through a series of chemical reactions which results in the formation of
monoacylglycerols, diacylglycerols, oxidized triacylglycerols, dimers,
trimers, polymers, free fatty acids, ketones, aldehydes, alcohols,
esters, and other minor products. In order to detect the rancidity of
oxidized soybean oil, carbon nanotube chemiresistor sensors have
been coated with polyethylenimine (PEI) to enhance the sensitivity
and selectivity. PEI functionalized SWCNTs are known to have a high
selectivity towards strong electron withdrawing molecules. The
sensors were very responsive to different oil oxidation levels and
furthermore, displayed a rapid recovery in ambient air without the
need of heating or UV exposure.
Abstract: Lipases are enzymes particularly amenable for
immobilization by entrapment methods, as they can work equally
well in aqueous or non-conventional media and long-time stability of
enzyme activity and enantioselectivity is needed to elaborate more
efficient bioprocesses. The improvement of Pseudomonas
fluorescens (Amano AK) lipase characteristics was investigated by
optimizing the immobilization procedure in hybrid organic-inorganic
matrices using ionic liquids as additives. Ionic liquids containing a
more hydrophobic alkyl group in the cationic moiety are beneficial
for the activity of immobilized lipase. Silanes with alkyl- or aryl
nonhydrolizable groups used as precursors in combination with
tetramethoxysilane could generate composites with higher
enantioselectivity compared to the native enzyme in acylation
reactions of secondary alcohols. The optimal effect on both activity
and enantioselectivity was achieved for the composite made from
octyltrimethoxysilane and tetramethoxysilane at 1:1 molar ratio (60%
increase of total activity following immobilization and enantiomeric
ratio of 30). Ionic liquids also demonstrated valuable properties as
reaction media for the studied reactions, comparable with the usual
organic solvent, hexane.