Conversion of lignocellulosics pretreated with liquid hot water to ethanol

Lignocellulosic materials pretreated using liquid hot water (LHW) (220°C, 5 MPa, 120 s) were fermented to ethanol by batch simultaneous saccharification and fermentation (SSF) usingSaccharomyces cerevisiae in the presence ofTrichoderma reesei cellulase. SSF of sugarcane bagasse (as received), aspen chips (smallest dimension 3 mm), and mixed hardwood flour (−60 +70 mesh) resulted in 90% conversion to ethanol in 2–5 d at enzyme loadings of 15–30 FPU/g. In most cases, 90% of the final conversion was achieved within 75 h of inoculation. Comminution of the pretreated substrates did not affect the conversion to ethanol. The hydrolysate produced from the LHW pretreatment showed slight inhibition of batch growth ofS. cerevisiae. Solids pretreated at a concentration of 100 g/L were as reactive as those pretreated at a lower concentration, provided that the temperature was maintained at 220°C.     

Alternative fuels from biomass and their impact on carbon dioxide accumulation

Applied Biochemistry and Biotechnology - A number of transportation fuels can be produced from renewable resources. The major fractions of lignocellulosic biomass, cellulose and hemicellulose, can...     

The determination of dissolved organic carbon in sea water

For most oceanographic applications, methods based on wet oxidation of the organic fraction, followed by stripping of the resulting CO₂ and measurement in the gas phase by non-dispersing infrared detectors give acceptable results. Oxidation by high-intensity ultraviolet light has advantages, particularly in ease of automation, over persulfate oxidation.     

Electrosynthesis of carboxylic acids from organic halides and carbon dioxide

The electrocarboxylation of a large variety of organic halides is achieved in simple and mild conditions in diaphragm-less cells.     

Cellulase production on bagasse pretreated with hot water

Because pretreatment of biomass with hot water only in differential flow systems offers very digestible cellulose and potentially less inhibition by liquid hydrolysate, solids and liquid hydrolysate from bagasse pretreated with hot water were fed to a batch cellulase production system using the Rut C30 strain of Trichoderma reesei to determine the suitability of these substrates for cellulase production. The organism was found to be sensitive to inhibitors in the liquid hydrolysate but could be adapted to improve its tolerance. In addition, filtering of the material reduced inhibitory effects. The organism was also sensitive to some component in the solids, and they had to be washed heavily to achieve good growth and cellulase production rates. Even then, a lag was found before enzyme production would commence on pretreated solids whereas no such lag was experienced with Solka Floc. However, once enzyme production began, as high and even somewhat greater cellulase productivities were realized with washed pretreated solids. Adding lignin to Solka Floc delayed enzyme production, suggesting that lignin or other materials in the lignin solids could cause the lag observed for pretreated bagasse, but more studies are needed to resolve the actual reason for this delay.     

Production of organic acids from biomass resources

Catalytic synthesis of valuable organic acids such as lactic acid, levulinic acid, formic acid, acetic acid, 2, 5-furandicarboxylic acid (FDCA), and sugar acids (e.g. gluconic acid and glucosaminic acid) from renewable carbon resources is of high interest for a sustainable chemical industry in the future. A number of efficient catalytic systems have been recently developed to convert biomass into organic acids. Herein we highlight new strategies and catalysts that are effective for the transformations. The mechanisms and catalyst functions involved in several typical reactions are analyzed for the rational design of more efficient catalytic systems.     

Vapor+liquid equilibrium of water, carbon dioxide, and the binary system, water+carbon dioxide, from molecular simulation

NVT- and NpT-Gibbs ensemble Monte Carlo (GEMC) simulations were applied to describe the vapor–liquid equilibrium of water (between 323 and 573 K), carbon dioxide (between 230 and 290 K) and their binary mixtures (between 348 and 393 K). The properties of supercritical carbon dioxide were determined between 310 and 520 K by NpT-MC simulations. Literature data for the effective pair potentials (for water: the SPC-, SPC/E-, and TIP4P potential models; for carbon dioxide: the EPM2 potential model) were used to describe the properties of the pure substances. The vapor pressures of water and carbon dioxide are calculated. For water, the SPC- and TIP4P models give superior results for the vapor pressure when compared to the SPC/E model. The vapor–liquid equilibrium of the binary mixture, carbon dioxide–water, was predicted using the SPC- as well as the TIP4P model for water and the EPM2 model for carbon dioxide. The interactions between carbon dioxide and water were estimated from the pair potentials of the pure components using common mixing rules without any adjustable binary parameter. Agreement of the predicted data for the compositions of the coexisting phases in vapor–liquid equilibrium and experimental results is observed within the statistical uncertainties of the simulation results in the investigated range of state, i.e. at pressures up to about 20 MPa.     

A vibrational spectroscopic study of structure evolution of water dissolved in supercritical carbon dioxide under isobaric heating

A combination of Raman scattering spectroscopy and infrared absorption was applied to investigate the structural evolution of water dissolved in supercritical carbon dioxide under isobaric heating (T=40-340 degrees C, P=250 bar). Quantitative analysis of experimental spectra allowed us to determine that at relatively moderate temperatures water dissolved in CO(2)-rich phase exists only under monomeric form (solitary water surrounding by CO(2) molecules), but hydrogen-bonded species, namely, dimers, begin to appear upon heating. At the same time, the ratio of dimers to monomers concentration increases with further temperature increase and at temperatures close to the temperature of total miscibility of the mixture (T=366 degrees C, P=250 bar), water dimers only are present in the CO(2)-rich phase.     

Dry ice-originated supercritical and liquid carbon dioxide extraction of organic pollutants from environmental samples

Packed in a high-pressure vessel and under calculated conditions, dry ice can be used as a source of carbon dioxide for supercritical CO₂ extraction or liquid CO₂ of organic compounds from environmental samples. Coupled with a fluid modifier such as toluene, dry ice-originated supercritical CO₂ (Sc CO₂) achieves quantitative extraction of many volatile organic compounds (VOCs) and semivolatile organic compounds (SOCs) including polycyclic aromatic hydrocarbons (PAHs), n-alkanes, and polychlorinated biphenyls (PCBs) from solid matrices. Compared to contemporary manual or automated supercritical fluid extraction (SFE) technologies, this novel technique simplifies SFE to a minimum requirement by eliminating the need of a high-pressure pump and any electrical peripherals associated with it. This technique is highly suitable to analytical areas where sample preservation is essential but difficult in the sampling field, or where sample collection, sample preparation, and analysis are to be done in the field.     

Automated quantitative and isotopic (13C) analysis of dissolved inorganic carbon and dissolved organic carbon in continuous-flow using a total organic carbon analyser

A method for the automated (13)C analysis of dissolved inorganic and organic carbon species has been developed to operate on a continuous-flow isotope ratio mass spectrometer (CF-IRMS). For natural and anthropogenic carbon species, the (13)C stable isotope has proven to be an excellent environmental tracer. Analytical performance tests were carried out on various organic compounds from easily oxidisable (sugar) to difficult (humic acid). A set of natural samples was also analysed to confirm the flexibility of the system. Analytical precision (2sigma) is typically <0.20 per thousand with sample reproducibility from 0.10-0.35 per thousand depending on reactivity of material. We believe this to be the first successful use of a total organic carbon (TOC) analyser for both dissolved inorganic and, specifically, dissolved organic species for (13)C stable isotope analysis in an automated CF-IRMS system. Routine analysis is achieved fairly quickly, is relatively simple with little or no sample manipulation, and will allow new and exciting studies for stable isotope research in both natural abundance and organic tracer studies not easily achieved before.     

Extraction of dissolved fatty acids from sea water

Summary During a cruise in the Baltic Sea in March/April 1991, dissolved lipids were concentrated from acidified sea water by adsorption on reversed phase material; the free fatty acids in the lipids were isolated. Titration of the acids with 0.01 mol/l methanolic KOH resulted in a very poor titration curve; assessing total concentration of organic acids in sea water by base titration appears to be impractical. After derivatization with p-phenylphenacyl bromide under crown ether catalysis the fatty acids were analyzed by micro-bore HPLC with UV-detection and comparison with standard reference substances. Some unknown fatty acids were characterized by GC/MS. Total concentrations were in the range from 1 to 4.5 nmol/l. They were the same in parallel samples liquid/liquid extracted with dichloromethane. The HPLC spectra of the fatty acids in both kinds of samples were also quite similar. This confirms earlier observations that adsorptive concentration of dissolved fatty acids and non-polar lipids from sea water is as effective as liquid/liquid extraction. Higher amounts of fatty acids can be concentrated by adsorption from large water volumes, thus lowering detection limits. Palmitic acid had by far the highest concentration in every sample followed by myristic acid, lauric acid, and stearic acid. Palmitoleic acid and oleic acid were the most abundant unsaturated acids. The other saturated and unsaturated acids had medium to low concentrations.     

Ionization of carbon acids in liquid ammonia

The acidities of various carbon acids in liquid ammonia (LNH(3)) at room temperature were determined by NMR and rates of D-exchange. There is a reasonable linear correlation of the pK(a)s in LNH(3) with those in water and DMSO of slope 0.7 and 0.8, respectively. Carbon acids with an aqueous pK(a) of less than 12 are fully ionized in liquid ammonia. Nucleophilic substitution of benzyl chloride by carbanions in liquid ammonia generates a Br?nsted β(nuc) = 0.38.     

Doping metal-organic frameworks for water oxidation, carbon dioxide reduction, and organic photocatalysis

Catalytically competent Ir, Re, and Ru complexes H(2)L(1)-H(2)L(6) with dicarboxylic acid functionalities were incorporated into a highly stable and porous Zr(6)O(4)(OH)(4)(bpdc)(6) (UiO-67, bpdc = para-biphenyldicarboxylic acid) framework using a mix-and-match synthetic strategy. The matching ligand lengths between bpdc and L(1)-L(6) ligands allowed the construction of highly crystalline UiO-67 frameworks (metal-organic frameworks (MOFs) 1-6) that were doped with L(1)-L(6) ligands. MOFs 1-6 were isostructural to the parent UiO-67 framework as shown by powder X-ray diffraction (PXRD) and exhibited high surface areas ranging from 1092 to 1497 m(2)/g. MOFs 1-6 were stable in air up to 400 °C and active catalysts in a range of reactions that are relevant to solar energy utilization. MOFs 1-3 containing [Cp*Ir(III)(dcppy)Cl] (H(2)L(1)), [Cp*Ir(III)(dcbpy)Cl]Cl (H(2)L(2)), and [Ir(III)(dcppy)(2)(H(2)O)(2)]OTf (H(2)L(3)) (where Cp* is pentamethylcyclopentadienyl, dcppy is 2-phenylpyridine-5,4'-dicarboxylic acid, and dcbpy is 2,2'-bipyridine-5,5'-dicarboxylic acid) were effective water oxidation catalysts (WOCs), with turnover frequencies (TOFs) of up to 4.8 h(-1). The [Re(I)(CO)(3)(dcbpy)Cl] (H(2)L(4)) derivatized MOF 4 served as an active catalyst for photocatalytic CO(2) reduction with a total turnover number (TON) of 10.9, three times higher than that of the homogeneous complex H(2)L(4). MOFs 5 and 6 contained phosphorescent [Ir(III)(ppy)(2)(dcbpy)]Cl (H(2)L(5)) and [Ru(II)(bpy)(2)(dcbpy)]Cl(2) (H(2)L(6)) (where ppy is 2-phenylpyridine and bpy is 2,2'-bipyridine) and were used in three photocatalytic organic transformations (aza-Henry reaction, aerobic amine coupling, and aerobic oxidation of thioanisole) with very high activities. The inactivity of the parent UiO-67 framework and the reaction supernatants in catalytic water oxidation, CO(2) reduction, and organic transformations indicate both the molecular origin and heterogeneous nature of these catalytic processes. The stability of the doped UiO-67 catalysts under catalytic conditions was also demonstrated by comparing PXRD patterns before and after catalysis. This work illustrates the potential of combining molecular catalysts and MOF structures in developing highly active heterogeneous catalysts for solar energy utilization.     

Dispersion of organic pigments using supercritical carbon dioxide

This research describes dispersion of organic pigments using supercritical fluids. With low surface tension and high diffusivity of fluids in supercritical states, aggregated particles may be effectively wetted and swelled to form the primary constituent of the dispersing solution by volume. In this paper, the conditions of temperature and pressure are used to control the density of supercritical carbon dioxide subject to PGMEA as cosolvent for dispersing organic powder in a solution. As shown from measurement with a laser scattering particle analyzer, the average diameter of phthalocyanine green 36 with the haloid structure can be significantly reduced to 93.5 nm; for aminoanthraquinone red containing and amino group (-NH(2)) and phthalocyanine blue 15:6 with symmetry benzene and inner hydrogen bond, the mean particle sizes are 178.5 and 188.7 nm, respectively, using supercritical CO(2). Additionally, the transmittance of UV light is used to confirm the dispersing performance in this study.     

Effect of water on the desorption of carbon dioxide from the surface of alumina

Based on investigations of temperature-programmed desorption of CO₂ from -Al₂O₃ surface, three forms of CO₂ adsorption differing considerably in quantitative contributions and temperature ranges of desorption have been distinguished. A significant inhibiting influence of water on CO₂ adsorption has been observed. Water adsorption results in gradual blocking of high and medium-energy adsorptive centers of CO₂ on -Al₂O₃.

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- CO₂ -Al₂O₃ CO₂, . CO₂. CO₂ Al₂O₃ .

     

The effects of dissolved halide anions on hydrogen bonding in liquid water

It is widely believed that the addition of salts to water engenders structural changes in the hydrogen-bond network well beyond the adjacent shell of solvating molecules. Classification of many ions as "structure makers" and "structure breakers" has been based in part on corresponding changes in the vibrational spectra (Raman and IR). Here we show that changes in O-H vibrational spectra induced by the alkali halides in liquid water result instead from the actions of ions' electric fields on adjacent water molecules. Computer simulations that accurately reproduce our experimental measurements suggest that the statistics of hydrogen-bond strengths are only weakly modified beyond this first solvation shell.     

Ratiometric fluorescence-based dissolved carbon dioxide sensor for use in environmental monitoring applications

The focus of this work is on the development and characterisation of a fluorescence-based ratiometric sol–gel-derived dissolved carbon dioxide (dCO₂) sensor for use in environmental monitoring applications. Fluorescence-based dCO₂ sensors are attractive as they facilitate the development of portable and low-cost systems that can be easily deployed outside the laboratory environment. The sensor developed for this work exploits a pH fluorescent dye 1-hydroxypyrene-3,6,8-trisulfonic acid, ion-paired with cetyltrimethylammonium bromide (HPTS-IP), which has been entrapped in a hybrid sol–gel-based matrix derived from n-propyltriethoxysilane along with the liphophilic organic base. The sensor spot deposited on a cover slip has been interrogated with a robust, ratiometric optical probe that combines effective fluorescence excitation and detection and thus facilitates the production of a highly sensitive sensor system using low-cost optoelectronic components. The probe design involves the use of dual-LED excitation in order to facilitate ratiometric operation and uses a silicon PIN photodiode. HPTS-IP exhibits two pH-dependent changes in excitation bands, which allows for dual excitation ratiometric detection as an indirect measure of the dCO₂. Such measurements are insensitive to changes in dye concentration, leaching and photobleaching of the fluorophore and instrument fluctuations unlike unreferenced fluorescence intensity measurements. The performance of the sensor system is characterised by a high degree of repeatability, reversibility and stability. Calculated limit of detection for the sensor was 35 ppb. The sensor probe was used to monitor dCO₂ levels in a laboratory-based aquatic habitat, and the expected diurnal pattern was clearly visible. The influence of temperature, biofouling and photobleaching on sensor performance has been also investigated.