Extrusion processing for ammonia fiber explosion (AFEX)

The ammonia fiber explosion (AFEX) process, previously run only in a batch reactor, has been adapted to run on a twin-screw extruder. The sugar yield of AFEX material after enzymatic hydrolysis has been increased up to 3.5 times over that of completely untreated material. The ruminant digestibility of corn fodder has been increased up to 32% (from 54–71%) over completely untreated material, and 23% (from 63–77%) over material extruded with no ammonia. Extrusion-treated material proved more digestible by the ruminant at 48 h than material treated in the batch reactor.     

Dilute-sulfuric acid pretreatment of corn stover in pilot-scale reactor

Corn stover is a domestic feedstock that has potential to produce significant quantities of fuel ethanol and other bioenergy and biobased products. However, comprehensive yield and carbon mass balance information and validated kinetic models for dilute-sulfuric acid (H₂SO₄) pretreatment of corn stover have not been available. This has hindered the estimation of process economics and also limited the ability to perform technoeconomic modeling to guide research. To better characterize pretreatment and assess its kinetics, we pretreated corn stover in a continuous 1 t/d reactor. Corn stover was pretreated at 20% (w/w) solids concentration over a range of conditions encompassing residence times of 3–12 min, temperatures of 165–195°C, and H₂SO₄ concentrations of 0.5–1.4% (w/w). Xylan conversion yield and carbon mass balance data were collected at each run condition. Performance results were used to estimate kinetic model parameters assuming biphasic hemicellulose hydrolysis and a hydrolysis mechanism incorporating formation of intermediate xylo-oligomers. In addition, some of the pretreated solids were tested in a simultaneous saccharification and fermentation (SSF) process to measure the reactivity of their cellulose component to enzymatic digestion by cellulase enzymes. Monomeric xylose yields of 69–71% and total xylose yields (monomers and oligomers) of 70–77% were achieved with performance level depending on pretreatment severity. Cellulose conversion yields in SSF of 80–87% were obtained for some of the most digestible pretreated solids.     

Water desorption isotherms of cellulose-acetate membranes

 The water desorption isotherms are determined in three cellulose acetate membranes with different acetyl content as a function of p/p ₀ at 10–40 °C. The partition coefficients (adsorbed water over water pressure) show a minimum at p/p ₀=0.5–0.6. This indicates a two energy mechanism. The agreement of our results with the BET adsorption isotherms only till p/p ₀<0.3 shows that a two energy adsorption mechanism is valid only for small water contents, probably one hydrate layer and a second more liquid-like water layer. At large p/p ₀, the adsorbed water becomes more and more liquid like by polarization of the hydrogen bonds. The heat of desorption is larger than the vaporization heat of water ΔH _vap(H₂O). It decreases with increasing water content asymptotically to ΔH _vap(H₂O). The cause may be a larger van der Waals interaction of the hydrate layer due to coordination numbers larger than 4.4 as in liquid water. Additionally, we found a hole adsorption process by sorbing unpolar solvents. The water and methonal adsorption are 100 times larger due to a swelling mechanism depending on the number of acetyl groups in the membranes. The amounts of n-alcohols sorbed decrease with their chain length. Received: 25 April 1997 Accepted: 10 June 1997     

Photodegradation of humic acid using spherical activated carbon contained Zn in a fluidized bed system

In this study, a strong acid ion-exchange resin, as the starting material of spherical activated carbon contained Zn (Zn-SPAC), was treated by 0.1 N zinc solution. Ion-exchange treatment was performed from one to three times for controlling the zinc content. The ion-exchanged resins were activated under N₂/H₂O vapor atmosphere at 900°C for 0.5 h, followed by carbonization treatment at 700°C under N₂ atmosphere. The Zn-SPAC samples were measured for their physicochemical characteristics, such as X-ray diffraction (XRD) patterns, scanning electron microscope (SEM) images, electron probe micro analyzer (EPMA) images, energy dispersive X-ray spectroscopy (EDXS), Brunauer–Emmett–Teller (BET) specific surface area, strength, and zinc content. Also, the samples were used in order to measure photochemical activities, such as the removal efficiency of humic acid (HA) in a fluidized batch reactor. The XRD patterns appeared as the ZnS type. The Zn-SPAC had a large BET specific surface area and their shape was spherical, with a diameter of about 350–400 μm. When the Zn-SPAC was dosed in a fluidized bed reactor with UV light, the HA removal efficiency increased by up to 60%. On the other hand, the HA removal efficiency by only UV-C (λ _max = 254 nm) irradiation was very low, about 15%. Therefore, we infer that Zn-SPAC has good photochemical activity and presented the possibility of being a useful photocatalyst for water purification.     

Effect of sulfuric and phosphoric acid pretreatments on enzymatic hydrolysis of corn stover

The pretreatment of corn stover with H₂SO₄ and H₃PO₄ was investigated. Pretreatments were carried out from 30 to 120 min in a batch reactor at 121°C, with acid concentrations ranging from 0 to 2% (w/v) at a solid concentration of 5% (w/v). Pretreated corn stover was washed with distilled water until the filtrate was adjusted to pH 7.0, followed by surfactant swelling of the cellulosic fraction in a 0–10% (w/v) solution of Tween-80 at room temperature for 12 h. The dilute acid treatment proved to be a very effective method in terms of hemicellulose recovery and cellulose digetibility. Hemicellulose recovery was 62–90%, and enzymatic digestibility of the cellulose that remained in the solid was >80% with 2% (w/v) acid. In all cases studied, the performance of H₂SO₄ pretreatment (hemicellulose recovery and cellulose digestibility) was significantly better than obtained with H₃PO₄. Enzymatic hydrolysis was more effective using surfactant than without it, producing 10–20% more sugar. Furthermore, digestibility was investigated as a function of hemicellulose removal. It was found that digestibility was more directly related to hemicellulose removal than to delignification.     

Effect of pretreatment of molasses and posttreatment of fermented broth in industrial production of ethanol

The aim of preclarification is to minimize sludge going to yeast separators. This purpose is partially fulfilled. However, it has been measured during the plant trial runs that preclarification does not noticeably improve fermentation. The aim of postclarification is to minimize sludge going to distillation. This purpose is well served as noted from the fact that cycle run of distillation columns using postclarification is three times longer (9–12 mo) as compared to the normal one (3–4 mo).     

Continuous fermentation of cellulosic biomass to ethanol

Experimental results are presented for continuous conversion of pretreated hardwood flour to ethanol. A simultaneous saccharification and fermentation (SSF) system comprised ofTrichoderma reesei cellulase supplemented with additional β-glucosidase and fermentation bySaccharomyces cerevisiae was used for most experiments, with data also presented for a direct microbial conversion (DMC) system comprised ofClostridium thermocellum. Using a batch SSF system, dilute acid pretreatment of mixed hardwood at short residence time(10 s, 220°C, 1% H₂SO₄) was compared to poplar wood pretreated at longer residence time (20 min, 160°C, 0.45% H₂SO₄). The short residence time pretreatment resulted in a somewhat (10–20%) more reactive substrate, with the reactivity difference particularly notable at low enzyme loadings and/or low agitation. Based on a preliminary screening, inhibition of SSF by byproducts of short residence time pretreatment was measurable, but minor. Both SSF and DMC were carried out successfully in well-mixed continuous systems, with steady-state data obtained at residence times of 0.58–3 d for SSF as well as 0.5 and 0.75 d for DMC. The SSF system achieved substrate conversions varying from 31% at a 0.58-d residence time to 86% at a 2-d residence time. At comparable substrate concentrations (4–5 g/l) and residence times (0.5–0.58 d), substrate conversion in the DMC system (77%) was significantly higher than that in the SSF system (31%). Our results suggest that the substrate conversion in SSF carried out in CSTR is relatively insensitive to enzyme loading in the range 7–25 U/g cellulose and to substrate concentration in the range of 5–60 g/L cellulose in the feed.     

Effect of the Preparation Methodof Al–Mg–O Catalysts on the Selective Decomposition of Ethanol

Summary.  Selective decomposition of ethanol was used as a test reaction at 350°C to evaluate the catalytic activity of two Al–Mg–O mixed oxides prepared by two different methods (wet impregnation and coprecipitation). The catalyst precursors were examined by TG and DTA and were calcined between 500–900°C for 5 h in air. The surface area of all catalysts was measured by N₂ sorption using the BET method. The total acidity and basicity were determined by TPD using pyridine and formic acid. The catalysts were characterized by XRD analysis. It was found that the preparation method of Al–Mg–O catalyst has a great effect on the selective decomposition of ethanol. Al–Mg–O (I) catalysts, prepared by wet impregnation, were more selective towards ethene formation during dehydration of ethanol. This is ascribed to their high total surface acidity. On the other hand, Al–Mg–O (II) catalysts, prepared by coprecipitation, were highly selective in the oxidative dehydrogenation of ethanol to yield acetaldehyde. This could be attributed to their high concentration of basic sites. In addition, the production of traces of diethyl ether was also observed (three times more for Al–Mg–O (II) than for Al–Mg–O (I)). Corresponding author. E-mail: shalawy99@yahoo.com Received October 12, 2001. Accepted (revised) January 7, 2002     

Chemotypical Variability of Leaf Oils in <Emphasis Type="Italic">Elephantopus scaber</Emphasis> from 12 Locations in China

The chemical constituents of leaf oils of Elephantopus scaber L. from 12 locations in Southern China, including three provinces and Hong Kong, were investigated using GC/MS. A total of 24 compounds were detected, of which 20 were identified by their mass spectra fragmentation patterns. The major compounds include hexadecanoic acid (8.19–39.22%), octadecadienoic acid (trace - 29.22%), five alkane homologues, i.e., n-tetradecane (1.19–5.26%), n-pentadecane (3.22–12.05%), n-hexadecane (2.38–16.26%), n-heptadecane (2.48–15.32%), and n-octadecane (1.39–9.59%), as well as tetramethylhexadecenol (2.06–4.31%). Hierarchical cluster analysis classified the leaf oils into two groups. Two main chemotypes of leaf oils in E. scaber were thus identified, one rich in hexadecanoic acid and octadecadienoic acid, and the other rich in the five alkane homologues. __________ Published in Kimiya Prirodnikh Soedinenii No. 5, pp. 403–404, September–October, 2005.     

Scaled quantum chemical studies of the structural and vibrational spectra of acetyl coumarin

The solid phase FT-IR and FR-Raman spectra of acetyl coumarin have been recorded in the regions 4000–50 cm⁻¹. The spectra were interpreted with the aid of normal coordinate analysis following full structure optimization and force field calculations based on density functional theory (DFT) and Hartree-Fock (HF) at 6–31G* and 6–311++G** basis sets. The resulting force fields were transformed to internal coordinates, the calculated vibrational frequencies and normal modes were utilized in the assignment of the observed vibrational fundamentals. The measured spectral data were used to refine the vibrational force constants by means of a small number of scaling factors.     

Copper Incorporated [Me2(15)dieneN4] Macrocyclic Complex for Fabrication of PVC based Membrane Electrode for Copper

Copper (II) complex of 2,4-dimethyl-1,5,9,12-tetraazacyclopentadeca-1,4-diene, [Me₂(15)dieneN₄] was synthesized and used in the fabrication of Cu²⁺ – selective ISE membrane in PVC matrix. The membrane having Cu(II) macrocyclic complex as electroactive material along with sodium tetraphenyl borate (NaTPB) as anion discriminator. Dibutyl phthalate (DBP) as plasticizer in poly(vinyl chloride) (PVC) matrix was prepared for the determination of Cu²⁺. The best performance was observed by the membrane having Cu(II) complex–PVC–NaTPB–DBP with composition 1:5:1:3. The sensor worked well over a concentration range 1.12 × 10⁻⁶ M–1.0 × 10⁻¹ M between pH 2.1–6.2 and a fast response time 10±2 s and a lifetime of 6 months. Their performance in partially non-aqueous medium was found satisfactory. Electrodes exhibited excellent selectivity for Cu²⁺ ion over other mono-, di-, trivalent cations. It can also be used as indicator electrode in the potentiometric titration of Cu²⁺ against EDTA as well as in the determination of Cu²⁺ in real samples.     

Acyl iodides in organic synthesis: XIII. Reaction of acyl iodides with nitrogen-containing heteroaromatic compounds

Reactions of acetyl iodide with pyridine at room temperature and with quinoline both at 20–25°C and on cooling to −50°C involve dehydrohalogenation of acetyl iodide with formation of ketene and pyridinium or quinolinium iodides. The reaction of acetyl iodide with pyridine at −5 to −50°C led to the formation of N-acetylpyridinium iodide. Benzoyl iodide reacted with both pyridine and quinoline at both −50°C and at 20–25°C to form stable N-benzoylpyridinium and N-benzoylquinolinium iodides. The reaction of pyrrole with acetyl iodide under analogous conditions was accompanied by polymerization.     

Cation π interaction between acetylcholine and the benzene ring

 Ab initio self-consistent-field second-order M?ller–Plesset perturbation theory computations including basis set superposition error and zero-point vibrational energy corrections have been performed on the complexation of benzene with the polar head of acetylcholine (ACh). The ACh–benzene complex is about 0.5 kcal/mol less stable than the corresponding tetramethylammonium (TMA)–benzene complex, with a structure a little distorted with respect to the latter. The electronic structure of ACh is little modified by the ligand. Overall, the replacement of one methyl group of TMA by the acetyl tail of ACh does not affect strongly the complexation to benzene, as far as the main interaction is concerned. Received: 1 April 1999 / Accepted: 19 October 1999 / Published online: 14 March 2000     

Synthetic analogs of Peganum alkaloids VI. Photochemical oxidation of 2,3-polymethylene-quinazoline derivatives

The rates of the photochemical oxidation of quinazoline alkaloids — deoxypeganine, peganine, pentamethylenequinazoline, and peganol — to the corresponding oxo derivatives have been studied. It has been shown by HPLC that the oxidation of deoxypeganine proceeds through a stage of the formation of a carbinolamine (peganol); in the case of its hydrochloride, the reaction takes place by the same scheme but four times more slowly. Tetra- and pentamethylenequinazolines have been synthesized and information on their melting points in the literature has been corrected. In the series trimethylenequinazoline-pentamethyl-enequinazoline-tetramethylenequinazoline the stability falls from left to right. Institute of Chemistry of Plant Substances, Academy of Sciences of the Uzbek SSR, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 4, pp. 528–532, July–August, 1991.     

Hydrodynamic characteristics in aerobic biofilm reactor treating high-strength trade effluent

Four 3–L aerobic biofilm reactors (ABRI, 2, 3, and 4) treating a highstrength food–processing waste water (10 g chemical oxygen demand [COD]/L) were subject to reactor liquor recirculation rates of 1, 3,15, and 30 L/h, respectively. Treatment performance in terms of COD removal rates of ABRI, 2, and 3 were similar at hydraulic loads of 2.0 g COD/L/d and below. At higher organic loads, ABR3 could achieve a COD removal rate that was over two times higher than that of ABRI and 2. ABR3 could be operated at a maximum organic load that was two times higher than that of ABRI and 2. ABR4 experienced a biofilm sloughing from the packing medium at the beginning of operation. Tracer studies showed that recirculation rate of 1 L/h resulted in a plug–flow pattern in the packed bed of the reactor. On the other hand, recirculation rate of 15 L/h, which was equivalent to recirculating the reactor liquor five times per hour, provided effective mixing in the packed bed. Superior performance of ABR3 was attributed to the effective recirculation of reactor liquor, which diluted and distributed the influent, particularly the oil and grease components.     

Thermodynamic Analysis of DSC Data for Acetaminophen Polymorphs

This article provides a thermodynamic analysis of DSC data for acetaminophen polymorphic forms I and II by measurement of heat capacity. Form I is found to have lower heat capacity and free energy and hence better stability than Form II down to at least –30°C. The transition temperature below which Form II becomes more stable was determined to be less than –120°C. Form I is more stable than Form II as a consequence of its higher entropy, since its crystallographic packing arrangement is of larger energy. This revised version was published online in August 2006 with corrections to the Cover Date.     

Semi-continuous Cultivation of <Emphasis Type="Italic">Chlorella vulgaris</Emphasis> for Treating Undigested and Digested Dairy Manures

The present study, based on a previous batch-wise experiment, investigated a lab-scale semi-continuous cultivation of green microalgae Chlorella vulgaris (UTEX 2714), as a useful means for nutrient reduction as well as production of algal biomass which can be used as potential feedstock for the production of biofuel and other commodities, on 20× diluted dairy manures. Both undigested and digested samples were applied in parallel experiments for comparison regarding the requirements of hydraulic retention times (HRTs), removal efficiencies of nitrogen, phosphorus, and chemical oxygen demand (COD), biomass productivities, and CO₂ sequestration abilities. It was demonstrated that algae grown in undigested dairy manure achieved removal rates of 99.7%, 89.5%, 92.0%, and 75.5% for NH₄⁺–N, TN, TP, and COD, respectively, under a 5-day HRT, while the HRT had to extend to 20 days in order to achieve 100.0% removal of NH₄⁺–N in digested one with simultaneous removals of 93.6% of TN, 89.2% of TP, and 55.4% of COD. The higher organic carbon contained in undigested dairy manure helped boost the growth of mixotrophic Chlorella, thus resulting in a much shorter HRT needed for complete removal of NH₄⁺–N. Moreover, algae grown in digested dairy manure provided more penitential than those grown in undigested one in CO₂ sequestration per milligram of harvested dried biomass (1.68 mg CO₂/mg dry weight (DW) vs 0.99 mg CO₂/mg DW), but did not surpass in total the amount of CO₂ sequestered on a 15-day period basis because of the better productivity gained in undigested dairy manure.     

Hydrogen production by the thermophilic bacterium Thermotoga neapolitana

Virtually all members of the order Thermotogales have demonstrated the ability to produce hydrogen; however, some members of this order produce considerably greater quantities than others. With one representative of this order, Thermotoga neapolitana, we have consistently obtained accumulation of 25–30% hydrogen with 12–15% carbon dioxide as the only other prominent product in the batch reaction. In contradistinction to information widely disseminated in the literature, we have also found that most members of this order tolerate and appear to utilize the moderate amounts of oxygen present in the gaseous phase of batch reactors (6–12%), with no apparent decrease in hydrogen production. Hydrogen accumulation has been widely reported to inhibit growth of Thermotogales. While this may be true at very high hydrogen tensions, we have observed log phase bacterial morphology (rods) even in the presence of 25–35% hydrogen concentrations. To maximize hydrogen production and minimize production of hydrogen sulfide, inorganic sulfur donors are avoided and the cysteine concentration in the medium is increased. We and others have demonstrated that different members of the order Thermotogales utilize a wide variety of feedstocks, including complex carbohydrates and proteins. Thus, it appears that organisms within this order have the potential to utilize a variety of organic wastes and to cost-effectively generate hydrogen.     

Radiation-thermal hydrodesulphurization of brown coal

The results of the investigation of radiation-thermal hydrodesulphurization of brown coal in presence of methane under accelerated electrons with a dose rate P=350 Gy/s in the intervals of temperatureT=200–500 °C, absorbed dose up to 60 kGy are presented. It has been established that at the more favourable conditions (T=400–450 °C,D>60 kGy) about 80% of sulphur is removed from the coal and in the solid product sulphur decreased up to 1.0–1.1%. In these conditions the selectivity of desulphurization processes iss=2.6–3.8 and energy consumption towards removal of sulphur isE=0.5–0.6 kW h/kg. The mechanism of selective activation by irradiation for the desulphurization process is discussed.     

Novel sol–gel reversible thermochromic materials for environmental sensors

Anhydrous cobalt(II) chloride has been encapsulated in several inorganic sol–gel matrices with different solvent/water ratios. Sols were cast into cuvettes and hermetically closed. Such sol–gel materials were found to be sensitive to temperature in the 10–50 °C range showing a change of colour. General characterisation of the sensitive materials was made by immersion into a thermostatic water bath and recording of the corresponding visible spectra. The optical response consisted of a change in colour from light pink to deep blue as the temperature increases. These temperature detectors behave as sensors showing good optical sensitivity in the range mentioned above and reversibility for more than 30 cycles. The sensors response time is at about 15 min and their lifetime is 2 months at least. These sol–gel materials have been designed to be applied for preservation and conservation purposes. High temperatures and cyclical temperature changes can yield severe consequences for the correct preservation of cultural heritage materials (textiles, archaeological ceramics and other remains, metallic objects and statues, stained glass windows, etc.) both in museums and outdoors.