Roles of inherent metallic species in secondary reactions of tar and char during rapid pyrolysis of brown coals in a drop-tube reactor

Two pairs of raw and acid-washed coal samples were prepared from Yallourn and Loy Yang brown coals, and subjected to rapid pyrolysis in a drop-tube reactor at 1073-1173 K in a stream of N₂ or H₂O/N₂ mixture. Examinations were made on the roles of the inherent metallic species in the secondary reactions of nascent tar and char that were formed by the intraparticle primary reactions. The experimental results revealed that the inherent metallic species were essential for vary rapid steam reforming/gasification of the nascent tar/char and simultaneous suppression of soot formation. In the absence of the metallic species, the soot formation from the tar accounted as much as 15-19 and 6-13% of the carbon in coal in N₂ and H₂O/N₂, respectively. The metallic species reduced the yield of soot to 6-8% in N₂ by enhancing the reforming of tar by H₂O generated from the pyrolysis of coal. In the H₂O/N₂ stream, instead of soot formation, a net gasification conversion up to 17% within 4.3 s was observed in the presence of the metallic species as a result of catalytic gasification of the nascent char. Moreover, the metallic species catalyzed the steam reforming of the nascent tar, giving its conversion up to 99%. Over the range of the conditions employed, a one-to-one stoichiometry was established between the steam consumption and the yield of carbon oxides formed by the steam reforming/gasification and water-gas-shift reaction.     

Phase structure in the blend of atactic poly(vinyl alcohol) with atactic poly(vinyl alcohol‐block‐vinyl acetate)

An almost fully saponified atactic poly(vinyl alcohol) and an atactic poly(vinyl alcohol‐block‐vinyl acetate) of which degree of saponification is 89 mol % were blended by a solution casting method. The phase structure of the blend film was analyzed by optical microscopy, ¹³C‐NMR, and differential scanning calorimetry. The most remarkable structure of the blend was composed of cylindrical domains penetrating the film. The swelling behavior of the blend films was also investigated in the dimethylsulfoxide and water mixed solvents to find differences in solubility and diffusion behavior between the matrix and the domain. The cylindrical domains could be selectively dissolved away in water and the film became porous. We tried to change the size of the cylindrical domain with various film preparation conditions. This aimed to turn the film into the useful filter membrane. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 1807–1815, 2002     

An absolute requirement of fructose 1,6-bisphosphate for the Lactobacillus caseiL-lactate dehydrogenase activity induced by a single amino acid substitution

Lactobacillus casei allosteric L-lactate dehydrogenase (L-LDH)absolutely requires fructose 1,6-bisphosphate [Fru(1,6)P2] forits catalytic activity under neutral conditions, but exhibitsmarked catalytic activity in the absence of Fru(1,6)P₂ underacidic conditions through the homotropic activation effect ofsubstrate pyruvate. In this enzyme, a single amino acid replacement,i.e. that of His205 conserved in the Fru(1,6)P₂-binding siteof certain allosteric L-LDHs of lactic acid bacteria with Thr,did not induce a marked loss of the activation effect of Fru(1,6)P₂or divalent metal ions, which are potent activators that improvethe activation function of Fru(1,6)P₂ under neutral conditions.However, this replacement induced a great loss of the Fru(1,6)P₂-independentactivation effect of pyruvate or pyruvate analogs under acidicconditions, consequently indicating an absolute Fru(1,6)P₂ requirementfor the enzyme activity. The replacement also induced a significantreduction in the pH-dependent sensitivity of the enzyme to Fru(1,6)P₂,through a slight decrease and increase of the Fru(1,6)P₂ sensitivityunder acidic and neutral conditions, respectively, indicatingthat His205 is also largely involved in the pH-dependent sensitivityof L.casei L-LDH to Fru(1,6)P₂. The role of His205 in the allostericregulation of the enzyme is discussed on the basis of the knowncrystal structures of L-LDHs.     

Glycoconjugated polymer 6. Synthesis of poly[styrene-<Emphasis Type="Italic">block</Emphasis>-(styrene-<Emphasis Type="Italic">graft</Emphasis>-amylose)] via potato phosphorylase-catalyzed polymerization

Summary The potato phosphorylase-catalyzed polymerization of α-D-glucose-1-phosphate (G-1-P) onto poly[styrene-block-(4-vinylbenzyl maltohexaoside)] (1) was performed at the molar ratios of [G-l-P]₀ and [maltohexaose]₀ of 35, 80, and 250. The product was found to be soluble in dimethyl sulfoxide, which was a good solvent for amylose, and showed the complex-formation with iodine, indicating that the product was assignable to poly[styrene-block-(styrene-graft-amylose)] (2). The quantitative analysis of the liberated phosphoric acid gave the average degree of polymerization o f the glucose unit (n) as 27, 5 1, and 180 for 2-I, 2-II, and 2-III, respectively. Received: 29 November 2002/Accepted: 22 December 2002 Correspondence to Toyoji Kakuchi     

Synthesis of well-defined poly(styrene)-b-poly(p-tert-butoxystyrene) multiblock copolymer from poly(alkoxyamine) macroinitiator

The stepwise insertion reaction of styrene (St) and p-tert-butoxystyrene (BOSt) into poly(alkoxyamine) macroinitiator was carried out to provide well-defined poly(St)-b-poly(BOSt) multiblock copolymers. Structural confirmation of the multiblock copolymers was accomplished by NMR and IR measurements. The model reaction also supported that the monomer insertion into the macroinitiator proceeded in accordance with a living fashion.     

Decomposition of Benzene Using Ag/TiO2 Packed Plasma-Driven Catalyst Reactor: Influence of Electrode Configuration and Ag-Loading Amount

This paper describes the effects of electrode configuration and the loading amount of Ag catalyst on the decomposition of gas-phase benzene using plasma-driven catalyst (PDC) reactors. Modification of ground electrode brought out a great enhancement in the energy efficiency for benzene decomposition by reducing abnormal discharges outside the reactor tube. The data of carbon balance and the selectivity of CO₂ indicated that the Ag catalyst played an important role in the decomposition of benzene, especially for the intermediates. The larger the Ag-loading amounts on the TiO₂, the better the performance of benzene decomposition in terms of the carbon balance and the selectivity of CO₂. Formation of NO₂ and N₂O indicated that the maximum specific input energy applicable to the PDC reactor should be determined not only by the decomposition efficiency but also by the formation of nitrogen oxides.     

NiZnCu Ferrite Thick Film with Nano Scale Crystallites Formed by the Aerosol Deposition Method

This paper describes the magnetic properties of NiZnCu ferrite film deposited at room temperature by an aerosol deposition method (ADM). The thickness of the film was 6 μm and the deposition rate was estimated as 2 μm/min. The microstructure of as-deposited at room temperature films consists of randomly oriented nanocrystallites with a size of 20 nm. As-deposited and annealed films exhibited the following magnetic properties: intensity of magnetization M _s= 0.147 T (117 emu/cm³), coercivity H _c= 40.58 kA/m (510 Oe); and M _s= 0.3 T (250 emu/cm³), H _c= 14.95 kA/m (188 Oe), respectively.     

Phase separation behavior and morphology development of phenolic resin/PMMA/hexamethylenetetrarnine blends

Summary In order to obtain materials with nanopores which will be applicable for many fields, the structures of the cured blends of phenolic resin (PhN), poly(methyl methacrylate) (PMMA) and curing agent were studied. After PMMA was extracted from cured blends, the structures of cured phenolic resins were observed with SEM. As a results, it was found that nanosized continuous pore structures were formed in extremely wide composition region if curing temperature was high.     

Preparation of micron-scale monodisperse oil-in-water microspheres by microchannel emulsification

Micron-scale monodisperse oil-in-water (O/W) micropheres (MS) were prepared using a novel microchannel (MC) emulsification technique. The characteristics of the MS preparation and the O/W-MS prepared were studied. Soybean oil and medium-chain triacyglycerol (MCT) were used as the disprrsed phase, and physiological saline was used as the continuous phase. Silicon MC with 1 to 3μm-equivalent channel diameters were employed. A novel MC module was devised to easily recover the O/W-MS prepared. The effects of the channel shape on the behavior of MS formation, on the MS size, and on the distribution were investigated. An MC with a terrace at the MC outlet stably yielded micron-scale monodisperse O/W-MS; the MS had diameters of about 5 μm, and their coefficients of variation were below 9%. Monodisperse food-grade O/W-MS with diameters of about 4 μm could be obtained by using polyglycerol fatty acid ester as the surfactant. The size and size distribution of the recovered O/W-MS remained almost constant over 60 d, demonstrating their long-term stability.     

Construction of an expression system of insect lysozyme lacking thermal stability: the effect of selection of signal sequence on level of expression in the Pichia pastoris expression system

Expression systems of human and silkworm lysozymes were constructedusing the methylotrophic yeast Pichia pastoris as a host. Theleader sequence and its prepro peptide of