Hyperbranched Polymers Containing Cyclopentadienyliron Complexes

A number of hyperbranched polymers containing cyclopentadienyliron moieties were prepared using the A₂+B₃ method. The A₂ compounds used were common diols, dithiols or dichloroarenecomplexes. B₃ compounds included either prepared star-shaped molecules or a purchased triol. The effect of the reaction conditions on the properties of the products was probed. Analysis of the prepared polymers was conducted using ¹H and ¹³C NMR, viscometry, differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). Viscometry values were generally found to be low, in the range of 0.175–0.300 dl/g. TGA showed losses starting at approximately 230°C and ending at 280°C, corresponding to the decomposition of the cyclopentadienyliron moiety. Degradation of the polyether backbone was found to occur starting at 390–567°C. Glass transition temperatures were found to be between 60 and 134°C, whereas melting temperatures ranged from 155 to 190°C.     

Methane and carbon dioxide emissions and nitrogen turnover during liquid manure storage

Animal slurry stored in-house and outside is a significant source of atmospheric methane (CH₄). The CH₄ source strength of stored slurry is greatly affected by temperature. To improve emission calculations on a global scale there is a need for knowledge about the relationship between production of CH₄ in slurry and temperature. In this study, the filling of slurry channels was reproduced in the laboratory by gradually filling 1 m-high PVC vessels during 9 days followed by incubation for 100–200 days. A preliminary test showed that little CH₄ was produced from animal slurry during 10 days of incubation at 20°C, if no inoculum (slurry incubated anaerobically at the test temperature for 1.5–2 months) was present. However, the addition of 7.6% inoculum supported an immediate production of CH₄. Vessels amended with inoculum and gradually filled with cattle or pig slurry were then incubated at 10, 15 and 20°C. Methane production from stored pig and cattle slurry was not significant at temperatures below 15°C, where CO₂ was the main product of decomposition processes. In contrast, the anaerobic production of CH₄ was high and significant relative to the production of CO₂ at 20°C. Peak emissions of CH₄ averaging 0.012 and 0.02 g C h⁻¹ kg⁻¹ volatile solids (VS) were reached within about 10 days at 10 and 15°C, respectively. At 20°C, the emission of CH₄ from pig slurry was about 0.01 g C h⁻¹ kg⁻¹ for 10 days, and thereafter emissions increased to about 0.10 g C h⁻¹ kg⁻¹ VS. For cattle slurry a peak emission of 0.08 g C h⁻¹ kg⁻¹ VS was measured after 180 days. Degradation of organic nitrogen (N) in cattle slurry was related to the reduction of organic material as reflected in CO₂ and CH₄ emission. The mineralization of organic N during storage represented 10–80% of organic N in cattle slurry, and 40–80% of the organic N in pig slurry.     

Influence of operating temperature on CO<Subscript>2</Subscript>-NH<Subscript>3</Subscript> reaction in an aqueous solution

Although aqueous ammonia solution has been focused on the removal of CO₂ from flue gas, there have been very few reports regarding the underlying analysis of the reaction between CO₂ and NH₃. In this work, we explored the reaction of CO₂-NH₃-H₂O system at various operating temperatures: 40 °C, 20 °C, and 5 °C. The CO₂ removal efficiency and the loss of ammonia were influenced by the operating temperatures. Also, infrared spectroscopy measurement was used in order to understand the formation mechanism of ion species in absorbent, such as NH₂COO⁻, HCO₃⁻, CO₃²⁻, and NH₄⁺, during CO₂, NH₃, and H₂O reaction. The reactions of CO₂-NH₃-H₂O system at 20 °C and 40 °C have similar reaction routes. However, a different reaction route was observed at 5 °C compared to the other operating temperatures, showing the solid products of ammonium bicarbonates, relatively. The CO₂ removal efficiency and the formation of carbamate and bicarbonate were strongly influenced by the operating temperatures. In particular, the analysis of the formation carbamate and bicarbonate by infrared spectroscopy measurement provides useful information on the reaction mechanism of CO₂ in an aqueous ammonia solution.     

Synthesis and characterization of poly(aryl ether ketone)s with fluorinated phenyl in the side chain

New bisphenol monomers, (4-fluorophenyl)hydroquinone (3b) and (3,4-difluoro phenyl)hydroquinone (3c), were synthesized in a two-step synthesis. Poly(aryl ether ketone)s (PAEKs) (4a–c) were derived from these fluorinated bisphenols and nonfluorinated bisphenol—phenylhydroquinone (3a) with 4,4′-diflourobenzophenone via a nucleophilic aromatic substitution polycondensation. The obtained polymers had inherent viscosities of 0.50–0.92 dL/g. Thermal analysis showed that the obtained PAEKs had excellent thermal properties, the glass transition temperatures ranged from 148 to 160 °C, and the temperatures at 5% weight loss (Td₅) were above 527 °C and the temperatures at 10% weight loss (Td₁₀) were above 544 °C in nitrogen. All the polymers showed excellent solubility and could dissolve in common organic solvents, such as DMSO, NMP, DMF, etc. So the films of them were easily cast from their solutions, which possessed good mechanical properties, with tensile strengths of 95.2–104.0 MPa, Young’s moduli of 2.68–3.06 GPa, and elongation at break of 15–32%. Furthermore, the prepared PAEKs displayed low dielectric constants (2.75–2.95 at 1 MHz) and hydrophobic character (contact angles for water: 83.9^o–98.4^o).     

Effects of extraction and fractionation pressures on supercritical extraction of cholesterol from beef tallow

Edible beef tallow was extracted by supercritical CO₂ in a dynamic mode at pressures from 138 to 345 bars and temperatures of 40 and 50°C. The lipid fractions were collected at 34.5 bar/40°C. A retrograde behavior of lipid solubility was observed around 170–175 bar. The ranges of the cholesterol concentration [chol.], were 300–450 mg/100 g and 50–200 mg/100 g lipid for the fractions extracted at 138 bar and 345 bar, respectively. Beef tallow was also extracted with sequentially varied pressures of 138, 345 and 138 bars at 40°C and collected at 34.5 bar/40°C. The results showed that after 20 kg CO₂ was used for extracting 100 g of loaded beef tallow the weight of the residual beef tallow remaining in the extractor was 23 g with [chol.] of 49 mg/100 g lipid. The lower [chol.] of the residual beef tallow represents a 60–70% reduction in cholesterol content, when compared with untreated beef tallow where [chol.] ranges from 130 to 160 mg/100 g lipid. To isolate lipid fractions containing higher [chol.], beef tallow was extracted at 345 bar/40°C and then fractionated into three separators connected in series with decreasing pressures of 173 bar, 117 bar, and 34.5 bar at 40°C, respectively. The results showed that the fractions collected from the third separator (34.5 bar) contained concentrated [chol.] ranging from 272 to 433 mg/100 g lipid. The fatty acid analysis revealed that the fractions containing high [chol.] generally consisted of high concentrations of myristic and palmitoleic acids but low concentrations of stearic and oleic acids.     

Supported Pt and Pt–Ru catalysts prepared by potentiostatic electrodeposition for methanol electrooxidation

Methanol electrooxidation was investigated on Pt–Ru electrocatalysts supported on glassy carbon. The catalysts were prepared by electrodeposition from solutions containing chloroplatinic acid and ruthenium chloride. Bulk composition analysis of the Pt–Ru catalyst was performed using an X-ray detector for energy dispersive spectroscopy analysis (EDX). Three different compositions were analyzed in the range 0–20 at.% Ru content. Tafel plots for the oxidation of methanol in solutions containing 0.1–2 M CH₃OH, and in the temperature range 23–50 °C showed a reasonably well-defined linear region. The slope of the Tafel plots was found to depend on the ruthenium composition. The lower slope was determined for the Pt catalyst, varying between 100 and 120 mV dec⁻¹. The values calculated for the alloys were higher, ranging from 120 to 140 mV dec⁻¹. The reaction order for methanol varies from 0.5 to 0.8, increasing with the ruthenium content. The activation energy calculated from Arrhenius plots was found to change with the catalyst composition, showing a lower value around 30 kJ mol⁻¹ for the alloys, and a higher value, of 58.8 kJ mol⁻¹, for platinum. The effect of ruthenium content is explained by the bifunctional reaction mechanism.     

Heat transfer in a high temperature fluidized bed

The heat transfer characteristics between the bed and immersed tube in a high temperature fluidized bed (7.5 cm I.D.×70 cm H) were investigated with sand and iron ore particles. The heat transfer coefficients were measured at operating temperatures of 200–600°C and gas velocities of 1–10 U_mf. The bed emissivity measured by the radiation probe was found to be 0.8–0.9. The experimentally obtained radiative heat transfer coefficient was in the range of 30–80 W/m²K for the operating temperature of 400–800°C and the contribution of radiation to total heat transfer was about 13% and 18% for the operating temperatures of 400°C and 600°C, respectively.     

Unperturbed molecular dimensions and the theta temperature of dextran in dimethylsulfoxide (DMSO) solutions

Summary The unperturbed molecular dimensions of dextran samples have been determined in dimethylsulfoxide (DMSO) solutions from intrinsic viscosity measurements at different temperatures. The unperturbed dimension parameter, K_o, has been calculated from extrapolation methods.The unperturbed root-mean-square end-to-end distance, <r²>_o ^1/2, found for the polymer samples in DMSO solutions, indicate that the polymer coils are contracted. This distance varies from 3.25 × 10⁻⁷ cm to 2.94 × 10⁻⁷ cm for the sample T 40 and from 8.28 × 10⁻⁷ cm to 7.48 × 10⁻⁷ cm for the sample T 500, in the chosen solvent as the temperature is raised from 25°C to 45°C. In the system of dextran/DMSO, the long-range interaction parameter, B, was also determined and a significant decrease is observed between 25°–45°C. The theta temperatures, Θ, were obtained as Θ= 327.25 K, Θ= 327.41 K and Θ= 323.38 K from the temperature dependence of the interaction parameter in Kurata-Stockmayer-Fixman, Berry and Inagaki-Suzuki-Kurata equations, respectively. Received: 19 January 1998/Revised version: 9 June 1998/Accepted: 10 June 1998     

Cu–ZrO2 Catalysts for Water-gas-shift Reaction at Low Temperatures

A series of Cu–ZrO₂ catalysts with Cu content in the range of 10–70 at.% Cu (=100×Cu/(Cu+Zr)) were prepared by coprecipitation, and their performances were tested for the water-gas-shift (WGS) reaction. The activity of the catalyst increased with Cu loading and, depending on the loading, the activity was comparable to or better than the activity of a conventional Cu–ZnO–Al₂O₃ catalyst at low temperatures below 473 K. Characterization of the catalysts revealed that the amount of Cu⁺ present on the catalyst surface, after being reduced by a H₂ mixture at 573 K, was well correlated with the activity of the catalyst, indicating that the Cu⁺ species were the active sites of the WGS reaction. The easy redox between Cu²⁺ and Cu⁺ during the WGS reaction was considered to be responsible for the high activity of Cu–ZrO₂ at low temperatures. A reaction mechanism based on the redox was proposed.     

Effects of Reaction Variables on Fischer–Tropsch Synthesis with Co-Precipitated K/FeCuAlO<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> Catalysts

Abstract  

The effects of reduction temperature and reaction temperature, pressure and space velocity on iron-based K/FeCuAlO _x Fischer–Tropsch catalysts prepared by co-precipitation were investigated. The catalyst reduced at 150 °C deactivated quickly due to an abundance of unreduced iron species. With increasing reduction temperature, the iron oxide’s phase transformed from hematite (α-Fe₂O₃) to magnetite (Fe₃O₄) and finally to metallic iron (α-Fe). The induction period to reach steady-state catalytic activity was reduced at increased reduction temperatures due to in situ reduction by syngas during reaction. CO conversion increased with increasing reaction temperature, and selectivity to C₅+ decreased with increasing reaction pressure and space velocity. At reaction temperatures up to of 300 °C, CO₂ formation by the water–gas shift reaction was linearly correlated with the extent of CO conversion, and CO₂ formation was slightly suppressed at ≥350 °C by a reverse water–gas shift reaction.     

Filamentous carbon templated SiO2–NiO aerogel: structure and catalytic properties for direct oxidation of hydrogen sulfide into sulfur

Silica aerogels comprising nickel oxide nanoparticles were synthesized with no use of supercritical drying. A high specific surface area (more than 1000 m²/g), mesoporous structure and considerable stability to sintering up to 900 °C are characteristic of these aerogels. The aerogels were synthesized using the sol–gel method. Filamentous carbon was templated by silica, tetraethoxysilane being used for supplying silica. Carbon was burnt later. Analysis of the aerogel structure revealed the presence of silica nanotubes and nanofibers. Aerogel testing for direct oxidation of H₂S into S⁰ demonstrated as high as 60% conversion of hydrogen sulfide at almost 100% selectivity under stoichiometric conditions at the temperature range of 300–350 °C and 73% conversion at 100% selectivity at a considerable excess of oxygen at 160 °C. This revised version was published online in July 2006 with corrections to the Cover Date.     

Formation of C m H n (m ≥ 3, n ≤ m) hydrocarbons from C1 and C2 molecules by high‐temperature (≥1000°C), short‐contact‐time (1–10 ms) nozzle beam reactions

A nozzle, fabricated from nickel, molybdenum, iron, palladium, and quartz was utilized to produce longer chain hydrocarbons, C _m H _n (m ≥ 3, n≤ m) from C₂ (ethane, acetylene) and C₁ (methane) reactants at nozzle temperature range 1000–1150°C. The conversion of ethane was close to 100% at T _noz = 1000°C, while that of methane reached 20% at T _noz = 1150°C. The contact time in the nozzle is in the 10^-3–10^-2 s range. The reactions are first and higher order in reactant pressure. The reaction mechanism involves the formation of free radicals at the nozzle surface followed by gas‐phase reactions. This revised version was published online in July 2006 with corrections to the Cover Date.     

Kinetics of the hydroformylation of soybean oil by ligand-modified homogeneous rhodium catalysis

The kinetics and mechanism of the hydroformylation of soybean oil by homogeneous ligand-modified rhodium catalysts were investigated at 70–130°C and 4000–11,000 kPa. The effects of reaction rates on systematic variations in reaction parameters were evaluated in order to develop an industrial process to convert vegetable oils to polyaldehydes. The activation energies in the presence of triphenylphosphine (Ph₃P) (61.1±0.8 kJ/mol) (mean±SD) and triphenyl phosphite [(PhO)₃P] (77.4±5.0 kJ/mol) were determined. The catalyst was deactivated at temperatures higher than 100°C. An evaluation of the effects of the reaction parameters on initial rates yielded the rate laws for Ph₃P {rate=k [olefin][Rh(CO)₂Acac]^1.1 [Ph₃P]^−0.5 (pH₂+pCO)^1.4, where Rh(CO)₂Acac is (acetylacetonato)dicarbonylrhodium (I)} and (PhO)₃P {rate=[olefin] [Rh(CO)₂Acac]^1.2 [(PhO)₃P]^−0.8 (pH₂+pCO)^0.9 at total pressures lower than 7000 kPa, and rate =[olefin] [Rh(CO)₂Acac]^1.2 [(PhO)₃P]^−0.8(pH₂+pCO)^1.7 at total pressures higher than 7000 kPa}.     

Synthesis and characterization of new polyamides and polyimides containing dioxypyrimidine moiety in the main chain with bulky imidazole pendent group: solubility, thermal and photophysical properties

A new symmetrical diamine monomer containing dioxypyrimidine and two diaryl imidazole bulky pendent group was synthesized by the nucleophilic substitution reaction of 4,6 dihydroxy pyrimidine with the synthesized 2-(2-chloro-5-nitrophenyl)-4,5-diphenyl-1H-imidazole (I). A series of novel fluorescent imidazole-containing polyamides (PAs) with inherent viscosities of 0.52–0.78 dL/g was prepared by direct polycondensation of the diamine with various dicarboxylic acids. These PAs were readily soluble in many organic solvents and could be solution-cast into tough and flexible films. The PAs exhibited glass transition temperatures (T_g)s between 202 and 260 °C, and 10% weight loss temperatures in the range of 345–470 °C in air. In addition, three novel polyimides (PIs) with inherent viscosities of 0.38–0.56 dL/g were prepared by addition reaction of the diamine with commercially available tetracarboxylic dianhydrides and subsequent chemical imidization. The PIs exhibited good solubility in polar solvents such as NMP. These polymers exhibited T_gs in the range of 237–285 °C and their 10% weight-loss temperatures varied from 440 to 520 °C.     

Amine-terminated aromatic and semi-aromatic hyperbranched polyamides: synthesis and characterization

A facile synthetic approach to aromatic and semiaromatic amine-terminated hyperbranched polyamides via direct polymerization of triamine (B₃) with different diacid chlorides (A₂) was explored. An aromatic triamine, 1,3,5-tris(4′-aminophenylcarbamoyl)benzene (TAPCB), was synthesized and monomers were characterized by elemental analysis, FTIR, ¹H and ¹³C NMR spectroscopy. Finally, the polycondensation reaction of TAPCB with terephthaloyl chloride (TPC), isophthaloyl chloride (IPC), sebacoyl chloride (SC) and adipoyl chloride (AC) resulted in the preparation of four hyperbranched polyamides i.e., HBPA 1, 2, 3 and 4, respectively. FTIR and ¹H NMR analyses confirmed the structures of the ensuing polymers and DB was found between 0.51–0.55. These thermally stable amorphous HBPAs were soluble in polar aprotic solvents at room temperature having glass transition temperatures (T_g) between 138–198 °C. Inherent viscosities (η_inh) and weight average molecular weights (M_w) were in the range of 0.27–0.35 dL/g and 1.3 × 10⁴–2.7 × 10⁴, respectively. Future prospects are envisaged.     

Synthesis of δ-eicosanolactone and δ-docosanolactone directly from meadowfoam oil

δ-Eicosanolactone and δ-docosanolactone were synthesized directly from the triacylglycerides of meadowfoam (Limnanthes) oil. Perchloric and sulfuric acids were used in stoichiometric quantities (0.5–4.0 mol equiv) to cyclize triglyceride to δ-lactone. When the reactions were run in the absence of solvent at 40°C, δ-lactone yields ranged from 17–75% where δ/γ ratios ranged from 6∶1 to 10.4.∶1. Sulfuric and perchloric acids gave similar yields for their individually optimized reactions. Perchloric acid-catalyzed reactions required less acid to produce similar amounts of δ-lactone (HClO₄ at 2.0 mol equiv gave 73% yield vs. H₂SO₄, which gave 75% yield at 2.5 mol equiv). The use of polar nonparticipating solvents during the reaction had little impact on δ-lactone formation or δ/γ ratio. Higher perchoric acid concentrations provided higher δ-lactone yields with δ/γ ratios remaining nearly constant. The effect of sulfuric acid on δ-lactone yield and δ/γ ratio was more direct; higher acid concentration improved, both. Both crystallization and short path distillation improved δ-lactone quality but short path distillation gave, higher recovered yields. The δ-lactones were converted to their corresponding 5-hydroxy acids in the same reaction vessel, separated, and cyclized back to δ-lactones upon heating under vacuum. This provided a convenient method for δ-lactone purification.     

Catalytic dry oxidation of aniline,benzene, and pyridine adsorbed on a CuO doped activated carbon

Adsorption of aniline, benzene and pyridine from water on a copper oxide doped activated carbon (CuO/AC) at 30 °C and oxidation behavior of the adsorbed pollutants over CuO/AC in a temperature range up to 500 °C are investigated in TG and tubular-reactor/MS systems. Results show that the AC has little activity towards oxidation of the pollutants and CuO is the active oxidation site. Oxidation of aniline occurs at 231–349 °C and yields mainly CO₂, H₂O and N₂. Oxidation of pyridine occurs at a narrower temperature range, 255–309 °C, after a significant amount of desorption starting at 150 °C. Benzene desorbs at temperatures as low as 105 °C and shows no sign of oxidation. The result suggests that adsorption-catalytic dry oxidation is suitable only for the strongly adsorbed pollutants. Oxidation temperatures of CuO/AC for organic pollutants are higher than 200 °C and pollutants desorbing easily at temperatures below 200 °C cannot be treated by the method. This work was presented at the 7 ^th China-Korea Workshop on Clean Energy Technology held at Taiyuan, Shanxi, China, June 26–28, 2008.     

Preparation of zeolitic adsorbents from waste coal fly ash

Power plants burning coal generate a large amount of fly ash as waste matter. The objective of this study is to produce zeolitic adsorbents that possesses high adsorptive capacity for toxic cations. The sample was first pretreated with a High Intensity Magnetic Separator for the removal of iron and magnetic materials (mainly Fe₂O₃ and TiO₂). The zeolitic adsorbents were prepared under the various conditions of NaOH concentration (1–5 N), reaction time from 3 to 96 hours and at the various temperatures of 60, 80 and 100°C. The results of the experiment showed that the coal fly ash should be synthesized with 4 N NaOH for 48 hours at 100°C in order to have good adsorptive capacity. The zeolitic adsorbents showed higher cation exchange capacity values than the natural zeolite in removing NH ₄ ⁺ , Pb²⁺, Ca²⁺and Cd²⁺ions.     

Synthesis of well-defined norbornene–lactone-functionalized polymers via ATRP

Well-defined norbornene–lactone-functionalized polymers were synthesized by atom transfer radical polymerization (ATRP) of 5-methacryloxy-6-hydroxynorbornene-2-carboxylic-6-lactone (MNL) and 5-acryloxy-6-hydroxynorbornene-2-carboxylic-6-lactone (ANL) monomers. The ATRP of MNL initiated by ethyl 2-bromopropionate (EBrP), in both N,N-dimethylformamide (DMF) and o-dichlorobenzene (ODCB) solvents was successfully carried out in the presence of CuCl/CuBr and N,N,N′′,N′′,N′′-pentamethyltriethylenetetramine (PMDETA) at 70 °C. The CuCl/ODCB catalyst system gave rise to a lower M _w/M _n (≦1.20) than CuBr/DMF catalyst system. The ATRP of ANL was feasible in the presence of CuBr and PMDETA at 70 °C but showed lower reactivity than MNL. The resulting polymers were characterized by means of gel permeation chromatography (GPC) and ¹H NMR spectroscopy.     

Purification and characterization of a thermophilic chitinase produced by <Emphasis Type="Italic">Aeromonas</Emphasis> sp. DYU-Too7

An extracellular chitinase, produced by Aeromonas sp. DYU-Too7, was purified in the following procedures: ammonium sulfate precipitation, ultrafiltration, chromatographic separation of DEAE-sepharose CL-6B and sephacrylS-100HR. The resulting chitinase has a molecular mass of 36 kDa, an optimal reaction pH of 5.0, and an optimal reaction temperature of 70°C. It retains almost 100% activity in the pH range of 5.0–8.0. This chitinase has a high thermal tolerance and retained 90% of its activity at 50°C and 75% at 60°C. Enzyme activity was inhibited by Ba²⁺, Hg²⁺, Mg²⁺ and Ag⁺ cations, but was not substantially inhibited by the K⁺ cation nor the chelating agent EDTA. The K _m and V _mα , using colloidal chitin as a substrate, are 6.3 g/L and 18.69 μmol/min/mg-protein, respectively. The 36 kDa chitinase of Aeromonas sp. DYU-Too7 is an exo-type enzyme, because chitobiose was the main hydrolysate in hydrolysis of colloidal chitin.