Effect of polymerization conditions on o‐phenylenediamine and o‐phenetidine oxidative copolymers

A series of new o‐phenylenediamine (OPD)/o‐phenetidine (PHT) copolymers with partly phenazine‐like structures has been successfully synthesized at three polymerization temperatures by chemically oxidative polymerization in four different polymerization media. The molecular structures and properties of the resulting OPD/PHT polymers were investigated by IR, UV–vis and high‐resolution ¹H NMR spectroscopies, and DSC, in order to ascertain the effect of reaction temperature, comonomer ratio and acid medium. The copolymerization mechanism of OPD with PHT monomers has been proposed. It is found that the statistical OPD/PHT copolymer obtained at a temperature of 118 °C has a higher degree of polymerization than that obtained at 12–17 °C. The OPD content in the copolymers calculated from NMR spectroscopic analysis is higher than that in the feed OPD content, whereas the OPD content calculated from element analysis is slightly lower than the feed OPD content. It can be predicted that denitrogenation takes place in the OPD units during the polymerization process at OPD/PHT molar ratios of 90/10 and 100/0. These OPD/PHT copolymers exhibit a much better solubility than the OPD homopolymer, hence suggesting an incorporation of PHT units into the phenazine structure of the homopolymer. The thermal behavior of the copolymers was also studied. Copyright © 2004 Society of Chemical Industry     

Effect of Plate Oscillation on Bubble Residence Time in an Aerated Stagnant Liquid

Gas transfer efficiency during absorption is an important factor in various technological processes involving the interaction between liquid and gaseous systems. It is known that gas bubble motion characteristics strongly affect the efficiency of mass transfer during gas absorption. A device for mechanical vibration of an aerated liquid was designed, based on a cylindrical column filled up with tab water and a plate oscillating in the vertical direction. The goal of the present study is to investigate the effect of vibration parameters such as amplitude, frequency and form of the applied signal on the efficiency of the oxygenation process. Bubble residence time in the liquid and bubble depth of submergence related to the oscillating plate surface were chosen as main parameters for measurements. Furthermore, experiments were conducted to study the effect of the design parameters of the vibrating plate on bubble motion characteristics. The resultant data show that bubble residence time and depth of submergence can be controlled by changing the amplitude, the frequency and the form of the vibration field applied.     

Morphology development in polyethylene/polystyrene blends: the influence of processing conditions and interfacial modification

The influence of processing conditions and interfacial modification on the morphology evolution and the composition range within which fully co‐continuous high density polyethylene/polystyrene blend structures can exist during blending in a single screw extruder was studied. Blends ranging from pure A to pure B component, with and without compatibilizer, were prepared under two different shear rates. It was found that high shear rates displaced the breakdown–coalescence balance of the dispersed nodules to the side of coalescence, narrowing the percolation domain and the critical composition for full co‐continuity decreased with increasing shear rates. The addition of a tri‐block compatibilizer induced the percolation threshold of the polystyrene phase to begin at lower percentages of polyethylene but the phase inversion point did not change. The experimental results are discussed in the light of various theoretical models. Copyright © 2005 Society of Chemical Industry     

Interconnected power systems with superconducting magnetic energy storage

The objective of this work is to discuss the concept of back‐to‐back interconnection systems with energy storage, especially with a Superconducting Magnetic Energy Storage (SMES) incorporated into a back‐to‐back DC link. In this case, each converter of the back‐to‐back system is used as a power conditioning system for the SMES coils. Since the AC–DC converter can be designed independently of the frequency of the power system, a two‐way switch is connected to the AC side of each converter. This two‐way switch can select the interconnected power systems. By using the two‐way switches, this system can provide the stored energy in the SMES system to each interconnected power system through two AC–DC converters. For instance, lower‐cost power of each power network can be stored through two converters during the off‐peak hours and made available for dispatch to each power network during periods of demand peak. Then this system increases the reliability of electric power networks and enables the economical operations depending on the power demand. This paper describes the unique operations of the back‐to‐back interconnection with SMES and discuses the optimal SMES configuration for a 300‐MW‐class back‐to‐back interconnection. © 2008 Wiley Periodicals, Inc. Electr Eng Jpn, 164(2): 37–43, 2008; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/eej.20482     

Zeolite synthesis from paper sludge ash with addition of diatomite

BACKGROUND: This study aimed to investigate the synthesis of zeolites from paper sludge ash (PSA) with added diatomite to remove both NH₄⁺ and PO₄^3? for water purification. The PSA had low Si and significant Ca contents. Four types of diatomite: white (T‐W) and brown (T‐B) from deposits of marine origin in Takanosu, and white (S‐W) and gray (S‐G) from lacustrine deposits in Shonai, were added to NaOH solution to increase the Si content and thereby synthesize zeolites with high cation exchange capacity (CEC). RESULTS: The order of the amounts of Si extracted from the diatomite to the alkali solution was S‐W > T‐W = T‐B > S‐G, which correlates with the amorphous SiO₂ content of diatomite. The original ash without addition of diatomite yielded hydroxysodalite with CEC of about 1.0 mmol g^?1. For all samples, the addition of diatomite to the solution yielded zeolite‐P with a higher CEC, but the addition of excess Si inhibited the synthesis of zeolite‐P, and the CEC of the product was low. A product with high CEC including zeolite‐P was obtained in a solution with around 500 mmol L^?1 of Si concentration, and had the ability to remove both NH₄⁺ and PO₄^3?. CONCLUSION: Diatomite has the potential for used as an additive for the synthesis of high CEC zeolite from PSA. The product with zeolite‐P exhibited relatively high CEC, capacity for NH₄⁺ uptake, and the ability to remove PO₄^3? by precipitation, which is preferable for water purification applications. Copyright © 2008 Society of Chemical Industry     

Photocatalytic degradation of 2,2‐bis(4‐hydroxy‐3‐methylphenyl) propane (BPP) based on molecular recognition interaction

BACKGROUND: Endocrine disruptors in the aquatic environment and their potential adverse effects are currently issues of concern. One of these endocrine disruptors is 2,2‐bis(4‐hydroxy‐3‐methylphenyl)propane (BPP). In this work the molecular recognition interaction of BPP with β‐cyclodextrin (β‐CD) was studied using IR spectroscopy and steady state fluorescence spectroscopy, and the photocatalytic degradation behaviour of BPP based on molecular recognition interaction was investigated in a TiO₂/UV–visible (λ_max = 365 nm) system. This might provide a new method for the treatment of some organic pollutants in wastewater. RESULTS: β‐CD reacts with BPP to form a 1:1 inclusion complex, the formation constant of which is 4.94 × 10³ L mol^?1. The photodegradation rate constant of BPP after molecular recognition by β‐CD showed a 1.42‐fold increase in the TiO₂/UV–visible (λ_max = 365 nm) system. The photodegradation of BPP depended on the concentration of β‐CD, the pH value, the gaseous medium and the initial concentration of BPP. The photodegradation efficiency of BPP with molecular recognition was higher than that without molecular recognition. After 100 min of irradiation the mineralisation efficiency of BPP after molecular recognition by β‐CD reached 94.8%, whereas the mineralisation efficiency of BPP before molecular recognition by β‐CD was only 40.6%. CONCLUSION: The photocatalytic degradation of BPP after molecular recognition by β‐CD can be enhanced in the TiO₂/UV‐visible (λ_max = 365 nm) system. This enhancement is dependent on the enhancement of the adsorption of BPP, the moderate inclusion depth of BPP in the β‐CD cavity and the increase in the frontier electron density of BPP after molecular recognition. Copyright © 2008 Society of Chemical Industry     

One‐step production of 2,3‐butanediol from starch by secretory over‐expression of amylase in Klebsiella pneumoniae

BACKGROUND: 2,3‐Butanediol (2,3‐BD) is a valuable chemical that can be biosynthesized from many kinds of substrates. For commercial biological production of 2,3‐BD, it is desirable to use cheap substrate without pretreatment, such as starch. However, there have been few reports on the production of 2,3‐BD directly from starch. RESULTS: In this work, gene malS coding for α‐amylase (EC 3.2.1.1) precursor was inserted into plasmid pUC18K, and secretory over‐expression of α‐amylase was achieved by engineered Klebsiella pneumoniae. The extracellular recombinant amylase accelerated the hydrolyzation of starch, and one‐step production of 2,3‐BD from starch was carried out by engineered K. pneumoniae. A 2,3‐BD concentration of 3.8 g L^?1 and yield of 0.19 g 2,3‐BD g^?1 starch were obtained after 24 h fermentation. CONCLUSION: The one‐step production of 2,3‐BD from starch was achieved by secretory over‐expression of amylase in K. pneumoniae. This would simplify the process and reduce the production cost considerably by enabling use of starch with minimal pretreatment. Copyright © 2008 Society of Chemical Industry     

Inhibition of sulfide on the simultaneous removal of nitrate and p‐cresol by a denitrifying sludge

BACKGROUND: Many industrial discharges, such as those generated from petrochemical refineries, contain large amounts of sulfurous, nitrogenous and organic contaminants. Denitrification has emerged as a suitable technology for the simultaneous removal of these pollutants in a single reactor unit; however, more evidence is demanded to clarify the limitations of denitrification on the simultaneous removal of sulfide and phenolic contaminants and to optimize the biological process. The aim of this study was to evaluate the capacity of a denitrifying sludge to simultaneously convert sulfide and p‐cresol via denitrification. RESULTS: Sulfide was the preferred electron donor over p‐cresol, imposing a 5 h lag phase (required for complete sulfide removal) on organotrophic denitrification. Addition of sulfide (20 mg S^2? L^?1) to p‐cresol‐amended denitrifying cultures also decreased the reduction rate of nitrate and nitrite, as well as the production rate of nitrogen gas. Nitrite reduction rate was the most affected step by sulfide, decreasing from 35 to 21 mg N (g VSS d)^?1. A synergistic inhibitory effect of nitrate and sulfide was also observed on nitrite reduction. Despite the effects of sulfide on the respiratory rates monitored, complete removal of nitrate, sulfide and p‐cresol could be achieved after 48 h of incubation. CONCLUSION: Our results suggest that simultaneous removal of sulfide and p‐cresol could be achieved in denitrifying reactors, but a large hydraulic residence time may be required to sustain an efficient process due to inhibitory effects of sulfide. Copyright © 2008 Society of Chemical Industry     

Synthesis of p‐aminophenol from the hydrogenation of nitrobenzene over metal–solid acid bifunctional catalyst

BACKGROUND: A single‐step conversion of nitrobenzene (NB) to p‐aminophenol (PAP) through catalytic hydrogenation is a widely used synthesis route for PAP. The main shortcoming of this route is the use of sulfuric acid for rearrangement of the phenylhydroxylamine (PHA) intermediate. In this paper, S₂O₈^2?/ZrO₂ (PSZ) solid acid and Pt‐S₂O₈^2?/ZrO₂ (Pt‐PSZ) bifunctional catalysts were prepared for the synthesis of PAP in non‐acid medium. RESULTS: Calcination temperature has a substantial effect on the acidity, structure and activity for PHA rearrangement of PSZ. The highest PAP yield was 33.8% over PSZ calcined at 823 K when the reaction was carried out in water at 423 K. A high PAP yield of 23.9% was achieved by a single‐step reaction of nitrobenzene over Pt‐PSZ bifunctional catalysts. CONCLUSION: PSZ solid acid exhibits high activity for PHA rearrangement. Perfect tetragonal ZrO₂ and much stronger acid sites play important roles in catalytic activity. Inhibiting the hydrogenation activity by reducing the amount of Pt loading on Pt‐PSZ can improve the competition of PHA rearrangement on acid sites with hydrogenation of PHA on metal active sites, resulting in better selectivity to PAP. Copyright © 2008 Society of Chemical Industry     

Photodegradation mechanism and stabilization of polyphenylene oxide and rigid‐rod polymers

Poly(2,4‐dimethyl‐1,4‐phenylene oxide) (PPO), poly(benzo[1,2‐d:5,4‐d′]bisoxazole‐2,6‐diyl‐1,4‐phenylene) (PBO) and poly(benzo[1,2‐d:4,5‐d′]bisthiazole‐2,6‐diyl‐1,4‐phenylene) (PBZT), which are polymers with extended conjugated structures, undergo a self‐sensitized photo‐induced electron‐transfer reaction. A second component is not required. This article presents many similar observations on these polymers when they are exposed to light and evidence to support the proposed photo‐induced electron‐transfer mechanism. Methods to stabilize these polymers against photo‐oxidation are also described. Workers investigating other conjugated polymeric systems may find the experimental methods, observations and polymer stabilization approaches discussed in this review useful. Copyright © 2005 Society of Chemical Industry