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     

Application of artificial neural networks to the analysis of two‐dimensional fluorescence spectra in recombinant E coli fermentation processes

A two‐dimensional (2D) spectrofluorometer was used to monitor various fermentation processes with recombinant E coli for the production of 5‐aminolevulinic acid (ALA). The whole fluorescence spectral data obtained during a process were analyzed using artificial neural networks, ie self‐organizing map (SOM) and feedforward backpropagation neural network (BPNN). The SOM‐based classification of the whole spectral data has made it possible to qualitatively associate some process parameters with the normalized weights and variances, and to select some useful combinations of excitation and emission wavelengths. Based on the classified fluorescence spectra a supervised BPNN algorithm was used to predict some of the process parameters. It was also shown that the BPNN models could elucidate some sections of the process's performance, eg forecasting the process's performance. Copyright © 2005 Society of Chemical Industry     

Production of silver‐doped analcime by isomorphous substitution technique

BACKGROUND: Metal‐exchanged zeolites have been reported to have significant limitations on cayalytic activity, such as counterbalancing the negative framework charges and limitation of active space. Alternative methods of incorporating silver ions into the framework of zeolites are therefore necessary. This paper reports on a technique for producing silver doped analcime by isomorphous substitution of silver ion into the framework of analcime. The amount of aluminium in the gel composition was reduced by a factor of 5%, 10% and 20% and an equivalent amount of silver was added to the gel and treated in a conventional manner for zeolite crystallisation. Some of the aluminium in the reaction gel was replaced with the silver. The silver‐doped analcime samples where characterised by X‐ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X‐rays (EDX), Fourier transform infrared (FTIR) spectroscopy and inductively coupled plasma‐atomic emission spectroscopy (ICP‐AES) analysis. RESULTS: The amount of silver ions loaded for each reduction of aluminium as determined by EDX were found to be (w/w) 0.29%, 1.41% and 2.10%, respectively. XRD pattern SEM images of the silver‐doped analcime showed the presence of zeolite P in addition to analcime. CONCLUSION: Silver‐doped analcime was successfully produced with different silver loadings and may exhibit higher anti‐microbial activities than silver‐exchanged counterparts. Copyright © 2008 Society of Chemical Industry     

Surface modification of starch nanocrystals through ring‐opening polymerization of ε‐caprolactone and investigation of their microstructures

Bionanoparticles of starch obtained by submitting native potato starch granules to acid hydrolysis conditions. The resulted starch nanoparticles were used as core or macro initiator for polymerization of ε‐caprolactone (CL). Starch nanoparticle‐g‐polycaprolactone was synthesized through ring‐opening polymerization (ROP) of CL in the presence of Sn(Oct)₂ as initiator. The detailed microstructure of the resulted copolymer was characterized with NMR spectroscopy. Thermal characteristic of the copolymer was investigated using DSC and TGA. By introducing PCL, the range of melting temperature for starch was increased and degradation of copolymer occurred in a broader region. X‐ray diffraction and TEM micrographs confirmed that there was no alteration of starch crystalline structure and morphology of nanoparticles, respectively. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Organic‐acid‐catalyzed sol–gel route for preparing poly(methyl methacrylate)–silica hybrid materials

In this study, a series of organic–inorganic hybrid sol–gel materials consisting of a poly(methyl methacrylate) (PMMA) matrix and dispersed silica (SiO₂) particles were successfully prepared through an organic‐acid‐catalyzed sol–gel route with N‐methyl‐2‐pyrrolidone as the mixing solvent. The as‐synthesized PMMA–SiO₂ nanocomposites were subsequently characterized with Fourier transform infrared spectroscopy and transmission electron microscopy. The solid phase of organic camphor sulfonic acid was employed to catalyze the hydrolysis and condensation (i.e., sol–gel reactions) of tetraethyl orthosilicate in the PMMA matrix. The formation of the hybrid membranes was beneficial for the physical properties at low SiO₂ loadings, especially for enhanced mechanical strength and gas barrier properties, in comparison with the neat PMMA. The effects of material composition on the thermal stability, thermal conductivity, mechanical strength, molecular permeability, optical clarity, and surface morphology of the as‐prepared hybrid PMMA–SiO₂ nanocomposites in the form of membranes were investigated with thermogravimetric analysis, differential scanning calorimetry, dynamic mechanical analysis, gas permeability analysis, ultraviolet–visible transmission spectroscopy, and atomic force microscopy, respectively. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008