Model-evaluation of the erosion behavior of activated sludge under shear conditions using a chemical-equilibrium-based model

The primary particles would erode from the sludge surface under shear conditions. As the primary particles have significant effects on the solid–liquid separation process, the erosion behaviors of activated sludge in biological wastewater treatment processes under shear conditions were investigated using a chemical-equilibrium-based model. The equilibrium dispersed mass concentration of the primary particles in the sludge solution was found to nonlinearly increase with the solid content and shear intensity, and could be well described by the model. Compared with other sludge reported in literatures, the activated sludge used in this study was found to be more stable during the shear test, with a high equilibrium constant K⁰ of 30.2 and a low Gibbs’ free energy of adhesion (ΔG⁰) of −3.41 at a shear intensity of 800 s⁻¹. The two parameters could be used to evaluate the strength of the sludge. The negative value of ΔH indicates the energy demand for the erosion process. The low value of ΔH for the activated sludge used in this study indicates that the erosion process was more energy demanding and the erosion process was less shear dependent for the activated sludge used in this study.     

Biological COD reduction and inorganic suspended solids accumulation in a pilot-scale membrane bioreactor for traditional Chinese medicine wastewater treatment

A pilot-scale test was conducted in a membrane bioreactor (MBR) for 452 days to treat high-strength traditional Chinese medicine (TCM) wastewater from two-phase anaerobic digest effluent. This study focuses on the chemical oxygen demand (COD) reduction and inorganic suspended solid (ISS) accumulation. The wastewater was high in COD, varying daily between 259 and 12,776 mg L⁻¹. Almost all the COD was removed by the MBR system, leaving a COD of <50 mg L⁻¹ in the MBR effluent. This indicated a great potential of the MBR in TCM wastewater reuse. ISS produced in the bioreactor by metabolism of microorganism increased from 265 to 4912 g h⁻¹, which showed that there were large numbers of ISS accumulation in the bioreactor. Two models, built on the material balances of COD and ISS, were developed for the simulation of MBR system performance in the biodegradation of TCM wastewater. Consequently, the kinetic constants including the maximum substrate specific biodegradation rate (V_max), the half-saturation coefficient (K_s) and the inorganic suspended solids growth rate (k) were calculated as V_max, 3.64, 3.82, 4.39 d⁻¹, K_s, 56.4, 225, 394 mg L⁻¹ and k, 265, 888, 4912 mg L⁻¹ d⁻¹ using the operational data at different hydraulic retention times (HRTs). The models well fitted the pilot-scale experimental data, and were able to simulate the COD reduction and ISS accumulation.     

In situ activated 3,5-dinitrobenzoic acid covalent attached to nanostructured platform for NADH electrooxidation

The activation of 3,5-dinitrobenzoic acid (3,5-DNBA) in situ is proposed for electrocatalytic detection of NADH at low overpotentials. Thus, 3,5-DNBA was strategically connected to a nanostructured surface based on MWCNTs and PEI (an amine rich polymer). Then, R–NO/R–NHOH was electrogenerated in situ by cycling the potential between 0.15 and −0.55 V versus SCE. The formation of an intermediate charge transfer complex is proposed for the reaction between NADH and redox mediator. The apparent Michaelis–Menten constant (K_M) obtained by RDE voltammetry and amperometry was in good agreement, around 10⁻⁵ mol L⁻¹. The k_obs for the catalytic reaction evaluated by chronoamperometry and RDE voltammetry, was in good agreement and was found to be around 10⁴ L mol⁻¹ s⁻¹. The sensor provides a linear response range for NADH from 4.0 up to 42.0 μmol L⁻¹ with a sensitivity of 71 nA L μmol⁻¹, detection and quantification limits of 1.2 and 4.0 μmol L⁻¹ respectively, with a response time of 0.16 s.     

一种新型反应器——生物气射流循环厌氧流化床的启动与运行特性

A novel anaerobic reactor, jet biogas inter-loop anaerobic fluidized bed （JBILAFB）, was designed and constructed. The start-up and performance of the reactor was investigated in the Process. of .artificial glucose wastewater treatment. With the wastewater recycle ratio of 2.5 ： 1, the recycled wastewater with biogas could mix sludge and wastewater in the JBILAFB reactor completely. The start-up of the JBILAFB reactor could be completed in less than 70 d through maintenance of hydraulic retention time （HR~I＂） and stepwise increase of feed total organic carbon （TOC） concentration. After the start-up, with the volumetric TOC loadings of 14.3 kg·m ^-3·d^-1, the TOC removal ratio, the effluent pH, and the volatile fatty acids （VFA）/alkalinity of the JBILAFB reactor were more than 80%, close to 7.0 and less than 0.4, respectively. Moreover, CH4 was produced at more than 70% of the theoretical value, The reactor exhibited high stability under the condition of high volumetric TOC loading. Sludge granules in the JBILAFB reactor were developed during the start-up and their sizes were enlarged with the stepwise increase of volumetric TOC loadings from 0.8 kg.m^-3.d ^-1 to 14.3 kg.m^-3.d^-1. Granules, an offwhite color and a similar spherical shape, were mainly comprised of global-like bacteria. These had good methanogenic activity and settleability, which were formed probably through adhesion of the bacteria. Some inorganic metal compounds such as Fe, Ca, Mg, Al, etc. were advantageous to the formation of the granules.     

Valorisation of hardwood hemicelluloses in the kraft pulping process by using an integrated biorefinery concept

A primary hydrolysis treatment (auto or acid-catalysed) of Eucalyptus globulus wood was performed before the cooking stage to extract part of the hemicelluloses that otherwise would be dissolved in the kraft liquor and burned. As xylose was the main monosaccharide Pichia stipitis was selected to produce bioethanol. Two methods were tested, with different alkalis, to reduce hydrolysates toxicity and adjust pH. A two-step method using Ca(OH)₂ leads to better fermentation results. Acid hydrolysates promoted higher ethanol concentrations (12 g L⁻¹) with high productivity and yield values (0.22 g_eth L⁻¹h⁻¹ and 0.48 g_eth/g_{xyl eqs}), whilst auto-hydrolysates, even after a secondary hydrolysis, gave low ethanol concentrations (2–4 g L⁻¹). The impacts on kraft cooking and pulp quality were also studied in order to fully understand the feasibility of this biorefinery concept (combining ethanol production and hardwood pulping). A decrease of the overall pulp yield (10% for auto- and 15% for acid-hydrolysis) was observed. However, a decrease on bleaching requirements (up to 15%) and on brightness reversion was registered. Moreover, auto-hydrolysis improves pulp viscosity, whilst acid-hydrolysis is more efficient in metals leaching. Overall, from the pulp production point of view, auto-hydrolysis conditions are more attractive than the acid-catalysed ones.     

Modelling and simulation of a gas–solids dispersion flow in a high-flux circulating fluidized bed (HFCFB) riser

Radial solids velocity profiles were computed on seven axial levels in the riser of a high-flux circulating fluidized bed (HFCFB) using a two-phase 3-D computational fluid dynamics model. The computed solids velocities were compared with experimental data on a riser with an internal diameter of 76 mm and a height of 10 m, at a high solids flux of 300 kg m⁻² s⁻¹ and a superficial velocity of 8 m s⁻¹. Several hundreds of experimental and numerical studies on CFBs have been carried out at low fluxes of less than 200 kg m⁻² s⁻¹, whereas only a few limited useful studies have dealt with high solids flux. The k– two-phase turbulence model was used to describe the gas–solids flow in an HFCFB. The model predicts a core–annulus flow in the dilute and developed flow regions similar to that found experimentally, but in the region of highest solids concentration it is somewhat overpredicted at the level close to the inlet.     

Bimetallic catalysts for the catalytic combustion of methane using microreactor technology

Pt–W and Pt–Mo based catalysts were evaluated for methane combustion using a sandwich-type microreactor. Alumina washcoated microchannels were impregnated with platinum in combination with and promoted with tungsten and molybdenum and compared with commercially available Pt/Al₂O₃ catalysts. Catalysts were tested in the range of 300–700 °C with flow rates adjusted to GHSV of 74,000 h⁻¹ and WHSV of 316 L h⁻¹ g⁻¹. Catalysts containing tungsten were found to be the most active and the most stable possibly due to a metal interaction effect. A Pt–W/γ-Al₂O₃ containing 4.6 wt% Pt and 9 wt% W displayed the highest activity with full conversion at 600 °C and a selectivity to CO₂ of 99%.     

Nickel inhibition of calcium precipitation by ureolytic mixed microorganisms under batch conditions

The respirometric assessment of the inhibitory impact of Ni(II) on substrate utilization and microbial carbonate precipitation (MCP) by ureolytic mixed microorganisms was investigated with a glucose containing mineral medium under batch conditions over an incubation period of 134 h. The IC₂₅ was determined as 224 mg Ni(II) L⁻¹ from the BOD values of samples. The interpretation of kinetic data showed that the substrate removal rate fitted a zero-order at the beginning of the incubation period and first-order during the last period, for a range of Ni(II) concentrations between 0 and 512 mg L⁻¹. Increasing Ni(II) concentrations from 0 to 512 mg L⁻¹ reduced the substrate degradation rate constant from 10.8 to 5.3 mg L⁻¹ h⁻¹ for zero-order rate constant (k₀), and from 0.015 to 0.002 h⁻¹ for first-order rate constant (k₁). The zero- and first-order reaction rates during incubation period were equalized to the reaction rate of the Monod equation in order to determine the kinetic constants, half saturation concentration (K_S) and maximum substrate removal rate (R_max). BOD removal rate was inhibited accordingly to mixed inhibition model with increasing Ni(II) concentrations during the calcification process. Also, the inhibition of calcium precipitation was observed at a higher Ni(II) concentration because of inhibition of ammonium production in these samples.     

Continuous operation of membrane bioreactor treating toluene vapors by Burkholderia vietnamiensis G4

A laboratory-scale biofilm membrane bioreactor inoculated with Burkholderia vietnamiensis G4 was examined to treat toluene vapors in a waste gas stream. The gas feed side and nutrient solution were separated by a composite membrane consisting of a porous polyacrylonitrile (PAN) support layer coated with a very thin (0.3 μm) dense polydimethylsiloxane (PDMS) top layer. After inoculation, a biofilm developed on the dense layer. The biofilm membrane bioreactor was operated continuously at different residence times (28–2 s) and loading rates (1.2–26.7 kg m⁻³ d⁻¹), with inlet toluene concentrations ranging from 0.21 to 4.1 g m⁻³. The overall performance of the membrane bioreactor was evaluated over a period of 165 days. Removal efficiencies ranging from 78% to 99% and elimination capacities from 4.2 to 14.4 kg m⁻³ d⁻¹ were observed after start-up period depending on the mode of operation. A maximum elimination capacity of 14.4 kg m⁻³ d⁻¹ was observed at a loading rate of 17.4 kg m⁻³ d⁻¹. Overall, the results illustrate that biofilm membrane reactors can potentially be more effective than conventional biofilters and biotrickling filters for the treatment of air pollutants such as toluene.     

Liquid flow texture analysis in trickle bed reactors using high-resolution gamma ray tomography

Trickle bed reactor performance and safety may suffer from radial and axial liquid maldistribution and thus from non-uniform utilization of the catalyst packing. Therefore, experimental analysis and fluid dynamic simulation of liquid–gas flow in trickle bed reactors is an important topic in chemical engineering. In the present study for the first time a truly high-resolution gamma ray tomography technique was applied to the quantitative analysis of the liquid flow texture in a laboratory cold flow trickle bed reactor of 90 mm diameter. The objective of this study was to present the comparative analysis of the liquid flow dynamics for two different initial liquid distributions and two different types of reactor configurations. Thus, the hydrodynamic behavior of a glass bead packing was compared to a porous Al₂O₃ catalyst particle packing using inlet flow from a commercial spray nozzle (uniform initial liquid distribution) and inlet flow from a central point source (strongly non-uniform initial liquid distribution), respectively. The column was operated in downflow mode at a gas flow rate of 180 L h⁻¹ and at liquid flow rates of 15 and 25 L h⁻¹.     

Effect of COD/NO3-N ratio on the performance of a hybrid UASB reactor treating phenolic wastewater

The effect of COD/O₃⁻-N ratio on the biodegradation of complex phenolic mixture was studied in bench scale hybrid upflow anaerobic sludge blanket (HUASB) reactors. HUASB reactor is a combination of a UASB unit at the lower part and an anaerobic fixed film at the upper end. The aim of this study was to evaluate the biodegradability of phenolic mixture (from synthetic coal wastewater) as the only carbon and energy source in continuous experiments using nitrate as the final electron acceptor. Synthetic coal wastewater contained phenol (490 mg/L); m-,o-,p-cresols (123.0 mg/L, 58.6 mg/L, 42 mg/L); 2,4-, 2,5-, 3,4- and 3,5 dimethyl phenols (6.3 mg/L, 6.3 mg/L, 4.4 mg/L and 21.3 mg/L) as major phenolic compounds representing the complex phenolic mixture. Nitrate nitrogen loading was increased from 0.11 g/m³/d to 0.5 g/m³/d in order to keep COD/NO₃⁻-N ratio as 20.1, 14.85, 9.9, 6.36 and 4.45. An input phenolics concentration of 752 mg/L and hydraulic retention time (HRT) of 24 h was maintained through out the study. Removal of phenolic mixture was found to increase with the lowering of COD/NO₃⁻-N ratio. Maximum phenolics removal of 98% was achieved at a COD/NO₃⁻-N ratio of 6.36. However, phenolics removal got adversely affected when COD/NO₃⁻-N ratio was reduced below 6.36. A nitrogen production efficiency of 78% was obtained according to nitrate consumption. Simultaneous denitrification and methanogenesis was observed in all the reactors throughout the study, demonstrating that denitrification is a feasible alternative for the treatment of coal wastewater. Granules degrading complex phenolic mixture were of diameter 1.6–2.25 mm.     

Kinetic studies on sorption of n-hexane in vanadium substituted MFI type zeolites of various crystal morphologies

The MFI type materials isomorphously substituted with vanadium form crystals of two morphology types. Investigations of sorption kinetics for n-hexane indicated for both morphologies a non-typical increase in the value of corrected transport diffusion coefficient with the crystals dimensions. An increase in the D₀ values with the vanadium content of the crystals has also been found, although it is not so well expressed as that with the dimensions. The increase in the D₀ values is from 1.1 × 10⁻¹¹ to 1.1 × 10⁻¹⁰ m²/s and may be a consequence of an additional system of larger pores, which is not reflected in the adsorption isotherms due to common occurrence of these pores in all crystals. It is also possible that vanadium causes a superior structure ordering and a decrease in/weakening of diffusion barriers.     

Magnetic properties of CNX whiskers

Carbon–nitrogen whiskers have been prepared by pyrolysis of 1,2-diaminopropane at 950 °C or of allylamine at 900 °C followed by quenching. They are scrolls of carbon film typically 250 nm thick and up to 1 mm long with about five layers in a structure like a “cigare russe” or “brandy snap”, about 50 μm in diameter. Approximately 8 wt% of nitrogen is incorporated into the carbon films, which are practically amorphous, exhibiting a broad diffraction peak at d = 0.34 nm. The whiskers are on the border of metallic conductivity with a resistivity of about 10⁻⁶ Ωm, and they may show either a positive or a negative temperature coefficient of resistance. The pyrolysis produces either whiskers, soot or both. Magnetization measurements of the whiskers made from 1,2-diaminopropane reveal a large diamagnetic susceptibility of χ = −170 × 10⁻⁹ m³  kg⁻¹ and a small ferromagnetic component of unknown origin with σ_S of up to 0.2 A m² kg⁻¹, whereas the soot shows a purely diamagnetic signal, with χ ≈ −40 × 10⁻⁹ m³ kg⁻¹.     

Catalytic NO–H2–CO–O2 reactions over Pt-supported mesoporous yttrium oxide

Catalytic light-off of a stream of NO, H₂, CO in an excess O₂ has been studied over various metal oxides loading 1 wt% Pt. Because a low-surface area Y₂O₃ (<5 m² g⁻¹) was found to exhibit the highest de-NO_x activity, a mesoporous Y₂O₃ was then synthesized from an yttrium-based surfactant mesophase templated by dodecyl sulfate , which was anion-exchanged by acetate (AcO = CH₃COO⁻). The product showed a 3-D mesoporosity with a large surface area (396 m² g⁻¹) and the Pt-supported catalyst achieved much improved light-off characteristics suitable for the low-temperature de-NO_x in the presence of CO and excess O₂.     

Solvent impregnated resins for the removal of low concentration phenol from water

The focus of this investigation is the development of a solvent impregnated resin for phenol removal from dilute aqueous solutions. Using a solvent impregnated resin (SIR) eliminates the problem of emulsification encountered in liquid–liquid extraction. Impregnated MPP particles and impregnated XAD16 particles are successfully used for phenol extraction. Impregnated MPP particles are preferred, as impregnated XAD16 particles show less mechanical strength and are more expensive. Impregnated MPP particles perform better compared to other synthetic adsorbents and basic ion exchangers. The maximum phenol capacity of impregnated MPP particles with 0.99 mol Cyanex 923 kg⁻¹ SIR is 4.1 mol kg⁻¹ SIR (386 mg g⁻¹ SIR) and of MPP particles containing 1.47 mol Cyanex 923 kg⁻¹ SIR it is 5.08 mol kg⁻¹ SIR (478 mg g⁻¹ SIR). The regenerability of impregnated MPP particles is easy and complete, and the particles are stable during several cycles. The equilibrium constants for the extraction of phenol are determined as K_chem = 37 L mol⁻¹ and K_phys = 18 (mol L⁻¹) (mol L⁻¹)⁻¹. With these values the SIR isotherms can be satisfactorily described.The results indicate that SIR technology is a promising alternative for the conventional phenol removal technologies at low phenol concentration levels.     

Steam reforming of n-hexadecane over noble metal-modified Ni-based catalysts

Steam reforming of n-hexadecane, a main constituent of diesel, over noble metal-modified Ni-based hydrotalcite catalyst was carried out in a temperature range of 700–950 °C, at an atmospheric pressure with space velocity of 10,000–100,000 h⁻¹ and feed molar ratio of H₂O/C = 3.0. The catalysts were prepared by a co-precipitation and dipping methods. The noble metal-modified Ni-based hydrotalcite catalyst displayed higher resistance for the sintering of active metal than the Ni-based hydrotalcite catalyst prepared by the conventional method. It was found that the Rh-modified Ni-based catalysts showed high resistance to the formation of carbon compared to Ni-based catalysts. The results suggest that Rh-modified Ni-based catalyst can be applied for the steam reforming (SR) reaction of diesel.     

Evaluation of atrazine degradation in UV/FeZSM-5/H2O2 system using factorial experimental design

Degradation of atrazine in model wastewater by UV/FeZSM-5/H₂O₂ system chosen as optimal for application of advanced oxidation process (AOP) has been studied in a batch photo reactor. The statistical study of the process was performed using two-level full factorial experimental design with the three process parameters. Individual parameters and their interaction effects on atrazine degradation were determined and statistical model of process was developed. The optimal operating conditions were established. This approach has also given a broader insight of the processes that were occurring in the reaction system, and it has finally led to simplification in terms of kinetics. Atrazine degradation was described by pseudo-first-order kinetics with observed rate constant k′ = 2 × 10⁻³ s⁻¹.     

A VOx/meso-TiO2 catalyst for methanol oxidation to dimethoxymethane

Mesoporous TiO₂ was prepared by simply controlling the hydrolysis of Ti(OBu)₄ with the help of acetic acid. The mesoporous TiO₂ had a well-crystallized anatase phase and a high surface area of 290 m² g⁻¹ with a pore size of about 4 nm. The anatase phase and the mesoporous structure were maintained in the VO_x/TiO₂ catalyst with a monolayer dispersion of V₂O₅, however, the surface area decreased to 126 m² g⁻¹. The catalyst was highly active and selective for methanol oxidation, giving about 55% conversion of methanol and 85% selectivity to dimethoxymethane at 423 K.     

The shear force amendments on the slugging behavior of upflow Anammox granular sludge bed reactor

The granulation of Anammox sludge plays an important role in improving the efficiency of high-rate Anammox bioreactors. The present study involved the use of anaerobic granular sludge to start up the Anammox process to accomplish granulation in Anammox reactor. The accumulation of nitrogen gas and subsequent slugging behavior were observed in the upflow Anammox granular sludge bed (AGSB) reactor, resulting in deteriorated effluent quality. Based on shear force analysis of the gas column under the quasi-steady state, the liquid-induced shear force was increased by progressively shortening of hydraulic residence time (HRT) and implementing effluent recycling. It appeared to be the right strategy to eradicate the slugging behavior which disappeared completely when HRT was shortened to 1.10 h with liquid upflow velocity of 1.30 cm min⁻¹. The application of high shear stress enhanced the nitrogen removal performance to 15.40 kg-N m⁻³ d⁻¹. Thus the amendments in the liquid-induced shear force by shortening HRT may be an appropriate strategy to overcome slugging behavior of the Anammox reactor.     

Ceria modified MnOx/TiO2 as a superior catalyst for NO reduction with NH3 at low-temperature

A series of cerium modified MnOx/TiO₂ catalysts were prepared by sol–gel method and used for low-temperature selective catalytic reduction (SCR) of NOx with ammonia. The experimental results showed that NO conversion could be improved by doping Ce from 39% to 84% at 80 °C with a gas hourly space velocity (GHSV) of 40,000 h⁻¹. This activity improvement may be contributed to the increase of chemisorbed oxygen and acidity after Ce doping. TPR results also verified that the redox property of Ce modified MnOx/TiO₂ was enhanced at low-temperature.