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.     

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.     

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.     

Removal of hydrogen sulfide, benzene and toluene by a fluidized bed bioreactor

The dominant off gases from publicly owned treatment works include hydrogen sulfide, benzene, and toluene. In this research, hydrogen sulfide oxidized byBacillus cereus, and benzene with toluene were removed by VOC-degrading microbial consortium. The optimum operating condition of the fluidized bed bioreactor including both microorganisms was 30 ‡C, pH 6–8, and 150 cm of liquid bed height. The critical loading rate of hydrogen sulfide, benzene and toluene in the bioreactor was about 15 g/m³h, 10 g/m³h and 12 g/m³h, respectively. The fluidized bed bioreactor showed an excellent elimination capacity for 580 hours of continuous operation, and maintained stable removal efficiency at sudden inlet concentration changes.     

Effect of the sulfide concentration on zinc bio-precipitation in a single stage sulfidogenic bioreactor at pH 5.5

Dissolved zinc is present in natural waters and process streams generated by the mining and metallurgical industry. These streams usually have a low pH. By using sulfate reducing bacteria, sulfide can be produced that precipitates with zinc as zinc sulfide (sphalerite), which can be easily separated from the wastewater and even reused as zinc concentrate. In this study, a sulfate reducing gas-lift bioreactor was operated at pH 5.5 using hydrogen as electron donor for sulfate reduction. We demonstrate effective zinc removal (7.2 mmol L⁻¹ d⁻¹) with low zinc effluent concentrations (0.65–8.8 μM) in a system combining sulfide generation by sulfate reducing bacteria (7.2–10.6 mmol SO₄²⁻ L⁻¹ d⁻¹) at low pH (5.5) with the bio-precipitation of crystalline sphalerite. To investigate the effect of the sulfide excess on the settling properties of the sphalerite precipitates, the sulfide excess concentration was varied about two orders of magnitude (0.008–2.2 mM). The results show that crystalline sphalerite was formed in all cases, but larger particles with better settling properties were formed at lower sulfide concentrations.     

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.     

Adsorption and photocatalytic degradation of phenol and 2,4 dichlorophenoxiacetic acid by Mg–Zn–Al layered double hydroxides

Mg–Zn–Al layered double hydroxides (LDHs) with varying amounts of zinc were prepared by the coprecipitation method. Solids were analyzed by XRD and N₂ physisorption, confirming the formation of pure LDH phase; and the production of mixed oxides with high specific surface areas (182–276 m² g⁻¹) after calcination. Band gap energy was also determined, presenting the expected decreasing tendency on increasing zinc amounts. These mixed oxides were tested both for the adsorption of 2,4 dichlorophenoxiacetic acid (2,4-d) and for the photocatalytic degradation of 2,4-d and phenol. Nearly total (97%) degradation of initial 1.45 mmol L⁻¹ of 2,4-d, with 1 g calcined LDH per liter, was accomplished in 9 h, while phenol half-life was as short as 3.5 h, with the catalyst with lowest zinc amount (5 wt.%). Langmuir adsorption isotherms are presented. Solids were also characterized by XRD and FTIR analysis after photocatalytic and adsorption activity, to determine the presence of 2,4-d. The versatility of LDH decomposition products in the elimination of different contaminants by different mechanisms puts them forward as a viable alternative for environmental remediation.     

Development of a membrane‐assisted hybrid bioreactor for ammonia and COD removal in wastewaters

A new membrane‐assisted hybrid bioreactor was developed to remove ammonia and organic matter. This system was composed of a hybrid circulating bed reactor (CBR) coupled in series to an ultrafiltration membrane module for biomass separation. The growth of biomass both in suspension and biofilms was promoted in the hybrid reactor. The system was operated for 103 days, during which a constant ammonia loading rate (ALR) was fed to the system. The COD/N‐NH₄⁺ ratio was manipulated between 0 and 4, in order to study the effects of different organic matter concentrations on the nitrification capacity of the system. Experimental results have shown that it was feasible to operate with a membrane hybrid system attaining 99% chemical oxygen demand (COD) removal and ammonia conversion. The ALR was 0.92 kg N‐NH₄⁺ m^?3 d^?1 and the organic loading rate (OLR) achieved up to 3.6 kg COD m^?3 d^?1. Also, the concentration of ammonia in the effluent was low, 1 mg N‐NH₄⁺ dm^?3. Specific activity determinations have shown that there was a certain degree of segregation of nitrifiers and heterotrophs between the two biomass phases in the system. Growth of the slow‐growing nitrifiers took place preferentially in the biofilm and the fast‐growing heterotrophs grew in suspension. This fact allowed the nitrifying activity in the biofilm be maintained around 0.8 g N g^?1 protein d^?1, regardless of the addition of organic matter in the influent. The specific nitrifying activity of suspended biomass varied between 0.3 and 0.4 g N g^?1 VSS d^?1. Copyright © 2004 Society of Chemical Industry     

Removal of dimethyl sulfide in a thermophilic membrane bioreactor

BACKGROUND: Several sources such as the paper and pulp industry and waste treatment plants emit waste gases containing volatile organic sulfur compounds at elevated temperature. Since cooling the hot gases increases the operational cost of biological reactors, application of thermophilic microorganisms could be a cost‐effective solution. The objectives of this study were to investigate the possibility of removal of dimethyl sulfide from waste gases under thermophilic conditions (52 °C) in a membrane bioreactor and to examine the long‐term stability of the reactor at elevated temperature. The effects of operating conditions such as gas residence time, nutrient supply, temperature decrease and short‐term shutdown on elimination capacity were investigated. RESULTS: A maximum elimination capacity of 54 g m^?3 h^?1 (0.108 g m^?2 h^?1) was obtained at a mass loading rate of 64 g m^?3 h^?1 (0.128 g m^?2 h^?1) with a removal efficiency of 84% at a gas residence time of 24 s. The long‐term operation of the thermophilic membrane bioreactor was followed for 9 months. Although the removal efficiency decreased to 50% after 3 months of continuous operation, it recovered (>96%) after the excess biomass was removed by applying high‐velocity liquid recirculation. CONCLUSION: This study demonstrated that the dimethyl sulfide removal is possible in a thermophilic membrane bioreactor with an elimination capacity of 54 g m^?3 h^?1 (0.108 g m^?2 h^?1) at a gas residence time of 24 s. Copyright © 2008 Society of Chemical Industry     

Properties of Nb-doped SrCo0.8Fe0.2O3−d perovskites in oxidizing and reducing environments

The phase stability of SrCo_0.8Fe_0.2O_3−d perovskite doped with niobium was studied by in situ high-temperature X-ray diffraction in the temperature range of 30–1000 °C and oxygen partial pressure 0.2–10⁻⁵ atm. The stability of the cubic perovskite structure in a wide range of oxygen partial pressures is the main advantage of SrCo_0.8−xFe_0.2Nb_xO_3−d (x = 0.1–0.3) system in comparison with SrCo_0.8Fe_0.2O_3−d. It is suggested that equilibrium of the thermal expansion with changes of the oxygen non-stoichiometry leading to the same lattice parameters in the oxidizing and reducing environments at the catalytic temperatures is a necessary requirement for stable operation of perovskite as an oxygen-conducting membrane. In the case of SrCo_0.8−xFe_0.2Nb_xO_3−d perovskite this condition is met at x = 0.2. This makes the SrCo_0.6Fe_0.2Nb_0.2O_3−d composition promising for application as oxygen-conducting membrane.     

Synthesis and dye separation performance of ferromagnetic hierarchical porous carbon

Ferromagnetic hierarchical porous carbon (FHPC) with nickel particles embedded in the hierarchical porous carbon skeleton was synthesized. The hierarchical macro–mesoporous skeleton was formed by dissolving a salt template of Na₂CO₃ and the ferromagnetic nickel particles were produced by in situ carbothermal reduction of nickel oxide. The saturation magnetization, remnant magnetization and coercive force of FHPC are 11.3 emu g⁻¹, 2.3 emu g⁻¹ and 55.7 Oe. The ferromagnetic property enables the magnetic separation of the FHPC from water. The surface chemical environments of the FHPC consist of different oxygen functional groups, like –OH, >COO and >CO groups, as well as a trace amount of aliphatic species of –CH₃ or -CH_2^- structures. Dye separation performance of the FHPC was investigated using methylene orange, and the adsorption capacity was 0.16 mg m⁻² with the adsorption kinetics constant of 2.2 m² mg⁻¹ min⁻¹, which is superior to that of magnetic carbon spheres.     

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.     

Relation between salt rejection and electrokinetic properties on Shirasu porous glass (SPG) membranes with nano-order uniform pores

The salt rejection by Shirasu porous glass (SPG) membranes having nano-order uniform pores was investigated for understanding the electrokinetic mechanism resulting from the surface charge developed on the membrane when in contact with salt solutions. Due to the dissociation of the hydroxyl groups such as silanol groups on the membrane surface, the membrane was negatively charged over a pH range of 3–10 from electrophoretic measurements. Cross-flow filtration experiments showed that up to 63% of NaCl was rejected by an SPG membrane having a mean pore diameters of 33 nm in a 1 mol m⁻³ NaCl solution at pH 7 under a transmembrane pressure of 74 kPa, even though the pore diameter is much larger than the ion diameter. This is a consequence of the electrostatic repulsive interaction between the co-ions (Cl⁻ ions) and the membrane surface. At the same pH, the rejection factor of NaCl decreased with increasing salt concentration due to an increase in the ionic strength. More negative charge on the membrane surface at higher pH resulted in higher rejection factors of NaCl for a fixed salt concentration. Higher rejection factors of NaCl by SPG membranes with smaller pore sizes for a fixed concentration are due to the higher ratio of the thickness of the electric double layer (Debye length) to the pore radius. The SPG membrane showed a salt rejection sequence: Na₂SO₄, NaCl and CaCl₂ at the same pH. This is because divalent anions (SO₄²⁻) are more strongly repelled by the negatively charged membrane, while divalent cations (Ca²⁺) adsorb specifically onto the membrane surface than monovalent cations (Na⁺). The salt rejection factor increased with increasing permeate volume flux. Due to the stronger acidity of the membrane materials, SPG membranes had a higher rejection factor and a lower isoelectric point (IEP < 3) than ceramic membranes.     

Effects of compressed carbon dioxide treatment on the specificity of oxidase enzymatic complexes from mate tea leaves

This work evaluates the enzymatic activity of peroxidase (POD) and polyphenoloxidase (PPO) present in the crude extract of mate tea leaves (Ilex paraguariensis St. Hill) submitted to compressed CO₂. The effects of temperature, exposure time, solvent reduced density, pressure, and depressurization rate on the activity of peroxidase and polyphenoloxidase were evaluated through a fractionated factorial experimental planning. Results show that temperature of 30 °C, pressure of 70.5 bar, exposure time of 1 h, depressurization rate of 10 kg m⁻³ min⁻¹ and carbon dioxide reduced density of 0.60 led to an enhancement of around 25% in the peroxidase activity and a polyphenoloxidase activity loss of 50%. Using this experimental condition, thermal stability at low temperature (−4 °C) and the influence of successive pressurization/depressurization cycles were determined. Results suggest that it is possible to increase the specificity of the enzymatic extract towards enhancing POD or PPO activity depending on the experimental condition employed, and that the processing of enzymatic complexes with compressed CO₂ may be a promising route to increase the specificity of enzymatic extracts.     

Electrochemical diamond sensors for TNT detection in water

An electrochemically stabilized boron doped diamond electrode prepared by chemical vapour deposition (CVD) is used for electrochemical TNT sensing in aqueous solutions. Square wave voltammograms (SWVs) exhibit three highly resolved peaks at −0.47, −0.62 and −0.76 V vs. Ag–AgCl reference electrode, respectively. The current vs. TNT concentration plot shows a linear relationship with a same slope for the two first TNT peaks at μg L⁻¹ and mg L⁻¹ concentration ranges. Detection and quantification limits of 10 and 25 μg L⁻¹, respectively, were obtained without any preconcentration step. Relative standard deviation (RSD) of less than 1% measured over 10 runs has been found for the −0.47 V peak current showing the very high stability of the electrode without any significant fouling effect. An interference study with nitro aromatic compounds of the same family (nitro toluene and dinitrotoluene) has shown that the −0.47 V reduction peak enables TNT discrimination. Measurement of TNT in a natural medium (sea water without any purification step except filtering) has been also investigated.     

Removal of COD from coking-plant wastewater in the moving-bed biofilm sequencing batch reactor

The objective of this paper is to investigate COD removal efficiency of the coking-plant wastewater by applying the moving-bed biofilm sequencing batch reactor (MBBSBR). The operation is simple and 30% WD-F10-4 BioM™ were packed as carrier materials. It was found that the coking-plant wastewater could be effectively treated with 92.9% of COD removal efficiency at a low organic loading rate (OLR) of 0.449 kgCOD·m⁻³·d⁻¹ The removal efficiency decreased gradually down to 70.9% when OLR increased to 2.628 kgCOD·m⁻³·d⁻¹. The system has strong tolerance to organic shock loading in this experiment. The COD removal results in the blank experiments of biofilm and sludge showed that the attached biofilm has higher activity than suspended sludge and contributes about 60% to the COD removal. This work was presented at the 7 ^th China-Korea Workshop on Clean Energy Technology held at Taiyuan, Shanxi, China, June 26–28, 2008.     

Analysis of tetramethylammonium–montmorillonite and retention of toluene from aqueous solution

Non-ionic organic contaminants, such as toluene, can be effectively absorbed by organo-montmorillionite. The tetramethylammonium (TMA)–montmorillonites were prepared by ion-exchange and used to evaluate toluene uptake from water. The TMA–montmorillonites were characterized by total organic carbon determinations, swelling index, X-ray diffraction, thermal analyses, and infrared spectroscopy. Toluene adsorption was measured by UV–visible spectrophotometry. The thermal stability of the TMA–montmorillonites decreased as TMA addition increased; the total mass loss decreased with increasing temperature up to 500 °C. The amount of carbon retained by the TMA–montmorillonites was proportional to the area of the infrared band at 1488 cm^− 1 (asymmetric C–H bending vibration of –CH3 group). The retention of toluene by TMA–montmorillonites increased from 0.2 to 0.22 mg g^− 1 mainly to interlayer adsorption. The adsorption of toluene influenced the OH-stretching vibration.     

Performance of a catalytically activated ceramic hot gas filter for catalytic tar removal from biomass gasification gas

Silicon carbide-based filter elements were catalytically activated to provide filter elements for catalytic tar removal from biomass-derived syngas. The filter element support was coated with CeO₂, CaO–Al₂O₃ and MgO with a specific surface of 7.4, 15.9 and 21.9 m²/g synthesized by exo-templating with activated carbon. Doping of a MgO coated filter element with 60 wt% NiO has led to an increase of the specific surface from 0.15 to 0.21 m²/g, whereas in case of a MgO–Al₂O₃ coated filter element a decrease from 1.18 to 0.91 m²/g was found. An increase of the NiO loading from 6 to 60 wt% on a MgO coated filter element resulted in an increase of the naphthalene conversion from 91 to 100% at 800 °C and a face velocity of 2.5 cm/s at a naphthalene concentration of 5 g/Nm³ in model biomass gasification gas. In case of a MgO–Al₂O₃ coated filter element with 60 wt% NiO in addition to complete naphthalene conversion in the absence of H₂S, a higher conversion of 66% was found in the presence of 100 ppmv H₂S compared to 49% of the MgO–NiO coated filter element. After scaling up of the catalytic activation procedure to a 1520 mm long filter candle, which shows an acceptable differential pressure of 54.9 mbar, 58 and 97% naphthalene conversion was achieved in the presence and absence of H₂S, respectively. The calculated WHSV value of 209.6 Nm³ h⁻¹ kg⁻¹ indicates the technical feasibility of a further increase of the catalytic performance by an increase of the NiO loading.     

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.     

Amperometric detection of hydrogen peroxide at nano-nickel oxide/thionine and celestine blue nanocomposite-modified glassy carbon electrodes

A simple procedure was developed to prepare a glassy carbon (GC) electrode modified with nickel oxide (NiOx) nanoparticles and water-soluble dyes. By immersing the GC/NiOx modified electrode into thionine (TH) or celestine blue (CB) solutions for a short period of time (5–120 s), a thin film of the proposed molecules was immobilized onto the electrode surface. The modified electrodes showed stable and a well-defined redox couples at a wide pH range (2–12), with surface confined characteristics. In comparison to usual methods for the immobilization of dye molecules, such as electropolymerization or adsorption on the surface of preanodized electrodes, the electrochemical reversibility and stability of these modified electrodes have been improved. The surface coverage and heterogeneous electron transfer rate constants (k_s) of thionin and celestin blue immobilized on a NiOx-GC electrode were approximately 3.5 × 10⁻¹⁰ mol cm⁻², 6.12 s⁻¹, 5.9 × 10⁻¹⁰ mol cm⁻² and 6.58 s⁻¹, respectively. The results clearly show the high loading ability of the NiOx nanoparticles and great facilitation of the electron transfer between the immobilized TH, CB and NiOx nanoparticles. The modified electrodes show excellent electrocatalytic activity toward hydrogen peroxide reduction at a reduced overpotential. The catalytic rate constants for hydrogen peroxide reduction at GC/NiOx/CB and GC/NiOx/TH were 7.96 (±0.2) × 10³ M⁻¹ s⁻¹ and 5.5 (±0.2) × 10³ M⁻¹ s⁻¹, respectively. The detection limit, sensitivity and linear concentration range for hydrogen peroxide detection were 1.67 μM, 4.14 nA μM⁻¹ nA μM⁻¹ and 5 μM to 20 mM, and 0.36 μM, 7.62 nA μM⁻¹, and 1 μM to 10 mM for the GC/NiOx/TH and GC/NiOx/CB modified electrodes, respectively. Compared to other modified electrodes, these modified electrodes have many advantages, such as remarkable catalytic activity, good reproducibility, simple preparation procedures and long-term stabilities of signal responses during hydrogen peroxide reduction.