废水中硫化物分析预处理方法的改进

采用负压作动力进行废水硫化物分析样品预处理的方法研究。通常的硫化物分析预处理是利用吹氮气(载气)进行的,但由于硫化氢极易挥发,在这种正压装置中容易产生泄漏,造成分析结果偏低。为了解决这个问题,本实验把整套预处理装置由正压改为负压,由吹气改为抽气,减少预处理过程中硫化氢的泄漏。实验回收率达96%以上,效果较好。     

Aerobic biodegradability of methyldiethanolamine (MDEA) used in natural gas sweetening plants in batch tests and continuous flow experiments

Mixtures of different amines including tertiary amines (methyldiethanolamine, MDEA) are commonly used for the removal of CO₂ from gas mixtures or in gas sweetening processes for the extraction of CO₂ and H₂S. The absorber solutions used can be released into the industrial waste water due to continuous substitution of degraded MDEA, periodically cleaning processes or an accidental spill. In this study, the aerobic biodegradability of MDEA was investigated in a standardised batch test and a continuous flow experiment (40 l/d). The results of the batch test indicated that the MDEA-solution was non-biodegradable during the test period of 28 days, whereas the continuous flow experiments showed biodegradation of more than 96% based on TOC-measurements. This was probably due to the adaptation of the microorganisms to this particular waste water contamination during continuous flow experiment.     

Identification of accident scenarios caused by internal factors using HAZOP to assess an organic hydride hydrogen refueling station involving methylcyclohexane

Organic hydride hydrogen refueling stations have been remarked as stations that can employ a practicable method based on the organic chemical hydride system involving methylcyclohexane (MCH) for the transport of hydrogen. This station has advantages in that the storage and transportation of MCH does not require a large amount of energy compared to compressed and liquefied hydrogen, and the system can use existing infrastructure. This type of station involves some hazardous materials, and thus, scenario identifications and risk assessments have been performed by researchers. However, the sample of studies available have employed a conceptual design model, and they did not identify concrete scenarios triggered by internal factors. Therefore, the purpose of this study is to identify accidental scenarios caused by internal factors that can affect an organic hydride hydrogen refueling station. In this study, we used Hazard and Operability study (HAZOP) and examined safety measures for the scenarios. As a result of the HAZOP, 105 accidental scenarios were identified and classified into the two following groups; (i) the scenarios assumed that the substances were ignited after they were released to the atmosphere, and (ii) the scenarios assumed that the substances were ignited in the process before they were released. Significant scenarios in group (i) were MCH or toluene pool fires, hydrogen jet fires, vapor gas explosions, or flash fires. The significant scenarios classified in (ii) were newly identified in this study. The scenarios include the explosion of the explosive mixture formed by the gaseous phase of toluene and oxygen from the vent line connected to the tank due to the static electric charge in the tank. For each scenario, safety measures to prevent the progression of the accident scenario were examined with reference to the current laws and regulations in Japan.     

LES – DFSD modelling of vented hydrogen explosions in a small-scale combustion chamber

Accidental explosions are a plausible danger to the chemical process industries. In the event of a gas explosion, any obstacles placed within the path of the flame generate turbulence, which accelerates the transient flame and raises explosion overpressure, posing a safety hazard. This paper presents numerical studies using an in-house computational fluid dynamics (CFD) model for lean premixed hydrogen/air flame propagations with an equivalence ratio of 0.7. A laboratory-scale combustion chamber is used with repeated solid obstacles. The transient compressible large eddy simulation (LES) modelling technique combined with a dynamic flame surface density (DFSD) combustion model is used to carry out the numerical simulations in three-dimensional space. The study presented uses eight different baffle configurations with two solid obstructions, which have area blockage ratios of 0.24 and 0.5. The flame speed, maximum rate of pressure-rise as well as peak overpressure magnitude and timing are presented and discussed. Numerical results are validated against available published experimental data. It is concluded that, increasing the solid obstacle area blockage ratio and the number of consecutive baffles results in a raised maximum rate of pressure rise, higher peak explosion overpressure and faster flame propagation. Future model development would require more experimental data, probably in a more congested configuration.     

Role of hydrogen bond capacity of solvents in reactions of amines with CO2: A computational study

Various computational methods were employed to investigate the zwitterion formation,a critical step for the reaction of monoethanolamine with CO_2,in five solvents(water,monoethanolamine,propylamine,methanol and chloroform) to probe the effect of hydrogen bond capacity of solvents on the reaction of amine with CO_2 occurring in the amine-based CO_2 capture process.The results indicate that the zwitterion can be formed in all considered solvents except chloroform.For two pairs of solvents(methanol and monoethanolamine,propylamine and chloroform) with similar dielectric constant but different hydrogen bond capacity,the solvents with higher hydrogen bond capacity(monoethanolamine and propylamine) facilitate the zwitterion formation.More importantly,kinetics parameters such as activation free energy for the zwitterion formation are more relevant to the hydrogen bond capacity than to dielectric constant of the considered solvents,clarifying the hydrogen bond capacity could be more important than dielectric constant in determining the kinetics of monoethanolamine with CO_2.     

Adsorption-oxidation of hydrogen sulfide on Fe/walnut-shell activated carbon surface modified by NH3-plasma

Walnut-shell activated carbon(WSAC) supported ferric oxide was modified by non-thermal plasma(NTP), and the removal efficiency for hydrogen sulfide over Fe/WSAC modified by dielectric barrier discharge(DBD) was significantly promoted. The sample modified for10 min and 6.8 k V output(30 V input voltage) maintained 100% H2 S conversion over a long reaction time of 390 min. The surface properties of adsorbents modified by NTP under different conditions were evaluated by the methods of X-ray photoelectron spectroscopy(XPS), Brunauer–Emmett–Teller(BET) analysis and in-situ Fourier transform infrared spectroscopy(FTIR), to help understand the effect of the NTP treatment. NTP treatment enhanced the adsorption capacity of Fe/WSAC, which could due to the formation of micro-pores with sizes of0.4, 0.5 and 0.75 nm. XPS revealed that chemisorbed oxygen changed into lattice oxygen after NTP treatment, and lattice oxygen is beneficial for H2 S oxidation. From the in-situ FTIR result,transformation of the reaction path on Fe/WSAC was observed after NTP modification. The research results indicate that NTP is an effective method to improve the surface properties of the Fe/WSAC catalyst for H2 S adsorption-oxidation.     

Combined zero valent iron and hydrogen peroxide conditioning significantly enhances the dewaterability of anaerobic digestate

The importance of enhancing sludge dewaterability is increasing due to the considerable impact of excess sludge volume on disposal costs and on overall sludge management. This study presents an innovative approach to enhance dewaterability of anaerobic digestate(AD) harvested from a wastewater treatment plant. The combination of zero valent iron(ZVI, 0–4.0 g/g total solids(TS)) and hydrogen peroxide(HP, 0–90 mg/g TS) under pH 3.0 significantly enhanced the AD dewaterability. The largest enhancement of AD dewaterability was achieved at 18 mg HP/g TS and 2.0 g ZVI/g TS, with the capillary suction time reduced by up to 90%. Economic analysis suggested that the proposed HP and ZVI treatment has more economic benefits in comparison with the classical Fenton reaction process. The destruction of extracellular polymeric substances and cells as well as the decrease of particle size were supposed to contribute to the enhanced AD dewaterability by HP + ZVI conditioning.     

The Danish incinerator dioxin study. Part 1

During the last two years an extensive series of dioxin measurements has been conducted on Danish municipal and hospital solid waste incinerators. The study was directed toward finding the total annual dioxin emissions from MSWI in Denmark, now estimated to be 3 kg. of dioxines and furanes. This sum is equivalent to 50 g. of 2,3,7,8-TCDD according to the Nordic Equivalents. Measurements were carried out according to a statistical design following a plan of pre-randomized sampling. This procedure allowed causal interpretation of the correlations found between the dioxin emissions and certain operating parameters. The statistical model obtained describes the emissions by variations between incinerators, by variation in time, and by changes in the load, the excess air and the HCl concentration in the flue gas.     

Experimental and modeling investigations on the unexpected hydrogen sulfide rebound in a sewer receiving nitrate addition: Mechanism and solution

Biogenic hydrogen sulfide is an odorous, toxic and corrosive gas released from sewage in sewers. To control sulfide generation and emission, nitrate is extensively applied in sewer systems for decades. However, the unexpected sulfide rebound after nitrate addition is being questioned in recent studies. Possible reasons for the sulfide rebounds have been studied, but the mechanism is still unclear, so the countermeasure is not yet proposed. In this study, a lab-scale sewer system was developed for investigating the unexpected sulfide rebounds via the traditional strategy of nitrate addition during 195-days of operation. It was observed that the sulfide pollution was even severe in a sewer receiving nitrate addition. The mechanism for the sulfide rebound can be differentiated into short-term and long-term effects based on the dominant contribution. The accumulation of intermediate elemental sulfur in biofilm resulted in a rapid sulfide rebound via the high-rate sulfur reduction after the depletion of nitrate in a short period. The presence of nitrate in sewer promoted the microorganism proliferation in biofilm, increased the biofilm thickness, re-shaped the microbial community and enhanced biological denitrification and sulfur production, which further weakened the effect of nitrate on sulfide control during the long-term operation. An optimized biofilm-initiated sewer process model demonstrated that neither the intermittent nitrate addition nor the continuous nitrate addition was a sustainable strategy for the sulfide control. To minimize the negative impact from sulfide rebounds, a (bi)monthly routine maintenance (e.g., hydraulic flushing with nitrate spike) to remove the proliferative microorganism in biofilm is necessary.     

苯酚液相臭氧氧化和复合氧化反应动力学

推导了苯酚液相臭氧氧化和复合氧化（O3/H2O2）反应动力学模型,研究了苯酚液相臭氧氧化和复合氧化过程的降解,得出了苯酚液相臭氧氧化和复合氧化在温度288～313K和pH3.2～9.8条件下的反应动力学,探讨了反应机理,认为：在酸性(pH3.2）及弱酸性（pH6.2～6.5）时,苯酚的臭氧化和复合氧化降解反应均为O3分子的直接氧化过程;在碱性（pH9.8）条件下,苯酚复合氧化降解机理以自由基反应为主。