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.     

载铁ACF/Ni阴极电化学体系除藻效能与机制

采用化学浸渍法将Fe@Fe₂O₃纳米线负载在活性炭纤维/泡沫镍上组成Fe@Fe₂O₃/ACF/Ni复合阴极,以钛基铂（Pt/Ti）为阳极,考察载铁量、初始pH值和不同电化学体系对除藻效果的影响,探究无供氧条件下Pt/Ti-Fe@Fe₂O₃/ACF/Ni电化学体系除藻的效能;基于·OH间接检测、铁离子浓度、H₂O₂浓度及pH值的分析和·O₂^-的检测研究Pt/Ti-Fe@Fe₂O₃/ACF/Ni中性电化学体系反应机制.结果表明,当制备阴极阶段投加0.03g FeCl₃×6H₂O,初始藻浓度为0.7×10⁹~0.8×10⁹个/L,电流密度为75mA/cm²,初始pH6.2时,电解60min,该体系除藻率可达到92.3%.在Pt/Ti-Fe@Fe₂O₃/ACF/Ni电化学体系中,Fe@Fe₂O₃/ACF/Ni阴极可通过电化学反应产生大量·OH和·O₂^-,使藻细胞破裂死亡;该体系除藻的主要机理是非均相电Fenton反应.     

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.     

过氧化钙(CaO2)联合生物炭对河道底泥的修复

底泥内源污染是导致河道黑臭反复的主要因素.为防止河道黑臭现象反复,以无锡市滨湖区某一河道为实验地点,采用CaO_2联合生物炭原位覆盖技术修复黑臭河道底泥,研究了该技术对泥水水质、底泥酸挥发性硫化物(AVS)和磷形态以及微生物的影响,探究该技术对黑臭底泥修复效果.结果表明, CaO_2联合生物炭覆盖可显著提高泥水体系溶解氧(DO)浓度和氧化还原电位(ORP),其中上覆水DO浓度和ORP分别保持在2 mg·L~(-1)和50 mV以上.间隙水氨氮(NH~+_4-N)、化学需氧量(COD)和总磷(TP)去除率分别达到了43.40%、 41.18%和50.97%.底泥AVS去除率达到了37.03%,高通量测序表明,底泥厌氧微生物相对丰度明显降低,出现热单胞菌属(Thermomonas)、Dechloromonas、变形菌属(Proteus hauser)、脱硫微菌属(Desulfomicrobium)和硫杆菌属(Thiobacillus)等脱氮除硫菌群.底泥中磷转化为稳定的铁铝结合态磷和钙结合态磷.因此,CaO_2联合生物炭原位覆盖对黑臭底泥具有良好的修复作用.     

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.     

强化UV/Fenton法降解水中苯酚的研究

研究了UV/Fenton法处理含苯酚废水时H2 O2 和FeSO4 加入量及苯酚初始浓度对酚去除效果的影响及C2 O2 -4 对UV/Fenton法的增强效果。 [H2 O2 ]=2 0mmol/L ,[FeSO4 ]=5mmol/L ,反应 2 0min ,苯酚初始浓度为 5 0mg/L时 ,酚去除率达 99%。UV/Fenton体系中引入C2 O2 -4 后可有效提高对紫外和可见光的利用率 ,进而提高了对高浓度苯酚废水去除效果