Sorption-enhanced chemical looping oxidative steam reforming of methanol for on-board hydrogen supply

Hydrogen is an indispensable energy carrier for the sustainable development of human society. Nevertheless, its storage, transportation, and in situ generation still face significant challenges. Methanol can be used as an intermediate carrier for hydrogen supplies, providing hydrogen energy through instant methanol conversion. In this study, a sorption-enhanced, chemical-looping, oxidative steam methanol-reforming (SECL-OSRM) process is proposed using CuO–MgO for the on-board hydrogen supply, which could be a promising method for safe and efficient hydrogen production. Aspen Plus software was used for feasibility verification and parameter optimization of the SECL-OSRM process. The effects of CuO/CH3OH, MgO/CH3OH, and H2O/CH3OH mole ratios and of temperature on H2 production rate, H utilization efficiency, CH3OH conversion, CO concentration, and system heat balance are discussed thoroughly. The results indicate that the system can be operated in auto-thermal conditions with high-purity hydrogen (99.50 vol％) and ultra-low-concentration CO (<50 ppm) generation, which confirms the pos-sibility of integrating low-temperature proton-exchange membrane fuel cells (LT-PEFMCs) with the SECL-OSRM process. The simulation results indicate that the CO can be modulated in a lower concentration by reducing the temperature and by improving the H2O/CH3OH and MgO/CH3OH mole ratios.     

Experimental investigation of the complex deflagration phenomena of hybrid mixtures of activated carbon dust/hydrogen/air

This paper aims to develop quantitative insights based on measured deflagration parameters of hybrid mixtures of activated carbon (AC) dust and hydrogen (H₂) gas in air. The generated experimental evidence is used to reject the claim of the null hypothesis (H₀) that severity of deflagrations of H₂/air mixtures always bound the severity of deflagrations of heterogenous combustible mixtures of AC dust/H₂/air containing the same H₂ concentrations as in the H₂/air binaries. The core insights of this investigation show that the maximum deflagration pressure rise (ΔP_MAX) and maximum rate of pressure rise ((dP/dt)_MAX) of this hybrid mixture are greater than those corresponding to deflagrations of H₂/air mixtures for all the dust and H₂ concentrations being examined. The deflagration severity indices (K_St and ES) of the hybrid mixture containing 29 mol% H₂ are found to be greater than those of the H₂/air mixture containing 29 mol% H₂. Also, the minimum explosible concentration (MEC) of the hybrid mixture is lower than that of the AC dust in air only. The insights gained should lead to better realization of the severity of a postulated safety-significant accident scenario associated with on-board cryoadsorption H₂ storage systems for fuel-cell (FC) powered light-duty vehicles. The identified insights could also be relevant to other industrial processes where combustible dusts are generated in the vicinity of solvent vapors. Moreover, these insights should be useful for supporting quantitative risk assessment (QRA) of on-board H₂ storage systems, designing improved safety measures for cryoadsorption H₂ storage tanks, and guiding H₂ safety standards and transportation regulations.     

Determination of the minimum ignition energy on the basis of a statistical approach

Based on existing MIE test results and new measurements, a statistical analysis for the MIE of hydrogen, ethene and propane is made by means of the logistic regression. The conditions necessary to carry out such an approach are discussed. It is shown that MIE values which are connected with a certain ignition probability could be determined adequately and lead to a more sophisticated result, also with regard to measurement uncertainties. This, in turn, leads to a better comparability and a higher informative content. At the same time, the MIEs of hydrogen, ethene and propane are reviewed. In doing so, a useful contribution to the discussion concerning the MIE of propane is made.     

Flame acceleration in unconfined hydrogen/air deflagrations using infrared photography

Flame behavior and blast waves generated during unconfined hydrogen deflagrations were experimentally studied using infrared photography. Infrared photography enables expanding spherical flame behaviors to be measured and flame acceleration exponents to be evaluated. In the present experiments, hydrogen/air mixtures of various concentrations were filled in a plastic tent of thin vinyl sheet of 1 m³ and ignited by an electric spark. The onset of accelerative dynamics on the flame propagation was analyzed by the time histories of the flame radius and the stretched flame speed. The results demonstrated that the self-acceleration of the flame, which was caused by diffusional-thermal and hydrodynamic instabilities of the blast wave, was influenced by hydrogen deflagrations in unconfined areas. In particular, it was demonstrated that the overpressure rapidly increased with time. The burning velocity acceleration was greatly enhanced with spontaneous-turbulization.     

有机过氧化物性质和安全性评价

介绍了有机过氧化物的性质、用途、安全性评价方法以及测试方法,要客观地评价有机过氧化物的安全性,必须通过多种方法来进行综合分析评定,为有机过氧化物的安全生产、使用、贮存和运输等提供科学的依据。     

常温下铁的硫化产物自燃性

含硫油品储运过程中H2S腐蚀产物是常温下硫铁化合物的主要来源,以H2S与铁粉反应制备的硫铁化合物来模拟设备内H2S的腐蚀产物,利用自然氧化的方法测定了硫化反应产物的一次氧化升温和二次氧化升温,考察了铁粉含水量对硫化反应及硫化反应产物自燃性的影响,采用XRD和SEM手段对硫化反应产物进行了表征。结果表明:H2S与铁粉的硫化反应产物为FeS,呈微小颗粒状,覆盖在铁粉表面;硫化反应产物具有自燃性,一次氧化升温最高达到87℃;未被完全氧化的硫化反应产物密封放置一段时间后自燃性明显增加,其二次氧化升温速率最高超过39℃/min;铁粉中含有适量的水可以增加硫化反应速率,提高硫化反应产物的自燃性。     

有机溶剂对过氧化环己酮热危险性的减敏效果评价

在纯过氧化环己酮(CYHPO)储运中常添加减敏剂,以降低其热危险性。为了对比评价减敏性能,采用绝热加速量热仪测试了纯CYHPO及加入等质量邻苯二甲酸二丁酯(DBP)、邻苯二甲酸二辛酯(DOP)、正己酸(HAA)和环己醇(CCH)后的热危险参数,并计算了上述5种样品的反应动力学常数和绝热校正数据,建立了包括初始放热温度T0和绝热反应加速度SARC的减敏效果判据,对4种减敏剂的热危险性减敏效果进行了评价。结果表明,DOP对CYHPO热危险性的减敏效果最好。     

Extinguishment of hydrogen laminar diffusion flames by water vapor in a cup burner apparatus

Transient computations with full hydrogen chemistry were performed to reveal the flame structure and extinguishment process of co-flow, hydrogen diffusion flame suppressed by water vapor. As the concentration of water vapor was increased, the flame detached away from the burner brim and formed an edge flame at the flame base. Water vapor showed larger chemical inhibition effect than nitrogen when extinguishing hydrogen flame, which was attributed to its enhanced third body effect in the reaction H + O₂ + M = HO₂ + M. The minimum extinguishing concentration (MEC) of water vapor and nitrogen was predicted by Senecal formula and perfectly stirred reactor (PSR) model respectively. The MECs predicted by PSR model agree with the MECs calculated by Fluent, which shows that 1) the flame extinction is controlled by the flame base, and 2) radiation absorption is negligible. The measured MECs are in a reasonable agreement with the values calculated by Fluent, which demonstrates the accuracy of the CFD model. A simple model was used to investigate the relative importance of extinguishing mechanisms of water vapor. The results show that in a co-flow configuration the thermal cooling and chemical inhibition effect are the main extinguishing mechanisms in suppressing hydrogen diffusion cup burner flame.     

Reuse of nickel recovered from spent Ni–Cd batteries for the preparation of C/Ni and C/Ni/Pd layered electrodes for energy sources

Nickel recovered in the recycling process of Ni–Cd batteries was used as a main component of bath for electrodeposition of nickel onto carbon fabric in order to obtain C/Ni composite. A part of the obtained composite was additionally coated with a thin layer of palladium (C/Ni/Pd composite). All the materials were investigated to assess the possibility of their use in the processes of electrochemical storage (sorption/desorption) of hydrogen and electrochemical oxidation of methanol. The obtained results showed the composites to be active electrode materials in these processes. The electrodes exhibited high activity and cyclability, especially in the process of methanol oxidation due to electrocatalytic activity of both nickel deposited onto carbon fabric and the outer layer of porous palladium coating nickel substrate.     

重庆开县井喷事故的环境影响分析

重庆开县“12.23”井喷事故中,大量富含硫化氢的天然气排入周围环境,致使以高桥镇为核心区的4个乡镇28个村,受到不同程度的硫化氢污染。笔者根据污染物排放情况以及当地的气候、水文等条件分析了井喷事故对该地区大气环境、水环境和土壤环境所造成的影响。结果表明,在距离井喷事故污染源下风方向5000m以内的区域,以及在与下风方向相垂直的方向500m以内的区域,大气环境均受到了不同程度的硫化氢污染,且在500～1500m区域内,污染最为严重。同时,由于硫化氢的沉降,该地区的水和土壤环境也受到了不同程度的影响。