An experimental study for H2S and CO2 removal via caustic scrubbing system

In this study, removal of hydrogen sulfide (H₂S) and carbon dioxide (CO₂) from simulated syngas has been studied on one column scrubbing system. Gas flow rate as a measure of gas residence time and superficial gas velocity, gas composition, inlet H₂S load, flow modes (countercurrent and cocurrent) and packing geometry were the parameters in the design and/or operation of an acid gas scrubber system. Better H₂S scrubbing efficiencies have been obtained in countercurrent flow mode than that of cocurrent flow mode. When accordingly designed, static mixer with its superior performance on H₂S removal overweighed to structured packings. The coexistence of CO₂ and H₂S has been shown to increase the sodium hydroxide (NaOH) consumption along the scrubber column thereby decreasing the H₂S removal efficiency at higher H₂S loads. The gas residence time as changing with the gas velocity was found to be more dominant on acid gas removal efficiency than the effect of superficial gas velocity within the experimented range. A gas residence times of equal or above 3 s were seemed to be closer to the optimum point.     

Removal of H2S by co-immobilized bacteria and fungi biocatalysts in a bio-trickling filter

Biological control of odor gases has gained more attention in recent years. In this study, removal performance of a vertical bio-trickling filter inoculated with bacteria and fungi was studied. Bacteria and fungi were isolated from activated sludge in a sewage treatment plant. By adopting “three step immobilization method”, the bio-trickling filter could degrade pollutant immediately once hydrogen sulfide (H₂S) passed. The optimal empty bed resident time was 20 s. The optimal elimination capacity was about 60 g H₂S m^?3 h^?1 with removal efficiency of 95%. And the maximum elimination capacity was 170 g H₂S m^?3 h^?1. Pressure drop was ranged between 5 and 15 mm H₂O per bed over the whole operation. Removal efficiency was not affected obviously after terminating nutrient supply. The bio-trickling filter could recover back after shut down H₂S gaseous and liquid supplies simultaneously. Microbial community structure in the bio-trickling filter was not changed significantly.Combining bacteria and fungi would be a better choice for inoculation into a bio-trickling filter because of the quickly degradation of H₂S and rapid recovery under shut-down experiment. This is the first study attempting to combine bacteria and fungi for removal of H₂S in a bio-trickling filter.     

Thermal hazard accident investigation of hydrogen peroxide mixing with propanone employing calorimetric approaches

Hydrogen peroxide (H₂O₂), historically, due to its broad applications in the chemical industries, has caused many serious fires and explosions around the world. Its thermal hazards may also be incurred by an incompatible reaction with other chemicals, and a runaway reaction may be induced in the last stage. This study applied thermal analytical methods to explore the H₂O₂ leading to these accidents by incompatibility and to discuss what might be formed by the upset situations. Thermal hazard analysis contained a solvent, propanone (CH₃COCH₃, so-called acetone), which was deliberately selected to mix with H₂O₂ for investigating the degree of thermal hazard. Differential scanning calorimetry (DSC) and vent sizing package 2 (VSP2) were employed to evaluate the thermal hazard of H₂O₂. The results indicated that H₂O₂ is highly hazardous while mixed with propanone, as a potential contaminant. The time to maximum rate (TMR) was used as emergency response time in the chemical industries. Therefore, TMR of H₂O₂ was calculated to be 70 min for runaway reaction (after T₀) and TMR of H₂O₂/propanone was discovered to be 27 min only. Fire and explosion hazards could be successfully lessened if the safety-related data are properly imbedded into manufacturing processes.     

Kinetic and 2D reactor modeling for simulation of the catalytic reduction of NOx in the monolith honeycomb reactor

Emission of NO_x is of primary environmental concern in the oil sands industry. Selective catalytic reduction (SCR) is one of the best NO_x reduction technologies. The present study discusses the testing of a mechanistic kinetic model for the SCR of NO_x to describe the kinetics of V₂O₅/TiO₂ catalysis at atmospheric pressure and a temperature of 623 K in a monolith honeycomb reactor. The modeling results impart insight into the significance of the diffusion with reaction steps and guidance for optimal monolith design for SCR. The validated expression would predict the conversion performance of the catalysts for different values of temperature inlet and ammonia concentration. A good agreement between experimental and model results has been obtained. A heterogeneous numerical model consisting of coupled mass and momentum balance equations was solved using the finite elements method without neglecting the axial dispersion term. The operating range for the catalyst relies on the NO conversion and emission. The optimum operating range for the best performance of the reactor is discussed.     

Hydrogen explosion incident mitigation in steam reforming units through enhanced inspection and forecasting corrosion tools implementation

Hydrogen (H₂) explosion effects recently examined, are confirming the devastating loss scenarios to humans, environment, assets, and associated business interruption. H₂ production is a core process in refineries used in further process steps. Steam reforming of natural gas or a mix with naphtha or LPG is a common hydrogen production technique, where the latest technologies have adopted enhanced metallurgies to minimize explosion risk and the associated maintenance cost following plant degradation owing to corrosion effects. However, corrosion rates are still high in specific areas of piping and process equipment. The aim of this paper is to present a methodology based on semi-quantitative RBI modeling according to regulations by API and recent EN standards, adopting a family of linear regression forecasting models that depict the yearly corrosion rate (per corrosion loop) of a hydrogen production steam reforming unit; this is done under different operating conditions (e.g., temperature, pressure, and fluid speed), metallurgy and other related physicochemical variables. The model is based on the examination of both ultrasonic wall thinning measurements and the examination of quantitative crosslinking total corrosion effects along with the physicochemical properties prevailing in different plant corrosion loops. The outcome of the regression analysis is an expansive family of multivariable equations describing, with a defined accuracy, the yearly corrosion rate and associated lifespan forecast per corrosion loop, and per examined part. These equations were further utilized in a custom-made database that can be used as an additional loss prevention tool by the hydrogen production unit management team. Evaluation results regarding the tool efficiency are presented in the following of this paper.     

循环减灾理论及其煤矿循环减灾模式

煤矿循环减灾是在矿业开发中,针对我国煤矿自然条件复杂、灾害多的实际,尽可能少采或不采目前条件不允许的煤炭资源,如必须开采则应减少危险源,综合利用、综合开发,把对煤炭开采有害的资源利用起来,化害为益,变废为宝,把目前认为无用的东西利用起来治理灾害,以废治害,从而实现资源开采最少化,环境影响最小化,资源利用充分化,煤矿生产灾害发生最少化。煤矿循环减灾的典型模式有化害为益模式和以废治害模式两种类型。化害为益模式中包括把煤矿瓦斯作为资源的先抽后采、边抽边采模式和充分利用地热,变热害为热能模式。以废治害模式中包括煤矸石井下直接用于采空区充填模式和粉煤灰回收利用模式。循环减灾是一种从根本上防止和减轻灾害的措施,在全国煤矿企业实施循环减灾对于遏止目前煤矿事故多发势头,实现煤矿企业可持续发展具有重要意义。     

Experimental study on CO and CO2 emissions from spontaneous heating of coals at varying temperatures and O2 concentrations

Laboratory experiments were conducted to investigate carbon monoxide (CO) and carbon dioxide (CO₂) emissions from spontaneous heating of three U.S. coal samples in an isothermal oven at temperatures between 50 and 110 °C. The oxygen (O₂) concentration of an oxygen/nitrogen (N₂) mixture flowing through the coal sample was 3, 5, 10, 15, and 21%, respectively. The temperature at the center of the coal sample was continuously monitored, while the CO, CO₂, and O₂ concentrations of the exit gas were continuously measured. The results indicate that the CO and CO₂ concentrations and the CO/CO₂ ratio increased when the initial temperature was increased. As the inlet O₂ concentration increased, the CO and CO₂ concentrations increased, while the CO/CO₂ ratios tended to converge to the same value. The ratio of CO/CO₂ was found to be independent of coal properties, approaching a constant value of 0.2. The maximum CO production rate correlated well with the maximum coal temperature rise. The apparent order of reaction for coal oxidation was estimated to be between 0.52 and 0.72. The experimental results in this study could be used for early detection and evaluation of a spontaneous heating in underground coal mines.     

反硝化细菌抑制石油集输系统中硫酸盐还原菌试验研究

建立了两个UASB反应器(UASB-1和UASB-2)。其中UASB-1模拟石油集输系统中硫酸盐还原菌的生存环境,强化系统中硫酸盐还原菌的滋生,使其不断产生硫化氢气体。该系统的液体进入后续UASB-2厌氧反应器,其主要作用是在其中形成反硝化作用的环境条件,以控制石油输集系统中不断滋生的硫酸盐还原菌,从而达到控制硫化氢气体的目的。结果表明,硫酸盐还原菌的最佳氧化还原电位(ORP)为-370～-300mV,而反硝化细菌的最佳ORP为-150～-50mV。向系统中投加亚硝酸钠可迅速增加反应器中的ORP,并为反硝化细菌提供充足的氮源。当系统中的w(SO24-)∶w(NO2-)=8∶1.2时,抑制效果最佳,可以将硫化氢的产生降低至10%。运用16S rDNA基因克隆-变性梯度凝胶电泳分析方法研究了系统中微生物种属的变化情况。结果表明,反硝化细菌能够有效抑制系统中硫酸盐还原菌繁殖,系统中3种典型硫酸盐还原菌(脱硫弧菌属、脱硫肠状菌属、脱硫单胞菌属)逐渐消失,同时反硝化细菌的种属和数量都显著增加。     

Flammability of methane,propane, and hydrogen gases

This paper reports the results of flammability studies for methane, propane, hydrogen, and deuterium gases in air conducted by the Pittsburgh Research Laboratory. Knowledge of the explosion hazards of these gases is important to the coal mining industry and to other industries that produce or use flammable gases. The experimental research was conducted in 20 L and 120 L closed explosion chambers under both quiescent and turbulent conditions, using both electric spark and pyrotechnic ignition sources. The data reported here generally confirm the data of previous investigators, but they are more comprehensive than those reported previously. The results illustrate the complications associated with buoyancy, turbulence, selective diffusion, and ignitor strength versus chamber size. Although the lower flammable limits (LFLs) are well defined for methane (CH₄) and propane (C₃H₈), the LFLs for hydrogen (H₂) and its heavier isotope deuterium (D₂) are much more dependent on the limit criterion chosen. A similar behavior is observed for the upper flammable limit of propane. The data presented include lower and upper flammable limits, maximum pressures, and maximum rates of pressure rise. The rates of pressure rise, even when normalized by the cube root of the chamber volume (V^1/3), are shown to be sensitive to chamber size.     

Hydrogen sulphide removal from landfill gas

Control of odours should be considered to be a fundamental issue in order to site, design and manage sanitary landfills. With regard to construction and demolition (C&;D) debris, landfilling was the mainly adopted solution in many European Countries; in particular, gypsum drywalls can produce high concentrations of hydrogen sulphide (H₂S) in landfill gas ranging from 7 ppm to 100 ppm. In some cases also dangerous concentrations until to 12,000 ppm were detected. In this paper H₂S removal efficiency in a lab-scale vertical packed scrubber was investigated. Hydrogen sulphide abatement was evaluated for inlet H₂S concentrations of 1000–100–10 ppm, adjusting scrubbing liquid pH in the range 9–12.5 by means of caustic soda (NaOH 2N solution). Moreover, best operating conditions for the system were defined as well as H₂S abatement along the tower and liquid recirculation effectiveness in case of inlet H₂S concentration of 10 ppm (typical odour concentration). Results showed that pH of 11.5 in scrubbing liquid could be considered the best value for removal of different inlet H₂S concentrations, also taking into account parasitical consumption of NaOH due to CO₂ absorption. Moreover, in case of continuous working of the system at H₂S concentration of 10 ppm, strong removal efficiency was already obtained with a packed bed height of about 70 cm. Significant performances were ensured after 1 h of constant activity, consuming about 3 ml of soda per cubic meter of polluted air. Subsequently liquid blowdown was necessary.     

Safe direct synthesis of H2O2 within the explosion limit of H2 enabled by low-temperature stable bcc-PdCu alloy membrane

Pd based membrane provides an inherently safer way to handle flammable mixture of hydrogen and oxygen, as it could selectively isolate hydrogen from other gases. However, due to their susceptibility to hydrogen embrittlement, pure Pd membranes are not suitable for processes at low temperature. To solve this problem, body-centered cubic (bcc)-PdCu alloy membranes were prepared by the combination of electroplating and electroless plating. The hydrogen permeation rate (J_H2), N₂ leak rate (J_N2) and H₂/N₂ selectivity (α_H2/N2) remained stable through 200 h continuous operation in H₂ at 298 K and ΔP_H2 = 100 kPa. The excellent low-temperature tolerance of bcc-PdCu membranes rendered them ideal materials for the capture and activation of hydrogen during the direct hydrogen peroxide synthesis from hydrogen and oxygen. The reaction could be performed safely within the explosive limit of hydrogen/oxygen by feeding the gases separately from the opposite sides of the membrane with no direct contact. 60 mmol m⁻² h⁻¹ formation rate, 40% H₂O₂ selectivity, and a nearly 100% hydrogen conversion was reached at 298 K, 500 kPa.     

A sulfur removal and disposal process through H2S adsorption and regeneration: Ammonia leaching regeneration

An iron oxide solid sponge H₂S adsorbent works by reacting H₂S and turning ferric oxide into ferric sulfide. The ferric sulfide will be converted back into ferric oxide and elemental sulfur when contacting oxygen or air. This study investigates the leaching of elemental sulfur from the solid sponge using anhydrous liquid ammonia as solvent. The leaching treatment expectedly results in effective regeneration of the adsorbent, which is able to lead to a sulfur removal and recovery process suitable for handling the small and mid-sized sulfur production cases, i.e., those less than 10 ton/day sulfur. The leaching does not significantly impair the physical properties, including the adsorbent pellet strength. The adsorption–regeneration (or leaching) cycle could be repeated at least three times. The cumulative sulfur loading can achieve as high as 50% (w/w), three times greater than that in the one-time use. The wash-off in leaching and the spent adsorbent can be made into slurry that is to be injected into underground formations such as depleted oil wells. It is anticipated that this underground injection is safer and more efficient than acid gas injection.     

Experimental study on biomass advanced reburning for nitrogen oxides reduction

Advanced reburning (AR) is effective for nitrogen oxides (NO_x) reduction, which integrates the basic reburning (BR) with the injection of nitrogen agents and additive compounds. The basic reburning of poplar, cornstalk, wheat-straw and peanut shell, is studied on a boiler simulator facility (BSF). The influence of operating parameters and the synergistic effect of the injection of ammonia, urea or/and sodium carbonate on NO_x reduction are investigated. The results show that an efficiency of 54–67% NO_x reduction could be achieved during the basic reburning process under the optimum operating conditions and the efficiency would be increased if nitrogen agent is injected with the over-fire air or into the burnout zone. Further, co-injection of sodium carbonate with the nitrogen agent could make the NO_x reduction process more thorough. On the whole, 85–92% NO_x reduction could be achieved during the advanced reburning process with a reburning fuel heat input of 15–20%.     

Experimental research on displacing coal bed methane with supercritical CO2

The high-gas and low-permeability are the common problems of China coal mine, which restrain the mining of coal-seam gas resources safely and efficiently. Hence, to solve the problem of low permeability of coal seam, an experimental system was set up and experimental research was conducted to investigate the effect of the displacement of methane by injecting supercritical CO₂ into coal samples. The experimental results indicated that, the extraction effect of supercritical CO₂ changes the coal’s porosity, and broadens the seepage channel for methane. Thus, the methane could be desorbed effectively from the coal matrix, and flow through more cracks at higher speed.     

A new simple methodology for evaluation of explosion risk in underground coal mines

The key objective of this paper is the presentation of a new risk assessment tool for underground coal mines based on a simplified semi-quantitative estimation and assessment method.In order to determine the risk of explosion of any work process or activity in underground coal mines it is necessary to assess the risk. The proposed method is based on a Risk Index obtained as a product of three factors: frequency of each individual scenario P_ucm, associated severity consequences C_ucm and exposure time to explosive atmospheres E_ucm. The influence of exposure time is usually not taken into account up to now. Moreover, the exposure to explosive atmospheres may affect factors of hazardous event probability as much as its consequences. There are many definitions of exposure to explosive atmospheres but in the case of underground coal mines the exposure is defined as frequency risk of firedamp and coal dust. The risk estimation and risk assessment are based on the developed of a risk matrix.The proposed methodology allows not only the estimation of the explosion risk but also gives an approach to decide if the proposal investment is well-justified or not in order to improve safety.     

An innovative and comprehensive approach for the consequence analysis of liquid hydrogen vessel explosions

Hydrogen is one of the most suitable solutions to replace hydrocarbons in the future. Hydrogen consumption is expected to grow in the next years. Hydrogen liquefaction is one of the processes that allows for increase of hydrogen density and it is suggested when a large amount of substance must be stored or transported. Despite being a clean fuel, its chemical and physical properties often arise concerns about the safety of the hydrogen technologies. A potentially critical scenario for the liquid hydrogen (LH₂) tanks is the catastrophic rupture causing a consequent boiling liquid expanding vapour explosion (BLEVE), with consequent overpressure, fragments projection and eventually a fireball. In this work, all the BLEVE consequence typologies are evaluated through theoretical and analytical models. These models are validated with the experimental results provided by the BMW care manufacturer safety tests conducted during the 1990's. After the validation, the most suitable methods are selected to perform a blind prediction study of the forthcoming LH₂ BLEVE experiments of the Safe Hydrogen fuel handling and Use for Efficient Implementation (SH₂IFT) project. The models drawbacks together with the uncertainties and the knowledge gap in LH₂ physical explosions are highlighted. Finally, future works on the modelling activity of the LH₂ BLEVE are suggested.     

CO2 corrosion control in steel pipelines. Influence of turbulent flow on the performance of corrosion inhibitors

Corrosion associated with aqueous environments containing carbon dioxide (CO₂) and/or hydrogen sulphide (H₂S), is a well-known phenomenon in oil and gas industries. This type of corrosion is of particular importance in transportation through steel pipelines. This transportation process could involve the movement of a complex mixture of gas and liquids. This moving mixture is in close contact with the inner surface of the steel pipelines and corrosion can occur. It has been demonstrated that this corrosion is influenced by flow.In oil and gas industries, film-forming corrosion inhibitors are the main tool used to control inner corrosion in pipelines. The movement of the environment generates mechanical shear stresses on the surface of the steel that can interfere with the formation of the film. This phenomenon is frequently not taken into account in corrosion control strategies and could cause problems. Despite the importance of this, there are few scientific studies available, which can provide control criteria.This work presents some ideas developed in order to understand the influence of flow on the corrosion process, making emphasis in the corrosion process associated with carbon dioxide (CO₂).     

Biotrickling filters for biogas sweetening: Oxygen transfer improvement for a reliable operation

An industrial-scale biotrickling filter for the removal of high concentrations of H₂S is described in this work. The system has been operating at H₂S inlet concentrations between 1000 and 3000 ppm_v at acidic conditions. A decrease of pH from 2.6 to 1.8 did not affect the biological activity inside the biofilter while reducing the water make-up consumption up to 75%. The current oxygen supply system, based on direct injection of air to the liquid phase, has demonstrated to be inefficient for a long-term operation leading to elemental sulfur accumulation in the packing material (i.e. promoting clogging episodes). The present study demonstrates it is possible to partially remove (40.3%) the deposited elemental sulfur by bio-oxidation when biogas is not fed. In normal operation conditions, the implementation of an aeration system based on jet-venturi devices has shown quite promising results in terms of oxygen transfer efficiency and robustness. Such improvement of oxygen transfer was translated in a better conversion of H₂S to sulfate, which increased around 17%, prolonging the lifespan operation at low-pressure drop.     

An explosion of a tank car carrying waste hydrogen peroxide

On the Metropolitan Expressway in Tokyo, a tank car exploded because it was carrying hydrogen peroxide (H₂O₂) in a compartment in which copper chloride (CuCl₂) remained. Although the main cause of the accident was trivial, the background on the accident suggested that an induction period in the reaction led to a mistake. This report describes the experimental investigation of the catalytic ability of CuCl₂, and comparing it with two other copper(II) compounds (nitrate: Cu(NO₃)₂; and copper sulfate: CuSO₄) and three iron(III) compounds (chloride: FeCl₃; nitrate: Fe(NO₃)₃; and sulfate: Fe₂(SO₄)₃).The experiments were performed using a reaction calorimeter. During the experiments at 35 °C, 2×10⁻⁵ mol of copper compounds slowly reacted with H₂O₂ and generated a precipitate. The iron compounds allowed the hydrogen peroxide to violently decompose. A 1×10⁻⁴ mol solution of CuCl₂, however, produced a violent decomposition at 35 °C. At 15 °C, a moderate heat release occurred.Based on these results, the concentration and temperature dependence of the catalytic ability of CuCl₂ were postulated to contribute to the induction period observed in the accident.     

动态群体安全投入博弈模拟*——以我国煤矿为例

为探究煤矿生产中的群体安全投入博弈特点,针对煤矿生产参与者面临的安全投入囚徒困境（SIPD）博弈,基于NetLogo模拟平台设计博弈模型,获取不同安全投入策略的工人群体变化、死亡情况和安全收益特征,探究不同安全环境对博弈结果的影响。研究结果表明:在低安全水平煤矿中,消极型工人（D-worker）可以利用积极型工人（C-worker）的安全投入,快速增加消极型群体规模,并攫取高达70%的安全收益,而在高安全水平煤矿中,在制裁型工人（T-worker）影响下,D-worker安全收益可被限制到20.4%。D-worker在恶劣安全环境中将成为主流,攫取最大安全收益,产生较高死亡率,并严重损害群体安全,扭转上述局面的短期方法为抑制群体消极心理,长期方法为逐步提高安全管理技术水平。研究结果可为我国煤矿安全水平提升提供安全投入策略参考。