Experiments on the influence of pre-ignition turbulence on vented gas and dust explosions

Experiments were performed on the influence of pre-ignition turbulence on the course of vented gas and dust explosions. A vertical cylindrical explosion chamber of approximately 100 l volume and a length-to-diameter ratio (l/d) of 4.7 consisting of a steel bottom segment and three glass sections connected by steel flanges was used to perform the experiments. Sixteen small fans evenly distributed within the chamber produced turbulent fluctuations from 0 to 0.45 m/s. A Laser-Doppler-anemometer (LDA) was used to measure the flow and turbulence fields. During the experiments the pressure and in the case of dust explosions the dust concentration were measured. In addition, the flame propagation was observed by a high-speed video camera. A propane/nitrogen/oxygen mixture was used for the gas explosion experiments, while the dust explosions were produced by a cornstarch/air mixture.It turned out that the reduced explosion pressure increased with increasing turbulence intensity. This effect was most pronounced for small vents with low activation pressures, e.g. for bursting disks made from polyethylene foil. In this case, the overpressure at an initial turbulence of 0.45 m/s was twice that for zero initial turbulence.     

Modelling and control of the dispersion of hazardous heavy gases

Dispersion of several common `heavy' gases (ethylene, propylene, ammonia, and chlorine) has been modelled on the basis of modifications in plume path theory. The model takes into account, among other things, the variations in temperature, density, and specific heat during the movement of the heavy gas plume. The effects of wind speed, density of the gas, and venting speed on the plume dispersion have been simulated. Based on the simulations a set of empirical equations has been developed. The equations have been validated by theoretical as well as experimental studies.Studies have also been carried out to simulate the effect of venting speed (manipulated by injecting hot air with the released gas) on the plume dispersion. The study reveals that the effect of venting speed on dispersion is very pronounced and can be used to reduce the risk posed by the accidental luxurious release of toxic/flammable gases. For example an increase of 20% in venting speed of chlorine (54.1 m/s) can reduce the distance up to which toxic concentration would occur by about 1100 meters.     

Experimental simulation of airbag deployment for pipeline closing

Small scale tests were carried out at ISL's shock tube facility STA (100 mm inner diameter) to study the problem of closing a pipeline by means of an airbag in case of explosions or gas leakages. Experiments were carried out to simulate the flow in a pipeline at velocities and gas pressures as present in pipeline flows. In this study the gas used was nitrogen at static pressures of 0.2 up to 5 MPa and at flow velocities of 25 m/s up to 170 m/s. A special Nylon airbag, deployed from the tube wall into the pipe, was used to simulate the airbag inflation in a real pipeline. For this purpose a special gas filling system consisting of a gas generator with a reservoir volume of up to 500 cm³ which permits air pressures up to 17 MPa to be generated inside the airbag was developed at ISL. With a fast pyrotechnically opened valve the reservoir gas was released for airbag filling. The airbag inflation was triggered in such a way that it opened in nearly 3 ms into the pipe flow generated by the shock tube and continued for about 10 ms. For this application a special measuring chamber was designed and constructed with 20 measuring ports. Through two window ports, located one in front of the other, the airbag inflation could be visualized with up to 50 successive flash sparks illuminating a fast rotating film inside a drum camera. Pressure measurements using commercially available PCB pressure gauges at 9 measuring ports placed along the inner tube surface gave some hints on the behaviour of the wall pressure during airbag deployment. As a result from the experiments performed it is to conclude, that, with the Nylon airbag samples available, the pipe flow cannot be blocked by the inflating airbag. The flow forces acting on the airbag during deployment are in the shock tube experiments of the order of about 1000 N, which are not balanced by the airbags' neck, fixing it to the shock tube wall. This outcome suggests that a mechanical support is required to fix the airbag in its place during inflation.     

Large scale high pressure jet fires involving natural gas and natural gas/hydrogen mixtures

A series of six large scale high pressure jet fires were conducted using natural gas and natural gas/hydrogen mixtures. Three tests involved natural gas and three involved a mixture of natural gas and hydrogen containing approximately 24% by volume hydrogen. For each fuel, the three tests involved horizontal releases from 20, 35 and 50 mm diameter holes at a gauge pressure of approximately 60 bar. During the experiments, the flame length and the incident radiation field produced around the fire were measured. The fires also engulfed a 1 m diameter horizontal pipe placed across the flow direction and about halfway along the flame. This pipe was instrumented to measure the heat fluxes to the pipe. The data obtained is compared with previous data obtained for various hydrocarbons at large scale.     

Flammability of hydrocarbon and carbon dioxide mixtures

The effect of carbon dioxide (CO₂) concentration on the ignition behaviour of hydrocarbon and CO₂ gas mixtures is examined in both jets and confined explosions. Results from explosion tests are presented using a 20 l explosion sphere and an 8 m long section of 1.04 m diameter pipeline. Experiments to assess the flame stability and ignition probability in free-jets are reported for a range of different release velocities. An empirically-based flammability factor model for free-jets is also presented and results are compared to ignition probability measurements previously reported in the literature and those resulting from the present tests.The results help to understand how CO₂ changes the severity of fires and explosions resulting from hydrocarbon releases. They also demonstrate that it is possible to ignite gas mixtures when the mean concentration is outside the flammable range. This information may be useful for risk assessments of offshore platforms involved in carbon sequestration or enhanced oil recovery, or in assessing the hazards posed by poorly-inerted hydrocarbon processing plant.     

Pb(II) adsorption from aqueous solutions by raw and treated biomass of maize stover – A comparative study

The potential to remove Pb(II) ion from wastewater treatment systems using raw and treated maize stover through adsorption was investigated in batch experiments. To achieve this, batch mode experiments were conducted choosing specific parameters such as pH (2–8), dosage concentration (2–30 g L⁻¹), contact time (5–180 min), temperature (20–45 °C) and metal ion concentrations (10–50 mg L⁻¹). Adsorption was pH-dependent showing a maximum at pH value 5. The equilibrium sorption capacities of raw and treated maize stover were 19.65 and 27.10 mg g⁻¹, respectively. The adsorption data fitted well to the Langmuir isotherm model. Kinetic studies revealed that the adsorption process followed pseudo-second-order model. The calculated thermodynamic parameters showed that the adsorption of Pb(II) was spontaneous and exothermic in nature. Consequently, this study demonstrated that both raw and treated maize stover could be used as adsorbents for the treatment of Pb(II) from industrial wastewaters.     

Method to analyze the regional life loss risk by airborne chemicals released after devastating earthquakes: A simulation approach

Widespread chemical plants render human life more vulnerable to major natural disasters such as earthquakes. Recognizing the potential cascading threats initiated by a devastating earthquake, a general methodology for assessing the life loss risks introduced by airborne hazardous chemical dispersion following seismically induced chemical release (SICR) was proposed. With a 600 km × 600 km region in North China as a demonstrative study area, the dispersion of ammonia released from multiple relevant chemical plants that were supposed to be damaged by a devastating earthquake was simulated in a probabilistic manner. Using an ammonia toxicity-fatality relationship and its toxicity concentration threshold, regional life loss and spatial spread were evaluated. The life loss risk was found to be non-prominent but would be very contingent on unfavorable meteorological conditions. Non-parametric correlation analysis revealed that the respective effects of meteorological mixing parameters on the risk exhibit new features in a disaster context, that is, stronger mixing would cause elevation of risk in a region. This preliminary research implied that the risk of chemical-induced life loss after a devastating earthquake deserves attention and a thorough uncertainty evaluation in the future.     

HRA in China: Model and data

Human reliability analysis (HRA) is generally viewed as quite an important part in probabilistic safety assessment (PSA). In this paper, a THERP + HCR HRA model is presented to model the operators’ post-accident behavior in Chinese nuclear power plants. The paper shows how the model is structured and how to consider and acquire the corresponding data, including HCR data modification and HRA event tree data. A case study is presented to make an illustration.     

Biosorption of Co(II) ions from aqueous solution using Chrysanthemum indicum: Kinetics,equilibrium and thermodynamics

The present study investigates the adsorption potential of Chrysanthemum indicum flower in its raw (CIF-R) and biochar (CIF-BC) form for the removal of cobalt ions from aqueous solution. The adsorbents were characterized for their surface area using BET analysis, surface morphology and elemental composition with SEM-EDAX and for the presence of functional groups by FTIR analysis. Batch adsorption experiments were carried out to evaluate the effect of process parameters, viz. pH, adsorbent dosage, initial metal ion concentration, contact time, stirring speed, presence of interfering ions and temperature on the adsorption of Co(II) ion using both the adsorbents. The optimum conditions for maximum removal of Co(II) ion was ascertained to be pH 5 for both adsorbents, adsorbent dose of 4 g/L and 3 g/L, equilibrium time of 60 min and 45 min, respectively, for CIF-R and CIF-BC. The maximum adsorption capacity of CIF-R and CIF-BC was found to be 14.84 mg/g and 45.44 mg/g, respectively, for the removal of Co(II) ion. The mechanism of adsorption was studied using different models of adsorption kinetics, isotherms and thermodynamics. It was inferred that Co(II) adsorption on both CIF-R and CIF-BC followed pseudo-second order kinetics and Langmuir isotherm model with the process being spontaneous and endothermic in nature.     

A study on the effect of trees on gas explosions

The downstream as well as the upstream oil and gas industry has for a number of years been aware of the potential for flame acceleration and overpressure generation due to obstacles in gas clouds caused by leaks of flammable substances. To a large extent the obstacles were mainly considered to be equipment, piping, structure etc. typically found in many installations. For landbased installations there may however also be a potential for flame acceleration in regions of vegetation, like trees and bushes. This is likely to have been the case for the Buncefield explosion that occurred in 2005 (Buncefield Major Incident Investigation Board, 2008), which led to the work described in the present paper. The study contains both a numerical and an experimental part and was performed in the period 2006–2008 (Bakke and Brewerton, 2008, Van Wingerden and Wilkins, 2008).The numerical analysis consisted of modelling the Buncefield tank farm and the surrounding area with FLACS. The site itself was not significantly congested and it was not expected to give rise to high overpressures in case of a hydrocarbon leak. However, alongside the roads surrounding the site (Buncefield Lane and Cherry Tree Lane), dense vegetation in the form of trees and bushes was included in the model. This was based on a site survey (which was documented by video) performed in the summer of 2006.A large, shallow, heavier-than-air gas cloud was defined to cover part of the site and surroundings. Upon ignition a flame was established in the gas cloud. This flame accelerated through the trees along the surrounding roads, and resulted in high overpressures of several barg being generated by FLACS. This is to the authors’ knowledge the first time a possible effect of vegetation on explosions has been demonstrated by 3D analyses.As a consequence of these results, and since the software had been validated against typical industrial congestion rather than dense vegetation, a set of experiments to try to demonstrate if these effects were physical was carried out as well. The test volume consisted of a plastic tunnel, 20 m long with a semi-circular cross-section 3.2 m in diameter allowing for representing lanes of vegetation. The total volume of the tent was approximately 80.4 m³. The experimental programme involved different degrees of vegetation size, vegetation density (blocking ratio) and number of vegetation lanes (over the full length of the tunnel). The experiments were performed with stoichiometric propane–air mixtures resulting in continuously accelerating flames over the full length of the tunnel for some of the scenarios investigated.The main conclusions of the study are that trees can have an influence on flame acceleration in gas–air clouds, and that advanced models such as FLACS can be used to study such influence. More research is needed, however, because even if FLACS predicts flame acceleration in dense vegetation, no evidence exists that applying the code to trees rather than rigid obstacles provides results of acceptable accuracy.     

Artificial neural network modelling of As(III) removal from water by novel hybrid material

The present study reported a method for removal of As(III) from water solution by a novel hybrid material (Ce-HAHCl). The hybrid material was synthesized by sol–gel method and was characterized by XRD, FTIR, SEM–EDS and TGA–DTA. Batch adsorption experiments were conducted as a function of different variables like adsorbent dose, pH, contact time, agitation speed, initial concentration and temperature. The experimental studies revealed that maximum removal percentage is 98.85 at optimum condition: pH = 5.0, agitation speed = 180 rpm, temperature = 60 °C and contact time = 80 min using 9 g L⁻¹ of adsorbent dose for initial As(III) concentration of 10 mg L⁻¹. Using adsorbent dose of 10 g L⁻¹, the maximum removal percentage remains same with initial As(III) concentration of 25 mg L⁻¹ (or 50 mg L⁻¹). The maximum adsorption capacity of the material is found to be 182.6 mg g⁻¹. Subsequently, the experimental results are used for developing a valid model based on back propagation (BP) learning algorithm with artificial neural networking (BP-ANN) for prediction of removal efficiency. The adequacy of the model (BP-ANN) is checked by value of the absolute relative percentage error (0.293) and correlation coefficient (R² = 0.975). Comparison of experimental and predictive model results show that the model can predict the adsorption efficiency with acceptable accuracy.     

Large scale experiments to study fires following the rupture of high pressure pipelines conveying natural gas and natural gas/hydrogen mixtures

As part of the EC funded Naturalhy project, two large scale experiments were conducted to study the hazard presented by the rupture of high pressure transmission pipelines conveying natural gas or a natural gas/hydrogen mixture containing approximately 22% hydrogen by volume. The experiments involved complete rupture of a 150 mm diameter pipeline pressurised to nominally 70 bar. The released gas was ignited and formed a fireball which rose upwards and then burned out. It was followed by a jet fire which continued to increase in length, reaching a maximum of about 100 m before steadily declining as the pipeline depressurised. During the experiments, the flame length and the incident radiation field produced around the fire were measured. Measurements of the overpressure due to pipeline rupture and gas ignition were also recorded. The results showed that the addition of the hydrogen to the natural gas made little difference to radiative characteristics of the fires. However, the fraction of heat radiated by these pipeline fires was significantly higher than that observed for above ground high pressure jet fires (also conducted as part of the Naturalhy project) which achieved flame lengths up to 50 m. Due to the lower density, the natural gas/hydrogen mixture depressurised more quickly and also had a slightly reduced power. Hence, the pipeline conveying the natural gas/hydrogen mixture resulted in a slightly lower hazard in terms of thermal dose compared to the natural gas pipeline, when operating at the same pressure.     

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.     

Investigation on removal of p-nitrophenol using a hybridized photo-thermal activated persulfate process: Central composite design modeling

The aim of this work is the study of p-nitrophenol (PNP) removal, as a nitroaromatic compound, using a hybridized photo-thermally activated potassium persulfate (KPS) in a fully recycled batch reactor. Response surface method was used for modeling the process. Reaction temperature, KPS initial dosage and initial pH of the solution were selected as variables, besides PNP degradation efficiency was selected as the response. ANOVA analysis reveals that a second order polynomial model with F-value of 41.7, p-value of 0.0001 and regression coefficient of 0.95 is able to predict the response. Based on the model, the process optimum conditions were introduced as initial pH of 4.5, [KPS]₀ = 1452 mg/L and T = 66 °C. Also experiments showed that using thermolysis and photolysis of the persulfate simultaneously, the role of thermolysis is not considerable. A pseudo first order kinetic model was established to describe the degradation reaction. Operational cost, as a vital industrial criterion, was estimated so that the condition of initial pH of 4.5, [KPS]₀ = 1452 mg/L and T = 25 °C showed the highest cost effective case. Under the preferred mild condition, the process will reach to 84% and 89% of degradation and mineralization efficiencies, after 60 and 120 min, respectively.     

Experimental investigation of the flow characteristics of jettisoning in a CO2 carrier

This experimental study was performed to investigate the flow characteristics in the jettisoning flow line of a liquid CO₂ carrier. When a pressurized liquid CO₂ container loses mechanical integrity, possibly by material or mechanical defects, the liquid inventory should be drained out rapidly for safety reasons using the so-called jettisoning process. In the course of jettisoning, the liquid CO₂ undergoes two phase change stages, from liquid to liquid + vapor and from liquid + vapor to solid + vapor. Consequently, the jettisoning release rate is affected by the characteristics of these phase changes. In this study, liquid CO₂ was discharged through a small tube, representing a jettisoning flow line. The temperature and pressure were measured along the tube, and the locations of the phase changes were inferred from the measured data. The experimental results showed that active nucleation occurred near the tube tip and that the phase change into solid and vapor occurred just after leaving the pipe, irrespective of the tube length in this study.     

Stochastic modeling of accident risks associated with an underground coal mine in Turkey

In this study, a methodology is proposed towards development of an uncertainty model that includes randomness in the occurrence of days-lost accidents in a coal mine. The accident/injury data consists of 1390 days-lost accident cases recorded at GLI-Tuncbilek underground lignite mine from January 1994 to December 2002. In the first step of proposed methodology, the frequency and the severity of the accidents have been modeled statistically by fitting appropriate distributions. The test done by BestFit software yields a chi-square value of 21.53 (p = 0.089) with 14 degrees of freedom and estimates the parameter of lambda for Poisson distribution as 12.87 accidents/month. For the severity component, a lognormal distribution is fitted to days-lost data and chi-square goodness-of-fit test calculates a value of 40.44 (p = 0.097) with 30 degrees of freedom. The parameters of lognormal distribution are estimated as a mean of 14.3 days and standard deviation of 23.1 days, respectively. Then, two distributions are basically combined by Monte Carlo simulation in order to construct relative risk levels in yearly base referring to the final cumulative distribution. Finally, a simple forecasting modeling is carried out in order to quantitatively predict the expected risk levels by using decomposition technique in time series analysis. Stochastic model estimates that although, there would be substantial reduction in the expected number of accidents in the near future, the higher level of risks still should be a concern for the mine management.     

Biohydrogen production using waste activated sludge as a substrate from fructose-processing wastewater treatment

Biohydrogen production by dark fermentation in a series of batch tests under different environmental control conditions was evaluated to determine the optimal initial cultivation pH and temperature for a continuous-flow kinetic test to validate the kinetic model system. The waste activated sludge (WAS) from fructose-processing manufacturing was used as the model substrate for biohydrogen production. The batch experiments for biohydrogen production were conducted in a 6 l bioreactor. Fifteen batch kinetic tests were investigated when pH was controlled at 6, 7, 8 and 9 as well as the temperature was controlled at 37 °C, 45 °C and 55 °C, respectively. The experimental results indicated that the optimal operational condition for hydrogen production occurred while pH was 7 and temperature was 55 °C with the highest hydrogen production of 7.8 mmol. The optimal recovery time for hydrogen was 25 h in the batch experiments. Furthermore, the kinetic test of biohydrogen production was performed by anaerobic mixed microbial culture in the continuous-flow experiment when pH and temperature was maintained at 7 and 55 °C. Approximately 60% and 7% of substrate solution was converted into acetate and hydrogen, respectively, at the steady state. Roughly only 0.77% and 2.7% of substrate solution was converted into propionate and butyrate, respectively, at a steady-state condition. The experimental and modeling approaches presented in this study could be employed for the design of pilot-scale and full-scale anaerobic biohydrogen fermentors using food-processing waste activated sludge (WAS) as a substrate solution.     

Refinery wastewater degradation with titanium dioxide,zinc oxide,and hydrogen peroxide in a photocatalytic reactor

This paper presents the photo-catalytic degradation of real refinery wastewater from National Refinery Limited (NRL) in Karachi, Pakistan, using TiO₂, ZnO, and H₂O₂. The pretreatment of the refinery effluent was carried out on site and pretreated samples were tested at 32–37 °C in a stirrer bath reactor by using ultra-violet photo oxidation process. The degradation of wastewater was measured as a change in initial chemical oxygen demand (COD) and with time. Optimal conditions were obtained for catalyst type, and pH. The titanium dioxide proved to be very effective catalysts in photo-catalytic degradation of real refinery wastewater. The maximum degradation achieved was 40.68% by using TiO₂ at 37 °C and pH of 4, within 120 min of irradiations. When TiO₂ was combined with H₂O₂ the degradation decreased to 25.35%. A higher reaction rate was found for titanium dioxide. The results indicate that for real refinery wastewater, TiO₂ is comparatively more effective than ZnO and H₂O₂. The experiments indicated that first-order kinetics can successfully describe the photo-catalytic reaction. The ANOVA results for the model showed satisfactory and reasonable adjustment of the second-order regression model with the experimental data. The ANOVA results also showed that pH is significant than reaction time and catalyst dosage of TiO₂; and in case of ZnO, reaction time is significant than pH and catalyst dosage. This study proves that real refinery wastewater reacts differently than synthetic refinery wastewater, oil field produced water or oil water industrial effluent.     

Effect of ultrasound irradiation and Ni-loading on properties and performance of CeO2-doped Ni/clinoptilolite nanocatalyst used in polluted air treatment

In this research nanocatalysts containing 5, 10 and 15 wt.% of Ni, dispersed by sonication over CeO₂–clinoptilolite composite support were compared toward total oxidation of toluene. Their catalytic performance at different temperatures between 150 and 350 °C was studied based on the oxidative destruction of toluene. The results indicated that the activity of Ni/CeO₂–clinoptilolite nanocatalyst for toluene oxidation increased from 33 to 44% at 250 °C by employing sonochemical method in synthesis of catalyst. Meanwhile, the catalytic activity was also improved when Ni content was increased from 5 to 10 and 15 wt.%. With the aid of several characterization techniques like XRD, FESEM, PSD, EDX, BET and FTIR, the correlation between nanocatalyst structure and its activity was addressed. It is indicated that sonochemical method can lift the catalytic activity due to the better dispersion of catalyst active components and also higher surface area. Among sonicated samples, 15 wt.% Ni nanocatalyst showed the highest toluene oxidation due to the better dispersion of catalyst active components and hence to more effective catalytic sites.