Prediction of methanol loss in liquid hydrocarbon phase during natural gas hydrate inhibition using rigorous models

Methanol is the most widely used natural gas hydrate inhibitor and it is only effective as a hydrate inhibitor in the aqueous phase. Methanol is not regenerated in natural gas inhibition process due to its intermittent application in most cases. However, a significant cost is associated with the process because of methanol loss while utilizing this inhibitor. In this work, several intelligent models along with a new mathematical correlation are presented in terms of methanol concentration in aqueous phase and temperature to precisely forecast the methanol loss in the saturated hydrocarbons phase. An excellent match was noticed between the calculated results and literature data.     

Simple Arrhenius-type function accurately predicts dissolved oxygen saturation concentrations in aquatic systems

A sufficient supply of dissolved oxygen (DO) is vital for life in higher organisms. In aquatic systems, oxygen regulates respiratory metabolism, mediates biogeochemical cycles, and is an integral component of water quality. In this work, a simple predictive tool for dissolved oxygen saturation concentrations in aquatic systems as a function of chloride concentration and temperature using a novel Arrhenius-type asymptotic exponential function has been formulated. The proposed method predicts the amount of dissolved oxygen saturation concentrations for temperatures up to 50 °C and chloride concentrations up to 25 g/l. Estimations are found to be in excellent agreement with the reliable data in the literature with average absolute deviation being 3%. The tool developed in this study can be of immense practical value for the engineers and scientists to have a quick check on the oxygen saturation concentrations in aquatic systems at various conditions without opting for any experimental measurements. In particular, environmental science experts would find the proposed approach to be user-friendly with transparent calculations involving no complex expressions.     

Estimation of displacement losses from storage containers using a simple method

Filling losses in tanks due to the expansion of the liquid into the tank and the vapors that are forced out of the tank are generally called displacement losses. Restrictions on vaporization loss of petroleum products give added emphasis to the accurate prediction of vapor pressure and hydrocarbon losses for petroleum products. In this work, firstly, a simple-to-use correlation is developed to estimate the true vapor pressure of liquefied petroleum gas (LPG) and natural gasoline as a function of Reid Vapor pressure (RVP) and temperature as well as the vapor pressure of different mixtures of propane and butane are correlated as a function of ambient air temperature and propane volume percent. Secondly, the filling losses from storage containers are estimated in percentage of liquid pumped in tanks as a function of working pressure and vapor pressure at liquid temperature. The study showed the proposed method to be in good agreement with the available reliable data in the literature. The average absolute deviation between reported data and the proposed correlation is less than 2%. The proposed simple-to-use approach can be of significant practical value for the process engineers and scientists to have a quick check on the prediction of the displacement losses from storage containers as well as for rapid estimation of vapor pressure of LPG and natural gasoline.     

Vapor flammability above aqueous solutions of flammable liquids

The flammability of vapors above aqueous solutions of ethanol and acetonitrile was studied experimentally in a 20-L combustion apparatus. No liquid was present in the apparatus, but the vapor concentrations were adjusted to correspond to the vapor in equilibrium with a specified aqueous solution. The experimental results for these two systems show that

• As water is added to the vapor, the lower boundary of the flammability zone decreases. For ethanol, the lower flammability limits (LFL) decreases from 3.7% for pure vapor to 3.2% with saturated water vapor. For acetonitrile, the decrease is from 4.2% to 3.8%. Thus, to a good approximation, the water vapor can be treated as an inert, enabling the data to be displayed on a single flammability triangle diagram. This provides a very simplified method for estimating the flammable behavior for aqueous solutions.

• The upper boundary of the flammability zone is unchanged with the addition of water.

• The limiting oxygen concentration (LOC) is essentially constant for all concentrations of aqueous solutions. The LOC for the pure solvent may be used as a universal LOC for all solvent concentrations.

• The vapor mixture above the aqueous solution is not flammable below a certain liquid mol fraction of flammable. The flammable concentration at which this occurs can be called the maximum safe solvent concentration (MSSC). A method is presented to determine the MSSC from experimental flammability data.

• The oxygen concentration defining the flammable boundary for the vapor decreases rapidly from the MSSC and then increases as the liquid solvent concentration increases.

The calculated adiabatic flame temperature (CAFT) method qualitatively predicts the same behavior as the experimental data.     

Quantification of source-level turbulence during LNG spills onto a water pond

The use of computational fluid dynamics (CFD) models to simulate LNG vapor dispersion scenarios has been growing steadily over the last few years, with applications to LNG spills on land as well as on water. Before a CFD model may be used to predict the vapor dispersion hazard distances for a hypothetical LNG spill scenario, it is necessary for the model to be validated with respect to relevant experimental data. As part of a joint-industry project aimed at validating the CFD methodology, the LNG vapor source term, including the turbulence level associated with the evaporation process vapors was quantified for one of the Falcon tests.This paper presents the method that was used to quantify the turbulent intensity of evaporating LNG, by analyzing the video images of one of the Falcon tests, which involved LNG spills onto a water pond. The measured rate of LNG pool growth and spreading and the quantified turbulence intensity that were obtained from the image analysis were used as the LNG vapor source term in the CFD model to simulate the Falcon-1 LNG spill test. Several CFD simulations were performed, using a vaporization flux of 0.127 kg/m² s, radial and outward spreading velocities of 1.53 and 0.55 m/s respectively, and a range of turbulence kinetic energy values between 2.9 and 28.8 m²/s². The resulting growth and spread of the vapor cloud within the impounded area and outside of it were found to match the observed behavior and the experimental measured data.The results of the analysis presented in this paper demonstrate that a detailed and accurate definition of the LNG vapor source term is critical in order for any vapor cloud dispersion simulation to provide useful and reliable results.     

Sensitivity analysis and optimization for gasoline vapor condensation recovery

Volatile organic compounds (VOCs) are easily evaporated and discharged from everywhere into the atmosphere, especially in various operations of gasoline. The emission of VOCs is always a significant environmental problem, and the control of VOCs pollution has been a hot topic in the field of air purification. In this paper, the condensation separation method for gasoline vapor recovery was investigated and four gasoline vapors of S1–S4 were selected for the sensitivity analysis and optimization of the condensation process, using the Model Analysis Tools from Aspen Plus. Generally, to control VOCs pollution efficiently, both the vapor recovery efficiency and the outlet vapor concentration of the condensation recovery system should be simultaneously considered. Then an optimized three-stage condensation process was proposed, whose condensation temperatures were optimized and designed at 1 °C, −40 °C and −110 °C, respectively. Further, based on the comprehensive consideration of both meeting the more strict VOCs emission standard and ensuring the condensation recovery system work stably and economically, it was recommended that the maximum total vapor recovery efficiencies for S1–S4 should be 99.73%, 99.79%, 99.82% and 99.19%, and the minimum outlet vapor concentrations be 2.87 g/m³, 2.75 g/m³, 3.04 g/m³ and 16.98 g/m³, respectively. Accordingly, the condensation temperature of the copious cooling stage should be set at −130 °C. Moreover, the total cooling duties for the single-stage and three-stage condensation processes were investigated and compared when the condensation temperature of the recovery system ranged from 20 °C to −110 °C. The total cooling duties of the three-stage condensation process for S1–S4 would be saved by 12.23%, 15.68%, 13.96% and 15.65%, respectively. Finally, a three-stage condensation system was developed for the industrial gasoline vapor recovery, which has performed well since its installation.     

Investigation of pool spreading and vaporization behavior in medium-scale LNG tests

A failure of a Liquefied Natural Gas (LNG) tanker can occur due to collision or rupture in loading/unloading lines resulting in spillage of LNG on water. Upon release, a spreading liquid can form a pool with rapid vaporization leading to the formation of a flammable vapor cloud. Safety analysis for the protection of public and property involves the determination of consequences of such accidental releases. To address this complex pool spreading and vaporization phenomenon of LNG, an investigation is performed based on the experimental tests that were conducted by the Mary Kay O'Connor Process Safety Center (MKOPSC) in 2007. The 2007 tests are a part of medium-scale experiments carried out at the Brayton Fire Training Field (BFTF), College Station. The dataset represents a semi-continuous spill on water, where LNG is released on a confined area of water for a specified duration of time. The pool spreading and vaporization behavior are validated using empirical models, which involved determination of pool spreading parameters and vaporization rates with respect to time. Knowledge of the pool diameter, pool height and spreading rate are found to be important in calculating the vaporization rates of the liquid pool. The paper also presents a method to determine the vaporization mass flux of LNG using water temperature data that is recorded in the experiment. The vaporization rates are observed to be high initially and tend to decrease once the pool stopped spreading. The results of the analysis indicated that a vaporization mass flux that is varying with time is required for accurate determination of the vaporization rate. Based on the data analysis, sources of uncertainties in the experimental data were identified to arise from ice formation and vapor blocking.     

Developing a CFD heat transfer model for applying high expansion foam in an LNG spill

Liquefied natural gas (LNG) is widely used to cost-effectively store and transport natural gas. However, a spill of LNG can create a vapor cloud, which can potentially cause fire and explosion. High expansion (HEX) foam is recommended by the NFPA 11 to mitigate the vapor hazard and control LNG pool fire. In this study, the parameters that affect HEX foam performance were examined using lab-scale testing of foam temperature profile and computational fluid dynamics (CFD) modeling of heat transfer in vapor channels. A heat transfer model using ANSYS Fluent® was developed to estimate the minimum HEX foam height that allows the vapors from LNG spillage to disperse rapidly. We also performed a sensitivity analysis on the effect of the vaporization rate, the diameter of the vapor channel, and the heat transfer coefficient on the required minimum height of the HEX foam. It can be observed that at least 1.2 m of HEX foam in height are needed to achieve risk mitigation in a typical situation. The simulation results can be used not only for understanding the heat transfer mechanisms when applying HEX foam but also for suggesting to the LNG facility operator how much HEX foam they need for effective risk mitigation under different conditions.     

Disposal of hexachlorodisilane and its hydrolyzed deposits

Hexachlorodisilane (Si₂Cl₆, HCDS) is an important precursor used in semiconductor device manufacturing. It is a flammable as well as a water reactive liquid which hydrolyzes rapidly upon contact with water or moisture. The hydrolyzed deposits are also known to be shock-sensitive with explosion energy equivalent to trinitrotoluene (TNT). In this work, two phases of test program including disposal of HCDS and disposal of the shock sensitive HCDS hydrolyzed deposits were conducted. The first phase of the program was to find an agent that can completely dissolve/react the HCDS vapor without forming shock sensitive deposits. The second phase of the program attempted to find a suitable agent to suppress the Si–Si bonds, one of the essential roles of chemical functional groups in shock sensitivity of the HCDS hydrolyzed deposits to suppress the shock sensitivity. A variety of agents such as sulfuric acid solutions, aqueous sodium hydroxide (NaOH) solutions, aqueous potassium hydroxide (KOH) solutions, KOH/alcohol solutions were utilized as the suppressants in this work. Samples mixed with suppressants were not only tested for shock sensitivity by a Fall-hammer apparatus but also analyzed for chemical functional groups to identify the effect of each agent. Concentrated sulfuric acid was found to suppress the shock sensitivity of the liquid HCDS hydrolyzed deposits by acting as a medium that helps the hydrolyzed deposit to retain moisture. KOH/alcohol solutions can turn HCDS vapor into non-hazardous silica, so that, it provided a safe way to dispose HCDS. Finally, practical recommendations about handling and eliminating the risk of shock sensitivity are given for HCDS liquid spill, HCDS vapor vent and HCDS hydrolyzed deposits.     

Experimental analysis of the evaporation process for gasoline

This paper presents the findings from a study on the evaporation process of 93 RON (research octane number) unleaded gasoline. The parameters measured in the experiment included the weight, the RVP (Reid vapor pressure) and the viscosity of gasoline, the concentration of NMHC (non-methane total hydrocarbon) in the oil vapor and the concentration of the main vapor constituent. Results showed that the parameters changed significantly as evaporation processed. The weight loss reached 86.36% after 300 days and presented a logarithmic curve with time. The RVP decreased from 38 kPa to 9.6 kPa. The viscosity of gasoline increased from 8.6 × 10^?4 Pa s to 1.51 × 10^?3 Pa s. All the concentrations of NMHC and the main constituent of vapor decreased in varying amounts. Most of the changes might be attributed to the evaporation of volatile hydrocarbons.     

隧道内甲醇液体蒸发及蒸气扩散规律数值模拟分析

为了研究隧道内甲醇液体蒸发及蒸气扩散规律,应用CFD方法进行了研究,分析了隧道内甲醇蒸气浓度分布规律。结果表明:浅液池上方、车辆底部及两侧位置出现甲醇蒸气的积聚,蒸气浓度分层具有一定的规律性,纵截面浓度分层较明显;甲醇蒸气主要分布于隧道中下部位置,尤其在距离地面1 m以下的空间,在泄漏源上方、车辆底部、车辆两侧均可能出现蒸气接近或超过爆炸极限的区域;隧道内障碍车辆底部和两侧较低位置蒸气产生积聚,同时车辆也阻碍了蒸气向对侧隧道口的扩散。     

Human Adaptation to Work in Two Different Climates

The processes of acclimation to hot-dry and to warm-humid climates were studied using two approaches: a quantitative analysis of literature data and an experimental study in the laboratory concerning the physiological parameters of heart rate, rectal temperature, sweat loss, and subjective assessment.

Analysis o f literature data: Data from 62 experiments with a total of 813 participants were pooled and recalculated. The experiments ranged from 6 to 24 days, air temperatures from 30.4 to 50.0°C, water vapor pressures from 1.5 to 6.5 kPa, and wet bulb globe temperatures (WBGT) from 27.4 to 38.6°C.

Laboratory studies: In the laboratory, 8 participants were acclimated during 15 consecutive days to a hot-dry climate and to a warm-humid climate, which were equivalent in terms of the WBGT (33.5 and 33.6°C, respectively). The participants walked four times for 25 min on a treadmill at a speed of 4 km/h. The hot-dry climate caused somewhat greater strain than the warm-humid condition. In the course of acclimation to the hot-dry climate, heart rate and rectal temperature started at higher levels, decreased slightly steeper but remained on a higher level throughout. Nevertheless, the differences between both thermal conditions were small, and both physiologic functions reached the point of acclimation almost at the same time under warm-humid and under hot-dry exposure. Sweat loss, which is not regarded as a valid predictor for acclimation, was considerably higher but increased less in the hot-dry than in the warm-humid climate.     

Determination of explosion limits – Criterion for ignition under non-atmospheric conditions

Many industrial processes are run at non-atmospheric conditions (elevated temperatures and pressures, other oxidizers than air). To judge whether and if yes to what extent explosive gas(vapor)/air mixtures will occur or may be generated during malfunction it is necessary to know the safety characteristic data at the respective conditions. Safety characteristic data like explosion limits, are depending on pressure, temperature and the oxidizer. Most of the determination methods are standardized for ambient conditions. In order to obtain determination methods for non-atmospheric conditions, particularly for higher initial pressures, reliable ignition criteria were investigated. Ignition tests at the explosion limits were carried out for mixtures of methane, propane, n-butane, n-hexane, hydrogen, ammonia and acetone in air at initial pressures up to 20 bar. The tests have been evaluated according to different ignition criteria: visual flame propagation, temperature and pressure rising. It could be shown that flame propagation and occasionally self-sustained combustion for several seconds occurred together with remarkable temperature rise, although the pressure rise was below 3%. The results showed that the combination of a pressure rise criterion of 2% and a temperature rise criterion of 100 K seems to be a suitable ignition criterion for the determination of explosion limits and limiting oxidizer concentration at higher initial pressures and elevated temperatures. The tests were carried out within the framework of a R&D project founded by the German Ministry of Economics and Technology.     

Thermodynamic method for the prediction of solid CO2 formation from multicomponent mixtures

The increase in GHG concentration has a direct effect on global climate conditions. Among the possible technologies to mitigate GHG emissions, CCS is being accepted to gain emission reduction. Such technology also involves cryogenic CO₂ capture processes based on CO₂ freeze-out or where the formation of solid CO₂ must be avoided. Captured CO₂ is usually transported in pipelines for the reinjection.The risk associated to the release of CO₂ is due to the changing temperatures and pressures the system may experience, which can lead to the deposition of solid CO₂ where it must be avoided. Prolonged exposure to dry ice can cause severe skin damage and its resublimation could pose a danger of hypercapnia. It is, thus, necessary to build up a tool able to predict the conditions in which CO₂ can freeze-out.A thermodynamic methodology based on cubic EoSs has been developed which is able to predict solid–liquid–vapor equilibrium of CO₂ mixtures with n-alkanes or H₂S which are usually found in equipment for acidic gas, mainly natural gas, treatment.The focus is a detailed analysis of the method performances when more than two components are present since, for such a case, literature does not provide significant modeling results.     

Dynamic simulation of the BP Texas City refinery accident

The paper investigates the causes and simulates the dynamics of the events that led to the catastrophic explosion on March 23, 2005 at the British Petroleum (BP) refinery in Texas City (USA) where 15 people died and 180 were injured.The paper follows the timeline of the accident, investigates the premises that characterized its phenomenology, and performs a critical analysis to fill the gaps that can be found in the scientific literature concerning the accident. In particular, a commercial dynamic process simulator (UNISIM) was adopted and integrated with ad hoc models to explain the column flooding and overfilling, the opening of the relief valves, and the flow of a two-phase mixture into the pipe connected to the blowdown system. The main findings are: (1) that the mass balance and the liquid thermal expansion cannot explain the complete flooding and overflow of the isomerization column; (2) the vapor cap used to explain the column overflow is unrealistic in our opinion; (3) the overflow can be explained by the partial vaporization of the feed stream after 1:00 PM and the consequent dispersion of vapor bubbles into the liquid holdup above the feed tray. In particular, tray holes smaller than 8 mm could cause the overflow; (4) there is a significant change in the thermodynamic conditions of the mixture emitted by the column head (temperature, pressure, vapor/liquid fractions) along the 270 m pipeline that connects the relief valves to the blowdown system; (5) the HEM model, together with the initial conditions we applied cannot explain the blowdown drum filling and release, therefore further studies are necessary.     

Modeling the vapor source term associated with the spill of LNG into a sump or impoundment area

The recent publication of evaluation protocols for vapor source term models and vapor dispersion models have influenced the modeling approaches that can be used for approval of new and expansion projects at LNG receiving terminals. In the past few years the scientific basis of integral vapor source term models has been questioned with growing concerns regarding their validity. In this paper, the shallow water equations (SWEs) were solved to study the characteristics of the evaporating LNG pool associated with a constant flow rate spill of LNG into a concrete sump. In the early stages of pool spreading, the leading edge thickness profile of the SWE model scales with the square root of the distance from the leading edge as the pool spreads. After the edge of the pool reaches the wall, the reflected wave forms a hydraulic jump that travels back towards the center of the pool at a speed that is considerably slower than the initial spreading of the pool. Once the hydraulic jump reaches the center, the pool assumes a nearly flat free surface for the rest of the spill. The pool spreading and the rate of evaporation from the SWEs were then compared to the solution provided by the integral model, PHAST. The two approaches were found to agree well with one another. The SWE model was also used to demonstrate the influence of an elevated spill source. With an elevated source, the LNG pool spreads faster, significantly increasing the initial rate of vaporization and peak vaporization rate. This increase in the initial rate of vaporization could lead to an increase in the vapor cloud hazard distance. The SWE model was also used to demonstrate the influence of an inclined sump floor in the shape of an inverted cone where the spilling LNG accumulates in the low vertex of the cone. Inclined sump floors can be used to significantly reduce the cumulative evaporation, making them attractive as a possible mitigation approach in cases where a containment sump is located close to a property boundary.     

Reduction of water usage in industry by using the MINLP coordinates technique

Natural resources are limited, so we need to handle them carefully. Wastewater also belongs as a significant natural resource. The re-usage of wastewater is to save fresh water and for the preparation of raw materials or/and utilities. The wastewater re-usage distribution can be optimised using mixed-integer nonlinear programming (MINLP), as a tool in combinations using the coordinates technique. The main goal of this MINLP coordinates technique was: i) wastewater and condensate, as produced during different industrial processes, could be collected for: utilities for steam-generation, and the preparations of raw materials; ii) wastewater and condensate could be collected within the main reservoir; iii) distributions from the main reservoir could be used with including different alternatives, which can reduce pollution, based on the re-usage of wastewater. Alternatives included in the optimization model represent potential solutions, which need to be evaluated on appropriate way.The MINLP coordinates technique for wastewater re-usage distribution was tested on existing formalin and methanol industrial processes, thus allowing the saving of water and generated by 280 kEUR/a profit.     

太阳辐射对纯液体蒸发行为影响的实验研究

通过蒸发实验,考察了太阳辐射对液体苯、甲苯和乙醇蒸发行为的影响.实验结果表明,苯和甲苯表面温度随时间呈现出先降低后升高的趋势,而乙醇则呈现出先降低后恒定的趋势,且环境风速越大,这种变化趋势就越明显.液体表面温度的变化不但与太阳辐射强度以及环境风速的大小有关,还与液体本身的物理性质(如热容、蒸发潜热和饱和蒸气压)有关.因此,在预测液体的蒸发速率时,必须考虑太阳辐射或周围热辐射源对液体表面温度的影响.     

Study of the explosion parameters of vapor–liquid diethyl ether/air mixtures

The knowledge of the vapor–liquid two-phase diethyl ether (DEE)/air mixtures (mist) on the explosion parameters was an important basis of accident prevention. Two sets of vapor–liquid two-phase DEE/air mixtures of various concentrations were obtained with Sauter mean diameters of 12.89 and 22.90 μm. Experiments were conducted on vapor–liquid two-phase DEE/air mixtures of various concentrations at an ignition energy of 40.32 J and at an initial room temperature and pressure of 21 °C and 0.10 MPa, respectively. The effects of the concentration and particle size of DEE on the explosion pressure, the explosion temperature, and the lower and upper flammability limits were analyzed. Finally, a series of experiments was conducted on vapor–liquid two-phase DEE/air mixtures of various concentrations at various ignition energies. The minimum ignition energies were determined, and the results were discussed. The results were also compared against our previous work on the explosion characteristics of vapor–liquid two-phase n-hexane/air mixtures.     

Correlation between flash points and vapor pressures of organic compounds

Correlations between flash points and vapor pressures at 25 °C for pure organic compounds were investigated. It was found that classification of organic compounds according to their chemical-structural characteristics (e.g., functional groups) was necessary for the correlation study. Under this classification, linearity seems to be the most appropriate correlation to explain the relationship between the inverse of flash points (°K) and the logarithm of vapor pressures (mm Hg) at 25°C for pure organic compounds. A test study to evaluate the validity of a regression line as an estimation of an unknown flash point from a known vapor pressure was carried out with a data set containing 31 alkanes and aromatics; 55% of the flash points were predicted within ±5°Cand89% were within ±10°C. Within limits of ± 5 to 10°C the procedure is useful but should be improved.