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.     

Study of dry ice formation during blowdown of CO₂-CH₄ from cryogenic distillation column

Cryogenic distillation columns are generally subjected to high-pressure loadings during the natural gas purification process. The high-pressure conditions inside the column cause safety risk e.g. rupture. When an emergency arises, blowdown is a typical way of minimizing the failure hazard. However, blowdown at the cryogenic conditions involves dry ice formation due to the rapid decrease in temperature driven by the Joule-Thomson effect. The dry ice formation intensifies the failure hazard due to the orifice blockage. Therefore, optimization of blowdown parameters is necessary to avoid the dry ice formation. So far, very limited studies are available in the literature for the blowdown of CO₂-CH₄ mixture, especially at the cryogenic conditions. In this study, a computational investigation followed by the experimental validation is accomplished to analyze the dry ice formation during blowdown of CO₂-CH₄ binary mixture from the cryogenic distillation column. The composition of mixture, orifice size, and initial conditions inside vessel have a high impact on blowdown path. A 3.00 mm orifice is the most suitable size for the blowdown at cryogenic conditions as it doesn't promote solidification and discharges the inventory quickly. Based on the experimental observation, an empirical correlation is also developed to instantly find out the optimum blowdown parameters.     

Experimental study on the suppression of gas explosion using the gas–solid suppressant of CO2/ABC powder

Gas explosion is the leading accident in underground coal mining in China. Using the self-improved 20 L spherical experimental system, the impacts of 8% CO₂, ABC powder at various concentrations and mixture of them on the suppression of mine gas explosion were investigated. The results indicate that cooperative synergism exists between ABC powder and CO₂. Their combination has a better effect than each of the two components acting alone, especially for the gas of larger concentration. When 0.25 g/L ABC powder was mixed with 8% CO₂, the explosion limits were reduced by about 55%, the time to reach the peak explosion pressure was prolonged 3.56 times on average. Meanwhile, the maximum explosion pressure declined on an average of 59.4% and the maximum explosion overpressure rising rate decreased on an average of 91.1%. A combination of 0.20 g/L ABC powder and 8% CO₂ completely suppressed 11% gas explosion. The explosion suppression mechanism of CO₂ and ABC powder were probed theoretically. CO₂ plays a key part in the whole explosion processes, and it can effectively suppress the forward reaction between gas and oxygen. While it is during the middle-later period of explosion processes that ABC powder plays a critical role. The particles decomposed from heated ABC powder such as nitrogen and phosphor will react with free radicals rapidly. Besides, atoms as N, P are capable of participating in chain reaction and reacting with active groups, significantly suppressing the gas explosion.     

Preoptimal analysis of phase characteristic indicators in the entire process of coal spontaneous combustion

To accurately predict the development degree of coal spontaneous combustion (CSC), the CSC process was investigated using a programmed high-temperature-heating experimental system, and the variation law of index gas concentration in the holistic process of CSC and oxidation is formulated. Additionally, the accuracy of the experimental system was evaluated using experimental design for thermal analysis, and the correlation between gas index and apparent activation energy was determined using grey correlation analysis. The results indicated the following. In the critical temperature stage (0–100 °C), φ(CO)/φ(CO₂) should serve as the main index and C₂H₄ should serve as the auxiliary index; in the crack-active-speedup temperature stage (100–260 °C), CO and φ(C₂H₄)/φ(C₂H₆) should serve as the main index and R₁, the Graham index, and φ(C₂H₄)/φ(CH₄) should serve as auxiliary indexes; in the speedup-ignition temperature stage (260–370 °C), R₂ and the Graham index should serve as main indexes and φ(CO)/φ(CO₂), C₂H₄, and R₁ should serve as auxiliary indexes; in the ignition temperature (370–500 °C), R₃ should serve as the main index and R₂, the Graham index and C₂H₄ should serve as auxiliary indexes. Among them, the grey correlation degrees among the Graham index, Grignard fire coefficient, and apparent activation energy were the highest, reaching 0.91.     

Emergency venting into redundant pipelines

The evolution of pressure, temperature, and gas inventory during containment of blowdown from two high pressure gas networks into a third lower pressure relatively large redundant pipeline is followed through a simple lumped parameter model. Numerical solution of the non-linear model equations enabled to study the effects of relevant operating conditions on the system's dynamics. The effects of initial pressure difference between the supply and receiving networks, ratio of discharge orifice to pipe diameters in the supply networks, and heat transfer from the surroundings are investigated. A set of computer generated results are presented to demonstrate vividly the effect of the above variables on the percent of gas recovered in the lower pressure pipeline, the blowdown time, and the minimum temperatures reached in the networks.     

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.     

Explosion parameters of wood chip-derived syngas in air

The wood gasification process poses serious concerns about the risk of explosion. The design of prevention and mitigation measures requires the knowledge of safety parameters, such as the maximum explosion pressure, the maximum rate of pressure rise and the gas deflagration index, K_G, at standard ambient temperature (25 °C) and pressure (1 bar) conditions. However, the analysis at specific process conditions is strongly recommended, as the explosion behavior of gas mixtures may be completely different.In the work presented in this paper, the explosion behavior of mixtures with composition representative of wood chip-derived syngas (CO/H₂/CH₄/CO₂/N₂ mixtures with and without H₂O) was experimentally studied in a closed combustion chamber. Experiments were run at two temperatures, 300 °C and 10 °C, and at atmospheric pressure. Test conditions were requested by the safety engineering designer of an existing industrial-scale wood gasification plant. In order to identify the specific fuel–air ratios to be analyzed, thus reducing the number of experimental tests, a preliminary thermo-kinetic study was performed.Results have shown that the mixtures investigated can be classified as low-reactivity mixtures, the higher value of K_G found (∼36 bar m/s) being much lower than the K_G value of methane (55 bar m/s @ 25 °C).     

Release and dispersion behaviour of carbon dioxide released from a small-scale underground pipeline

The development of carbon capture and storage (CCS) brings challenges for safety issues regarding carbon dioxide (CO₂) transmission pipelines. Once a pipeline is punctured or full-bore ruptured, the leaked CO₂ is hazardous to personnel and the environment. Small-scale devices were established with the aim of studying the release and dispersion behaviour of gas and liquid CO₂ from a punctured underground pipeline. A sandbox was built to simulate the underground conditions. The parameters of the sand used in the experiments were tested. CO₂ concentrations on the ground and temperatures around the release orifice in the sand were analysed. The results indicate that in the CO₂ gas release experiments, the CO₂ concentration on the sand surface decreases with increasing horizontal distance in the form of a power function. CO₂ concentrations in upward release are slightly larger than those in horizontal release at the same location but are obviously bigger than values in downward release. The temperature-drop region is much smaller than that in air. A frozen ice ball can be generated near the release orifice during the gas phase of the CO₂-release process. In the liquid phase of CO₂-release experiments, a large amount of dry ice is generated near the release orifice. Dry ice can only be generated in the area close to the release orifice, especially in the near-field area.     

The influence of impurities on the transportation safety of an anthropogenic CO2 pipeline

Transportation safety is a key aspect of carbon capture and storage (CCS), which is a major technology used to reduce greenhouse gas emissions. Supercritical CO₂ pipelines have been certified as an optimised choice for CO₂ transportation. The results of this study show that the Peng–Robinson (PR) equation of state is recommended for analysis of the properties of supercritical CO₂. The influence of nonpolar and polar impurities on the two-phase region and the location of the sharp discontinuity in the density are found by analysing the ternary phase equilibrium and physical parameters using the PR equation of state. A transitional area between the supercritical phase and the dense phase, where the density changes abruptly, is defined as the quasi-critical region. This study describes the functional relation between the temperature and the pressure that defines the quasi-critical line by calculating the partial derivative equations and then determines the effect of impurities on the quasi-critical region of transported CO₂. Operational recommendations for pipeline transportation of flue CO₂ are developed using a pipeline operated by Sinopec as an example, demonstrating the influence of impurities in flue CO₂ on saturation pressure for control and prevention of fractures in CO₂ pipelines.     

Fracture criterion and control plan on CO2 pipelines: Theory analysis and full-bore rupture (FBR) experimental study

Pressurized pipelines are the most reliable and cost-effective option for the long-distance transportation of CO₂ from an emitter to an onshore storage site. Propagating or unstable factures are considered catastrophic pipeline failures, resulting in a massive escape of inventory within a short period of time. The decompression curve for CO₂ exhibits a large drop in decompression wave speed at the phase transition pressure, leading to a higher driving force for crack propagation. The study of fracture control plans is very important for assessing the possibility of fracture propagation and preventing unstable fracturing along CO₂ pipelines. Three full-bore rupture (FBR) experiments were performed using an industrial-scale (258 m long, 233 mm inner diameter) CO2 pipeline with initial CO2 states of gaseous, dense and supercritical phases, respectively. The relation between the decompression velocity and the pipeline fracture propagation velocity was analyzed during the process of buried CO2 pipeline release. A fracture propagation criterion was established for the buried CO₂ pipeline. For the gaseous CO₂ leakage, the pressure plateau corresponding to the decompression wave velocity only appeared near the closed end of the pipeline. For the dense CO₂ leakage, the pressure plateau corresponding to the decompression wave velocity was observed near the saturation pressure after rapid decompression. For the supercritical CO₂ leakage, the pressure plateau corresponding to the decompression wave velocity was observed in the stage when the supercritical CO₂ transformed into the two phases of gas and liquid. Compared with the gaseous and dense CO₂, for the supercritical CO_2, the initial decompression wave velocity was the smallest, and the requirement of the pipeline safety factor was the highest.     

Risk assessment methodology for high-pressure CO2 pipelines incorporating topography

This paper presents a risk assessment methodology for high-pressure CO₂ pipelines developed at the Health and Safety Laboratory as part of the EU FP7 project CO2Pipehaz.Traditionally, consequence modelling of dense gas releases from pipelines at major hazard impact levels is performed using integral models with limited or no consideration being given to weather bias or topographical features of the surrounding terrain. Whilst dispersion modelling of CO₂ releases from pipelines using three-dimensional CFD models may provide higher levels of confidence in the predicted behaviour of the cloud, the use of such models is resource-intensive and usually impracticable. An alternative is to use more computationally efficient shallow layer or Lagrangian dispersion models that are able to account for the effects of topography whilst generating results within a reasonably short time frame.In the present work, the proposed risk assessment methodology for CO₂ pipelines is demonstrated using a shallow-layer dispersion model to generate contours from a sequence of release points along the pipeline. The simulations use realistic terrain taken from UK topographical data. Individual and societal risk levels in the vicinity of the pipeline are calculated using the Health and Safety Laboratory's risk assessment tool QuickRisk.Currently, the source term for a CO₂ release is not well understood because of its complex thermodynamic properties and its tendency to form solid particles under specific pressure and temperature conditions. This is a key knowledge gap and any subsequent dispersion modelling, particularly when including topography, may be affected by the accuracy of the source term.     

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.     

Modelling three-phase releases of carbon dioxide from high-pressure pipelines

This paper describes the development and experimental validation of a three-phase flow model for predicting the transient outflow following the failure of pressurised CO₂ pipelines and vessels. The choked flow parameters at the rupture plane, spanning the dense-phase and saturated conditions to below the triple point, are modelled by maximisation of the mass flowrate with respect to pressure and solids mass fraction at the triple point. The pertinent solid/vapour/liquid phase equilibrium data are predicted using an extended Peng–Robinson equation of state.The proposed outflow model is successfully validated against experimental data obtained from high-pressure CO₂ releases performed as part of the FP7 CO2PipeHaz project (www.co2pipehaz.eu).The formation of solid phase CO₂ at the triple point is marked by a stabilisation in pressure as confirmed by both theory and experimental observation. For a fixed diameter hypothetical pipeline at 100 bar and 20 °C, the flow model is used to determine the impact of the pipeline length on the time taken to commence solid CO₂ discharge following its rupture.     

Inhibiting effects of gas–particle mixtures containing CO2, Mg(OH)2 particles,and NH4H2PO4 particles on methane explosion in a 20-L closed vessel

The main risk factors from methane explosion are the associated shock waves, flames, and harmful gases. Inert gases and inhibiting powders are commonly used to prevent and mitigate the damage caused by an explosion. In this study, three inhibitors (inert gas with 8.0 vol% CO₂, 0.25 g/L Mg(OH)₂ particles, and 0.25 g/L NH₄H₂PO₄ particles) were prepared. Their inhibiting effects on methane explosions with various concentrations of methane were tested in a nearly spherical 20-L explosion vessel. Both single-component inhibitors and gas–particle mixtures can substantially suppress methane explosions with varying degrees of success. However, various inhibitors exhibited distinct reaction mechanisms for methane gas, which indicated that their inhibiting effects for methane explosion varied. To alleviate amplitude, the ranking of single-component inhibitors for both explosion pressure (P_ex) and the rate of explosion pressure rise [(dP/dt)_ex] was as follows: CO₂, NH₄H₂PO₄ particles, and Mg(OH)₂ particles. In order of decreasing amplitude, the ranking of gas‒particle mixtures for both P_ex and (dP/dt)_ex was as follows: CO₂–NH₄H₂PO₄ mixture, CO₂‒Mg(OH)₂ mixture, and pure CO₂. Overall, the optimal suppression effect was observed in the system with the CO₂–NH₄H₂PO₄ mixture, which exhibited an eminent synergistic effect on methane explosions. The amplitudes of P_ex with methane concentrations of 7.0, 9.5, and 11.0 vol% decreased by 37.1%, 42.5%, and 98.6%, respectively, when using the CO₂–NH₄H₂PO₄ mixture. In addition, an antagonistic effect was observed with CO₂‒Mg(OH)₂ mixtures because MgO, which was generated by the thermal decomposition of Mg(OH)₂, can chemically react with water vapor and CO₂ to produce basic magnesium carbonate (xMgCO₃·yMg(OH)₂·zH₂O), thereby reducing the CO₂ concentration in a reaction system. This research revealed the inhibiting effects of gas‒particle mixtures (including CO₂, Mg(OH)₂ particles, and NH₄H₂PO₄ particles) on methane explosions and provided primary experimental data.     

Explosion regions of 1,3-dioxolane/nitrous oxide and 1,3-dioxolane/air with different inert gases - Experimental data and numerical modelling

In this study, experimental determination and modelling investigations for the explosion regions of 1,3-dioxolane/inert gas/N₂O and 1,3-dioxolane/inert gas/air mixtures were carried out and compared. The experimental measurements were carried out at 338 K and atmospheric pressure according to EN1839 method T using the inert gases N₂, CO₂, He and Ar. The results showed that the ratio of the lower explosion limit in N₂O (LEL_N2O) to the lower explosion limit in air (LEL_air) is 0.52 and the ratio of the maximum oxygen content in air (MOC_air) to the limiting oxidizer fraction in nitrous oxide (LOF_N2O) is 0.36 ± 0.02 independent of the inert gas. When comparing the inert gas amount at the apex based on the pure oxidizing component, which is O₂ in case of air, N₂O-containing mixtures need less inert gas to reach the limiting oxidizer quantity whereas the efficiency of inert gases is in the same order. The coefficients of nitrogen equivalency however were found to differ to some extent. The explosion regions of 1,3-dioxolane/inert gas/oxidizer mixtures were modelled using the calculated adiabatic flame temperature profile (CAFTP) method as well as corrected adiabatic flame temperatures. The results indicate good agreement with experimental data for CO₂, N₂ and Ar- containing mixtures. The noticeable deviations that occur when He is the inert gas are due to the lacking transport data of that mixture.     

Experimental study on explosion inhibition by heptafluoropropane and its synergy with inert gas

The inhibition effect of heptafluoropropane (CF₃CHFCF₃) on methane explosions under different inhibitor concentrations in a closed vessel was studied. A high-speed camera and a pressure sensor were adopted respectively to record flame propagation characteristics and pressure data. Results indicate that the relationship between flame propagation and pressure rising was correlated. As the equivalent ratio (ϕ)≤1, the pressure presented a trend of rising firstly and then decreasing with increasing CF₃CHFCF₃ concentration, and it was found that there existed a critical concentration for pressure decrease. As ϕ > 1, the pressure exhibited a decreasing trend. Although the pressure appeared to seemingly increase, the moment that the pressure began to rise (t_rise) and the moment that the maximum explosion overpressure appeared (t_Pmax) were obviously delayed. The average rate of pressure rise ((dP/dt)_ave) was decreased as the concentration of CF3CHFCF3 increased. It indicates that CF₃CHFCF₃ can effectively reduce the explosion reaction rate. The critical concentration of CF₃CHFCF₃ for complete inhibition was determined. Meanwhile, the synergy of CF₃CHFCF₃-inert gas can improve the inhibition effect. Compared with CF₃CHFCF₃–N₂, the synergy of CF₃CHFCF₃–CO₂ presented a better inhibition effect, and the inhibition effect was increased with increasing inert gas concentration. And the mechanisms of physical and chemical effects on explosion inhibition were analyzed.     

A risk assessment methodology for high pressure CO2 pipelines using integral consequence modelling

This paper presents a risk assessment methodology for high pressure CO₂ pipelines developed at the Health and Safety Laboratory (HSL) as part of the EU FP7 CO2Pipehaz project. Until recently, risk assessment of dense phase and supercritical CO₂ pipelines has been problematic because of the lack of suitable source term and integral consequence models that handle the complex behaviour of CO₂ appropriately. The risk assessment presented uses Phast, a commercially available source term and dispersion model that has been recently updated to handle the effects of solid CO₂. A test case pipeline was input to Phast and dispersion footprints to different levels of harm (dangerous toxic load and probit values) were obtained for a set of pipeline specific scenarios. HSL's risk assessment tool QuickRisk was then used to calculate the individual and societal risk surrounding the pipeline. Knowledge gaps that were encountered such as: harm criteria, failure rates and release scenarios were identified and are discussed.     

冷冻取芯过程煤样温度变化特性研究

为探究冷冻取芯过程煤样温度变化特性,基于模拟试验的相似性,自主设计冷冻取芯模拟测试试验装置,选取榆家梁矿、首山一矿、六龙煤矿、九里山矿4个矿区不同变质程度煤样,用以测定瓦斯吸附平衡压力为0、1.0、2.0、3.0 MPa下冷冻取芯过程煤样的温度实时变化数据,并统计分析各条件下的数据。研究结果表明:冷冻取芯技术的冷冻效果与煤变质程度及瓦斯吸附平衡压力呈正相关关系;冷冻取芯对含瓦斯煤冷冻效果优于不含瓦斯煤;冷冻取芯对高变质煤冷冻效果优于低变质煤;冷冻取芯过程中,煤样温度随时间变化曲线符合指数函数关系。     

Effect of CO2 corrosion behavior of mild steel in oilfield produced water

The corrosion rates of API X65 mild steel alloy in CO₂ – containing produced water have been studied by weight loss technique, potentiodynamic polarization technique and characterization of the corroded surface techniques. The effect of temperature, speed of rotation, pH and acetic acid concentration were studied. The optimum condition in presence and absence of protective film were also addressed. The kinetic parameters and reaction behavior were discussed in details. Corrosion rates increases with increasing temperature, acetic acid concentration, and speed of rotation, and decreased with increasing solution pH. The primary corrosion product of API X65 mild steel is ferrous carbonate (FeCO₃) at high temperatures, high pH's (alkaline media) and absence of acetic acid, which could act as a protective film so that CO₂ corrosion rate can be reduced.     

Law of variation for low density polyethylene dust explosion with different inert gases

To reveal the effects of different inert gases on explosion characteristics during low density polyethylene (LDPE) dust explosion and optimize the explosion-proof process, eight N₂ (CO₂)/air mixed inerting conditions were experimentally studied. Typical inerting conditions with 12 L cylindrical explosive tank were used to study the characteristics on the flame propagation. The thermogravimetric analysis with related theories were used to further explain the mechanism and quantities in low density polyethylene (LDPE) dust explosion with different inert gases. The results showed that the reduction of O₂ concentration could effectively delay the progress of flame growth process and weaken the effect of dust combustion reaction. The flame growth process of condition (N₂/air (18% O₂)) was 2.05 times slower than that of the non-inert condition. The explosion strength was obviously reduced, and the characteristic parameters such as explosion pressure and flame propagation speed were also affected by the decrease of O₂ concentration. For LDPE powder, the smaller the median diameter, the greater the explosion intensity and the lower the limiting oxygen content (LOC). The LOC with CO₂ was usually higher than that with N₂ and the effect of CO₂ was significantly better than N₂ in inerting.