Safer management of process changes in chemical reactors

Nowadays many chemical industries are SMEs where multi-purpose batch or semi-batch reactors are commonly used. Vent sizing for realistic runaway scenario is not an easy task for such enterprises since they have usually few resources and use multi-purpose reactors with fast process turnovers. As a consequence these batch and semi-batch reactors are usually equipped with emergency relief systems sized once forever when the reactor is designed. This can lead to a large underestimation of the vent area in case of runaway reactions occurring when processes different from the ones considered for originally sizing the vent are carried out.The approach proposed in this work aims to identify the maximum reactor load leading to safe conditions even in case of runaway phenomena to be handled with the emergency relief system already installed (or even with a smaller vent area). This approach allows avoiding the change of the emergency relief system with a larger vent area (as required every time a new more hazardous process has to be carried out on existing reactors) at the price of lower plant productivity.     

Database-supported documentation and verification of pressure relief device design in chemical plants

In this paper the results of a multi-year analysis of the pressure relief devices located in several plants in major chemical sites are summarized. The analysis consisted of a systematic evaluation of existing safety valves and rupture discs including the identification of the service conditions and design cases as well as the sizing calculations of the individual device and associated piping. Furthermore, from the total amount and the hazardous potential of the effluents the necessity of retention systems is evaluated to ensure a safe disposal.Because the knowledge in the field of emergency pressure relief changed very rapidly in recent years, the design of some safety devices was not according to the state of the art. An essential part of the verification program was the recommendation of measures to find the most economical yet technically correct way to correct these deficiencies. Rather than by carrying out wholesale replacement of an incorrectly sized safety device or vent line, often a reduction of the mass flow rate to be discharged, for example, by an orifice in a supply line, is sufficient.Results of the analysis were recorded on a novel database to capture the sizing information and maintain correct pressure relief device sizing into the future. The systematic databased approach has been used for the evaluation of about 4000 safety devices so far. The procedure has been proven to enable an experienced design engineer to carry out the analysis of a great number of pressure relief devices in a time-saving, reliable and reviewable way.     

Study of chemical supply system of high-tech process using inherently safer design strategies in Taiwan

The photoelectric, semiconductor and other high-tech industries are Taiwan's most important economic activities. High-tech plant incidents are caused by hazardous energy, even when that energy is confined to the inside of the process machine. During daily maintenance procedures, overhauling or troubleshooting, engineers entering the interior of the machines are in direct contact with the source of the energy or hazardous substances, which can cause serious injury. The best method for preventing such incidents is to use inherently safer design strategies (ISDs); this approach can fully eliminate the dangers from the sources of hazardous energy at a facility.This study first conducts a lithography process hazard analysis and compiles a statistical analysis of the causes of the fires and losses at high-tech plants in Taiwan since 1996, the aim being to establish the necessary improvement measures by using the Fire Dynamics Simulation (FDS) to solve relevant problems. The researchers also investigate the lithography process machine in order to explore carriage improvement measures, and analyse the fires' causes and reactive materials hazardous properties, from 1996 to 2012. The effective improvement measures are established based on the accident statistics. The study site is a 300 mm wafer fabrication plant located in Hsinchu Science Park, Taiwan.After the completion of the annual maintenance jobs improvement from September 2011 to December 2012, the number of lithography process accidents was reduced from 6 to 1. The accident rate was significantly reduced and there were no staff time losses for a continuous 6882 h. It is confirmed that the plant safety level has been effectively enhanced. The researchers offer safety design recommendations regarding transport process appliances, chemical storage tanks, fume cupboard devices, chemical rooms, pumping equipment, transportation pipelines, valve manual box (VMB) process machines and liquid waste discharge lines. These recommendations can be applied in these industries to enhance the safety level of high-tech plants, facilities or process systems.     

Conceptual design of pressure relief systems

Conceptual design of pressure relief systems is an important stage in the design of a safe process plant. The conceptual design stage consists of the following steps: deciding on the location of pressure relief devices, selecting the general type of pressure relief device for each identified location, i.e. safety valve and/or bursting disc (rupture disc), or other relief device, and selecting the special features for the chosen device type. Some regulations, codes and standards, and a decision tree for the selection of a relief device have been described in the literature. This paper presents four decision trees that have been developed for the different steps in the conceptual design stage. Only positive pressure in pressure vessels is considered here.     

Numerical study of choked two-phase flow of hydrocarbons fluids through orifices

Valves and orifices are the most widely devices of flow control used in oil and gas industry. In particular, they are installed in relief piping system in order to control the discharge flow during potential plant overpressuring scenarios, thus ensuring plant safety. It is a common practice to flow liquid and gas mixtures through such restriction devices.Rigorous models are available to precisely size pressure relief devices operating in single phase flow; however for two-phase flow, no models are considered sufficiently reliable for predicting the relevant flow conditions.In the present paper, two-phase flow of hydrocarbons fluids through an orifice under critical conditions has been numerically investigated.The existing literature has been analyzed and data on two-phase flow of highly volatile mixtures of hydrocarbons through openings have been collected. A comparison has been carried out with numerical simulations carried out by the multiphase flow simulation tool OLGA by SPT.The Henry–Fauske model has been used as orifice choke model and the orifice discharge flow coefficient, required as input by OLGA, has been calculated by Chisholm's model.Comparison between OLGA's results and experimental data shows that Henry–Fauske model markedly underestimates the mass flow rate through the orifice, if Chisholm's model is used to calculate discharge coefficient. It was found that the error of the model could be minimized using different values of orifice discharge coefficient (C_d).A new discharge flow coefficient model, suitable for choked two-phase flow across orifices, is proposed in this study and it has been determined to match the above mentioned experimental measurements.     

A new approach to determine relieving temperature and thermodynamic behavior of trapped single and multi-phase fluid exposed to fire

Process safety plays a key role in modern industries. This is more significant specifically in off-shore oil and gas platforms where releasing hydrocarbons could cause irreversible damages to both environment and personnel. An important instrument device which can provide safety for process equipment in oil and gas fields is safety relief valve. Correct sizing procedure of such devices depends strongly on physical properties of fluid and relieving condition. The present study revolved around applying thermodynamic concepts and modeling to throw some light on the behavior of trapped fluid exposed to fire in order to evaluate precise temperature and fluid properties at relieving condition. Peng–Robinson equation of state together with a three phase flash has been utilized to handle the calculation. Effect of different design parameters has been evaluated for three distinct categories of fluids namely natural gas, gas-condensate mixture, and gas-oil mixtures. These parameters encompass of operating temperature, operating pressure, Difference of Operating and Design Pressure, gas and oil specific gravities, gas-oil ratio, and water cut. The study depicted that American Petroleum Institute practice number 521 which suggests an ideal gas assumption fails to provide reliable predictions as it significantly overestimate the relieving temperature. Moreover, black oil correlations were also used for the relief temperature estimation of gas-oil-water mixtures. Comparison with HYSYS results as a prominent engineering software proved that black oil models are reliable tools to predict relief temperature.     

安全阀失效模糊综合评价方法的研究

针对安全阀在实际使用过程中的失效涉及诸多因素影响的特点,运用模糊综合评价的数学模型,将安全阀失效的相关影响因素作为因素集,把可能产生故障的元件作为评价集,按照权重的大小对安全阀的故障进行综合评价,以提高维修人员对安全阀故障的判断能力和综合检修能力,达到设备稳定运行的目的。     

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.     

Safety valve sizing according to EN ISO 4126-4 and industrial practice in case of highly viscous liquid duty

The calculation of the minimum relief area on the basis of the iterative procedure, as reported in EN ISO 4126-4 and by adopting an explicit method as carried out in the industrial practice, leads to the same valve size. This applies to valves with a high and low value of the related lift, respectively, with a valve nozzle orifice according to API RP 526. However, under extraordinary conditions it may be possible that the discharge areas differ due to the graduation of the valve sizes within a suppliers' production program. Indeed, neither method gives systematically larger relief areas than the other, the procedures are equivalent.     

Methodology for global sensitivity analysis of consequence models

A methodology is presented for global sensitivity analysis of consequence models used in process safety applications. It involves running a consequence model around a hundred times and using the results to construct a statistical emulator, which is essentially a sophisticated curve fit to the data. The emulator is then used to undertake the sensitivity analysis and identify which input parameters (e.g. operating temperature and pressure, wind speed) have a significant effect on the chosen output (e.g. vapour cloud size). Performing the sensitivity analysis using the emulator rather than the consequence model itself leads to significant savings in computing time.To demonstrate the methodology, a global sensitivity analysis is performed on the Phast consequence model for discharge and dispersion. The scenarios studied consist of above-ground, horizontal, steady-state discharges of dense-phase carbon dioxide (CO₂), with orifices ranging in diameter from ½ to 2 inch and the liquid CO₂ stagnation conditions maintained at between 100 and 150 bar. These scenarios are relevant in scale to leaks from large diameter above-ground pipes or vessels.Seven model input parameters are varied: the vessel temperature and pressure, orifice size, wind speed, humidity, ground surface roughness and height of the release. The input parameters that have a dominant effect on the dispersion distance of the CO₂ cloud are identified, both in terms of their direct effect on the dispersion distance and their indirect effect, through interactions with other varying input parameters.The analysis, including the Phast simulations, runs on a standard office laptop computer in less than 30 min. Tests are performed to confirm that a hundred Phast runs are sufficient to produce an emulator with an acceptable degree of accuracy. Increasing the number of Phast runs is shown to have no effect on the conclusions of the sensitivity analysis.The study demonstrates that Bayesian analysis of model sensitivity can be conducted rapidly and easily on consequence models such as Phast. There is the potential for this to become a routine part of consequence modelling.     

危化品罐车自封堵式安全截断阀设计与分析

为解决危化品罐车的储罐阀门管线等关键部件易损坏造成危化品泄漏的问题,基于系统本质安全原理设计1种内置自封堵式安全截断阀并对其关键部件强度进行校核计算,建立实现阀芯阀座有效密封的三维实体模型并完成有限元分析。结果表明:在阀座密封面与球形阀芯接触处出现最大应力,阀座承受的最大应力小于材料的最大屈服应力,内置自封堵式安全截断阀具有较高的可靠性,可为危化品储运相关安全装置设计提供理论参考。     

Effects of ignition energy on fire and explosion characteristics of dilute hybrid fuel in ventilation air methane

Deflagration explosions of coal dust clouds and flammable gases are a major safety concern in coal mining industry. Accidental fire and explosion caused by coal dust cloud can impose substantial losses and damages to people and properties in underground coal mines. Hybrid mixtures of methane and coal dust have the potential to reduce the minimum activation energy of a combustion reaction. In this study the Minimum Explosion Concentration (MEC), Over Pressure Rise (OPR), deflagration index for gas and dust hybrid mixtures (K_st) and explosive region of hybrid fuel mixtures present in Ventilation Air Methane (VAM) were investigated. Experiments were carried out according to the ASTM E1226-12 guideline utilising a 20 L spherical shape apparatus specifically designed for this purpose.Resultsobtained from this study have shown that the presence of methane significantly affects explosion characteristics of coal dust clouds. Dilute concentrations of methane, 0.75–1.25%, resulted in coal dust clouds OPR increasing from 0.3 bar to 2.2 bar and boosting the K_st value from 10 bar m s⁻¹ to 25 bar m s⁻¹. The explosion characteristics were also affected by the ignitors’ energy; for instance, for a coal dust cloud concentration of 50 g m⁻³ the OPR recorded was 0.09 bar when a 1 kJ chemical ignitor was used, while, 0.75 bar (OPR) was recorded when a 10 kJ chemical ignitor was used.For the first time, new explosion regions were identified for diluted methane-coal dust cloud mixtures when using 1, 5 and 10 kJ ignitors. Finally, the Le-Chatelier mixing rule was modified to predict the lower explosion limit of methane-coal dust cloud hybrid mixtures considering the energy of the ignitors.     

An economic evaluation framework for membrane reactor modules in the presence of uncertainty: The case for process safety investment and risk reduction

A comprehensive Net Present Value (NPV) model has been developed to demonstrate the economic advantages of process safety and risk reduction investments on Pd/Au-based membrane reactors. In particular, the economic viability of Pd/Au-based membrane reactor modules incorporated into Integrated Gasification Combined Cycle (IGCC) plants is evaluated within the aforementioned framework by pro-actively following sound process safety design principles. Sources of irreducible uncertainty (market, technological, operational) as well as safety risk are explicitly recognized, such as the Pd/Au prices, membrane life-time and loss in the power plant capacity factor due to possible accidents. The effect of the above uncertainty drivers on the membrane module cost along with production disruption and associated revenue losses is elucidated using Monte-Carlo simulation techniques that enable the propagation of the above uncertain inputs through the NPV-model, and therefore, generate a more realistic distribution of the process system's value rather than a single-point/estimate that overlooks these uncertainties. Pre-investment on risk reducing measures, such as spare safety relief systems (cautionary redundancy) for membrane reactor modules operating at high pressures (e.g. 50 atm), is shown to be economically more attractive than cases where analogous safety measures are not implemented. Since accidents and possibly catastrophic events do happen in an uncertain world, additional investment on safety measures could ensure a safer and more profitable operation of the process system under consideration giving credence to the thesis that process safety investments may result in enhanced techno-economic performance in the presence of irreducible uncertainties.     

Are micro reactors inherently safe? An investigation of gas phase explosion propagation limits on ethene mixtures

A method for the determination of safety properties for micro reactors and micro structured components is presented. Micro structured reactors are not inherently safe but the range of safe operating conditions of micro reactors are extended since the explosion region is reduced. The λ/3 rule was demonstrated to be applicable to micro scale tubes for stoichiometric mixtures of ethane–oxygen and ethane–nitrous oxide. Furthermore first results from an investigation concerning detonation propagation through a micro reactor of non-ideal geometry are shown. Initial pressure investigated is ranging from low pressure up to 100 kPa.     

Benchmarking of two-phase flow through safety relief valves and pipes

This paper compares calculated results for two-phase flows through safety relief valves and pipes using the TPHEM, CCFLOW and RRERSP computer programs. These studies were conducted to locate errors in the programs as well as to further our understanding of how each program worked. For most low-to-moderate viscosity flow examples, and for the frozen flow examples, the program results agreed despite differences in the calculation methods. Current thinking is that the TPHEM computer program gets better results for high viscosity flows through safety relief valves (nozzles) and for pipe down flows. This is because this program successively iterates nozzle flows to achieve results consistent with the choke pressure, temperature and quality and successively iterates pipe flows to achieve results consistent with the pipe length. Safety relief valve flows from the RRERSP computer program are reduced by the inlet pipe non-recoverable pressure loss. This effect is significant for several cases.     

API Standard 521 new alternative method to evaluate fire relief for pressure relief device sizing and depressuring system design

Since the 1950's, API Standards have provided guidance on determining relief loads for equipment exposed to pool fires. The API method is empirical based on tests performed in the 1940's. There is increasingly widespread interest in analytical methods based on heat transfer principles to model fire heat input. The API committee agreed to include an analytical method in the 6th edition of API Standard 521 to establish relief loads for pressure relief devices and to design depressuring systems for the fire scenario. The analytical method provides more flexibility than the empirical method but has limitations (e.g., too many permutations are possible leading to potential under-sizing of the pressure relief device).This paper discusses the basis for the empirical method in API Standard 521 and provides comparisons of the empirical and analytical method with two more recent large-scale pool fire tests. This pool fire test data indicates that the empirical method will provide a conservative estimate of pool fire heat input for most applications and is still the method of choice when designing pressure relief systems. However, these recent tests indicate the empirical method needs to be modified when a vessel or equipment is partially confined by adjacent embankments or walls equal or greater than the vessel height. In such cases, the wetted area exponent should be 1.0 instead of 0.82.The analytical method is useful in determining time-versus-temperature profiles for heating unwetted vessels of varying wall thicknesses and materials of construction. These profiles, which depend upon the type of fire (e.g., unconfined pool fire, jet fire, etc.), can be combined with tensile strength and stress-rupture data to specify a depressuring system's pressure-versus-time profile. This will minimize failure and/or mitigate the effects of failure due to overheating from fire exposure.     

关于呼吸器用气瓶阀国家标准的探讨

呼吸器是一种自给式的呼吸保护器具,被广泛运用到消防、化工、船舶、石油、矿山等行业,其主要分为空气呼吸器、氧气呼吸器、氮氧混合呼吸器和潜水呼吸器。一直以来,作为特种设备的呼吸器用气瓶阀并没有相关的国家标准,而GB 15382-2011《气瓶阀通用技术条件》并不包括呼吸器用气瓶阀,因此有必要制定相关的国家标准来对其进行规范。目前,《空气呼吸器用气瓶阀技术条件》国家标准已经出台征求意见稿,本文针对意见稿的相关内容,对阀门进出气口连接型式、过滤装置、限流要求、泄压装置及爆破压力等方面提出相关意见和建议。     

The dynamic response of pressure relief valves in vapor or gas service. Part II: Experimental investigation

An experimental testing program designed to evaluate the opening stability characteristics of direct acting pressure relief valves (PRV) in gas/vapor service is described. Three different valve sizes from each of three different manufacturers were tested at two different set pressures to determine their opening characteristics (disk lift vs. time). The valves were tested with several different lengths of inlet piping as well as with and without discharge piping to determine the conditions under which unstable operation (chatter) would occur. Part I of this program described a mathematical model for predicting the dynamic response of PRV's, and the data described in this test program were used to evaluate the accuracy of the model, as described in Part III of this study to follow.