Fugitive emissions in chemical processes: The assessment and prevention based on inherent and add-on approaches

Fugitive emissions are among the major concerns of industrial process releases. The emissions cause problem to various aspects including the environment, health, and economic. Early evaluation of process hazards is beneficial because process can be made inherently benign at lower cost. This paper discusses two important aspects of fugitive emissions assessment during process design – the quantification and the prevention strategies.For the quantification part, three methods are presented for fugitive emissions estimation during the process design. They are tailored to data available in simple process flow diagram (PFD), detailed PFD, and piping & instrumentation diagram (PID). Such methods are needed as early emissions estimation allows production routes and process designs with lower emissions to be selected. The fugitive emissions estimation and methods to abatement are demonstrated on a benzene process case study. Valves are found to be the major emission source with 50% of fugitive emissions of process area in a base case of petrochemical process, in which no fugitive emission reductions are yet made. Pumps without mechanical seals come second with 30% and flanges with 8% of emissions. Inherently safer design keywords can be applied to prevent fugitive emissions in the process plants. Substitution is the most applicable keyword in fugitive emission reduction of existing plants.The emission rate calculations together with estimation of health risk give a sound background for the decision making on elimination of emissions at source through equipment and piping changes. The case study presented reveals that by substituting emission prone components by inherently low-leaking ones, the plant emissions can be reduced over 90% in practice. This is created mainly by replacing rising stem valves with ball valves, installing double mechanical pump seals or hermetic pumps and making changes in sampling and relief systems. Ideally by also changing flanges to welded connections, which is not viable for various reasons, the emissions could be reduced nearly to zero.     

Occupational chemical exposure and risk estimation in process development and design

Each year more people die from diseases caused by work than are killed in industrial accidents. Therefore, methods are needed to evaluate occupational health hazards as early as possible when the process is still under development. A method for estimating inhalative exposures and risks in petrochemical and related plants is presented. The method is simple and suffices with the limited data availability during the early design stages.The steps of the method, which utilizes preliminary process flow diagrams are as follows: first the fugitive emissions and process plot areas are estimated based on precalculated process modules representing the typical process sections (such as a distillation unit). Chemical concentration in the air is then calculated based on the wind velocity probability and the estimated process cross-sectional area. For this purpose a typical wind velocity distribution in the area is used. The worker risk of exposure to chemicals is evaluated either based on the concentration in air by using the hazard quotient method or calculating the carcinogenic chemicals intake and the resulting risk of cancer. The values are compared to the benchmarks.As a result the process route health characteristics such as fugitive emissions rate, critical wind speed, chemical concentration in air and intake amount as well as the corresponding risk of exposure are produced. By using statistical meteorological data, health risks of occupational exposure can be estimated more realistically as probabilities. The approach is capable of comparing alternative processes to select the concept which is inherently occupationally healthier. Using this method, the exposure problems of a process can be identified earlier and proper decisions can be made early in process development or predesign stage.The concentration-based method is demonstrated by a case study of six competing manufacturing routes for methyl methacrylate (MMA). The C3 is found to be the most harmful alternative to health. Both concentration-based and intake-based methods are applied. The study indicates that the intake-based risk estimation benchmark is stricter than the exposure limit-based benchmark for carcinogens.     

Inherent occupational health assessment during preliminary design stage

Chemical process routes can already be assessed as early as in the development and design phases. Process screening should not look at economic and technical aspects only, but also the safety, health, and environmental performances. In this paper, a method called the Health Quotient Index (HQI) is presented for the preliminary process design phase. The HQI provides a simple approach to quantify workers' health risk from exposure to fugitive emissions e.g. in petrochemical plants. The method utilizes process data from flow sheet diagram, which is already available at the preliminary design stage. Since the mechanical details of the process are still unknown, a database of the precalculated fugitive emissions for typical operations in chemical plants was created to simplify the assessment. The HQI can be used to rank alternative process concepts or to quantify the risk level of processes. As a case study, six process routes for producing methyl methacrylate are discussed. Three health indexes are compared in the case study. The HQI is able to highlight the difference of hazard levels between the routes better as a result of more detailed assessment of the exposures.     

大型碳化硅生产园区面源源强及减排指标核算

以某年产25万吨大型碳化硅园区无组织排放面源为例,提出基于多个地面站气象数据的CALPUFF模型地面浓度反推方法,优化流场模拟,使得无组织面源源强核算结果更加准确,并以环境保护目标空气质量达标为原则,核算其大气污染物减排指标,得出具体结论:园区大气污染物SO2、NOX、CO、PM10年排放量分别为449.06t、86.98t、5158.58t、115.06t;无组织排放SO2、CO及PM10的减排比例分别为63.5%、19.2%、42.44%,对应减排量分别为285.16 t/a、990.45 t/a、48.83 t/a。     

污水生化处理过程中N2O的产生特征研究进展

N2O是大气中重要的温室气体之一,而污水生化处理已被报道是导致N2O产生的潜在人为源之一。大量研究表明,污水生化处理过程中N2O主要产生于微生物的硝化和反硝化代谢过程中。从微生物学和生物化学反应角度,阐述了硝化和反硝化过程中N2O的生成机理,同时给出了几种典型污水处理工艺N2O的产生量和相关影响因素,并对A/A/O工艺中不同处理单元N2O的释放情况进行重点论述。研究发现,对于几种典型的污水处理工艺,由于工艺条件和主要影响因素的不同,N2O的释放量存在较大的差异;对于同一污水处理工艺,不同处理单元N2O的释放量也存在很大差别。污水处理厂中,好氧处理单元是N2O的主要排放单元,而在好氧单元中,DO质量浓度及NO2--N质量浓度是影响N2O释放量的主要因素。在综合分析硝化和反硝化过程N2O产生机理的基础上,进一步总结了污水生化处理过程中DO质量浓度、NO3-和NO2-质量浓度、pH值、C/N比、污泥龄等对N2O释放的影响。     

松针燃烧排放物的热重桥/质谱在线监测方法

森林火灾排放物主要包含气体、挥发性有机化合物(VOCs)、和半挥发性有机化合物(SVOCs),这些物质会严重威胁消防队员和居民的健康。森林火灾烟气是一种包含固体颗粒、液体和气体化合物的复杂混合物。在火前锋附近(靠近消防队员)或者离火前锋很远(但靠近居民)的地方,当苯、甲苯、烯烃等有机化合物的浓度超过各健康安全组织规定的极限值,就可能对健康产生影响。本文给出了一种使用室内热重桥一质谱联用对炉内松针燃烧实验进行火前锋排放物在线监测的新方法。该燃烧实验被认为含氧量较低,这是真实森林火灾中通常的情形。使用这种方法测量得到的苯和甲苯的最大浓度分别是1050和2050ppm。CO2的最大浓度超过10．000ppm。     

Inherent occupational health assessment during basic engineering stage

Each year more people die from work-related diseases than are killed in industrial accidents. Therefore it is essential to evaluate occupational health aspect during the process design. Early evaluation of safety, health, and environmental (SHE) performance is advantageous, since the opportunities to make the process inherently benign are greater and the cost therefore lower. The methods for occupational health assessments need to be tailored to specific design stages, since the data availability is changing as the design proceeds. In this paper, an index-based method called the Occupational Health Index (OHI) is presented for the basic engineering stage. The OHI is the final of the three methods in series proposed for health assessment in development and design stages. The OHI is based on the information available in piping and instrumentation diagrams (PIDs) and the plot plan. Four health aspects are considered; chronic inhalation risks to noncarcinogens and carcinogens, acute inhalation risk, and dermal/eye risk. The index is demonstrated on separation system of a toluene hydrodealkylation process. The assessment results allow the level of occupational health risks to be evaluated, the sources of exposures be detected, and corrective actions taken in a focused way.     

Strategies for assessing and reducing inherent occupational health hazard and risk based on process information

Over the last few decades, the concept of inherent occupational health has gained increasing attention to reduce occupational hazards that may adversely impact workers’ health. In order to assess occupational hazards in the chemical process, different inherent occupational health assessment methods have been developed at the early stages of process development and design. The methods in the order of process information availability – ranging from the detailed piping and instrumentation diagrams to a simple sketch of process concepts are the: occupational health index (OHI), health quotient index (HQI) and inherent occupational health index (IOHI). This paper proposes systematic heuristic frameworks to assist process designers and engineers in assessing and reducing inherent occupational health hazards or risks based on process information availability. Strategies for reducing health hazards or risks in the OHI, HQI and IOHI methods based on inherently safer design (ISD) keywords of minimization, substitution, moderation and simplification are included in this study. It is worth mentioning that the proposed frameworks act as guidelines for design engineers in systematically selecting the appropriate index and methodology to assess and reduce health hazards/risks based on the availability of the process information. A case study is solved to illustrate the proposed framework.     

Design as a contributor to chemical process accidents

The paper discusses the design errors in chemical process industry (CPI) by analyzing major equipment related accident cases from Failure Knowledge Database (FKD). The aim is to recognize the contribution of design to chemical process accidents and to evaluate the time of occurrence of the errors in a plant design project. The analysis of accident cases found out that the contribution of design to accidents is very significant: 79% of accident cases analyzed were contributed by design errors. The most critical design errors were poor layout (17%), insufficient consideration of chemical reactivity and incompatibility (16%) and incorrectly chosen process conditions (16%). The design errors were initiated at basic (32%), detailed (32%) and preliminary (22%) design phases of the project. Errors in fundamental aspects of chemical processes e.g. route selections are more severe (as compared to others errors class) and might creates many similar errors in later phases of design project. Based on the accident information gathered, a straightforward point-to-look list for error detection and elimination was suggested for process lifecycle stages.     

Inherent safety concept based proactive risk reduction strategies: A review

The growing scale and complexity of process industries have brought safety, health, and environmental issues to the forefront. As a result, proactive risk reduction strategies (RRSs) are commonly employed to address these issues by reducing the frequency or mitigating the consequences of potential incidents. Among these strategies, inherent safety, which is a proactive measure of loss prevention and risk management, is considered to be the most effective method. This review aims to provide a comprehensive analysis of RRSs for achieving inherency, as well as techniques for evaluating the performance of inherent safety, health, and environmental aspects. Background information is presented, including the development and implementation of the inherently safer process design, as well as the approaches for achieving inherently healthier and environmentally friendlier processes. Subsequently, the execution approaches and practical applications of other RRSs are discussed to highlight the distinctiveness and benefits of inherent safety. Next, this study examined the characteristics of inherency assessment tools (IATs) based on available information at different process stages. Furthermore, the evaluation methods and historical development of IATs are investigated from the perspectives of safety, occupational health, and environmental considerations, followed by a statistical analysis of IATs. It is concluded that the no-chemical hazards-based IATs have not been extensively studied yet, which may improve the safety level of process plants from the perspective of comprehensive inherency risk reduction. As a way forward, future research opportunities are proposed to promote the implementation of greater optimized risk management.     

Health risk assessment of emissions from a coal-fired power plant using AERMOD modelling

Current electricity generation mix in Malaysia consists of 58% gas, 33% coal and 9% hydro. It is anticipated that by year 2019, the generation mix will be at 64% coal, 32% gas and 4% hydro. Due to the increase in coal consumption for power generation, there is a critical need to evaluate the health risks for the population living in the vicinity of a coal-fired power plant in Malaysia. To date, such study related to the plant in Malaysia has never been published. In this study, health risk assessment (HRA) for air emission from a coal-fired power plant in Malaysia was carried out. Two pollutants from the Proposed New Environmental Quality (Clean Air) Regulation 201X (Draft) (i.e. SO₂ and Hg) were assessed for non-carcinogenic health risk, and two trace elements (i.e. As and Cr) were assessed for carcinogenic health risk. Both short-term and long-term health effects were evaluated. Air dispersion modelling (AERMOD) was used to predict the ground level concentration (GLC) within 10 km radius of the emission source. Based on the HRA, different health risks were identified for short-term and long-term dispersion of the studied pollutants. The findings indicate that a detailed assessment on the short-term and long-term health effects of the emissions from coal-fired power plant in Malaysia with meteorological factor as one of the significant factors influencing the emissions level is needed.     

Model-based hazard identification in multiphase chemical reactors

Chemical productions operated in extreme conditions (high pressure, high temperature) require a detailed analysis of all potentially dangerous situations that can lead to a major industrial accident and thus cause a loss of life and property. Many accidents in the near or distant history underline the need of a detailed safety analysis in process industries, not only in the phase of plant design but also during the operation of the plant. It would be shown that simulation of a chemical unit using an appropriate mathematical model and the nonlinear analysis theory can be a suitable tool for safety analysis. This approach is based on mathematical modeling of a process unit where both the steady-state analysis, including the analysis of the steady states multiplicity and stability, and the dynamic simulation are used. Principal objective of this paper is to summarize problems regarding the model-based hazard identification in processes. A case study, focused on phenomena of multiple steady states in ammonia synthesis reactor will be presented. The influence of the model complexity and model parameters uncertainly on the quality of safety analysis would be underline.     

Method for identifying contributors to chemical process accidents

The paper presents a new method for identifying contributors to chemical process accidents by exploiting knowledge on causes of past accident cases. Accident reports from the Failure Knowledge Database were analyzed and utilized for hazard identification. The accident information gathered was used as a basis to develop an accidents ranking and points-to-look-for approach for the safe design and operation of chemical process equipment. In the method, accident contributors including technical, design and operation errors of major process equipment types and piping are identified. The method is applicable throughout the process lifecycle, even for process changes in the early design stages. The Bhopal tragedy is used as a case study to demonstrate and test the method. The proposed method can predict on average up to 85% of accident causes and design and operation errors.     

苯和甲苯硝化及磺化反应热危险性分级研究

首先介绍了化工工艺热安全性的内涵,并从反应过程热危险性分析的方法学出发,介绍间隙、半间歇化学反应工艺热危险性分级研究的总体思路及方法。然后,围绕甲苯和苯的硝化、磺化反应,用全自动反应量热仪(RC1e)和加速度量热仪(ARC)测定其反应过程的绝热温升(△Tad)、目标反应所能达到的最高温度(TM)、分解反应最大速率到达时间(θD)等参数。运用风险评价指数矩阵法(方法1)和基于失控过程温度参数的热危险评估法(方法2)分别对其硝化和磺化反应过程的热危险性进行了分级评估。结果表明,这两种方法具有良好的一致性;给定工艺条件下甲苯和苯的一段硝化反应过程的热危险度等级较低;而磺化反应的热危险较高。尽管这两种方法还有一定的局限性,但对于间歇、半间歇合成工艺的本质安全化设计、工艺热危险性的评估具有重要的参考价值和实用意义。     

Assessment of chemical process hazards in early design stages

A new method called SREST-layer-assessment method with automated software tool is presented that in a hierarchical approach reveals the degree of non-ideality of chemical processes with regard to SHE (safety, health and environment) aspects at different layers: the properties of the chemical substances involved (substance assessment layer (SAL)), possible interactions between the substances (reactivity assessment layer (RAL)), possible hazard scenarios resulting from the combination of substances and operating conditions in the various equipments involved (equipment assessment layer (EAL)), and the safety technologies that are required to run a process safely and in accordance with legal regulations (safety-technology assessment layer (STAL)). In RAL, EAL and STAL the main focus is put on process safety. A case study is used to show the principles of the method. It is demonstrated how the method can be used as a systematic tool to support chemical engineers and chemists in evaluating chemical process safety in early process development stages.     

Process analysis of an industrial waste-to-energy plant: Theory and experiments

Thermal conversion is fundamental in an integrated waste management system due to the capability of reducing mass and volume of waste and recovering energy content from unrecyclable materials. Indeed, power generation from industrial solid wastes (ISW) is a topic of great interest for its appeal in the field of renewable energy production as well as for an increasing public concern related to its emissions. This paper is based on the process engineering and optimization analysis, commissioned to the University Campus-Biomedico of Rome by the MIDA Tecnologie Ambientali S.r.l. enterprise, ended up in the construction of an ISW thermo-conversion plant in Crotone (Southern Italy), where it is nowadays operating. The scientific approach to the process analysis is founded on a novel cascade numerical simulation of each plant section and it has been used initially in the process design step and after to simulate the performances of the industrial plant. In this paper, the plant process scheme is described together with the values of main operating parameters monitored during the experimental test runs. The thermodynamic and kinetic basics of the mathematical model for the simulation of the energy recovery and flue gas treatment sections are presented. Moreover, the simulation results, together with the implemented parameters, are given and compared to the experimental data for 10 specific plant test runs. It was found that the model is capable to predict the process performances in the energy production as well as in the gas treatment sections with high accuracy by knowing a set of measurable input variables. In the paper fundamental plant variables have been considered such as steam temperature, steam flow rate, power generated as well as temperature, flow rate and composition of the resulting flue gas; therefore, the mathematical model can be simply implemented as a reliable and efficient tool for management optimization of this kind of plants.     

Inherent safety tool for explosion consequences study

The lack of formal integration between process design stages with risk and consequence estimation is a hurdle to designing inherently safe process plants. Conventional risk assessment methodologies are often not carried out concurrently with process design. Therefore, process designers lack the information about risk levels and consequence that may result from the process conditions being considered in a particular process route until the design is completed. Hence, effects of changes in process conditions on risk levels and consequence cannot be studied in a time effective manner during the design stages. Few studies have been identified on the possibility and viability of integrating risk estimation with process design. But viable framework and methodology for doing so has not yet been reported. This paper presents a feasible framework in which risk and consequences estimation can be part of design stages. A demonstrative tool named as integrated risk estimation tool (iRET) was developed by using process simulation software, HYSYS and spreadsheet, MS Excel as the platforms. iRET estimates risk due to explosions by using TNT equivalence method and the TNO correlation method. iRET has a potential to be extended to include all forms of risk such as fire, explosion, toxic gas releases and boiling liquid expanding vapour explosion (BLEVE). The paper also presents case studies to demonstrate the functionality and viability of using iRET in conjunction with process design. The results of these case studies have successfully shown that the risk due to explosion can be assessed during the initial design stage ensuring a safer plant. The framework and iRET there by presented here provide systematic methodology and technology to design inherently safer plants.     

Simple graphical method for inherent occupational health assessment

The concept of inherently safer design was introduced to design a fundamentally safer process so that hazards can be avoided or minimized rather than controlled or managed. The ideology has later been extended to the environmental, but not health criteria due to its complicated underlying principles. Even though health risk methods are already established, majority are for existing plants assessment. Early consideration of health aspect starting from process design stage however, has received much less attention. This paper introduces a simple graphical method to evaluate the inherent occupational health hazards of chemical processes during the R&D stage. A survey was conducted to identify the important health parameters for the graphical method development, involving nine world inherent safety and health experts. Based on their input, process mode, material volatility, operating pressure and chemical health hazard (toxicity and adverse effect) are the significant factors affecting inherent health hazards of chemical processes. The choice of parameters was bounded by the information availability at this stage. The method was applied on six routes to methyl methacrylate and ten routes to acetic acid. The parameters were plotted for each subprocess of the alternative routes. The ‘healthiest’ route was selected based on thorough hazards assessment across all the subprocesses. The first case study reveals the tertiary butyl alcohol as the ‘healthiest’ one as it poses relatively lower, or at least comparable hazards to the other routes due to exposure and health impacts. Meanwhile the acetic acid case study indicates ethanol oxide and ethyl oxide based routes as the inherently healthier as they operate at lower operating pressure besides posing comparable hazards level for the other three parameters, compared to the other routes. The case studies show that the inherent occupational health of a chemical process can already be evaluated easily in the R&D stage with the simple graphical method proposed.     

Monitoring of pathogenic microorganisms contamination during heat drying process of sewage sludge

The sewage sludge from wastewater treatment plant is a potential source of infectious organism. The number and type of pathogens in sludge depends on various factors namely, the wastewater source, the type of treatment plant, and other environmental factors such as the biological medium offered by the sewage sludge. The principal sludge-borne diseases are presented followed by discussion on biological aspect of growth and occurrence. The overall objective of this work is to estimate kinetic reduction of pathogen population in sludge during different thermal-drying process including: the agitated conductive drying, drum drying, solar drying, and fry-drying. The temperature curves were reported from literature except frying data which were determined in experiment. In order to apply the temperature influence on pathogens population, kinetic parameters for the thermal inactivation (D, z-values) were chosen from literature. Values of concentrations of each pathogen were also extracted from scientific review of pathogens in bio-solids. This study conducted to resolve the survival kinetic of Hepatitis A viruses. The result showed that a concentration of 7 × 10⁴ cfu/100 ml initially present in the sewage sludge is significantly reduced during the heat drying processes except the solar plant. The sewage sludge is completely disinfected when heated for 20 min, 10 min, and 10 s, respectively, during the agitated conductive process, vacuum fry-drying, and drum drying process.     

钢铁行业碳排放量核算方法的实证性研究

介绍了碳排放量核算的基本原理与通用方法。以某钢铁公司焦化厂CO2排放量计算为实例,对比分析了物料衡算法和经验计算法的合理性和准确性。研究发现,对于钢铁企业来说,采用IPCC方法进行CO2排放量的计算是可行的。