石化企业危险化工工艺风险等级评估指标分解

伴随石化企业的迅猛发展,危险品越来越多,生产条件越来越苛刻,同时带来的是更为重大的风险隐患以及安全事故,因此对危险工艺的风险评估就显得尤为重要.考虑到目前还没有什么好的方法来判别某种工艺就一定是危险化工工艺,因此本文在国家安监总局划分的15种危险化工工艺的基础上,根据危险化工工艺表征涉及的影响因素,结合化工工艺的实际情况,选择具有典型代表意义的重要性评价指标作为研究对象,建立了由67个具体指标形成的动态指标体系,并运用指标分类分解方法对各个指标进行量化,最后采用模糊数学综合评价对危险化工工艺进行了软件化评估,从而为政府和企业加强安全管理提供了便利,进一步实现石化企业的本质安全化.     

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。     

Wet bench reactive hazards of cleaning stages in semiconductor manufacturing processes

According to the research from FM Global (Factory Mutual Insurance Company), most of the incidents that have occurred in semiconductor plants in the past two decades were reported as “Fire Cases”. They claim that the fires in wet chemical cleaning processes were mainly caused by heater failure. However, depending on the process conditions, electrical heaters are designed to turn off automatically when the temperature reaches a set point. Therefore, a thorough study of the situations related to possible fires in wet chemical cleaning processes is necessary.

This study focused on the incompatible behaviors of cleaning materials used in the wet bench stage. These results can be applied to determine the causes of fires in the wet bench stage from using reactive chemicals for cleaning purposes.

Another purpose of this study was to investigate the potential hazards of widely used chemicals (hydrogen peroxide, concentrated sulfuric acid, hydrochloric acid and isopropyl alcohol) within similar processes in semiconductor plants. Experimental data were also verified in order to establish a concentration triangular diagram, which could be used to identify a combustion, deflagration or even detonation zone. Finally, this study can provide basic design data for an inherently safer process to avoid potential hazards caused by dangerous mixtures, which may result in large property loss in semiconductor plants.     

探究土壤中萘提取液的浓缩方法比较

随着科学技术的发展,工业产品越来越丰富。工业工艺过程、缺氧燃烧、垃圾焚烧和填埋等生产活动,产生了大量的多环芳烃物质。这些物质通过复杂的物理迁移、化学及生物转化反应,进入土壤,严重污染环境,给人类及其生物的安全带来严重危害。如何快速、准确检测土壤中多环芳烃的含量,成为治理污染等相应策略实施的首要条件。当前测定土壤中多环芳烃的前处理方法有加压流体萃取、索式萃取、超声波萃取、微波萃取等。在这些成熟萃取手段中,浓缩又是一个关键步骤。目前浓缩的手段有KD浓缩、氮吹浓缩、旋转蒸发浓缩、旋转与氮吹合用浓缩。本文对四种浓缩手段对多环芳烃中的萘提取液进行浓缩分析比较,并获得了一定结论,望给行业内提供有效的参考意见。     

Occupational Exposure to Harmful Chemical Substances While Processing Phenol-Formaldehyde Resins

Air pollutants emitted while processing phenol-formaldehyde resins have been investigated. Gas chromatography-mass-selective detection was used to separate and identify chemical compounds. It was determined that workers were exposed to formaldehyde in all workplaces. Besides, phenol, acetaldehyde, acrylaldehyde, 2-furaldehyde, xylene, ethylbenzene, toluene, tetrachlorethene, ethyl acetate, butyl acetate were found during the production of frictional materials; and 2-furaldehyde, phenol, naphthalene, 2-furan-methanol, polycyclic aromatic hydrocarbons (PAHs) during the production of abrasive materials. Quantitative analyses were performed with gas chromatogra-phy and high performance liquid chromatography. Assessment of occupational exposure indicated that chemical compounds emitted during the investigated processes might be dangerous for human health, mainly because of suspected carcinogenic compounds: formaldehyde and PAHs.     

A little knowledge is a dangerous thing – Unexpected reaction case studies make the case for technical discipline

The old saying, “what you don't know can't hurt you,” implies that ignorance is bliss. “A little knowledge is a dangerous thing,” may be closer to the truth; however, it is not the little that we know that is dangerous, but that which is not known. By design, the processes used in the chemical industry are reactive, and the intended reaction receives much scrutiny. However, other reactions occur, often unexpectedly, and possibly with severe consequences. The lessons we learn from these reactions must drive the improvement of our process development and technology management processes and the culture that shapes those processes, a culture of Technical Discipline.Technical Discipline, analogous to Operating Discipline in the manufacturing organization, is a culture committed to fully identifying and characterizing chemical and reaction hazards, and properly documenting and communicating those hazards to create a permanent knowledge and understanding within the organization operating that process.A culture of Technical Discipline will reveal reaction hazards that might otherwise remain unknown until being unveiled in a dramatic and unexpected fashion. Until you fully identify and characterize the hazards of the materials you handle in your processes…what you don't know can hurt you.     

生物反应器中投加含硅聚铁混凝剂的协同作用研究

比较了将含硅聚铁混凝剂分别投加到反应器和出水中两种工艺对COD和磷的去除效果.结果表明: 混凝剂投加量在40 mg/L以下时,前者出水中的磷低于后者,此时将混凝剂投加到反应器中具有生物协同作用,30 mg/L时协同作用最明显; 当混凝剂的投加量增加到50 mg/L时两种工艺出水中的磷没有明显差别,不再具有生物协同作用; 混凝剂投加量为10～50 mg/L时,两种工艺的出水COD差别不大,没有协同作用.将混凝剂直接投加到反应器中可省去混凝、沉淀所需的设备及构筑物,从而节约投资.因此为提高对TP和COD的去除效果,可直接将混凝剂投加到生物反应器中.     

Computer-aided assessment of occupationally healthier processes during research and development stage

Each year more people die from occupational related diseases than are killed in industrial accidents. Therefore it is critical to start considering health aspect early when developing a new chemical process. In this paper, a computer-aided tool for assessing inherent occupational health is proposed for chemical process research and development stage. The method was developed based on the reaction chemistry data, which is the only data available at this stage. Three types of approaches were formulated to calculate the route index value using additive type, average type and worst case type calculations. The tool can be used to rank the alternative chemical synthesis routes by their health properties as well as characterize the hazard level of single process. Finally the tool was applied to six process routes for methyl methacrylate production for demonstration. The case study revealed hazards of the processes from different perspectives, e.g. the results from the additive-type calculation were mainly affected by the total number of steps in the route, which indicates the impact of process complexity on the level of hazard. The introduction of such tool provides a swift yet reliable means that will encourage health criteria to be considered earlier in process development besides economic, safety and environment.     

Cause analysis of the fire and explosion during crude oil desulfurization in China

A serious fire and explosion accident that resulted in massive crude oil leakage and severe environmental pollution occurred on 16 July, 2010, in Dalian Port, China. To investigate the root cause of accident and conduct a wide-range investigation, desulfurizing agent JH02, which has a similar ingredient to the desulfurizing agent HD used in Dalian Port, and TS02 were employed in this study to determine the role of desulfurizing agents in the accident. The thermal behavior of crude oil, desulfurizing agents, and their mixtures was measured by using a C80 calorimeter. By using the calorimetric data, the kinetic parameters of the chemical reaction, such as activation energy, pre-exponential factor, and self-accelerating decomposition temperature of crude oil, as well as JH02, TS02, and their mixtures, were calculated and compared. The results indicated that the direct cause of the accident was the thermal runaway initiated by the increasing instability of the crude oil–desulfurizing agent mixture. Excess pressure in the oil pipeline triggered the physical explosion, but it alone was not enough to cause a serious damage. Furthermore, a stable desulfurizing agent such as TS02 could not ensure a safe desulfurizing process. The results of this study would benefit the safety management of desulfurizing processes during production and storage.     

二恶英的毒性及环境来源

介绍了二恶英的结构、理化性质、毒性和环境来源.二恶英是由2个或1个氧原子联接2个被氯取代的苯环组成的三环芳香族亲脂性固体有机化合物,非常稳定,难以自然降解,是目前发现的无意识合成的副产品中毒性最强的化合物,已经成为当今环境界和国际媒体关注的热点.其来源可分为工业来源和非工业来源,工业来源包括有机氯化学品的生产与纸浆氯气漂白过程、固体废物焚烧、热电以及金属生产等,非工业来源包括汽油,家庭固体燃料(木材和煤)以及木制品和家庭废物等的不完全燃烧、光化学反应和生化反应等.     

Study of Major Accidents Involving Chemical Reactive Substances: Analysis and Lessons Learned

The objective of this paper is to present the results of the analysis performed on a selection of accidents included in the MARS database. This is a database of past accidents that occurred in Europe maintained by the European Commission, in order to help the Member States to meet the requirements of the Seveso and Seveso II directives. The study is focused on those accidents that involve reactions between chemical substances, whether wanted or unwanted, that generated a hazardous situation by loss of control of such reactions. Runaway reactions are known to be especially dangerous, given that many times they are unexpected, or their possible consequences underestimated, so sometimes chemical industries are not ready to cope with the effects of loss of control of reactive processes. The aim of the analysis is to obtain lessons learned from past accidents in order to prevent similar situations in the future, or to reduce their consequences. Understanding the causes of past accidents, including equipment failures, deviations in the expected course of a reaction, or deficiencies in process operations performed, can help to a better understanding of similar processes. Industries working with potentially dangerous chemicals should consider introducing lessons learned into their safety management systems.     

一种新型危险化工工艺安全评估方法的设计

在安全生产过程中,建设项目风险评价在我国经过几十年的发展,无论在模型亦是方法上均有所进步,但对化工项目进行危险化工工艺风险等级评价的研究并不多见。本文按照危险化工工艺表征涉及的影响因素,在参考了日本劳动省"六阶段"的定量评价表以及危险度评价法并对15种危险化工工艺定性分析的基础上,提出了一种基于危险度评价法的更为全面的危险化工工艺辨识方法。该评价方法可用于确定危险化工工艺的风险等级。为化工企业工艺危险的实时评估和安全管理提供技术支撑和科学途径。     

内源性稀土元素对土壤中氮素分布特征的影响

在离子型稀土开采过程中,由于部分防渗层渗漏、收集系统不完善等原因,有大量的氮化合物进入矿区周边土壤及地下水中,给当地居民生活环境带来了严重威胁。应用土柱实验,研究内源性稀土元素对矿区土壤氮化物吸附与解吸作用的影响。     

Numerical analysis on the hot spot in reactive chemical storage

In an exothermic reactive chemical storage tank, a thermal explosion can occur when the heat generation within the storage tank is greater than the heat removal from the storage tank. In a solid system, the existence of an inflection point in the temperature versus time curve is often used as a criterion for thermal explosion. In this study the applicability of this criterion to fluid storage is examined by investigating the hot spot in the system. Transient natural convection of an exothermically reactive fluid in a vertical, cylindrical storage tank with isothermal walls is investigated numerically. The axisymmetric 2-D Navier–Stokes equations governing the flow fields are reduced by introducing the stream function–vorticity formulation and solved by the alternating-direction-implicit (ADI) technique. The reactive heat sources are represented by a zeroth-order rate expression with an Arrhenius-type rate constant. It is found that the hot spot is no longer located in the center of the tank due to the buoyancy effect. In a particular range of Rayleigh number and Frank-Kamenetskii number, the hot spot is found to move periodically. A stable steady regime, stable oscillatory regime and thermal explosion regime can be specified based on the dependence of the critical Frank-Kamenetskii number on the Rayleigh number. In the stable oscillatory regime multiple inflections in temperature versus time are found. Therefore, the existing criterion, which defines thermal explosion by the appearance of an inflection in the temperature versus time curve, is no longer applicable in reactive fluid systems. The results of nonconvective systems do, however, provide a preliminary and conservative estimate for thermal explosion of a reactive storage tank.     

基于多Agent的危险化学品安全生产信息采集系统设计

安全生产监管是政府的重要职责,直接关系到国家财产和人民生命安全.安全生产监管中,以危险化学品的监管为重中之重.提高安全生产监管的信息化程度是降低监管强度、提高监管效率行之有效的方法.构建了由管理Agent、采集Agent、故障诊断Agent、通信Agent组成的分布式信息采集多Agent系统,将安监局监管中心对危险化学品生产过程监管的信息采集任务下移到企业端,利用多Agent系统实现危险源生产状态参数的采集、监控及分析;设计了该信息采集系统各类Agent的结构和功能.利用多Agent系统实现分散于各企业的危险源生产状态参数的信息采集、监控及分析,预测和诊断生产过程中的异常状况.通过Agent之间的合作、并行求解使危险化学品安全生产信息采集的问题得到较好地解决.     

氧化锆生产废水处理工艺

以调节沉淀-汽提处理技术作为氧化锆生产废水的处理工艺,对主要构筑物做出工艺设计,运行结果表明该工艺具有出水水质稳定、处理效率高、流程简洁、操作简便等特点.是处理含高浓度氨氮、可生化性差的工业废水的一种适用技术.     

低温制高纯氮生产过程危险性分析及安全对策

针对低温冷冻制取高纯度(≥99.999%)氮气和液氮的生产工艺及装置,对其生产过程中存在或潜在的危险、有害因素进行辨识和分类,并作出危险和有害程度评价;明确物料泄漏、设备缺陷、人为因素等事故致因,特别对氮窒息事故进行案例剖析。同时,应用目的树分析方法,从工艺技术和安全管理角度,提出消除或减少生产性危险及职业性危害的安全对策和措施。结果表明:在低温制高纯氮生产过程中,采取技术上和管理上的安全对策与措施,能有效预防火灾、爆炸、氮中毒等事故发生,避免低温冻伤等职业危害,从而防患于未然。     

A new intelligent assistant system for HAZOP analysis of complex process plant

There are several problems that should be solved in the practical application of HAZOP analysis, such as the inheritance instrument of experience knowledge, the classification of accident reasons, the recurrence of analysis process and the verification of analysis results. This paper presents a new HAZOP assistant program named HELPHAZOP, which can be used to cope with these problems. With the aid of this program, a number of influence relationship models, which can be utilized to present the relationship structure of the whole system, can be established, and a variety of spread paths, which can be employed to describe the occurrence of the accidents, can be identified. These models and paths can help analyzers to understand the analysis process of different chemical processes and to verify the analysis results. Experience knowledge or information of process parameters stored in this program, including deviations, abnormal reasons, consequences and disaster-causing ways, can contribute to the analysis of some new plants. The program has been applied in the HAZOP analysis process of residuum hydrotreating process. The probability of the human errors which would be happened because of the misunderstanding or the deficiency of plant experience in the HAZOP analysis has been reduced and the accuracy, practicability and analysis efficiency of the accident forecast have been greatly improved.     

芳烃类化合物结构表征及-lgK_(ow)定量预测

为探寻芳烃类有机物结构与正辛醇/水分配系数(-lgK_(ow))的关系,应用分子顶点及顶点相互作用矢量对芳烃类有机物进行了结构表征.采用多元线性回归及逐步回归建立了3个定量结构-性质关系的-lgK_(ow)模型.经过比较,发现模型M3具有最佳模拟结果,此时模型的复相关系数为0.946,标准偏差为0.392.为检验模型的稳定性,采用留一法(leave-one-out)对模型进行了交互检验,复相关系数为0.920,标准偏差为0.429.