Determining a realistic ranking of the most dangerous process equipment of the ammonia production process: A practical approach

OCI Nitrogen seeks to gain knowledge of (leading) indicators regarding the process safety performance of their ammonia production process. The current research determines the most dangerous process equipment by calculating their effects resulting from a loss of containment using DNV GL's Phast™ dispersion model. In this paper, flammable and toxic effects from a release from the main equipment of an ammonia plant have been calculated. Such an encompassing approach, which can be carried out for an entire plant, is innovative and has never been conducted before. By using this model, it has been demonstrated that the effects arising from an event of failure are the largest in process equipment containing pressurized synthesis gas and ‘warm’ liquid ammonia, meaning the ammonia buffer tanks, ammonia product pumps, and the ammonia separator. Most importantly, this document substantiates that it is possible to rank the most hazardous process equipment of the ammonia production process based on an adverse impact on humans using the calculated effect distance as a starting point for a chance of death of at least 95%. The results from the effect calculations can be used for risk mapping of an entire chemical plant or be employed and applied in a layer of protection analysis (LOPA) to establish risk mitigation measures.     

氯胺消毒管网“三氮”与总氯变化的预测模型

为探讨氯胺消毒供水管网的水质问题,建立了一种试验规模的氯胺消毒供水管网水质模拟系统。基于质量守恒原理和双Monod方程建立了该系统的硝化与氯胺衰减动力学耦合模型,并通过试验对该模型进行了验证。模型中的部分参数采用非线性多项式回归方法进行估计。应用该模型确定了活性氨氧化菌(AOB)和亚硝酸盐氧化菌(NOB)的数量。该模型对管网模拟系统内氨氮、硝酸盐氮与总氯的预测值与实测值基本一致,但对亚硝酸盐氮的预测值与实测值存在较大偏差。     

水力负荷对3种滤料生物挂膜和溶解无机氮去除效果的初步研究

以人工模拟海水养殖废水为处理对象,探讨了PE(聚乙烯)环、珊瑚石和PP(聚丙烯)方便面净水板3种生物滤料对氨氮的吸附性能,获得了动态吸附的穿透曲线。研究了3种滤料的生物挂膜情况以及挂膜成熟后在不同水力负荷下的净水效果。结果表明,珊瑚石滤料的挂膜成熟时间明显短于PE和PP材质的滤料,生物膜厚度与水流流速呈负相关。水力负荷对3种滤料生物滤器的净水效果有显著影响,当水力负荷为19～51 m3/(m2.h)时,生物滤器对TAN、TOC和NO2--N有较为理想的去除效果。     

一种新型泡沫凝胶成胶时间及灭火特性的实验研究

为研究新型无氨泡沫凝胶的胶凝特性和灭火特点,采用倾斜试管法分别测试了不同反应物浓度、温度、pH值和发泡剂浓度等参数对新型泡沫凝胶成胶时间的影响,同时通过灭火实验对泡沫凝胶的消防特性进行了研究。结果显示：当水玻璃与促凝剂的质量比在1．33—4．0时材料成胶时间满足煤矿灭火要求;pH值在6．9—8．5时成胶最快;成胶时间随温度升高而减小;发泡剂浓度对成胶时间影响不大;泡沫凝胶灭火效果良好且有效延长了复燃周期。因此泡沫凝胶在矿井消防中有很强的实用价值,并且可通过限制反应物浓度、pH值、温度等参数,更高效的控制成胶时间。     

青海湖氮素分布特征及其对藻类生长的影响

以青海湖水体的11个样点为研究对象,测定不同形态氮素(总氮、硝酸盐氮、亚硝酸盐氮、氨氮)质量浓度、藻类数量及叶绿素质量浓度,同时测定其他相关因子,并对氮素对藻类生长的影响进行分析。结果表明:青海湖水体中总氮、硝酸盐氮及氨氮质量浓度分别为0.80mg/L、0.28 mg/L和0.20mg/L,且湖心区(深水区)样点质量浓度大于岸边区(浅水区)样点,浅水区植物生长及沙柳河等外源输入均对氮素质量浓度有一定程度的影响;亚硝酸盐氮质量浓度为9.70μg.L-1,浅水区质量浓度高于深水区;浅水区氨氮的氧化作用可能是亚硝酸盐氮质量浓度在浅水区高于深水区的主要原因,同时溶解氧是此过程的限制因子;水体氮素与藻类数量为显著的负相关性,但与叶绿素质量浓度为显著正相关性。青海湖水体不同形态氮素分布具有不同特征,且氮素对藻类的生长和繁殖具有不同的影响。     

苯酚对硝化颗粒污泥性能的影响

采用序批实验研究了苯酚对硝化颗粒污泥性能的影响.结果表明.苯酚的存在显著地降低了氨氮降解率,抑制了硝化颗粒污泥中氨氧化菌的活性和亚硝酸氧化菌的活性,显著地降低了氨氮的比降解速率和硝氮的比生成速率,降低了硝化颗粒污泥的硝化性能.苯酚去除后,硝化颗粒污泥中氨氧化菌的活性可以完全恢复,而亚硝酸氧化菌的活性不能完全恢复.苯酚的降解是硝化颗粒污泥中的好氧异养菌、硝化菌和厌氧的反硝化菌共同作用的结果.     

CFD simulations of ammonia dispersion using “dynamic” boundary conditions

Ammonia is stored in liquid form at ambient temperature and under high pressure. During an accident, ammonia will flash out of the vessel and disperse in the surrounding area. This paper provides a comparison of the results obtained by the FLADIS field experiments and those of CFD modeling by Fluent 6.3. FLADIS experiments were carried out by the Risø National Laboratory using pressure liquefied ammonia. Time series of meteorological conditions as wind speed, wind direction and source strength were determined from the experimentally measured data and used as the inflow boundary conditions. Furthermore, for more realistic simulation of air flow in the computation domain for the desired atmospheric stability, periodic boundary conditions were used on both side boundaries. The initial two-phase flow of the released ammonia was also included. The liquid phase was modeled as droplets using discrete particle modeling, i.e., the Euler–Lagrangian approach for continuous and discrete phases.     

鸡粪除臭菌的筛选、培养条件优化及其应用

为了筛选出具有高效除臭能力的菌株,采用驯化富集、平板划线的方法从鸡粪中筛选除臭微生物,采用初筛、复筛相结合的方法检测所筛选微生物的除臭效果。初筛采用嗅阈值法,复筛以氨气和硫化氢的去除率为检测指标,最终获得除臭效果最好的菌株CCJZ022。经过形态学观察、生理生化鉴定和16S rRNA基因序列分析,确定菌株CCJZ022为红平红球菌(Rhodococcus erythropolis)。对其初始pH值、培养温度及接种量进行优化,发现该菌株在初始pH值为7.0、培养温度为30℃、接种量为12%时除臭效果最好,对氨气和硫化氢的去除率分别可达66.73%和54.51%。利用该菌株进行鸡粪除臭的小试也取得了很好的效果,表明该菌株可以应用于鸡粪除臭。     

曝气量及亚硝酸盐浓度对SBBR单级自养脱氮系统性能的影响

为了提高单级自养脱氮工艺的脱氮性能及稳定性,采用SBBR反应器,通过连续试验及间歇试验研究了曝气量对单级自养脱氮系统脱氮效率及脱氮负荷的影响,分析了反应器内不同曝气条件下氨氮降解特征、亚硝酸盐质量浓度与氨氮降解速率的关系,并探讨了污泥的亚硝酸盐氧化活性与SBBR反应器稳定性的关系。连续试验结果表明,曝气量从48 L/h提高到88 L/h,总氮平均去除率由72.46%增长至93.00%,总氮平均去除负荷由0.29 kg N/(m3·d)提高至0.57kg N/(m3·d)。间歇试验结果表明:氨氮降解速率随曝气量增加而提高,出水氨氮及总氮质量浓度随曝气量增加而降低;同时曝气期DO质量浓度随曝气量增加而有所升高;在整个SBBR周期内未出现亚硝酸盐积累的现象,亚硝酸氮质量浓度一直较低(低于2.00mg/L),向反应器中添加亚硝酸盐可以促进氨氮的降解;随曝气量增加,由于污泥的亚硝酸盐氧化活性较低,硝化作用产生的硝酸盐并未大幅增长,系统表现出了较好的稳定性;氨氮未完全降解时,反应器内DO质量浓度曲线缓慢下降或基本保持不变,当氨氮完全被去除时,系统不再耗氧,DO质量浓度迅速升高,曲线出现拐点,DO拐点对单级自养脱氮控制有重要参考价值。     

不同液气比条件下氨法脱碳工艺影响因素试验研究

基于氨法脱碳工艺,对不同液气比下各工艺参数对CO_2脱除率的影响开展了试验研究。结果表明,氨水浓度和烟气停留时间的提升能够有效提高CO_2的脱除率,而反应温度、CO_2体积分数及CO_2负载量的提高不利于CO_2的脱除。通过调整液气比可以缓解各工艺参数对CO_2脱除率的影响,维持系统稳定。综合对比试验结果,认为液气比合适的应用范围为6~8 L/m3。     

红外气体分析仪比对防护试验检测方法的探究

本文通过比对检测方法,即化学法检测氨气防护试验的浓度和仪器法进行比对试验,得出两种方法准确度为2.77%,一致性良好,并且红外气体分析仪自动化程度高,测定简便、迅速,适用于防护试验。     

Process hazards review applied to the use of anhydrous ammonia in agriculture: an example of chemical process safety for small business

Process hazards review (PHR) techniques have generally been applied by large, sophisticated companies in the nuclear, aerospace, and chemical process industries. There remains, however, a large population of smaller distributors and consumers of hazardous materials which could benefit equally from the application of PHR. These consumers unfortunately are generally less sophisticated and individually lack the necessary resources required to apply such state-of-the-art safety techniques.

Where common processes can be identified, it is possible to conduct a more generic PHR that will provide a sound technical basis for recognizing and preventing the development of hazards wherever these processes are used. Some facility-specific issues will always need to be considered, but the existence of the generic PHR should make the conduct of a PHR by each facility considerably easier and less costly.

Researchers from the National Institute for Occupational Safety and Health (NIOSH) contracted with DNV Technica Inc. to lead a hazard and operability study (HAZOP) of agricultural handling of anhydrous ammonia, from the receipt of ammonia at the retail distribution centre to the application of the ammonia by farmers to the fields. The multidisciplinary HAZOP team consisted of representatives from NIOSH, an agricultural chemical trade association, an ammonia producer, state ammonia facility inspectors, a retail distributor, and an equipment manufacturer. Several participants were part-time farmers with ammonia application experience.

Some specific aspects of applying the HAZOP technique in the context of this study, the findings obtained, and the plans to disseminate the important safety information developed during the course of the PHR are discussed. Finally, it is suggested that this approach could prove to be a useful addition to the product stewardship activities of chemical producers.     

污水地下渗滤系统基质床特性模拟

为提高污水地下渗滤系统(Subsurface Waste-water Infiltration System,SWIS)的生物脱氮效率,改进了基质床体结构组成,采用土柱模拟试验对比了基质床改进前后ORP特征及氨化、硝化及反硝化细菌数量的变化。结果表明,在地下渗滤系统中,氨氮的去除率(Q)随基质层深度的变化规律为Q(100 cm)Q(80 cm)Q(20 cm)≈Q(40 cm)Q(60 cm)。改进后基质铺设顺序依次为:0~60 cm填充炉渣和草甸棕壤(两者体积比为3∶7),60~130 cm铺设活性污泥、炉渣和草甸棕壤(三者体积比为1∶2∶7)。基质床结构组成改进后,20~60 cm区域氧化电位(ORP)大幅提高,尤其60 cm深度处ORP从0提高到180 m V,有效促进了硝化反应的进行;床体氨化、硝化及反硝化细菌数量大幅度提高,对NH+4-N及TN的脱除效率分别较改进前提高了12.6%和10.5%,出水NH+4-N及TN质量浓度满足城市景观地表水水质标准(GB/T 18921—2002)。     

A modified steady-state model for evaluation of ammonia concentrations behind a water curtain

Water curtain system has been proved an effective mitigation measurement for ammonia spill dispersion. Calculating of ammonia cloud concentration with water curtain was less studied. This paper presents a steady-state calculation model to calculate open and forced ammonia spill dispersion. The formula of ammonia absorption was built and integrated into the calculation model. The calculated downwind ammonia concentrations for open and forced spill dispersion were reproduced and compared with literature using a statistical method. In addition, the relationship between ammonia concentration in water droplet and the droplet diameter was studied. The results display that the formula of ammonia absorption is suitable for calculating mass transfer process between the ammonia cloud and the water curtain. The calculation model presents good performances for open and forced ammonia spill dispersion. This study indicates that the calculation model can be satisfactory in determining the impact of open and forced ammonia spill dispersion and the design of water curtain mitigation system.     

耦合式SCR还原剂供给调节装置及控制技术的研究与应用

阐述了SCR喷氨调节控制常用的方法及存在的问题,提出了一种新型耦合式SCR还原剂供给调节装置及控制技术,并通过电厂实际案例对该调节装置与控制技术进行了说明。研究结果表明:该调节装置及控制技术可使脱硝效率相对稳定、出口NO_x的浓度不超标、喷氨不过量。     

Ammonia large scale atmospheric dispersion experiments in industrial configurations

A programme of large-scale experiments for atmospheric dispersion was carried out by INERIS over a period extending from December 1996 to April 1997. The objectives of the test campaign were to measure anhydrous ammonia concentrations in a range of few meters to 2 km from the release, in order to generate data to be used to improve 2-phase discharge and dispersion modelling.

The discharges were released from a 6-tonne storage tank of pressurised liquid ammonia and through a discharge device with an outlet diameter of 2 in. Fifteen trials were carried out with various release configurations corresponding to industrial situations (impinging jets on the ground and on a wall at various distances, release through a flange without seal…). The quantity of ammonia discharged from the liquid phase varied according to the tests, from 1.4 to 3.5 tons for durations between 7 and 14 min and, therefore, at flow rates between 2 and 4.5 kg/s. Approximately 200 sensors were settled downwind to measure ammonia concentrations and temperature in the plume. These tests showed that for discharges with identical flow rates the distances corresponding to the same concentration vary a lot according to the configurations. These distances tend to be reduced by the presence of obstacles or retention dikes that collected liquid ammonia. In the paper, the main experimental results are presented. In order to enable the comparisons with numerical predictions, more detailed information are given in [Bouet R. (1999). Ammoniac—Essais de dispersion atmosphérique à grande échelle. INERIS rapport, ref INERIS-DRA-RBo-1999-20410 (available at http://www.ineris.fr/recherches/recherches.htm).     

氨制冷系统压力管道安装及实验的要点

近年来,液氨管道事故的不断发生,引起了人们对氨制冷管道系统工程的高度重视.首先介绍了氨的性质,然后介绍了氨制冷管道安装及实验应该注意的一些要点,希望能对氨制冷工程的管道安装质量起到一些作用.     

液氨储罐事故性泄漏扩散过程模拟分析

液氨是化工企业常用的原料，而每年因为液氨储罐的泄漏造成的事故也十分频繁，液氨属于高度危险性物质，一旦泄漏极可能造成灾难性后果。本文探讨了描述液氨储罐事故性泄漏及扩散过程的数学模型，并用所建模型针对某市化学园区某化工公司液氨储罐工程建设项目进行模拟分析。从模拟结果来看，采用数学模型的方法对事故后果进行预测和分析具有一定程度的可靠性，对于救灾、重大危险源编制应急事故预案以及对新建项目进行危险性预评价都具有一定程度的指导意义。     

基于动力学与混合核函数LS-SVM的厌氧发酵产气量预测模型研究

利用农业生产中产生的牲畜粪便牛粪和秸秆进行厌氧发酵试验,以产气量为参考指标,研究牛粪和秸秆厌氧发酵的产气量预测模型。试验过程中测量发酵物的氧化还原电位(ORP)、p H值、挥发性脂肪酸(VFA)、氨氮含量、化学需氧量(COD)、电导率及产气量,并用灰色关联分析法筛选出与产气量关联较强的参数,将筛选出的参数作为多项式核函数和高斯径向基核函数构建的混合核函数LS-SVM模型的输入量,训练出预测能力较强的混合核函数LS-SVM模型,然后在混合核函数LS-SVM模型中融入微生物动力学构建产气量预测模型,并用验证集验证模型性能。仿真结果表明,筛选得到关联较强的参数为ORP、p H值、VFA、氨氮含量;融入动力学的混合核函数LS-SVM模型与混合核函数LS-SVM模型相比,产气量的预测更准确,误差更小,最小误差减少了近一个数量级,试验证明该模型有效。