过氧丙酸分解反应的失控泄放特性研究

为研究过氧丙酸分解反应的失控泄放特性,利用泄放模式实验装置对过氧丙酸在不同泄放口径和泄放压力下的顶部和底部的泄放过程进行了试验模拟,得到了过氧丙酸的失控特性参数和不同条件下的泄放特征。结果表明:过氧丙酸失控反应泄放易出现二次峰值现象,初次峰值为气相泄放,二次峰值为气液两相泄放;二次峰值的出现取决于泄放口径及泄放时的物料温度,与泄放压力无关;恒压泄放容易出现非平衡泄放,导致较高最大累积压力和较高的釜内物料温度;底部泄放能够使釜内物料快速排空。     

沸石在环境保护中的新应用

本综述了沸石在控制环境中亚硝胺污染,净化处理废水以及沸石在农业生产和其他环境保护领域中应用的新进展。沸石是香烟添加剂的首选材料,能使侧流烟气中的亚硝胺减少一半,主流烟气中减少约70％,减轻吸烟和被动吸烟的污染危害。沸石的净化作用源于其对亚硝胺特殊的催化和吸附作用。香烟燃烧所产生的亚硝胺如果在高温下接触沸石,将被催化裂解;如果亚硝胺在较低温度下接触沸石,也会被沸石吸附而不再污染环境。沸石的特殊吸附功能使之成为缓释肥料的重要组成部分。沸石和高分子材料组装、分散之后,能制成调控植物根苗附近小环境水含量的功能性复合材料。     

Reduction of Bed Agglomeration in CFB Combustion Biomass with Aluminium-Contain Bed Material

Two kinds of bed materials were used as bed materials when a biomass of cotton stalk was burnt in a circulation fluidized bed (CFB) combustion pilot plant (0.2 MW). After a long time operation, silica bed materials were found sintered while aluminous bed materials slightly changed. The particles of both kinds of bed materials were sampled and three instrumental approaches were performed (XRF, SEM/EDS, XRD) to identify the bed materials in order to find out the mechanics of agglomeration.The result shows that both of the bed materials were enriched with alkali metals but the changing speed of enrichment of aluminous particles was much slower than that of silica particles. The CFB could go steadily and well at least 72 h under our experimental condition when aluminous particles were used as bed material. Agglomeration of aluminous bed materials was reduced due to the protective element aluminous.     

Numerical simulation of flue gas desulfurization characteristics in CFB with bypass ducts

A new process of flue gas desulfurization in circulating fluidized bed with flue gas bypass ducts is presented. k–? Model, Discrete Phase Model and Finite-Rate Chemistry Model are proposed to simulate the desulfurization process characteristics in circulating fluidized bed reactor. The proposed model is validated by the comparison of experimental data and simulation results. The results show that the desulfurization reactor with bypass ducts is superior to the reactor without bypass ducts. The reactor with bypass ducts has higher desulfurization efficiencies and lower flow resistances than the reactor without bypass ducts, and it is more suitable for flue gas flow variation. Desulfurization reaction rate is controlled by absorption reaction on sorbent particles surface. When water content and Ca/S ratio increase, desulfurization efficiency of the reactor with bypass ducts increases. When SO₂ concentration increases, desulfurization efficiency decreases.     

浸渍液pH值对V-Mo/Ti脱硝催化剂性能的影响研究

为提升V-Mo/Ti催化剂的脱硝性能,在催化剂制备过程中调节浸渍工艺参数,制备了一系列不同浸渍液pH值的催化剂,采用XRD、N2-吸附脱附、拉曼光谱、UV-Vis、H2-TPR、NH3-TPD等手段对催化剂进行表征,考察了pH值的变化对催化剂物理化学性能的影响,采用固定床微型反应器对催化剂的脱硝性能进行评价。结果表明,降低浸渍液pH值,可以抑制催化剂上VOx物种的聚合,提升催化剂的还原性能,有利于提升催化剂的脱硝效率,降低脱硝反应过程中N2O生成量。同时,浸渍液pH值的变化,也会影响催化剂的酸性性能。当浸渍液pH值低于3.64时,催化剂酸性性能显著降低,造成催化剂脱硝性能降低;当浸渍液pH值控制在3.64时,催化剂的还原性能和酸性性能匹配较好,从而显示了较高的脱硝性能。     

Thermal risk in batch reactors: Case of peracetic acid synthesis

The present paper deals with accidents risk in batch reactors. It identifies the conditions for the occurrence of a thermal runaway and develops a probabilistic approach to assess the relevant risk. It investigates also the conditions for optimal synthesis of peracetic acid (PAA) with hydrogen peroxide (HP) and acetic acid (AA). The kinetic model of reversible reaction and side reaction of PAA synthesis is used to predict reactor temperature and molar ratio of PAA by ASPEN PLUS software. A sensitivity analysis is performed under different conditions such as constant temperature or adiabatic process with different concentrations of sulfuric acid. Assuming a prior cooling system failure, the conditions for reaction runaway triggering a thermal accident are identified in the case of PAA synthesis. Monte Carlo simulations are used in order to calculate the conditional probability of accident and optimize the synthesis of PAA.     

硫磺回收装置尾气回收系统安全分析

阐述了硫磺回收装置尾气回收系统的概况、工艺原理和工艺流程,对影响安全生产的加氢反应器床层温度、急冷塔堵塞和吸收塔中吸收效果等各种因素,从尾气中SO2的浓度、加氢反应器入口温度、加氢反应器入口H2浓度、加氢反应器出入口O2浓度、胺液H2S的吸收能力、贫胺液质量、贫液温度、胺液浓度及循环量、吸收塔压力等方面进行了安全分析,针对各种影响因素,提出了相应的安全对策措施,以确保系统的安全运行。     

移动床生物膜反应器充氧能力的试验研究

对移动床生物膜反应器的充氧能力进行了试验研究，结果表明：反应器充氧能力在添加填料比无填料时大；在悬浮载体能够均匀流化的填充率范围内，反应器充氧能力随着填充率的增大而增大；当填充率大于可以均匀流化的最大填充率时，反应器的充氧能力略有下降。     

Aging estimation of reactor pressure vessel in the field using magnetic properties

Many researchers have been interested in the nondestructive measurement methods for estimating components damage in order to assure the safe service of steel structures. It is recognized that the evaluating techniques based on magnetic measurement can offer a great potential because of high susceptibility to the change of several metallurgical factors. Magnetic property such as coercive force was measured. The coercive force at room temperature monotonously increased with the increase of frequency. The correlation between the magnetic properties of used material and that of un-used material was studied. The coercive force gradient at room temperature increased with the increase of aging. Hence the estimating method using magnetic properties allows one to evaluate the extent of material aging for reactor pressure vessel.     

Critical runaway conditions and stability criterion of RDX manufacture in continuous stirred tank reactor

The energetic material cyclo-1,3,5-trimethylene-2,4,6-trinitramine (RDX) has been widely used as explosive and propellant ingredients in the military industry. It is usually produced by hexamine nitration reaction in continuous stirred tank reactor (CSTR). This manufacturing process is quite dangerous and always causes fire incidents or explosion owing to its thermal instability in its nitration reaction or purification processes. In this investigation, we used its reaction kinetics parameters to evaluate the thermal hazard conditions and stable reaction criteria in the reaction systems of continuous stirred tank reactor.     

Emission of Oxygenated Species from the Combustion of Pine Wood and its Relation to Soot Formation

Combustion tests of pine wood cribs have been performed in different airflows in a fire test chamber. VOC in the flue gas has been monitored on-line using FTIR. Soot was collected at different heights above the bed on to quartz fibre filters and was characterized using pyrolysis-GC-MS. Correlation between combustion conditions and emission profiles were elucidated. The soot contained significant amounts of adsorbed oxygenated material derived from pyrolysis of the wood. Three types of material were identified: pyrolysis products, pyrolysis recombination products and PAH, and significant proportions of O-PAH are also present. Oxygenated PAH increased with temperature and higher air flow rate whereas oxygenated phenolic type material increased with lower temperature and lower air flow rate. Cooler flames from oxygen-starved fires akin to conditions in household fires produce significant higher proportions of phenolic material.Oxygen appears to play a significant role in the production of soot and there appear to be two routes by which PAH material can be synthesized. Firstly through conventional hydrocarbon mechanisms such as the HACA method and secondly through a route involving the polymerization of biomass pyrolysis fragments. A number of important species are identified which could be intermediates between these pyrolysis products and PAH.     

Optimum parameters for fault detection and diagnosis system of batch reaction using multiple neural networks

Batch process usually differs from the continuous process because of its time-varying variables and the process parameters. An early detection and isolation of faults in the process will help to reduce the process upsets and keep it safe and reliable. This paper discusses on the application of multi-layer perceptron neural network in detecting various faults in batch chemical reactor based on an esterification process that involves the reaction of ethanol and acetic acid catalyzed by sulfuric acid. A multi-layer feed forward neural network with double hidden layers has been used in the neural network architecture. The detection was based on the different patterns generated between normal and faulty conditions. An optimum network configuration was found when the network produced the minimal error with respect to the training, testing and data validation.     

Characterization of Products from the Pyrolysis of Municipal Solid Waste

Pyrolysis of municipal solid waste (MSW) in the form of refuse-derived fuel (RDF) was performed in a fixed bed reactor to recover char, oil/wax and combustible gases. It was established that the yield and composition of the products recovered depended on temperature; the percentage yield of char fell as the pyrolysis temperature was raised from 400°C to 700°C, whereas that of oil/wax and gaseous products rose. The chars recovered were also found to have properties which depended on the size fraction analysed. The gaseous product evolved during the pyrolysis had a high calorific value, making the gases suitable for use as a fuel. Fourier transform infrared spectrometry (FT-ir) of the derived oils, indicated that they were chemically very complex and highly oxygenated, and have the potential of being used either as a petrochemical feedstock or as a substitute liquid fuel.     

苯硝化工艺HAZOP分析的定量化研究

为提高危险化工工艺过程风险评估的准确性,通过工艺仿真模拟,研究工艺参数波动对生产装置安全性能的影响。以苯硝化工艺为例,采用危险与可操作性分析对该过程进行定性的风险评估;同时利用Aspen Plus建立苯硝化装置的模拟流程。结合HAZOP分析中偏差与模拟中硝化釜的流程变量之间的联系,以进料混酸的流量和1号硝化釜热负荷及出口温度为量化指标,观察混酸流量在正常操作点17.6 m3/h的±100%范围波动下1号硝化釜热负荷及出口温度的变化。研究结果表明,保持1号硝化釜温度为正常值,随着混酸流量的增大,硝化釜热负荷先增大后减小;保持硝化釜热负荷不变,随着混酸流量的增大,硝化釜温度先增大后减小。其中混酸流量值超过22.95 m3/h时,温度超过报警阈值60℃。     

医院含病毒污水的安全处理技术

针对医院在治疗病毒疾病病人如非典型肺炎病人过程中排出的传染性病毒污水,分析了污水处理中消除细菌及病毒病原的消毒方法如氯气、二氧化氯、臭氧和紫外线消毒等的特点,结合医院含病毒污水的水质组成和处理过程无病毒扩散和二次污染的要求,分别从高级氧化技术、新型生物技术及其结合提出医院病毒污水安全处理发展的方向。     

Emergy analysis of cassava vinasse treatment

Vinasse has great pollution to the environment. A number of technologies have been explored for reducing the pollution of vinasse. Sustainability has become an important factor when discussing wastewater treatment techniques. Emergy analysis was used to evaluate the treatment of cassava vinasse in this paper. Cr (emergy consumption ratio) as a new emergy index was proposed to measure the impact of waste treatment to the society. Centrifugal solid–liquid separation, UASB (up-flow anaerobic sludge bed), and SBR (sequencing batch reactor activated sludge process) are used in the treatment process. The emergy indices for cassava vinasse treatment system were as follows: EYR (emergy yield ratio) was 6.20, ELR (environmental loading ratio) was 5.81, ESI (emergy sustainability index) was 1.07, and Cr was 4.60E+12 sej/m³. The emergy of coal electricity accounts for 46% of all purchased inputs. It is necessary to improve the treatment technology to reduce the electricity used.     

PTA锻焊反应器的制造

本文对PTA装置上的大型铬钼钢锻焊反应器,在制造过程中的几个关键技术进行了介绍：控制材料的化学成分提高铬钼钢材料的抗回火脆化能力;采用先进的冶炼工艺和锻造技术保证大型锻件的质量;优化铬钼钢封头正火热处理中的冷却工艺来保证材料的性能指标;采用合理的焊接工艺,既保证了厚壁环焊缝的焊接质量,又降低了制造成本;优化堆焊工艺,保证了反应器内壁的堆焊质量;正确选择热处理规范,对铬钼钢压力容器至关重要。     

Process safety aspects in water-gas-shift (WGS) membrane reactors used for pure hydrogen production

The syngas produced by coal gasification processes can be utilized in Pd-based water-gas-shift membrane reactors for the production of pure H₂. Pd/alloy composite membrane reactors exhibit comparative advantages over traditional packed bed reactors such as simultaneous reaction/separation in one compact unit and increased reaction yields. Furthermore, the development of comprehensive process intensification strategies could further enhance membrane reactor performance resulting in a substantially smaller and functional, inherently safer, environmentally friendlier and more energy efficient process.A systematic non-isothermal modeling framework under both steady state and dynamic/transient conditions for a catalytic high temperature water-gas shift reaction in a Pd-based membrane reactor has been developed to characterize the dynamic behavior of the process system at various operating conditions from a process safety standpoint. In particular, various reaction conditions as well as key process variables such as feed temperature and flow rate, catalyst loading, driving force for H₂ permeation are considered as they are critically related to various safety aspects in the operation of a Pd-based membrane reactor. Within the proposed framework, process parameters and operating conditions which may induce hazards and compromise process safety are identified, analyzed and characterized. Finally, the proposed approach is evaluated through detailed simulation studies in an illustrative case study involving a real Pd-based membrane reactor used for pure hydrogen production and separation that exhibits complex behavior over a wide operating regime.     

Alternative method to prevent thermal runaway in case of error on operating conditions continuous reactor

Thermal runaway was studied in a continuous tubular pilot reactor under steady-state regime. Different accident scenarii were conducted by making some errors on reactant concentrations and/or temperature feed. To prevent thermal runaway, control by direct contact by solvent injection was used at different reactor locations. This injection allowed controlling the maximum reaction temperature. A simplified analytical method to estimate the maximum reaction temperature along the reactor was used.Benefit of this control method was the diminution of computational time. Furthermore, by injecting solvent to control maximum reaction temperature, there is no need to shut down the unit. The control method was validated experimentally.     

Stable and eco-friendly solid acids as alternative to sulfuric acid in the liquid phase nitration of toluene

Liquid-phase nitration of toluene was carried out using a silica supported Cs salt of phosphomolybdic acid (Cs_2.5H_0.5PMoO₄₀) as catalyst with dilute nitric acid under mild conditions. The Cs_2.5H_0.5PMoO₄₀ particles with Keggin-type structure were well dispersed on the surface of silica, and the catalysts exhibited strong acidity, which may be responsible for the high catalytic nitration activity. The effects of various parameters on nitration were tested, which included reaction temperature, reaction time, catalyst amount and reactants ratio. Under suitable conditions, the nitrations gave high toluene conversion (99.6%) and good mono-nitration selectivity. Compared to the conventional process, there was no other organic solvent or sulfuric acid used in the reaction system, which made it more environment-friendly. Moreover, the supported catalyst was proven to have excellent stability in the nitration process.