绿色技术评价磺化反应过程热危险性

反应量热仪RC1研究磺化反应过程中热危险性具有评价路线简单、易于操作、过程绿色环保等优势,近年来逐渐成为研究的热点.磺化反应过程中由于工艺的不同,不同磺化反应过程的热危险性也具有很大的差别.通过反应量热仪RC1、差示扫描量热DSC、绝热加速量热仪ARC对10种不同工艺的磺化反应过程的热危险进行了深入的研究,对企业实践生...     

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。     

绝热加速量热仪在化工生产热危险性评价中的应用

本文介绍了一种新型热危险性分析仪器--绝热加速量热仪的设计原理和内部结构,运行模式以及所能获得的温度、压力和最大温升速率时间等数据类型.并通过阐述其在化学动力学研究、自加速分解温度的计算、化学工艺安全性分析和化学工艺过程开发以及热爆炸事故原因调查等方面的应用,指出了绝热加速量热仪在化工生产危险评价方面的特点和优势.     

Thermal hazard evaluation for iso-octanol nitration with mixed acid

2-Ethylhexyl nitrate (2-EHN), an important additive to diesel fuel, is produced from the nitration of iso-octanol with HNO₃–H₂SO₄ mixed acid. In this study, the differential scanning calorimeter (DSC), accelerating rate calorimeter (ARC) and reaction calorimeter were used to analyze the thermal stability of 2-EHN and the thermal hazard of iso-octanol nitration. Four samples with different ratios of 2-EHN to mixed acid were tested using DSC. The results indicated that more mixed acid could catalyze the decomposition of 2-EHN. Three samples were tested using ARC and the results showed that sample 4 contained the lowest onset temperatures, T_D8 and T_D24. This shows that there is a higher probability of triggering the decomposition of the product 2-EHN from the iso-octanol nitration process. This conclusion was verified using RC1e tests at different temperatures. The RC1e experiments also indicated that the overall heat generation of these reactions was considerably large despite the high yields of the nitration process at 45 °C and 55 °C. This heat generation makes these semi-batch processes difficult to control, especially on a pilot or plant scale. Based on the maximum temperature of the synthesis reaction (MTSR) corrected by the yield, the only acceptable semi-batch process is the nitration reaction at 10 °C.     

基于CONE和MCC的典型电缆燃烧性能研究

采用锥形量热仪和微燃烧量热仪对四类不同护套材料的八种电缆样品进行燃烧性能分析,研究结果表明：电缆燃烧热释放过程不仅与护套、绝缘的材料密切相关,也与电缆结构密不可分;对于护套材料相同而大小或结构不同的电缆点燃时间和到达第一个峰值的时间以及第一个峰值最大热释放速率基本一致;聚烯烃无机阻燃材料电缆能够有效降低热释放速率峰值,CO2、CO释放量也明显低于橡胶电缆、普通PVC电缆和阻燃PVC电缆;微燃烧量热仪和锥形量热仪实验数据存在一定的相关性,微燃烧量热仪实验数据可以对电缆锥形量热仪实验的第一燃烧阶段燃烧行为进行预测。     

Pressure relief sizing of reactive system using DIERS simplified methods and dynamic simulation method

Incidents involving uncontrolled chemical reactions continue to result in fatality, injury and economic loss. These incidents are often the result of inadequate pressure relief system designs due to a limited knowledge of the chemical reactivity hazard. A safe process design requires knowledge of the chemical reactivity of desired as well as undesired chemical reactions due to upset conditions. Simplified, cost effective methods to relief system sizing are presented by The Design Institute of Emergency Relief Systems (DIERS). They require multiple experiments, and sizing is only valid for the system composition and thermal inertia represented by the small scale experiments. Results are often conservative, especially for gassy systems. Detailed, dynamic computer simulation is highly accurate and can be used for iterative design and multiple scenario evaluation.In this study, an accelerating rate calorimeter (ARC^®) and a low thermal inertia calorimeter (automatic pressure tracking adiabatic calorimeter – APTAC™) were used to collect chemical reactivity data for the dicumyl peroxide and toluene system. Results of the pressure relief system sizing using the dynamic simulation method are presented and compared with DIERS simplified methods.     

Thermal decomposition kinetic of liquid organic peroxides

This study demonstrates the application of isothermal calorimeter for investigating the thermal decomposition of several liquid organic peroxides, such as t-Butyl peroxy acetate (TBPA), Di-tert butyl peroxide (DTBP), and Cumene hydroperoxide (CHP). The decomposition mechanism and kinetic can be identified from case to case. TBPA and DTBP undergo first order reaction, whereas CHP occurs autocatalysis. Accurate kinetic can be assessed on the basis of discerning these various schemes of given samples. Consequently, the thermal runaway or reactive hazards potential of organic peroxides can be determined, for instance as a self accelerating decomposition temperature (SADT).     

硝酸甲胺反应过程的安全性研究

用反应量热仪(RC1e)对硝酸溶液与一甲胺溶液在反应过程中的热安定性进行初步研究,分别测试不同反应温度、加料速度和初始硝酸浓度下反应的放热情况。实验结果表明:该中和过程反应迅速,在室温就能进行;与反应温度、加料速度相比,起始硝酸浓度对反应安全性影响最大,且硝酸浓度越高,反应的速度和反应的完全程度也越高。实验还表明:RC1e是研究反应过程中热安定性情况的有效工具,能通过反应过程的热量变化体现反应速率,所得结果对硝酸甲胺的工业化生产具有重要的参考价值。     

混酸中甲苯半间歇硝化过程的危险性研究

为了解甲苯在混酸中硝化的危险性,用差示扫描量热法(DSC)测试甲苯、混酸及一硝基甲苯的热分解情况,用反应量热仪(RC1e)研究搅拌速度、温度及硝酸过用率3因素对目的反应的影响。结果表明,混酸分解温度最低,而当目的反应的3因素出现异常,以及反应过程中发生冷却失效时,均可导致硝化反应体系不稳定,此时若不停止加料,并采取措施,易引起混酸的分解,进一步可引起一硝基甲苯的分解,导致严重后果。     

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.     

Combustion characteristics of asphalt and sodium compounds

Risk evaluation of mixtures of asphalt and inorganic salts such as sodium nitrate, sodium nitrite, sodium carbonate and sodium dihydrogenphosphate was conducted. The ignition and the combustion characteristics of mixtures of asphalt and oxidizing salts were obtained. Quasi-heat-accumulation experiments of asphalt–salt mixtures were conducted using about 1 kg samples. Six types of asphalt–salt mixtures were made and their ignition characteristics were examined in the quasi-heat-accumulation experiments. Then to clarify burning behavior of the asphalt–salt mixtures, experiments for understanding their combustion characteristics were conducted using a cone calorimeter.

The main results are as follows.

(1) In the quasi-heat-accumulation experiment, a region with high concentration of the salt mixture particles was made at the bottom of the sample vessel through the process of their sedimentation. An exothermic reaction started in this region. Just before the asphalt–salt mixture was ignited, a huge amount of white smoke was released. A kind of jet flame of a few meters in height was created.

(2) Based on the data of ignition temperature from the cone calorimeter experiments, ignition of asphalt was caused by a chemical reaction of asphalt with an oxidizing salt. The combustion of the asphalt–salt mixture contained the self-heating reaction.     

二甲亚砜热稳定性的实验研究

采用先进的绝热加速量热仪为手段,对二甲亚砜的热稳定性进行了系统研究,其内容涉及纯二甲亚砜的热稳定性、加酸碱和硫化物等杂质后二甲亚砜的热稳定性,包括初始放热温度、温升速率、温度-压力等;通过修正试验数据,消除了热惰性因子的影响;得到了二甲亚砜的热稳定性特性。研究表明,在酸、碱存在时,二甲亚砜在室温下即可发生强烈的放热反应,导致二甲亚砜的分解温度提前。该实验研究结果,对二甲亚砜的安全生产工艺过程控制具有重要参考价值。     

三种液体稳定剂对过氧乙酸稳定效果的实验研究

利用绝热加速量热仪对三种过氧乙酸液体稳定剂的稳定效果进行了实验分析,并与常规实验方法获得的结论进行了比较。绝热条件下加入三种液体稳定剂后,初始分解温度分别提高了1.85℃、17.52℃和14.73℃,绝热温升分别升高了3.77℃、降低了12.56℃和17.88℃,到达最大温升速率的时间分别延长了508.93min、319.92min和247.92min,稳定效果为磷酸乙酸丁酯磷酸三丁酯,对过氧乙酸的安全生产、储存和使用具有一定指导意义。     

有机酸对H发泡剂分解历程的影响及作用机制分析

为研究有机酸对H发泡剂热分解特性的影响,采用量热仪测试不同质量分数苯甲酸、水杨酸、邻苯二甲酸与H发泡剂混合物的热分解特性参数.结果表明:H发泡剂分解时,随着升温速率增加,外推起始分解温度Te、峰值温度Tp与最大放热速率随之升高.3种有机酸的加入均可以促进H发泡剂的分解,随着有机酸质量分数的增加,其外推起始分解温度和峰值...     

固化剂对矿用充填泡沫固化行为的影响

为提高泡沫的充填堵漏风效果,选取有机强酸A,有机磺酸B,无机强酸C等3种固化剂,通过测定泡沫的发泡时间、发泡温度、承压强度和氧指数等参数,分析不同组合固化剂对矿用充填泡沫固化行为的影响。结果表明:乳化时间、起泡时间和表干时间随固化剂用量的增加而明显缩短;泡沫的发泡倍数和发泡温度随固化剂用量的增加而增加;单独使用有机强酸A或有机磺酸B时,泡沫都存在不同程度的收缩,当添加较高量的无机强酸C时,泡沫的尺寸稳定性变好。当复合固化剂有机强酸A用量∶有机磺酸B用量∶无机强酸C用量=1.2∶1∶1时,泡沫的固化效果最优。     

自反应性化学物质的热危险性评价方法

笔者进行的研究工作 ,给出了利用C80微量量热仪所测得的自反应性化学物质的热流速曲线 ,从而求解该物质的化学反应动力学参数 ,以及在Semenov模型下求解其自加速分解温度SADT(Self AcceleratingDecompositionTemperature)的方法 ,并将一些有机过氧化物、氧化剂和可燃剂的混合物的自加速分解温度的推算结果与实测值进行了比较。实验证明 ,该推算方法结论准确 ,是一种安全、简便、实用的反应性化学物质热危险性的评价方法     

Research on the critical temperature of thermal decomposition for large cartridge emulsion explosives

Emulsion explosives are one type of main industrial explosives. The emergence of the large cartridge emulsion explosives has brought new security incidents. The differential scanning calorimeter (DSC) and the accelerating rate calorimeter (ARC) were selected for the preliminary investigation of the thermal stability of emulsion explosives. The results showed that the initial thermal decomposition temperatures were in the range of 232–239 °C in nitrogen atmosphere (220–232 °C in oxygen atmosphere) in DSC measurements and 216 °C in ARC measurements. The slow cook-off experiments were carried out to investigate the critical temperature of the thermal decomposition (T_c) of the large cartridge emulsion explosives. The results indicated that the larger the diameter of the emulsion explosives, the smaller the T_c is. For the large cartridge emulsion explosives with diameter of 70 mm, the T_c was 170 °C at the heating rate of 3 °C h⁻¹. It is a dangerous temperature for the production of the large cartridge emulsion explosives and it should cause our attention.     

Hazard evaluation for chlorination and amination reactions of fluorocytosine production process

Reaction thermal runaway is one of the most important reasons leading to chemical accidents. With the rapid development of the chemical industry in the world, especially the fine chemical industry, various safety accidents also occur frequently. Therefore, it is necessary to study the exothermic behavior of the reaction process. In this study, reaction calorimeter was used to study the exothermic phenomena during the chlorination reaction and amination reaction. Differential scanning calorimetry was performed on the reactants, and thermogravimetric experiments were performed on the products. In addition, adiabatic experiment was performed to study the thermal runaway behavior of amination products under adiabatic conditions. The results showed that the target reactions generated a large amount of heat in the initial stage. The maximum temperature of amination reaction is higher than the initial decomposition temperature of the amination product under adiabatic condition. The pyrolysis of amination product was divided into three stages. The product had a high apparent activation energy at the beginning of decomposition, and the apparent activation energy decreased as the decomposition progressed.     

过氧乙酸溶液的热爆炸分析

为有效预防生产、储运和使用中过氧乙酸引发的火灾爆炸事故,采用绝热加速量热仪模拟了15%和10%浓度的过氧乙酸溶液的热爆炸过程,得到了两种浓度的PAA溶液的热分解温度、压力、温升速率随时间变化的关系曲线,并用速率常数法分别计算了反应级数n、表观活化能Ea和指前因子A。经过绝热修正,得到最危险状态下的温度和压力等相关热危险参数,并基于Semenov热爆炸理论推算了三种包装条件下两种样品的不可逆温度和自加速分解温度。结果表明,15%PAA和10%PAA溶液热分解反应级数均为一级,表观活化能分别为1044kJ·mol-1和1032kJ·mol-1;绝热条件下初始放热温度分别为429℃和293℃;自加速分解温度受反应系统到达最大反应速率的时间、物料存储规模及散热条件的影响,建议PAA应储存在通风背阴处且单个包装容积应控制在25L以下。