高效厌氧反应器处理啤酒废水的试验研究

在(35±1)℃条件下,采用高效厌氧反应器对青岛啤酒股份有限公司的生产废水进行处理,研究了厌氧反应器的启动和运行情况,分析了回流比、温度和上升流速等因素对反应器的影响.结果表明,厌氧反应器的容积负荷可达21 kg COD/(m3·d),COD去除率稳定在80%以上,出水挥发酸质量浓度低于350 mg/L,平均每去除1 kgCOD产生0.26 m3沼气.启动结束后,颗粒污泥的平均沉降速度由40.3 m/h提高到73.4 m/h,污泥密度由0.78 g/cm3升高至1.02 g/cm3,0.5～1.5 mm粒径的颗粒污泥占66%.同时,在25℃的运行条件下反应器的容积负荷降至9 kg COD/( m3·d),温度升高后反应器的运行可以较快得到恢复.     

丁二烯聚合放热危险特性和安全泄放面积计算

为探讨丁二烯的聚合放热危险特性,并为某化工厂丁二烯储罐安全泄放设计提供依据,利用新型绝热量热仪VSP2,对丁二烯的聚合放热过程及加有阻聚剂对叔丁基邻苯二酚(TBC)的丁二烯的聚合放热过程进行试验研究,得到温度、压力随时间变化的数据。用Leung法和平衡速率模型(ERM),分别计算得到该厂丁二烯储罐的安全泄放流量和泄放能力,并最终确定其安全泄放面积。结果表明:丁二烯聚合反应的起始放热温度为70.26℃,反应失控后体系的最高温度和最高压力分别达到194.07℃和1.06 MPa,具有较大的危险性;阻聚剂TBC能有效阻止丁二烯的聚合;丁二烯聚合反应的泄放类型为蒸气型泄放,计算得到该化工厂丁二烯储罐的安全泄放面积为0.06 m2。     

聚磷酸铵对糖粉火焰传播特性的影响研究

为明确聚磷酸铵(APP)对糖粉粉尘火焰燃烧特性的影响,采用竖直开口方管道燃烧试验平台,研究不同质量分数APP对糖粉粉尘爆燃火焰特征、火焰速度、火焰温度等参数的影响,并采用热分析仪对糖粉及其APP混合物的热解行为进行了分析。结果表明:随着APP质量分数的增加,糖粉粉尘火焰的亮度逐渐降低;添加质量分数为6%的APP后,糖粉火焰在管道中的最大传播速度由17. 3 m/s降低到2. 8 m/s,火焰最高温度降低了46. 46%,糖粉热解残余量由0. 71%提高到16. 06%; APP对糖粉火焰抑制作用包括物理抑制和化学抑制,APP热分解反应可吸收燃烧反应中的热量,分解产物可捕捉提燃烧反应中的自由基,从而达到抑制糖粉火焰传播的目的。     

基于PLC控制的内循环回流式流化床反应器的设计

针对传统反应器在有机废水处理中存在的问题,在结合UASB和IC反应器特点的基础上,通过设置布水器进行均衡布水,引进固定化微生物填料防止反应器堵塞,改进三相分离器提高回流比,设置内循环回流管减少水头损失及布置多级取样口方便采样,设计可自动控制的厌氧/好氧一体化内循环回流式流化床反应器,并且采用PLC控制器控制进出水水量、水流上升速度、曝气量、进气时间及水力停留时间等参数,用于处理高氨氮有机废水.屠宰废水室内试验结果表明:在进水流量为1 m3/d,水力停留时间为3h,pH值7.2,25℃的条件下,好氧微曝气使溶解氧为2 mg/L,厌氧好氧自动交替运行,水流上升速控制在约1.0 m/h,约40％的污水无动力回流处理,填料无堵塞,采样方便.经50d驯化后,出水CODcr、NH+4-N、油脂及色度的去除率分别达到了87％、63.6％、74.7％和84.7％,且每天能获得生物质气体约0.32 m,平均处理费用为0.15元/t,比传统处理工艺费用要低.这说明内循环回流式流化床反应器较传统反应器在高氨氮有机废水处理,特别是脱氮方面有较大提高,可用于高氨氮有机废水的处理.     

腐蚀管道寿命可靠性的步降应力加速试验研究

为保障油气管道安全运营,需研究腐蚀管道寿命的可靠性。首先基于管道失效机理,采用步降应力加速寿命试验(SDSALT)方法,获得不同温度下腐蚀率样本;其次利用加速因子和逆幂律加速方程建立数据折算模型,将腐蚀率样本转换为应力作用失效时间并截尾抽样后作为输入,求得含未知参数的准样本;然后通过准样本估计Weibull分布的3个参数,进而得到以温度和时间为自变量的管道可靠性函数;最后以H_2S/CO_2环境中运营的N80管道为例,验证所建腐蚀管道寿命预测方法的可靠性。结果表明,该方法大幅缩短试验时间,对管道寿命预测准确,并分析出管道可靠性的降低速度随温度和时间的增加先增大后减小,可应用于管道的适用性评价。     

醋酸乙烯聚合体系热失控风险评估及失控抑制

为实现对醋酸乙烯(VAC)聚合反应热失控行为的风险评估及紧急抑制,采用VSP2绝热量热仪对醋酸乙烯聚合反应体系在不同危险场景条件下的热失控过程和失控抑制进行试验模拟。依据苏黎世危险性分析法(ZHA)中的失控反应严重度评估判据,评估醋酸乙烯聚合反应的热失控风险程度,提出紧急情况下抑制剂的加入时间及加入量。结果表明,醋酸乙烯聚合反应失控后绝热温升(ΔT_(ad))超过100℃,最大反应速率到达时间(TMRad)约为10 min,其热失控风险程度仅次于不可接受水平。聚合体系温度不高于73℃时,通过加入不低于参与聚合反应的醋酸乙烯质量20%的常温溶剂,可有效阻止失控反应发生。     

反应量热仪RC1在化工热危险性分析中的应用

介绍了一种新型热危险性分析仪器--反应量热仪RC1的设计原理和内部结构,运行模式以及所能获得的温度、传热系数、热转化率、绝热温升、最大合成反应温度等数据类型,并通过阐述其在过程安全、工艺过程开发及优化和基础研究等方面的应用,指出了反应量热仪在化工热安全领域中的特点和优势.     

气相爆轰实验系统设计

设计了一套内径139 mm、总长10 m的气体、粉尘爆轰管道式反应装置,装置由试验管道系统、测试系统、辅助实验系统和控制系统4部分构成。测试系统包括高频响动态压力传感器、火焰传感器、超动态应变仪、数据采集卡、高速摄像系统等设备,以便测试可燃气体、粉尘的爆轰参数和管道的动力学响应特征参数。实验装置可用于可燃气云和粉尘的燃烧、爆炸特性以及爆轰波对结构加载作用的研究,研究成果可用于燃气输送管道的设计、校核,为安全生产保驾护航。     

EGSB反应器的低温运行性能研究

对膨胀颗粒污泥床(EGSB)反应器在低温(10～15℃)条件下的运行状况和污泥特性进行研究.结果表明,EGSB反应器在10～15℃的低温条件下能够稳定高效运行.当进水COD质量浓度低至114mg/L或高达3600mg/L(有机负荷高达23kg COD·m-3·d-1)时,COD去除率均能维持在70%左右.与中温(32～35℃)相比,低温时颗粒污泥的沉速相对较低,但不低于15m/h,不会被冲出反应器而造成污泥流失.低温时,颗粒污泥的产甲烷活性明显降低,COD去除率也明显降低,但液体上升流速的提高能改善泥水的传质效果,提高COD去除率.在HRT=0.9h、液体上升流速Vup=3.0m/h左右的运行条件下,反应器内温度由35℃降到15℃时,K由0.391 × 103降到0.107×103,COD去除率由84.32%降到68.9%.但当Vup由3.0m/h提高到4.2m/h时,K由0.107×103提高到0.254×103,COD去除率也由68.9%提高至76.7%.低温时,EGSB反应器的抗温度冲击能力很强.低浓度时,EGSB反应器的抗pH冲击能力不强,但随着进水COD浓度的提高,其抗DH冲击能力逐渐增强.EGSB反应器在低温低浓度条件下运行时需添加碱度以维持反应器内适宜的pH值.     

V2O5/TiO2催化剂选择性催化还原脱除NOx的研究

通过浸渍法制备V2O5/TiO2催化剂,在固定床反应器中进行NH3选择性催化还原脱除NOx的研究.结果表明,对于100/140目催化剂,NOx转化率随反应时间线性增加,NH3选择性催化还原NOx反应为一级反应,反应活化能为98.23 kJ*mol-1.对于片状催化剂,气体流量和催化剂的厚度对脱氮反应有较大的影响,气体流量增加,NOx转化率提高,当流量增至120 L*h-1后,NOx转化率趋于稳定;催化剂厚度由0.1 cm增至0.2 cm, NOx转化率从83%降至40%, 催化剂有效因子从0.254降至0.127.对于0.1 cm厚的片状催化剂,在573 K和空速1.4 s-1条件下,NOx转化率可达92%.     

Thermal hazards analysis of styrene in contact with impurities

Styrene is a reactive monomer commonly used to produce polystyrene and other copolymers. Unintended thermal runaway polymerization reactions of styrene keep reoccurring and have led to catastrophic consequences. One of the possible causes of these runaway incidents involves the contamination of the styrene monomer by incompatible species, which was not adequately investigated and documented. This study focuses on the quantification of thermal runaway hazards of styrene in contact with a series of contamination substances by adopting calorimetric analysis. Both Differential Scanning Calorimeter (DSC) and Advanced Reactive System Screening Tool (ARSST) were employed to examine the exothermic characteristics of styrene mixed with contaminating substances at different concentration levels and mixing conditions. Key safety parameters of the exothermic reaction, such as the onset temperature, the overall heat release, the maximum self-heating rate, as well as the activation energy, were obtained. The results indicated that the thermal runaway polymerization of purified styrene was significantly altered by the presence of contaminant species. Water effectively retarded and quenched the runaway polymerization at a higher temperature range. Alkaline had no substantial effect on the thermal runaway characteristics. The presence of acid solution under both static contact and vigorous mixing condition significantly promoted the thermal polymerization of styrene. A trace amount of concentrated acid initiated violent exothermic activity even at room temperature; and the severity of the reaction was profoundly impacted by the mass-transfer. Our study demonstrates significant implications in the prevention of runaway incidents during transportation and storage of styrene.     

Thermal research on the uncontrolled behavior of styrene bulk polymerization

Thermal runaway can occur during the styrene bulk polymerization process because of easily formed local hotspots resulting from the high viscosity of reactants and the difficulty of heat dissipation. To obtain the thermal hazard characteristics, the polymerization behavior of styrene was investigated using differential scanning calorimetry (DSC) at a scanning rate of β = 2 °C/min. Experimental results showed that the exothermic peaks obtained for heat initiation were different from those obtained when initiator was added. The exothermic peak changed from one to two after the initiator was added. The exothermic onset temperature (T₀) was also reduced. Phi-tech II was utilized to study the bulk polymerization of styrene in an adiabatic environment. The adiabatic temperature rise (ΔT_ad), starting temperature of uncontrolled polymerization (T_star), maximum temperature (T_end), and heat of polymerization (ΔH) under different conditions were acquired. When the dose of the additive was increased, the starting temperature of uncontrolled polymerization (T_star) decreased and the adiabatic temperature rise (ΔT_ad) increased gradually. Severity grading was performed based on the severity evaluation criteria of runaway reaction. The results can help designers decide whether it is necessary to take certain measures to reduce risk.     

基于VSP2的引发剂质量分数对醋酸乙烯聚合反应失控特性及安全泄放设计影响研究

为了解决醋酸乙烯聚合反应失控所引起的超压问题,通过VSP2绝热量热仪研究了醋酸乙烯聚合反应的失控特性,并通过Leung's法对某醋酸乙烯聚合反应器的安全泄放面积进行了计算;然后,在其他条件不变的情况下,研究引发剂质量分数对失控特性和泄放面积的影响,结果表明,引发剂质量分数对反应总放热量的影响不大,体系绝热温升为105~115℃;但引发剂质量分数越大,失控反应的最大温升速率和最大压升速率越大。这是因为引发剂质量分数越大,在相同泄放压力和最大累积压力下,单位质量反应物的放热速率就越大,也就需要更大的泄放面积;最后,引入无量纲数W~*、G~*和A~*,拟合出它们与引发剂质量分数X*的关系式,结果表明,在研究范围内所需安全泄放面积随引发剂质量分数线性增大。     

Evaluation of thermal hazard characteristics of four low temperature reactive azo compounds under isothermal conditions

The polymerization reaction can lower the threshold of the required energy by the initiator to improve the efficiency of the overall process reaction. Emerging polymerization initiators are also a major focus of process improvement and technological progress. Azo compounds (azos), which used in dyeing applications, are subsequently used in polymerization reactions due to their highly exothermic reaction characteristics. Although higher heat release can promote polymerization and modify the product, heat generation may also cause process hazards.These thermal hazard parameters were studied by selecting dimethyl 2,2′-azobis(2,4-dimethylvaleronitrile) (ABVN), 2,2′-azobis(2-methyl propionate) (AIBME), 2,2′-azobis(2-methylpropionamide) dihydrochloride (AIBA), and 2,2′-azobis(isobutyronitrile) (AIBN), which are common azo initiators at present. Thermal hazards are closely related to the reaction kinetics of the substance itself. The form of the reaction, the apparent activation energy and the thermodynamic parameters of the exothermic mode were also obtained.Kinetic analysis of the actual process using the experimental data of the isothermal calorimetry model is rarely used in the evaluation of related thermal hazard characteristics. The simulation results revealed the kinetic azo models and were further applied to calculate the runaway situations of azo under specific boundary conditions.     

过氧化苯甲酰合成工艺热危险性分析

采用RC1e反应量热仪对过氧化苯甲酰(BPO)合成工艺危险性进行研究,测试不同Na OH溶液初始浓度(1.96 mol/L、3.93 mol/L、7.14 mol/L)下反应的放热历程,获得BPO合成反应过程中的热危险性参数,并采用PHI-TECⅡ绝热加速量热仪对产物进行热稳定性分析,最后评估该反应热风险。结果表明,Na OH浓度为7.14 mol/L时,反应初期放热速率慢,热累积度大,后期反应剧烈,绝热温升(ΔTad)及热失控时工艺反应达到的最高温度(MTSR)最大。热稳定性试验表明,合成的粗产物BPO初始分解温度、活化能、指前因子、最大放热速率到达时间为24 h时的对应温度(TD24)均低于纯BPO。利用合成粗产物BPO的TD24对反应进行危险度评估,该工艺热危险性等级均为5级,工艺危险性大。     

The critical runaway condition and stability criterion in the phenol–formaldehyde reaction

The procedure of phenol–formaldehyde polymerization is a rather important and complicated reaction in the chemical industry. This exothermic polymeric reaction releases a huge amount of heat. The high amount of energy accumulated and increasing temperature in this reaction process always lead to runaway reaction and a hazard situation owing to the high released heat and improper operation. In this investigation, we used sodium hydroxide as alkali–catalyst in the phenol–formaldehyde polymerization and estimated the reaction kinetics parameters to evaluate the thermal hazard conditions. The critical temperatures and stable criteria of the runaway reaction in this exothermic polymerization were evaluated. This technique is important and useful for safe operation in the phenol–formaldehyde polymerization process.     

简单放热化学反应体系热安全性研究判据

许多危险化学物质在发生热化学反应的同时通常会放出热量,如果能量不能有效释放就可能引起火灾和爆炸事故,考虑到化学物质对热的响应方式非常复杂,从分析绝热条件下化学物质的热化学反应动力学入手,利用化学物质的物理化学特性参数计算化学反应体系在绝热条件下发生热化学反应的温升速率dT/dt,进而获得有关的动力学因子A,E等。结果表明,尽管在近似绝热条件下化学反应体系的热化学反应与其本身的特性和反应容器有关,但温升速率dT/dt只与物质的物理化学特性参数有关。含氯酸钾的几种简单放热反应体系的ARC实验结果进一步验证了这一结论。因此,同一种化学物质与不同物质构成的多元混合反应体系在相同近似绝热条件下的热化学反应特征参数,可以作为判据用来比较并评价体系的相对安全性,该判据对表征热化学反应的难易程度以及物质的相对安全性起到一定的指导意义。     

数值分析方法在一起高危工艺分析中的应用

以二级放热反应为研究对象,在反应体系温度、浓度均匀分布的假设基础上,根据反应速率方程和热平衡方程,建立高危工艺反应的温度和转化率随时间变化的数学模型。采用数值计算技术,以一阶差分代替微分,并结合工艺中的恒温过程、绝热过程和飞温过程,编写计算程序求得其转化率、温度在不同时间点的数值解,揭示爆炸事故的发展过程,定量分析操作参数的影响和转化率、温度随时间分布的规律。同时通过对绝热反应时间、冷凝器的冷却能力的分析,结合冷凝器的移热能力和反应放热对反应体系热积累的影响,讨论防止反应失控发生的可能性。最后探讨冷凝器热负荷余量、反应物投料浓度比等因素对控制反应失控的影响。     

Using thermal analysis with kinetic calculation method to assess the thermal stability of azo compound on construction materials

The application of construction polymers in engineering and alternative materials has always occupied a place in the market. In the production process of polymer resins, initiators can be used to lower the polymerization reaction energy threshold, which can improve reaction efficiency and reduce energy loss. However, as a commonly used energetic substance in the polymerization process, azos have caused related process hazards due to their exothermic characteristics. Because of this, it is essential to examine and analyze the thermal hazard characteristics of emerging azo substances, such as 2-cyanopropan-2-imemicarbazide (CABN). Although previous literature performs the calculation on related thermal hazard parameters of CABN, there is still exists a void for discussion in estimating the reaction model to avoid analogous hazards and enhance the existing thermal analysis. Based on the past literature, the reaction model is improved with thermogravimetric analysis as evidence. The revised thermal hazard parameters are calculated as the basis of control and mitigation measures, the kinetic model is used to estimate the modified safety parameters, and in the judgment of the runaway reaction, the critical temperature of the runaway is found by analyzing the influence of slight changes in ambient temperature on the reaction temperature. The results show that the critical temperature that causes CABN to enter the runaway reaction is delayed, and the hazard is lower than in the storage situation. Therefore, the thermal hazard to CABN mainly focuses on the safety environment and measures during storage.     

Thermal hazard assessment for synthesis of 3-methylpyridine-N-oxide

The exothermic oxidation of 3-methylpyridine with hydrogen peroxide was analyzed by Reaction Calorimeter (RC1e) in semi-batch operation. Heat releasing rate and heat conversion were studied at different operating conditions, such as reaction temperature, feeding rate, the amount of catalyst and so on. The thermal hazard assessment of the oxidation was derived from the calorimetric data, such as adiabatic temperature rise (ΔT_ad) and the maximum temperature of synthesis reaction (MTSR) in out of control conditions. Along with thermal decomposition of the product, the possibility of secondary decomposition under runaway conditions was analyzed by time to maximum rate (TMR_ad). Also, risk matrix was used to assess the risk of the reaction. Results indicated that with the increase of the reaction temperature, the reaction heat release rate increased, while reaction time and exotherm decreased. With the increase of feeding time, heat releasing rate decreased, but reaction time and exotherm increased. With the amount of the catalyst increased, heat releasing rate increased, reaction time decreased and exothermic heat increased. The risk matrix showed that when the reaction temperature was 70 °C, feeding time was 1 h, and the amount of catalyst was 10 g and 15 g, respectively, the reaction risk was high and must be reduced.