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。     

Evaluation of thermal reaction for two azo compounds by using 20-L apparatus and calorimetry

Azo compounds are widely involved in the industrial processes of dyes, pigments, initiators, and blowing agents. Unfortunately, these compounds have a bivalent unstable –NN– composition, which can be readily broken when the ambient temperature is elevated. Self-accelerating decomposition might cause a runaway reaction and lead to a fire, explosion, or leakage when the cooling system fails or other events occur. This study investigated the explosion properties, thermal stability parameters, and thermal hazard and mechanism of 2,2′–azobisisobutyronitrile (AIBN) and 2,2′–azobis–2–methylbutyronitrile (AMBN). We used a 20-L apparatus, vent sizing package 2, synchronous thermal analysis, and differential scanning calorimetry under explosive, adiabatic, and dynamic conditions to acquire the explosive curves, thermal curves, and thermodynamic parameters of the substances. Moreover, the differential isoconversional method (Friedman method) and ASTM E698 equation were employed to obtain the apparent activation energy E_a. All the experimental results revealed that AIBN is more dangerous than AMBN. The E_a of AIBN was lower than that of AMBN. The results can be used to construct an azo compound thermal hazard database for use for searches and reference examples by industry and related research areas.     

308 nm光作用下α-Fe2O3表面HNO3的光解

采用紫外可见光谱(UV-Vis)、傅立叶变换红外光谱(FTIR)及离子色谱(IC)技术对HNO3在α-Fe2O3表面暗反应和308nm下光解反应进行了研究.考察了时间、HNO3浓度、相对湿度(RH)等条件对反应的影响.结果表明,随着HNO3浓度、光照时间的增加,HNO3在气相与α-Fe2O3表面光解产物浓度均呈指数增加;HNO3在α-Fe2O3表面光解产生的NO2、NO分别为气相产生的3.27及3.87倍,而无论气相还是表面光解的NO2浓度均约为NO的2倍.随着RH的增加,HNO3光解产生的HONO的浓度随之呈指数增大,其产率从RH 20%时的0.023增加到90%时的0.087.α-Fe2O3的表面效应在HNO3的表面光解反应中起主导作用.     

固体云爆剂热分解性能研究

目的研究固体云爆剂的热分解特性。方法利用差示扫描量热(DSC)和热重分析(TG)测定该固体云爆剂的热分解过程。分别得到固体云爆剂在不同温度下的DSC和TG曲线,以及同一温度下云爆剂不同组分的DSC和TG曲线。结合线性回归分析的方法,利用Ozawa法、Starink法以及Kissinger法计算了反应活化能。结果其表观活化能为208 k J/mol左右。结论该固体云爆剂的热分解是一个连续的过程,具有良好的安定性。     

工业园区综合难降解废水深度处理实验研究

某工业园区综合废水处理厂设计规模5.0×104m3/d,原设计出水执行《城镇污水处理厂污染物排放标准》(GB 18918-2002)一级B标准,需将出水标准提高到一级A排放标准.分别采用混凝沉淀法和高级氧化法深度处理二级生化出水.小试试验结果表明:二级生化出水CODcr在62~75 mg/L左右,PAC、Al2(SO4)3及PFS三种絮凝沉淀药剂处理出水CODcr去除效果均不明显,不能稳定达到一级A排放标准.芬顿催化氧化的pH=5,FeSO4+H2O2投加量为(200+100)mg/L;臭氧氧化的O3投加量33 mg/L,其出水CODcr均能达到一级A排放标准.     

水溶液中臭氧和溴离子的反应研究

为探明O3氧化Br-的反应机制,采用离子色谱、PDA紫外-可见光度仪研究了水中Br-被O3氧化的反应过程.离子色谱分析表明,被氧化的Br-中只有约10%被O3氧化成BrO3-.进一步研究表明,除了生成BrO3-外,Br-被O3氧化过程中还产生了Br2,Br2又与溶液中存在的Br-结合形成Br3-,并首次得到了Br3-的吸收光谱,测得Br3-的最大吸收峰λmax为260 nm,提出了Br-与O3的基元反应.该研究补充和完善了O3氧化Br-的反应机制,也为O3处理含Br-水时Br-的归趋提供了有益信息.     

土壤重金属钝化修复剂生物炭对镉的吸附特性研究

目前以生物炭为代表的生物质对重金属的吸附表现出良好的应用前景.为确定生物炭对溶液中镉的吸附性能,选用由棉花秸秆制备的生物炭,研究吸附等温线、吸附动力学以及温度、pH和离子强度等对生物炭吸附Cd2+的影响.研究表明,生物炭对Cd2+的吸附可以用Freundlich等温线较好地拟合,在不同温度下其饱和吸附量分别为9.738 mg.g-1(288.15 K)、10.14 mg.g-1(298.15 K)、10.40 mg.g-1(308.15 K)和10.71 mg.g-1(318.15 K),热力学参数表明生物炭吸附Cd2+的过程是自发的吸热过程;吸附动力学过程符合二级动力学模型,在40 min即可达到平衡;pH对生物炭吸附Cd2+的影响较大,在pH2～8范围时,生物炭对Cd2+的吸附量随pH的增加先上升后下降;生物炭对Cd2+的吸附量随着溶液离子强度的增大呈降低趋势.该项研究可为生物炭在土壤重金属污染修复中的应用提供一定的理论基础.     

Quantitative analysis of microbial biomass yield in aerobic bioreactor

We have studied the integrated model of reaction rate equations with thermal energy balance in aerobic bioreactor for food waste decomposition and showed that the integrated model has the capability both of monitoring microbial activity in real time and of analyzing biodegradation kinetics and thermal-hydrodynamic properties. On the other hand, concerning microbial metabolism, it was known that balancing catabolic reactions with anabolic reactions in terms of energy and electron flow provides stoichiometric metabolic reactions and enables the estimation of microbial biomass yield (stoichiometric reaction model). We have studied a method for estimating real-time microbial biomass yield in the bioreactor during food waste decomposition by combining the integrated model with the stoichiometric reaction model. As a result, it was found that the time course of microbial biomass yield in the bioreactor during decomposition can be evaluated using the operational data of the bioreactor (weight of input food waste and bed temperature) by the combined model. The combined model can be applied to manage a food waste decomposition not only for controlling system operation to keep microbial activity stable, but also for producing value–added products such as compost on optimum condition.     

Homogeneous and heterogeneous reactions of anthracene with selected atmospheric oxidants

The reactions of gas-phase anthracene and suspended anthracene particles with O3 and O3-NO were conducted in a 200-L reaction chamber, respectively. The secondary organic aerosol (SOA) formations from gas-phase reactions of anthracene with O3 and O3-NO were observed. Meanwhile, the size distributions and mass concentrations of SOA were monitored with a scanning mobility particle sizer (SMPS) during the formation processes. The rapid exponential growths of SOA reveal that the atmospheric lifetimes of gas-phase anthracene towards O3 and O3-NO are less than 20.5 and 4.34 hr, respectively. The particulate oxidation products from homogeneous and heterogeneous reactions were analyzed with a vacuum ultraviolet photoionization aerosol time-of-flight mass spectrometer (VUV-ATOFMS). Gas chromatograph/mass spectrometer (GC/MS) analyses of oxidation products of anthracene were carried out for assigning the time-of-flight (TOF) mass spectra of products from homogeneous and heterogeneous reactions. Anthrone, anthraquinone, 9,10- dihydroxyanthracene, and 1,9,10-trihydroxyanthracene were the ozonation products of anthracene, while anthrone, anthraquinone, 9-nitroanthracene, and 1,8-dihydroxyanthraquinone were the main products of anthracene with O3-NO.