A numerical study of the auto-ignition temperatures of CH4–Air,C3H8–Air,CH4–C3H8–Air and CH4–CO2–Air mixtures

The auto-ignition temperature (AIT) is an important parameter in the process industries. In order to ensure a safe working environment in process industries, it is important to predict the AIT of combustible gases or vapors. In this study, the AITs of natural gas mixtures (CH₄–Air, C₃H₈–Air, CH₄–C₃H₈–Air and CH₄–CO₂–Air) are calculated based on a detailed kinetic model. To create a more practical model, different ignition criteria and convective heat transfer coefficients are investigated and compared against one another, resulting in the temperature criterion and a convective heat transfer coefficient of h = 50 W/(m² K). The results showed that the AITs of CH₄–Air and C₃H₈–Air decrease with an increase of equivalence ratios. While the propane ratio increasing, the AIT of CH₄–C₃H₈–Air decreasing. Reaction path analysis of natural gas mixtures (CH₄–C₃H₈) was also carried out to explain this phenomenon, yielding results showing that C₃H₈ is the main reaction during the ignition induction period. In addition the AIT of CH₄ increases slowly in positive correlation with CO_2, which plays a role of an inert gas. Comparing the results with literature work revealed a deviation of about 10%. Thus, it can be reasonably concluded that the AIT of a low hydrocarbons mixtures such as natural gas can be reliably predicted with detailed kinetic model.     

硝酸铵与硝铵磷热稳定性对比研究

为了研究硝铵磷的热稳定性,用DSC－TG同步热分析仪测试了硝酸铵的热分解过程,根据升温速率分别为5,10,15 K／min的DSC和TG－DTG曲线,利用Ozawa法和Kissinger法求得的硝酸铵的活化能基本一致。用Rogers公式和Arrhenius公式求得指前因子和速率常数分别为1．62×1010 s－1,1．07×10－18 s－1（120℃）;硝酸铵在升温速率为5 K／min时,分解峰值温度的活化焓、活化熵、活化自由能分别为102．76 kJ／mol ,－62．35 J／（K·mol ）,134．98 kJ／mol;对比了硝酸铵和硝铵磷的DSC曲线,结果表明硝铵磷的吸热分解峰值温度低于硝酸铵,热稳定性更好。     

辣根过氧化物酶处理酚和氯酚的催化特性研究

为了研究辣根过氧化物酶处理酚和氯酚的动力学过程,采用人工配不试验,测定了ｐＨ对酶催化反应的影响,Ｈ２Ｏ２抑制酶催化反应的动力学参数和不同度物的酶催化反应动力学参数,结果表明,在试验的ｐＨ范围内,ｐＨ为９时过氧化物酶对苯酚和对氯苯酚的去除效率最高,分别达到９９．５％和９５％。     

几种低分子量有机酸对红壤中DDTs类物质释放动力学的影响

采用自行设计的动力学试验装置,系统研究了3种低分子量有机酸(草酸、酒石酸和柠檬酸)和水对红壤中滴滴涕(DDTs)类物质的释放动力学行为.结果表明:10 mmol/L的低分子量有机酸可使DDTs类物质的释放百分率相对于水提高15～18个百分点,特别在淋洗液的前250mL更为明显.水对DDTs类物质的释放动力学数据可用表观一级动力学方程很好拟合(R²>0.99,p<0.000 1),说明DDTs的释放可能以土壤矿物表面扩散为主,而有机酸存在体系中的该类物质的释放却更好符合抛物线方程、双常数方程,说明低分子量有机酸的存在使DDTs的释放机理复杂化,这可能与有机酸对矿物的溶解、对矿物表面固有有机质结构的干扰有关.     

诱导动力学光度法测定废水中微量砷

依据As(Ⅲ)对Cr(Ⅵ)-Fe(phen)_3~(2+)氧化还原反应在酸性条件下的诱导作用,提出了一种测定微量砷的动力学方法.并建立了测定最佳条件:[Cr(Ⅵ)]=3.2×10~(-4)mol/L;[Fe~(2+)]=1.2×10~(-4)mol/L;[phen]/[Fe~(2+)=5.6;pH=1.2;512nm.线性范围为0-3.0μg/ml As(Ⅲ),方法检测限为0.01μg/ml.除S~(2-)外,多数常见离子均有较大允许共存量.用本法测定工业废水中的微量砷,所得结果满意.样品加标回收率为95.8％—103.3％,变异系数RSD<4.64％.     

Fenton试剂处理腐殖酸废水影响特性和降解动力学模型

研究了Fenton试剂降解腐殖酸废水的影响特性,并在理论分析反应过程的基础上建立动力学方程,同时根据实验进行动力学方程参数估算。研究表明,Fenton试剂通过氧化和混凝共同作用有效去除腐殖酸。在初始pH=4,40mmol/L FeSO4和160 mmol/L H2O2投量下,腐殖酸60 min氧化去除率、混凝去除率分别达到78.6%和11.5%,其初始氧化速率达到最大59.6 mg/(L.min)。腐殖酸的氧化降解动力学模型值与实验值吻合良好,说明采用该动力学模型能较好预测腐殖酸废水的氧化降解情况,且Fenton氧化降解腐殖酸的机理符合自由基的理论和实践。     

天然及CaCl2改性沸石对四环素的吸附

通过静态吸附实验研究了水中四环素在天然和CaCl2改性沸石上的吸附行为及机制。实验表明,天然沸石对四环素具有吸附能力,CaCl2改性可以提高沸石对四环素的吸附能力。天然和改性沸石对四环素的吸附符合拟二级动力学模型,颗粒内扩散不是吸附过程的主要控制步骤。Freundlich和Dubinin-Radushkevich(D-R)等温吸附模型可以较好地描述实验所用2种沸石对四环素的吸附行为,D-R等温方程拟合结果显示吸附过程包含离子交换作用。通过对天然和改性沸石吸附四环素前后溶液中主要阳离子浓度变化分析证实了该吸附过程包含离子交换作用。实验研究了pH值变化对沸石吸附四环素的影响,当pH=3～5时,天然和改性沸石对四环素的吸附量均随pH值的增加而急剧下降,而pH=5～10时,天然和改性沸石对四环素的吸附量变化均不明显,推测可能是离子交换作用和化学沉淀吸附作用所致。另外,实验还初步探索了溶液离子强度对沸石吸附四环素的影响情况,随着溶液中Na+和Ca2+离子强度的增加,吸附量先急剧降低随后趋向平稳,进一步说明了沸石对四环素的吸附过程不是由单一机制控制的。     

改性TiO2光催化降解三苯甲烷类污染物

以硫酸钛为原料采用水热法制备了掺Fe3+TiO2晶体粉末,采用X射线衍射仪(XRD)对样品的结构进行了表征。在可见光条件下,用溴酚蓝、甲基绿、甲基蓝、孔雀石绿、甲基紫和碱性品红等6种典型三苯甲烷类化合物为目标降解物,研究了以自制的掺Fe3+TiO2晶体粉末对它们的催化降解作用。实验结果表明,制备的掺Fe3+TiO2晶体属于锐钛矿型。6种化合物的光催化降解反应遵循拟一级动力学规律,且可用Langmuir-Hinshelwood(L-H)动力学模型描述,其表观反应速度常数(k)的大小顺序为:溴酚蓝<甲基绿<甲基蓝<孔雀石绿<甲基紫<碱性品红,大小变化次序与其半衰期t1/2成反比,并从分子结构上对它们的降解规律进行定性解释。     

液/固体系中硅藻土对Pb2+和Cd2+的吸附机制

为了提高硅藻土在重金属废水处理上的应用水平,采用静态吸附实验考察了液/固体系中硅藻土对Pb2＋、Cd2＋的吸附影响因素、吸附等温线和吸附动力学属性。结果表明,随着投加量的减少,离子初始浓度的提高,pH值的增大,吸附作用时间的延长,硅藻土对Pb2＋、Cd2＋吸附量不断上升;硅藻土对Pb2＋、Cd2＋的等温吸附都符合Langmuir模型,硅藻土对Pb2＋、Cd2＋最大吸附量分别为10.428 mg/g和7.916 mg/g,硅藻土对Pb2＋具有更好的吸附能力;Pb2＋具有较低的水合自由能,更容易脱去水膜与硅藻土孔道内的活性基团发生吸附作用;双常数扩散方程可以很好地描述硅藻土对Pb2＋、Cd2＋的吸附动力学属性,硅藻土对Cd2＋有较快的吸附速率。     

Factors affecting the growth rates of ammonium and nitrite oxidizing bacteria

The maximum specific growth rates of both ammonium oxidizing bacteria (AOB) and nitrite oxidizing bacteria (NOB) were investigated under varying aerobic solids retention time (SRT_a) and in the presence/absence of anoxic (alternating) conditions. Two bench SBRs, reactor R1 and R2, were run in parallel for 150 d. Reactor R1 was operated in aerobic conditions while R2 operated in alternating anoxic/aerobic conditions. The feed (synthetic wastewater), temperature, hydraulic retention time and mixing were identical in both reactors. The SRT_a in both reactors was, sequentially, set at four values: 5, 4, 3 and 2 d.Kinetic tests with the biomasses from both reactors were carried out to estimate the maximum specific growth rates (μ_max) at each tested SRT_a and decay rates, in both aerobic and anoxic conditions. The kinetic parameters of nitrifier were estimated through the calibration of a two step nitrification-denitrification activated sludge model.The results point to a slightly higher μ_max,AOB and μ_max,NOB in alternating conditions, while both μ_max,AOB and μ_max,NOB were shown not to vary in the tested range of SRT_a (from 2 to 5 d) at 20 °C. They were relatively high when compared to literature data: 1.05 d⁻¹ < μ_max,AOB < 1.4 d⁻¹ and 0.91 d⁻¹ < μ_max,NOB < 1.31 d⁻¹. The decay coefficients of both AOB and NOB were much higher in aerobic (from 0.22 d⁻¹ to 0.28 d⁻¹) than in anoxic (0.04 d⁻¹ to 0.16 d⁻¹) conditions both in R1 and R2, which explained the higher nitrification rates observed in the alternating reactor.