三甲氧苄二氨嘧啶的热解动力学研究

采用热重法(TG)和微分热重法(DTG)对合成的磺胺增效剂三甲氧苄二氨嘧啶(TMP)进行了热稳定性研究.研究结果表明:在25℃～700℃范围内有一次失重过程.运用Kissinger和Ozawa等方法计算了其活化能,并运用Satava-Sestak积分方程得到了TMP的热解动力学参数,其中热分解积分函数采用[-ln(1-a)]1/n的形式.求得的热解反应活化能Ea=70.2276 kJ/mol,反应级数n=2.02298.得到的热解动力学方程为:dα/dt=3.3576×106exp(-7.0228×104/RT)(1-α)[-ln(1-α)]0.4967     

Cl与CH4反应机理及动力学性质的理论研究

用MP2(FULL)/6-311G(d,p)方法优化了Cl与CH4反应的各驻点的几何构型,用高水平方法 QCISD(T)/aug-cc-pvtz计算了单点能,得到两个反应的表观活化能分别为15.82 kJ/mol和165.40 kJ/mol.采用变分过渡态理论加小曲率隧道效应的方法计算了两个反应在200～2000 K的速率常数,与实验值符合得较好.     

三醋酸甘油酯合成的热力学和动力学分析

采用Benson基团贡献法估算了三醋酸甘油酯的合成反应热．计算结果表明：该反应的焓变分别为ΔHf1＝－41．1 kJ/mol、ΔHf2＝－12．3 kJ/mol、ΔHf3＝－12．3 kJ/mol ,所得的计算结果与实验测定数据基本相符合．考察了在采水条件下温度对三醋酸甘油酯合成的影响,建立了拟一级反应动力学模型,结果表明,该模型能较好的拟合实验数据．     

一水邻苯二甲酸钙的热分解及其脱水动力学分析

采用TG-DTA分析研究了一水邻苯二甲酸钙热分解过程,对其中的脱水过程进行了动力学计算. 由Friedman和Ozawa-Flynn-Friedman法得到脱水过程的活化能和指前因子,用Archar方法计算拟合了几种机理函数,确定了脱水过程的优化动力学参数及最佳机理模型. 脱水过程的活化能Ea为141.1576 kJ/mol,反应的机理模型为Bna,即f(α) =(1-α)n*αn.     

O+CH4→OH+CH3反应的矢量相关研究

在扩展的London-Eyring-Polanyi-Sato(LEPS)势能面上,运用准经典轨线法在碰撞能Ecol=53.35 kJ/mol条件下研究了O+CH4→OH+CH3反应.在质心系下计算得到了广义极化微分反应截面PDDCS、k-j'两矢量相关的p(θr)分布和k-k'-j'三矢量相关的p(Φr)分布.结果与有关实验和理论符合得很好,很好地再现了反应过程和生成物的分布特点.     

C_2(a~3Π_u)自由基与C_2H_6反应的动力学计算

用密度泛函理论B3LYP方法,在6-311G(d,p)基组下,优化得到C2(a3Πu)+C2H6→C2H+C2H5反应各驻点(反应物、过渡态和产物)的几何构型,对其进行振动分析,并计算了它们的能量.在CCSD/6-311G(d,p)水平下单点能计算得到的反应势垒为24.47kJ/mol.采用传统过渡态理论,计算了温度范围50K～2000K的反应速率常数.实验结果表明,随着反应温度的升高,反应速率逐渐升高,反应的平均活化能也随着温度的不断升高而不断增大.     

煤液化过程热解动力学特性的研究

煤的热重实验数据动力学分析表明，煤热解反应由在三个一级反应构成，即两个热分解反应和一个热缩聚反应。以log[-log(1-a)]=log(AE/Rφ）－0.054E/T-2.884作动力学模型，计算出煤的热解特性参数，热解各阶段的表观活化能Ea，反应速率常数K，指前因子A，以及最大失重率F，最大反应速率Rm%和反应活性参数Ra,作为表征煤热解反应活性的指标，Ra越大或Rm越大，则煤的反应活性越好。由TG和DTG曲线定义Tb和Tf两个温度可以初步确定煤液化反应温度区间为：杨村煤390－480℃、神木煤425－525℃。     

MP2-R12方法在分子间相互作用研究的运用

本文对MP2-R12方法运用于研究分子间相互作用进行了初步的理论探讨,通过对一些有代表性的体系的计算,得到的结合能与用CCSD(T)方法得到的结合能相差大都是在2 kJ/mol左右,最大的也不超过4J/mol.     

氯化锌与2-氨基嘧啶配合物的热化学性质研究

制备了2-氨基嘧啶(AP)与锌的配合物Zn(AP)2C12,并对其组成进行了测定．采用具有恒温环境的溶解-反应量热计,分别测定了298．15 K时[Zn(NO3)2·6H2O(s) 2 KCl(s) 2 AP (s)]和[Zn(AP)C12(s) 2 KNO3(s)]在100．00mL 2 mol．L-1HCl溶液中的溶解焓．通过设计热化学循环得到2-氨基嘧啶(AP)与硝酸铜和氯化钾反应的反应焓为-34．5±2．49 kJ·mol-1,进而计算出配合物Zn(AP)2C12在298．15 K时的标准摩尔生成焓为-602．20±3．02kJ．mol-1．     

联吡咯构象异构的理论计算

构象分析是阐明分子结构的最重要手段之一,理论计算能够给出分子构象异构的一般信息。采用HF/6-31G*、B3LYP/6-31G*、BHHLYP/6-31G*和MP2/6-31G*方法,对3种联吡咯构造异构体进行了构象分析。采用BHHLYP/6-31++G**方法进行势能面上稳定点和过渡态的计算。结果表明,气相中6个联吡咯能量极小构象体能量差最大达14.56kJ/mol,转化能垒最大达10.19kJ/mol。采用自洽反应场极化连续模型溶剂理论,探讨了水溶剂对优势构象异构体的几何结构和能量的影响。结果表明,水相中6个联吡咯能量极小构象体的能量差最大达9.40kJ/mol,转化能垒最大达11.68kJ/mol。这种系统化研究有助于理解联吡咯各构造异构体之间构象能量与几何结构的关系。     

Vacuum pyrolysis characteristics of waste epoxy printed circuit boards

Vacuum pyrolysis was employed to dispose scrap brominated epoxy printed circuit boards (PCBs). Pyrolysis characteristics of waste PCBs under normal pressure and vacuum were investigated in this paper. A detailed study on the analysis of the elemental composition of PCBs and the pyrolysis products was performed. The thermal decomposition kinetics was measured by a thermogravimetric (TG) analyzer. The activation energy of pyrolysis under nitrogen atmosphere and vacuum were 193 kJ/mol to 206 kJ/mol and 145 kJ/mol to 165 kJ/mol, respectively. The composition of materials was analyzed by elemental analyzer. The pyrolysis products were analyzed by GC (gas chromatograph), GC-MS (chromatography and mass spectrometry) and FT-IR (Fourier transform infrared spectroscopy). Vacuum helped to increase the yield of pyrolysis oil. The liquid yield of PCBs pyrolysis at 15 kPa and normal pressure were 31.3? and 23.5?, respectively. The main components in pyrolysis oils were phenol, isopropyl-phenol, and their brominated substitution.     

Non-Isothermal Kinetics of Thermal Decomposition of a Novel Antitumor Agent 4-{5-[3,4-Dimethyl-5-（3,4,5 -Trimethoxyphenyl ）Thiophen-2-yl]-2-Methoxyphenyl}Morpholine

IN REEENT YEARS，MUEH ATTENTION HAS BEEN PAID TO DIARYL一SUBSTITUTED HETEROEYELES THAT ARE ASSOEIATED WITH HIGH BIOLOGIEAL AETIVITIES AS SELEETIVE COX一2 INHIBI- TORS[L〕AND ANRITUMOR AGENTS[21.A NEW EOM卯UND， NAMELY4一{5一[3，4一DIMETHYL一5一(3，4，5一T     

应用改性粉煤灰处理含铅废水的研究

对改性粉煤灰处理含铅废水进行了实验研究,结果表明,对铅离子的去除效果优于等量未改性粉煤灰和活性炭。吸附时间、废水的pH值、吸附剂用量、温度以及废水中Pb2＋浓度都能影响改性粉煤灰的吸附效果。最适宜的吸附条件是：在室温,pH=8．0,吸附剂用量为1．0g,Pb2＋含量小于0．005mol／L,吸附15min时,改性粉煤灰对废水中Pb2＋的吸附达到饱和。     

Quantum chemical study on the catalytic mechanism of Na/K on NO-char heterogeneous reactions during the coal reburning process

Quantum chemical simulation was used to investigate the catalytic mechanism of Na/K on NO-char heterogeneous reactions during the coal reburning process. Both NO-char and NO-Na/K reactions were considered as three-step processes in this calculation. Based on geometry optimizations made using the UB3LYP/6-31G（d） method, the activation energies of NO-char and NO-Na/K reactions were calculated using the QCISD（T）/6-311G（d, p） method; Results showed that the activation energy of the NO-Na/K reaction （107.9/82.0 kJ/mol） was much lower than that of the NO-char reaction （245.1 kJ/mol）. The reactions of NaO/KO and Na2O/K2O reduced by char were also studied, and their thermodynamics were calculated using the UB3LYP/6-31G（d） method; Results showed that both Na and K can be refreshed easily and rapidly by char at high temperature during the coal reburning process. Based on the calculations and analyses, the catalytic mechanism of Na/K on NO-char heterogeneous reactions during the coal reburning process was clarified.     

聚丙烯纤维对高性能混凝土强度与耐久性影响的试验研究

研究了掺加聚丙烯纤维、矿渣及粉煤灰对C50高性能混凝土抗渗性、立方体抗压强度、干燥收缩变形以及抗氯离子渗透性能的影响,同时分析了聚丙烯纤维的合理掺量。     

粉煤灰脱色性能的试验研究

根据粉煤灰的结构及特点,研究粉煤灰处理印染废水的脱色机理及其性能.将酸化处理的粉煤灰对印染废水进行脱色试验,考察粉煤灰投加量、酸的种类、浓度和搅拌时间等因素对脱色效果的影响.通过正交实验找出最佳参数,探索了酸化处理的粉煤灰处理印染废水的机理和效果.     

Experiment and mechanism investigation on advanced reburning for NOx reduction： influence of CO and temperature

Pulverized coal reburning, ammonia injection and advanced reburning in a pilot scale drop tube furnace were investigated. Premix of petroleum gas, air and NH3 were burned in a porous gas burner to generate the needed flue gas. Four kinds of pulverized coal were fed as reburning fuel at constant rate of 1g/min. The coal reburning process parameters including 15%～25% reburn heat input, temperature range from 1100 ℃ to 1400 ℃ and also the carbon in fly ash, coal fineness, reburn zone stoichiometric ratio, etc. were investigated. On the condition of 25% reburn heat input, maximum of 47% NO reduction with Yanzhou coal was obtained by pure coal reburning. Optimal temperature for reburning is about 1300 ℃ and fuel-rich stoichiometric ratio is essential; coal fineness can slightly enhance the reburning ability. The temperature window for ammonia injection is about 700 ℃～1100 ℃. CO can improve the NH3 ability at lower temperature. During advanced reburning, 72.9% NO reduction was measured. To achieve more than 70% NO reduction, Selective Non-catalytic NOx Reduction (SNCR) should need NH3/NO stoichiometric ratio larger than 5, while advanced reburning only uses common dose of ammonia as in conventional SNCR technology. Mechanism study shows the oxidization of CO can improve the decomposition of H2O, which will rich the radical pools igniting the whole reactions at lower temperatures.     

改性粉煤灰对含铅废水的吸附研究

通过对粉煤灰的硫酸改性得到酸改性粉煤灰,用其对含铅模拟废水进行吸附实验,探讨改性的最佳条件,并在最佳改性条件下制得改性粉煤灰,研究改性粉煤灰投加量、吸附时间、吸附温度以及pH值对Pb2＋吸附效果的影响.结果表明,在投加量为10 g/L,吸附时间为50 min,吸附温度为50℃,pH-6时,改性粉煤灰对40 μg/mL的Pb2＋的去除率可达90.34％,能够较好的去除废水中的Pb2＋.     

Comparative study on activating fly ash by quick lime and slaked lime: effects and kinetics

Lime, which is a frequently used activating agent of fly ash （FA）, has two main states： slaked lime and quick lime. We studied the effects of slaked lime and quick lime on activating FA, and discussed their kinetics. The results show that slaked lime is more beneficial for activating FA than quick lime given the condition of equivalent CaO amount. The use of slaked lime has superiority in technology and economy on activating FA. Theoretical analysis revealed that the kinetic constant of the activation reaction using slaked lime is higher than using quick lime, credited to the better volume stability and fineness, and smaller water demand of slaked lime.