超临界水氧化五氯硝基苯生产废水的研究

在间歇式反应器中进行超临界水氧化五氯硝基苯生产废水试验.采用3因素3水平正交试验设计法,判断影响氧化处理效果的主次顺序为温度、压力、时间,并得到最佳工艺条件为反应温度500 ℃、反应压力28 MPa、停留时间30 s.进行单因素试验,考察了反应温度、压强两个主要因素对氧化效果的影响,温度升高和压强增大都有利于污染物去除.单因素试验结果表明,SCWO处理后出水水质达到国家规定的<污水综合排放标准>中的1级标准,验证了该最佳工艺条件的合理性.进行了均相催化和非均相催化超临界水氧化试验.结果表明,催化剂的加入可以显著提高COD的去除率.非均相催化剂中,采用TiO2/ZnO双金属组合催化氧化的效率高于单一金属,均相催化剂Zn(NO3)2和Fe(NO3)3的催化效率相差无几,且都高于Cu(NO3)2催化效率,Na2CO3的催化效果最高.     

超临界水氧化法处理焦化废水

对超临界水氧化技术处理焦化废水进行了试验研究,以H2O2作为氧化剂,研究了氧化剂用量、反应温度、停留时间和压力等影响因素.试验结果表明H2O2用量的增加有利于污染物降解,但是当用量为理论用量1.6倍时,其影响已不明显.废水的CODCr,去除率随着反应温度、压力和停留时间的增大而提高.另外,在所有影响因素中反应温度是影响焦化废水降解的主要因素.试验确定了最适宜工艺条件为:H2O2用量为理论用量1.6倍,反应温度540℃,反应压力28MPa,反应时间大于120 s.在此工艺条件下,废水的CODCr,去除率达99.4%.     

偏二甲肼超临界水氧化动力学研究

利用一套连续式超临界水氧化实验装置,以H2O2为氧化剂,在480～550℃、30 MPa条件下,进行了超临界水氧化偏二甲肼实验,建立了COD去除宏观动力学方程.实验结果表明,在超临界条件下,偏二甲肼氧化分解很快,当温度为550℃、压力为30 MPa、停留时间为5.8 s时,COD去除率可高达93.5%以上.偏二甲肼的去除率随反应温度升高、停留时间延长而提高.在H2O2过量50%的情况下,偏二甲肼氧化分解反应对有机物为1.13级,对氧气为0.29级;反应活化能Ea为44.65 kJ·mol-1;指前因子A为4.93×103.     

超临界水氧化法测定TOC装置的建立和初步试验

利用超临界水氧化技术(Super Critical Water Oxidation,SCWO)能迅速彻底氧化各种有机污染物的特点,将其应用于废水总有机碳(Total Organic Carbon,TOC)的检测.自行构建了一套利用超临界水氧化法连续检测废水TOC的试验装置.选取邻苯二甲酸氢钾作为典型有机污染物,首先在p=24.0 MPa,T=380～440℃,m=1.0～20.0条件下,验证了本方法的可行性与可重复性.通过试验初步研究了超临界水氧化温度与氧化系数m对TOC检测的影响机制,得出测试水样TOC转化率随反应温度和氧化系数m的增加先增加而后趋于平稳;并得出随着反应温度的升高、氧化系数的增大,TOC降解率也随之提高,当m≥6.0,T≥420℃时,TOC几乎完全降解.测试水样邻苯二甲酸氢钾溶液适宜检测条件为T=420℃,p=24 MPa,m=6.0,此时TOC降解率达到99％.同时,分别用岛津TOC分析仪(高温催化燃烧法)和SCWO-NDIR装置对葡萄糖和苯酚混合溶液的TOC进行了测定,两者的测定结果线性拟合关系较好,证明利用超临界水氧化法测定TOC可行.     

印染废水的光催化氧化研究现状及其进展

在光催化氧化法降解染料废水的研究中,通常使用金属氧化物为催化剂,其中TiO2最为理想;催化负载方式很多,以溶胶-凝胶法更具应用前景;同时,催化氧化过程中的催化剂的用量、废水的pH值和初始浓度、温度、光照强度和光源类型等因素对氧化效果有着不同程度的影响;在各式反应器中,管式反应器被认为最具有发展前景.要使这项技术成功走向工业化,必须解决好催化剂的活性、负载技术和反应器设计等方面的问题.     

超临界水中含油污泥与甲醛共氧化研究

在温度为390～450 ℃,压力为25 MPa,反应时间为1～10 min的条件下,在间歇式反应釜中采用超临界水共氧化方法处理含油污泥,考察共氧化添加物种类、时间、甲醛质量浓度和温度对氧化效果的影响.结果表明,添加甲醛对含油污泥的转化具有明显的促进作用,450 ℃反应10 min,含油污泥COD去除率达99.0%.甲醛质量浓度至少要与含油污泥初始COD处于同一数量级时,才具有显著的促进作用.氧化中间产物CO和醋酸产率随甲醛质量浓度提高而增加.反应温度低时甲醛的促进作用明显.随着反应温度的提高,CO产率增加,醋酸产率降低.     

碱对含油污泥超临界水氧化的影响研究

在间歇反应釜中进行含油污泥超临界水氧化试验,反应压力为25 MPa,反应温度为390～450 ℃,反应时间为1～10 min条件下,研究添加Na2CO3和NaHCO3对含油污泥超临界水氧化的影响.结果表明,添加Na2CO3和NaHCO3均有利于COD的去除,且NaHCO3的处理效果优于Na2CO3.NaHCO3的适宜添加质量浓度为100 mg/L,且低温下的处理效果优于高温,而高温甚至起到了抑制作用.在390 ℃、25 MPa、NaHCO3添加质量浓度100 mg/L、过氧量427%条件下,反应5 min后含油污泥的COD去除率达86%,比添加前提高了10.7%,同时也降低了中间产物CO和醋酸的收率.本研究为开发超临界水氧化含油污泥无害化处理新技术和新方法提供了参考.     

湿式过氧化氢氧化法处理吡虫啉农药废水研究

为优化反应条件,在2 L压力反应器内,对吡虫啉农药废水进行湿式过氧化氢氧化(WPO)和催化湿式过氧化氢氧化(CWPO)降解处理,考察了过氧化氢加入量、反应温度、进水pH值和催化剂等对反应过程与污染物降解的影响规律.结果表明,WPO和CWPO能在温和的条件下降解难于生物降解的吡虫啉农药废水.温度为110℃,压力为0.6 Mpa,过氧化氢用量为理论用量.进水pH值为3.5的条件下,WPO处理吡虫啉农药废水,COD去除率为47.7%;采用非均相Cu-Ni-Ce/SiO2催化剂,pH值为7.0.其他条件相同时,CWPO对相同吡虫啉农药废水的COD去除率可达89.1%.计算得CWPO和WPO基于COD的第1阶段表观活化能分别为11.2 kJ/mol和29.6 kJ/mol.湿式过氧化氢氧化法为农药废水的处理提供了一种经济有效的方法.     

基于BP神经网络的间硝基苯磺酸钠CWPO降解条件优化

为了对电镀废水中的间硝基苯磺酸钠催化湿式过氧化氢氧化(CWPO)降解条件进行模拟及优化,建立了间硝基苯磺酸钠CWPO降解过程BP神经网络模型.经验证,模型预测值与试验值的平均相对偏差为0.81%,相关系数r和Nash-Suttcliffe模拟效率系数NSC分别为0.992 5和0.983 9.相对灵敏度分析表明,影响间硝基苯磺酸钠去除率(以TOC表示)的顺序从大到小为: 反应温度、间硝基苯磺酸钠质量浓度、pH值、H2O2用量、反应时间、初始氧分压、催化剂用量.结合遗传算法以TOC去除率最高作为优化目标,分别对降解条件进行优化.经对比,带成本约束的优化降解结果(99.36%)比试验中的TOC去除率平均值(85.51%)提高了10%以上,同时,优化后的降解成本(2.03元)相比无成本约束条件下的降解成本(2.38元)降低了近15%(0.35元).     

基于BFGS-BP神经网络岩爆分类研究

BP神经网络模型是岩爆预测中的常用模型，为了强化预测效果，选取BFGS算法对BP神经网络模型进行优化。选取应力系数■、脆性系数■和弹性能量指数W_et作为预测指标，国内外46组案例作为样本库，分别建立BFGS-BP神经网络模型和传统BP神经网络模型，对比验证其优化效果，将建好的模型用于锦屏二级水电站和秦岭隧道加以检验，得到一种有应用前景的机器学习预测模型。     

Inherently safer reactors: Improved efficiency of 3-picoline N-oxidation in the temperature range 110–125 °C

Alkylpyridine N-oxides are important intermediates in the pharmaceutical and agrochemicals industries. The N-oxides are produced via the homogeneously catalyzed oxidation of the respective alkylpyridines using a 50% excess of hydrogen peroxide. The competitive hydrogen peroxide decomposition produces oxygen in the flammable environment of alkylpyridines and thus forms a key hazard for this reaction. In this work, the N-oxidation was performed under pressure in the temperature range of 110–125 °C with different catalyst concentrations. It was shown that temperature had an undisputable positive effect on the N-oxidation efficiency. The accurate measurement of the pressure rise due to decomposition was difficult. However, only 5% of the added H₂O₂ decomposed when stoichiometric quantities were employed, even in the temperature of 110 °C. The N-oxidation was very efficient, even when the lowest concentration of catalyst employed in this study was used.     

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.     

Cu/γ-Al2O3的制备及对活性艳红X-3B的脱色性能研究

为实现活性染料X-3B废水在常温常压下高效地脱色,以过渡金属为活性组分、活性氧化铝(γ-Al_2O_3)为载体,采用等体积浸渍法制备了一系列M/γ-Al_2O_3(M=Cu2+、Fe3+、Zn2+、Mn2+)负载型催化剂,并考察其对活性艳红X-3B模拟染料废水的脱色性能,同时考察了活性组分、焙烧温度、负载量、催化剂投加量、氧化剂用量及pH值等因素对活性艳红X-3B脱色性能的影响规律。结果表明,常温常压下,以Cu2+为活性组分,焙烧温度为350℃、负载量为4%(质量分数)、氧化剂H_2O_2浓度为58 mmol/L、催化剂投加量为1.2 g/L、pH值为5~7、反应50 min时,催化剂对活性艳红X-3B废水的脱色效果最佳,脱色率可达95%以上。平行试验表明,Cu2+的存在可增加载体表面的吸附中心,H_2O_2可分解产生HO·,当两者共存时,活性艳红X-3B在催化剂表面主要发生化学吸附与催化氧化两种反应过程,且染料在Cu/γ-Al_2O_3上发生的吸附作用明显大于H_2O_2分解产生HO·而引发的催化氧化作用。动力学试验表明,活性艳红X-3B反应过程动力学模型与初始质量浓度有关,大于等于200 mg/L时,符合准一级动力学方程。     

Investigation of the decomposition reaction and dust explosion characteristics of crystalline dicumyl peroxide

The dicumyl peroxide (DCP) is widely used as a polymerization initiator, catalyst and vulcanizing agent in the chemical industry. A number of accidents have been caused by its thermal instability in storage or manufacturing process. Thus, its hazard characteristics have to be clearly identified. First of all, the differential scanning calorimeter (DSC) is used to measure the heat of decomposition reaction, which can contribute to understanding the reaction characteristics of DCP. The accelerating rate calorimeter (ARC) is used to measure the rates of temperature and pressure rises of decomposition reaction, and then the kinetics parameters are estimated. Furthermore, the MIKE 3 apparatus and the 20-l-Apparatus are used to measure and analyze the dust explosion characteristics of DCP at room temperature and atmospheric pressure. Finally, Semenov's thermal explosion theory is applied to investigate the critical runaway condition and the stability criterion of decomposition reaction, and to build the relationship of critical temperature, convective heat transfer coefficient, heat transfer surface area and ambient temperature. These results contribute to improving the safety in the reaction, transportation and storage processes of DCP.     

Use of isoperibolic calorimetry for the study of the effect of water concentration,temperature and reactor venting on the rate of hydroxylamine thermal decomposition

Hydroxylamine, NH₂OH, thermal decomposition has been responsible for two serious accidents. However, its reactive behavior and the synergy of factors affecting the rate of its decomposition are not understood. In this work, isoperibolic calorimetric measurements were performed in a metal reactor, in the temperature range 130–150 °C, employing 30–80 ml solutions containing 1.4–20 g of pure hydroxylamine (2.8–40 g of the supplied reagent). The calorimetric measurements were performed in order to assess the effects that NH₂OH concentration, temperature and reactor venting has on NH₂OH rate of decomposition. The measurements showed that increased concentration or temperature, results in faster reactions and probably higher pressure generation per mass of reactant, with concentration having a more pronounced effect. However, when both factors work synergistically the result is dramatically worse in terms of reaction rate. The pressure generation is also different, thus indicating that different reaction pathways predominate each time. Venting the produced gases in stages resulted in the highest mass loss of the solution.     

Thermal risk analysis of cumene hydroperoxide in the presence of alkaline catalysts

Many studies have been performed to clarify the basic thermal runaway hazards and kinetics of cumene hydroperoxide (CHP) decomposition. However, materials that are incompatible with CHP have not been clearly identified. Alkaline solutions have been used as a catalyst to form dimethylphenyl carbinol (DMPC) and dicumyl peroxide (DCPO); however, these solutions also affect the reaction and storage temperature of CHP. In this study, thermal calorimeters, differential scanning calorimetry (DSC) and vent sizing package 2 (VSP2), were used to compare the effects of various bases on the decomposition of CHP in cumene. Specifically, the exothermic onset temperature, change in pressure over time, self-heating rate and heat of decomposition were evaluated. Moreover, to appraise the degree of hazard associated with the use of CHP, the compatibility of CHP with various substances was analyzed, and a risk matrix for thermal runaway reactions was obtained. The results of the present study could be used to design safety procedures for the production of CHP and its derivatives.     

A novel pretreatment process of mature landfill leachate with ultrasonic activated persulfate: Optimization using integrated Taguchi method and response surface methodology

A novel advanced oxidation process (AOP) using ultrasonic activated persulfate oxidation was used to pretreat mature landfill leachate. The effects of different operating variables (e.g., the initial S₂O₈²⁻ concentration, pH, temperature, ultrasonic power and reaction time) on the oxidation performance were investigated regarding the total organic carbon (TOC) removal efficiency, and the variables were optimized using the integrated Taguchi method and response surface methodology (RSM). Based on the Taguchi method under L₁₆ (4⁵) arrays and a grey relational analysis, the most significant variables included the initial S₂O₈²⁻ concentration, temperature and reaction time. The concentrations of these variables were further optimized using RSM. Using the integrated optimization method, the optimal conditions included an initial S₂O₈²⁻ concentration of 8.5 mM, a reaction temperature of 70 °C and a reaction time of 2.46 h, which resulted in a TOC removal efficiency of 77.32%. The experimental results showed that the enhanced TOC removal from mature landfill leachate by sono-activated persulfate oxidation could be attributed to the combined effects of ultrasonic catalysis and sulfate radical-AOP. Overall, ultrasonic activated persulfate oxidation is a promising method for the pretreatment of landfill leachate.     

固定化漆酶对水中邻苯二胺的去除研究

以壳聚糖为载体,戊二醛为交联剂,采用交联法与吸附法相结合的方法对漆酶进行固定化,研究固定化漆酶在水处理中的应用,并进行了酶促反应的动力学和热力学分析,探讨了戊二醛质量浓度、交联时间、固定化时间以及漆酶质量浓度对固定化漆酶活性的影响。结果表明,漆酶固定化的最佳条件如下:戊二醛质量分数为5%,交联时间为8 h,固定化时间为6.5 h,酶质量浓度为20g/L。此条件下得到的固定化漆酶的比活力达到15 015.4U/g。利用制得的固定化漆酶对水中邻苯二胺进行处理。在最适温度50℃,最适pH=6条件下,利用12000U的固定化漆酶催化处理100mL质量浓度为200mg/L的邻苯二胺溶液,反应6 h后邻苯二胺的去除率达到94.8%。连续5次重复使用固定化漆酶处理邻苯二胺,6 h降解率均在60%以上。用自来水代替蒸馏水配制邻苯二胺溶液时,底物的去除率为55.1%,去除效果明显降低。固定化漆酶处理邻苯二胺反应属于一级反应,反应活化能约为44.1 kJ。     

Ti/SnO2-RuO2-Sb电极电氧化处理五氯苯酚模拟废水研究

采用刷涂-热解法制备了Sb、Ru掺杂的Ti/SnO2电极。通过SEM、EDX、XRD和循环伏安扫描(CV)表征了电极表面形态、组成、结构和电化学性质,并通过正交试验考察了电催化氧化降解五氯苯酚的影响因素。结果表明,各因素对五氯苯酚转化率影响的大小顺序依次为:底物初始质量浓度、反应温度、反应时间、电流密度、初始溶液pH值。在底物质量浓度为50mg.L-1,反应温度50℃,反应时间180min,电流密度40mA.cm-2,溶液初始pH值为8的条件下五氯苯酚的转化率达到97.6%。     

硝酸异辛酯热安定性的实验研究

使用加速量热仪(ARC)研究硝酸异辛酯(EHN)的热分解,得到热分解温度随时间的变化曲线,自放热速率、分解压力随温度的变化曲线以及分解压力随升温速率的变化曲线。分析在绝热条件下硝酸异辛酯的热分解反应动力学和热分解过程,计算表观活化能、指前因子和反应热等参数。根据绝热热分解的起始温度和反应热数据,给出硝酸异辛酯在反应危险度等级中的分类,并计算在75℃时的反应风险指数。