Remediation of 2,4-dichlorophenol-contaminated groundwater using nano-sized CaO2 in a two-dimensional scale tank

• Nano CaO₂ is evaluated as a remediation agent for 2,4-DCP contaminated groundwater. • 2,4-DCP degradation mechanism by different Fe²⁺ concentration was proposed. • 2,4-DCP was not degraded in the system for solution pH>10. • The 2,4-DCP degradation area is inconsistent with the nano CaO₂ distribution area. This study evaluates the applicability of nano-sized calcium peroxide (CaO₂) as a source of H₂O₂ to remediate 2,4-dichlorophenol (2,4-DCP) contaminated groundwater via the advanced oxidation process (AOP). First, the effect and mechanism of 2,4-DCP degradation by CaO₂ at different Fe concentrations were studied (Fenton reaction). We found that at high Fe concentrations, 2,4-DCP almost completely degrades via primarily the oxidation of •OH within 5 h. At low Fe concentrations, the degradation rate of 2,4-DCP decreased rapidly. The main mechanism was the combined action of •OH and O₂^•−. Without Fe, the 2,4-DCP degradation reached 13.6% in 213 h, primarily via the heterogeneous reaction on the surface of CaO₂. Besides, 2,4-DCP degradation was significantly affected by solution pH. When the solution pH was>10, the degradation was almost completely inhibited. Thus, we adopted a two-dimensional water tank experiment to study the remediation efficiency CaO₂ on the water sample. We noticed that the degradation took place mainly in regions of pH<10 (i.e., CaO₂ distribution area), both upstream and downstream of the tank. After 28 days of treatment, the average 2,4-DCP degradation level was ≈36.5%. Given the inadequacy of the results, we recommend that groundwater remediation using nano CaO₂: (1) a buffer solution should be added to retard the rapid increase in pH, and (2) the nano CaO₂ should be injected copiously in batches to reduce CaO₂ deposition.     

Catalytic activity of noble metal nanoparticles toward hydrodechlorination: influence of catalyst electronic structure and nature of adsorption

In this study, stabilized Pd, Pt and Au nanoparticles were successfully prepared in aqueous phase using sodium carboxymethyl cellulose (CMC) as a capping agent. These metal nanoparticles were then tested for catalytic hydrodechlorination toward two classes of organochlorinated compounds (vinyl polychlorides including trichloroethylene (TCE), tetrachloroethylene (PCE), and alkyl polychlorides including 1,1,1-trichloroethane (1,1,1-TCA), and 1,1,1,2-tetrachloroethane (1,1,1,2-TeCA)) to determine the rate-limiting steps and to explore the reaction mechanisms. The surface area normalized reaction rate constant, k_SA, showed a systematic dependence on the electronic structure (the density of states at the Fermi level) of the metals, suggesting that adsorption of organochlorinated reactants on the metal catalyst surfaces is the rate-limiting step for catalytic hydrodechlorination. Hydrodechlorination rates of 1,1,1-TCA and 1,1,1,2-TeCA agreed with the bond strength of the first (weakest) dissociated C-Cl bond, suggesting that C-Cl bond cleavage, which is the first step for dissociative adsorption of the alkyl polychlorides, controlled the catalytic hydrodechlorination rate. However, hydrodechlorination rates of TCE and PCE correlated with the adsorption energies of their molecular (non-dissociative) adsorption on the noble metals rather than with the first C-Cl bond strength, suggesting that molecular adsorption governs the reaction rate for hydrodechlorination of the vinyl polychlorides.     

填埋场产气规律的模型预测

垃圾填埋产气率预测对于评估填埋场能源气体产生潜力,确定填埋气体利用方式极为关键. 通过对南京水阁垃圾填埋场的现场取样、抽气试验及工程运行等数据的分析,讨论了对于填埋气体产生的两步一级反应耦合模型的求解方法;建立了基于有机物分解数据和现场抽气试验数据的2类求解途径,并对各自的适用范围进行了分析;给出了最大产气率、最大产气率发生时间和最大产气率发生时已产气量的解析解,其中最大产气率与反应速率常数(K)和总产气量(L0)有关,最大产气率发生时间仅与K有关,而最大产气率发生时的已产气量占总产气量的比率为常数,与反应介质、反应条件等均无关. 结果表明,填埋气体两步一级反应耦合模型的预测结果与实测结果较吻合.      

酸性废水处理试验研究

精细化工厂生产过程中排放酸性废水,盐化工厂产生碱性盐泥,可用之中和酸性废水。用两种方案确定反应比例关系。经过讨论建议选用方案二为实际应用方案。     

光合细菌与酵母跨界融合(杂合)子发酵味精废水研究

光合细菌球形红假单胞菌（Ｒｈｏｄｏｐｓｅｕｄｏｍｏｎａｓ ｓｐｈａｅｒｏｉｄｅｓ）酿酒酵母（Ｓａｃｃｈａｒｏｍｙｃｅｓ ｃｅｒｅｖｉｓｉａｅ）细胞分别经溶菌酶和蜗牛酶脱壁形成原生质体，在聚乙二醇（ＰＥＧ）和Ｃａ＾２＋诱导下实现了真核与原核细胞的超远缘杂交，经抗菌素培养基初步鉴定，融合产物能同时在含有链霉素和制霉菌素的培养基中生长，而双亲细胞只能在含有单一抗菌素的培养基中生长，经初筛与得获得高絮弟性     

颗粒活性炭吸附染料的类分形动力学特征的研究

建立了复杂分子吸附反应时指数h与分形子谱维数ds、分形介质的表面分形维数Ds 的关系式.对吸附动力学数据的模拟表明,不同温度下6种染料在颗粒活性炭表面的吸附过程符合非线性动力学.吸附速率一般随着温度的升高而增加,反应活化能在0 2 0～1 75kJ·mol- 1 之间.上述反应为快速反应.进一步分析表明,该吸附过程具有类分形动力学特征,吸附反应的逐时速率系数k与反应时间t呈指数关系;相应的分形子谱维数ds<2 .随着染料的初始浓度的增加,ds 也随之增加,而h和k0 值通常会随之降低.吸附3种酸性染料时,h和k0 值在本实验的温度范围内均随着温度的升高而增加;其它3种直接性染料也大都呈现h随着温度的升高而增加的趋势.上述吸附反应中有效反应级数x也与ds、Ds 有关,呈现分数反应级数     

京津冀城市群冬季二次PM2.5的时空分布特征

二次组分是造成京津冀城市群冬季PM_2.5污染的重要因素.采用CO示踪法,估算2017～2021年冬季京津冀城市群二次PM_2.5浓度,并分析其时空分布特征,探讨区域二次PM_2.5的影响因素.结果表明,2017～2021年冬季京津冀区域PM_2.5浓度下降趋势明显,河北中南部一次PM_2.5下降幅度最大,二次PM_2.5浓度年际波动平稳,北京和天津二次PM_2.5占比明显高于其他城市.随着污染程度加剧,一次PM_2.5和二次PM_2.5质量浓度均有不同程度的增加,二次PM_2.5占比呈显著增大趋势.与直接测量结果相比,CO示踪法获得的结果偏低,与冬季CO浓度较高,一次PM_2.5浓度高估有关,选取合适的一次气溶胶基准值是改进该方法,获取合理估算值的关键.     

Hazard evaluation for chlorination and amination reactions of fluorocytosine production process

Reaction thermal runaway is one of the most important reasons leading to chemical accidents. With the rapid development of the chemical industry in the world, especially the fine chemical industry, various safety accidents also occur frequently. Therefore, it is necessary to study the exothermic behavior of the reaction process. In this study, reaction calorimeter was used to study the exothermic phenomena during the chlorination reaction and amination reaction. Differential scanning calorimetry was performed on the reactants, and thermogravimetric experiments were performed on the products. In addition, adiabatic experiment was performed to study the thermal runaway behavior of amination products under adiabatic conditions. The results showed that the target reactions generated a large amount of heat in the initial stage. The maximum temperature of amination reaction is higher than the initial decomposition temperature of the amination product under adiabatic condition. The pyrolysis of amination product was divided into three stages. The product had a high apparent activation energy at the beginning of decomposition, and the apparent activation energy decreased as the decomposition progressed.     

抛光铝粉爆炸及ABC粉体抑爆特性的实验研究

为研究抛光铝粉的爆炸危险和ABC粉体的抑爆特性,在对实验粉体粒径分布进行分析的基础上,采用20 L粉尘爆炸特性实验装置,分别对不同铝粉尘浓度、不同抑爆剂浓度条件下的爆炸特性参数进行测试。研究结果表明:在实验条件下,铝粉的爆炸下限为45 g/m3＜C＜60 g/m3;随铝粉浓度增加,爆炸烈度呈现出先增强后减弱的变化趋势,在浓度为400 g/m3时爆炸烈度最大。ABC抑爆剂能够有效抑制铝粉爆炸超压和爆炸反应进程,随着惰性粉体浓度的增加,抑制效果愈加明显,爆炸逐渐减弱。当ABC惰性粉体的质量占比增加到50%时,相较单一铝粉爆炸,反应过程时间由72 ms增加至785 ms,爆炸最大压力、最大压力上升速率分别下降了61.7%,89.5%;当ABC粉体质量占比为53%时,铝粉被完全惰化,未发生爆炸。     

影响大气汞化学过程的敏感因子分析

为了分析汞在大气中的化学行为,在一个化学模式中加入汞的气相、气液平衡和液相反应,模拟大气汞及其化合物的演变规律,并分析了气象因子(云、光解率、温度)和化学因子(气态O3、H2O2、HO2、OH和气态零价汞Hg0(g))的初始体积分数对各形态汞及其化合物浓度和Hg0(g)转化率的影响.模拟结果表明,在中等大气污染条件下,Hg0(g)的每小时平均转化率为2.91%.敏感性试验结果表明,云量、光解率、温度、O3和Hg0(g)的初始体积分数对不同形态汞的影响较为显著.云量的增加、光解率的增加、臭氧初始体积分数的升高,各形态汞的平衡时间缩短,除气态氧化汞和一价汞离子外,其他形态汞的平衡浓度均会降低,Hg0(g)的转化率增加.温度增加将抑制Hg0(g)的转化.Hg0(g)的初始体积分数增加,各形态汞的浓度升高,但其平均转化率没有显著变化.不同因子对汞化学过程的相对作用对区域或全球大气汞的环境模拟具有指导意义.