矿用润湿型压裂液的制备与性能分析*

为有效减少煤矿开采时粉尘的生成量,降低综采区粉尘含量。基于自由基聚合和季铵化反应制备1种润湿型压裂液。通过单因素实验,确定最优配比是200 mL水,5 g油酸,0.3 g过硫酸钾,3 g N,N′-亚甲基双丙烯酰胺,2 mL环氧氯丙烷,2 g氯化钾和2 g水杨酸钠。对压裂液的反应过程、微观结构、剪切黏度、剪切稳定性、滤失性、润湿型性和清洁性进行研究。研究结果表明:该压裂液具有较高的剪切黏度和较佳的剪切稳定性,有利于注入煤层;具有较低的滤失性,便于压裂造缝;具有良好的润湿能力,能够有效地渗透到煤层中去;具有残渣含量少等特点,清洁性良好。     

稀土对植物抗逆作用的自由基机制

通过研究及收集的资料，提出在植物生长期中，稀土元素能增加植物的抗逆性，当植物受到酸雨、重金属及盐胁迫时，稀土表现出抗氧化性质，而且稀土对植物的抗逆作用是由于其具有清除含氧自由基的作用。     

Effects of copper chloride on formation of polychlorinated dibenzo-p-dioxins in model waste incineration

Combustion experiments in a laboratory-scale fluidized-bed reactor were conducted to elucidate the effects of copper chloride as a catalyst on polychlorinated dibenzo-p-dioxins (PCDDs) formation in municipal waste incineration. We used model wastes with and without copper chloride (CuCl₂ · 2H₂O), both of which contained polyvinyl chloride as a chlorine source. Combustion temperature was set to 900 °C, and the amount of air supplied was twice the stoichiometric ratio. The experimental setup was carefully planned to suppress the influences of experimental conditions except the waste composition. Results of these experiments showed that copper chloride in the waste increased the amount of PCDDs formed and made the homologue profile to shift towards the highly chlorinated species. Copper chloride contributes to the PCDDs formation by promoting chlorination, whereby the reaction is important in that organic matter is chlorinated directly by copper compounds. Copper chloride did not exert a great influence on the isomer distribution patterns of PCDDs, while there appeared a significant difference in the case of PCDFs. This points out the difference of the major formation mechanisms between PCDDs and PCDFs. PCDDs are less formed by the catalytic reactions from carbon/polycyclic aromatic hydrocarbons than PCDFs in our experimental conditions.     

Calorimetric behaviors of hydroxylamine and its salts caused by Fe(III)

The objective of this study is to obtain information on the calorimetric behaviors of aqueous solutions of hydroxylamine (HA), hydroxylamine chloride (HACl), and hydroxylamine nitrate(HAN) caused by different Fe(III) states (free Fe(III) from Fe(NH₄)(SO₄)₂, Fe(CN)₆³⁻, and Fe(EDTA)⁻). The calorimetric data were obtained with a small-scaled reaction calorimeter, Super-CRC.

In the mixing with Fe(III), HA showed the highest reactivity among three substrates. Free Fe(III) and Fe(EDTA)⁻ showed catalytic effects in the reactions. In the overall heat of reactions, Fe(EDTA)⁻ exceeded free Fe(III), which precipitated as Fe(OH)₃ and decreased the chances of interactions with HA. It was suggested that the generation of NH₃ had taken place in the process of reducing HA along with Fe(II) oxidation. Fe(CN)₆³⁻ was less reactive than free Fe(III) and Fe(EDTA)⁻.

The ability of masking Fe(III) was estimated for CyDTA. The HA including CyDTA had no exothermic peak; however, there was an endothermic peak of the heat flow at Fe(III) injection. CyDTA was found to have the ability to inhibit a violent exothermic reaction of HA.     

电化学氧化除氨氮过程中羟基自由基及中间产物定量分析

采用高效液相色谱对电化学氧化除氨氮过程,不同电流密度,Cl-浓度及初始pH值的·OH进行定量检测和分析,同时,对不同初始pH值和电流密度下,电化学氧化除氨氮的中间产物进行了定量分析,结果表明:·OH产生量与电流密度成正比,当有Cl-存在,且在碱性条件下会抑制·OH的产生;初始pH值为偏碱性时,NO2-和氯胺的产量均有所增加.建议电化学氧化脱氨氮过程,尽量保持溶液pH值在中性或酸性条件下;电流密度对氨氮电化学氧化过程中各中间产物的量有着较大影响,在电流密度为10mA/cm2时,活性物质产量最高,且有害中间产物产量最低.     

不同来源腐殖酸对三价锑的光氧化作用及影响因素

三价锑是有毒金属锑生物地球化学循环中的不稳定还原态,其在腐殖酸体系中的光氧化过程可能是水体环境中Sb（Ⅲ）转化的重要途径.通过室内模拟实验,探讨了光照条件下不同来源腐殖酸对Sb（Ⅲ）的光氧化反应特征,并考察腐殖酸浓度、Sb（Ⅲ）初始浓度、溶液pH值、环境中普遍存在的阴阳离子等环境因素对光氧化作用的影响.结果表明：Sb（Ⅲ）在腐殖酸溶液中的光化学反应过程符合准一级动力学规律.反应体系中腐殖酸浓度的升高有利于促进Sb（Ⅲ）的光氧化作用,而Sb（Ⅲ）初始浓度增加则抑制其光氧化作用,Sb（Ⅲ）的光氧化速率常数随溶液pH值的升高而逐渐增大,褐煤来源腐殖酸对Sb（Ⅲ）的光氧化速率常数高于土壤来源腐殖酸.水环境中NO₃^-的存在促进了腐殖酸对Sb（Ⅲ）的光氧化作用,而Cl^-、SO₄^2-和Na⁺未对Sb（Ⅲ）的光氧化作用产生显著影响.羟基和超氧自由基是Sb（Ⅲ）光氧化反应中的主要活性基团,其中在酸性条件下,羟基自由基对Sb（Ⅲ）的光氧化反应起主导作用,而在中性和碱性条件下超氧自由基起主要作用.     

基于详细化学动力学的甲烷热着火影响因素分析

利用化学动力学软件CHEMKIN4.1,在不同初始温度、浓度、湿度和压强下,对甲烷热着火进行了详细化学动力学 模拟。通过对主要组分摩尔浓度分析和温度敏感性分析,得到了甲烷热着火过程的主要基元反应和引发热着火发生的主 要原因。通过对甲烷热着火的延迟时间、热着火发生后主要生成物摩尔浓度和反应后的温度的对比分析,揭示了初始浓 度、湿度和压强对甲烷热着火的影响规律。本研究可以为甲烷为主的气体如瓦斯、天然气等可燃气体的燃烧和爆炸提供 理论支撑,从而有效利用这些可燃气体,降低灾害的发生。     

沼液中溶解游离氨基酸的测定——柱前衍生-反相高效液相色谱法

针对沼液特点开发pH值调节（pH 10.2）旋蒸浓缩（去除氨氮和挥发性生物胺）联合3K Millipore超滤离心分离的预处理方法.并以邻苯二甲醛（OPA）和氯甲酸芴甲酯（FMOC-Cl）为柱前衍生化试剂,结合反向高效液相色谱和荧光检测分析,对沼液中溶解游离氨基酸（DFAA）进行了定性和定量考察.该方法保证了各氨基酸在一定浓度范围内呈现良好的线性关系（R²均大于0.99）,标准样品中所选用的24种氨基酸,除谷氨酸回收率为70.5%外,其它氨基酸回收率为89%～115%,相对标准偏差为1.1%～5.0%.用所建立的方法对样品中溶解游离氨基酸的测定结果为：原料即剩余污泥中的溶解游离氨基酸量为2.0mol/L,5%和20%含固率反应器的沼液中的溶解游离氨基酸量分别为0.04mol/L和1.94mol/L,且种类不同,初步表明了不同厌氧消化反应系统中氨基酸的利用和产生机制的差异.     

Degradation of carbon tetrachloride in thermally activated persulfate system in the presence of formic acid

The thermally activated persulfate (PS) degradation of carbon tetrachloride (CT) in the presence of formic acid (FA) was investigated. The results indicated that CT degradation followed a zero order kinetic model, and CO ₂ ^– · was responsible for the degradation of CT confirmed by radical scavenger tests. CT degradation rate increased with increasing PS or FA dosage, and the initial CT had no effect on CT degradation rate. However, the initial solution pH had effect on the degradation of CT, and the best CT degradation occurred at initial pH 6. Cl^– had a negative effect on CT degradation, and high concentration of Cl^– displayed much strong inhibition. Ten mmol·L^–1HCO ₃ ^– promoted CT degradation, while 100 mmol·L^–1NO ₃ ^– inhibited the degradation of CT, but SO ₄ ^2– promoted CT degradation in the presence of FA. The measured Cl–concentration released into solution along with CT degradation was 75.8% of the total theoretical dechlorination yield, but no chlorinated intermediates were detected. The split of C-Cl was proposed as the possible reaction pathways in CT degradation. In conclusion, this study strongly demonstrated that the thermally activated PS system in the presence of FA is a promising technique in in situ chemical oxidation (ISCO) remediation for CT contaminated site.     

Enhanced degradation of trichloroethene by calcium peroxide activated with Fe(III) in the presence of citric acid

Trichloroethene (TCE) degradation by Fe(III)-activated calcium peroxide (CP) in the presence of citric acid (CA) in aqueous solution was investigated. The results demonstrated that the presence of CA enhanced TCE degradation significantly by increasing the concentration of soluble Fe(III) and promoting H₂O₂ generation. The generation of HO? and O₂^-? in both the CP/Fe(III) and CP/Fe(III)/CA systems was confirmed with chemical probes. The results of radical scavenging tests showed that TCE degradation was due predominantly to direct oxidation by HO?, while O₂^-? strengthened the generation of HO? by promoting Fe(III) transformation in the CP/Fe(III)/CA system. Acidic pH conditions were favorable for TCE degradation, and the TCE degradation rate decreased with increasing pH. The presence of Cl^-, HCO₃^-, and humic acid (HA) inhibited TCE degradation to different extents for the CP/Fe(III)/CA system. Analysis of Cl^- production suggested that TCE degradation in the CP/Fe(III)/CA system occurred through a dechlorination process. In summary, this study provided detailed information for the application of CA-enhanced Fe(III)-activated calcium peroxide for treating TCE contaminated groundwater.