过一硫酸盐的活化及其降解水中有机污染物机理的研究进展

基于活化过一硫酸盐（PMS）产生SO₄^-·的新型高级氧化技术,在芬顿和类芬顿催化降解水中有机污染物的研究中占有重要地位。本文从活化PMS方法的特点和用途出发,对目前活化PMS的主要方法进行了论述,并对活化PMS降解水中有机污染物的机理进行了探讨,最后对该领域研究中存在的问题进行了分析。指出,开发高效的协同活化PMS的方法将成为该领域研究的必然趋势。     

贵州省三岔河流域水化学特征及其控制因素

对乌江源区三岔河流域枯水期和丰水期河水样品离子浓度及组成特征分析表明,河水主要的阴阳离子分别是HCO_3~–和Ca~(2+),分别占到总阴离子量的55%和总阳离子量的70%,与喀斯特地区流域相似。主要离子的时空分布的对比分析表明,Ca~(2+)、Mg~(2+)、Na~+、HCO_3~–、Cl~–枯水期浓度略高于丰水期,而K+、SO_4~(2–)、NO_3~–两期浓度变化相对较小;空间分布的多样化,反映了不同小流域在地质背景、生态环境、人为活动等方面的差异对河水离子的影响。通过Gibbs图分析表明,研究区河水水化学主要受到岩石风化的影响,通过阴阳离子三角图分析表明,研究区河水水化学主要受到碳酸岩盐的影响,并且硫酸广泛参与到岩石风化中,人为活动对流域水化学组成也有一定影响。     

赣南小流域的水文地球化学特征和主要风化过程

对赣南花岗岩小流域进行采样、测试及分析,发现其河水含有较低的矿化度,水化学组成以Na ,Ca2 ,Cl-1和HCO-3为主,溶解性Si的含量明显较高,代表了典型硅酸盐地区河流的相应化学组成.通过Gibbs图分析,赣南流域大部分地区受大气降水的影响比较显著,"蒸发-浓缩"类型的小流域也较多.根据主成分分析和因子分析的结果,定量地估算了大气中CO2和三类岩石对河水中各种离子的贡献比例.与黄河相比,赣南流域受硅酸盐岩风化作用强烈,但主要影响因素仍是碳酸盐和蒸发盐岩,二者对赣南流域溶解质的贡献率分别为42.8%和29.2%,大气中CO2对河水溶解质的贡献率为21.4%,低于世界平均水平.主要风化反应以岩盐和方解石的溶解为主,Si/(Na* K)比值较低,说明风化反应在表生环境中进行,其产物是富含阳离子的次生矿物.     

用于干式脱污的CaO蒸汽活化实验研究

利用小型活化转炉实验台对以CaO为主要成分的钙基脱污剂在300～650℃的温度范围内进行蒸汽活化处理,结合X射线衍射和压汞仪的分析结果,初步探讨了蒸汽活化的机理.研究表明,蒸汽活化温度在600℃以上时,脱污剂孔隙结构有显著的改善,比孔容积和比表面积有着显著的增加,微孔(＜100nm)的数量大量增加,而低温下蒸汽活化的效果不是十分明显;研究还发现高温下延长活化时间有利于改善脱污剂的孔隙结构.     

Oxidative degradation of phenol by sulfidated zero valent iron under aerobic conditions: The effect of oxalate and tripolyphosphate ligands

After adding either organic or inorganic ligands, sulfidated nano-zero-valent iron (SnZVI) was used for aerobic degradation of phenol, and the effect of the ligand species on oxidation performance was investigated. We found that SnZVI hardly degraded phenol in the absence of ligand addition. Ligands initiated and promoted the degradation of pollutants by SnZVI. The data herein show that a characteristic inorganic ligand, tripolyphosphate (TPP), is more effective in enhancing oxidation than a characteristic organic ligand oxalate. In addition to the scavenging of reactive oxidants by the organic ligand, more ferrous ion (Fe(II)) dissolution from SnZVI in the TPP system is another cause for the superior enhancement by the inorganic ligand. In the oxalate system, as the sulfur content of SnZVI increased, the oxidation efficiency increased because FeS shell promoted the transfer of electrons to produce more reactive oxygen species (ROS). In TPP system, the effect of sulfur content on oxidation performance is more complex. The SnZVI with low sulfur content showed poor oxidation performance compared with that of nZVI. Further experiments proved that sulfidation might weaken the complexation of TPP with surface bound Fe, which would slow down the ionic Fe(II) dissolution rate. Therefore, sulfidation has the dual effects of enhancing electron transfer and inhibiting the complexation of inorganic ligands. In addition, the mechanisms of ROS generation in different ligand systems were investigated herein. Results showed that the critical ROS in both the oxalate and TPP systems are hydroxyl radicals, and that they are produced via one-electron activation of O₂.     

活化后钾改性正硅酸锂吸附CO2的性能评价及动力学研究

制备了钾改性正硅酸锂(K-Li4SiO4),并对其进行了自活化,考察了活化后K-Li4SiO4吸附剂在不同温度和CO2浓度气氛中吸附CO2的性能及动力学行为。总体而言,吸附剂的CO2吸附能力随着温度的升高、CO2浓度的增加而提升。在700℃、100%体积分数CO2气氛中吸附剂的吸附量最大,可达7.9 mmol/g,吸附剂的利用率为95.2%。利用双指数模型能够很好地描述吸附剂在各个温度以及各个CO2浓度气氛下的CO2吸附过程。吸附活化能随着CO2气氛浓度的升高而降低,CO2体积分数为20%,50%,100%时的吸附活化能分别为26448,14035,6178 J/mol。     

Effect of pyrolysis and oxidation characteristics on lauric acid and stearic acid dust explosion hazards

The effect of pyrolysis and oxidation characteristics on the explosion sensitivity and severity parameters, including the minimum ignition energy MIE, minimum ignition temperature MIT, minimum explosion concentration MEC, maximum explosion pressure P_max, maximum rate of pressure rise (dP/dt)_max and deflagration index K_st, of lauric acid and stearic acid dust clouds was experimentally investigated. A synchronous thermal analyser was used to test the particle thermal characteristics. The functional test apparatuses including the 1.2 L Hartmann-tube apparatus, modified Godbert-Greenwald furnace, and 20 L explosion apparatus were used to test the explosion parameters. The results indicated that the rapid and slow weight loss processes of lauric acid dust followed a one-dimensional diffusion model (D1 model) and a 1.5 order chemical reaction model (F1.5 model), respectively. In addition, the rapid and slow weight loss processes of stearic acid followed a 1.5 order chemical reaction model (F1.5 model) and a three-dimensional diffusion model (D3 model), respectively, and the corresponding average apparent activation energy E and pre-exponential factor A were larger than those of lauric acid. The stearic acid dust explosion had higher values of MIE and MIT, which were mainly dependent on the higher pyrolysis and oxidation temperatures and the larger apparent activation energy E determining the slower rate of chemical bond breakage during pyrolysis and oxidation. In contrast, the lauric acid dust explosion had a higher MEC related to a smaller pre-exponential factor A with a lower amount of released reaction heat and a lower heat release rate during pyrolysis and oxidation. Additionally, due to the competition regime of the higher oxidation reaction heat release and greater consumption of oxygen during explosion, the explosion pressure P_m of the stearic acid dust was larger in low concentration ranges and decayed to an even smaller pressure than with lauric acid when the concentration exceeded 500 g/m³. The rate of explosion pressure rise (dP/dt)_m of the stearic acid dust was always larger in the experimental concentration range. The stearic acid dust explosion possessed a higher P_max, (dP/dt)_max and K_st mainly because of a larger pre-exponential factor A related to more active sites participating in the pyrolysis and oxidation reaction. Consequently, the active chemical reaction occurred more violently, and the temperature and overpressure rose faster, indicating a higher explosion hazard class for stearic acid dust.     

肥煤自燃全过程热动力学特征参数研究

实验测定了林西矿肥煤样品30~900℃煤自燃全过程热动力学特征参数,得出:TG/DTG曲线显示煤样DTG初始临界温度45℃,干裂温度122℃,活性温度195℃,增速温度265℃,质量极大值温度342℃,着火温度465℃,最大热失重速率温度515℃和燃尽温度690℃;DSC曲线显示,煤样初始放热温度60℃、最大热释放速率温度511℃。结合TG-DTG-DSC曲线综合分析可知,煤温达到510℃左右时煤样反应最剧烈。由煤自燃标志气体测定实验系统得出:煤温130℃后CO,CO 2释放量迅速增加,210℃增加速度下降;CH 4,C 2 H 6含量变化具有规律性且两者变化相近;C 2 H 4出现温度为130℃;C 2 H 4/C 2 H 6比值在190~350℃有较强的规律性,呈上升趋势且上升速度较快;350℃之后,CH 4,C 2 H 6,C 2 H 4体积分数均开始急剧增大;C 2 H 4/CO与C 2 H 4/CO 2变化趋势大致相同,在130~350℃时缓慢增长,达到350℃后比值呈指数形式上升。经拟合曲线,得到活化能的3个突变点温度:70,180,220℃,其中180℃与交叉点温度相吻合。通过以上研究,得到了肥煤自燃全过程的热力学特征参数,为实际生产中防治煤自燃提供了理论依据。     

硫化废气污泥活性炭净化处理技术研究

以污泥厂剩余活性污泥作为原料,采用KOH为活化剂制备污泥活性炭,探讨了活化温度及时间、热解温度、洗涤温度及方式在污泥活性炭制备过程中的最佳工艺条件。以品红吸附量及产率作为污泥活性炭的考察指标,采用单因素实验筛选出了制备污泥活性炭的最佳工艺条件,并对污泥活性炭脱硫剂的脱硫性能进行了实验研究。实验研究结果显示,烟气中O2、水蒸气含量的多少及脱硫温度的高低会影响污泥活性炭脱硫剂的脱硫性能。     

单轴应力对煤自燃特性参数和导热系数的影响研究

为探究单轴应力作用下煤氧化和传热特性,利用自制荷载加压煤自燃特性参数测定装置对炉体内长焰煤煤样进行程序升温。结合程序升温过程中煤临界温度Tc和Tg,对其进行阶段划分:阶段1为30℃~Tc;阶段2为Tc~Tg。计算了不同单轴应力下2个阶段煤表观活化能和平均耗氧速率。根据能量守恒得出程序升温过程煤导热系数随温度的变化,进一步分析煤导热系数与单轴应力的关系。结果表明:阶段1单轴应力为4 MPa时为临界轴压,煤表观活化能最大,平均耗氧速率最小;阶段2煤表观活化能和平均耗氧速率随单轴应力增大均呈抛物线变化,单轴应力为2.7 MPa时为临界轴压,煤表观活化能最大,平均耗氧速率最小;阶段1和2煤导热系数随温度升高均先减小后增大,并且煤导热系数随单轴应力增大呈三次函数变化。