酒石酸淋洗过程中土壤重金属解吸动力学特征

采用批处理淋洗的方法,研究了酒石酸淋洗修复张士污灌区土壤过程中镉、铅、铜、锌4种重金属离子解吸动力学特征。结果表明,酒石酸在12h条件下,达到对污染土壤中镉离子的最大去除率,铅、铜、锌3种重金属离子达到最大去除率则需要24h。4种重金属离子的解吸动力学过程可以用Elovich方程很好的描述,说明酒石酸去除重金属离子的过程是一种非均相扩散过程。此外,解吸速率曲线显示,反应初期相同时刻上酒石酸对铅离子的解吸速率最快,其次是铜和锌,最后是镉离子;反应后期同一时刻上铜和锌的解吸速率大于铅和镉。     

Thermal hazard and decomposition kinetics of 1-butyl-2,3-dimethylimidazolium nitrate via TGA/DSC and FTIR

1-Butyl-2,3-dimethylimidazolium nitrate ([Bmmim][NO₃]), a kind of versatile and novel ionic liquids, is widely applied in the modern petrochemical industry. Nevertheless, its thermal hazard safety data at high temperature or thermal disturbance conditions are currently unavailable. Therefore, this study aimed to characterize the thermal risk of [Bmmim][NO₃] through auto-ignition temperature measurements, flash point analysis, thermal gravimetric analysis/differential scanning calorimetry (TGA/DSC), TGA-Fourier transform infrared spectroscopy (TGA-FTIR) and thermal decomposition kinetics analysis. Additionally, [Bmmim][NO₃] was examined using isothermal thermogravimetric analysis at different temperatures (220, 230, 240, 250, 260 and 270 °C). The experimental results show that the flash point of [Bmmim][NO₃] is 305.70 ± 9.30 °C and the auto-ignition temperature is 341.00 ± 21.60 °C with an ignition delay time of 8.6 s. In addition, using the nitrogen atmosphere TGA data to calculate the activation energy according to the Friedman, Kissinger and Flynn-Wall-Ozawa methods, roughly the same results were obtained. Finally, TGA-FTIR results show that [Bmmim][NO₃] produced acetylene, butane, butanol and carbon dioxide during the thermal decomposition process. This study could provide data support and some guidance for the thermal hazard assessment and safety control of [Bmmim][NO₃] during its use and storage.     

废弃印刷线路板熔融盐气化特性:Ⅱ气化反应动力学模型

为评价不同气化方案对印刷线路板熔融盐气化的影响,针对印刷线路板的熔融盐气化反应过程建立了反应动力学模型.模型计算结果表明,气化反应体系首先发生CO、H2和焦炭的氧化反应.生成较大量的CO2和H2O2,此后反应体系内CO2和HO2与焦炭进行氧化还原反应而逐渐减少,在参加反应的焦炭被消耗完全后,反应体系随着水气变换可逆反应的平衡而达到平衡.     

水稻和玉米的热氧化分解特性及几种动力学方法结果的比较

利用热重分析仪在空气气氛、不同的升温速率下对带壳稻谷粉和玉米粒粉进行了热重测试,依据热重实验数据,采用多种热解动力学分析方法计算了水稻和玉米的活化能数值并进行比较,结果表明水稻和玉米的热氧化反应活化能随着转化率出现先增加后降低的趋势,并在转化率为70%左右达到了极大值。     

苯酚的褐煤吸附过程及影响因素分析

以污染物苯酚为研究对象,褐煤作为吸附剂,通过批量实验研究了褐煤对废水中苯酚的吸附特性,考察了褐煤粒径、褐煤投加量、反应温度、反应p H、反应时间对吸附作用的影响,并对吸附过程进行了分析。采用Lagergren动力学方程和拟二级吸附动力学方程分析苯酚吸附过程,结果表明,褐煤对苯酚的吸附动力学曲线更符合拟二级吸附动力学方程,反应初始速率随着苯酚初始浓度的升高而增大,但随着煤粉粒径的增大而减小。颗粒内扩散模型对苯酚的吸附动力学曲线分析结果表明:苯酚在褐煤上的吸附首先经历了速率较快的膜扩散控制阶段,进而经历了吸附较缓慢的颗粒内扩散控制阶段,最后到达吸附平衡,褐煤对苯酚的吸附过程主要受到颗粒内扩散控制。     

Kinetics characteristics of coal low-temperature oxidation in oxygen-depleted air

The longwall gob (mined-out) area is one of the main places that are prone to coal spontaneous combustion and most of the residual coal in it is in oxygen-depleted air as it is a semi-enclosed space. A DSC (Differential scanning calorimetry) test system was designed to accurately test the heat generation of coal oxidation in different oxygen concentration atmosphere, based on which the kinetics parameters (activation energy and pre-exponential factor) of coal low-temperature oxidation in oxygen-depleted air were solved out. The results show that the kinetics parameters present obvious stage features and the lower the oxygen concentration is, the smaller is the difference of the kinetics parameters that in different oxidation stages. When the oxygen concentration is lower than 5% and 3% for jet coal and meagre coal respectively, the kinetics parameters of slow oxidation start to be greater than that of rapid oxidation. Both in the slow oxidation and rapid oxidation stage, with the decrease of oxygen concentration, kinetics parameters present significant decline on the whole while in different oxygen concentration range, the decline rate is different. It's concluded that when assessing the residual coal's self-heating risk, we need to use the corresponding kinetics parameters of coal oxidation in the oxygen concentration of the location where the residual coal is and the safety factor will be greater to only use the kinetics parameters of coal oxidation in slow oxidation stage. This study is of great significance for the assessment and control of the self-heating risk of coal that in different oxygen concentration atmospheres of the longwall gob areas.     

Removal kinetics of phosphorus from synthetic wastewater using basic oxygen furnace slag

Removal kinetics of phosphorus through use of basic oxygen furnace slag (BOF-slag) was investigated through batch experiments. Effects of several parameters such as initial phosphorus concentration, temperature, BOF-slag size, initial pH, and BOF-slag dosage on phosphorus removal kinetics were measured in detail. It was demonstrated that the removal process of phosphorus through BOF-slag followed pseudo-first-order reaction kinetics. The apparent rate constant (k_obs) significantly decreased with increasing initial phosphorus concentration, BOF-slag size, and initial pH, whereas it exhibited an opposite trend with increasing reaction temperature and BOF-slag dosage. A linear dependence of k_obs on total removed phosphorus (TRP) was established with k_obs = (3.51 ± 0.11) × 10^− 4 × TRP. Finally, it was suggested that the Langmuir–Rideal (L–R) or Langmuir–Hinshelwood (L–H) mechanism may be used to describe the removal process of phosphorus using BOF-slag.     

Removal kinetics of phosphorus from synthetic wastewater using basic oxygen furnace slag

Removal kinetics of phosphorus through use of basic oxygen furnace slag(BOF-slag)was investigated through batch experiments. Effects of several parameters such as initial phosphorus concentration, temperature, BOF-slag size, initial p H, and BOF-slag dosage on phosphorus removal kinetics were measured in detail. It was demonstrated that the removal process of phosphorus through BOF-slag followed pseudo-first-order reaction kinetics. The apparent rate constant(kobs) significantly decreased with increasing initial phosphorus concentration, BOF-slag size, and initial p H, whereas it exhibited an opposite trend with increasing reaction temperature and BOF-slag dosage.A linear dependence of kobson total removed phosphorus(TRP) was established with kobs=(3.51 ± 0.11) × 10- 4× TRP. Finally, it was suggested that the Langmuir–Rideal(L–R)or Langmuir–Hinshelwood(L–H) mechanism may be used to describe the removal process of phosphorus using BOF-slag.     

Application of a hydroxylamine nitrate stability model to plutonium purification process equipment

A mathematical model that predicts hydroxylamine nitrate (HAN) (NH₂OH·HNO₃) stability is applied to aqueous solutions containing HAN, nitric acid and plutonium that are used in plutonium purification processes. The model estimates the stability of these solutions with respect to the rapid, hazardous, autocatalytic reaction of HAN with nitric acid that generates heat and gas. It also accounts for reaction kinetics, temperature changes, gas generation rates, solution volumes and flow rates, and distribution of plutonium and nitric acid between aqueous and organic phases. The model is applied to three typical process vessels used in solvent extraction purification of plutonium – a countercurrent aqueous/organic plutonium stripping column, an oxidation column used for HAN and hydrazine destruction, and a plutonium rework tank. Both normal and off-normal process scenarios are modeled. Two of the off-normal scenarios lead to the rapid autocatalytic reaction of HAN with nitric acid where heat and gas are generated and that could lead to damage of the process equipment and/or release of hazardous plutonium solution from the vessel. In these two cases, stationary aqueous solutions containing HAN, Pu(III), and nitric acid were allowed to slowly react until conditions for the autocatalytic reaction were reached.     

厌氧氨氧化工艺脱氮及其污泥形态的研究

为研究厌氧氨氧化工艺对高浓度含氮废水的脱氮性能,在以聚乙烯海绵作为填料的上流式厌氧固定床反应器中利用人工配置高浓度含氮废水进行了实验研究.实验中通过添加充足无机碳源,实现了厌氧氨氧化反应器在总氮浓度900～1 210 mg/L长期稳定的运行,脱氮效率在80％以上,最高氮负荷为5.9 kg/m3·d.结果表明:充足的无机碳源在一定程度上可有效地降低高浓度亚硝氮对厌氧氨氧化菌的抑制作用.通过对污泥性状的研究,明确寻找出污泥上浮的原因所在.通过Stover-Kincannon模型确定系统动力学参数KB和Umax分别为30.2 g/L·d和2L2g/L·d,这将有助于对该厌氧氨氧化系统各控制条件的有效调节和准确设定,也为日后应用于实际工程中提供重要的理论依据.