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。     

磷酸活化植物基活性炭对水溶液中铅的吸附

以棉秆与互花米草为原料,采用磷酸活化法制备了低成本的植物基活性炭,通过静态实验研究了其对重金属铅的吸附性能。结果表明,在活化温度为500℃、活化时间为2 h条件下,制备的棉秆和互花米草活性炭比表面积为1 570m2/g和856 m2/g,含氧酸官能团含量分别为1.43 mmol/g和1.27 mmol/g。在25℃下,两种活性炭对重金属铅的Langmuir最大吸附量分别为119 mg/g和111 mg/g,吸附最佳pH为4.3,吸附平衡符合Freundlich方程,离子交换在吸附过程中发挥了重要作用。     

罐底含油泥热解动力学参数计算方法的优选

在化学反应设计中反应动力学是较重要的因素。为得到更合理的污泥热解动力学参数计算方法,利用热重分析仪,在氮气气氛下对罐底含油污泥的热解特性进行研究。根据热重实验数据,分别采用Coats-Redfern法、Kissinger法、FWO法和Popescu法计算污泥热解动力学参数,并获取罐底泥热解制油的主要阶段(第2阶段)的反应活化能E、频率因子A并分析各种方法反应机理。通过对比不同计算方法得到动力学参数及拟合曲线与实验曲线的相关性,确定了最佳罐底含油污泥热解动力学参数计算方法。研究表明,Popescu法得到罐底泥的热解过程符合Jander方程,活化能E为101.43 kJ/mol,与FWO法得到的91.20 kJ/mol相近,且预测曲线与实验曲线有较好的相关性(0.9816),说明Popescu法计算罐底泥热解动力学参数更合适。     

Phenol depletion by thermally activated peroxydisulfate at 70°C

The ability of thermal activated peroxydisulfate (PS) of mineralizing phenol at 70 °C from contaminated waters is investigated. Phenol in concentrations of 10⁻⁴ to 5 × 10⁻⁴ M is quantitatively depleted by 5 × 10⁻³ to 10⁻² M activated PS in 15 min of reaction. However, mineralization of the organic carbon is not observed. Instead, an insoluble phenol polymer-type product is formed. A reaction mechanism including the formation of phenoxyl radicals and validated by computer simulations is proposed. High molecular weight phenolic products are formed by phenoxyl radical H-abstraction reactions. This is not the case for the room temperature degradation of phenol by sulfate radicals where sulfate addition to the aromatic ring mainly leads to the generation of hydroxycyclohexadienyl radicals leading to hydroxybenzenes and oxidized open chain products. Therefore, a change in the reaction mechanism is observed with increasing temperature, and thermal activation of PS at 70 °C does not lead to the mineralization of phenol. Thus PS activation at 70 °C may be considered a potential method to reduce the load of phenol in polluted waters by polymerization.     

Batch sorption dynamics and equilibrium for the removal of lead ions from aqueous phase using activated carbon developed from coffee residue activated with zinc chloride

Lignocellulosic materials are good precursors for the production of activated carbon. In this work, coffee residue has been used as raw material in the preparation of powder activated carbon by the method of chemical activation with zinc chloride for the sorption of Pb(II) from dilute aqueous solutions.The influence of impregnation ratio (ZnCl₂/coffee residue) on the physical and chemical properties of the prepared carbons was studied in order to optimize this parameter. The optimum experimental condition for preparing predominantly microporous activated carbons with high pore surface area (890 m²/g) and micropore volume (0.772 cm³/g) is an impregnation ratio of 100%. The developed activated carbon shows substantial capability to sorb lead(II) ions from aqueous solutions and for relative impregnation ratios of 75 and 100%, the maximum uptake is practically the same. Thus, 75% represents the optimal impregnation ratio.Batch experiments were conducted to study the effects of the main parameters such as contact time, initial concentration of Pb(II), solution pH, ionic strength and temperature. The maximum uptake of lead(II) at 25 °C was about 63 mg/g of adsorbent at pH 5.8, initial Pb(II) concentration of 10 mg/L, agitation speed of 200 rpm and ionic strength of 0.005 M. The kinetic data were fitted to the models of pseudo-first order and pseudo-second order, and follow closely the pseudo-second order model. Equilibrium sorption isotherms of Pb(II) were analyzed by the Langmuir, Freundlich and Temkin isotherm models. The Freundlich model gives a better fit than the others.Results from this study suggest that activated carbon produced from coffee residue is an effective adsorbent for the removal of lead from aqueous solutions and that ZnCl₂ is a suitable activating agent for the preparation of high-porosity carbons.     

一种新型活性半焦吸附剂的制备及其表面特征分析

对一种原料半焦进行粉碎、筛分,取其中10～20目的颗粒;用去离子水冲洗后高温下烘干至恒重;依次进行HNO3活化、KOH活化和加压水热化学活化,制备出活性半焦吸附剂。经实验证明,该活性半焦吸附剂对甲苯的吸附等温线符合Langmuir模型,其甲苯吸附容量可达207 mg/g,穿透时间由80 min延长至235 min。该活性半焦吸附剂的比表面积为555.56 m2/g,碘值为811.38 mg/g,表面酸碱总量为0.8649 mmol/g,并通过SEM扫描进行了表面微观形态分析。数据表明,经改性后制备出的新型活性半焦对甲苯的去除率明显增加,其表面物化性质也有明显改变,是一种优良的有机废气吸附剂。