气体临界温度以上吸附平衡的预测研究

采用容积法测定了CH4和N2 在微孔活性炭K0 2上的吸附平衡数据 ,温度为 2 73～ 333K ,压力为 0～12MPa .提出了一个可以从单一气体吸附等温线预测其它条件下吸附平衡的理论模型 .该模型考虑了临界温度以上吸附相密度和饱和吸附量与温度的关系 ,并采用孔径分布来表征吸附剂表面吸附势场的不均一性 ,局部方程使用Langmuir描述 .利用此模型预测了CH4和N2 在K0 2活性炭上的吸附平衡 ,在所研究的温度、压力范围内的整体预测偏差不超过 3% .另外 ,对文献中不同实验条件下气体临界温度以上的吸附平衡进行了研究 ,在较宽的范围内也取得了很好的预测结果     

吸附制冷用复合吸附剂的吸附热

本文推导出由一条吸附等温线和同一吸附质的汽化潜热,计算吸附热的简化模型。对水和乙醇在自制复合吸附剂、13X分子筛、硅胶和活性炭上的吸附热进行了计算;对吸附热与吸附量的关系进行了关联,给出了拟合方程。结果表明:在相同的吸附量条件下,水在复合吸附剂上的积分吸附热比在13X分子筛上低11％～17％;乙醇在复合吸附剂上的积分吸附热较在活性炭上低23％～27％。该研究为吸附制冷系统结构设计提供了计算吸附热的简便算法。     

纸质活性炭纤维的制备及性能表征

通过KOH活化纸巾制备活性炭纤维, 比表面积高达1388 m²/g. 用制得的活性炭纤维作为吸附剂进行亚甲基蓝吸附实验研究,用Langmuir和Freundlich吸附模型分析实验数据,并研究pH值对活性炭纤维吸附亚甲基蓝影响. 活性炭纤维吸附速率更适于Pseudo-second-order动力学模型,相关系数高达0.998. 整个浓度变化区间Langmuir吸附等温线比Freundlich吸附等温线更适合实验数据. 所制备活性炭纤维对亚甲基蓝最大平衡吸附量为520 mg/g,实验发现,pH值越高活性炭纤维对亚甲基蓝吸附量越大.     

CuO掺杂C3N对C5F10O分解组分吸附性能的第一性原理研究

全氟五碳酮（C5F10O）作为可替代SF6的新型环保绝缘气体已被投入到实际应用中. 在绝缘设备内部不可避免的会发生局部放电等故障，造成C5F10O绝缘气体分解产生弱绝缘性能甚至剧毒的分解组分，为保证绝缘设备的安全运行，在不影响气敏传感器正常检测绝缘设备内部故障的情况下，需对这些分解组分进行有选择地吸附去除. 新型类石墨烯C3N材料在气体吸附领域具有良好的应用前景，文中基于第一性原理计算了CuO分子掺杂C3N对主要分解组分CF4、C2F6及剧毒产物CF2O、HF的吸附过程，计算并分析了各分解组分吸附时的吸附能、态密度、电荷转移量、差分电荷密度以及不同环境温度下的恢复时间. 结果表明，CuO-C3N对HF表现出良好的吸附性，CF2O次之，但其无法吸附CF4与C2F6，因此CuO-C3N可以作为一种高性能的气体吸附剂对C5F10O绝缘设备内的剧毒分解组分HF进行吸附去除.     

固化块状活性炭--甲醇的吸附性能实验分析

为提高固体吸附式制冷系统中吸附床的有效传热,本文提出了一种具有较高导热系数和较快吸附速度的固化块状活性炭,并对其物性和吸附性能进行实验研究.针对采用不同材料配比的块状活性炭,测试了活性炭-甲醇在吸附温度35℃,蒸发温度3～5℃条件下的吸附性能曲线,对比分析了粘结剂比例、固化密度及不同的床换热条件对吸附性能的影响,并由此给出了块状活性炭作吸附剂时的合适的粘结剂比例、固化密度、吸附制冷循环中的循环吸附量和循环时间.     

非链式HF激光器能量稳定性影响因素实验研究

为提高非链式电激励脉冲HF激光的能量稳定性,分析了激光产生反应动力学和影响激光能量稳定性的主要因素,得知基态HF分子的生成、工作气体的温度上升以及工作气体C2H6的消耗是激光能量快速下降的主要原因。经实验研究,没有采用任何反应产物去除方法的情况下,激光器输出1600个脉冲激光后,激光能量下降率达31%,采用沸石分子筛吸附单元对基态HF分子进行吸附后,同样输出1600个脉冲激光,激光能量基本趋于平稳状态,且输出约5500个脉冲激光后,激光能量较初始平均值仅有10%的下降;另外,在激光器运行过程中,恢复工作气体的初始温度和补充少量的C2H6也能改善激光能量的稳定性,其中补充25%的C2H6气体可使激光能量提高近8%。由激光产生反应动力学和实验研究结果可知,增加分子筛吸附单元、工作气体温控单元和工作气体实时补给单元可提高激光能量的稳定性。     

BC3复合纳米管的储氢性能研究

采用巨正则蒙特卡罗方法（GCMC）研究了BC3复合纳米管的物理吸附储氢性能,获得了该纳米管在不同温度和压强下的吸附等温线,及其在不同条件下的物理储氢吸附量,并和相应的碳纳米管进行了对比研究。结果表明,BC3纳米管在所有条件下的储氢性能均优于相应的碳纳米管,因而它是一种比碳纳米管更强的氢存储介质,并从纳米管和H2分子以及H2分子和H2分子之间的平均总相互作用能的分布情况等因素出发解释了这两种纳米管有不同储氢行为的原因。     

BC3复合纳米管的储氢性能研究

采用巨正则蒙特卡罗方法(GCMC)研究了BC3复合纳米管的物理吸附储氢性能,获得了该纳米管在不同温度和压强下的吸附等温线,及其在不同条件下的物理储氢吸附量,并和相应的碳纳米管进行了对比研究.结果表明,BC3纳米管在所有条件下的储氢性能均优于相应的碳纳米管,因而它是一种比碳纳米管更强的氢存储介质,并从纳米管和H2分子以及H2分子和H2分子之间的平均总相互作用能的分布情况等因素出发解释了这两种纳米管有不同储氢行为的原因.     

桤木木屑对废水中Hg~（2＋）的静态吸附

研究了未改性、HNO3改性和NaOH改性桤木木屑对水中Hg2＋的吸附特性,并探讨了Hg2＋初始浓度、吸附时间和吸附温度对吸附率的影响。结果表明,在实验条件下,3种木屑对水中Hg2＋均有较好的吸附效果,吸附率可达99%以上。其中,N aOH改性木屑的吸附效果最好,平衡吸附量为3.00μg/g。结果表明,利用N aOH改性桤木木屑制备废水中Hg2＋吸附材料具有很好的应用前景。     

硫化氢在金属-有机骨架材料中吸附与分离的计算模拟

摘 要: 采用优化的DREIDING力场参数,通过巨正则系综蒙特卡洛(GCMC)模拟方法对天然气中的两种气体CH4和H2S在Cu6(BTTC)4(H2O)6·xS (1)和[(CH3)2NH2]3[(Cu4Cl)3(BTTC)8]·yS (2)两种金属有机骨架(MOFs)材料中的吸附与分离性能进行了比较研究.结果证明了聚合物2的吸附量和分离性能相比之下高于聚合物1,且两种材料的吸附机理存在差异,聚合物1中金属Cu和有机基团对于吸附两种气体没有明显的作用,主要分布在小孔道和大孔道;然而聚合物2中H2S和CH4主要吸附在有机基团、金属Cu和-Cl基团周围.则含有-Cl基团的聚合物2展现了优越的吸附能力和稳定性.总而言之,本文获得的结果可以应用于此类研究领域,因此在环境范围中吸附去除污染物可以产生更深层次定性和定量的作用.     

Adsorption isotherms and kinetics of methylene blue on a low-cost adsorbent recovered from a spent catalyst of vinyl acetate synthesis

A regenerated activated carbon used as catalyst support in the synthesis of vinyl acetate has been tested as a low-cost adsorbent for the removal of dyes. After a thorough textural characterization of the regenerated activated carbon, its adsorption isotherms and kinetics were determined using methylene blue as model compound at different initial concentrations. Both Langmuir and Freundlich isotherm models were developed and then compared. It was found that the equilibrium data were best represented by the Langmuir isotherm model. The kinetic data were fitted to pseudo-first-order, pseudo-second-order and intraparticle diffusion models, and it was found that the best fitting corresponded to the pseudo-second-order kinetic model. The results showed that this novel adsorbent had a high adsorption capacity, making it suitable for use in the treatment of methylene blue enriched wastewater.     

Adsorption of aromatic compounds from the biodegradation of azo dyes on activated carbon

The adsorption of three selected aromatic compounds (aniline, sulfanilic acid and benzenesulfonic acid) on activated carbons with different surface chemical properties was investigated at different solution pH. A fairly basic commercial activated carbon was modified by means of chemical treatment with HNO₃, yielding an acid activated carbon. The textural properties of this sample were not significantly changed after the oxidation treatment. Equilibrium isotherms of the selected compounds on the mentioned samples were obtained and the results were discussed in relation to their surface chemistry. The influence of electrostatic and dispersive interactions involved in the uptake of the compounds studied was evaluated. The Freundlich model was used to fit the experimental data. Higher uptakes are attained when the compounds are present in their molecular form. In general, adsorption was disfavoured by the introduction of oxygen-containing groups on the surface of the activated carbon.     

The influence of nonpolar organics adsorption on the electrochemical behaviour of powdered activated carbon electrodes in aqueous electrolytes

Adsorption and electrochemical studies were carried out on three activated carbon samples first oxidized, then heat-treated under vacuum (at 180, 500 and 900 °C). The investigations were performed with aqueous electrolyte (Na₂HPO₄ and H₃PO₄) solutions containing selected nonpolar organics (benzene and n-hexane). Adsorption measurements were carried out on solution with a wide range of organics concentration (up to saturation point). Cyclovoltammetric curves of powdered electrodes prepared from the activated carbon samples were recorded for the organics in saturated solutions. The electric double layer capacities of the anodic and cathodic parts were estimated, and the surface anodic and cathodic charge was calculated both in absence and presence of organics in the electrochemical systems. The relative surface charge (in relation to systems without organics) was found to decrease with a reduction in the concentration of surface oxygen-containing groups. Other physicochemical parameters characterizing the degree of surface oxidation (total oxygen concentration, primary water adsorption centres) were also taken into consideration. The correlation between adsorption capacity towards the nonpolar organic compounds (obtained from adsorption isotherms) and change of surface charge was analyzed.     

Adsorption of molecular gases on porous materials in the SAFT-VR approximation

A simple molecular thermodynamic approach is applied to the study of the adsorption of gases of chain molecules on solid surfaces. We use a model based on the Statistical Associating Fluid Theory for Variable Range (SAFT-VR) potentials [A. Gil-Villegas, A. Galindo, P.J. Whitehead, S.J. Mills, G. Jackson, A.N. Burgess, J. Chem. Phys. 106 (1997) 4168] that we extend by including quasi-two-dimensional approximation to describe the adsorption properties of these types of real gas [A. Martínez, M. Castro, C. McCabe, A. Gil-Villegas, J. Chem. Phys. 126 (2007) 074707]. The model is applied to ethane, ethylene, propane, and carbon dioxide adsorbed on activated carbon and silica gel, which are porous media of significant industrial interest. We show that the adsorption isotherms obtained by means of the present SAFT-VR modeling are in fair agreement with the experimental results provided in the literature.     

Characterization of synthetic carbons activated with phosphoric acid

The structural heterogeneity of synthetic phosphoric acid activated carbons has been analyzed using pore-size distributions (PSDs) obtained from nitrogen at −196 °C and carbon dioxide at 0 °C isotherms. PSDs where obtained by the BET–Kelvin method. It is shown that the BET–Kelvin method is in good agreement with DFT and provides a fast means for assessment of the porous structure of adsorbents. PSDs obtained by the BET–Kelvin method using different adsorbates give results consistent with each other. Due to the restricted pressure range for carbon dioxide adsorption isotherm the PSD gives information only about pores in the micropore range. The agreement between different methods is better for small micropores.     

Removal of naphthalene from petrochemical wastewater streams using carbon nanoporous adsorbent

Ordered mesoporous carbon, OMC, was synthesized using ordered mesoporous silica MCM-48 as hard template, the structural order and textural properties of the synthesized materials were studied by XRD, SEM, and nitrogen adsorption-desorption analysis. Adsorption of naphthalene over various porous adsorbents such as OMC, MCM-48, and commercial activated carbon was studied from solutions with different concentration at ambient temperature (25 ± 2 °C) and pH 7. The adsorption isotherms of naphthalene were in agreement with a Langmuir model, moreover, the uptake capacity of naphthalene followed the order: OMC > commercial activated carbon > mesoporous silica (MCM-48).     

Wettability modification of pitch-based spherical activated carbon by air oxidation and its effects on phenol adsorption

The surface chemistry of pitch-based spherical activated carbon (PSAC) was modified by air oxidation to enhance its wettability as well as adsorption properties. Changes of PSAC after modification in texture, surface chemistry and wettability were studied by different techniques including N₂ adsorption, X-ray photoelectron spectroscopy (XPS) and dynamic contact angle analyzer (DCA). Phenol adsorption characteristics in different solvents on PSAC were also investigated. When PSAC was modified under an atmosphere with 20 vol.% oxygen at 400 and 450 °C for 5 h, surface acidic groups increased from 0.11 to 1.22 and 1.60 meq/g, while basic groups decreased from 0.52 to 0.03 and 0.02 meq/g, respectively. After PSAC was modified, the increase of the oxygen-containing groups, especially carboxylic and phenolic ones, is responsible for the increasing of the surface acidity and the significant improvement of the wettability of PSAC. PSAC with a relatively high oxygen content provided a low adsorption capacity to phenol in aqueous solution, and the adsorption isotherms change from Langmuir class (L) to the S-shaped curve; while the solvent is changed into cyclohexane, all adsorption isotherms are type L, and the adsorption capacity to phenol increases with increasing oxygen-containing groups. Possible reasons, including the solvent effect, π-π dispersion and donor-acceptor interactions are discussed.     

非局域密度泛函理论表征活性炭孔径分布的改进算法

为提高由NLDFT计算值确定活性炭孔径分布(PSD)的精度,根据测得的77K氮在非石墨化碳黑BP460和椰壳活性炭K05上的吸附数据,比较了吸附空间及壁面结构采取不同假设对计算结果的影响。结果表明,常规将活性炭吸附空间近似为无限尺寸的石墨化碳黑表面构成的狭缝孔,并由Lorenz-Berthelot混合法则确定相互作用参数,计算值在较低压力区域和试验值之间的偏差明显;而将吸附壁面结构近似为非石墨化碳黑,并由表面粗糙度和石墨晶格分布的误差函数修正相互作用参数后,计算结果和试验值吻合良好。分析结果时发现,归一化方法和考虑周边吸附质分子作用的加权函数是影响NLDFT计算结果准确性的关键因素。     

碳纳米纤维吸附储氢性能分析

文中综合碳纳米纤维微观结构的表征结果以及氢吸脱附等温线的实验测量结果,对碳纳米纤维的吸附储氢性能进行了综合分析,分析发现:比表面积和中孔容积均与氢吸附量成线性关系;微孔容积对材料吸附性能影响较大,微孔容积与氢吸附量成抛物线关系;氢在常温左右以及77K下的吸附等温线呈现超临界气体的吸附特征,氢在273K和353K下的吸脱附等温线也基本重合,呈现的是物理吸附的特征。实验结果还说明:常温左右,甚至是77K下,碳纳米纤维均不适合于氢的吸附储存。     

ICP-OES研究活性炭无纺布对镉的吸附

重金属污染是一个相当严重的环境问题。镉具有很强的生物毒性和不可降解性,对生态环境和人体健康有极大威胁,被列为优先控制污染物。环境中镉的主要污染源是电镀、采矿和化学工业等部门的废水,如何简单高效去除水中的镉,有重要的社会意义和经济意义。目前,水中重金属的去除方法有化学沉淀、膜分离、离子交换、吸附、电解等,其中吸附法因简单高效而广泛应用。活性炭纤维是一种新型活性炭,孔径小且均匀,表面官能团发达,吸附性能好,逐步应用于水处理领域。以电感耦合等离子体光谱为检测手段,佐以比表面积分析,X射线衍射,元素分析和傅里叶变换红外光谱,研究比较了三种活性炭纤维(纤维炭网、活性炭无纺布、活性炭纤维毡)的结构特点及其对水中镉的吸附性能。三种活性炭纤维结构基本类似,具有较发达的孔隙结构。活性炭无纺布极性较强,表面有丰富的羟基、羧基、醛基等含氧官能团,对水中镉的吸附作用最大。因此,选择活性炭无纺布为吸附剂进行后续实验。研究了活性炭无纺布吸附镉的影响因素,如溶液pH,吸附时间等。溶液pH影响吸附剂表面电荷及水中镉的存在状态。水中镉的去除效率随溶液初始pH的增大而增大,在较低pH时,吸附剂与Cd2+间存在静电斥力,同时H+和Cd2+存在竞争吸附,pH>9时,镉的去除是吸附与沉淀协同作用的结果,选择pH为6～7。在吸附的初始阶段,活性炭无纺布对Cd2+的吸附量迅速增加,10 min时,吸附率达到72%。随着吸附位点逐渐被Cd2+所填充,吸附速率逐渐变慢,300 min时,吸附容量基本无变化,吸附趋于平衡。优化了镉的吸附条件后,进行等温吸附实验和动力学实验。结果表明,25 ℃时,吸附时间为300 min,pH 6.0条件下,当镉的平衡浓度在20.00 mg·L-1时,活性炭无纺布对镉的单位质量吸附量和单位比表面积吸附量分别是3.04 mg·g-1和0.035 mg·m-2。用Langmuir方程(R2=0.997, K_L =1.796 L·mg-1)和Freundich方程(R2=0.895, K_F=0.918 L·mg-1, n=2.12)拟合活性炭无纺布对镉的等温吸附数据,Langmuir方程计算的理论吸附量为3.07 mg·g-1,与实验值相当,并且线性系数更高,说明该体系的吸附符合Langmuir方程,主要为单分子层吸附。Langmuir分离因子介于0和1之间,表明活性炭无纺布对镉的吸附容易进行。用准一级动力学方程、准二级动力学方程、颗粒内扩散方程和Elovich方程四种动力学模型拟合吸附过程。在吸附的前5 min,镉在活性炭无纺布上的吸附符合颗粒内扩散方程(R2=0.985),吸附主要受颗粒内扩散控制。在吸附的5～300 min,颗粒内扩散方程拟合较差。整个吸附过程符合准二级动力学方程(R2=0.999,k₂=0.367 g·mg-1·min-1),Elovich方程(R2=0.981,a=0.271 mg·g-1, b=0.083 mg·g-1·(lg min)-1)和准一级动力学方程(R2=0.927,k₁=0.008 8 min-1)次之,颗粒内扩散方程(R2=0.785)最差。活性炭无纺布对镉的吸附过程是一种化学作用为主的吸附过程。对5.00 mg·L-1含镉水样,活性炭无纺布投放量为10 g·L-1时,吸附后水中镉的浓度小于0.10 mg·L-1,符合《污水综合排放标准》(GB 8978-1996)。活性炭无纺布可同时吸附镉,铜,铅,铬等重金属离子,选择性较差。但在电镀、采矿等实际废水中重金属种类复杂,适当提高吸附剂投放量,可同时去除多种重金属。利用活性炭无纺布吸附处理含镉水样,处理效果好、操作简单,可以作为去除水中镉的吸附剂,为含镉废水的处理提供了技术支持和理论基础。