Comparison of the adsorption dynamics of air on zeolite 5A and carbon molecular sieve beds

Adsorption and desorption in zeolite 5A and CMS beds were compared by using a ternary mixture (N₂/ O₂/Ar; 78 : 21 : 1 vol%). Because the breakthrough curves for both beds show a tail by temperature variance, a non-isothermal mathematical model was applied to the simulation of adsorption dynamics. The LDF model with a constant rate parameter was enough to predict the experimental breakthrough and temperature curves of an equilibrium separation bed, while the modified LDF model with a concentration-dependent parameter should be applied to a kinetic separation bed. In the CMS bed initially saturated with He, Ar was the first breakthrough component with N₂ following after a short interval. Then, after a long interval, the breakthrough of O₂ occurred with a broad roll-up due to its fast diffusion rate and the relatively slow diffusion rate of N₂. In the CMS bed initially saturated with O₂, the breakthrough curves of O₂ and N₂ showed a very broad shape because of the slow diffusion of N₂ into CMS. In the zeolite 5A bed, the breakthrough time sequence was Ar, O₂, and N₂ at very close time intervals. After the sharp roll-ups of O2 and Ar, the variation of the breakthrough curves was negligible. The inflection of the temperature profile in the zeolite 5A bed was caused by the crossover of the O₂ and N₂MTZs, while in the CMS bed it was caused by the difference in the diffusion rates of O₂ and N₂.     

发泡剂对沸石分子筛吸附/脱附性能的影响

采用XRD和SEM等手段分别测定了添加发泡剂处理前后的13X沸石分子筛的晶体结构和微观形貌的变化,并用容量法考察了发泡处理对13X沸石分子筛-乙醇吸附/脱附性能的影响.发现在空气氛围中,500℃下对13X沸石分子筛进行发泡处理,能提高沸石的渗透性,而并不破坏其晶体结构.     

Adsorption equilibrium and kinetics of H2O on zeolite 13x

The adsorption characteristics of H₂O on zeolite 13X were measured by a gravimetric method. The adsorption isotherm showed type II isotherm and was fitted by using both the excess surface work (ESW) model and Langmuir-Freundlich model. The results predicted by the Langmuir-Freundlich model were much smaller than the experimental results at higher-pressure region. However, the ESW model agreed well with the experimental data over the whole pressure region. In this case, a plot of the change in chemical potential versus the amount adsorbed gave two linear regions due to secondary effects such as capillary condensation. The experimental uptake curves were well fitted by several LDF models and solid diffusion model with the error range of 1.5-3.5%. Unlike the expectation that the more rigorous solid diffusion model would fit better, Nakao-Suzuki model showed the best agreement with experimental uptake data.     

A study on the thermal behavior of low silica X-type zeolite ion-exchanged with alkaline earth cations

Pure and high crystalline low silica X-type zeolite with Si/Al ratio of 1 was synthesized under specific hydrothermal conditions. After preparation and characterization of Na form of the zeolite (Na-LSX) from the synthesized zeolite, Na cations were exchanged by three alkaline earth cations. The amount of the exchanged cations per 1 g of the zeolite for each cation was determined by wet chemical method. Among the various prepared samples, those containing approximately equal amount of different cations were selected and characterized by XRD, IR, and XRF techniques. TGA/DTG/DTA and XRD techniques were employed to investigate thermal behavior of the cation exchanged zeolites.     

AgCo13X改性分子筛的制备与吸附脱硫性能

采用液相离子交换法制备了以金属离子Co2+和Ag+共同改性的AgCo13X分子筛吸附剂,并用XRD、NH3-TPD、BET和TG等技术对其结构进行表征。在模拟柴油中考察了吸附剂对二苯并噻吩(DBT)的脱硫性能。结果表明:AgCo13X分子筛的脱硫性能优于单一离子改性的Co13X和Ag13X分子筛;而Co13X和Ag13X分子筛的脱硫性能又明显高于未改性的13X分子筛。当Ag+离子交换浓度为0.1 mol/L时制备的Co2+和Ag+共同改性的AgCo13X分子筛具有最好的脱硫性能,其脱硫率为99.91%。剂油比为0.02 g/mL,当吸附时间为1 h即可达到吸附平衡;吸附剂具有良好的稳定性和再生性,再生后的脱硫率达到98.21%。     

Effects of zeolite structure and aluminum content on thiophene adsorption, desorption, and surface reactions

The adsorption and desorption of thiophene and the reactions of thiophene-derived adsorbed species in He, H₂, and O₂ were examined on H-ZSM5, H-Beta, and H-Y with varying Si/Al ratios. Thiophene adsorption uptakes (per Al) were independent of Al content, but were above unity and influenced by zeolite structure (1.7, 2.2, and 2.9 on H-ZSM5, H-Beta, and H-Y). These data indicate that thiophene oligomers form during adsorption and that their size depends on spatial constraints within zeolite channels. Adsorption and oligomerization occur on Brønsted acid sites at 363 K. Thiophene/toluene adsorption from their mixtures show significant thiophene selectivity ratios (10.3, 7.9, and 6.4, for H-ZSM5, H-Beta, and H-Y zeolites), which exceed those expected from van der Waals interactions and reflect specific interactions with Brønsted acid sites and formation of toluene–thiophene reaction products. Treatment of thiophene-derived adsorbed species above 363 K in He or H₂ led to depolymerization of thiophene oligomers and to the formation of unsaturated adsorbed species with a 1:1 thiophene/Al stoichiometry on all zeolites and at all Si/Al ratios. These unsaturated species desorb as stable molecules, such as H₂S, hydrocarbons, and larger organosulfur compounds, formed via ring opening and hydrogen transfer from H₂ or co-adsorbed species, and also form stranded unsaturated organic deposits. Smaller channels and higher Al contents preferentially formed H₂S, benzotiophenes, and arene products during treatment in He or H₂, as a result of diffusion-enhanced of secondary reactions of desorbed thiophene molecules with adsorbed thiophene-derived species. Only oxidative regeneration treatments led to full recovery of thiophene uptake capacities. A preceding treatment in H₂, however, led to the partial recovery of thiophene-derived carbon atoms as useful hydrocarbons and decreased the amount of CO₂ and SO₂ formed during subsequent oxidative treatments required for regeneration.     

载金属离子的13X分子筛对噻吩的吸附性能研究

采用Zn2+,Cu2+,N i2+,Ag+分别负载到13X分子筛制得吸附剂,考察了它们对噻吩的吸附能力,发现Ag+-13X吸附效果最好,与软硬酸碱理论解释的结果一致。测定了噻吩在Ag+-13X上的吸附动力学数据,并测定了其不同温度下的吸附平衡数据,采用Langmu ir模型进行拟合,与平衡数据吻合得很好,说明Langmu ir模型能够描述本体系的特征,从微观上探讨了其吸附机理,是分子尺寸和化学键的共同作用;考察了Ag+-13X对真实汽油的脱硫性能,结果表明对汽油中的噻吩类硫化物都有脱除效果,为其工业设计提供基础数据。     

Cu+-13X上噻吩与苯并噻吩的竞争吸附

以噻吩(TP)、苯并噻吩(BT)和正己烷配制模拟汽油,就如何提高Cu+-13X分子筛对噻吩的选择性进行了一系列的静态吸附及动力学吸附研究。结果表明:增加模拟汽油中噻吩的初始质量分数,可以增大Cu+-13X对噻吩的吸附量,提高噻吩对苯并噻吩的竞争吸附性能。当模拟汽油中苯并噻吩、噻吩的初始质量分数分别为500,700μg/g时,Cu+-13X对噻吩的吸附量就大于苯并噻吩;当模拟汽油中苯并噻吩、噻吩的初始质量分数分别为350,850μg/g时,Cu+-13X对噻吩的选择性大于苯并噻吩,噻吩在竞争吸附中占优势。     

超声法制备Ce^4＋/13X分子筛的吸附脱硫性能

采用在离子交换过程中引入超声的方法制备了Ce4 /13X分子筛,考察了超声法对分子筛的制备及脱硫性能的影响,并考察了静态吸附条件对Ce4 /13X在低硫模型汽油(硫含量为23 mg/kg)中的脱硫性能影响。结果表明,超声法可显著缩短分子筛离子交换平衡的时间,提高离子交换度,且能有效地提高活性组分Ce在分子筛表面的含量,脱硫实验结果也显示吸附容量有明显的提高。常温常压,吸附时间为2.5 h,剂油质量比为0.0072的条件下,Ce4 /13X对噻吩的脱硫效果最好,吸附量为0.07653mmol/g,脱硫率可达到76.5%。Freundlich等温式能很好地关联噻吩在Ce4 /13X上的吸附平衡数据。450℃空气气氛中焙烧4 h的方法,可较好地再生Ce4 /13X。     

噻吩在Cu+-13X上吸附平衡和动态数据测定

对噻吩在Cu -13X分子筛上的吸附平衡和动态数据进行了测定。对噻吩的吸附平衡数据用Langmuir模型进行拟合,得到了303、323 K下噻吩在Cu -13X上的饱和吸附量分别为232.86、74.78 mg/g;采用固定床测定了不同停留时间及不同初始浓度下的动态透过曲线,结果表明,在透过点以前动态吸附可以实现噻吩的零含量,缩短停留时间和增加初始浓度会影响吸附的透过曲线,实验结果为吸附工艺设计提供了一定的基础数据。     

载铜13X的制备及其对噻吩的吸附动力学

研究了载铜13X的制备以及吸附噻吩的动力学性能.实验考察了负载溶液、还原时间、还原温度以及预处理等方面对吸附剂制备的影响,得到了制备载铜13X吸附剂所需要的最优化条件.采用Crank单孔模型对测定的吸附动力学数据进行拟合,确定了不同温度下的噻吩在载铜13X上的扩散系数.实验结果表明,Crank单孔模型可很好地描述噻吩在载铜13X分子筛上的吸附过程.     

13X沸石吸附处理水中苯胺的性能及应用

用天然岩石矿物为原料,经过较简单的工艺过程合成13X沸石去除水中苯胺,模拟废水的实验结果表明：沸石对苯胺的吸附速率非常快,吸附时间为10min时,吸附基本达饱和;一般当沸石用量为10g/L时,水蝇苯胺的吸附率达95％,随着pH值的增加,苯胺在沸石上的吸附率较小;温度增加,吸附率有所增加。但常温下,苯胺的吸附率也能达到93％,13X沸石对苯胺的最大吸附量可达10mg/g,其吸附规律较好地符合Freundlich吸附等温式,饱和了苯胺的沸石,用质量分数为20％,温度为60℃的氯化钠溶液洗脱,解吸率近于100％,且解吸后的沸石在未经任何处理的情况下仍能吸附苯胺;对实际苯胺废水的处理结果,也表明13X沸石不仅可有效地去除苯胺,还可以有效地去除废水中的SS,CODCr,氨氮及油等。     

Polymer nanocomposites using zinc aluminum and magnesium aluminum oleate layered double hydroxides: Effects of LDH divalent metals on dispersion, thermal, mechanical and fire performance in various polymers

Oleate-containing layered double hydroxides of zinc aluminum (ZnAl) and magnesium aluminum (MgAl) were used to prepare nanocomposites of polyethylene, poly(ethylene-co-butyl acrylate) and poly(methyl methacrylate). The additives and/or their polymer composites were characterized by X-ray diffraction, FTIR, elemental analysis, thermogravimetric analysis, mechanical testing, and cone calorimetry. The unusual packing of the monounsaturated oleate anions in the gallery of these LDHs facilitates the dispersion of these nanomaterials. The inorganic LDH protects the polymer from thermal oxidation, shown by enhancement of the thermal and fire properties of the corresponding polymer nanocomposites. There is a qualitative difference in the morphology of the two LDHs in PE and PMMA. ZnAl is better dispersed in PE while MgAl is better dispersed in PMMA. The zinc-containing material led to a large reduction in the peak heat release rate in polyethylene, while the magnesium-containing material led to enhancement of the fire properties of the more polar poly(methyl methacrylate). These fire properties are consistent with the morphological differences. Neither of these LDHs shows efficacy with poly(ethylene-co-butyl acrylate), which indicates a selective interaction between the LDH and the various polymers.     

稀土元素Ce对硫化物在Cu~+-13X上动态竞争吸附的影响

采用液相离子交换法制备了Cu+-13X及负载稀土元素Ce的Ce/Cu+-13X分子筛吸附剂。采用固定床动态吸附实验考察了Ce/Cu+-13X对2,5-二甲基噻吩、苯并噻吩动态吸附性能。研究结果表明,稀土元素Ce的引入可以促进Cu+-13X对2,5-二甲基噻吩和苯并噻吩的吸附性能,同时减弱竞争吸附。在床层高度为16 cm、进样速度为16 mL/h、停留时间为30 min时,效果最佳。     

In situ growth of layered double hydroxide films on anodic aluminum oxide/aluminum and its catalytic feature in aldol condensation of acetone

Mg/Al layered double hydroxide (LDH) films were fabricated in situ with anodic aluminum oxide (AAO)/aluminum as both the substrate and the sole aluminum source by means of urea hydrolysis. The structure and morphology of the LDH films were investigated by X-ray diffraction (XRD), attenuated total reflectance-Fourier transform infrared (ATR-FT-IR) and scanning electron microscopy (SEM), which show that hexagonal plate-shaped LDH crystallites grow perpendicularly on the substrate via a strong chemical interaction. After being activated by a calcination/rehydration procedure, the rehydrated LDH (RLDH) platelets remain firmly immobilized on the AAO/aluminum substrate and retain the hexagonal platelet morphology of the LDH precursor. The catalytic activity of the resulting material was tested by using aldol condensation of acetone as a probe reaction, showing that the RLDH/AAO is superior in catalytic performance to the powdered RLDH analogue. The kinetic feature of this catalytic reaction was also analyzed, which suggests that it obeys the D₁ kinetic model, a one-dimensional diffusion-controlled mechanism.     

Dynamical adsorption and temperature-programmed desorption of VOCs (toluene, butyl acetate and butanol) on activated carbons

The elimination of solvent vapors from paint shop atmospheres and their recovery for possible re-use is a current environmental requirement. We have studied the dynamical adsorption at 23 °C of typical car paint solvents, i.e. toluene, butylacetate and butanol, on two microporous activated carbons, and the thermal regeneration of these carbons with hot air at 150 °C. A sequence of seven adsorption-desorption cycles with a mixture of these solvents left the carbons with some textural changes but the adsorption capacity remained virtually unaffected. Heavy volatile compounds, proceeding from the possibly unstabilized binder, are eliminated in the course of the first adsorption-desorption runs. Differential scanning calorimetry applied to the desorption in argon of pure solvents showed that the desorption enthalpies ΔH_des are close to, or slightly larger than, the evaporation enthalpies ΔH_vap except for butanol, which exhibited a particularly high ΔH_des value. Temperature-programmed desorption experiments, obtained with carbon samples heated in a helium flow containing oxygen traces, evidenced the desorption of numerous oxidation products. This finding may have consequences for hot air regeneration processes.     

轻石脑油中C_6烷烃在5A分子筛上的吸附/脱附等温线研究

测定了轻石脑油中正、异构C6烷烃在5A-1分子筛上的低温(25～80℃)及高温(150～300℃)吸附/脱附等温线,分析了吸附温度、吸附压力、脱附压力对5A-1分子筛吸附/脱附性能的影响。结果表明:正己烷在5A-1分子筛上低温(25～80℃)及高温(150～300℃)下的吸附等温线均为I型吸附等温线,且随着吸附温度的升高,等温线优惠程度逐渐降低。吸附温度25℃、平衡压力7.5kPa时,异构C6烷烃在5A-1分子筛上的吸附量较小,对正己烷平衡吸附量影响不大。对于轻石脑油中的C_6烷烃来说,较适宜的吸附温度优选200～250℃,在该温度范围内,正己烷平衡吸附量为5.68～9.03g/(100g);脱附压力为1.4 kPa时,正己烷脱附量为0.69～2.35g/(100g),能够满足变压吸附的操作要求。     

碳纳米管对水体重金属污染物的吸附/解吸性能研究进展

详细阐述了碳纳米管(CNTs)对水体中和重金属离子的吸附/解吸影响因素和吸附机理,展望了碳纳米管在环境治理方面应用前景。     

沸石吸附废水中磷污染物的研究

含磷化学物质的普遍使用以及目前很低的污水处理率．导致含磷废水大量排放．水体富营养化和水污染日益严重,采用合成的13X沸石,作为一种新型磷吸附剂．研究其在不同吸附时间、水体pH值、沸石用量和振荡速度等条件下对水体中磷的吸附规律。研究表明．该沸石作为废水除磷吸附剂具有很好的发展前景。     

Study of SO2 adsorption and thermal regeneration over activated carbon-supported copper oxide catalysts

The mechanisms of SO₂ adsorption and regeneration over activated carbon-supported copper oxide sorbent/catalysts were analyzed. Studies were carried out in a fixed-bed reactor equipped with a non-dispersive infrared gas analyzer to detect the reaction products and by using X-ray powder diffraction (XRPD) and temperature-programmed desorption (TPD) experiments to characterize the nature of the sulfate species and surface oxygen complexes. The results indicate that SO₂ was catalytically oxidized to SO₃ over a copper phase in the presence of gaseous oxygen, and then reacted with a copper site to form a sulfate linked to copper without desorption into the gas phase. The activated carbon support did not participate in this sulfation reaction. After the adsorption of SO₂, the exhausted sorbent/catalysts could be regenerated by direct heat treatment in inert gas at temperatures between 260 and 480 °C, while the neighboring surface oxygen complexes on the carbon surface were acting as the reducing agents to reduce CuSO₄ to Cu. During the subsequent adsorption process, the copper is rapidly oxidized by oxygen in the flue gas.