超声波对活性炭吸附苯酚相平衡的影响

研究了超声波条件下的苯酚水溶液 +活性炭体系的相平衡以及超声波强度和第三组分的加入对这种相平衡关系的影响。研究结果表明 :与无超声波同温度下的常规脱附过程相比 ,超声波能够通过空化作用将能量施加于体系的分子上 ,使体系的相平衡明显向固相吸附量减少的方向移动 ;将乙醇或乙酸乙酯作为第三组分加入苯酚水溶液 +活性炭吸附体系 ,也可改变原有的吸附相平衡关系 ,使体系的相平衡向固相吸附量减少的方向移动 ,在超声场的同时作用下 ,这种相平衡关系的变化更为明显     

Thermodynamic and Kinetic Behaviors of Trinitrotoluene Adsorption on Powdered Activated Carbons

Abstract

Regulations on the removal of trinitrotoluene (TNT) from wastewater have become increasingly more stringent, demanding faster, less expensive, and more efficient treatment. This study focuses on the adsorption equilibrium and kinetics of TNT on powered activated carbons (PAC). Three types of PACs (i.e., wood based, coal based, and coconut‐shell based) were studied as functions of temperature and pH. Thermodynamic properties including Gibbs free energy, enthalpy, and entropy, were evaluated by applying the Van't Hoff equation. In addition, the adsorption energy distribution functions which describe heterogeneous characteristics of porous solid sorbents were calculated by using the generalized nonlinear regularization method. Adsorption kinetic studies were carried out in batch adsorber under important conditions such as PAC types, temperature, pH, and concentration. We found that fast and efficient removal of TNT dissolved in water can be successfully achieved by PAC adsorption.     

Adsorption Equilibrium and Fixed Bed Adsorption of Aniline onto Polymeric Resin and Activated Carbons

The adsorption of aniline on several adsorbents including resin Sepabeads SP206 and activated carbons Jacobi and Norit, has been studied. The influence of temperature in the adsorption capacity was obtained by batch method. Langmuir and Bi-Langmuir were the best models to represent the equilibrium sorption isotherm of aniline in the resin and the activated carbons, respectively. Higher adsorption capacity was obtained for both activated carbons than that for resin, being the maximum adsorption capacity three times higher. Nevertheless, the aniline adsorption capacity onto resin is much more influenced by the temperature.

The dynamic behavior of aniline onto Sepabeads SP206 resin and activated carbon Jacobi was also studied. Breakthroughs and reverse breakthroughs were carried out in a laboratory-scale column to study the adsorbent regeneration. A Linear Driving Force (LDF) model was used to predict the experiments for the two adsorbents. The results demonstrated that Sepabeads SP206 resin can be easily regenerated by using water, while around 50% of aniline remains adsorbed in the activated carbon. Furthermore, after 4 cycles of adsorption-desorption, only around 60% of aniline can be recovered from the activated carbon Jacobi; this behavior can be explained by the aniline that is chemically adsorbed into the activated carbon.     

吸附法去除电厂汞的研究进展

重金属汞是电厂烟气中的主要污染物。主要介绍了活性炭、飞灰、钙基、矿物类及金属、生物质等吸附剂应用于烟气中脱汞的研究进展,评价了各种吸附剂的应用特点,并对今后需要开展的工作提出建议,为我国燃烧电厂汞排放控制提供参考。     

Chemical Surface Characterization of Activated Carbons by Adsorption Excess of Probe Molecules

Activated carbons are one of the most common industrial adsorbents in liquid‐phase applications. It is known that the surface groups of the activated carbon can have a significant influence on the adsorption process from the liquid phase. Therefore, it is desirable to measure surface groups on activated carbons. This opens up the possibility to use group‐contribution methods to model and predict adsorption isotherms. An idea is presented to characterize the inner surface of activated carbons by three types of surface groups: aromatic, polar, and nonpolar surface groups. The amounts of these surface groups were calculated from excess adsorption isotherms of probe molecules on ten activated carbons. This lays the groundwork for further simulation studies of liquid‐phase adsorption using group‐contribution methods.     

Thermal desorption of gases and solvents from graphite and carbon nanotube surfaces

The interaction of 23 gases and solvents with the basal plane of highly oriented pyrolytic graphite (HOPG) and with single-wall carbon nanotube (SWCNT) samples is studied using thermal desorption spectroscopy. Pre-exponential frequency factors used for analysis of desorption traces are obtained from vapor pressure data. Activation energies for desorption at monolayer coverage are determined using the Redhead peak-maximum method. Binding energies of non-polar adsorbates to the HOPG surface are found to scale with the adsorbate polarizability providing clear evidence for the van der Waals character of the interaction. Low coverage desorption temperatures on SWCNT samples are found to be 50-100% higher than on HOPG. Such increase has previously been attributed to physisorption in higher coordinated sites such as grooves on the external SWCNT rope surfaces. Polar adsorbates on the other hand typically desorb at much higher temperatures from SWCNT samples which is here tentatively attributed to stronger interaction with defect sites.     

Adsorption of dyes on activated carbons: influence of surface chemical groups

The surface chemistry of a commercial activated carbon has been selectively modified, without changing significantly its textural properties, by means of chemical treatments, using HNO₃, H₂O₂, NH₃, and thermal treatments under a flow of H₂ or N₂. The resultant samples were characterized in terms of their surface chemistry and textural properties, and subsequently tested in the removal of different classes of dyes. It was shown that the surface chemistry of the activated carbon plays a key role in dye adsorption performance. The basic sample obtained by thermal treatment under H₂ flow at 700 °C is the best material for the adsorption of most of the dyes tested. For anionic dyes (reactive, direct and acid) a close relationship between the surface basicity of the adsorbents and dye adsorption was shown, the interaction between the oxygen-free Lewis basic sites and the free electrons of the dye molecule being the main adsorption mechanism. For cationic dyes (basic) the acid oxygen-containing surface groups show a positive effect but thermally treated samples still present good performances, showing the existence of two parallel adsorption mechanisms involving electrostatic and dispersive interactions. The conclusions obtained for each dye individually were confirmed in the colour removal from a real textile process effluent.     

Temperature Programmed Hydrogenation of Toluene

Supported Ni, Co, Pt and Ir catalysts were studied by temperature programmed gas phase hydrogenation (TPH) of toluene to evaluate the performance of the catalysts and to obtain information about the applicability of temperature programming to hydrogenation studies. On all catalysts the reaction rate passed through a maximum as the temperature increased. The maximum reaction rate was reached at slightly lower temperatures with the Co catalyst than the Ni, Pt and Ir catalysts. This work demonstrates that TPH is a rapid method for evaluating the performance of hydrogenation catalysts and, combined with temperature programmed desorption, provides information on the reaction mechanism unobtainable from isothermal experiments.     

苯在改性活性炭上的脱附活化能

采用浸渍法制备了KH560/改性活性炭、1706/改性活性炭和A172/改性活性炭等3种活性炭,并利用程序升温脱附技术测定了苯在这3种改性活性炭上的脱附活化能. 结果表明,苯在经改性的活性炭上的脱附活化能均大于其在未改性活性炭上的脱附活化能,表明用有机硅烷改性活性炭可以提高其对苯的吸附能力. IGC分析结果表明,经硅烷改性的活性炭的特殊作用吸附自由能DGs均小于原始活性炭的DGs,这4种活性炭表面与苯的特殊作用吸附自由能DGs大小顺序与苯在这些活性炭上的脱附活化能大小顺序正好相反,这表明DGs越小,吸附质与活性炭表面形成的吸附越牢固,吸附质从其表面脱附所需的活化能越大.     

氯霉素在活性炭上的吸附平衡与动力学

为去除水体中残留的氯霉素,采用生物相容性佳的活性炭作吸附剂,测定了25,30,35℃下氯霉素在自制活性炭上的吸附平衡与动力学,并与商用竹炭作对比。结果表明高比表面积活性炭是去除水体中残留氯霉素的高效吸附剂,活性炭的吸附容量随着吸附剂比表面积和孔容的增大而增大,但随温度从25,30到35℃升高而减小,自制高比表面积活性炭的吸附容量达到3种市售活性炭样品吸附容量的10倍以上;Freundlich吸附等温线方程可较好地描述氯霉素在活性炭上的吸附平衡,准二级方程是用来描述氯霉素在活性炭上吸附的合适动力学模型,并通过拟合得到了其动力学参数。随着温度的升高吸附容量逐渐减小。本研究为活性炭对水体中残留氯霉素的吸附处理提供了科学依据。     

Adsorption of methimazole on the mercury electrode

The electrosorption behaviour of methimazole (vetranal) at the mercury/1 M NaClO₄ interface was determined from a double layer differential capacity measurements extrapolated to zero frequency. Methimazole is the thiourea derivative, which is used as a drug in the overactivity of the thyroid gland. The values of zero charge potential were shifted to negative potentials ca. 230 mV with an increasing methimazole concentration from 10⁻⁴ M to 10⁻¹ M. The relative surface excesses Γ′ of methimazole were calculated from surface pressure at the density of surface charge σ = constant. The values of Γ′ increase with the increase of σ. Adsorption of methimazole was analyzed on the basis of the constants obtained from the Frumkin and virial isotherms. The values of the standard Gibbs energy of adsorption ΔG° increase with the increase of σ while the values of interaction parameters A and B decrease.     

Surface oxygen complexes as governors of neopentane sorption in multiwalled carbon nanotubes

Multiwalled carbon nanotube (MWCNT) samples were obtained by purification and ball-milling of a MWCNT sample synthesized by catalytic chemical vapor decomposition. These samples were oxidized with KMnO₄-H₂SO₄ solution. A heat treatment was employed to decompose the oxygenated groups created by the oxidation treatment. The samples were characterized by transmission electron microscopy (TEM), adsorption of nitrogen, pore size distribution, and by thermogravimetric analysis combined with mass spectroscopy (TG-MS). The dynamics of 2,2-dimethyl-propane (neopentane) sorption was studied by frequency-response (FR) spectroscopy. The FR spectra obtained clearly demonstrate the effect of (a) the ball-milling, (b) the oxidative treatment and (c) the heat treatment on the sorption uptake processes involved in these treated samples.     

H2S adsorption on polycrystalline UO2

We report results on the adsorption and desorption of H₂S on polycrystalline UO₂ at 100 and 300 K, using ultrahigh vacuum X-ray photoelectron spectroscopy (XPS), low energy ion scattering (LEIS), and temperature programmed desorption (TPD). Our work is motivated by the potential for using the large stockpiles of depleted uranium in industrial applications, e.g., in catalytic processes, such as hydrodesulfurization (HDS) of petroleum. H₂S is found to adsorb molecularly at 100 K on the polycrystalline surface, and desorption of molecular H₂S occurs at a peak temperature of 140 K in TPD. Adsorption rates of sulfur as a function of H₂S exposure are measured using XPS at 100 K; the S 2p intensity and lineshapes demonstrate that the saturation coverage of S-containing species is 1 monolayer (ML) at 100 K, and is 0.3–0.4 ML of dissociation fragments at 300 K. LEIS measurements of adsorption rates agree with XPS measurements. Atomic S is found to be stable to >500 K on the oxide surface, and desorbs at 580 K. Evidence for a recombination reaction of dissociative S species is also observed. We suggest that O-vacancies, defects, and surface termination atoms in the oxide surface are of importance in the adsorption and decomposition of S-containing molecules.     

Adsorption of Radon and Water Vapor on Commercial Activated Carbons

Abstract

Equilibrium adsorption isotherms are reported for radon and water vapor on two commercial activated carbons: coconut shell Type PCB and hardwood Type BD. The isotherms of the water vapor were measured gravimetrically at 298 K. The isotherms of radon from dry nitrogen were obtained at 293, 298, and 308 K while the data for the mixture of radon and water vapor were measured at 298 K. The concentrations of radon in the gas and solid phases were measured simultaneously, once the adsorption equilibrium and the radioactive equilibrium between the radon and its daughter products were established. The shape of the isotherms was of Type III for the radon and Type V for the water vapor, according to Brunauer's classification. The adsorption mechanism was similar for both the radon and the water vapor, being physical adsorption on the macropore surface area in the low pressure region and micropore filling near saturation pressure. The uptake capacity of radon decreased both with increasing temperature and relative humidity. The heat of adsorption data indicated that the PCB- and the BD-activated carbons provided a heterogeneous surface for radon adsorption. The equilibrium data for radon were correlated with a modified Freundlich equation.     

噻吩、苯和正辛烷在NaY和CeY分子筛上的热脱附

采用智能质量分析仪(IGA),利用程序升温脱附法(TPD)研究了噻吩、苯和正辛烷在NaY和CeY分子筛上的热脱附行为,测定了升温速率为15 K/min时3种吸附质在NaY和CeY上的热重(TG)和微分热重(DTG)曲线。结果表明,3种吸附质在NaY上脱附比较容易,苯和正辛烷在CeY上脱附也很容易,但噻吩在CeY上脱附比较困难,噻吩有一部分不能完全脱附。CeY对噻吩具有较好的吸附选择性,而NaY的吸附选择性不好。     

Adsorption of toluene onto activated carbons exposed to 100 ppb ozone

The effects of 100 ppb ozone exposure on the adsorption of 1 ppm toluene on activated carbon are presented for dry (less than 5% RH) and humid (55% RH) air. In dry air, the 10% toluene breakthrough times of granular carbon beds exposed to ozone for 208 days are 17% less than those of unexposed carbon beds. At 55% RH, the corresponding reduction in toluene breakthrough time is 78%. For a humid environment with 100 ppb ozone, filter life would be reduced by more than half compared to the expected life based on tests in the absence of ozone. This degradation is attributed to changes in carbon surface chemistry, surface area, and pore volume that occur with relatively brief exposure to the ozone.     

Adsorption of Phenol on Different Activated Carbons Prepared from Date Pits

The potential use of different activated carbons (ACs) prepared from dates pits and phosphoric acid for the removal of phenol from aqueous solutions was investigated. Date pits were converted into five different types of activated carbons by air and phosphoric acid activation. The specific surface area (BET) of the prepared ACs varied from 794 m²/g, for the phosphoric acid:date pit ratio of 5:1, to 1707 m²/g for a ratio of 2:1. Batch adsorption experiments revealed that the adsorption of phenol varied among all of the prepared ACs, where the 2:1 AC showed the highest uptake. Equilibrium pH studies showed that the phenol removal was pH dependent and the maximum phenol uptake occurred at an equilibrium pH of 3.0. Dynamics studies indicated that the initial uptake of phenol on 2:1 AC at pH 4 was rapid, where 80% of the maximum uptake was achieved during the first 30 minutes; both surface adsorption and intraparticle diffusion were involved in the adsorption process and the data followed the pseudo second-order reaction. The equilibrium adsorption data of phenol on 2:1 AC at solution pH 3 was best described by the Redlich-Peterson, Sips, and Langmuir models.     

活性污泥对垃圾渗滤液吸附等温线的研究

采用MLSS为6000mg／L的活性污泥为吸附剂,对水样进行三级吸附试验,研究了在不同的曝气时间、pH和污泥浓度对活性污泥吸附量的影响及活性污泥吸附深度处理垃圾渗滤液的吸附等温线。试验结果表明：活性污泥吸附平衡时间为2h,pH为3～9时,活性污泥吸附量几乎不变。随着污泥浓度的升高,活性污泥的吸附量增大,污泥浓度升至6000mg／L后吸附量变化不大。一级、二级活性污泥吸附等温线更好的符合Freundlich公式等温式,吸附常数n介于1～10之间,说明活性污泥是良好的吸附剂,三级活性污泥吸附等温线则更好的符合Iangmuir公式等温式。     

Influence of pore structure and surface chemistry on electric double layer capacitance in non-aqueous electrolyte

The performance as electric double layer capacitors (EDLC) in non-aqueous electrolyte of a series of alkaline agent-activated carbons with high surface area is presented in this work. The results obtained show that, in general, capacitance increases with surface area. However, the results obtained in this study confirm that capacitance not only depends on surface area, but also on two other parameters: pore size distribution and surface chemistry. It has been shown that capacitance is higher for a sample with wider micropore size distribution than for a sample with higher surface area but too narrow micropore size distribution. In addition, it has been observed that the sample with a very high amount of surface groups presents very high capacitance values. In the present study, a KOH-activated carbon with a capacitance as high as 220 F/g was prepared. Finally, the results obtained with a mesoporous sample have shown that the presence of mesopores in activated carbons with very high surface area (e.g. >2000 m²/g), do not seem to be effective for double layer capacitors.