Kinetics and Equilibria of Synthesized Anionic Surfactant onto Berea Sandstone

We present static adsorption studies of anionic surfactants on crushed Berea sandstone. The maximum adsorption density was 0.9604 mg/g. The kinetics of adsorption process was modeled using pseudo-first-order and pseudo-second-order rate equations at 25°C and 70°C. The equilibrium adsorption process was validated using Langmuir and Freundlich adsorption models. In addition, the effects of different parameters that govern the effectiveness of these surfactants such as pH and temperature were also investigated. The kinetic study results show that the surfactant adsorption is a time dependent process. The apparent rate constant of adsorption process determined by the first-order kinetic model at 25°C and 70°C were 0.11768 and ?0.04513, respectively. The rate constant for pseudo-second-order kinetic model was 0.0086 at 25°C and 0.0101 at 70°C. The adsorption of anionic surfactant followed pseudo-second-order kinetic model. The Freundlich and Langmuir model constant were 1.6509 × 10^?4 and ?9.775 × 10^?5, respectively. The equilibrium results showed that the adsorption of anionic surfactant onto Berea sandstone was well described by Langmuir adsorption model. It was concluded that anionic surfactants performed better at higher pH and temperature.      

Application of mass spectrometry for study of the adsorption of multicomponent surfactant mixtures at the solid/solution interface

The selective adsorption of the components of a polydisperse gemini surfactant blend (alkylbenzenesulfonate-Jeffamine salt, ABSJ) in aqueous solution onto Berea sandstone, a reference material in enhanced oil recovery (EOR), was investigated. The individual adsorption isotherms of the four, benzene-ring containing ABSJ components with different alkyl chain lengths (ranging from decyl to tridecyl of the alkyl chain length) were simultaneously determined by using a four-channel electrospay ionization mass spectrometer (ESI-MS) for concentration analysis. This analytical device provided selective information (based on the differences in the mass to charge ratio) on the adsorption of each component in the mixed surfactant system. The overall isotherm obtained from the superposition of the individual isotherms determined by ESI-MS agreed well with the isotherm determined by UV spectrometry; the UV equipment is benzene-ring sensitive, irrespective of the alkyl chain length. The S-shaped isotherms reached a plateau at the critical micelle concentration. Longer-chain surfactants adsorbed preferentially over the short chain homologs, independently of solution concentration. This analytical device provided the net adsorption isotherm. Most analytical methods are not component selective, and thus they are not able to measure the individual isotherms in multicomponent solutions. Here, we report on a novel method which describes the selective determination of the individual adsorption isotherms of surfactants in a multicomponent mixture. The theoretical background of the method is described in detail.     

Zn(II)/α-FeOOH 吸附体系的固体浓度效应

采用宏观吸附-解吸实验系统地研究了Zn(II)在针铁矿(α-FeOOH)表面吸附的固体浓度(Cp)效应, 并考察了温度对固体浓度效应的影响, 揭示了固体浓度效应产生的机理. 实验结果表明: Zn(II)/α-FeOOH的吸附等温线随固体浓度的增加明显下移, 表现出显著的固体浓度效应; 随着固体浓度的升高, 平衡浓度相近的实验点的解吸滞后角(θ)和热力学不可逆系数(TII)均明显升高, 说明体系的可逆性随固体浓度的增大而显著降低, 这一结果符合亚稳平衡吸附(MEA)理论对固体浓度效应产生机制的预测. 本研究还发现Zn(II)/α-FeOOH体系在低温下的固体浓度效应比在高温下更为显著. 不同温度下的吸附-解吸实验表明,该体系的吸附可逆性随温度的升高而明显增强(θ和TII明显降低), 这再次证明了吸附可逆性对Cp效应的控制作用, 并从另一角度证实了MEA理论对固体浓度效应机制的解释. 实验测得Zn(II)/α-FeOOH体系的吸附热力学参数△H、△S分别为34.07 kJ·mol-1和195.71 J·mol-1·K-1, 表明Zn(II)可在针铁矿表面发生吸热的化学吸附反应.     

Lindane Adsorption-Desorption on Chitin in Sea Water

Abstract

The adsorption and desorption processes by solid materials are important in determining the movement and fate of pesticide compounds in aquatic systems. Chitin is one of the constituents of natural organic matter and may serve as a model organic phase for studying the pesticide adsorption-desorption in marine systems. The lindane adsorption-desorption to chitin has been studied as a function of chitin concentration (2.5 gl^?1 to 12.5 gl^?1), temperature (5 to 45°C), pH (1.5 to 8) and salinity (15‰ to 36‰). Both, Freundlich and linear isotherms for the adsorption and desorption processes were used to represent the experimental data. Two-site Langmuir isotherm can describe well the measured sorption isotherm. The adsorbent-concentration effect and the adsorption-desorption hysteresis show the existence of different classes of site with different accessibility. Thus, the adsorption-desorption reaction of lindane is the result of more than a single mechanism. An increase in temperature (ΔH = ?4.0 ± 0.7 Kcal mol^?1) and a decrease in salinity resulted in both lower lindane adsorption and in a more reversible process. An increase of pH resulted in lower adsorption partition coefficients.     

Surface science of DNA adsorption onto citrate-capped gold nanoparticles

Single-stranded DNA can be adsorbed by citrate capped gold nanoparticles (AuNPs), resulting in increased AuNP stability, which forms the basis of a number of biochemical and analytical applications, but the fundamental interaction of this adsorption reaction remains unclear. In this study, we measured DNA adsorption kinetics, capacity, and isotherms, demonstrating that the adsorption process is governed by electrostatic forces. The charge repulsion among DNA strands and between DNA and AuNPs can be reduced by adding salt, reducing pH or by using noncharged peptide nucleic acid (PNA). Langmuir adsorption isotherms are obtained, indicating the presence of both adsorption and desorption of DNA from AuNPs. While increasing salt concentration facilitates DNA adsorption, the desorption rate is also enhanced in higher salt due to DNA compaction. DNA adsorption capacity is determined by DNA oligomer length, DNA concentration, and salt. Previous studies indicated faster adsorption of short DNA oligomers by AuNPs, we find that once adsorbed, longer DNAs are much more effective in protecting AuNPs from aggregation. DNA adsorption is also facilitated by using low pH buffers and high alcohol concentrations. A model based on electrostatic repulsion on AuNPs is proposed to rationalize the DNA adsorption/desorption behavior.     

非离子表面活性剂的吸附机理和表面胶团化对二氧化硅悬浮液稳定性的影响

测定了CAB-O-SIL在290.7K和304.2K时自水和1mol/LNaCl溶液中吸附非离子表面活性剂TritonX-100(TX100)的吸附等温线。结果表明,吸附量随温度升高而增加。NaCl的存在也使吸附量增加。运用生成表面胶团的吸附理论处理了实验结果,求得了表面胶团化的平衡常数、表面胶团的平均聚集数、临界表面胶团浓度和表面胶团化的标准热力学函数。实验表明,随TX100浓度的增大,CAB-O-SIL悬浮液稳定性出现不规则的变化。加入NaCl的效应是使悬浮液的稳定性下降和促进表面胶团的形成。结合吸附研究结果,提出了一个涉及表面胶团的颗粒相互作用模型,合理地解释了悬浮液稳定性的实验结果。     

超高交联树脂NXD-4对水中邻苯二甲酸单丁酯的去除性能

以新合成的超高交联吸附树脂NXD-4为吸附剂,以邻苯二甲酸单丁酯(MBP)为目标污染物,通过吸附等温线和动力学实验,考察了NXD-4对MBP的去除性能并与活性炭AC-1进行了对比。结果表明,NXD-4和AC-1对MBP的去除均以物理吸附为主,在288~313 K温度范围内,最大吸附量随温度的升高而降低;相同条件下,NXD-4对MBP的吸附量明显大于AC-1的;而且,它们对MBP均具有较快的去除速率,在1750min左右即可达到吸附平衡,但AC-1对MBP的吸附速率大于NXD-4的;脱附再生实验表明,相比于AC-1,NXD-4的脱附再生效果更好,脱附率可以达到96%以上。因此,NXD-4作为吸附剂,对水体中邻苯二甲酸单酯的去除方面具有良好的应用前景。     

Adsorption of nonionic surfactants on cellulose surfaces: adsorbed amounts and kinetics

Kinetic and equilibrium aspects of three different poly(ethylene oxide) alkylethers (C12E5, C12E7, C14E7) near a flat cellulose surface are studied. The equilibrium adsorption isotherms look very similar for these surfactants, each showing three different regions with increasing surfactant concentration. At low surfactant content both the headgroup and the tail contribute to the adsorption. At higher surface concentrations, lateral attraction becomes prominent and leads to the formation of aggregates on the surface. The general shape of the isotherms and the magnitude of the adsorption resemble mostly those for hydrophilic surfaces, but both the ethylene oxide and the aliphatic segments determine affinity for the surface. The adsorption and desorption kinetics are strongly dependent on surfactant composition. At bulk concentrations below the CMC, the initial adsorption rate is attachment-controlled. Above the CMC, the micellar diffusion coefficient and the micellar dissociation rate play a crucial role. For the most hydrophilic surfactant, C12E7, both parameters are relatively large. In this case, the initial adsorption rate increases with increasing surfactant concentration, also above the CMC. For C12E5 and C14E7 there is no micellar contribution to the initial adsorption rate. The initial desorption kinetics are governed by monomer detachment from the surface aggregates. The desorption rate constants scale with the CMC, indicating an analogy between the surface aggregates and those formed in solution.     

Adsorption and solvent desorption behavior of ion-exchanged modified Y zeolites for sulfur removal and for fuel cell applications

Typical ion-exchanged modified Y zeolites (AgY and CeY) were prepared for sulfur removal. The adsorption and desorption behavior of typical sulfur and hydrocarbon molecules in various Y zeolites has been investigated by the adsorption breakthrough and on site solvent washing experiments, as well as computer simulation. Breakthrough experiments showed that the adsorption capacity for thiophenic sulfur increased for the studied adsorbents as follows: CeY > AgY > NaY. The higher initial sulfur concentration accelerated the appearance of breakthrough, and the outlet sulfur concentration, in all cases, cannot reach the corresponding initial sulfur level. The concentration profile of washing solvent during desorption process showed that most of the sulfur compounds could be recovered at initial desorption stage. The desorption rates of typical Y zeolites follow the order: NaY > AgY > CeY, which is the reverse as that found in adsorption capacity. The distinct adsorption and desorption behavior of CeY, AgY, and NaY zeolites was markedly related with their various binding force (S-M coordination, π-complexation, and Van der Waals force) with sulfur compounds. The adsorption isotherms and density distribution snapshots study by computer simulation confirmed the preferential adsorption of thiophenic sulfur.     

Removal of 2.4-dichloro phenoxyacetic acid from aqueous solution by adsorption on activated carbon. A kinetic study

The sorption of 2.4-dichloro phenoxyacetic acid (2.4-D) on two different activated carbons was determined using the batch equilibration technique. The calculated slopes of the Freundlich sorption isotherms were significantly less than 1. The (K) values were higher for the activated carbon which has the higher specific surface, and increased with NaCl concentration. The rate of attaining equilibrium of 2.4-D increased with a decrease in absorbent concentration. Dynamic modelling of the adsorption showed that a first order reversible kinetic model was followed for the adsorption process. The overall rate constant K′, the adsorption rate K₁, the desorption rate constant K₂, and the equilibrium constant K_c for the adsorption process were calculated.     

Effect of Nanofluid Treatment on Water Sensitive Formation to Investigate Water Shock Phenomenon,An Experimental Study

Permeability reduction in porous media as a result of frail and tenuous fine particles migration would decrease the productivity index in the subterranean reservoirs. During reservoir stimulation by injecting fluids into the reservoir, as the salinity condition of the formation brine changes, fine particles initiate the triggering process. In this study, MgO-based nanofluid as a fines fixation agent was stably prepared based on the particle size distribution and characterized through transmission electron microscopy analysis. Afterward, several core flooding tests were performed using Berea sandstone cores to study the effect of nanofluid injection on fines fixation in the water shock phenomenon. Permeability reduction occurred up to 95% of inchoate permeability for no treatment case, which was also confirmed by scanning electron microscopy analysis. Finally, MgO nanofluid with 0.03 wt% concentration and 120 minutes soaking time in the core mitigated the fine particles release and fixed them on the pore walls' surfaces critically reducing the formation damage. The analysis shows that outweighing the attraction potentials compared to repulsions was the main mechanism after nanofluids treatment.     

717型阴离子交换树脂吸附水溶性芳香族有机污染物研究

研究了717型阴离子交换树脂对苯酚、苯甲酸和十二烷基苯磺酸钠(SDBS)等水溶性芳香族污染物吸附过程的基本化学问题.研究结果表明:717型树脂对苯酚、苯甲酸和SDBS的吸附过程均符合Lagergren二级吸附动力学方程,吸附速率均随着温度的升高而加快,吸附表观活化能Ea分别为13.2kJ/mol、59.5kJ/mol和48.1kJ/mol,吸附过程△H0和△S0均为正值,△G0均为负值,吸附能够自发进行;吸附等温模型符合Langmuir等温式;318K时,717型树脂在pH=9.1对SDBS的饱和吸附容量为360mg/g;在pH=10.2,对苯酚和苯甲酸的饱和吸附容量分别为194mg/g和286mg/g.用浓度均为0.5mol/L,体积比为5∶1的NaCl-NaOH混合溶液可快速洗脱树脂上吸附的污染物,洗脱率达98％以上.该树脂对水溶性芳香族污染物吸附容量大,易于再生和循环利用,可用于环境水体中水溶性芳香族有机污染物的吸附治理.     

Highly removal of anionic dye from aqueous medium using a promising biochar derived from date palm petioles: Characterization,adsorption properties and reuse studies

The present work investigates the preparation of promising biochar derived from date palm petioles powder (DPB) via a thermal treatment. DPB was characterized through various techniques to analyze the chemical (FTIR), morphological (SEM) and point of zero charges to investigate changes incorporated through the pyrolysis process.The adsorption of methyl orange (MO) onto the biochar was investigated using batch experiments according to different parameters which influence the adsorption process such as: initial dye concentration, equilibrium time, pH, and temperature. Isothermal and reuse studies of MO adsorption onto DPB were also investigated.Results of MO removal on DPB have demonstrated that the adsorption process was initial dye concentration-dependent, and equilibrium time was occurred in 60 min. The biochar presented high stability of MO adsorption capacity in a large domain of pH. Thermodynamic analysis of this process revealed that methyl orange adsorption was exothermic and spontaneous in nature.The experimental data were analyzed by pseudo-first-order, pseudo-second-order model, and the intraparticle-diffusion for kinetics and Langmuir, Freundlich, and Temkin models for isotherms.Kinetic adsorption followed the pseudo-second-order model and the intraparticle-diffusion within pores controlled the adsorption rate. The experimental data yielded good fits with in the following isotherms order: Langmuir > Temkin > Freundlich, The maximum adsorption capacity of MO on DPB was found 461 mg.g^?1. The reusability study reveals the possibility of the reuse of DPB for three (03) cycles of adsorption–desorption, a slight decrease in the ability of methyl orange adsorption has noticed with the increase of the number of adsorption–desorption cycles : 81.03 %, 67.84 %, and 51.72 %, respectively. The found results of the present study show that the biochar derived from date palm petioles have the potential to be used as a promising adsorbent for the treatment of MO dye.     

铝离子和钛离子化学改性MCM-41介孔材料的制备及其对污水中镉离子的吸附性能(英文)

通过在MCM-41材料中引入Al 3+和Ti 4+两种诱因金属离子合成了化学改性介孔材料Al-Ti-MCM-41和Ti-Al-MCM-41;评价了两种介孔材料对污水中镉离子的吸附行为.利用氮气吸附-脱附等温线对Al-Ti-MCM-41(1∶1)样品的吸附行为进行了详细分析,考察了吸附剂投加量、Cd2+初始质量浓度和吸附温度对其吸附行为的影响.结果表明:改性Al-Ti-MCM-41(1∶1)介孔材料的最可几孔径和比孔容分别为16nm和0.04cm3/g,由BJH法计算得到的平均孔径为17.02nm;其对污水中Cd2+的吸附率达99.8%.Cd2+的吸附率随Al-Ti-MCM-41(1∶1)介孔材料投加量的增加先增加而后降低最终达到平衡,吸附容量随Cd2+初始浓度的增大而增加;吸附温度对吸附行为基本无影响.     

Characterization and determination of the thermodynamic and kinetic properties of the adsorption of the molybdenum(VI)-calmagite complex onto active carbon

The extraction of the Mo(VI)-calmagite complex by adsorption onto active carbon is investigated in the present paper. Thermodynamic and kinetic properties and different adsorption isotherms were determined. The adsorption studies have shown that both the empirical Freundlich and the classical Langmuir isotherms successfully fit the experimental results. The overall adsorption process was exothermic and spontaneous in the temperature range from 283 to 323 K; namely, DeltaH(0) and DeltaS(0) values were found to be -8.15 kJ mol(-1) and -3.86 J mol(-1) K, respectively. The high activation energy demanded for desorption of the Mo(VI)-calmagite complex surface indicated that the overall process was controlled by the slow desorption, while a fast and low activated adsorption of the complex onto active carbon surface was fairly favored. These features indicate that active carbon may be very useful for preconcentration of molybdenum from diluted solutions.     

Adsorption of cadmium ions from aqueous solutions using nano-montmorillonite: kinetics,isotherm and mechanism evaluations

With increasing industrial development, heavy metal pollution, e.g., cadmium (Cd) pollution, is increasingly serious in soil and water environments. This study investigated the sorption performance of nano-montmorillonite (NMMT) for Cd ions. Adsorption experiments were carried out to examine the effects of the initial metal ion concentration (22.4–224 mg/L), pH (2.5–7.5), contact time (2–180 min) and temperature (15–40 °C). A simulated acid rain solution was prepared to study the desorption of Cd adsorbed on NMMT. After the adsorption or desorption process, the supernatant was analyzed using a flame atomic absorption spectrometry method. The Cd removal rate increased as the pH and contact time increased but decreased as the initial metal ion concentration increased. The maximum adsorption capacity was estimated to be 17.61 mg/g at a Cd²⁺ concentration of 22.4 mg/L. The sorption process can be described by both the Langmuir and Freundlich models, and the kinetic studies revealed that the pseudo-second-order model fit the experimental data. The Cd desorption rate when exposed to simulated acid rain was less than 1%. NMMT possesses a good adsorption capacity for Cd ions. Additionally, ion exchange was the main adsorption mechanism, but some precipitation or surface adsorption also occurred.     

ADSORPTION OF 1,2,4-ACID BY WEAKLY BASIC RESIN： ISOTHERMS, THERMODYNAMICS AND KINETICS

The adsorption properties, including the adsorption isotherms, thermodynamics and kinetics, of l-amino-2-naphthol-4-sulfonic acid (1,2,4-acid) onto weakly basic resin ND900 are investigated. Both the Langmuir and Freundlich equations can give a good fit to the adsorption isotherms, which indicates an endothermic and a favorable adsorption in our study range. A high yield in elimination of about 45.21%-97.28% is obtained for the tested adsorption systems. The capacity and affinity of the adsorption increase with temperature, due to the phenomena of “solvent-motivated” effects. The value of ΔH is 51.59 kJ/mol, which indicates a chemical adsorption and then expects the poor desorption property of ND900. The negative value of ΔG indicates the spontaneous nature of the adsorption process, and the positive value of ΔS shows the increased randomness at the solid/solution interface during the adsorption process. The value of the adsorption rate constant lower than 0.013 min^-1 is indicative of a slow adsorption rate. The intra-particle diffusion must be one of the rate limiting steps.     

Morphology and surface properties of fumed silicas

Several series of fumed silicas and mixed fumed oxides produced and treated under different conditions were studied in gaseous and liquid media using nitrogen and water adsorption-desorption, mass spectrometry, FTIR, NMR, thermally stimulated depolarization current (TSDC), photon correlation spectroscopy (PCS), zeta potential, potentiometric titration, and Auger electron spectroscopy methods. Aggregation of primary particles and adsorption capacity (Vp) decrease and hysteresis loops of nitrogen adsorption-desorption isotherms becomes shorter with decreasing specific surface area (S(BET)). However, the shape of nitrogen adsorption-desorption isotherms can be assigned to the same type independent of S(BET) value. The main maximum of pore size distribution (gaps between primary nonporous particles in aggregates and agglomerates) shifts toward larger pore size and its intensity decreases with decreasing S(BET) value. The water adsorption increases with increasing S(BET) value; however, the opposite effect is observed for the content of surface hydroxyls (in mmol/m2). Associative desorption of water (2(SiOH)-->SiOSi+H2O) depends on both the morphology and synthesis conditions of fumed silica. The silica dissolution rate increases with increasing S(BET) and pH values. However, surface charge density and the modulus of zeta-potential increase with decreasing S(BET) value. The PCS, 1H NMR, and TSDC spectra demonstrate rearrangement of the fumed silica dispersion depending on the S(BET) value and the silica concentration (C(SiO2)) in the aqueous suspensions. A specific state of the dispersion is observed at the C(SiO2) values corresponding to the bulk density of the initial silica powder.     

Micellization and adsorption of a zwitterionic surfactant: N-dodecyl betaine-effect of salt

Time-resolved fluorescence quenching, self-diffusion measurements and calorimetric investigations have been used in order to investigate the effect of salt on aggregation in aqueous solutions and the adsorption onto silica gel of the zwitterionic surfactant N-dodecyl betaine (NDB).

The micelle aggregation number of NDB stays constant when the NDB or salt concentration increases but decreases with an increase of temperature. Evidence is presented for the binding of cations and anions to micellar aggregates. The degree of binding has been obtained for Na⁺, Ca²⁺ and Cl⁻ ions; it is always larger for the anion.

Enthalpies of micellization were obtained directly from calorimetric curves of NDB in dilution experiments. The observed decrease of the endothermic enthalpies of micellization with increasing temperature or salinity is attributed to a structural change in the water molecules around the alkyl chain of the free monomers.

The adsorption isotherms of NDB onto silica gel depend very little on temperature, and a plateau is reached near the CMC. At saturation, the adsorbed amount of NDB depends on the salt and follows the sequence NDB < (NDB + NaCl) < (NDB + CaCl₂).

The exothermic differential molar enthalpies of adsorption demonstrate the same behaviour as the enthalpies of micellization with varying temperature or salinity. Adsorption onto silica gel depends on the NDB concentration, the salt concentration and temperature.     

Kinetics and isotherms of asphaltene adsorption in narrow pores

New data relating to the kinetics and adsorption isotherms of asphaltene in consolidated sandstone core samples are reported. The data were obtained from the measurements of electrokinetics of consolidated sandstone core samples in asphaltene/toluene solutions and petroleum oils. The numerical reduction in the (negative) zeta potential of the sandstone samples were attributed to the adsorption of positively charged molecules of asphaltenes. The hydrodynamics thickness δ of adsorption of asphaltene were followed by monitoring the pressure increase that occurred as the adsorbed layer restricted the rock pores and applying Poiseuille's equation. The flow rates indicated a plateau of asphaltene adsorption at a pore blocking thickness of about δ/r = 0.3, which was also the point at which the streaming current reached a plateau. After increasing to about 30% of the pore radius, the adsorbed layer thickness δ stopped growing either with time or with concentration of asphaltene in the flowing liquid. Alternative hypotheses involving asphaltene adsorption isotherms have been investigated. A theoretical treatment advanced describing particle adsorption in the same terms as molecular adsorption and the Langmuir isotherm, with the free energy of asphaltene adsorption on the rock surface (modeled on silica) calculated on the basis of van der Waals attraction. Acceptable agreement was obtained with the electrokinetic measurements.