Kinetics Studies of Metallic Ions Adsorption by Immobilised Chitosan

Immobilised chitosan on glass plates was used as an adsorbent for metallic ions from aqueous solutions in a batch adsorption system. Experiments were carried out as a function of contact time and initial metallic ions concentration. The adsorption efficiency increased with increasing initial metallic ions concentration (5 – 20 mg L-1) and the observed trend was: Ag2+ > Cu2+ > Ni2+ > Fe3+ > Cd2+ > Zn2+. The experimental data were fitted to pseudo-first, pseudo-second-order, intra-particle, and liquid film diffusion kinetic models. The applicability of the pseudo-second-order kinetic model indicated that the adsorption behaviour was ascribed by chemisorption. Further data analysis by the diffusion kinetic models suggested that the metallic ions adsorption was controlled by more than one step; adsorption at the active sites, intra-particle, and liquid film diffusion.

Adsorption of Cr(VI) onto cross-linked chitosan-almond shell biochars: equilibrium, kinetic, and thermodynamic studies

In this study, to remove Cr(VI) from the solution environment by adsorption, the almond shell was pyrolyzed at 400 and 500 °C and turned into biochar (ASC400 and ASC500) and composite adsorbents were obtained by coating these biochars with chitosan (Ch-ASC400 and Ch-ASC500). The resulting biochars and composite adsorbents were characterized using Fourier transform infrared (FTIR) spectroscopy; Brunauer, Emmett, and Teller (BET) surface area; scanning electron microscopy/energy-dispersive X-ray spectroscopy (SEM/EDX); and the point of zero charge pH (pHpzc) analyses. The parameters affecting the adsorption were examined with batch adsorption experiments and the optimum parameters for the efficient adsorption of Cr(VI) in 55 mg L−1 solution were determined as follows; adsorbent dosages: 5 g L−1 for biochars, 1.5 g L−1 for composite adsorbents, contact time: 120 min, pH: 1.5. It was seen that the temperature did not affect the adsorption much. Under optimum conditions, Cr(VI) adsorption capacities of ASC400, ASC500, Ch-ASC400, and Ch-ASC500 adsorbents are 11.33, 11.58, 37.48, and 36.65 mg g−1, respectively, and their adsorption percentages are 95.2%, 97.5%, 94.3%, and 94.0%, respectively. Adsorption data were applied to Langmuir, Freundlich, Scatchard, Dubinin-Radushkevic, and Temkin isotherms and pseudo-first-order kinetic model, pseudo-second-order kinetic model, intra-particle diffusion model, and film diffusion model. The adsorption data fitted well to the Langmuir isotherm and pseudo-second-order kinetic models. From these results, it was determined that chemical adsorption is the dominant mechanism. Also, both intra-particle diffusion and film diffusion is effective in the adsorption rate. For all adsorbents, the Langmuir isotherm proved to be the most appropriate model for adsorption. The maximum monolayer adsorption capacities calculated from this model are 24.15 mg g−1, 27.38 mg g−1, 54.95 mg g−1, and 87.86 mg g−1 for ASC400, ASC500, Ch-ASC400, and Ch-ASC500, respectively. The enthalpy change, entropy change, and free energy changes during the adsorption process were calculated and the adsorption was also examined thermodynamically. As a result, adsorption occurs spontaneously for all adsorbents.

Research on Cadmium Adsorption-Desorption Dynamics of Biochars

Biochar has high potential usage in retaining various contaminants, wastewater treatment, and water purification. In this study, three rice husk derived biochars with pyrolysis temperature 300, 400 and 500 ºC, respectively, and pristine rice rusk were used to remove cadmium from aqueous solution. The results showed that about 70% or more of Cd2+ adsorption occurred in the first 960 mins of adsorption kinetics. The Cd2+ adsorption capacity under equilibrium increased with increasing pyrolysis temperature, probably attributed to the increased specific surface area (SSA) under higher pyrolysis temperature noting that significant linear correlation occurred between Cd2+ adsorption capacity and SSA. The Cd2+ adsorption could be best fitted by pseudo-second order model relative to Elovich model and pseudo-first order model. The Cd2+ adsorption rates were higher in film diffusion stage, indicating that film diffusion stage was significant and fast in the early stage of Cd2+ adsorption. In contrast, Cd2+ adsorption by intra-particle diffusion accounted for 47.0%, 47.9% and 43.9% on average of the total Cd2+ adsorption, respectively, indicating that intra-particle diffusion of Cd2+ played a more predominant role in limiting Cd2+ adsorption rate. When reaching Cd2+ desorption equilibrium, removal ratio (RR) values were averaged 0.96, 0.91, and 0.90 under three initial concentrations. More than 90 percentage on average of Cd2+ was removed from aqueous solution by biochars and rice rusk as well, thus biochars can be used to efficiently remove contaminants from aqueous environment. Cation exchange, electrostatic attraction, and the complexation with surface functional groups could be the main dominant mechanisms for Cd2+ adsorption-desorption on biochars.

Hydrogel Based on Tricarboxi-Cellulose and Poly(Vinyl Alcohol) Used as Biosorbent for Cobalt Ions Retention

A biomaterial based on poly(vinyl alcohol) reticulated with tricarboxi-cellulose obtained by TEMPO oxidation (OxC25) was used as a new biosorbent for Co(II) ions retention from aqueous solutions. The biosorption process of Co(II) ions was studied while mainly considering the operational factors that can influence it (i.e., biosorbent concentration, pH of the aqueous media, temperature and contact time of the phases). The maximum adsorption capacity was 181.82 mg/g, with the biosorption well fitted by the Langmuir model. The kinetic modeling of the biosorption process was based on certain models: Lagergreen (pseudo first order model), Ho (pseudo second order model), Elovich (heterogeneous biosorbent model), Webber–Morris (intraparticle diffusion model) and McKay (film diffusion model). The corresponding kinetic model suggests that this biosorption process followed a pseudo-second order kinetic model and was developed in two controlled steps beginning with film diffusion and followed by intraparticles diffusion.

Sorption of Organic Pollutants onto Soils: Surface Diffusion Mechanism of Congo Red Azo Dye

For the protection of human and ecological receptors from the effects of soil pollution with chemical compounds, we need to know the behavior and transport of pollutants in soil. This work investigated the Congo red (CR) acid dye sorption on three natural soils collected from central and northeastern regions of Romania, symbolized as IS-65, IS-T, and MH-13. To define the mechanism of sorption and identify the rate governing step, various diffusion models such as Weber–Morris intraparticle diffusion, Boyd, film and pores diffusion, and mass transfer analysis have been verified. The intraparticle diffusion analysis of Congo red sorption onto soils has been described by a multi-linear plots, showing that the sorption process takes place by surface sorption and intraparticle diffusion in macro, meso, and micropores. The values of intraparticle diffusion coefficient kid increased with any rise of the initial concentration of pollutant. The results show that the values of pore diffusion coefficient (Dp) and film diffusion coefficient (Df) are found to be from 10−8 to 10−10 cm2 s−1, indicating that film diffusion influences the sorption rate limiting step. The intraparticle diffusion analysis shows that the plots did not pass through the origin and have two distinct parts, confirming that intraparticle diffusion is not the single determining mechanism involved in the sorption of Congo red on soils IS-65, IS-T, and MH-13. The results revealed that the sorption process has a complex nature, since both external diffusion and internal diffusion are involved in the sorption of CR from solution onto the investigated soils.

Study of the adsorption of an organic pollutant onto a microporous metal organic framework

In this study, the microporous Metal Organic Framework-5 (MOF-5) has been synthesized to be used to remove methyl orange by adsorption. The adsorption experiments exhibit a good adsorption capacity at a catalyst dose of 0.1 g L−1 and for an initial concentration of 200 mg L−1, whereas the performance is stable over a wide pH range. The equilibrium adsorption data showed a sigmoidal course, which is well fitted by the Dubinin-Astakhov model applicable for physical adsorption processes (E = 0.055 kJ mol−1) onto heterogeneous surfaces and a more homogeneous pore structure (n = 9.9), with a maximum adsorption capacity of 1248.35 mg g−1. As can be observed from the evaluation of the kinetic data, the surface of the adsorbent is heterogeneous with different active sites for Methyl Orange (MO) adsorption. Moreover, based on the rate constant, it can be suggested that there is a specific interaction like electrostatic interaction between MO and the adsorbent for rapid and high uptake of the dye, whereas the adsorption phenomenon is reversible. According to the adsorption mechanisms, intra-particle and film diffusion models simultaneously controlled the rate sorption, which was confirmed by the calculated intra-particle diffusion and the film diffusion coefficients. The evaluation of the thermodynamic parameters revealed that the MO adsorption is spontaneous, endothermic and the randomness increases with the adsorption of MO.

Cu(II) and As(V) Adsorption Kinetic Characteristic of the Multifunctional Amino Groups in Chitosan

Amino groups in the chitosan polymer play as a functional group for the removal of cations and anions depending on the degree of protonation, which is determined by the solution pH. A hydrogel beadlike porous adsorbent was used to investigate the functions and adsorption mechanism of the amino groups by removal of Cu(II) as a cation and As(V) as an anion for a single and mixed solution. The uptakes of Cu(II) and As(V) were 5.2 and 5.6 μmol/g for the single solution and 5.9 and 3.6 μmol/g for the mixed solution, respectively. The increased total capacity in the presence of both the cation and anion indicated that the amino group (NH2 or NH3+) species was directly associated for adsorption. The application of a pseudo second-order (PSO) kinetic model was more suitable and resulted in an accurate correlation coefficient (R2) compared with the pseudo first-order (PFO) kinetic model for all experimental conditions. Due to poor linearization of the PFO reaction model, we attempted to divide it into two sections to improve the accuracy. Regardless of the model equation, the order of the rate constant was in the order of As(V)-single > Cu(II)-single > As(V)-mixed > Cu(II)-mixed. Also, the corresponding single solution and As(V) showed a higher adsorption rate. According to intraparticle and film diffusion applications displaying two linear lines and none passing through zero, the rate controlling step in the chitosan hydrogel bead was determined by both intraparticle and film diffusion.