Adsorpcja 4-chlorofenolu z roztworów wodnych na mieszanych adsorbentach: węgiel aktywny - nanorurki węglowe

Celem pracy było zbadanie kinetyki adsorpcji oraz adsorpcji równowagowej 4-chlorofenolu (4-CP) z wody na węglu aktywnym (AC) i nanorurkach węglowych (CNT) oraz na ich mieszaninach o różnym składzie (25/75, 50/50 i 75/25% mas.). Kinetyka adsorpcji przebiegała zgodnie z modelem pseudo 2. rzędu, równowaga adsorpcyjna ustalała się po około 30 minutach w przypadku nanorurek i po około 4 godzinach w przypadku węgla aktywnego. Szybkość adsorpcji 4-CP zwiększała się wraz ze wzrostem ilości nanorurek w mieszaninie adsorbentu, wartość k2 wzrastała z 0,030 g/mmol·min dla AC do 0,709 g/mmol·min dla CNT. Adsorpcja w warunkach równowagowych została opisana za pomocą równań Freundlicha i Langmuira - adsorpcja 4-CP z wody zachodziła zgodnie z modelem Langmuira. Wzrost udziału węgla aktywnego w mieszaninie adsorbentu zwiększał jej zdolność do usuwania 4-CP z roztworu. Wartość maksymalnej pojemności adsorpcyjnej q_m wzrosła z 0,296 mmol/g dla CNT do 2,037 mmol/g dla AC.

The adsorption process by solid adsorbents is one of the most efficient methods for the removal of organic pollutants from water. Adsorption is attractive for its relative flexibility and simplicity of design, ease of operation and regeneration as well as no or low generation of toxic substances. Among all the applied adsorbents, the activated carbons are the most widely used adsorbents due to their excellent adsorption abilities for organic compounds. The high adsorption capacities of the activated carbons are usually related to their high surface area and pore volume. Recently carbon nanotubes are also used as adsorbents, mainly due to their high rate of adsorption of organic pollutants. The aim of this study was to investigate the adsorption of 4-chlorophenol (4-CP) from aqueous solutions on mixed adsorbents: activated carbon (AC) and carbon nanotubes (CNT). Such a mixed adsorbent combines the advantages of both activated carbon (high adsorption capacity) as well as carbon nanotubes (excellent kinetic properties). Various adsorbents compositions were tested: 0/100, 25/75, 50/50, 75/25 and 100/0 wt.% of activated carbon/carbon nanotubes. The results showed that the adsorption equilibriums were achieved after 30 min for the carbon nanotubes and after about 4 hours for the activated carbon. For the description of the experimental data, the equations of the pseudo-first and pseudo-second order were considered. The correlation coefficients for the pseudo-first order kinetic model were relatively low, whereas the pseudosecond order model gives an excellent fitting with the high R² values (> 0.99). This indicates that the adsorption system belongs to the second-order kinetic model. The adsorption rate of 4-CP increased with the increase in the amount of carbon nanotubes in the adsorbent mixture from 0.030 g/mmol·min for pure activated carbon to 0.709 g/mmol·min for CNT. In order to investigate the mechanism of the adsorption, the intraparticle diffusion model (Weber-Morris model) was also used. The results showed that the intraparticle diffusion was not the only rate-controlling step. Moreover, the Weber-Morris plots (q_t vs. T^1/2) were not linear over the whole time range, suggesting that more than one process affected the adsorption. The adsorption was also analyzed as a function of the solution concentration at the equilibrium. Adsorption isotherms of 4-CP were analyzed using the Freundlich and Langmuir models. The R² values show that the equilibrium data were better represented by the Langmuir isotherm compared to the Freundlich equation. The increase in the amount of activated carbon in the adsorbent mixture resulted in an increase in the adsorption capacity of the adsorbent from 0.296 mmol/g for CNT to 2.037 mmol/g for AC.