Monoaromatic hydrocarbons including benzene, toluene, ethylbenzene and xylene isomers (BTEX) are a very important category of water pollutants. These volatile compounds are very hazardous because of their fast migration in soil and water bodies and their acute and chronic toxicities when inhaled or ingested, especially benzene which is a known carcinogenic molecule. In this study, a natural zeolite (i. e., clinoptilolite-rich tuffs) was modified by two cationic surfactants (i. e., hexadecyltrimethyl ammonium chloride (HDTMA-Cl), and N-cetylpyridinium bromide (CPB)). The prepared adsorbents were then characterized, and their adsorptive capabilities for BTEX examined at different experimental conditions. The results of adsorption tests at 24 h revealed that the adsorption capacity of the modified zeolites improved by increasing the surfactant loading (i. e., less than the critical micelle concentration (CMC), to higher than the CMC), which caused an increase in sorption capacity from 60 to 70% for HDTMA-modified samples, and from 47 to 99% for CPB-modified zeolite. Adsorption kinetic tests showed the optimum contact time was 48 h with an average BTEX removal of 90 and 93% for HDTMA-modified and CPB-modified zeolite, respectively. Results showed that by increasing of pH from 3 to 11, the sorption capacity of the adsorbent decreased markedly from 97 to 75%. Analyzing the influence of temperature showed that the adsorption efficiency of adsorbents for benzene reduced from 93% at 208C to 10% at 48C. However, the influence of temperature on other compounds was not remarkable. Overall, CPB-modified zeolite exhibited higher selectivity toward BTEX compounds at optimum experimental conditions. Although commercial powder activated carbon (PAC) showed a higher capacity for all BTEX compounds and faster adsorption kinetics, the adsorption capacity of the CPB-modified zeolite at optimized conditions was competitive with PAC results.
Increasing release of organic pollutants to the environment has caused one of the largest world crises for water resources. Volatile organic compounds are toxic monoaromatic pollutants of soil and water. In this research, natural zeolite nanoparticles were produced mechanically by means of a milling technique, modified using two cationic surfactants of hexadecyltrimethylammonium chloride and n-cetyl pyridinium bromide and formed as granules using a novel technique already developed by our group. The granulated adsorbents were used to uptake benzene, toluene, ethylbenzene, and xylenes (BTEX) from contaminated water. Two intra-particle diffusion models (i.e., Weber and Morris and Vermeulen models) and three surface reaction models (i.e., pseudo-first order, pseudo-second order, and Elovich) were applied to evaluate the kinetics of adsorption and the best fitted model was chosen. Results of the adsorption kinetic evaluations were shown that uptake of granulated nanozeolites are higher than natural zeolites (in the order of four). Kinetic results revealed that the adsorption follows a pseudosecond order indicating existence of chemisorption in the studied conditions. It was noticed that the intraparticle diffusion is prevailing in the first stage of adsorption for a relatively short time (i.e., first 25 min).
In this paper, a novel adsorbent developed by means of granulating of natural zeolite nanoparticles (i.e., clinoptilolite) was evaluated for possible removal of the petroleum monoaromatics (i.e., benzene, toluene, ethylbenzene, and xylene, BTEX). To do this, the natural zeolite was ground to produce nanosized particulate, then modified by two cationic surfactants and granulated. The effect of various parameters including temperature, initial pH of the solution, total dissolved solids (TDS), and concentration of a competitive substance (i.e., methyl tert-butyl ether, MTBE) were studied and optimized using a Taguchi statistical approach. The results ascertained that initial pH of the solution was the most effective parameter. However, the low pH (acidic) was favorable for BTEX adsorption onto the developed adsorbents. In this study, the experimental parameters were optimized and the best adsorption condition by determination of effective factors was chosen. Based on the S/N ratio, the optimized conditions for BTEX removal were temperature of 408C, initial pH of 3, TDS of 0 mg/L, and MTBE concentration of 100 mg/L. At the optimized conditions, the uptake of each BTEX compounds reached to more than 1.5 mg/g of adsorbents.
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