This study investigated the production of powdered activated carbon derived from carbon black of pyrolyzed waste tires, and their adsorptive capacity on vapor-phase mercury chloride (HgCl2) using both adsorption column and thermogravimetric adsorption systems. The adsorption isotherms and kinetic models were further simulated in the study. In addition, an innovative compositive impregnation process was developed to increase the sulfur content of powdered activated carbon derived from waste tires. The activation of carbon black to form powdered activated carbon was performed in a tubular oven. The operating parameters including activation temperatures, activation time, and water feed rates were investigated in this study. Experimental results indicated that the yield of carbon-black derived powdered activated carbon (CBPAC) decreased with the increase of activation temperature, activation time, and water feed rate, while the BET surface area and pore volume decreased. In the comparison of activation time and water feed rate in the activation process, activation time had an important impact on the production of specific surface area than water feed rate. The optimal operating parameters included activation temperature of 900¢J, activation time of 180min, water feed rate of 0.5 mLH2O/gC-sec, and water injection behind activation process of 17.5 min. From the analysis of carbon surface, the carbon contents of powdered carbon black (PCB), CBPAC, commercial powdered activated carbon (CPAC) were 89.5%, 87.6%, and 88%, respectively. The C (1s) peak region of PCB consisted of 49.8% C-C, 38.9% C-O, 10.5% C=O or O-C-O. Similar analysis results showed that the total area of the C (1s) peak region of CBPAC consisted of 57.5% C-C, 26.8% C-O, 8.1% C=O or O-C-O, and 7.6% O-C=O. Similar to CPAC, the C (1s) peak region consisted of 42.6% C-C, 41.8% C-O, and 15.6% O-C=O. Furthermore, the sulfur contents of PCB and CBPAC were both 0.5%. The S (2p) peak region of PCB consisted of 58.9% ZnS (zinc sulfide) and 41.1% S=C=S. For CBPAC, the S (2p) peak region solely contained S=C=S. The comparison of two sulfur impregnation processes revealed that the innovative compositive impregnation process could simultaneously increased the sulfur content and the BET surface area of powdered activated carbon (PAC), however, the direct impregnation process increased the sulfur content while the BET surface area of PAC decreased linearly. Without the disadvantages of time and energy consumption associated with direct impregnation, the compositive impregnation is an efficient and energy-saving process for producing sulfurized PAC with a high BET surface area and high sulfur content. Experimental results obtained from the adsorption column tests indicated that the influence of the adsorption depth on the adsorptive capacity of CBPAC did not vary much, while the adsorptive capacity of CBPAC increased with HgCl2 concentration. Furthermore, the adsorptive capacity of CBPAC on vapor-phase HgCl2 was less than that of CPAC at the adsorption temperatures of 25~150¢J and high humidity of 12.3 wt %. The difference of adsorptive capacity for CBPAC and CPAC correlated closely with BET surface area and sulfur content. Results form the thermogravimetric adsorption analysis indicated that the adsorptive capacity of CBPAC and initial adsorption rate on vapor-phase HgCl2 increased with HgCl2 concentration and decreased with adsorption temperature. In the kinetic modeling, the deviation of experimental and simulated values simulated by the pseudo-first-order model was lower than those of pseudo-second-order models. Furthermore, the r (correlation coefficient) of pseudo-first-order and pseudo-second-order models were 0.9745~0.9977 and 0.9217~0.9780, respectively. It suggested that the pseudo-first-order model could simulate the adsorption of HgCl2 onto CBPAC better than pseudo-second-order model.

The objective of this study was to remove mercury vapor from municipal waste incinerator (MWI) by the adsorption of powder activated carbon (PAC) prepared from the pyrolysis of waste tire. The study focused on the measurement of mercury concentration in flue gas emitted from municipal waste incinerator, the preparation of PAC from the pyrolysis of the waste tire and impregnated with sulfur, and the adsorption capacity of mercury by the self-made PAC. The measurement of heavy metals in flue gas emitted from four typical MWIs was conducted in this study. Experimental results obtained from the measurement of mercury from flue gas indicated that the removal efficiency of mercury ranged from 83.71%~96.22%for the tested MWIs. This study revealed that the injection of PAC in flue gas would enhance the removal efficiency of mercury. Besides, oxided mercury (Hg2+) can be removed much more easily than elemental mercury (Hg0). Experimental results obtained from the pyrolysis of waste tires indicated that the pyrolysis temperature of waste tire was approximately 400~500¢J, and the percentage of carbon residue is 35~37%. With higher temperature and water feed rate and longer activation time, the specific surface area and total pore volume of PAC increased while the average pore radius decreased. The highest specific surface area of PAC obtained in this study was 996 m2/g. In addition, experimental results obtained from sulfur impregnation process indicated that the specific surface area of PAC decreased dramatically as sulfur was added to PAC. Experiment results obtained from the adsorption capacity of HgCl2 on PAC by column test indicated that PAC with higher specific surface area could adsorb more HgCl2 at room temperature (25¢J). The adsorption capacity of sulfur impregnated PAC decreased at 25¢J was due to the decrease of specific surface area of PAC. However, results from the comparison of two PAC with similar specific surface area indicated that the PAC with higher sulfur content had higher adsorption capacity. It suggested that the addition of sulfur to PAC could enhance the adsorption of HgCl2 at 25¢J. Experimental results obtained from column tests at 150¢J showed that the adsorption capacity of PAC increased as sulfur content of PAC increased. These results suggested that the adsorption mechanism of HgCl2 by PAC was mainly physical adsorption at lower temperature and it was chemisorption at higher temperature. Besides, the self-made PAC demonstrated the similar adsorption capacity of HgCl2 with commercial PAC used in MWIs.

This study investigated the adsorptive and desorption capacity of HgCl2 onto powdered activated carbon derived from carbon black of pyrolyzed waste tires (CPBAC) via thermogravimetric analysis (TGA). Due to incomplete classification and recycling of municipal solid wastes (MSW), they still mix with a lot of hazardous materials, which unfortunately can not be removed by incinerators and air pollution control devices(APCDs). Among them, mercury and its pollutants attract more attention by people. Mercury and its pollutants emitted from the incineration of municipal solid wastes could cause severely adverse effects on human health and ecosystem since they exist mainly in vapor phase due to high vapor pressure. If they can not be remove by the air pollution control devices, they will be emitted to the atmosphere and cause serious effects on environmental ecology via various routes. Activated carbon has been widely applied to the treatment of organic compounds and heavy metals in wastewater and waste gas stream. However, the adsorptive capacity of activated carbon decreases with adsorption temperature. The low adsorptive capacity of activated carbon at high temperature (>150 oC) can be overcome by impregnated activated carbons. Previous study reported that sulfur impregnated powdered activated carbons could effectively remove the vapor-phase elemental mercury (Hgo) emitted from MSW incinerators and utility power plants. However, the impregnated typically used is sulfur (S) which is solely applied for the adsorption of elemental mercury (Hgo). Besides, these studies seldom investigate the distribution of impregnated sulfur in the inner pores of activated carbon and its effects on the specific surface area and pore size distribution. Thus, this study was to investigate the fundamental mechanisms for the adsorption/desorption of HgCl2 by/from sulfur impregnated PAC. Experimental results indicated that the sulfur content of sulfur impregnated CBPAC decreased with increasing impregnation temperatures form 400 to 650 oC; while the surface area of sulfur impregnated CBPAC increased with impregnation temperatures. In this study, TGA was applied to obtain the adsorptive capacity of HgCl2 onto CBPAC with adsorption temperature (150oC) and influent HgCl2 concentration (100~500 £gg/m3). Experimental results indicated that the adsorptive capacity of CBPAC increased with the increase of influent HgCl2 concentration and surface area of the activated carbon. This study revealed that the impregnation of sulfur on CBPAC could increase its adsorption capacity at high temperatures. Desorption experimental parameters included desorption temperature (400, 500, and 600 oC), heating rate (10, 15, and 20 oC /min) and regeneration cycle (1~7 cycles). In probing into the regeneration efficiency of CBPAC, experiments were conducted at the desorption times of 60 and 30 min. The results suggested the regeneration efficiency of carbon under 30 min was generally highter than that under 60 min. Because the desorption time was more longer and the sulfur content was lesser. Therefore, the regeneration times was reduce. Experimental results indicated that the mechanism of HgCl2 desorption from the spent CPBAC was strongly affected by desorption temperature. Both the desorption efficiency and the desorption rate of HgCl2 increased dramatically with desorption temperature. The desorption heat of HgCl2 (823 KJ/mole) was much higher than the vaporization heat of HgCl2 (59.2 KJ/mole), indicating that the adsorption of HgCl2 on sulfur impregnated CBPAC was chemical adsorption. Consequently, raising desorption temperature could enhance the desorption of HgCl2 and shorten the duration for HgCl2 desorption. Moreover, the formation of HgS during the desorption of HgCl2 from activated carbons can be proved by the surface characteristics of sulfur impregnated activated carbons. Results obtained from the regeneration of sulfur impregnated activated carbons indicated that the regeneration cycles decreased as the desorption duration increased. It was attributed to the potential desorption of sulfur from actived carbons, which thus decreased the adsorptive capacity and the regeneration cycles.

The objective of this study is to investigate the influence of sulfur compounds (S and Na2S) for powdered activated carbon derived from carbon black of pyrolyzed waste tires (CPBAC). Besides, this study investigated the distribution of impregnated sulfur in the inner pores of activated carbon and its effected on the specific surface area and pore size distribution. This study investigated the fundamental mechanisms by analysis of thermodynamic properties and to establish the kinetic models for the adsorption/desorption of HgCl2 by/from sulfur impregnated CBPAC. Furthermore, this study investigated the adsorptive and desorption capacity of HgCl2 onto CPBAC via thermogravimetric analysis (TGA). Experimental results indicated that the specific surface area of sulfur impregnated CBPAC with elemental S (S0) was larger than sulfur impregnated CBPAC with Na2S. Besides, the sulfur content of sulfur impregnated CBPAC increased with increasing the surface area of CBPAC under the same impregnated temperature. And, the adsorptive capacity of CBPAC increased with the increase of influent HgCl2 concentration and surface area of the activated carbon. According to the experimental results of the adsorption capacity under the differential sulfur content, its indicated that the affection of sulfur content for adsorption capacity of HgCl2 was much than HgCl2 concentration and surface area of the activated carbon. The desorption energys were 266 and 282 kJ/mole for HgCl2 desorption from saturated CBPAC-S0 and CBPAC-Na2S, respectively. The results showed the process of HgCl2 adsorption onto CBPAC was in favor of a physisorbed state of HgCl2 at the adsorption temperature of 150 oC but the process of HgCl2 adsorption onto CBPAC which impregated was in favor of a chemisorbed state of HgCl2 at the adsorption of 150 oC. The value of ∆G for CBPAC at the adsorption temperature of 30 ~150 oC were ranged from -15.28 kJ/mole to -26.63 kJ/mole. The value of ∆G for CBPAC-S0 at the adsorption temperature of 30~150 oC ranged from -23.45 kJ/mole to -32.09 kJ/mole. The value of ∆G for CBPAC-Na2S at the adsorption temperature of 30~150 oC ranged from -22.84 kJ/mole to -32.72 kJ/mole. The results showed negative values of ∆G confirmed the feasibility of adsorption process and the spontaneous nature for the adsorption of HgCl2. The value of ∆H for CBPAC at the adsorption temperature of 30 ~150 oC ranged from -35.58 kJ/mole to -35.82 kJ/mole. The value of ∆H for CBPAC-S0 at the adsorption temperature of 30 ~150 oC ranged from -38.07 kJ/mole to -52.49 kJ/mole. The value of ∆H for CBPAC-Na2S at the adsorption temperature of 30~150 oC was -37.45 kJ/mole to -53.12 kJ/mole. A negative ∆H suggested that the adsorption of HgCl2 is an exothermic process. Besides, the adsorptive behavior of HgCl2 for two activated carbons (CBPAC-Na2S and CBPAC-S0) at high temperature (110 ¢J and 150 ¢J ) was the same chemical reaction mechanism due to the same ∆H. Besides, the results of model simulation indicated that modified adsorption kinetic model based on pore diffusion scheme developed in this study could successfully simulate the transport and adsorption of HgCl2 by considering the chemical reaction within the inner pores of carbon grains at 150 oC.