Influence of Activated Carbon Surface Oxygen Functionality on Elemental Mercury Adsorption from Aqueous Solution

Mercury (Hg), though naturally occurring, is a toxic element. Exposure to various forms of mercury can be harmful for humans and ecosystems. Mercury-contaminated wastewater can be treated using activated carbon to adsorb the mercury, allowing for safe discharge. Wet chemical oxidation of activated carbon was performed to enhanced surface oxygen functionality, with the objective of enhancing aqueous ionic (Hg(II)) and elemental (Hg(0)) mercury adsorption. Characterization of the modified carbons included nitrogen adsorption-desorption, elemental analysis, point of zero charge, and total acidity titration. The concentration and identity of the modifying reagent influenced the characteristics of the carbons, including the surface oxygen functionality. These carbons with enhanced surface oxygen (C(O)) were applied to trace-level Hg solutions (50 μg/L). Adsorption of Hg(II) demonstrated a strong positive correlation with the carbon’s oxygen content, with the greatest Hg(II) removal associated with the highest oxygen content. Interestingly, this correlation was not seen in Hg(0) adsorption. A four variable model best fit the data, identifying surface area, pore volume, point of zero charge, and oxygen content as important variables. The point of zero charge was identified as the primary independent variable. To ensure proper waste handling, it was determined that none of the carbon samples leached mercury at levels that would necessitate treatment and disposal as a hazardous waste

Optimization of Magnetic Powdered Activated Carbon for Aqueous Hg(II) Removal and Magnetic Recovery

Activated carbon is known to adsorb aqueous Hg(II). MPAC (magnetic powdered activated carbon) has the potential to remove aqueous Hg to less than 0.2 mg/L while being magnetically recoverable. Magnetic recapture allows simple sorbent separation from the waste stream while an isolated waste potentially allows for mercury recycling. MPAC Hg-removal performance is verified by mercury mass balance, calculated by quantifying adsorbed, volatilized, and residual aqueous mercury. The batch reactor contained a sealed mercury-carbon contact chamber with mixing and constant N2(g) headspace flow to an oxidizingtrap. Mercury adsorption was performed using spiked ultrapure water (100 mg/L Hg). Mercury concentrations were obtained using EPA method 245.1 and cold vapor atomic absorption spectroscopy. MPAC synthesis was optimized for Hg removal and sorbent recovery according to the variables: C:Fe, thermal oxidation temperature and time. The 3:1 C:Fe preserved most of the original sorbent surface area. As indicated by XRD patterns, thermal oxidation reduced the amorphous characteristic of the iron oxides but did not improve sorbent recovery and damaged porosity at higher oxidation temperatures. Therefore, the optimal synthesis variables, 3:1 C:Fe mass ratio without thermal oxidation, which can achieve 92.5% (± 8.3%) sorbent recovery and 96.3% (±9%) Hg removal. The mass balance has been closed to within approximately ±15%

The Effect of Photon Source on Heterogeneous Photocatalytic Oxidation of Ethanol by a Silica-Titania Composite

The objective of this study was to distinguish the effect of photon flux (i.e., photons per unit time reaching a surface) from that of photon energy (i.e., wavelength) of a photon source on the silica-titania composite (STC)-catalyzed degradation of ethanol in the gas phase. Experiments were conducted in a bench-scale annular reactor packed with STC pellets and irradiated with either a UV-A fluorescent black light blue lamp ((gamma)max=365 nm) at its maximum light intensity or a UV-C germicidal lamp ((gamma)max=254 nm) at three levels of light intensity. The STC-catalyzed oxidation of ethanol was found to follow zero-order kinetics with respect to CO2 production, regardless of the photon source. Increased photon flux led to increased EtOH removal, mineralization, and oxidation rate accompanied by lower intermediate concentration in the effluent. The oxidation rate was higher in the reactor irradiated by UV-C than by UV-A (38.4 vs. 31.9 nM/s) at the same photon flux, with similar trends for mineralization (53.9 vs. 43.4%) and reaction quantum efficiency (i.e., photonic efficiency, 63.3 vs. 50.1 nmol CO2 (mu)mol/photons). UV-C irradiation also led to decreased intermediate concentration in the effluent . compared to UV-A irradiation. These results demonstrated that STC-catalyzed oxidation is enhanced by both increased photon flux and photon energy

Final Report

Forest products provide essential resources for human civilization, including energy and materials. In processing forest products, however, unwanted byproducts, such as volatile organic compounds (VOCs) and hazardous air pollutants (HAPs) are generated. The goal of this study was to develop a cost effective and reliable air pollution control system to reduce VOC and HAP emissions from pulp, paper and paperboard mills and solid wood product facilities. Specifically, this work focused on the removal of VOCs and HAPs from high volume low concentration (HVLC) gases, particularly methanol since it is the largest HAP constituent in these gases. Three technologies were developed and tested at the bench-scale: (1) A novel composite material of activated carbon coated with a photocatalyst titanium dioxide (TiO{sub 2}) (referred to as TiO{sub 2}-coated activated carbon or TiO{sub 2}/AC), (2) a novel silica gel impregnated with nanosized TiO{sub 2} (referred to as silica-titania composites or STC), and (3) biofiltration. A pilot-scale reactor was also fabricated and tested for methanol removal using the TiO{sub 2}/AC and STC. The technical feasibility of removing methanol with TiO{sub 2}/AC was studied using a composite synthesized via a spay desiccation method. The removal of methanol consists of two consecutive operation steps: removal of methanol using fixed-bed activated carbon adsorption and regeneration of spent activated carbon using in-situ photocatalytic oxidation. Regeneration using photocatalytic oxidation employed irradiation of the TiO{sub 2} catalyst with low-energy ultraviolet (UV) light. Results of this technical feasibility study showed that photocatalytic oxidation can be used to regenerate a spent TiO{sub 2}/AC adsorbent. A TiO{sub 2}/AC adsorbent was then developed using a dry impregnation method, which performed better than the TiO{sub 2}/AC synthesized using the spray desiccation method. The enhanced performance was likely a result of the better distribution of TiO2 particles on the activated carbon surface. A method for pore volume impregnation using microwave irradiation was also developed. A commercial microwave oven (800 W) was used as the microwave source. Under 2450 MHz microwave irradiation, TTIP was quickly hydrolyzed and anatase TiO2 was formed in a short time (< 20 minutes). Due to the volumetric heating and selective heating of microwave, the solvent and by-products were quickly removed which reduced energy consumption and processing time. Activated carbon and TiO{sub 2}/AC were also tested for the removal of hydrogen sulfide, which was chosen as the representative total reduced sulfur (TRS) species. The BioNuchar AC support itself was a good H{sub 2}S remover. After coating TiO{sub 2} by dry impregnation, H{sub 2}S removal efficiency of TiO{sub 2}/AC decreased compared with the virgin AC due to the change of surface pH. Under UV light irradiation, H{sub 2}S removal efficiency of TiO{sub 2}/AC composite doubled, and its sulfate conversion efficiency was higher than that of AC. The formation of sulfate is preferred since the sulfate can be removed from the composite by rising with water. A pilot-scale fluidized bed reactor was designed to test the efficiency of methanol oxidation with TiO{sub 2}/AC in the presence of UV light. TiO{sub 2}/AC was prepared using the spray desiccation method. The TiO{sub 2}/AC was pre-loaded with (1) methanol (equivalent to about 2%wt) and (2) methanol and water. When the TiO{sub 2}/AC loaded with methanol only was exposed to UV light for one hour in the reactor, most of the methanol remained in the carbon pores and, thus, was not oxidized. The TiO{sub 2}/AC loaded with methanol and water desorbed about 2/3 of the methanol from its pores during fluidization, however, only a small portion of this desorbed methanol was oxidized. A biofilter system employing biological activated carbon was developed for methanol removal. The biofilter contained a mixed packing with Westvaco BioNuchar granular activated carbon, perlite, Osmocote slow release ammonium nitrate pellets, and Agrasoke water crystals in a 4:2:1:1 ratio by volume. The biofilter was inoculated with a bacterial culture collected from a Florida pulp and paperboard plant. A non-inoculated biofilter column was also tested. Use of a biological inoculum enriched from biofilm in the pulp and paper process has the potential to enhance the performance of a GAC biofilter. During testing, packing material was removed from the inlet and oulet of the biofilters and analyzed for genetic diversity using molecular techniques. The biofilter inoculated with specifically-enhanced inoculum showed higher bacterial diversity for methylotrophs and all bacteria, as compared to a non-inoculated biofilter. Mixed methylotrophic cultures, selected as potential biofilter inocula, showed increased methanol removal with highest concentrations of nitrogen provided as nitrate

Visible-Light-Responsive Photocatalysis: Ag-Doped TiO2 Catalyst Development and Reactor Design Testing

In recent years, the alteration of titanium dioxide to become visible-light-responsive (VLR) has been a major focus in the field of photocatalysis. Currently, bare titanium dioxide requires ultraviolet light for activation due to its band gap energy of 3.2 eV. Hg-vapor fluorescent light sources are used in photocatalytic oxidation (PCO) reactors to provide adequate levels of ultraviolet light for catalyst activation; these mercury-containing lamps, however, hinder the use of this PCO technology in a spaceflight environment due to concerns over crew Hg exposure. VLR-TiO2 would allow for use of ambient visible solar radiation or highly efficient visible wavelength LEDs, both of which would make PCO approaches more efficient, flexible, economical, and safe. Over the past three years, Kennedy Space Center has developed a VLR Ag-doped TiO2 catalyst with a band gap of 2.72 eV and promising photocatalytic activity. Catalyst immobilization techniques, including incorporation of the catalyst into a sorbent material, were examined. Extensive modeling of a reactor test bed mimicking air duct work with throughput similar to that seen on the International Space Station was completed to determine optimal reactor design. A bench-scale reactor with the novel catalyst and high-efficiency blue LEDs was challenged with several common volatile organic compounds (VOCs) found in ISS cabin air to evaluate the system's ability to perform high-throughput trace contaminant removal. The ultimate goal for this testing was to determine if the unit would be useful in pre-heat exchanger operations to lessen condensed VOCs in recovered water thus lowering the burden of VOC removal for water purification systems

Adsorption of Manganese(II) Ions by EDTA-treated Activated Carbons

The adsorption of manganese(II) ions from aqueous solution onto three different granular activated carbons treated with ethylenediamine tetraacetic acid (EDTA) and its sodium salt was investigated. Characterization of the chelate-treated carbons showed that EDTA altered the physical and chemical properties of the sorbents relative to their untreated counterparts. Furthermore, the modified sorbents exhibited a heightened capacity towards the adsorption of Mn(II) ions from aqueous media. Manganese(II) ion removal increased from 0 to 6.5 mg/g for the lignite coal-based sorbent, from 3.5 to 14.7 mg/g for the wood-based sorbent and from 1.3 to 7.9 mg/g for the bituminous coal-based sorbent. The increased removal is attributed, in part, to the creation of Lewis base sites that participate in covalent interactions and hydrolysis reactions

Influence of Activated Carbon Surface Oxygen Functionality on Elemental Mercury Adsorption from Aqueous Solution

Mercury (Hg), though naturally occurring, is a toxic element. Exposure to various forms of mercury can be harmful for humans and ecosystems. Mercury-contaminated wastewater can be treated using activated carbon to adsorb the mercury, allowing for safe discharge. Wet chemical oxidation of activated carbon was performed to enhanced surface oxygen functionality, with the objective of enhancing aqueous ionic (Hg(II)) and elemental (Hg(0)) mercury adsorption. Characterization of the modified carbons included nitrogen adsorption-desorption, elemental analysis, point of zero charge, and total acidity titration. The concentration and identity of the modifying reagent influenced the characteristics of the carbons, including the surface oxygen functionality. These carbons with enhanced surface oxygen (C(O)) were applied to trace-level Hg solutions (50 μg/L). Adsorption of Hg(II) demonstrated a strong positive correlation with the carbon’s oxygen content, with the greatest Hg(II) removal associated with the highest oxygen content. Interestingly, this correlation was not seen in Hg(0) adsorption. A four variable model best fit the data, identifying surface area, pore volume, point of zero charge, and oxygen content as important variables. The point of zero charge was identified as the primary independent variable. To ensure proper waste handling, it was determined that none of the carbon samples leached mercury at levels that would necessitate treatment and disposal as a hazardous waste

Removal of methanol from pulp and paper mills using combined activated carbon adsorption and photocatalytic regeneration

Methanol is one of the major hazardous air pollutants emitted from chemical pulp mills. Its collection and treatment is required by the Maximum Achievable Control Technology portion of the 1998 Cluster Rule. The objective of this study is to investigate the technical feasibility of combined adsorption and photocatalytic regeneration for the removal and destruction of methanol. To facilitate the regeneration, activated carbon (AC) was coated with commercially available photocatalyst by a spray desiccation method. Laboratory-scale experiments were conducted in a fixed-bed reactor equipped with an 8 W black light UV lamp (peak wavelength at 365 nm) at the center. The photocatalyst loaded onto AC had no significant impact on the adsorption capacity of the carbon. High humidity was found to greatly reduce the material's capacity in the adsorption and simultaneous adsorption and photocatalytic oxidation of methanol. The photocatalytic regeneration process is limited by the desorption of the adsorbate. Increasing desorption rate by using purge air greatly increased the regeneration capacity. When the desorption rate was greater than the photocatalytic oxidation rate, however, part of the methanol was directly desorbed without degradation

Optimization of Magnetic Powdered Activated Carbon for Aqueous Hg(II) Removal and Magnetic Recovery

Activated carbon is known to adsorb aqueous Hg(II). MPAC (magnetic powdered activated carbon) has the potential to remove aqueous Hg to less than 0.2 mg/L while being magnetically recoverable. Magnetic recapture allows simple sorbent separation from the waste stream while an isolated waste potentially allows for mercury recycling. MPAC Hg-removal performance is verified by mercury mass balance, calculated by quantifying adsorbed, volatilized, and residual aqueous mercury. The batch reactor contained a sealed mercury-carbon contact chamber with mixing and constant N2(g) headspace flow to an oxidizingtrap. Mercury adsorption was performed using spiked ultrapure water (100 mg/L Hg). Mercury concentrations were obtained using EPA method 245.1 and cold vapor atomic absorption spectroscopy. MPAC synthesis was optimized for Hg removal and sorbent recovery according to the variables: C:Fe, thermal oxidation temperature and time. The 3:1 C:Fe preserved most of the original sorbent surface area. As indicated by XRD patterns, thermal oxidation reduced the amorphous characteristic of the iron oxides but did not improve sorbent recovery and damaged porosity at higher oxidation temperatures. Therefore, the optimal synthesis variables, 3:1 C:Fe mass ratio without thermal oxidation, which can achieve 92.5% (± 8.3%) sorbent recovery and 96.3% (±9%) Hg removal. The mass balance has been closed to within approximately ±15%