Carbon dioxide capture by functionalized solid amine sorbents with simulated flue gas conditions

A novel solid amine sorbent was prepared using KIT-6-type mesoporous silica modified with tetraethylenepentamine (TEPA). Its adsorption behavior toward CO(2) from simulated flue gases is investigated using an adsorption column. The adsorption capacities at temperatures of 303, 313, 333, 343, and 353 K are 2.10, 2.29, 2.58, 2.85, and 2.71 mmol g(-1), respectively. Experimental adsorption isotherms were obtained, and the average isosteric heat of adsorption was 43.8 kJ/mol. The adsorption capacity increases to 3.2 mmol g(-1) when the relative humidity (RH) of the simulated flue gas reaches 37%. The adsorption capacity is inhibited slightly by the presence of SO(2) at concentrations lower than 300 ppm but is not significantly influenced by NO at concentrations up to 400 ppm. The adsorbent is completely regenerated in 10 min at 393 K and a pressure of 5 KPa, with expected consumption energy of about 1.41 MJ kg(-1) CO(2). The adsorption capacity remains almost the same after 10 cycles of adsorption/regeneration with adsorption conditions of 10 vol % CO(2), 100 ppm SO(2), 200 ppm NO, 100% relative humidity, and a temperature of 393 K. The solid amine sorbent, KIT-6(TEPA), performs excellently for CO(2) capture and its separation from flue gas.     

Using bromine gas to enhance mercury removal from flue gas of coal-fired power plants

Bromine gas was evaluated for converting elemental mercury (Hg0) to oxidized mercury, a form that can readily be captured by the existing air pollution control device. The gas-phase oxidation rates of Hg0 by Br2 decreased with increasing temperatures. SO2, CO, HCl, and H2O had insignificant effect, while NO exhibited a reverse course of effect on the Hg0 oxidation: promotion at low NO concentrations and inhibition at high NO concentrations. A reaction mechanism involving the formation of van der Waals clusters is proposed to accountfor NO's reverse effect. The apparent gas-phase oxidation rate constant, obtained under conditions simulating a flue gas without flyash, was 3.61 x 10(-17) cm3 x molecule(-1) x s(-1) at 410 K corresponding to a 50% Hg0 oxidation using 52 ppm Br2 in a reaction time of 15 s. Flyash in flue gas significantly promoted the oxidation of Hg0 by Br2, and the unburned carbon component played a major role in the promotion primarily through the rapid adsorption of Br2 which effectively removed Hg0 from the gas phase. At a typical flue gas temperature, SO2 slightly inhibited the flyash-induced Hg0 removal. Conversely, NO slightly promoted the flyash induced Hg0 removal by Br2. Norit Darco-Hg-LH and Darco-Hg powder activated carbons, which have been demonstrated in field tests, were inferred for estimating the flyash induced Hg0 oxidation by Br2. Approximately 60% of Hg0 is estimated to be oxidized with the addition of 0.4 ppm of gaseous Br2 into full scale power plant flue gas.     

Novel mercury control technology for solid waste incineration: sodium tetrasulfide (STS) as mercury capturing agent

Traditional pollution control technologies are able to capture oxidized forms of mercury to some extent; however, they show low efficiency for the control of elemental mercury emissions. This study developed a novel mercury removal technology: injection of sodium tetrasulfide (Na2S4) dissolved in the sodium hydroxide (NaOH) solution in the spray-dryer system. The effects of flue gas temperature and Na2S4 level in flue gas on the mercury removal efficiency were investigated. Na2S4 was decomposed into Na2S (S2-) and elemental S (S0), which reacted with HgCl2 and elemental Hg (Hg0), and HgS was then formed. Under the optimized operation parameters, this technology can simultaneously remove over 88% of HgCl2 and more than 90% of Hg0 from a flue gas stream containing about 400 microg m(-3) Hg0 and 1200 microg m(-3) HgCl2. The increased flue gas temperature (>170 degrees C) and the decreased Na2S4-to-Hg mass ratio (S-Hg-R) (<2.0) had negative effects on the reactions of gaseous mercury (HgCl2 + Hg0) with ionic sulfur (S2-) and S0. All the experiments were conducted in a full scale hospital-waste incinerator with a capability of 20 tons per day (TPD).     

Development of cost-effective noncarbon sorbents for Hg(0) removal from coal-fired power plants

Noncarbonaceous materials or mineral oxides (silica gel, alumina, molecular sieves, zeolites, and montmorillonite) were modified with various functional groups such as amine, amide, thiol, urea, and active additives such as elemental sulfur, sodium sulfide, and sodium polysulfide to examine their potential as sorbents for the removal of elemental mercury (Hg(0)) vapor at coal-fired utility power plants. A number of sorbent candidates such as amine- silica gel, urea- silica gel, thiol- silica gel, amide-silica gel, sulfur-alumina, sulfur-molecular sieve, sulfur-montmorillonite, sodium sulfide-montmorillonite, and sodium polysulfide-montmorillonite, were synthesized and tested in a lab-scale fixed-bed system under an argon flow for screening purposes at 70 degrees C and/or 140 degrees C. Several functionalized silica materials reported in previous studies to effectively control heavy metals in the aqueous phase showed insignificant adsorption capacities for Hg(0) control in the gas phase, suggesting that mercury removal mechanisms in both phases are different. Among elemental sulfur-, sodium sulfide-, and sodium polysulfide-impregnated inorganic samples, sodium polysulfide-impregnated montmorillonite K 10 showed a moderate adsorption capacity at 70 degrees C, which can be used for sorbent injection prior to the wet FGD system.     

Remediation of elemental mercury using in situ thermal desorption (ISTD)

In situ thermal desorption (ISTD) is a soil heating method that simultaneously applies heat and vacuum to the subsurface at temperatures up to 600 degrees C. As the soil is heated, the vapor pressure of the contaminant increases allowing mass transfer to the gas phase and extraction from the soil using vacuum wells. The overall goal of this research is to assess the feasibility of using ISTD to remove elemental mercury from soils. The initial phase of research included design of a laboratory soil column apparatus and preliminary soil column experiments with surrogate nonaqueous phase liquids (perfluorocarbons) to test the apparatus and investigate the effects of air flow rate and temperature on the ISTD process. Following the preliminary experiments, a mercury off-gas treatment system was added and mercury experiments were conducted. Experiments performed using elemental mercury showed greater than 99.8% removal of the mercury from Ottawa sand. These results show that ISTD can remove mercury from soil at temperatures well below its boiling point and that perfluorodecalin can be used as a surrogate for elemental mercury in laboratory experiments. A flow and transport simulator was used to model the results from both the perfluorocarbon and the mercury experiments.     

Novel regenerable sorbent for mercury capture from flue gases of coal-fired power plant

A natural chabazite-based silver nanocomposite (AgMC) was synthesized to capture mercury from flue gases of coal-fired power plants. Silver nanoparticles were engineered on zeolite through ion-exchange of sodium ions with silver ions, followed by thermal annealing. Mercury sorption test using AgMC was performed at various temperatures by exposing it to either pulse injection of mercury or continuous mercury flow. A complete capture of mercury by AgMC was achieved up to a capture temperature of 250 degrees C. Nano silver particles were shown to be the main active component for mercury capture by amalgamation mechanism. Compared with activated carbon-based sorbents, the sorbent prepared in this study showed a much higher mercury capture capacity and upper temperature limit for mercury capture. More importantly, the mercury captured by the spent AgMC could be easily released for safe disposal and the sorbent regenerated by simple heating at 400 degrees C. Mercury capture tests performed in real flue gas environment showed a much higher level of mercury capture by AgMC than by other potential mercury sorbents tested. In our mercury capture tests, the AgMC exposed to real flue gases showed an increased mercury capture efficiency than the fresh AgMC.     

XAS and XPS characterization of mercury binding on brominated activated carbon

Brominated powdered activated carbon sorbents have been shown to be quite effective for mercury capture when injected into the flue gas duct at coal-fired power plants and are especially useful when burning Western low-chlorine subbituminous coals. X-ray absorption spectroscopy (XAS) and X-ray photoelectron spectroscopy (XPS) have been used to determine information about the speciation and binding of mercury on two commercially available brominated activated carbons. The results are compared with similar analysis of a conventional (non-halogenated) and chlorinated activated carbon. Both the XAS and XPS results indicate that the mercury, though introduced as elemental vapor, is consistently bound on the carbon in the oxidized form. The conventional and chlorinated activated carbons appeared to contain mercury bound to chlorinated sites and possibly to sulfate species that have been incorporated onto the carbon from adsorbed SO2. The mercury-containing brominated sorbents appear to contain mercury bound primarily at bromination sites. The mechanism of capture for the sorbents likely consists of surface-enhanced oxidation of the elemental mercury vapor via interaction with surface-bound halide species with subsequent binding by surface halide or sulfate species.     

Development of a Cl-impregnated activated carbon for entrained-flow capture of elemental mercury

Efforts to discern the role of an activated carbon's surface functional groups on the adsorption of elemental mercury (Hg0) and mercuric chloride demonstrated that chlorine (Cl) impregnation of a virgin activated carbon using dilute solutions of hydrogen chloride leads to increases (by a factor of 2-3) in fixed-bed capture of these mercury species. A commercially available activated carbon (DARCO FGD, NORITAmericas Inc. [FGD])was Cl-impregnated (Cl-FGD) [5 lb (2.3 kg) per batch] and tested for entrained-flow, short-time-scale capture of Hg0. In an entrained flow reactor, the Cl-FGD was introduced in Hg0-laden flue gases (86 ppb of Hg0) of varied compositions with gas/solid contact times of about 3-4 s, resulting in significant Hg0 removal (80-90%), compared to virgin FGD (10-15%). These levels of Hg0 removal were observed across a wide range of very low carbon-to-mercury weight ratios (1000-5000). Variation of the natural gas combustion flue gas composition, by doping with nitrogen oxides and sulfur dioxide, and the flow reactor temperature (100-200 degrees C) had minimal effects on Hg0 removal bythe Cl-FGD in these carbon-to-mercury weight ratios. These results demonstrate significant enhancement of activated carbon reactivity with minimal treatment and are applicable to combustion facilities equipped with downstream particulate matter removal such as an electrostatic precipitator.     

Rapid response concentration-controlled desorption of activated carbon to dampen concentration fluctuations

Fluctuations in concentration of organic vapors in gas streams that are treated by devices such as biofilters or oxidizers make it challenging to remove the vapors from the gas streams in an efficient and economic manner. Combining adsorption with concentration-controlled desorption provides an active buffer between the source of vapors and the control device for better control of concentration and flow rate of the gas stream that is treated by the secondary control device, hence further enhancing the performance or reducing the size of the devices. Activated carbon fiber cloth is used with microwave swing adsorption to remove methyl ethyl ketone (MEK) from air streams and then provide a readily controllable feed stream of that vapor in air at a specified concentration and gas flow rate with steady-state tracking desorption. MEK was captured with >99.8% efficiency during the adsorption cycle. The MEK concentration during the regeneration cycle was readily controlled at concentration set-points between 170 and 5000 ppmv, within relative standard deviations of 1.8 and 4.9%, respectively, and at 20% of the gas flow rate that was treated during the adsorption cycle. Such capability of the system allows the secondary control device to be optimized for select constant concentrations and low gas flow rates that is not possible without such pretreatment.     

Impact of surface heterogeneity on mercury uptake by carbonaceous sorbents under UHV and atmospheric pressure

Chemical and morphological heterogeneities of carbon sorbents play important roles in gas-phase adsorption. However, the specific chemical complexes and topological structures of carbon that favor or impede elemental mercury uptake are not well understood and are the subject of this study. Temperature programmed desorption (TPD) with a model carbonaceous material (highly oriented pyrolytic graphite, HOPG) under ultrahigh vacuum (UHV) conditions and fixed bed adsorption by activated carbon (BPL) at atmospheric pressure were combined to investigate the effects of chemical and morphological heterogeneities on mercury adsorption by carbonaceous surfaces. TPD results show that mercury adsorption at 100 K onto HOPG surfaces with and without chemical functional groups and topological heterogeneity created by plasma oxidation occurs through physisorption. The removal of chemical functionalities from the HOPG surface enhances mercury physisorption. Plasma-oxidation of HOPG provides additional surface area for mercury adsorption. However, the pits created by plasma oxidation are more than 10 nm in diameter and do not simulate microporosity that predominates in activated carbons. Mercury adsorption by activated carbon at atmospheric pressure occurs through two distinct mechanisms. Physisorption governs mercury adsorption at lower temperatures (i.e., below 348 K), while chemisorption predominates at high adsorption temperatures (i.e., above 348 K). Presence of water on activated carbon surface enhances mercury uptake by both physisorption and chemisorption. Oxygen containing functional groups reduce mercury uptake by physisorption by blocking access to the micropores. No significant impact of oxygen functionalities was observed in the chemisorption regime. The key findings of this study open the possibility to apply scientific information obtained from the studies with simple surfaces such as HOPG under ideal conditions (UHV) to industrial sorbents under realistic process conditions.     

Sulfur dioxide treatment from flue gases using a biotrickling filter-bioreactor system

Complete treatment of sulfur dioxide (SO2) from flue gases in a two-stage process consisting of a biotrickling filter followed by biological post-treatment unit was investigated. The biotrickling filter could remove 100% of influent SO2 from simulated flue gas at an empty bed residence time of 6 s for a concentration range of 300-1000 ppm(v). All the absorbed SO2 was recovered in the biotrickling filter liquid effluent as sulfite (a product of chemical reaction of SO2) and sulfate (product of biological oxidation of sulfite). The biotrickling filter liquid effluent was further processed biologically in a single post-treatment unit consisting of a combined anaerobic and microaerophilic reactor for the simultaneous reduction of sulfate and sulfite to sulfide and oxidation of sulfide to elemental sulfur. The post-treatment unit could effectively treat the biotrickling filter effluent and produce elemental sulfur. The sulfur production efficiency of the reactor reached about 80% of the SO2 treated. This new biological treatment system seems to be a promising alternative for flue gas desulfurization.     

Iron blast furnace slag/hydrated lime sorbents for flue gas desulfurization

Sorbents prepared from iron blast furnace slag (BFS) and hydrated lime (HL) through the hydration process have been studied with the aim to evaluate their reactivities toward SO2 under the conditions prevailing in dry or semidry flue gas desulfurization processes. The BFS/HL sorbents, having large surface areas and pore volumes due to the formation of products of hydration, were highly reactive toward SO2, as compared with hydrated lime alone (0.24 in Ca utilization). The sorbent reactivity increased as the slurrying temperature and time increased and as the particle size of BFS decreased; the effects of the liquid/solid ratio and the sorbent drying conditions were negligible. The structural properties and the reactivity of sorbent were markedly affected by the BFS/HL ratio; the sorbent with 30/70 ratio had the highest 1 h utilization of Ca, 0.70, and SO2 capture, 0.45 g SO2/g sorbent. The reactivity of a sorbent was related to its initial specific surface area (Sg0) and molar content of Ca (M(-1)); the 1 h utilization of Ca increased almost linearly with increasing Sg0/M. The results of this study are useful to the preparation of BFS/HL sorbents with high reactivity for use in the dry and semidry processes to remove SO2 from the flue gas.     

Survey of catalysts for oxidation of mercury in flue gas

Methods for removing mercury from flue gas have received increased attention because of recent limitations placed on mercury emissions from coal-fired utility boilers by the U. S. Environmental Protection Agency and various states. A promising method for mercury removal is catalytic oxidation of elemental mercury (Hg0) to oxidized mercury (Hg2+), followed by wet flue gas desulfurization (FGD). FGD cannot remove Hg0, but easily removes Hg2+ because of its solubility in water. To date, research has focused on three broad catalyst areas: selective catalytic reduction catalysts, carbon-based materials, and metals and metal oxides. We review published results for each type of catalyst and also present a discussion on the possible reaction mechanisms in each case. One of the major sources of uncertainty in understanding catalytic mercury oxidation is a lack of knowledge of the reaction mechanisms and kinetics. Thus, we propose that future research in this area should focus on two major aspects: determining the reaction mechanism and kinetics and searching for more cost-effective catalyst and support materials.     

Adsorption enhancement mechanisms of silica-titania nanocomposites for elemental mercury vapor removal

A novel nanocomposite that combines high-surface area silica with the photocatalytic properties of titania has been developed that allows for effective capture of elemental mercury vapor. The adsorption capability of the developed material has been found to improve after periods of photocatalytic oxidation. In this study, the mechanisms for adsorption enhancement were identified. BET nitrogen adsorption and mercury porosimetry were used to evaluate pore structure, and the results suggest that a decrease in contact angle was likely to be responsible for improved mercury capture over time. Contact angle measurements showed a significant change of more than 10 degrees, indicating greater attraction to mercury for the used pellets due to deposited mercuric oxide. ICP and TGA analyses showed that mercury was captured as both elemental mercury (Hg0) and mercuric oxide (HgO). In addition, it was shown that pellets used for nearly 500 h still showed greater than 90% removal efficiency and had an average capacity of 10 mg of Hg/g based on mass balance calculations, while some pellets had a capacity over 30 mg of Hg/g according to ICP and TGA analyses. Mercuric oxide doped pellets removed 100% of elemental mercury without pretreatment. The superior mercury removal efficiency combined with various advantages of the novel composite demonstrates its use as an effective alternative to conventional activated carbon injection technology.     

Characteristics of PCDD/F distributions in vapor and solid phases and emissions from the Waelz process

The Waelz process is a classic method used for recovering zinc from electric arc furnace (EAF) dusts containing relatively high concentrations of PCDD/Fs (polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans) as well as volatile metals, such as Zn, Pb, and Cu, and chlorine. As a result of the operating temperature in the cooling process and high carbon and chlorine contents, significant PCDD/Fs are formed in the typical Waelz process, causing public concerns regarding PCDD/F emissions. In this study, flue gas and ash samplings are simultaneously conducted at different sampling points to evaluate the removal efficiency and the partitioning of PCDD/Fs between the vapor and solid phases in the Waelz plant investigated. With the environment (temperature window, sufficient retention time, chlorine, and catalysts available) conducive to PCDD/F formation in the dust settling chamber (DSC), a significantly high PCDD/F concentration (1223 ng TEQ/Nm3) is measured in flue gas downstream from the DSC of the Waelz plant investigated. In addition, the cyclone and bag filter adopted in this facility can only remove 51.3% and 69.4%, respectively, of the PCDD/Fs in the flue gas, resulting in a high PCDD/F concentration (145 ng TEQ/Nm3) measured in the stack gas of the Waelz plant investigated. On the basis of treating 1 ton of EAF dust, the total PCDD/F discharge (stack gas emission + ash discharge) is 840 ng TEQ/kg EAF dust of the Waelz plant investigated. Because of the lack of effective air pollutant control devices for PCDD/Fs, about 560 ng TEQ/kg EAF dust are discharged via stack gas in this facility.     

Impact of sulfur oxides on mercury capture by activated carbon

Recent field tests of mercury removal with activated carbon injection (ACI) have revealed that mercury capture is limited in flue gases containing high concentrations of sulfur oxides (SOx). In order to gain a more complete understanding of the impact of SOx on ACl, mercury capture was tested under varying conditions of SO2 and SO3 concentrations using a packed bed reactor and simulated flue gas (SFG). The final mercury content of the activated carbons is independent of the SO2 concentration in the SFG, but the presence of SO3 inhibits mercury capture even at the lowest concentration tested (20 ppm). The mercury removal capacity decreases as the sulfur content of the used activated carbons increases from 1 to 10%. In one extreme case, an activated carbon with 10% sulfur, prepared by H2SO4 impregnation, shows almost no mercury capacity. The results suggest that mercury and sulfur oxides are in competition for the same binding sites on the carbon surface.     

Electrically regenerated ion exchange for removal and recovery of Cr(VI) from wastewater

Ion exchange is widely used for removal and recovery of Cr(VI) from wastewater. Generally, the exhausted ion exchanger is regenerated using chemicals. Although chemical regeneration is efficient, contaminants are introduced, leading to difficulty for the subsequent recovery of Cr(VI). To overcome such a problem, a new regeneration method, namely electrical regeneration, which is carried out on the principle of electrodialysis, is presented in this paper. Experimental results showed that the weak-base resin used could be effectively regenerated electrically. About 93% capacity of the resin was restored under a constant current of 0.25 A over a period of 24 h. The pure chromic acid was recovered in the anode chamber with a concentration of 5.03 g Cr(VI)/L. It was found that the weak-base resin regenerated electrically could remove Cr(VI) from wastewater as effectively as that regenerated chemically. The Cr(VI) concentration was reduced from initial 50 mg/L to lower than the detectable limit, 0.01 mg/L, after treatment.     

Mercury vapor pressure of flue gas desulfurization scrubber suspensions: effects of pH level, gypsum, and iron

Calcium-based scrubbers designed to absorb HCl and SO(2) from flue gases can also remove oxidized mercury. Dissolved mercury halides may have an appreciable partial vapor pressure. Chemical reduction of the dissolved mercury may increase the Hg emission, thereby limiting the coremoval of mercury in the wet scrubbing process. In this paper we evaluate the effects of the pH level, different gypsum qualities, and iron in flue gas desulfurization (FGD) scrubber suspensions. The impact of these parameters on mercury vapor pressure was studied under controlled laboratory conditions in model scrubber suspensions. A major influence is exerted by pH values above 7, considerably amplifying the mercury concentration in the vapor phase above the FGD scrubber suspension. Gypsum also increases the mercury re-emission. Fe(III) decreases and Fe(II) increases the vapor pressure significantly. The consequences of the findings for a reliable coremoval of mercury in FGD scrubbers are discussed. It is shown that there is an increased risk of poor mercury capture in lime-based FGD scrubbers in comparison to limestone FGD scrubbers.     

Control of electrothermal heating during regeneration of activated carbon fiber cloth

Electrothermal swing adsorption (ESA) of organic gases generated by industrial processes can reduce atmospheric emissions and allow for reuse of recovered product. Desorption energy efficiency can be improved through control of adsorbent heating, allowing for cost-effective separation and concentration of these gases for reuse. ESA experiments with an air stream containing 2000 ppm(v) isobutane and activated carbon fiber cloth (ACFC) were performed to evaluate regeneration energy consumption. Control logic based on temperature feedback achieved select temperature and power profiles during regeneration cycles while maintaining the ACFC's mean regeneration temperature (200 °C). Energy requirements for regeneration were independent of differences in temperature/power oscillations (1186-1237 kJ/mol of isobutane). ACFC was also heated to a ramped set-point, and the average absolute error between the actual and set-point temperatures was small (0.73%), demonstrating stable control as set-point temperatures vary, which is necessary for practical applications (e.g., higher temperatures for higher boiling point gases). Additional logic that increased the maximum power application at lower ACFC temperatures resulted in a 36% decrease in energy consumption. Implementing such control logic improves energy efficiency for separating and concentrating organic gases for post-desorption liquefaction of the organic gas for reuse.     

Application of amine-tethered solid sorbents for direct CO2 capture from the ambient air

While current carbon capture and sequestration (CCS) technologies for large point sources can help address the impact of CO(2) buildup on global climate change, these technologies can at best slow the rate of increase of the atmospheric CO(2) concentration. In contrast, the direct CO(2) capture from ambient air offers the potential to be a truly carbon negative technology. We propose here that amine-based solid adsorbents have significant promise as key components of a hypothetical air capture process. Specifically, the CO(2) capture characteristics of hyperbranched aminosilica (HAS) materials are evaluated here using CO(2) mixtures that simulate ambient atmospheric concentrations (400 ppm CO(2) = "air capture") as well as more traditional conditions simulating flue gas (10% CO(2)). The air capture experiments demonstrate that the adsorption capacity of HAS adsorbents are only marginally influenced even with a significant dilution of the CO(2) concentration by a factor of 250, while capturing CO(2) reversibly without significant degradation of performance in multicyclic operation. These results suggest that solid amine-based air capture processes have the potential to be an effective approach to extracting CO(2) from the ambient air.