Development of nano-niO/Al2O3 catalyst to be used for tar removal in biomass gasification.

The objective of this study isto develop a novel supported nano-NiO catalyst for tar removal in biomass gasification/pyrolysis, to significantly enhance the quality of the produced gases. For this purpose, the supported nano-NiO/gamma-Al2O3 catalyst was prepared by deposition-precipitation (DP) method. Different analytical approaches such as XRD, BET, TEM and SEM/EDX were used to characterize the synthesized catalysts. The results showed thatthe prepared nano-NiO/gamma-Al2O3 catalysts had a coated structure with a loading of NiO in catalysts over 12 wt %, and they had also a higher BET surface area over commercial nickel based catalysts. The active components of catalyst were spherical NiO nanoparticles coated on the surface of supports with a size range of 12-18 nm. Furthermore, the activity of the catalysts to remove tar in the process of biomass pyrolysis was also investigated using a bench-scale combined fixed bed reactor. The experiments demonstrated that the tar yield after addition of the catalyst was reduced significantly; the tar removal efficiency reached to 99% for catalytic pyrolysis at 800 degrees C, and the gas yield after addition of the catalyst increased markedly. The compositions of gas products before and after addition of the catalyst in the process also changed significantly. The percentages of CO2 and CH4 in the product gas after addition of the catalysts were obviously reduced, while those of the valuable H2 and CO strongly increased. Therefore, using the prepared NiO/gamma-Al2O3 catalyst in biomass gasification/pyrolysis can significantly improve the quality of the produced gas and meanwhile efficiently eliminate the tar generation.

Characteristics of rapidly formed hydrogen-producing granules and biofilms.

The physicochemical and microbiological characteristics of rapidly formed hydrogen-producing granules and biofilms were evaluated in the present study. Microbial species composition was examined using the 16S rDNA-based separation and sequencing techniques, and spatial distribution and internal structure of microbial components were evaluated by examining the confocal laser scanning microscope (CLSM) images. Phylogenetic analysis indicated that a pure culture of Clostridium pasteurianum-like bacterium (98% similarity) was found in microbial community of granules and biofilms. It is postulated that containing such a species favored the rapid immobilization of hydrogen-producing culture. Manure granules and biofilms secreted 24-35 mg extracellulous proteins and 142-175 mg extracellulous polysaccharides in each gram of culture (in VSS). Such a high productivity of extracellulous polymers (ECP), a bio-glue to facilitate cell-to-cell and/or cell-to-substratum interaction, may work as the driving forces for the immobilization of C. pasteurianum. As abundant proteins were noted in the granule cores, it can be derived that rapid formation of the hydrogen-producing granules could be due to the establishment of precursor protein-rich microbial nuclei.

Aerobic granulation under the combined hydraulic and loading selection pressures.

Two SBR reactors were set up to investigate the feasibility of aerobic granulation under the combined selection pressures of hydraulic shear force and substrate loading. Aerobic granulation was studied at superficial upflow air velocity of 3.2 and 2.4 cm/s under an organic loading rate (OLR) range of 6.0-15.0 kg COD/m3d. Good reactor performance and well granule characteristics were achieved in a wide OLR range from 6.0 high up to 15.0 kg COD/m3d at 3.2 cm/s. While under the velocity of 2.4 cm/s, stable operation was limited in the OLR range of 6.0-9.0 kg COD/m3d and failed to operate with granule deterioration under further higher OLRs. The optimal combination of hydrodynamic shear force and loading selection pressure was demonstrated to be an important factor that influence aerobic granulation and govern the granule characteristics and reactor performance.

Biodegradation and kinetics of aerobic granules under high organic loading rates in sequencing batch reactor.

Biodegradation, kinetics, and microbial diversity of aerobic granules were investigated under a high range of organic loading rate 6.0 to 12.0 kg chemical oxygen demand (COD) m(-3) day(-1) in a sequencing batch reactor. The selection and enriching of different bacterial species under different organic loading rates had an important effect on the characteristics and performance of the mature aerobic granules and caused the difference on granular biodegradation and kinetic behaviors. Good granular characteristics and performance were presented at steady state under various organic loading rates. Larger and denser aerobic granules were developed and stabilized at relatively higher organic loading rates with decreased bioactivity in terms of specific oxygen utilization rate and specific growth rate (muoverall) or solid retention time. The decrease of bioactivity was helpful to maintain granule stability under high organic loading rates and improve reactor operation. The corresponding biokinetic coefficients of endogenous decay rate (kd), observed yield (Yobs), and theoretical yield (Y) were measured and calculated in this study. As the increase of organic loading rate, a decreased net sludge production (Yobs) is associated with an increased solid retention time, while kd and Y changed insignificantly and can be regarded as constants under different organic loading rates.

Structure and stability of aerobic granules cultivated under different shear force in sequencing batch reactors.

The cultivation of stable aerobic granules as well as granular structure and stability in sequencing batch reactors under different shear force were investigated in this study. Four column sequencing batch reactors (R1-R4) were operated under various shear force, in terms of superficial upflow air velocity of 0.8, 1.6, 2.4, and 3.2 cm s(-1), respectively. Aerobic granules were formed in all reactors in the experiment. It was found that the magnitude of shear force has an important impact on the granule stability. At shear force of 2.4 and 3.2 cm s(-1), granules can maintain a robust structure and have the potential of long-term operation. Granules developed in low shear force (R1, 0.8 cm s(-1) and R2, 1.6 cm s(-1)) deteriorated to large-sized filamentous granules with irregular shape, loose structure and resulted in poor performance and operation instability. Granules cultivated under high shear force (R3, 2.4 cm s(-1) and R4, 3.2 cm s(-1)) stabilized to clear outer morphology, dense and compact structure, and with good performance in 120 days operation. Fractal dimension (Df) represents the internal structure of granules and can be used as an important indicator to describe the structure and stability of granules. Due to the combined effects of shear force and growth force, the mature granules developed in R3 and R4 also displayed certain differences in granular structure and characteristics.

Rapid formation of hydrogen-producing granules in an anaerobic continuous stirred tank reactor induced by acid incubation.

A novel approach to rapidly initiate granulation of hydrogen-producing sludge was developed in an anaerobic continuous stirred tank reactor at 37 degrees C. To induce microbial granulation, the acclimated culture was subject to an acid incubation for 24 h by shifting the culture pH from 5.5 to 2.0. The culture was resumed to pH 5.5 after the incubation and the reactor was operated at hydraulic retention times (HRTs) of 12, 6, 2, 1, and 0.5 h in sequence. Microbial aggregation took place immediately with the initiation of acid incubation and granules were developed at 114 h. No granule was observed in the absence of acid incubation in the control test. Changing the culture pH resulted in improvement in surface physicochemical properties of the culture favoring microbial granulation. The zeta potential increased from -11.6 to -3.5 mV, hydrophobicity in terms of contact angle improved from 31 degrees to 43 degrees and extracellular proteins/polysaccharides ratio increased from 0.2 to 0.5-0.8. Formation of granular sludge facilitated biomass retention of up to 32.2 g-VSS/L and enhanced hydrogen production. The hydrogen production rate and hydrogen yield increased with the reduction in HRT at an influent glucose concentration of 10 g/L once steady granular sludge layer was formed, achieving the respective peaks of 3.20 L/L x h and 1.81 mol-H(2)/mol-glucose at 0.5 h HRT. The experimental results suggested that acid incubation was able to initiate the rapid formation of hydrogen-producing granules by regulating the surface characteristics of microbial aggregates in a well-mixed reactor, which enhanced the hydrogen production.

Influence of surface properties on the mechanism of H2S removal by alkaline activated carbons.

Alkaline activated carbons are widely used as adsorbents of hydrogen sulfide (H2S), one of the major odorous compounds arising from sewage treatment facilities. Although a number of studies have explored the effects of various parameters, mechanisms of H2S adsorption by alkaline carbons are not yet fully understood. The major difficulty seems to lie in the fact that little is known with certainty about the predominant reactions occurring on the carbon surface. In this study, the surface properties of alkaline activated carbons were systematically investigated to further exploit and better understand the mechanisms of H2S adsorption by alkaline activated carbons. Two commercially available alkaline activated carbons and their representative exhausted samples (8 samples collected at different height of the column after H2S breakthrough tests) were studied. The 8 portions of the exhausted carbon were used to represent the H2S/carbon reaction process. The surface properties of both the original and the exhausted carbons were characterized using the sorption of nitrogen (BET test), surface pH, Boehm titration, thermal and FTIR analysis. Porosity and surface area provide detailed information about the pore structure of the exhausted carbons with respect to the reaction extent facilitating the understanding of potential pore blockages. Results of Boehm titration and FTIR both demonstrate the significant effects of surface functional groups, and identification of oxidation products confirmed the different mechanisms involved with the two carbons. From the DTG curves of thermal analysis, two well-defined peaks representing two products of surface reactions (i.e., sulfur and sulfuric acid) were observed from the 8 exhausted portions with gradually changing patterns coinciding with the extent of the reaction. Surface pH values of the exhausted carbons show a clear trend of pH drop along the reaction extent, while pH around 2 was observed for the bottom of the bed indicating sulfuric acid as the predominant products. Although both carbons are coal-based and of KOH impregnated type, performances of different carbons differ significantly. A correlation is well established to link the reaction extent with various surface properties. In summary, not only the homogeneous alkali impregnation and physical porosity but also the carbon surface chemistry are significant factors influencing the performances of alkaline activated carbons as H2S adsorbents.

Control of mercury vapor emissions from combustion flue gas.

GOAL, SCOPE AND BACKGROUND: Mercury (Hg) emission from combustion flue gas is a significant environmental concern due to its toxicity and high volatility. A number of the research efforts have been carried out in the past decade exploiting mercury emission, monitoring and control from combustion flue gases. Most recently, increasing activities are focused on evaluating the behavior of mercury in coal combustion systems and developing novel Hg control technologies. This is partly due to the new regulatory requirement on mercury emissions from coal-fired combustors to be enacted under the U.S. Title III of the 1990 Clean Air Act Amendments. The aim of this review work is to better understand the state-of-the-art technologies of flue gas mercury control and identify the gaps of knowledge hence areas for further opportunities in research and development. MAIN FEATURES: This paper examines mercury behaviors in combustion systems through a comprehensive review of the available literature. About 70 published papers and reports were cited and studied. RESULTS AND DISCUSSION: This paper summarizes the mechanisms of formation of mercury containing compounds during combustion, its speciation and reaction in flue gas, as well as subsequent mobilization in the environment. It also provides a review of the current techniques designed for real-time, continuous emission monitoring (CEM) for mercury. Most importantly, current flue gas mercury control technologies are reviewed while activated carbon adsorption, a technology that offers the greatest potential for the control of gas-phase mercury emissions, is highlighted. CONCLUSIONS AND RECOMMENDATIONS: Although much progress has been achieved in the last decade, techniques developed for the monitoring and control of mercury from combustion flue gases are not yet mature and gaps in knowledge exist for further advancement. More R&D efforts are required for the effective control of Hg emissions and the main focuses are identified.

Kinetic study of hydrated lime reaction with HCl.

Hydrochloride (HCl) is an acidic pollutant present in the flue gas of most municipal or hazardous waste incinerators. Hydrated lime (Ca(OH)2) is often used as a dry sorbent for injection in a spray reactor to remove HCI. However, due to the short residence time encountered, this control method has generally been found to have low conversion efficiencies which results in the high lime usage and generates large amount of fly ash as solid wastes. A fundamental study was carried outto investigate the kinetics of HCl-lime reaction under simulated flue gas conditions in order to better understand the process thereby providing a basis for an optimized lime usage and reduced fly ash production. The initial reaction rate and conversion of three limes were studied using a thermogravimetric analyzer by varying the gas flow rate, temperature (170-400 degrees C), and HCI concentrations (600-1200 mg/m3) as well as the associated particle size and surface area of the limes. The initial lime conversions were found to rely mostly on the residence time, while the ultimate lime conversions were strongly influenced by temperature and the reaction products. CaOHCI was found to be the primary product in most cases, while for one specific lime, CaCl2 was the ultimate conversion product after an extended time period. The true utilization of lime in flue gas cleanup is thus higher when CaOHCl is considered as the final product than those based on CaCl2 as the final product, which has been commonly used in previous studies. The initial reaction was controlled by diffusion of HCl in gas phase and the subsequent reaction by gaseous diffusion through the developing product layer. Increasing the HCI concentration raised the initial rate as well as conversion. However, overloading the lime with excessive HCI caused clogging at its surface and a drop in the ultimate conversion. Limes with smaller particle diameters and higher surface areas were found to be more reactive. The effect of gas-phase mass transfer was minimized when an optimum flow rate was chosen, and in the absence of internal diffusion the reaction was found to be first order with respect to HCI concentration.

Kinetics and mechanisms of H2S adsorption by alkaline activated carbon.

Activated carbon adsorption is widely used to remove hydrogen sulfide (H2S), one of the major odorous compounds, from gas streams. In this study, the mechanisms of H2S adsorption by alkaline activated carbon were systematically studied. Two brands of commercial activated carbons were used as H2S adsorbents. A series of designed experiments were carried outto understand on a fundamental basis the differences in H2S removal capacity observed for the two types of carbons and samples for the same carbon obtained from different batches. The physicochemical and structural characteristics of the original and exhausted activated carbons were identified using several analytical approaches (i.e., XRF, SEM, XRD, and BET). The relationships between the adsorption performances of activated carbon for H2S and its physicochemical characteristics were discussed. The kinetics of the H2S adsorption was also studied using TGA/DSC system. Both physical adsorption and chemisorption played an important role in the H2S adsorption mechanisms with the studied carbons. Chemisorption was rapid and occurred mostly at the carbon surface whereas physical adsorption was relatively slow and mostly took place at the inner pores of carbon. Carbon II demonstrated the best performance of H2S removal due to its high capacity of both physical adsorption and chemisorption. Catalytic effects of transition metals might also contribute to enhancing the H2S oxidation.