Regenerative thermal oxidation of airborne N, N-dimethylformamide and its associated nitrogen oxides formation characteristics

In this study, a two-bed electrically heated regenerative thermal oxidizer (RTO) was used to test the thermal destruction and oxides of nitrogen (NOx) formation characteristics in burning airstreams that contain either N, N-dimethylformamide or dimethylformamide (DMF) mixed with methyl ethyl ketone (MEK). The RTO contained two 0.152 m x 0.14 m x 1 m (L x W times] H) beds, both packed with gravel particles with an average diameter of approximately 0.0111 m and a height of up to 1 m with a void fraction of 0.42 in the packed section. The thermal recovery efficiency (TRE) and the gas pressure drop over the beds were also studied. Experimental results reveal that, with a valve shifting time (ts) of 1.5 min, a superficial gas velocity (Ug) of 0.39 m/sec (evaluated at an influent air temperature of around 30 degrees C) and preset maximum destruction temperatures (Ts) of 750-950 degrees C, no NOx was present in the effluent gas from the RTO when it was loaded with DMF-free air. When only DMF was present in the influent air, the average destruction efficiencies exceeded 96%, and increased with the influent DMF concentration from 300 to 750 mg/N x m3. The "NOx-N formation/DMF-N destruction" mass ratios were in the range 0.76-1.05, and decreased as the influent DMF concentration increased within the experimental range. When both DMF and MEK were present in the influent gas, the NO, formation ratio was almost the same and the DMF destruction efficiency increased with the influent MEK/DMF ratio from 150/300 to 4500/300 (mg/mg) and in the preset temperature range. The NOx formation ratios were in the range 0.75-0.96. The TRE decreased as Ug increased but was invariant with Ts. The Ergun equation was found to suffice in the estimation of the pressure drop when the gas flowed over the packing beds.     

Bioconversion of Dimethylformamide in Biofilters

ABSTRACT

Bioconversion of dimethylformamide (DMF) was studied using two sets of three-stages-in-series biofilters, one packed with inoculated pig manure and the other with coconut fiber compost-based media. The two media were different in carbon/nitrogen (C/N) ratio and specific area. Tests were made to compare effects of different C/N ratio and specific area on the performance of the filter and on the variation of physicochemical properties of the media for treating DMF. DMF concentration in the influent air stream was in the range of 100 to 4,500 mg/m³. The gas retention time (GRT) in the first stages of both filters was 19 to 76 sec. The volumetric loading of DMF (L) to the first stages of both filters was 3 to 97 g DMF-N/m³.h (15.6 to 506 g DMF/m³.h). Results indicated that DMF was successively hydrolyzed to ammonia and nitrified to nitrite and nitrate or incorporated into microbial cell. Inlet portions of the media subjected to high DMF or ammonia loading varied greatly in pH due to insufficient buffering capacity. The middle portions of the media subjected to moderate ammonia loading were suitable for nitrification. The coconut fiber compost media with a higher initial C/ N ratio and porosity favored the elimination of DMF. For the media, DMF-N removal efficiencies of larger than 90% were obtained with L < 50 g DMF-N/m³.h and GRT > 23 sec. The pig manure compost media with a lower initial C/N ratio favored the nitrification reaction; its maximum capacity was 8.58 g NO₃ ^--N/m³.h.     

Performance Characteristics of a Regenerative Catalytic Oxidizer for Treating VOC-Contaminated Airstreams

ABSTRACT

A pilot apparatus of a regenerative catalytic oxidizer (RCO) equipped with two electrical heaters and two 20-cm i.d. × 200-cm height regenerative beds was used to treat methyl ethyl ketone (MEK) and toluene, respectively, in an airstream. The regenerative beds were packed with gravel (approximate particle size 1.25 cm, specific area 205 m²/m³, and specific heat capacity 840 J/kg °C) as a solid regenerative material and K-type thermal couples for measuring solid and gas temperatures, respectively. The catalyst bed temperature was kept around 400 °C and the gas superficial velocity was operated at 0.234 m/sec. This investigation measured and analyzed distributions of solid and gas temperatures with operating time and variations of volatile organic compound (VOC) concentrations in the regenerative beds. The overall VOC removal efficiency exceeded 98% for MEK and 95% for toluene. Degradation of VOCs will exist for MEK on the surface of solid material (gravel) in the temperature range of 330-400 °C, but toluene does not exhibit this phenomenon.     

Sub-region (district) and sector level SO2 and NOx emissions for India: assessment of inventories and mitigation flexibility

Sub-regional and sector level distribution of SO₂ and NO_x emissions inventories for India have been estimated for all the 466 Indian districts using base data for years 1990 and 1995. Although, national level emissions provide general guidelines for assessing mitigation alternatives, but significant regional and sectoral variability exist in Indian emissions. Districts reasonably capture this variability to a fine grid as 80% of these districts are smaller than 1°×1° resolution with 60% being smaller than even 1/2°×1/2°. Moreover, districts in India have well-established administrative and institutional mechanisms that would be useful for implementing and monitoring measures. District level emission estimates thus offer a finer regional scale inventory covering the combined interests of the scientific community and policy makers. The inventory assessment methodology adopted is similar to that prescribed by the Intergovernmental Panel on Climate Change (IPCC) for greenhouse gas (GHG) emissions. The sectoral decomposition at district level includes emissions from fossil fuel combustion, non-energy emissions from industrial activities and agriculture. Total SO₂ and NO_x emissions from India were 3542 and 2636 Gg, respectively (1990) and 4638 and 3462 Gg (1995) growing at annual rate of around 5.5%. The sectoral composition of SO₂ emissions indicates a predominance of electric power generation sector (46%). Power and transport sector emissions equally dominate NO_x emissions contributing nearly 30% each. However, majority of power plants are situated in predominantly rural districts while the latter are concentrated in large urban centers. Mitigation efforts for transport sector NO_x emissions would therefore be higher. The district level analysis indicates diverse spatial distribution with the top 5% emitting districts contributing 46.5 and 33.3% of total national SO₂ and NO_x emissions, respectively. This skewed emission pattern, with a few districts, sectors and point sources emitting significant SO₂ and NO_x, offers mitigation flexibility to policy makers for cost-effective mitigation.     

Adsorptive conversion of nitrogen dioxide from etching vent gases over activated carbon

Some metal etching operations emit limited flow rates of waste gases with reddish-brown NO₂ fume, which may cause visual and acidic-odor complaints, as well as negative health effects. In this study, tests were performed by passing caustic-treated waste gases vented from Al-etching operations through columns packed either with virgin or regenerated granular activated carbon (GAC) to test their adsorptive conversion performance of NO₂ in the gases. The gases contained 5–55 ppm NO₂ and acetic and nitric acids of below 3 ppm. Exhausted carbon was regenerated by scrubbing it with caustic solution and water, and dried for further adsorption tests. Results indicate that with an (empty bed residence time (EBRT) of 0.15 sec for the gas through the GAC-packed space, around 60% of the influent NO₂ of 54 ppm could be removed, and 47% of the removed NO₂ was converted by and desorbed from the carbon as NO. GAC used in the present study could be regenerated at least twice to restore its capacity for NO₂ adsorption. Within EBRTs of 0.076–0.18 sec, the adsorptive conversion capacity was linearly varied with EBRT. In practice, with an EBRT of 0.20 sec, a conversion capacity of 0.80 kg NO₂ (kg GAC)^?1 with an influent NO₂ of 40 ppm can be used as a basis for system design.

Implications: Some metal etching operations emit waste gases with reddish-brown (yellow when diluted) NO₂ fume which may cause visual and acidic-odor complaints, as well as negative health effects. This study provides a simple process for the adsorptive conversion of NO₂ in caustic-treated waste gases vented from metal-etching operations through a GAC column. With an EBRT of 0.20 sec, a conversion capacity of 0.80 kg NO₂ (kg GAC)^?1 with an influent NO₂ of 40 ppm can be used as a basis for system design. Saturated GAC can be regenerated at least twice by simply scrubbing it with aqueous caustic solution.     

Nitrogen oxides emissions from the MILD combustion with the conditions of recirculation gas

The nitrogen oxides (NO_x) reduction technology by combustion modification which has economic benefits as a method of controlling NO_x emitted in the combustion process, has recently been receiving a lot of attention. Especially, the moderate or intense low oxygen dilution (MILD) combustion which applied high temperature flue gas recirculation has been confirmed for its effectiveness with regard to solid fuel as well. MILD combustion is affected by the flue gas recirculation ratio and the composition of recirculation gas, so its NO_x reduction efficiency is determined by them. In order to investigate the influence of factors which determine the reduction efficiency of NO_x in MILD coal combustion, this study changed the flow rate and concentration of nitrogen (N₂), carbon dioxide (CO₂) and steam (H₂O) which simulate the recirculation gas during the MILD coal combustion using our lab-scale drop tube furnace and performed the combustion experiment. As a result, its influence by the composition of recirculation gas was insignificant and it was shown that flue gas recirculation ratio influences the change of NO_x concentration greatly. Implications: We investigated the influence of factors determining the nitrogen oxides (NO_x) reduction efficiency in MILD coal combustion, which applied high-temperature flue gas recirculation. Using a lab-scale drop tube furnace and simulated recirculation gas, we conducted combustion testing changing the recirculation gas conditions. We found that the flue gas recirculation ratio influences the reduction of NO_x emissions the most.     

Radical precursors and related species from traffic as observed and modeled at an urban highway junction

Nitrous acid (HONO) and formaldehyde (HCHO) are important precursors for radicals and are believed to favor ozone formation significantly. Traffic emission data for both compounds are scarce and mostly outdated. A better knowledge of today's HCHO and HONO emissions related to traffic is needed to refine air quality models. Here the authors report results from continuous ambient air measurements taken at a highway junction in Houston, Texas, from July 15 to October 15, 2009. The observational data were compared with emission estimates from currently available mobile emission models (MOBILE6; MOVES [MOtor Vehicle Emission Simulator]). Observations indicated a molar carbon monoxide (CO) versus nitrogen oxides (NO_x) ratio of 6.01 ± 0.15 (r ² = 0.91), which is in agreement with other field studies. Both MOBILE6 and MOVES overestimate this emission ratio by 92% and 24%, respectively. For HCHO/CO, an overall slope of 3.14 ± 0.14 g HCHO/kg CO was observed. Whereas MOBILE6 largely underestimates this ratio by 77%, MOVES calculates somewhat higher HCHO/CO ratios (1.87) than MOBILE6, but is still significantly lower than the observed ratio. MOVES shows high HCHO/CO ratios during the early morning hours due to heavy-duty diesel off-network emissions. The differences of the modeled CO/NO_x and HCHO/CO ratios are largely due to higher NO_x and HCHO emissions in MOVES (30% and 57%, respectively, increased from MOBILE6 for 2009), as CO emissions were about the same in both models. The observed HONO/NO_x emission ratio is around 0.017 ± 0.0009 kg HONO/kg NO_x which is twice as high as in MOVES. The observed NO₂/NO_x emission ratio is around 0.16 ± 0.01 kg NO₂/kg NO_x, which is a bit more than 50% higher than in MOVES. MOVES overestimates the CO/CO₂ emission ratio by a factor of 3 compared with the observations, which is 0.0033 ± 0.0002 kg CO/kg CO₂. This as well as CO/NO_x overestimation is coming from light-duty gasoline vehicles.

Implications: Nitrous acid (HONO) and formaldehyde (HCHO) are important precursors for radicals that ultimately contribute to ozone formation. There still exist uncertainties in emission sources of HONO and HCHO and thus regional air quality modeling still tend to underestimate concentrations of free radicals in the atmosphere. This paper demonstrates that the latest U.S. Environmental Protection Agency (EPA) traffic emission model MOVES still shows significant deviations from observed emission ratios, in particular underestimation of HCHO/CO and HONO/NO_x ratios. Improving the performance of MOVES may improve regional air quality modeling.     

中小型工业窑炉NO_x废气的净化技术与应用

介绍了中小型工业窑炉生产过程中排放NOx的现状,并针对NOx的治理问题,从工程应用角度,简述了湿法和干法净化NOx的原理和化学反应过程。讨论了NOx排放特性和NOx废气中NO2/NOx比例的问题。提出了影响NOx治理的主要因素,包括吸收剂、吸附剂、催化剂和设备的部分应用参数,并结合工程实例指出工程需要注意的问题。介绍了多项采用湿法和干法净化NOx的工程应用项目,丰富了中小工业窑炉NOx废气的治理的实践经验,为中小工业窑炉排放NOx治理奠定了基础。     

NOX Levels in the Caracas Valley

An analysis of air quality data from 1970-1975 in the Los Angeles (LA) Basin has been made with emphasis on factors relevant to high hourly NO₂ concentrations, (NO₂). Detailed analysis of CO and SO₂ air quality and the (NO _x )/(CO) and (CO)/(SO₂) ratios reveals that high (NO₂) result mainly from vehicular sources; contributions from stationary sources to these high (NO₂) of greater than 10% occur rarely. Meteorological conditions (very low early-morning inversion base height and low wind speed) favoring the formation of high (NO₂) restrict the impact of elevated point NO _x sources on the ground level (NO₂) during the early to mid-morning hours. The overnight leftover NO _x during high NO₂ days is shown to originate largely from local sources near the monitoring sites. A regression analysis using NO₂, NO _x and HC data from downtown LA shows that a 50% reduction in (NO _x ) reduces high (NO₂) by 40-45%; a 50% reduction in (HC) reduces high (NO₂) by 5-10%. The present analysis supports assumptions used in an earlier generalized rollback model that related NO _x emissions to high 1-h average (NO₂) observed at downtown LA.     

生物滤塔和NRB在有氧条件下去除废气中的NOx

研究了有氧条件下氮氧化物在生物滤塔内的传质机理,结果表明,当含NOx废气中氧气含量为20%、氧化度为80%时,被生物滤塔内微生物吸附分解的NOx仅占被净化的NOx的12%左右,而88%左右的NOx没有被微生物及时分解,而是转入液相中形成NO3-和NO2-.在此基础上,提出了采用生物滤塔和硝酸盐脱除反应器(nitrate...     

NOx Reduction in a Gas Fired Utility Boiler by Combustion Modifications

Data on the effect of several combustion modifications on the formation of nitrogen oxides and on boiler efficiency were acquired and analyzed for a 110 MW gas fired utility boiler. The results from the study showed that decreasing the oxygen in the flue gas from 2.2% to 0.6% reduced the NO_x formation by 33% and also gave better boiler efficiencies. Flue gas recirculation through the bottom of the firebox was found to be ineffective. Staged combustion was found to reduce the NO_x emissions by as much as 55 % while decreasing the efficiency by about 5%. Adjustment of the burner air registers reduced the NO_x formation by about 20 ppm. The lowest NO_x emissions of 42 ppm (at about 3% O₂) in the stack was obtained for air only to one top burner and 0.5% oxygen in the flue gas.     

Four Common Diagnostic Problems that Inhibit Radon Mitigation

Abstract

An activated sludge aeration tank (40 × 40 × 300 cm, width × length × height) with a set of 2-mm orifice air spargers was used to treat gas-borne volatile organic compounds (VOCs; toluene, p-xylene, and dichloromethane) in air streams. The effects of liquid depth (Z), aeration intensity (G/A), the overall mass-transfer rate of oxygen in clean water (K _L a _O2 ), the Henry’s law constant of the tested VOC (H), and the influent gaseous VOC concentration (C ₀) on the efficiency of removal of VOCs were examined and compared with a literature-cited model. Results show that the measured VOC removal efficiencies and those predicted by the model were comparable at a G/A of 3.75–11.25 m³/m²·hr and C ₀ of ～1000–6000 mg/m³. Experimental data also indicated that the designed gas treatment reactor with K _L a _O2 = 5–15 hr^?1 could achieve >85% removal of VOCs with H = 0.24–0.25 at an aerated liquid depth of 1 m and >95% removal of dichloromethane with H = 0.13 at a 1-m liquid depth.     

Effect of Hydrocarbon and NO x on Photochemical Smog Formation under Simulated Transport Conditions

The body of information presented in this paper is directed to those individuals concerned with the effect of urban pollution on downwind areas. Concern has been expressed over the appropriate hydrocarbon and NO _x control strategy to be used in minimizing the effects of ozone and NO₂ on urban population centers and their downwind environs. O₃ and NO₂ formation were studied in smog chamber irradiations as a function of the initial NO _x concentration at three hydrocarbon concentrations. By carrying out the irradiations for a period of time equivalent to one solar day in a continuously diluting system, smog formation in a chemically reacting pollutant system under transport was simulated. The results of this experimental simulation suggest that hydrocarbon reduction reduces O₃ in urban as well as downwind areas while NO _x reduction increases O₃ in the urban area and has little effect on O₃ in downwind areas. Both hydrocarbon and NO _x reduction will reduce atmospheric NO₂ levels, with the effect of NO _x reduction generally being more pronounced.     

Influence of nocturnal vertical stability on daytime chemistry: A one-dimensional model study

Nocturnal chemistry can play an important role in determining the initial morning conditions for daytime chemistry in urban areas. However, the impact on daytime O₃ levels is difficult to assess as the suppression of vertical trace gas transport leads to highly altitude dependent nocturnal chemistry, in particular with respect to the removal and conversion of nitrogen oxides (NO_x) and volatile organic compounds (VOC). One-dimensional (1-D) chemical transport model calculations for different nighttime vertical stabilities and different ozone formation regimes (i.e. NO_x- vs. VOC-sensitive) were performed assuming a 1000 m high daytime boundary layer and a growing nocturnal boundary layer reaching 200 m height at the end of the night. Exclusion of NO₃ chemistry from the model leads to daytime O₃ concentration changes from ?4% to +16% for different O₃ sensitivities. In all cases strong nocturnal vertical concentration profiles of NO_x, O₃, NO₃ and N₂O₅ and a dependence of these profiles on vertical stability were found at night. The nocturnal NO_x loss averaged over the lowest 1000 m changes by 9–24% for different vertical stabilities and ozone sensitivities. The impact of nocturnal vertical stability leads to 7–12% difference in O₃ concentration in the morning and ～0–2.5% in the afternoon.     

Controlling NOx Emissions From Steam Generators

The information presented is directed to those individuals concerned with reducing nitrogen oxides (NO _x ) emissions from gas, oil, or coal fired utility steam generators. First, this paper presents NO _x emission data obtained in the testing of tangentially fired utility boilers; second, it relates these data to the general body of information developed by other investigators in the areas of theoretical analysis and bench scale and full scale testing; and finally, it discusses current design practice in relation to NO _x emission control and the continuing R&D effort required to assure acceptable control technology.     

北京市交通道路空气中NO_x的污染现状及时空变化规律研究

基于2008年及2009年分4个季节对北京市3种类型道路(开阔型、交叉路口型和峡谷型)空气中的NOx的现场监测结果,分析了3种类型道路空气中NOx的污染现状和时空变化规律及影响因素。实验结果表明,昼间北京市各类型街道空气中NOx浓度呈早晚浓度高、中午浓度低的变化规律,NOx浓度随季节和车流量变化较明显。交通道路空气中NO占NOx的分担率高,且有较好的相关性,而NO2分担率较低,与NOx相关性较差。     

Formation of Oxides of Nitrogen in Pulverized Coal Combustion

Nitrogen oxides are a potential atmospheric pollutant. Their formation and decomposition were studied in an experimental pulverized-coal-fired furnace. The concentration of nitrogen oxides (NO_x) was a maximum in the combustion zone and decreased as the combustion gas cooled. At a coal burning rate of 2 Ib/hr and 22% excess air, reduction of nitrogen oxides was obtained by selective secondary-air distribution. With 105% cf the stoichiometric air fed to the coal-combustion zone and 17% additional air fed just beyond the flame front, 62% reduction of NO_x occurred with good combustion efficiency. Lowering the quantity of excess air lowered the NO_x concentration, but at the expense of combustion efficiency. When 22% excess air was fed to the primary combustion zone, NO_x concentration in the effluent was 550 ppm and carbon in the fly ash 2.0%. With 5% excess air, the NO_x concentration fell to 210 ppm and carbon in the fly ash rose to 13.8%. With stoichiometric combustion the NO_x was 105 ppm a reduction of 81 %, and the carbon was 42.3%. Recirculation of combustion gas was not an effective means of lowering NO_x formation.     

Diurnal and Weekday Variations in the Source Contributions of Ozone Precursors in California’s South Coast Air Basin

Abstract

For at least 30 years, ozone (O₃) levels on weekends in parts of California’s South Coast (Los Angeles) Air Basin (SoCAB) have been as high as or higher than on weekdays, even though ambient levels of O₃ precursors are lower on weekends than on weekdays. A field study was conducted in the Los Angeles area during fall 2000 to test whether proposed relationships between emission sources and ambient nonmethane hydrocarbon (NMHC) and oxides of nitrogen (NO_x) levels can account for observed diurnal and day-of-week variations in the concentration and proportions of precursor pollutants that may affect the efficiency and rate of O₃ formation. The contributions to ambient NMHC by motor vehicle exhaust and evaporative emissions, estimated using chemical mass balance (CMB) receptor modeling, ranged from 65 to 85% with minimal day-of-week variation. Ratios of ambient NO_x associated with black carbon (BC) to NO_x associated with carbon monoxide (CO) were approximately 1.25 ± 0.22 during weekdays and 0.76 ± 0.07 and 0.52 ± 0.07 on Saturday and Sunday, respectively. These results demonstrate that lower NO_x emissions from diesel exhaust can be a major factor causing lower NO_x mixing ratios and higher NMHC/NO_x ratios on weekends. Nonmobile sources showed no significant day-of-week variations in their contributions to NMHC. Greater amounts of gasoline emissions are carried over on Friday and Saturday evenings but are, at most, a minor factor contributing to higher NMHC/NO_x ratios on weekend mornings.     

Measurements of nitrogen oxides from Hudson Bay: Implications for NOx release from snow and ice covered surfaces

Measurements of NO and NO₂ were made at a surface site (55.28 °N, 77.77 °W) near Kuujjuarapik, Canada during February and March 2008. NO_x mixing ratios ranged from near zero to 350 pptv with emission from snow believed to be the dominant source. The amount of NO_x was observed to be dependent on the terrain over which the airmass has passed before reaching the measurement site. The 24 h average NO_x emission rates necessary to reproduce observations were calculated using a zero-dimensional box model giving rates ranging from 6.9 × 10⁸ molecule cm^?2 s^?1 to 1.2 × 10⁹ molecule cm^?2 s^?1 for trajectories over land and from 3.8 × 10⁸ molecule cm^?2 s^?1 to 6.6 × 10⁸ molecule cm^?2 s^?1 for trajectories over sea ice. These emissions are higher than those suggested by previous studies and indicate the importance of lower latitude snowpack emissions. The difference in emission rate for the two types of snow cover shows the importance of snow depth and underlying surface type for the emission potential of snow-covered areas.     

A new environmental chamber for evaluation of gas-phase chemical mechanisms and secondary aerosol formation

A new state-of-the-art indoor environmental chamber facility for the study of atmospheric processes leading to the formation of ozone and secondary organic aerosol (SOA) has been constructed and characterized. The chamber is designed for atmospheric chemical mechanism evaluation at low reactant concentrations under well-controlled environmental conditions. It consists of two collapsible 90 m³ FEP Teflon film reactors on pressure-controlled moveable frameworks inside a temperature-controlled enclosure flushed with purified air. Solar radiation is simulated with either a 200 kW Argon arc lamp or multiple blacklamps. Results of initial characterization experiments, all carried out at 300–305 K under dry conditions, concerning NO_x and formaldehyde offgasing, radical sources, particle loss rates, and background PM formation are described. Results of initial single organic–NO_x and simplified ambient surrogate–NO_x experiments to demonstrate the utility of the facility for mechanism evaluation under low NO_x conditions are summarized and compared with the predictions of the SAPRC-99 chemical mechanism. Overall, the results of the initial characterization and evaluation indicate that this new environmental chamber can provide high quality mechanism evaluation data for experiments with NO_x levels as low as 2 ppb, though the results indicate some problems with the gas-phase mechanism that need further study. Initial evaluation experiments for SOA formation, also carried out under dry conditions, indicate that the chamber can provide high quality secondary aerosol formation data at relatively low hydrocarbon concentrations.