Field enhancements of packed-bed performance for low-concentration acidic and basic-waste gases from semiconductor manufacturing process

Low-concentration acidic and basic-waste gas pollutants contribute significantly in the total emission of a facility. Previous results show that the control of high volumetric flow rate (approximately 500 m3/min), low-concentration acidic (< 1 ppm by vol) and basic (< 3 ppm by vol) gases from semiconductor process vent, by conventional wet scrubbing technique is a challenging task. This work was targeted to enhance the performance of packed beds for high-volumetric flow rate, low-concentration acidic (HF, HCl), and basic (NH3)-waste gases from the semiconductor manufacturing process. The methodology used to meet the goal was the application of fine-water mist over the inlet stream before entering to the packed bed and use of the surfactant with mist/packed-bed liquid in low concentration. An experimental study was carried out in two acid-packed beds to optimize the operating conditions, such as pH of the liquid, circulating liquid flow rate, blow-down cycle, and so forth. The relationship among liquid pH, liquid ionic concentration, and the removal efficiency of the packed bed for the pollutants has been discussed considering chemical equilibrium, two-film theory, and Henry's law. For the potential utilization of scrubbing water, the dependency of the efficiency on blow-down cycle was studied, and a mechanism is suggested. The proposed water-mist surfactant system was installed in two acid-packed beds, and performance of the packed beds was compared. The background efficiencies of the acid-packed beds for HF, HCl, and NH3 were found max to be (n = 11) 53, 40, and 27%, whereas after installation of the system, they increased significantly and became 76 +/- 13% (n = 10), 76 +/- 8% (n = 7), and 78 +/- 7% (n = 7), respectively, for inlet concentrations of HF and HCl < 1 ppm and NH3 < 14 ppm. The mechanism by which the surfactants operate to enhance the removal in scrubbing process is suggested considering the hydrodynamic effect and the interfacial effect with the charge-generating characteristic of surfactants on water surface, when dissolved into water. The results show that a proposed rectification system can effectively reduce the emission rates below the regulatory level (0.6 kg/hr) at the present conditions of the facility.     

The effects of watercress growing on chalk headwater streams in Dorset and Hampshire

Chalk stream headwaters are of high value for water supply, amenity, game fishing and fish farming. The water quality implications of modern watercress growing watercress beds are reflected in increasing concentrations of phosphorus and potassium downstream of the beds. Zinc concentrations in both suspended solids emanating from the beds and in sediments downstream of the watercress farms reach high levels in some cases. Ranunculus plants downstream of the watercress farms show elevated levels of zinc. Large amounts of suspended solids enter the receiving streams from watercress beds and in many cases the stream bed directly downstream of the farms has a high proportion of fine organic sediments derived from the watercress farms.     

Evaluating the performance of a turbulent wet scrubber for scrubbing particulate matter

A turbulent wet scrubber was designed and developed to scrub particulate matter (PM) at micrometer and submicrometer levels from the effluent gas stream of an industrial coal furnace. Experiments were conducted to estimate the particle removal efficiency of the turbulent scrubber with different gas flow rates and liquid heads above the nozzle. Particles larger than 1 µm were removed very efficiently, at nearly 100%, depending upon the flow rate, the concentration of the dust-laden air stream, and the water level in the reservoir. Particles smaller than 1 µm were also removed to a greater extent at higher gas flow rates and for greater liquid heads. Pressure-drop studies were also carried out to estimate the energy consumed by the scrubber for the entire range of particle sizes distributed in the carrier gas. A maximum pressure drop of 217 mm H₂O was observed for a liquid head of 36 cm and a gas flow rate of 7 m³/min. The number of transfer units (NTU) analysis for the efficiencies achieved by the turbulent scrubber over the range of particles also reveals that the contacting power achieved by the scrubber is better except for smaller particles. The turbulent scrubber is more competent for scrubbing particulate matter, in particular PM_2.5, than other higher energy or conventional scrubbers, and is comparable to other wet scrubbers of its kind for the amount of energy spent.

Implications: The evaluation of the turbulent scrubber is done to add a novel scrubber in the list of wet scrubbers for industrial applications, yet simple in design, easy to operate, with better compactness, and with high efficiencies at lower energy consumption. Hence the turbulent scrubber can be used to combat particulate from industrial gaseous effluents and also has a scope to absorb gaseous pollutants if the gases are soluble in the medium used for particles capture.     

PISCES: Tracking Trace Chemicals in Power Plants

PISCES, Power Plant Integrated Systems: Chemical Emissions Studies, is a multimedia chemical species project on plant emissions. Products generated in the PISCES project will help utilities design and operate their plants to minimize chemical species emissions. PISCES takes a holistic approach to the control of toxics by acknowledging that a chemical removed from a gas stream will appear in a liquid or solid stream.     

Information Required for the Selection and Performance Evaluation of Wet Scrubbers

The term “wet scrubber” or simply “scrubber,” for the purpose of this report, is intended to include any device using liquid to effect the removal of solid or liquid particles which are entrained in process air or gas streams. This guide is intended to provide information required for the selection and performance evaluation of all types of scrubbers installed for the primary purpose of removing such particulates from any process gas stream. It is not intended to cover scrubbers for the collection of gaseous and/or vapor constituents which involve gas absorption mechanisms.     

Atomization and Cloud Behavior In Venturi Scrubbing

The exact collection mechanism of a venturi scrubber has been unknown up to this time. Photographic stop-action techniques and glass venturi scrubbers have made it possible to establish where and how particles are captured and to speculate on possible gas removal possibilities. This report extends the knowledge of pneumatic atomization which is used in gas scrubbing and many other applications by providing further information on cloud-type atomization. Cloud-type atomization which is produced by pneumatic atomization of liquid streams (not drops) results in the formation of liquid droplets which appear to be less than 10 microns in diameter. These droplets coalesce and form clouds which move as single entities. Effective overall cloud diameters are determined to be a function of the velocity of the atomizing gas stream. The effective cloud diameters start at 170 [a and increase as throat gas velocities increase from 150 ft/sec. Throat velocities and liquid inlet nozzle diameters necessary to obtain water clouds of specific effective diameters can be estimated.

These large clouds are efficient impaction targets and stop most of the particulate matter within 0.5 cm from the throat scrubbing liquid inlets. High gas absorption is expected for the clouds of droplets because turbulent gas movement can exist inside and outside the clouds and the 10 μ droplets provide exceptional surface area.     

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.     

Feasibility study of using brine for carbon dioxide capture and storage from fixed sources

A laboratory-scale reactor was developed to evaluate the capture of carbon dioxide (CO2) from a gas into a liquid as an approach to control greenhouse gases emitted from fixed sources. CO2 at 5-50% concentrations was passed through a gas-exchange membrane and transferred into liquid media--tap water or simulated brine. When using water, capture efficiencies exceeded 50% and could be enhanced by adding base (e.g., sodium hydroxide) or the combination of base and carbonic anhydrase, a catalyst that speeds the conversion of CO2 to carbonic acid. The transferred CO2 formed ions, such as bicarbonate or carbonate, depending on the amount of base present. Adding precipitating cations, like Ca++, produced insoluble carbonate salts. Simulated brine proved nearly as efficient as water in absorbing CO2, with less than a 6% reduction in CO2 transferred. The CO2 either dissolved into the brine or formed a mixture of gas and ions. If the chemistry was favorable, carbonate precipitate spontaneously formed. Energy expenditure of pumping brine up and down from subterranean depths was modeled. We conclude that using brine in a gas-exchange membrane system for capturing CO2 from a gas stream to liquid is technically feasible and can be accomplished at a reasonable expenditure of energy.     

Liquid Entrainment from a Mobile Bed Scrubber

Liquid entrainment rate and drop size distribution were measured in the exhaust gas stream from a mobile bed scrubber. The pilot plant scrubber was 46 cm (18 in.) square and was packed with 3.8 cm (1.5 In.) diameter hollow polyethylene spheres to a static depth of 25 cm (10 in.). Entrainment flow rate depends on both gas and liquid rates. At a liquid/gas ratio of 6.7 l/m³ (50 gal/Mcf) and a superficial gas velocity of 2.6 m/sec (8.5 ft/sec) the entrainment flow rate was 0.0064 l/m³ (0.05 gal/Mcf) and at 3.75 m/sec (12.3 ft/sec) it was 0.031 l/m³ (0.23 gal/Mcf). The mass median drop diameter was about 400 nm at a liquid/gas ratio of 6.7 l/m³. The drop size distribution appears to be bimodal. Dye impregnated paper and cascade impactor techniques were used to measure drop size.     

New High-Efficiency Mist Collector

The recently developed York Type P acid mist scrubber collects phosphoric acid mists and other very fine liquid particulates with very high efficiency with moderate pressure drop and high throughput. The collector consists of a single vessel containing two stainless steel wire mesh contactors. The collector converts submicron size acid mist into larger liquid particles which are collected and separated from the gas stream before being discharged from the collector. The first commercial unit started operation in July 1964, and four additional units have since been installed. Collection efficiency is 99.9+% at a pressure drop of 35-40 in W.G. The scrubber is compact and has no moving parts. Collected acid drains by gravity to a receiving tank. Experimental development work is described and design parameters such as efficiency, gas velocity, and pressure drop are discussed.     

Treatment of ethylether in air stream by a biotrickling filter packed with slags.

This paper reports results of studies using a biotrickling filter with blast-furnace slag packings (sizes = 2-4 cm and specific surface area = 120 m2/m3) for treatment of ethylether in air stream. Effects of volumetric loading, superficial gas velocity, empty bed gas retention time, recirculation liquid flow rate, and biofilm renewal on the ethylether removal efficiency and elimination capacity were tested. Results indicate that ethylether removal efficieincies of more than 95% were obtained with an empty bed retention time (EBRT) of 113 sec and loadings of lower than 70 g/m3/hr. At an EBRT of 57 sec, removal efficiencies of more than 90% could only be obtained with loadings of lower than 35 g/m3/hr. The maximum elimination capacities were 71 and 45 g/m3/hr for EBRT = 113 and 57 sec, respectively. The maximum ethylether elimination capacities were 71 and 96 g/m3/hr, respectively, before and after the renewal at EBRT = 113 sec. With an EBRT of 113 sec and a loading of lower than 38 g/m3/hr, the removal efficiency was nearly independent of the superficial liquid recirculation velocity in the range of 3.6 to 9.6 m3/m2/hr. From data regression, simplified masstransfer limited, and reaction- and mass-transfer limited models correlating the contaminant concentration and the packing height were proposed and verified. The former model is applicable for cases of low influent contaminant concentrations or loadings, and the latter is applicable for cases of higher ones. Finally, CO2 conversion efficiencies of approximately 90% for the influent ethylether were obtained. The value is comparable to data reported from other related studies.     

Solid‐phase extraction and GC analyses of select agricultural pesticides and metabolites in stream water

Abstract

The occurrence of agricultural pesticides in surface waters around the USA has created a concern over the status of safe drinking water. Solid‐phase extraction (SPE) or liquid‐liquid extraction (LLE) is usually employed to concentrate trace levels of pesticides in water samples to concentrations that are measurable with advanced chromatographic instruments. We describe here a SPE and capillary gas chromatographic (GC) procedure to extract and concentrate trace levels of select agricultural pesticides and metabolites from stream water. Our SPE and GC method provides high sensitivity, with recoveries between 85% to 95%, and high reproducibility for 9 of the pesticides studied. The described method provided marginal recoveries of 19 and 60% for the atrazine metabolites.     

Effect of Water and Carbon Dioxide in Chemiluminescent Measurement of Oxides of Nitrogen

ABSTRACT

This paper reports results of studies using a biotrickling filter with blast-furnace slag packings (sizes = 2–4 cm and specific surface area = 120 m²/m³) for treatment of ethylether in air stream. Effects of volumetric loading, superficial gas velocity, empty bed gas retention time, recirculation liquid flow rate, and biofilm renewal on the ethylether removal efficiency and elimination capacity were tested. Results indicate that ethylether removal efficiencies of more than 95% were obtained with an empty bed retention time (EBRT) of 113 sec and loadings of lower than 70 g/m³/hr. At an EBRT of 57 sec, removal efficiencies of more than 90% could only be obtained with loadings of lower than 35 g/m³/hr. The maximum elimination capacities were 71 and 45 g/m³/hr for EBRT = 113 and 57 sec, respectively. The maximum ethylether elimination capacities were 71 and 96 g/m³/hr, respectively, before and after the renewal at EBRT = 113 sec. With an EBRT of 113 sec and a loading of lower than 38 g/m³/hr, the removal efficiency was nearly independent of the superficial liquid recirculation velocity in the range of 3.6 to 9.6 m³/m²/hr. From data regression, simplified mass-transfer limited, and reaction- and mass-transfer limited models correlating the contaminant concentration and the packing height were proposed and verified. The former model is applicable for cases of low influent contaminant concentrations or loadings, and the latter is applicable for cases of higher ones. Finally, CO₂ conversion efficiencies of approximately 90% for the influent ethylether were obtained. The value is comparable to data reported from other related studies.     

Mitigation of low stream pH and its effects on salmonids

Crushed limestone (200 tonnes) was spread in bars on the bed of an acidic brook (mean pH 5.0) in Nova Scotia, Canada. A seasonally variable but significant increase in pH of running water resulted, and a longitudinal pH gradient over the limed section extended to the mouth of the brook. The effectiveness persisted after 3 years, during which pH downstream of the limestone increased an average of 0.4 pH units (range < 0.1-1.3 pH units) along with significantly increased Ca, Mg and acid neutralizing capacity. Total and exchangeable Al were not altered by the limestone and non-exchangeable forms dominated. The interstitial water was nearly neutral (mean pH 7.1) in limestone beds but it was acidic (mean pH 5.4) in gravel beds of the control section upstream. Spawning Atlantic salmon (Salmo salar) dug three times more redds in gravel of the limed section than in the control. Salmon fry survived and they were significantly more abundant in the limed section than in the control. The density of juvenile salmon increased over time, indicating a recovery of the population. The density of brook trout (Salvelinus fontinalis) also increased and trout fry were usually more abundant in the limed section than in the control. The observed benefits for salmonids suggest that small-scale application of limestone to stream beds and spawning sites can be used to mitigate the effects of low stream pH.     

Regenerative Thermal Oxidation of Airborne N,N-Dimethylformamide and Its Associated Nitrogen Oxides Formation Characteristics

Abstract

In this study, a two-bed electrically heated regenerative thermal oxidizer (RTO) was used to test the thermal destruction and oxides of nitrogen (NO_x) 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 × 0.14 m × 1 m (L × 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 (t _s) of 1.5 min, a superficial gas velocity (U _g) of 0.39 m/sec (evaluated at an influent air temperature of around 30 °C) and preset maximum destruction temperatures (T _S) of 750–950 °C, no NO_x 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?m³. The “NO_x-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_x 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 NO_x formation ratios were in the range 0.75–0.96. The TRE decreased as U _g increased but was invariant with T _s. The Ergun equation was found to suffice in the estimation of the pressure drop when the gas flowed over the packing beds.     

Impact of atrazine-bearing agricultural tile drainage discharge on planktonic drift of a natural stream

Preliminary results are reported from a co-operative study between Agriculture Canada and Environment Canada on environmental impacts of atrazine measured in a field stream receiving agricultural drainage. Systematically, tile drained plots of known crop rotation, area, flow and pesticides use were used in the study. A maximum tile drainage concentration of 13.9 microg liter(-1) atrazine was measured while the maximum measured stream concentration was 1.89 microg liter(-1). Phytoplankton and zooplankton samples were collected on a bi-monthly basis during the growing season. The study indicated possible negative impacts of low concentrations of atrazine on planktonic drift populations, when natural stream flow was reduced, resulting in a lower dilution capacity. A 20 m section of the stream was affected by the tile drainage waters as measured by the resident biological community. Both atrazine and ambient environmental conditions were felt to be contributing to the measured results. No negative impacts on planktonic drift populations were evident beyond 50 m downstream of the tile drainage and stream confluence.     

Performance characteristics of a regenerative catalytic oxidizer for treating VOC-contaminated airstreams

A pilot apparatus of a regenerative catalytic oxidizer (RCO) equipped with two electrical heaters and two 20-cm i.d. x 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 degree 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 degrees 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 degrees C, but toluene does not exhibit this phenomenon.     

Effect of liquid inhibitors on PCDD/F formation. Prediction of particle-phase PCDD/F concentrations using PLS modelling with gas-phase chlorophenol concentrations as independent variables

Emissions of polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) from municipal waste incineration are currently a subject of considerable public concern because of their extreme toxicity. PCDD/F formation in incineration processes is being studied widely, but little work has been done on their inhibition. We studied the effect of two liquid inhibitors, sodium ammonium hydrogen phosphate (NAHF) and urea (H2NCONH2), on PCDD/F formation in the combustion of liquid fuel doped with copper and chlorine using a pilot-scale plant. The inhibitors were injected into the flue gas stream at a temperature of 725 degrees C, whereupon both the chlorophenol and PCDD/F concentrations decreased. Particle-phase PCDD/F concentrations in particular decreased by up to 90% with NAHF and 70% with urea, but gas phase reduction took place only with urea. The results suggest that the formation of PCDD/Fs is hindered in the particle phase at the early stages of the PCDD/F formation chain, probably even before precursors such as chlorophenols have been formed. As a consequence, particle-phase PCDD/F concentrations can be predicted by a PLS (partial least-squares) approach with the gas-phase chlorophenol concentrations as independent variables. The structure and partial charges of Cu(+)-urea complex were calculated by the HF/3-21G basis set.     

Gas Cleaning in a Wetted Butterfly Valve

An attempt was made to demonslrate the utility of a wetted butterfly valve for cleaning flue gases from industrial wastes. Butterfly valves are extensively in use to control the gas pressures in various processes. A small pilot plant with a maximum airflow rate of 400 cfm and water flow rate of 4 gpm was constructed to provide the desired testing conditions. The results indicate that for a pressure drop greater than 30 in. water a collection efficiency of greater than 95% for submicron particles can be obtained. For particles larger than 1.7;u diameter efficiencies of greater than 99% were obtained. The exceptional suitability of wet butterfly valves for gas cleaning is demonstrated by the flexibility to adjust to large variations of gas and liquid flow rates.     

Development of a Method for the Analysis of NO2 and NH3 by NO-Measuring Instruments

Adaptation of available instruments to the analysis of NO₂ and NH₃ became important with the introduction of the Federal Constant Volume Sampling procedure for exhaust analysis in 1970. Two instruments, the NO optical detector (NOOD) and the non-dispersive infrared analyzer (ND1R), are both fast and accurate. The use of a system of two converters in conjunction with either of these instruments permits the analysis of a gas stream for NO, NO₂, and NH₃. NO is measured on the gas stream before conversion; NO₂ is determined after the gas stream has passed over a C-Mo converter at 475°C; and NH₃ is determined after the gas has been conducted over a C-Cu converter.