Inorganic Acid Emission Factors of Semiconductor Manufacturing Processes

Abstract

A huge amount of inorganic acids can be produced and emitted with waste gases from integrated circuit manufacturing processes such as cleaning and etching. Emission of inorganic acids from selected semiconductor factories was measured in this study. The sampling of the inorganic acids was based on the porous metal denuders, and samples were then analyzed by ion chromatography. The amount of chemical usage was adopted from the data that were reported to the Environmental Protection Bureau in Hsin-chu County according to the Taiwan Environmental Protection Agency regulation. The emission factor is defined as the emission rate (kg/month) divided by the amount of chemical usage (L/month). Emission factors of three inorganic acids (i.e., hydrofluoric acid [HF], hydrochloric acid [HQ], and sulfuric acid [H₂SO₄]) were estimated by the same method. The emission factors of HF and HCl were determined to be 0.0075 kg/L (coefficient of variation [CV] = 60.7%, n = 80) and 0.0096 kg/L (CV = 68.2%, n = 91), respectively. Linear regression equations are proposed to fit the data with correlation coefficient square (R²) = 0.82 and 0.9, respectively. The emission factor of H₂SO₄, which is in the droplet form, was determined to be 0.0016 kg/L (CV = 99.2%, n = 107), and its R² was 0.84. The emission profiles of gaseous inorganic acids show that HF is the dominant chemical in most of the fabricators.     

Emission characteristics of volatile organic compounds from semiconductor manufacturing

A huge amount of volatile organic compounds (VOCs) is produced and emitted with waste gases from semiconductor manufacturing processes, such as cleaning, etching, and developing. VOC emissions from semiconductor factories located at Science-Based Industrial Park, Hsin-chu, Taiwan, were measured and characterized in this study. A total of nine typical semiconductor fabricators (fabs) were monitored over a 12-month period (October 2000-September 2001). A flame ionization analyzer was employed to measure the VOC emission rate continuously in a real-time fashion. The amount of chemical use was adopted from the data that were reported to the Environmental Protection Bureau in Hsin-chu County as per the regulation of the Taiwan Environmental Protection Administration. The VOC emission factor, defined as the emission rate (kg/month) divided by the amount of chemical use (L/month), was determined to be 0.038 +/- 0.016 kg/L. A linear regression equation is proposed to fit the data with the correlation coefficient (R2)=0.863. The emission profiles of VOCs, which were drawn using the gas chromatograph/mass spectrometer analysis method, show that isopropyl alcohol is the dominant compound in most of the fabs.     

Emission Characteristics of Volatile Organic Compounds from Semiconductor Manufacturing

Abstract

A huge amount of volatile organic compounds (VOCs) is produced and emitted with waste gases from semiconductor manufacturing processes, such as cleaning, etching, and developing. VOC emissions from semiconductor factories located at Science-Based Industrial Park, Hsin-chu, Taiwan, were measured and characterized in this study. A total of nine typical semiconductor fabricators (fabs) were monitored over a 12-month period (October 2000-September 2001). A flame ionization analyzer was employed to measure the VOC emission rate continuously in a real-time fashion. The amount of chemical use was adopted from the data that were reported to the Environmental Protection Bureau in Hsin-chu County as per the regulation of the Taiwan Environmental Protection Administration. The VOC emission factor, defined as the emission rate (kg/month) divided by the amount of chemical use (L/month), was determined to be 0.038 ± 0.016 kg/L. A linear regression equation is proposed to fit the data with the correlation coefficient (R²) = 0.863. The emission profiles of VOCs, which were drawn using the gas chromatograph/mass spectrometer analysis method, show that isopropyl alcohol is the dominant compound in most of the fabs.     

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.     

Simulation of stack plume opacity

The visual impact of primary particles emitted from stacks is regulated according to stack opacity criteria. In-stack monitoring of the flue gas opacity allows plant operators to ensure that the plant meets U.S. Environmental Protection Agency opacity regulations. However, the emission of condensable gases such as SO3 (that hydrolyzes to H2SO4), HCl, and NH3, which may lead to particle formation after their release from the stack, makes the prediction of stack plume opacity more difficult. We present here a computer simulation model that calculates the opacity due to both primary particles emitted from the stack and secondary particles formed in the atmosphere after the release of condensable gases from the stack. A comprehensive treatment of the plume rise due to buoyancy and momentum is used to calculate the location at which the condensed water plume has evaporated (i.e., where opacity regulations apply). Conversion of H2SO4 to particulate sulfate occurs through nucleation and condensation on primary particles. A thermodynamic aerosol equilibrium model is used to calculate the amount of ammonium, chloride, and water present in the particulate phase with the condensed sulfate. The model calculates the stack plume opacity due to both primary and secondary particles. Examples of model simulations are presented for three scenarios that differ by the emission control equipment installed at the power plant: (1) electrostatic precipitators (ESP), (2) ESP and flue gas desulfurization, and (3) ESP and selective catalytic reduction. The calculated opacity is most sensitive to the primary particulate emissions. For the conditions considered here, SO3 emissions showed only a small effect, except if one assumes that most H2SO4 condenses on primary particles. Condensation of NH4Cl occurs only at high NH3 emission rates (about 25 ppm stack concentration).     

Regulated and unregulated emissions from modern 2010 emissions-compliant heavy-duty on-highway diesel engines

The U.S. Environmental Protection Agency (EPA) established strict regulations for highway diesel engine exhaust emissions of particulate matter (PM) and nitrogen oxides (NO_x) to aid in meeting the National Ambient Air Quality Standards. The emission standards were phased in with stringent standards for 2007 model year (MY) heavy-duty engines (HDEs), and even more stringent NO_X standards for 2010 and later model years. The Health Effects Institute, in cooperation with the Coordinating Research Council, funded by government and the private sector, designed and conducted a research program, the Advanced Collaborative Emission Study (ACES), with multiple objectives, including detailed characterization of the emissions from both 2007- and 2010-compliant engines. The results from emission testing of 2007-compliant engines have already been reported in a previous publication. This paper reports the emissions testing results for three heavy-duty 2010-compliant engines intended for on-highway use. These engines were equipped with an exhaust diesel oxidation catalyst (DOC), high-efficiency catalyzed diesel particle filter (DPF), urea-based selective catalytic reduction catalyst (SCR), and ammonia slip catalyst (AMOX), and were fueled with ultra-low-sulfur diesel fuel (~6.5 ppm sulfur). Average regulated and unregulated emissions of more than 780 chemical species were characterized in engine exhaust under transient engine operation using the Federal Test Procedure cycle and a 16-hr duty cycle representing a wide dynamic range of real-world engine operation. The 2010 engines’ regulated emissions of PM, NO_X, nonmethane hydrocarbons, and carbon monoxide were all well below the EPA 2010 emission standards. Moreover, the unregulated emissions of polycyclic aromatic hydrocarbons (PAHs), nitroPAHs, hopanes and steranes, alcohols and organic acids, alkanes, carbonyls, dioxins and furans, inorganic ions, metals and elements, elemental carbon, and particle number were substantially (90 to >99%) lower than pre-2007-technology engine emissions, and also substantially (46 to >99%) lower than the 2007-technology engine emissions characterized in the previous study.

Implications:?Heavy-duty on-highway diesel engines equipped with DOC/DPF/SCR/AMOX and fueled with ultra-low-sulfur diesel fuel produced lower emissions than the stringent 2010 emission standards established by the U.S. Environmental Protection Agency. They also resulted in significant reductions in a wide range of unregulated toxic emission compounds relative to older technology engines. The increased use of newer technology (2010+) diesel engines in the on-highway sector and the adaptation of such technology by other sectors such as nonroad, displacing older, higher emissions engines, will have a positive impact on ambient levels of PM, NOx, and volatile organic compounds, in addition to many other toxic compounds.     

Particulate matter emission rates from beef cattle feedlots in Kansas-reverse dispersion modeling

Open beef cattle feedlots emit various air pollutants, including particulate matter (PM) with equivalent aerodynamic diameter of 10 microm or less (PM10); however limited research has quantified PM10 emission rates from feedlots. This research was conducted to determine emission rates of PM10 from large cattle feedlots in Kansas. Concentrations of PM10 at the downwind and upwind edges of two large cattle feedlots (KS1 and KS2) in Kansas were measured with tapered element oscillating microbalance (TEOM) PM10 monitors from January 2007 to December 2008. Weather conditions at the feedlots were also monitored. From measured PM10 concentrations and weather conditions, PM10 emission rates were determined using reverse modeling with the American Meteorological Society/U.S. Environmental Protection Agency Regulatory Model (AERMOD). The two feedlots differed significantly in median PM10 emission flux (1.60 g/m2-day for KS1 vs. 1.10 g/m2-day for KS2) but not in PM10 emission factor (27 kg/1000 head-day for KS1 and 30 kg/1000 head-day KS2). These emission factors were smaller than published U.S. Environmental Protection Agency (EPA) emission factor for cattle feedlots.     

PCDD/PCDF reduction by the co-combustion process

A novel process, termed the co-combustion process, has been developed and designed to utilise the thermal treatment of municipal solid waste (MSW) in cement clinker production and reduce PCDD/PCDF emissions. To test the conceptual design; detailed engineering design of the process and equipment was performed and a pilot plant was constructed to treat up to 40 tonnes MSW per day. The novel process features included several units external to the main traditional cement rotary kiln: an external calcinations unit in which the hot gas calcined the limestone thus making significant energy savings for this chemical reaction; the lime generated was used in a second chamber to act as a giant acid gas scrubber to remove SOx and particularly HCl (a source of chloride); an external rotary kiln and secondary combustion unit capable of producing a hot gas at 1200 degrees C; a gas cooler to simulate a boiler turbogenerator set for electricity generation; the incorporation of some of the bottom ash, calcined lime and dust collector solids into the cement clinker. A PCDD/PCDF inventory has been completed for the entire process and measured PCDD/PCDF emissions were 0.001 ng I-TEQ/Nm(3) on average which is 1% of the best practical means [Hong Kong Environmental Protection Department, 2001. A guidance note on the best practicable means for incinerators (municipal waste incineration), BPM12/1] MSW incineration emission limit values.     

Thermodynamic analysis and kinetic modelling of dioxin formation and emissions from power boilers firing salt-laden hog fuel

Both organic chlorine (e.g. PVC) and inorganic chlorides (e.g. NaCl) can be significant chlorine sources for dioxin and furan (PCDD/F) formation in combustion processes. This paper presents a thermodynamic analysis of high temperature salt chemistry. Its influence on PCDD/F formation in power boilers burning salt-laden wood waste is examined through the relationships between Cl2, HCl, NaCl(g) and NaCl(c). These analyses show that while HCl is a product of combustion of PVC-laden municipal solid waste, NaCl can be converted to HCl in hog fuel boilers by reactions with SO2 or alumino-silicate materials. Cl2 is a strong chlorinating agent for PCDD/F formation. HCl can be oxidized to Cl2 by O2, and Cl2 can be reduced back to HCl by SO2. The presence of sulphur at low concentrations thus enhances PCDD/F formation by increasing HCl concentrations. At high concentrations, sulphur inhibits de novo formation of PCDD/Fs through Cl2 reduction by excess SO2. The effect of NH3, CO and NOx on PCDD/F formation is also discussed. A semi-empirical kinetic model is proposed. This model considers both precursor and de novo formation mechanisms. A simplified version is used as a stack emission model. The kinetic model indicates that stack dioxin emissions will increase linearly with decreasing electrostatic precipitator (ESP) efficiency and exponentially with increasing ESP temperature.     

Emissions from charbroiling and grilling of chicken and beef

Emission rates for fine particle (<2.5 microm) mass (PM2.5), carbon (organic/elemental), inorganic ions (SO4(2-), NO3-, NH4+), elements (primarily metals), and speciated organic compounds are reported for charbroiling hamburger, steak, and chicken. The PM2.5 rates for charbroiling meats ranged from 4.4 to 11.6 g/kg of uncooked meat in this study. No mass-emission rates are available from grilling, but the speciated organic data are available for these samples. Emission rates varied by type of appliance, meat, meat-fat content, and cooking conditions. High-fat hamburger cooked on an underfired charbroiler emitted the highest amount of PM2.5. The emissions were almost exclusively composed of organic carbon, with small amounts of elements and inorganic ions. Water-soluble K+ and Cl-, which are used as indicators of wood smoke in source apportionment studies, were also present in meat-cooking emissions. The speciated organic compounds that were measured include polycyclic aromatic hydrocarbons (PAHs), cholesterol, and the long-chain gamma-lactones. Charbroiling emissions yielded an average of approximately 3-5 times more PAHs, approximately 20 times more cholesterol, and approximately 10 times more lactones than grilling. These data were utilized in the ambient source apportionment analysis for the 1997 Northern Front Range Air Quality Study source apportionment.     

污泥热干化和燃烧特性试验研究

分别在桨叶式干化机和热重仪上进行污泥干化和燃烧试验,研究了污泥干化特性和污染物排放特性,并对污泥的燃烧特性进行分析。结果表明,污泥干化过程分为黏稠区、粘滞区和颗粒区3个阶段。干化过程排放的污染气体有氨气、氯化氢、氟化氢、氰化氢、甲烷和挥发性有机酸等,其中氨气为主要污染气体。经冷凝吸收和活性炭吸附处理后,各种污染气体浓度均显著降低,其中氨气去除率最高,达97.04%。污泥干化冷凝液的BOD5和COD质量浓度分别为4 040、8 510mg/L,氨氮的质量浓度为1 025mg/L,pH为9.84,属于高浓度有机废水。污泥的燃烧过程可以分为3个失重阶段:水分析出阶段(50～150℃),挥发分燃烧阶段(150～450℃),固定碳燃烧阶段(450～650℃)。分别用Kissinger法和Ozawa法计算挥发分燃烧阶段和固定碳燃烧阶段的活化能和动力学方程,挥发分燃烧阶段的活化能低于固定碳燃烧阶段,表明挥发分燃烧阶段污泥更易燃烧。污泥的燃烧过程在650℃时基本完成,因此实际工程应用中,设计干化污泥的焚烧温度在750℃比较合理。     

The impact of wet flue gas desulfurization scrubbing on mercury emissions from coal-fired power stations

This article introduces a predictive capability for Hg retention in any Ca-based wet flue gas desulfurization (FGD) scrubber, given mercury (Hg) speciation at the FGD inlet, the flue gas composition, and the sulphur dioxide (SO2) capture efficiency. A preliminary statistical analysis of data from 17 full-scale wet FGDs connects flue gas compositions, the extents of Hg oxidation at FGD inlets, and Hg retention efficiencies. These connections clearly signal that solution chemistry within the FGD determines Hg retention. A more thorough analysis based on thermochemical equilibrium yields highly accurate predictions for total Hg retention with no parameter adjustments. For the most reliable data, the predictions were within measurement uncertainties for both limestone and Mg/lime systems operating in both forced and natural oxidation mode. With the U.S. Environmental Protection Agency's (EPA) Information Collection Request (ICR) database, the quantitative performance was almost as good for the most modern FGDs, which probably conform to the very high SO2 absorption efficiencies assumed in the calculations. The large discrepancies for older FGDs are tentatively attributed to the unspecified SO2 capture efficiencies and operating temperatures and to the possible elimination of HCl in prescrubbers. The equilibrium calculations suggest that Hg retention is most sensitive to inlet HCl and O2 levels and the FGD temperature; weakly dependent on SO2 capture efficiency; and insensitive to HgCl2, NO, CA:S ratio, slurry dilution level in limestone FGDs, and MgSO3 levels in Mg/lime systems. Consequently, systems with prescrubbers to eliminate HCl probably retain less Hg than fully integrated FGDs. The analysis also predicts re-emission of Hg(O) but only for inlet O2 levels that are much lower than those in full-scale FGDs.     

Emission projections for the U.S. Environmental Protection Agency Section 812 second prospective Clean Air Act cost/benefit analysis

Section 812 of the Clean Air Act Amendments (CAAA) of 1990 requires the U.S. Environmental Protection Agency (EPA) to perform periodic, comprehensive analyses of the total costs and total benefits of programs implemented pursuant to the CAAA. The first prospective analysis was completed in 1999. The second prospective analysis was initiated during 2005. The first step in the second prospective analysis was the development of base and projection year emission estimates that will be used to generate benefit estimates of CAAA programs. This paper describes the analysis, methods, and results of the recently completed emission projections. There are several unique features of this analysis. One is the use of consistent economic assumptions from the Department of Energy's Annual Energy Outlook 2005 (AEO 2005) projections as the basis for estimating 2010 and 2020 emissions for all sectors. Another is the analysis of the different emissions paths for both with and without CAAA scenarios. Other features of this analysis include being the first EPA analysis that uses the 2002 National Emission Inventory files as the basis for making 48-state emission projections, incorporating control factor files from the Regional Planning Organizations (RPOs) that had completed emission projections at the time the analysis was performed, and modeling the emission benefits of the expected adoption of measures to meet the 8-hr ozone National Ambient Air Quality Standards (NAAQS), the Clean Air Visibility Rule, and the PM2.5 NAAQS. This analysis shows that the 1990 CAAA have produced significant reductions in criteria pollutant emissions since 1990 and that these emission reductions are expected to continue through 2020. CAAA provisions have reduced volatile organic compound (VOC) emissions by approximately 7 million t/yr by 2000, and are estimated to produce associated VOC emission reductions of 16.7 million t by 2020. Total oxides of nitrogen (NO(x)) emission reductions attributable to the CAAA are 5, 12, and 17 million t in 2000, 2010, and 2020, respectively. Sulfur dioxide (SO2) emission benefits during the study period are dominated by electricity-generating unit (EGU) SO2 emission reductions. These EGU emission benefits go from 7.5 million t reduced in 2000 to 15 million t reduced in 2020.     

Inorganic PM2.5 at a U.S. agricultural site

In this study, we present approximately two years (January 1999-December 2000) of atmospheric NH3, NH4+, HCl, Cl-, HNO3, NO3-, SO2, and SO4= concentrations measured by the annular denuder/filter pack method at an agricultural site in eastern North Carolina. This site is influenced by high NH3 emissions from animal production and fertilizer use in the surrounding area and neighboring counties. The two-year mean NH3 concentration is 5.6 (+/-5.13) microg m(-3). The mean concentration of total inorganic PM2.5, which includes SO4=, NO3-, NH4+, and Cl-, is 8.0 (+/-5.84) microg m(-3). SO4=, NO3-, NH4+, and Cl- represent, respectively, 53, 24, 22, and 1% of measured inorganic PM2.5. NH3 contributes 72% of total NH3 + NH4+, on an average. Equilibrium modeling of the gas+aerosol NH3/H2SO4/HNO3 system shows that inorganic PM2.5 is more sensitive to reductions in gas + aerosol concentrations of sulfate and nitrate relative to NH3.     

Throughfall chemistry in a spruce chronosequence in southern Poland

The chemical composition of throughfall and canopy leaching, as well as the acid neutralizing capacity and alkalinity depended on the age of Norway spruce (Picea abies Karst) stands and season of the year. A higher amount of sulphur and strong acids was deposited to the soil in the older age classes. Concentrations of SO(4)(2)(-), K(+), H(+), Mn(2+), Fe(2+) and Zn(2+) in throughfall were higher than in bulk precipitation in any season. This suggests that these ions were washed out or washed from the surface of needles and/or barks. The other ions NO(3)(-), NH(4)(+), Ca(2+) and Mg(2+) were retained by the canopy, in particular Ca(2+) and Mg(2+) during the growing season in young stands. Principal component analysis identified five factors responsible for the data structure and suggested the major anthropogenic emission sources were acidic emission (SO(4)(2)(-)+NO(3)(-)), heavy metals-dust particles (Fe(2+)+Mn(2+)+Zn(2+)), ammonium (NH(4)(+)) and H(+), while the natural-origin emission was mineral dust (Na(+)+K(+)+Ca(2+)+Mg(2+)).     

Remote sensing-based estimates of annual and seasonal emissions from crop residue burning in the contiguous United States

Crop residue burning is an extensive agricultural practice in the contiguous United States (CONUS). This analysis presents the results of a remote sensing-based study of crop residue burning emissions in the CONUS for the time period 2003-2007 for the atmospheric species of carbon dioxide (CO2), methane (CH4), carbon monoxide (CO), nitrogen dioxide (NO2, sulfur dioxide (SO2), PM2.5 (particulate matter [PM] < or = 2.5 microm in aerodynamic diameter), and PM10 (PM < or = 10 microm in aerodynamic diameter). Cropland burned area and associated crop types were derived from Moderate Resolution Imaging Spectroradiometer (MODIS) products. Emission factors, fuel load, and combustion completeness estimates were derived from the scientific literature, governmental reports, and expert knowledge. Emissions were calculated using the bottom-up approach in which emissions are the product of burned area, fuel load, and combustion completeness for each specific crop type. On average, annual crop residue burning in the CONUS emitted 6.1 Tg of CO2, 8.9 Gg of CH4, 232.4 Gg of CO, 10.6 Gg of NO2, 4.4 Gg of SO2, 20.9 Gg of PM2.5, and 28.5 Gg of PM10. These emissions remained fairly consistent, with an average interannual variability of crop residue burning emissions of +/- 10%. The states with the highest emissions were Arkansas, California, Florida, Idaho, Texas, and Washington. Most emissions were clustered in the southeastern United States, the Great Plains, and the Pacific Northwest. Air quality and carbon emissions were concentrated in the spring, summer, and fall, with an exception because of winter harvesting of sugarcane in Florida, Louisiana, and Texas. Sugarcane, wheat, and rice residues accounted for approximately 70% of all crop residue burning and associated emissions. Estimates of CO and CH4 from agricultural waste burning by the U.S. Environmental Protection Agency were 73 and 78% higher than the CO and CH4 emission estimates from this analysis, respectively. This analysis also showed that crop residue burning emissions are a minor source of CH4 emissions (< 1%) compared with the CH4 emissions from other agricultural sources, specifically enteric fermentation, manure management, and rice cultivation.     

The effect of coal combustion flue gas components on low-level chlorine speciation using EPA method 26A

U.S. Environmental Protection Agency (EPA) Method 26A is the recommended procedure for capturing and speciating halogen (X2) and hydrogen halide (HX) stack emissions from combustion sources. Previous evaluation studies of Method 26A have focused primarily on hydrogen chloride (HCl) speciation. Capture efficiency, bias, and the potential interference of Cl2 at high levels (> 20 ppm [microgram/m3]) and NH4Cl in the flue gas stream have been investigated. It has been suggested that precise Cl2 measurement and accuracy in quantifying HX or X2 using Method 26A are difficult to achieve at Cl2 concentrations < 5 ppm; however, no performance data exist to support this. Coal contains low levels of Cl, in the range of 5-2000 ppmw, which results in the presence of HCl and Cl2 in the products of combustion. HCl is the predominant Cl compound formed in the high-temperature combustion process, and it persists in the gas as the products of combustion cool. Concentrations of Cl2 in coal combustion flue gas at stack temperatures typically do not exceed 5 ppm. For this research, bench-scale experiments using simulated combustion flue gas were designed to validate the ability of Method 26A to speciate low levels of Cl2 accurately. This paper presents the results of the bench-scale tests. The effect of various flue gas components is discussed. The results indicate that SO2 is the only component in coal combustion flue gas that has an appreciable effect on Cl2 distribution in Method 26A impingers, and that Method 26A cannot accurately speciate HCl and Cl2 in coal combustion flue gas without modification.     

Determination of volatile organic profiles and photochemical potentials from chemical manufacture process vents

The main objective of this study was to monitor the volatile organic compounds (VOCs) in the stack gas released from organic chemical industrial plants to determine emission factors. Samples from 52 stacks, with or without air pollution control devices (APCDs), from seven industrial processes were taken and VOCs measured using U.S. Environmental Protection Agency (EPA) Method 18. These 7 processes, including 26 plants, were the manufacturers of acrylonitrile-butadiene-styrene (ABS), polyvinyl chloride (PVC), polystyrene (PS), acrylic resin (ACR), vinyl chloride (VC), para-terephthalic acid (PTA), and synthetic fiber (SYF). The results clearly indicate significant variations of emission factors among the various industrial processes, particularly emission factors for those without APCDs. As expected, those with APCDs yield much less emission factors. Regardless of those with or without APCDs, the order of manufacturing processes with regard to VOC emission factors is SYF > ABS > PS >ACR > PTA > PVC > VC. The emission factors for some processes also differ from those in EPA-42 data file. The VOC profiles further indicate that some VOCs are not listed in the U.S. VOC/Particulate Matter Speciation Data System (SPECIATE). The potential O3 formation is determined from the total amount of VOC emitted for each of seven processes. The resultant O3 yield varied from 0.22 (ACR) to 2.33 g O3 g(-1) VOC (PTA). The significance of this O3 yield is discussed.     

Indoor Emissions from Conversion Varnishes

ABSTRACT

Conversion varnishes are two-component, acid-catalyzed varnishes that are commonly used to finish cabinets. They are valued for their water and stain resistance, as well as their appearance. They have been found, however, to contribute to indoor emissions of organic compounds. For this project, three commercially available conversion varnish systems were selected. A U.S. Environmental Protection Agency (EPA) Method 24 analysis was performed to determine total volatile content, and a sodium sulfite titration method was used to determine uncombined (free) formaldehyde content of the varnish components. The resin component was also analyzed by gas chromatography/mass spectroscopy (GC/MS) (EPA Method 311 with an MS detector) to identify individual organic compounds. Dynamic small chamber tests were then performed to identify and quantify emissions following application to coupons of typical kitchen cabinet wood substrates, during both curing and aging. Because conversion varnishes cure by chemical reaction, the compounds emitted during curing and aging are not necessarily the same as those in the formulation. Results of small chamber tests showed that the amount of formaldehyde emitted from these coatings was 2.3–8.1 times the amount of free formaldehyde applied in the coatings. A long-term test showed a formaldehyde emission rate of 0.17 mg/m²/hr after 115 days.     

Fenton/絮凝工艺深度处理制浆造纸废水的工程应用分析

以某制浆造纸厂生化出水Fenton/絮凝深度处理工艺长期运行数据为依据,系统分析了H2O2、废酸液（FeSO4含量约8%）、硫酸铝、PAM及氧化钙等处理药剂用量与水量、进水负荷和COD去除量之间的关系。结果表明,H2O2、废酸液、硫酸铝、PAM及氧化钙的单位水量平均投加量分别为0.05、2.18、0.07、0.0075和0.27 kg/m3,而去除单位COD的药剂平均消耗量分别为0.20、8.48、0.27、0.029和1.06 kg/（kg COD）;H2O2、废酸液、硫酸铝和氧化钙的用量随进水负荷的增大而增加,而PAM随进水负荷的变化较小。H2O2和FeSO4的投加摩尔比（MH2O2/Fe2＋）主要集中在1.0-2.0之间,其中在1.0-1.6之间的累积频率达到93%。该工艺的出水COD和SS分别为65-100 mg/L和20-30 mg/L,达到《制浆造纸工业水污染物排放标准》（GB 3544-2008）排放要求。废水深度处理成本约为1.01元/m3,其中药剂费用约0.58元/m3,占56.98%。