小型燃油锅炉大气污染物的排放管理控制

燃料燃烧过程是大气污染物的重要来源之一,对人体健康,空气质量和气候变化具有非常重要的影响;管理控制是控制污染物排放的重要手段.以85台小型燃油锅炉(≤10.5 MW)燃料特性分析数据和污染物排放实测数据为基础,通过统计分析方法,分析了中国在用燃油品质以及大气污染物的排放现状,讨论了小型燃油锅炉大气污染物排放管理控制的潜力与可行性.结果表明,对燃油品质的管理控制是有效控制燃烧过程大气污染物排放的重要措施,分别有95%和98%燃油的灰分和含硫量符合国家相关规定;所有测试锅炉PM排放浓度远低于<锅炉大气污染物排放标准>(GB/T 13271-2001)规定的最高允许排放限值,有90%以上的锅炉达到GB/T 13271～2001中SO2最高允许排放限值,有84%的锅炉达到GB/T 13271-2001中NOx最高允许排放限值;与其他国家相比,中国对小型燃油锅炉常规大气污染物排放的管理控制处于中等水平,应当适时开展对有害空气污染物的管理控制.     

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.     

Comparison of particle size distributions and elemental partitioning from the combustion of pulverized coal and residual fuel oil

U.S. Environmental Protection Agency (EPA) research examining the characteristics of primary PM generated by the combustion of fossil fuels is being conducted in efforts to help determine mechanisms controlling associated adverse health effects. Transition metals are of particular interest, due to the results of studies that have shown cardiopulmonary damage associated with exposure to these elements and their presence in coal and residual fuel oils. Further, elemental speciation may influence this toxicity, as some species are significantly more water-soluble, and potentially more bio-available, than others. This paper presents results of experimental efforts in which three coals and a residual fuel oil were combusted in three different systems simulating process and utility boilers. Particle size distributions (PSDs) were determined using atmospheric and low-pressure impaction as well as electrical mobility, time-of-flight, and light-scattering techniques. Size-classified PM samples from this study are also being utilized by colleagues for animal instillation experiments. Experimental results on the mass and compositions of particles between 0.03 and > 20 microns in aerodynamic diameter show that PM from the combustion of these fuels produces distinctive bimodal and trimodal PSDs, with a fine mode dominated by vaporization, nucleation, and growth processes. Depending on the fuel and combustion equipment, the coarse mode is composed primarily of unburned carbon char and associated inherent trace elements (fuel oil) and fragments of inorganic (largely calcium-alumino-silicate) fly ash including trace elements (coal). The three coals also produced a central mode between 0.8- and 2.0-micron aerodynamic diameter. However, the origins of these particles are less clear because vapor-to-particle growth processes are unlikely to produce particles this large. Possible mechanisms include the liberation of micron-scale mineral inclusions during char fragmentation and burnout and indicates that refractory transition metals can contribute to PM < 2.5 microns without passing through a vapor phase. When burned most efficiently, the residual fuel oil produces a PSD composed almost exclusively of an ultrafine mode (approximately 0.1 micron). The transition metals associated with these emissions are composed of water-soluble metal sulfates. In contrast, the transition metals associated with coal combustion are not significantly enriched in PM < 2.5 microns and are significantly less soluble, likely because of their association with the mineral constituents. These results may have implications regarding health effects associated with exposure to these particles.     

燃油锅炉燃烧过程SO2的生成与排放特征

燃料燃烧过程是大气污染物的重要来源之一,对人体健康、空气质量和气候变化产生非常重要的影响。以62台燃油锅炉（≤10.5 MW）的燃料特性分析数据和SO₂排放实测数据为基础,通过统计分析方法,研究了燃油燃烧过程中燃油硫含量S和过量空气系数α对硫的转化率、SO₂排放因子和排放浓度的影响,获得了基于燃料消耗量、燃料发热量的SO₂排放因子EF_C、EF_H以及SO₂标态折算浓度C′_SO2与硫含量S间的关联式。结果表明,在过量空气系数α＞1的燃油燃烧过程中,EF_C、EF_H、C′_SO2与燃油硫含量S呈现出显著的线性正相关性,而与过量空气系数α无关,其关系式分别为：EF_C=18.86602×S,EF_H=443.78751×S ,C′_SO2＝1 509.28337×S;硫转化率η和基于燃料硫含量的SO₂排放因子EF_S则与燃油硫含量S和过量空气系数α无关,其平均值分别为96.3％和1.93 kg/kg。     

Pyrolysis-GC-MS analysis of crude and heavy fuel oil asphaltenes for application in oil fingerprinting

A Pyrolysis – Gas Chromatography – Mass Spectrometry (Py-GC-MS) method was developed for the analysis and profiling of crude and heavy fuel oil asphaltenes, for application in oil fingerprinting. Asphaltenes were precipitated from ten geographically different oils using n-pentane, and analysed by Py-GC-MS. Alkane profiles and sulphur/aromatic profiles were used to compare the oils, and to correctly differentiate oils from different geographical regions. Py-GC-MS could not differentiate a weathered oil sample and a fresh oil sample from the same source. The results of this study support the findings from a previously developed FTIR method for asphaltene profiling.     

Characterization of methane emissions from five cold heavy oil production with sands (CHOPS) facilities

Cold heavy oil production with sands (CHOPS) is a common oil extraction method in the Canadian provinces of Alberta and Saskatchewan that can result in significant methane emissions due to annular venting. Little is known about the magnitude of these emissions, nor their contributions to the regional methane budget. Here the authors present the results of field measurements of methane emissions from CHOPS wells and compare them with self-reported venting rates. The tracer ratio method was used not only to analyze total site emissions but at one site it was also used to locate primary emission sources and quantify their contributions to the facility-wide emission rate, revealing the annular vent to be a dominant source. Emissions measured from five different CHOPS sites in Alberta showed large discrepancies between the measured and reported rates, with emissions being mainly underreported. These methane emission rates are placed in the context of current reporting procedures and the role that gas-oil ratio (GOR) measurements play in vented volume estimates. In addition to methane, emissions of higher hydrocarbons were also measured; a chemical “fingerprint” associated with CHOPS wells in this region reveals very low emission ratios of ethane, propane, and aromatics versus methane. The results of this study may inform future studies of CHOPS sites and aid in developing policy to mitigate regional methane emissions.

Implications: Methane measurements from cold heavy oil production with sand (CHOPS) sites identify annular venting to be a potentially major source of emissions at these facilities. The measured emission rates are generally larger than reported by operators, with uncertainty in the gas-oil ratio (GOR) possibly playing a large role in this discrepancy. These results have potential policy implications for reducing methane emissions in Alberta in order to achieve the Canadian government’s goal of reducing methane emissions by 40–45% below 2012 levels within 8 yr.     

Speciated hydrocarbon emissions from small utility engines

Partially speciated hydrocarbon (HC) emissions data from several small utility engines, as measured by a Fourier Transform Infrared analyzer, are presented. The engines considered have nominal horsepower ratings between 3.7 and 9.3 kW. Both side-valve and overhead-valve engines are studied, and four different fuels are used in the engines. The results indicate that the small HCs present in the exhaust tend to be in the form of either methane or unsaturated HCs. Other small alkanes, such as ethane and propane, are present in only relatively small concentrations. In terms of ozone formation potential, the HCs in the form of methane will lead to little ozone, but the distribution of the C2 and C3 species is not ideal from an ozone reduction stand-point. It is also found that the presence of oxygen in the fuels appears to lead to somewhat more complete combustion, although the effects are not large. Finally, the overhead-valve engines appear to have lower HC emissions than side-valve engines, which is primarily due to higher operating A/F ratios and the engine geometry.     

Fast preparation of the seawater accommodated fraction of heavy fuel oil by sonication

The seawater accommodated fraction (SWAF) of oil is widely used for the assessment of its toxicity. However, its preparation in the laboratory is time consuming, and results from different authors are difficult to compare as preparation methods vary. Here we describe a simple and fast set up, using sonication, to produce reproducible SWAF in the laboratory. The system was tested on heavy fuel oil placed on seawater at different salinity and temperature conditions. Maximum dissolution of the oil was achieved after 24 h, independently of both seawater salinity and temperature. Our findings are discussed in relation to the fate of the oil from the deep spill of the Prestige tanker. Changes in temperature in the open ocean are bound to have larger impact in the concentration of the SWAF than the corresponding values of sea water salinity. We anticipate that in this type of incident the highest SWAF, as the oil reaches the sea surface, should be expected in the warmest and less saline waters of the water column.     

Fast preparation of the seawater accommodated fraction of heavy fuel oil by sonication

The seawater accommodated fraction (SWAF) of oil is widely used for the assessment of its toxicity. However, its preparation in the laboratory is time consuming, and results from different authors are difficult to compare as preparation methods vary. Here we describe a simple and fast set up, using sonication, to produce reproducible SWAF in the laboratory. The system was tested on heavy fuel oil placed on seawater at different salinity and temperature conditions. Maximum dissolution of the oil was achieved after 24 h, independently of both seawater salinity and temperature. Our findings are discussed in relation to the fate of the oil from the deep spill of the Prestige tanker. Changes in temperature in the open ocean are bound to have larger impact in the concentration of the SWAF than the corresponding values of sea water salinity. We anticipate that in this type of incident the highest SWAF, as the oil reaches the sea surface, should be expected in the warmest and less saline waters of the water column.     

Traffic generated non-exhaust particulate emissions from concrete pavement: A mass and particle size study for two-wheelers and small cars

This study aimed to understand the non-exhaust (NE) emission of particles from wear of summer tire and concrete pavement, especially for two wheelers and small cars. A fully enclosed laboratory-scale model was fabricated to simulate road tire interaction with a facility to collect particles in different sizes. A road was cast using the M-45 concrete mixture and the centrifugal casting method. It was observed that emission of large particle non exhaust emission (LPNE) as well as PM₁₀ and PM_2.5 increased with increasing load. The LPNE was 3.5 mg tire⁻¹ km⁻¹ for a two wheeler and 6.4 mg tire⁻¹ km⁻¹ for a small car. The LPNE can lead to water pollution through water run-off from the roads. The contribution of the PM₁₀ and PM_2.5 was smaller compared to the LPNE particles (less than 0.1%). About 32 percent of particle mass of PM₁₀ was present below 1 μm. The number as well as mass size distribution for PM₁₀ was observed to be bi-modal with peaks at 0.3 μm and 4–5 μm. The NE emissions did not show any significant trend with change in tire pressure.     

Control of PCDD/PCDF emissions from refuse-derived fuel combustors

This paper presents preliminary results of performance tests conducted at the Mid-Connecticut Refuse-Derived Fuel Facility in February 1989. The objectives of these performance tests were to evaluate the effects of combustion and flue gas cleaning process conditions on air pollution emissions and residue properties.     

Pronounced decrease of ambient particle number emissions from diesel traffic in Denmark after reduction of the sulphur content in diesel fuel

Measurements of particle number concentration and size distributions in a Copenhagen street canyon in January–March 1999, and one year later in 2000, have revealed that the number of particles in the ultrafine size range below 100 nm decreased significantly in the period between the two campaigns. The decrease was especially large in the size range below 30 nm. By two common factors, we found high co-variance between ultrafine particles, nitrogen oxides, and carbon monoxide. The co-variation can be used to assess the contributions and size distributions of particles from the two main sources, petrol traffic and diesel traffic. Here, we show that the drop in particle concentrations can be consistently explained by a 56% fall in the average particle emission from the diesel vehicles in the street. In the same period, we found no change in the particle emission from petrol cars. The change is probably due to the reduction of the sulphur content in diesel fuel from approximately 0.05% to less than 0.005%, implemented in all parts of Denmark in July 1999.     

Mixed-model statistical analysis of fuel, equipment, mileage, and driving schedule effects on particulate matter emissions from heavy diesel-powered vehicles

An extensive experimental program has been conducted to evaluate the comparative effects of California Air Resources Board diesel fuel and an ultra-low-sulfur (S) diesel (with and without aftermarket passive filtering devices) on mass emissions of particulate matter (PM) in heavy vehicles. Tests have been performed on 20 Class 8 trucks at two high-mileage levels using two different driving schedules. The design of the test program facilitates the use of mixed-model statistical analysis, which allows more appropriate treatment of the explanatory variables than normally achieved. The analysis suggests that the ultra-low-S diesel fuel yields extremely low mean PM emissions when used in conjunction with a particulate filter, even at high mileage, but that the estimates are highly variable. The high degree of uncertainty, caused at least in part by large vehicle-to-vehicle variation, may obscure the true PM response and adversely impact attainment of increasingly more stringent diesel PM emissions standards in the United States.     

Hazardous air pollutant emissions from gas-fired combustion sources: emissions and the effects of design and fuel type

Air emissions from gas-fired combustion devices such as boilers, process heaters, gas turbines and stationary reciprocating engines contain hazardous air pollutants (HAPs) subjected to consideration under the federal clean air act (CAA). This work presents a recently completed major research project to develop an understanding of HAP emissions from gas-fired boilers and process heaters and new HAP emission factors based on field emission tests of gas-fired external combustion devices used in the petroleum industry. The effect of combustion system design and operating parameters on HAP emissions determined by both field and research tests are discussed. Data from field tests of gas-fired petroleum industry boilers and heaters generally show very low emission levels of organic HAPs. A comparison of the emission data for boilers and process heaters, including units with and without various forms of NOx emission controls, showed no significant difference in organic HAP emission characteristics due to process or burner design. This conclusion is also supported by the results of research tests with different burner designs. Based on field tests of units fired with natural gas and various petroleum industry process gases and research tests in which gas composition was intentionally varied, organic HAP emissions were not determined to be significantly affected by the gas composition. Research data indicate that elevated organic HAP emission levels are found only under extreme operating conditions (starved air or high excess air combustion) associated with poor combustion.     

小型锅炉烟气喷雾分离法脱硫的试验研究

以4t燃煤锅炉为对象，重点研究了喷雾分离法脱硫技术的工艺流程和主要设备，并给出了相应的试验结果。结果表明以清水为吸收剂，液气比≤0．1L／m^3，脱硫效率达到了60％—70％。本装置具有工艺简单、占地省、投资少、运行费用低的优点，特别适合用于中小型锅炉的改造。     

Volatile organic compound emissions from dry mill fuel ethanol production

Ethanol fuel production is growing rapidly in the rural Midwest, and this growth presents potential environmental impacts. In 2002, the U.S. Environmental Protection Agency (EPA) and the Minnesota Pollution Control Agency (MPCA) entered into enforcement actions with 12 fuel ethanol plants in Minnesota. The enforcement actions uncovered underreported emissions and resulted in consent decrees that required pollution control equipment be installed. A key component of the consent decrees was a requirement to conduct emissions tests for volatile organic compounds (VOCs) with the goal of improving the characterization and control of emissions. The conventional VOC stack test method was thought to underquantify total VOC emissions from ethanol plants. A hybrid test method was also developed that involved quantification of individual VOC species. The resulting database of total and speciated VOC emissions from 10 fuel ethanol plants is relatively small, but it is the most extensive to date and has been used to develop and gauge compliance with permit limits and to estimate health risks in Minnesota. Emissions were highly variable among facilities and emissions units. In addition to the variability, the small number of samples and the presence of many values below detection limits complicate the analysis of the data. To account for these issues, a nested bootstrap procedure on the Kaplan-Meier method was used to calculate means and upper confidence limits. In general, the fermentation scrubbers and fluid bed coolers emitted the largest mass of VOC emissions. Across most facilities and emissions units ethanol was the pollutant emitted at the highest rate. Acetaldehyde, acetic acid, and ethyl acetate were also important emissions from some units. Emissions of total VOCs, ethanol, and some other species appeared to be a function of the beer feed rate, although the relationship was not reliable enough to develop a production rate-based emissions factor.     

The history of mercury emissions from fuel combustion in Maritime Canada

In this study, we present an inventory of historical emissions of mercury resulting from combustion of wood, coal and refined petroleum products in Maritime Canada. The pattern of emissions illustrates the strong influences of population growth, industrial development and prevailing fuel preferences in the region. According to our calculations, anthropogenic mercury releases from fuel combustion in Maritime Canada have cumulatively totaled more than 50 tonnes since 1800. We have compiled both high and low estimates of annual mercury releases in this region. Mercury emissions from fuel combustion in Maritime Canada reached a maximum level in the 1940s. At this time, emissions were between 778 (low) and 1494 (high) kg per year, coinciding with the period of most intensive coal use in Maritime Canada. In 1995, emissions were approximately 54% of the level reached in 1940, at 427 (low)-800 (high) kg per year. In presenting this emissions inventory, we hope to refine past estimates with current information on the mercury content of different fuel types, and create a comprehensive database on how mercury emissions from various sources have changed over time.     

小型燃油锅炉NOx的排放特征与管理控制

以68台燃油锅炉（≤10.5 MW）NO_x排放实测数据为基础,通过统计分析方法,研究了NO_x的排放特征;通过对比分析,探讨了我国燃油锅炉NO_x排放控制与管理现状,讨论了进一步加强我国燃油锅炉NO_x排放管理控制的可能性与可行性,并提出了相应的管理控制建议。结果表明,NO_x平均排放浓度为318.2 mg/m³,