Theoretical and Observational Assessments of Flare Efficiencies

ABSTRACT

Flaring of waste gases is a common practice in the processing of hydrocarbon (HC) materials. It is assumed that flaring achieves complete combustion with relatively innocuous byproducts such as CO₂ and H₂O. However, flaring is rarely successful in the attainment of complete combustion, because entrainment of air into the region of combusting gases restricts flame sizes to less than optimum values. The resulting flames are too small to dissipate the amount of heat associated with 100% combustion efficiency.

Equations were employed to estimate flame lengths, areas, and volumes as functions of flare stack exit velocity, stoichiometric mixing ratio, and wind speed. Heats released as part of the combustion process were then estimated from a knowledge of the flame dimensions together with an assumed flame temperature of 1200 K. Combustion efficiencies were subsequently obtained by taking the ratio of estimated actual heat release values to those associated with 100% complete combustion.

Results of the calculations showed that combustion efficiencies decreased rapidly as wind speed increased from 1 to 6 m/sec. As wind speeds increased beyond 6 m/sec,combustion efficiencies tended to level off at values between 10 and 15%. Propane and ethane tend to burn more efficiently than do methane or hydrogen sulfide because of their lower stoichiometric mixing ratios.

Results of theoretical predictions were compared to nine values of local combustion efficiencies obtained as part of an observational study into flaring activity conducted by the Alberta Research Council (ARC). All values were obtained during wind speed conditions of less than 4 m/sec. There was generally good agreement between predicted and observed values. The mean and standard deviation of observed combustion efficiencies were 68 ± 7%. Comparable predicted values were 69 ± 7%.     

Characterization of Emissions from Diffusion Flare Systems

ABSTRACT

Emissions from flares typical of those found at oil-field battery sites in Alberta, Canada, were investigated to determine the degree to which the flared gases were burned and to characterize the products of combustion in the emissions. The study consisted of laboratory, pilot-scale, and field-scale investigations. Combustion of all hydrocarbon fuels in both laboratory and pilot-scale tests produced a complex variety of hydrocarbon products within the flame, primarily by pyrolytic reactions. Acetylene, eth-ylene, benzene, styrene, ethynyl benzene, and naphthalene were some of the major constituents produced by conversion of more than 10% of the methane within the flames. The majority of the hydrocarbons produced within the flames of pure gas fuels were effectively destroyed in the outer combustion zone, resulting in combustion efficiencies greater than 98% as measured in the emissions.

The addition of liquid hydrocarbon fuels or condensates to pure gas streams had the largest effect on impairing the ability of the resulting flame to destroy the pyrolytically produced hydrocarbons, as well as the original hydrocarbon fuels directed to the flare. Crosswinds were also found to reduce the combustion efficiency (CE) of the co-flowing gas/condensate flames by causing more unburned fuel and the pyrolytically produced hydrocarbons to escape into the emissions.

Flaring of solution gas at oil-field battery sites was found to burn with an efficiency of 62-82%, depending on either how much fuel was directed to flare or how much liquid hydrocarbon was in the knockout drum. Benzene, styrene, ethynyl benzene, ethynyl-methyl benzenes, toluene, xylenes, acenaphthalene, biphenyl, and fluorene were, in most cases, the most abundant compounds found in any of the emissions examined in the field flare testing. The emissions from sour solution gas flaring also contained reduced sulfur compounds and thiophenes.     

Characterization of emissions from diffusion flare systems

Emissions from flares typical of those found at oil-field battery sites in Alberta, Canada, were investigated to determine the degree to which the flared gases were burned and to characterize the products of combustion in the emissions. The study consisted of laboratory, pilot-scale, and field-scale investigations. Combustion of all hydrocarbon fuels in both laboratory and pilot-scale tests produced a complex variety of hydrocarbon products within the flame, primarily by pyrolytic reactions. Acetylene, ethylene, benzene, styrene, ethynyl benzene, and naphthalene were some of the major constituents produced by conversion of more than 10% of the methane within the flames. The majority of the hydrocarbons produced within the flames of pure gas fuels were effectively destroyed in the outer combustion zone, resulting in combustion efficiencies greater than 98% as measured in the emissions. The addition of liquid hydrocarbon fuels or condensates to pure gas streams had the largest effect on impairing the ability of the resulting flame to destroy the pyrolytically produced hydrocarbons, as well as the original hydrocarbon fuels directed to the flare. Crosswinds were also found to reduce the combustion efficiency (CE) of the co-flowing gas/condensate flames by causing more unburned fuel and the pyrolytically produced hydrocarbons to escape into the emissions. Flaring of solution gas at oil-field battery sites was found to burn with an efficiency of 62-82%, depending on either how much fuel was directed to flare or how much liquid hydrocarbon was in the knockout drum. Benzene, styrene, ethynyl benzene, ethynyl-methyl benzenes, toluene, xylenes, acenaphthalene, biphenyl, and fluorene were, in most cases, the most abundant compounds found in any of the emissions examined in the field flare testing. The emissions from sour solution gas flaring also contained reduced sulfur compounds and thiophenes.     

Theoretical and observational assessments of flare efficiencies

Flaring of waste gases is a common practice in the processing of hydrocarbon (HC) materials. It is assumed that flaring achieves complete combustion with relatively innocuous byproducts such as CO2 and H2O. However, flaring is rarely successful in the attainment of complete combustion, because entrainment of air into the region of combusting gases restricts flame sizes to less than optimum values. The resulting flames are too small to dissipate the amount of heat associated with 100% combustion efficiency. Equations were employed to estimate flame lengths, areas, and volumes as functions of flare stack exit velocity, stoichiometric mixing ratio, and wind speed. Heats released as part of the combustion process were then estimated from a knowledge of the flame dimensions together with an assumed flame temperature of 1200 K. Combustion efficiencies were subsequently obtained by taking the ratio of estimated actual heat release values to those associated with 100% complete combustion. Results of the calculations showed that combustion efficiencies decreased rapidly as wind speed increased from 1 to 6 m/sec. As wind speeds increased beyond 6 m/sec, combustion efficiencies tended to level off at values between 10 and 15%. Propane and ethane tend to burn more efficiently than do methane or hydrogen sulfide because of their lower stoichiometric mixing ratios. Results of theoretical predictions were compared to nine values of local combustion efficiencies obtained as part of an observational study into flaring activity conducted by the Alberta Research Council (ARC). All values were obtained during wind speed conditions of less than 4 m/sec. There was generally good agreement between predicted and observed values. The mean and standard deviation of observed combustion efficiencies were 68 +/- 7%. Comparable predicted values were 69 +/- 7%.     

Computational fluid dynamics modeling of laboratory flames and an industrial flare

A computational fluid dynamics (CFD) methodology for simulating the combustion process has been validated with experimental results. Three different types of experimental setups were used to validate the CFD model. These setups include an industrial-scale flare setups and two lab-scale flames. The CFD study also involved three different fuels: C₃H₆/CH₄/Air/N₂, C₂H₄/O₂/Ar, and CH₄/Air. In the first setup, flare efficiency data from the Texas Commission on Environmental Quality (TCEQ) 2010 field tests were used to validate the CFD model. In the second setup, a McKenna burner with flat flames was simulated. Temperature and mass fractions of important species were compared with the experimental data. Finally, results of an experimental study done at Sandia National Laboratories to generate a lifted jet flame were used for the purpose of validation. The reduced 50 species mechanism, LU 1.1, the realizable k-? turbulence model, and the EDC turbulence–chemistry interaction model were used for this work. Flare efficiency, axial profiles of temperature, and mass fractions of various intermediate species obtained in the simulation were compared with experimental data and a good agreement between the profiles was clearly observed. In particular, the simulation match with the TCEQ 2010 flare tests has been significantly improved (within 5% of the data) compared to the results reported by Singh et al. in 2012. Validation of the speciated flat flame data supports the view that flares can be a primary source of formaldehyde emission.

ImplicationsValidated computational fluid dynamics (CFD) models can be a useful tool to predict destruction and removal efficiency (DRE) and combustion efficiency (CE) under steam/air assist conditions in the face of many other flare operating variables such as fuel composition, exit jet velocity, and crosswind. Augmented with rigorous combustion chemistry, CFD is also a powerful tool to predict flare emissions such as formaldehyde. In fact, this study implicates flares emissions as a primary source of formaldehyde emissions. The rigorous CFD simulations, together with available controlled flare test data, can be fitted into simple response surface models for quick engineering use.     

Radon exhalation and ultrafine fraction of radon progeny in closed room air

The influence of ²²²Rn exhalation from walls and air exchange (low ventilation rates ν<0.3 h^-1) upon its concentration in room air has been considered. It was found that the radon concentration reachs 84 Bq m^-3 at exhalation and ventilation rates of 66 Bq hm^-2 and 0.28 h^-1, respectively. The radon concentration and the ultrafine fraction f_p of potential α energy concentration as well as the equilibrium factor F of the short-lived radon progeny were also determined in three different completely closed rooms. An electroprecipitation method was applied for determining the ²²²Rn concentration while a single wire-screen technique was used for the determination of ultrafine radon progeny. During the measurements, the radon concentrations were varied between 33 and 134 with a mean value 89 Bq m^-3. A mean ultrafine fraction (f_p) of 0.16 was obtained at a mean aerosol particle concentration (Z) of 1700 cm^-3 and a mean equilibrium factor (F) of 0.33. The obtained mean value of f_p was found to be about five times higher than the value reported in the ICRP publication (f_p=0.03). The attachment rate (X), the deposition rate (q^f) and the deposition velocity (v^f_d) of the ultrafine radionuclide ²¹⁸Po were calculated. A mean value of X was found to be 49 h^-1 at a mean q^f of 46 h^-1 and a mean v^f_d of 4.6 m h^-1. The attachment coefficient β of ²¹⁸Po was found to vary between 0.016 and 0.047 with a mean value 0.028 cm³ h^-1.     

Gas-phase rate coefficients for the reactions of NO3, OH and O3 with α,β-unsaturated esters and ketones: Structure−activity relations (SARs)

Gas-phase rate coefficients for the atmospherically important reactions of NO₃, OH and O₃ are predicted for 55 α,β-unsaturated esters and ketones. The rate coefficients were calculated using a correlation described previously [Pfrang, C., King, M.D., C. E. Canosa-Mas, C.E., Wayne, R.P., 2006. Atmospheric Environment 40, 1170–1179]. These rate coefficients were used to extend structure–activity relations for predicting the rate coefficients for the reactions of NO₃, OH or O₃ with alkenes to include α,β-unsaturated esters and ketones. Conjugation of an alkene with an α,β-keto or α,β-ester group will reduce the value of a rate coefficient by a factor of ∼110, ∼2.5 and ∼12 for reaction with NO₃, OH or O₃, respectively. The actual identity of the alkyl group, R, in −C(O)R or −C(O)OR has only a small influence. An assessment of the reliability of the SAR is given that demonstrates that it is useful for reactions involving NO₃ and OH, but less valuable for those of O₃ or peroxy nitrate esters.     

Impact of clouds and aerosols on ozone production in Southeast Texas

A radiative transfer model and photochemical box model are used to examine the effects of clouds and aerosols on actinic flux and photolysis rates, and the impacts of changes in photolysis rates on ozone production and destruction rates in a polluted urban environment like Houston, Texas. During the TexAQS-II Radical and Aerosol Measurement Project the combined cloud and aerosol effects reduced j(NO₂) photolysis frequencies by nominally 17%, while aerosols reduced j(NO₂) by 3% on six clear sky days. Reductions in actinic flux due to attenuation by clouds and aerosols correspond to reduced net ozone formation rates with a nearly one-to-one relationship. The overall reduction in the net ozone production rate due to reductions in photolysis rates by clouds and aerosols was approximately 8 ppbv h^?1.     

Prediction of gas diffusion in complicated terrain by a potential flow model

A numerical model was developed to simulate gaseous diffusion in complicated terrain. This model calculates the air flow as a potential flow by the Boundary Element Method, and gaseous diffusion by an analytical Gaussian equation in the potential flow. Plume spreads σ_y and σ_z are modified by multiregression equations derived from wind tunnel experiments, and the terrain height is elongated depending on the atmospheric stability.First, tracer data from Cinder Cone Butte in the U.S. measured by the U.S.-EPA were predicted by the model in order to examine the prediction accuracy under stable conditions. The averaged ratio of the observed concentration to predicted concentration for 12 runs was better than a factor of 10. Next, tracer data from the Geysers area in the U.S. measured by the U.S.-DOE were used to examine the prediction accuracy under neutral conditions. The ratio of the observed concentration to predicted concentration for two runs under neutral conditions was better than factor of two at most locations, but prediction capability is poor in blocked or separated flow conditions.     

A study of gas/particle partitioning of SVOCs in the tropical atmosphere of Southeast Asia

Gas- and particle-phase polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs) were collected at a tropical site in Southeast Asia over 12-h periods during November and December 2006 to determine their gas/particle distributions by analyzing integrated quartz filter and polyurethane foam samples. Gas/particle partitioning coefficients, K_p, were calculated, and their relationship with the subcooled liquid vapor pressure p_L^o for both PAHs and PCBs was investigated. The regressions of log K_p vs. log p_L^o for most of samples gave high correlations for both PAHs and PCBs and the slopes were statistically shallower than ?1, but they were relatively steeper than those obtained in temperate zones of the Northern Hemisphere. By comparison, the particle-bound fraction of low molecular weight (LMW) PAHs was underestimated by both Junge-Pankow adsorption and K_OA (octanol–air partition coefficient) absorption models, while the predicted values agree relatively better with those observed ones for high molecular weight (HMW) PAHs. In addition, the adsorption onto the soot phase (elemental carbon) predicted accurately the gas/particle partitioning of PAHs, especially for LMW compounds. On the other hand, the K_OA absorption model using the measured organic matter fraction (f_OM) value fitted the PCB data much better than the adsorption model did, indicating the sorption of nonpolar compounds to aerosols might be dominated by absorption into organic matters in this area.     

Emissions from Slash Burning and the Influence of Flame Retardant Chemicals

Pollutants sampled during the burning of 30 lb ponderosa pine fuel beds yielded emission factors for CO, hydrocarbon gases, and par-ticulate matter of 146, 8.4, and 9.1 lb/ton of fuel, respectively. When similar beds were treated with diammonium phosphate flame retardant, these factors increased to 166, 11.7, and 19.3 lb/ton of fuel, respectively.

Gas chromatographic analysis of hydrocarbon gases showed that 15-40% of this material was composed of methane and eth-ylene. Ethane and acetylene were the next most abundant materials, with photochemically important materials constituting minor portions of this gaseous component. Fuel beds treated with flame retardant produced more oiefins, and this production lasted throughout the smoldering phase of burning.

These tests showed that the smoldering phase of combustion is of major importance to air pollutant production during slash burning. The initial 80% of the fuel burned accounted for only 20-30% of HC and CO emissions. This suggests that a rapid mop-up of slash burns could substantially reduce air pollutant production.     

Solubility of organic acids in various methanol and salt concentrations: the implication on organic acid sorption in a cosolvent system

The well-known cosolvency-induced sorption model is not applicable to predict the sorption of carboxylic acids in cosolvent system. To investigate the phenomenon, sorption and solubility of chlorinated phenols (2,4-dichlorophenol (2,4-DCP) and 2,4,6-trichlorophenol (2,4,6-TCP)) and carboxylic acids (benzoic acid and 2,4-dichlorophenoxyacetic acid (2,4-D)) were measured in soil-methanol mixture with various ionic strengths. The sorption (K_m) of chlorinated phenols was explained by a cosolvency-induced sorption model; the inverse log-linear relationship between the K_m and methanol volume fraction (f_c). However, the K_m of carboxylic acids increased with increasing f_c. This discrepancy was attributed to the effect of the carboxylic moiety. To explain the effect, solubility was measured for benzoic acid and 2,4,6-TCP from various liquid conditions. For both solutes, the cosolvency power (σ) increased with CaCl₂ concentrations and the salting constant (K^s) became smaller as f_c increased. However, the σ value at a given salt concentration and the K^s value at a given f_c were greater for 2,4,6-TCP than for benzoic acid, both of which were due to the greater hydrophobicity of the former. Overall, the solubility profiles of the both solutes on combination of f_c and CaCl₂ concentration evidenced no specific role of the carboxylic moiety. Therefore, it can be reasonably concluded that the positive relationship between K_m and f_c for carboxylic organic acid can be attributed to the modification of the activity coefficient occurred in the solid phase, which cannot be traceable by cosolvency-based model.     

An Advective Model for Predicting Air Pollution within an Urban Heat Island With Applications to New York City

A simple air pollution model has been tested for New York City with data from five mornings which were characterized by urban heat island effects. The model is nondiffusive and relies primarily upon conservation of mass. The correlation coefficient between over 400 predicted and observed values of SO₂ mixing ratio was 0.83.     

Sorption of acidic organic solute onto kaolinitic soils from methanol-water mixtures

The fate of the acidic organic solute from the soil-water-solvent system is not well-understood. In this study, the effect of the acidic functional group of organic solute in the sorption from cosolvent system was evaluated. The sorption of naphthalene (NAP) and 1-naphthoic acid (1-NAPA) by three kaolinitic soils and two model sorbents (kaolinite and humic acid) were measured as functions of the methanol volume fractions (f _c ≤ 0.4) and ionic compositions (CaCl₂ and KCl). The solubility of 1-NAPA was also measured in various ionic compositions. The sorption data were interpreted using the cosolvency-induced sorption model. The K _m values (= the linear sorption coefficient) of NAP with kaolinitic soil for both ionic compositions was log linearly decreased with f _c. However, the K _m values of 1-NAPA with both ionic compositions remained relatively constant over the f _c range. For the model sorbent, the K _m values of 1-NAPA with kaolinite for the KCl system and with humic acid for both ionic compositions decreased with f _c, while the sorption of 1-NAPA with kaolinite for the CaCl₂ system was increased with f _c. From the solubility data of 1-NAPA with f _c, no significant difference was observed with the different ionic compositions, indicating an insignificant change in the aqueous activity of the liquid phase. In conclusion, the enhanced 1-NAPA sorption, greater than that predicted from the cosolvency-induced model, was due to an untraceable interaction between the carboxylate and hydrophilic soil domain in the methanol-water system. Therefore, in order to accurately predict the environmental fate of acidic pesticides and organic solutes, an effort to quantitatively incorporate the enhanced hydrophilic sorption into the current cosolvency-induced sorption model is required.     

Spectroscopic behavior of oxygenated combustion by-products

The oxygenated species, massively produced in the energy production plants based on combustion processes, constitute one of the most numerous categories of hazardous air pollutants. Therefore, development of real time diagnostic tools are needed in order to study their formation during combustion processes and to reveal their presence both in the exhaust and in the atmosphere. In this work, oxygenated compounds were identified inside fuel-rich premixed ethylene/air flames by means of ultraviolet fluorescence spectroscopy with the support of qualitative chemical analysis of the sampled combustion gases.

Strong band progression, typical of aldehydic functionality, were recognized in fluorescence spectra (λ_exc=355 nm) measured in the early oxidation region of premixed flames varying the equivalence ratio from 3.0 up 21.6. Downstream of the oxidation region, spectroscopic signatures of pyrolytic species were found to prevail on those peculiar of oxygenated compound. The position and the extension of the two main flame zones were found to depend on the flame conditions (C/O ratio) due to the effect of the C/O ratio on the temperature history along the flame axis. This correlation was interpreted on the basis of the measured axial temperature profiles.     

Carbon dioxide and methane fluxes in the littoral zones of two lakes,east Antarctica

During the summertime of 2007/2008, carbon dioxide (CO₂) and methane (CH₄) fluxes across air–water interface were investigated in the littoral zones of Lake Mochou and Lake Tuanjie, east Antarctica, using a static chamber technique. The mean fluxes of CO₂ and CH₄ were ?70.8 mgCO₂ m^?2 h^?1 and 144.6 μgCH₄ m^?2 h^?1, respectively, in the littoral zone of Lake Mochou; The mean fluxes were ?36.9 mgCO₂ m^?2 h^?1 and 109.8 μgCH₄ m^?2 h^?1, respectively, in the littoral zone of Lake Tuanjie. Their fluxes showed large temporal and spatial dynamics. The CO₂ fluxes showed a significantly negative correlation with daily total radiation (DTR) and a weakly negative correlation with air temperature and water temperature, indicating that sunlight intensity controlled the magnitude of CO₂ fluxes from the open lakes. The CH₄ fluxes significantly correlated with local air temperature, water table and total dissolved solids (TDS), indicating that they were the predominant factors influencing CH₄ fluxes. Summertime CO₂ budgets in the littoral zones of Lake Mochou and Lake Tuanjie were estimated to be ?152.9 gCO₂ m^?2 and ?79.7 gCO₂ m^?2, respectively, and net CH₄ emissions were estimated to be 312.3 mgCH₄ m^?2 and 237.2 mgCH₄ m^?2, respectively. Our results show that shallow, open, alga-rich lakes might be strong summertime CO₂ absorbers and small CH₄ emitters during the open water in coastal Antarctica.     

Linking chemical extraction to microbial degradation of 14C-hexadecane in soil

Chemical extractions have been shown to measure the biodegradable fraction of aromatic contaminants in soil; however, there is little research on the chemical prediction of aliphatic hydrocarbon degradation. The aim of this study was to investigate the potential for cyclodextrin extractions to predict hexadecane biodegradation in soil. Soils were amended with 10 or 100 mg kg⁻¹ of a model alkane n-hexadecane and 100 Bq g⁻¹¹⁴C-n-hexadecane. Correlations between the extents of mineralisation and extractions of the ¹⁴C-contaminant were determined. Solvent shake extractions and aqueous CaCl₂ extractions were poor predictors of hexadecane bioaccessibility. However, the novel HP-α-CD shake extraction showed close correlation (r² = 0.90, n = 36, p < 0.05) to the mineralisation data. This novel extraction technique has the potential to be used to assess the biodegradable aliphatic hydrocarbon fraction in contaminated soils.     

Recovering CO2 From Large− and Medium-Size Stationary Combustors

This paper summarizes the results of research conducted at Ar-gonne National Laboratory (ANL) to develop and design a novel method for the recovery of CO₂ from flue gases. The basic process concept Involves the combustion of a hydrocarbon fuel using a mixture of oxygen and carbon dioxide (or CO₂ and H₂0) rather than air as the oxidant, which results In a product stream that contains primarily CO₂ and H₂O. This stream Is then dried and conditioned to meet the specifications of the end user, A slip stream of CO₂ (or CO₂, and H₂0) is used as a diluent in the combustion chamberto maintain a flame temperature equivalent to the temperature that would otherwise be obtained using air as an oxidant. The cost-effectiveness of the process in recovering C0₂ is dependent on the scale of the operation, the type of fuel used, the cost of oxygen, and the cost of capital. The sensitivity of the cost of the recovered C0₂ to these variables Is discussed, and a model for estimating the cost of CO₂ recovered using the ANL process Is presented.     

Validation of ADMS against wind tunnel data of dispersion from chemical warehouse fires

Comparisons are presented of the predictions of the atmospheric dispersion modelling system (ADMS) and wind tunnel data for plume dispersion from chemical warehouse fires. The focus of the comparisons is dispersion from structurally intact buildings with open roofs and dispersion of plumes flush with the ground without obstacles, however, dispersion from building shells and doors is also considered. Both buoyancy driven and momentum driven flows are treated, although emphasis is on buoyancy driven flows as these are generally more likely to occur in warehouse fires. The study shows that the ADMS building module is able to reproduce many of the features of dispersion observed in the wind tunnel. These include a recirculating region behind the building in which material may be trapped, a main wake which brings material down towards the surface, and appropriate sensitivity to the buoyancy and momentum of the emitted material, and the location of sources on the building roof. The comparisons suggest that the ADMS building model can be used to predict dispersion from the stages of fire development studied. The precise level of agreement depends (but not in a systematic way) on the buoyancy flux parameter F_B, the momentum flux parameter F_M and the number of roof lights. There are some significant differences between the wind tunnel boundary layer and the simulated atmospheric boundary layer in ADMS which have to be considered when making wind tunnel model comparisons. These relate mainly to the near surface where the wind tunnel underestimates turbulent velocities, the boundary layer height which in the wind tunnel corresponds to an atmospheric boundary layer depth of 82.5 m (atmospheric boundary layers are frequently an order of magnitude deeper), and the boundary layer top where the ADMS boundary layer is capped by an inversion and has low turbulence levels whereas the wind tunnel boundary layer has higher levels of turbulence and no capping inversion.