Absorption and reaction kinetics of amines and ammonia solutions with carbon dioxide in flue gas

The removal system for the absorption of CO2 with amines and NH3 is an advanced air pollution control device to reduce greenhouse gas emissions. Absorption of CO2 by amines and NH3 solutions was performed in this study to derive the reaction kinetics. The absorption of CO2 as encountered in flue gases into aqueous solutions of monoethanolamine (MEA), diethanolamine (DEA), and NH3 was carried out using a stirred vessel with a plane gas-liquid interface at 50 degrees C. Various operating parameters were tested to determine the effect of these variables on the absorption kinetics of the reactants in both gas and liquid phases and the effect of competitions between various reactants on the mass-transfer rate. The observed absorption rate increases with increasing gas-liquid concentration, solvent concentration, temperature, and gas flow rate, but changes with the O2 concentration and pH value. The absorption efficiency of MEA is better than that of NH3 and DEA, but the absorption capacity of NH3 is the best. The active energies of the MEA and NH3 with CO2 are 33.19 and 40.09 kJ/mol, respectively.     

Quality Assured Measurements of Animal Building Emissions: Gas Concentrations

Abstract

Comprehensive field studies were initiated in 2002 to measure emissions of ammonia (NH₃), hydrogen sulfide (H₂S), carbon dioxide (CO₂), methane (CH₄), nonmethane hydrocarbons (NMHC), particulate matter <10 µm in diameter, and total suspended particulate from swine and poultry production buildings in the United States.

This paper focuses on the quasicontinuous gas concentration measurement at multiple locations among paired barns in seven states. Documented principles, used in air pollution monitoring at industrial sources, were applied in developing quality assurance (QA) project plans for these studies. Air was sampled from multiple locations with each gas analyzed with one high quality commercial gas analyzer that was located in an environmentally controlled on-farm instrument shelter. A nominal 4 L/min gas sampling system was designed and constructed with Teflon wetted surfaces, bypass pumping, and sample line flow and pressure sensors. Three-way solenoids were used to automatically switch between multiple gas sampling lines with ≥10 min sampling intervals. Inside and outside gas sampling probes were between 10 and 115 m away from the analyzers. Analyzers used chemiluminescence, fluorescence, photoacoustic infrared, and photoionization detectors for NH₃, H₂S, CO₂, CH₄, and NMHC, respectively. Data were collected using personal computer-based data acquisition hardware and software. This paper discusses the methodology of gas concentration measurements and the unique challenges that livestock barns pose for achieving desired accuracy and precision, data representativeness, comparability and completeness, and instrument calibration and maintenance.     

填料塔中Na_2CO_3吸收高浓度H_2S的传质特性

在填料吸收塔中考察了Na2CO3溶液吸收高浓度H2S气体的气液传质特性。通过测量填料塔进出口气体中H2S浓度计算了Na2CO3溶液吸收高浓度H2S气体的总体积传质系数(KGa),并研究了进气流速、吸收液流量、吸收温度和吸收液浓度对KGa的影响。结果表明,KGa随Na2CO3浓度、吸收液流量的增加而增加,随吸收温度、进气流速的升高而降低;在高浓度H2S吸收过程中液相传质阻力不能忽略。     

混合胺MEA+DETA吸收CO2的影响因素

以MEA为主体,DETA 为添加剂,考察1 h内,在温度298~338 K,压力300~700 kPa,混合胺溶液初始浓度(质量分数)4%~20%范围内,MEA+DETA不同配比的混合吸收剂吸收CO₂的特性。获得MEA+DETA混合胺吸收CO₂的最佳吸收条件为:308 K、500 kPa、总胺质量浓度为20%,MEA与DETA 的配比为8:2。     

The Recovery of Ammonia and Hydrogen Sulflde from Ground-Level Area Sources Using Dynamic Isolation Flux Chambers: Bench-Scale Studies

Abstract

Controlled bench-scale laboratory experiments were conducted to evaluate the recovery of ammonia (NH₃) and hydrogen sulflde (H₂S) from dynamic isolation flux chambers. H₂S (80–4000 ppb) and NH₃ (5000–40,000 ppb) samples were diffused through the flux chamber to simulate ground level area source emissions while measuring the inlet and outlet flux chamber concentrations simultaneously. Results showed that the recovery of H₂S during a 30-min sampling time was almost complete for concentrations >2000 ppb. At the lowest concentration of 80 ppb, 92.55% of the H₂S could be recovered during the given sampling period. NH₃ emissions exhibited similar behavior between concentrations of 5000–40,000 ppb. Within the 30-min sampling period, 92.62% of the 5000-ppb NH₃ sample could be recovered. Complete recovery was achieved for concentrations >40,000 ppb. Predictive equations were developed for gas adsorption. From these equations, the maximum difference between chamber inlet and outlet concentrations of NH₃ or H₂S was predicted to be 7.5% at the lowest concentration used for either gas. In the calculation of emission factors for NH₃ and H₂S, no adsorption correction factor is recommended for concentrations >37,500 ppb and 2100 ppb for NH₃ and H₂S, respectively. The reported differences in outlet and inlet concentration above these ranges are outside the full-scale sensitivity of the gas sensing equipment. The use of 46–90 m of Teflon tubing with the flux chambers has apparently no effect on gas adsorption, because recovery was completed almost instantaneously at the beginning of the tests.     

Biological elimination of H2S and NH3 from wastegases by biofilter packed with immobilized heterotrophic bacteria

Biotreatment of various ratios of H₂S and NH₃ gas mixtures was studied using the biofilters, packed with co-immobilized cells (Arthrobacter oxydans CH8 for NH₃ and Pseudomonas putida CH11 for H₂S). Extensive tests to determine removal characteristics, removal efficiency, removal kinetics, and pressure drops of the biofilters were performed. To estimate the largest allowable inlet concentration, a prediction model was also employed. Greater than 95% and 90% removal efficiencies were observed for NH₃ and H₂S, respectively, irrespective of the ratios of H₂S and NH₃ gas mixtures. The results showed that H₂S removal of the biofilter was significantly affected by high inlet concentrations of H₂S and NH₃. As high H₂S concentration was an inhibitory substrate for the growth of heterotrophic sulfur-oxidizing bacteria, the activity of H₂S oxidation was thus inhibited. In the case of high NH₃ concentration, the poor H₂S removal efficiency might be attributed to the acidification of the biofilter. The phenomenon was caused by acidic metabolite accumulation of NH₃. Through kinetic analysis, the presence of NH₃ did not hinder the NH₃ removal, but a high H₂S concentration would result in low removal efficiency. Conversely, H₂S of adequate concentrations would favor the removal of incoming NH₃. The results also indicated that maximum inlet concentrations (model-estimated) agreed well with the experimental values for space velocities of 50–150 h⁻¹. Hence, the results would be used as the guideline for the design and operation of biofilters.     

Diurnal Odor,Ammonia, Hydrogen Sulfide,and Carbon Dioxide Emission Profiles of Confined Swine Grower/Finisher Rooms

Abstract

The objective of this study was to obtain diurnal variation profiles of odor and gas (ammonia [NH₃], hydrogen sulfide [H₂S], carbon dioxide [CO₂]) concentrations and emission rate (OGCER) from confined swine grower/finisher rooms under three typical weather conditions (warm, mild, and cold weather) in a year. Two grower/finisher rooms, one with a fully slatted floor and the other with partially slatted floors, were measured for 2 consecutive days under each weather condition. The results revealed that the diurnal OGCER in the room with a fully slatted floor was 9.2–39.4% higher than that with a partially slatted floor; however, no significant differences in the diurnal OGCER were found between these two rooms, except for the NH₃ concentrations in August, the NH₃ and H₂S concentrations and emissions in October, and odor concentrations and emissions in February (p > 0.05). The OGCER variations presented different diurnal patterns as affected by time of day, season, type of floor, ventilation rate, animal growth cycles, in-house manure storage, and weather conditions. Significant diurnal fluctuations in the OGCER (except for the odor concentrations and H₂S emissions) were observed in August (p < 0.05); all of the gas emissions in October and the CO₂ concentrations and emissions in February also showed significant diurnal variations (p < 0.05). These significant diurnal variations indicated that the OGCER during different periods of a day should be monitored when quantifying OGCER concentrations and emissions; for example, source emission data used in air dispersion modeling to decrease the great incertitude of setback determination using randomly measured data.     

旋转填充床吸收模拟工业废气中SO2的研究

选择3%SO2作为模拟工业废气,一乙醇胺(MEA)作为吸收剂在超重力条件下对模拟工业废气中脱硫工艺进行了实验研究,考察了旋转填充床转速、气液比、吸收剂入口温度以及吸收剂浓度对脱硫率的影响,确定了MEA作为吸收剂时适宜的操作条件.同时在旋转填充床中考察了几种不同吸收剂对3%SO2脱除率的影响.研究表明,1 mol/L哌嗪...     

Protection from wintertime rainfall reduces nutrient losses and greenhouse gas emissions during the decomposition of poultry and horse manure-based amendments

Manure-based soil amendments (herein “amendments”) are important fertility sources, but differences among amendment types and management can significantly affect their nutrient value and environmental impacts. A 6-month in situ decomposition experiment was conducted to determine how protection from wintertime rainfall affected nutrient losses and greenhouse gas (GHG) emissions in poultry (broiler chicken and turkey) and horse amendments. Changes in total nutrient concentration were measured every 3 months, changes in ammonium (NH₄⁺) and nitrate (NO₃^?) concentrations every month, and GHG emissions of carbon dioxide (CO₂), methane (CH₄), and nitrous oxide (N₂O) every 7–14 days. Poultry amendments maintained higher nutrient concentrations (except for K), higher emissions of CO₂ and N₂O, and lower CH₄ emissions than horse amendments. Exposing amendments to rainfall increased total N and NH₄⁺ losses in poultry amendments, P losses in turkey and horse amendments, and K losses and cumulative N₂O emissions for all amendments. However, it did not affect CO₂ or CH₄ emissions. Overall, rainfall exposure would decrease total N inputs by 37% (horse), 59% (broiler chicken), or 74% (turkey) for a given application rate (wet weight basis) after 6 months of decomposition, with similar losses for NH₄⁺ (69–96%), P (41–73%), and K (91–97%). This study confirms the benefits of facilities protected from rainfall to reduce nutrient losses and GHG emissions during amendment decomposition.

Implications: The impact of rainfall protection on nutrient losses and GHG emissions was monitored during the decomposition of broiler chicken, turkey, and horse manure-based soil amendments. Amendments exposed to rainfall had large ammonium and potassium losses, resulting in a 37–74% decrease in N inputs when compared with amendments protected from rainfall. Nitrous oxide emissions were also higher with rainfall exposure, although it had no effect on carbon dioxide and methane emissions. Overall, this work highlights the benefits of rainfall protection during amendment decomposition to reduce nutrient losses and GHG emissions.     

Laboratory testing of a continuous emissions monitor for hydrochloric acid

Continuous monitoring of exhaust flue gas has become a common practice in power plants in response to Federal Mercury and Air Toxics Standards (MATS) standards. Under the current rules, hydrochloric acid (HCl) is not continuously measured at most plants; however, MATS standards have been proposed for HCl, and tunable diode laser (TDL) absorption spectroscopy is one method that can be used to measure HCl continuously. The focus of this work is on the evaluation and verification of the operation performance of an HCL TDL over a range of real-world operating environments. The testing was conducted at the University of California at Riverside (UCR) spectroscopy evaluation laboratory. Laboratory tests were conducted at three separate temperatures, 25ºC, 100ºC, and 200ºC, and two distinct moisture levels for the enhanced temperatures, 0%, (2 tests) and 4%, over a concentration range from 0 ppmv to 25 ppmv-m at each of the elevated temperatures. The results showed good instrument accuracy as a function of changing temperature and moisture. Data analysis showed that the average percentage difference between the ammonia concentration and the calibration source was 3.33% for varying moisture from 0% to 4% and 2.69% for varying temperature from 25 to 100/200ºC. An HCl absorption line of 1.742 μm was selected for by the manufacturer for this instrument. The Hi Tran database indicated that CO₂ is probably the only major interferent, although the CO₂ absorption is very weak at that wavelength. Interference tests for NO, CO, SO₂, NH₃, and CO₂ for a range of concentrations typical of flue gasses in coal-fired power plants did not show any interference with TDL HCl measurements at 1.742 μm. For these interference tests, CO₂ was tested at a concentration of 11.9% concentration in N₂ for these tests. Average precision over the entire range for all 10 tests is 3.12%.

Implications: The focus of this study was an evaluation of the operation performance of a tunable diode laser (TDL) for the measurement of hydrochloric acid (HCl) over a range of real-world operating environments. The results showed good instrument accuracy as a function of changing temperature from 25ºC to 200ºC and moisture from 0% to 4%. Such as an instrument could be used for continuous monitoring of exhaust flue gas in power plants once the Federal Mercury and Air Toxics Standards (MATS) standards have been fully implemented.     

Performance of the Annular Denuder System with Different Arrangements for HNO3 and HNO2 Measurements in Taiwan

ABSTRACT

Experiments on different annular denuder system (ADS)arrangements for sampling nitrous acid (HNO₂) and ni-tric acid (HNO₃) gases were conducted in this study toevaluate their sampling artifacts. The evaluation basis isthe one that employed one sodium chloride denuder forsampling HNO₃ gas and two sodium carbonate (Na₂CO₃)denuders for sampling HNO₂ gas, which is a commonlyemployed ADS arrangement in many field applicationsin the United States. A field study was conducted inHsinchu, Taiwan, and the results indicated that this ADSarrangement may yield over 80% relative errors for HNO₃gas. It also showed that the relative errors for HNO₂ gascan be less than 10% as sampled with only one Na₂CO₃denuder. This is attributed to the fact that the ambientHNO₃ concentration measured in this study was relativelylow while the HNO₂ concentration was high, as comparedto typical concentrations of these two gases measured inthe United States.

The sampling error of HNO₃ gas may be due to highconcentrations of N-containing interfering speciespresent in Taiwan’s atmosphere. Because the relative sam-pling errors of HNO₃ and HNO₂ gases depend mainly ontheir concentrations in the atmosphere as well as con-centrations caused by interfering species, the risk for higherror while measuring low HNO₂ concentrations by onlyone Na₂CO₃ denuder is also possible. As a result, it is sug-gested that pretests are necessary to evaluate possiblesources and degrees of sampling errors before fieldsampling of HNO₂ and HNO₃ gases. The sampling errorsof these two gases can, therefore, be minimized with abetter arrangement of the ADS.     

Dry Deposition of Ammonia at Environmental Concentrations on Selected Plant Species

The deposition velocity of NH₃ on six plant species at environmental concentrations has been studied in a dynamic plant gas exchange reactor. The total resistance to the transport of NH₃ was studied. The aerodynamic resistance was determined directly by NH₃ gas absorption in aqueous solutions at environmental concentrations in a two-phase gradientless reactor modeling the transfer processes through the stomata in a leaf. The concentration of NH₃ in the gas phase ranged from 50 to 1000 ppb and the temperature varied from 25 to 30°C. The results for the deposition velocity for NH₃, during the day, varied from 0.3 to 1.3 cm/s. The deposition velocities at night were about one order of magnitude smaller. These results are compared with estimates from the Frdssling equation which consistently yields higher values of the same order of magnitude. To determine accurate atmospheric transport models or global budget models, a variable deposition velocity should be used to account for the diurnal and seasonal variations in the surface resistance.     

Nitrogen Dioxide Absorption and Sulfide Oxidation in Aqueous Sulfide

ABSTRACT

Rates of nitrogen dioxide (NO₂) absorption and sulfide oxidation were measured in a highly characterized stirred cell contactor at 55 °C, with O₂ present in the gas phase. The rate constant of the reaction between NO₂ and sul-fide at 55 °C was determined to be 26.4 x10⁵ M^-1sec^-1. A reaction mechanism was proposed that is consistent with the kinetic data. NO₂ absorption initiates sulfide oxidation in the presence of oxygen. The rate of sulfide oxidation increased with sulfide and oxygen concentration and with the rate of NO₂ absorption. Furthermore, thiosulfate was an effective inhibitor of sulfide oxidation.     

Operational Characteristics of Effective Removal of H2S and NH3 Waste Gases by Activated Carbon Biofilter

Abstract

Simultaneous removal of hydrogen sulfide (H₂S) and am- gases. monia (NH₃) gases from gaseous streams was studied in a biofilter packed with granule activated carbon. Extensive studies, including the effects of carbon (C) source on the growth of inoculated microorganisms and gas removal efficiency, product analysis, bioaerosol emission, pressure drop, and cost evaluation, were conducted. The results indicated that molasses was a potential C source for inoculated cell growth that resulted in removal efficiencies of 99.5% for H₂S and 99.2% for NH₃. Microbial community observation by scanning electron microscopy indicated that granule activated carbon was an excellent support for microorganism attachment for long-term waste gas treatment. No disintegration or breakdown of biofilm was found when the system was operated for 140 days. The low bioaerosol concentration emitted from the biofilter showed that the system effectively avoided the environmental risk of bioaerosol emission. Also, the system is suitable to apply in the field because of its low pressure drop and treatment cost. Because NH₃ gas was mainly converted to organic nitrogen, and H₂S gas was converted to elemental sulfur, no acidification or alkalinity phenomena were found because of the metabolite products. Thus, the results of this study demonstrate that the biofilter is a feasible bioreactor in the removal of waste gases.     

Technique for Measuring the Total Concentration of Gaseous Fixed Nitrogen Species

This paper reports the development of a rapid, continuous technique for analyzing fixed nitrogen species (NH₃, HCN, CH₃NH₂, etc.). The technique uses a platinum catalyst at low pressure in combination with a conventional chemiluminescent NO _x analyzer. Previous workers observed that conventional stainless steel catalysts, and platinum catalysts operated at atmospheric pressure, do not reliably convert NH₃ to NO. The most serious problem was the variation in the efficiency of these catalysts with operating conditions. Changes in temperature, gas composition, or X_NH3 could change the conversion efficiency from 99.9% to <30%. The new conversion technique, however, is quantitative up to several thousand ppm NH₃ in either O₂/He or O₂/CO₂/N₂.     

Adsorption of Hydrochloric Acid on Solid Slaked Lime for Flue Gas Clean Up

The reaction between hydrochloric acid and solid slaked lime was investigated by passing simulated flue gas through a fixed bed reactor. The influence of CO₂ and H₂O present in the flue gas was studied, as well as the influence of the reaction temperature in the range 423 to 673 K. The reaction was found to be of first order with respect to the two reactants. Expressions to account for the temperature and the CO₂ and H₂O concentrations were derived from the experimental data.     

Nonthermal Plasma Chemical Processing of Bromomethane

ABSTRACT

Nonthermal plasma chemical decomposition of bromomethane (CH₃Br) was investigated with a coaxial type packed-bed plasma reactor. It has been demonstrated that plasma chemical processing is an effective approach to decompose CH₃Br in a wide concentration range. It has been shown that CH₃Br decomposition reactivity depends on reactor operating factors such as background gas, O₂ concentration, and humidification. Higher decomposition efficiencies can be obtained in dry N₂. However, organic byproducts such as BrCN are concurrently produced under deaerated conditions. Water suppresses CH₃Br decomposition and also affects the yields of CO_x (CO and CO₂) and organic byproducts due to the involvement of some active species generated from water. The presence of O₂ retards CH₃Br decomposition by quenching high-energy electrons, while it suppresses organic byproducts and improves CO_x yield. The reacted carbons in CH₃Br are recovered as CO_x almost quantitatively in air. Higher CO₂ selectivities cannot be achieved by increasing O₂ concentration. NO_x formation, which is accompanied by CH₃Br decomposition, can be effectively suppressed by decreasing O₂ concentration down to 2%. Furthermore, reaction mechanisms are discussed by comparing the reactivities of CH₃Br and its congeners.     

Development of a 24-Hour Method for Analysis of SO2 and CO2 from Electric Utility Units Equipped with Flue Gas Desulfurization Scrubbers

A procedure was developed for the 24-h determination of SO₂ and CO₂ in effluent gas from fossil fuel combustion sources. Laboratory experiments were conducted to test absorption of SO₂ in hydrogen peroxide solution and absorption of CO₂ by sodium hydroxide on an inert substrate at expected ambient temperatures of 15 to 45°C. Isopropyl alcohol cannot be used to trap sulfuric acid and particulates because it permeates the sampling train and prevents complete absorption of CO₂. Elemental analysis of stack particulates revealed that at least 31 elements were present. Iron and other elements interfered with SO₂ analysis. These particulates were completely removed by a heated borosilicate glass filter. Both laboratory and field experiments showed that molecular sieves are a promising alternative for CO₂ absorption. Statistical evaluation of data collected at three units equipped with flue gas desulfurization scrubbers proved that the new procedure is accurate and precise.     

Direct and indirect effects of ammonia, ammonium and nitrate on phosphatase activity and carbon fluxes from decomposing litter in peatland

Here we investigate the response of soils and litter to 5 years of experimental additions of ammonium (NH₄), nitrate (NO₃), and ammonia (NH₃) to an ombrotrophic peatland. We test the importance of direct (via soil) and indirect (via litter) effects on phosphatase activity and efflux of CO₂. We also determined how species representing different functional types responded to the nitrogen treatments. Our results demonstrate that additions of NO₃, NH₄ and NH₃ all stimulated phosphatase activity but the effects were dependent on species of litter and mechanism (direct or indirect). Deposition of NH₃ had no effect on efflux of CO₂ from Calluna vulgaris litter, despite it showing signs of stress in the field, whereas both NO₃ and NH₄ reduced CO₂ fluxes. Our results show that the collective impacts on peatlands of the three principal forms of nitrogen in atmospheric deposition are a result of differential effects and mechanisms on individual components.