Desulfurization of Flue Gases in A Fluidized Bed of Modified Limestone

This publication concerns the dry removal of SO₂ from gases using limestone absorbents. It reports bench-scale experiments made with commercial samples of powdered limestone (CaCO₃) activated by addition of a cheap substance, namely CaCl₂. The absorption was carried out in a fluidized bed traversed by the flue gases, between 600° and 900° C. The degree and rate of transformation of CaCO₃ to CaSO₄ in the presence of SO₂ and air have been compared for unmodified and modified absorbents. Initial rates of reaction, and the variation of the rate of absorption with time have been measured. The influence of the SO₂ content of the gas has been assessed. At 700° C, the maximum degree of transformation of activated limestone to sulfate exceeds 90%, whereas untreated CaCO₃ transforms only to 16–20%. At the same temperature, more than 90% of SO₂ contained In a gas carrying 0.35% SO₂ is removed. Because of the much smaller quantity of solid absorbent required, dry absorption processes based on the modified absorbents might get renewed interest. The modified absorbents might also be used for in situ absorption in fluidized bed combustion, in which the temperatures are in the range studied in the present paper.     

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.     

Removal of SO2 From Flue Gases Using Carbon at Elevated Temperatures

The interaction of a typical flue gas with active charcoal and bituminous coal char at temperatures between 600 and 800°C and atmospheric pressure has been studied. The SO₂ in the flue gas interacts with the carbon to form primarily H₂S, COS, and a carbon-sulfur surface complex. H₂S and COS break through the carbon bed much in advance of SO₂. At 800°C, sulfur retention on the bed exceeds at least 11% before SO₂ breakthrough occurs. The reaction of H₂S and COS with O₂ over active charcoal at 100–140°C to produce sulfur, which deposits on the carbon, has also been studied and found to be feasible. As a result of this study, a new process is outlined for the removal of SO₂ from flue gas, with the ultimate conversion     

Ni-Co bimetallic catalysts on coconut shell activated carbon prepared using solid-phase method for highly efficient dry reforming of methane

Ni-Co bimetallic catalysts supported on coconut shell activated carbon are synthesized using solid-phase method and investigated for dry reforming of methane, to explore the impact of Ni:Co ratio on the catalyst activity and stability. The catalyst performances are evaluated under the temperature varying from 600 to 900 °C and gas hourly space velocity (GHSV) of 7200 mL/h·g-cat. The characterization results show that metal nanoparticles are produced on the support, and the bimetallic catalyst with an explicit Ni:Co ratio (2:1) is the most beneficial for metal particle dispersion and acquires the minimum particle size of 4.41 nm. The bimetallic catalysts with an explicit Ni:Co ratio of 1:2 and 1:1 exhibit a synergistic effect towards the conversions of CH₄ and CO₂, respectively. The experimental results reveal that the highest CH₄ and CO₂ conversions rise to 94.0% and 97.5% within 12 h at 900 °C on average, respectively, assisted with the two bimetallic catalysts. The intensity of disordered carbon and thermal stability are enhanced with the extension of reforming process, contributing to a long-term catalytic stability. Besides, no obvious carbon deposition is detected, leading to a highly catalytic stability for the bimetallic catalysts.

     

Current Status of the ADVACATE Process for Flue Gas Desulfurization

The following report discusses current bench- and pilot-plant advances in preparation of ADVAnced siliCATE (ADVACATE) calcium silicate sorbents for flue gas desulfurization. It also discusses current bench- and pilot-plant advances in sorbent preparation. Fly ash was ground in a laboratory scale grinder prior to slurring in order to decrease the slurring time needed for the sorbent to be reactive with SO₂. Reactivity of ADVACATE sorbents with SO₂ in the bench-scale reactor correlated with their surface area.

ADVACATE sorbents produced with ground fly ash were evaluated in the 50 cfm (85 m³/h) pilot plant providing 2 s duct residence time. ADVACATE sorbent was produced by slurrying ground fly ash (median particle size of 4.3 µm) with Ca(OH)₂ at the weight ratio of 3:1 at 90°C (194°F) for 3hto yield solids with 30 weight percent of initial free moisture. When this sorbent was injected into the duct with 1500 ppm SO₂ and at 11°C (20°F) approach to saturation, the measured SO₂ removal was approximately 60percent at a Ca/S stoichiometric ratio of 2. Previously, when ADVACATE sorbent was produced at 90°C (194°F) and at the same fly-ash-to-Ca(OH)₂ weight ratio using unground fly ash, removal under the same conditions in the duct was approximately 50 percent following 12 h slurring. The report presents the results of pilot-scale recycle tests at the recycle ratio of 2. Finally, the report discusses future U.S. Environmental Protection Agency plans for commercialization of ADVACATE.     

Development and Pilot Plant Evaluation of Silica- Enhanced Lime Sorbents for Dry Flue Gas Desulfurization

EPA’s efforts to develop low cost, retrofitable flue gas cleaning technology include the development of highly reactive sorbents. Recent work addressing lime enhancement and testing at the bench-scale followed by evaluation of the more promising sorbents in a pilot plant are discussed here.

The conversion of Ca(OH)₂ with SO₂ increased several-fold compared with Ca(OH)₂ alone when Ca(OH)₂ was slurrled with fly ash first and later exposed to SO₂ in a laboratory packed bed reactor. Ca(OH)₂ enhancement increased with the increased fly ash amount. Dlatomaceous earths were very effective reactivity promoters of lime-based sorbents. Differential scanning calorimetry of the promoted sorbents revealed the formation of a new phase (calcium silicate hydrates) after hydration, which may be the basis for the observed Improved SO₂ capture.

Fly ash/lime and diatomaceous earth/lime sorbents were tested in a 100 m³/h pilot facility incorporating a gas humidifier, a sorbent duct injection system, and a baghouse. The inlet SO₂ concentration range was 1000-2500 ppm. With once-through dry sorbent injection into the humidified flue gas [approach to saturation 10–20°C (18–36°F) in the baghouse], the total SO₂ removal ranged from 50 to 90 percent for a stoichiometric ratio of 1 to 2. Recycling the collected solids resulted in a total lime utilization exceeding 80–90 percent. Increased lime utilization was also investigated by the use of additives.     

Evaluation of the Iron-o-Phenanthroline Procedure For Determining S02 in Turbine Exhaust Gases

Several wet chemical methods have been used or suggested for the determination of SO₂ concentrations in air pollution work. These include the iron-O-phenanthroline procedure reported by Stephens and Lindstrom, the Scaringelli-modified West-Gaeke method and the Schulze method. This paper describes a laboratory study to evaluate the usefulness of the iron-o-phenanthroline procedure and is directed to individuals concerned with the analysis of gases from the exhaust of gas turbine engines and other combustion processes, including stationary power plants. The variables considered were: range of usefulness in terms of concentration of SO₂, efficiency of collection, effect of contaminants, specifically oxides of nitrogen, olefin and aldehyde and effect of storage prior to spectrophctometric measurement. The Stephens-Lindstrom method was found to be suitable for measuring higher levels of SO₂ concentrations. It can accurately measure amounts totalling 6000 µl of SO₂ and above whereas the other mentioned methods are generally used for lower levels. Collection efficiency was satisfactory. Contaminants, particularly oxides of nitrogen, are a problem only at low levels of SO₂. NO₂ interference may be eliminated by absorption of the NO₂ on Ultraport S impregnated with ANEDA/H₂SO₄ solution. Temperature control during SO₂ addition is necessary. Storage of exposed reagents prior to measurement produce only small errors if stored at 0°C or at room temperature.     

Opacity of monodisperse sulfuric acid aerosols

The plume opacity and droplet diameters of a monodisperse sulfuric acid aerosol were calculated as a function of the initial H₂SO₄ concentration, initial H₂O concentration and final gas temperature after cooling from an original stack gas temperature of 300°C. Calculation assumptions include heterogeneous heteromolecular condensation of H₂SO₄ and H₂O onto monodisperse nuclei of 0.05 μm dia., three aerosol particle nuclei concentrations of 10⁶, 10⁷ and 10⁸ cm⁻³ (at 300°C and 760 mm Hg); and a stack or plume diameter of 6 m. The calculated results show that for the conditions considered and with the stack temperatures in excess of 125°C, initial H₂SO₄ stack gas concentrations of 10ppm or less will result in calculated opacities of less than 20 % for a plume diameter of 6 m. The results show that the calculated opacity is significantly affected by the initial H₂SO₄ and initial H₂O concentrations and the final gas temperature. The increases in the calculated opacities upon cooling of the stack gases are similar in general to the increases in the measured opacities between instack and outstack reported by Nader and Conner (1978) for an oil-fired boiler.     

Atmospheric corrosion effects of HNO3—Comparison of laboratory-exposed copper,zinc and carbon steel

The influence of nitric acid (HNO₃) on the atmospheric corrosion of copper, zinc and carbon steel was investigated in laboratory exposures at 65% relative humidity (RH), 25 °C and 0.03 cm s⁻¹ air velocity. The deposition velocity (V_d) of HNO₃ on the specimens, the corrosion rates and corrosion products were determined by gravimetry, ion chromatography, X-ray diffraction (XRD) and Fourier transform infrared (FT-IR) microspectroscopy. Comparisons were also made with literature data on the corrosion effects of sulfur dioxide (SO₂), nitrogen dioxide (NO₂) and ozone (O₃).At 65% RH, the V_d of HNO₃ on all metals was at least 70% of that of an ideal absorbent, i.e., an impregnated filter with perfect absorption for HNO₃. The V_d of HNO₃ was much higher than that of SO₂, NO₂ or O₃, which is mainly attributed to the relatively high sticking coefficient, high solubility and high reactivity of HNO₃ compared to the other gases. During identical exposures to HNO₃, the corrosion rate of carbon steel was nearly three times higher than that of copper or zinc. However, when comparing the corrosion effects induced by HNO₃ with those induced by SO₂ alone or in combination with either NO₂ or O₃, HNO₃ turned out to be far more aggressive than SO₂. Relative to SO₂, zinc is the metal most sensitive to HNO₃, followed by copper and with carbon steel least sensitive to HNO₃.     

Hydrogen Sulfide Removal From Hot Producer Gas With Sintered Absorbents

The Bureau of Mines prepared three sintered materials capable of removing H₂S from producer gas at 1000° to 1500°F. They are mixtures of ferric oxide and fly ash, ferric oxide and pumice stone, and red mud (a ferric oxide-containing residue from processing bauxite). All three absorbents were virtually completely regenerable with air. A sintered Fe₂O₃; (25%)-fly ash [75%) mixture was tested through nine H₂S absorption-air regeneration cycles without loss of absorplion capacity or attrition of the pellets. The absorbent with the greatest capacity was a red mud, absorbing 16.0% by weight of sulfur at 1000° F, 24.0% at 1250° F, and 45.1 % at 1 500° F.     

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.     

Simultaneous removal of sulfur dioxide and polycyclic aromatic hydrocarbons from incineration flue gas using activated carbon fibers

Incineration flue gas contains polycyclic aromatic hydrocarbons (PAHs) and sulfur dioxide (SO₂). The effects of SO₂ concentration (0, 350, 750, and 1000 ppm), reaction temperature (160, 200, and 280 °C), and the type of activated carbon fibers (ACFs) on the removal of SO₂ and PAHs by ACFs were examined in this study. A fluidized bed incinerator was used to simulate practical incineration flue gas. It was found that the presence of SO₂ in the incineration flue gas could drastically decrease removal of PAHs because of competitive adsorption. The effect of rise in the reaction temperature from 160 to 280 °C on removal of PAHs was greater than that on SO₂ removal at an SO₂ concentration of 750 ppm. Among the three ACFs studied, ACF-B, with the highest microporous volume, highest O content, and the tightest structure, was the best adsorbent for removing SO₂ and PAHs when these gases coexisted in the incineration flue gas.

ImplicationsSimultaneous adsorption of sulfur dioxide (SO₂) and polycyclic aromatic hydrocarbons (PAHs) emitted from incineration flue gas onto activated carbon fibers (ACFs) meant to devise a new technique showed that the presence of SO₂ in the incineration flue gas leads to a drastic decrease in removal of PAHs because of competitive adsorption. Reaction temperature had a greater influence on PAHs removal than on SO₂ removal. ACF-B, with the highest microporous volume, highest O content, and tightest structure among the three studied ACFs, was found to be the best adsorbent for removing SO₂ and PAHs.     

Reduction of atmospheric emissions due to switching from fuel oil to natural gas at a power plant in a critical area in Central Mexico

ABSTRACT

A case study was conducted to evaluate the SO₂ emission reduction in a power plant in Central Mexico, as a result of the shifting of fuel oil to natural gas. Emissions of criteria pollutants, greenhouse gases, organic and inorganic toxics were estimated based on a 2010 report of hourly fuel oil consumption at the “Francisco Pérez Ríos” power plant in Tula, Mexico. For SO₂, the dispersion of these emissions was assessed with the CALPUFF dispersion model. Emissions reductions of > 99% for SO₂, PM and Pb, as well as reductions >50% for organic and inorganic toxics were observed when simulating the use of natural gas. Maximum annual (993 µg/m³) and monthly average SO₂ concentrations were simulated during the cold-dry period (152–1063 µg/m³), and warm-dry period (239–432 µg/m³). Dispersion model results and those from Mexico City’s air quality forecasting system showed that SO₂ emissions from the power plant affect the north of Mexico City in the cold-dry period. The evaluation of model estimates with 24 hr SO₂ measured concentrations at Tepeji del Rio suggests that the combination of observations and dispersion models are useful in assessing the reduction of SO₂ emissions due to shifting in fuels. Being SO₂ a major precursor of acid rain, high transported sulfate concentrations are of concern and low pH values have been reported in the south of Mexico City, indicating that secondary SO₂ products emitted in the power plant can be transported to Mexico City under specific atmospheric conditions.

Implications: Although the surroundings of a power plant located north of Mexico City receives most of the direct SO₂ impact from fuel oil emissions, the plume is dispersed and advected to the Mexico City metropolitan area, where its secondary products may cause acid rain. The use of cleaner fuels may assure significant SO₂ reductions in the plant emissions and consequent acid rain presence in nearby populated cities and should be compulsory in critical areas to comply with annual emission limits and health standards.     

Silica-Enhanced Sorbents for Dry Injection Removal of SO2 from Flue Gas

Novel silica-enhanced lime sorbents were tested in a bench-scale sand-bed reactor for their potential for SO₂ removal from flue gas. Reactor conditions were 64°C (147°F), relative humidity of 60 percent [corresponding to an approach to saturation temperature of 10°C (18°F)], and inlet SO₂ concentration of 500 or 1000 ppm. The sorbents were prepared by pressure hydration of CaO or Ca(OH)₂ with siliceous materials at 100°C (101 kPa) [212°F (14.7 psi)] to 230°C (2793 kPa) [446°F (405 psi)] for 15 min to 4 h. Pressure hydration fostered the formation of a sorbent reactive with SO₂ from fly ash and Ca(OH)₂ in a much shorter time than did atmospheric hydration. The conversion of Ca(OH)₂ in the sand-bed reactor increased with the increasing weight ratio of fly ash to lime and correlated well with B.E.T. surface area, increasing with increasing surface area. The optimum temperature range for the pressure-hydration of fly ash with Ca(OH)₂ was between 110 and 160°C (230 and 320 °F). The pressure hydration of diatomaceous earth with CaO did not offer significant reactivity advantages over atmospheric hydration; however, the rate of enhancement of Ca(OH)₂ conversions was much faster with pressure hydration. Scanning electron microscope (SEM) and x-ray diffraction studies showed solids of different morphology with different fly ash/lime ratios and changing conditions of pressure hydration.     

Removal of SO2 from Simulated Flue Gases Using Non-Thermal Plasma-Based Microgap Discharge

Abstract

The removal of sulfur dioxide (SO₂) from simulated flue gases streams (N₂/O₂/H₂O/SO₂) was experimentally investigated using microgap discharge. In the experiment, the thinner dielectric layers of aluminum oxide (Al₂O₃) were used to form the microgap discharge. With this physical method, a high concentration of hydroxyl (OH·) radicals were produced using the ionization of O₂ and H₂O to further the conversion of SO₂ into sulfuric acid (H₂SO₄) at 120° C in the absence of any catalysts and absorbents, which were captured with the electrostatic precipitator (ESP). As a result, the increase of discharge power and concentrations of O₂ and H₂O increased the production of OH· radicals resulting in enhanced removal of SO₂ from gas streams. With the test and analysis, a number of H₂SO₄ droplets were produced in experiment. Therefore, a new method for removal of SO₂ in semidry method without ammonia (NH₃) additive was found.     

Selective Reduction of Nitrogen Oxides In Combustion Flue Gases

The body of Information presented in this paper is directed to those Individuals concerned with the removal of NO_x in combustion flue gases. A catalytic process for the selective reduction of nitrogen oxides by ammonia has been investigated. Efforts were made toward the development of catalysts resistant to SO_x poisoning. Nitrogen oxides were reduced over various metal oxide catalysts in the presence or absence of SO_x(SO₂ and SO₃). Catalysts consisting of oxides of base metals (for example, Fe₂O₃) were easily poisoned by SO₃, forming sulfates of the base metals. A series of catalysts which are not susceptible to the SO_x poisoning has been developed. The catalysts possess a high activity and selectivity over a wide range of temperatures, 250—450°C. The catalysts were tested in a pilot plant which treated a flue gas containing 110-150 ppm NO_x, 660-750 ppm SO₂, and 40-90 ppm SO₃. The pilot plant was operated at 350°C and at a space velocity of 10,000 h^-1. The removal of nitrogen oxides was more than 90% for several months.

A mechanism of the NO-NH₃ reaction has also been investigated. It is found that NO reacts with NH₃ at a 1:1 mole ratio in the presence of oxygen and the reaction is completely inhibited by the absence of oxygen. The experimental data show that the NO-NH₃ reaction in the presence of oxygen is represented byNO + NH₃ + 1/4 O₂ = N₂ + 3/2 H₂O.     

A Study on the Treatment of CO2, SO2, Nox,and Fly Ash by Pulse Activation

ABSTRACT

This paper presents a technique for the complete, simultaneous decomposition of CO₂, SO₂, and NO_x, as well as the simultaneous removal of fly ash by ultra-high voltage pulse activation. Ultra-high voltage narrow pulse is used to make the gases in the reactor become active molecules, which are then dissociated into nonpoisonous gas molecules and solid particles under the control of a directional reaction model. By using a sufficient charge and a strong electric field, the fly ash can be removed. It becomes the carrier of C and S, and its efficiency is 99.5%. Owing to the action of catalyst B (using Ni as the mother's body), the activation energy of CO₂, SO₂, and NO_x gases is reduced in great magnitude, and their removal efficiency can reach 75~90% at normal pressure and 180 °C.     

Synthetic SO2 Sorbents for Fluidized-Bed Coal Combustors

The information presented in this paper is directed to engineers who are involved with environmental emissions from coal conversion plants. Synthetic sorbents were investigated as an alternative to natural sorbents (limestone) for the removal of SO₂ from the combustion gas in a fluidized-bed coal combustor. The sulfation rate of a synthetic sorbent, CaO in α-AI₂O₃, was determined as a function of gas composition, temperature, and calcium concentration in the sorbent. The reaction was found to be diffusion-controlled above 850°C and kinetically controlled at lower temperatures. The physical characteristics of the support material have a major effect oh the sulfation kinetics. Porosity measurements indicated that supports containing large pores (>0.2 µm) produced sorbents having high sulfation rates and that pores with diameters less than 0.2 µm did not contribute significantly to the capture of SO₂. The sorbents SrO in α-AI₂O₃ and BaO in α-AI₂O₃ had lower SO₂ capture rates than did CaO in α-AI₂O₃. The alkali metal oxide sorbents K₂O and Na₂O in α-AI₂O₃ captured SO₂ much faster than did the alkaline earth metal oxides.     

Absorption and Reaction Kinetics of Amines and Ammonia Solutions with Carbon Dioxide in Flue Gas

Abstract

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 °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.     

Impact of Indoor Environmental Parameters on Formaldehyde Concentrations in Unoccupied Research Houses

An environmental parameters study has examined the impact of indoor temperature (T) and relative humidity (RH) levels on formaldehyde (CH₂O) concentrations inside two unoccupied research houses where the primary CH₂O emitter is particleboard underlayment. The data were fit to a simple three-term, steady state model describing the T and RH dependence of CH₂O concentration in a single compartment with a single CH₂O emitter. The model incorporates an Arrhenius T dependence and a nonlinear RH dependence of the CH₂O vapor concentration within the solid CH₂O emitter. The RH dependence is based on Freundlich's theory of the adsorption of water vapor on solid surfaces. The model is used to estimate potential seasonal variation in CH₂O concentrations under specified experimental conditions inside the research houses. The modeled results indicate six- to ninefold variation between 18°C, 20% RH and 32°C, 80% RH, simulating potential winter/summer conditions with minimal indoor climate control. In comparison, Indoor conditions ranging from 20°C, 30% RH to 26°C, 60% RH yielded approximate two- to fourfold fluctuations in CH₂O concentration.

The research house data were also used to evaluate the limitations and applicability of more complex five-term models developed from small-scale chamber studies of the environmental dependence of CH₂O emissions from particleboard underlayment. These models also incorporate a linear T and RH dependence of the CH₂O transport rate through the CH₂O emitter in addition to the T and RH dependence of the CH₂O concentration within the emitter. Good correlation is observed between the results of the research house studies and 1) a selected (i.e., single) underlayment model over a broad range of environmental conditions and 2) a combined underlayment model over a restricted range of environmental conditions.