Simultaneous Removal of NOx and SOx from Flue Gas of a Glass Melting Furnace using a Combined Ozone Injection and Semi-dry Chemical Process

In this study, we propose a plasma-chemical hybrid NO_x removal process using nonthermal plasma for the treatment of flue gases emitted from glass melting furnaces; the process is demonstrated through a laboratory-scale model experiment conducted using a semi-dry desulfurization apparatus. The performance of the system for simultaneous removal of SO₂ and NO_x is investigated. As a result, NO is effectively oxidized to NO₂ by injecting ozone into the spray region and the removal efficiencies of 90% and 50% were obtained for NO and NO_x, respectively. In addition, the SO₂ removal efficiency of 84% was achieved.     

Simultaneous removal of SO2 and NOx by microwave with potassium permanganate over zeolite

Simultaneous sulfur dioxide (SO₂) and nitrogen oxides (NO_x) removal from flue gas can be achieved with high efficiency by microwave with potassium permanganate (KMnO₄) over zeolite. The experimental results showed that the microwave reactor could be used to oxidation of SO₂ to sulfate with the best desulfurization efficiency of 96.8% and oxidize NO_x to nitrates with the best NO_x removal efficiency of 98.4%. Microwave accentuates catalytic oxidation treatment, and microwave addition can increase the SO₂ and NO_x removal efficiency by 7.2% and 12.2% separately. The addition of zeolite to microwave potassium permanganate increases from 16.5% to 43.5% the microwave removal efficiency for SO₂, and the NO_x removal efficiency from 85.6% to 98.2%. The additional use of potassium permanganate to the microwave zeolite leads to the enhancement of SO₂ removal efficiency up from 53.9% to 95%, and denitrification efficiency up from 85.6% to 98.2%. The optimal microwave power and empty bed residence time (EBRT) on simultaneous desulfurization and denitrification are 259 W and 0.357 s, respectively. SO₂ and NO_x were rapidly oxidized in microwave induced catalytic oxidation reaction using potassium permanganate with zeolite being the catalyst and microwave absorbent.     

Recent developments in novel sorbents for flue gas clean up

Coal combustion is one of the most important energy sources for electricity generation, but also produces airborne pollutants. The amount of SO₂ and NO_x for example, is in the order of hundreds to thousands of ppm, and tens to hundreds of ppm, respectively, while Hg in flue gases could be up to tens to hundreds of ppb. Flue gas desulphurization technology is already in place for SO₂ removal, and new sorbents such as zeolites are being investigated for such an application. NO_x can be removed by selective catalytic reduction with various catalysts. Mercury is the hardest to remove due to its persistent nature and relatively low concentration in flue gases. New sorbents have also been developed for mercury removal applications. A current trend in flue gas emission control is to remove Hg, NO_x and SO₂ simultaneously. Various catalytic sorbents have been investigated to remove two or more of these pollutants concurrently. This article reviews recent developments made for emission control of coal-fired power plant flue gases using novel sorbents to target individual or multiple pollutants.     

Regeneration/Optimization of Activated Carbon Monolith in Simultaneous SO2/NOx Removal from Flue Gas

Due to the adverse effects of SO₂/NO_x on humans and the environment, environmental regulations necessitate the control of their emission. In this study, an activated carbon monolith was synthesized with cobalt oxide (ACM‐Co₃O₄) for the purpose of simultaneous SO₂/NO_x removal from flue gas generated by coal combustion. Average regeneration efficiencies of 92.7 and 94.2 % were obtained for SO₂ and NO_x, respectively. The Langmuir model can adequately describe the experimental results of the ACM‐Co₃O₄ adsorbent in SO₂ and NO_x removal. The key regeneration parameters were optimized by using the response surface methodology (RSM). The RSM results revealed that the statistical prediction and experimental results were in agreement.     

Verfahren zur Minderung von NOx-Emissionen in Rauchgasen

Processes for lowering NO_x emissions in flue gases . The authors survey processes currently under development for reducing NO_x emission levels of combustion units. Primary measures, i.e. acting upon the combustion process itself, do not suffice to meet the recently stiffened limiting emission values; particular attention is therefore paid to secondary measures involving the flue gases. The article describes both wet processes and dry catalytic and non-catalytic processes, some of which can also be employed for simultaneous removal of NO_x and SO₂. In view of the fast large-scale implementation demanded, only a few, already extensively developed processes will presumable be accepted, and will play a considerable role on an industrial scale.     

Removal of sulfur dioxide and nitrogen oxides by using ozone injection and absorption–reduction technique

A two-step process capable of removing NO_x and SO₂ simultaneously was proposed, which was made up of an ozonizing chamber and an absorber containing a reducing agent solution. Nitrogen oxides (NO plus NO₂) in most practical exhaust gases consist chiefly of NO. The injection of ozone into the exhaust gas gives rise to a rapid oxidation of NO to NO₂. Compared to NO, NO₂ has relatively high solubility in water, and it can readily be reduced to N₂ when the NO₂-rich exhaust gas is brought into contact with the reducing agent solution. Sodium sulfide (Na₂S) used as the reducing agent in this study can also remove SO₂, effectively. As the exhaust gas passed through the ozonizing chamber and the absorber sequentially, NO_x removal efficiency of about 95% and SO₂ removal efficiency of 100% were obtained. The formation of H₂S from sodium sulfide could be suppressed by using a basic reagent, together with the reducing agent. The rate of depletion of the reducing agent during the treatment of the exhaust gas was much faster than expected by reaction stoichiometry, obviously due to the oxygen in the exhaust gas. The amount of sodium sulfide required was found to be about four times the amount of NO_x and SO₂ removed.     

Electron beam flue gas treatment (EBFGT) technology for simultaneous removal of SO2 and NOx from combustion of liquid fuels

Electron beam flue gas treatment technology was applied for removal of SO₂ and NO_x from flue gas, emitted from combustion of high-sulfur fuel oils. The detailed study of this process was performed in a laboratory by irradiating the exhaust gas from the combustion of three grades of Arabian fuels with an electron beam from accelerator (800 keV, max. beam power 20 kW). SO₂ removal is mainly dependent on ammonia stoichiometry, flue gas temperature and humidity and irradiation doses up to 8 kGy. NO_x removal depends primarily on irradiation dose. High removal efficiencies up to 98% for SO₂ and up to 82% for NO_x were obtained under optimal conditions. The flue gas emitted from combustion of high-sulfur fuel oils, after electron beam irradiation, meets the stringent emission standards for both pollutants. The by-product, which is a mixture of ammonium sulphate and nitrate, can be used as a fertilizer as such or blended with other components to produce commercial agricultural fertilizer.     

Microwave catalytic NOx and SO2 removal using FeCu/zeolite as catalyst

Non-thermal plasma technology is a promising process for flue gas treatment. Microwave catalytic NO_x and SO₂ removal simultaneously has been investigated using FeCu/zeolite as catalyst. The experimental results showed that a microwave reactor with FeCu/zeolite only could be used to microwave catalytic oxidative 91.7% NO_x to nitrates and 79.6% SO₂ to sulfate; the reaction efficiencies of microwave catalytic reduction of NO_x and SO₂ in a microwave reactor with FeCu/zeolite and ammonium bicarbonate (NH₄HCO₃) as a reducing agent could be up to 95.8% and 93.4% respectively. Microwave irradiation accentuates catalytic reduction of SO₂ and NO_x treatment, and microwave addition can increases SO₂ removal efficiency from 14.5% to 18.7%, and NO_x removal efficiency from 13.4% to 18.7%, separately. FeCu/zeolite catalyst was characterized by X-ray diffraction (XRD), X-ray photoelectron spectrum analysis (XPS), scanning electron microscopy (SEM) and the Brunauer Emmett Teller (BET) method. Microwave catalytic NO_x and SO₂ removal follows Langmuir-Hinshelwood (L-H) kinetics.     

Combined SO2 and NOx removal at moderate temperature by a dual bed of potassium-containing coal-pellets and calcium-containing pellets

The combined removal of both SO₂ and NO_x from a gas mixture that contains NO_x, SO₂, O₂, and N₂ was carried out in a dual bed of calcium-containing pellets and potassium-containing coal-pellets. The calcium-containing pellets retain SO₂ and nitrogen oxides are reduced to N₂ by the potassium-containing coal-pellets. The NO_x-carbon reaction is catalysed by the potassium species on pellets, which also avoid the massive consumption of carbon by O₂. The optimum temperature for the combined removal of SO₂ and NO_x is around 450 °C. This temperature is high enough to ensure the decomposition of Ca(OH)₂, used as CaO precursor [CaO is much more effective for SO₂ retention than Ca(OH)₂], and low enough to avoid an important combustion of carbon by O₂. The ratio between mass_Ca-pellets/mass_{K/carbon-pellets} is a key factor in this process in order to avoid the potassium catalyst poisoning by SO₂ chemisorption. Under the experimental conditions of this study, an appropriate mass_Ca-pellets/mass_{K/carbon-pellets} ratio of 10/1 was found. With this ratio, the efficiency of the potassium-containing coal-pellets for NO_x reduction is similar to that observed in the absence of the calcium-containing pellets for a SO₂-free gas mixture.     

Removal of elemental mercury from simulated coal-combustion flue gas using a SiO2–TiO2 nanocomposite

A novel silica–titania (SiO₂–TiO₂) nanocomposite has been developed to effectively capture elemental mercury (Hg⁰) under UV irradiation. Previous studies under room conditions showed over 99% Hg⁰ removal efficiency using this nanocomposite. In this work, the performance of the nanocomposite on Hg⁰ removal was tested in simulated coal-fired power plant flue gas, where water vapor concentration is much higher and various acid gases, such as HCl, SO₂, and NO_x, are present. Experiments were carried out in a fix-bed reactor operated at 135 °C with a baseline gas mixture containing 4% O₂, 12% CO₂, and 8% H₂O balanced with N₂. Results of Hg speciation data at the reactor outlet demonstrated that Hg⁰ was photocatalytically oxidized and captured on the nanocomposite. The removal efficiency of Hg⁰ was found to be significantly affected by the flue gas components. Increased water vapor concentration inhibited Hg⁰ capture, due to the competitive adsorption of water vapor. Both HCl and SO₂ promoted the oxidation of Hg⁰ to Hg(II), resulting in higher removal efficiencies. NO was found to have a dramatic inhibitory effect on Hg⁰ removal, very likely due to the scavenging of hydroxyl radicals by NO. The effect of NO₂ was found to be insignificant. Hg removal in flue gases simulating low rank coal combustion products was found to be less than that from high rank coals, possibly due to the higher H₂O concentration and lower HCl and SO₂ concentrations of the low rank coals. It is essential, however, to minimize the adverse effect of NO to improve the overall performance of the SiO₂–TiO₂ nanocomposite.     

Metal chelate absorption coupled with microbial reduction for the removal of NOx from flue gas

A novel process for the removal of NO_x from flue gas by a combined Fe(II)EDTA absorption and microbial reduction has been demonstrated. Fe(II)EDTA–NO and Fe(III)EDTA (EDTA: ethylenediaminetetraacetate) can be effectively reduced to the active Fe(II)EDTA in the reactor containing microorganisms. In a steady‐state absorption and regeneration process, the final removal efficiency of NO is up to 88%. The effects of four main parameters (i.e. NO, O₂ and SO₂ concentrations, and the amount of cyclic solution) on NO_x removal efficiency were experimentally investigated at 50 °C. The results provide some insight into conditions required for the successful removal of NO_x from flue gas using the approach of Fe(II)EDTA absorption combined with microbial reduction. Copyright © 2005 Society of Chemical Industry     

Removal of so x and NO x from flue gas with ceria

Ceria (CeO₂) is considered as one of materials for the simultaneous removal of SO_x and NO_x from flue gas. Ceria was coated on honeycomb and tested for adsorption of SO₂ and reduction of NO with ammonia. Experimental results showed the characteristics similar to copper oxide but reactivity for NO reduction was higher in broader temperature range compared with the latter.     

Simultaneous removal of SO2 and NO by sodium chlorite solution in wetted-wall column

The effect of feeding rate of NaClO₂ solution, inlet SO₂ and NO concentration, [NaClO₂]/[SO₂+NO] molar ratio (η), L/G ratio and, solution pH on the simultaneous removal of SO_x/NO_x has been investigated in a wetted-wall column. Both SO_x and NO_x removal efficiencies are enhanced with the increasing feeding rate of NaClO₂ solution and attain a steady state. NO_x removal efficiency increases with increasing SO₂ concentration, but SO_x removal remains unaffected with increasing NO concentration. In an acidic medium, DeSO_x and DeNO_x efficiency increased with increasing [NaClO₂]/[SO₂+NO_x] molar ratio and attained a steady state. NO_x removal starts only after the complete removal of SO_x. The excess of NaClO₂ does not enhance NO_x removal efficiency. Solution pH does not affect the DeSO_x and DeNO_x efficiency. The maximum SO_x and NO_x removal efficiencies achieved at the typical operating conditions of commercialized FGD processes are about 100 and 67%, respectively.     

Investigations on bromine corrosion associated with mercury control technologies in coal flue gas

Mercury control technologies are often associated with adding halogens to the flue gas to enhance oxidation of elemental mercury. The present research was to evaluate the corrosion characteristics of iron in a flue gas containing bromine to simulate mercury control applications in coal-fired utility plants. An AISI 1008 cold rolled steel was exposed to a synthetic flue gas (7.1 vol% O₂, 14.3 vol% CO₂, 2.0 vol% H₂O, 51 ppmv HBr, 510 ppmv SO₂, 51 ppmv NO_x, and the balance N₂). Exposure times ranged from 30 days to 6 months. Metal coupons were exposed with simulated flue gases at 300°, 150°, and 80 F (149°, 66°, and 27 °C), respectively. The corroded coupons were analyzed using scanning electron microscope and micrometer measurements to determine the deposit chemistry and corrosion loss. The corrosion products consisted mainly of iron oxides and iron bromide. A mechanism for HBr corrosion is suggested. Bromine dew point corrosion took place on metal surfaces at temperatures below or close to the dew point of HBr, while active oxidation occurred at higher temperatures.     

Katalysatoren für den Umweltschutz

Catalysts for environmental protection. The main emitters of anthropogenic air pollution are internal combustion engines, power plants, and production processes. Components of exhaust gases which are regarded as pollutants are hydrocarbons (HC), carbon monoxide (CO), nitrogen oxides (NO_x), sulfur dioxide (SO₂), and dust. Three main types of catalyst are understood to improve the environment; namely automotive emission control, NO_x abatement and oxidation. To reduce the pollutants HC, CO, and NO_x in automobile exhaust gas, three-way catalysts are currently applied. The reduction of particle emissions in diesel exhaust gas is achieved by diesel filters and oxidation catalysts. Pollutants from power plants are mainly the inorganic components NO_x and SO₂. In the SCR process, NO_x is catalytically reduced to nitrogen and water. The DESONOX process is suited for the simultaneous catalytic abatement of NO_x and SO_x. Exhaust gases from production processes in many areas require after-treatment. Therefore catalyst formulations depend on process parameters and exhaust gas components. This overview presents and explains catalyst types, design, mode of operation, and processes.     

Application of Water‐Swollen Thin‐Film Composite Membrane in Flue Gas Purification

A water‐swollen thin‐film composite membrane, which was a reverse osmosis membrane with a thin polyamide layer, was used to separate a model mixture of N₂, CO₂, and SO₂. The polyamide swells with water, and thus, becomes more permeable to polar gases. The flue gas contains water vapor, which must be removed before it is subjected to SO₂ removal. Here moisture is employed to keep the membrane swollen. Using the model mixture, the humidified feed stream is brought to the membrane, where it is cooled below the dew point, so that water condenses on the membrane to keep the polyamide swollen. The membrane showed high CO₂ and SO₂ permeance, but low selectivity, so it could be applied to separate these two gases from N₂, and thus, is suitable for flue gas purification.     

Computational screening of porous carbons,zeolites, and metal organic frameworks for desulfurization and decarburization of biogas,natural gas,and flue gas

Eighteen kinds of porous materials from carbons, zeolites, and metal organic frameworks (MOFs) have been extensively investigated for desulfurization and decarburization of the biogas, natural gas, and flue gas by using a molecular modeling approach. By considering not only the selectivity but also capacity, Na‐5A, zeolite‐like MOF (zMOF), and Na‐13X, MIL‐47 are screened as the most promising candidates for removal of sulfide in the CH₄? CO₂? H₂S and N₂? CO₂? SO₂ systems, respectively. However, for simultaneous removal of sulfide and CO₂, the best candidates are zMOF for the natural gas and biogas (i.e., CH₄? CO₂? H₂S system) and MOF‐74‐Zn for the flue gas (i.e., N₂? CO₂? SO₂ system). Moreover, the regeneration ability of the recommended adsorbents is further assessed by studying the effect of temperature on adsorption. It is found that compared to the zMOF and MIL‐47 MOFs, the Na‐5A and Na‐13X zeolites are not easily regenerated due to the difficulty in desorption of sulfide at high temperature, which results from the stronger adsorbent–adsorbate interactions in zeolites. The effect of sulfide concentration on the adsorption properties of the recommended adsorbents is also explored. We observe that the zMOF and MIL‐47 are also superior to the Na‐5A and Na‐13X for desulfurization of gas mixtures containing high sulfide concentration. This is because MOFs with larger pore volume lead to a greater sulfide uptake. The effects of porosity, framework density, pore volume, and accessible surface area on the separation performance are analyzed. The optimum porosity is about 0.5–0.6, to meet the requirements of both high selectivity and uptake. It is expected this work provides a useful guidance for the practical applications of desulfurization and decarburization. © 2013 American Institute of Chemical Engineers AIChE J, 59: 2928–2942, 2013     

Simultaneous removal of SO2, NO and particulate by pilot-scale scrubber system

SO _x and NO _x have both previously been identified as primary precursors of acid rain, and thus the abatement of SO _x and NO _x emissions constitutes a major target in the field of air pollution control. In this study, the efficacy of a pilot-scale scrubber was evaluated with regard to the simultaneous removal of SO₂, NO and particulate with wet catalysts. The removal efficiencies of particulate were measured to be 83, 92 and 97% with catalyst flux of 0.5, 0.8 and 1.5 L/min, respectively. The average removal efficiencies of particulate with different nozzles were approximately 94 and 90% with FF6.5 (5/8 in.) and 14 W (1.0 in.) nozzles, respectively. At least 96–98% of particulate and SO₂ were removed, regardless of the stage number of reactor. In a one-stage scrubber, 83.3% removal efficiency of NO was achieved after 48 hours; however, the two-stage scrubber achieved an NO removal efficiency of 95.7%. Regardless of the liquid-gas ratio, SO₂ and particulate were removed effectively, whereas NO was removed about 84% and 74% under liquid-gas ratio conditions of 39.32 L/m³ and 27.52 L/m³, respectively. In experiments using STS and P.P. pall ring as packing material, particulate and SO₂ removal efficiency values in excess of 98% were achieved; however, NO removal was correlated with the different packing materials tested in this study. With the above optimum operation conditions, even after 20 hours, the removal efficiency for NO stayed at 95% or higher, the removal efficiency for SO₂ stayed at 97% or higher, and the removal efficiency for particulate stayed at 92% or higher. In accordance, then, with the above results, it appears that this process might be utilized in scrubber systems, as well as systems designed to simultaneously remove particulate, SO₂ and NO from flue gas.     

Novel method for removal of NO x and SO2 by sustainable electrochemical process using Ag(I)/Ag(II) redox mediator

The objective of this work was to develop a process for removal of industrial waste gases like NO, NO₂ and SO₂ by electrochemically generated Ag(I)/Ag(II) redox mediator system in aqueous nitric acid medium. 100% removal efficiencies were achieved in these studies for removal of NO _x and SO₂ with Ag(II) ions in room temperature and atmospheric pressure. This Ag(I)/Ag(II) redox mediator system can be regenerated continuously during the scrubbing process.     

Removal of NOx with radical injection caused by corona discharge

Removal of NO_x (namely DeNO_x) from simulated flue gas with direct current (d.c.) corona radical shower system was investigated. Steady streamer coronas occur when the flow rates of the fed gases are adjusted properly. The experimental results show that both the composition and the flow rate of the gas fed into the nozzles influence the V-I characteristic of corona discharge. The vapor in the flue gas restrains the discharge, reduces the discharge current, but enhances the DeNO_x efficiency. Furthermore, removal of NO_x from flue gas by radical injection associated with alkali solution (26% by weight of NaOH in water) scrubbing was carried out. Oxygen together with water vapor is fed into the nozzle electrode and the oxygen and water molecules are decomposed in the corona zone. It is found that NO and NO₂ can be converted into HNO₂ and HNO₃, respectively, by radicals formed during the discharge process and the conversion efficiency of NO_x in the plasma reactor is more than 60%. The overall DeNO_x efficiency of the system reaches 81.7% after the flue gas was scrubbed by the NaOH solution.