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.     

Reaction behavior of SO2 in the sintering process with flue gas recirculation

The primary goal of this paper is to reveal the reaction behavior of SO₂ in the sinter zone, combustion zone, drying–preheating zone, and over-wet zone during flue gas recirculation (FGR) technique. The results showed that SO₂ retention in the sinter zone was associated with free-CaO in the form of CaSO₃/CaSO₄, and the SO₂ adsorption reached a maximum under 900ºC. SO₂ in the flue gas came almost from the combustion zone. One reaction behavior was the oxidation of sulfur in the sintering mix when the temperature was between 800 and 1000ºC; the other behavior was the decomposition of sulfite/sulfate when the temperature was over 1000ºC. However, the SO₂ adsorption in the sintering bed mainly occurred in the drying–preheating zone, adsorbed by CaCO₃, Ca(OH)₂, and CaO. When the SO₂ adsorption reaction in the drying–preheating zone reached equilibrium, the excess SO₂ gas continued to migrate to the over-wet zone and was then absorbed by Ca(OH)₂ and H₂O. The emission rising point of SO₂ moved forward in combustion zone, and the concentration of SO₂ emissions significantly increased in the case of flue gas recirculation (FGR) technique.

Implications: Aiming for the reuse of the sensible heat and a reduction in exhaust gas emission, the FGR technique is proposed in the iron ore sintering process. When using the FGR technique, SO₂ emission in exhaust gas gets changed. In practice, the application of the FGR technique in a sinter plant should be cooperative with the flue gas desulfurization (FGD) technique. Thus, it is necessary to study the influence of the FGR technique on SO₂ emissions because it will directly influence the demand and design of the FGD system.     

Studies on the Removal of Sulfur Dioxide from Hot Flue Gases to Prevent Air Pollution

The pollution of the atmosphere by sulfur dioxide is one of the gravest of all in public nuisance problems, especially in the industrial regions. A practically applicable method in industry for the removal of sulfur dioxide has been studied. The Kiyoura-T .I .T. process utilizes the oxidation method to convert S0₂ of the flue gas to S0₃ in the presence of vanadium oxide. A limited amount of water vapor present in the flue gas reacts with S0₃ to form H₂SO₄. Ammonia is then introduced to the gaseous mixture, which is now at the suitable temperature, to form ammonium sulfate. Conditions are controlled to produce ammonium sulfate of the right size to produce aggregate that may be removed by a dry cyclone separator.     

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.     

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.     

Summary of the 1991 EPRI/EPA/DOE SO2 Control Symposium

The 1991 SO₂ Control Symposium was held December 3-6, 1991, in Washington, D.C. The symposium, jointly sponsored by the Electric Power Research Institute (EPRI), the U.S. Environmental Protection Agency (EPA), and the U.S. Department of Energy (DOE), focused attention on recent improvements in conventional sulfur dioxide (SO₂) control technologies, emerging processes, and strategies for complying with the Clean Air Act Amendments of 1990. Its purpose was to provide a forum for the exchange of technical and regulatory information on SO₂ control technology. Over 800 representatives of 20 countries from government, academia, flue gas desulfurization (FGD) process suppliers, equipment manufacturers, engineering firms, and utilities attended. In all, 50 U.S. utilities and 10 utilities in other countries were represented. In 11 technical sessions, a diverse group of speakers presented 111 technical papers on development, operation, and commercialization of wet and dry FGD, Clean Coal Technologies, and combined sulfur dioxide/nitrogen oxides (SO₂/NO_x processes.     

Effect of Oxidizing and Reducing Conditions on the Reaction of Water with Sulfur Bearing Blast Furnace Slags

The evolution of H₂S and SO₂ from hot blast furnace slags by reaction with H₂O has been found to be dependent upon the presence of O₂ or H₂ in the reaction zone as well as on the temperature. H₂ has been found to produce a small increase in H₂S and a small decrease in SO₂ emission, while O₂ has been found to produce a very great inhibiting effect on H₂S emission and only a small increase in SO₂ emission. The total emission of sulfur bearing gases is much less when H₂O + air is blown at the slag than when H₂O + Ar is blown at the slag, particularly at 1200°C and above. These effects may be useful in attempts to design systems for slag quenching which will produce less pollution.     

Effect of Flue Dust on the Vanadium Oxide Catalyst Utilized by the Contact Oxidation Process

Concepts for controlling SO₂ from fossil fuels can be separated into two main categories: (1) Residual and vacuum gas oil desulfurization and (2) Flue gas desulfurization. The Kiyoura-T.I.T. process confines itself to the desulfurization of flue gas. It employs vandium oxide as a catalyst which oxidizes the sulfur dioxide to trioxide, followed by a gaseous phase reaction of ammonia. The end product, ammonium sulfate is removed by an electrostatic precipitator. (The details were presented at annual meetings of APCA in 1966 and 1967 as 1 and II.) Flue gas is passed through cyclone and dust filter to remove dust. Under normal operating conditions almost all of the dust is removed at the filters. The author carried out experiments to determine whether there was any effect on the activity of the catalyst, assuming that a portion of the dust escapes into the stream along the flue. It has been generally accepted that in fuel oil firing steam power plants, about 100 mg./nm³ of dust including carbon, hydrocarbon, and ash are normally contained in the flue stream. The carbon and hydrocarbon is oxidized readily at the filters and exists only as ash. An amount of ash equivalent to the amount assumed to have settled on the catalyst over a period of 3–12 months, was placed on the catalyst, and experiments were carried out. The SO₂ conversion efficiency was measured and found to be over 93%. The results showed that at the actual operational temperature of 450°C, ash had practically no effect at all.     

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.     

Control of Claus Plant Sulfur Compound Emissions

The body of information of this paper is directed to those individuals charged with selecting a process to control atmospheric sulfur emissions from Claus plants serving refineries, gas processing installations, and chemical plants. The TGT process developed by the French Petroleum Institute (IFP) is an extension of the Claus reaction itself in the liquid phase. Mixed H₂S and SO₂ in tail gas from Claus units is fed to a packed tower in which a solution of proprietary catalyst in a high BP polyglycol circulates countercurrent to the gas flow. The mixed gases react with the catalyst to form a complex, which in turn reacts with more gases to produce elemental sulfur. Reaction temperature keeps the sulfur above its melting point. Product accumulates in the boot of the tower and is drawn off continuously through a seal leg.

The IFP TGT process is simple in design and units have simple construction, characterized by use of low carbon steel and the use of very few pieces of equipment. Of all processes used today to take effluent sulfur values down to 1000 ppm SO₂ after incineration, the IFP TGT process requires the least capital investment and the lowest operating costs. Twenty-six full scale plants are operating or under design or construction: nine each in the U.S. and Japan, five in the U.S.S.R. and Poland, two in western Europe and one in Canada. Capacities of the Claus plants served range from 45 to 800 Lt/d sulfur.     

Laboratory and Field Evaluation of the Controlled Condensation System for S03 Measurements in Flue Gas Streams

The study reported by this paper involves the use of the Controlled Condensation System (Goksoyr/Ross Coil) for flue gas S0₃ measurements in both the laboratory and the field, under low and high mass loadings. The Controlled Condensation System cools the flue gas to below the dewpoint of H₂S0₄ but above the H₂0 dewpoint. The resulting aerosol is collected either on the coil walls or on the back-up glass frit. The laboratory recovery of the H₂S0₄ in streams of varying S0₂, H₂0, and H₂S0₄ content was found to be 95 ± 6%. A new quartz filter holder was designed to meet the filtration problems encountered in collecting S0₃ from particle laden flue gas streams. This quartz system, when heated to above 250°C, quantitatively passed the H₂S0₄ into the condensation coil. Later studies with this filter system preloaded with fly ash equivalent to a mass loading of 1.3 g/m³ yielded a 80-85% recovery of H₂S0₄. The laboratory system was simultaneously tested at a 150 megawatt, pulverized coal-fired power plant prior to and after a wet limestone FGD. The inlet grain loading to the FGD ranged from 0.06 g/m³ to 11.4 g/m³ with S0₂ concentrations as high as 4000 ppm. The average inlet H₂S0₄ value was 8.3 ppm and the outlet from the FGD was 3.1 ppm. The source fluctuation value was determined to be ±65%.     

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.     

Emissions of Sulfur Trioxide from Coal-Fired Power Plants

Abstract

Emissions of sulfur trioxide (SO₃) are a key component of plume opacity and acid deposition. Consequently, these emissions need to be low enough to not cause opacity violations and acid deposition. Generally, a small fraction of sulfur (S) in coal is converted to SO₃ in coal-fired combustion devices such as electric utility boilers. The emissions of SO₃ from such a boiler depend on coal S content, combustion conditions, flue gas characteristics, and air pollution devices being used. It is well known that the catalyst used in the selective catalytic reduction (SCR) technology for nitrogen oxides control oxidizes a small fraction of sulfur dioxide in the flue gas to SO₃. The extent of this oxidation depends on the catalyst formulation and SCR operating conditions. Gas-phase SO₃ and sulfuric acid, on being quenched in plant equipment (e.g., air preheater and wet scrubber), result in fine acidic mist, which can cause increased plume opacity and undesirable emissions. Recently, such effects have been observed at plants firing high-S coal and equipped with SCR systems and wet scrubbers. This paper investigates the factors that affect acidic mist production in coal-fired electric utility boilers and discusses approaches for mitigating emission of this mist.     

Low Concentration Mercury Sorption Mechanisms and Control by Calcium-Based Sorbents: Application in Coal-Fired Processes

ABSTRACT

The capture of elemental mercury (Hg⁰) and mercuric chloride (HgCl₂) by three types of calcium (Ca)-based sor-bents was examined in this bench-scale study under conditions prevalent in coal-fired utilities. Ca-based sorbent performances were compared with that of an activated carbon. Hg⁰ capture of about 40% (nearly half that of the activated carbon) was achieved by two of the Ca-based sorbents. The presence of sulfur dioxide (SO₂) in the simulated coal combustion flue gas enhanced the Hg⁰ capture from about 10 to 40%. Increasing the temperature in the range of 65-100 °C also caused an increase in the Hg⁰ capture by the two Ca-based sorbents. Mercuric chloride (HgCl₂) capture exhibited a totally different pattern. The presence of SO₂ inhibited the HgCl₂ capture by Ca-based sorbents from about 25 to less than 10%. Increasing the temperature in the studied range also caused a decrease in HgCl₂ capture. Upon further pilot-scale confirmations, the results obtained in this bench-scale study can be used to design and manufacture more cost-effective mercury sorbents to replace conventional sorbents already in use in mercury control.     

Predicting Extents of Mercury Oxidation in Coal-Derived Flue Gases

Abstract

The proposed mercury (Hg) oxidation mechanism consists of a 168-step gas phase mechanism that accounts for interaction among all important flue gas species and a heterogeneous oxidation mechanism on unburned carbon (UBC) particles, similar to established chemistry for dioxin production under comparable conditions. The mechanism was incorporated into a gas cleaning system simulator to predict the proportions of elemental and oxidized Hg species in the flue gases, given relevant coal properties (C/H/O/N/S/Cl/Hg), flue gas composition (O₂, H₂O, HCl), emissions (NO_X, SO_X, CO), the recovery of fly ash, fly ash loss-on-ignition (LOI), and a thermal history. Predictions are validated without parameter adjustments against datasets from lab-scale and from pilot-scale coal furnaces at 1 and 29 MW_t. Collectively, the evaluations cover 16 coals representing ranks from sub-bituminous through high-volatile bituminous, including cases with Cl₂ and CaCl₂ injection. The predictions are, therefore, validated over virtually the entire domain of Cl-species concentrations and UBC levels of commercial interest. Additional predictions identify the most important operating conditions in the furnace and gas cleaning system, including stoichiometric ratio, NO_X, LOI, and residence time, as well as the most important coal properties, including coal-Cl.     

Dynamic NO adsorption characteristics of iron-treated activated carbon fibers

The breakthrough curve for NO adsorption on the activated carbon fibers treated in iron salt solutions was determined. They can adsorb much more NO than granular activated carbon by a factor of more than 10 from a flowing 300 ppm NO-N₂ mixed gas at 100°C and 20 ml min⁻¹; the most effective one of the iron-treated carbon fibers of 0.2 g is able to reduce the NO concentration from 300 ppm to 30 ppm. These adsorbents can adsorb the same amount of NO from even a 300 ppm NO-500 ppm SO₂-10% CO₂-10% H₂O-1% O₂-N₂ mixed gas.     

Odor Threshold Measurement by Dynamic Olfactometry: Significant Operational Variables

Abstract

Combustion flue gases of three different industrial boilers firing miscellaneous fuels were monitored for a twoweek period. Nitric oxide (NO), sulfur dioxide (SO₂), carbon monoxide (CO), carbon dioxide (CO₂), and total hydrocarbons (CxHy) were continuously measured using single-component gas analyzers in parallel with a lowresolution Fourier Transform Infrared (FTIR) gas analyzer. Hydrogen chloride (HCl) was measured continuously using the FTIR analyzer and semi-continuously using a traditional liquid-absorption technique. Nitrous oxide (N₂O), nitrogen dioxide (NO₂), and water vapor (H₂O) were continuously measured using the FTIR analyzer only. Laboratory tests were conducted prior to the field measurements to assess the detection limits of the different measurement methods for each gas component. No significant differences were found between the results of the low-resolution FTIR analyzer and the single-component analyzers or the liquid absorption method.     

Mixotrophic cultivation of microalgae using industrial flue gases for biodiesel production

In the present study, an attempt has been made to grow microalgae Scenedesmus quadricauda, Chlorella vulgaris and Botryococcus braunii in mixotropic cultivation mode using two different substrates, i.e. sewage and glucose as organic carbon sources along with flue gas inputs as inorganic carbon source. The experiments were carried out in 500 ml flasks with sewage and glucose-enriched media along with flue gas inputs. The composition of the flue gas was 7 % CO₂, 210 ppm of NO _x and 120 ppm of SO _x . The results showed that S. quadricauda grown in glucose-enriched medium yielded higher biomass, lipid and fatty acid methyl esters (FAME) (biodiesel) yields of 2.6, 0.63 and 0.3 g/L, respectively. Whereas with sewage, the biomass, lipid and FAME yields of S. quadricauda were 1.9, 0.46, and 0.21 g/L, respectively. The other two species showed closer results as well. The glucose utilization was measured in terms of Chemical Oxygen Demand (COD) reduction, which was up to 93.75 % by S. quadricauda in the glucose-flue gas medium. In the sewage-flue gas medium, the COD removal was achieved up to 92 % by S. quadricauda. The other nutrients and pollutants from the sewage were removed up to 75 % on an average by the same. Concerning the flue gas treatment studies, S. quadricauda could remove CO₂ up to 85 % from the flue gas when grown in glucose medium and 81 % when grown in sewage. The SO _x and NO _x concentrations were reduced up to 50 and 62 %, respectively, by S. quadricauda in glucose-flue gas medium. Whereas, in the sewage-flue gas medium, the SO _x and NO _x concentrations were reduced up to 45 and 50 %, respectively, by the same. The other two species were equally efficient however with little less significant yields and removal percentages. This study laid emphasis on comparing the feasibility in utilization of readily available carbon sources like glucose and inexpensive leftover carbon sources like sewage by microalgae to generate energy coupled with economical remediation of waste. Therefore on an industrial scale, the sewage is more preferable. Because the results obtained in the laboratory demonstrated both sewage and glucose-enriched nutrient medium are equally efficient for algae cultivation with just a slight difference. Essentially, the sewage is cost effective and easily available in large quantities compared to glucose.