SO2 and NO selective adsorption properties of coal-based activated carbons

The aim of this paper is to study binary gas adsorption on the activated carbon in the fixed-bed reactor. Coal-based granular activated carbons can selectively adsorb SO₂ and NO. Physically adsorbed NO is replaced and desorbed by SO_2. Chemically adsorbed NO can promote the absorption of SO₂. The presence of SO₂ and NO can enhance the chemical adsorption of NO and SO₂, respectively. When the diameter of granular activated carbon decreases and the specific surface area increases, both the penetration time of the activated carbon bed and SO₂ removal efficiency increase. The whole removal efficiency of SO₂ is more than 99% in the penetration time, but the whole removal efficiency of NO is only 55% in the coexistence of SO₂ and NO. SO₂ adsorption capacity of HNO₃ dipped granular activated carbon is higher than that of non-treated one. The two experimental results are agree with each other.     

SO2 and NO removal from flue gas over V2O5/AC at lower temperatures — role of V2O5 on SO2 removal

Supporting V₂O₅ onto an activated coke (AC) has been reported to significantly increase the AC's activity in simultaneous SO₂ and NO removal from flue gas. To understand the role of V₂O₅ on SO₂ removal, V₂O₅/AC is studied through SO₂ removal reaction, surface analysis, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared (FTIR) techniques. It is found that the main role of V₂O₅ in SO₂ removal over V₂O₅/AC is to catalyze SO₂ oxidation through a VOSO₄-like intermediate species, which reacts with O₂ to form SO₃ and V₂O₅. The SO₃ formed transfers from the V sites to AC sites and then reacts with H₂O to form H₂SO₄. At low V₂O₅ loadings, a V atom is able to catalyze as many as 8 SO₂ molecules to SO₃. At high V₂O₅ loadings, however, the number of SO₂ molecules catalyzed by a V atom is much less, due possibly to excessive amounts of V₂O₅ sites in comparison to the pores available for SO₃ and H₂SO₄ storage.     

Modeling of SO2 removal in fabric filter

Fabric filters are involved in most semi-dry flue gas desulfurization process and represent ability of SO₂ removal. SO₂ removal efficiency in fabric filter after a semi-dry scrubber is investigated. Experimental results showed that SO₂ inlet concentration has little effect on SO₂ removal efficiency, SO₂ removal efficiency increases as flue gas inlet temperature increases and relative humidity affects SO₂ removal efficiency significantly. The kinetic model based on shrinking core theory has been presented. It is found that, in the beginning, when calcium hydroxide conversion ratio is less than 0.3, SO₂ removal process is mainly controlled by chemical reaction (Model-2); and when calcium hydroxide conversion ratio is greater than 0.3, SO₂ diffusion through product layer is rate limiting (Model-3). The experimental results in fabric filter are successfully correlated by Model-3.     

Adsorption of CO2 and SO2 on activated carbons with a wide range of micropore size distribution

The adsorption isotherms of N₂ at 77K, CO₂ at 251, 273 and 298K, and SO₂ at 262 and 273K have been determined on a series of physically activated carbons with a wide range of micropore size distributions. Since the series includes carbons with very high burn-off, it shows the problems involved in the characterization of microporsity in superactivated carbons. On the other hand, the results show that the carbon surface-adsorbate interactions for SO₂ at low relative pressures are weaker than for N₂ and CO₂, as a result of the strong adsorptive-adsorptive interactions in the bulk gas phase.     

Activity and characterization of Rh/Al2O3 and Rh-Na/Al2O3 catalysts for the SCR of NO with CO in the presence of SO2 and HCl

SO₂ and HCl are major pollutants emitted from waste incineration processes. Both pollutants are difficult to remove completely and can enter the catalytic reactor. In this work, the effects of SO₂ and HCl on the performance of Rh/Al₂O₃ and Rh-Na/Al₂O₃ catalysts for NO removal were investigated in simulated waste incineration conditions. The characterizations of the catalysts were analyzed by BET, SEM/EDS, XRD, and ESCA. Experimental results indicated the 1%Rh/Al₂O₃ catalyst was significantly deactivated for NO and CO conversions when SO₂ and HCl coexisted in the flue gas. The addition of between 2 and 10 wt.% Na promoted the activity of the 1%Rh/Al₂O₃ catalyst for NO removal, but decreased the CO oxidation and BET surface area. The catalytic activity for NO removal was inhibited by HCl as a result of the formation of RhCl₃. Adding Na to the Rh/Al₂O₃ catalyst decreased the inhibition of SO₂ because of the formation of Na₂SO₄, which was observed in the XRD and ESCA analyses. SEM mapping/EDS showed that more S was residual on the surface of the Rh-Na/Al₂O₃ catalyst than Cl.     

Elemental sulfur production through regeneration of a SO2-adsorbed V2O5-CoO/AC in H2

H₂ regeneration of an activated carbon supported vanadium and cobalt oxides (V₂O₅-CoO/AC) catalyst–sorbent used for flue gas SO₂ removal is studied in this paper. Elemental sulfur is produced during the H₂-regeneration when effluent gas of the regeneration is recycled back to the reactor. The regeneration conditions affect the regeneration efficiency and the elemental sulfur yield. The regeneration efficiency is the highest at 330 °C, with SO₂ as the product. The production of elemental sulfur occurs at 350 °C and higher with the highest elemental sulfur yield of 9.8 mg-S/g-Cat. at 380 °C. A lower effluent gas recycle rate is beneficial to elemental sulfur production. Intermittent H₂ feeding strategy can be used to control H₂S concentration in the gas phase and increase the elemental sulfur yield. Two types of reactions occur in the regeneration, reduction of sulfuric acid to SO₂ by AC and reduction of SO₂ to elemental sulfur through Claus reaction. H₂S is an intermediate, which is important for elemental sulfur formation and for conversion of CoO to CoS that catalyzes the Claus reaction. The catalyst–sorbent exhibits good stability in SO₂ removal capacity and in elemental sulfur yield.     

Full-scale measurements of SO2 gas phase concentrations and slurry compositions in a wet flue gas desulphurisation spray absorber

Two measurement campaigns were carried out at ENERGI E2's Asnæs Power plant, unit 5. The unit has a capacity of 620 MW_e and is equipped with a wet flue gas desulphurisation (FGD) plant employing a counter-current spray absorber with five spray levels. In the first campaign, the power plant was firing Orimulsion^® with 2.85 wt% S resulting in a flue gas concentration of SO₂ exceeding 2000 ppmv. In the second campaign, the fuel applied was a low-S blended coal and the SO₂ concentration in the raw gas was around 400 ppmv. A novel probe for in situ sampling of gas phase concentrations in wet FGD spray absorbers was developed and applied for measuring axial profiles of the SO₂ gas phase concentrations in the absorber. The expected decrease in SO₂ concentrations along the height of the absorber was found in the spray section (from height 26.5 to 36.2 m) whereas the SO₂ concentration above the holding tank and below the gas inlet was quite low probably due to long local residence times in the region. Horizontal variations, due to somewhat different flow conditions near the column wall were investigated and the SO₂ concentrations were found to be higher near the wall. Measurements at different gross loads showed that the SO₂ gas phase concentration at a given position inside the absorber was roughly linearly related to the L/G ratio in the measuring interval. Turning off one of the lower spray levels, while burning coal with low S content, did not lower the overall removal efficiency of the absorber. However, the SO₂ gas phase concentration inside the lower part of the absorber was increased by a factor of 2-3. Measurements of slurry pH at different positions showed a decrease of approximately 0.5 units from the upper to the lower part of the absorber. The full-scale measurements provide a detailed set of experimental data for validation of mathematical models of a wet FGD spray absorber.     

Sulphur dioxide (SO2) electrotransfer in electric field generated by corona discharge

The mechanism of the forming SO₂ negative ions and their electrotransfer in the corona discharge electric field was investigated in this paper. The experimental results showed that SO₂ electrotransfer occurred in the electric field with corona discharge, which had potential applications in removal of SO₂ of the flue gas from coal-fired power plants by electrotransfer. SO₂ electrotransfer was enhanced by higher electric-field intensity or a larger discharging area. Assistant uniform electric field after the corona discharge electric field would improve SO₂ electrotransfer. The increment of the desulphurization efficiency by SO₂ electrotransfer might reach as high as 50%.     

Impact of SO2 concentration on the corrosion rate of X70 steel and iron in water-saturated supercritical CO2 mixed with SO2

The corrosion behavior of X70 steel and iron in water-saturated supercritical CO₂ mixed with SO₂ was investigated using weight-loss measurements. As a comparison, the instantaneous corrosion rate in the early stages for iron in the same corrosion environment was measured by resistance relaxation method. Surface analyzes using SEM/EDS, XRD and XPS were applied to study the morphology and chemical composition of the corroded sample surface. Weight-loss method results showed that the corrosion rate of X70 steel samples increased with SO₂ concentration, while the corrosion rate increased before decreasing with SO₂ concentration for iron sample. Comparing resistance relaxation method results with weight-loss method results, it is found that the instantaneous corrosion rate of iron is much higher than the uniform corrosion rate of the iron tablet specimens which are covered with thick corrosion product films after a long period of corrosion. The corrosion product films were mainly composed of FeSO₄ and FeSO₃ hydrates. The possible reaction mechanism under such environment was also analyzed, and the electrochemical reaction between the dissolved SO₂ in the condensed water film with iron is the critical reaction step.     

Computational modeling of furnace sorbent injection for SO2 removal from coal-fired utility boilers

Furnace sorbent injection (FSI) is used to remove SO₂ formed during coal combustion by injecting sorbent into the high temperature zone of a furnace above the fireball. FSI is cost effective for older coal-fired boilers, especially when space or capital budgets are limited. To optimize the design and performance of FSI, an SO₂/sorbent modeling scheme that simultaneously considers calcination (or dehydration), sintering, and sulfation has been developed and implemented. It is coupled with a three-dimensional combustion model based on computational fluid dynamics to determine the most desirable locations for sorbent injection and to optimize the amount of sorbent needed to achieve a targeted SO₂ removal efficiency. A sensitivity analysis was conducted to determine the effect of flue gas temperature, particle diameter, and SO₂ concentration on the extent of sulfation. This SO₂/sorbent sub-model was applied to a 126-MW front-wall fired boiler firing eastern bituminous coal. The SO₂ removal efficiencies predicted by the model agreed well with those measured in the field. The modeling results indicated that sorbent injected directly into the furnace through boosted over-fired air ports is more effective at removing SO₂, due to longer residence time and better mixing, relative to ports higher in the furnace with poor mixing. This modeling approach is optimized for full-furnace application to facilitate the design process.     

Cobenefit of SO3 reduction on mercury capture with activated carbon in coal flue gas

Parametric experiments were carried out to study the interactions of mercury, SO₃, and injected activated carbon (AC) in a coal flue gas stream. The levels of SO₃ vapor in flue gas were altered by individually varying flue gas temperature, moisture, or sodium fume injection in the flue gas. Meanwhile, mercury emissions with AC injection (ACI) upstream of an electrostatic precipitator (ESP) were evaluated under varied SO₃ concentrations. SO₃ measurements using a condensation method indicated that low temperature, high moisture content, and sodium fume injection in flue gas shifted SO₃ partitioning from the vapor to particulate phase, subsequently improving mercury capture with ACI. 0.08 g/m³ of DARCO^® Hg-LH injection only provided approximately 20% mercury reduction across the ESP in a bituminous coal flue gas containing 28 ppm SO₃, but mercury capture was increased to 80% when the SO₃ vapor concentration was lowered less than 2 ppm. Experimental data clearly demonstrate that elevated SO₃ vapor is the key factor that impedes mercury adsorption on AC, mainly because SO₃ directly competes against mercury for the same binding sites and overwhelmingly consumes all binding sites.     

Influence of SO3 on mercury removal with activated carbon: Full-scale results

Activated carbon injection is considered one of the most cost-effective options for mercury control at PRB-fired power plants. However, roughly 30% of sites firing PRB coal use SO₃ for flue gas conditioning. The presence of SO₃ in flue gas can decrease mercury capture by activated carbon, sometimes dramatically. Overcoming activated carbon performance limitations caused by SO₃ conditioning for units with this configuration is essential to enable these plants to cost-effectively meet pending mercury emission regulations. Ameren's Labadie Unit 2 fires PRB coal and uses SO₃ to enhance particulate capture in the electrostatic precipitator (ESP). Full-scale sorbent injection tests at Labadie were conducted from 2005–2007. Six sorbents were tested at SO₃ injection concentrations ranging from 0 to 10.7 ppm. Sorbent performance was evaluated at two injection locations (the air preheater (APH) inlet and outlet). Native mercury capture on fly ash was typically less than 15%. When the mercury sorbents were injected downstream of the air preheater, the SO₃ concentration resulted in a decrease in mercury capture from 85% (no SO₃ injection) to 17% (SO₃ injection set at 10.7 ppm). Mercury sorbents were more effective when injected upstream of the air preheater. With the SO₃ system off, mercury removal increased from 75% when injecting 5.1 lb/MMacf of brominated carbon at the APH outlet, compared to 95% when injecting at the inlet. With the SO₃ system on, test results indicated an increase from about 30% injecting at the outlet to 58% injecting at the inlet. Tests evaluating the ADA-ES patented onsite milling process showed that 85% mercury capture was achieved injecting 4 lb/MMacf of milled activated carbon compared to a requirement of 10 lb/MMacf to achieve the same removal using as-received carbon, representing a 60% reduction in activated carbon consumption. No changes in opacity, APH and ESP performance, or other balance-of-plant effects were observed in these tests.     

Influence of low concentration of SO2 for selective reduction of NO by C3H8 in lean-exhaust conditions on the activity of Ag/Al2O3 catalyst

The effect of SO₂ for the selective reduction of NO by C₃H₈ on Ag/Al₂O₃ was investigated in the presence of excess oxygen and water vapor. The NO_x conversion decreased permanently even in the presence of a low concentration of SO₂ (0.5–10 ppm) at <773 K. The increase in SO₂ concentration resulted in a large decrease in NO_x conversion at 773 K. However, when the reaction temperature was more than 823 K, the activity of Ag/Al₂O₃ remained constant even in the presence of 10 ppm of SO₂. The sulfate species formed on the used Ag/Al₂O₃ were characterized by a temperature programmed desorption method. The sulfated species formed on silver should mainly decrease the deNO_x activity on the Ag/Al₂O₃. The sulfated Ag/Al₂O₃ was appreciably regenerated by thermal treatment in the deNO_x feed at 873 K. The moderate activity remains at 773 K in the presence of 1 ppm SO₂ for long time by the heat treatment at every 20 h intervals.     

Simultaneous reduction of NOx and SO2 emissions from coal combustion by calcium magnesium acetate

The potential of calcium magnesium acetate (CMA) as a medium for the simultaneous control of NO_x and SO_x emissions has been investigated using a pulverized coal combustion rig operating at 80 kW. A US and a UK coal of significantly different sulphur contents were used as primary fuel and CMA was injected in solution form into the combustion gases by horizontally opposed twin-fluid atomisers at temperatures of 1100-1200 °C. SO₂ reductions typically greater than 80 and 70% were found for initial SO₂ levels of 1000 and 1500 ppm, respectively, at Ca/S ratios greater than 2.5. There did not appear to be significant limitation on sulphation by pore blockage using CMA due to the open structure formed during calcination and there is clear potential for zero SO₂ emissions at higher Ca/S ratios. The Ca content of the CMA in the form of CaO, via a droplet drying/particle calcination process, absorbs SO₂ by sulphation processes by penetration into the open pore structure of these particles. The effect of primary zone stoichiometry (λ₁=1.05, 1.15 and 1.4) on NO_x reduction was investigated for a range of CMA feed rates up to a coal equivalent of 24% of the total thermal input. NO_x reductions of 80, 50 and 30% were achieved at a primary zone stoichiometry of λ₁=1.05, 1.15 and 1.4, respectively, for a reburn zone residence time of 0.8 s. At lower equivalent reburn fuel fractions, coal gave greater NO_x reductions than CMA but similar levels were achieved above Rff=18%. The mechanism for NO_x reduction involves the organic fraction of CMA which pyrolyses into hydrocarbon fragments (CH_i), but to a lesser degree than coal, which may then react with NO_x in a manner similar to a conventional ‘reburn’ mechanism where NO_x is partly converted to N₂ depending on the availability of oxygen.     

等速升温流态化下CaO/生物质焦的SO2/NO联合脱除特性

燃煤锅炉污染物超低排放标准对电厂脱硫和脱硝系统提出了更高的要求。CaO作为脱硫剂可以实现循环流化床锅炉烟气中SO₂的高效脱除,焦炭作为还原剂直接还原NO,同时CaO的存在对焦炭还原NO起催化作用,可以实现燃煤烟气中SO₂/NO的联合脱除。为了探究连续温度变化对CaO/生物质焦联合脱硫脱硝性能的影响,在钙循环捕集CO₂技术背景下,研究了等速升温流态化下CaO/生物质焦的SO₂/NO联合脱除特性。探究了烟气中O₂和CO₂对CaO/椰壳焦脱除SO₂/NO的影响。结果表明,O₂通过对椰壳焦表面碳原子的活化作用降低了异相还原NO温度,在300~950℃等速升温过程中CaO/椰壳焦的NO脱除效率逐渐增加,780℃以上能实现100%脱硝。O₂也提高了CaO/椰壳焦的脱硫效率。CO₂与CaO的碳酸化反应以及与椰壳焦的气化反应对同时脱除SO₂/NO有明显抑制作用。O₂和CO₂共同作用下,在500~800℃内CaO/椰壳焦的脱硝效率随温度升高而增加,脱硫效率先降低后升高。NO促进了CaO/椰壳焦脱除SO₂,而SO₂对脱硝有抑制作用。800℃时CaO/椰壳焦同时脱除SO₂和NO的效率分别为97.7%和93.9%。     

Advanced experimental analysis of the reaction of Ca(OH)2 with HCl and SO2 during the spray dry scrubbing process

This work evaluates both the removal efficiencies of HCl and SO₂ at different points in a spray dryer using Ca(OH)₂ as the absorbent. The operating conditions were specified in terms of the temperature of the flue gas (200-300 °C), the HCl concentration (120-1000 ppm), the SO₂ concentration (150-500 ppm) and the amount of CaCl₂ added (10-30 wt.%).The experimental results showed that the SO₂ removal efficiencies were higher in the presence of HCl (120-500 ppm) than in the absence of HCl at 250 °C and 20% relative humidity (RH). However, the removal efficiency of SO₂ decreased as the HCl concentration increased. The removal efficiency of SO₂ also increased with the amount of CaCl₂ in the spray dryer.     

Study of the preasphaltenes of coal liquefaction and its hydro-conversion kinetics catalyzed by SO4/ZrO2

The investigation of hydro-conversion behavior of the heavy intermediate products derived from coal direct liquefaction is advantageous to optimize the technological conditions of direct coal liquefaction and improve the oil yield. In this paper, the hydro-conversion of preasphaltenes catalyzed by SO₄²⁻/ZrO₂ solid acid was investigated based on the structural characterization of preasphaltenes and its hydro-conversion products, and the determination of products distribution and the kinetics of preasphaltenes hydro-conversion. The results indicated that the content of condensed aromatic rings increased, and the contents of hydrogen, oxygen and aliphatic side chains of preasphaltenes decreased with the increase of coal liquefaction temperature. The preasphaltenes showed higher hydro-conversion reactivity while SO₄²⁻/ZrO₂ solid acid was used as catalyst. Higher temperature and longer time were in favor of increasing the conversion and the oil + gas yield. The conversion of preasphaltenes hydro-conversion under 425 °C, for 40 min reached 81.3% with 51.2% oil + gas yield. SO₄²⁻/ZrO₂ solid acid was in favor of the catalytic cracking rather than the catalytic hydrogenation in the hydro-conversion of preasphaltenes. The activation energy of preasphaltenes conversion into asphaltenes was 72 kJ/mol. The regressive reactions were only observed at a higher temperature.     

Reduction of NO by CO on Cu/ZrO2/Al2O3 catalysts: Characterization and catalytic activities

ZrO₂, γ-Al₂O₃ and ZrO₂/γ-Al₂O₃-supported copper catalysts have been prepared, each with three different copper loads (1, 2 and 5 wt%), by the impregnation method. The catalysts were characterized by nitrogen adsorption (BET), X-ray diffraction (XRD), temperature programmed reduction (TPR) with H₂, Raman spectroscopy and electronic paramagnetic resonance (EPR). The reduction of NO by CO was studied in a fixed-bed reactor packed with these catalysts and fed with a mixture of 1% CO and 1% NO in helium. The catalyst with 5 wt% copper supported on the ZrO₂/γ-Al₂O₃ matrix achieved 80% reduction of NO. Approximately the same rate of conversion was obtained on the catalyst with 2 wt% copper on ZrO₂. Characterization of these catalysts indicated that the active copper species for the reduction of NO are those in direct contact with the oxygen vacancies found in ZrO₂.     

NO reduction with H2 in the presence of excess O2 over Pd/MFI catalyst

The NO SCR (selective catalytic reduction) activity with H₂ in the presence of excess O₂ was investigated over Pd/MFI catalyst prepared by sublimation method. With GHSV=90?000 h⁻¹, a very high steady-state conversion of NO to N₂ (70%) is achieved at 100 °C. Significant reorganizations take place inside the catalyst upon its first contact with all reactants and products at the reaction temperature. Pd⁰, which has a significant role in the NO-H₂-O₂ reaction, is possibly the active site for NO reduction. The formation of Pd-β hydride deactivates the catalyst for NO reduction. Throughout the entire NO-H₂-O₂ reaction, no N₂O or NO₂ is formed; N₂ is the only N-containing product. The presence of O₂ inhibits the formation of undesirable NH₃. The rate of the NO+H₂ reaction is fast or comparable to that of the H₂+O₂ reaction. The oxidation of Pd⁰ and subsequent agglomeration of PdO are responsible for the decreased NO reduction activity at high temperature.