Flue gas treatment by activated carbon obtained from oil-fired fly ash

The treatment of the solid particulates derived from the combustion of heavy oils (that is, oil-fired fly ash) with acidic solutions (HCl and HF) followed by activation at 900 °C with CO₂ and then with O₂ (1%) in N₂ at 800 °C, produces activated carbon having high surface area values (measured both by N₂ adsorption at 77 K and by CO₂ adsorption at 273 K) and surface basic characteristics. This carbon appears to be suitable for SO₂ and NO_X adsorption and hence for industrial flue gas treatment processes. By submitting the activated carbon thus obtained to some adsorption/desorption cycles of gaseous mixtures having a similar composition to that of flue gases, its general characteristics (surface areas, sorbent properties etc.) change as expected of a typical activated carbon. Based on the results obtained, these particulate materials, produced in large amounts by heavy oil combustion, are assumed to be fully exploitable for flue gas treatment.     

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.     

Py-MS Study of Sulfur Behavior during Pyrolysis of High-sulfur Coals under Different Atmospheres

In this study sulfur pyrolysis behavior of two Chinese high sulfur coals and their treated coal samples was investigated by Py-MS at a heating rate of 5 °C/min from room temperature to 1025 °C under hydrogen, helium and 2% O₂-He. It is found that the internal and external hydrogen do not show hydrogenation ability at temperature below 400 °C, due to no H₂S formation at this temperature region for all the coal samples. At temperature higher than 400 °C, not only the indigenous hydrogen but also indigenous oxygen can react with sulfur-containing radicals to form H₂S or SO₂. The evolution of H₂S and SO₂ displays the same profiles in pyrolysis of ZY pyrite-free coal under He, further revealing that after the breakage of C-S bond in the organic sulfur structure in coal to form sulfur-containing radicals, which can equally react with indigenous hydrogen and oxygen. The similar tendency between evolution of CO₂ and SO₂ and the same ending temperature also shows that not only C-S but also C-C bond can be broken in pyrolysis of ZY coals under 2% O₂-He atmosphere. However, unlike SO₂ evolution, CO₂ emission increases in the temperature ranging from 500 °C to 800 °C in LZ raw and deashed coals, implying the breakage of C-C bond at high temperature, which might be related to their low coal rank and high pyrite content.     

Influence of preparation conditions on porous structures of olive stone activated by H3PO4

An olive factory residue was used as a precursor in the preparation of granular activated carbon by chemical activation with H₃PO₄. Effects of final activation temperature, time, and H₃PO₄ concentration used in the impregnation stage on the porous development were investigated. SO₂ adsorption experiments were also performed for some of the activated carbon samples to represent their adsorption performance. Activation at low temperature represented that micropores were developed first at early stages of the temperatures. Mesoporosity developed at around 250 °C, enhanced up to 400 °C, and then started to decrease due to possibly shrinking of pores. The optimum temperature for olive stone was found to be around 400 °C on the basis of total pore volume and BET surface area. It was clearly demonstrated that H₃PO₄ concentration used in the impregnation stage was not only effective for development of surface area and pore volumes but also an effective tool for tailoring the pore structure and size distribution.     

Analysis of the behaviour of pollutant gas emissions during wheat straw/coal cofiring by TG-FTIR

The behaviour of pollutant gas emissions during the firing of wheat straw and coal blends was examined experimentally by using thermogravimetric analysis (TGA). Typical anthracite coal and wheat straw in central China were selected in this study. The ratio of coal to wheat straw by mass was set as 10:90, 15:85, 40:60 and 60:40 and the firing was carried using simulated air with oxygen and nitrogen gases. The emission characteristics of gas pollutants such as HCl, SO₂, CO₂ and NO_x were determined by coupled Fourier transform infrared (FTIR) measurements. The results showed that HCl, SO₂, CO₂ and NO_x emissions were closely related to the volatile combustion and char reacting stages. HCl emission was mainly released during the volatile combustion at the temperature between 220 and 450 °C. The profiles of HCl against temperature exhibit a single-peak, and the HCl peak occurred at 310 °C for all blends no matter what the ratio. The emission profiles of SO₂, and NO_x against temperature had the characteristic of two peaks. The first peak occurred around 320 °C for all blends, and however the second peak shifted towards higher temperatures as the coal content was increased in the blends. The study showed that combining the straw and coal can produce better emission control by reducing the magnitude of the peak releases. The analysis showed that the blended sample with 40% coal and 60% straw by mass produced the lowest levels of HCl, NO_x and SO₂ gas emissions. The CO₂ emission was mainly produced in the char combustion stage and purely increased with the carbon content in the blends.     

European inter-laboratory comparison of high pressure CO2 sorption isotherms. I: Activated carbon

In order to assess and improve the quality of high-pressure sorption isotherms of carbon dioxide (CO₂) on coals, an inter-laboratory study (“Round Robin”) has been conducted among four European research laboratories. In a first round of measurements, excess sorption isotherms were determined on Filtrasorb 400 (F400) activated carbon at 318 K using the manometric (TU Delft and RWTH Aachen University) and the gravimetric (FP Mons and INERIS) method up to 16 MPa. The study shows that CO₂ sorption in the supercritical range can be determined accurately with both gravimetric and manometric equipment but requires thorough optimization of instrumentation and measuring as well as proper sample preparation procedures. For the characterization of the activated carbon F400, which we used as benchmark, we have determined a surface area of 1063 m² g⁻¹, and Dubinin-Radushkevich (DR) micropore volume of 0.51 cm³ g⁻¹. Additionally, we analysed the elementary near-surface composition by energy dispersive X-ray spectroscopy (EDX). To characterise the bulk composition of the F400 activated carbon, a proximate and ultimate analysis was performed.The observed excess sorption maxima around 5 MPa have values around 8.0 mol kg⁻¹, which are consistently higher (by upto 0.8 mol kg⁻¹) than literature data.     

In situ nitrogen enriched carbon for carbon dioxide capture

In situ nitrogen enriched carbon was synthesized from locally available low cost soybean as the proteinaceous source. The material was synthesized by chemical activation using zinc chloride followed by physical activation using CO₂. The surface area of synthesized nitrogen enriched carbon was found to be 811 m²/g which is comparable with commercially available activated carbon. The nitrogen enriched carbon was having a breakthrough adsorption capacity of 23 mg/g at 120 °C which was almost three times higher in comparison with the commercially available activated carbon for a gas mixture comprising 15% CO₂ balanced with helium. This high adsorption capacity was attributed to the presence of nitrogen group within the carbon matrix, which was estimated to be about 0.64% as determined using the Kjeldahl’s method. The presence of different nitrogen containing groups assisting the adsorption of CO₂ in the synthesized sample was also confirmed by infrared analysis. For checking the consistent performance of the synthesized carbon, multi-cycle adsorption-desorption studies were carried out at 30 and 75 °C in binary mixture of CO₂/N₂.     

SO2 retention on CaO/activated carbon sorbents. Part II: Effect of the activated carbon support

The present paper analyses the role of the activated carbon (AC) properties on the SO₂ uptake capacity of CaO/AC sorbents prepared by AC impregnation or ionic exchange with calcium acetate water solutions. Gas adsorption and mercury porosimetry have been used for textural characterization of the AC and surface oxygen groups have been characterized by temperature programmed desorption (TPD). Thermogravimetry has been used for SO₂ retention tests and CO₂ chemisorption at 300 °C for CaO dispersion (d) determinations. The results show that the surface calcium on CaO/AC samples, determined as “Ca loading · CaO dispersion” (parameter Ca(%) · d), governs the SO₂ uptake. The surface oxygen content is the AC property that mainly controls both the calcium loading and surface calcium on CaO/AC samples, which could be explained by the fact that the surface oxygen lowers the hydrophobic character of the AC supports therefore favouring the interaction with the calcium acetate water solutions. The combination of high calcium loading and dispersion leads to SO₂ uptakes up to 123 mg SO₂/g. The textural properties of the supports have some influence in the calcium loading. However, the effect is masked by the blockage of AC porosity by the calcium loaded.     

Enhancement of nitric oxide removal by ammonia on a low-rank coal based carbon by sulphuric acid treatment

This work presents a study of the effect of wet sulphuric acid treatment and gas-phase treatment with SO₂ + O₂ + H₂O on the catalytic activity of a low-rank coal-based carbon for the nitric oxide reduction with ammonia. Carbons were characterized by N₂ adsorption, TPD, and FTIR in order to assess how the surface chemistry and the texture of carbons change after the treatments. A great amount of oxygenated functional groups both CO₂ and CO evolving ones are produced by liquid-phase sulphuric acid treatment. However, the amount of those groups after gas-phase treatment with SO₂ + O₂ + H₂O is lower, in particular the CO₂ evolving groups. The catalytic activity of carbons was examined in a fixed bed reactor at 150 °C in a gas flow containing NO, O₂, N₂ and NH₃, the effluent concentration being monitored continuously during the reaction. The obtained results indicate that an appropriate balance between the type of oxygen functional groups and surface area available to the reactant gas are required to reach high levels of NO conversion.     

Impacts of acid gases on mercury oxidation across SCR catalyst

A series of bench-scale experiments were completed to evaluate acid gases of HCl, SO₂, and SO₃ on mercury oxidation across a commercial selective catalytic reduction (SCR) catalyst. The SCR catalyst was placed in a simulated flue gas stream containing O₂, CO₂, H₂O, NO, NO₂, and NH₃, and N₂. HCl, SO₂, and SO₃ were added to the gas stream either separately or in combination to investigate their interactions with mercury over the SCR catalyst. The compositions of the simulated flue gas represent a medium-sulfur and low- to medium-chlorine coal that could represent either bituminous or subbituminous. The experimental data indicated that 5–50 ppm HCl in flue gas enhanced mercury oxidation within the SCR catalyst, possibly because of the reactive chlorine species formed through catalytic reactions. An addition of 5 ppm HCl in the simulated flue gas resulted in mercury oxidation of 45% across the SCR compared to only 4% mercury oxidation when 1 ppm HCl is in the flue gas. As HCl concentration increased to 50 ppm, 63% of Hg oxidation was reached. SO₂ and SO₃ showed a mitigating effect on mercury chlorination to some degree, depending on the concentrations of SO₂ and SO₃, by competing against HCl for SCR adsorption sites. High levels of acid gases of HCl (50 ppm), SO₂ (2000 ppm), and SO₃ (50 ppm) in the flue gas deteriorate mercury adsorption on the SCR catalyst.     

Removal of elemental mercury by activated carbon impregnated with CeO2

Mercury emission from coal-fired power plants becomes a great environmental concern due to its high toxicity and volatility in particularly for elemental mercury. Activated carbon adsorption is considered to be a potential technology to control elemental mercury emission. In this work, a novel CeO₂/AC (activated carbon impregnated with cerium dioxide) sorbent was studied with an attempt to produce economical and effective sorbent for capturing mercury. The influencing factors researched include loading values changing from 1 wt% to 10 wt% and adsorption temperature changing from 30 to 200 °C. Some physicochemical techniques such as BET and XRD were used to characterize the properties of the sorbents. The adsorption test results show that CeO₂ impregnation significantly enhanced the AC adsorption ability for elemental mercury. When the CeO₂ load was below 3%, Hg⁰ adsorption ability of ameliorated AC enhanced with the increase in the loading value, and then decreased at higher loading. The influence of temperature on the mercury removal efficiency was also studied, the trend of which was similar to the effect of loading value. The maximum removal efficiency was obtained at 100 °C.     

Electrochemical decomposition of CO2 and CO gases using porous yttria-stabilized zirconia cell

Electrochemical decomposition of CO₂ and CO gases using a porous cell of Ru-8 mol% yttria-stabilized zirconia (YSZ) anode/porous YSZ electrolyte/Ni–YSZ cathode system at 400–800 °C was studied by analyzing the flow rate and composition of outlet gas, current density, and phases and elementary distribution of the electrodes and electrolyte. A part of CO₂ gas supplied at 50 ml/min was decomposed to solid carbon and O₂ gas through the cell at the electric field strengths of 0.9–1.0 V/cm. The outlet gas at a flow rate of 3 ml/min included 61–63% CO₂ and 37–39% O₂ at 700–800 °C and the outlet gas at a flow rate of 50 ml/min included 73–96% (average 85%) CO₂ and 4–27% (average 15%) O₂ at 800 °C. On the other hand, the supplied CO gas was also decomposed to solid carbon, O₂ and CO₂ gases at 800 °C. The fraction of outlet gas at a flow rate of 50 ml/min during the CO decomposition at 800 °C for 5 h was 11–36% CO, 59–81% O₂ and 2–9% CO₂. The detailed decomposition mechanisms of CO₂ and CO gases are discussed. Both Ni metal in the cathode and porous YSZ grains under the DC electric field have the ability to decompose CO gas into solid carbon and O²⁻ ions or O₂ gas.     

α-Fe2O3 nano-platelets prepared by mechanochemical/thermal processing

A new method to prepare plate-shaped Fe₂O₃ nanoparticles was investigated and their magnetic properties were characterised. First, Fe₂O₃ nanoparticles of ~ 6 nm in diameter were synthesised by mechanochemical processing, involving the solid-state exchange reaction Fe₂(SO₄)₃ + 3 Na₂CO₃ → Fe₂(CO₃)₃ + 3 Na₂SO₄ → Fe₂O₃ + 3 Na₂SO₄ +  3 CO₂ (g) effected by high-energy ball milling and subsequent heat treatment at 400 °C. Next, nano-platelets were grown from the nanoparticles by further heat treatment in a salt matrix at 700 °C. Removal of the salt and by-product phases after heat treatment led to well-dispersed platy haematite particles of 20-200 nm in diameter with aspect ratio of 4-10. The hematite nano-platelets were weakly ferromagnetic with coercivity of ~ 160 Oe and remanent magnetisation of 0.2 emu/g.     

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.     

Flue gas desulphurization by activated carbon fibers obtained from polyacrylonitrile by-product

By pyrolysis of a polyacrylonitrile textile by-product, subsequent activation by CO₂ and treatment (at high temperature) with a N₂ flow containing a low percentage of O₂ or of NH₃, three carbonaceous matrices are obtained having a high surface area and surface sites with basic characteristics. The SO₂ sorption properties of these carbon samples (in the temperature range between 100 and 160 °C) from gaseous mixtures having a similar composition to flue gases, seems to be promoted by nitrogen bonded to carbon. The SO₂ adsorbed by the carbons can be divided, by suitable extraction with distilled water, into: (i) desorbable, such as SO₂ or H₂SO₃, (ii) desorbable, such as SO₃ or H₂SO₄, (iii) non-desorbable. Following 10 SO₂ adsorption and desorption cycles, the surface area values of the activated carbons remain practically constant, while both the content of the acidic surface sites and the amount of non-desorbable SO₂ increase; this results in the decrease in the SO₂ carbon sorption property seeming to be even more marked for the carbon sample containing nitrogen.     

Fate of the chlorine and fluorine in a sub-bituminous coal during pyrolysis and gasification

The fate of the chlorine and fluorine present in a sub-bituminous coal from Indonesia during pyrolysis and gasification has been studied with fixed and entrained bed reactors. The rate profile for HCl evolved in the temperature programmed pyrolysis exhibits the main and shoulder peaks at 480 and 600 °C, respectively. Model experiments and subsequent Cl 2p XPS measurements show that HCl reacts with metal impurities and carbon active sites at 500 °C to be retained as inorganic and organic chlorine forms, from which HCl evolves again at elevated temperatures. It is suggested that the HCl observed in the coal pyrolysis may originate from the above-mentioned chlorine functionalities formed by secondary reactions involving the nascent char. In the CO₂ gasification of the 900 °C char at 1000 °C and 2.5 MPa, any measurable amounts of HCl and HF could not be detected even at a high conversion of 75 wt% (daf), suggesting the accumulation of these halogens in the residual char. When the coal is injected into an O₂-blown, entrained bed gasifier at 1200-1400 °C under 2.6 MPa, the partial oxidation proceeds to a larger extent at a higher O₂/coal ratio, whereas the chlorine and fluorine are enriched in the remaining char, and the extent of the enrichment at the latter stage of gasification is larger with the fluorine. The XPS measurements of the chars reveal the presence of the broad F 1 s peak, which can cover a wide range of binding energies attributable to inorganic and organic fluorine. The halogen enrichment during gasification is discussed in terms of secondary reactions of HCl and HF with char.     

Overcoming the barrier to graphitization in a polymer-derived nanoporous carbon

A new pathway to synthesize a carbon with both nanoporosity and pre-graphitic structures has been discovered by annealing at 2000 °C a CO₂ activated, non-graphitizing, nanoporous carbon originally derived from polyfurfuryl alcohol. The activation process with CO₂ overcomes the barrier to graphitization normally present in this carbon even when treated at high temperature. Gas adsorption analysis, skeletal density measurements, X-ray diffraction, and transmission electron microscopy are utilized to probe the structure of both the non-activated and the activated carbons at 800, 1200, 1800, and 2000 °C. The influence of activation time is also examined. Prior to activation the nanopore walls are comprised of several layers of disordered graphenes. Activation eliminates the barrier to graphitization by reducing the number of layers below the limit of detection and by removing carbon material highly susceptible to oxidation. Annealing at 2000 °C of the carbon activated to 84% burnoff induces the formation of pre-graphitic domains amongst the nanoporous carbon. The (0 0 2) bands corresponding to 2θ = 24.3°, 26°, and 26.5° are identified and assigned to amorphous, turbostratic, and graphitic morphologies. A pore volume of 0.50 cm³ g⁻¹ localized in pores below 2 nm in size is preserved after annealing.     

Modified activated carbons for catalytic wet air oxidation of phenol

This study aims at testing several activated carbons for the catalytic wet air oxidation (CWAO) of phenol solutions. Two commercial activated carbons were used both as received and modified by treatment with either HNO₃, (NH₄)₂S₂O₈, or H₂O₂ and by demineralisation with HCl. The activated carbons were characterised by measuring their surface area, distribution of surface functional groups and phenol adsorption capacity. The parent and treated activated carbons were then checked for CWAO using a trickle bed at 140 °C and 2 bar of oxygen partial pressure. The treatments increase the acidic sites, mostly creating lactones and carboxyls though some phenolic and carbonyl groups were also generated. Only (NH₄)₂S₂O₈ treatment yields a significant decrease in surface area. CWAO tests show that catalytic activity mainly depends on the origin of the activated carbon. The modifications generally had a low impact on phenol conversion, which correlates somewhat with the increase in the acidity of the carbons. Characterisation of the used activated carbon evidences that chemisorbed phenolic polymers formed through oxidative coupling and oxygen radicals play a major role in the CWAO over activated carbon.     

活性焦汞吸附特性及动力学机理分析

通过固态吸附剂汞吸附效能测定系统进行了太西活性焦吸附单质汞的实验,考察单质汞Hg⁰入口浓度和温度对太西活性焦脱汞性能的影响并探讨了吸附机理。结果表明:在CO₂/N₂/O₂/NO/Hg⁰体系中,不同Hg⁰入口浓度获得的汞脱除效率曲线相似,脱除效率随Hg⁰入口浓度增大而增加;变入口浓度工况下,汞的吸附全过程遵循准二级动力学反应模型,该吸附过程以化学吸附为主;在反应温度从403 K升高到423 K的过程中,系统发生了化学吸附或者化学反应,423 K可作为活性焦的最佳除汞温度;Bangham方程可对变温工况下活性焦脱除单质汞的吸附过程进行准确描述,并获得不同温度下活性焦脱汞的吸附速率常数存在k_423K>k_463K>k_403K的关系。