多层生物滤塔净化硫化氢废气研究

以木屑为填料,采用多层生物滤塔净化H2S气体,研究其适宜的工艺条件及生物降解宏观动力学.结果表明,填料分层可提高H2S去除率,当进气容积负荷＜153.2 g H2S/(m3·d)时,H2S的去除率保持在90%以上;进气浓度低于70 mg/m3,下层200mm填料对H2S总去除率的贡献在50%以上;填料含水率为50%～6...     

Long-term evaluation of activated carbon as an adsorbent for biogas desulfurization

ABSTRACT

In this study, granular activated carbon (GAC) was used as an adsorbent for biogas desulfurization. Biogas containing 932–2,350 ppm of H₂S was collected from an anaerobic digester to treat the wastewater from a dairy farm with about 200 cows. An adsorption test was performed by introducing the biogas to a column that was packed with approximately 50 L of commercial GAC. The operation ceased if the effluent gas had an H₂S concentration of over 100 ppm. The GAC was replaced by a given weight of new GAC in a subsequent test. According to the results, for H₂S concentrations in the range of 932–1,560 ppm (average±SD = 1,260 ± 256 ppm), 1 kg of the GAC yielded biogas treatment capacities of 568 ± 112 m³ and H₂S adsorption capacities of 979 ± 235 g. For the higher influent H₂S concentrations of 2,110 ± 219 ppm, the biogas treatment and H₂S-adsorption capacities decreased to 229 ± 18 m³ and 668 ± 47 g, respectively. An estimation indicated a requisite cost of US$16.5 for the purification of 1,000 m³ of biogas containing 2,110 ppm of H₂S. This cost is approximately 5% of US$330, the value of 1,000 m³ of biogas.     

Resource Recovery from Flue Gas Desulfurization Systems

The cost effective benefits of yielding a flue gas desulfurization (FGD) sludge predominantly composed of CaSO₄·2H₂O, have been previously established. The recovery of this material as FGD by-product gypsum has been demonstrated abroad. Recently U.S. wallboard manufacturers have recognized the viability of this recovery practice. Such techno-economic decision making variables as a) by-product specification, b) transportation costs, and c) location of suitable FGD systems enable the recognition of FGD by-product recovery. Recent investigations of resultant solids content and chloride washing reflect the technical possibility of delivering a suitable product. Commercial and economic factors favor recovery based upon rising disposal and transportation costs. Existing and near term proposed systems surface the technical and commercial problems faced by utilities considering recovery.

Generation of an oxidized FGD sludge consisting of 90⁺% CaSO₄·2H₂O and dewatered to 80⁺% solids is technically achievable by air sparging within the FGD system. Although the product is suitable for land disposal, electric power utilities should consider and evaluate by-product recovery. U.S. wallboard manufacturers have established technical criteria for FGD by-product gypsum. Percent CaSO₄·2H₂O, final solids content, particle size, and chloride content are primarily technical parameters. Technology exists within the FGD industry to satisfy these criteria and results are discussed.

Economic factors comparing mining costs, transportation costs, and disposal costs are developed for specific utility projects. Such comparison established generalized financial criteria for a given utility to develop the economic reasonableness of considering FGD byproduct recovery.

End product user perspectives are presented providing electric utilities with a realistic appreciation for by-product recovery potential. Location of existing wallboard plants highlight potential recovery regions. Quality control problems are discussed in terms of generating a by-product rather than a disposable material.     

Status and Problems of Regenerable Flue Gas Desulfurization Processes

Fourteen sulfur and/or sulfuric acid producing regenerate FGD processes were discussed at the 1974 FGD Symposium in Atlanta. During the period elapsed since then, considerable status change has occurred on many of these regenerable processes. Other regenerable processes which were not as well known during 1974 have surfaced in 1975. The problems of obtaining reducing gases (hydrogen sulfide, carbon monoxide, and hydrogen) for the reduction of sulfur dioxide product streams to elemental sulfur have become severe due to shortages of natural gas or other petroleum based feedstock. A new sulfur producing process which employs CO and H₂ directly (rather than the H₂S required for liquid and vapor base Claus reactions) is gaining attention. This paper discusses briefly: (1) the announced status of the many regenerable FGD processes, (2) the problem of reductant gas supply, and (3) the effect on FGD processes of using coal based reducing gas instead of reformed natural gas.     

The Effect of Coal Combustion Flue Gas Components on Low-Level Chlorine Speciation Using EPA Method 26A

ABSTRACT

U.S. Environmental Protection Agency (EPA) Method 26A is the recommended procedure for capturing and speci-ating halogen (X₂) and hydrogen halide (HX) stack emissions from combustion sources. Previous evaluation studies of Method 26A have focused primarily on hydrogen chloride (HCl) speciation. Capture efficiency, bias, and the potential interference of Cl₂ at high levels (>20 ppm [u,g/m³]) and NH₄Cl in the flue gas stream have been investigated. It has been suggested that precise Cl₂ measurement and accuracy in quantifying HX or X₂ using Method 26A are difficult to achieve at Cl₂ concentrations <5 ppm; however, no performance data exist to support this. Coal contains low levels of Cl, in the range of 5-2000 ppmw, which results in the presence of HCl and Cl₂ in the products of combustion. HCl is the predominant Cl compound formed in the high-temperature combustion process, and it persists in the gas as the products of combustion cool. Concentrations of Cl₂ in coal combustion flue gas at stack temperatures typically do not exceed 5 ppm. For this research, bench-scale experiments using simulated combustion flue gas were designed to validate the ability of Method 26A to speci-ate low levels of Cl₂ accurately. This paper presents the results of the bench-scale tests. The effect of various flue gas components is discussed. The results indicate that SO₂ is the only component in coal combustion flue gas that has an appreciable effect on Cl₂ distribution in Method 26A impingers, and that Method 26A cannot accurately speciate HCl and Cl₂ in coal combustion flue gas without modification.     

The Fate and Behavior of Mercury in Coal-Fired Power Plants

Abstract

For the past 22 years in the Netherlands, the behavior of Hg in coal-fired power plants has been studied extensively. Coal from all over the world is fired in Dutch power stations. First, the Hg concentrations in these coals were measured. Second, the fate of the Hg during combustion was established by performing mass balance studies. On average, 43 ± 30% of the Hg was present in the flue gases downstream of the electrostatic precipitator (ESP; dust collector). In individual cases, this figure can vary between 1 and 100%. Important parameters are the Cl content of the fuel and the flue gas temperature in the ESP. On average, 54 ± 24% of the gaseous Hg was removed in the wet flue-gas desulfurization (FGD) systems, which are present at all Dutch coal-power stations. In individual cases, this removal can vary between 8% (outlier) and 72%.

On average, the fate of Hg entering the power station in the coal was as follows: <1% in the bottom ash, 49% in the pulverized fuel ash (ash collected in the ESP), 16.6% in the FGD gypsum, 9% in the sludge of the wastewater treatment plant, 0.04% in the effluent of the wastewater treatment plant, 0.07% in fly dust (leaving the stack), and 25% as gaseous Hg in the flue gases and emitted into the air. The distribution of Hg over the streams leaving the FGD depends strongly on the installation. On average, 75% of the Hg was removed, and the final concentration of Hg in the emitted flue gases of the Dutch power stations was only ~3 μg/m_STP ³ at 6% O₂. During co-combustion with biomass, the removal of Hg was similar to that during 100% coal firing.

Speciation of Hg is a very important factor. An oxidized form (HgCl₂) favors a high degree of removal. The conversion from Hg⁰ to HgCl₂ is positively correlated with the Cl content of the fuel. A catalytic DENOX (SCR) favors the formation of oxidized Hg, and, in combination with a wet FGD, the total removal can be as high as 90%.     

Application of the Active Soda Process for Removing Sulphur Dioxide from Flue Gases

The active soda process1 was applied for desulfurlzatlon of flue gases emitted by a plant burning heavy fuel oil In a rotary drum drier for stone aggregate. The flue gas capacity of the plant was about 6,7 m³/s at normal conditions. The SO₂ concentration varied between 400– 500 ppm. The solid, dry and fine-grained NaHCO₃ of good quality was fed directly into the hot gas stream at the outlet of the rotary drier In two variants—with and without grinding. The mean particle size was 0.180 m^-3 or 0.070 m^-3, respectively. The achieved desulfurizatlon degree was shown to be directly dependent on the flue gas temperature and on the grinding effect, as well as on the normalized stoichiometric ratio. The highest achieved desulfurization degree amounted up to 74 percent. During the design of the desulfurization process no pilot plant installations and tests were necessary, and for the final process no special chemical reactor was used.     

Improved Spray Dry Scrubbing through Grinding of FGD Recycle Material

A laboratory size spray dry scrubbing unit consisting of a spray dryer and a pulse Jet baghouse was used to study the effect of grinding recycle waste on SO₂ removal across the spray dryer and on sorbent utilization. The equipment treats simulated flue gas with a dry flow rate of 1.5 m³ h^?1 (stp) and utilizes an ultrasonic nozzle for atomization. The apparatus was initially tested over a broad range of operating conditions; a close agreement in SO₂ removal was found with data from much larger units. The effect of grinding the FGD recycle material on the SO₂ removal across the spray dryer was found to be great. Grinding the recycle material can enhance the SO₂ removal efficiency to a level comparable to operation with a large excess of fresh lime.     

Simulation of Stack Plume Opacity

ABSTRACT

The visual impact of primary particles emitted from stacks is regulated according to stack opacity criteria. In-stack monitoring of the flue gas opacity allows plant operators to ensure that the plant meets U.S. Environmental Protection Agency opacity regulations. However, the emission of condensable gases such as SO₃ (that hydrolyzes to H₂SO₄), HCl, and NH₃, which may lead to particle formation after their release from the stack, makes the prediction of stack plume opacity more difficult.

We present here a computer simulation model that calculates the opacity due to both primary particles emitted from the stack and secondary particles formed in the atmosphere after the release of condensable gases from the stack. A comprehensive treatment of the plume rise due to buoyancy and momentum is used to calculate the location at which the condensed water plume has evaporated (i.e., where opacity regulations apply).

Conversion of H₂SO₄ to particulate sulfate occurs through nucleation and condensation on primary particles. A thermodynamic aerosol equilibrium model is used to calculate the amount of ammonium, chloride, and water present in the particulate phase with the condensed sulfate. The model calculates the stack plume opacity due to both primary and secondary particles. Examples of model simulations are presented for three scenarios that differ by the emission control equipment installed at the power plant: (1) electrostatic precipitators (ESP), (2) ESP and flue gas desulfurization, and (3) ESP and selective catalytic reduction. The calculated opacity is most sensitive to the primary particulate emissions. For the conditions considered here, SO₃ emissions showed only a small effect, except if one assumes that most H₂SO₄ condenses on primary particles. Condensation of NH₄Cl occurs only at high NH₃ emission rates (about 25 ppm stack concentration).     

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.     

Simultaneous removal of NOx,SO2, and Hg from flue gas in FGD absorber with oxidant injection (NaClO2)– full-scale investigation

ABSTRACT

This article presents the results of an industrial-scale study (on 400 MW_e lignite fired unit) of simultaneous NO_x, SO₂, and Hg^T removal in FGD absorber with oxidant injection (NaClO₂) into flue gas. It was confirmed that the injection of sodium chlorite upstream the FGD (Flue Gas Desulfurization) absorber oxidize NO to NO₂, Hg⁰ to Hg²⁺, and enhancing NO_x and Hg^T removal efficiency from exhaust gas in FGD absorber. Mercury removal efficiency grows with the rise of degree of oxidation NO to NO₂ and was limited by the phenomenon of re-emission. For NO_x removal the most critical parameters is slurry pH and temperature. There was no negative effect on sulfur dioxide removal efficiency caused by oxidant injection in tested FGD absorber. Based on the data provided, NO_x and Hg^T emissions can be reduced by adjusting the FGD absorber operating parameters combined with oxidant injection.     

An Analysis of Extinction Coefficients of Particles and Water Moisture in the Stack after Flue Gas Desulfurization at a Coal-Fired Power Plant

ABSTRACT

Two important factors that affect in-stack opacity—light extinction by emitted particles and that by water moisture after a flue gas desulfurization (FGD) unit—are investigated. The mass light extinction coefficients for particles and water moisture, k _p and k _w, respectively, were determined using the Lambert-Beer law of opacity with a nonlinear least-squares regression method. The estimated k _p and k _w values vary from 0.199 to 0.316 m²/g and 0.000345 to 0.000426 m²/g, respectively, and the overall mean estimated values are 0.229 and 0.000397 m²/g, respectively. Although k _w is 3 orders of magnitude smaller than k _p, experimental results show that the effect on light extinction by water moisture was comparable to that by particles because of the existence of a considerable mass of water moisture after a FGD unit. The mass light extinction coefficient was also estimated using Mie theory with measured particle size distributions and a complex refractive index of 1.5-ni for fly ash particles. The k _p obtained using Mie theory ranges from 0.282 to 0.286 m²/g and is slightly greater than the averaged estimated k _p of 0.229 m²/g from measured opacity. The discrepancy may be partly due to a difference in the microstructure of the fly ash from the assumption of solid spheres because the fly ash may have been formed as spheres attached with smaller particles or as hollow spheres that contained solid spheres. Previously reported values of measured k _p obtained without considering the effects of water moisture are greater than that obtained in this study, which is reasonable because it reflects the effect of extinction by water moisture in the flue gas. Additionally, the moisture absorbed by particulate matter, corresponding to the effect of water moisture on the particulates, was clarified and found to be negligible.

IMPLICATIONS In-stack opacity is used as a surrogate for particle concentration and can be measured using light transmission meters as part of a continuous emission monitoring system. Because emission standards have become increasingly strict, FGD with wet scrubbing is generally used for coal-fired power plants. However, after a FGD unit with wet scrubbing is set up, the concentration of water moisture increases, affecting the measured opacity. This study evaluates the contributions of particles and water moisture to opacity. The results should provide useful information and can be utilized for modifying measurements for monitoring particulate emissions using opacity.     

Asbestos: Rationale Behind A Proposed Air Quality Standard

A computerized simulation model has been developed to compute energy requirements of a limestone slurry flue gas desulfurization (FGD) system as a function of FGD system design parameters, power plant characteristics, coal properties, and sulfur dioxide emission regulation. Results are illustrated for a "base case" plant of 500 MW, burning 3.5% sulfur coal, meeting the federal new source performance standard of 1.2 lb SO₂/10⁶ Btu. The flue gas is cleaned by an electrostatic precipitator followed by a limestone FGD system with a TCA scrubbing vessel and an optimized in-line steam reheater. The total FGD system energy requirement for this case was found to be 3.4% of the total energy input to the boiler. Sensitivity analyses were then performed in which the nominal values of ten system parameters were individually varied. This caused the total FGD system energy requirement to vary between 2.5 % and 6.1 % of the gross plant output for the range of parameters tested. The most sensitive parameters were found to be scrubbing slurry pH, which affects pumping requirements, and stack gas exit temperature, which affects reheat requirements. In all cases, FGD energy requirements were minimized when the SO₂ emission standard was met by partially bypassing the scrubber. In light of the recent Clean Air Act Amendments this option may not be feasible in the future.     

Technical Description of Parameters Influencing the pH Value of Suspension Absorbent Used in Flue Gas Desulfurization Systems

Abstract

As a result of the large limestone deposits available in Poland, the low cost of reagent acquisition for the large-scale technological use and relatively well-documented processes of flue gas desulfurization (FGD) technologies based on limestone sorbent slurry, wet scrubbing desulfurization is a method of choice in Poland for flue gas treatment in energy production facilities, including power plants and industrial systems. The efficiency of FGD using the above method depends on several technological and kinetic parameters, particularly on the pH value of the sorbent (i.e., ground limestone suspended in water). Consequently, many studies in Poland and abroad address the impact of various parameters on the pH value of the sorbent suspension, such as the average diameter of sorbent particles (related to the limestone pulverization degree), sorbent quality (in terms of pure calcium carbonate [CaCO₃] content of the sorbent material), stoichiometric surfeit of CaCO₃ in relation to sulfur dioxide (SO₂) absorbed from flue gas circulating in the absorption node, time of absorption slurry retention in the absorber tank, chlorine ion concentration in sorbent slurry, and concentration of dissolved metal salts (Na, K, Mg, Fe, Al, and others). This study discusses the results of laboratory-scale tests conducted to establish the effect of the above parameters on the pH value of limestone slurry circulating in the SO₂ absorption node. On the basis of the test results, a correlation equation was postulated to help maintain the desirable pH value at the design phase of the wet FGD process. The postulated equation displays good coincidence between calculated pH values and those obtained using laboratory measurements.     

Improvement of Air Quality in a Small Indoor Ice Arena by Effective Emission Control in Ice Resurfacers

ABSTRACT

The effectiveness of a new emission control system in the ice resurfacer was tested in an exhaust gas emission laboratory, and the improvement of the air quality in a small, enclosed ice arena was demonstrated in a 4.5-month follow-up study. The emission control system consisted of a lambda sensor-controlled fuel supply and a three-way metallic catalyst that were applied to a propane-fueled resurfacer. In the laboratory tests, the engine emissions of carbon monoxide (CO), hydrocarbons (HC), and nitrogen oxides (NO ) reduced simultaneously by 91, 90, and 96%, respectively. During the air quality follow-up the median 1-hour average nitrogen dioxide (N0₂) concentration inside the ice arena decreased from 430 ug/m³ (230ppb) to 58 ug/m³ (31 ppb), and that of CO decreased from 4.4 mg/m³ (3.8 ppm) to 1.5 mg/m³ (1.3 ppm). The new emission control system proved to be a feasible, reliable, and effective means to improve the indoor air quality in the ice arena. However, continuous mechanical ventilation was necessary during all business hours in order to achieve and maintain a fully acceptable air quality with this technology.     

Performance of an Innovative Two-Stage Process Converting Food Waste to Hydrogen and Methane

Abstract

This study was conducted to evaluate the performance of an innovative two-stage process, BIOCELL, that was developed to produce hydrogen (H₂) and methane (CH₄) from food waste on the basis of phase separation, reactor rotation mode, and sequential batch technique. The BIOCELL process consisted of four leaching-bed reactors for H₂ recovery and post-treatment and a UASB reactor for CH₄ recovery. The leaching-bed reactors were operated in a rotation mode with a 2-day interval between degradation stages. The sequential batch technique was useful to optimize environmental conditions during H₂ fermentation. The BIOCELL process demonstrated that, at the high volatile solids (VS) loading rate of 11.9 kg/m³-day, it could remove 72.5% of VS and convert VS_removed to H₂ (28.2%) and CH₄ (69.9%) on a chemical oxygen demand (COD) basis in 8 days. H₂ gas production rate was 3.63 m³/m³ ·day, while CH₄ gas production rate was 1.75 m³/m³ ·day. The yield values of H₂ and CH₄ were 0.31 and 0.21 m³/kg VS_added, respectively. Moreover, the output from the post-treatment could be used as a soil amendment. The BIOCELL process proved to be stable, reliable, and effective in resource recovery as well as waste stabilization.     

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.     

Performance of a Semi-Industrial Scale Gasification Process for the Destruction of Polychlorinated Biphenyls

Abstract

A semi-industrial scale test was conducted to thermally treat mixtures of spent oil and askarels at a concentration of 50,000 ppm and 100,000 ppm of polychlorinated biphenyls (PCBs) under a reductive atmosphere. In average, the dry-basis composition of the synthesis gas (syngas) obtained from the gasification process was: hydrogen 46%, CO 34%, CO₂ 18%, and CH₄ 0.8%. PCBs, polychlorinated dibenzo-p-dioxins, and polychlorinated dibenzofurans (PCDDs/PCDFs) in the gas stream were analyzed by high-resolution gas chromatography (GC)-mass spec-trometry. The coplanar PCBs congeners 77, 105, 118, 156/157, and 167 were detected in the syngas at concentrations <2 ×10^?7 mg/m³ (at 298 K, 1 atm, dry basis, 7% O₂). The chlorine released in the destruction of the PCBs was transformed to hydrogen chloride and separated from the gas by an alkaline wet scrubber. The concentration of PCBs in the water leaving the scrubber was below the detection limit of 0.002 mg/L, whereas the destruction and removal efficiency was >99.9999% for both tests conducted. The concentration of PCDDs/PCDFs in the syngas were 8.1 ×10^?6 ng-toxic equivalent (TEQ)/m³ and 7.1 × 10^?6 ng-TEQ/m³ (at 298 K, 1 atm, dry basis, 7% O₂) for the tests at 50,000 ppm and 100,000 ppm PCBs, respectively. The only PCDD/F congener detected in the gas was the octachloro-dibenzo-p-dioxin, which has a toxic equivalent factor of 0.001. The results obtained for other pollutants (e.g., metals and particulate matter) meet the maximum allowed emission limits according to Mexican, U.S., and European regulations for the thermal treatment of hazardous waste (excluding CO, which is a major component of the syngas, and total hydrocarbons, which mainly represent the presence of CH₄).     

Study on the removal of elemental mercury from simulated flue gas by Fe<Subscript>2</Subscript>O<Subscript>3</Subscript>-CeO<Subscript>2</Subscript>/AC at low temperature

Fe₂O₃ and CeO₂ modified activated coke (AC) synthesized by the equivalent-volume impregnation were employed to remove elemental mercury (Hg⁰) from simulated flue gas at a low temperature. Effects of the mass ratio of Fe₂O₃ and CeO₂, reaction temperature, and individual flue gas components including O₂, NO, SO₂, and H₂O (g) on Hg⁰ removal efficiency of impregnated AC were investigated. The samples were characterized by Brunauer–Emmett–Teller (BET), X-ray diffraction (XRD), scanning electron microscopy (SEM), and X-ray photoelectron spectroscopy (XPS). Results showed that with optimal mass percentage of 3 % Fe₂O₃ and 3 % CeO₂ on Fe3Ce3/AC, the Hg⁰ removal efficiency could reach an average of 88.29 % at 110 °C. Besides, it was observed that O₂ and NO exhibited a promotional effect on Hg⁰ removal, H₂O (g) exerted a suppressive effect, and SO₂ showed an insignificant inhibition without O₂ to some extent. The analysis of XPS indicated that the main species of mercury on used Fe3Ce3/AC was HgO, which implied that adsorption and catalytic oxidation were both included in Hg⁰ removal. Furthermore, the lattice oxygen, chemisorbed oxygen, and/or weakly bonded oxygen species made a contribution to Hg⁰ oxidation.