Effect of Refractory on the Thermal Stability of SF6

The thermal decomposition of SF₆ is known to be oxygen-independent. Nevertheless, because of its high stability, the use of SF6 as a "conservative" surrogate in incinerator performance evaluation has been advocated and researched. This paper shows that refractory decreases markedly the stability of SF₆. The resulting increase in SF₆ decomposition was from 0 percent to 95 percent at 900°C, and the temperatures at which 90-99 percent decomposition occurred were lowered by 300-150°C. Refractory also decreased the stability of CCl₄ and C₂Cl₄, but to a lesser extent. The difference between the decompositions of C₂Cl₄ and SF₆ was reduced from several orders of magnitude to a factor of 2-4. Such a drastic and adverse change in relative stability could render SF₆ unsuitable as a "conservative" surrogate. The requirements for a "conservative" surrogate and the need for caution in its use are discussed, and further research areas are indicated.     

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.     

A Study of Primary Sulfate Emissions From a Coal-Fired Boiler with FGD

A study was carried out to investigate the emissions of SO₂ and primary sulfate materials (H₂SO₄ and inorganic particulate matter) from a boiler burning fossil fuel and using a wet-limestone scrubber for SO₂ removal. Experiments were designed to assess the scrubbing efficiency for SO₂ and sulfate, as well as the potential for scrubber liquor reentrainment. The boiler studied was an 820 MW cyclone-fired unit equipped with a wet, limestone scrubber, consisting of eight two-stage venturi-absorber modules designed to treat a flue gas flow rate of 2,760,000 acfm. The boiler fuel was a low-grade sub-bituminous coal with ash and sulfur contents of 25 and 5%, respectively. Multiple-sampling methods were employed concurrently on the inlet and outlet of a candidate absorber module to measure SO₂, total water-soluble sulfate, and free H₂SO₄. Samples were collected during three field experiments from September 1977 through April 1978. The average SO₂ scrubbing efficiency was 76% and was observed to decrease over the 5 day operation/maintenance cycle of the module. The total water-soluble sulfate input to the scrubber amounted to approximately 1% of the total sulfur oxides and was composed of a 5:1 ratio of H₂SO₄ to particulate sulfate. The total sulfate scrubbing efficiency, averaging about 29%, was invariant with respect to SO₂ removal. The sulfate emissions measured in the scrubber exit gas consisted of about 85 % H₂SO₄ as a fine aerosol. Mass emissions of acid and particulate sulfate were calculated as 1730 Ib/hr and 305 Ib/hr, respectively.     

Predicting Cutoff Aerodynamic Diameter and Sharpness of Single Round-Nozzle Impactors with a Finite Impaction Plate Diameter

Abstract

This investigation numerically examined the cutoff aerodynamic diameter (da₅₀) and the sharpness (GSD) of the particle collection efficiency curve of impactors with a finite impaction plate diameter. Results revealed that the inertial impactors have a limited cutoff aerodynamic diameter at different air velocities. The extreme value of the cutoff aerodynamic diameter increases with the nozzle diameter (W)/the plate diameter (D_c). The computed da₅₀/D_c values of the impactors increase with W/D_c at various Reynolds numbers (Re) and with the nozzle-toplate distance (S)/D_c when Re is 100. The value of GSD slightly increases with W/D_c for Re of 10 and 100, although the effect of S/D_c on GSD is not evident at various Res. The particle collection efficiency curve of the impactor with a lower Re is less sharp than that with a high Re at various W/D_c and S/D_c values. Statistical equations closely fitted the obtained numerical results for Res of 10–3000. The equations are useful for directly calculating the cutoff aerodynamic diameter and the sharpness of the particle collection efficiency curve for single round-nozzle impactors with a finite impaction D_c.     

Characterization of Fugitive Material within a Primary Lead Smelter

ABSTRACT

The primary production of Pb via the sinter plant-blast furnace method resulted in a large number of Pb and other phases, reflecting the complex reactions occurring within each of the processes. Optical microscopy and X-ray diffraction (XRD) techniques have been used to characterize fugitive emissions and dusts generated during sintering, smelting, Cu drossing, refining, and slag fuming at a primary Pb-Zn smelter. The results displayed a complex array of phases, with the mineralogy of the dusts and fume reflecting conditions of the particular metallurgical operation. The principal Pb species followed a transformation from PbS through PbSO₄ and PbO to Pb° (metal) from raw materials to the refinery. The fugitive emissions generated by the blast furnace were of a finer size with more complex chemistry than fugitive material from other source areas. XRD identified a mixture of PbS, ZnO, and ZnS, associated with one or more of the Cl-bearing phases Pb(OH)Cl, PbCl₂, Pb₄O₃Cl₂, Na₃Pb₂(SO₄)₃Cl, Pb₁₀(SO₄)Cl₂O₈, Pb₄SCl₆, and Pb₇S₂Cl₁₀. The presence of Cl-bearing phases in the fume has possible health implications.     

Decomposition of SF6 in an RF Plasma Environment

Abstract

Sulfur hexafluoride (SF₆)-contained gas is a common pollutant emitted during the etching process used in the semiconductor industry. This study demonstrated the application of radio-frequency (RF) plasma in the decomposition of SF₆. The decomposition fraction of SF₆ [η_SF6 (C_in–C_out)/C_in x 100%] and the mole fraction profile of the products were investigated as functions of input power and feed O₂/SF₆ ratio in an SiO₂ reactor. The species detected in both SF₆/Ar and SF₆/O₂/Ar RF plasmas were SiF₄, SO₂, F₂, SO₂F₂, SOF₂, SOF₄, S₂F₁₀, S₂OF₁₀, S₂O₂F₁₀, and SF₄. The results revealed that at 40 W, η_SF6 exceeded 99%, and the reaction products were almost all converted into stable compounds such as SiF₄, SO₂, and F₂ with or without the addition of oxygen. Sulfur oxyfluorides such as SO₂F₂, SOF₂, SOF₄, S₂OF₁₀, and S₂O₂F₁₀ were produced only below 40 W. The results of this work can be used to design a plasma/chemical system for online use in a series of a manufacturing process to treat SF₆-containing exhaust gases.     

Synthetic SO2 Sorbents for Fluidized-Bed Coal Combustors

The information presented in this paper is directed to engineers who are involved with environmental emissions from coal conversion plants. Synthetic sorbents were investigated as an alternative to natural sorbents (limestone) for the removal of SO₂ from the combustion gas in a fluidized-bed coal combustor. The sulfation rate of a synthetic sorbent, CaO in α-AI₂O₃, was determined as a function of gas composition, temperature, and calcium concentration in the sorbent. The reaction was found to be diffusion-controlled above 850°C and kinetically controlled at lower temperatures. The physical characteristics of the support material have a major effect oh the sulfation kinetics. Porosity measurements indicated that supports containing large pores (>0.2 µm) produced sorbents having high sulfation rates and that pores with diameters less than 0.2 µm did not contribute significantly to the capture of SO₂. The sorbents SrO in α-AI₂O₃ and BaO in α-AI₂O₃ had lower SO₂ capture rates than did CaO in α-AI₂O₃. The alkali metal oxide sorbents K₂O and Na₂O in α-AI₂O₃ captured SO₂ much faster than did the alkaline earth metal oxides.     

Technique for Measuring the Total Concentration of Gaseous Fixed Nitrogen Species

This paper reports the development of a rapid, continuous technique for analyzing fixed nitrogen species (NH₃, HCN, CH₃NH₂, etc.). The technique uses a platinum catalyst at low pressure in combination with a conventional chemiluminescent NO _x analyzer. Previous workers observed that conventional stainless steel catalysts, and platinum catalysts operated at atmospheric pressure, do not reliably convert NH₃ to NO. The most serious problem was the variation in the efficiency of these catalysts with operating conditions. Changes in temperature, gas composition, or X_NH3 could change the conversion efficiency from 99.9% to <30%. The new conversion technique, however, is quantitative up to several thousand ppm NH₃ in either O₂/He or O₂/CO₂/N₂.     

Fe_3O_4@SiO_2/TiO_2核壳结构纳米颗粒降解TNT溶液

针对TNT炸药废水具有成分复杂、排放量大、有毒等特点,立足于炸药废水在排放前的降解处理,研究开发一种基于核壳结构Fe3O4@SiO2/TiO2纳米颗粒的高效、可控回收、无二次污染且成本低的光催化降解方法。利用高温碳还原法和溶胶凝胶法制备了具有核壳结构的Fe3O4@SiO2/TiO2纳米颗粒。XRD分析表明,内核Fe3O4呈现磁铁矿特征,表面覆盖的纳米TiO2为锐钛矿型。磁滞回线测试结果显示,复合颗粒的饱和磁化强度为46.5 emu/g,N2吸附-解吸分析结果表明,该颗粒具有典型的介孔结构。使用Fe3O4@SiO2/TiO2纳米颗粒在紫外光下对含TNT废水进行降解,降解率达到81.9%,且颗粒的回收率达到88.4%,为实现高效、可控回收、无二次污染光催化-吸附降解TNT奠定了基础。     

An evaluation of artifact SO42− formation on nylon filters under field conditions

The extent of SO₂ conversion on Membrana (Ghia) Nylasorb nylon filters under field conditions has been evaluated and found to be quite variable. The S-SO₄²⁻ loading on the nylon filters is higher at higher SO₂ concentrations, and on a long term basis approaches a saturatio limit of 2.5 μg S-SO₄²⁻ on a 47mm disc, at a dosage of 230 μg SO₂ approximately. The % conversion decreases as the SO₂ concentration increases. On a long term basis, at an SO₂ concentration range of 1.0–7.7 μg m⁻³, the conversion ranges from 8.2% to 2.1%. The dependence of SO₂ conversion on nylon filters on relative humidity displays a diurnal pattern. An expression has been derived to explain the observed % SO₂ conversion on nylon filters as a combined effect of the ambient SO₂ concentration and relative humidity.     

Laboratory and field measurements of NOx produced from corona discharge

This research consists of a laboratory study and a field study. The laboratory research reports the formation of NO_x from a point to plane corona discharge. Discharge polarity and relative humidity determined the amount of NO_x that was produced. The positive point discharge caused more NO_x to form than the negative point discharge. For both polarities NO_x production showed a nonlinear increase with current. Relative humidity enhanced the NO_x formation for both polarities. In each case, the amount of NO_x formed was comparable to the quantity of N₂O produced from corona discharge. The research also reports the results from a field study that measured the amounts of 03 and NO₂ produced by corona discharge during a thunderstorm. The study found that the ambient concentrations of 03 and NO₂ increased several fold due to corona discharge and returned to original levels after the thunderstorm.     

Recovering CO2 From Large− and Medium-Size Stationary Combustors

This paper summarizes the results of research conducted at Ar-gonne National Laboratory (ANL) to develop and design a novel method for the recovery of CO₂ from flue gases. The basic process concept Involves the combustion of a hydrocarbon fuel using a mixture of oxygen and carbon dioxide (or CO₂ and H₂0) rather than air as the oxidant, which results In a product stream that contains primarily CO₂ and H₂O. This stream Is then dried and conditioned to meet the specifications of the end user, A slip stream of CO₂ (or CO₂, and H₂0) is used as a diluent in the combustion chamberto maintain a flame temperature equivalent to the temperature that would otherwise be obtained using air as an oxidant. The cost-effectiveness of the process in recovering C0₂ is dependent on the scale of the operation, the type of fuel used, the cost of oxygen, and the cost of capital. The sensitivity of the cost of the recovered C0₂ to these variables Is discussed, and a model for estimating the cost of CO₂ recovered using the ANL process Is presented.     

Influence of operational key parameters on the photocatalytic decolorization of Rhodamine B dye using Fe2+/H2O2/Nb2O5/UV system

The present research deals with the development of a new heterogeneous photocatalysis and Fenton hybrid system for the removal of color from textile dyeing wastewater as Rhodamine B (RhB) solutions by using Fe²⁺/H₂O₂/Nb₂O₅ as a photocatalytic system. The application of this photocatalytic system for the decolorization of dye contaminants is not reported in the literature yet. Different parameters like dye concentration, Nb₂O₅/Fe²⁺ catalyst amount, pH, and H₂O₂ concentration have been studied. The optimum conditions for the decolorization of the dye were initial concentration of 10 mg L^?1 of dye, pH 4, and Nb₂O₅/Fe²⁺ catalyst concentration of 0.5 g L^?1/50 mg L^?1. The optimum value of H₂O₂ concentration for the conditions used in this study was 700 mg L^?1. Moreover, the efficiency of the Nb₂O₅/photo-Fenton hybrid process in comparison to photo-Fenton alone and a dark Fenton process as a control experiment to decolorize the RhB solution has been investigated. The combination of photo-Fenton and Nb₂O₅ catalysts has been proved to be the most effective for the treatment of such type of wastewaters. The results revealed that the RhB dye was decolorized in a higher percent (78 %) by the Nb₂O₅/photo-Fenton hybrid process (Fe²⁺/H₂O₂/Nb₂O₅/UV) than by the photo-Fenton process alone (37 %) and dark Fenton process (14 %) after 120 min of treatment. Moreover, the Nb₂O₅ catalyst as a heterogeneous part of the photocatalytic system was demonstrated to have good stability and reusability.     

Facile synthesis of magnetic ZnFe2O4–reduced graphene oxide hybrid and its photo-Fenton-like behavior under visible iradiation

A magnetic ZnFe₂O₄–reduced graphene oxide (rGO) hybrid was successfully developed as a heterogeneous catalyst for photo-Fenton-like decolorization of various dyes using peroxymonosulfate (PMS) as an oxidant under visible light irradiation. Through an in situ chemical deposition and reduction, ZnFe₂O₄ nanoparticles (NPs) with an average size of 23.7 nm were anchored uniformly on rGO sheets to form a ZnFe₂O₄–rGO hybrid. The catalytic activities in oxidative decomposition of organic dyes were evaluated. The reaction kinetics, effect of ion species and strength, catalytic stability, degradation mechanism, as well as the roles of ZnFe₂O₄ and graphene were also studied. ZnFe₂O₄–rGO showed to be a promising photocatalyst with magnetism for the oxidative degradation of aqueous organic pollutants and simple separation. The combination of ZnFe₂O₄ NPs with graphene sheets leads to a much higher catalytic activity than pure ZnFe₂O₄. Graphene acted as not only a support and stabilizer for ZnFe₂O₄ to prevent them from aggregation, largely improving the charge separation in the hybrid material, but also a catalyst for activating PMS to produce sulfate radicals at the same time. The ZnFe₂O₄–rGO hybrid exhibited stable performance without losing activity after five successive runs.     

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.     

铜铈掺杂六铝酸盐的脱硝性能

用共沉淀法制备用于脱除NO的六铝酸盐催化剂LaMxAl12-xO19(M =Cu,Ce,CuCe).用XRD、H2-TPR和BET对催化剂进行了结构和物性表征.用微型催化反应装置考察了催化剂在CO选择性催化还原NO中的活性.结果表明,Cu离子易于进入六铝酸盐晶格内,形成完整的六铝酸盐结构.Ce离子不易于进入六铝酸盐晶格内,主要以CeO2的形式存在.在CO+ NO条件下,3种催化剂都表现出较好的脱硝活性,LaCuCeAl10O19中由于Cu离子与Ce离子间产生协同作用,该催化剂的脱硝活性有所增加.加入SO2后,3种催化剂都有不同程度的失活现象发生,其中LaCuAl11O19催化剂受SO2中毒影响最严重,LaCuCeAl10O19催化剂的脱硝活性在三者中最好.     

A Combined Ca(OH)2/NH3 Flue Gas Desulfurization Process for High Sulfur Coal: Results of a Pilot Plant Study

The removal of SO₂ with atomization of a slaked lime slurry and supplemental injection of gaseous NH₃ were tested in a conventional spray dryer/baghouse system for SO₂ concentrations of 2000 ppm and 3000 ppm and a 30° F approach to saturation. Results at 3000 ppm of SO₂ showed an average SO₂ removal efficiency of 90.3 percent at a combined stoichiometric ratio of 0.95-1.10 and an average overall sorbent utilization of 91.6 percent. The overall molal ratio of NH₃/SO₂ reaction was found to be 2:1 under the test conditions Particle size analyses, and EP toxicity tests were conducted on the products of the reactions.     

Continuous Infrared Analysis of N2O in Combustion Products

Nitrous oxide (N₂O) levels in the atmosphere are increasing, potentially contributing to the greenhouse effect and depletion of stratospheric ozone. From a limited data base, combustion sources have been identified as a major anthropogenic source of N₂O. However, the existing data base (obtained by traditional grab sampling techniques followed by gas chromatographic analysis) is in question due to the discovery of a sampling artifact. A continuous on-line N₂O analyzer would enable and facilitate the accurate characterization of combustion sources over a range of operating conditions, and also aid in the development of an appropriate sampling technique. This paper addresses the development of a continuous measurement technique, and the evaluation and initial use of a field prototype continuous N₂O analyzer developed at the UCI Combustion Laboratory in cooperation with a major instrument manufacturer. The analyzer is capable of measuring N₂O levels down to a few ppm. The analyzer has been evaluated and used to study the N₂O emissions from a pulverized coal-fired boiler. The N₂O levels found with the analyzer are substantially lower than levels previously attributed to such sources. Initial N₂O measurements made with the analyzer suggest that N₂O levels are not a substantial fraction of the NO_X levels, as previously suggested.     

Photocatalytic degradation of acetaminophen in modified TiO2 under visible irradiation

This study investigated the photocatalytic degradation of acetaminophen (ACT) in synthetic titanium dioxide (TiO₂) solution under a visible light (λ >440 nm). The TiO₂ photocatalyst used in this study was synthesized via sol–gel method and doped with potassium aluminum sulfate (KAl(SO₄)₂) and sodium aluminate (NaAlO₂). The influence of some parameters on the degradation of acetaminophen was examined, such as initial pH, photocatalyst dosage, and initial ACT concentration. The optimal operational conditions were also determined. Results showed that synthetic TiO₂ catalysts presented mainly as anatase phase and no rutile phase was observed. The results of photocatalytic degradation showed that LED alone degraded negligible amount of ACT but with the presence of TiO₂/KAl(SO₄)₂, 95 % removal of 0.10-mM acetaminophen in 540-min irradiation time was achieved. The synthetic TiO₂/KAl(SO₄)₂ presented better photocatalytic degradation of acetaminophen than commercially available Degussa P-25. The weak crystallinity of synthesized TiO₂/NaAlO₂ photocatalyst showed low photocatalytic degradation than TiO₂/KAl(SO₄)₂. The optimal operational conditions were obtained in pH 6.9 with a dose of 1.0 g/L TiO₂/KAl(SO₄)₂ at 30 °C. Kinetic study illustrated that photocatalytic degradation of acetaminophen fits well in the pseudo-first order model. Competitive reactions from intermediates affected the degradation rate of ACT, and were more obvious as the initial ACT concentration increased.     

Foliar responses of five plant species to ozone and a sulphur dioxide/ozone mixture after a sulphur dioxide pre-exposure

Plants that were pretreated with 0.15 ppm SO₂ for either 2 or 3 d before an intermittent O₃ or SO₂/O₃ exposure exhibited differences in per cent visible foliar injury that often varied significantly from plants that received no SO₂ pretreatment. Differences that were observed could not be explained on the basis of leaf diffusive resistance alone. The SO₂ pretreatment for 2 d caused a decrease in visible O₃ injury in white bean, an increase in visible O₃ injury in cucumber and radish, and had no effect on soybean and tomato. The same pretreatment caused an increase in visible injury from the SO₂/O₃ mixture in white bean, a decrease in visible injury for cucumber and tomato, and had no effect on soybean and radish. However, these same trends did not occur when the SO₂ pretreatment was increased to 3 d. Pretreatment with sub-acute levels of SO₂ can significantly alter a plant's response to O₃ or a mixture of SO₂/O₃, the change in response being sensitive to the pretreatment SO₂ dosage. The nature of the visible injury symptoms from O₃ or the pollutant mixture were not altered for any of the plant species regardless of the length of time of the SO₂ pretreatment and, generally, the onset of visible injury was not greatly altered.