湿法脱硫中石灰石溶解特性的模型及实验研究

在石灰石-石膏湿法烟气脱硫中,石灰石的溶解影响到浆液吸收SO2的能力及吸收塔持浆池的大小.根据传质及化学离子平衡理论,建立了石灰石的溶解模型,并通过实验对模型进行了验证,结果表明,模拟结果与实验值基本一致,模型较好地反映出石灰石的溶解过程;在浆液pH较低的情况下,通过增强搅拌强度,可以明显提高石灰石的溶解速率,而在浆液...     

Characterization of metal adsorption kinetic properties in batch and fixed-bed reactors

Copper adsorption kinetic properties in batch and fixed-bed reactors were studied in this paper. The isothermal adsorption experiments showed that the copper adsorption capacity of a granular activated carbon (Filtrasorb 200) increased when ionic strength was higher. The presence of EDTA diminished the adsorption. An intraparticle diffusion model and a fixed-bed model were successfully used to describe the batch kinetic and fixed-bed operation behaviors. The kinetics became faster when the solution pH was not controlled, implying that the surface precipitation caused some metal uptake. The external mass transfer coefficient, the diffusivity and the dispersion coefficient were obtained from the modeling. It was found that both external mass transfer and dispersion coefficients increased when the flow rate was higher. Finally effects of kinetic parameters on simulation of fixed-bed operation were conducted.     

添加剂促进亚硫酸钙氧化的实验研究

在湿式石灰石-石膏法脱硫工艺中，副产物——亚硫酸钙的氧化是其中重要的化学过程。利用自行设计的实验室规模的反应装置，通过改变pH、亚硫酸钙浓度、空气流量、催化剂浓度和温度等条件，实验研究了多种添加剂对亚硫酸钙氧化的促进作用。实验结果可为湿法脱硫工艺的设计提供有益的参考。     

Solubilization, solution equilibria, and biodegradation of PAH's under thermophilic conditions

Biodegradation rates of PAHs are typically low at mesophilic conditions and it is believed that the kinetics of degradation is controlled by PAH solubility and mass transfer rates. Solubility tests were performed on phenanthrene, fluorene and fluoranthene at 20 degrees C, 40 degrees C and 60 degrees C and, as expected, a significant increase in the equilibrium solubility concentration and of the rate of dissolution of these polycyclic aromatic hydrocarbons (PAHs) was observed with increasing temperature. A first-order model was used to describe the PAH dissolution kinetics and the thermodynamic property changes associated with the dissolution process (enthalpy, entropy and Gibb's free energy of solution) were evaluated. Further, other relevant thermodynamic properties for these PAHs, including the activity coefficients at infinite dilution, Henry's law constants and octanol-water partition coefficients, were calculated in the temperature range 20-60 degrees C. In parallel with the dissolution studies, three thermophilic Geobacilli were isolated from compost that grew on phenanthrene at 60 degrees C and degraded the PAH more rapidly than other reported mesophiles. Our results show that while solubilization rates of PAHs are significantly enhanced at elevated temperatures, the biodegradation of PAHs under thermophilic conditions is likely mass transfer limited due to enhanced degradation rates.     

Egg mass and shell thickness in dippers Cinclus cinclus in relation to stream acidity in Wales and Scotland

The shell thickness and mass of eggs of the dipper (Cinclus cinclus) collected on streams of different pH in Wales and Scotland were measured. The aluminium, phosphorus and calcium content of their invertebrate prey were also measured. In a regression analysis, significant at p<0.05, stream pH accounted for up to 7% of the variance in shell thickness, with shells decreasing by 2.5% of the overall mean with each unit of pH decline. In the Welsh sample, differences in shell thickness due to pH were small compared with differences between years across all sites. In data pooled between Scotland and Wales, pH accounted for 17% of the variance in egg mass, but a greater proportion (25%) in Scottish eggs alone. Aluminium concentrations in invertebrates showed no relationship with stream pH, but calcium levels in two insect orders increased significantly with pH. Calcium rich prey, such as Gammarus, were found only in circumneutral streams. The importance of calcium in the diet of dippers before and during egg formation is discussed. No evidence that aluminium in prey adversely affected dipper eggs was found.     

Effect of acid rain on building material of the El Tajín archaeological zone in Veracruz, Mexico

Three limestone slabs (approx. 20 cm2 each) were extracted from the El Tajin archaeological zone in Veracruz, Mexico. X-ray diffraction analysis revealed three components: calcite (81.2%), quartz (17.9%) and feldspar (0.9%). Calcite content by x-ray diffraction analysis was slightly higher than that determined by chemical reaction between the limestone sample and nitric acid. The latter analysis, carried out in triplicate, yielded a calcite content of 77.1%. Mean water absorption, density and porosity of the limestone samples were also determined. Dissolution of limestone samples was investigated using an experimental rainfall simulation chamber, in which the stone samples were irrigated with artificial rain matching the pH and the ionic composition with 40 rainfall samples collected at El Tajin from August 18, 2002, to April 9, 2003. According to calcium and bicarbonate net concentrations found in the effluent of the chamber, a chemical mechanism by which limestone at El Tajin is dissolved by acid rain is proposed. A model used to investigate the air transport pathways corresponding to precipitation events at El Tajin shows that air parcels come mainly from the Gulf of Mexico, although no directional preference is evident for acidic vs. non-acidic events.     

Dissolution kinetics of sub-millimeter Composition B detonation residues: role of particle size and particle wetting

The dissolution of the 2,4,6-trinitrotoluene (TNT), hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX), and octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) from microscale particles (<250 μm) of the explosive formulation Composition B was examined and compared to dissolution from macroscopic particles (>0.5 mm). The dissolution of explosives from detonation soot was also examined. The measured mass transfer coefficients for the microscale particles were one to two orders of magnitude greater than the macroscopic particles. When normalized to particle surface area, mass transfer coefficients of microscale and macroscale particles were similar, indicating that the bulk dissolution processes were similar throughout the examined size range. However, an inverse relationship was observed between the particle diameter and the RDX:TNT mass transfer rate coefficient ratio for dry-attritted particles, which suggests that RDX may be more readily dissolved (relative to TNT) in microscale particles compared to macroscale particles. Aqueous weathering of larger Composition B residues generated particles that possessed mass transfer coefficients that were on the order of 5- to 20-fold higher than dry-attritted particles of all sizes, even when normalized to particle surface area. These aqueous weathered particles also possessed a fourfold lower absolute zeta-potential than dry-attritted particles, which is indicative that they were less hydrophobic (and hence, more wettable) than dry-attritted particles. The increased wettability of these particles provides a plausible explanation for the observed enhanced dissolution. The wetting history and the processes by which particles are produced (e.g., dry physical attrition vs. aqueous weathering) of Composition B residues should be considered when calculating mass transfer rates for fate and transport modeling.     

Consolidation of degraded ornamental porous limestone stone by calcium carbonate precipitation induced by the microbiota inhabiting the stone

Although it has already been shown that calcareous stone can be consolidated by using a bacterially inoculated culture medium, a more user-friendly method is the in situ application of a sterile culture medium that is able to activate, among the microbial community of the stone, those bacteria with a potential for calcium carbonate precipitation. In order to test this new method for stone consolidation, non-sterilized decayed porous limestone was immersed in sterile nutritional media. Results were compared to those of the runs in which stone sterilized prior to the treatment was used. The effects of the microbial community on stone consolidation were determined by recording the evolution of the culture media chemistry. The treated stone was tested for mechanical resistance and porosity. Results demonstrate that the tested media were able to activate bacteria from the microbial community of the stone. As a consequence of the growth of these bacteria, an alkalinization occurred that resulted in calcium carbonate precipitation. The new precipitate was compatible with the substrate and consolidated the stone without pore plugging. Therefore, a good candidate to in situ consolidate decayed porous limestone is the application of a sterile culture medium with the characteristics specified in the present study.     

Nonequilibrium sorption of phenols onto geosorbents: the impact of pH on intraparticle mass transfer

While the pH effect on sorption equilibrium of weak acids on natural sorbents was investigated in a number of studies, less is known about the pH dependence of sorption kinetics. This paper investigates the impact of pH on sorption kinetics during the transport of some selected phenols through a sandy aquifer material. Breakthrough curves measured in column experiments were analyzed using a mass transfer based nonequilibrium model designated as dispersed flow, film and particle diffusion model (DF-FPDM). In this model, the rate limiting intraparticle diffusion is characterized by the mass transfer coefficient, kSaV, which can be determined from breakthrough curves by curve fitting. The experimental results indicate that the kSaV is pH-dependent and inversely correlated with the pH-dependent distribution coefficient, K(d,app). Regression equations are presented that may be used to estimate approximate values of intraparticle mass transfer coefficients on the basis of experimentally determined or LFER predicted distribution coefficients.     

无机盐对SO2—H2O—CaCO3气液固三相反应系统pH值的影响

研究了硫酸钠、硝酸钠和氯化钠及相应钙盐对石灰石浆液烟气脱硫条件下ＳＯ２－Ｈ２Ｏ－ＣａＣＯ３气、液、固三相反应系统中ｐＨ值的影响。发现硫酸钠能明显提高系统的ｐＨ值，硝酸钠和氯化钠使ｐＨ值提高的幅度不大，而３种钙盐均使ｐＨ值降低。根据膜模型的分析结果，认为无机盐影响该反应系统ｐＨ值的主要原因是无机盐的加入改变了石灰石表面的ｐＨ值。     

Kinetic analysis of constructed systems for the recovery of contaminated areas by acid mine drainage

INTRODUCTION: Flowing of the acid mine drainage may contaminate the adjacent water bodies causing substantial changes in the aquatic ecosystem. This aspect is the most relevant problem in the southern of Santa Catarina once the contaminated areas are inserted in the watershed of the Araranguá, Urussanga, and Tubar?o rivers, increasing the need for recovery studies. These areas are between Criciúma, I?ara, Urussanga, Siderópolis, Lauro Müller, Orleans, and Alfredo Wagner towns where a conservation unit exist called the Environmental Preservation Area of Baleia Franca. Aiming to compare the kinetics of the ash derived from burning coal and to neutralize acid mine drainage, different neutralizer, limestone, fly, and bottom ash, was mounted on a pilot scale experiment. DISCUSSION: The transport parameters showed the same order of infiltration and dispersion: fly ash < bottom ash < limestone. The order of measured alkalinity was: limestone < fly ash < bottom ash, with pH values of 9.34, 12.07, and 12.25, respectively. The limestone kinetics of acidic drainage neutralization was first order with reaction rate constant k?=?0.0963 min(-1), bottom ash was 3/4 with k?=?0.0723 mol(1/4) L(-1/4) min(-1), and the fly ash had higher order kinetics, 4/3, with reaction rate constant k?=?27.122 L(1/3) mol(-1/3) min(-1). However, by mathematical modeling, it was found that due to a combination of transport and kinetics, only limestone treatment reached a pH above 6 within 5 years, corresponding to the ideal as planned.     

The significance of heterogeneity on mass flux from DNAPL source zones: an experimental investigation

Understanding the process of mass transfer from source zones of aquifers contaminated with organic chemicals in the form of dense non-aqueous phase liquids (DNAPL) is of importance in site management and remediation. A series of intermediate-scale tank experiments was conducted to examine the influence of aquifer heterogeneity on DNAPL mass transfer contributing to dissolved mass emission from source zone into groundwater under natural flow before and after remediation. A Tetrachloroethylene (PCE) spill was performed into six source zone models of increasing heterogeneity, and both the spatial distribution of the dissolution behavior and the net effluent mass flux were examined. Experimentally created initial PCE entrapment architecture resulting from the PCE migration was largely influenced by the coarser sand lenses and the PCE occupied between 30 and 60% of the model aquifer depth. The presence of DNAPL had no apparent effect on the bulk hydraulic conductivity of the porous media. Up to 71% of PCE mass in each of the tested source zone was removed during a series of surfactant flushes, with associated induced PCE mobilization responsible for increasing vertical DNAPL distributions. Effluent mass flux due to water dissolution was also found to increase progressively due to the increase in NAPL-water contact area even though the PCE mass was reduced. Doubling of local groundwater flow velocities showed negligible rate-limited effects at the scale of these experiments. Thus, mass transfer behavior was directly controlled by the morphology of DNAPL within each source zone. Effluent mass flux values were normalized by the up-gradient DNAPL distributions. For the suite of aquifer heterogeneities and all remedial stages, normalized flux values fell within a narrow band with mean of 0.39 and showed insensitivity to average source zone saturations.     

氧化镁烟气脱硫反应特性研究

利用实验室规模的鼓泡式反应装置,对比了碳酸钙、氧化镁和氧化镁/硫酸镁脱硫剂的反应活性,证实脱硫液中高浓度硫酸镁的存在是保证镁法脱硫效率高于钙法的重要因素,并考察了硫酸镁浓度、脱硫剂(氧化镁)浓度、烟气量、SO2浓度和吸收液温度等因素对脱硫效率的影响。结果表明,脱硫反应可以根据pH分为2个不同阶段;反应过程中脱硫效率随着硫酸镁浓度的增加而显著升高;烟气量增加将会导致脱硫效率有所下降;入口SO2浓度升高,脱硫效率下降;氧化镁浓度、温度对脱硫效率影响不显著。结合实验现象进行推断,氧化镁脱硫的反应过程受SO2在气液两相界面的传质扩散和其水解产物在液相的扩散控制。     

On the dissolution kinetics of humic acid particles. Effect of monocarboxylic acids

The dissolution kinetics of humic acid particles has been studied in batch experiments, and the effects of monocarboxylic (formic, acetic, and propionic) acids are reported. The dissolution rate of the particles is significantly affected by the presence of monocarboxylic acids in the pH range 4–10. At pH 7, for example, propionic acid increases 30 times this dissolution rate. The capacity of increasing the dissolution rate is in the order formic acid < acetic acid < propionic acid, and this dissolving capacity of carboxylics seems to be directly related to their affinity for HA molecules located at the surface of the solid particles. The results indicate that carboxylics and related compounds may affect markedly the mobility and transport of humic substances in the environment.     

Investigation of solid-phase buffers for sulfur-oxidizing autotrophic denitrification.

This paper investigates biological denitrification using autotrophic microorganisms that use elemental sulfur as an electron donor. In this process, for each gram of nitrate-nitrogen removed, approximately 4.5 g of alkalinity (as calcium carbonate) are consumed. Because denitrification is severely inhibited below pH 5.5, and alkalinity present in the influent wastewaters is less than the alkalinity consumed, an external buffer was needed to arrest any drop in pH from alkalinity consumption. A packed-bed bioreactor configuration is ideally suited to handle variations in flow and nitrate loading from decentralized wastewater treatment systems, as it is a passive system and thus requires minimal maintenance; therefore, a solid-phase buffer packed with the elemental sulfur in the bioreactor is most suitable. In this research, marble chips, limestone, and crushed oyster shells were tested as solid-phase buffers. Bench- and field-scale studies indicated that crushed oyster shell was the most suitable buffer based on (1) the rate of dissolution of buffer and the buffering agent released (carbonate, bicarbonate, or hydroxide), (2) the ability of the buffer surface to act as host for microbial attachment, (3) turbidity of the solution upon release of the buffering agent, and (4) economics.     

The dissolution of benzene, toluene, m-xylene and naphthalene from a residually trapped non-aqueous phase liquid under mass transfer limited conditions

The results of dissolution experiments for benzene, toluene, m-xylene and naphthalene (BTXN) from a relatively insoluble oil phase (tridecane), residually trapped in a non-sorbing porous medium, are described. This mixture was chosen to simulate dissolution of soluble aromatic compounds from a petroleum hydrocarbon mixture, e.g., crude oil, for which a large fraction of the mixture is relatively insoluble. The experiments were carried out at a small source length to interstitial velocity ratio, L/v, so that dissolution would be mass transfer limited (MTL). When fitted to data for toluene, a multiregion mass transfer model was found to predict the experimental data satisfactorily for the other components without adjustment of the mass transfer rate parameters. These results indicate that the dissolution process can be generalized for various hydrophobic organic compounds present in a multicomponent non-aqueous phase liquid (NAPL) when mass transfer limitations are present. This also suggests that dissolution data obtained for one compound can be useful for predicting the dissolution histories for other compounds from petroleum hydrocarbon mixtures.     

烟气脱硫过程锰催化氧化亚硫酸钙的研究

利用直径280 mm、高320 mm的间歇式搅拌槽,在MnSO4加入浓度为0～0.05 mol/L的情况下,对亚硫酸钙悬浮液进行了催化氧化实验研究.实验结果表明,锰离子的加入会改变亚硫酸钙的氧化机理及氧化过程,表现为终点氧化率和氧化速率的变化.当Mn2 浓度为0.05 mol/L时,亚硫酸钙的终点氧化率比未加入Mn2 时高30%;此外,与非催化反应过程相比,Mn2 的加入能使亚硫酸钙在一个更宽的浓度范围内(0.02～0.073 mol/L)和一个更宽的时间范围内(20～100 min)均保持较高的氧化速率水平.     

Embryonic sulphated black crusts on carbonate rocks in atmospheric simulation chamber and in the field: role of carbonaceous fly-ash

Experimental conditions characteristic of the urban pollution in many European cities over the last decades were reproduced in a simulation chamber in which samples of limestone were exposed for a period of 12 months, both naked or sprinkled with carbonaceous fly-ash. In agreement with the findings reported in the literature the fly-ash emitted by heavy fuel combustion are highly reactive, undergoing chemical and morphological transformations which give rise to crystals growth, especially gypsum. The development of gypsum crystals was observed overall in close proximity of fly-ash anchoring them to the limestone surface. Samples of the same limestone exposed in the field in a polluted environment for the same period of time led to similar results. The preliminary mechanisms leading to the genesis of sulphated black crusts in polluted environments were thus highlighted. Because of their roughness the embryonic black crusts increase the development of the crust by trapping new particles. This trapping is also facilitated by the wetness of the stone surface leading to the development of hydrated mineral (gypsum) in the water meniscus between fly-ash and stone surface.     

Mass flux from a non-aqueous phase liquid pool considering spontaneous expansion of a discontinuous gas phase

The partitioning of non-aqueous phase liquid (NAPL) compounds to a discontinuous gas phase results in the repeated spontaneous expansion, snap-off, and vertical mobilization of the gas phase. This mechanism has the potential to significantly affect the mass transfer processes that control the dissolution of NAPL pools by increasing the vertical transport of NAPL mass and increasing the total mass transfer rate from the surface of the pool. The extent to which this mechanism affects mass transfer from a NAPL pool depends on the rate of expansion and the mass of NAPL compound in the gas phase. This study used well-controlled bench-scale experiments under no-flow conditions to quantify for the first time the expansion of a discontinuous gas phase in the presence of NAPL. Air bubbles placed in glass vials containing NAPL increased significantly in volume, from a radius of 1.0 mm to 2.0 mm over 215 days in the presence of tetrachloroethene (PCE), and from a radius of 1.2 mm to 2.3 mm over 22 days in the presence of trans-1,2-dichloroethene (tDCE). A one-dimensional mass transfer model, fit to the experimental data, showed that this expansion could result in a mass flux from the NAPL pool that was similar in magnitude to the mass flux expected for the dissolution of a NAPL pool in a two-fluid (NAPL and water) system. Conditions favouring the significant effect of a discontinuous gas phase on mass transfer were identified as groundwater velocities less than ~0.01 m/day, and a gas phase that covers greater than ~10% of the pool surface area and is located within ~0.01 m of the pool surface. Under these conditions the mass transfer via a discontinuous gas phase is expected to affect, for example, efforts to locate NAPL source zones using aqueous concentration data, and predict the lifetime and risk associated with NAPL source zones in a way that is not currently included in the common conceptual models used to assess NAPL-contaminated sites.     

石灰石湿法脱硫过程中SO2吸收数学模型

为揭示石灰石湿法脱硫体系中喷淋塔内SO2的浓度和脱硫效率的变化情况,针对喷淋塔内石灰石在气膜控制、气液膜控制和固体溶解控制的3个不同阶段,以双膜理论为基础,以单个石灰石颗粒为研究对象,通过石灰石在不同阶段的转化率和粒径变化,得到SO2在不同阶段脱硫效率随时间的变化规律,建立SO2吸收的数学模型.模型计算结果表明,在烟气行程上,脱硫效率受SO2气膜传质阻力和石灰石溶解速率限制.在吸收塔底部和上端SO2吸收速率较低,在SO2和石灰石摩尔比在适宜条件下,有效吸收段高度为2 m左右.理论模型揭示的规律对喷淋塔的设计和运行参数选取有一定借鉴意义.