Nonideal transport of reactive contaminants in heterogeneous porous media: 7. distributed-domain model incorporating immiscible-liquid dissolution and rate-limited sorption/desorption

The purpose of this work is to present a distributed-domain mathematical model incorporating the primary mass-transfer processes that mediate the transport of immiscible organic liquid constituents in water-saturated, locally heterogeneous porous media. Specifically, the impact of grain/pore-scale heterogeneity on immiscible-liquid dissolution and sorption/desorption is represented in the model by describing the system as comprising a continuous distribution of mass-transfer domains. With this conceptualization, the distributions of the initial dissolution rate coefficient and the sorption/desorption rate coefficient are represented as probability density functions. Several sets of numerical experiments are conducted to examine the effects of heterogeneous dissolution and sorption/desorption on contaminant transport and elution. Four scenarios with different combinations of uniform/heterogeneous rate-limited dissolution and uniform/heterogeneous rate-limited sorption/desorption are evaluated. The results show that both heterogeneous rate-limited sorption/desorption and heterogeneous rate-limited dissolution can significantly increase the time or pore volumes required to elute immiscible-liquid constituents from a contaminated porous medium. However, sorption/desorption has minimal influence on elution behavior until essentially all of the immiscible liquid has been removed. For typical immiscible-liquid constituents that have relatively low sorption, the asymptotic elution tailing produced by heterogeneous rate-limited sorption/desorption begins at effluent concentrations that are several orders of magnitude below the initial steady-state concentrations associated with dissolution of the immiscible liquid. Conversely, the enhanced elution tailing associated with heterogeneous rate-limited dissolution begins at concentrations that are approximately one-tenth of the initial steady-state concentrations. Hence, dissolution may generally control elution behavior of immiscible-liquid constituents in cases wherein grain/pore-scale heterogeneity significantly influences both dissolution and sorption/desorption.     

Multiphase flow and transport through fractured heterogeneous porous media

The migration of Dense, Non-Aqueous Phase Liquid (DNAPL) and dissolved phase contamination through a fractured heterogeneous porous medium has been investigated through the use of a multiphase compositional model. The sensitivity of the timescales of migration and the distribution of contaminant in the subsurface to the mean permeability, the variance of the permeability, and the degree of fracturing of the domain were examined. It was found that increasing the mean permeability of the domain allowed the DNAPL to penetrate deeper into the subsurface, while decreasing the mean permeability caused the DNAPL to pool at shallower depths. The presence of fractures within the system was found to control the infiltration only in the most fractured domain. Moment analysis of the nonwetting phase showed that large-scale movement had ceased after approximately 9 years (maximum duration of the source-on condition was approximately 4.5 years). This tended to be due to a redistribution of the DNAPL towards a residual configuration, as was evidenced by the gradual trending of average nonwetting phase saturations within the domain to a static value. The dissolved phase plume was found to migrate at essentially the same rate as the nonwetting phase, due to the reduced relative permeability of lenses containing DNAPL, and due to diffusive losses of mass to the matrix of fractured clay and silty-clay lenses. Some exceptions to this were found when the DNAPL could not overcome the displacement pressure of a lens, and could not by-pass the lens due to the lack of available driving force after the source had been shut off.     

Magnetic resonance imaging of nonaqueous phase liquid during soil vapor extraction in heterogeneous porous media

Soil vapor extraction (SVE) is commonly used to remediate nonaqueous phase liquids (NAPLs) from the vadose zone. This paper aims to determine the effect of grain size heterogeneity on the removal of NAPL in porous media during SVE. Magnetic resonance imaging (MRI) was used to observe and quantify the amount and location of NAPL in flow-through columns filled with silica gel grains. MRI is unique because it is nondestructive, allowing three-dimensional images to be taken of the phases as a function of space and time. Columns were packed with silica gel in three ways: coarse grains (250-550 microm) only, fine grains (32-63 microm) only, and a core of fine grains surrounded by a shell of coarse grains. Columns saturated with water were drained under a constant suction head, contaminated with decane, and then drained to different decane saturations. Each column was then continuously purged with water-saturated nitrogen gas and images were taken intermittently. Results showed that at residual saturation, a sharp volatilization front moved through the columns filled with either coarse-grain or fine-grain silica gel. In the heterogeneous columns, the volatilization front in the core lagged just behind the shell because gas flow was greater through the shell and decane in the core diffused outward to the shell. When decane saturation in the core was above residual saturation, decane volatilization occurred near the inlet, the relative decane saturation throughout the core dropped uniformly, and decane in the core flowed in the liquid phase to the shell to replenish volatilized decane. These results indicate that NAPL trapped in low-permeability zones can flow to replenish areas where NAPL is lost due to SVE. However, when residual NAPL saturation is reached, NAPL flow no longer occurs and diffusion limits removal from low-permeability zones.     

[Cu—γ—Al2O3]催化剂处理染料废水工艺条件研究

采用「Ｃｕ－γ－Ａｌ２Ｏ３」催化剂对由活性艳红Ｘ－３Ｂ配制的ＣＯＤｃｒ为５７００ｍｇ／Ｌ色度３１００倍的实际染料废水进行了催化氧化试验，试验表明，在控制ｐＨ＝４－５，Ｈ２Ｏ２用量为５．０ｍｇ／Ｌ，催化剂用量为３．０ｇ／Ｌ，ｔ＝７０℃和反应时间为２ｈ条件下，可获得ＣＯＤｃｒ去除率为７７％－７８％，脱色率为９９％的良好效果，且催化剂可再生使用。     

Using X-ray computed tomography and micro-Raman spectrometry to measure individual particle surface area, volume, and morphology towards investigating atmospheric heterogeneous reactions

Heterogeneous reactions on the aerosol particle surface in the atmosphere play important roles in air pollution, climate change, and global biogeochemical cycles. However, the reported uptake coefficients of heterogeneous reactions usually have large variations and may not be relevant to real atmospheric conditions. One of the major reasons for this is the use of bulk samples in laboratory experiments, while particles in the atmosphere are suspended individually. A number of technologies have been developed recently to study heterogeneous reactions on the surfaces of individual particles. Precise measurements on the reactive surface area, volume, and morphology of individual particles are necessary for calculating the uptake coefficient, quantifying reactants and products, and understanding the reaction mechanism better. In this study, for the first time we used synchrotron radiation X-ray computed tomography(XCT) and micro-Raman spectrometry to measure individual CaCO_3 particle morphology, with sizes ranging from 3.5–6.5 μm. Particle surface area and volume were calculated using a reconstruction method based on software threedimensional(3-D) rendering. The XCT was first validated with high-resolution fieldemission scanning electron microscopy(FE-SEM) to acquire accurate CaCO_3 particle surface area and volume estimates. Our results showed an average difference of only 6.1% in surface area and 3.2% in volume measured either by micro-Raman spectrometry or X-ray tomography. X-ray tomography and FE-SEM can provide more morphological details of individual Ca CO3 particles than micro-Raman spectrometry. This study demonstrated that X-ray computed tomography and micro-Raman spectrometry can precisely measure the surface area, volume, and morphology of an individual particle.     

催化臭氧化在水处理中的应用

催化臭氧化是高级氧化技术的一种,本文从均相和非均相催化两方面对催化臭氧化进行了综述,阐述了催化臭氧化的反应机理及影响因素,介绍了近年来催化臭氧化在水处理中的应用,并对今后深入研究的方向进行了展望。     

Application of heterogeneous catalysis to biodiesel synthesis using microalgae oil

• Microalgae oil application for biodiesel synthesis is discussed. • Catalytic effectiveness of ferment preparations and chemical catalyst is disputed. • Application of heterogeneous catalysts for biodiesel synthesis is reviewed. • Possibilities of catalyst regeneration is shown. Recently, there is a growing interest in the use of microalga in various fields. Microalgae have properties such as rapid reproduction and high biomass accumulation, and under certain conditions, some are able to accumulate a large amount of oil. However, microalgae oil often contains more free fatty acids than the vegetable oil and is therefore unsuitable for biodiesel synthesis using alkaline catalysts. For this reason, some authors suggest the application of heterogeneous catalysis. A particular interest in the use of immobilized enzymes has developed. Other solid substances can also be used as heterogeneous catalysts are usually metal oxides, carbonates or zeolites. The use of these catalysts results in simpler biodiesel synthesis, especially purification processes, a cleaner end product and a less polluted environment. The molar ratio of alcohol to oil is lower during enzymatic transesterification, and more than 90% ester yield is obtained using a molar ratio of alcohol to oil of 3:1 to 4.5:1. The alcohols do not have a negative effect on the effectiveness of chemical catalysts, so it is possible to use alcohols in molar ratio from 4:1 to 12:1. The optimal temperature of enzymatic process is 30℃‒50℃. An ester yield of more than 95% was obtained in 12‒48 h. Using chemical catalysts, greater than a 95% yield of esters was obtained at higher temperatures in a shorter time. Material costs of enzymatic catalysis can be reduced by reusing the catalysts directly or after regeneration.     

Modeling quenching distance and flame propagation speed through an iron dust cloud with spatially random distribution of particles

In this research combustion of iron dust particles in a medium with spatially discrete sources distributed in a random way has been studied using a numerical approach. A new thermal model is generated to estimate flame propagation speed and quenching distance in a quiescent reaction medium. The flame propagation speed is studied as a function of iron dust concentration and particle diameter. The predicted propagation speeds as a function of these parameters are shown to agree well with experimental measurements. In addition, the minimum ignition energy has also been investigated as a function of equivalence ratio and particle diameter. The quenching distance has been studied as a function of particle diameter and validated by the experiment. Considering random distribution of particles, the obtained results provide more realistic and reasonable predictions of the combustion physics compared to the results of the uniform distribution of particles.     

Heterogeneous firms and the environment: a cap-and-trade program

Currently, cap-and-trade programs are a cornerstone of many countries' climate change policies and proposals. This paper investigates the economic and environmental effects of different climate change policy designs in a general equilibrium setting with heterogeneous firms and monopolistic competition. The analysis predicts that the cap on emissions perfectly defines the environmental quality but has no effect on firms' profits, or decisions to enter or exit the market. In contrast, increasing the share of free allocations of emission allowances, as opposed to auctions, has no effect on environmental quality but reallocates resources among firms toward the most productive ones which has an impact on firms' entry and exit decisions, the mass of firms, and the composition of the market. Firm heterogeneity magnifies these economic effects of changes in the initial allocation of allowances. The paper provides a decomposition of the change in aggregate emissions which takes account of the changes at sector level, across the firms within a sector, and at the firm level.