Combustion Kinetics of Athabasca Bitumen from 1D Combustion Tube Experiments

There are two basic requirements for heavy-oil recovery processes: first, mobilize the bitumen, and second, have a drive mechanism deliver the mobilized bitumen to a production wellbore. In situ combustion has the potential to be an important heavy-oil recovery method. Before design of in situ combustion recovery processes can start, it is necessary as a first step to understand the kinetics of various complex chemical reactions and determine kinetic constants associated with the reactions. Even with modern reservoir simulation capabilities, this is a significant challenge. In this research, an Athabasca bitumen combustion tube experiment, conducted by the ISC Research Group at the University of Calgary, was history matched by using a reservoir thermal simulator to determine a set of kinetic parameters as well as the transport parameters for the system. The main results of the history match was a match of air injection rate, bitumen and gas production volumes, average product gas compositions, temperature profiles along the tube through time, and pressure. Gridding sensitivities were examined to determine if the derived kinetic and transport parameters were dependent on gridblock size. The results revealed that the grid was refined enough to sufficiently capture thermal, mass transfer, and reaction length scales. After this single match was achieved, the same constants were used to successfully predict several other combustion tube experiments. The results suggest that the fuel (coke) for high-temperature oxidation (HTO) originates mainly from low-temperature oxidation (LTO) and not from thermal cracking. This implies that the major control on HTO is upstream oxygen transfer into the LTO region. If LTO does not occur, then a relatively small amount of coke is deposited in the matrix due to thermal cracking and this may be insufficient to start or sustain HTO.     

Adsorption kinetics, isotherm, and thermodynamic studies of adsorption of pollutant from aqueous solutions onto humic acid

In the present study,humic acid was used as an adsorbent for the investigation of the adsorption kinetics,isotherms,and thermo-dynamic parameters of hexavalent chromium from aqueous solution at varying pH,temperatures,and concentrations.Adsorption isotherms and equilibrium adsorption capacities were determined by the fittings of the experimental data to three well-known iso-therm models:Langmuir,Freundlich,and Redlich-Peterson.The results showed that the Langmuir and Redlich-Peterson models appear to fit the adsorption better than did the Freundlich adsorption model for the adsorption of chromium onto humic acid.The equilibrium constants were used to calculate thermodynamic parameters such as the change of free energy,enthalpy,and entropy.The derived adsorption constants (logaL) and their temperature dependencies from Langmuir isotherm have been used to calculate the corresponding thermodynamic quantities such as the free energy of adsorption,heat,and entropy of adsorption.The thermo-dynamic data indicate that Cr (VI) adsorption onto humic acid is entropically driven and characterized by physical adsorption.     

Comments on “Two-dimensional concentration distribution for mixing-controlled bioreactive transport in steady-state” by O.A. Cirpka and A.J. Valocchi

In this comment we present a re-analysis of the analytical solution presented by Cirpka and Valocchi for steady-state concentrations of dissolved bioreactive compounds and bacterial biomass in porous media. We discuss the validity range of the analytical solution. In particular, the criterion used to determine the sustainability of biomass is revisited. This re-analysis shows that the ω$\omega$ criterion used by Cirpka and Valocchi is only a necessary but not a sufficient criterion to determine the bioreactive zones. As a consequence, the analytical solution does not provide the exact distribution of compounds throughout the domain, but can serve as upper or lower boundaries for species concentrations at a given location. These conclusions are supported by the simulation results obtained from an established reactive transport model.     

Performance of A Combination Process of UV/H2O2/Micro‐Aeration for Oxidation of Dichloroacetic Acid in Drinking Water

The decomposition of dichloroacetic acid (DCAA) in water using a UV/H₂O₂/micro‐aeration process was investigated in this paper. DCAA cannot be removed by UV radiation, H₂O₂ oxidation or micro‐aeration alone, while UV/H₂O₂/micro‐aeration combination processes have proved effective and can degrade this compound completely. With initial concentrations of about 110 μg/L, more than 95.1% of DCAA can be removed in 180 min under UV intensity of 1048.7 μW/cm², H₂O₂ dosage of 30 mg/L and micro‐aeration flow rate of 2 L/min. However, more than 30 μg/L of DCAA was left after 180 min by UV/H₂O₂ combination process without micro‐aeration with the same UV intensity and H₂O₂ dosage. The effects of applied UV radiation intensity, H₂O₂ dose, initial DCAA concentration and pH on the degradation of DCAA have been examined in this study. Degradation mechanisms of DCAA with hydroxyl radical oxidation have been discussed. The removal rate of DCAA was sensitive to operational parameters. There was a linear relationship between rate constant k and UV intensity and initial H₂O₂ concentration, which indicated that a higher removal capacity can be achieved by improvement of both factors. A newly found nitrogenous disinfection by‐product (N‐DBP)‐DCAcAm, which has the potential to form DCAA, was easier to remove than DCAA by UV/H₂O₂ and UV/H₂O₂/micro‐aeration processes. Finally, a preliminary cost comparison revealed that the UV/H₂O₂/micro‐aeration process was more cost‐effective than the UV/H₂O₂ process in the removal of DCAA from drinking water.     

Rice Husk Ash as a Low Cost Adsorbent for the Removal of Methylene Blue and Congo Red in Aqueous Phases

Adsorption is of significant importance for effluent treatment, especially for the treatment of colored effluent generated from the dyeing and bleaching industries. Low cost adsorbents have gained attention over the decades as a means of achieving very high removal efficiencies to meet effluent discharge standards. The present article reports on batch investigations for color removal from aqueous solutions of Methylene Blue (MB) and Congo Red (CR) using Rice Husk Ash (RHA) as an alternative low cost adsorbent. The performance analysis was carried out as a function of various operating parameters, such as initial concentration of dye, adsorbent dose, contact time, shaker speed, interruption of shaking and ionic concentration. Performance studies revealed that a very high percentage removal of color was achievable for both dyes. The maximum percentage removal of MB was 99.939%, while 98.835% removal was observed for CR. These percentage removals were better than existing systems. Detailed data analysis indicated that adsorption of MB followed the Temkin isotherm, while CR followed the Freundlich isotherm. These isotherms were feasible within the framework of experimentation. Batch kinetic data, on the other hand, indicated that pseudo second order kinetics governed adsorption in both cases. Sensitivity analysis further indicated that the effects of initial dye concentration, shaker speed, pH and ionic strength had no noticeable effect on the percentage dye removal at equilibrium. Batch desorption studies revealed that 50% acetone solution was optimum for CR, while desorption of MB varied directly with acetone concentration.     

A Study of the Thermodynamics and Kinetics of Copper Adsorption Using Chemically Modified Rice Husk

The use of rice husk as a low cost adsorbent for the removal of copper from wastewater has been explored in a laboratory scale experiment. The rice husk used for the study was treated with alkali to increase the sorption properties. The influence of metal ion concentration, weight of biosorbent, stirring rates, temperature and pH were also evaluated, and the results are fitted using adsorption isotherm models. From the experimental results it was observed that almost 90–98% of the copper could be removed using treated rice husk. The Langmuir adsorption isotherm, Freundlich isotherm and Tempkin isotherm models were used to describe the distribution of copper between the liquid and solid phases in batch studies, and it was observed that the Langmuir isotherm better represented the adsorption phenomenon. The experimental rate constant, activation energy, Gibbs free energy, enthalpy and entropy of the reaction were calculated in order to determine the mechanism of the sorption process.     

Heating rate dependency of petroleum-forming reactions: implications for compositional kinetic predictions

The generation of bulk petroleum, liquid and gaseous hydrocarbons from the Duvernay Formation was simulated by heating immature kerogens in a closed system (MSSV pyrolysis) at four different heating rates (0.013, 0.1, 0.7 and 5.0 K/min). Using the established parallel reaction kinetic model, temperature and compositional predictions were tested to be suitable for geological conditions by comparing the laboratory results with natural changes in source bitumens and reservoir oil maturity sequences from the Duvernay Formation. In the case of bulk liquid and gaseous hydrocarbons, the above kinetic calculations can be considered valid because their maximum yields are independent of laboratory heating rates. In contrast, the contents of paraffins, aromatics and sulfur compounds show a pronounced heating rate dependence. Extrapolated to geological heating rates, the compositional predictions are consistent with the bulk composition of natural products in the Duvernay-petroleum system showing an increase of paraffinicity and hydrogen content. In contrast to that, the “hump” decreases with decreasing heating rate, a trend which is confirmed by the low amounts of unresolved compounds in natural high maturity products. Because of these heating-rate dependent compositional changes, geological predictions of natural molecular composition by the commonly used kinetic models are not suitable.     

江西大布铀矿床溶浸地质条件及溶浸方法研究

本文围绕溶浸采矿这个主题 ,从岩、矿石的物质成分 ;矿石结构构造 ;铀的存在形式 ;岩、矿石物理力学参数 ;矿体形态、产状、规模及矿床水文地质等诸多方面阐述了大布铀矿床溶浸的天然地质条件 ,并通过一系列矿石铀浸出工艺试验 ,获得大量溶浸工艺参数 ,提出大布铀矿床以原地破碎浸出辅以堆浸为最佳采矿方案。     

塔里木盆地熟化有机质成烃动力学模型原始参数的恢复及意义

针对塔里木盆地主力源岩层大多埋深较大、成熟度较高,对这些源岩所进行的模拟实验不能反映或描述样品在达到现今埋深这前所经历的成烃演化过程的难题,本文先由模拟实验数据出发,建立和标定各样品的化学动力模型,在此基础上,推导和建立了恢复化学动力的始参数的方法并利用塔里木盆地的样品进行了应用。结果表明,深埋样品有机质中有相当部分的低活化能组分已在其前期演化过程中被成烃反应所消耗。因此,要客观描述样品的全部成烃