Effect of high stirring speed on the agglomerate behaviors for cohesive SiO2 powders in gas fluidization

The effects of superficial gas velocity and mechanical stirring speed on the precise regulation of flow regimes for cohesive SiO₂ powders (mean diameter is 16 μm) were experimentally investigated in a stirring-assisted fluidized bed. The results showed that compared with the agglomerates formed in the non-assisted fluidization of cohesive SiO₂ powders, the introduction of mechanical stirring could effectively reduce the size of agglomerates and well disperse the agglomerates during fluidization. The best regulation range of agglomerate particulate fluidization can be achieved at 600 rpm when agglomerate sizes were reduced to below 200 μm. Further investigation based on the operational phase diagram revealed that transformations of flow regimes were dominated by both stirring speed and gas velocity. The stirring applied enlarges the operational range of agglomerate particulate fluidization (APF) with a delayed onset of bubbling for cohesive particles. However, the exorbitant speed increases the collision velocity and contact area between small agglomerates, which results in the formation of unstable agglomerates and the whirlpool of powder.     

Effect of acoustic field on CO2 desorption in a fluidized bed of fine activated carbon

Adsorption using solid sorbents has the potential to complement or replace current absorption technology, because of its low energy requirements. Among the commercially available adsorbent materials, attention is focused on activated carbons because they are easily regenerable by reason of their low heat of adsorption. These sorbents are generally available in the form of fine powders. Sound-assisted fluidization can process large amounts of fine powders, promoting and enhancing CO₂ capture on fine sorbents, because it maximizes gas–solid contact. Temperature swing adsorption (TSA), consisting of inducing sorbent regeneration and CO₂ recovery by appropriate temperature increase and gas purge, is one of the most promising techniques. This study investigates the CO₂ desorption process by TSA in a sound-assisted fluidized bed of fine activated carbon. Desorption tests were performed under ordinary and sound-assisted fluidization conditions to assess the capability of sound to promote and enhance the desorption efficiency in terms of CO₂ recovery, CO₂ purity, and desorption time. The results show that the application of sound results in higher desorption rates, CO₂ recovery and purity. Regular and stable desorption profiles can be obtained under sound-assisted fluidization conditions. This stability makes it possible to successfully realize a cyclic adsorption/desorption process.     

Competitive Methane Desorption by Supercritical CO2 Injection in Coal

A large diameter (∼70 mm) dry coal sample was used to study the competitive displacement of CH₄ by injection of supercritical CO₂, and CO₂–CH₄ counter-diffusion in coal matrix. During the test, a staged loading procedure, which allows the calibration of the key reservoir modelling parameters in a sequential and progressive manner, was employed. The core-flooding test was history matched using an Enhanced Coalbed Methane (ECBM) simulator, in which Fick’s Law for mixed gas diffusion and the extended Langmuir equations are implemented. The system pressure rise during the two loading stages and the CO₂ breakthrough time in the final production stage were matched by using the pair of constant sorption times (9 and 3.2 days) for CH₄ and CO₂, respectively. The corresponding diffusion coefficients for CH₄ and CO₂ were estimated to be 1.6 ×  10⁻¹² and 4.6 ×  10⁻¹² m²/s, respectively. Comparison was made with published gas diffusion coefficients for dry ground samples (ranging from < 0.063 to ∼3 mm) of the same coal at relatively low pressures (< 4 MPa). The CO₂/CH₄ gas diffusion coefficient ratio was well within the reported range (2–3), whereas the CH₄ diffusion coefficient obtained from history matching of the core-flooding test is approximately 15 times smaller than that arrived by curve-fitting the measured sorption uptake rate using a unipore diffusion model. The calibrated model prediction of the effluent gas composition was in good agreement with the test data for CO₂ mole fraction of up to 20%.     

Li2SiO3 fast microwave-assisted hydrothermal synthesis and evaluation of its water vapor and CO2 absorption properties

A series of lithium metasilicate (Li₂SiO₃) powder materials has been successfully synthesized by the microwave-assisted hydrothermal route using lithium hydroxide and tetraethyl-orthosilicate-derived sol precursors. Ceramic powders were obtained under hydrothermal conditions of autogenous pressure in the presence of a nonionic surfactant. The production of pure and well-crystallized Li₂SiO₃ using very short reaction times at low temperatures was shown by X-ray diffraction, scanning electron microscopy, and N₂ adsorption-desorption analyses. Synthesized Li₂SiO₃ particles were nanocrystalline and exhibited different morphologies and specific surface areas depending on the synthesis conditions. Additionally, the capability of selected Li₂SiO₃ samples to absorb H₂O and CO₂ was evaluated via thermogravimetric analyses by varying the temperature, carrier gas, and water vapor concentration. Li₂SiO₃ particles exhibited interesting textural and morphological characteristics that make them suitable for use as a CO₂ absorbent and which suggest that they also have the potential to be used in other applications.     

Fabrication of nano-sized Ca(OH)2 with excellent adsorption ability for N2O4

Uniform nano-sized calcium hydroxide (Ca(OH)₂) monocrystal powder was synthesized from calcium oxide in a surfactant solution via a digestion method by decreasing the surface tension of the reaction system to control the growth of crystalline Ca(OH)₂. The Ca(OH)₂ monocrystal powder samples were characterized by means of scanning electron microscopy (SEM), transmission electron microscopy (TEM), high resolution transmission electron microscopy (HRTEM), X-ray diffraction (XRD), Brunauer–Emmett–Teller (BET), and Fourier transform-infrared spectroscopy (FT-IR). The NO_x adsorption ability of the samples was evaluated, and the influence of various types and concentrations of surfactants on powder agglomeration and then the specific surface area in the precipitation process were studied. The specific surface area of the samples was found as high as 58 m²/g and 92 m²/g and the particle size, 300–400 nm and 200–300 nm in the presence of 10 wt% PEG600 and 0.086 mL/L SDS at a reaction time of 5 h, respectively. The product has an exceptionally strong adsorption ability for NO_x, which makes it a highly promising adsorbent for emission control and air purification.     

Preparation of NiFe2O4 nanopowder via EDTA precursor and study of its properties

An ethylene diamine tetra acetic acid (EDTA) precursor-based chemical method is reported for preparing single-phase nickel ferrite (NiFe₂O₄) nanopowder. The synthesized powder was characterized by thermogravimetric analysis, differential scanning calorimetric analysis, X-ray diffraction, particle size analysis and scanning electron microscopy. DC electrical resistivity and magnetic property of the synthesized NiFe₂O₄ were measured by using a two-probe method and a vibrating sample magnetometer respectively. The DC resistivity behaviour of the NiFe₂O₄ nanopowder was correlated with the change of microstructure, during sintering. This EDTA precursor-based method is capable of producing nanostructured single-phase NiFe₂O₄ powder at a comparatively low calcination temperature and offers the potential of a simple and cost-effective route, including the preparation of other ferrite nanoparticles.     

Experimental investigation on micro-dynamic behavior of gas explosion suppression with SiO2 fine powders

To study the effect of inert dust on gas explosion suppression mechanism, SiO₂ fine powders were sprayed to suppress premixed CH₄-Air gas explosion in a 20 L spherical experimental system. In the experiment, high speed schlieren image system was adopted to record explosion flame propagation behaviors, meanwhile, pressure transducers and ion current probes were used to clearly record the explosion flame dynamic characteristics. The experimental results show that the SiO₂ fine powders suppressed evidently the gas explosion flame, and reduced the peak value of pressure and flame speed by more than 40 %. The ion current result shows that the SiO₂ super fine powders were easy to contact with and absorb free radicals near the combustion reaction region, which greatly reduced the combustion reaction intensity, and in turn influenced the flame propagation and pressure rising.     

Controlled synthesis of Ce(OH)CO3 flowers by a hydrothermal method and their thermal conversion to CeO2 flowers

Highly uniform Ce(OH)CO₃ flowers were successfully prepared in large quantities using a facile hydrothermal approach from the reaction of Ce(NH₄)(NO₃)₄ with CO(NH₂)₂ at 160 °C in a water–N₂H₄ complex. The influences of the N₂H₄ content and temperature on flower formation were discussed. CeO₂ flowers were prepared by thermal conversion of Ce(OH)CO₃ flowers at 500 °C in air. Both Ce(OH)CO₃ and CeO₂ flowers were characterized by X-ray powder diffraction (XRD), and scanning electron microscopy (SEM). The UV–vis adsorption spectrum of the CeO₂ flowers showed that the band gap energy (E_g) is 2.66 eV, which is lower than that of bulk ceria.     

Modelling the Flow of Carbon Dioxide Through Beds of Cereal Grains

The insect population in grain stores can be kept under control by maintaining a high concentration of CO₂ gas (greater than 35%) throughout the grain bed. In this paper the initial phase of this process is considered, where the gas is introduced into the bed. The flow of CO₂ through the grain bulk is modelled as fluid flow in a porous medium and the effect of advection, dispersion, sorption and curvilinear isobars and streamlines are considered. An analytic solution to this problem is developed using perturbation expansions and the analysis is restricted to the dominant term in each expansion. In curvilinear flow, a useful variable is the traverse time; the time taken for the gas to travel from the inlet duct. It is shown that lines of constant traverse time are also lines of constant CO₂ concentration throughout the grain bed except in the narrow region called the front, where the concentration gradient is large. For most grain stores the isobars have a negative curvature and in these situations the front moves more slowly than in uniform flow and the width of the front increases more rapidly as it travels through the grain bed. It is shown that sorption has an effect on the CO₂ concentration in the air for some grains such as canola but not for others such as wheat.     

Validation of surface coating with nanoparticles to improve the flowability of fine cohesive powders

Fluidization of fine cohesive powders is seriously restricted by the strong interparticle cohesion. The rational combination of nanoparticles with fine cohesive powders is expected to obtain composite particles with improved flowability. In this work, we firstly reviewed the sandwich and three-point contact models regarding the fundamental principles of nano-additives in reducing cohesiveness. Based on these previous models, the effects of the size of nanoparticles, their agglomeration and coverage on the surface of cohesive powders in reducing interparticle forces were theoretically analyzed. To validate the theory effectiveness for the irregularly shaped cohesive powders, an extreme case of cubic powders coated with silica nanoparticles was fabricated, and the flowability of the composite particles was determined experimentally. Ultimately, based on force balance of a single particle, a semi-theoretical criterion for predicting the fluidization behavior of coated powders was developed to guide the practical applications of improving the flowability of cohesive powders through structural design and modulation.     

In situ preparation of hydrophobic CaCO3 nanoparticles in a gas–liquid microdispersion process

This study presents a novel process of in situ surface modification of CaCO₃ nanoparticles using a multiple-orifice dispersion microreactor. CO₂/Ca(OH)₂ precipitation reaction was employed to prepare CaCO₃ nanoparticles with sodium stearate surfactant. Synthesized CaCO₃ products were characterized by thermogravimetric analysis (TGA), infra-red (IR), X-ray diffraction (XRD), transmission electron microscopy (TEM) and Brunauer–Emmet–Teller analysis (BET). The effect of various operation parameters on nanoparticles and the dosage of sodium stearate were determined. The results showed that the preparation process could be precisely controlled with efficient mass transfer process. The particles were highly hydrophobic with a contact angle of 117° and monodisperse with an average size of 30 nm. The adsorptions of sodium stearate and calcium ion on solid particles during the in situ surface modification process were investigated.     

An Experimental Study of CO<Subscript>2</Subscript> Exsolution and Relative Permeability Measurements During CO<Subscript>2</Subscript> Saturated Water Depressurization

Dissolution of CO₂ into brine is an important and favorable trapping mechanism for geologic storage of CO₂. There are scenarios, however, where dissolved CO₂ may migrate out of the storage reservoir. Under these conditions, CO₂ will exsolve from solution during depressurization of the brine, leading to the formation of separate phase CO₂. For example, a CO₂ sequestration system with a brine-permeable caprock may be favored to allow for pressure relief in the sequestration reservoir. In this case, CO₂-rich brine may be transported upwards along a pressure gradient caused by CO₂ injection. Here we conduct an experimental study of CO₂ exsolution to observe the behavior of exsolved gas under a wide range of depressurization. Exsolution experiments in highly permeable Berea sandstones and low permeability Mount Simon sandstones are presented. Using X-ray CT scanning, the evolution of gas phase CO₂ and its spatial distribution is observed. In addition, we measure relative permeability for exsolved CO₂ and water in sandstone rocks based on mass balances and continuous observation of the pressure drop across the core from 12.41 to 2.76 MPa. The results show that the minimum CO₂ saturation at which the exsolved CO₂ phase mobilization occurs is from 11.7 to 15.5%. Exsolved CO₂ is distributed uniformly in homogeneous rock samples with no statistical correlation between porosity and CO₂ saturation observed. No gravitational redistribution of exsolved CO₂ was observed after depressurization, even in the high permeability core. Significant differences exist between the exsolved CO₂ and water relative permeabilities, compared to relative permeabilities derived from steady-state drainage relative permeability measurements in the same cores. Specifically, very low CO₂ and water relative permeabilities are measured in the exsolution experiments, even when the CO₂ saturation is as high as 40%. The large relative permeability reduction in both the water and CO₂ phases is hypothesized to result from the presence of disconnected gas bubbles in this two-phase flow system. This feature is also thought to be favorable for storage security after CO₂ injection.     

等离子体辅助球磨制备表面修饰纳米TiO2的摩擦学性能分析

以季铵盐和月桂酸钠为过程处理剂,利用等离子体辅助球磨制备表面修饰纳米TiO_2粉体,并测试其摩擦学性能.结果表明:在等离子体的热爆效应及脉冲电子轰击效应的协同作用下,辅助球磨11 h制备的表面修饰纳米TiO_2粉体粒径在20 nm左右,晶型发生由锐钛矿型向金红石型的转变.等离子体辅助球磨使得纳米TiO_2获得了良好的亲油疏水表面特性,在40CA船用润滑油中表现出稳定的分散性.由于纳米TiO_2粉体的"微轴承"作用,复合润滑油的摩擦系数降低,摩擦副的磨损失重量减少.纳米TiO_2粉体在摩擦过程中容易吸附沉积在摩擦副表面并修补磨痕,使得复合润滑油具备良好的减摩及自修复性能.     

Hydrothermal preparation of nanocrystalline ZnO2

A green hydrothermal method was proposed for the synthesis of nanocrystalline ZnO₂, using Zn₅(CO₃)₂(OH)₆ powder and 6 vol% H₂O₂ aqueous solution as the starting materials. Characterization results from X-ray diffraction, Raman, high resolution transmission electron microscopy and selected area electron diffraction revealed that the products synthesized at 80–120 °C for 6–18 h were pure cubic phase ZnO₂ nanocrystals. Room temperature photoluminescence spectra of the as-synthesized ZnO₂ nanocrystals displayed a wide and strong emission band in the visible region of about 525–570 nm upon laser excitation at 325 nm, which may have originated from their surface state and other crystal defects.     

IMPROVEMENT OF FLUIDIZABILITY OF FINE POWDERS ——A COMPUTER STUDY

Simulations of the gas fluidization of a cohesive powder were performed using the Stokesian Dynamics method and an agglomeration-deagglomeration model to investigate methods of improving the fluidizability of fine powders. Three techniques (a) high gas velocity (b) vibration-assisted fluidization and (c) tapered fluidizer were used in the simulations which provided detailed information on the bed microscopy such as the motion of 1 O0 particles in a fluidizing vessel along with the formation and destruction of cohesive bonds dudng collisions. While all three techniques were found to effectively improve the fluidizability of a strongly cohesive powder, we suggest a combination of high velocity fluidization assisted by extemal vibration of the fluidized bed to minimize entrainment of particles.     

Modeling of CO<Subscript>2</Subscript> Leakage up Through an Abandoned Well from Deep Saline Aquifer to Shallow Fresh Groundwaters

This article presents a numerical modeling application using the code TOUGHREACT of a leakage scenario occurring during a CO₂ geological storage performed in the Jurassic Dogger formation in the Paris Basin. This geological formation has been intensively used for geothermal purposes and is now under consideration as a site for the French national program of reducing greenhouse gas emissions and CO₂ geological storage. Albian sandstone, situated above the Dogger limestone is a major strategic potable water aquifer; the impacts of leaking CO₂ due to potential integrity failure have, therefore, to be investigated. The present case–study illustrates both the capacity and the limitations of numerical tools to address such a critical issue. The physical and chemical processes simulated in this study have been restricted to: (i) supercritical CO₂ injection and storage within the Dogger reservoir aquifer, (ii) CO₂ upwards migration through the leakage zone represented as a 1D vertical porous medium to simulate the cement–rock formation interface in the abandoned well, and (iii) impacts on the Albian aquifer water quality in terms of chemical composition and the mineral phases representative of the porous rock by estimating fluid–rock interactions in both aquifers. Because of CPU time and memory constraints, approximation and simplification regarding the geometry of the geological structure, the mineralogical assemblages and the injection period (up to 5 years) have been applied to the system, resulting in limited analysis of the estimated impacts. The CO₂ migration rate and the quantity of CO₂ arriving as free gas and dissolving, firstly in the storage water and secondly in the water of the overlying aquifer, are calculated. CO₂ dissolution into the Dogger aquifer induces a pH drop from about 7.3 to 4.9 limited by calcite dissolution buffering. Glauconite present in the Albian aquifer also dissolves, causing an increase of the silicon and aluminum in solution and triggering the precipitation of kaolinite and quartz around the intrusion point. A sensitivity analysis of the leakage rate according to the location of the leaky well and the variability of the petro-physical properties of the reservoir, the leaky well zone and the Albian aquifers is also provided.     

Modeling of Rocks and Cement Alteration due to CO<Subscript>2</Subscript> Injection in an Exploited Gas Reservoir

The injection of CO₂ in exploited natural gas reservoirs as a means to reduce greenhouse gas (GHG) emissions is highly attractive as it takes place in well-known geological structures of proven integrity with respect to gas leakage. The injection of a reactive gas such as CO₂ puts emphasis on the possible alteration of reservoir and caprock formations and especially of the wells’ cement sheaths induced by the modification of chemical equilibria. Such studies are important for injectivity assurance, wellbore integrity, and risk assessment required for CO₂ sequestration site qualification. Within a R&D project funded by Eni, we set up a numerical model to investigate the rock–cement alterations driven by the injection of CO₂ into a depleted sweet natural gas pool. The simulations are performed with the TOUGHREACT simulator (Xu et al. in Comput Geosci 32:145–165, 2006) coupled to the TMGAS EOS module (Battistelli and Marcolini in Int J Greenh Gas Control 3:481–493, 2009) developed for the TOUGH2 family of reservoir simulators (Pruess et al. in TOUGH2 User’s Guide, Version 2.0, 1999). On the basis of field data, the system is considered in isothermal (50°C) and isobaric (128.5 bar) conditions. The effects of the evolving reservoir gas composition are taken into account before, during, and after CO₂ injection. Fully water-saturated conditions were assumed for the cement sheath and caprock domains. The gas phase does not flow by advection from the reservoir into the interacting domains so that molecular diffusion in the aqueous phase is the most important process controlling the mass transport occurring in the system under study.     

Manipulation of polymer foam structure based on CO2-induced changes in polymer fundamental properties

Foaming of polymers with CO2 has attracted increasing attention in polymer processing studies. Some of the fundamental properties of polymer/CO2 systems is discussed in this short review, including solubility and diffusivity of CO2 in the polymer, polymer crystallization, interfacial tension between the polymer and the gas, and rheology of the CO2/polymers melt. These properties understandably affect the foaming process, and the structures of the foam products. Meanwhile, these properties can be changed via manipulation of CO2 in polymer. The proposed idea is to manipulate the foaming process and the foam structure by CO2-induced changes in these properties. Two cases from the authors＇ laboratory are presented for elucidating how to use the changes to manipulate the foaming process.     

Production of nanomaterials by vaporizing ceramic targets irradiated by a moderate-power continuous-wave CO<Subscript>2</Subscript> laser

The efficiency of utilization of CO ₂ laser energy for vaporization of Al ₂ O ₃ ceramics is evaluated using a mathematical model for the interaction of laser radiation with materials. It is shown that the calculated efficiency of radiation-energy utilization is not higher than 15% at a radiation power density of 10⁵ W/cm ² on the target. On the experimental facility designed for the synthesis of nanopowders, a vaporization rate of 1 g/h was achieved for Al ₂ O ₃, which corresponds to a 3% efficiency of radiation-energy utilization. The dependence of the characteristic particle size of a zirconium oxide nanopowder on helium pressure in the range of 0.01–1.00 atm was studied. Results of experiments on vaporization of multicomponent materials (LaNiO ₃ and the Tsarev meteorite) are given. __________ Translated from Prikladnaya Mekhanika i Tekhnicheskaya Fizika, Vol. 48, No. 2, pp. 172–184, March–April, 2007.     

Alkali-activation reactivity of chemosynthetic Al2O3–2SiO2 powders and their 27Al and 29Si magic-angle spinning nuclear magnetic resonance spectra

Pure Al₂O₃–2SiO₂ powders were prepared by sol–gel and coprecipitation methods, and their alkali-activation reactivities were compared. The alkali-activation reactivity of the powder prepared by the sol–gel method was higher than that of the powder prepared by the coprecipitation method. The powders were investigated by ²⁷Al and ²⁹Si magic-angle spinning nuclear magnetic resonance spectroscopy (MAS NMR) to understand the relationship between their structure and alkali-activation reactivity. The ²⁷Al MAS NMR data showed that the five-coordinate Al content of the powder prepared by the sol–gel method was higher than that of the powder prepared by coprecipitation. The higher content of five-coordinate Al corresponded to higher alkali-activation reactivity. The ²⁹Si MAS NMR data showed that for the powder prepared by the sol–gel method, silicon was replaced by aluminum at secondary coordination sites of the central Si atoms during calcination. However, for the powder prepared by single-batch coprecipitation, the main change was from a low degree of polycondensation to a high degree of polycondensation.