Thresholds of secondary organic aerosol formation by ozonolysis of monoterpenes measured in a laminar flow aerosol reactor

The reactions of ozone with a series of monoterpenes (α-pinene, sabinene, limonene and myrcene) were investigated in a novel flow reactor dedicated to the investigation of secondary organic aerosol (SOA) formation. Rate constants for the gas phase reactions and nucleation thresholds were determined at T～296 K, P～764 Torr under dry conditions (dew point ≤?33 °C) and in absence of OH radicals scavenger and seed particles. Comparison with the literature as well as data from a simulation chamber showed good agreement. The experiments also show that the novel flow reactor improves the accuracy in evaluating the nucleation thresholds during the ozonolysis of monoterpenes and show that aerosol flow reactor is a useful tool to study the SOA nucleation step. Given as an upper limit, the nucleation thresholds obtained are (in molecule cm^?3/ppb): α-pinene, 3.9×10¹⁰/1.56; sabinene, 6.2×10⁹/0.26; limonene, 1.1×10¹⁰/0.43 and myrcene 2.1×10¹⁰/0.83.     

Modeling of nano-particle precipitation process in a membrane dispersion micro-structured reactor

In our previous work, a membrane dispersion micro-structured reactor has been successfully applied to the preparation of nano-particles. It is a general requirement to model the process for large scale production. The classic precipitation theory, population balance model (PBM), as the main model has been tested in this work, and it has been found that the classic model by introducing a parameter of mixing scale can reliably simulate the process. The model is used to calculate the precipitation of BaSO₄ nano-particles. The diffusion of reactants, nucleation, growth and particle agglomeration have been considered in the model. The evolutions of supersaturation ratio and particle number density distribution with the model can be predicted clearly, which help us to understand the effect of mixing scale on the three stages of pre-nucleation, nucleation and growth. The particle size and its distribution are also calculated and the results are in good agreement with the experimental data.     

Controlled synthesis of alumina in a spray flame aerosol reactor

In this study, a spray flame aerosol reactor (S-FLAR) is used to synthesize alumina nanoparticles. The as-produced powders are then characterized by X-ray diffraction, N₂ physisorption, and transmission electron microscopy to determine the crystal phase, surface area, particle size distribution, and morphology. The effects of the precursor, dispersion oxygen, and sheath oxygen rates on the characteristics of synthesized alumina were investigated. On increasing the precursor rate, decreasing the dispersion oxygen rate or sheath oxygen rate; the alumina powder surface area decreased. With increasing precursor rates and decreasing dispersion oxygen rates, the proportion of theta alumina increased and that of eta alumina decreased. When using an S-FLAR to synthesize alumina, the dispersion oxygen rate offers the best control of the surface area, while the precursor rate controls the crystal phase proportions. This result is useful for the design and operation of spray flame aerosol reactors to produce alumina-based catalysts.     

A numerical investigation of aerosol dynamics in a wall-less reactor

This paper describes a numerical investigation of aerosol formation during silane decomposition in a wall-less reactor. The wall-less reactor is amenable to numerical investigation because the homogeneous chemical reactions leading to the formation of solid particles are isolated from heterogeneous effects, such as occur at the walls of a laminar flow aerosol reactor. The flow/heat transfer and gas-phase chemical kinetics are simulated utilizing separate one-way coupled models. The aerosol dynamics model is based on a simplified sectional model originally developed by Okuyama et al. This model is modified to allow for the simulation of particle growth via condensation. Simulations have been performed which indicate that particle growth via condensation may be an important process. Additionally, the effects of total reactor pressure, temperature and inlet silane concentration on the dynamics of the aerosol population have been investigated. Conditions which result in the formation of larger and more numerous particles have been identified.     

Evaporative cooling of micron-sized droplets in a low-pressure aerosol reactor

The results of experimental and computational investigation of evaporative cooling of micron-sized droplets in a low-pressure aerosol reactor (LPAR) are reported. The cooling rate of the aerosol was found to be about . A constant low pressure, the flow rates of the carrier gas and solution are major factors that affect droplet cooling. A higher total pressure accelerated the change in droplet radius. For some regimes it was predicted that an aerosol undergoes freezing and then melting. The characteristic time required for evaporative cooling is about 1 ms. The agreement between experimental results and calculated values, based on the free molecular approximation of heat and mass transfer processes, is reasonably good.     

Small bubble formation via a coalescence dependent break-up mechanism

A mechanism has been elucidated for the coalescence-mediated break-up of bubbles in gas-liquid systems. Images taken from dynamic systems (a coalescence cell and laboratory-scale bubble columns) show that in some instances the coalescence of two bubbles is accompanied by the formation of a much smaller daughter bubble. Following the coalescence process an annular wave is formed due to the very rapid expansion of the hole following the instant of film rupture. As the wave moves along the length of the bubble, away from the point of rupture it causes a rippling effect which distorts the newly coalesced bubble and may result in the formation of an unstable extension. Instabilities due to the annular wave pinch off a portion of this extension, resulting in the generation of a small daughter bubble. In coalescence dominated systems the process results in the generation of significant numbers of bubbles much smaller (100- diameter) than the Sauter mean diameter (3-).     

Single-step processing of copper-doped titania nanomaterials in a flame aerosol reactor

Synthesis and characterization of long wavelength visible-light absorption Cu-doped TiO2 nanomaterials with well-controlled properties such as size, composition, morphology, and crystal phase have been demonstrated in a single-step flame aerosol reactor. This has been feasible by a detailed understanding of the formation and growth of nanoparticles in the high-temperature flame region. The important process parameters controlled were: molar feed ratios of precursors, temperature, and residence time in the high-temperature flame region. The ability to vary the crystal phase of the doped nanomaterials while keeping the primary particle size constant has been demonstrated. Results indicate that increasing the copper dopant concentration promotes an anatase to rutile phase transformation, decreased crystalline nature and primary particle size, and better suspension stability. Annealing the Cu-doped TiO2 nanoparticles increased the crystalline nature and changed the morphology from spherical to hexagonal structure. Measurements indicate a band gap narrowing by 0.8 eV (2.51 eV) was achieved at 15-wt.% copper dopant concentration compared to pristine TiO2 (3.31 eV) synthesized under the same flame conditions. The change in the crystal phase, size, and band gap is attributed to replacement of titanium atoms by copper atoms in the TiO2 crystal.     

Analysis of iron particle growth in aerosol reactor by a discrete-sectional model

The growth of iron particles by thermal decomposition of Fe(CO)₅ in a tubular reactor was analyzed by using a one dimensional discrete-sectional model with the coalescence by sintering of neighboring particles incorporated in. A thermal decomposition of Fe(CO)₅ vapor to produce iron particles was carried out at reactor temperatures varying from 300 to 1,000°C, and the effect of reactor temperature on particle size was compared with model prediction. The prediction exhibited good agreement with experimental observation that the primary particle size of iron was the largest at an intermediate temperature of 800°C. Model prediction was also compared with Giesen et al.’s [1] experimental data on iron particle production from Fe(CO)₅. Good agreement was shown in primary particle size, but a considerable deviation was observed in primary particle size distribution. The deviation may be due to an inadequate understanding of the sintering mechanism for the particles within an agglomerate and to the assumption of an ideal plug flow in model reactor in contrast to the non-ideal dispersive flow in actual reactor.     

Simulation of hydrocarbons pyrolysis in a fast-mixing reactor

Currently, thermal decomposition of hydrocarbons for the production of basic petrochemicals (ethylene, propyl-ene) is carried out in steam-cracking processes. Aside from the conventional method, under consideration are alternative ways purposed for process intensification. In the context of these activities, the method of high-temperature pyrolysis of hydrocarbons in a heat-carrier flow is studied, which differs from previous ones and is based on the ability of an ultra-short time of feedstock/heat-carrier mixing. This enables to study the pyrolysis process at high temperature (up to 1500 K) at the reactor inlet. A set of model experiments is conducted on the lab scale facility. Liquefied petroleum gas (LPG) and naphtha are used as a feedstock. The detailed data are obtain-ed on temperature and product distributions within a wide range of the residence time. A theoretical model based on the detailed kinetics of the process is developed, too. The effect of governing parameters on the pyrolysis process is analyzed by the results of the simulation and experiments. In particular, the optimal temperature is detected which corresponds to the maximum ethylene yield. Product yields in our experiments are compared with the similar ones in the conventional pyrolysis method. In both cases (LPG and naphtha), ethylene selectivity in the fast-mixing reactor is substantial y higher than in current technology.     

The effect of aerosol reactor residence time distribution on product aerosol characteristics

A theoretical study of the performance of continuous stirred tank and tubular flow aerosol reactors is presented. In all reactors considered, the aerosol properties are determined by chemical reaction, nucleation and aerosol growth in the free molecule regime in the absence of coagulation. Three to five dimensionless groups, depending on reactor type, affect the product aerosol characteristics (polydispersity, concentration, average size, surface area and yield). The uniformity of the product aerosol can be substantially improved by seeding. Aerosol reactors can be used in powder production or in chemical vapor deposition.     

Population balance modelling of droplet coalescence and break-up in an oscillatory baffled reactor

This paper presents new population balance analysis to describe simultaneous coalescence and break-up in the formation of methylmethacrylate droplets in a batch oscillatory baffled reactor. It is concluded that the droplet data can very well be described by a model in which coalescence is taken to be shear induced, selection for break-up proceeds at a rate proportional to droplet volume and approximately four equally sized break-up fragments are produced per break-up event. It is shown that the experimental droplet size distribution data are self-similar in form and exhibit asymptotic behaviour characteristics also seen in the model. The coalescence rate is found to vary as the square of the oscillation frequency and the selection rate to vary with the oscillation frequency to the power five. As a result the asymptotic mean droplet volume is inversely proportional to the oscillation frequency.     

Simulation of ethylene epoxidation in a multitubular transport reactor

It has been demonstrated that increased yields of ethylene oxide are obtained with a fixed-bed reactor operating with multiple injection of oxygen and cyclic adsorption-desorption of the desired reaction product. In certain conditions, this reactor simulates the operation of a larger two-tube transport reactor; the latter reactor may, in turn, be used to simulate large-scale commercial multitubular transport reactors. The small fixed-bed reactors may also be used for optimization of the process. The reaction of ethylene epoxidation on a silver catalyst is a good illustration of the advantages of a multitubular transport reactor and of this new method of simulation and optimization.     

乙苯脱氢规整反应器的模拟研究

采用COMSOL Multiphysics软件对规整及散堆固定床反应器内的乙苯脱氢反应进行了模拟计算,对比了等温和绝热条件下2种反应器的性能,研究了反应器串联段数、工艺条件、催化剂结构对绝热规整反应器内乙苯脱氢反应性能的影响。结果表明:等温和绝热条件下,与颗粒散堆固定床相比,规整反应器的乙苯转化率更高、苯乙烯选择性更高、反应器压降更小。进料温度为893 K、压力为104 k Pa时,绝热规整反应器中乙苯转化率为54.81%,苯乙烯选择性为94.84%,而绝热散堆固定床仅为39.55%和92.52%。对于绝热规整反应器,三段工艺的乙苯转化率和苯乙烯收率比一段或二段工艺高;升高温度、降低压力可以提高乙苯转化率,且较低的温度和压力可得到较高的苯乙烯选择性;减小催化剂孔壁厚度可以得到更高的乙苯转化率和苯乙烯选择性,适宜孔壁厚度为0.2 mm;催化剂孔密度对反应性能几乎没影响。     

Simulation of fluid dynamics in a microchannel Fischer-Tropsch reactor

Fluid dynamics in a microchannel of a new-generation Fischer-Tropsch reactor for artificial petroleum synthesis is reported. Liquid and gaseous product downflows are modeled in the annular flow approximation. The conjugate flow of gaseous and liquid products is investigated in terms of integral momentum balance equations with capillary effects and microchannel wall roughness taken into consideration. A simulation procedure appropriate for the method of deposition of catalyst particles onto the inner wall is suggested for modeling a random inner surface of the microchannel. The simulation procedure takes into account the variation of the synthesis product composition and the variation of the thermal properties of the liquid and gas phases along the microchannel length. A stable computational procedure has been devised for calculating fluid dynamic parameters of the two-phase flow. The effects of the synthesis gas flow rate and conversion, microchannel diameter, chain propagation constant, temperature, and pressure on the two-phase flow parameters and on the aerodynamic resistance of the gas have been investigated.     

Chemical absorption of mercaptan in an aerosol operated loop reactor

A mechanistic mathematical model for the chemical absorption of mercaptan in sodium hypochlorite solution has been derived. In order to describe the process adequately, a semi-verified complex scheme of the involved kinetic reactions based on stopped-flow measurements with UV-detection has been implemented. The overall system of differential equations has been solved numerically. For some asymptotic cases, approximation formulae are given. The process has been carried out in an aerosol operated jet loop reactor which is characterized by high interfacial areas at low liquid flow rates. Fitting the model solution to the experimentally obtained conversion data enabled determination of the unknown hydrodynamic parameters. By means of a sensitivity analysis, the influences of the different parameters are discussed.     

Coke formation during naphtha pyrolysis in a tubular reactor

The effect of run time, temperature, conversion and inlet steam-to-naphtha ratio on the rate of coke deposition during naphtha pyrolysis in an annular tubular reactor has been investigated. Rates of coke deposition increased with increasing temperature, conversion and inlet naphtha partial pressure. Pyrolysis and coking models available for naphtha cracking were used to calculate the total coke deposited by treating the temperature difference between the reacting fluid and the outer reactor wall as a parameter. For all the runs, the experimental and calculated coking rates were in close agreement for an assumed temperature difference of 35-45°C.     

Simulation of heat and mass transfer in the coalescence of droplets in a gas-drop flow

The simplified mathematical model for calculating the renewal of the surface and intensification of heat and mass transfer in the coalescence of two drops in a gas-drop flow has been proposed. The model is based on the energetic analysis of the dynamics of collisions and the coalescence of drops.