Effect of Ru addition to CO/SiO2/HZSM-5 catalysts on Fischer-Tropsch synthesis of gasoline-range hydrocarbons

Microporous HZSM-5 zeolite and mesoporous SiO2 supported Ru-Co catalysts of various Ru adding amounts were prepared and evaluated for Fischer-Tropsch synthesis (FTS) of gasoline-range hydrocarbons (C-5-C-12). The tailor-made Ru-Co/SiO2/HZSM-5 catalysts possessed both micro- and mesopores, which accelerated hydrocracking/hydroisomerization of long-chain products and provided quick mass transfer channels respectively during FTS. In the same time. Ru increased Cor reduction degree by hydrogen spillover, thus CO conversion of 62.8% and gasoline-range hydrocarbon selectivity of 47%, including more than 14% isoparaffins, were achieved simultaneously when Ru content was optimized at 1 wt% in Ru-Co/SiO2/HZSM-5 catalyst.

Chaotic behavior of pulsating heat pipes

Chaotic behavior of closed loop pulsating heat pipes (PHPs) was studied. The PHPs were fabricated by capillary tubes with outer and inner diameters of 2.0 and 1.20 mm. FC-72 and deionized water were used as the working fluids. Experiments cover the following data ranges: number of turns of 4, 6, and 9, inclination angles from 5 degrees (near horizontal) to 90, (vertical), charge ratios from 50% to 80%, heating powers from 7.5 to 60.0 W. The nonlinear analysis is based on the recorded time series of temperatures on the evaporation, adiabatic, and condensation sections. The present study confirms that PHPs are deterministic chaotic systems. Autocorrelation functions (ACF) are decreased versus time, indicating prediction ability of the system is finite. Three typical attractor patterns are identified. Hurst exponents are very high, i.e., from 0.85 to 0.95, indicating very strong persistent properties of PHPs. Curves of correlation integral versus radius of hypersphere indicate two linear sections for water PHPs, corresponding to both high frequency, low amplitude, and low frequency, large amplitude oscillations. At small inclination angles near horizontal, correlation dimensions are not uniform at different turns of PHPs. The non-uniformity of correlation dimensions is significantly improved with increases in inclination angles. Effect of inclination angles on the chaotic parameters is complex for FC-72 PHPs, but it is certain that correlation dimensions and Kolmogorov entropies are increased with increases in inclination angles. The optimal charge ratios are about 60-70%, at which correlation dimensions and Kolmogorov entropies are high. The higher the heating power, the larger the correlation dimensions and Kolmogorov entropies are. For most runs, large correlation dimensions and Kolmogorov entropies correspond to small thermal resistances, i.e., better thermal performance, except for FC-72 PHPs at small inclination angles of theta < 15 degrees.

Molecular Dynamics Simulation of Methane Hydrate Dissociation Process in the Presence of Thermodynamic Inhibitor

The dissociation of methane hydrate in the presence of ethylene glycol (11.45 mol.L-1) at 277.0 K was studied using canonical ensemble (NVT) molecular dynamics simulations. Results show that hydrate dissociation starts from the surface layer of the solid hydrate and then gradually expands to the internal layer. Thus, the solid structure gradually shrinks until it disappears. A distortion of the hydrate lattice structure occurs first and then the hydrate evolves from a fractured frame to a fractional fragment. Finally, water molecules in the hydrate construction exist in the liquid state. The inner dissociating layer is, additionally, coated by a liquid film formed from outer dissociated water molecules outside. This film inhibits the mass transfer performance of the inner molecules during the hydrate dissociation process.

Numerical simulations of interrupted and conventional microchannel heat sinks

We provide three-dimensional numerical simulations of conjugate heat transfer in conventional and the newly proposed interrupted microchannel heat sinks. The new microchannel heat sink consists of a set of separated zones adjoining shortened parallel microchannels and transverse microchambers. Multi-channel effect, physical property variations, and axial thermal conduction are considered. It is found that flow rate variations in different channels can be neglected, while heat received by different channels accounts for 2% deviations from the averaged value when the heat flux at the back surface of the silicon chip reaches 100 W/cm(2). The computed hydraulic and thermal boundary layers are redeveloping in each separated zone due to shortened flow length for the interrupted microchannel heat sink. The periodic thermal developing flow is responsible for the significant heat transfer enhancement. Two effects influence pressure drops across the newly proposed microchannel heat sink. The first one is the pressure recovery effect in the microchamber, while the second one is the head loss when liquid leaves the microchamber and enters the next zone. The first effect compensates or suppresses the second one, leading to similar or decreased pressure drop than that for the conventional microchannel heat sink, with the fluid Prandtl number larger than unity.

Effect of pulse heating parameters on the microscale bubble dynamics at a microheater surface

We study the effects of pulse heating parameters on the micro bubble behavior of a platinum microheater (100 mu m x 20 mu m) immersed in a methanol pool. The experiment covers the heat fluxes of 10-37 MW/m(2) and pulse frequencies of 25-500 Hz. The boiling incipience is initiated at the superheat limit of methanol, corresponding to the homogeneous nucleation. Three types of micro boiling patterns are identified. The first type is named as the bubble explosion and regrowth, consisting of a violent explosive boiling and shrinking, followed by a slower bubble regrowth and subsequent shrinking, occurring at lower heat fluxes. The second type, named as the bubble breakup and attraction, consists of the violent explosive boiling, bubble breakup and emission, bubble attraction and coalescence process, occurring at higher heat fluxes than those of the first type. The third type, named as the bubble size oscillation and large bubble formation, involves the initial explosive boiling, followed by a short periodic bubble growth and shrinking. Then the bubble continues to increase its size, until a constant bubble size is reached which is larger than the microheater length. 

Periodic bubble emission and appearance of an ordered bubble sequence (train) during condensation in a single microchannel

Condensation of steam in a single microchannel, silicon test section was investigated visually at low flow rates. The microchannel was rectangular in cross-section with a depth of 30 pm, a width of 800 mu m and a length of 5.0 mm, covered with a Pyrex glass to allow for visualization of the bubble formation process. By varying the cooling rate during condensation of the saturated water vapor, it was possible to control the shape, size and frequency of the bubbles formed. At low cooling rates using only natural air convection from the ambient environment, the flow pattern in the microchannel consisted of a nearly stable elongated bubble attached upstream (near the inlet) that pinched off into a train of elliptical bubbles downstream of the elongated bubble. It was observed that these elliptical bubbles were emitted periodically from the tip of the elongated bubble at a high frequency, with smaller size than the channel width. The shape of the emitted bubbles underwent modifications shortly after their generation until finally becoming a stable vertical ellipse, maintaining its shape and size as it flowed downstream at a constant speed. These periodically emitted elliptical bubbles thus formed an ordered bubble sequence (train). At higher cooling rates using chilled water in a copper heat sink attached to the test section, the bubble formation frequency increased significantly while the bubble size decreased, all the while forming a perfect bubble train flowing downstream of the microchannel. The emitted bubbles in this case immediately formed into a circular shape without any further modification after their separation from the elongated bubble upstream. The present study suggests that a method for controlling the size and generation frequency of microbubbles could be so developed, which may be of interest for microfluidic applications. The breakup of the elongated bubble is caused by the large Weber number at the tip of the elongated bubble induced by the maximum vapor velocity at the centerline of the microchannel inside the elongated bubble and the smaller surface tension force of water at the tip of the elongated bubble.

Gasoline-range hydrocarbon synthesis over cobalt-based Fischer-Tropsch catalysts supported onSiO2/HZSM-5

Two types of SiO2 with different mesopore size and HZSM-5 zeolite were used to prepare hybrid supported cobalt-based catalysts. The textual and structural properties of the catalysts were studied using N-2 physisorption, X-ray diffraction (XRD), and H-2 temperature-programmed reduction (TPR) techniques. Fischer-Tropsch synthesis (FTS) performances of the catalysts were carried out in a fixed-bed reactor. The combination effects of the meso- and micropores of the supports as well as the interaction between supports and cobalt particles on FTS activity are discussed. The results indicate that the catalyst supported on the tailor-made SiO2 and HZSM-5 hybrid maintained both meso- and micropore pores during the preparation process without HZSM-5 particles agglomerating. The mesopores provided quick mass transfer channels, while the micropores contributed to high metal dispersion and accelerated hydrocracking/hydroisomerization reaction rate. High CO conversion of 83.9% and selectivity to gasoline-range hydrocarbons (C-5-C-12) of 55%, including more than 10% isoparaffins, were achieved simultaneously on this type of catalyst.

Two-dimensional numerical simulations of shock waves in micro convergent-divergent nozzles

The steady two-dimensional Navier-Stokes equations with the slip wall boundary conditions were used to simulate the supersonic flow in micro convergent-divergent nozzles. It is observed that shock waves can take place inside or outside of the micronozzles under the earth environment. For the over-expanded flows, there is a boundary layer separation point, downstream of which a wave interface separates the viscous boundary layer with back air flow and the inviscid core flow. The oblique shock wave is followed by the bow shock and shock diamond. The viscous boundary layer thickness relative to the whole nozzle width on the exit plane is increased but attains the maximum value around of 0.5 and oscillates against this value with the continuous increasing of the nozzle upstream pressures. The viscous effect either changes the normal shock waves outside of the nozzle for the inviscid flow to the oblique shock waves inside the nozzle, or transfers the expansion jet flow without shock waves for the inviscid flow to the oblique shock waves outside of the nozzle. 

Transient flow patterns and bubble slug lengths in parallel microchannels with oxygen gas bubbles produced by catalytic chemical reactions

Transient flow patterns and bubble slug lengths were investigated with oxygen gas (O-2) bubbles produced by catalytic chemical reactions using a high speed camera bonded with a microscope. The microreactor consists of an inlet liquid plenum, nine parallel rectangular microchannels followed by a micronozzle, using the MEMS fabrication technique. The etched surface was deposited by the thin platinum film, which is acted as the catalyst. Experiments were performed with the inlet mass concentration of the hydrogen peroxide from 50% to 90% and the pressure drop across the silicon chip from 2.5 to 20.0 kPa. The silicon chip is directly exposed in the environment thus the heat released via the catalytic chemical reactions is dissipated into the environment and the experiment was performed at the room temperature level. It is found that the two-phase flow with the catalytic chemical reactions display the cyclic behavior. A full cycle consists of a short fresh liquid refilling stage, a liquid decomposition stage followed by the bubble slug flow stage. At the beginning of the bubble slug flow stage, the liquid slug number reaches maximum, while at the end of the bubble slug flow stage the liquid slugs are quickly flushed out of the microchannels. Two or three large bubbles are observed in the inlet liquid plenum, affecting the two-phase distributions in microchannels. The bubble slug lengths, cycle periods as well as the mass flow rates are analyzed with different mass concentrations of hydrogen peroxide and pressure drops. The bubble slug length is helpful for the selection of the future microreactor length ensuring the complete hydrogen peroxide decomposition. Future studies on the temperature effect on the transient two-phase flow with chemical reactions are recommended.

Boundary conditions at the solid-liquid surface over the multiscale channel size from nanometer to micron

The boundary condition at the solid surface is one of the important problems for the microfluidics. In this paper we study the effects of the channel sizes on the boundary conditions (BC), using the hybrid computation scheme adjoining the molecular dynamics (MD) simulations and the continuum fluid mechanics. We could reproduce the three types of boundary conditions (slip, no-slip and locking) over the multiscale channel sizes. The slip lengths are found to be mainly dependent on the interfacial parameters with the fixed apparent shear rate. The channel size has little effects on the slip lengths if the size is above a critical value within a couple of tens of molecular diameters. We explore the liquid particle distributions nearest the solid walls and found that the slip boundary condition always corresponds to the uniform liquid particle distributions parallel to the solid walls, while the no-slip or locking boundary conditions correspond to the ordered liquid structures close to the solid walls. The slip, no-slip and locking interfacial parameters yield the positive, zero and negative slip lengths respectively. The three types of boundary conditions existing in "microscale" still occur in "macroscale". However, the slip lengths weakly dependent on the channel sizes yield the real shear rates and the slip velocity relative to the solid wall traveling speed approaching those with the no-slip boundary condition when the channel size is larger than thousands of liquid molecular diameters for all of the three types of interfacial parameters, leading to the quasi-no-slip boundary conditions.

Study on methane hydration process in a semi-continuous stirred tank reactor

The methane hydration process is investigated in a semi-continuous stirred tank reactor. Liquid temperatures and reaction rates without stirrer are compared with those occurring with stirrer, while at the same time better stirring conditions of the methane hydration process are given by the experiments. Some basic data of fluid mechanics, for example, stirring Reynolds number, Froucle number and stirrer power, are calculated during the methane hydration process, which can be applied to evaluate stirrer capacity and provide some basic data for a scaled up reactor. Based on experiment and calculations in this work, some conclusions are drawn. First, the stirrer has great influence on the methane hydration process. Batch stirring is helpful to improve the mass transfer and heat transfer performances of the methane hydration process. Second, induction time can be shortened effectively by use of the stirrer. Third, in this paper, the appropriate stirring velocity and stirring time were 320 rpm and 30 min, respectively, at 5.0 MPa, for which the storage capacity and reaction time were 159.1 V/V and 370 min, respectively. Under the condition of the on-flow state, the initial stirring Reynolds number of the fluid and the stirring power were 12,150 and 0.54 W, respectively. Fourth, some suggestions, for example, the use of another type of stirrer or some baffles, are proposed to accelerate the methane hydration process. Comparing with literature data, higher storage capacity and hydration rate are achieved in this work. Moreover, some fluid mechanics parameters are calculated, which can provide some references to engineering application.

Effects of forced solution flow on lysozyme crystal growth

In order to study quantitatively the effects of forced solution on crystal growth, we designed a new set of experimental equipment, in particular, a microchannel mixer was used as crystallization container so that the consumption of protein samples was much reduced and thus an exact syringe pump could be used for precise control of the flow rates. Since the mixer’s section was designed to be rectangular, the solution velocity in its center was steady and constant, and thus repeatable experiments were facilitated. Experimental results showed that the effects of forced solution on protein crystal growth were different under different levels of supersaturation, and new results were obtained for cases of high supersaturation. When the supersaturation is σ = 2.3, with increasing flow rates the growth rates of the lysozyme crystal’s (110) face hardly change when the flow rates are lower than 1300 μm/s, and decrease quickly afterwards. When the flow rate reaches 2000 μm/s, the crystal nearly ceases to grow. When the supersaturation is σ = 2.7, with increasing flow rates the (110) face growth rates increase at the beginning then reach the maximum values at 1700 μm/s – 1900 μm/s and decrease afterwards, approaching zero or so when the flow rate reaches 12000 μm/s. The higher the supersaturation, the larger the flow rate at which the crystal ceases to grow. © 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim