Influence of 3A molecular sieve to tetrahydrofuran(THF) hydrate formation

Visual observation of the THF hydrate formation process in the presence of a 3A molecular sieve has been made at normal atmosphere and below a temperature of zero by microscopy. The results indicate that a 3A molecular sieve can induce the nucleation of the THF hydrate and promote the THF hydrate growth. With the existence of a 3A molecular sieve, the growth rate of THF hydrate is between 0.01 and 0.05 mu m/s. In comparison with the system without any 3A molecular sieve, the growth rate increases about 4 nm/s. After the THF hydrate grows into megacryst, the crystals will recombine and partially change under the same condition.

Use of electrical resistance to detect the formation and decomposition of methane hydrate

The changes of electrical resistance (R) were studied experimentally in the process of CH4 hydrate formation and decomposition, using temperature and pressure as the auxiliary detecting methods simultaneously. The experiment results show that R increases with hydrate formation and decreases with hydrate decompositon. R is more sensitive to hydrate formation and decompositon than temperature or pressure, which indicates that the detection of R will be an effective means for detecting natural gas hydrate (NGH) quantitatively.

Determination of appropriate condition on replacing methane from hydrate with carbon dioxide

This paper is intended to determine the appropriate conditions for replacing CH4 from NGH with CO2. By analyzing the hydration equilibrium graphs and geotherms, the HSZs of NGH and CO2 hydrate, both in permafrost and under deep sea, were determined. Based on the above analysis and experimental results, it is found that to replace CH4 from NGH with gaseous CO2, the appropriate experimental condition should be in the area surrounded by four curves: the geotherm, (H-V)(CO2), (L-V)(CO2) and (H-V)(CH4), and to replace CH4 from NGH with liquid CO2, the condition should be in the area surrounded by three curves: (L-V)(CO2), (H-L)(CO2) and (H-V)CH4. For conditions in other areas, either CO2 can not form a hydrate or CH4 can release little from its hydrate, which are not desirable results.

Hydrate dissociation conditions for gas mixtures containing carbon dioxide, hydrogen, hydrogen sulfide, nitrogen, and hydrocarbons using SAFT

A new method, a molecular thermodynamic model based on statistical mechanics, is employed to predict the hydrate dissociation conditions for binary gas mixtures with carbon dioxide, hydrogen, hydrogen sulfide, nitrogen, and hydrocarbons in the presence of aqueous solutions. The statistical associating fluid theory (SAFT) equation of state is employed to characterize the vapor and liquid phases and the statistical model of van der Waals and Platteeuw for the hydrate phase. The predictions of the proposed model were found to be in satisfactory to excellent agreement with the experimental data.

Control mechanisms for gas hydrate production by depressurization in different scale hydrate reservoirs

The methane hydrate was formed in a pressure vessel 38 mm in id and 500 mm in length. Experimental works on gas production from the hydrate-bearing core by depressurization to 0.1, 0.93, and 1.93 MPa have been carried out. The hydrate reservoir simulator TOUGH-Fx/Hydrate was used to simulate the experimental gas production behavior, and the intrinsic hydration dissociation constant (K-0) fitted for the experimental data was on the order of 104 mol m(-2) Pa-1 s(-1), which was one order lower than that of the bulk hydrate dissociation. The sensitivity analyses based on the simulator have been carried out, and the results suggested that the hydrate dissociation kinetics had a great effect on the gas production behavior for the laboratory-scale hydrate-bearing core. However for a field-scale hydrate reservoir, the flow ability dominated the gas production behavior and the effect of hydrate dissociation kinetics on the gas production behavior could be neglected.

Clathrate Dissociation Conditions for Methane + Tetra-n-butyl Ammonium Bromide (TBAB) + Water

Hydrate equilibrium data of the CH4 + tetra-n-butyl ammonium bromide (TBAB) + water have been measured by using the isothermal pressure search method for four components of TBAB aqueous solutions. The three-phase equilibrium lines obtained in the present study are shifted to the low-temperature or high-pressure side from that of the stoichiometric TBAB solution. Moreover, methane uptake into semi-clathrates is confirmed by a shift in the clathrate regions when methane is present. The experiments are carried out in the pressure range of (0.5 to 11) MPa and in the temperature range of (281.15 to 295.15) K.

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.

Study on the kinetics of hydrate formation in a bubble column

Gas hydrate formation experiments were performed using methane in the presence of tetrahydrofuran (THF) in aqueous solution in a transparent bubble column in which a single pipe or a sintered plate was used to produce bubbles. The mole fraction of THF in aqueous solution was fixed at 6%. The hydrate formation kinetic behaviors on the surface of the rising bubble, the mechanical stability of hydrate shell formed on the surface of the bubble, the interactions among the bubbles with hydrate shell were observed and investigated morphologically. The rise velocities of individual bubbles with hydrate shells of different thickness and the consumption rates of methane gas were measured. A kinetic model was developed to correlate the experimentally measured gas consumption rate data. It was found that the hydrate formation rate on the surface of the moving bubble was high, but the formed hydrate shell was not very easy to be broken up. The bubbles with hydrate shells tended to agglomerate rather than merge into bigger bubble. This kind of characteristic of hydrate shell hindered the further formation of hydrate and led to the lower consumption rate of methane. The consumption rate of methane was found to increase with the decrease of temperature or increase of pressure. The increase of gas flux led to a linear increase in consumption rate of methane. It was demonstrated that the developed kinetic model could be used to correlate the consumption rate satisfyingly.

Polarization patterns control based on photoinduced anisotropy of photochromic fulgide

We investigate the photoinduced anisotropy of a photochromic material of pyrrylfulgide/PMMA films. It is proven that when the film is illuminated with a linear polarization light, an optical axis that has the same polarization as the excitation light could be induced in the film. A matrix of light spots with different polarizations is recorded on the pyrrylfulgide/PMMA film. When reading out with non-polarization light, the matrix of light spots shows no information of patterns. However, when reading out with different linear polarization lights, different patterns could be observed. The experiment confirms that the pyrrylfulgide/PMMA film could be used to record two different polarization patterns in a matrix of spots. This property may be applied in camouflage technology.

Bleaching kinetics of indoly-benzylfulgimide in PMMA

Indoly-benzlfulgimide belongs to the photochromic fulgide family and follows photochemical first order kinetics. Its bleaching kinetics is investigated at 633 nm and 640 nm by spectroscopy, by the time dependence of transmission and of diffraction from holographically induced gratings. The non-exponential decay law resulting for diffraction experiments with a Gaussian beam profile is calculated and verified experimentally. For a quasi-homogeneous beam profile the time constant determined from diffraction decay is half the one for absorbance decay. The photochemical reaction rate of indoly-benzylfulgimide in PMMA is (3.9 +/- 0.3) cm(2)/J at 650 nm. (c) 2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Absorbance kinetics of dye-doped systems with photochemical first order kinetics

Often it is assumed that absorbance decays in photochromic materials with the time dependence of the photochemical kinetics, i.e. exponentially for first order kinetics. Although this may hold in the limiting case of vanishing absorbance, deviations are to be expected for realistic samples, because the local photochemical kinetics slows down with increasing initial absorption and penetration depth of the radiation. We discuss the theory of the kinetics of initially homogeneous photochromic samples and derive analytical solutions. In extension of Tomlinson's theory we find an analytical solution that holds with good approximation even for samples that exhibit a small residual absorption in the saturation limit. The theoretical time dependence of the absorbance originating from photochemical first order kinetics of dye-doped systems is compared with experimental data published by Lafond et al. for fulgides doped in different polymer matrices. (c) 2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Photochromic fulgide for holographic recording

(N-4'-methoxy-2-methyl-5-phenyl)-3-pyrryl-ethylidene (isopropylidene) succinic anhydride fulgide, doped in PMMA matrix, exhibits photochromic behavior. The fatigue resistance experiment shows no photodegradation is detected after more than 450 writing-erasing cycles. Study of fulgide material for holographic recording media shows the optimal exposure and the diffraction efficiency is 1047 mJ/cm(2) and 2.26%, respectively, with 10 mum thickness polymer film. Holographic grating with 1680 lines/mm at writing angle theta = 30degrees is also obtained. (C) 2004 Elsevier B.V. All rights reserved.

Preparation and luminescence properties of Eu2+ in SiO2 xerogels

Al-doped and B, Al co-doped SiO2 xerogels with Eu2+ ions were prepared only by sol-gel reaction in air without reducing heat-treatment or post-doping. The luminescence characteristics and mechanism of europium doping SiO2 xerogels were studied as a function of the concentration of Al, B, the europium concentration and the host composition. The emission spectra of the Al-doped and B, Al codoped samples all show an efficient emission broad band in the blue violet range. The blue emission of the Al-doped sample was centered at 437 nm, whereas the B, Al co-doped xerogel emission maximum shifted to 423 nm and the intensity became weaker. Concentration quenching effect occurred in both the Al-doped and B, Al co-doped samples, which probably is the result of the transfer of the excitation energy from Eu2+ ions to defects. The highest Eu2+ emission intensity was observed for samples with the Si(OC2H5)(4):C2H5OH:H2O molar ratio of 1:2:4. (c) 2006 Elsevier B.V. All rights reserved.

Dual-wavelength photochromic fulgides for parallel recording memory

Two photochromic fulgides, 2-{2-[4-(N,N-dimethylnilino)-5-methyl-4-oxazoly]}ethylidene-4-(1-methylethylidene) tetrahydrofuran-2,5-dione (A) and 3-(1,2-dimethyl-5-phenyl-3-pyrolloethylidene)-4-(1-methylethylidene)tetrahydrofuran-2,5-dione (B), doped in PMMA as candidates of dual-wavelength optical memory for parallel recording has been investigated. With 488 nm-laser and 650 nm-laser, both "cross" and "star" images are recorded on the fulgides-PMMA film and read out clearly, respectively. Crosstalk between two fulgides in PMMA matrix and nondestructive readout has also been explored. The results show that no significant cross-talk is detected between them, and nondestructive readout is up to 201 times. (C) 2005 Elsevier B.V. All rights reserved.

Experimental investigation of parallel optical data storage using pyrrylfulgide photochromic material

The optical storage characteristics of a new kind of organic photochromic material-pyrrylfulgide were experimentally investigated in the established parallel optical data storage system. Using the pyrrylfulgide/PMMA film as a photon-mode recording medium, micro-images and encoded binary digital data were recorded, readout and erased in this parallel system. The storage density currently reaches 3 x 10(7) bit/cm(2). The recorded information on the film can be kept for years in darkness at room temperature.