scholarly journals Adsorption Compression Analysis for Supercritical Fluids using Ono-Kondo Model

2012 ◽  
Vol 11 (2) ◽  
pp. 45
Author(s):  
Panita Sumanatrakul ◽  
Chayanoot Sangwichien ◽  
Gregory Aranovich ◽  
Marc D Donohue
Keyword(s):  
Supercritical Fluids ◽  
High Pressures ◽  
The Other ◽  
Kondo Model ◽  
Zeolite 13X ◽  
Adsorbed Phase ◽  
Supercritical Adsorption ◽  
Attractive Region ◽  
Linear Sections ◽  
Low Pressures

In this paper, supercritical data has been evaluated and shown to demonstrate adsorption compression. Ono-Kondo analysis of adsorption isotherms for supercritical systems (including nitrogen, methane, and carbon dioxide on activated carbon Filtrasorb 400 and on zeolite 13X) indicates adsorption compression phenomenon at high pressure end just as in subcritical systems. Experimental isotherms for adsorption of supercritical fluids are plotted in Ono-Kondo coordinates with the Henry’s constant estimated based on results of modeling as well as calorimetric and chromatographic measurements. The linear sections of the results show the range of applicability of the classical Ono-Kondo model with constant energies of interactions. The slopes of these linear sections represent values and signs of these energies: negative slopes indicate repulsive interactions in adsorbed phase due to adsorption compression. Switching interactions from attractive to repulsive with an increase in the pressure for supercritical adsorption suggests that adsorbed phase has two regions. One is an attractive region at low-pressures and the other is a repulsive region at high pressures. It can be indicated that the shape of isotherms in Ono-Kondo coordinates can help to understand adsorbate-adsorbate energies; the slope of the line in Ono-Kondo coordinates gives the sign and magnitude of the energy as a function of adsorbate density.

A mathematical model for hydrocarbon autoignition at high pressures

1975 ◽  
Vol 346 (1647) ◽  
pp. 515-538 ◽  
Keyword(s):  
Mathematical Model ◽  
High Pressures ◽  
The Other ◽  
Chain Mechanism ◽  
Rapid Compression Machine ◽  
High Pressure And Temperature ◽  
Cool Flame ◽  
Induction Periods ◽  
Branched Chain ◽  
Low Pressures

We have developed a generalized mathematical model for the autoignition of hydrocarbons under the conditions of high pressure and temperature achieved in a rapid-compression machine. The model is able to simulate the essential phenomena of the two-stage autoignition of alkanes under these conditions; these are a well-defined cool flame that is often quenched rapidly and completely before the onset of a sharp ignition. It also pre­dicts correctly the transition to single-stage autoignition at even higher temperatures and the variation with temperature of the characteristic induction periods. The model is based on a degenerate-branched-chain mechanism. We show that it must contain as necessary features two termination processes, one linear and the other quadratic in radial concen­tration, and two routes for the formation of branching agent, one of which involves intermediate products of oxidation. The model also predicts, without any adjustment of the kinetic parameters, the essential pheno­mena of cool-flame and ignition behaviour that are observed at low pressures.

On the diffusion of gases through metals

1936 ◽  
Vol 32 (4) ◽  
pp. 657-662 ◽  
Author(s):  
Jwu-Shi Wang
Keyword(s):  
High Pressures ◽  
Adsorbed Layer ◽  
Experimental Results ◽  
The Other ◽  
Important Process ◽  
Low Pressures ◽  
Diffusion Of Hydrogen ◽  
Diffusion Of Gases

The results of experiments on the diffusion of hydrogen through metals from a pressure p on one side to a vacuum on the other show that at high pressures the amount diffusing varies linearly with p½ but that at low pressures it varies more rapidly. The difficulty usually encountered when diffusion from an adsorbed layer into the solid is considered theoretically is that the theory indicates that saturation should be reached. In this paper it is shown that this difficulty is due to the omission of an important process at the surface and that by including this process the experimental results can be explained.

On the Negative Excess Isotherms for Methane Adsorption at High Pressure: Modeling and Experiment

SPE Journal ◽  
2019 ◽  
Vol 24 (06) ◽  
pp. 2504-2525 ◽  
Author(s):  
Jing Li ◽  
Keliu Wu ◽  
Zhangxin Chen ◽  
Kun Wang ◽  
Jia Luo ◽  
...  
Keyword(s):  
High Pressure ◽  
Mass Balance ◽  
High Pressures ◽  
Pore Wall ◽  
Void Volume ◽  
Excess Adsorption ◽  
Experimental Conditions ◽  
Accessible Volume ◽  
Adsorbed Phase

Summary An excess adsorption amount obtained in experiments is always determined by mass balance with a void volume measured by helium (He) –expansion tests. However, He, with a small kinetic diameter, can penetrate into narrow pores in porous media that are inaccessible to adsorbate gases [e.g., methane (CH4)]. Thus, the actual accessible volume for a specific adsorbate is always overestimated by an He–based void volume; such overestimation directly leads to errors in the determination of excess isotherms in the laboratory, such as “negative isotherms” for gas adsorption at high pressures, which further affects an accurate description of total gas in place (GIP) for shale–gas reservoirs. In this work, the mass balance for determining the adsorbed amount is rewritten, and two particular concepts, an “apparent excess adsorption” and an “actual excess adsorption,” are considered. Apparent adsorption is directly determined by an He–based volume, corresponding to the traditional treatment in experimental conditions, whereas actual adsorption is determined by an adsorbate–accessible volume, where pore–wall potential is always nonpositive (i.e., an attractive molecule/pore–wall interaction). Results show the following: The apparent excess isotherm determined by the He–based volume gradually becomes negative at high pressures, but the actual one determined by the adsorbate–accessible volume always remains positive.The negative adsorption phenomenon in the apparent excess isotherm is a result of the overestimation in the adsorbate–accessible volume, and a larger overestimation leads to an earlier appearance of this negative adsorption.The positive amount in the actual excess isotherm indicates that the adsorbed phase is always denser than the bulk gas because of the molecule/pore–wall attraction aiding the compression of the adsorbed molecules. Practically, an overestimation in pore volume (PV) is only 3.74% for our studied sample, but it leads to an underestimation reaching up to 22.1% in the actual excess amount at geologic conditions (i.e., approximately 47 MPa and approximately 384 K). Such an overestimation in PV also underestimates the proportions of the adsorbed–gas amount to the free–gas amount and to the total GIP. Therefore, our present work underlines the importance of a void volume in the determination of adsorption isotherms; moreover, we establish a path for a more–accurate evaluation of gas storage in geologic shale reservoirs with high pressure.

THE ISOPIESTIC METHOD APPLIED TO SORPTION ISOTHERMS

1949 ◽  
Vol 27b (2) ◽  
pp. 87-100 ◽  
Author(s):  
S. Barnartt ◽  
J. B. Ferguson
Keyword(s):  
Carbon Tetrachloride ◽  
Linear Relation ◽  
Sorption Isotherms ◽  
Sorption Process ◽  
The Other ◽  
Isopiestic Method ◽  
Simple Criterion ◽  
Water Vapors ◽  
Linear Sections ◽  
Wide Pressure

The isopiestic method has been applied to the sorption of carbon tetrachloride and water vapors by activated coconut shell charcoals. The isopiestic charges were found to be linearly related over wide pressure ranges. Isotherms formed by plotting the isopiestic charges of two charcoals one against the other consisted of three linear sections for both carbon tetrachloride and water. If the pressure isotherm of one charcoal be known, those of other charcoals may be computed from it by weighing relatively few isopiestic charges. Errors inherent in the measurement of equilibrium pressures, as well as those caused by the drift of the pressure isotherms towards higher sorption capacities at a given pressure, are eliminated in the isopiestic method of comparing charcoals. The linear relation between the isopiestic charges affords a simple criterion of rejection for equations proposed to fit the pressure isotherms. It also throws into relief the structural regularities in activated charcoals. The existence of discontinuities m the sorption process, reported by previous experimenters, is supported by the isopiestic data.

scholarly journals The thermal decomposition of nitrogen pentoxide at low pressures

1925 ◽  
Vol 109 (751) ◽  
pp. 526-540 ◽  
Keyword(s):  
Thermal Decomposition ◽  
The Other ◽  
Nitrogen Tetroxide ◽  
Nitrogen Pentoxide ◽  
Other Hand ◽  
Rate Of Reaction ◽  
Reaction Proceeds ◽  
Products Of Reaction ◽  
Glass Surfaces ◽  
Low Pressures

Unimolecular reactions possess a unique interest in that, as Perrin (‘Ann. Physique,’ vol. 11, p. 5, 1919) first pointed out, for the occurrence of such, some type of interaction between radiation and matter must take place. Although such reactions appear to be extremely rare, many physical processes such as evaporation, ionisation in gases at high temperatures and radio-active decay, proceed at rates conforming to a unimolecular law; true chemical reactions which are definitely unimolecular and not pseudo-unimolecular in character are, on the other hand, stated by many ( e. g ., Lowry, ‘Trans. Farad. Soc.,’ vol. 17, p. 596 (1922) ) to be non-existent. In order to substantiate this statement, it is clearly necessary to prove the more complex character of any reaction which satisfies the usual criteria of unimolecular change. The thermal decomposition of gaseous nitrogen pentoxide apparently fulfils these conditions, for Daniels and Johnston (‘J. Am. C. S.,’ vol. 43, p. 53 (1921)) showed that the reaction proceeded according to a unimolecular law over wide ranges of variation of pressure, and Lueck ( ibid ., vol. 44, p. 757 (1922)) obtained practically identical unimolecular constants for the decomposition in solution in carbon tetrachloride and chloroform. On the other hand, Daniels, Wulf and Karrer ( ibid ., vol. 44, p. 2402 (1922) ) suspected the reaction to be autocatalytic, owing to the apparent retardation of the reaction velocity in the presence of ozone, but the experiments of one of us (Hirst, ‘J. C. S.,’ vol. 127, p. 657 (1925), and of White and Tolman (‘J. Am. C. S.’ vol. 47, p. 1,240 (1925)) proved this to be erroneous. In addition, it has been shown that the reaction proceeds uniformly according to the unimolecular law even in the presence of extensive glass surfaces, or of gases which may be either indifferent, such as argon and nitrogen, or the products of reaction, such as nitrogen tetroxide or dioxide or oxygen. The rate of reaction may be expressed in the form - d C/ dt = 4·98 × 10 13 e -24.700/RT . C. Attempts have been made to interpret the experimental results on the hypothesis that the reaction is in reality bimolecular, and only apparently unimolecular in character; but owing to the abnormally large value of the energy of activation, namely, 24,700 calories per gram. molecule, the number of molecules which could be activated per second by inelastic collision, calculated according to the kinetic theory, falls far short of the observed reaction rate, being, in fact, some 10 5 times smaller.

scholarly journals Comparison of gas dehydration methods based on energy consumption

2016 ◽  
Vol 20 (2) ◽  
pp. 253-258
Author(s):  
B.S. Kinigoma ◽  
G.O. Ani
Keyword(s):  
Energy Consumption ◽  
Natural Gas ◽  
High Pressures ◽  
Energy Requirement ◽  
Chemical Properties ◽  
Triethylene Glycol ◽  
Design Engineers ◽  
Natural Gas Dehydration ◽  
Physical And Chemical ◽  
Low Pressures

This study compares three conventional methods of natural gas (Associated Natural Gas) dehydration to carry out the dehydration process and suitability of use on the basis of energy requirement. These methods are Triethylene Glycol (TEG) absorption, solid desiccant adsorption and condensation. Analyses performed were based on dehydration of Natural Gas saturated with 103Nm3/h water content at a temperature range of -10O C to 30oC, and gas pressure variation between 7MPa and 20MPa. This analysis and study showed that energy required for all three processes decreases with increase in pressure, but condensation dehydration requires the least energy at high pressures. Results obtained shows that, both at high pressures and low pressures, TEG dehydration is most suitable and in cases where very low Tdew is required, solid desiccant adsorption is preferable. In conclusion, the findings in this paper will aid natural gas process design engineers to decide on what method to use base  on energy consumption and on the physical and chemical properties of the final products.Keywords: Dehydration, Absorption, Desiccant, Condensation, Triethylene Glycol (TEG)

THE KINETICS OF THE DECOMPOSITION REACTIONS OF THE LOWER PARAFFINS: I. n-BUTANE

1938 ◽  
Vol 16b (5) ◽  
pp. 176-193 ◽  
Author(s):  
E. W. R. Steacie ◽  
I. E. Puddington
Keyword(s):  
Reaction Rate ◽  
High Pressures ◽  
The Other ◽  
First Order ◽  
Decomposition Reactions ◽  
Temperature And Pressure ◽  
Products Of Reaction ◽  
Kinetics Of ◽  
Good Agreement ◽  
Mechanism Of The Reaction

The kinetics of the thermal decomposition of n-butane has been investigated at pressures from 5 to 60 cm. and temperatures from 513 to 572 °C. The initial first order rate constants at high pressures are given by[Formula: see text]The results are in good agreement with the work of Frey and Hepp, but differ greatly from that of Paul and Marek. The reaction rate falls off strongly with diminishing pressure; this is rather surprising for a molecule as complex as butane. The first order constants in a given run fall rapidly as the reaction progresses. The last two facts suggest that chain processes may be involved.A large number of analyses of the products of reaction have been made at various pressures, temperatures, and stages of the reaction, the method being that of low-temperature fractional distillation. The products are virtually independent of temperature and pressure over the range investigated. The initial products, obtained by extrapolation to zero decomposition, are:—H2, 2.9; CH4, 33.9; C3H6, 33.9; C2H4, 15.2; C2H6, 14.1%. The mechanism of the reaction is discussed, and the results are compared with those of the other paraffin decompositions.

scholarly journals Sorption, Structure and Dynamics of CO2 and Ethane in Silicalite at High Pressure: A Combined Monte Carlo and Molecular Dynamics Simulation Study

Molecules ◽  
2018 ◽  
Vol 24 (1) ◽  
pp. 99 ◽  
Author(s):  
Siddharth Gautam ◽  
Tingting Liu ◽  
David Cole
Keyword(s):  
Molecular Dynamics ◽  
Monte Carlo ◽  
Time Scales ◽  
Rotational Motion ◽  
High Pressures ◽  
Sorption Isotherms ◽  
Md Simulations ◽  
Dynamics Simulation ◽  
Structure And Dynamics ◽  
Low Pressures

Silicalite is an important nanoporous material that finds applications in several industries, including gas separation and catalysis. While the sorption, structure, and dynamics of several molecules confined in the pores of silicalite have been reported, most of these studies have been restricted to low pressures. Here we report a comparative study of sorption, structure, and dynamics of CO2 and ethane in silicalite at high pressures (up to 100 bar) using a combination of Monte Carlo (MC) and molecular dynamics (MD) simulations. The behavior of the two fluids is studied in terms of the simulated sorption isotherms, the positional and orientational distribution of sorbed molecules in silicalite, and their translational diffusion, vibrational spectra, and rotational motion. Both CO2 and ethane are found to exhibit orientational ordering in silicalite pores; however, at high pressures, while CO2 prefers to reside in the channel intersections, ethane molecules reside mostly in the sinusoidal channels. While CO2 exhibits a higher self-diffusion coefficient than ethane at low pressures, at high pressures, it becomes slower than ethane. Both CO2 and ethane exhibit rotational motion at two time scales. At both time scales, the rotational motion of ethane is faster. The differences observed here in the behavior of CO2 and ethane in silicalite pores can be seen as a consequence of an interplay of the kinetic diameter of the two molecules and the quadrupole moment of CO2.

scholarly journals How Far Can One Push the Noble Gases Towards Bonding?: A Personal Account

Molecules ◽  
2019 ◽  
Vol 24 (16) ◽  
pp. 2933 ◽  
Author(s):  
Ranajit Saha ◽  
Gourhari Jana ◽  
Sudip Pan ◽  
Gabriel Merino ◽  
Pratim Kumar Chattaraj
Keyword(s):  
Electron Density ◽  
High Pressures ◽  
Noble Gases ◽  
Activation Barrier ◽  
Covalent Bond ◽  
The Other ◽  
Personal Account ◽  
Covalent Bonds ◽  
Other Hand ◽  
Different Types

Noble gases (Ngs) are the least reactive elements in the periodic table towards chemical bond formation when compared with other elements because of their completely filled valence electronic configuration. Very often, extreme conditions like low temperatures, high pressures and very reactive reagents are required for them to form meaningful chemical bonds with other elements. In this personal account, we summarize our works to date on Ng complexes where we attempted to theoretically predict viable Ng complexes having strong bonding to synthesize them under close to ambient conditions. Our works cover three different types of Ng complexes, viz., non-insertion of NgXY type, insertion of XNgY type and Ng encapsulated cage complexes where X and Y can represent any atom or group of atoms. While the first category of Ng complexes can be thermochemically stable at a certain temperature depending on the strength of the Ng-X bond, the latter two categories are kinetically stable, and therefore, their viability and the corresponding conditions depend on the size of the activation barrier associated with the release of Ng atom(s). Our major focus was devoted to understand the bonding situation in these complexes by employing the available state-of-the-art theoretic tools like natural bond orbital, electron density, and energy decomposition analyses in combination with the natural orbital for chemical valence theory. Intriguingly, these three types of complexes represent three different types of bonding scenarios. In NgXY, the strength of the donor-acceptor Ng→XY interaction depends on the polarizing power of binding the X center to draw the rather rigid electron density of Ng towards itself, and sometimes involvement of such orbitals becomes large enough, particularly for heavier Ng elements, to consider them as covalent bonds. On the other hand, in most of the XNgY cases, Ng forms an electron-shared covalent bond with X while interacting electrostatically with Y representing itself as [XNg]+Y−. Nevertheless, in some of the rare cases like NCNgNSi, both the C-Ng and Ng-N bonds can be represented as electron-shared covalent bonds. On the other hand, a cage host is an excellent moiety to examine the limits that can be pushed to attain bonding between two Ng atoms (even for He) at high pressure. The confinement effect by a small cage-like B12N12 can even induce some covalent interaction within two He atoms in the He2@B12N12 complex.

Sign in / Sign up

Export Citation Format

Share Document