A statistical method for evaluation of the experimental phase equilibrium data of simple clathrate hydrates

We, herein, present a statistical method for diagnostics of the outliers in phase equilibrium data (dissociation data) of simple clathrate hydrates. The applied algorithm is performed on the basis of the Leverage mathematical approach, in which the statistical Hat matrix, Williams Plot, and the residuals of a selected correlation results lead to define the probable outliers. This method not only contributes to outliers diagnostics but also identifies the range of applicability of the applied model and quality of the existing experimental data. The available correlation in the literature in exponential form is used to represent/predict the hydrate dissociation pressures for three-phase equilibrium conditions (liquid water/ice–vapor-hydrate). The investigated hydrate formers are methane, ethane, propane, carbon dioxide, nitrogen, and hydrogen sulfide. It is interpreted from the obtained results that the applied correlation for calculation/estimation of the phase behavior of simple clathrate hydrate systems is statistically valid and correct, 5 hydrate dissociation data are found to be probable doubtful ones and 10 data points are out of applicability domain of the applied correlation.

[1]  Guangjin Chen,et al.  Experimental and modeling studies on the hydrate formation of CO2 and CO2-rich gas mixtures , 2000 .

[2]  D. Robinson,et al.  Hydrates In the PropaneCarbon Dioxide- Water System , 1971 .

[3]  A. Mohammadi,et al.  Thermodynamic Consistency Test for Experimental Solubility Data in Carbon Dioxide/Methane + Water System Inside and Outside Gas Hydrate Formation Region , 2011 .

[4]  Colin R. Goodall,et al.  13 Computation using the QR decomposition , 1993, Computational Statistics.

[5]  E. Hammerschmidt.  Formation of Gas Hydrates in Natural Gas Transmission Lines , 1934 .

[6]  Cor J. Peters,et al.  Gas hydrate phase equilibria for propane in the presence of additive components , 2002 .

[7]  Paola Gramatica,et al.  Principles of QSAR models validation: internal and external , 2007 .

[8]  A. Mohammadi,et al.  Equilibrium Data of Carbonyl Sulfide and Hydrogen Sulfide Clathrate Hydrates , 2009 .

[9]  A. Mohammadi,et al.  Ice−Clathrate Hydrate−Gas Phase Equilibria for Air, Oxygen, Nitrogen, Carbon Monoxide, Methane, or Ethane + Water System† , 2010 .

[10]  Huen Lee,et al.  Clathrate phase equilibria for the water–phenol–carbon dioxide system , 1997 .

[11]  Amir H. Mohammadi,et al.  Application of gas hydrate formation in separation processes: A review of experimental studies , 2012 .

[12]  Hideyuki Tsuji,et al.  Structure-I and Structure-H Hydrate Formation Using Water Spraying , 2002 .

[13]  Peter Englezos,et al.  Kinetics of Ethane Hydrate Growth on Latex Spheres Measured by a Light Scattering Technique , 2000 .

[14]  S. Saito,et al.  Hydrates at high pressures: Part I. Methane‐water, argon‐water, and nitrogen‐water systems , 1964 .

[15]  M. Kharrat,et al.  Experimental determination of stability conditions of methane hydrate in aqueous calcium chloride solutions using high pressure differential scanning calorimetry , 2003 .

[16]  K. Ohgaki,et al.  Formation of CO2 Hydrate in Pure and Sea Waters , 1993 .

[17]  Amir H. Mohammadi,et al.  Equilibrium Data and Thermodynamic Modeling of Nitrogen, Oxygen, and Air Clathrate Hydrates , 2003 .

[18]  Farhad Gharagheizi,et al.  A novel method for evaluation of asphaltene precipitation titration data , 2012 .

[19]  Takeshi Sugahara,et al.  Thermodynamic stability and structure of nitrogen hydrate crystal , 2002 .

[20]  Ali Eslamimanesh,et al.  Gas Hydrate Formation in Carbon Dioxide + Nitrogen + Water System: Compositional Analysis of Equilibrium Phases , 2011 .

[21]  Benjamin James Falabella,et al.  A STUDY OF NATURAL GAS HYDRATES. , 1975 .

[22]  Ali Eslamimanesh,et al.  Thermodynamic consistency test for experimental data of water content of methane , 2011 .

[23]  V. A. Kamath,et al.  Experimental determination of dissociation pressures for hydrates of the cis- and trans-isomers of 2-butene below the ice temperature , 1982 .

[24]  H Dijstelbergen,et al.  International gas research conferenceTokyo, Japan, November 1989 , 1990 .

[25]  D. C. Bond,et al.  Effect of Antifreeze Agents on the Formation of Hydrogen Sulphide Hydrate , 1949 .

[26]  Ross Anderson,et al.  Carbon monoxide clathrate hydrates: Equilibrium data and thermodynamic modeling , 2005 .

[27]  J. V. D. Waals,et al.  Thermodynamic properties of gas hydrates II: Phase equilibria in the system H2S‐C3H3‐H2O AT −3°C , 2010 .

[28]  R. L. Allen,et al.  Thermodynamic Properties of Gases , 1946 .

[29]  M. Clarke,et al.  Determination of the intrinsic rate of ethane gas hydrate decomposition , 2000 .

[30]  T. Guo,et al.  Hydrate Formation of CO2-Rich Binary and Quaternary Gas Mixtures in Aqueous Sodium Chloride Solutions , 1999 .

[31]  Takeshi Sugahara,et al.  Stability boundaries of gas hydrates helped by methane-structure-H hydrates of methylcyclohexane and cis-1,2-dimethylcyclohexane , 2003 .

[32]  P. S. Chappelear,et al.  Experimental measurement of hydrate numbers for methane and ethane and comparison with theoretical values , 1970 .

[33]  A. Mohammadi,et al.  Experimental Data Assessment Test for Composition of Vapor Phase in Equilibrium with Gas Hydrate and Liquid Water for Carbon Dioxide + Methane or Nitrogen + Water System , 2012 .

[34]  Farhad Gharagheizi,et al.  Evaluation of Thermal Conductivity of Gases at Atmospheric Pressure through a Corresponding States Method , 2012 .

[35]  Yoshiyuki Tanaka,et al.  THERMODYNAMIC PROPERTIES OF R13 (CCIF3), R23 (CHF3), R152a (C2H4F2), AND PROPANE HYDRATES FOR DESALINATION OF SEA WATER , 1984 .

[36]  Peter J. Rousseeuw,et al.  Robust regression and outlier detection , 1987 .

[37]  B. H. Sage,et al.  Phase Behavior in the Hydrogen Sulfide-Water System , 1952 .

[38]  Peter Englezos,et al.  Incipient equilibrium data for propane hydrate formation in aqueous solutions of sodium chloride, potassium chloride and calcium chloride , 1993 .

[39]  M. Wendland,et al.  Experimental pressure-temperature data on three- and four-phase equilibria of fluid, hydrate, and ice phases in the system carbon dioxide-water , 1999 .

[40]  Peter Englezos,et al.  Experimental study on the equilibrium ethane hydrate formation conditions in aqueous electrolyte solutions , 1991 .

[41]  L. R. Oellrich,et al.  Experimental determination of hydrate equilibrium conditions for pure gases, binary and ternary mixtures and natural gases , 1997 .

[42]  Huen Lee,et al.  Measurement and prediction of phase equilibria for water + methane in hydrate forming conditions , 2001 .

[43]  E. D. Sloan,et al.  The effect of pressure on methane hydration in pure water and sodium chloride solutions , 2001 .

[44]  A. Mohammadi,et al.  An improved Clapeyron model for predicting liquid water-hydrate-liquid hydrate former phase equilibria , 2011 .