1、,I , . . , Technical Publication TP-11 Pro cess ors Associatiofi I 1812 First Place Vapor-Liquid-Equilibria Study of Light Gases in Hydrogen-Coal Liquid Model Compound Systems Tulsa, Okla. 74103 Tor Kragas Riki Kobayashi Rice University Houston, Texas August, 1983 Phone: 918/582-5112 GPA TP-11 83 m
2、3824699 001119.5 8T9 m FOREWORD Through the use of sophisticated new equipment, a high pressure tracer perturbation chromatograph, Rice University has obtained Henrys constants over a wider range of pressure, temperature, and composition than has been possible in the past. the 9-methylanthracene sys
3、tems were obtained. Data for Henrys constants for several light gases in Data were of such accuracy and value as to warrant distribution since they can be used to expand our knowledge of coal liquids. Henrys constants with other appropriate, and available data can provide information to deter- mine
4、interaction parameters in mixture equation of state. Professor Kobayashi and Dr. Tor Kragas are to be commended for their work and for making the data available for distribution. Thanks are also extended to Karl Kilgren, Chairman of the GPA Phase Equilibria Steering Com- mittee, for editing the repo
5、rt. cc Carl Sutton, Secretary i GPA TP-LL 3 3824b99 DOLL196 735 TABLE OF CONTENTS Foreword Table of Contents. . List of Tables . List of Figures. Abstract Results and Conclusions. The Experiment and the Measurements. References . Tables . Figures. . . . . . . . . . . Page .i . ii . iii . iv .1 .2 .3
6、 .7 .8 . 29 ii GPA TP-LL 83 II 3824697 OOLLL97 671 II Table 1 7 8 9 10 11 12 13 14 15 16 LIST OF TABLES Title Infinite Dilution K-Values for Methane in the Hydrogen-Dibenzofuran System Infinite Dilution K-Values for Ethane in the Hydrogen-Dibenzofuran System Infinite Dilution K-Values for Propane in
7、 the Hydrogen-Dibenzofuran System Infinite Dilution K-Values for N-Butane in the Hydrogen-Dibenzofuran System Infinite Dilution K-Values for Carbon Dioxide in the Hydrogen-Dibenzofuran System Infinite Dilution K-Values for Hydrogen Sulfide in the Hydrogen-Dibenzofuran System Infinite Dilution K-Valu
8、es for Methane in the Hydrogen-9-Methylanthracene System Infinite Dilution K-Values for Ethane in the Hydrogen-9-Methylanthracene System Infinite Dilution K-Values for Propane in the Hydrogen-9-Methylanthracene System Infinite Dilution K-Values for N-Butane in the Hydrogen-9-Methylanthracene System
9、Infinite Dilution K-Values for Carbon Dioxide in the Hydrogen-9-Methylanthracene System Infinite Dilution K-Values for Hydrogen Sulfide in the Hydrogen-9-Methylanthracene System Henrys Constants in 9-Met-ylanthracene Henrys Constants and Infinite Dilution Fugacity Coefficients for Light Hydrocarbon
10、Gases in the Hydrogen-9-Methylanthracene System Second Cross Viria1 Coefficients of Light Hydro- carbon Gases with Hydrogen Heats of Solution in Hydrogen-9-Methylanthracene Mixtures Page 8 - 9 10 11 12 13 14 16 18 19 20 21 22 23 27 28 ii i GPA TP-LL 83 I 3824699 OOLLL98 508 = Figure 1 2 3 4 5 6 7 8
11、9 10 11 12 13 14 15 16 17 18 19 20 LIST OF FIGURES Title Infinite Dilution P x K-Values in the H2-Dibenzofuran System at 100 C Infinite Dilution P x K-Values in the H2-Dibenzofuran System at 100 C Infinite Dilution P x K-Values in the H2-Dibenzofuran System at 125 C Infinite Dilution P x K-Values in
12、 the H2-Dibenzofuran System at 125 C Infinite Dilution P x K-Values in the H2-9-Methylanthracene System at 100 C Infinite Dilution P x K-Values in the H2-9-Methylanthracene System at 100 C Infinite Dilution P x K-Values in the H2-9-Methylanthracene System at 125 C Infinite Dilution P x K-Values in t
13、he H2-9-Methylanthracene System at 125 C Infinite Dilution P x K-Values in the H2-9-Methylanthracene System at 150 C Infinite Dilution P x K-Values in the H2-9-Methylanthracene System at 150 C Infinite Dilution P x K-Values in the H2-9-Methylanthracene System at 175 C Infinite Dilution P x K-Values
14、in the H2-9-Methylanthracene System at 175 C Infinite Dilution P x K-Values in the H2-9-Methylanthracene System at 200 C Infinite Dilution P x K-Values in the H2-9-Methylanthracene System at 200 C Henrys Constants in 9-Methylanthracene Henrys Constants in 9-Methylanthracene Henrys Constants for Meth
15、ane in H2-9-Methylanthracene Mixtures Henrys Constants for Ethane in H2-9-Methylanthracene Mixtures Henrys Constants for Propane in H2-9-Methylanthracene Mixtures Henrys Constants for N-Butane in H2-9-Methylanthracene Mixtures Schematic of Chromatographic System Page 29 - 30 31 32 33 34 35 36 37 38
16、39 40 41 42 43 44 45 46 47 48 21 v 49 GPA TP-LL 3 I 3824699 OOLLL99 444 I ABSTRACT The most pervasive of the limiting laws describing the solubility of supercritical gases in a less volatile solvent is Henrys Law. Accordingly, we report Henrys constants for several supercri ti cal gases in 9-methyla
17、nthracene and in the H2-9-methylanthracene mixtures. The latter Henrys constants are to be distinguished from the former because they are Henrys constants in mixtures of and 9-methylanthracene rather than in a pure component. While the solubility of H2 in the pressure range of this study is rather l
18、ow, the effect of the solubility on the Henrys constants is quite significant. Infinite dilution K-values for the supercritical gases in dibenzofuran are also presented. The K-values at infinite dilution are presented as products of the total pressure and the K-values versus pressure (P x K plots).
19、These plots provide an immediate visual consistency check, with the low pressure limit yielding the Henrys constant in the pure solvent. Each of the infinite dilution K- values reported has the potential of being converted into its corresponding Henrys constant at the particular fixed H2-solvent con
20、centration. Thus, the data presented represents a massive amcwnt of information. 1 GPA TP-II 83 = 3824699 DOLL200 T9b RESULTS AM!) CONCLUSIONS Through the uti 1 i zati on of a sophi sti cated hi gh pressure tracer perturbation chrom tography apparatus, it has been possible to obtain K-values and der
21、ived quantities such as Henrys constants for a number of volatile gases in 9-methylanthracene and in the H2-9-methylanthracene system. While it was not possible to attain data applicable to reactor conditions, the data should be applicable to the development of software for most downstream processin
22、g conditions. Extensive V-L-E measurements are presented in Tables 1 through 12 for CH4, C2H6, C3H8, n-C4H10, CO2, and H2S in the form of K-values at essentially infinite dilution in: the Hp-dibenzofuran system at temperatures of 100 and 125OC and pressures to 900 psia; and the H2-9-methylanthracene
23、 system at temperatures of 100, 125, 150, 175, and 200C to pressures as high as 3000 psia. The K-values are also presented as products of the total pressure and the K-value as a preliminary assessment of their consistency. The Henrys constants of the same gases in 9-methylanthracene have been evalua
24、ted and are presented in Table 13. Henrys constants and gas phase infinite dilution fugacity coefficients based on a second virial coefficient approximation for the light hydrocarbon gases in the hydrogen-9-methylanthracene systems are deri ved and presented in Table 14 for liquid phase hydrogen con
25、centration ranges of 0.00, 0.01, 0.02, 0.03, 0.04, and 0.05 mol percent. The Henrys constants are shown to vary significantly both with hydrogen liquid phase concentration and temperature. The pressure and vapor phase fugacity associated with each liquid phase composition and temperature are also ta
26、bulated. The second cross virial coefficients of the light hydrocarbon gases in hydrogen (Hirschfelder et al, 2 GPA TP-IL 83 3824677 OOIL20L 922 1954; Chu et al, 1975) are tabulated in Table 15. Finally the heats of solution of the light hydrocarbon gases at essentially infinite dilution in the H2-9
27、-methylanthracene mixtures are tabulated in Table 16. P x K plots of the V-L-E data are presented in Figures 1 through 14. The H2S K-val ues cou1 d not be determi ned beyond 150C because of thermal /pressure decomposition of H2S. The Henrys constdnt of the same components in 9- methyldnthracene, if
28、stable, are presented in Figures 15 and 16. The Henrys constant for the hydrocarbons methane, ethane, propane, and n-butane in the H2-9-methylanthracene mixtures are presented in Figures 17 through 20. A similar analysis for CO2 and H2S was not possible because of the absence of the basic data neede
29、d to carry out the calculations (Kragas, 1983). The data presented herein are of sufficient accuracy such that the experimental points, individually or col lecti vely, can be used to evaluate interaction parameters to develop calculational procedures using appropriate equations of state. An analysis
30、 of the data by various means to obtain derived quantities attests to the consistency of the data. THE EXPERIMENT AND THE MEASUREMENTS A schematic diagram of the high temperature, hi gh pressure chromatographic system used to conduct the experiments is presented in Figure 21. The experimental appara
31、tus, while in principle possesses the basic features of any gas chromatograph, carries a number of features required to obtain quantitative V-L-E data to the best of our abilities. Among the features are: (1) a tandein proportioning pump to cause a known, uniform flow of 3 GPA TP-LL 83 = 3824699 OOL
32、L202 869 the carri er gas through the chromatographic column, high temperature chromatographic injection valves (modified Valco Valves), to inject the tracer perturbation gases into the flowing system, a special low volume, “laminar“ ionization chamber to pick up the radi oacti ve perturbations, an
33、electrometer and associated electronic components to pick up the extremely low currents ( amps.) associated with the radioactive perturbation peaks, an on-1 i ne mi crocomputer (Commodore Pet) and i nterfaci ng components to integrate and obtain the first moment of the chromatographic peak and hence
34、 yield improved values of the net retention volume, (VRi-Vs), in Equation 1 below, and a high temperature DPI to isolate the external pressure measurement system from the system undergoing study. The basic equation for systems in which the elution gas is appreciably soluble in the liquid phase was d
35、eveloped by Stalkup and Kobayashi (1963); where: (3) (4) (5) Z,RTw Ki = K value of component i at infinite dilution, i # 1, 2, 3, . n. Z, = compressibility factor of the elution gas at the pressure and temperature of the experiment, R = gas constant T = absolute temperature 4 GPA TP-11 83 .I 3824b99
36、 OOLL203 7T5 w = moles of the fixed liquid phase (on the packing) P = total pressure = retention volume of component i “Ri Vg = free gas volume Y19 Y2*Yn In order to eliminate V the retention time of tritium or deuterium and the K previously determi ned in sol ubi 1 i ty experiments conducted by Nas
37、i r and Kobayashi (1981) were utilized. The final working equation obtained becomes: = composition of 1, 2, . n in the gas phase. 9 RT- w Pf (t Ri - +RT w where: = volumetric flow rate of elution gas at T and P fP P tRi = retention time of component i tRT = retention time of tritium or deuterium = c
38、ompressibility factor of the elution gas at the zP TP “2 pump temperature and pressure pump temperature in absolute units = K = K-value of H2 determined froin independent hydrogen sol ubi 1 i ty data It was found that column “bleeding“ introduced serious noise in the detection scheme shown. Therefor
39、e it was necessary to introduce a chilled surface prior to the ionization chamber. The temperature of the chilled surface was maintained below the freezing point of 9-inethylanthracene so ds not to contribute to the retention time of the perturbation species. A presaturator was also used to minimize
40、 vaporization losses from the chromatographic column. The moles of fixed 1 iquid on the chromatographic 5 GPA TP-LL 83 D 3824697 0011204 631 column was checked periodically by weighing the column. The maximum uncertainties in the K-values as estimated by Kragas (1983) are as follows: 16.2 for methan
41、e, 5.5 mol % for ethane, 5.3 mol X for propane, 4.0 mol % for n-C4H10, 6.8 mol % for CO2, and 3.6 mol % for H2S. The results reported herein demonstrate that the perturbation chromatographic method can be extended to pressures rather higher than attained before (by a factor of three), to higher temp
42、eratures than attained before (by 15OoC), and K-values rather higher than we have been able to obtain in past studies (by a factor of 3 to 4). The generation of Henrys constants of soluble gases in a higher molecular weight model compound found in coal liquids provides a means of effectively expandi
43、ng our knowledge/understandi ng about such systems. The Henrys constants, together with vapor pressures (Sivaraman et al, 1982) and fugacity coefficients (this study), provide the basic data needed to generate i nteracti on parameters in mixture equations of state. The perturbation chromatographic m
44、ethod provides a convenient , accurate method of measuring the K-values and Henrys constants for volatile gases in a rather low volatility liquid. The basic measurements are pressure, temperature, flow rate, mass, and retention times, all measurements that can be made with extreme precision. 6 GPA T
45、P-II 83 3824699 OOLL205 578 = REFERENCES Chu, To-C., Chappelear, P.S., and Kobayashi, R., (1975). Hirschfelder, J.O., Curtiss, C.F., and Bird, R.B., 1954. Molecular Theory of Kragas, T.K., 1983. Ph.D. Thesis, Rice University, Houston, Texas. Nasir, P., and Kobayashi, R., 1981. J. Chem. Eng. Data, 26
46、:321. Sivaraman, A., and Kobayashi, R., 1982. J. Chem. Eng. Data, 27:264. Stalkup, F.I., and Kobayashi, R., 1963. AIChE J., 9:121. AIChE J., 21:173. Gases and Liquids, John Wiley and Sons, Inc., New York. 7 GPA TP-III 83 I 3824677 OOLL2Ob 404 TABLE 1 Infinite Dilution K-values for Methane in the Hyd
47、rogen - D i ben tofu ran System Temperature C Pressure psia CH4 K 100.0 125.0 107 99.85 20 1 59.21 298 37.83 449 25.73 498 22.64 643 16.41 828 12.43 cH4 PxK psia 10684 11901 11273 11553 11275 10552 10292 179 59.63 10674 237 43.26 10253 319 31.73 10122 412 24.37 10040 544 18.88 10271 712 15.91 11328
48、873 13.58 11855 8 GPA TP-11 83 m 3824699 0011207 340 = TABLE 2 Infinite Dilution K-values for Ethane in the Hydrogen-Di benzofuran System Temperature Pressure C psia 100.0 125.0 107 200 298 449 607 739 795 113 179 237 319 413 543 712 873 KC2H6 22.10 12.44 8.20 5.68 4.20 3.40 3.27 25.28 15.61 12.36 8
49、.90 7.44 5.51 4.35 3.51 PX KC2 H6 psia 2365 2488 2444 2550 2549 2513 2600 2857 2794 2929 2839 3073 2992 3097 3064 9 GPA TP-LL 83 3824699 DOLL208 287 = TABLE 3 Infinite Dilution K-values for Propane in the Hydrogen-Di benzofuran System Temperature Pressure C psia 100.0 125.0 107 2 O0 298 440 449 607 739 795 KC3H8 PxKC3H8 psia 8.61 4.86 3.37 2.27 2.20 1.66 1.39 1.33 113 10.59 179 6.77 237 5.06 318 3.92 407 3.09 542 2.37 713 1.78 873 1.54 921.3 972 .O 1004.3 998.8 987.8 1007.8 1027.2 1057.4 1197. 1212. 1199. 1247. 1258. 1285. 1269. 1344. 10 G
