1、GPA TP-4 74 W 3824b99 OULU790 815 E Tec hnica I Publication TP-4 . An investigat sponsored by Gas Processa Association Lowk+mature Data from Rice University for Vapor-Liquid and P-V-T Behavior Work performed by: Chappelear, T. W. Leland, and Co-workers . Riki Kobayashi, Patsy S. . ion the irs Suppli
2、ers 1812 First Place Compiled and assessed by: Patsy Chappelear Rice University Houston, Texas April, 1974 a Research Engineer Phone 918:582-51 2 d GPA TP-4 74 3824699 001079L 751 1 FOREWORD Since the late 50s the Rice University Low Temperature Vapor-Liquid Lab has been producing physical equilibri
3、a data for hydrocarbons, under the direction of Dr. Riki Kobayashi. It began with a study of the methane- ethane-propane ternary K-values at temperatures down to -200F. In the years of its operation, dozens of investigators have contributed their efforts to produce data which have been of vital inte
4、rest to the Natural Gas Processing Industry. The work is continuing, with pertinent infor- mation constantly being published. numberous technical journals, theses, monographs, and the like. These data have been publised in It is the intended purpose of this Technical Publication to put together in o
5、ne place such of this data as is deemed useful either for development of correlations or helpful directly in the design of gas processing plants. Since there is some variation in the quality of data presented in this com- pilation, it was decided that the data be graded so that the casual user would
6、 have some knowledge of the quality of a given system. pose, Mrs. Patsy Chappelear has compiled, graded and comnented on the systems included. Mrs. Chappelear has worked closely with Dr. Kobayashi and his co- workers over the years and has a first-hand knowledge of the work included in this publicat
7、ion. She has attempted to use this knowledge to present a compilation useful both to the practicing engineer engaged in process design as well as the engineer attempting to develop generalized correlations which describe the laws of nature. To this pur- This Technical Publication has been made possi
8、ble by a grant from the GPSA, and we wish to express our appreciation for their financial support. Warren E. White GPA TP-4 74 3824699 0030792 698 I 2 Permission from the publishers has been granted to reproduce portions of articles which appeared in the following journals, with the copyright holder
9、 in parentheses: Advances in Cryogenic Engineering (Plenum Press) A.1.Ch.E. Journal (American Institute of Chemical Engineers) Chemical Engineering Science (Pergamon Press) I these included the National Science Foundation, NGPA, Petro- leum Research Fund of ACS, American Gas Association, Columbia Ga
10、s Systems Service Corporation, Phillips Petroleum Company, Shell Oil Company, and Brown it is deposited at the University and with University MZcrolms. alga depoaited at Ehe University und UniversiLy MicrDfllms. The results and conclusions from such studies are then extracted and published in the op
11、en literature in various scientific journals. Such has been the procedura for the work in low temperature v-1-e and p-v-t performed at Rice University under Professor Riki Kbayeshi. Some poet-doctoral studies are reported as a Monograph, which i0 The problem for the practicing engineer is to .secure
12、 the daca if it exists, He also needs some idea of the quality of the data. ta ansver those two problems for the v-1-e ara from Rice University. the course of the work iL became evident that sodit other data should also be included; these are givn in Section II. The soltition has been presented prim
13、arily by the cut-and-paste method in order tu eliminate one more possibility for errar, that of transcrlption. All known ermr8 ia the various rrieduacripts have been corrected. This compilation attempts During General Comments The coqilation is presented in the order indicated in the Table of Conten
14、ts. Ir ia strongly recammended that the user first study Section i11 which gives some guidance or use of the data presented in Sections I and II. Secrion TV presents some class notes of Professor Kchayashi that have been in- cluded by the compiler as recornended reading. to date of Profemor Kobeyash
15、i and the compiler. Attention TWO articles have been reproduced in their entirety: One from Hydrocarbon Proceasing on pages 6 and 7 which discusses the importance of critical re- strictions. The other paper on pages 63 through 68 is from the Journal of Chemical 6r Engineering Data and uL11 provide i
16、nformation on the basic ternary i thane-ethane-propane. as well as soum guidance to the interpretation of data. Page 46 haa been left blank for arderly arrangemenK. and 29 have been omitted, Meanfng of Ratings The data have been given relative ratings for quality or reliability by the eompller. pear
17、s ta a large oval has the following meanings: In addition, Section V Lista the publications Pageg 28 This is diecussed in detail in Section III. The number which ap- I. Excelient, superior, frilly reliable. 2. 3 4. Very good, may have some regions or points which could beer further irives t iga tiri
18、n. Good, sufficient for engineering calculat3one. Fair, the 0ri1y data that exists at the th of compilation, probably should have further experimental investigation if warranted by en- giaeeriiig operations. GPA TP-4 74 3824697 00110794 460 I 5 SECTION I Vapor-Liquid-Equilibr ia Data Pages A. Binary
19、 Systems 1. Hydrocarbon: Methane-Ethane Methane-Propane Methane-n-Butane Methane-n-Pentane Methane-n-Hexane Methane-n-Heptane Methane-Methylcyclohexane Methane-Toluene Methane-n-Decane E thane-Propane n-Butane-n-Dodecane 2. Other: C4s in Furfural Methane-Carbon Monoxide Ethylene Glycol-Methane Ethyl
20、ene Glycol-Hydrogen Sulfide Ni trogen-Methane Nitrogen-Ethane B. Ternary Systems Methane-Ethane-Propane Methane-Ethane-n-Heptane Methane-Propane-n-Heptane Methane-Ethane-Toluene Methane-Propane-Toluene Methane-Ethane-n-Decane Methane-Propane-n-Decane Methane-n-Butane-n-Decane Methane-Propane-n-Hexad
21、ecane Carbon Dioxide-Methane-n-Octane Hydrogen Sulfide-Methane-n-Octane Hel ium-Me thane-n- Oc tane Neon-Methane-n-Octane Argon-Methane-n-Octane Nitrogen-Methane-Ethane Ethylene Glycol-Methane-Hydrogen Sulfide 6-7, 8-14, 61-62 6-7, 15-19, 61-62 20-27 30-31 32-34, 36 35, 37-39, 42 40-42 42-43 44-45 6
22、1-62 47 47 48-49 92-94 92-94 50-55 56-59 60-70 72, 74-75 71, 72, 76-77 73 72-73 78 79-84 85 78 86 86 87 87 87 88-91 92-94 GPA TP-4 74 a 3824699 0010795 3T7 M 6 Caution! pinch point in Y-X curve! Ivan Wichterle, Riki Kobayashi and Patsy S. Chappelear, Rice University, Houston ALL BINARY SYSTEMS have
23、a pinch point at high pres- sures which must be considered in designing high pressure, high purity separations (Fig. 1 ) . If this phenomena is ig- uquid- CanPo- Fig. 1-X-Y pinch point. owl I l O8 O .90 10 X .MIXE FRPCTION Oc ME- N LlOlDPWE Y VERSUS X DIAGRAM FOR METHANE -ETHANE SYSTEM (MPANDED SCAL
24、E 1 Fig. 2-Expanded scale Y-X diagram for methaneethane system. nored, the separation may require infinite stages or may operate near the minimum reflux ratio! Are you designing or operating in a region which is affected by critical phenomena? Examples are ethane recovery plantss and the production
25、of very high purity ethylene. In fact, the top of any distillation column could be a region of serious consideration if conditions are close to the critical region of the light components. Are you using or developing a K-value correlation? At present no K-value correlation has even qualitatively tak
26、en into account this behavior. In brief, the effect is an observed inflection or pinch bi I I I I I ow O90 1m x .-E mmim OF YETW IN mio msf Fig. Expanded scale Y-X diagram for methanepropane systems. / I O O9 x, YXE FRIICTION OF METHNE IN UMJD Rip9 Y VERSUS X LSOBARS FOR METHANE-ETHANE SYSTEM Fig 4-
27、Y-X isobars for methaneethane system. HYDROCAILBON PROCESSINO November 1971 GPA TP-4 74 EH 3824699 0030796 233 W CAUTION1 PINCH POINT IN Y-X CURVEI o Y Y i 0985 ! 1 I 04 o1 06 07 O8 09 IO X.WE FRACTION WUETWNE INLIOUD PM the vast majority of the dota has error less than 1%. The improved method made
28、possible measurements of ,- very dilute mixtures close to critical conditions. Figure 2, Pressure-composition diagram for the metham- ethane system on an expanded xale for the, earlier investigation, but the resultant average maximum per- cent errnr is i% il. the K-values as compared to 1.6% for the
29、 methanephpane system. This improvement in the accuracy arose from the increase in manipulatory skill of the investiga- tor, which decreased the error in the concentration measure- ments. the -50“ and were verified in the The error analysis is the same type as reported 0F data of Price and KobayGhi
30、preliminary stages of this investigation. 06 07 O O9 IO METHANE Figure 1. Pressure-composition diagram for methantethana system Materiais Used. The same “ultrahigh purity“ methane, purchased from Matheson Gas Products CO., WS used. The reported analysis was at least 99.97% methane with a total amoun
31、t of major impurities of 105 ppm. The charge gas passed through a molecular sieve purifier to remove water, oil, and particles down to 12 p. Research-grade (99.99%) ethane was donated by The Phillip Petroleum Co. It was used without further purification. NO impurities in the methane or ethane were d
32、etected by the in- vestigators gas chromatographic analysis. The sequence of the investigations by Wichterle were: 1. Initial examination and evaluation of Prices data by new experimental measurements. 2. Experiments on the methane-propane system reported in JCED. 3. Experiments on the methane-ethan
33、e system reported in JCED. 4. Experiments on the ternary system. 5. Experiments on Methane-Ethane for critical exponents. GPA TP-4 74 - romtournal of Chemical and Engineering Data, Vol. 17, No. 1, 1972 9 Table I. Vapor-liquid Equilibrium for MefhaneEham System CHI mole CH, mole fraction Piesrmre K-V
34、due 2 Il Psi 20.40 25.50 30.60 35.40 37.45 39.45 41.50 43.50 44.30 45.10 45.50 45.65cJ 1W 37.4 19.7 10.3 7.00 3.58 2.66 2.13 1.76 1.49 1.28 1.122 1.051 l.OO0 380 24.5 14.3 10.1 7.71 3.87 2.49 1.84 1.43 1.28 1.17 1.093 1.038 1.020 1.OOO 4m 22.9 13.9 9.24 7.09 3.61 2.35 1.70 1.32 1.137 1.038 1.017 1.0
35、11 1.OOO 44P 2.26 1.77 1.435 1.22 1.142 1.085 1.047 1.020 1.012 1.008 1.02 1.ooO 1 .o00 0.238 O. 135 O. 0782 O. 0573 0.0414 0.0408 0.0443 0.0525 0.0711 O. 113 0.253 O. 508 1.000 1.000 0.0786 O. O492 0.0365 O. 0295 0.0208 O. 0196 0.0221 0.0314 o. o419 0.0614 O. O985 o. 181 O. 317 1.000 1.000 0.0673 O
36、. o429 0.0315 0.0251 O. 0173 O. 0174 0.0208 O. 0328 0.0597 o. 140 0.206 O. 276 1.000 1.000 O. 0151 O. 0178 0.0237 O. O380 O. 0521 0.0757 o. 108 o. 169 O. 208 0.250 0.331 (1.OOO) Temp = 190.58E = -82.57OC = -116.6“F 615. O 41.85 1.035 o. 124 638.0 43.40 1.017 o. 163 654.0 44.50 1.001 0,218 661.0 45.0
37、0 1.0034 0.242 663.0 45. LO 1.0025 0.239 667.0. 45.40 1.Ooo (0.W) (Cbntmrr# on nQt poge) GPA TP-4 74 3824699 OOLOOb TO2 17 o from: Journal of Chemical and Engineering Data, Vol. 17, No. 1, 1972 Table II. Vapor-Liquid Equilibrium for Methane-Propane System (Continued CHI mole fraction Pressure K-valu
38、e 2 O.ooO0 0.0629 O. 1506 O. 3042 O. 4769 O. 6728 O. 8450 o. 9230 O. 9623 0.9810 1.oooO 0.oooO O. O692 O. 1196 O. 2270 O. 4909 O. 6907 0.8423 O. 9032 O. 9650 1.oooO O.oo00 O. 0873 O. 1791 0.3510 O. 5450 0.8000 O. 8738 0.9135 0.9497 1.oooO O. oooO o. 2109 O. 3005 0.5258 0.7200. 0.8306 0.9287 1.oooO O
39、. m 0.3924 0.5007 0.6982 1.oooO Y O.oo00 O. 9656 o. 9839 0.9907 0.9929 O. 9937 O. 9947 o. 9958 O. 99675 O. 9980 1.oooO O.oo00 O. 9862 O. 9915 O. 99505 o. 9973 o. 9979 O. 99845 O. 99880 O. 99925 1.oooO 0.oooO o. 9958 o * 99793 0.99888 O. 99921 o. 99956 O. 99965 O. 99972 o. 99979 1.0000 0.oooO O. 9994
40、0 O. 99959 O. 99975 0.99986 0.99990 o. 999952 1.oooO 0.oooO 0.999921 0.999935 0.999962 Psia Atm Methane Temp = 187.54% = -85.61“C = -122.3F 1.2840 O. 087370 5u)s 41.0 2.79 15.35 100.0 6.80 6.53 200.0 13.60 3.26 300.0 20.40 2.08 400.0 27.20 1.48 490.0 33.35 1.18 540. o 36.75 1.08 565. O 38.45 1.036 5
41、86. O 39 * 85 1.017 606.0 41.25. 1.000 Temp = 172.04“K = -101.11“C = -150.0F O. 3850“ O. 0262W 115W 30.8 2.10 14.25 52.6 3.57 8.29 100.0 6.80 4.38 200. O 13.60 2.03 260. o 17.70 1.44 300.0 20.40 1.185 320.0 21.75 1.106 342.0 23.25 1.035 361.5. 24.80 1.000 Temp = 158.15% = -115.00C = -175.O“F O. 0968
42、0“ O. 006587“ 29oob 25.0 1.70 11.4 51.5 3.50 5.57 100.0 6.80 2.85 138.5 9.42 1.83 176.0 12.00 1.25 187. O 12.70 1.14 194.0 13.20 1.094 201.5 13.70 1.053 213.5- 14.50. 1.OOO Temp = 144.26“K = -128.89OC = -200.0F O. 018660 O. 001270“ 82ooS 31.0 2.11 4.74 48.0 3.27 3.33 74.0 5.04 1.90 91.0 6.19 1.39 98
43、.0 6.67 1.20 108.0 7.35 1.076 114.0. 7.75. 1.OOO Temp = 130.37“K = -142.78“C = -225.O“F O. 002591 0.000176. 28o00, 27.0 1.84 2.55 34.0 2.31 2.00 42.0 2.86 1.43 Propane 1.OOO O. 0367 0.0190 O. 0136 O. 0136 O. 0193 0.0342 O. 0545 O. 0862 o. 1052 0.51 1.OOO O. 0148 0.00965 0.00640 o. 00530 O. 00679 0.0
44、0983 0.0123 O. 0214 O. 035 1.OOO 0.00460 O. O0252 O. O0172 O. O0174 o. 00220 O. 00277 O. 00324 O. O0417 o. 0053 1.000 o. 000760 O. 000586 0.000527 0.000500 o.Ooo590 O. 000673 O.Ooo71 1.000 O. O00130 o. O00130 o. o00128 l.oo00 54.0 3.67 1.ooO o. O0013f Saturated vapor preasure of C! r = -59.950 = -51
45、.WC 20.3 0.m 25.1 0.0562 50.3 0.0294 100.2 o.ois0 150.3 O.Oi17 200.3 0.00966 300.3 0.00765 500.3 0.00702 400.3 0.00702 600. 0.007 r = -79.9 = -62.21% 20.0 0.0340 25.1 0.0270 50.0 0.0144 100.0 o.Oo809 150.0 0.00566 200.0 0.00494 300.0 o.Oo408 400.1 o.mm 500.1 o.oM01 600. o.oI)154 The overall error in
46、 the dew-point data is either less than 2% or 0.00001 in mole fraction of n-butane. depend- ing on which is larger. Materials The n-butane used in this investigation was donated by Phillips Petroleum Co. The n-butane was research grade with Purity Of 99.93%. The pure methane was purchased from Mathe
47、son Gas Products. It was ultra high-purity grade with purity of 99.97% minimum. No further checks for purity over these manufacturers specifications were made. Since the signals from the thermoconductivity de- tector were obtained by comparing the mixture and pure methane stream which were originate
48、d from the same source, any slight effects on the signals owing to impurity would be canceled out. r = -99.WF = r = -119.37“F = _.- - . r = -116.62“F =. -73.27C -82.57% -84.WC Press, fraction of Press, fraction of Press, fraction of psia n-butane psia ,butane psia n-butane 25.0 0.0125 25.1 0.00596 2
49、5.0 0.00524 50.3 0.00654 50.1 0.0033 51.2 0.00278 100.1 0.00367 100.1 0.00186 101.1 0.00165 150.1 0.00280 150.1 0.00134 151.0 0.00118 200.1 0.00243 199.7 0.00120 201.0 0.00105 300.3 0.00206 299.7 0.00105 300.3 0.000917 4Ml.3 0.00205 399.7 0.00111 400.0 o.Oo0951 500.1 0.00230 500.1 0.00134 500.7 0.00125 600. 0.00285 600. 0.00177 550. 0.00139 700. 0.00416 625. 0.00176 600. 0.00127 750. 0.00555 650. 0.00137 615. 0.00104 763. O.Oo605 660. 0.000909 631. O.OOO359 800. 0.00770 805. 0.00853 r = -139.96.F = -95.5392 Mole Mole Mole 20.1 0.0154 20.1 0.00743 19.8
