273
Ind. Eng. Chem. Process Des. Dev. 1984, 2 3 , 273-276
WESTERN KENTUCKY
Acknowledgments The authors with to thank the Office of Fossil Energy, Department of Energy, for support of this work (Contract No. E (49-18)-2035),R. Sharma for experimental assistance, and D. Thakkar and S. Holiman for assistance with the analyses. The authors also wish to thank J. C. Dooley and C. H. Thompson of Bartlesville Energy Technology Center for supplying the sample, Dr. C. V. Philip of Texas A & M University furnished the gas chromatograph-mass spectrometer results. Literature Cited
DISTILLATE
1000
.-
,800
-
x
is00
-
4
+ w400
.
-
415 XPO
4 690
200
-
'
0
PP
&
IL
l;O
2 k
250
3k
i(m
345CKPO
3iO
4bo
TEMPERATURE, .C
Figure 2. Enthalpy as a function of temperature for the Western Kentucky distillate at several pressures.
brown in color, but it became much darker with time. The results of the enthalpy measurements on the distillate sample are presented as raw data in Table S3 of the Supplementary Material and shown in Figure 2. The liquid, two-phase, and vapor regions are clearly distinguishable as is the significant effect of pressure on the enthalpy of a vapor. Unfortunately, there are no other existing data for coal-derived liquids for comparison. Again, however, the figure at least offers an indication of the experimental precision.
"Technical Data Book-Petroleum Refining", 2nd ed; American Petroleum Institute Division of Refining, Washington, DC, 1970; pp 5-19. Andrew, J. R. M.S. Dissertation, Colorado School of Mines, Golden, CO, 1978. Hoiiiman, S. L. M.S. Dissertation, Colorado School of Mines, Golden, CO, 1979. Kesier, M. G., Lee, B. I. Hydrocarbon Process. 1978, 55(3) 153. McConneil, J. R. M.S. Dissertation, Colorado School of Mines, Golden, CO, 1976. McConnell, J. R.; Fleckenstein, R. R.; Kidnay, A. J.; Yesavage, V. F. Ind. Eng Chem . Process Des. Dev. 1884, preceding paper in this issue. Omid, H. Ph.D. Dissertation, Colorado School of Mines, Golden, CO, 1977. Sturm, G. P., Jr.; Woodward, P. W.; Vogh, J. W.; Holmes, S. A,; Dooiey, J. E. "Analyzing Syncrude from Western Kentucky Coal", Bartiesvilie Energy Research Center, Report of Investigation Number: BERC/RI-75/ 12, Bartlesville, OK, 1975.
.
Received for review February 2, 1982 Accepted June 28, 1983
Supplementary Material Available: Tables of GC-MS results and enthalpy data for the coal liquids (9 pages). Ordering information is given on any current masthead page.
Enthalpy Measurements on Distillates Produced from a Utah Coal by the Char-Oil-Energy-Development Process and from a Kentucky Bituminous Coal by the Synthoil Process James R. Andrew, Raj Sharma, Arthur J. Kldnay, and Victor F. Yesavage' Department of Chemical and Petroleum Refining Engineerlng, Colorado School of Mines, Golden, Colorado 8040 1
Enthalpy data for a light distillate of a coalderived liquid produced from a Utah coal by the Char-Oil-Energy-Development (COED) process are presented at pressures of 415, 690, 3450, 6895, and 10340 kPa (60, 100, 500, 1000, 1500 psia) for temperatures between 18.3 and 383 OC (65 to 721 OF). Results for a distillate of a syncrude produced from a Kentucky bffuminous coal by the synthoil process are also presented at pressures of 1035, 1380, 3450, 6895, and 10340 kPa (150, 200, 500, 1000, 1500 psia) at temperatures between 18.3 and 395 O C (65 and 742 OF). The data were obtained in a Freon-11 (CFCI,) reference-fluid boil-off calorimeter.
Introduction This is the third in a series of papers reporting the results of an extensive set of measurements on coal-derived liquids and model compounds. The data were obtained in a Freon-11 (CFC1,) reference-fluid boil-off calorimeter that was developed specifically for measurements on coal-derived liquids. In a previous paper (McConnell et al., 1984), which described the calorimeter evaluation, results with water and n-heptane as test fluids indicate that the uncertainty in the measurements should be less than 0196-4305/84/ 1 123-0273$01.50/0
f1.0% of the measured enthalpy values (McConnell et al., 1984). Initial data were reported for a syncrude and a distillate produced from a Western Kentucky coal by the COED process (Omid et al., 1984). In the present study measurements are reported for a distillate from a Utah coal using the COED process and a distillate from a Kentucky bituminous coal using the Synthoil process. Experimental Section The boil-off calorimeter system is described in detail elsewhere (McConnellet al., 1984). As discussed previously 0 1984 American Chemical Society
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Table I
Table 111. Synthoil Distillate. ASTM Distillation (D-86) 70 recovered
Physical Properties Synthoil distillate molecular weight, wt av (no. av) bromine no., g/lOO g, ASTM D 1 1 5 9 refractive index, n z o specific gravity, (60" 160" ) kinematic viscosity, (100 O F ) , ASTM D 4 4 5 " API K Watson
140 (130)
Utah distillate 135 (125) 16.3
8.1 1.5400 0.978 5.9 13.2 10.0
1.4992 0.879 2.12 29.4 10.8
Elemental Analysesa element C
83.52
H
9.24
N
1.60
S
0.13
75.5Bb (74.30) 10.39 (9.8) 0.99 (1.12) 0.00
a Data in parentheses measured at Texas A&M UniverAverage of t w o independent measurements for C, sity. H, N, and S. The analyses were done by different operators o n the same equipment.
Table 11. Utah Distillate. ASTM Distillation (D 86) % recovered
(by v 0 1 ) ~ IBP 10 20 30 40 50 60 70 80 90
endpoint
temp, "C ( O F ) at 0.81 a t m b 66 108 146 179 198 220 231 246 260 282 304
(150) (227) (294) (355) (388) (428) (447) (475) (500) (539) (580)
corr temp, "C 71 114 153 187 206 228 238 254 267 293 314
(160) (237) (308) (368) (402) (442) (460) (490) (513) (559) (598)
a 4.8 mL was left in the bottom of the distilling flask of 100 mL charged. Ambient pressure at Golden, CO. Temperature corrected t o 1 a t m using API (1970). Distillation performed by Colorado School of Mines.
(Omid et al., 1984), a major concern during operation is the occurrence of sample decomposition at high temperatures. The ensure that sample decomposition had a negligible effect on the enthalpy measurements, low-temperature runs were repeated after high-temperature runs were obtained. As a check of the system reliability, measurements on n-heptane were periodically repeated. Based on these studies the accuracy of the data is believed to be within f1.0% of the measured enthalpy values. Experimental details are reported elsewhere (Sharma, 1977; Andrew, 1978). Both coal-derived liquids were analyzed in detail and the results are listed in Tables 1-111. The measurements include physical properties, elemental analysis, and ASTM distillation. A gas chromatographic-mass spectrometer (GC-MS) analysis performed by Dr.C . V. Philip of Texas A&M University is presented in Table S1 as Supplementary Material. As can be seen from Table I, the elemental analyses for the Utah distillate after several replications consistently produced combined carbon, hydrogen, and nitrogen results of about 85%. The sulfur content was very low in this sample. The results from the GC-MS show that the
(by vel)' IBP 10 20 30 40 50 60 70 80 90
endpoint
temp, "C ( O F ) at 0.81 atm 91 207 216 224 232 241 253 263 280 310 326
(196) (404) (420) (436) (449) (466) (487) (506) (536) (590) (618)
corr temp, "C 98 216 224 232 239 249 262 274 291 318 335
(208) (420) (435) (450) (462) (480) (504) (525) (555) (605) (635)
a 7.0 mL was left a t the bottom of the distilling flask of 100 mL charged. Ambient pressure at Golden, CO. Temperature corrected t o 1 atm using API (1970). Distillation performed by Colorado School of Mines.
sample contains significant quantities of oxygen compounds, but oxygen alone cannot account for the anomalous values. Perhaps there is some interference between species present in the sample and the instrument used, a Carlo Erba Elemental Analyzer, or perhaps there is a fundamental flaw in the analytical method. In the GC-MS analysis, for unambiguous spectra, it is usually possible to identify 90% to 98% of the major peaks, at least as far as compound type. However, for the Synthoil sample only 76% of the peaks could be identified (Holliman, 1979). Utah Distillate The Utah distillate was derived from a syncrude produced by the COED process using a Utah coal. The syncrude was furnished by the Bartlesville Energy Technology Center and was selected for measurement because the sample and the feed coal had been characterized in detail by the Bartlesville Laboratory (Dooley et al., 1975). The whole oil sample was filtered three times with Whatman No. 1filter paper to remove the large amount of solid residue. After charging the system and heating the syncrude to a temperature of 180 "C a very large pressure drop (2750 kPa) was observed across the calorimeter. One data point was measured, but the inlet pressure continually increased from 4070 kPa (590) to 4310 kPa (625 psia) in the course of the 10-min data collection period. Before another data point could be taken the pressure drop had increased to 5000 kPa (800 psia) and the measurement was terminated. The system was drained and at the outlet of the calorimeter a very viscous, thick substance was obtained. This material was a much lighter brown than the original liquid and was obviously the source of the very large pressure drop. The system was cleaned and recharged with a new filtered sample and operation was resumed. Within a few minutes after starting the pump and without heating the oil, the pressure drop across the calorimeter had increased to over 6200 kPa (900psia). Upon draining the calorimeter the same light brown material was obtained. This substance became less viscous upon heating but remained more viscous than the original sample. The whole oil sample viscosity was significantly altered by pumping and thus routine enthalpy measurements could not be made. It was decided therefore to concentrate on measurements of distillate samples. A batch distillation was performed on the whole oil to obtain the three products shown in Table IV. The distillate was light reddish-brown in color and tended to become darker with time, while the vacuum distillate was greenish-black in color.
Ind. Eng. Chem. Process Des. Dev., Vol. 23, No. 2, 1984 275
Table V. Data for Sample of Centrifuge Synthoil
Table IV. Distillation of Utah Syncrude
This Synthoil product was made from a blend of Kentucky bituminous coal. Analysis of this coal and its source follows
total sample charged products distillate atmospheric distillation ( = 6 2 0 mmHg) (cut point 2 7 1 "C, 7 6 0 mmHg) vacuum distillate vacuum distillation ( 23-4 mmHg) (cut point P 3 2 1 "C, 7 6 0 mmHg) residue ( 3 2 1 "C+, 7 6 0 mmHg)
1 0 060 g
total products loss
10 012 g 48 g P 0.48%
JTAH
4 056 g 1250 g 4706 g
D'STL.
proximate analysis, w t % moisture ash volatile matter fixed carbon ultimate analysis, wt % moisture ash carbon hydrogen nitrogen oxygen, by difference sulfur as sulfate as pyrite as organic analysis typical of this Synthoil product are S in product, wt % ash in product, wt % viscosity of product, SSF a t 1 8 0 "F specific gravity of product solvent analysis (wt W ) (ash-free) organic benzene insols asphaltenes (pentane insols from benzene sols) oils (pentane sols from benzene sols)
6.1 15.5 36.3 42.1 6.1 15.5 60.3 4.9 1.2 12.8 5.3 0.58 2.69 2.03 0.4 0.7 26.5 1.100 1.8 23.5 74.7
Table VI. Synthoil Material Balance I
I
0
/ I
I
50
00
50
I
I
I
I
20C
25C
300
350
TEMPERATURE,
I 400
"C
Figure 1. Enthalpy as a function of temperature for a Utah coalderived distillate at several pressures.
Several runs reported elsewhere (Sharma, 1977) were obtained on the vacuum distillate; however, due to system leaks and the small amount of sample, sufficient quantities of this oil were not available for characterization. For the light distillate, data were obtained at pressures of 415,690,3450,6895, and 10340 kPa (60,100,500,1000, 1500 psia) between temperatures of 18.3 and 383 "C (65 to 721 O F ) . Experimental data are reported in Table S2 presented as Supplementary Material and are illustrated in Figure 1. These data were adjusted to an outlet temperature of 18.3 "C (65.0 OF) by use of a heat capacity obtained from the slope of the enthalpy measurements at low temperatures. This correction was less than f1.0 kJ/kg. The selected reference state is the liquid at 18.3 OC and 1atm. The adjustment to 1 atm was made with the Kesler-Lee (1976) correlation and this correction was less than 2%. Thus, even significant percent errors in the correlation would not affect the overall reported accuracy. Figure 1 illustrates the transition from liquid to twophase to vapor, showing the small effects of pressure on enthalpy in the liquid, the gradual sample vaporization, and the appreciable effect of pressure on enthalpy in the vapor phase. The figure also indicates the precision of the experimental results. Synthoil Distillate The Synthoil was obtained from the Pittsburgh Energy Technology Center. The sample analysis received with the sample is shown in Table V. The Synthoil sample was a tar-like substance which was so viscous at room temperature that no attempt was made to take enthalpy data on the whole oil. Instead, an atmospheric distillate was prepared in a laboratory batch distillation apparatus. An overall material balance for the batch distillation is presented in Table VI. The atmospheric cut was a light,
15 865 g
total synthoil charged products atmospheric distillation ( 6 2 0 mmHg) (cut point, 3 2 1 "C, 7 6 0 mmHg) residue ( 3 2 1 "C+, 760 mmHg) total products
1200
11774 g 1 5 809 g 56 g 0.36%
SYNTHOIL
0
4 035 g
1 50
I 100
DISTILLATE
I I50
I
200
I 250
I
I
I
300
350
400
TEMPERATURE,
Figure 2. Enthalpy as a function of temperature for a Synthoil distillate at 1380 and 3450 kPa.
transparent golden-brown liquid which darkened with the passage of time, probably due to oxidation of the nitrogen compounds. The residue from the distillation was a black viscous substance that was solid at room temperature. The enthalpy measurements were made at pressures of 1035,1380,3450,6895,and 10340 kPa (150,200,500,1000, 1500 psia) at temperatures between 18.3 and 395 "C (65 and 742 OF). Data are presented in Table S3 presented as Supplementary Material and illustrated in Figure 2. Again the reference state is 18.3 "C and 1.0 atm. From Figure 2 the transition from the liquid to the two-phase
Ind. Eng. Chem. Process
276
region can be clearly seen. Due to the high viscosity of this sample and large pressure drop across the calorimeter, it was not possible to operate at lower inlet pressures. Thus, the two-phase vapor transition and data in the vapor region were not obtained. Acknowledgments
This work was supported by the Office of Fossil Energy, Department of Energy (Contract No. E (49-18)-2035). The authors wish to thank H. Omid and M. C. Hiza for experimental assistance and D. Thakkar and S. Holliman for assistance with the analyses. J. E. Dooley and C. H. Thompson of Bartlesville Energy Technology Center sumlied the Utah COED samde while P. M. Yavorskv of Pittsburgh Energy Technolo& Center supplied the Synthoil sample. Dr. c. V. Philip of Texas A & M University supplied the GC-MS results.
Des. Dev. 1904, 23, 276-278
Literature Cited "Technlcal Data Book-Petroleum Refining", 2nd ed., American Petroleum Institute, Division of Refinlng, Washington, DC, 1970; pp 5-19. Andrew, J. R. M.S. Dissertation, Colorado School of Mines, Goklen, CO, 1978. Dooley, J. E.;Sturm, G. P.; Woodward, P. W.; Vogh. J. N.; Thompson, C. H. "Analyzing Syncrude from Utah Coal"; Bartlesville Energy Research Center, Report of Investlgatlon No. BERC/RI-75/7, Bartlesvllie, OK, 1975. Holliman, S. L. M.S. Dissertation, Colorado School of Mlnes, Golden, CO, 1979. Kesier, M. G.; Lee, B. I . Hydrocarbon Process. 1976, 55(3), 153. McConnell, J. R.; Fleckenstein, R. R.; Kldnay, A. J.; Yesavage, V. F. Znd. fng . Cbem. Process Des. Dev. 1984, previous paper in this issue. Omid, H.; Andrew, J. K.; Yesavage, V. F.; Kidnay, A. J. Znd. Eng. Chem. Process Des. D e v . 1984, previous paper in this issue. Sharma, R. M.S. Dissertatlon, Colorado School of Mines, Golden, CO, 1977.
Received for review February 2, 1982 Accepted June 28, 1983
Supplementary Material Available: Tables of GC-MS results and enthalpy data for the coal liquids (10 pages). Ordering information is given on any current masthead page.
Enthalpy Measurements on DDstDllate Cuts of Syncrudes Produced from the Solvent Refined Coal Processes RaJ Sharma, James R. Andrew, Victor F. Yesavage,' and Arthur J. Kldnay Depatfment of Chemical and Petroleum Refining Engineering, Colorado School of Mines, Golden, Colorado 8040 1
Enthalpy data are presented at 14 pressures between 210 and 10340 kPa (30 and 1500 psia) for temperatures between 18.3 and 382 OC (65 to 720 OF) for a naphtha cut distilled from a coalderived liquid produced by the Solvent Refined CoaCI (SRCI) process. Data are also reported for two distillates produced by the Solvent Refined Coal-I1 (SRC-11) process. Measurements for the naphtha were obtained at pressures of 690, 1380, and 2060 kPa (100, 200, 300 psia) at temperatures from 18.3 to 237 OC (65 to 459 OF), and measurements for the middle boiling range distillate were obtained at pressures of 895, 1035, 2070,and 6895 kPa (130, 150, 300, 1000 psia) at temperatures from 18.3 to 357 OC (65 to 675 OF). The data were obtained in a Freon-11 (CFCI,) reference fluid boil-off calorimeter.
Introduction As a part of a continuing effort to obtain enthalpy measurements for coal-derived liquids and model compounds representative of coal-derived liquids, enthalpy measurements are presented for three distillate liquids produced from the two solvent refined coal processes, SRC-I and SRC-11. The data were obtained in a Freon 11 (CFClJ reference fluid boil-off calorimeter that has been described previously (McConnell et al., 1984). Based on previous evaluation studies, uncertainty in the measurements should be less than *LO% of the measured enthalpy values. Data have been previously reported for coal-derived liquids produced by the Char-Oil-Energy-Development (COED) (Omid et al., 1984; Andrew et al., 1984) and the Synthoil processes (Andrew et al., 1984). Experimental Section The boil-off calorimeter is described in detail elsewhere (McConnell et al., 1984). As in previous studies with coal liquids (Omid et al., 1984; Andrew et al., 1984), a major concern was the occurrence of sample decomposition at high temperatures. This was a particularly severe problem for the liquids of this investigation. To determine whether sample decomposition had an effect on the enthalpy measurements, low-temperature runs were repeated after high-temperature runs had been obtained. It was often 0196-4305/84/1123-0276$01.50/0
necessary to discard data in regions where it was believed that sample decomposition resulted in uncertainties greater than f1.0%. The details of the experimental difficulties are reported elsewhere (Andrew, 1978; Sharma, 1980). The three coal liquids were analyzed in detail and the results are listed in Tables I-IV. The measurements include physical properties, elemental analysis, and ASTM distillation. A gas chromatographic-mass spectrometer (GC-MS) analysis performed by Dr. C. V. Philip of Texas A&M University is presented as Supplemental Material in Table S l . For the GC-MS analyses 90% to 95% of the major peaks are identified, at least as far as compound type, for the two naphtha samples, but for the SRC-I1 middle distillate it appears that the separation techniques was not effective, for only 25% of the peaks could be identified. SRC-I Naphtha The sample, produced by the Pittsburg and Midway Coal Mining Company at the SRC-I pilot plant in DuPont, WA, was a light, amber-colored liquid and was charged to the calorimeter as received. Severe operational difficulties were often encountered at higher temperatures due to extreme compositional changes in the sample. At lower pressures and temperatures above 175 "C, a solid black product would often form 0 1984 American
Chemical Society
