EXTREME CONDITION PROCESSING Henry, H. M., Gas Age 115, 36-7, 40-9, 70, 72, 73 (March 10,
amounts. Product gas volumes and heating values were calculated for the conditions of 60” F., 30 inches of mercury absolute pressure, and saturation with water vapor assuming the ideal gas law. Specific gravities were calculated on a dry basis from the average molecular weight of the gas referred to air of molecular weight 28.972. Since gas samples were taken intermittently as the run proceeded and only the exit gas volume could be measured directly, i t was necessary to calculate the gas volumes during the run from the observed pressure and temperature. The ideal gas law was used since exit gas volumes calculated by this method did not deviate by more than 3’% from values measured by wet test meter. For the tests with petroleum oils, product gas volume calculations were based on the full system volume of 1006.8 ml., whereas for the coal tests the free volume was assumed t o be the difference between the system volume and the volume of the coal charge (weight divided by bulk density).
1955).
Ipatieff, V. N., Natl. Petroleum News 23, 49-54 (March 25, 1931); Ibid., 61-5, 99 (April 1, 1931). Kling, A., Florentin, M. D., “Proceedings of Second International Conference on Bituminous Coal,” val. 2, pp. 523-41, Carnegie Inst. Technol., Pittsburgh, 1928. Linden, H. R., Bair, W. G., Pettyjohn, E. S., Am. Gas Assoc. Proc. 1954, pp. 616-27 [GUS Age 113, 19-26, 68, 170 (May 20, 1954); Gas World 140, 98-104 (1954)l. Linden, H. R., Guyer, J. J., Pettyjohn, E. S., Am. Gas Assoc. Proc. 1954, pp. 639-54. Linden, H. R., Reid, J. M., Bair, W. G., Pettyjohn, E. S., “Initial Operation of a Four-Shell Cyclic Regenerative Pressure Oil Gas Pilot Unit,” CEP-55-16, Am. Gas Assoc. Chem. Eng. Mfd. Gas Production Conference, New York, N. Y . , May 23-25, 1955. Lowry, H. H., “Chemistry of Coal Utilization,” Wiley, New York, 1945. McAfee, J., Montgomery, C. T.V., Hirsch, J. N., Horne, W.A., Summers, C. R., Jr., Petroleum Refiner 34, KO.5, 156-62 (1955).
Mizoshita, T., J . Sac. Chem. I n d . J a p a n 44, Suppl. Binding 247 (1941).
literature Cited
Ogawa, T., Yokota, T., Bull. Chem. Sac. J a p a n 5 , 266-75
(1) Austin, G. T., Ph.D. thesis, Purdue University, Lafayette, Ind., 1943. (2) Benson, H. E., Field, J. H., Jimeson, R. M., Chem. Eng. Progr. 50,356-64 (1954). (3) Bergius, F., Brennstof-Chem. 6, 164 (1925); Fuet 4 , 458 (1925). (4) Bergius, F., 2. Ver. deut. Ing. 69, 1313-20, 1359-62 (1925). (5) Booth, N., Williams, F. A,, J . Inst. Fuel 11, 493-502 (1938). (6) Bray, J. L., Howard, R. E., Purdue Uniz.. Eng. Erpt. Station Bull., Research Ser. 90 (September 1943). (7) Bray, J. L., Morgal, P. W., Ibid., 93 (July 1944). (8) Dent, F. J.,Blackburn, W-.H., Millett, H. C., Gas J. 220, 4705 (1937) [Inst. Gas Engrs. N o . 167/56 (1937)l. (9) Ibid., 224, 442-5 (1938) [Inst. Gas Engrs. No. 190/73 (1938)l. (10) Dent, F. J., Gas Council Research Commun. GC 1 (1952). (11) Dent, F.J., Gas J. 244, 502-07 (1944) [Gas World 121, 378-87 (1944) 1. (12) Dent, F. J., Gas Research Board GRB 13/3 (1950). (13) Dunstan, A. E., Nash, A. W., Tizard, Henry, Brooks, B. T., “Science of Petroleum,” vol. 3, pp. 2130-63, Oxford Univ. Press, New York, 1938. (14) Eickmeyer, A . G., Marshall, W. H., Jr., Chem. Eng. Progr. 51, 418-21 (1955). (15) Ellis, C., “Hydrogenation of Organic Substances,” 3rd ed., pp. 499-586, Van Nostrand, Kew York, 1930. (16) Graham, J. I., Skinner, D. G., “Proceedings of Third International Conference on Bituminous Coal,” vol. 2, pp. 17-27, Carnegie Inst. Technol., Pittsburgh, 1931. (17) Greyson, M., Demeter, J. J., Schlesinger,M. D., Johnson, G. E., Jonakin. J.. Mvers. J. W.. U . S. Bur. Mines Rmt. Invest. 5137 (1955). (18) Griffith. R. H., Dent, F. J., Gas Council Research Commun. GC 8 (1953). (19) Hall, C. C., Fuel 12, 76-93 (1933).
(1930). Pier, M., Brennstof-Chem. 32, 129-33 (1951). Pyrcioch, E. J., Dirksen, H. A., Von Fredersdorff, C. G., Pettyjohn, E. S., Am. Gas Assoc. Proc. 1954, pp. 813-36. Rossini. F. D., Pitzer, K. S., Arnett, R. L., Braun, R. >I.,
Pimentel, G. C., “Selected Values of Physical and Thermodynamic Properties of Hydrocarbons and Related Compounds,” Carnegie Press, Pittsburgh, 1953. Schlesinger, $1. D., Demeter, J. J., Greyson, ILI., IKD. ENG. CHEM.48,68-70 (1956). Searight, E. F., Boyd, J. R., Parker, R., Linden, H. R., Am. Gas Assoc. Proc. 1954, pp. G75-97 [Inst. Gas Technol. Research
Bull 24 (January 1956) 1. Shatwell, H. G., Fuel 2, 229-32 (1923). Shatwell, H. G., J . Inst. Petroleum Technol. 10, 903-11 (1924). Spilker, A,, Zerbe, K., 2. angew. Chem. 39, 1138-43 (1926). Stockman, C. H., Bray, J. L., Purdue Univ. Eng. Expt. Station Bull., Research Ser. 111 (November 1950). Starch, H. H., Fisher, C. H., Hawk, C. O., Eisner, A., U . S. Bur. Mines Tech. Paper, No. 654 (1943). Strimbeck, G. R., Holden, J. H., Rockenbach, 12. P., Cordiner, J. B., Jr., Schmidt, L. D., Am. Gas Assoc. Proc. 1954, 50163.
Tropsch, H., Fuel 11, 61-6 (1932). U . S . Bur. Mines, Rept. Invest. 4865, (1952).
Utermohle, C. E., Am. Gas Assoc. Monthly 30, No. 11, 27-8. 54-5 (1948). Van Fredersdorff, C . G., Pyrcioch, E. J., Am. Gas Assoc. Proc. 1953, 968-1001. Waterman, H. I., Perquin, J. N. J., J . Inst. Petroleum Technol. 10,670-7 (1924). Weir, H. M., IND.ENG.CHEM.39,48-54 (1947). Wiley, J. L., Anderson, H. C., U . S. Bur. Mines Bull. 485 (1951). Zielke, C. W., Gorin, E., IND.ENGI.CHEM.47, 820-5 11965).
(HYDROGASIFICATION OF PETROLEUM OILS AND BITUMINOUS COAL)
Hydrogenolysis of Petroleum Oils EUGENE B. SHULTZ, JR.,
AND
H. R. LINDEN
lnsfifufe of Gas Technology, Chicago, Ill.
T
HE high pressure hydrogenolysis of oils a t high temperatures (1200’ t o 1350” F. or 649’ t o 732” C . ) has not been reported. However, many investigations a t temperatures u p t o 500’ C. (932’ F.) have been carried out t o develop processes for upgrading heavy petroleum crudes and residuums to higher value liquid fuels. The results of early investigations of hydrogena-
review was published earlier by Shatwell(S5), and another review (IS) includes discussions o€ batch reactor tests by Bergius and Ipatieff and descriptions of commercial scale plants by Russell and King. A comprehensive bibliography on all phases of pressure hydrogenation was prepared by the U. s. Bureau of &Tinesin
tion of petroleum crudes and fractions, shale oils, pitch, asphalt, and paraffin wax were compiled by Ellis (15) in 1930. A brief
I n the early studies carried out in batch reactors, conversions t o gas not exceeding 17 weight per cent (46)were observed
May 1956
1951 (47).
INDUSTRIAL AND ENGINEERING CHEMISTRY
a95
ENGINEERING, DESIGN, AND PROCESS DEVELOPMENT 200
I80
4
Table I.
I N I T I A L PRESSURE; 1045 PSIG M A X I M U M P R E S S U R E = 3065 P S l G Ht/OIL F E E D R A T I O = 1 7 4 . 8 S C F I G A L . OPERATING T E M P = 12OOOF.
Oil type Gpecific gravity
160
60' F./60° F.
OAPI
i
Distillation, %, O F. Initial boiling point
4
a 140
~~
2 0
10 20 30 40 50
v)
a-120 -1
w
60
>v)
70 80 90
100
Q
a W
1
End point Viscosity, Saybolt 5ec. at 122" B. Aniline point, O F. Conradson carbon residue, wt. % Heating value, B.t.u./ lb. Ultimate analysis, wt. % Carbon Hydrogen Sulfur Carbon-hydrogen weight ratio
80
l-
a
-I
2
60
3
0
40
20
0
Figure 1.
40 80 120 160 200 240 RESIDENCE T I V Z ABOVE 8 . 7 5 0 ~ MIN.
Effect of residence time at 1200" gas yields from reduced crude
896
Diesel Oil
Reduced Crude
0.846 35.7
0.925 21.4
Bunker C Fuel Oil (Texas Crude) 1 .QO1 9.9
354 426
446 465
483 497 517 535
555 588 656 32.5
(Universal) 144.1 0.01
247.0
93.7
(Universal)
(Furol)
4.42
10.73
...
.*.
19,390
19,201
18,774
86.I
85.43
89.55
12.79
12.13
1.90
10.52 0.86
7,04
8.51
...
6.74
280
F. on product
because of the low temperatures employed. Conversions were generally improved by higher temperatures, longer reaction times, and higher initial hydrogen pressures. Methane mis the predominant hydrocarbon gas produced and was reported in concentrations as high as 73.6 mole per cent ( 3 6 ) . More recent data including continuous reactor studies confirm these results (91,98,41). Some work was also carried out with pure compounds, mostly in an attempt to locate the temperature a t which rapid dissocia-
Figure 2.
Analyses of Oils
tion into fixed gases begins. This temperature appears to be a function of pressure as well as compound type. Pier (30) determined the half life of lower molecular weight paraffins a.t 200 to 250 atm. hydrogen pressure and 360" to 460" 6.in the presence of tungsten sulfide. Ogawa and Yokota ( $ 9 ) investigated the effect of nickel catalyst on hydrogenation of cyclic hydrocarbons a t 450" to 500" C. Kling and Florentin ( 2 6 ) found that a t sufficiently high initial hydrogen pressures in the absence of catalysts, appreciable gasification n-as initiated from 410" to 440" C. for higher molecular Iyeight pa.raffins, a t 440" C. for anthracene and a t 475" C. for naphthalene. Other studies with polynuclear aromatics have generally confirmed these values (29, 37). From these data, it appeared that substantial conversion of
Effects of residence time and temperature on gaseous product yields from Bunker C fuel oil
INDUSTRIAL AND ENGINEERING CHEMISTRY
voi. 48, N ~ 5.
EXTREME CONDITION PROCESSING oils to gas by hydrogenation at high pressures and temperatures could be realized most readily by increasing the reaction temperature above the dissociation ranges. I n the first part of this study typical petroleum oils were gasified in a batch reactor a t temperatures from 1200' t o 1350" F., reactor pressures from 2000 t o 4400 lb. per sq. inch gage, and hydrogen-oil feed ratios from 92 t o 299 stand. cu. ft. per gal.
Effects of Residence l i m e and Temperature During the heat-up period of the batch hydrogasification tests with distillate and residual petroleum oils (see Table I for analyses), very little gasification occurred until the temperature reached a level of approximately 900' F. The variation of pressure with temperature was virtually linear until a threshold temperature was reached, when the moles of gas present began t o increase suddenly and the gas properties began to change very rapidly. This threshold temperature was measured a t the break in the temperature-pressure curve during the initial portion of the run, and, since it was affected somewhat by rate of heatup as well as hydrogen partial pressure and oil properties] i t was reported for each run (Table 11). As shown in Figures 1 and 2, increases in residence time during the period between attainment of threshold and run temperatures (27 to 42 minutes) resulted in rapid changes in gas composition accompanied by high rates of gaseous hydrocarbon prcduction (shown in Table I1 as space-time yield-the volume of gaseous hydrocarbons produced per unit reactor volume in the time elapsed after attainment of threshold temperature). The hydrogen concentration decreased rapidly during this period, and the concentrations of propane, butanes, and olefins initially formed soon reached maxima. Accompanying the disappearance of propane, higher paraffins, and olefins as run temperatures of 1200" t o 1350" F. were approached, ethane concentrations reached a maximum of 15 to 25 mole per cent. As the temperature was held Constant, benzene and toluene concentrations passed through a maximum, whereas methane concentrations continued to increase and hydrogen and ethane concentrations t o decrease until a n approximate balance between the hydrogenation and dehydrogenation reactions waB achieved. For hydrogasification of reduced crude a t a nominal run temperature of 1200' F., the time a t which this balance occurred increased from approximately 30 minutes a t a hydrogen-oil feed ratio of 92 stand. cu. ft. per gal. to approximately 150 minutes at a hydrogen-oil feed ratio of 228 stand. cu. ft. per gal. (see Runs 3, 15, 8, and 14, Table 11). A typical gas composition a t this approximate balance point was 90% methane, 3% ethane, and 3% hydrogen; the other 4% consisted of higher hydrocarbons and inerts. When the run was continued, the hydrogen concentration began to increase slowly from its minimum of 2 to 4%, and a set of reactions, more typical of pyrolysis than hydrogenolysis, occurred. The net B.t.u. recovery (the product of gas yield and heating value, minus the initial hydrogen heat of combustion) and the conversion t o gas passed through maxima a t the same time (Table 11). For reduced crude this appeared to occur as the run temperature of 1200" F . was attained. At comparable conditions the maxima for Bunker C fuel oil were observed a t much longer residence times, about 100 minutes after the attainment of 1200' F. The accuracy of the reported maximum B.t.u. recoveries of 164,000 B.t.u. per gal. for Run 8 and 176,000 B.t.u. per gal. for Run 7 are in doubt since the corresponding conversions of oil to gas were 117 and 123 weight per cent, respectively. The maximum B.t.u. recovery corresponding t o complete conversion should not exceed the heat of combustion of the oil referred t o liquid water and gaseous carbon dioxide a t 60' F. and 1 atm. (148,000 B.t.u. per gal. for the reduced crude and 157,000 B.t.u. per gal. for the Bunker C fuel oil) less the exothermic heat of the overall hydrogenolysis reaction at the same reference conditions
May 1956
(15,000 t o 20,000 B.t.u. per gal.). This estimate of a B.t.u. recovery of approximately 135,000 B.t.u. per gal. at complete gasification of residual oils is confirmed by the results of Table I1 for conversions t o gas of 90 weight per cent or more. The effects of temperature on hydrogasification results for Bunker C fuel oil are illustrated by a comparison of Runs 7 , 17, and 20 (Table I1 and Figure 2) carried out at 1200", 1275O, and 1350' F., respectively, at otherwise similar conditions. Although the effects of time and temperature cannot be separated when reaction occurs to such a great extent during the heatup period, it can be seen that, in general, an increase in temperature caused a n increase in the rates of the hydrogasification reactions, resulting in substantial increases in t h e rates of hydrogen utilization and in the gaseous hydrocarbon space-time yields. I n the production of 1000 t o 1100 B t.u. per stand. cu. ft. and 0.6 specific gravity gases from Bunker C fuel oil with approximately 200 stand. cu. ft. of hydrogen per gal., net B.t.u. recoveries increased from 117,000 t o 125,000 B.t.u. per gal. with decreases in temperature from 1350' to 1200' F. Conversions t o gas were limited t o a maximum of 86.5 weight per cent in this range of operating conditions because of a slightly inadequate hydrogen supply. Residence times above threshold temperature necessary for the production of approximately 90 mole per cent paraffin content gases were 192 minutes for Run 7 (1200' F.), 52 minutes for Run 17 (1275' F.), and 47 minutes for Run 20 (1350" F.).
Effects of Hydrogen-Oil Feed Ratio Four 1200" F. runs were made with 0.1-pound samples of reduced crude at hydrogen-oil feed ratios from 92 to 228 stand. cu. ft.per gal., representing a range of 40 t o 100% of the hydrogen requirements for complete conversion of this oil t o a high methane content gas of 1000 B.t.u. per stand. cu. ft. Decreasing the feed ratio through this range resulted in a faster utilization of the hydrogen charged and a more rapid approach to a n equilibrium gas composition as shown by increasing methane contents of the gases a t equivalent residence times (Table 11). Increases in the hydrogen-oil feed ratio from 92 to 228 stand. cu. ft. per gal. uniformly increased the yields of 1000 to 1100 B.t.u. per stand. cu. ft. and 0.6 specific gravity gas from about 125 to 190 stand. cu. ft. per gal., corresponding t o increases in conversions of from 70 t o nearly 100 weight per cent and increases in net B.t.u. recoveries from about 100,000 t o 130,000 B.t.u. per gal. Since equivalent gases were produced in greater quantities but a t longer residence times as hydrogen-oil feed ratios were increased, the effect of feed ratio upon gaseous hydrocarbon space-time yields was not well defined; values ranged without significant trend from 47 to 86 stand. cu. f t . per cu. ft. per hr. Bunker C fuel oil showed a significant increase in conversion, accompanied by a n increase in unreacted hydrogen in the product gas when the hydrogen-oil feed ratio was increased from 197 to 299 stand. cu. ft. per gal. (Runs 20 and 42, Table 11). However, complete conversion t o 1000 B.t.u. per stand. cu. f t . product gas did not seem attainable in the batch reactor because of excessive carbon formation a t hydrogen-oil feed ratios meeting the stoichiometric requirements for conversion of .Bunker C fuel oil t o equilibrium methane-ethane-hydrogen product gas (approximately 300 stand. cu. f t . of hydrogen per gal.). I n such an externally heated batch reactor extended exposure of feed and intermediate product hydrocarbons t o high temperatures, without adequate contacting with free hydrogen] appears unavoidable. Effects of Feed Oil Properties Comparing of Runs 16,8, and 7 (Table 11) made with Diesel oils reduced crude, and Bunker C fuel oil, respectively, at 1200" F.
INDUSTRIAL AND ENGINEERING CHEMISTRY
897
ENGINEERING, DESIGN, AND PROCESS DEVELOPMENT
Table II. Run 3 Reduced crude,
Run 16 Diesel oil, 0.105 Ib.
Charge Operating conditions Temp., F. Initial pressure, lb./sq. in. gage Hydrogen/oil ratio, stand. cu. ft./ gal. Threshold temp., 'F. Time to reach threshold temp., min.
0.098 Ib.
Batch Reactor Test Data for High (Data corrected for gas
Run 15 Reduced crude, 0.104 lb.
1200 1020
1200
510
1200 755
1200 1045
155.0 860
92.4 850
123.1 875
174.8 875
42
51
43
No. 1 No. 2 No. 3 No. 4 No. 1 No. 2 No. 3 No. 1 No. 2 No. Time above room temp., min. 54 Time at run temp., min. Reactor pressure, Ib./sq. in. gage 2855 Reactor temp., F. 1002 Operating results NetB.t.u.recovery,MB.t.u./gal 31.1 Productgas yield, stand. cu.ft./gal. 168.3 Conversion to gas, net wt. % of chargea 22.8 Gaseous hydrocarbon space-time 39.8 yieldh,stand. cu.ft./cu. ft.-hr. Condensate, wt. % of charge Carbon residue, wt. rC of charge Material balance, yo Product gas properties Gas composition, mole % 0.8 Nz CO COz
...
+
HzS Hz CHI
+
0
6 c
75
0 2965 1200
120 45 2940 1200
180 105 3090 1200
105 15 2040 1193
109.6 112.4 112.4 154.9 152.7 160.4
137 47 2085 1200
200 110 2105 1197
110.6 103.9 100.0 124.4 126.5 128.0
. .46. . . 70.
1985 910
2170 1165
52 3
105 30 2430 1205
No. 4 No. 1 No. 2 No. 3 No. 4 145
70 2455 1200
11.2 100.4 100.5 103.5 137.8 127.1 138.9 140.8
65
...
2900 1017
115 25 2920 1199
200 110 3015 1200
300 210 3065 1200
164.3 120.4 128.9 121.9 184.2 165.3 170.6 173.4
84.2
87.3
86.7
73.2
68.6
65.0
7.1
70.2
68.5
71.5
116.9
87.3
94.4
88.9
......... ......... .........
85.2
47.6
29.3 9.4 6.3 98.6
47.4
30.4
17.9 4.9 22.2 89.7
35.6
86.2
49.5
31.0
144.2
50,O
26.7
.........
4.0 17.4 90.4
17.0 14.2 8.4 105.7
1.5 0.1 25.9 46.6 24.4 0.2
0.8 0.1 2.6 93.5 1.9
0.9 0.2 3.3 83.3 9.7
0.6
0.4
4.4 89.8 2.7
6.3 90.0 1.5 0.2
...
1.3 0.1 54.5 6.8 8.2 11.7 9.1 3.0 5.2 0.1
1.0 0.2 17.5 60.9 17.0 0.3 0.4
1.2 0.3 3.4 88.9 2.3 0.1
1.4 0.1 4.0 91.6 0.6
1.5
3.4 0.2
1.9 0.4
...
CzHs CaHs Butanes Pentanes plus Olefins Benzene Toluene Xylenes Ethylbenzene CSAromatics Total Heatingvalue, B.t.u./stand. cu.ft. Specific gravity (air = 1-00)
Run 8 Reduced crude, 0.105 lb.
87.9 4.9 2.7 2.0 0.6 0.2
0.7
... ...
0.9 0.1 2.5 85.4 10.0 0.2
... ... ... ... ... ...
* . a
. I .
9 . .
0.4 0.4 0.1
0.2 0.6
0.3
.0.1. . . 0.. 1. . ... . . ... ... . . a
-
0.1 0.1 100.0 100.0 100.0 100.0
_
_
_
. I . _ .
~
479 1031 1064 1012 0.191 0.581 0.609 0.575
0.8
95.8 1.1 0.7 0.4 0.3 0.1 0.8
1.5 0.3 17.4 53.8 23.6 0.4
0.4 0.2 3.2 92.4 3.0 0.1
... ...... 0.1 ... 0.8 ... 0.2 ... ... 1.9 ... 0.2 0.2 ... 1.2 ... 0 . 2 0.6 0.9 0.7 ... 0 . 1 0.1 0.9 0.3 0.8 *.. . . . . . . . . 0.2 0.2
.0.2. . . ... . . ... ... 0.6 0.2 0.1
... ...
.. .. .. .. .. .. .. .. ..
~
0.1 0.3 0.2 0.1 _ _ e . . 0 . 1 __ 100.0 100.0 100.0
1126 1053 1010 0.655 0.606 0.569
1.0 0.2 3.7 92.0
1.3
... ... ...
0.1 1.3 0.4
......... ......... .........
...
...... ... . . . . . . 1.1 0.1 ... 0.1
... ... ... . . . . . . . . . . . . . . . ... ... ... 0.1 ... ... __ -_ . . ._ . . . .-. . ~... __ ... __ _ 0 . .
100.0 100.0 100.0 100.0 100.0 100 * 0 100.0 100.0
367 1107 1012 1019 0.115 0.639 0.571 0.586
1195 1065 1082 1023 0.716 0.614 0.638 0.594
Calculated a s total wt. of gas minus initial hydrogen wt., divided by wt. of charge. Based on time elapsed after threshold temp. was reached, a n d reactor volume of 1006.8 in!. Furnace was not preheated before insertion of reactor.
and a t comparable hydrogen-oil feed ratios (22 to 25 stand. cu. ft. per lb.) shows t h a t increases in the carbon-hydrogen weight (C/H) ratio of the feed substantially reduced the rate of gaseous hydrocarbon formation. For example, a t the time of initial production of 1000 to 1100 B.t.u. per stand. cu. ft. and Q.6 specific gravity gas, gaseous hydrocarbon space-time yields mere 85 etand. cu. f t . per cu. f t . per hr. for Diesel oil ( C / H ratio = 6.74), 50 stand. cu. ft. per cu. ft. per hr. for reduced crude ( C / H ratio = 7.04), and 36 stand. cu. f t . per cu. ft. per hr. for Bunker C fuel oil ( C / H ratio = 8.51). I n each case this resulted in comparable gas yields (21 t o 22 stand. cu. ft. per lb.), conversions (81 to 87 weight per cent), and net B.t.u. recoveries (about 14,000 to 16,000 B.t.u. per lb.).
Conclusions This exploratory study of high pressure hydrogasification of petroleum oils in a laboratory reactor has indicated t h a t it is practical t o produce high methane content gases of 900 to 1100 B.t.u. per stand. cu. ft. and 0.5-0.6 specific gravity by direct hydrogenation of the low cost residual oils.
898
Complete conversion of reduced crude was approached a t 1200' F., 3400 Ib. per sq. inch gage, and a hydrogen-oil feed ratio of approximately 230 stand. cu. f t . per gal. This corresponded to a 1000 B.t.u. per stand. cu. f t . gas yield of 200 stand. cu. ft. per gal. For Bunker C fuel oil, 80 t o 85% conversions were obtained at 1200" to 1350" F., 2600 t o 3100 lb. per sq. inch gage, and a hydrogen-oil feed ratio of approximately 200 stand. cu. ft. per gal. At a hydrogen t o oil feed ratio of 300 stand. cu. f t . per gal. it was possible to convert approximately 90% of Bunker C fuel oil a t 1350' F. and 4000 lb. per sq. inch gage to a gas containing approximately 90% methane and 10% hydrogen. Under these conditions the equivalent of 220 stand. cu. ft. per gal. of 1000 B.t.u. per stand. cu. f t . product gas was obtained. The residence times in the batch reactor required t o produce high methane content gases from reduced crude oil a t 1200" F. and from Bunker C fuel oil a t 1275" to 1350" F. were in the order of 30 t o 60 minutes after the initial gasification temperature (usually 850' t o 1000' F.) had been reached. This corresponds to product gas space-time yields of u p to 100 stand. cu. ft. per cu. ft. reactor volume per hr. and indicates that commercial
INDUSTRIAL AND ENGINEERING CHEMISTRY
Vol. 48, No. 5
EXTREME CONDITION PROCESSING Pressure Hydrogasification of Petroleum Oils losses due t o sampling)
Run 14 Reduced crude, 0.104 lb.
Run 7 Bunker C fuel oil, 0.096 lb.
Run 17 Bunker C fuel oil, 0.106 lb.
Run 20 Bunker C fuel oil, 0.102 Ib.
Run 42 Bunker C fuel oil, 0.102 lb.
1355
1200 1050
1275 1065
1350 1050
1350 1650
228.1 875
208.4 930
191.4 940
196.6 1020
298.5 1222
35
48
43
40
1200
No. 1 No. 2 No. 3 No. 4 No. 1 No. 2 No. 3 No. 4
119
No. 1 No. 2 NO.3 NO.4 NO. 1 NO.2 NO.3 No. 4
NO.1 NO.2 No. 3 No. 4
87 145 215 22 80 150 3380 3305 3315 962 1200 1200 1195
60 120 180 240 45 105 165 2885 2690 2620 2595 1078 1205 1202 1200
51 67 95 130 17 52 2950 2990 2890 2980 1015 1187 1270 1275
55 67 87 125 5 43 2960 2950 3050 3070 1158 1265 1357 1350
101 121 144 164 1 21 4265 4380 4060 4020 1110 1207 1354 1350
25.1 132.1 127.4 117.7 223.5 193.6 189.4 190.5
44.8 118.1 175.7 124.6 208.7 179.9 175.6 174.4
32.2 90.1 110.6 117.7 202.5 183.9 169.4 174.1
85.7 106.9 117.2 108.8 192.5 180.0 176.8 178.6
10.4 91.1 118.7 121.5 282.0 273.8 235.8 233.8
43
i&k
21.2
98.3
96.7 89.9
40.1
.. .. .. ..62.5 .. .. ..35.8 .... ......... 1.4
24.1 8.2 1.9 96.2
0.9 0.8 0.2 0.2 92.3 24.8 8.6 2.2 2.4 52.0 77.6 92.9 0.7 17.9 10.7 3.6 0.4 0.2 0.1 0.1 0.4 0.2 0.6 0.5 1.7 1.5 0.1 0.1 1.3
......
...
......
28.2 80.7 123.0 86.5
21.9 59.6 75.8
80.7
61.9 36.0 23.0 16.8 15.8 9.0 105.8
67.1
41.3
......... ......... .........
0.2 0.6 .81.5 . . .25.5 ..
0.5 0.1
0.4 0.1 12.0 7.8 61.8 79.9 10.8 8.5 0.1 0.1
10.8 54.5 4.4 16.1 1.8 0.3 0.5 0.1 0.1. 0.6 0.2 2.0 14.2 0.4 0.4 0.2 0.1 0.1 0.1
.. .. .. ..88.0 .. .. ..65.2 .. .. ......... 1.5
1.1
......
86.1 45.1 7.4 35.6 2.6 17.2 1.3 0.7 0.4 0.3 0.4 0.2 0.1
7.1 6.3 92.0
0.7 0.7 0.1 0.1 5.7 4.8 87.2 91.1 5.1 0.7
.. .. .. ... ... ... ... ... ... . . . . 2.4 . . ... 0.1 ... 0.9 2.3 ... ... 1.5 1.7 0.1 0.5 . . . . . . 0.2 0.3 ... 0.1 0.1 .... ... ...... ............ .O.. I.. .. .. . . .. ....... .. ... .. .. .. .. .. .. .. .. .. .. .. .. . . . . . 00.2 .1. . . . . . . . . .. . . . . . .----100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0
.. .. .. .. .. ..
...... ........
--___.-
534 1030 1391 1098 438 1061 1060 1001 0.168 0.604 0.609 0.568 0.219 0.580 0.868 0.633
......
55.8
72.3
84.0
74.3
112.0 86.0 70.8
41.4 7.1 .. .. .. .. .. .. .. .... 22.6 . . . . . . . . . 101.3
0.7 ... 56.9
0.9 2.8 0.8 0.1 O.I... 36.4 6.2 6.5 25.1 42.7 86.6 91.8 12.1 16.4 1.3 0.4 3.7 0.9 0.1 0.2
... . . . . . . . .1.1. . . 0.6 . . .. .. .. .. ... ...
8.7 62.1
86.0 88.4
.. .. .. .. .. .. .139.0 90.5 . . 2.0 .. .. .. .. .. .. .. .. .. 102.2 12.1 ... 0.4 0.2 0.3 ............
95.9 62.1 17.3 10.2 1.9 24.6 78.2 88.6 1.1 11.9 4.0 0.7 0.6 0.1 0.3 0.1
......
. . . . . . . ... .. .. .. .. 0.2 0.3 . . . . . . 0.2 1.4 2.6 0.4 ... 0 . 5 ' 0.3 0.2 0.3 0.2 0.1 ............ ............ ............ ... 0.3 0.1 ... ............ . . . . . . . . . . . . --_____ ............ ---100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 e . .
461 824 I018 1032 772 944 1021 961 0.186 0.433 0.578 0.593 0.392 0.522 0.606 0.538
reaction times could be obtained in a continuous reactor after suitable pretreatment of the oil feed. For operation with reiatively high hydrogen content oils, preheating of the feed in the presence of hydrogen to initial gasification temperature before injection into the hydrogasification reactor may be adequate. For Bunker C fuel oil operation, the feed stock would probably have to be upgraded by liquid phase prehydrogenation at 800" to 900" F. over a suitable catalyst under conditions similar to the Gulf HDS process ($7). Hydrogen requirements could be met by pressure reforming of natural gas, if available, or by pressure reforming of approximately one third of the product gas. When using product gas as a source of hydrogen, one barrel (42 gal.) of Bunker C fuel oil would give a net yield of approximately 6000 cu. ft. of 1000 B.t.u.
......
375 683 914 934 0.108 0.329 0.497 0.513
per stand. cu. ft. gas or its equivalent. The remaining 3200 cu. ft. of the 9200 cu. ft. per barrel total yield would be used for producing 13,000cu. f t . of hydrogen. Total fuel requirements for product gas reforming and for preheating of process oil and hydrogen are estimated a t 2 to 2.5 gal. per thousand cu. ft. of total product gas. Most of the steam requirements for hydrogen production, including carbon dioxide removal, and for hydrogen compression could probably be satisfied by recovery of waste heat and of the exothermic heat of hydrogenation (approximately 8% of the heat of combustion of the total product gas). On that basis, one barrel of Bunker C process feed and fuel would produce 4000 cu. f t . of 1000 B.t.u. per stand. cu. ft. gas which would represent a basic cost of 65 cents per thousand cu. f t . a t a Bunker C fuel oil price of $2.60 per barrel.
(Continued on page 900)
May 1956
INDUSTRIAL AND ENGINEERING CHEMISTRY
899
