ENGINEERING, DESIGN, AND PROCESS DEVELOPMENT
Hydrogasification of P Bituminous Coal to Natura I
N TWO articles, Linden and coworkers a t the Institute of Gas
Technology evaluate the feasibility of converting residual petroleum oils and low rank coals to pipeline gas by direct hydrogenation, and present results of batch reactor tests conducted a t 1200" to 1350' F and 1400 to 4400 lb. per sq. inch gage. Increases in the field cost of natuial gas and in costs of processing, transmission, and storage have resulted in greater interest in the production of fuel gases suitable for supplying local peak demands and supplementing base load requirements. A major portion of peak load gas can be produced economically by cyclic high temperature thermal cracking of petroleum oils a t atmospheric pressure (20,43); however, the high olefin-content product gases typical of low pressure thermal cracking operations have unsatisfactory combustion characteristics ( S 4 ) . Further, a large fraction (30 to 60%) of the process oil is converted to tar, and by-product handling, stand-by, and maintenance costs are high. IThile substantial improvements of thermal cracking processes have been developed on a laboratory and pilot plant scale by the use of moderate pressures (50 to 80 lb. per sq. inch gage) and limited quantities of process hydrogen (up to 100 stand. cu. ft. per gal.), essentially complete conversion to gases with methane contents approaching those of natural gases has not been achieved with feeds Those molecular weights and carbon-hydrogen ratios exceed those of natural gasolines (85-26). Studies of methods for supplementing base load natural gas requirements have indicated that conversion of coal t o high methane content gas, in areas where long distance transmission lines pass through coal fields near the major market areas, may be the most economical method for transporting this source of energy to the domestic consumer in readily usable form ( S I ) . The process for conversion of coal to pipeline (900 B.t.u. per stand. cu. ft.) gas, which has been studied most extensively, requires the gasification of coal n-ith steam and oxvgen to produce synthesis gas (40, 48,44, 4 6 ) adjustment of the hydrogencarbon monoxide ratio of the synthesis gas over water gas shift catalyst, removal of sulfur compounds, methanation over nickel catalyst (17, 53), and finally, carbon dioxide iemoval ( 2 ) . h re-evaluation of the problem of converting residual petroleum fuels and the more reactive, low rank coals to high methane content pipeline gas has indicated that direct hydrogenation a t 1200' t o 1400" F. and 1500 to 3000 lb. per sq inch gage (hydrogasification) may have many advantages over the conversion processes now most actively considered The success of this approach would depend largely upon the availability of low cost process hydrogen. Production of 90 to 95% purity hydrogen by catalytic steam reforming of natural gas a t 100 to I50 lb. per sq. inch gage ( I 4 ) , followed by water gas, shift and caibon dioxide removal by hot carbonate scrubbing (8), can be accomplished a t a total conversion cost (not including process natural gas costs and fixed charges) of approximately 15 cents per thousand cu. f t . of hydrogen, and an investment cost of approximately $135 per thousand cu. ft. daily hydrogen capacity. Where natural gas is not available, product gas can be used as a source of hydrogen Partial hydrogasification of low rank COak, in a process where the more reactive constituents are converted to gas and the residual char is used for hydrogen production by suspension
894
gasification with steam and oxygen, also appears to offer an attractive alternative to the partial oxidation and methanation process since the catalytic step would be eliminated and the oxygen requirements substantially reduced. The objective of this study is, therefore, the exploration of operating conditions and process requirements for the production of natural gas substitutes by hydrogasification of low cost petroleum oils and coals.
Apparatus and Procedure The 1-liter reactor used for this study was constructed from 19-9DL alloy. The vesael 1%-asof 2-inch i.d., 43/8-inch o.d., and 20-inch inside length, mith an Autoclave Engineers closure (modified Bridgman self-sealing type). The reactor cover was equipped with a 3/8-inch-o.d. thermocouple n-ell which protruded into the center of the reaction zone; the over-all system volume xyas 1006.8 mi. The furnace was constructed from trvo 5-inch-i.d., 12-inch-long cylindrical electric heaters having a rating of 2.25 kw. each, housed in a 14-inch-diameter, 24-inch-long shell with insulation filling the space between shell and heating elements. The entire furnace mas supported in a rocking mechanism which oscillated 60 cycles per minute through an angle of about 15" belon to 15" above horizontal. The procedure used Tvas to charge the reactor with oil or -60mesh coal at room temperature. After making the seal and flushing t o remove air, the vessel v a s filled v i t h cylinder hydrogen (about 99.3% pure) to the desired initial pressure. After preheating the furnace a t full input for 1 hour, the run wah started by inserting the charged reactor into the hot furnace. Heating a t full input \vas continued with reactor temperatures rising about 1.3' F. per minute t o within about 30' F. of the desir ed run temperature. Manual control with a variable transformer m-as then used. Temperatures were sensed with a Chromel-Alumel thermocouple and measured with a Leeds & Northrup portable galvanometer equipped with an ice-v-ater reference. Pressures were measured n-ith a 10-inch-diameter Heise gage of the Bourdon tube type, calibrated against a dead-weight gage. Simultaneous readings of temperature and pressure were made a t intervals throughout the progress of the run. Gas samples were taken a t intervals by stopping the rocking motion momentarily, and bleeding the sample into an evacuated 10-ml. gas analysis bottle, without passage through absorbers or condensers. At the conclusion of the run, a final gas sample vias taken, the electric current m-as shut off, and the gaseous and liquid products were immediately recovered by expanding all the gas from the reactor through a dry ice-acetone condenser and a wet test meter. After the reactor cooled, it was opened and the solid residue was recovered. Product gas samples were analyzed with a Consolidated Engineering Co. Model 21-103 mass spectrometer, and specific gravities and heating values -were calculated from the analyses. Whenever direct determination of carbon monoxide and nitrogen was not possible, they were assumed t o be present in equal
INDUSTRIAL AND ENGINEERING CHEMISTRY
Vol. 48, No. 5
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).
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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
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