FUEL, GAS, A N D PETROLEUM CHEMISTRY sible synthetic substitutes. E . J. Hewitt and others from the Evans Research and Development Laboratories, N e w York, de scribed an oil obtained from black pepper, one part of which seems to contribute vitally to the pepper aroma. Fractions were distilled separately, and the com pounds obtained in additional treatment were described. T h e higher fractions were found to yield the semicarbazone of citral, with preliminary evidence of the pres ence of citronellal. Norene E . Kennedy, Quartermaster Gen eral Laboratories, Philadelphia, reported on part of an investigation into the taste and flavor of black pepper, Piper nigrum, with a v i e w to developing a synthetic sub stitute. N e w analogs of piperine, piperoyl piperidide and capsiufri, deceienoyl vanillylamide, were all synthesized. The paper, prepared in collaboration with T . Hasselstrom and H. W. Coles, after discussing the pungency and biting characteristics of piperine and unsaturated piperidides, said that the effect of the amine part o f the acid-amide molecule oh pungency was investigated. The research showed that the 5-phenyln-valeroyl pipecolides had the same bit ing characteristics as piperine, with n o offtaste and flavor, while the acid-amides of 5-phenyl-n-valeric acid and isobutylamine? and vanillylamine were strong irritarxts. Food for Rubber Tree. I n t h e mineral nutrition of Hevea brasiliensis, rubber tree, J. McGavack and coworkers at the Pas saic laboratories of the United StatesRubber Co. reported that potassium, -phos phate, and magnesium are deficient min erals most likely to retard developmentThe elimination of sulfur severely retards the Hevea while very small amounts in duce normal growth. Growth also i s ex cellent at very l o w calcium levels. A s t o minor elements, a high requirement o £ iron was exhibited but the study d i d not: bring out requirements of zinc, manganese,, or boron. Floyd- W . Dunn, Abilene Christian Col lege, Texas, reported o n the extension o f studies which showed previously that pep tides from the amino acid antagonist β-%— thienylalanine inhibited the growth of Ε . coliy while certain other peptides d e r i v e d from phenylalanine reversed the toxicity of the antagonist. The more recent work shows that the growth of rats is retarded! by peptide analogs such as carbobenzoxyglycil-£-2-thienylalanine, glycyl-/3-24hi enylalanine, and chloroacetyl-/3-2-thienyialanine. Sugar Cane Juice. Based o n questions from the floor, much interest was showrn in studies of amino acid contents m raw sugar cane juice. M. L. Wolfrom,. Ohio State University, outlined the procedure's which involved, in part, two-dimensional paper chromatography, followed h>y d e ionization with ion exchange resins. .Aminto acids revealed included valine, l e u c i n e , glycine, and alanine.
VOLUME
2 9, N O .
3 9 .
FUEL. G A S . A N D PETROLEUM
CHEMISTRY
Continuous Gas Stream Analysis Announced to Petroleum Industry •
Thiourea adduction requirements defined
• High temperature retorting of shale produces variety of aromatics >-p:HE petroleum industry, highly instru*· mentized as it is, h a s long awaited the commercial adaptation of mass spectrom etry to continuous analysis of gas streams. This is now a reality through the work of the Esso Laboratories, and although only prototypes o f the instruments have been used, it is thought that such instruments will be available commercially within a year. C. E. Starr, Jr., described this work, including application o f the leak detector type of mass spectrometer to continuous monitoring of single components and the application of the larger and specially con structed instrument to rnulticomponent gas analysis. This latter work included con tinuous determination of methane, ethane, and ethylene in gas streams from an ethyl ene recovery unit and continuous analysis for C 5 and lighter components in gas streams from a catalytic reforming unit. A pilot reforming unit has actually been operated in w h i c h spectrometric analyses, furnished t o an electronic computing unit, enabled control o f the process without the necessity of ordinary sample taking. Carbon Deposits. Coke deposits on cracking catalysts represent one of the most universal products in catalytic crack ing, and loss of otherwise valuable mate rials b y degradation. These deposits have been shown to decrease with increasing temperature, and R. C. Archibald, Shell Development Co., described a n e w lab scale unit for investigating the possible beneficial effects of increasing temperature considerably above t h e normal cracking range, and reducing the contact time to minimize thermal cracking reactions. A quartz spherical joint section was used, with 1 mm. diameter gold wire packing in the bottom of the column and granular silica-alumina catalyst above the wire. By induction heating of the gold wire, feed materials passing over it could he raised to 7 0 0 ° C. in contact times as low as 10 milliseconds. A small electric fur nace was used around the catalyst bed and a quench water tube at the top of the section allowed quenching of the vapors as they came off the catalyst. Car bon deposits were found to fall off con tinuously with increasing temperatures, with no minimum reached, and it was determined that catalytic activity at higher temperatures varies considerably with particle size of the catalyst. This indicates
SEPTEMBER
2 4,
1951
that for any given temperature there is a maximum particle size beyond which full utilization of the catalyst is not attained. Oxygen Determination in Liquids. Im provement of the MacHattie-Maconachie method for determining traces of oxygen in gases by reaction with copper has been made and the method extended to deter mine dissolved oxygen in liquids, accord ing to Louis Lykken, Shell Development Co. Postpaper conversation brought out the suggestion that this stripping tech nique is much superior to the conven tional Winkler method as used b y water chemists to determine oxygen, and could well b e adapted to their uses.
>> Thiourea Adduction Although adduction of hydrocarbons with urea has been reasonably well studied, previous workers have never defined ad duction requirements for thiourea. David Flitter, having a large number of pure hydrocarbons at his disposal at Penn State, made adduction tests using 30 of these compounds with urea and 4 8 with thiourea. He has found no adducting by thiourea with aromatic structures or with normal paraffins, and reports that the presence of phenyl groups interferes with adduction in the case of both urea and thiourea. Study ing the Fisher-Hirschfelder-Taylor models of hydrocarbons (scaled o n e centimeter to one Angstrom u n i t ) , Dr. Flitter and R. W . Schiessler have concluded that the cross sectional dimensions of the hydrocarbon model must approximate the range 5.8 to 6.8 A. in the molecule before adduction will take place. Pressure Effect on Hydrocarbon Vis c o s i t y . Work that m a y have considerable practical importance was that reported b y Ε. Μ. Griest, Corning Glass, on API Proj ect 4 2 . Very little is known about the effect of pressure o n viscosity, as related to molecular structure. Griest, with W a y n e W e b b and R. W . Schiessler of Penn State, has studied the viscosity of a number of pure hydrocarbons and binary mixtures at pressures from 15 to 50,000 pounds per square inch and temperatures from 100° to 275° F . Their work suggests that increase of viscosity at constant tem perature is related to the concurrent de crease in specific volume through the L e n nard-Jones potential function.
3955
INTERNATIONAL CONGRESS Synthetic Liquid Fuels. Great interest w a s shown in the several papers presented on the Fischer-Tropsch process and on the production of liquid fuels from oil shale. This was particularly evidenced in the lively discussions of economic and technical aspects of the problems, which followed die two sessions. Cost of the actual reaction step in the Fischer-Tropsch synthesis is minor compared to that of the oxygen and synthesis gas starting materials. Oxygen C o s t s . A. R. Powell of Koppers Co. estimated that under today's inflated costs, a 1000-ton-per day oxygen unit, operating at 1 0 0 % capacity, with electric power costs at 0.6 cent per k.w.h. and a 15-year capital investment write-off, could produce 95% oxygen at a cost of $5.00 per ton, or 20 cents per 1000 cubic feet. Dr. Powell further said that this raises the serious question of whether air should b e used instead of oxygen if synthesis gas is to be made from coal. Disagreement on the costs was voiced by L·. C. Kemp of the Texas Co., who thinks that the Koppers' estimate on investment costs is much too high. Oxygenated Compounds from FischerTropsch. A statement of the current status of me Stanolind Oil and Gas C o / s plant for separating oxygenated by-products from the Carthage Hydrocol plant was given b y J. E . Latta of Stanolind. Although neither plant has operated continuously because of mechanical and engineering difficulties, Stanolind has produced from primary- and wash-water streams over considerable periods a number of compounds containing four oxygen atoms or less, and work is being done on separation of the oil-soluble oxygenated compounds. Physical methods, largely distillation, are sufficient for separating into marketable chemicals the 10% of the water stream which consists of these compounds. H . H. Storch and R. B. Anderson, U . S. Bureau of Mines, examining FischerTropsch pilot plant at Pittsburgh. Dr. Anderson reviewed the progress in obtaining liquid fuels from coal and shale
Acid bottoms yield acetic, propionic, and butyric acids, and the overhead nonacid distillate is fractionated and further distilled. H. H. Storch, U. S. Bureau of Mines, who presided over die session, voiced the opinion that even at the Brownsville plant operations will not be feasible when the price of natural gas reaches 25 cents per 1000 cubic feet, but that the cost of the project has been justified in the information obtained and the lessons learned.
>> Aromatics from Shale T h e retorting of shale at high temperatures (1200° to 1800° F.) to yield benzene, toluene, xylenes, naphthalene, and higher hydrocarbons was described by F. E . Brantley, U. S. Bureau of Mines. This method appears to offer a good means of recovering valuable products from the fine shale which is usually rejected as feed to conventional retorts. In this connection S. S. Kurtz, Sun Oil, asked whether it might not be more feasible in the long run to make aromatics rather than fuel from shale, and to concentrate on petroleum and coal hydrogénation as fuel sources. Dr. Storch indicated that this did not appear to b e the best avenue since
INDUSTRIAL A N D E N G I N E E R I N G CHEMISTRY
Prediction: Atomic Fuel Cheaper Than Coal • Annual U. S. phosphorus capacity to reach 4 3 0 million pounds by 1953 • N e w theory for pressure reactions chemists, engineers
excites
• Criteria suggested for laboratory experiments to yield d a t a for design of industrial reactors TNDUSTRXAL and engineering chemistry in *•• its broadest, deepest, and widest aspects was represented on the program of the section so identified. T h e 4 4 papers that were scheduled ranged in approach from a fundamentally new concept of chemical reaction under pressure to a prospecting report on a mafor new potash deposit in Northeast England. In technical content they varied from discussion of the human element in antibiotics production to a many-factored calculation for determining the efficiency of countercurrent stagewise mass transfer processes. In scope they included such specialized subjects as the molten state theory of the vanadium oxide catalyst for sulfuric acid manufacture to topics of such broad scope as the U. S. phosphorus and phosphate
3956
mine costs for shale are now down to about 50 cents per ton, retorting techniques are in good shape, and over-all figures for production of gasoline from shale are far more optimistic than from coal. Dr. Powell said that from the short term standpoint, the petroleum industry can best supply aromatics, but that eventually shale and coal will have to supply a great deal of the greatly increasing demand. He estimates that by the end of the next two decades the annual requirements for benzene in this country will be one billion gallons. Shale Oil Costs. Tentative estimates of a 10,000-barrel-per-day refinery, producing gasoline from shale oil retorting and refining, would be $ 3 5 million, with a 5.5-year payout time, indicated K. L. Berry, Bureau of Mines, during the discussion. Dr. Storch said that $2.00 per barrel (including pipeline transportation costs) in Los Angeles or Chicago appears to be a reasonable estimate for viscositybroken shale oil and that Union Oil Co/s proposal to hydrogenate coker distillate at 1500 pounds per square inch pressure appears to be the best way for utilizing conventional refinery equipment in producing motor fuels from shale.
CHEMICAL
chemicals industry. Foreign authors were well represented, and the international flavor of the audience was similarly most evident. Atomic Fuel for Peace. The staggering implications of atomic energy for peaceful human -itilization around the world held spellbound the audience attending the Tuesday luncheon of the Section on Industrial and Engineering Chemistry. John J. Grebe, research consultant to D o w and participant in high-level AEC technical studies of nuclear energy, was the speaker. He pointed out that the average nuclear energy potential in the uranium and thorium of the world's continents is equivalent to 20 to 50 pounds of coal per pound of earth. In some land masses, for example, the Allegheny mountain range in
AND
ENGINEERING
Ν Ε WS
