Symposium on Utilization of Gaseous Hydrocarbons Presented before the Division of Petroleum Chemistry at the 82nd Meeting of the American Chemical Society, Buffalo, N. Y., August 31 to September 4, 1931.
G
ASEOUS hydrocarbons present an excellent potential source of raw material for chemical manufacture. Everyone is cognizant of this fact but few appreciate why this potential source does not become a real source. At least two important reasons can be given for this failure to utilize our gaseous hydrocarbons. First, most chemical reactions involving gaseous hydrocarbons take place with an evolution of heat. It is difficult to obtain the necessary heat transfer in order to maintain proper temperature conditions. Proper temperature conditions or the confining of the reaction temperature within narrow limits arc absolutely necessary in order to produce the pure products desired, instead of a complex mixture. A second reason is evident when we consider that even though there is no great evolution of heat in certain reactions involving gaseous hydrocarbons, nevertheless there is great difficulty in operating these reactions under what might be considered reasonable equilibrium conditions. This is probably due to the fact that reasonable equilibrium conditions necessitate reactions a t very high temperatures and high pressures. Satisfactory equipment t o meet such conditions has only recently been developed.
Lately there has been an attempt on the part of investigators in this general field to utilize pure organic compounds rather than mixtures. This is apparently a step in the right direction as shown by the increase of interesting results obtained in this field. It is believed that the papers in this symposium will clearly substantiate the statements made above. One peculiar economic feature of the general problem should be noted. The present large use for hydrocarbons is as motor fuel; approximately 20 billion gallons are produced per year in this country. The next largest use for these hydrocarbons that has been proposed is in the production of solvents with only 200 million gallons per year possible consumption. Between the two uses there should be developed a third field before the oil refineries can afford t o spend the large sums necessary to utilize the hydrocarbon gases. Two possibilities have recently appeared. One is the use of hydrocarbons in the manufacture of synthetic resins to be used in paints, varnishes, lacquers, and plastics The other is the use of hydrocarbon gases in the manufacture of new synthetic textiles-for example, the polymers of glycol sebacate. D. B. KEYES,Chairman
Partial Oxidation of Hydrocarbons Catalyzed by Oxides of Nitrogen C . H. BIBB,Oxidation Products Company, Jersey City, N . J .
T H E O X I D A l I O N of methane to formaldeof heating; form of r e a c t i o n hyde and methanol has been involved in most of the c h a m b e r ; and the nature of of nitrogen to catalyze work sf the past. However, considerable quanthe hydrocarbon all have prothe p a r t i a l o x i d a t i o n nounced effects on the r e s u l t s Of hydrocarbons with air has tities of formaldehyde can be obtained f r o m obtained. principally been described propane and other hydrocarbons by the process, i n a r t i c l e s b y L~~~~ a n d S o u k u p (s), S m i t h a n d and, as has been described, phenol is the prinOXIDATIONOF NATURAL Milner ( 4 ) , a n d Bibb and cipal oxidation product when benzene is used. GAS L u c a s (8); and in P a t e n t s I n this article, operative conditions of a f e w In addition t o the simplest t o t h e a u t h o r ('1. The runs are described which show better yields on m e t h o d of partially oxidizing process con si s t s e s s e n t i a l l y i n m i x i n g a i r and a gaseous the hydrocarbons and oxides of nitrogen to t h e hydrocarbons of n a t u r a l hvdrocarbon t o g e t h e r with a formaldehyde than have heretofore been pubgas, which c o n s i s t s in only a single pass of the gaseous mixr e l a t i v e l y s m i l l amount of Zished. ture through the reaction zone oxides of nitrogen, heating the mixture to a reaction temperature which may vary between and the condensation of the oxidation products, the tail 500" and 900' C., cooling the mixture, and condensing out gases were oxidized successively four times. I n another the aqueous solution formed from the fixed gases. The series of experiments the recycle principle was used whereby fixed or exit gases may be processed again for additional the tail gases from the condensation apparatus were conoxidation products by mixing with more air, with or with- veyed back to the inlet of the reaction zone and reoxidized. out the further addition of nitrogen oxides, or they may be I n some experiments the recycle rate was over fifteen times recycled in the original heating chamber. The proportions the amount of input into the system. A bleed-off of the of hydrocarbon, air,, and nitrogen oxides; temperature; gases was, of course, necessary in order to maintain constant velocity of the gases through the reaction zone, or the time pressure.
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HE u s e of t h e oxides
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