July 1947
INDUSTRIAL AND ENGINEERING CHEMISTRY
drocarbon conceritratiori j however, no great advantage can be gained by operating this process with a hydrocarbon-nitric acid mole ratio greater than l 5 : l (IO). I t has been found that the yields, hased on hydrocarbon consumed, may be increased by diluting the reactants n i t h nitrogen (17 ) ; however, yields based on nitric acid are lowered unless a large hydrocarbon-acid ratio i.q used. When the nitration reaction is performed with large nit,ric acid-hydrocarbon ratios, temperature control is difficult, and, thus. hiirning or explosion of the reactants ma?- occur. RULE 13
Catalystc accelerate osidation rather than iiitration. Silica gel, nitric oside, platinum oside, iron, copper, lead, and the heavy metal oxides catalyze osidatiuii and thus result in poor yields of nitro paraffins ( 7 ) , whereas light (BI), aluminum nitrate, or carbon monoxide have no appreciable eiTect. Levy (13) report? that a borosilicate gla+ contuining 0.23" reaction of paraffin; with nitric acid or nitroge:i dioxide: however. several inveitigatorr have been uiiable t o confirm these results. Since the yields obt:ii:ied in this laboratory in the a b s e x e of catalysts are much higher thuii tliohe claimed by Levy (14). it is poquihle that the priiicipal fmction of the catalyst was t o help maintain proper temperature control by causing turbulent flow, Constraction material.< \vliich have no appreciable effect on the nitratioii reaction are glass, silica, platinum, and gold, whereas ferrous surfaces promote rapid osidation aad decomposition of the reaction mixture. I t has been found that the chromium-nickel steels which resist the corrosive action of nitric acid at high temperst,ure will not greatly afEect the osidatioii and decomposition reactions if a mixture of sodium and potassium nitrate is sprayed continuously into the reactor (f2). Reactor tubes of small diameter allow escellent heat transfer: hon-ever, they have a high ratio of surface area to volume, so that the effect of depozited catalysts is greatly magnified. Correspondingly, the effect of osidation catalysts is diminished in tuhes of larger diameter, but temperatiire control s u f m (12).
82 1
ACKNOWLEDGMENT
The assistance of the Commercial Solvents Corporatioil, ivhich supported financially the research upon which this paper is hased, is hereby gratefully acknowledged. LITERATURE CITED
(1) Alexander, L. G., private communication. :2) Blickenstaff, R. T., and Hass, H. B., J . Am. Chsm. Soc.. 68,
1431 (1946).
(3) Boyd, T., and Hass, H. B., IND.ENG.CHEM.,34, 300-4 (1942). (4) Danzig, 51. H., and Hass, H. B., J . A m . Chem. SOC.,66, 2017- 19
(1944). i 5 ~ 1H a s . H . B., Dorsky, J., and Hodge, E. B., ISD. E s n . CHEM., 33, 1138-43 (1941). 161 H a s , H. B., Hodge, E . R., and Yanderbilt, B. SI., P. R. Patent 1,987,667 (July 21, 1943). t i ) Hass. H. B., Hodge, E. B., arid Vanderhilt, B. &I.. ISD. l,;s(,. CHEM.,28, 3.39-44 (1936). ( 8 ) Has?, H. B., and Patterson, J. .i., I b i d . , 30, 67-9 (1938). (9) Hais. H B . , and Riley, E. F.. C'hem, Revs , 32, 373-430 (1943). (10) Hass. 11. B., Shechtei., H., A'exanda., I.. G . , and H a t c h e r , 13. B.. ISD. ESG.C H E M . , 39, 919 (1947). (11, Howe. A . P., and Has3, H . B.. I b i d . , 38, 251-3 (1946) 112) Laiidoii, G . K., U. S. Patents 2,161,476 (Julie 6, 19391 aiid 2,lfi4.774 (July 4 , 1939). ( 1 3 1 L P ~K., (to Imperial Chemical Industries, Ltd.). IbiO., 2.382.241 (.August 14, 19451. (14)I b i l . , 3,394,315 (Feb. 5, 1946). (15) Ss:iietkin. 9. S.,Dobrovolskab-a, Xl. K., and Opariria. X1. P., J . R I I S Phys. ~. Chem. Soc., 47, 405-9, 409-15 (1916) (161 Platinol-, SI. S., a n d Shaikind. S.P., J . Grn. C'hem. (I 4, 434 (1934). (17) Ridout, 0. \V.,E. S. Patent 2,291,345 (July 2 8 , 19421. (18) Seigle, L. \T., P1i.D. thesis. Purdue Univ. (1939). (19) Seigle, L. \I7.,and Hass, H. B., IND.E v c . (.HEX.. 31. 648 -50 (1939). (20) dhechter, IT., Ph.D. thesis, Purdue Cniv. (1946). (21) Shoruigen, P. P.. and Topchier, A , , Ber., 67, 1362 (1934). (22) Tvree, J . T . , XI. S. thesis, Purdue Unir. (1946). (23) Urhsnski, T., and Slon, M., Roczniki Chem., 17, 161-1 (1937) PREFESTED as p a r t of the Unit Process Symposium before the Di\-ision oi Industrial a n d Engineering Chemistry a t t h e 110th Neeting of the C H E V I C A L S O C I E T Y , Chicago, 111.
.$MFRI~AS
Production of Citric Acid in Submerged Culture EDWARD 0. KAROWl ~ N DSELXIAN A. FAKSRIAS .%eicJersey 4gricultctral Experiment Station. R u t p e r s I nirersity, >\-eu.brunsicich., 4. J
T h e hubmerged culture fermentation method haa been applied to the production of citric acid. A strain of A s pergillus wentii has been found to produce citric acid with complete absence of oxalic acid. 4 definite balance of minerals in the medium and highly aerobic conditions are necessary. Sucrose, glucose, and cane molasses purified by various means can be utilized for the production of citric acid. N'eutralization of a portion of the fermentation arid with calcium rarhonate results in higher yields.
'T
HE industrial advaiitagea of deep tank feririentatiunb as applied both to anaerobic bacteria and to yeasts (true ferrnentations) and l o arrohir processes (so-called oxidative frrnientations and submerged inold fermentations) over surface riroctmea arp well known. Allthough such deep tank fernienta1
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tiona brought about by molds and other aerobic niicroorgariisni~ have, been applied with considerable success to the production of certain orgsnic acids, such as gluconic and fumaric, and t o antibiotic substances, notably penicillin and streptomycin, consid(xrable difficulty has been encountered in the mse of other procwscs, particularly the production of citric acid. Since Wehmer's tlisc o w r y (34) of the ability of certain fungi belonging t o the I'enicilIiitrn group, which he designated Cilromgces, to produrc citric acid from sugar, a n extensive literature has accumulated (18). Included arr numerous reports on largely unsuccessful at tcmpts to carry out the procrss in a deep or submerged state (1, 2. .i,.9< 26, 29, .33). Kluyvrr and Perquin (15) drvclopetl t h e "shalring method" for the stud>-of citric acid production t)y niolds. The organism was inoculated into a medium placed in bottles. These werc simultaneously shaken and aerated in a special shaking apparatus. T h e mold grew throughout the mcdium in the frirm of
INDUSTRIAL AND ENGINEERING CHEMISTRY
a22 T.%BLE 1.
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.el:,11.. Biorhem. %.. 202, 1 3 - 5 6 (l9:38). eiiiherg. 11. A , , J . d y r . Hcaearch, 51, 413-24 (1935). J.,U. S. Patent 2,353,771 (Jiili-18, 1944). IT., Zrntr. Bukf. Parasiteiik. 11, 82, 321-47 (1930). n u n , S.A%.. Soil S c i . , 3, 505-89 (1917). \Taksman. Y. A,, U. S.Patent 2,328,988 ( d u g . 17, 1944). TI'nrd. 0 . E., Lockwood, L. B.. Tabenkin, B.. and Well:, P..I., ISD. ESG. CHE.\I.,30, 1233-7 (193s). \17elitiier, C., Chem.-Zty., 36, llOG-7 (1912). Tl~elinter.C., Compt. ~ 7 d . 117, , 832-3 (1893). a:td Ward. G . l,:., I s n . 1;s~.(,'HEM,, 31, 172-7 TVells, P. 1.. (1939). TT-oodruff, H. E.. aiiil l ' i i - t ~ i,,I . \\-., . i , ~ h .Biochcm., 2, 301-15
(1943).
