THE FERMENTATION INDUSTRY DURING WORLD WAR I1
I943 1944
C. S. BORUFF AND J. M. VAN LAKEN
1945
H i r u m W'alker & Sons Inc., Peorin, I l l . I
1946 5
0 ,
,
I
#
15
IO 1
1
,
1
1
1
,
25
20 #
PENICILLIN UNITS
I
,
I
30
+
X 10It
grain most coniriionly utilized i i i graiii alcohol distillcries. This forretl the industry to turn to sorghum grains and t o wheat arid tvhwt products since t h r y ww more rradily available. Kot only were distillers unfamiliar with the procwsing of wheat and grariular Lvheat flour, but relatively fe\v had the preferred facilities foi, adequately processing the grain and for completely recovering thtl much needed by-product fec& T o avoid lossrs of valuabk~grain and alcohol and to assurc thc the War Product ioii rubber pivgram of its alcohol requirc~mc~nts, 13oartl appc)inted a \Vheai-.-\lcohol Resrarch C'ommittce to solvithe problems associated w i t h the fermentation of wheat. With the S o r t h e r n Regional Research Laborat ory of the I'nited State.. Department of Agriculture ai; the coordinating agency, a prograni of collaborative research was t'ormulatetl. T h c first wheat alcohol conference \\-as held in Peoria in Soveniber 1942. This was followed by another in February 1043 t o discuss the informatioii which had been accuniulated from t h r various research proieet?. From reports presented, it \vas evident t h a t many disti1lt.i~;;had sc~lvedthe problems involved in pwcessing wheat and were obtaining t:fficienries and plant capacitic.6 nearly equal to those ohtaincd from corn. However, by this tinic there \vas a serious shortage of high protc,in feeds, ant1 further ivork was rrquired to improvc tht, rocovei'y of fcrnicntation residues to fill this need. This portion 0 1 the problem was satisfactorily coverid in a third confert~ncc~ held in September 1943. privatr research groups, government agencies participated in the \vkAeat-alco1iol1.rogram. T h e group submitted and discussed over sixty rcsearch rc8port.q (9). From late 1942 to July 1945 nt,ai,ly 700,000,000 galloirr of alcohol were produced from wheat and wheat products, an ( s x ccsllcnt example of the ac.coiiil)lishiiierit of cwoperativr effort. Figure I summarizes the role ~ ~ l a by y dt lie fermrntatioii intluctry in the wartime production of industrial alcohol ( 2 2 ) ; i t shon:, the quantities of alcohol made from grain, molasses, and ethyIr~iii* from 19-10 through 1946. In 1943 and succeeding years, graiii contributed the bulk of the alcohol, vihile t h a t from ethyltmc. inciea ed slightly and that from molassei decreased slightly. S o t indicated in Figure 1 are minor sources of alcohol sucli as fruit wastes, whey, sulfite liquor, and potatoes. Althouph these materials accounted for only 0 . 5 5 of the total in 1945, they contributed about 2% in 1946, largcly as a result of ~ I ' I J C essing surplus potatoes and ivood pulping wastes. Govcr I I nient-sponsored plants were erected at Bellingham, Wash., t 11 utilize sulfite liquor, a n d a t Springfield, Ore., t o sacmarify anti ferment wood waste. T h e combined output of these two plants was estimated t o be 6,000,000 gallons of industrial alcohol annually (7). Provided alcohol can be made competitively f r , o r i i
During the recent war the fermentation intiustr? conFerted itself to meet increased needs for \arious chemicals and biologicals. It also participated in the development and conimercial production of antibiotics and biological warfare agents. These accomplishments not only habe resulted in greater diversification of the industrg but also haFe enhanced interest in the industrial applications of microorganisms.
THE
contributions of the fermentation industry t o o w country's industrial accomplishments during World \Tar I1 h a w , for thc most part, remained untold. I t has seenicd appropriate, therefore, t o summarize available information on this subject. Prior to World War I the only fermentation product manufactured in appreciable quantities was ethyl alcohol. During World War I the acetone-butanol fermentation was developed t u commercial scale a n d provided much-needed acetone for the manufacture of explosives. Within ten t o fifteen years after the war there was a sharp increase in the production of organic acids by fermentation. During the period 1941 t o 1946, which is reviewed here, the alltJime peak of volume production of conventional fermentation products was reached. Over and above this production the industry contributed much t o the outstanding developments in the field of antibiotics, germ warfare, etc. As a result of this progress, interest in the industrial utilization of microorganisms has been greatly enhanced. ETHYL ALCOHOL
Ethyl alcohol, one of our oldest and most versatile organic chemicals, still ranks first in tonnage production in the fermcntation industry. During the five years prior t o 1941, a n average of 123,000,000 wine gallons of industrial alcohol was made (all figures at 190' proof); about 72y0 came from the fermentation of molasses, 20m0 by synthesis from ethylene, and the remaining 8% b y fermentation of grains and other carbohydrate materials. With the advent of the war, the need for industrial alcohol \\-as increased tremendously, largely for the manufacture of both butadiene and styrene in the synthetic rubber program, but also for a variety of other essential processing and synthetic operations. Early in the war the'main source of fermentable raw material (molasses) \vas largely cut off, and the industry was obliged to turn to grain. Production problems were further complicated by the necrssity of maintaining an adequate carry-over of corn, th(,
934
I N D U S T R I A L A N D E N G I N E E R I N G CHEMISTRY
August 1947
.
these materials, considerable quxntities of aood p-aste and sulfite liquor could be put t o use in this manner. T h a t industrial alcohol filled a wide variety of wartime needs is apparent from Table I, which s h o w the disposition of industrial alcohol from January 1, 1942, to June 30, 1845 (10). Over this period synthetic rubber required 611,000,000 gallons, or nearly 40% of the total alcohol consumed. I n 1943 and 1914 approsimntcJly two thirds of the but,atliene arid a large part of the styrene were made from alcohol. Allocations for indirect military and rivilian needs, which included that utilized in the synthesis of other chemicals, required over ~500,000,000gallons. The remaining alcohol, about 3076 of the total, [vent to Lend-Lease, antifreeze, and direct military uses. The story of the original government estimates as to wartime alcohol demands and their abrupt change due to the rubber situation, the installation and expansion of high-proof alcohol product i o n facilities in beverage plants, the conversion of eastern seah a r d molasses to grain, the construction of three largely governiiwnt-sponsored and -financed grain alcohol plants in the Midwest, :ind t,he problems of the various iiidustry committees and governnwnt agencies relative t o grain allocation, production, storage, m d transportat>ionof alcohol would make interesting reading, but \viotiId not be appropriate for this discussion. The war also brought about the development and adoption of n>ctifyingcolumns packed with fiber glass ( 5 ) . .\[any have asked why the \Tar Production Board and other :igoncics saw fit to proceed with an expanding grain alcohol program in view of the grain shortage situation. The ansffer is readily apparent when it is realized that large quantities of espensive, acid-resistant equipment are essential for the conversion of ethylI , I I ( ~ ,\yith the result that construction costs are nearly three times :is high for synthetic alcohol ILS for grain plants, including comIlk'te feed recovery facilities. The cost of a complete grain alcohol I)lant averaged $275,000 per annual million gallons of alcohol as ,.ompared to $800,000 per annual million gallons from ethylene. T h e total construction time required and the critical materials iiei.(l are also murh less for grain plants. B Y -PRODUCT 5
TABLE
I. CONSUMPTIOY JASU~RY
.
TION
a
O F INDUSTRIAL E T H Y L L%LCOHOL FROM
1, 1042, THROVGH JUXE 30, 1945
C-:e Total" TOTAL COWJUMPDirect military Lend-Lease Synthetic rubber Antifreeze Indirect niilitary and ciri!ian
935
Per Cent
.Jan. 1- ,Jan. 1- J a n . 1- .Jan. IDec. 31. Dec. 31, Dec. 31, .June 19420 1043u 1944" 1945
3,o
1.543.500 134,200 167,900
100 8.i 10.9
226.000 52,000
611,200 121,100
39.6 i.8
29:OOO
509,100
33.0
i2o,oon
25,000
425.900 605.800 288,200 39.900 27.200 15,100 63,000 56,900 23.000 126,900 329.€00 154.700 5C',800 31,800 9,500
i4i.900
160.300
The gas from alcoholic fermentation is about 99.87; carbon dioxide. Besides its application as a refrigerant, carbon dioside was utilized as a gas in soda ash manufacture arid as a liquid in fire rstinguishers. One war-born use \vas that (of protecting planes against engine fires in the air as well as on the ground. Dry ice found a variety of new uses and interesting applications, including the cooling and hardening of aluminum rivets arid the shrinkiug of i.ivets in the manufacture of airplanes. Fusel oil is a misture of alcohols derived from the action of !cast upon amino acids and related compounds; consequently its composition varies from one substrate to another. The major portion is composed of propyl, butyl, and amyl alcohols. Fusel oil is produced in alcoholic fermentations at the rate of 20 to 30 pounds per 1000 gallons of 190" proof alcollol. In 1945, 11,000,000 pounds were recovered or just under 20 pounds per 1000 gallons of alcohol. This by-product is fractionated to meet specific weds, one of uhich-the use of the amyl fraction as a source of amyl acetatr?--\vas vital in the recovery of penicillin. BUTYLENE GLYCOL
Much research and development \vas done in thc Criitetl dtates and Canada on the butylene glycol fermentation. A rcsearch program similar to that for industrial alcohol production \vas set up and functioned during most of the mir period. From this collaborative research effort, the production, recovery, and conversion of butylene glycol to butadiene were successfully carried
By-products rccoverable during the production of grain alcohol di5tillers' erains and solubles. carbori dioside. and fusel oil .lctually these represent approximately ti70 I hirds by weight of the grain entering the disiillery. Each played an important role in filling uxrtinie requirements. The recovery of total feed, both grains and solubles, reached an all-time high figure in 1945 LEGEND of 633,000 tons as compared with a preaar prorluction of about 175,000 tons ( 2 ) . This high SYNTHETIC figure reflects not only the peak of grain utiiizaGRAIN tion but also the influence of the installation of wiiditional equipment for distillers' feed reMOLASSES Khereas in 1943 only about 10%; of t h e distilleries had complete recovery equipment, present facilities are capable of recovering of the residues from grain alcohol fernientaI ion (3). The annual production of solid carbon dioside iri the United States during World War I1 ranged from 429,000,000 pounds i n 1941 to 659,000,000 in 1045. The quantity of liquid and gaseous carbon dioxide produced during the -:*me period ranged from 217,000,000 pounds i n 1941 t o 332,000,000 in 1944 ( 1 ) . A iul~stantialportion of this carbon dioside was 1940 1941 1942 1943 194d iwovcred from fermentation gases, that from ( I t hyl alcohol fermentations being especially Figure 1. Annual Production of Industrial ;ilcohol ~ i t 4 i x h I cbecause of its relatively high purity. (Tear Ending June 30) tiria
Y
r30.900
I n thousands of gallons a t 190' proof.
M
936
INDUSTRIAL AND ENGINEERING CHEMISTRY
Vol. 39, No. 8
.\.s Tablr Y I A E G ..~t ~ lu c a ~ r .\L,Iu. c I1 shon.s, not only was thew an apprt’riable increasc i t ] vinegar productiuii ACETONE ACETONE (luring the n-ar years. but also a sui#ACETONE -tantial aniouiit of vinegar \vas further MOLASSES I rfined to acetic. acid (6 CITRICACID. So production data &IC‘ available beyond those given for 194?. Production figures for ic.rmentatioi! ritric acid, which reprewits more thaii 8OC; of the total, ior 1941 and 19-12 a r t ’ listed as 22,533,000 and 23,638,000 pounds, respectively ( 6 ) . It ise~tiiiiatetl that the total productioii duriiig t h i , NOL years follon-ing was in the neighbuhood of 26,000,000 pounds annually. .ihout two thirds of the total wartime output n-as utilized in pharmaceutictii preparations, most of the remaindri I w irig consumed in foods and beverage,.. GLCCOSIChcru SALTS. Productiuii I943 I944 1941 1942 1945 informatioil on gluconic acid and t h t , Figure 2 . Annual Production of Acetone-Butanol (Tear Ending J u n e 30) irniainiiig organic acids is iragnientar>.. Some 871,000 pounds of gluconic acid salts were manufactured in I945 it: . out on a large pilot plant scale. !dost iinpoi tant contiibutions Most of this \vas in the l o ~ mof t h r calcium salt for use i r i phwrti:~were made in the development of methods for the continuous acid ceuticals. saccharification of grains t o fermentable sugar, the efficient I ecovery of butylene glycol from fermented mashes, and the esteriYEAS?‘ fication and pyrolysis of butylene glycol to butadiene. I t was \ \ M e thc productioli of all yeast iteins was greatiy iiirrt.aw(I found late in the war period that 13 to 14 pounds of butylene glyduring the war, the development of active dry bakers’ yeast t i i l i l col, convertible to 6.3-6.8 pounds of butadiene, could be produced the expanded use of yeast products in pharmaceutical prepartifrom a bushel of grain at a cost about equivalent to that f o l hutations were outstanding. The reported quantities (6) of active d r y diene from alcohol (3). yeast produced during the war years follow: 1940, 3,000,000 pounds: 1043, 7,000,000; 1045 (11 months only), 13,285,000: ACETONE
1 .
ACETOYE-BUTAYO L
The production of acetone-butanol by fernleiitation is, in order of volume, esceeded only by the industrial alcohol industry. The history of this industry and its role in supplying acetone during Korld War I is common knoJTledge. Khile the emphasis n-as shifted from acetone t o butanol during World \Tar 11, the industry continued to provide large quantities of required solvents. During World V a r I1 acetone and butanol vere niade iii four ( ~five r plants in the United States and by a single plant in I’uerto Rico. Figure 2 shows graphically our total Ti-artinie production of acetone-butanol and the proportions of this output provided by synthetic and fermentative processes (61. Althougli small quantities of acetone and butanol were made in the United States by the fermentation of whey, this source provided in 19-15 (it, most productive year) less than 1% of the butanol manufactured. By-product feed from this industry, tvhile appreciably lcss than that from industrial alcohol production, is valuable hccauae of its high potency of riboflavin. Other by-product.: are carb, These have been used for t h e synthesis of nicthanol. The ethyl nlcoliol produwd I Jtliis ~ iiidustry v a s included under the previous discussion on iiitiustr~ial alcohol.
1946,4,000,000. Active dry yeast was developed for and utilized alniost exclusively by the arnied forces. I t is produced in it manner similar to conventional bakers’ yeast but is dried in specially designed equipment to about 8C;. moisture. In this operation viability and activity are retained, with the result that the product caii t , t > stored for long periods in tropical climates. Hccausc>of its longel. shelf life, active dry ycasr seems drstined t o supplant t h e o l i l type baliei,~’yeas^. .4leo nianufacturctl in increased aniouiit q during the ivar \vel t . yeast products rich in vitamine. Yeast rich iii exgosterol n a produced and irradiatrd tu supplement our reduced su~~plic+ IJI’ vitamin L) n-hich normally conics from marine sourccs. 1-t.a.r produrts fortified with B vitaniins n-ere eniplnyed exteiisivc~l~ i:l foods and pharmaceuticals. Some 12 to 14 million pounck or. Lre\t-ers’ yeitst rverc recovered annually, a third of v h i r h \{-abti(,bittered for the pliarmaceuticnl trade arid the remainder dried H I I ~ I u s t ~ das an ingi,edient of livestock feeds. 01ie other hugtr poreritial ~ ( J U I ’ C C ui’ yeast, p ~ , u l x i t ~fot1dc.1 l~. yexst, is til!. sulfiti. n.astr. liquor froni the piil~iiridustriec. Thi:
ORGASIC ACIDS
L - t c i ~ cI c r u . This acid is produced by feriiieiiting augaIs, starches, and whey. Three grades are made-technical, fiiie edible, and medicinal. In 1940 five firms reported production of technical grade, five the edible grade! and trt-o the medicinal grade. Lactic acid production has expanded considerably during the past ten years with the result that little, if any, lactic acid has been inipurtcd since 1937. Figure 3 shows production from 1040 through 1946 (6).
___
\Yine Galluxis of 190’ l’rouf hlcol-ul C u n i e r t e d t o Total Vinegar i c e t i c aciil
1i.cal y,>aT Ending Juue 30 1940 1941 1942 1943 1944 1945 a
S o breakdurvn
7,718.558a 7,876,631a
8,c55,53ly 13,,51,221 19,341,007 16,426,668 18
,..... ...... ......
6,926,489 7,592,501 7,174,609
...... ... . ......
8,824,732 11,748,506 9,252,059
given; presmiably tliis is largely vinegar.
August 1947
INDUSTRIAL AND ENG
Tvere produced. By March 1946 this had been increased to 27 kg. and by December 1916, t o about 35 kg. a month. Several 'plants are now in production and the figures given are certain to incrpase tremendously. I n addition to these two antibiotics, considerable tyrothricin has been made and marketed for specific uses, such as for surface applications, and numerous other antibiotics such as subtilin and bacitracin have received laboratory st'udy and drvelopmcn t .
e--
BIOLOGICAL WAR FARE
Biological warfare, as defined ill t h e 1Ierck report ( 4 ) , involves the use of
/
1944
Figure 3.
.Lnnual Production of 100% Lactic (.411 G r a d e s )
source aloric, It is eatiniated, could supplv about 270,000 tuiia uf dry yeast annually if fully developed (13). Fermentative utilization of sulfite liquor to manufacture lactic acid, ethyl alcohol, acetone-butanol, etc , wa? given additional study arid seem%t o be entirely feasihlr. FUA-GAL ENZYhlES
Eiizymes from microorganisms found many new and extended applications during the war, and their increased commercial production in the future is indicated. 1Iold enzymes of the mold bran type were manufactured for the first time on a large scale as a substitute for barley malt in grain alcohol fermentations. Later, similar preparations n-ere employed successfully as malt adjuncts in making food sirups. T h e Eagle Grove, Iowa, plant of the Mold Bran Company has a daily output of about 10 tons of enzyniat,ically active material (8). Bacterial enzyme preparations rich in am?-lase were also manufactured. These have the property of retaining amylolytic a d o n a t relatively high temperatures and for this reason are especially suitable in preliquefying grain mashes and in the testile industry.
ACKNOB LEDGMEYT
T h e authors are especially indebted t o P. 13. Jacobs, Northern Regional Research Laboratory, and to C. 4. Rager, U. S. Department of Commerce, for supplying numerous data on the production of fermentation products. LITERATURE
Crrm
(1) .hiiigton, L. G., "Carbon Dioxide," U. S. Dept. of Conimerce, hNTIBIOTICS 1 1 1 I)i,c,ciiiiret, 1'341
the sul)ply of penicillin v a s nut sufficient single patient, wherras today we esport a considerablr The increase in production from 1943 through sui,plus. l!M f f f 1 is shown by the graph on page 034. T h e huge inercasc during this period coincided not only n-ith the construction of plants utilizing deep tank methods but also with the ns arid with the rcfinement of to t r w t
A
Iiid. Reference Service, March 1946. (2) Boruff. c. S., 1x0. ESo. CHEM.. 39,602 ( 1 9 l i ) . ( 3 ) Jacobs, P. B., Sorthcrii Regiorial Research Lab.. d I C ' H d l . 95 (July 1946). (4) Slerck, G. V., Ch em. Etig. A ' e i c ~ x . 24, 1346 (1946). ( 5 ) Miriaid, G. FT., Koffolt, J. H., and Withrcriv, J. K..Trarla. A m . I 7 ~ a t .Chem. E ~ Q T s39, . , 81:3 (19431. (6) Ilager, C. A , , U. S. Dept. of Coriiniercr, ('iiein. and Drug Sect., private communicatiori.
(7) Tousley, R . D., Wash. State College, Bur. (if t:run. and Business Re$earch, Bull. 3 (1945). (Y,,~Undwkofler. L. A , . Seversoil. ( > ,11.. Goei inn. K . ,J , and Christenyen, L.'hl., CereuZ Chem.,~24,1'(1947)..' (9) t-.8.Dept. of d g r . , Sorthem Regional Research Lab., "Production of Alcohol from Theat," (summa,ryof conferences and ~
I n 1944 the nhnlesalc value of the 1.6 trillion units of penicilliri was given as %33!000,000(11 I . Estimated a t S0.35 per vial of 100,000 units, tho 1946 production had a n-holesale value of approxiinatclly 8100,000,000. T h r penicillin industry is indeed onc of our most important coniniercial fermentations. The search for other useful antibiotics has received intensive study, especiallj- with a view toward the treatment of diseases caused by acid-fast and Gram-negative organisms. Foremost anioiig the newly developed antibiotics of this type is streptomycin, the discovery and development of which is attributed wholly t o American scientists. I t is particularly effective against tularemia and shows promise when combined with conventional
collaborative work), March 1944. (10) U. S. Dept. of Commerce, "Industria! Alcohol in the W a r Prograin. Wai,tinie End T2.e Pattern," Oc?. 29, 1946. (11) U. 5. Dept. of Commerce, "U.8. Production and Sales of Syn-
thetic Organic Chemicals 1944, 1945, 1946." (12) U. S . Treasury Dept., Ann. Repts. of Coirmissioner of Internal Revenue for Fiscal Years 1945 and 1946. (13) R'iley, A. J., Inst. of Paper Chem., Sulfite Pulp Rlfrs. Conini. on
Waste Disposal, private communication. beioie t h e Division of Agiicultural and Food Chemistry st the 111th Meeting of the A J I E R I C C . ~H~E M I C ASOCIETY, L htlantic City, N. J.
PREbEXTED
