were within our power, no one else would ever preseiit the Perkiii Rledal. 1 have the pleasure of presenting, rather than
introducing, the Dean of the American chemical profession. Professor Charles Frederick Chandler. N A T l O N I L GUM AND Mrcn COMPANY ?Taw Y O R Z CITY
PRESENTATION ADDRESS By
c. 17.
A I R . CIIAnIMnN AND BROTHI:R
CsnnDrilK
CIftZirWSs:
I h . Twitchcii's ieost iinport;nit contributions to Industrial Chemistry involve new wid iniyroved methods ior the hydrolysis of oils and fats for the production 01 the free fatly acids and glrccrin. These iriethods liarw very largdy superseded theold mcthotis suclinsthat of ChevreulandGay-Lussac (in r 8 q ) , who saponified in open kettles with ; t I M i . Tliis Ijincecs was improvcd I,? Alilly in 1 x 3 1 , who rubstituled milk of lime for alkali, and Iatcr b y w n d w t i u s thc s:+ponificutioii iu closed 1- lirosiiir, reduced mount oi lime required r c n 1 of the (at lo as z IW cciil. Then came f I)iil~iuni:*iit.rirst d Imxtically iii ,842 by i l w i i , i t ) wliicli tlir iat w;i\ iapouifird hy suliuric x i t i , a i i d the fttlty acids
It is m y privilege and very pleasant diity as Senior Past l>resi. dent of the Society of Chemical Industry, rcsidinp i n lhis country, t o presen't t o Izrnst Twitchell, R.S. and li.Sc., thc eleventh impression of ai,plivd liiii tiiswvwies of the Perkin Medal, in recoglei i t i i t l Xileisens in a nition of h i s most origiiid in nliiclr the fat and valuable work iii Apcornliorcd lry superplied Chemistry. heiiicd steam a u d s u b s Dr. Twitcliell was bani in qurnt distilkition, which Cincinnati, on February WAS practiced ;it thr works 26, 1863. He ,graduated of thc I'iicis Candle Co., in 1886 from the University 1liitt.ersra. Firrally in 1854, of Cincinnati with the deTilghmnnri introduced his gree of B.S, and in r 9 r j pro~ess in which the fat, received from his elme mater cniiilsidrd in water, was the honorary degree of Docforced through u coil a t a tor of Science. On Itis tengxrature of 020' C. graduation in 1886, he was Mnrix iuund tliat by adding appointed chemist to the it little calcirim UT m a ~ l i e Emery Candle Co., of sium carbonate to the water, Cincintiati. and has been t l x teniixmtiirc and presconnected with that firm sure could be very mateever since. rially reduced to as low as At present he is Chemical eYen 3 t" 5 attnosphercs. Director to the Emery The art of saponifying Candle Company, President ilie fats lind reached this of the AmericanOilTreating stage of de>wInpmcnt when atid Hardening Company, Di. Twitchell made an and Chairman of the Board eiitirely n e w de(mtiire by ofDirectors of the Twitchell the application of uew Process Company. reagents, whicb by acting Dr. Twitchell has devoted as cntalyzcrs, w e n when the past thirty years chiefly used in sudi small proporto the chemistry of fats. tions such 3s 1 to 2 per His investigations ;tnd discellt, are ii~,ie to coveries have keen given to the fats 'completely. The the chemical world in the oprmtion may Re conform of articles in various ducted by simply boiling chemical journals and in the fat with water and the letters patent oi the United roper qiiantity of the States and other countries. ponifier." The agents In 1891 he published first empluyed by D r his method ior the dcterTwitchell wcre the sulfomination of rosin in the acids of the fatty acids, fatty acids of suai>. The ERNST TWIZCAELL. PIIRKIIU' M R m i . I s r . 1917 such :is sulk-stearic acid, method is based on the a d d , eic. Later Ur. Twitchell found that by infact, observed by him, that the fatty acids, when dissolved in s~~lio-oleic ahsolute alcohol, are readily and completely converted into troducing ail aromatic radical inio the sulio-acid, a much ethyl ethers by the action of dry hydrochloric wid gas which, morc satisfactory catalyzer was obtained~.a sulio-fatty-aromatic acid. Such ixmnatic radicals a ore furnished by bcnzcne, ahsorbing the water set free, acts to reduce the reaction. On the other hand the rosin acids, under the same trcatment, re- phcnol, imd naphthalene are employed, naphthalene stearomain unchanged, and may be determined voluinctrieally with sulfonic acid being a favorite catalyzer. These acids when converted into salts of such mctds as barium, standard soda solution, or gravimetrically. calcium, xmgiiesitim, aluminum, etc., can he produced as stable Lewkowitsch, in his comprehensive work 011 "Oils, Fats Waxes." remarks: "Of all t h e methods for deterniiiiing rosiii dry powders, to be used with a suitable tiroportion 01 sulfuric ncids in the presence of fatty acids, the Twitchell method gives acid, or hydrochloric acid to make them active. I t woiild giw me great pleasure'to dwell longer on these the best results."
9
T H E J O 11R A L O F IiVDUSTRIAL A N D E N G I N E E H N G C H E M I S T R Y DR.
March July February April December February
29, 11, 19, 20, 30,
1898 1899 1907 1909 1913 1, 1915
601,603 628,503 814,426 918,612 1,082,662 1,170,468
Vol.
Q,
No.
2
TWITCHELL’S U. S. PATENTS
Process of Decomposing F a t s or Oils into F a t t y Acids and Glycerin. F a t t y Aromatic Sulfa Compound and Process of Making Same. Process of Effecting a Combination between Selected Members of t h e Alcohols and F a t t y Acid. Process of Separating Liquid from Solid F a t t y Acids. Process of Manufacturing F a t t y a c i d s and Glycerin. Sulfo-Fatty-Aromatic Acid Salt.
interesting inventions and improvements made by Dr. Twitchell, but inasmuch as you are t o hear from the Doctor himself, and also from Dr. Langmuir and Dr. Ittner on the subject, I will limit myself t o the following statements: The Twitchell process has made possible the large scale saponification of fats for the production of crude glycerin free from salt and of fatty acids for direct combination with soda so as to make soap instead of using the more expensive caustic lye on the neutral fat. Low-grade fats, such as garbage grease, cottonseed oil foots, etc. were formerly with difficulty used in the soap or candle industry. Such materials can now be readily worked up by the Twitchell process, the fatty acids being distilled to remove color before use. This releases a large quantity of the higher grade fats for use as food products. The bulk of the soap used in Belgium, Holland, Germany and Scandinavia is said to be prepared from fatty acids direct, and 75 per cent of these acids are made by the Twitchell method. Millions of pounds of fats are saponified yearly in the United States by this process, and practically all of the larger soap factories have Twitchell plants. All of the recent books in German and English on the soap and fat industries discuss the Twitchell process in full. DR. TWITCHELL’S PUBLICATIONS
“ T h e Determination of Rosin in I t s Mixtures with F a t t y Acids,” J . A n a l . and A p p . Chem., Vol 6 (July, 1891). “ T h e Separation of Solid a n d Liquid F a t t y Acids,” Jour?ial of the American Chemical Society, Vol. 17 (April, 1895). “Sulfuric Acid a s a Reagent in t h e Analysis of F a t t y Acids,” Journol of the Society of Chemical Industry, Vol. 16 (December, 1897). “Benzene-Stearo-Sulfonic Acid and Other Sulfonic Acids Containing t h e Stearic Radical,” Jourizal of the American Chemical Society, Vol 17 (January, 1900). “A Reagent in t h e Chemistry of Fats,” Journal of the Amcrican Chemical Society. Vol. 28 (February. 1906); Vol. 29 (April. 1907). “ T h e Melting and Solidifying Points of Mixtures of F a t t y Acids, a n d t h e Use of These Points t o Determine t h e Composition of Such Mixtures,” Journal of Indusirial and Engineering Chemistry, Vol. 6 (July. 1014). “Gnsaponifiable M a t t e r in Greases,“ Journal of Industrial and Engineering Chemistry, Vol. 7 (March, 1915). CONFERRING THE MEDAL
ERNSTTWITCHELL,BACHELOROF SCIENCE AND DOCTOROF SCIENCE: It gives me the greatest pleasure, as the representative of the Affiliated Chemical and Electrochemical Societies of America, to place in your hands this beautiful Perkin Medal, as a token of the appreciation and affection of your fellow chemists. COLUMBIA UNIVERSITY NEW Y O R K CITY
ADDRESS OF ACCEPTANCE B y ERNSTTWITCHELL The first suggestion which led to my discovery of a special catalyzer for hydrolyzing fats came to me in studying the socalled Acidification Process. This was one of the oldest methods used in candle factories for separating glycerol from fatty acids. It consisted in treating the fat a t a fairly high temperature, over 100’C., with a small amount of concentrated sulfuric acid; 4 per cent or considerably less could be used; the product was then boiled with an excess of water. The result is a layer of fatty acids floating on the acid water containing the glycerol. This reaction could not be explained by the assumption that there is a combination of sulfuric acid with the fat or fatty acid and glycerol, which decomposes during the subsequent operation of boiling with water, because there was not enough sul-
furic acid to combine with all of the fat. I have seen various theories given to explain the Acidification Process, some quite absurd. For instance, in one text-book it is stated that fats consist of minute globules surrounded by membranes and that the function of the sulfuric acid is simply to char and destroy these membranes, leaving the fat in a condition to be hydrolyzed by water a t 100’. Another theory I have frequently seen even in recent articles, is that compounds are formed which cause the f a t to emulsify with water, and the idea evidently is that if a good enough emulsion is obtained, hydrolysis will take place even a t 100’ I have seen this theory given to account for the action of my hydrolyzing reagent. As a matter of fact, fats do not hydrolyze at IOO’, practically speaking, with water alone, even though they may be perfectly emulsified. A t higher temperatures than IOO’, and under pressure, hydrolysis takes place, as is illustrated in the autoclave process of separating glycerol. I n the course of practical experiments with the Acidification Process I found that I could reduce the amount of sulfuric acid used very considerably and yet obtain complete decomposition; but often the boiling with water had to be decidedly prolonged. It seemed clear that there was some catalytic agent which caused the reaction between the fat and the water in this process of boiling, and it would naturally occur to any one that this catalyzer was probably some sulfur compound produced by the action of sulfuric acid on fat. I found that compounds of this nature could be roughly separated from the fat which contained them by treating with petroleum ether in which they were insoluble. They could be f u r t h e purified by solution in ether and extraction with water and were easily identified as sulfonic acids by their acidity, the formation of potassium sulfate on fusion with caustic potash, and other characteristics. It occurred to me to prepare this catalyzer outside of the body of the fat, thus avoiding the action of the sulfuric acid in forming with the fat undesirable compounds, in charring, discoloring, and partially destroying it. As these sulfonic acids were probably produced by the action of the sulfuric acid on the oleic acid constituent of the fat, I first studied the results of the action of sulfuric acid on pure oleic acid under various conditions of temperature, quantity, etc. The action of sulfuric acid on oleic acid a t low temperatures, as was known, produces a compound of sulfuric acid, stearosulfuric acid, an acid sulfuric ester. This was not the catalyst that I was seeking. I t very probably has all the properties of a catalyst for the hydrolysis of fats except one, it is decomposed on boiling with water. and as the hydrolysis of a fat hardly takes place a t all under any circumstances a t a lower temperature than IOO’, i t is plain that this compound would not serve my purpose The compounds obtained on treating oleic acid with sulfuric acid a t a temperature of 100’or over are not sulfuric acid compounds but are true sulfonic acids. The principal one seemed to be derived from two molecules of oleic acid and contained one sulfonic acid group and one carboxyl group. I have never seen this sulfonic acid described, but believe that I had in my hands a fairly pure compound of the composition C,7H8~(SO~H)CO0.C,7H&OOH.This was my first hydrolyzing reagent or “Saponifier ” But as i t was difficult to prepare commercially in fair yield and of any degree of purity. I dropped further investigation along this line on the accidental discovery of the fatty aromatic sulfonic acids, described in the Journal of the American Chemical Socaety, January, goo.
