Aug. 28, 1945. HD. ALLEN ETAL 2,383,579 PROCESS FOR TREATING FATS AND FATTY OILS Filed March 30, 1945 steam coouine PREREATER ‘CONDENSER asowee [aco ‘Sean SALT FILTER owrcerswe ——J INvenToRS HAROLD OWAINE ALLEN WILLIAM ASHLEY KLINE By, ‘ATTORNE)Patented Aug. 28, 1945 2,388,579 PROCESS FOR TREATING FATS AND FATTY Harold Dwaine Allen, Glen Rock, and William ‘Ashley Kline, Morris Plains, N. 5, assignors to Colgate-Paimolive-Peet Company, Jersey City, NJ, a corporation of Delaware ‘Application March 80, 1948, Serial No. 481,080 2,383,579 UNITED STATES PATENT OFFICE 18 Claims. ‘The present invention relates to @ process for the aleoholysis of fatty materials and, more par- Hoularly, to an improved high temperature proc ess for reacting fatty glycetides with alcohols, ‘whereby fatty acld esters and glycerine are Pro- 5 dduced in a relatively short time. ‘The methods of alcoholysis or radical inter- change between a glyceride and an alcohol d ‘scribed by the prior art have had certain dis- advantages, especially in continuous operation. 10 ‘Thus, the time required for a reaction between the alcohol and the fatty elyceride to provide sat~ isfactory yields of fatty ester and glycerine on ‘an industrial scale varied in the case of alkaline Aleoholyals from about twenty minutes to several 1 hours and usually ran about thirty minutes to an hour, and when using an acidic catalyst var- fed from about three hours to about twenty hours, ‘This not only tied up equipment and stock in provess but, in operating continuously by 20 passing the reactants together through a reaction Coll, it was necessary to provide a reaction coil of Telatively great length if satisfactory ylelds were to be produced. IIS an object of the present invention to pro- vide an improved process for reacting fatty glye- cerides (or other fatty acid ester of a higher alco hhoD) with an sloohol to produce fatty esters and slyeerine (or other higher aleohol) in high yield in g relatively short time. a0 Tt is also an object of the invention to provide a novel continuous process for producing a high Field of fatty esters and glycerine from fats and falty olls in relatively inexpensive and space- conserving equipment. % ‘Other objects and advantages of the invention ‘will be apparent from the following description, taken in conjunction with the accompanying drawing, where! ‘The figure represents @ flow diagram illustrat- 4” ‘ng the flow of materials in the operative steps of ‘a process in accordance with this invention, ‘According to the present invention, a fatty acid ester of @ higher alcohol (e. ¢., a elyceride) 1s contacted with an alcohol, preferably in the pres- 45 fence of an alcoholysis catalyst. The mixture is heated to a temperature above the normal boll- {ng point of the alcohol, and a pressure suficient to preserve a liquid aleghol phase is maintained. Avery rapid reaction takes place, with formation 60 of allyl esters and the higher alcoho! (say, glye- rine) ina relatively short time, Unreacted al- cohol is removed, and the products are separately reoovered. ‘The redction may be brourht to the desree of 65 (ct. 2604109) completion desired in a single hot contacting of the materlals, or, as disclosed by Joseph Henry Percy in United States patent application Serial ‘No, 462,369 (fled October 17, 1942), the glycerides may be partially esterified with the alcohol in a first treatment to form a pool of partially reacted ‘material containing monoglycerides and digiycer- Ides, so that the reaction mixture is substantially homogeneous. The partial esterification may be accomplished by Keeping the glyeeride and the ‘leanol in contact in a pool at moderate or a ele vated temperatures for a time interval insuffi ‘lent for the reaction to go to completion under ‘the operating conditions, as by continuously run~ rning fatty glyceride, alcohol and catalyst into = ool or mixing chamber and continuously with Grawing a substantially equivalent amount of par- tally reacted material at a rate designed to main. tain uniform conditions in the pool. ‘The reac- ton of the constituents of the withdrawn mate- rlal is then brought toward completion at a tem- erature above the normal bolling point of the Alcohol involved and at a pressure which Keeps fan alcohol liquld phase, It may be preferred at is point, when using an alkaline catalyst, to ‘add suflelent aoid to decampose any soap formed from the eatalyst, and in certain cases, espectally when alcohols higher than methanol are em- ployed in the process, the appearance of two phases does not occur until after acidification ‘or removal of unreacted alcohol. ‘While the phases may be separated, with or without acidifeation, before removal of the excess aleohol, it is generally preferred to vaporize un- reacted aleobol prior to settling, as disclosed by ‘Walter Russell Trent sn United States patent ap- pplication Ser. No. 462,370 (filed October 11, 1942) ‘After removal of the alcohol, the residue is al- lowed to settle; glycerine separates out as a lower layer and is withdrawn, and the upper layer eon taining alkyl esters, and in somo cases incom- pletely reacted glycerides, 1s also Temoved for further processing. Various ways of treating the ‘upper layer, which comprises the esterifleg mate~ ‘Hal, have been pointed out in application Ser. No. 462,369. a one procedure in accordance with the pres lent process, the fatty glyceride is premixed with fan alcohol and a catalyst and is passed through a contactor coil. ‘There the mixture is heated to a temperature above the boiling point of the alcohol ‘but below its critical temperature and below the temperature of substantial degradation of the ‘materials. Suffcient back pressure is applied to maintain a substantial proportion of the aleohol2 4n the Uquld state. ‘The mixture remains in the contactor coll for a relatively short time, sey of the order of up to about ten aintites for alkaline ‘leoholysis and up to about thirty minutes when using an acidic catalyst, and is then run to a 5 preheater, where it is heated under substantially ftmospheite pressure to a temperature sufficient to volatilize the excess alcohol. The resulting Uquid-vapor mixture is passed into a separating chamber from which the volatilized unreacted al conol is withdrawn and preferably passed to & condenser and receiver. The remaining material Comprises alkyl esters and giyourine, which are separately recovered, This may be accomplished hy codistitiation and settling the distillate or by running the material directly into a settling tank. ‘The glycerine separates out as a lower layer and fs withdrawn, and the esters (and glycerides, if present) are also removed, The process of any step thereof may be carried out in bateh, inter ‘mittent or continuous operation. Im general, the fatty oll, alcohol and catatyst ‘may be premixed in a homogenizer at about room. temperature before being run into the reaction coil. ‘When carrying out the aleohotysis with an alkatine catalyst, it is preferred thus to mix the reactants at a moderate temperature if small amounts of water are present, in order to avoid ‘the possibility of excessive looal saponification of the resulting esters. "Such saponifleation removes the catalyst from the reaction body before the reactants have been thoroughly mixed and al- lowed to react. When using an acid catalyst oF ‘when, even with an alkaline catalyst, the veact= ants are substantially anhydrous, the olf and the alcohol may be separately preheated to the de~ sired reaction temperature and thoroughly mixed directly in the reaction coll, whereby the reaction ‘can be completed in an extremely short reaction. time. In the presence of an alkaline catalyst and of small amounts of waler, preheating and ‘hot contacting tend to decrease the yield of esters, ‘The reaction coll is heated to provide tempera: ‘ures above the bolling point of the alcohol at atmospheric pressure, say to a temperature of ‘about 60° C. to about 160°C, or higher, but below ‘the temperature of substantial degradation of the materials. Where an alkaline catalyst ts em. ployed, this may also be below the temperature of substantially complete removal of the alkaline catalyst by saponification of the resulting esters. However, a temperature may be emplayed which ‘will produce high ester and glycerine yields in a very short and practical reaction time with simul~ ‘taneous conversion of the alkaline catalyst to soap. ‘This yield will be @ maximum at a par ticular temperature for a given combination of reactants. In acid or alkaline aleoholysls with elther methanol or ethanol, it is preferred to ‘maintair. temperatures of about 80°C. to about 160" C, and temperatures of about 90° G, to about 180° C. have given particularly satisfactory re- sults, ‘The mixture in the reaction colt is kept under ' pressure sufficient to maintain a liquid alcohol phase, If desired, the pressure may be low enough to permit the volatilization of a portion of the alcohol during the reaction, but, in general, eMiciency of operation 1s iniproved’ when the ‘amount of alcoho! volatilized in the coil is rela tively low. ‘Thus, at a reaction temperature of 100° ©. for methanol, it is preferred to employ a ‘gauge pressure of 55’ pounds per square inch or hhigher, say about 75 pounds per square inch, ‘whereby the alcoho! is substantially unvaporized. 75 0 6 20 0 50 0s © 6s 70 2,883,570 A similar pressure is applied in ethanolysis at 100° C., although at this temperature an even, lower pressure would-keep substantially all of the cetyl alcoho! in the liquid state. As the reaction temperature rises, higher pressures are requived, 4 suitable pressure for reaction with methanol ai ‘bout 125° C. being of the order of 150 pounds ber square inch absolute, ‘The reaction mixture Teaves the coi! and, if hecessary, may then be heated to volatilize the excess alcoho}, with or without prior neutrallza. tion. “Where the reaction mixture contain unt converted catalyst and 1s not neutralized before Yolatilizing the excess aleohol, it is advantageous to carry out such volatilization below the tem: erature of substantial reversal of the reaction ‘upon removal of the alcohol. In general, the oor eration may be carried out at reduced pressures, at atmospheric pressure, or at supertamospheric Dressures, ‘The fatty material treated by the process muy be any of the natural fatty acid esters, such as the fats and fatty oils suitable for employment by the soap-making art in any of the processes heretofore known, or any other fatty acid ester ofa higher alcohoi, such as glycerol or other poly. hydric alcohols or long-chain (say, about twelve to about twenty carbons) monohydrie alcohols, ‘oF mixtures of these esters, especially elycerides of fatty acids having about eight to about twenty. six, and preferably about twelve to about twenty, carbon atoms per molecule of fatty acid, These ¢gsters includes coconut oll, palm oi, olive oll, cots tonseed oll, com off, tung oll, ova bean oll, wool fat, tallow, whale and fish oils, ete. Althoush a refined oil containing substantially no moisture 4s preferably employed, as the presence of water Gecreases the yield of esters in alkaline alco holysis and slows down the reaction when an acid catalyst is used, small amounts of water can be tolerated when carrying out the reaction with the lower alcohols, such as methyl or etiyt alco hol and especially methanol, Similarly, where acid aleoholysis is employed or where, in alkaline alcoholysis, acidification of the reaction mixture 4s contemplated, either before or after volatilnes tion of the unreacted alcohol, free fatty acid may ‘be present in the glyeeride in the proportion at 10% to 20% or even higher. In carrying out the alcoholysis according to {this invention, short-chain aliphatic monohydrie alcohols, ineliding aryl-substituted aliphatic al. Cobos, are preferably employed, particularly thie ‘saturated, primary alcohols, especially alcohols having a boiling point in the presence of water {in excess of the azeotrople composition of lower ©. at atmospheric pressure and, more Particularly, the lower alcohols having ¢ne to bout six carbon atoms per molectle. ‘Thus, al- ccohols satisfactory for use in forming esters ‘ith the fatty acid components of the glycerides treat ed include such low molecular weight monchydris alcohols as methy! alcohol, ethyl alcohol, props] aleohol, isopropyl alcohol, n-butyl aleotio, iso- secondary butyl alcohol, tertiary butyl alcohol, the amyl alcohols, benzyl alcohol etc. While any proportion of fatty material and alcohol may be used, it is preferred to employ an amount of alcohol at least. about 50% in excess Of the calculated theoretical amount necessary for aleoholysis of the particular glyeerides treat ed, and particularly satisfactory results have been objained when using an excess of at least three to five times the stoichiometric amount required, n selecting an aleoholysis catalyst, an alkaline