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Aug. 28, 1945. H. D._ALLEN ET AL ~ 2,383,579 PROCESS FOR TREATING FATS AND FATTY OILS Filed March 30, 1943 STEAM COOLING . WATER PRESSU RE CONTROL PREHEATER CONDENSER REACTION COIL ALCOHOL FLAS H CHAMBER STEAM ALCOHOL ACID (CAUSTIC SODA) MXXING CHAMBER ESTERS SALT FILTER I INVENTORS HAROLD DWAINE ALLE N WILLIAM ASHLEY KLI_NE BY ‘ ATTORNE Patented Aug. 28, 1945 _ 2,383,579 UNITED‘ STATES PATENT OFFICE raoonss FOR 'rarghigo 2,383,579 FATS AND FATTY Harold Dwaine Allen, Glen Rock, and William Ashley Kline, Morris Plains, N. J ., assignors to Colgate-Palmolive-Peet Company, Jersey City, N. J ., a corporation of Delaware ' Application March 30, 1943, Serial No. 481,080 18 Claims. (Cl. 260-4109) The present invention relates to a process for ' completion desired in a single hot contacting of - the materials, or, as disclosed by Joseph Henry the alcoholysis of fatty materials and, more par Percy in United States patent application Serial ticularly, to animproved- high temperature proc— No. 462,369 (?led October 17, 1942) -, the glycerides ess for reacting fatty glycerides with alcohols, whereby fatty acid esters and glycerine are pro (.1 may be partially esteri?ed with the alcohol in a ?rst treatment to form a pool of partially reacted duced in a relatively short time. material containing monoglycerides and diglycer The methods of alcoholysis or radical inter ides,‘ so that the reaction mixture is substantially homogeneous. The partial esteri?cation may be scribed by the prior art have had certain dis advantages, especially in continuous operation. 10 accomplished by keeping the glyceride and the alcohol in contact in a pool at moderate or at ele Thus, theltime required for a reaction between vated temperatures for a time interval ‘insum the alcohol and the fatty glyceride to provide sat cient for the reaction to go to completion under isfactory yields of vfatty ester and glycerine ‘on the operating conditions, as by continuously run an industrial scale varied in the case of alkaline ning fatty glyceride, alcohol and catalyst into a alcoholysis from about twenty minutes toseveral pool or mixing chamber and continuously with hours and usually ran about thirty minutes to drawing a substantially equivalent amount of par an hour, and when using an acidic catalyst var- tially reacted material at a rate designed to main led from about three hours to about twenty tain uniform conditions in the pool. The reac hours. This not only tied up equipment and stock-in process but, in operating continuously by 20 tion of the constituents of the withdrawn mate rial is then brought toward completion at a tem passing the reactants together through a reaction peratureoabove the normal boiling point of the coil, it was necessary to provide a reaction coil of alcohol involved and at a pressure which keeps relatively great length if satisfactory yields were an alcohol liquid phase. It may be preferred at to be produced. this point, when using an alkaline catalyst, to It is an object of the present invention to ‘pro add suf?cient acid to decompose any soap formed vide an improved process for reacting fatty glyc from the catalyst, and in certain cases, especially erides (or other fatty acid ester of a higher alco when alcohols higher than methanol are em hol) with an alcohol to produce fatty esters and ployed in the process, the appearance of two glycerine (or other higher alcohol) in high yield phases does not occur until after acidi?cation in a relatively short time. or removal of unreacted alcohol‘. It is also an object of the invention to provide a While the phases may be separated, with or novel continuous process for producing a high without acidi?cation, before removal of the excess yield of fatty esters and glycerine from fats and ’ alcohol, it is generally preferred to vaporize un fatty oils in relatively inexpensive and space reacted alcohol prior to settling, as disclosed by conserving equipment. ' Walter Russell Trent in United States patent ap- ' Other objects and advantages of the invention plication Ser. No. 462,370 (?led October 1'7, 1942) . . will be apparent from the following description, After removal of the alcohol, the residue is al taken in conjunction with the accompanying lowed to settle; glycerine separates out as a lower drawing, wherein: ‘layer and is withdrawn, and the upper layer con The ?gure represents a flow diagram illustrat taining alkyl esters, and in some cases incom ing the ?ow of materials in the operative steps of pletely reacted glycerides, is also removed for a process in accordance with this invention. further processing. Various ways of treating the According to the present invention, a fatty acid upper layer, which comprises the esteri?ed mate ester of a higher'alcohol (e. g., a glyceride) is contacted with an alcohol, preferably in the pres 45 rial, have been pointed out in application Ser. No. change between a glyceride and an alcohol de ence of an alcoholysis catalyst. The mixture is heated to a temperature above the normal boil ing point of the alcohol, and a pressure suf?cient to preserve a liquid alcohol phase is maintained. A very rapid reaction takes place, with formation of alkyl esters and the higher alcohol (say. glyc erine) in a relatively short time. Unreacted al cohol is removed, and the products are separately recovered. » ' _ The reaction may be brought to the degree of 55 462,369. In one procedure in accordance with the pres ent process, the fatty glyceride is premixed with an 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. Sufficient back pressure is applied to _maintain a substantial proportion of the alcohol 2 2,383,579 in the‘llquid state. The mixture remains in the contactor coil for a relatively short time, say of the order of up to about ten minutes for alkaline alcoholysis and up to about thirty minutes when using an acidic catalyst, and is then run to a preheater, where it is heated under substantially atmospheric pressure to a temperature su?icient to volatilize the excess alcohol. The resulting liquid-vapor mixture is passed into a separating chamber from which the volatilized unreacted al cohol is withdrawn and preferably passed to a A similar pressure is applied in ethanolysis at 100° 0., although at this temperature an even lower pressure would'keep substantially all of the ethyl alcohol in the liquid state. As the reaction temperature rises, higher pressures are required, a suitable pressure for reaction with methanol at about 125° C. being of the order of 150 pounds per square inch absolute. . The reaction mixture leaves the coil and, if necessary, may then be heated to volatilize the excess alcohol, with or without prior neutraliza tion. Where the reaction mixture contains un converted catalyst and is not neutralized before condenser and receiver. The remaining material comprises alkyl esters and glycerine, which are separately recovered. This may be accomplished the excess alcohol, it is advantageous by codistillation and settling the distillate or by 15 volatilizing to carry out such volatilization below the tem running'the material directly into a settling tank. perature of substantial reversal of the reaction The glycerine separates out as a lower layer and upon removal of the alcohol. In general, the op is withdrawn, and the esters (and glycerides, if , eration may be carriedout at reduced pressures, present) are also removed. The process or any at atmospheric pressure, or at supertamospheric step thereof may be carried out in batch, inter 20 pressures. mittent orcontinuous operation. The fatty material treated by the process may In general, the fatty oil,.,alcohol,and catalyst be any of the natural fatty acid esters, such as maybe premixed in a homogenizer at about room the fats and fatty oils suitable for employment temperature before being run into the reaction coil. When carrying out the alcoholysis with an 25 by the soap-makingart in any of the processes heretofore known, or any other fatty acid ester alkaline catalyst, it is preferred thus- to. mix the of a higher alcohol, such as glycerol or other poly reactants at a moderate-temperature if small hydric alcohols or long-chain (say, about twelve amounts of water are present, in order to avoid . to about twenty carbons) monohydric alcohols, the possibility of excessive local saponi?cation of .ormixtures'of these esters, especially glycerides the resulting esters. Such saponi?cation removes the catalyst from the reaction body before the 30 offatty acids having about eight to about twenty six, and preferably about twelve to about twenty, reactants have been thoroughly mixed and al— carbon atoms per molecule of fatty acid. These lowed'to react. When using an acid catalyst or esters includes coconut oil, palm oil, olive oil, cot when, even with an alkaline catalyst, the react tonseed oil, corn oil,- tung. oil, soya bean oil, wool ants are substantially anhydrous, the oil and the fat, tallow, whale and ?sh oils, etc. Although a alcohol may be separately preheated’ to the de re?ned oil containing substantially no moisture sired reaction temperature and thoroughly mixed is preferably employed, as the presence of water ' directly in the reaction coil, whereby the reaction decreases the yield of esters in alkaline alco can be completed in an extremely short reaction time. In the presence of an alkaline catalyst 40 holysis and slows down the reaction when an acid catalyst is used, small amounts of water can be ' ‘ andJof-small amounts of water, preheating and hot contacting tend to decrease the yield of esters, The reaction coil is heated to provide tempera-_ 'tures above the boiling point of the alcohol at atmospheric pressure, say to a temperature of about 80° C. to about 160° C. or higher, but below the temperature of substantial degradation of the materials. Where an alkaline catalyst is em ployed, this may also be below the temperature of substantially complete removal of the alkaline 50 catalyst by saponi?cation of the resulting esters. However, a. temperature may be employed 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 55 tolerated when, carrying out the reaction with the lower alcohols, such as methyl or ethyl alco hol and especially methanol. Similarly, Where acid alcoholysis is employed or where, in alkaline alcoholysis, acidi?cation of the reaction mixture, is contemplated, either before or after volatilize. tion of the unreacted alcohol, free fatty acid may be present in the glyceride in the proportion of 10% to 20% or even higher. In carrying out the alcoholysis according to this invention, short-chain aliphatic monohydric alcohols, including aryl-substituted aliphatic al- I cohols, are preferably employed, particularly the saturated, primary alcohols, especiallyalcohols having a boiling point in the presence of water in excess of the azeotropic composition of lower ticular temperature for a given combination of than 100° C. at atmospheric pressure and, more reactants. In acid or alkaline alcoholysis with particularly, the lower alcohols having one to either methanol or ethanol, it is preferred to maintain temperatures of about 80° C. to about 60 about six carbon atoms per molecule. Thus, al cohols satisfactory for use in forming esters with 160° C., and temperatures of about 90°‘ C. to about soap. This yield will be a maximum at a par 130° C. have given particularly satisfactory re sults. The mixture in the reaction coil is kept under ' a pressure su?icient to maintain a liquid alcohol 65 phase. If desired, the pressure may be low enough to permit the volatilization of a portion the fatty acid components of the glycerides treat ed include such low molecular weight monohydric alcohols as methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, n-butyl alcohol, iso butyl alcohol, secondary butyl alcohol, tertiary butyl alcohol, the amylk 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 ‘ amount of alcohol volatilized in the coil is rela 70 of the calculated theoretical amount necessary tively low- Thus, at a reaction temperature of for alcoholysis of the particular glycerides treat? 100° C. for methanol, it is preferred to employ a ed, and particularly satisfactory results have been ' gauge pressure of 55 pounds per square inch or obtained when using an excess of at least three of the alcohol during the reaction, but, in general, e?iciency of operation is improved when the higher, say about '75 pounds per square inch, ?ve times the stoichiometric amount required. whereby the alcohol is substantially unvaporized. 75 to In selecting an alcoholysis catalyst. an alkaline 2,888,579 I or anacidic catalyst may be employed. vAmong those which have been found suitablefor use in the present process are sodium hydroxide, sodium 101° C. and 103° C." A su?icient back pressure is maintained upon the coil to prevent volatilization of the alcohol. The coil is equipped with outlet cocks at various points therealong for the pur pose of withdrawing'the material after any de methylate, sodium carbonate, barium oxide, lime, tetramethyl ammonium hydroxide, boron tri?uo ride, aluminum chloride, hydrochloric acid, tri sired interval of reaction time. After 3.1 min- ‘ chloracetic acid, phosphoric acid, glycerine mono acid sulphate, sulphuric acid, organic sulphonic acids, alkyl sulphuric acids, etc. While- it is pos sible to obtain good yields with proportions of 10 utes in the coil, a portion of the reaction mixture is withdrawn-and promptly acidi?ed with dilute sulphuric acid to halt the reaction. The acidi?ed mixture is allowed to settle, and a'lower glycerine catalyst up to about 0.30 mol per equivalent of layer is withdrawn. The upper layer is washed fatty glycerides and higher, it is preferred to use with water to remove unreacted alcohol, residual large excesses. of alcohol and to introduce rela glycerine and excess mineral acid, and it is then tively small amounts of catalysts, say of the order dried and vacuum distilled. An ester. yield of of about 0.03 mol to about 0.10 mol per equivalent approximately 96.2% of the calculated theoreti of glycerides. A convenient way of introducing cal yield is obtained. the catalyst into the reaction mixture is in ad A second portion of the reaction mixture is re mixture with and, where practical, advanta moved from the reaction coil after an additional geously in solution in the alcohol employed. In 4.1 minutes and is treated in a manner similar to alkaline alcoholysis, when the glyceride treated 20 the treatment of the ?rst portion. A yield of contains free fatty acid, su?icient alkalinecata methyl esters equivalent to about 96.5% of the lyst is added to provide an excess of alkali above calculated theoretical yield is obtained. that destroyed by the free fatty acid present. Example III After acidi?cation with an acid stronger than the fatty acid of the glyceride, the fatty acid goes into the ester layer. However, acid catalysts are 25 particularly appropriate for use with oils contain ing a large proportion of free fatty acids, as the ' acids are esteri?ed during the process. The following examples illustrate the present invention, but it will be understood that the in vention is not limited thereby. . Example I 1 Using the same proportions of cottonseed oil, ' methanol and sodium hydroxide as set forth in Example 11, the materials are mixed and run into a reaction coil, as there described. The mixture is heated in the coil to a temperature of 131° C. 30 and is maintained at a pressure suf?cient to keep the alcohol in the liquid state. A portion of the reaction mixture is withdrawn from the reaction coil after 3.1 minutes therein and, after treat ment ‘as described in Example II, gives a yield of About 224 c. e. per minute of re?ned anhydrous 35 96.8% of methyl esters of cottonseed oil fatty coconut oil is pumped to a homogenizer and is there contacted with 96 c. 0. per minute of an hydrous ethyl alcohol containing 0.7 5% of sodium hydroxide. The materials are thoroughly mixed acids. Ea‘ample IV About 100 parts by weight of coconut oil are charged into a stainless steel bomb with 72 parts of methyl alcohol and 1 part of concentrated sul phuric acid. The bomb is brought to a tempera mately ten minutes. The coil is jacketed with ture of 135° C. and maintained at approximately low pressure steam at a temperature of about that temperature for some forty-?ve minutes 100° C. and is equipped with means for maintain‘ with intermittent shaking. It is then cooled to ing a back pressure upon the contents thereof. 45 about 25° C., and its contents are washed with The reaction mixture is kept under a pressure water, dried and ?ltered. Theyield of distillable‘ in the homogenizer, and the mixture is run into a reaction coil having a holding time of approxi of about 90 pounds per square inch absolute and is run from the reaction coil at a temperature of about 100° C. The mixture is passed with reduc ‘ material obtained, comprising methyl esters of the coconut oil fatty acids, is about 97.3% of the calculated theoretical yield. tion in pressure through a preheater, which is 50 Example V also steam jacketed, and the temperature of the mixture is there raised to 110° C. The ethyl al Employing the same equipment and procedure cohol is vaporized within the preheater pipe, and as in Example IV, 285 parts by weight of No. 4 the liquid-vapor mixture is run into a packed tallow containing about 14% of free fatty acids column for separation of the vapor. A series of 55 are charged into a bomb with 160 parts of methyl steam coils is located at the bottom of the column alcohol and about 3 parts of concentrated sul and serves as a reboiler. The ethyl alcohol is phuric acid. After forty-?ve minutes at a tem removed at the top of the column to- a condenser perature of about 135° C. and removal of excess and receivers, and the ethyl esters of coconut oil alcohol, a yield approximately 96.4% of the cal acids, glycerine and any soap present drop 60 culated theoretical is obtained. through the series of steam coils into a settling Example VI chamber. Glycerine separates out in the lower A substantially anhydrous mixture of coconut layer, which is withdrawn, and theupper layer. oil and ethyl alcohol in approximately equal parts comprising the ethyl esters is removed for puri ?cation and further processing. 65 by weight is heated to about 130° C. under su?i cient pressure to keep the alcohol in the liquid Example II phase. The mixture is passed into a stainless About 285. parts by weight per minute of sub steel homogenizer at a rate of about 200 parts by stantially anhydrous cottonseed oil is mixed with weight per minute and is contacted there with 160 parts per minute of substantially anhydrous 70 about 1' part per minute of concentrated sul methanol and 1.6 parts per minute of sodium hy phuric acid, meanwhile maintaining the pres droxide (about 0.04 mol of sodium hydroxide per sure. The materials are thoroughly mixed at equivalent of oil) during a period of 4.1 minutes. ' 140° C. for about four minutes, and the e?iuent After thorough mixing, the materials are into is run into a steam-jacketed reaction coil having a reaction coil, where they are heated to between 75 a holding time of approximately ?ve minutes. 4 2,383,579 The temperature is kept at about 140° C. and a back pressure of 165 pounds per square inch as solute is maintained within the coil. The reac tion mixture is ?ashed into a vaporization cham ber maintained at 135° C.,' and excess ethyl al cohol is volatilized and removed. The remainder of the mixture is passed into, a settling tank, from which glycerine and ethyl esters are sepa ume per minute. The oil mixture and the alcohol run through the pump together and are mixed therein during a period of about six seconds. The alcohol contains about 0.75% anhydrous caustic soda based on the oil used. The reaction mixture in the coil is heated to about 123° C. and is under a gauge pressure therein of about 125 pounds per square inch. The coil has a holding rately withdrawn. time of about thirty-seven seconds at the present 10 throughput rate, and at the end of this period Example VII the eiliuent at about 123° C. is ?ashed into a About 215 parts by weight per minute of coco vaporization chamber maintained at about 129° nut oil are run into a homogenizer and are there C. and atmospheric pressure. The excess meth mixed with about 230 parts per minute of ethyl anol is volatilized, and the residue is passed to alcohol containing about 0.6% of sodium hy an acidi?cation and settling tank, where it is droxide. The materials are thoroughly mixed acidi?ed, washed, dried and distilled. A yield of for about three minutes, and the mixture is run esters equivalent to about 97.5% of the calculated into a heated reaction coil of such dimensions as theoretical yield is obtained. to be able to contain 3,200 parts of material, that Example X is, having a holding time of about seven minutes at the present rate of feed. The materials are A substantially anhydrous mixture of coconut heated therein to about 100° C. and are main oil and tallow in the proportion of about 1 to 4 tained under a back pressure of about 90 pounds is heated to about 75° C. and run at about 785 per square inch absolute. The'e?iuent from the parts by volume per minute directly into a reac reaction coil is run. into a preheater at substan- . tion coil having a capacity of about 785 parts by tially atmospheric pressure and it is there heated volume. Substantially anhydrous methyl alcohol to about 110° C. Unreacted ethyl alcohol is va containing about 0.75% anhydrous caustic soda porized, and the liquid-vapor mixture is passed on the basis of oil used is also run directly into to a packed column which is situated over a series the coil at a rate of about 500 parts by volume of steam coils. The steam coils serve as a re 30 per minute. The reactants mix in the coil and v boiler, and steam is furnished to them at a pres are heated to about 123° C. under a pressure of sure su?icient to provide an outside surface tem 125 pounds per square inch gauge during the perature of about 130° C. vaporized unreacted period of 0.61 minute when they are passing alcohol is withdrawn at the top of the column therethrough. The e?iuent passes through a so and is condensed and stored for reuse in the lution heater at atmospheric pressure and is process. The residue ?ows through the reboiler vaporized in a ?ash chamber at 115° C. Excess and into ar acidi?cation tank, where su?icient methyl alcohol is volatilized, and the ‘residue is sulphuric acid is added to provide an acidic re treated as in Example IX, a yield of esters equiv action mixture having a pH of about 4.0. The alent to about 97.5% of the calculated theoretical acidi?ed mixture is then settled, and a lower 40 yield being recovered. glycerine layer is removed. The upper layer comprising the ethyl esters of coconut oil acids over?ows through an outlet in the upper portion of the settling tank. and coconut oil in'the ratio of 4 to 1 is heated ‘ Example VIII About 285 parts by weight per minute of cot tonseed oil are thoroughly mixed with about 160 parts per minute of methyl alcohol and about 1.6 parts per minute of sodium hydroxide for a period of about thirty seconds, the reactants be ing at about 25° C. throughout. The mixture is then run into a reaction coil having a holding time of about thirty seconds and the tempera ture is raised to about 130° C. Example XI A substantially anhydrous mixture of tallow Suiilcient pres sure is maintained within the coil to keep methyl alcohol in the liquid state. The e?iuent from the coil is ?ashed into a vaporization chamber at > to 113° C. and run to the inlet of a .pump at a rate of about 785 parts by volume per minute. Substantially anhydrous methanol containing 0.75% dry sodium_hydroxide on an oil basis is heated under pressure to about 119° C‘. and run to the same pump inlet at about 500 parts per minute. The capacity of the pump is such that the reactants pass through at these rates in about six seconds. The materials are pumped into a reaction coil, through which they pass in about seventy-eight seconds, and the temperature of the reaction mixture is raised to about 138° C. under a gauge pressure of about 163 pounds per square inch. The ef?uent from the coil passes atmospheric pressure and then into a second ‘ into a tube under atmospheric .pressure, where chamber under a vacuum of about 26 inches of 60 the temperature is reduced to about 133° C., and mercury, and excess methanol is volatilized and it is then treated in an atmospheric vaporization withdrawn. The residue flows into a settling chamber at about 129° C., where excess alcohol tank, where a lower glycerine-containing layer is is volatilized. The residue is treated as in Exam withdrawn. The upper layer is removed, washed, dried, and vacuum distilled, and a yield of methyl esters of cottonseed oil equivalent to about 97.0% of the calculated theoretical yield is obtained. Example IX A dry mixture of about 80% tallow to about 20% coconut oil is preheated to about 73° C. and is pumped into a reaction coil at a rate of about 785 parts by volume per minute. Substantially anhydrous methanol at about 22° C. is pumped into the coil at a rate of about 500 parts by vol ple IX, and a yield of esters equivalent to about 98% of the calculated theoretical yield is obtained. Example XII Referring to the ?gure, a mixture of about 20% of coconut oil and 80% of tallow is drawn from a calibrated supply tank through a salt ?lter to remove moisture therefrom and is pumped into a mixing chamber. Solid substantially anhydrous caustic soda is dissolved in substantially anhy drous methyl alcohol in the proportion of 0.17 part by weight of caustic to 10.4 parts of meth 5 2,388,679‘ anol, and the alcoholic solution is also pumped from the principles and true ‘spirit ,of the in from a supply tank to the mixing chamber. The ~ vention. fatty oil mixture is pumped to the- chamber at the rate of 22.3 pounds per hour, and the alkaline - alcohol is pumped into the chamber in con?uence therewith at the rate of 10.57 pounds per hour. The mixing chamber is equipped with' twenty motor-driven impeller blades adapted to run at 800 R. P. M., and the temperature of the, mixing We claim: ' - . ' 1. The process which comprises heating a fatty acid ester of an aliphatic polyhydric alcohol with an aliphatic monohydric alcohol having one to about six carbon atoms per molecule in the pres ence of an alcoholysis catalyst at a temperature above the normal ‘boiling point of said aliphatic chamber is 40° C. Under these conditions in the 10 monohydric alcohol and at a pressure sufficient mixing chamber, the two-phase system reaches a ?nely-divided state and the reaction is initiated. The volume of the mixing chamber is such to maintain the monohydric alcohol in liquid phase, thereby providing a liquid body contain ing alkyl esters and polyhydric alcohol; and re covering the alkyl esters and the polyhydric that its‘ holding time is about four minutes, and the e?iuent passes into a reaction coil which 15 2. The process which comprises heating a fatty comprises a series bank of double pipe units, glyceride, with a monohydric alcohol having one the volume of which is equivalent to about ten to about six carbon atoms per molecule in the minutes’ reaction time. Low pressure steam is presence of an alcoholysis catalyst at a tempera supplied to the outer pipe, which forms an an ture above the normal boiling point of said alco nular jacket ‘for the reaction coil, and a reaction 20 hol and at a, pressure suf?cient to maintain a temperature of about 100° C. is thereby main substantial proportion of said alcohol in a liquid tained. The coil outlet is furnished with a pres phase, thereby providing a liquid body contain sure controller which maintains a gauge pressure ing monohydric alcohol esters and glycerine; and of about '75 pounds per square inch within the separately recovering said esters and glycerine. coil. Under these conditions of temperature and 25 3. A process for treating fatty materials which pressure, the alcohol is substantially unvolatil comprises heating a fatty glyceride with a satu-' 'ized, and a high yield of methyl esters and glyc ' rated, aliphatic, monohydric alcohol having one erine is obtained within the reaction time and to about six carbon atoms per molecule in the with the simultaneous conversion of substantially 80 presence of an alcoholysis catalyst at a tempera all of the catalyst to soap. ture about 80° C. to about 160° C. but above the The reaction mixture ?owing from the coil is normal boiling point of the alcohol and at a released to substantially atmospheric pressure pressure substantially above the vapor pressure within a steam-heated tubular preheater, in of said alcohol at the temperature employed, which the latent heat of vaporization of steam 35 thereby providinga liquid body containing alkyl is added to the vaporizing unreacted alcohol at esters and glycerine; and recovering alkyl esters about 100° C. The liquid-vapor mixture is passed and glycerine from said liquid body. alcohol. to a steam-heated separation or ?ash chamber - ‘ 4. The process as set forth in claim 3 wherein at substantially atmospheric pressure. The va ' the alcohol employed is methyl alcohol and porized alcohol is withdrawn and is condensed 40 wherein the alkyl esters produced are methyl in a tubular condenser as substantially anhydrous alcohol for reuse. The residue after vaporiza tion of the alcohol flows into a settling tank, where it is cooled to about 52° C. and is acidi?ed with dilute sulphuric acid. The acidi?ed mix ture is allowed to stand, and two layers are ob esters. 5. The process as set forth in claim 3 wherein the alcohol employed is ethyl alcohol and where in the alkyl esters produced are ethyl esters. 6. A process for treating fatty materials which comprises heating a fatty glyceride with an ex cess of a saturated, aliphatic, monohydric alco The lower layer, comprising glycerine together hol having one to about‘ six carbon atoms per molecule, said ‘excess being about three to about with the water and salt resulting from acidi?ca tion of the mixture, is withdrawn. The upper 50 ?ve times the stoichiometric amount of said alco tained. hol required fOr alcoholysis of said glyceride, in layer, comprising the methyl esters of the tallow the presence of an alcoholysis catalyst in the pro and coconut oil fatty acids, the fatty acids made portion of about 0.3 mol to about .10 mol of by acid splitting of the soap formed by saponi? said catalyst per equivalent of glyceride, at a cation of the esters with the caustic catalyst, and partially reacted mono- and, di-glycerides, 55 temperature of about 80° C. to about 160° C. but above the normal boiling point of the alcohol is also removed. This operation gives about 98% and at a pressure substantially above the vapor conversion of available fatty acid to methyl pressure of said alcohol at the temperature em esters and about 94% liberation of the available ployed, thereby providing a liquid body contain glycerine, based upon the calculated theoretical yields. _ 60 ing alkyl esters, glycerine and unreacted alcohol; removing unreacted alcohol therefrom; and sep The ester fractions obtained according to the arately recovering alkyl esters and glycerine, present invention, with or without washing 7. A process for treating fatty materials which and/or subsequent puri?cation, can be employed comprises mixing a fatty glyceride with a sat in many chemical processes and products, as in the paint, perfumery, lubricating oils, medicinals 65 urated, straight-chain, monohydric alcohol hav and other ?elds. They may be used for chemical reductions and in many chemical syntheses and ing one to about six carbon atoms per molecule and with an alcoholysis catalyst; heating the one of their greatest outlets for volume con mixture at a temperature of about 80° C. to sumption is in the soap-making industry. Although the present invention has been de about 160° C. but above the normal boiling point I scribed with reference to particular embodiments and examples, it will be apparent to those skilled in the art that variations and modi?cations of this invention can be made and that equivalents can be substituted therefor without departing 70 of the alcohol and at a pressure substantially above the vapor pressure of said alcohol at the temperature employed, thereby providing a liquid body containing alkyl esters and glycerine; and recovering alkyl esters and glycerine from said liquid body. - 6 2,388,579 8. A process for treating fatty materials which comprises establishing a liquid pool containing a fatty glyceride, a saturated, straight-chain, cohol therefrom; and recovering ethyl esters and glycerlne from said liquid body. monohydric alcohol having one to about six car bon atoms per molecule, alkyl esters, glycerine and partially reacted glycerides; continuously in troducing a fatty glyceride and a saturated, straight-chain, monohydric alcohol having one to about six carbon atoms per molecule together with an alcoholysis catalyst into said liquid pool; continuously withdrawing a. portion of said liquid pool; regulating the rates ofsaid introduction and said withdrawal with respect to the size of the liquid pool to keep the fatty glyceride and presence of an acidic alcoholysis catalyst‘for up to about thirty minutes at a temperature above the normal boiling point of said alcohol and at a pressure substantially above the vapor pressure of said alcohol at the temperature employed, thereby providing a liquid body containing alkyl esters and glycerine; and recovering alkyl esters and glycerine from said liquid body. 14. A process for treating fatty materials which the alcohol in contact in the pool in the presence of the alcoholysis catalyst for a period of time comprises heating a fatty glyceride with an excess of a saturated, straight-chain, monohydric alco hol having one to about six carbon atoms per sumcient to provide thorough mixing and insuffi cient for the reaction to go to completion; heat ing the withdrawn portion at a temperature above the normal boiling point of the alcohol molecule in the presence of an acid alcoholysis catalyst for up to about thirty minutes at a tem perature of about 80° C. to about 160° C. but above and at a pressure substantially above the vapor _ pressure of said alcohol at the temperature em the normal boiling point of the alcohol and at a pressure substantially above the vapor pressure of ployed, thereby providing a liquid body contain ing alkyl esters and glycerine; and recovering alkyl esters and glycerine from said liquid body. 9. A process for treating fatty materials which said alcohol at the temperature employed, there by providing a liquid body containing alkyl esters, glycerine and‘unreacted alcohol; volatilizing un comprises heating a fatty glyceride with a satu reacted alcohol from said liquid body at a tem perature below the temperature of substantial re versal of the reaction upon removal of the alco rated, aliphatic, monohydric alcohol having one to about six carbon atoms per molecule in the presence of an alkaline alcoholysis catalyst for up to about ten minutes at a temperature above the normal boiling point of said alcohol and at a pressure substantially above the vapor pressure , 13. A process for treating fatty materials which comprises heating a fatty glyceride with a satu rated, aliphatic. monohydric alcohol having one to about six carbon atoms per molecule in the a hol; and recovering alkyl esters and glycerine, from said liquid body. 15. A process for treating fatty'materials which comprises heating a fatty glyceride with an excess of methyl alcohol in the presence of an acid alco 35 holysis catalyst at a temperature of about 90° C. esters and glycerine; and recovering alkyl esters to about 130° C. and at a pressure substantially and glycerine from said liquid body. _ above the vapor pressure of methyl alcohol at the 10. A process for treating fatty materials which temperature employed, thereby providing a liquid comprises heating a fatty glyceride with an ex body containing methyl esters, glycerine and un cess of a saturated, straight-chain, monohydric 40 reacted methyl alcohol; removing unreacted alcohol having one to about six carbon atoms per methyl alcohol therefrom; and recovering methyl molecule in the presence of an alkaline alcoholy esters and glycerine from said liquid body._ sis catalyst for up to about ten minutes at a tem 16. A process for treating fatty materials which perature of about 80° C. to about 160° C.'but above comprises heating a fatty glyceride with an ex~ the normal boiling point of the alcohol and at a 45 cess of ethyl alcohol in the presence of an acid pressure substantially above the vapor pressure alcoholysis catalyst at a temperature of about 90° of said alcohol at the temperature employed, C. to about 130° C. and at a pressure substantially thereby providing a liquid body containing alkyl above the vapor pressure of ethyl alcohol at the of said alcohol at the temperature employed, thereby providing a liquid body containing alkyl esters, glycerine and unreacted alcohol; volatiliz temperature employed, thereby providing a liquid ing unreacted alcohol from said liquid body ‘at a 50 body containing ethyl esters, glycerine and unre temperature below the temperature of substan acted ethyl alcohol; removing unreacted ethyl al tial reversal of the reaction upon removal of the cohol therefrom; and recovering ethyl esters and alcohol; and recovering alkyl esters and glycerine glycerine from said liquid body. from said liquid body. . ‘.17. The‘ process which comprises bringing a 11. A process for treating fatty materials which 55 stream of fatty material from the class consisting comprises heating a fatty glyceride with an ex of fats and oils into con?uence with a stream of cess of methyl alcohol in the presence of an al lower aliphatic monohydric alcohol in the pres kaline alcoholysis catalyst at a temperature of ence of an alcoholysis catalyst and under turbu about 90° C. to about 130° C. and at a pressure lent conditions, subjecting the mixture ‘to a tem substantially above the vapor pressure of methyl 60 perature above the normal boiling point of said alcohol at the temperature employed, thereby alcohol and at a pressure su?icient to maintain. providing a liquid body containing methyl esters, the alcohol in liquid phase whereby alcoholysis of glycerine and unreacted methyl alcohol; remov fatty material takes place, introducing the reac ing unreacted methyl alcohol therefrom; and re tion mixture into a zone of lower pressure to vola covering methyl esters and glycerine from said 65 tilize unreacted alcohol therefrom and leave a liquid body. residue containing glycerine and alkyl esters, and 12. A process for treating fatty materials which thereafter separately recovering glycerine and al comprises heating a fatty glyceride with an ex cess of ethyl alcohol in the presence of an alkaline kyl esters from said residue. ' 18. The continuous alcoholysis process which alcoholysis catalyst at a temperature of about 90° 70 comprises continuously bringing a stream of fatty C. to about 130° C. and at a pressure substantially material from the class consisting of fats and oils ‘above the vapor pressure of ethyl alcohol at the I into con?uence with a stream of lower aliphatic temperature employed, thereby providing a liquid monohydric alcohol in the presence of an alco body containing ethyl esters, glycerine and unre holysis catalyst and under turbulent conditions. acted ethyl alcohol; removing unreacted ethyl al 75 subjecting the mixture to a temperature above 2,383,579 the normal boiling point of said alcohol and at a pressure sumcient to maintain the alcohol in 7 continuously withdrawing the volatilized alcohol from said zone, continuously withdrawing the res idue from said zone, and separately recovering glycerine and alkyl esters from said withdrawn reaction mixture into a zone of lower pressure to 5 residue. liquid phase whereby alcoholysis of the fatty ma terial takes place, continuously introducing the volatilize unreacted alcohol therefrom and leave HAROLD DWAINE ALLEN. a residue containing glycerine and alkyl esters, WILLIAM ASHLEY KLINE. Certi?cate of Correction Patent No. 2,383,;579 August 28, 1945 HAROLD DWAINE ALLEN ET AL. ' It is hereby certi?ed that error appears in the printed speci?cation of the above numbered patent requiring correction as follows: ‘ Page 5, second column, line 53, for “about 0.3 mol” read about .03 11ml;-v same may conform to the record of the case in the Patent O?ice. Signed and sealed this 6th day of February, A. ‘D. 1951. [we] THOMAS F. MURPHY, Assistant Oommz'ssz'oner of Patents.