2,182,179 RH. POTTS ET AL Dec. 5, 1939. TREATMENT OP GLYCERIN LYBS AND OP CRUDE GLYCERIN Filed Nov. 8, 1937 douwoavax or xr Garopdenrcx ata sexu] xsi cpasen ox 5 Saray Arsiat susox09} SOA fowasnse Jrventors apn CONE, Ralph 7. Po, De extoemeyPatented Dec. 5, 1939 2,182,179 TREATMENT OF GLYCERIN LYES AND OF CRUDE ‘GLYCERIN Ralph H. Potts, La Grange, and Edwin W. Colt, ‘Evanston, Ii, assignors io Armour and Com- any, Chicago, HL, a corporation of Iilinols Application November 8, 1937, Serial No. 173,539 2,182,179 UNITED STATES PATENT OFFICE 20 Claims. ‘This invention relates to the treatment of elycerin-containing materials such as soap lyes, Soap lye crudes, and similar materials, and it comprises processes wherein such glycerin-con- 5 taining materials, prior to the recovery of ely- cetin therefrom, are acidified and then extracted with a solvent for caprylic and eaproie acids, or other organic materials therein, without, how- ever, dissolving the glycerin, in order to remove caprylic and caproic acids and other organic im- purities from the glycerin-containing material before subjecting the material to processes for the recovery of glycerin therefrom. In the manufacture of soap, animal and vegeta~ ble fats, or mixtures thereof, are saponified with solution of an alkali, usually caustic soda, and the soap salted out of the reaction mixture.” The liguid from which the soap has been salted out is commonly referred to as a soap lye. Soap lyes contain all the products of the soap Kettle that are not thrown out by the salt, and, con: sequently, these lyes are aqueous solutions of salt, caustic soda, and glycerin associated with rela” tively stall amounts of impurities. ‘The impur- {ies are mainly sodium salts of iow molecular Weight fatty acids, namely those fatty acids con- taining from 6 to 10 carbon atoms, such as sodium captoate, caprylate and caprate, and sodium salts of low molecular weight hydroxy and similar oxidized acids. ‘These salts are not thrown out of solution when common salt (sodium chlo- Tide) is added to salt out the soap. Other com- plex organic materials may also be present. An average soap ive may contain about, 0.11% of normal aliphatic acids (as sodium salts) having an average molecular weight corresponding to straight-chain aliphatic acids of 10 carbon atoms, and a similar amount of hydroxy or otherwise oxidized acids having an average molecular weight corresponding to about 8 carbon atoms in the molecule. ‘These iyes, however, vary consid- erably in the nature and quantity of impurities, depending upon the kind of fats being saponified. It has been recognized in the art that before giye- 8 erin is recovered from the soap lye the im- purities in the lye should be removed to the high- est possible degree consistent with practical plant operations. ‘Their presence materially affects the yield of glycerin which can be obtained from the lye. Since the average amount of glycerin in 8 soap lye is about 5%, traces of low molecular Weight aliphatic acids materially reduce the amount of glycerin recovered. The quality of the glycerin is also affected by the presence of 10 1s 30 3 0 50 (Cl. 260637) these fatty acids, most of whicn are quite volatile and distil over with the glycerin, ‘Hitherto the glycerin manufacturer has treated soap lyes with chemical reagents to precipitate the soluble fatty acid salts as insoluble salts. 5 Ferric chloride, for example, will form insoluble fron salts of caprylic, eaproie and capric acids. Some of the ferric chloride may also hydrolyze to insoluble ferric hydroxide which may carry down much of the other organic impurities also. 10 This has, of course, necessitated filtration of the lye and ‘the glycerine lost in the press-cake 1s, significant. ‘The thus treated lye is then eval orated to give a crude glycerin, most all of the salt used for salting-out being thrown out of 15 solution at this stage, and the crude glycerin 1s, then distilled to give a distillate of substantially Dure glycerin. In the ferrie ebloride or other Precipitation method, there is a relatively large Press-cake loss of available griyeerin, Much 29 available glycerin is also lost during the distill tion of the crude, ‘We have set ourselves to the problem of de- veloping improved ways of treating soap lyes rior to recovery of the glycerin therefrom, so as 25 to reduce the glycerin loss and to improve the quality of the glycerin, and we have discovered that relatively low molecular weight fatty acids, namely those having from 6 to 10 carbon atoms, either simple aliphatic acids or oxidized forms 30 thereof, existing in the original soap lye as sodium salts, can be extracted from the lye with solvents provided the lye is first acidified to liberate the free fatty acids from thelr salts, The sodium salts of the Ce to Cue fatty actds 35 only amount to about 0.2% to 0.3% of the soap Ive and they are thus soluble in the lye in spite of its high salt concentration, Before we can ex- tract the soap Iye with our solvents, it is neces sary that the Ce to Cio fatty acids ‘be Uberated 49 from their sodium salts. Consequently, we first acidity the soap lye with any sultable acid. Hy- drochloric acid is the best because it forms sodium chloride coincident with the Uberation of free fatty acid. Sulfurle acid, which would form 45 sodium sulfate, can, of course, be used instead of hydrochloric, and'we do not wish to be limited to any particular acid so long as it is one which will displace the aliphatic acids from their sodium salts, ‘This acidification step is advantageously 5y such that the pH of the acidified lye lies between about 3 and 4. ‘The pH value can be decreased below 3 but this requires additional acid which for economic reasons should be avoided. In broad aspects then, our process comprises gg10 18 20 ™ 2 the steps of acldifying soap ye and then extract ing the acidified lye with solvents for the Cs to Cro ‘aolds and other organic impurities present, which Solvents do not dissolve significant amounts of giyeerin. ‘That is our major contribution to the art, Thereafter, we neutralize the acidity of the extracted lye and recover its glycerin content therefrom. ‘The extracted, acidified lye is neu- tralized to avoid any danger of corroding the stills. ‘This step is readily performed by simply adding enough alkall to the acidified extracted Ive until its pH is 6 or higher. Recovery of the glycerin from the treated lye is done in the man- ner usual in this art. ‘In consequence of our discovery we are able to markedly increase the yield of available glycerin. ‘We avoid the press-cake loss which 1s inherent in any type of precipitation process, such as the ferric process method. We are also able to re- cover more glycerin from the evaporated lye, In ‘addition, our process permits us to recover com~ mercial quantities of the valuable low molecular Weight acs, namely, expr, enprote and capric ‘There are many solvents which we can use in our process, All of them should be water- insoluble and have the property of dissolving low molecular weight fatty acids, such as caprylic, faprole and caprie without, however, dissolving any substantial quantity of glycerin. “These sol- Yents include aliphatic solvents, such as ethyl ether, chloroform, trichlorethane and petro~ Jeu ether. Aromatic solvents, such as ben- zene, toluene and xylene can also be used. We have further discovered that one particularly advantageous group of solvents is fatty acids having molecular weights higher than the mo- Yeoular weights of the fatty acid impurities in ‘the acidified lye. ‘Thus, for example, if the acid- ified lye contains mostly caproic acid, extraction of the lye with any fatty acid having a higher molecular welght than caproic will remove the caproio acid and leave an extracted lye substan- tially free of organic acid impurities. If the tye, after acidification contains eaprylic acid as an impurity then any fatty acid having a mo- Jeoular weight higher than caprylic will remove caprylic acid, For most purposes we find it best to use fatty acids having sixteen or more carbon atoms as the extraction agent. These fclds can be palmitic, stearic, oleic end linoleic, or mixtures thereof. "All of these acids are in- Soluble in the acidified lye and are readily avail~ able commercially. But, more broadly, our in- Yention comprises the extraction of the lve with 2 fatty acid, or mixtures thereof, having a mo- Jecular welght higher than that of the acld in the lye. ‘Neutral oils, namely triglycerides, are also insoluble in the acidified lye and can be used instead of the fatty acids. A triglyceride of any fatty acid, or mixtures of fatty acids, will work regardless of the molecular weight of the fatty geld radical, since these are all relatively insol- luble in the acidified lye, and will not dissolve the glycerin therein under the conditions of our process, Since the extraction is in liquid phase fhe extraction liquid or solvent should be one which is normally fluid or can be made so at moderately elevated temperatures. The tem- perature of extraction is not a factor, and we tan operate at temperatures as hish as 180° F. or up to a temperature just below the boiling point of the mixture being treated. Pure stearic Bold, while it can be used as the extraction lig- 2,182,179 ‘uld, would have to be liquefied by the applica- tion of heat, and, of course, the soap lve would have to be treated while hot. For this reason we prefer to use solvents which are normally fluid at room temperature or slightly above. ‘One very advantageous mixture of fatty acid for use as the solvent is that obtained as a frac- tion in the distillation of cottonseed fatty acids. ‘On the average such a fraction will contain about 5% palmitic acid, 55% of linoleic acid and 40% of oleic acid. Ox We can use ordinary oleic acid of commerce, commonly referred to as red oll. For greater convenience in processing op- erations, it is best that the extraction liquid be either a normally liquid fatty acid, such as oleic, or, when normally solid fatty acids are used, they can be first mixed with enough oleic or lin- noleic so that the final mixture is liquid. One of the major advantages of our process is that the extraction liquid can be a common product of the soap works. Fats can be split to liberate free fatty acids, such as mixtures of oleic with palmitic and stearic, and these mixtures can be used as the extraction liguld. If the split fatty acids contain large quantities of normally solid acids they can be fractionally distilled to get a fraction which is normally liquid, or enough of the solid fatty acids can be pressed from the fatty acid mixture so that the mixed acids used for extraction are fluid. However, as stated, we do not intend to be limited to the use of only normally liquid mixtures because mixtures which, may be solid or pasty at, for example, 70° F. may be fluid enougth for use at extraction tem- peratures of 180° F. or higher. ‘With respect to fatty acids as extraction la uids, our invention, however, is not limited to the ‘use of palmitic, stearic, olele and linoleic ‘acids, Caprylic acid will remove caproic acid from the lye and, although eaprylic acid is very ‘slightly soluble in the acidified lye, the amount ‘thereof in the lye will be less than the amount of caproic in the lye prior to extraction, Laurie, myristic, palmitic, stearic and the unsaturated fatty acids are entirely insoluble and these are est for commercial purposes. “Most all of the triglycerides we use are liquid at room temperature or can be made so at mod: erately elevated temperatures. Cottonseed oil is one such triglyceride which works well. ‘Tri- lein, tripalmitin, and like triglycerides or mix- ‘tures thereof are operative. ‘In order that our invention may be more clearly understood, we have, on the appended flow-sheet indicated o suitable apparatus set ‘up for practising our process. ’referring to the drawing, the hot aqueous soap lye is first collected in a storage tank 1. "The average composition of this lye may be about 5% glycerin, 12% salt, 0.2% to 0.4% of a mixture of sodium’ salts of Cs to Cio fatty acids ‘and sodium salts of oxidized fatty acids having approximately this carbon chain length. The ‘hot soap lye is pumped from tank | by pump 2 through line 3 to a filter 4 wherein suspended dirt and other insolubles are removed. Since the amount of material removed is very small there is practically no press-cake loss of glycerin. ‘The filtrate is then passed by line § to @ mixing ‘vessel 6 in which it is mixed with hydrochloric or other suitable acid. Advantageously the amount ‘of acid added can be carefully controlled by means of hydrogen ion control devices not shown, Enough acid is added until the pH of the soap lye is reduced to between 3 and 4 al- 10 30 40 0 %10 6 20 25 ao 60 6 2,182,170 though, as stated above, the acidification can bbe more drastic. It should not be less than suf- ficient to give a pH of about 4.5 to 5 since at higher pH values there is relatively little con- version of these sodium salts of the organic acids to free acids. The acidified lye then passes by line 1 to a storage tank 8 from which it is withdrawn by line 9 and pumped by pump 10 to the upper art of the extraction tower If through line 12. ‘The extraction liquid or solvent maintained in storage tank 18 flows by line 14 to pump 18 by which it is pumped into the lower part of tower {1 through line 16, ‘The extration liquid, advantageously the mix- ture of palmitic, oleic and linole'e acids referred to above, meets the down-coming stream of acid- ified soap lye and the extraction process is thus countercurrent. Since the specific gravity of the fatty aclds is less than that of the acidified soap lye, the fatty acids naturally rise in the tower and collect at the top thereof. The fatty acids which we use are, of course, substantially insoluble in the soap lye. Countereurrent ex- fraction is especially advantageous because of its high efficiency. We can, however, use othe: extraction methods, either batch or multi-stage ‘methods wherein lye extracted in one vessel asses to another and so on through a series of vessels, and extraction fluid passes through the series of vessels in the opposite direction. The extracted lye leaves the bottom of the tower 11 by lines (7 and 19 and passes to a stor- age vessel (9 from which it flows to a centrifuge 20 for the removal of any fine suspended globules of fatty acid extraction fluid, In the centrifuge, hydroxy fatty acids in the original lye also sepa. rate out. We have discovered that although the extraction liquid will effect 100% removal of nor- mal acids, such as caproic, eaprylic and capric, it only removes about 50% to 70% of the oxidized acids. But as the normal fatty acids are removed from the soap lye the solubility of the oxidized acids in the acidified lye decreases, consequent~ ly, any remaining quantities of oxidized acids tend to separate out in the centrifuge. Or we can alternatively filter the lve from storage tank 19 prior to further treatment since filtration at this, stage will remove any remaining traces of oxi- dized acids. ‘The point at which line (8 is set with, respect to the column of liquid in tower {1 deter- mines the position of the fatty acid-lye interface. During the extraction the acidified lye can be the continuous phase and the extracting liquid the discontinuous phase, or the extracting liquid can bbe the continuous phase and the acidified lye the discontinuous phase. By maintaining the in- terface at some intermediate level both methods can be employed. ‘The use of a centrifuge or a filter for the ‘treatment of lye flowing from storage tank 19 is optional and depends entirely on whether the extracted lye coming from the bottom of tower 11 needs the further treatment stated, In any event, the lye from storage tank 19 passes by line 21 to a, mixing vessel 22 wherein it is substantially neu- tralized with any suitable alkali, such as caustic soda, prior to passing to the evaporators for the recovery of glycerin and salt. The amount of alkali added, such as caustic soda, should be enough to raise the pH value to about 6 or 7, or even higher if desired. Advantageously the neu- tralized lye is conducted to a further storage tank 23 from which it passes as required to the evap- 3 orators. The extraction process indicated on the drawing {s continuous, ‘The fatty acld, or triglyceride, extraction fluld with its content of dissolved impurities extracted from the lye leaves the top of the tower by way 5 of discharge outlet 26 to a settling vessel 25. In. this vessel any occluded Iye is given an oppor- tunity to separate out. The extraction liquid then passes by Une 26 to a stripping column 27 which can be of any conventional type wherein the volatile organic acids, such as caprole, ca~ prylic, and capric can be stripped with steam and Vacuum from the extraction liquid. ‘These vola- tile acids are then condensed and collected, and the higher fatty acid extraction liquid {s returned to container 13 for reuse by way of line 2 ‘The above description, together with the draw- ing indicates the principles of our invention. ‘There are many modifications possible. For ex- ample, we can recycle a portion of the contents of separator 25 after it leaves settling device 25 back to the tower by way of line 29, pump 30 and mixer 3f. “Various other recycling features com- mon in the art of extraction generally can, of course, be employed. ‘The amount of extraction fluid necessary is not critical. Ordinarily we use from about 2 to 4 volumes of fatty acid or triglyceride extraction liquid for each 100 volumes of soap lye since this uantity appears to be adequate for all purposes. Our process of treating soap lyes for the re~ moval of impurities prior to distillation enables Us to increase markedly the yleld of glycerin which can be obtained from the soap lye, and we are also able to get a better giyterin distillate with respect to quality. Moreover, we are able to re~ cover from the lye sizeable amounts of eaprole, caprylic and eapric acids which have a market value. Our process is also adaptable to the treatment of soap lye crudes and residues from the distilla- tion of glycerin, “A soap lye erude consists large- ly of glycerin about 80%, salt about 12%, and about 1% of fatty acid salts, such as soditim ca- roate. ‘These crudes are the product of evapo. rating most of the water and removing most of the common salt from the original lye prior to istilling glycerin from the crude. Our process can be used to further purify crudes which have been partially purified by other methods. ‘The crudes are first diluted with an equal quantity of water, then acidified to liberate the free fatty acids, ‘and then extracted as described above for the soap iye. When treating crudes it is better to increase the amount of extraction liquid to about 1.5% based on the volume of diluted crude. ‘In addition to getting a higher yield of good quality slycerin we also are able to recover the valuable Cs to Cwo acids therein. The residues trom the distillation of glycerin commonly contain glycerin that is not recoverable in the presence of large Quantities of salt and organie impurities. ‘These residues contain large quantities of organic im- purities because the impurities in the original Soap lye or soap lye crude tend to concentrate in the residue during distillation of the residue from the crude. If the impurities have been but par- tially removed from a soap lye, and the thus treated soap lye evaporated to get a crude, and the crude then distilled for the recovery of slyc- erin, the residue from the distillation of the giye- erin can be extracted by our invention to effect ‘removal of organic impurities and the thus purl- fied residue again distilled to recover more glyc- erin therefrom. By our process, we can recover 75 10 35 45 50 60 010 6 30 35 40 4 more glycerin of better grade from these residues and in treating these materials we first. dilute them with water, then acidity to berate free fatty acids, and then extract as described above. ‘Since our process can be used for the treat- ment of soap lyes, soap lye crudes, and residues Dur to the distillation thereof for the recovery Bf their glycerin content, we wish to cover all of these materials in the appended clalms. ‘In the above more specific description of our invention we have deseribed the use of fatty acids thd trigiyeerides as the extraction fluid or sol- Gent. Ib is to be understood that our other sol- ‘Yents can be sed in exactly the same manner as we have described above. “Having thus described claim is: L. ‘The process of treating glycerin-containing materials of the class of acidified soap lyes, acidi- fed soap lye crudes and acidified residues prior {fo the recovery of glycerin therefrom which com= prises the step of extracting material of the class Reseribed with @ water-insoluble solvent for or genic impurities therein which solvent does not SSpstantially dissolve glycerin in said material. 2 ‘The process asin claim 1 wherein the acidity of the giycerin-containing material during the extraction is about 3 to 4 expressed in pH units. '3, The process of recovering caprylic and ca- proic acids from glycerin-containing materials Bf the class of soap lyes, soap lye orudes and resi- Ques which comprises acidifying such elycerin= Containing material and then extracting the Seldified material with a water-insoluble solvent for said acids, which solvent does not, substan~ tially dissolve glycerin in. said material. “{eethe process as in claim 3 wherein the sol- vent is a fatty acid having @ molecular weight greater than caproic acid. 'b. The process of treating glycerin-containing materials of the class of acidified soap lyes, Rcldified soap lye crudes and acidified residues prior to the recovery of the glycerin therefrom Tinich comprises the step of extracting material Br the class described with a fatty material Ghosen from the group consisting of water insol- Sle triglycerides and fatty acids having a molec- Uilar weight higher than that of the fatty acids in the acidified material. 6. ‘The process of treating glycerin-containing materials of te class consisting of acidified soap. Ives, acidified soap lye crudes and acidified resi~ dues prior to recovery of glycerin therefrom Which comprises the step of extracting such ma~ Yerlal while at pL of about 3 to 4 with a fatty material chosen from the group consisting of Water insoluble triglycerides and fatty acids hav- jng a molecular weight higher than that of the fatty acids In the acidified material. 7 the process as in claim 5 wherein the fatty material is at least one water insoluble fatty acid. 8. ‘The process as in claim 6 wherein the fatty material is at least one water insoluble fatty acid. 9. ‘The process of treating soap lyes which com prises acidifying the lye until the pH thereof is hot more than about 4 and then extracting the acidified lye with @ fatty material chosen from the group consisting of water insoluble triglyce- ‘our invention, what we 2,189,170 rides and fatty acids having a molecular weight higher than that of the fatty acids in the acldi- fled material. 10, ‘The process of treating soap lyes which ‘comprises acidifying the lye until the pH thereof is not more then about 4 and then extracting the acidified lye with at least one water insoluble fatty acid. Ii, The process of treating soap Iyes which ‘comprises adding hydrochioric acid to the tye un- til the pH thereof is about 3 to 4 and then ex- tracting the acidified lye with a liquid mixture of palmitic, olelc and linoleic acids. 12. In the recovery of glycerin from soap lyes the steps which comprise acidifying the lye, ex- tracting the lye with a fatty material chosen from the group consisting of water insoluble tri- siyeerides and fatty aclds having a molecular Weight higher than that of fatty acids in the acidified material, neutralizing the acidified ex- tracted soap Wve and recovering ‘lyeerin there- (rom. 13. In the recovery of glycerin from soap lyes the steps which comprise acidifying the lye to a pi of about 3 to 4, extracting the lye with a fatty ‘material chosen from the group consisting of wa~ ter insoluble triglycerides and fatty acids having a molecular weight higher than thet of fatty acids in the acidified material, neutralizing the acidified extracted lye and recovering glycerin therefrom. 14. In the recovery of glycerin from soap lyes the steps which comprise acidifying the soap Ive with hydrochloric acid, extracting the acidified lye with a fatty material chosen from the group consisting of water insoluble triglycerides and fatty acids having a molecular weight higher than that of fatty acids in the acidified material, neutratizing the acidified extracted lye and re~ covering glycerin therefrom. 15. In the recovery of glycerin from soap lyes the steps which comprise acidifying the lye with hydrochloric acid until the pH of the lye is about 3 to 4, extracting the acidified lye with a fatty material chosen from the group consisting of w ter insoluble triglycerides and fatty acids having @ molecular weight higher than thet of fatty acids in the acidified material, neutralizing the ‘acidified extracted lye and recovering glycerin therefrom. 16, The process as in tatty material comprises soluble fatty acid. YI, ‘The process as in fatty material comprises soluble fatty acid. 18, The process as in fatty material comprises soluble fatty acid. 19. The process as in fatty material comprises soluble fatty acid. ‘20. ‘The process as in claim 12 wherein the fatty material comprises a Wuid mixture of palmitic, oleic and linolele acids. claim 12 wherein the fat least one water in- claim 13 wherein the at least one water in- claim 14 wherein the at least one water in- claim 15 wherein the at least one water in- RALPH H. POTTS. EDWIN W. COLT. 25 30 35 “0 50 65 oo 6