Патент USA US2412113код для вставки
2,412,113 Patented Dec. 3, 1946 UNITED‘ STATES PATENT o1=1=1cs 2,412,113 , . PURIFYING vOF ALKYLOLAMIDES Harland‘ H. Young, Chicago, 111., and David Rubinstein, Brooklinc, Mass., assignors to In dustrial ‘Patents Corporation, Chicago, 111., a corporation of Delaware No Drawing. Application April 14, 1943, ‘Serial No. 483,062 4 Claims. 1 I V ' (Cl. 260-404) 2 , This invention relates tothe purifying of Val kylolamides and more particularly to the removal . . , . soluble precipitates or, foots separable from the mixture in any desired manner such as settling, ?ltration, or centrifugal separation. By treat ing the reaction mixture with the acidic material kylolamides including mixtures resulting from reacting fatty or other organic acids oresters 5 in the presence of a small amount of‘ water the of such acids with alkylolamines in order to proneutralization reaction is facilitated and. other materials such as the glycerol or other alcohol duce alkylolamides. Esters of fatty or other orof basic substances from mixtures containing al ganic ' acids with glycerol or with other m'onohydroxy, dihydroxy or trihydroxy alcohols will react with alkylolamines to produce reaction 10 which may be present in the mixture are usually removed as part of the foots. . It is, therefore, the object of the present in-. mixtures in which a large number of compounds exist in‘ equilibrium. This reaction,‘ if carried vention to remove basic and other impurities from mixtures containing alkylolamides so as olamine on in theand presence under of carefully an excess controlled of the condialkyl- to Another produce puri?ed object of alkylolamides. the inventionxis ' to . provide - 1: tions can be made to consist predominantly of 15 a process by which basic impurities are removed from crude alkylolamides as an insoluble precipi alkylolamides of the acids. Similarly, reaction mixtures can be produced by reacting the acids tate. - 1 Another object of the invention is to provide themselves with alkylolamines. Thus by reacting alkylolamines with fatty acids an equilibrium a process of purifying alkylolamides containing mixture is produced containing the fatty acids, 20 basic impurities by the employment of‘ acidic the alkylolamine, alkylolamine- soaps, alkylolmaterials forming insoluble precipitates or foots. amine esters, alkylolamides and alkylolamide Another object of the invention is to provide a process of purifying alkylolamides of fatty acids esters. If the reaction is carried on between an alkylolamine and esters of fatty acids, the reacin which strong mineral acids or compounds of tion mixture may also contain the ester as well 25 such acids with weak bases are employed to form insoluble precipitates with basic reacting impuri as the alcohol of the ester. Other by-products of unknown structure may exist but such by- ties.‘ .. ‘ _ ; I . products are in general basic in reaction because A further object of the invention is to provide _ a process of purifying alkylolamides of fatty of free nitrogen functions. The present invention is directed to removing 30 acids containing basic impurities in which the the basic impurities in such mixtures and is paralkylolamides are dissolved in an inert solvent ticularly applicable to reaction products between and the impurities are neutralized to form com glycerides of higher fatty acids such as vegetable pounds insoluble in the solvent. _ ' or animal oils and either mono-alkylolamines or A still further object of the invention is to dialkylolamines. By reacting the glyceride with 35 provide a process of purifying alkylolamides 0011 an alkylolamine in the presence of an excess of taining basic impurities in ‘which a solidvacid the alkylolamine a reaction’ mixture consisting reaction material is employed to remove such predominantly of alkylolamides of the higher fatty acids can be produced which alkylolamides impurities ' I . ’ ' 7 The preferred practice of the present invention exist in equilibrium with . alkylolamine, glycer- 40 includes the addition of a strong mineral acid in ides, glycerol, alkylolamine soaps and alkylol- ‘a small quantity of water to the reaction prod amine esters as well as alkylolamide esters. nets of an alkylolamine and a glycerol ester of If the reaction is with a dialkylolamine‘ there are‘ higher fatty acids which reaction products con-1 also other possible reaction products such as the tain basic impurities such as the alkylolamine, dialkylolamine monoacid ester and the dialkyl- 45 alkylolamine esters, alkylolamine ‘soaps, etc. Sufficient acid is preferably added and thor olamide monoacid ester. The basic reacting materials, among Which arealkylolamine soaps, oughly admixed with the reaction products to excess alkylolamine and alkylolamine esters neutralize all of the basic impurities. A precipi cause the reaction products to develop off ?avors tate forms which is insoluble in the alkyolamides and odors which deleteriously affect the mixtures 50 or any glycerol esters or alkylolamide esters for use in edible and other products” It has been which are present. This precipitate in most' found that substantially all of the materials cases readily settles and can be removed by de.-. causing such deleterious flavors, or odors, can canting the alkylolamides or by ?ltration or’cen be removed from the mixture by neutralization trifugal separation. This precipitate is generallyv with an acidic material which willproduce in-, 55 ?occulent and resembles, the foots.._obtained. in 2,412,113 3 the re?ning of ordinary vegetable and animal 4 re?ning agent. Many other acid reacting mate rials such as lower fatty acids neutralize the fats or oils. If the alkylolamide is to be incorpo alkaline impurities in the reaction mixtures above rated in glyceride oils, which is many times the referred to but yield compounds which retain case, the crude alkylolamide may be added to the glyceride oil prior to re?ning in accordance with (a their solubility in the mixture, which compounds cannot be easily removed from the mixture. The the present. invention. Thus the glyceride oil invention, therefore, is concerned with the em or fat functions as a solvent for the alkylolamide ployment of acids or acidic materials which form during the re?ning operation and assists in sep arating the precipitate from the alkylolamides as ~ insoluble precipitates with the basic impurities, this precipitate is also insoluble in the glyceride 10 mineral acids or their salts with weak bases being the preferred acidic material, but any acid react oil. Any alkylolamide esters present are also re ' ing-material either organic or inorganic which is tained in the glyceride oil and‘are not objection sufficiently acid'to neutralize the basic materials able. The temperature of re?ning will vary with and which produces insoluble foots which may be different alkylolamides depending upon the al removed from the reaction mixture may be em kylolamine employed or the fatty acids present ployedin the present invention. Materials other in the alkylolamide and upon the nature of the than strong acids which are contemplated for use glyceride oil solvent, if one is employed. In gen in the invention include sodium dihydrogen phos eral the temperature should be suiiiciently high to render ?uid the crude reaction mixture or phate, sodium acid sulphate, potassium acid tar the glyceride oil in which it is incorporated. 20 trate and aluminum sulphate. Other salts of like nature ,andedible could also be used. Thus, when re?ning alkylolamides or alkylol While the invention has been speci?cally de amides admixed with glyceride oils containing scribed with respect to reaction mixtures pro substantially saturated fatty acid radicals, such duced by reacting an alkylolamine with a. glycerol materials should be'heated to a temperature sui’?ciently’ above the melting point to render 25 ester of higher fatty acids, it is also applicable to re?ning of reaction mixtures of alkylolamines them ?uid prior to the re?ning operation. Thus with the fatty acids themselves, with esters other the temperatures employed may range between than the glycerol esters of fatty acids, acid an approximately 70° F. and 180° F. although in - hydrides, acid chlorides, or other acylating agents some cases higher temperatures may be desir able. 30 all of which acylating agents are included in the term lypophyllic acylating agents. In general it The preferred reagent is phosphoric acid in a is desired to remove all of the materials in the concentration‘between approximately 50% and reaction mixture which have a, free nitrogen 90%, as such phosphoric acid also makes it pos function which includes any alkylolamine present sible to selectively remove the impurities. Thus, or the alkylolamine esters. Any alkylolamine the alkylolamine phosphate is somewhat more soaps are also decomposed to liberate the amine insoluble than the alkylolamine ester phosphate so thatthe amine portion of such compounds and. can be selectively precipitated to remove it may likewise be removed from the mixture. Also, from either the alkylolamide alone or from the, alkylolamide dissolved in a glyceride oil or other glyceride oils or fats have‘been described as a ester of a. higher fatty acid. By adding just 40 solvent for the reaction material during the re?n ing operation. It will be apparent that any inert slightly more phosphoric acid solution than that solvent for the alkylolamides being treated may necessary to react with the alkylolamine, this be employed.‘ The foots produced by the re?ning material can be substantially completely removed operation may be removed from such admixtures from the mixture after which additional phos phoric acid solution can be added to precipitate 45 by ?ltration, decantation or centrifugal separa tion and other impurities such as coloring matter, the alkylolamine ester phosphate. Other strong mineral acids such as sulfuric and hydrochloric acids in substantially the same concentration referred to above can, however, be employed to remove the basic impurities from the ialkylol amides. ' Other acid reacting materials "may. also be em ployed to remove basic impurities. For example, various salts of strong acids such as sulfuric, hy drochloric, and phosphoric with weak bases in r the form of granular salts can be employed as ?lters through whichthe crude alkylolamide mix ture is passed. The admixture of a small amount of moisture or Water with the crude. alkylolamide etc., are to a large extent removed with the foots by adsorption thereon. While we have described the preferred embodi ments of our invention, it is understood that the details thereof may be varied within the scope of the following claims. We claim: 1. The method of purifying alkylolamides asso ciated with other reaction products formed in reacting alkylolamines with fatty acids and their esters and containing alkylolamides, and other basic substances of bitter ?avor, which comprises treating thecrude alkylolamides with‘ an aqueous mixture facilitates the removal ofthe basic im 60 solution of a mineral acid material in a glyceride solvent for said alkylolamides and alkylolamine purities. 'It ~is-also possible to suspend such acid‘ esters to neutralize said basic substances and to reacting salts by agitation in the crude mixture ‘or-crude mixture combined with a solvent, and allow the same to settle. Such operation causes precipitate the same as insoluble compounds, the basic ingredients of the crude mixture to react with the salts andinsolu-ble products formed thereby to be removed from the mixture. The dampening of the granular vsalt with a small amount of water prior to admixing the same with highduring the treatment to render'the solution of .alkylolamides in a liquid condition and there after separating said compounds from the puri?ed while maintaining the temperature su?icien-tly alkylolamides. ' 2. The method of purifying crude alkylolamides the mixture to be re?ned or the addition of a of higher f-at-tyacidsformed by reacting an excess ‘ small .amount ‘of Water to the ‘mixture during re?ning ‘with the granular material assists in the reaction with'the basic materials. It is apparent that concentrated solutions or .s'lurri'es of such acid reactingsalts may also be employed as ya 75 of ' alkylolamines with higher‘ fatty acids and glycerides thereof, said crude alkylolamides con taining alkylolamides, and other side reaction products of a basic nature and having a bitter ‘ ?avor, which’ comprises contacting a solution of 2,412,113 5 . 6 said crude alkylolamides in a glyceride oil with 3. The method according to claim 2 in which an aqueous solution of a neutralizing agent conthe neutralizing agent is aqueous phosphoric acid taming a mineral acid to convert said basic subof about 50% ‘to 90% concentration. stances into insoluble salts, supplying su?icient ‘i. The method according to claim 2 in which heat during the operation to keep the solution of 5 the glyceride oil is triglyceride fat. alkylolamides in a liquid condition and then sepa rating said insoluble salts from the solution of HARLAND H. YOUNG. puri?ed alkylolamides. DAVID RUBINSTEIN.