2,024,683 GELATN PRODUCT AND METHOD OF AKING SAME Chester E. Epstein, Highland Park, and Nathan R. Gotthoffer, Grayslake, ill assignors to Grayslake Gelatin Co., Grayslake, it a corpo ration No Drawing. Application Iay 5, 1932, Serial No. 609,49. 6 Claims. (C. 99-) This invention relates to a gelatin product and simply by tinning the flow of a gelatin solution the process of manufacturing the same. It has through a tube containing a small orifice, the for its object the production of a very high qual gelatin solution being kept at a definite concen ity gelatin possessing the desirable character tration and temperature. The particular tube istics of exceptional purity and freedom from employed is first calibrated so that the seconds Odor, high gelatinizing value and high viscosity. of flow can readily be converted to the standard As a further object it effects the formation of millipoise units. an edible gelatin product by a process employing Other characteristics of a good quality gelatin Only edible materials. product are as follows: It should dissolve readily It may be well first to consider the character in hot water and when immersed in cold water 0 istics of a gelatin product which determines its should soak up very rapidly and also should ab duality. In the first place purity of the product sorb a large quantity of the cold water. This is essential, and this is determined in large meas “Water absorption power' may be readily meas lure by the appearance and odor of the product ured by simply adding a weighed quantity of gela 5 in Solution and also by its ash content. A good tin to a definite volume of water at a constant 5 gelatin product should be sparkling clear in solu temperature and noting the amount of Water tion, should have a pale amber, color, should be soaked up after an established time of contact free from all objectionable odor and its ash con between the Water and the gelatin. s tent should be at a minimum value. Still another feature of a good quality gelatin 20 Another qualitative feature of gelatin is its product is its ability to whip up or beat up rapidly 20 gelatinizing value or gel strength. This is deter and yield a stable foam, that is, one which will mined by various mechanisms practically all of not break down quickly. Finally a good quality which operate on the same principle. Samples gelatin should have excellent emulsifying qual of the gelatin to be tested are dissolved under ities as determined by practical tests. 25 Standard conditions and at a definite concentra The invention of the digestor by Papin in 1682 25 tion after which they are kept at 50° E. for a marked the beginning of the preparation of gela period of sixteen hours. A plunger is then ad tin on a commercial scale. Papin's digestor con justed to the Surface of the jelly and the weight sisted simply of a contrivance for cooking bones required to depress this plunger a given distance With steam. The next step in the evolution of tarugh the jelly is determined and recorded as gelatin production was the discovery made in the 30 the jelly strength of the gelatin. Gelatins hav early eighteenth century that if the bones were ing higher gelatinizing values will for stiffer treated with inorganic acid prior to cooking with jellies and thus offer greater resistance to the the steam the gelatin could be much more read plunger So that more weight will be required to depress the plunger the fixed distance and higher ily extracted from them and, indeed, the product obtained would be of a higher quality than re- 35 values accordingly-obtained. his factor of gelatinizing value is of the ut sulted when this inorganic acid treatment was not employed. For this purpose, hydrochloric most importance in practically all the applica- . . acid was commonly used. v ions of gelatin and is a direct measure of the All of these early processes employed bones aS value of the gelatin to the consumer. Thus in a gelatia dessert product, for example, a gelatin the raw material source for the gelatin. Today 40 practically all of the gelatin commercially pro of high gelatinizing value will replace a corre duced is prepared from three classes of raw ma Sporadingly greater quantity of a lower test gela terials, namely: bones, calf-skins and pig-skins. is a So that a lesse' amount of the higher test While there is a great diversification of processes 23'ciuct caxa be employed. in like manner a high viscosity is a desirable ences betweenthese for treating them materials, the essential differ- 4 lie chiefly in details of op feature is a gelati product because a gelatin eration and in Enethods of handling. Practically of high viscosity will set to a jelly faster than all of the processes call for acidulation of the raw a product of like strength but lower viscosity, material at some point during the manufacture when the two products are prepared in identical and prior to the extraction of the gelatin. The 50 manner. A higher viscosity will also in part conditioned raw material is then treated with hot more body to a gelatin solution which is desira Water or steam to extract the gelatin and the ble in many of the applications to which gelatin gelatin Solution thus obtained is clarified and is put. The viscosity is measured in any of the dried by various methods. standard type viscosimeters Or may be dietermined Bones are generally degreased with organics 2 2,024,683 solvents and the mineral matter is then removed namely to the class of compounds comprising the by treatment with acid, yielding a product called Organic acids, and in one particular embodiment ossein, which is employed to a great extent for of this invention, to the edible organic acids, such the manufacture of gelatin, This material is as, for example, tartaric acid or citric acid, treated with a lime Solution Over an extended We have found that when tartaric acid, for is period to Soften the material and dissolve out example, is used as the sole acidulating agent in the mucins and foreign proteins after which it is the treatment of pigskins, the final gelatin, ex washed free of lime, acid being employed in the tracted is of a very high quality, possessing, among other advantages, a high gelatinizing value "...later stages of the deliming process. O Calfskins, as commonly used by the gelatin and Superior viscosity. We have also observed manufacturer, are the trimmings from tanner's that the products obtained by this new method have a distinct advantage over the older products stocks and are first limed for a period of from six to twelve Weeks. After the Skins have been in that they are comparatively free from odor. thoroughly limed they are Washed free of the Another particular consideration in connection 5 lime and in this step inorganic acid is employed, with the production of gelatin from pigskins acidulated by tartaric acid is that such a process hydrochloric and phosphoric acids being usually used for gelatin manufacture and Sulphurous comprises the manufacture of an edible gelatin acid where glue is the desired end product. product by a method employing.only edible mate It is with the third class of raw materials, rials. namely pigskins, that this invention more A possible explanation for the benefits derived 20 particularly, but by no means exclusively, deals. from the employment of these organic acids may The pigskins employed by the edible gelatin be found in the fact that they are very poorly manufacturer reach the plant in a fresh frozen ionized in comparison with the inorganic acids state, are an edible product, and bear the stamp commonly employed. When, for example, sul 25 of the U. S. Department of Agriculture-Bureau phuric acid is used as the acidulating agent the 25 l of Animal Industry. The method of procedure pH value of the dilute acid solution employed with these skins is somewhat different from the for the purpose may reach a value in the neigh processes described above, which are employed borhood of 1.0. On the other hand, when tartaric with bones and calfskins. The frozen pigskins acid is utilized in the requisite amounts the pH value of the solution is considerably higher, being 30 are washed with cold water in large vats to re in the neighborhood of 2.4. There is no doubt move any surface dirt and to thaw out the solidly but that the exposure of the skins to the lower frozen bundles. During the later stages of the washing period a dilute inorganic acid solution pH value obtained with the inorganic acids com may be employed which is absorbed by the skins monly employed, even though only for a short and which can be controlled to any desired end time, does effect some damage to these skins and is consequently to the quality of the gelatin product point. The acid serves to facilitate the subse ultimately obtained therefrom. When the poorly quent extraction of the gelatin from the skins, on ionized organic acids, such as tartaric acid, are treatment with hot water, and plays a very im employed with their resulting higher pH value in portant part in the quality and quantity of the Solution, this deleterious effect is minimized and 40 40 gelatin obtained. consequently a higher grade gelatin product re Gelatin, as such, does not exist in the animal Sults. skin but is obtained by hydrolysis of the protein It will be apparent that many possible varia collagen. This hydrolysis, which is accomplished in practice by cooking the washed skins with hot tions of this process can be employed, ail of t water, is by no means a simple process but is which, however, come within the scope of our is invention, in manufacturing a gelatin product v accompanied by complex reactions involving a by secondary hydrolysis of the gelatin obtained to areaemployed process in which one or more organic acids as acidulating agents. Thus, par various peptones and amino acids which have no. tial benefits can gelatinizing value and are therefore worthless in or more organic be derived from the use of one 50 connection with the various uses to which gelatin or more inorganic acids,inand acids combination with one 50 is put. The extent of this secondary conversion combination as coming withinWethe consider such a scope of our can, of course, be gauged by the quality of the invention. In another variation, one or more resulting product as determined by the various inorganic acids may be employed in combination tests for gelatinizing value, viscosity, water ab with one or more salts of organic acids, thus 55 55 Sorption power, emulsifying action, beating Or Serving to form the organic acids in affect. It whipping qualities, etc., as described above. It is also possible to use organic acids and organic' has been found that by careful control of the salts in combination, the salts acting as buffer amount of acid absorbed by the skins one can salts, and Serving further to depress the ioniza reach a point where the hydrolysis of collagen to tion of the organic acid or acids employed. How- 80 gelatin takes place very rapidly while at the same ever, this particular procedure cannot be car time the secondary, undesirable hydrolysis of ried too far, as we have found that when the gelatin to peptones is kept at or near a minimum, pH value of the acidulating solution becomes too thus yielding a gelatin product of very high high, the raw material will not take up the acid . quality. readily so that some of the benefits of the process 65 It is to this very important step of acidulation that Our invention directly relates. We have are sacrificed. All of these variations, and in found that not only is the amount of acid emi fact any other combinations involving organic ployed of vast importance but also that the char acids or a mixture of substances resulting in the acter or nature of the acid used exerts a very formation of organic acids, we consider as com 70 important influence in determining the quality ing within the scope of this invention. Thus 70 of the resultant gelatin product. In place of the various inorganic salts may also be employed or acids commonly employed for acidulation, Suchi combinations of inorganic acids and inorganic as sulphuric, phosphoric and hydrochloric acids, salts with organic acids and Organic salts. we resort to an entirely different class of con We do not further limit ourselves to any par. 5 pounds for accomplishing the desired acidulation, ticular procedure or concentration in connection is 2,024,683 3 with the addition of the organic acid. It may citric acids, in conjunction with one or more inorganic acids, then hydrolyzing. be added all at one time or in two or more astages at different times. When employed in 9. In a method of manufacturing gelatin the conjunction with an inorganic acid, the organic step which consists in acidulating the gelatin acid may be added at the same time as the in yielding raw material with one or more inorganic 5 Organic acid or it may be added at an earlier acids in conjunction with one or more organic or later stage of process as desired. All of these salts of the group of organic acids consisting differences are regarded as merely variations in of 10. tartaric and citric acids, then hydrolyzing. As a new composition, a gelatin derivative details of procedure and as essentially coming 0. within the scope of our invention. of an organic acid of the group consisting of 10 What we claim as new and desire to secure. by tartaric and citric acids, resulting from the hy United States Letters Patent is: drolysis of collagen in the presence of said acid. 1. In a method of manufacturing gelatin from li. As a new composition, a gelatin citrate pigskins the step which consists in acidulating complex resulting from the hydrolysis of collagen 5 the pigskins with citric acid. in the presence of citric acid. s 2. In a method of manufacturing gelatin from 12. As a new composition, a gelatin tartrate pigskins the step which consists in acidulating complex resulting from the hydrolysis of collagen the pigskins with tartaric acid. in the presence of tartaric acid, then hydrolyzing. 3. As a new composition, a gelatin citrate 13. In a method of manufacturing gelatin from corplex resulting from the hydrolysis of the pigskins the step which consistS in acidulating 20 coliagen of pigskins in the presence of citric acid. the pigskins with one or more organic acids of 4. As a new composition, a gelatin tartiate the group consisting of tartaric and citric acids, complex resulting from the hydrolysis of the then hydrolyzing. collagen of pigskins in the presence of tartaric 14. In a method of manufacturing gelatin from acid. pigskins the step which consists in acidulating 25 5. In a method of manufacturing gelatin the the pigskins with one or more organic acids of step which consists in acidulating the gelatin the group consisting of tartaric and citric acids yielding raw material with one or more organic in conjunction with one or more inorganic acids, acids of the group consisting of tartaric and then hydrolyzing. citric acids, then hydrolyzing. 15. In a method of manufacturing gelatin from 30 6. In a method of manufacturing gelatin the pigskins the step which consists in acidulating step which consists in acidulating the gelatin the pigskins with one or more inorganic acids . yielding raw material with citric acid, then hy in conjunction with One or more organic salts . drolyzing. of the group of organic acids consisting of tar- . 7. In a method of manufacturing gelatin the taric and citric acids, then hydrolyzing. 35 step which consists in acidulating the gelatin of 16. As a new composition, a gelatin derivative an organic acid of the group consisting of tar yielding raw material with tartaric acid, then hydrolyzing. taric and citric acids, resulting from the hy 8. In a method of manufacturing gelatin the drolysis of the collagen of pigskins in the pres 0. step which consists in acidulating the gelatin ence of said acid. yielding raw material with one or more organic CBESTER. H. EPSEN. acids of the group consisting of tartaric and NATHAN. R. GOTTE OFFER
H. R. Bolliger, M. Brenner, H. Gänshirt, Helmut K. Mangold, H. Seiler, Egon Stahl, D. Waldi Auth., Egon Stahl Eds. Thin-Layer Chromatography A Laboratory Handbook