Patented Apr. 18, 1939 UNITED STATES 2,154,452 PATENT OFFICE PABA ASE METHOD OF CONTROLLING THE PLASTIC- ITY OF HYDROGENATED GLYCERIDE on Leslie G. Jenness, Brooklyn, N. ¥., aasienor to jewark, Intermetal Corporation, Ni ‘No Drawing. 10 Claims, ‘This invention relates to a method of control ling the plasticity of semi-solid fats produced ‘by hydrogenating glyceride ols and the product resulting therefrom, and more particularly to a ‘5 method of controling the plasticity of semi-solid {fats prepared from glyceride oils containing sub- stantial quantities of acid radicals of other than nd the resulting product. ple of lls containing substantial 10 Guantities of other than Cis acid radicals, the fish ‘lls of commerce are made up of a mixture of slycerides having Cie, Cxo and Cza acid radicals with a small amount of Cu radicals, in which the Cx and Cx aeld radicals are present in substan- 16 tial amounts, ‘These fish olls also contain large quantities of higher unsaturates, such as acid radleals with three, four and five double bonds, and probably radicals containing triple bonds are resent. ‘Th my copending application, Serial No, 44,635, filed October 11, 1935, T have disclosed how such higher unsaturates of giyceride olls ean be elim- inated and mixed glyceride molecules formed in the liquid oll, in order to form a stable quid gg oll, and T have further disclosed how, after such pretreatment, the liquid oll can be converted into a highly stable semi-solid fat by a further hy- Grogenation, ‘This pretreatment largely deter- mines the stability of the semi-solid fat as the 30 final stability of the fat depends upon the sta~ bility of the pretreated liquid oil and the extent to which acld radicals having more than one dou- ble bond remain in the fat. In general, a more stable semi-solid fat can be produced by pre- gg treatment of the liquid oll if the stability of the Hquid elyceride oll can be improved by the pre- treating operation. For shortening purposes, semi-solid fats must have sultable plasticity; that is, the congeal point 49 and the Wiley melting point must differ consid erably, so that the fat assumes a plastic condl- tlon between the temperature at which the fat congeals and the temperature at which the fat melts. ‘The plasticity of semi-solid fats produced 4s from olls which are almost entirely composed of slycerides having Cis acid radicals, such as the vegetable olls of commerce, can be controlled by the nature of the hydrogenation following the pretreatment operation. By lowering the tem- perature of hydrogenation and increasing the rate of hydrogenation in the final hydrogenation of such olls, the congeal point and the Wiley melt- ing point may be made to diverge, and a semi- solid fat of desired plasticity produced. In gen- eral, the lower the temperature of the final hy- NT & Cor Application April 11, 1986, ‘Serial No, 73,934 (cu 99—118) drogenation and the faster the rate, the greater ‘will be the plasticity of the semi-solid fat and ‘the stabillty will not be measurably decreased unless the temperature is decreased and the rate of hydrogenation increased to such an extent ‘that Telatively large quantities of acid radicals hhaving two double bonds remain in the oll. Also such low temperatures and high rate of hydro- genation may produce a product having too much plasticlty. In accordance with this invention, highly stable fats having desirable plasticity can be produced. ‘The plasticity of the Cue glyceride oils may also bbe Increased by. discontinuing the final hydro- genation before fat of the hardness desired 1s obtained and then adding » small. percentage of vegetable oll stearin, or by adding vegetable stearin before hydrogenation, and then bringing the fat down to the desired consistency. By the latter procedure, the temperature of hydrogena- tlon and the rate of hydrogenation may be main tained sufficiently high in the final hydrogena~ tion to reduce the acid radicals having two dou- le bonds to a desired minimum in order to ob- tain stability and still produce a product of the required plasticity. ‘However, with oils containing mixtures of Cus, Cw and Cx acid radicals in which the radicals of higher molecular weight are substantially all unsaturated, nelther of these procedures mate- rlally affect’ tho plasticity of the semi-solid fat. T have discovered that in hydrogenating such lis solid fats having the same number of car- bon atoms in thelr acld radicals as the radicals, of the unsaturated components of the oils being hydrogenated, must be added to the process elther before or after hydrogenation in order to inerease the plasticity of the resulting semi-solid fat. For example, in the case of fish of! which, contains unsaturated Ci and Cz acid radicals fn substantial proportions, as well es Cis acid radicals, a solid fat containing Cz» or Cz, or at east one of these radicals, in substantial quan- tity, must be added. ‘As stated above, this solld fat may be added at any time during the process and within the range of fat hardness suitable for shortening ‘purposes, the result is substantially the same whether the solid fat Is added before pretreat~ ment, after final hydrogenation, or at an inter- mediate stage. If added before or during hy- Grogenation, the fat is brought down to the de- sired consistency by the final hydrogenation, or it added after the final hydrogenation, this final hydrogenation Is merely carried far enough so x 20 3 5010 6 20 38 40 4s 2 that the addition of the solid fat will produce the desired consistency. A convenient source of solid fats having the desired acld radicals is the fat resulting from the*substantially complete hydrogenation of the oll being treated. Thus, in ‘order to control plasticity of hydrogenated fish olf, or mixtures of fish and vegetable oils, sub- stantially completely hydrogenated fish oil may bbe added. ‘As a specific example of the practice of the present invention, an oil blend containing 70 parts of whole fish ofl, 22 parts of soya bean ofl and 8 parts of coconut oll, after being pretreated at 820° F. in accordance with the process of my above-mentioned copending application, was hy- Grogenated at a temperature of 260° F., also in accordance with the process disclose in my sald copending application, to an fodine number of 125 where it showed a Wiley melting point of 32.5 C., and a congeal point of 25° C., or a dif- ference of 7.5* C. ‘These congeal and melting points are, how- ever, too close together to produce the required plasticity. The blended oils were used in order to show the effect of even a reduced amount of Cie and Cz: acid radicals and, furthermore, 0o- conut ofl is known to be favorable to increase plasticity. Even under these favorable condi- tions in which the amount of Cio and Cm acid radieals had been reduced and coconut of! em- ployed, and an extremely low temperature of hydrogenation used, still the resultant semi-solid fat was not sufficiently plastic. ‘To this semi-solid fat, 2% of solid fat, prepared by substantially completely rydrogenating fish oil to the saturated state, was added. ‘The re- sultant, product possessed an fodine number of ‘10, @ Wiley melting point of 37° C., and a con~ geal point of 27° C., or a difference of 10°C. ‘The plasticity of this ‘product was entirely in line ‘with commerelal shortenings having satisfactory plasticity. ‘As another specific example, a blended oi! having the same proportions of Ash oll, soya, bean ofl and coconut oll was hydrogenated un- der the same conditions but two parts of com- pletely hardened fish oll was added before hydro- genatlon. ‘The resulting characteristics were al~ most identical, at todine numbers of 70 and 72, with those of the former example to which hard- ened fish oll had been added after hydrogenation, Further hydrogenation caused a higher congeal point in the presence of the hardened fish oil than occurred when the oll was hydrogenated to the corresponding point before adding the hard- ened fat. ‘The reasons why the addition-of solid fat hav- ing aeld radicals with the same number of car- ‘bon atoms as the oil being hydrogenated {s nec essary to improve plasticity, are probably as fol- lows. T have found that in oils containing mixtures of glycerides having acid radicals of different ‘numbers of carhon atoms, the hydrogenation un~ der conditions favorable to producing increased plasticity is selective as to the radicals contain- ing the lowest number of carbon atoms, ‘Thus, in fish olls, the Cis and Cus acid radicals hydro- genate in preference to the acid radicals of high molecular weight, such as the Cz and Cz. acid radicals, In a semi-solid fat produced from fish oil or biends containing substantial amounts of Cxe and Cz2 acid radicals, the solid phase is com- posed largely of glycerides having Cx and Cis acid radicals, and the liquid phase is composed, 2,154,453 largely of glycerides containing Cx and Cn acid radicals. It is probable that a divergence of the ‘Wiley melting point and the congeal point Is ‘caused by @ solution of saturated fats in the un- saturated liquid olls, and that solid fats of a given molecular weight are more soluble in liquid oils of the same molecular welght. ‘Thus, adding 2 Cis solid fat to a semi-solid fat containing Co and Czz liquid oils does not substantially increase the solution of solid fats in the liquid oll. How- ever, when Cao and Cn solid fats are added, these readily dissolve in the Cup and Cas liquid olls and the plasticity of the semi-solid fat increases due to the divergence of the Wiley melting point and ‘congeal point caused thereby. ‘Thus, it is neces- sary to add a solid fat containing acid radicals, of the same number of carbon atoms as that of ‘the liquid phase of the ofl. In the claims, the expression “incorporating with said semi-solid fat”, is employed to cover and embrace adding the ‘solid fat either before or after hydrogenation or at an intermediate stage of the hydrogenation. While I have disclosed the preferred embodi- ments of my invention, and have given a theory of operation, it is understood that the present in= vention is not to be-limited to any precise theory of operation, nor it 1s to be limited to fish oils, or the details of the present disclosure, but may be varied within the scope of the following claims. T claim as my invention: 1, The method of controlling the plasticity of a hydrogenated semi-solid fat prepared from flyeeride oils including substantial quantities of Cie acld radicals and substantial quantities of other than Cis acid radicals, which comprises adding to sald fat a substantially completely saturated solid fat containing substantial quan- tities of acid radicals having the same number of carbon atoms as the acid radicals of the oll being hydrogenated which have the greater num~ ber of carbon atoms. 2. The method of controlling the plasticity of fa semi-solid fat prepared by partially hydro- genating ols containing fish olls and having sub- stantial amounts of acid radicals having difter- ‘ent numbers of carbon atoms therein, which com- prises incorporating with said semi-solid fat a Substantially completely hydrogenated fish oil containing substantial quantities of acid radicals having the same number of carbon atoms as the acid radicals of the partially hydrogenated oil which have the greater number of carbon atoms. 3. ‘The method of controlling the plasticity of a semi-solid fat prepared by hydrogenating giyceride oils containing substantial quantities of Cw and Ci acid radicals and other acid radicals, substantially all of which contain less than 20 carbon atoms, which comprises incorporating witir sald semi-solid fat a substantially com- pletely saturated solid fat containing substantial ‘quantities of saturated Cz» and Cz acid radicals 4, The method of-increasing the plasticity of a semi-solid fat prepared by hydrogenating fish ‘oll, which comprises adding a solid fat prepared bby substantially completely hydrogenating fish ‘ll to the fish oll being hydrogenated. 5. The method of increasing the plasticity of ‘semni-solid fats prepared by hydrogenating a glye- ride oil containing substantial amounts of acid radicals having different numbers of carbon atoms therein, which comprises incorporating with sald semi-solid fat, a substantially com- pletely saturated solid fat containing acid radi- als having the same number of carbon atoms 10 uw 85 0 61s 3,104,408 as the acid radicals of the hydrogenated ofl which have the greater number of carbon atoms. 6. The method of increasing the plasticity of semi-solid fat prepared by hydrogenating a glyeeride of! containing substantial quantities of Cus, acid radicals and substantial quantities of other than Cue acid radicals, which comprises incorporating with said semi-solid fat a fat con- taining substantial amounts of saturated acid radicals having the same number of carbon atoms as those of sald glyceride ofl which have the greater number of carbon atoms, 7. ‘The method of increasing the plasticity of a semi-solid fat prepared by hydrogenating a glyceride oil containing substantial quantities of Cw acid radicals and substantial quantities of other than Cus acid radicals, which comprises adding to said glyceride oll during hydrogena- tion, a fat containing substantial amounts of saturated acid radicals having the same number of carbon atoms as those of sald giyceride oll which have the greater number of carbon atoms. 8. The method of increasing the plasticity of semi-solid fat prepared by hydrogenating a siyceride oll including substantial quantities of Cie acid radicals and substantial quantities of other than Cus acid radicals, which comprises 3 adding to the semi-solid fat a fat containing substantial amounts of saturated acid radicals having the same number of carbon atoms as those of said glyceride ofl which have the greater number of carbon atoms. 9. The method of increasing the plasticity of semi-solid fats prepared by hydrogenating glyc- eride ofls containing Cus acid radicals and sub- stantial amounts of another acid radical having @ greater number of carbon atoms than said Cis radicals, which comprises incorporating with said semi-solid fat, a fat containing substantial amounts of saturated acid radicals having the ‘same number of carbon atoms as sald other acid radical. 10. The method of increasing the plasticity of semi-solid fats prepared by hydrogenating alyceride olls containing substantial amounts of acid radicals having different numbers of carbon atoms, the step which comprises incorporating with sald semi-solid fat, a fat containing a sub- stantial amount of saturated acid radicals hav- ing carbon atoms corresponding in number to the radicals of said ofl having the greatest num- ber of carbon atoms. LESLIE G. JENNESS. 10 6