-Patented Feb. 14, 1939 2 s l 4 7 p l 7 7 UNITED STATES PATTNT OFFICE 2,147il77 MTHOD OF MMROGENATI[OPT OF FATTY. ACIID GLYCERIDES lwao Seto and' Masanori Sato, Dairen, Manchukno, assignors to Mnami Nlanshn Tetsudo Rabushfld Kaisha (South Manchuria Railway Co.), Dairen, ?4&nchukao, a corporation of Japan APPUcation February 26, 1935, @Serial No. 8,409 2 Claims. (Cl. 204-31) The present invention relates to a method of eaecting contiziuous hydrogqnation and other catalytic reactions, characterized by the fact that when hydrogenation and other catalytic reactions are performed, by employing a catalyzer in suspension for oils, fats and other or anic I 9 compounds, an electrode is pr6vided In a reaction chamber, so that reaction may be carried out,. applying high tension alternating current 10 to said electrqde during hydrogeiiation and ti@at immediately u@on the completion of the reactign the alternating current Is changed to dir6et current, whereby the catalyier is accumulated on the waH of -the chamber, in the meantime with1.3 drawing the reaction.product alone from the vessel and then giving a fresh supply of the material to the chamber to renew the reaction. The object of this invention is to obtain a continuously hydrogenating method which by the suit20 able alternate employment of altqrnating and direct currents does not only accelerate the speed of r6action, but also enables the same catalyzer to be employed repeatedly without Impairing its function. 25 The accompanying drawing shows diagrammatically an example of an a aratus in a Ionpp gitudinal section for carrying the present inven-tion Into practice. it is well known in the hydrogenation of oils, ,3( fats and other organic compounds to pt6viously activate hydrogen by applying high tension current or to carry out reaction directly in a high tensi.on electric fleld. However, aU thesl! known methods do no i3iore than attempt to effect reaction chiefly by electric power.. Now, this invention unlike the methodshitherto proposed employs L-lectric power merely in a subsidiary -manner. In electro-catalytic reaction by which the hydrogenation of organic material is effected, there is employed..the sa@me reaction temperature iind uses the same quantity of a catalyzer and the same'other conditions as in ordinary catalytic reaction. In addition to the 'ordinary catalytic reaction, the present invention embodies the activation oi the hydrogen gas introduced into a reaction cli@mber provided with an electrode, so that during hydrogenation high tension alternating current (the tension belng'so high as to produce coronal discharge) 50 may be appl;ed. At the same time, by the discharge of electricity the stirring. action in thi reaction chamber is made unifbrni '4)2d perfect. T4t;s, it is not only possiblt@ to obtain very lilgh reae-tion speed as compared with the knowxi catm alytic reaction, but after the completion of the reaction, the catalyzer Is being very easuy accumulated on the waU of the chamber by changIng the current to direct current, the reaction product alone being dischgrged from the vessel, after which a fresh supply of raw material Is delivered to the vessel and the current Is obanged again to alternating current, Eind thus employing the same catalyzer repeatedly. Therefore, quite unlike known methods In which in order to restore its function the ca@alywr is necissarfly 10 removed from the chrlmber every time the reaction is completed, is separated fiom reactive material by filtiation and then is recovered by complicated chemical operation, the catalyzer is allowe d to stak in the chamber, wh e It is gepa- 15. or rated electricafly by simple means and Is used for fresh material. Accordingly, by carrying out the ' two operations alternately using a certain quantity of a catalyzer, it Is possible to effect hydrogenation intermittently. COnse- 20 quentl y, the co,nsumpti.on of a catalyzer for my pilrtic ular material is considerably reduced and yet the operation Is greatly simplified. The following. Is the manner of performing this invention:- 25 One electrode- Is formed by the wall of a cylindric al reactlon vessel 2 which is'grbunded.and is surrounded by iL heating device I and a second iplectr ode 3 Is provided at the center of mUd vessel, the electrodes being Insulated froift each 30 other by an Insulator 4. . The vessel 2 Is provided 4t @ Its bottom with an inlet pipe 5 for reactive materi al, an Inlet pipe 6 for birdrogen and a stirrer 7, and at the upper portion with an outlet pipe 8 for hydrqgen and an outlet,pipe 9 for 35 the reaction product. A source of electricity Is conne cted with th6 ejectrode 3 through a switch IC, a transformer I I and a rectifier 12. A more satisfa ctory result may be obtgined ff the surface of the electrode 3 Is coated with a thin 4o smooth layer of a dielectrie resistai2ce material such as porcelaii2, enamel, or glass. In operation, the above reacuon chamber is charged with reactive inaterial mlxed with a desired quantity of a catalyzer. Controlling prol)- 45 erly- the temperature. the voltsie of cxirrent and the Introduction of hydrogen and rotating,the stirrer 7 to.prevent the catalyzer from being de'posited on the bottom of the chamber, cataWHe hydrogenating reaction Is started, utilwnlg the 50 discharge of high tension altemate current till the reactive material undergoes t;he desiredh@,drogenation, when the switelz id is tumed togive direct electrie curtent by the rectifler 12, so that the electrode 3 may -be @paused to 55

2 2,147,177 act as an anode. Then, the catalyzer suspending in the reaction zone will be accumulated on the electrode immediately. It now a suitable quantity 6f fresh reactive material is introduced from the inlet -5, it will raise the level of the liquid in the chamber and discharge the reaction product at the ilpper part from the chamber through the outlet S. Then, changing from. direct currerit to alternating current, hydrogen10 ating reaction is agairi carried out, after which the ciirrent is again changed to direct current, as before and the reaction product is taken out. In this way, using the same catalyzer repeatedly, it is possible to obtain the reaction product with-15 out introducing new or reactivated catalyzer. As a practicable example, when the sahie catalyzer was employed repeatedly thirty eight times, the Iodine value of the hydrogenated oil in each time was. 20 Time Iodine value 59.4 L - -------------------------------------------------- 2 ---------------------- ------------------------------ .8.3 $-- 3,5.0 25 35.6 5 ----------------------------------------------------- 29.1 6 ----------------------------------- ----------------- 29-5 .7 ----------------------------------------------------- 32.5 8@ 40.5 : 39.7 10 ---------------------------------------------------- 41.3 30 11 39.1 37-4 13 ---------------------------------------------------- 40.5 14-@ -------------------------------------------------- 42.6 15 45.1 55.7 62.6 18 ---------------------- ------------- 55.6 1:1 19 --- ----------------------------------------------------- -- 46.0 20 ---------------------------------------------------- 62.3 21 -------------- ------------------------------------- 67.6 22 --------------------------------------------------- 67.1 23 ---------------------------------------------------- 62.8 24 --------------------- ------------------------------ r,13- 4 25 ----------------- ----------- - ------------------ 57.6 40 w ---------------------------------------------------- 62.8 27 --------------- --- 61.8 28 - ----------------- :--: ----------------------------- 66.2 29 ------------ --------------------------------------- 70.7 30- --: --------------------- : ------------------------- 737 31-:: -- ---------------------------------------------- 76'0 32 --------------------------------------------------- 68.5 33 ------------------------------------------- --------- 77,3 45 34 ----------------- ---------------------- 77.5 35 ----------------------------------------- 75:8 36 ------------------------------------------------- -- 780 37 -------------- - ---------------------------------- 796 38 --------------------------------------------------- 95:3 - - .50 -The conditions of operation are the same at all times, aud the example showsthe degree of the lowering of the iodine value, using th6 same eatalyst repeatedly. The oil, of course, is fresbly suppiied each 55 time. - Pbr the llrst operation, it has the iodine value lowered to 59A, to be discharged subsequently. On supplying fresh oil of the same quahty for the second operation, the iodine was lowered to 38.5, which clearly shows.that the cat60 alytic power of the catalyst Is successively elevated up to the fifth time. This shows how the =me catalyst may be utiuzed practically more than thirty tiines. The temperature is about 170-2001 C. as in the known methods. As regards the time, voltage, etc., thts has been explained in the a mendment flled on June 3, 1936. The nickel Is the common reduced nickel, preterilbly In the form of finely divided particles, which per se is not different from the ordinary hy&ogenation of oil pnd is nbt peculiar, so it is understood by any chemist and therefore it has not been described in the @original specification. The quantity of a catalyzer used for the entire raw oil quantity is 0.024% as m(,'tallic nickel, and thus with such small quantity of a cat as compared with the known methods it is possible to attain the object of hardening perfectly. 10 In sfiort, according to tWs invention an excellent hydrogenating metho(f hitherto unknown is obtained by employing a catalyzer in a suspending condition, utilizing both high tension alternate and direct electro-currents at the time of performing catalytic hydrogenation and thus effecting the separation and dispersion of the catalyzer simply in a reaction chamber. The following are examples to indicate the amount of v@oltage, the area of electrodes, the 20 size of the vessel and the reaction time, necessary to properly effect hydrogenation in accordance with the present invention: In the manufacture of hqrdened soya bean oil, the electrode is spaced 50 cm' from the wall of the vessi,-I.and th6 electrical charge to be applied is 150 kv., and if the space between the electrode and the vessel is 5 cm:, the charge will be 30 kv. The time required for hydrogenation when the product is to have an iodine value of 60, is 40 30 minutes. Vlhen the product is to have an iodine value of 10-20, the tiine Is from 11/2 to 2 hours. In the manufacture of aniline from nitrobenzene, the time required is 8 to 10 hours. It is to be understood that the amouht of voltage, the area of the electrodes., the size of the ... vessel and the reaction time, vary according to the class of the raw material used and the quality of the product desired. We