PROCEDURE FOR THE SELECTIVE HYDROGENATION OF SEVERAL TIMES INSATIATED ONE ORGANIC COMPOUNDS

The invention refers to a procedure for the selective hydrogenation of several times ungesättJgten organic compounds, for example from edible Triglyceriden. As is common knowledge is, essentially consists oils and fat of a mixture of Triglyeeriden of fatty acids. The fatty acid containing usually about 16 to 22 C-atoms and can be satisfied, like stearic acid; they can also moneungesättigt, like oleic acid; diungesättigt, like Linolsäure; or triinsatiated, as Linolensäure, its eder show even a still higher Ungesättigtheit. In Ölund fat technology it is usual to hydrogenate oils to give in order to remove a part of the Ungesättigtheit and thus the hydrogenated oil desired characteristics, as higher fusion point and/or increased stability. While steps the hydrogenation, both one behind the other and at the same time, a number of reactions up. For example the hydrogenation can be represented by the following simplified pattern for hydrogenating Linolensäure: K, K2 K3 Linolensäure Linolsäure oleic acid” Starinsäure, whereby Kl designate, K2 etc. such as asking constants of the which are possible reactions. Besides secondary reactions arise, like a shift and an isomerization of double bonds. The isomerization leads to the transformation of cis double bonds in trans double bonds, whereby the appropriate have, the trans acids of containing oils usually a higher fusion point. Oils and fats, which contain a high portion of stearic acid, have a too high Sehmelzpunkt, in order to be organoleptisch acceptable for most application purposes. Therefore it was so far usual to direct the hydrogenation in such way that as little stearic acid became to receive as possible formed and a high portion of trans-01säure, in order the oil with the desired fusion point to result in. Nowadays the cis trans isomerization is regarded as less desired, because a shift to liquid, however sturdy oils is present, which as such or as Bestandtei] e for soft Margarinen is used, which in Kfih] is stored. The Selektivitäten with the Hydrierungsreaktienen is defined usually as follows: K2 Kl SI = _ _ SII = -- K3 K2 if the selectivity SI of the reaction is high, small portions of satisfied acids is produced. If the SE] SII ektivität is high, is possible it to hydrogenate Linolensäure while a high percentage of the essential fatty acid remains Linolsäure. SI is defined as the portion of trans isomers, which is formed regarding the hydrogenation degree. As mentioned, one wishes to direct nowadays the hydrogenation in such way that SI a oiedrigen value has a SE as possible. OS with the normal hydrogenation practice, which is usually implemented with the help of a nickel catalyst on a carrier at high temperatures and increased pressures, cannot be avoided a substantial isomerization of Doppe] connections. Some catalysts were suggested, since they are selective, e.g. to copper catalysts. Such catalysts give however, although they are selective, for instance the same degrees of 0 to isomerization as nickel. It was now found that the process of the reactions, which enters during the Hydrierun8 with the help of a metallic catalyst be affected it can, by implementing the hydrogenation in presence of a catalyst, to which before beginning of the hydrogenation an exterior electrical potential is put on, which of the naturally occurring G] eichgewichtspotentia] versohieden is, while it with an E solved in a liquid] ektrolyten in contact is. The potential has a SE] a chen value that no electro-chemical hydrogen production takes place. The new procedure is to be differentiated from there from the electro-chemical hydrogenations to, with which for llydrierung the necessary hydrogen by e] ektrochemisohe Umwand] ung from e.g. water or an acid is produced. The same catalyst can be used both without and with an outside potential or with different potentials again and again. The invention is not limited by any theoretical explanation of the features, which arise at the catalyst surface. • at the time of execution of the procedure according to invention the substance which can be hydrogenated is loosened or dispersed preferably in a liquid, like e.g. an alcohol or a Keton. The liquid is not to react preferably with hydrogen in presence of the catalyst and on the applied reaction conditions. Water, methanol, Äthano], isopropanol, Glycerin, acetone, Äthy] englykolmonomethyläther (Methylcellosolve), acetonitrile, witches, Benzo] and mixtures hievon can be used. If however an alcohol is used as liquid, occasionally a certain Alkoho can enter] yse. It is not substantial that the substance which can be hydrogenated (i.e. the substrate) is soluble in the selected liquid. Dispersions e.g. a Triglyceridöls in methanol have equal good results as solutions of the oil in acetone or in a acetone Met hano] - mixture result in. The relationship from liquid to substrate is not critical. Preferably conditions of 20 become: 1 to 1: I or even still lower applied. A portion for the release of the E] ektro] yts is already sufficient. It was found that with more concentrated systems the selectivity is usually higher. The system is to possess a certain electrical conductivity. For this purpose an electrolyte can be added to the system. As electrolyte a substance is to be selected, those not reacted with the hydrogen. Furthermore the electrolyte is to be sufficient soluble in the selected liquid and not react with the substrate on the applied reaction conditions. Good results orat obtained Tetrabutylammoniumperchlorat, Tetraäthylammoniumphosphat, Tetraäthylammoniumbromid, Tetraäthy] -, Tetramethylammonlumacetat ammoniumparatoluolsulfonat, and furthermore with atriumdodecy] - 6-sulfonat, Natriumacetat, sodium hydroxide, Natriummethano] RK and Ammoniumaeetat with quaternären Ammoniumsa] zen, like Tetraäthylammoniumperch]. The portion applied electrolytes is not critical, and usually a concentration from approximately 0.001 to approximately 0.1 M is sufficient. The procedure according to invention is insensitive opposite water. Systems with a content up to 10% water resulted in good hydrogenation results. It is not necessary from there that the liquids mentioned, electrolytes are free and other components of the system from humidity. As catalyst each metallic catalyst can find such as palladium, platinum, rhodium, ruthenium, nickel u.dg], or an alloy hievon to application. Such catalysts can take the form of an extracted alloy, like a Raney nodding]. The catalyst can be used in the form of porously Metal] call on an F] more attenträger, which is immersed into a system, or he can preferably arrive in the form of small particles suspended in the system at application, in] the etztgenannten case preferably is the metallic component on a carrier. As Katalysatorträger can be used for example metals, ion exchange resins, soot, graphite and silicon dioxide. On the catalyst with the help of an inert electrode an electrical is set potential, which electrode is a part of a three-electrode system, which from a collector, exists a backplate electrode and a Bezugse] ektrode. The potential at the collector can be regulated regarding the Bezugselektrodo with the help of a voltage regulator or a d.c. supply, in order to keep the potential constant during the hydrogenation at any value. It is however also a regulation possible over the Zellenspannung in a two-electrode system. Tensions to the Arbeitse] ektrode are determined and measured generally regarding the reference electrode, which knows liquid connection between the electrolytic solution of the reaction mixture and the solution of the reference electrode through is facility-reached, those by a low electrical resistance as well as through: a small Flüssigkeltsdurehgang characterized, as for example a diaphragm end in the proximity of the surface of the collector or a Luggin Kapillarsystem well-known in the electrochemistry is. The collector and the Gegenelektrcde can be by suitable Einriehtungen, which let the river through, for example a glass frit, from each other separated. The collector can be made from any material, for example a Platinfelie, or of a gauze from platinum or stainless steel. The backplate electrode can consist the reference electrode of platinum or stainless steel and can any reference electrode, as for example a mercury-chloride-satisfied electrode or an SI] a ber /Silberchleridelektrode, be. The potential from the collector to the catalyst either by direct contact, for example by a platinum foil üherzogene with palladium, whereby the palladium is the catalyst, or thus will transfer that the Katalysaterteilchen is brought by strong agitating with the electrode in contact. Such so-called Sch] ammelektroden is well-known, S. e.g. P.Boutry, O.Bloch and J.C.Ealanceanu, Comp.Rend. 254, 2583 (1962). It is also possible to increase the potential transition thereby that an electrically leading firm powder, for example aluminum powders, is added to the system, in particular if a Scblammelektrcde is used. The potential put on depends on the nature of the catalyst and the used solvent. It can be easily determined, which potential should be put on, in order the desired selectivity to obtain. For example with a palladium catalyst in methanol the formation of satisfied fatty acids is called with maintaining a tension the Calomel electrode, in the following SCE, satisfied by -0,9 V opposite, suppressed completely. Generally the outside tension put on amounts to 0 to -3 V opposite the SCE. Although the creation of a constant potential is preferred, how this was indicated in the understanding, one achieves also a increased selectivity of the hydrogenation reaction, if the potential varies during the hydrogenation. Sometimes it is even possible to set a potential on the catalyst and to switch then the energy input or the voltage regulator off used if necessary. In this case the potential at the catalyst will first drop, however the remaining potential remaining at the catalyst will often be sufficient to achieve a increased selectivity and suppression of the trans education. For the introduction of the hydrogenation the potential can be set on the collector, after the device was filled with the solvent containing the Elektrelyten and the catalyst was added and the device contains a hydrogen atmosphere. After the potential was put on during a certain period, the mass which can be hydrogenated is brought into the device. The device can be filled also with a liquid, which contains the electrolytes, the catalyst and the mass which can be hydrogenated, and with nitrogen to be filled. Then the desired potential is set on the collector during a certain period. The hydrogenation is introduced thereby that the nitrogen is replaced by hydrogen. Generally the introduction procedure specified last is more practical, and the selectivity ttydrierungsreaktion is somewhat better than with the first introduction procedure. In accordance with a third t ethode is put on the potential during a certain period at the liquid with electrolytes and suspended catalyst in a device, which is filled with oxygen or nitrogen. Then the mixture is transferred into a reactor, which contains the mass which can be hydrogenated, which can resemble solved in or be dispersed in another liquid or. The temperature, at which the hydrogenation is accomplished, is not critical and depends on the activity of the selected catalyst. With palladium, platinum u.dgl, the reaction rates are sufficient at ambient temperature, although lower and higher temperatures can be used. With less active catalysts higher temperatures up to 100*C can be even more highly necessary or. The temperatures amounted to generally -20 to 200°C, the reaction can be accomplished also with atmospheric pressure or with higher pressures or even with a pressure which is under atmospheric pressure. Generally the pressure amounts to 1 to bar. Naturally pressures over the atmospheric pressure are needed, if one liked to work at a temp RA - 5 - a Nr.36563Z tur over your boiling point the liquid. The procedure in accordance with the invention can be used for the hydrogenation of connections with more than one double bond, in order to increase the selectivity of the hydrogenation reaction. Examples hiefür are Triglycerid5le, like soy bean oil, Leinsamenö], Fischöle, Palmöl etc., fatty acid aster, like methyl, Äthylund other alkyl esters, soaps, Alkoho] e and other fatty acid derivatives, as well as polyunöesättigte cyclische connections, 'like Cyclododecatrien. The following Beispie] e is to describe the invention more near, without this is to be limited however on that. With the examples, with which the portions of the components do not constitute 188%, the less meaning components, like C, are ù, C, -, C20 -, C22 - etc. fatty acids, does not mention. The percentages mentioned are in mol--°6 indicated. Other percentages refer to the mass. In the tables the fatty acids are indicated, i.e. by the number of carbon atoms and the number of double bonds, which they contain, C 18: Linolensäure, C 18 means 3: 2 Lino] acid etc. is example 1: The hydrogenation was accomplished under atmospheric pressure and at ambient temperature in the device shown in Fig.1. 188 ml a container --1-- possesses a magnetic agitator --2--, a landing on water EFF inlet --8-- and two electrodes from Platinfo] IE with a surface of 5,5 cm2, of those the one, i.e. --4--, and as catalyst is used, and the other one is covered with palladium, i.e. --5--, when backplate electrode serves. Furthermore the container possesses (Luggin) a capillary system --6--, that over one in a closed cock --8-- formed liquid connection to an aqueous satisfied calomel Bezugse] ektrode --7-- leads, which with Natriumch] erid is satisfied. Finally the container points a combination --9-- from a cock with an essay up, which permits the addition and withdrawal of liquids with the help of a 2s syringe, the piston and the cover were with a broad flange --10-- connected. The reactor was with one on 200 ml calibrated burette connected, which with hydrogen (over a BTS Kata cleaned] ysator and CaC] 2) and Paraffinö] was filled. Regular tensions put on over one tension-move] it (the chemicals Electronics CO., Durham, England). Dia. catalyst cutting were measured regarding the reference electrode with a voltmeter PM 2440 company Philips exhibiting a negative pressure pipe}. After lqeaktor and (Luggin} Kapil] arsystem up to the cock with a 0,1n solution by Tetrabutylammoniumperchlorat in exp. ethanol (in the reactor about 80 valley) it had been fed the reactor was repetitive evacuated and cleaned with hydrogen, on which the solution and the catalyst satisfied with the hydrogen under agitating, originating from the burette, wutden. The tension was measured. It reached a value of -0,82 V opposite the SCE in the GI eiehgewichtszustand. Then 0.641 g (2.18 mMol) were ineleat Methy]] (M = 294.5} admitted under constant agitating of the solution. The composition of the Beaktionsmischung was then determined by gas liquid chromatography (GLC) according to admission of 51,7 ml hydrogen (necessary for the hydrogenation of only one Doppe] connection, i.e. 190 mol) and according to decrease of the Linoleatgeha] ts on 29. With this attempt no outside tension was applied. The attempt was repeated, and this time an outside tension was applied by -1,10 V opposite the SCE. In this case 0.669 g (2.27 mMol} methyl] were brought in ino] eat into the Beaktionsgefäß, whereby 55.2 was necessary for the Deppelbindung ml hydrogen. During this attempt a weak river passed through by the system, which corresponded to the electro-chemical equivalent of approximately 0.5 of the available double bonds. The results are summarized in the table I, whereby the compositions in Mo] - is indicated. thus to the table I and also the later following table II that the second pair of the values in the column mol-refers completely right to an absorption of hydrogen of 100, D, h is noticed. the quantity, which for the hydrogenation of a Doppe] connection per molecule is necessary. Also these values show very clearly the very large selectivity improvement, which is reached by creation of the outside potential. Table I (in relation to V the SCE) exterior potential put on - 1.10 no exterior potential put on - i, i0 Linoleat of 2 2 36 6 mono esters Stearat 14 93 32 92 84 3 32 2.5 H =-Aufnahme {mol) of 187,102 ioo IO0 a bright foil did not lead übarhaupt not to a hydrogenation, which shows that the tension put on possesses an effect only if a catalytically active substance is present. Example 2: Example 1 was eat hydrogenated with the exception repeated that Methy] o]. Without outside tension the oleate ester was hydrogenated completely to Methylstearat. With an outside tension of -1,10 V opposite the SCE hardly hydrogen was taken up and the oleate remained in not-converted condition. , Even after 4stündiger reaction, no Methylstearat was determined by gas Plüssigchromatographie. Were also formed no for trans isomers. Example 3: Example 1 was repeated with the exception that Methyllinolenat in place of Methyllinoleat was given to the reaction container and a potential was put on by -0,90 V in place by -1,10 V opposite the SCE. The results are summarized in table II. Table II (in relation to V the SCE) exterior potential put on - 0.90 no exterior potential put on - 0.90 Linolenat of 2 2 serving acid esters 4 43 Moncenester 31.5 53 Stearat 61,1.5 52.5 34 6 36.5 29 20.5 13 0.5 H =-Aufnahme (mol) 262,170,100,100 the above examples 1 to 3 it does not show that the creation of a potential to the catalyst a very large influence on the SE] ektivität. The formation of satisfied connections is implied suppressed, whereby a very high SE] ektivität SI, while SII is likewise considerably increased, which can be concluded from the high portion of serving acid esters. Example 4: On the way described in example 1 Methyllinolenat were used hydrogenated, whereby Pa] ladiumruß and platinum soot as catalyst. The composition of the reaction mixture wutde determined, after 95 of the Linolenats had been converted. The results are specified in the following table III. Table II! Catalyst Pt Pd (in relation to V the SCE) no potential put on 0.60 no potential put on - 0.90 Linolenat serving acid ester 32.5 5.5 Monoßnester 12.5 39 36 47.5 Stearat of 23.5 53 examples 5, 6 and 7: These examples were accomplished with a mud electrode in the device shown in Fig.2. The device shown in Fig.2 possesses a cathode chamber --1-- with a platinum gauze serving as collector --2-- and a bell agitator --3--, that over a magnet --4--one propels. The cathode chamber is over a MediumfrJtte --5-- with the anode chamber --6-- connected, the one platinum foil --7-- as backplate electrode contains, hydrogen becomes over an inlet --B-- supplied. (Luggin) a capillary system --9-- leads across a medium frit --10zu of a satisfied Calomel Bezugeelektrode --11--, some aqueous, satisfied Natriumch] oridlösung contains. In this device the Methyllinoleat was used hydrogenated, whereby as catalyst palladium powders, Raney nickel and Pa]] adium on carbon with 5 palladium and once an LS outside tension and other time to comparison purposes an outside tension was not put on. The reaction medium consisted of 0,05 M Tetraäthylammoniumperchlorat in methanol. The tension was regulated in the way described in example 1. The composition of the reaction mixture was determined, after 90% of the Methyllinoleats were converted. The results are summarized in table IV. Tabe] le IV example catalyst Pd-powder Pd-powder Raney nickel Raney nodding] Pd on coal Pd on coal (in relation to V the lake) no potential - 0.9 l0 no potential put on - 0.3 no potential put on put on - O, g I0 82 8 90 87 3 89.5 0.5 82 8 90 cycle per second admission hydrogenation time in Molin min 97 90 9O g7 88 37 53 28 33 footnote to table IV: *) L = Linoleat, M = Honoenester, S - Stearat these examples show likewise an increase of the selectivity of the hydrogenation reaction by the creation of a potential to the catalyst surface, since the education is suppressed by Stearat. Example 8: In the examples 5 to 7 described device about 4 g soy bean oil with and without a anöelegtes exterior potential were hydrogenated by -0,9 V opposite the SCE. The oil became in an O, 05I - solution of Tetraäthylammoniumperchlorat in acetone in a relationship of oil: Liquid of 1: 2 solved. 1% palladium powder, related to the Jl, was added to the system le. The hydrogenation was accomplished at ambient temperature and under Atmosphärendruek. The results are summarized in table V. Table V fatty acid C 18 C 18 C 18 C 18 C 16: 3: 2: 1: 0: 0 entirely () cycle per second consumption (ml/g oil) transGehalt Hydrlerungszelt (m n) composition of the output bus 7 53 21. 4 12 composition of the hydrogenated product (%) without exterior put on potential 2 41 4 12 14 15.6 116 with outside potential put on of -0,9 V opposite the SCE 2 48 34 4 12 I0 14.0 150 this attempt shows the high selectivity SII and the small portion during the Bydrierung formed trans isomers, if in accordance with the invention an exterior potential is put on. Example 9: Example 8 was repeated, whereby however methanol as liquid in a relationship of oil: Liquid of approximately 1: q was used and the portion of palladium powder 2.5% amounted to. Since the soy bean oil is weakly soluble in methanol, a Zweiphasensystem developed contrary to a phase system of the example 8. The results are summarized in table VI. Fatty acid C18: 3 C18: 2 C18: 1 C18: 0 C16: 0 entirely () example 10 transGehalt: Table V1 composition the output poles 8 53 4 RST composition of the hydrogenated product () without ange] egtes Potentia ußePes with put on! outside potential of -0,9 V in relation to the SCE 3 0 3 0 16 52 46 67 31 51 6 7 4 4 10 10 13 19.3 27 37.0 69 4.7 20.5 68 C 18 C 18 C 18 C 18 C 16: 3: 2: 1: 0: 0 entirely transGehalt (Z) 0 fusion point (degrees) Jodzah] 133 table UII composition of the Aus9angsöls 8 53 4 composition hydrlerL of the n of product () without put on with put on exterior potential outside potential by - O, g V more gegenUher the SCE 2 1 31 52 4 18 8 < 0,115,118 FeLts ure example 9 oil became with a Anteilsverhä] tnis: Liquid of 1: 4 repeats. The hydrogenation was so for a long time continued, until the oil exhibited an iodine number of approximately 110. The results sindin table VII in summary. Table VII (continuation) fatty acid cycle per second consumption composition of the exit LS composition of the hydrogenated product () without exterior put on potential 2 with outside potential put on of - o, g V opposite the SCE 2 8 14,0 the attempt shows that the portion of the formed trans acid is very low and is lowered the fusion point of the product by the voltage regulation. Example 11: Example 8 was repeated, whereby acetone with 0,05M Tetraäthylammoniumperchlorat was used as liquid. The relationship of oil: Liquid amounted to 1: 6 and the system contained 10% Raney nickel as catalyst. The results are summarized in table VIII. Table VlIl fatty acid ClB=3 C18: 2 C18: 1 C18: 0 C16: 0 Hydrlerungszeit (in) composition of the output oil 7 53 24 4 12 composition of the hydrogenated product () without exterior put on Potentia! it shows 2 26 52 8 12 13 33.0 i with put on outside potential of -1,5 V opposite the SCE 2 37 12 24 200 of this BeJspJel that also with BaneyickeJ as catalyst the selectivity of the BydrJerung increased and the portion is strongly lowered formed trans isomers due to the outside potential. Example 12: In Fig.3 is a device from a double-walled container --1-- with a capacity of 600 ml shown. By the coat of the double-walled Gäfäßes regulated water can flow by a thermostat. The container is with four guide plates --2-- and an agitator --3-- provided. Furthermore the container contains one as Arbeitse] cktrode serving gauze --4-- from stainless steel and a chamber --5--, those over a glass frit --6-- and a Gegene] ektrode is connected with a chamber taking up the collector --7-- from stainless steel or platinum contains. The chamber of the backplate electrode has an open connection roll the head area of the container --1-- to printing expenditures] calibrate. A satisfied Calomel Bezugselektrode --8-- ektrode ceramic diaphragm ne over e stands with the chamber of the Arbeitse] --9-- and a salt bridge --10-- in contact. The cover of the container is with inlets--IL and 12-- provide for the oil and the hydrogen. The cover is during the hydrogenation by means of a suitable, the flanges --14-- spreading l0 clamping device --13-- fastened. In this device 90 g soy bean oil were hydrogenated with 24°C and under atmospheric pressure, whereby an exterior potential was put on by -0,95 V opposite the SCE and agitated with 850 Umdr/min. Acetone was used as liquid, whereby the Volumsverhältnls from oil to liquid 1: 4,5 amounted to. The electrolyte was Tetraäthylammoniumperch] orat (TEAP), which was used in different concentrations. The catalyst was palladium powder in a portion of 1,4. The results are shown in table IX. Table IX fatty acid C18: 3 C18: 2 C18: 1 C18: 0 Cl6: 0 of entire tPansGehalt () hydrogenation time (min) composition of the output oil 7 22 4 II < 1 composition of the hydPierten product () with a TE@-Konzentration put on by O, 05M 2 36 4 11 O, 02H 2 36 4 12 43 O, O05H 2 4 11 39 exterior Poland TLA] bel O, 05H TEAP 2 33 49 11 16 21 this example does not show that the electrolyte concentration has an influence on the result of the hydrogenation hardly. Example 13: Rübsamenöl was hydrogenated with 24°C and under atmospheric pressure in the device drawn in Fig.3. As catalyst Pal was used] adium on soot with 3-% Pd in a portion of I00 TpM palladium. The liquid was acetone and the relationship from Rübsamenöl to acetone amounted to 1st 4,5. The liquid contained 0,05M Tetraäthylammoniumperchlorat (TEAP) as electrolyte. The results are summarized in table X. Table X fatty acid C18=3 C1@: 2 C18: 1 Cl@: O C1G: O entire transGehalt (%) Hydrlerungszeit (min) composition of the Ausgan9söls lg 19 59 2 composition of the hydrogenated product no Nu8eres potential angelegtl) 2 3 11 < 1 with outside potential put on of -0,95 V gegenUbeù of the SCE 2 19 GG 2 as catalyst 1.4 Palladlumpulver uses example 14: Tallow of first-class white was hydrogenated fuel element 40°C and under atmospheric pressure in the device drawn in Fig.3, used as catalyst 0.3% palladium powders. The liquid was acetone with a content of 0,05M TEAP as electrical] yt, which in a relationship of oil: Liquid of 1: 4,5, the results is summarized in table X£ was used. Table XI fatty acid C18: 3 C18: 2 C18: 1 C18: 0 C16: 0 composition of the AusgangsUls (z) 0.2 3 4t 24 composition of of the hydrogenated product (%) with put on ußere potential ven - O, g5 in relation to V the SCE entirely transGehalt () 3 g Hydrlerungszeit (min) - 36 GG iodine number of 49 4G 4G 2 43 24 no exterior potential put on 2 44 24 although the influence on the selectivity to be rather small seems, is the portion of formed trans isomers strongly decreased, which has a considerable influence on the Dilatationswerte of the oil, as in table XII shown. Dil atation hydrogenated by Ausöangsöl without a potential put on hydrogenates ange with] egtern outside potential the 580,820,665 table XII Dzo I Dze 505,370,675,505,570,420 D30 255 35O 290,215,180 D o D 0 example 15: Pa] möl was hydrogenated with 40°C and under atmospheric pressure in the device represented in Fig.3. As catalyst 0.5% palladium powders were used. Acetone with a content of 0,05M TEAP as electrolyte was the liquid. which in a relationship from oil to liquid of 1: 4,5 one used. The results are summarized in table XIII. Table XIII fatty acid C18: 3 (: 18: 2 C18: 1 C18: O ClB: 0 entire Iran content () (min) iodine number of composition of the output oil (Z) 0.3 10.5 38.7 B, 7 43.6 ydrierungszeit < I 53.6 composition of the hydrogenated product () no exterior potential put on 2.5 46 5.7 43.8 52 4 hurry put on outside potential by - o, g5 V opposite the SCE 2.5 46.5 5.2 43.4 71 example 16: 90 g Fischöl were hydrogenated with 24°C in the device represented in Fig.3. 1.5 g of a catalyst, consisting of 3% Pal] adium on carbon, were used, the liquid were acetone, which in a relationship of oil: Liquid of 1: 4,5 and 0,0SM TEAP was used as electrical] yt contained. The hydrogenation continued, until the Wasserstoffverbraueh amounted to tal/ö, bie results are summarized in table XIV and with the Ergebntssen, which became to receive, when the Fischöl nods in usual way with the help of one] kaLa] ysators in two stages with 150 and 180°C and with a pressure from approximately 4 bar had been hydrogenated, comparative. Table XIV Jodzah] entire transGehalt (%) Di] atation: D15 D20 D s D30 of the D o Ausgangsö] 163 < 1 in usual way using one nods] - catalyst hydrogenated oil 42,935,730,565,330 10o RST with outside potential put on of -0,95 V i i IL 37,555,400,225 0 0 without creation of the outside potential with an iodine number of was formed for 49% trans isomers, whereby palladium was used on coal as catalyst and worked in acetone. Examples 17 and 18: 100 m] Palmöl were solved in 450 ml acetone with a content from 0,05M TEAP. The solution was hydrogenated with 40°C under a pressure by 163740 Pa in the device represented in Pig.3. In example 17 the used catalyst was 0.5 g Pal] adiumpu]. In example 18 0.225 g palladium were used on Rohle with a content of 3% Pd as catalyst. The results of the attempts are summarized in table XV. Table XV KaLalysaLor hydrogen consumption (ml) output oil without exterior put on potential miL put on ußere potential by -0,95 V opposite the SCE 0.5 g Pd 0.5 g Pd with put on outside Poland A] of - O, g5 V in relation to the SCE 0.225 g 3 Pd/C 860 78g 781 hydrogenation tent (min) 21 73 56 iodine number of 53.5 45.0 5.0 45.0 C 6: 0 () 42.2 42.0 41.8 42.5 Tabel] e XV (continuation) output oil without put on put on with exterior put on Pntentlal mlt outside potential by outside Pntential by - o, g5 in relation to V the SCE - o, g5 V opposite the SCE catalyst 01 5 g Pd 0.5 g Pd 01,225 g 3% pd/c C! 8: 0 () 6.0,7.7,6.4,6.6 C 18; 1 () 38.0 46, g 46, g 47.7 C 18: 2 (%) 12.5 2.0,2.2,2.0 total drink content () < 1 g 6 6 extinction E 232 E 268 Dilatatlon the Dzo 02s 030 of the Owo D4s Oso Oss 2.250 1.518 750,595,405,265,155 0 0 0 2.101 0.411 12BO 1130 860,560 36O 140 0 0,0 2.003 0.309!!! o g25 565,425,255 IO RST o example 19: 10B g of trans, trans, cis l, 5,9-Cyc] ododecatrien (CDT) in 450 ml acetone with a content from 0, O5M TEAP were solved. The hydrogenation was accomplished in the device represented in Fig.3 at a temperature of 24°C and a pressure by 103740 Pa with 3% Pd/C as catalyst. Without creation of an outside potential 42.6 I hydrogen were taken up to 6 h, with an outside potential put on of -0,95 V opposite the SCE only 19.5 I hydrogen to 6 h. The latter IIydrierung had been taken up after 13 1/2 h, when 26.6] hydrogen was continued, because hydrogen consumption had practically stopped. I0 converted with both attempts that of trans, trans, cis-1,5,9-Gyc] ododecatrien with the same relationship. The outside potential put on reduced the portion on trans, trans, trans - CDT. Furthermore less Cyclododecan was gebiIdet. During the reaction with the outside potential put on the serving portion is ever higher in the ReaktionsmisGhung, compared to the attempt. with no exterior is put on potential. Furthermore the process of the hydrogenation is shown in the Fig.4A and 4B. The different curves result in the concentrations of the components of the system as function of hydrogen consumption. With “A! 'characteristic curves show the concentration of a special component. if no exterior potential is put on. The accordingly numbered, curves named “b” are issued the concentrations of the same component during the hydrogenation with one] ange] egten outside potential of -0,95 V opposite the SCE. To assist in the understanding the designations of the different curves are summarized in table XVI. Table XVI component without put on with put on exterior potential cls, trans, trans Trien of trans, trans, trans Trlen of trans, Lrans, trans serving Cyclododecan entire Henken cis Honoen trans Monoen Al a2 a3 a4 a5 a6 a7 outside potential - o, g5 V opposite the SCE bi b2 b3 b “b5 J remarks Fig.4A Fig. “B l) the curves A! and bl examples 20 to 24 tune Oberein: In the device represented in Fig.3 soy bean oil was hydrogenated. In example 20 the potential was set electrolyte and catalyst in a hydrogen atmosphere on a mixture from liquid, and after the production of the equilibrium the hydrogenation was introduced by injecting the oil into the device. In the examples 21 to 24 the catalyst, and the oil were brought in the liquid, the electrolyte into the reaction container, whereupon a nitrogen atmosphere was put on above the system and begun after the production of the equilibrium with the hydrogenation, as the nitrogen was replaced by hydrogen. The further conditions of the hydrogenation and the results are summarized in table XVII. Table XVII example Sojabehnenöl 21 22 23 24 exit $o, 100 l1 100 ml 200 ml 200 el 200 ml Elektrelyt! ösung abehnenöl 450 el O, 05H TEAP acetone 500 ml O, 05M TEAP acetone 300 ml O, 05H TEAP acetone 300 ml O, 05H TEAP Ameten 300 el O, 05M TEAP Ameton atmosphere with put on potential put on} u8eres potential (in relation to V the SCE) cycles per second of Nz N2 Nz N2 -0.95 - o, g5 ù0,95 -1.2 -1.5 HydrlePun9szelt (min) 57 88 189,245 cycle per second consumption (mZ) 1450 1500 300O 2350 2300 entire transGehalt (%) < I C16: 0 (z) 11.0 11.1 tons, 8 I0,0 10.8 I0,8 C18: 0 (z) 3.6,3.9,3.8,3.8,3.7,3.8 C18=1 21.9 35, g 35.0 35.4 3t, 6 30.6 C18: 2 54.8 45.0 46.9 46.2 50.3 51, “C18 3 (z) 2.0” 2.0” 2.0” 2.0 I *) C 18: 0.41 isomers, designation as 6, g, 12-Octadecatriensäure contained 3 into all 8elsplelen became 1.25 g Pa! LOD [more umpulver than catalyst Z Lo uses these attempts shows that in the examples 21 to 24 described output procedures {with that the potential under a nitrogen atmosphere is put on) to a higher selectivity of the hydrogenation reaction leads. In particular SII is improved. Furthermore the table shows that by creation of a more negative potential the selectivity is improved and also the trans content of the hydrogenation product is reduced. Example 25: In the device shown in Fig.8 100 m] Sojabohnenö were hydrogenated], solved in 450 ml acetone, with a content from 0.05M TEAP, with 1,25 mg palladium powders as catalyst. In this case the potential was not put on on the catalyst by a tensiometer, but a potential between the collector and the backplate electrode was put on with the help of a direct current supply, whereby the tension was increased, until the potential between the working electrode and the reference electrode {SCE) -1.5 V amounted to. During the creation of this potential in the device a nitrogen atmosphere was maintained, switched off after 1/2 h the current supply and begun it with the hydrogenation, as nitrogen was replaced by hydrogen. During the hydrogenation the potential was based on the collector. This attempt was accomplished at a temperature of 24°C and with a pressure by 103740 Pa. The results of this attempt are indicated in table XVIII. Table XVIII 83,197,237 2gg Ausgangsö! o 500 1150 1500 2000 potential (in relation to V the SCE) PaRS Fettsäurezusa evse zung () C18: 0 Cl8: l [C18: 2 I 10.8 3.55 20.7 55.6 II, 0,3.6 24.4 54, g 10.9 3.7 30.2 51.6 10.9 3.7 34.0 48,6! 0,8,3.7 39.9 43.6 -1.14 -1.03 - I, 02 -0.98 -0.93 < 1 ice: 0 C18: 3 ii 7,5* 4.5 " 2.0 " 1,2W 0,7* *) C 18: 0,4Z isomers, bezelchnet as 6, contains 3 g, 12-Octadecatriensäure this example shows that to the catalyst angelegto the potential drops after switching the current supply off first fast from -1,5 V opposite opposite the SCB on approximately -1 V the SCE; this tension is reduced in the process of the hydrogenation only very slowly, the selectivity of the hydrogenation is very good. Example 26: In the device represented in Fig.3 soy bean oil was hydrogenated. The device fed with 100 ml oil, 450 ml acetone with a content ven 0,05M TEAP and a catalyst. The potential was not put on by a tensiometer put on” it however a potential between the collector and the backplate electrode with the help of a direct current supply (D050-10 delta lektronika), whose tension was increased, until the potential between the collector and the reference electrode (SCE) - I, 5 V amounted to. %Vä'hrend put on the potential in the device a Stiokstoffatmosphäre one maintained. With beginning of the hydrogenation nitrogen was replaced by hydrogen. During the hydrogenation the potential of the system was held with the help of a G'1 ei0 hstr0 mzufuhr -1,5 V opposite the SCE. The hydrogenation was accomplished with 24°C and under atmospheric pressure. Several catalysts were examined. The results are shown in table XIX. Table XIX catalyst {8eschlckun9) i output oil Rh/C (200 mg Rh/kg oil) h/C (500 ml Rh/kg 51) Ru/C (12oo mg Ru/kg oil) Ru/C (3000 mg Ru/kg I) s Ptlc (1oo 9 Pt/ki oil) Pt/C (600 mg Pf/kg oil) Raney Ni (0.8 Ni) Raney ni (3 egg) Pd/C (50 mg Pd/kg oil) 3 Pd/C (150 mg Pd/kg oil) potential put on (in relation to V the SCE) no -1.5 no -1.5 no -1.5 no -1.5 no -1.5 hydrogenation time of Trans (min) () i 150 I19 600 53 241,112 2g6 163 63 14 < I 18 tons of 31 32 4 2! 2 7 16 FetLsäurezusanenseLzung () C18: 0,3.6 14.1 4.1+ 16.4 5.2 17.7 5.6,6.3,3.8,5.1,3.7 C18: 1 20.7 38 37.4 36.2 38.2 39.4 37.0 43, g 36.5 45.3 27.5 C18: 2 55.6 32.5 B2,) 31.7 39.9 28.1 42.6 35.6 45.0 34.4 53.8 C18: 3 " 7.5,2.0,2.0,2.0,2.0,2.0,2.0,2.0,2.0,2.0,2.0 *) C 18: 3 contained 0.4 isomers, designation as 6,9,12-Octadecatrlensäure in the attempt with Rh/C 0.2 to 0.3 conjugated serve formed. Formed with the catalyst Ru/C about 1.5 conjugated serve during the hydrogenation procedures. It is shown that with potential put on the content of the satisfied fatty acid is reduced and the content of the Linolsäure increases, Beispi61 27: In the device shown in Fig.2 the potential was set on the catalyst with a d.c. supply. The gesättiote Calomel electrode was brought to chamber of the working electrode however with the cathode chamber {) over a ceramic diaphragm and a Salzbrüoke in contact, i.e. the contact is the same as in example 12. The Vorriohtung was fed with acetone with a content by 0,05M TEAP and the catalyst. Under a nitrogen atmosphere a potential up to -1,4 V was long put on opposite the SCE to this system with the help of a Gleichstromque] le (D 050-10 delta Elektronika) 45 min. It became a device in accordance with Fig.3, as described 12 in example, when hydrogenation reactor uses. The device was filled with 10O ml soy bean oil uncl 450 ml acetone, the acetone in the hydrogenation reactor contained no electrolytes. Contents of approximately 30 ml in the cathode chamber of the device shown in Fig.2 were supplied to the chamber of the collector of the hydrogenation reactor. This reactor was not connected with a voltage regulator or a d.c. supply. The potential between the working electrode and the Bezugselektrede (SCE) in ltydrierungsreaktor was measured with a voltmeter exhibiting a negative pressure pipe. The results are summarized in table XX. Catalyst: 1 g Pa] ladiumpulver, temperature " 24°C. Atmosphär “ndruck. - 20 - NR, 365632 table XX time () 150,270,352,398 cycle per second admission potential (el) (V gegengbeP the SCE) Aus9an9s-SojabohnenOl 500 -1.03 1000 -1.02 1400 -1.00 2000 -0.97 TPeRS < I 018:0 3.6,3.7,3.7,3.7,3.8 C18: 1 20.7 24.3 27.7 31.0 38.5 010:2 55.6 54.1 52.9 50.8 44.0 *) C 18: 0.4 isomers, designation as 6,9,12-Octadecatrlens ure C18 contained 3: 3 " 7.5,5.1,3.2,2.0,1.1 example 28: Example 27 was repeated, whereby 3% Pd were used on coal as catalyst (catalyst portion of 25 mg Pd/kg oil). It was egt 60 min long under a nitrogen atmosphere a potential up to -1,3 V opposite the SCE to the catalyst in the device ange shown in Fig.2]. Contents of the cathode chamber were brought into a 3 l-Glasreaktor, which exhibited a Rfihrer. Into the reactor 650 mI soy bean oil and 650 mI acetone BingefüI became] t. After 100 min hydrogenation had the soy bean oil the following Ana] yse Eisenschaften: Iodine number: 120,9. Iran content: 5%. Palladium concentration: 0.2 mg Pd/kg oil after filtering. Fettsäiurezusammensetzung (%): C 16: 0 = 10.5, C 18: 0 = 3.8, C 18: 1 = 31.6, C 18: 2 = 50.8, C 18: 3 = 1,9. The hydrogenated (91 one refined and on taste and ha] tbarkeit evaluates. After refining the Palladiumantei] of the oil up to 0,03 mg Pd/kg oil, the oil rose had after lg weeks still another rather good taste. Example 29: Example 27 was repeated. The device shown in Fig.2 was filled however with a catalyst and a liquid, which contained electrolytes specified in table XXI. A potential up to -1,0 V opposite the SOE was set on this system under a nitrogen atmosphere with the help of a Gleichstromquel] e. The hydrogenation in the device shown in Fig.3 accomplished, which with 100 m] SojabohneoSl and 450 ml acetone filled was. Temperature 24°C. Atmosphttrendruck. The results are shown in table XXI. As methanol the Flüsslgkeit for the electrolytes (in the device shown in Fig.2) during the creation of the potential was, Methylester in the hydrogenated products was determined, table XXI electrolytic solution in the device O, 02N shown in Fig.2 Natclumdodecyl O sulfonat in acetone (5t water content) O, 05H Tetraäthylameonium - 03H Tetraäthylammoniumbromid in Acet “n O, 05M Tetramethylammonlumacetat in methanol O, 05H Natrluemethanolat p-toluolsulfonat £n Retinol catalyst (Beschlckung mg Pd/kg oil) i i i Ausgengsö in acetone O! Pd/C (2oo) hydrogenation time tensions in relation to the SCE during that hydrogenating (min) after 500 ml with C1B: 3 cycle per second admission = 2% i -0.02 V of Trans C10: 0 fatty acid composition () C18: 0 C18: 1 C18: 2 IL 3, g -0.83 V -0.83 V s P “/c (2o0) 3 Pd/C (“00) 40, -0.72 V -0.86 V C18: 3 ii 21.5 53, g 8.5 < I 10.5 I0,6 4, “40.0 “1.5,2.0 3% Pd/C (200) 24 -0.07 V 10.5 4.1 35.4 $6, G, l -0.87 V 7 10.5 “, 0 33.0 49.2 2.0,2.0 o. - o, gg V 5 10.5 3, g 31.2 51.3 2.0 3% Pd/C (200) “B -0 3 V - o, go V 7 10.5 3, g 34.7 47.3 2.0 O, 05N Tetraäthylammonlumphosphat in acetone 3 Pd/C (500) 29 -0.64 V -0.72 V 7 10.4 4.1 35.4 40.4 2.0 O, O5N Natrlumacetat in methanol 5 Pd/C (700) 350 - o, g6 V - o, go V* 7 10.6 3, g 27.6 52.8 3.0,0.1 Natrlumhydroxyd $n methanol (5 Wassergeha] t) 5 Pd/C (700) 330 - O, g6 V - o, gB V* 6 10.8 3, g 26.6 53,3 3.6 I Z FI Q footnotes to table XXI: *) Potential opposite the SCE with C 18: 3 = 3,6 ) Oer Mr. 5 Pd/C (200) was used meant that of a Katalysa%er, consisting of Palladlum on a carbon carrier, entbElt Selcher 5 palladium, thus vleZ, Trade Union of German Employees altogether 20 mg PaZZadium per kg of 01 available rare, example 30: Example 29 was repeated. The device shown in Fig.g became with the catalyst (3% Pd on coal) and G [ycerin with a content of 10M CH ONa filled, a potential up to -0,93 V opposite the SCE was long put on at a temperature of 45°C under a Stiokstoffatmosphäre 3 h. The hydrogenation was accomplished in the device shown in Fig.3, which was filled with 100 ml soy bean oil and 450 ml PropanoI-1. Temperature: 40°C. Atmospheric pressure. Catalyst portion: 2.4 g 3% Pd on coal, the results are shown in table XXII. Table XXII i Ausgangsö! with Potentia put on! Hydrogenation time (min) 46 of Trans < 1 C16: 0 10.5 10.4 fatty acid composition (%) C18: 0,3.9,3.9 C18: 1 C18: 2 21.5 53.9 28.2 53.8 C18: 3,8.5,2.0 " * *) C 18: 0.4% isomers, designation as 6,9,12-Octadecatriensäure **) C 18 contained 3: 1.4% 6,9,12-Octadecatriensäure and other isomers example 31 contained 3: Example 27 was repeated, whereby palladium was used on ion exchange resin as catalyst. The catalyst was adsorbed thereby manufactured that the Pa] ladiumch] orid on the ion exchange resin (Amberlyst A27) in diluted acetic acid. Subsequently, the catalyst with NaBHù was reduced. The resin contained 14.2% palladium. A potential up to -1,4 V opposite the lake was set on the catalyst 135 min long in acetone with a content by 0,05M TEAP. /Ydrierungsreaktor with 100 ml soy bean oil and 450 were filled ml the acetones. Temperatur' 24°C. Atmosphärendruek. 130 mg catalyst were used. The results are shown in table XXIII. Output oil hydrogenation time (min} table XXIII of Trans 1%) Fettsäurezusammensetzun g {mol %) C18: 0 IL C18: 0 10.5 10.4 C18: 2 i C18: 1 21.5 30.5 C18: 3 i < $ 3.9 53.9 8.5 hydrogenated oil 191 4 4.0 52.0 2.0 example 3Z: Example 31 was used repeated, whereby 2% Pal] adium on SI] iciumdioxyd as catalyst (catalyst portion: 100 mg Pd/kg oil). A potential up to -1,25 V was long put on opposite the SCE 60 min. The results are shown in table XXIV. Table XXIV hydrogenation time (min) Trans fatty acid composition (%) 016:0 C18: 0 C18: 1 C18: 2 C18: 3 output oil < 1 10.5 3.9 21.5 53.9 8.5 hydrogenated 01,133 6 I0,5 4.0 33.1 48.8 2.0 example 33: The potential was set on the catalyst in accordance with example 27 in the device shown in Fig.2. A potential of -1,3 V opposite the SCE was set on the catalyst with 5% Pd/C and acetone with a content by 0,05M TEAP. Contents of the Kathodsnkammer were brought to Parr autoclaves into a I], which was filled with 200 ml soy bean oil and 400 ml acetone. Afterwards contents the autoclaves under a nitrogen atmosphere to a temperature up to 60°C were warmed up. With beginning of the hydrogenation the nitrogen was replaced by hydrogen. With a second attempt, without creation of a potential, 30 ml 0,05M TEAP in acetone were admitted to contents the autoclaves. The hydrogenation was accomplished at a temperature of 60°C and a pressure by approximately 3 bar. The results are represented in table XXV. Table XXV potential, i with potential put on without angelegLee potential KaLalysaLor (filling) (mg Pd/kg) Ausgangsö] 2O0 HydrierungszeiL (min) 4B 21 of Trans < I 16 C16: 0 10.5 10.5 10.4 fatty acid composition () C18: 0 C18: l! C18: 2,3.9 21.5 53.9 B, O 32.3 49.7 6.3 4g, l 31, I C18: 3,8.5,2.0,2.0 example 34: Example 33 was repeated. The device shown in Fig.2 was filled with acetone with a content of 0,0SM TEAP and 1.8 g 5% Pd on coal as catalyst. A potential up to -1,0 V opposite the SCE S was long put on 85 min. The hydrogenation in a 1 1 Parr autoclaves accomplished, which with 500 ml Sojabohnenö] filled was. Temperature: 100°C. Pressure: 4 bar. The results are indicated in the table XXVI. Table XXVI hydrogenation time {min) output oil 13 example 35: Trans i i < 1 13 O16: 0 10.5 10.5 fatty acid composition (%] C18: 0 C18: 1 C18: 2,3.9,4.0, l 21.5 53.9 35.5 46.5 C10: 3 i 8.5,2.0 example 27 one repeated. The device shown in Fig.2 was filled with acetone with a content of 0,05M TEAP and 450 mg 3% palladium on coal as catalyst. A potential up to - i, 4 in relation to V the SCE was put on. With beginning of the hydrogenation contents of the cathode chamber of the chamber of the collector of the hydrogenation reactor were supplied. The hydrogenation took place in the device shown in Fig.3, which was filled with 100 ml flax seed oil and 450 ml acetone. The hydrogenation was accomplished with 24°C and under Atmosphärendruek. The device shown in Fig.2 was filled again with acetone with a content of 0,0SM TEAP and 300 mg 3% palladium on coal as catalyst. A potential up to -1,4 V was put on opposite the SCE. After the flax seed oil had taken up 4000 ml H=, contents of the cathode chamber of the device shown in Fig.2 were supplied again to the hydrogenation reactor. The results are summarized in table XXVII. Table XXVII output oil 2500 ml 5.7,3.5 19.4 38.3 32.8 Bs-admission 5000 ml 7000 ml 8000 ml 5.7,5.7,3.5,3.7 27.0 40.7 51.0 48.4 12.2 1, l 19 G 16: 0 {%) 5.7,5.7 C 10: 0 (%} 3.5,4.0 C 18: 1 (%) 15.4 52.0 G 18. : 2 (%) * 16.1 37.2 C 18: 3 (%} 58.9 0.0 (%) < I 29 “} C I8: 2 contained some isomers of Linolsäure with shifted double bonds.