DE1418884B - Process for obtaining fat fractions with a melting behavior that differs from the starting material - Google Patents

Description

1 2

The physical properties of fats, not directed transesterification in the presence of an alkali their melting points and their behavior lischen transesterification catalyst, subsequent Inbeim Melting or solidification depends on the activation of the transesterification catalyst with water essentially depends on the structure and amount of the deposited, with the formation of soaps and separation Triglycerides present in fats 5 differentiate solid fat fractions from liquid fat away. This applies above all to fats with narrow proportions and is therefore characterized by the melting range and preferably for those on the net that one after inactivating the alkaline Melting range of body temperature. These fats transesterification with water by addition found as special fats in the production of baking water, which is not insoluble with soap goods, confectionery and chocolate articles or, in the case of precipitation, salts which form in dissolved form, a disperser Manufacture of pharmaceutical preparations, sion of separated solid and liquid fat such as for example suppositories, use. A particle in the aqueous salty soap solution A useful natural product for this is cocoa, after which this dispersion is used in the usual way butter, which is relatively sharp for fats in a solid bowl centrifuge in an im Has a melting point that is slightly below the body-15 consisting essentially of an oil lighter temperature is. Attempts have been made to use cocoa butter as a phase and a suspension of solid fat particles Manufacture similar fats synthetically or from heavier ones obtained in the aqueous soap solution natural fats fractions with cocoa butter-like phase separates.

to separate borrowed properties. While it was known to include natural fatty acid triglycene, too Processes in which the glyceride structure is rendered non-natural with the aid of alkaline catalysts Fats due to controlled or non-controlled esterification and the catalyst after the transesterification Transesterification has changed. through. Addition of water and the formation of a

The "non-directed" transesterification means inactivating aqueous caustic alkali solution, but has

one transesterification at temperatures at which it is recommended to use this alkali as quickly as possible

the entire glyceride mixture in the liquid state must be removed before it becomes a larger amount of neutral

located. Under these circumstances, a move takes place triglycerides saponified. It was therefore from this

the fatty acid residues present in the fat take place, methods were not familiar with the teaching,

this change of place not only to allow within the soap formation, but also

of a glyceride molecule as well as between different further separation of the solid and liquid fractions

which glyceride molecules can accomplish. Of the 30 tions of the fat mixture on the presence of the

A state of equilibrium is reached when the soap builds up.

different fatty acid residues present in the fat As starting materials for the implementation of the method according to the invention according to statistical criteria, the glyceride molecules are mainly used. The so-called things natural fats, primarily triglycerides, "directed" transesterification differs from the 35 such as palm oil, palm kernel oil, coconut oil, tallow "uncontrolled" transesterification by the working and lard. But there can also be fractions of this temperature. One works using so-called fats. Finally, you can not use the usual low-temperature catalysts at temperature natural fats and above all, in which the glyceride-like fats present in the glyceride mixture or their fractions, such as higher-4 ° sperm oil formed during or during the transesterification, for example. To the glyceride molecules to be fused, working fat fractions include, among other things, can. This removes the constituents that crystallize out at higher temperatures, such as those that crystallize out in other separation processes, for example those of transesterification equilibrium during winterization, and solid fat constituents that occur in edible oils are formed. However, depending on the amount of triglyceride fractions in the liquid fat for the formation of higher-melting glycerides, the triglyceride fractions whose capable fatty acid residues have a higher-melting glyceride melting point that is substantially above or substantially rises, which in turn crystallize out. This is below the desired fraction, again as a process takes place until a practically starting material is used in the implementation of the inventive saturated solution of the higher-melting triglycene process according to the invention,
ride in the liquid that has remained liquid and there is no The starting material to be used will reproduce the higher melting point. The controlled, expediently selected in this way or by mixing and the non-controlled transesterification is in itself composed of different fats in such a way that one is known and one of its various embodiments is described in as much detail as possible in the literature in its various embodiments when the fat mixture is cooled. There will be 55 large amount of triglycerides with the desired excretion here on the AE Bailey works, “Industrial Oil Composition. In the production and Fat Products ", New York, 1951, pp. 826 to 839, of fats that are as similar as possible to the composition of the natural or EW Eckey," Vegetable Fats and Oils ", cocoa butter, is said to be in the from New York , 1954, pp. 145 to 149, and the divorced fats cited therein refer to the ratio of saturated older literature. The desired fat fraction of saturated fatty acids, in particular oleic acid, has been isolated from such transesterification products with 14 to 18 carbon atoms, for example with the aid of organic solvents, so that they are in the range of 2: 1; this fraction should preferably be obtained in an amount and / or glyce molar ratio of the rid structure present in the starting material, such as was not present in the starting material with stearic acid, palmitic acid and oleic acid residues. 65 will be approximately the same. The amount of

The invention relates to a method for obtaining different fats present, completely saturated

of fat fractions with a triglyceride from the starting material should not be significantly greater than

deviating melting behavior due to controlled or natural cocoa butter.

3 4

For those who are not guided and / or for those who walk. The one directed by non-directed transesterification Transesterification to be used catalysts holding triglyceride mixture can then be cooled and are known per se. Be separated from particular importance; but it cannot apply to them either are the transesterifications directed by lower monovalent or polyvalent hydrocarbons to attract a directed transesterification, d. H. close those with 1 to 8 and preferably with 5, whereby one to carry out the 1 to 3 carbon atoms derived alcoholates directed transesterification necessary low temperature Alkali and alkaline earth metals. In addition, the catalyst can advantageously only clog when but also the free metals or their alloys, the triglycerides of the desired melting range can be applied. In particular, those who have left with are here.

Room temperature liquid alloys of sodium io In the manufacture of a cocoa butter substitute fat and potassium useful. If the palm oil to be used is, for example, left slowly at first Catalysts in solid form before - cool alkali alcoholates so far that the highest melting are in solid form on the market - then it recommends that parts crystallize out, which reaches around 30 ° C itself, this is mechanical with the help of suitable devices. Then gradually cool down to about nisch well to distribute in the starting material. Man 15 20 ° C, whereby those in palm oil can be but also the finely divided solid catalysts excrete existing natural glycerides that the first in an inert solvent, similar to natural cocoa butter. Then sets for example, aliphatic or aromatic carbons are added to the conversion catalyst and omitted Hydrogen, and these dispersions disperse the conditions of the directional transesterification and add to the starting material. Alcoholates can optionally with further cooling to about but also in the 16 ° C immediately after their production the newly formed glycerides with two saturating ones Solution of the alcoholate in alcohol and one unsaturated fatty acid residue per mole can be used. Strong organic bases can also crystallize out naturally.

already as catalysts for the transesterification. B. in the cases

been hit. The amounts of catalyst used are 25, in which the distribution of the fatty acid

at least about 0.05 to 0.1 percent by weight, residuals on the glyceride molecules the statistical

preferably 0.1 to 0.5 percent by weight sodium equilibrium or only a little of the statistical

methylate, based on the triglyceride to be transesterified. tical equilibrium deviates. Contains example

You can also use larger amounts, for. B. up to wise a starting material to be processed

1 or 2 percent by weight will work. When using 30 no or only very small amounts of tri-

other transesterification catalysts than sodium glycerides, which melt much higher than the

methylate, equivalent amounts of alkali are to be used. triglyceride fraction to be produced, then you can

The transesterification that takes place when the non-directed transesterification and process are carried out according to the invention cannot begin immediately with the directed transesterification.
directs, directed or a combination of not 35 In directed transesterification, the diverted and directed transesterification can be. esterification catalyst, unless it is made from a

In the case of non-directed transesterification, which occurs in previous, non-directed transesterification already in the tri-temperatures up to 250 ° C, for example, a glyceride mixture is present, can be added, are also less active catalysts, such as when there are already small amounts of solid triglycees, for example Alkali hydroxides or their soaps, 40 riden have formed, however, it is recommended to use the applicable. It is therefore not absolutely necessary to also use a transesterification catalyst for the controlled conversion for a non-directed transesterification intended for esterification first in the completely melted starting fats To distribute completely fatty acid or anhydrous to nen triglyceride mixture and then quickly do. Those intended for the directed transesterification to cool down to the temperature at which the starting materials are made should, on the other hand, be as free as possible from the solid Trivon to be isolated later Be fatty acids and water, d. i.e., the content of glyceride fractions begins.

of free fatty acid should, if possible, be 0.2 percent by weight and the water content should be 0.01 percent by weight NEN glycerides can be through the transesterification and not exceed. Dry soaps or metal- largely influence the crystallization. Provided hydroxyde, as it depends on a previous 50, from a present Trinicht controlled transesterification still present in the oil glyceride mixture the triglycerides with the highest level can, however, do not interfere. to gain possible melting point, one leaves the

If the starting material has a significant amount of controlled transesterification time to stop the

genes of triglycerides with an above the enamel equilibrium, before the highest-

point of the desired triglyceride, for example 55 melting triglycerides by removing heat

crystallize the desired cocoa butter substitute fat, d. i.e., one makes the crystalline

Contains melting point, one can initially make this sation speed smaller than the transesterification

higher melting parts and possibly also speed. But if you want to leave the

the triglyceride fraction present in the starting fat in favor of the highest melting triglycerides

of the desired composition in whole or in part- 60 the formation of a lower-melting triglyceride-

Let it crystallize out wisely and only then prevent fractions, as is the case with the

Addition of the catalyst with the directed Um- Production of a cocoa butter substitute fat the case

start esterification. In this way one avoids is, then one makes the crystallization speed

the formation of even larger amounts of undesirable speed greater than the rate of transesterification. on

refractory products. 65 In this way one passes through the temperature

But you can also pre-area in the starting material, in which only the higher melting tri

existing higher melting triglycerides can excrete faster than with the non-glyceride

Directed transesterification in the lower melting process described first and achieved very

soon the temperature range in which the triglycerides crystallize with the desired melting point. Once this temperature has been reached, the rate of crystallization can of course be reduced make, because in this temperature range the setting of the equilibrium and as complete as possible Crystallization of all glycerides melting in this temperature range is desirable.

The rate of transesterification can be determined in the controlled transesterification by the choice of catalyst, by its amount and, especially in the case of solid catalysts, by the stirring speed. The rate of transesterification increases with the activity and amount of the catalyst and with it the stirring intensity. The rate of crystallization depends on the temperature control dependent: The faster the heat is removed from the triglyceride mixture, the greater the rate of crystallization.

The temperature ranges within which the transesterification takes place, depending on the composition the starting fat may be different. In general, when the solid crystallizes out Fat components reached the final temperature by 5 to 20 ° C below the melting temperature of the desired one Fixed portion lie. The duration of the controlled transesterification can vary within wide limits and will generally be between 5 and 75 hours. Of course, the directed transesterification can also proceed more slowly - there are already transesterification processes with cooling times of a week and more has been described - but one is made for economic reasons hardly go beyond a cooling time of 3 days.

There are several ways to determine whether the rate of crystallization is greater is than the transesterification rate, or vice versa. These possibilities are more or less based less on an analytical comparison of the composition of the solid and liquid components or in simplified form on the control of the change in the properties of the excretory Fixed portion. The fatty acid composition of the starting mixture is obtained by methods known per se established, then it is also known which highest melting glycerides in a theoretically optimal guided transesterification would have to crystallize. The melting behavior the actually crystallized triglycerides and the content of the liquid triglyceride to form Fatty acids capable of high melting triglycerides can easily be tracked during transesterification and assess the crystallization. Most processed fats contain various fatty acids Degree of saturation. One can therefore determine whether and in which one by determining the iodine numbers Extent in the solid fractions less saturated fatty acids have been incorporated, which lower the melting point of the solid parts. The iodine number can be determined by determining the im Replace or supplement the solid fraction of existing, fully saturated triglycerides. Should be the one to be processed Glyceride mixture consisting essentially of saturated fatty acids of various chain lengths exist, then the change in the saponification number is a measure of the composition of the liquid or. Fixed portion. Also allow the changes in the melting points of the two fractions a control of the transesterification or crystallization process.

The determination of the hardness of the excreted fat by penetration measurement is particularly suitable to get an insight into the composition of the fat. The more uniform the excreted Is composed of fat, the greater the hardness, i.e. H. the lower the penetration. As lower-melting fat components are excreted, the hardness of the fat decreases and the penetration values increase. Likewise, the determination of the dilatation of the excreted Use solid fat to control the transesterification process.

In order to carry out this control in practice, a glyceride sample is taken during the transesterification from about 100 to 500 g, sets so much of a wetting agent solution with stirring that a Forms dispersion of separated solid and liquid fat particles in the aqueous wetting agent solution, Transfer this dispersion into centrifuge tubes and centrifuge in a standard laboratory centrifuge. Man then separates the solid from the liquid phase and examines the fractions after having them beforehand has dried. The iodine number, the saponification number or the melting point are determined in usual way. To determine the saturated triglycerides, the dried solid fraction is used in about 55 ° C dissolved in ten times the amount of acetone and then heated to 20 ° C with vigorous stirring chilled. After about 30 minutes at this temperature, practically all are completely saturated Triglycerides crystallized out. It is filtered off, washed with acetone at 18 ° C. and driven off on the filter residue still adhering acetone and determines the amount of this residue. Of course are other analytical methods can also be used, such as, for example, the determination of the molecular refraction etc.

The transesterification is followed by the separation of the solid glyceride fraction from the remaining liquid on. The separation process used here is a variation of the well-known, here briefly called the "rewetting process" designated separation method, in which the with the surface of the solid glyceride particles liquid glycerides in contact are displaced by aqueous wetting agent solution, d. h., the solid glyceride particles are rewetted. The variation described here differs from the known method in that the formation of the soap used as a wetting agent is formed with the formation the dispersion of solid and liquid glyceride particles combined in an aqueous soap solution. To this Purpose one mixes the catalyst-containing fat with water, which with the transesterification catalyst under Formation of lye reacts. It is advisable to add a little water first, i. H. about 0.1 to 1 percent by weight, based on fat, so that a lye that is as concentrated as possible is formed reacts quickly with the fat, and only then add the rest of the water.

The amount of water to be added to the fat should be at least so large that it is easy to flow Suspension of solid and liquid fat particles is formed in an aqueous soap solution. The entire amount of water should be at least about 0.5 times the weight of the triglyceride mixture. In general one aligns with the amount of water

I 418 884
7 8

according to the amount of solid glyceride fat particles to be separated in aqueous soap solution. The disper components. If this amount is about 30 weight sion is separated in a laboratory centrifuge, percent of the total glyceride mixture is sufficient. while with a 5 colored, optionally in a pure white consistency, content of 50 to 60 percent by weight of solids is obtained. If you change the conditions of the um-glycerides expediently twice that of the wetting, for example the concentration of soap, the amount of weight of the entire triglyceride mixture of water or the other components of the water-water applied. You can of course also use some soap solution, then you can use even more water on the changed, up to about 5 times the color intensity of the solid fraction of the conditions of the glyceride mixture, as long as this allows you to recognize the concentrations that are necessary for separating the most tration of the soap solution For a light-colored or a pure white solid triglyce-satisfactory wetting and emulsifying effect necessary rids are necessary.
Limit is pressed. Provided that the solid glycerides to be separated are included

The water contains salts, which with the soap no 15 completed transesterification already in the solid state Form insoluble precipitates, such as are present, the separation can be directly an-sodium chloride or sodium sulfate. It can also be closed. But it may also be desirable NEN other known emulsion stabilizers, such as the glyceride mixture after the addition less For example, methyl cellulose, carboxymethyl cellu- water quantities to be heated so as to cause the formation of loose, ether made from celluloses and oxyalkylsulfonic acids, 20 soap to speed up. In this case must then Cellulose sulfates, alginates or other water-soluble ones, however, cause the higher melting derivatives to crystallize out High molecular carbohydrates, like the two fat components, made again for example of cellulose or starch, polydene. This variation of the veracrylate according to the invention or polymethacrylates, etc. may be added. driving gives you the option of initially using the

When converting the alkaline transesterification process, fat fractions are undesirable catalyst in soap or in the production of the high melting point, e.g. B. in larger quantities Dispersion of completely saturated triglycerides, ab triglyceride particles, formed separately from one another, solid and liquid in aqueous soap solution can separate and now from that with this first separation the soap can be precipitated due to the hardness of the water. accrued liquid portion by cooling the If this is kept within tolerable limits, d. i.e., 30 fat fraction with the desired melting range if the still existing, not precipitated water is to be excreted and using the at the Soluble alkali soap is sufficient to disperse the soap solution formed by destroying the catalyst To maintain the state, the water hardness needs to be separated again.

not to be considered. But if this is still undesirable in the solid fat fraction

In the case of insoluble soaps, there may be 35 high-melting ingredients present then it is advisable to mix softened water together with the desired fat fraction turn and / or add substances to the water, remove the fat components that have remained liquid, which bind the hardness or are able to be separated, in order to make them again insoluble in water Separate metal soaps from this in water-soluble steps. This separation process To transfer alkali soaps. These substances 40 can be done in any way; with special include the well-known complex-forming alkali Advantages if the suspension of the solid fatty phosphates is heated, such as alkali tripoly, tetra components in the aqueous wetting agent solution, where Poly- and -hexamethaphosphate or other alkali either on the fat fraction to be processed poly- and metaphosphates or the alkali salts that heat the elevated separation temperature or they entirely known organic complexing agents, e.g. B. the 45 melts and cools to the separation temperature, so Nitrilotriacetic acid, ethylenediaminetetraacetic acid that in any case the undesirable high-melting or other aminopolycarboxylic acids. These sub- den glycerides in solid form and the glyceride fractions are then added to the water, tion with the desired melting behavior as when alkaline earth compounds are obtained as transesterification liquids.

catalysts, because then all of the 50 die formed after the liquid triglycerides have been separated off Soap as water-insoluble alkaline earth soap together with the aqueous soap solution obtained would exist. In such a case, solid triglycerides could be derived from this solution the complex-forming substances mentioned have already been filtered or centrifuged off after melting add to the water that will be the reaction between. Should the severing of the solid or the the transesterification catalyst and fat release liquefied triglycerides from the aqueous soap; But you can make the complex-forming substances solution difficulties, so you can also add later. As with soap formation, so soap concentration is achieved by acidifying the solution Here, too, it is advisable to reduce the complex-forming substances. The resulting free fatty acids In order to achieve high concentrations, first of all go into the triglyceride fraction and must to use a little water and the soap obtained, optionally from this by alkali refining then dilute the solution later. removed. This alkali refining can

To control the rewetting process, for example bypass when using synthetic Kapillaraktivsubder optimal soap concentration or the optimal punch, especially those made from sulphate or sulphate water, the following method can be used: fonattyp, added to the aqueous soap solution. Have it The mixture to be separated is solidified and, for example, fatty alcohol sulfates and alkylbenzene liquids are added Triglyceride a fat-soluble dye to sulfonate and in particular the tetrapropylene benzene and then forms the dispersesulfonate in the manner described, which has been found to be useful. An addition to this sion of separate, solid and liquid synthetic capillary active substances causes a

easier separation of the higher-melting triglyceride fraction dispersed in the aqueous soap solution. If you melt this triglyceride fraction before separating it, you can get the optimal one Conditions of this separation operation, in particular the concentration of soap and possibly synthetic Capillary active substances can easily be determined by looking at a sample of this dispersion which has melted Stains triglycerides with the help of a fat dye and then carries out the separation.

The amount obtained when carrying out the process according to the invention is too high or too low Melting glycerides can be fed back into the process as starting material.

Although the production of cocoa biscuit replacement fats in the description of the invention Process was particularly emphasized, this process can not only be applied to the production of fat fractions that melt in the cocoa butter area. You can also make fats, whose melting point is significantly above body temperature. Such fats are for example as an additive to dietary fats, e.g. B. to diet margarines, which are not by hydrogenation should contain manufactured hard fats. In addition, according to the method according to the invention Manufacture drawing fats used in the bakery industry that are not supposed to melt as sharply like cocoa butter, but which does not contain any components that melt significantly above 37 ° C should.

The previous description of the method according to the invention is essentially based on those cases in which a triglyceride solid at normal temperature, preferably a cocoa butter substitute fat, should be produced. Of course, the method according to the invention can also be used to advantage for the production of triglyceride mixtures with special properties that are liquid at normal temperature use. When cooking oils are winterized, for example, those at higher temperatures separated melting products. These are triglycerides, which melt at higher temperatures not exclusively from saturated fatty acids, so that the oil in the separation of the higher melting Parts of unsaturated fatty acids are lost. According to the invention you can now first with the oil carry out a controlled transesterification with the aim of removing those present in the higher-melting fractions Residues of unsaturated fatty acids as largely as possible due to such saturated fatty acids substitute. If the higher-melting triglycerides present after the transesterification are then separated off, then you get a higher yield of oil, but without reducing the cold resistance of the oil.

The rise, flow or clear melting points and dropping points mentioned in the examples were after the "German standard methods for the investigation of fats, fat products and related substances", CIV 3 a and C rV 3 b, determined.

example 1

The transesterification of the fat took place in a tapering container with a capacity of 12 cbm instead, which was provided with a cooling jacket. The contents of the container were slowed down with the help of a running anchor stirrer kept in motion, d. i.e., the agitator shaft protruded from the top almost to the lowest point and the agitator rod was approximately U-shape; it stroked at a short distance over the container wall.

5 tons of deacidified, bleached and dried coconut oil (V ⁰ = 1.4491; SZ = 0.08; water content = 0.005%; slip melting point = 23.9 ° C; JZ = 9.5) were heated to 70 ° C in this container, mixed with 0.3 percent by weight of dusty sodium methylate and stirred under nitrogen for 30 minutes at this temperature. After this time, the transesterification equilibrium had been established in the liquid phase, which was evident from the fact that the slip melting point, which was 26.9 ° C. towards the end of this time, no longer changed. The mixture was then cooled to 29 ° C. over the course of an hour with stirring and then stirred further without cooling. As the crystallization began, the temperature rose to 30 ° C over the course of an hour.

In order to control the course of the directional transesterification which then follows, during this Repeated transesterification samples of 100 g fat each taken and each with 100 ecm 3% sodium sulfate solution, which had the same temperature as the removed fat, stirred for 30 minutes. This formed a dispersion of separated solid and liquid fat particles in the sodium sulfate soap solution. Then the dispersion was in a laboratory centrifuge into an oily phase and into a Dispersion of solid fat particles separated in aqueous solution. The aqueous phase was of the separated oily, and the solid fractions were by boiling and acidifying the aqueous solution deposited. The higher-melting fat fraction obtained in this way was separated from the acidic aqueous Phase separated, dried, and the slip melting point of this phase was determined.

The further crystallization of the fat mixture to be transesterified was then carried out in such a way that the slip melting point of the solid fat constituents present at a final temperature of the controlled transesterification of 25 ° C was not below 30 ° C. To this end, the mixture was within 5 hours from 30 to 27 ° C, cooled within further 5 hours, from 27 to 26 ° C and then in the course of 10 hours from 26 to 25 ⁰ C. During this time, when the temperatures 26 and 25 ° C. were reached, samples were taken, and slip melting points of 35.9 and 32.0 ° C. were determined on the solids isolated according to the above procedure. Then the fat was stirred for a further 4 hours at 25 ° C.

To prepare the dispersion, 5 t of tap water (6 ° German Hardness) 3% sodium sulphate solution at 25 ° C was added. The mixture was 1 hour stirred for a long time, resulting in a dispersion of separated solid and liquid fat particles in aqueous Soap solution made up. The dispersion was carried out continuously in a solid-jacketed centrifuge of conventional design separated into phases of different specific weights, the lighter phase being the im essentially anhydrous oil and, as the heavier phase, a suspension of solid fat particles in the aqueous Soapy solution was obtained. This dispersion was made by boiling in aqueous soap solution and liquid Fat broken down. The liquid fat, which was produced in an amount of 2.3 t, had a slip melting point of 30.5 ° C, a flow melting point of 31.8 ° C,

II 12

a clear melting point of 32.4 ° C and an iodine half of 48 hours cooled from 47 to 20 ° C. When the number was 6.5 and represented the desired cocoa butter - 32, 25 and 20 ° C, samples were taken and the replacement fat fraction. Iodine numbers of 12, 18 were found on these samples. · _{] 9} ^unc * 25 found. When 25 ° C. was reached, _the transesterification was terminated in example 2 5 by stirring the 5 t of coconut oil treated in this way according to example 1 under fat with 7.5 cbm of a solution at 20 ° C. initially not under the conditions described there , 5 percent by weight tetrapropylenebenzene-steered, ie in the liquid phase, interesterified. The directed transesterification including ansulfonate and 4 percent by weight sodium sulfate was prevented. The further processing took place as in the Beisicht, the formation of the highest melting triglycerides io game 1.

In favor of the formation of less high-melting points, 2 t of a higher-melting fraction were used to push back triglycerides, carried out more quickly with a rising melting point of 54 and an iodine in Example 1, that is, the fat was given less number of 26 and 3 t of liquid components with a rising time adjusting the Umesterungsgleichgewichtes melting point below 10 ⁰ C and an iodine value of relaxed as when trying to obtain example 1. to this 15 63rd

The purpose was the fat mixture, after it had reached the temperature of 30 ° C, within hard fat components for plastic fats, for diet 2 hours at 26 ° C and within 2 more margarines and for production Cooled purely vegetable hours to 25 ⁰ C. After that, the fat became unhardened drawing fats and drawn margarines. Stirring was continued for 4 hours at a temperature of 25 ° C. This can be determined by separating the lower-melting fat fraction contained in the solid fat fraction, which contains the most favorable conditions for wetting, a sample of 100 g of the fat, which has been frozen in an excellent cocoa butter substitute fat, was dyed with "fat red" and included. The liquid phase is added as liquid edible oil, 100 ecm of the 3 ° / aigen used in Example 1, for example for the production of mayonnaise, and sodium sulfate solution. After 30 minutes of stirring as a vegetable oil for the production of margarine, the resulting dispersion was usable,
divided and some of the divided portions with changeable.
varying amounts of tetrapropylene benzene sulfonate ± 5 e 1 s ρ 1 e 1 4
puts. When the dispersion was separated in a laboratory 5 t of the palm oil processed in Example 3 were ratorium centrifuge, it was found that the under 30 under the conditions specified in Example 1 using an aqueous phase with an additional one so long not directed transesterified until in the content of 0.3 percent by weight of tetrapropylene liquid phase had made the transesterification equilibrium of a benzenesulfonate solid fraction obtained pure white. Then the mixture was so oil-free in the course. Cooled one hour to 41 ° C, where the crystallization The main amount of transesterified fat was used 35 sation. The cooling was switched off and, as described in Example 1, by stirring with the temperature rose to 47 ° C within 2 hours due to the crystallization of a 3% sodium sulfate solution in this dispersion.
The fat was used with the intention of producing a softer solid fraction than in the 1.5 times the amount by weight of sodium sulphate solution in the preceding example. Sufficient 4 ° of tetrapropylene benzene sulfonate was then added to the dispersion within only 5 hours from 47 to 20 ° C. that the aqueous solution cooled and at this temperature still contained 0.3 percent by weight of it for 4 hours. held.

The dispersion was then as in Example 1 in the manner indicated in Example 2 was described, further processed, and it fell 3.9 t found that one can achieve optimal separation results with of a solid fat with a slip point of 45 1.5 times the amount by weight of an aqueous solution of 28.2 ° C and an iodine number of 9.0. This solid solution received 4 percent by weight of sodium sulfate Fat fraction was softer than that of Example 1 and 0.6 percent by weight of tetrapropylene benzene sulfonate produced and was suitable for the production of a contained. It was therefore the mixture of the old summer margarine. different and the remaining liquid glycerides with. 50 7.5 cbm of a solution at 20 ° C stirred, the 4 Ge example 3 percent by weight sodium sulfate and 0.6 percent by weight 5 t palm oil deacidified by distillation (SZ contained tetrapropylene benzene sulfonate. The dispersion = 1.0; JZ = 52; Water content = 0.006 percent by weight was stirred for another 30 minutes and then concentrated) were used under the continuously operating solid jacket centrifuges described in Example 1 not steered interesterified. Then 55 was separated.

the fat was cooled to 41 ° C. in the course of an hour. 53 percent by weight of a higher melting point and the cooling was switched off. Obtained by the onset of zenden glyceride, which had a riser melt crystallization, the temperature rose within point of 44 ° C and an iodine number of 41. 2 hours at 47 ° C. This fraction was suitable as a solid fraction for summer with the intention of producing a solid fat fraction, 60 margarine. The oil that remained liquid had a triglycerides which, statistically speaking, were about a third of the slip melting point of 20 ^° C. and an iodine number completely saturated and about 64.
two thirds from triglycerides with two saturated. .
and an unsaturated fatty acid residue became examples
the further crystallization was carried out in such a way that the iodine 65 To winterize cottonseed oil was the number of solid fat excreted at 20 ° C - 10 kg of this oil (content of free fatty acids components not greater and not significantly less = 0.056 percent by weight; water content = 0.006 geals 29. For this purpose, the fat was weight percent; n _D ⁱ⁰ = 1.4650) in one with a

Cooling jacket and a stirrer provided container first transesterified with stirring and then with dispersed aqueous sodium sulfate solution. The oil, heated to 40 ° C., was used for transesterification with 0.4 percent by weight mixed with dusty sodium methylate, then initially from 40 to in the course of 20 minutes 25 ° C and then cooled from 25 to 0 ° C in the course of 48 hours. Because the amount of catalyst is greater was than in the previous attempts and for the elimination of the compared to the previous ones Examples of relatively small amounts of solids were available for 48 hours the transesterification equilibrium is established to a very large extent during the controlled transesterification.

When trying out the optimal wetting conditions, it was found that the soap concentration was proportionate was high. The fat was therefore with 1.5 times the amount by weight of a 3% sodium sulfate solution added the 0.5 weight percent tetrapropylene benzene sulfonate and so much sulfuric acid contained that the concentration of the produced soap was 0.2% by weight. The dispersion was separated in a conventional, continuously operating solid jacket centrifuge and the resulting Phases worked up. 8.8 kg of liquid oil with an iodine number of 107 were obtained, at 0 ° C. after 5 hours has not yet shown any eliminations. 1.2 kg of higher melting fractions were obtained from the aqueous phase obtained with an iodine number of 67.

With a winterization carried out in the usual way, in which the same starting oil within 72 hours, while carefully stirring, cools from 15 to 0 ° C and the coarse crystals formed were separated in a filter press, only 73 percent by weight of oil fell in addition to 27 percent by weight fixed proportions.

Example 6

This example describes the production of a solid fat that is used in the production of suppositories serves and therefore should melt below 37 ° C, but should also have a certain plasticity, so Medicines can be easily incorporated.

For this purpose, 7 t of palm kernel ^fat (n _D i0 = 1.4510; content of free fatty acids = 0.05 percent by weight; water content = 0.006 percent by weight; JZ = 18.5) were processed under such conditions that the transesterification equilibrium is reached during the crystallization of the could not set the highest melting solids. To achieve this, the amount of sodium methoxide to 0.2 percent by weight was lowered, and 30 minutes carried out long after the at 7O ⁰ C, non-steered transesterification the mixture was cooled within 4 hours at 28 ° C, where a strong crystallization started and the temperature of the fat rose to 30 ° C without cooling. The further crystallization was carried out in such a way that the iodine number of the ^{proportions precipitated at 25 °} C. was in the range from 10 to 12. This was achieved by cooling the fat from 30 to 25 ° C within 48 hours.

To prepare the dispersion, 20 t of a previously obtained aqueous solution were used Contained 0.3 percent by weight soap and 3.5 percent by weight sodium sulfate. After 30 minutes Stirring, the dispersion was separated with the help of centrifuges, as are used to separate the "soapstock" used in oil refining. There were 30 weight percent solids with an iodine number of 10.9 and 70 percent by weight of liquid fractions with an iodine number of 21.8.

Example 7

30 kg of a refined bleached and dried coconut fat (n _D * ° = 1.4491; SZ = 0.09; water content = 0.006%) were, as described in the previous examples, after adding 0.3 percent by weight of sodium methylate for 1 hour at 70 ° C not steered interesterified. It was then cooled to 30.degree. C. over the course of 2 hours. For this purpose, the fat from the storage container was returned to the storage container via a scraped surface cooler with a capacity of 41 (this device is described in German Auslegeschrift 1088 490). The cooling rate was adjusted so that the temperature was lowered over the course of 23 hours from 30 to 25.5 ⁰ C. In addition, at the start of cooling, 100 g of solids obtained in a previous separation were added as seed crystals. The fat was pumped another 20 hours at 25.5 ⁰ C, with well-trained needle-shaped crystals formed.

. When trying out the optimal wetting conditions by adding a fat dye to the dispersion formed from fat and soap solution, a wetting agent solution with a reduced soap content proved to be optimal. It was the total amount of fat with 30 therefore kg of a 3% sodium sulfate solution of 23.5 ⁰ C processed 2,3 kg l ° / o sulfuric acid had been added. This dispersion was separated after stirring for 30 minutes in a full bowl centrifuge; during working up of the removed from the centrifuge phases, 10.6 kg of a very sharp-melting hard fat with a slip melting point of 30.2 ⁰ C and a clear melting point of 30.6 ° C and 39.4 kg of a liquid product were obtained, the need to do is to be used together with a high-melting triglyceride, for example a tristearin, in a renewed transesterification.

Example 8

31 kg of deacidified bleached and dried palm kernel fat were added after adding 0.5 percent by weight dust-fine sodium ethylate for 1 hour at 70 ° C not steered interesterified. Then it became Fat in the apparatus used in the previous example initially on within 3 hours 31 ° C and then cooled to 26.5 ° C over a further 25 hours. After adding 100 g finely divided Seed crystals from a previous experiment developed over a further 22 hours well formed crystals at 26.5 ° C. The rate of transesterification and crystallization were not controlled in this experiment. The fat mixture was with 31 kg of a 3 ° A> strength sodium sulfate solution of 26.5 ° C, to which the amount of 3.1 kg recognized as optimal in previous experiments 10% sulfuric acid had been added. After stirring for 30 minutes, the dispersion, as described in the previous examples, separated in a full-walled centrifuge and the phases worked up. 10.1 kg of hard fat with a flow melting point of 36.1 ° C. and a clear melting point were obtained of 36.4 ° C. The liquid product, which was obtained in an amount of 20.9 kg,

was suitable for use as a liquid component in a new transesterification.

Example 9

A mixture of 80 g of dehydrated and hydrogenated soybean oil (JZ = 1; content of free fatty acids = 0.1 percent by weight) and 120 g of palm oil that has been deacidified by distillation (JZ = about 50; content of free Fatty acids = 0.23%) after the addition of 1 g of finely divided solid sodium methylate for 1 hour Heated to 70 ° C. This non-directed transesterification resulted in a glyceride mixture that was about 40% 3-fold saturated, about 40% double saturated and about 20% double and triple unsaturated glycerides. To the Inactivation of the catalyst, 0.1 g of water was dispersed in the oil by vigorous stirring. After that the mixture was cooled from 46 to 38 ° C. within 7 hours with stirring. It crystallized a large part of the higher melting parts contained in the fat.

The resulting mixture of solid and liquid fat was then at 38 ° with a solution of 16 g sodium sulfate and 0.45 g concentrated sulfuric acid added to 400 g of water. Over the course of three hours of stirring, the mixture neither heated and cooled, the sodium hydroxide solution formed from the catalyst saponified some of the Glycerides to form soap. This resulted in a dispersion of solid and separated from one another liquid glyceride particles in the aqueous solution. When throwing off a small portion of the with A dispersion added to a fat dye in a centrifuge was found to be in the solid fractions liquid substances were still retained. The dispersion was therefore 10 ecm an aqueous Solution of 1.6 g of alkylbenzenesulfonate added. The resulting dispersion was in a centrifuge into a lighter aqueous phase and into a heavier dispersion of solid fat components in aqueous solution separated. After working up, 87 g of oil and 111 g of solid glyceride were obtained. The iodine number of the solid Glycerides was 21.

The oily glyceride obtained in the manner described was cooled from 40 to 15 ° C. over the course of 20 hours with stirring, some of the fat crystallizing out. This mixture was stirred with twice the amount by weight of an aqueous solution containing 2% alkylbenzenesulfonate and 4% sodium sulfate. The resulting dispersion was separated in a conventional manner in a centrifuge into a lighter liquid phase and a heavier suspension of solid fat components in aqueous solution. After work-up 59 of a solid fat fraction was obtained g, which had an iodine value of 37 and at 20 ⁰ C, a dilatation of the 1200th This fat was suitable as a cocoa butter substitute and could also be used together with natural cocoa butter. The liquid phase obtained in the second separation stage (dropping point 12 ° C.; JZ = 56) could be used as a liquid oil in margarine production.

The solid phase obtained during the first separation could be used in a repetition of the experiment can be used in place of the hydrogenated soybean oil or used together with it. One could but also this fraction by a repeated separation carried out at a somewhat higher temperature separate into a higher and lower melting fraction, with the lower melting fraction also as Cocoa butter substitute was suitable.

Claims (7)

Patent claims: 1. Process for obtaining fat fractions with a different from the starting material Melting behavior due to directed or non-directed transesterification in the presence of an alkaline Transesterification catalyst, subsequent inactivation of the transesterification catalyst with Water with the formation of soaps and separation of the separated solid fat fraction from the Fractions remaining liquid, characterized in that after inactivation the alkaline transesterification catalyst with water by adding more water, which does not contain any insoluble, precipitate-forming salts dissolved with soaps, a dispersion of one another separate solid and liquid fat particles in the aqueous salty soap solution forms, after which this dispersion in the usual way in a solid bowl centrifuge in a lighter phase consisting essentially of an oil and one as a suspension of the solid Fat particles in the aqueous soap solution accumulating heavier phase separates. 2. Application of the method according to claim 1 on the separation of a maximum melting point which can be produced under the conditions of controlled transesterification Glyceride fraction, in particular for the winterization of edible oils, characterized in that that the rate of transesterification is set greater than the rate of crystallization during the controlled transesterification. 3. Application of the method according to claim 1 to the production of glyceride fractions which melt lower than that which can be produced under the conditions of a directed transesterification The highest melting glyceride fraction, in particular for the production of cocoa butter substitute fats, characterized in that the Temperature range in which the highest melting glycerides crystallize under the conditions the controlled transesterification progresses so quickly that the rate of crystallization is greater than the transesterification rate. 4. Modification of the method -according to claim 3, characterized in that one off Fats that contain such high-melting glycerides or that are made up of under the Directed transesterification conditions could form such high melting point glycerides that The highest melting glycerides can crystallize before the start of the controlled transesterification and optionally separated, then the transesterification catalyst is added and the controlled transesterification performs. 5. The method according to claim 4, characterized in that one prior to the start of the steered Transesterification the amounts of triglyceride of the desired in the starting material Can crystallize melting range. 6. The method according to claim 3 to 5, characterized 009154/192 I 418 884 characterized in that in the presence or absence of a catalyst for the directed transesterification first at temperatures up to 30 ° C the highest melting and then at temperatures up to 20 ⁰ C the less high melting portions can crystallize and then in the presence of a catalyst for the controlled transesterification allows the newly formed, less high-melting fractions to crystallize out, optionally cooling to about 16 ° C. 7. The method according to claim 2 to 6, characterized in that one in the processing of fats that contain appreciable amounts of triglycerides with a melting point that is about the melting range of the desired triglyceride fraction is contained, initially not directed and then controlled transesterified.