HUT65567A

HUT65567A - Process for separating steroids from lipids

Info

Publication number: HUT65567A
Application number: HU553088A
Authority: HU
Inventors: Corran Norman Stuart Mclachlan; Bruce Hamilton; Owen Catchpole
Original assignee: Mclachlan; Piper
Priority date: 1988-09-09
Filing date: 1988-09-09
Publication date: 1994-07-28
Also published as: HU885530D0

Abstract

A találmány tárgya eljárás szteroidok lipidektől (például koleszterinnek vajzsírtól) való elválasztására. Az eljárás szerint egy szteroid/zsír elegyet tartalmazó anyagból nagynyomású folyadékkal (vagy szub- vagy szuperkritikus nagynyomású gázzal) extrahálják a szteroid/zsír elegyet, vagy a szteroid/zsír elegyet ebben oldják, és a kapott nagynyomású folyadékelegyből bázisos fémek oxidjait vagy oxigéntartalmú sóit (például kalcium- vagy magnézium-oxidot, -karbonátot, -szulfátot stb.) tartalmazó adszorbensre szelektíve adszorbeáltatják a szte roido(ka)t, majd a lényegében szteroidmentes oldatból — kívánt esetben frakcionáltan — kinyerik a szteroidmentes lipideket, az adszorbensről pedig leoldják a szteroidokat.The present invention relates to a method for separating steroids from lipids (e.g., cholesterol from butter fat). According to the process, a steroid / fat mixture is extracted from a steroid / fat mixture material with high pressure liquid (or sub- or supercritical high pressure gas) or the steroid / fat mixture is dissolved therein and the oxides or oxygen-containing salts of the base metals from the resulting high-pressure liquid mixture (e.g. selectively adsorb the steroid (s) to an adsorbent containing calcium or magnesium oxide, carbonate, sulfate, etc., and then extract the steroid-free lipids from the substantially steroid-free solution, optionally fractionally, and release the steroids from the adsorbent.

Description

COPIES

A method for separating steroids from lipids / ·.

PIPER dames, William, AUCKLAND

MCLACHLAN Corran, Norman, Stuart, AUCKLAND, ÚD ZÉLAND

Date of announcement of 'Rem ^ eíkóz.i': 09/09/88.

International entry report number: PCT / GB88 / 00739

International Publication Number: W0 90/02788

The present invention relates to a method for separating steroids from lipids (e.g., cholesterol from butter fat).

According to the process, a steroid / fat mixture is extracted from a steroid / fat mixture material with high pressure liquid (or sub- or supercritical high pressure gas) or the steroid / fat mixture is dissolved therein and the oxides or oxygen-containing salts of the base metals from the resulting high-pressure liquid mixture (e.g. selectively adsorb the steroid (s) to an adsorbent containing calcium or magnesium oxide, carbonate, sulfate, etc., and then extract the steroid-free lipids from the substantially steroid-free solution, optionally fractionally, and release the steroids from the adsorbent.

•• Ο és ν ν «· · · · · · ő · · · · · · · · · · · · · · ·

A method for separating cholesterol from butterfat, characterized in that

i) dissolving the butterfat in a high pressure physiologically acceptable liquid (or high pressure liquid or high pressure sub or supercritical gas);

ii) selectively adsorbing the cholesterol on the adsorbent material by contacting the resulting high-pressure liquid mixture with calcium hydroxide, calcium oxide, calcium carbonate, magnesium carbonate, magnesium hydroxide or the like; and iii) recovering substantially the steroid-free butterfat from the high pressure liquid.

The process for separating cholesterol from butter fat according to claim 5, characterized in that the substantially cholesterol-free butter fat is separated from the high-pressure liquid by increasing the temperature of the high-pressure liquid or by reducing the pressure of the high-pressure liquid or combining the two.

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DISCLOSURE EXAMPLE

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A method for separating steroids from lipids

PIPER James, William, AUCKLAND

MCLACHLAN Corran, Norman, Stuart, AUCKLAND,

NEW ZEALAND

Inventors: CATCHPOLE Owen, John, WELLINGTON,

HAMILTON Bruce, Henry,. WELLINGTON,

MCLACHLAN Corran, Norman, Stuart, AUCKLAND,

NEW ZEALAND

CftA International Application Date: 1988. 09.

International Application Number: PCT / GB88 / 00739

International Publication Number: WO 90/02788

The present invention relates to a process for separating steroids (especially cholesterol) from lipids, such as naturally occurring fats and oils. The process can be used mainly, but not exclusively, in the manufacture of low cholesterol or cholesterol-free butter or tallow.

There have already been attempts to fractionate triglycerides to produce better spreadable butter and / or to remove cholesterol in butter. However, none of the prior art techniques has proved satisfactory since either cholesterol has not been satisfactorily removed or the taste of butter has been altered by removing cholesterol, or otherwise reducing the value of butter by altering its physical properties or impairing its shelf life.

Today, cholesterol in foods is becoming increasingly important. In addition to taking care of the saturated fats in our diet, in some countries, legislation will probably require that cholesterol content be displayed on the food sold, along with other nutritional values.

The primary source of cholesterol in foods is lipid-containing foods such as red or white meat, crustaceans and dairy products such as butter or cheese.

The lipid / components in question are lipids known as neutral lipids. This group of lipids include: mono-, di-, and triacylglycerides, which are collectively referred to as fat; free and esterified cholesterol and other steroids; free fatty acids, fatty alcohols and wax esters. The most important are fat and cholesterol components, and in the case of butter it is desirable to remove cholesterol from the butter without any damage to the fat components.

EP 0174848, published on behalf of the New Zealand Dairy Research Institute, describes a method for removing cholesterol from anhydrous milk fat by adding 70 to 90 ° C of powdered activated carbon which is stirred for one hour in the heated fat, ·

- 3 are then removed by filtration and then the heated fat is treated once more with powdered activated carbon until the milk fat is cholesterol-free or at least substantially free of cholesterol. However, such treatment damages the milk fat by heating, which is manifested by oxidation and unpleasant odor and requires the subsequent use of deodorizers and antioxidants, which in turn damages or removes the flavor and color components of the milk fat. The milk fat thus requires additional treatment and addition of additives to aid in restoring the original color and taste.

U.S. Patent No. 4,504,503 to Lever Brothers Company discloses another method. This patent describes a process for the preparation of a triglyceride mixture having buttery properties by fractionation of liquefied gas or gas under supercritical conditions. The preferred gas is supercritical carbon dioxide, which is used to treat fat or hardened butterfat at 60 to 100 ° C and subsequently to separate the various triglycerides by fractional condensation by varying the pressure or temperature of the carbon dioxide. This results in a preferred separation of a mixture of 24 to 42 C-triglycerides for margarine production. There is no mention of the removal of cholesterol in this patent.

Shishikura et al., In U.S. Patent No. 13,402, and a similar modification of Grease Grease by Extraction with Supercritical Carbon Dioxide [Shishikura · ··· »· · · * · · · · · · · · 9 ·

- 4 et al., Agric. Biol. Chem., 50 (5), 1209-1215 (1986), concluded that the preparation of low cholesterol butter fat by simple extraction with supercritical carbon dioxide is impossible. This article describes an attempt to convert butter fat to dissolve the butterfat at 40 ° C and 300 to 350 bar in supercritical carbon dioxide and pass the supercritical fluid onto a column filled with silica gel.

Shlshikura et al. Said that they were able to achieve a significant (over 90%) reduction in cholesterol, but only at a very high (50%) yield loss. Under conditions that could still be considered acceptable (15-20%), cholesterol removal fell to 70-80%. Experiments have also been conducted with a mixture of activated carbon and silica gel. This resulted in about 75% recovery of cholesterol, but almost completely removed both the flavor and color components.

The present invention relates to an improved method of separating steroids from lipids, in particular an improved method of removing cholesterol from butter.

We have discovered in the present invention that it is possible to separate steroids, especially cholesterol, from fats by dissolving the cholesterol / fat mixture in a high pressure liquid or sub- or supercritical gas, such as carbon dioxide, and selectively adsorbing from the dissolved fat mixture. cholesterol, high-pressure liquid mixture is contacted with an adsorbent • · * · · · · · · · · · · ·

It is preferred that the sorbent material be passed through the material containing or containing the basic metals containing oxygen, such as oxides, hydroxides, carbonates, sulfates, or the like.

leaving the high-pressure liquid mixture on a basic additive bed or a charged column so that the cholesterol is selectively adsorbed so that the high-pressure fluid leaving the bed contains a fat product that is substantially free of cholesterol.

Accordingly, the present invention provides a method for separating steroids from lipids comprising the following operations:

(a) dissolving the steroid / lipid mixture in a high pressure physiologically acceptable liquid (or in a high pressure liquid or a high pressure sub- or supercritical gas); (b) contacting the high pressure liquid mixture with an adsorbent material that comprises the oxygen-containing salts of the base metals such as oxides , consisting of hydroxides, carbonates, sulfates, or the like, or comprising steroids selectively adsorbing on the adsorbent material; and (c) recovering substantially steroid-free lipids from the high pressure liquid.

Preferably, the cholesterol or other steroids can be removed selectively from the adsorbent material by washing the adsorbent material with the same or other high pressure liquid or organic solvents, such as isopropyl alcohol or chloroform / methanol mixtures, to provide cholesterol or • "· · ·". • · · · · · · · · · · · ·

- 6 other steroids for pharmaceutical or other purposes.

Explanation of the illustrations:

The foregoing provides a broad description of the invention, the preferred embodiment of which is illustrated in more detail in the Examples, with reference to the accompanying drawings.

Figure 1 is a flowchart illustrating the extraction of fat and cholesterol from food containing cholesterol, such as meat, egg powder or milk powder by high pressure liquid, and the separation of cholesterol from the cholesterol / fat mixture by selective adsorption of cholesterol onto an adsorbent material.

Figure 2 is a flowchart illustrating a similar process, wherein the food is a fat or oil, such as butter, vegetable oil or fish oil, which is dissolved in the high pressure liquid, and selectively removed by adsorption to an adsorbent material and substantially free of cholesterol. the oil is separated from the high pressure liquid.

In these two processes, the high pressure liquid is either used to dissolve the fat or oil if the food is butter or an animal or vegetable oil, or if the food is a fat and cholesterol-containing matrix, such as meat, cheese, milk powder, egg powder or the like, then the fat and cholesterol is extracted using high pressure liquid.

Examples of suitable extraction liquids include carbon dioxide, disodium monoxide, trifluoro-chloromethane, difluorodichloromethane, 1,1-difluoroethane, sulfur hexafluoride, trifluoromethane, difluoro chloromethane;

difluoroethylene, octafluoropropane, ethane, ethylene, or mixtures thereof, and other non-health related gases, which may be suitable for the processing of food in suitable sub- or supercritical temperature and pressure ranges. Solubilizers (which are discussed later) can also be used in conjunction with high pressure fluid. The high pressure liquid may be a liquid or a sub- or supercritical gas.

In a high-pressure liquid extraction process, pressure and temperature are controlled parameters. A mother is in the supercritical state when her temperature and pressure are above the critical temperature (Te) and critical pressure (Pc). In this state, it cannot be compressed into liquid under any pressure.

In the case of carbon dioxide, the critical temperature (Te) = 31 _/ 3 ° C and critical pressure (Pc) = 72.8 bar. The pressure of a subcritical fluid is higher than Pc, but its temperature is lower than Tc. All for horses.

sub- and supercritical fluids

Appropriate extraction pressures may be used for the extraction

50 to 400 bar, preferably a

They range from 200 to 250 bar.

The appropriate extraction temperature is in the range of 30-60 ° C, preferably 35 ° C.

(The appropriate optional parameters include carbon dioxide

When using a grid, the preferred extraction pressure falls within the range of 200-300 bar, and the preferred temperature is in the range of 30-50'C. If cholesterol is extracted from a protein-containing raw material, it is preferable not to work at temperatures above 60 ° C to avoid denaturation of the protein. * * * * * «·· • · • ·

carbon dioxide, because it has physiologically inert, bacteriostatic / bactericidal properties, has a relatively low critical temperature and pressure, is particularly suitable for treating food products and is compatible with the adsorbent materials that we have.

Preferred methods for recovering cholesterol or other steroids dissolved in high-pressure fluid using adsorption techniques. Cholesterol or other steroids are separated by selective adsorption from a mixture of natural sources, such as triacylglycerides, derived from animals, plants, yeasts, or the like. The mixture to be separated can be produced in the following ways:

(1) Extraction from a solid matrix, such as meat, egg powders, milk powders, and other animal products containing fat containing a certain amount of cholesterol.

(2) Extraction of liquid or solid purified animal fats such as lard, butter, fish oils, wool grease, vegetable oils or the like.

The lipid mixture is extracted or dissolved in liquids of high pressure (liquid or sub- or supercritical).

Separation of cholesterol or other steroids (detailed below) from the dissolved lipid mixture is achieved by contacting the high pressure liquid mixture with an adsorbent which contains the basic metals containing oxygen, such as oxides, hydroxides, carbonates, sulfates, phosphates, acetates, or made of carbonates or discovered them · · *

- 9 glazes. A wide variety of basic metal oxides, hydroxides, carbonates, sulfates and other oxygen-containing salts can be used. Examples include magnesium oxide, calcium oxide, strontium oxide, barium oxide, cadmium (II) oxide, cobalt (II) oxide, manganese oxide, nickel oxide, zinc oxide, and hydroxides, carbonates of these metals , sulphates and other oxygen-containing salts.

Preferred adsorbents according to the present invention adsorb cholesterol and other steroids, while other lipids are only adsorbed to a minimal extent. Consequently, a substantially cholesterol-free lipid blend is available from the high pressure fluid,

U when it is discharged from the adsorbent or otherwise separated from it.

In most cases, this operation consists in passing the high-pressure liquid over a column filled with the adsorbent material or passing it through an adsorbent bed, although it is also possible to add the adsorbent material in the form of a fine powder to the high-pressure liquid, e.g. mix with it, and then separate the powder from the liquid by filtration, hydrocyclone, centrifuge or other solid / liquid separation technique.

The degree of separation depends on the amount of high pressure fluid used. For example, when the bed or column of the adsorbent material is used, the adsorbent bed or column can be regenerated with a larger amount of the same high pressure liquid. However, other liquids can be used for regeneration, which can wash cholesterol or other steroids faster. The final step of the process is the separation of the purified lipid mixture «4 ·· 4 ·

- 10 pounds of high pressure fluid. The following options are available to resolve this:

(1) Feeding into a solid matrix, such as meat, milk powder or egg powder.

(2) Dosage and mixing with insoluble residues such as butter.

(3) Simple separation and collection, for example for pork lard and butter.

Procedure 1 (Figure 1): Isolation of cholesterol from a solid matrix

The lipids are extracted with high pressure liquid from the nutrient, for example, minced meat and at least partially dried meat. The preferred liquid is sub- or supercritical carbon dioxide ¹ preferably at a pressure ranging from 150 to 300 bar and preferably from 30 to 60 ° C.

Extracted lipids dissolved in the high pressure liquid, especially fat and cholesterol, are then passed through a column tightly filled with the adsorbent material. This is preferably granulated or granulated to a particle size that provides a good flow of ______ on the column, but at the same time it also has a maximum surface area of adsorbent material.

As will be apparent from the Examples, various basic oxides, hydroxides, carbonates and other oxygen-containing salts may be used as adsorbent materials. It is preferred that the column has multiple input and output points so that different portions of the bed can be used at different times for adsorption of cholesterol. Suitable selection of different parts of the bed makes it possible to use one part of the bed for adsorption while dissolving cholesterol on the other side

The flow rate of the high-pressure fluid and the amount of the dissolved fat / cholesterol in the liquid is preferably controlled to selectively adsorb substantially all of the cholesterol on the bed (with minimal fat adsorption, unless there is a controlled separation of the triglycerides), thus leaving the high-pressure fluid leaving the bed. in most cases it contains essentially all of the fat from which we have completely or almost completely removed the previously present cholesterol.

The high pressure fluid leaving the bed is then subjected to various operations to separate the fat from the high pressure liquid. This can be achieved in various ways, for example, by increasing the temperature, reducing the pressure or combining the two.

The preferred method of separating the fat from the high pressure liquid is to raise the temperature to a level where the solubility of the fat in the high pressure liquid is reduced or negligible. This is 10 to 30 ° C higher for carbon dioxide than the extraction temperature. The liquid will then remain under high pressure and be returned to the process (recyclable).

Fat can also be extracted from the liquid to reduce its pressure. This can also be combined with a temperature change if desired. The pressure can also be reduced to atmospheric, but the liquid cannot be returned to the process; or the pressure of the high pressure fluid can be reduced to a value in the range of 50 to 100 bar and then recycled. In many cases the combination of the two methods can be the most economical.

Since the fat in this case is obtained from a meat product, such as beef, the resulting beef tallow can be returned to the meat, thereby restoring the structure of the meat product. In this way, some of the fat or all the fat can be returned, depending on what fat content is desired in the meat product. For example, it is possible, if desired, to produce a low-fat (cholesterol-free) meat product, in which case part of the beef fat is removed and only the residue is returned to the meat product.

Procedure 2 (Figure 2): Cholesterol-free butter.

This procedure is similar to that shown in Figure 1, except that the nutrient is butter fat and is dissolved in a high pressure liquid such as sub- or supercritical carbon dioxide. This solution is then passed through a column filled with the adsorbent material described above, so that the cholesterol is selectively adsorbed on the material, and the high-pressure liquid leaving the column contains the bulk of the fat and is substantially free of cholesterol.

This cholesterol-free fat is then preferably separated from the high-pressure liquid by increasing the temperature as described above, although it is also possible to separate by pressure reduction. Preferably, the high pressure liquid is recycled to the process (recycled) and used to dissolve additional butter fat, which is then passed through the adsorbent material and the process continues as shown in the flow diagram.

Preferably, the cholesterol is dissolved from the adsorbent material as described above to yield cholesterol in substantially pure form.

Referring to the methods described with reference to Figures 1 and 2, it is to be considered that the adsorbent material must be selected to substantially adsorb the total cholesterol on the bed, and that the resulting cholesterol-free fat is suitable for use as a food product. This is preferably achieved by the choice of a physiologically acceptable and relatively inexpensive adsorbent material that does not primarily bind the triacylglycerides, fatty acids or sensitive components of naturally occurring foods such as flavors, odors, colorants, or the like.

Of the basic oxides, hydroxides, carbonates and other oxygenated salts tested, it is preferred to use the oxides, hydroxides and carbonates of magnesium and calcium. Even when high pressure liquid other than carbon dioxide is used, it is preferred to use the appropriate carbonate.

Although calcium carbonate is the preferred material for high-pressure carbon dioxide, it has been found in our experiments that, when used with supercritical carbon dioxide, basic oxides or hydroxides are converted to the corresponding carbonates in the adsorption column. Since calcium carbonate is an inexpensive, naturally occurring mineral, it is a preferred material for use in this cholesterol / steroid adsorption process.

The method according to the invention can be used in a number of possible embodiments, some of which are described below.

Optional parameters of the procedure:

adsorbents:

Preferred adsorbent materials are oxides of basic metals as well as here

- 14 hydroxides, carbonates, sulphates and other oxygen-containing salts thereof. Calcium carbonate, calcium oxide, magnesium carbonate, magnesium oxide and magnesium hydroxide are the most preferred naturally occurring adsorbent materials, but the oxides, hydroxides of magnesium, calcium, strontium, barium, cadmium, cobalt, manganese, nickel and zinc carbonates, sulphates and other oxygen-containing salts are also suitable (but not exclusive) adsorbents. They can be used on their own or in mixtures, and use their naturally occurring forms.

Some of these are not suitable for the production of a food grade product, but steroid-free fat obtained when separating steroids is not always intended for the production of food grade products, so some or all of these materials may be used in such cases.

The properties of the adsorbent material depend on the crystal structure (and thus on the surface structure) and on the polar nature (acidic or basic). The choice of adsorbent material depends on the design of the plant; the strength of the adsorption capacity of the material, the particle / size and the strength of the material (in the case of a bed or column) are important for avoiding channeling so that the high pressure fluid does not pass through the column without adsorption, and it is desirable to avoid the fragmentation of the material into fine powder. blocking the column can cause the opposite effect. Thus, the adsorbents are preferably used in granular or granular form, or as naturally occurring minerals or in suitable substrates such as glass beads or rings.

In our experience, the most suitable materials are the oxides, hydroxides, carbonates, sulphates or other oxygen-containing salts of the base metals, and the adsorbent material must be selected with respect to its relative adsorption bond strength. It has been found that for a given anion, the strongest adsorption of steroids to basic salts containing oxygen is shown by magnesium salts, and this adsorption bond strength decreases towards nickel, cadmium, cobalt, zinc, calcium, strontium and barium; the latter shows the weakest adsorption from the group.

In our experience, acidic oxides are not suitable for use with high-pressure liquids, because they adsorb all lipid materials too strongly, making it difficult to separate without overloading the adsorbent. Examples of such acid oxides are silica gel, Florisil (magnesium sulfate-activated silica gel) and aluminum oxide, and as such are not useful in the process of the invention.

Any liquid that exhibits high-pressure (or liquid or sub-supercritical) properties may be used in the process of the present invention.

The following gases are those whose critical properties fall within the appropriate range and are not objectionable from a health point of view: carbon dioxide, ethane, propane, ethylene, nitrogen dioxide, sulfur hexafluoride, trifluoromethane, difluorodichloromethane, 1 , 1-difluoroethylene, octafluoropropane, trifluoromethane and mixtures thereof, as well as other healthally unsuitable gases suitable for processing food in sub- or supercritical temperature and pressure ranges.

• · · · · · · · · · · · · · · ··· ·· *

- 16 Dissolution Enhancers:

Subcritical additives that appear to enhance the solubility of liquids or cholesterol. Examples include isopropyl alcohol, ethanol, acetone, methanol, diethyl ether, ethylene dichloride and ethyl acetate. Other dissolution enhancers known to those skilled in the art may also be used to increase the solubility of lipids and especially cholesterol or other steroids in high pressure liquids.

Operational parameters (preferred carbon dioxide solvent and preferred magnesium carbonate, magnesium oxide, calcium carbonate, calcium oxide adsorbents):

Pressure: A pressure of 100 to 400 bar can be used and a pressure range of 150 to 300 bar is preferred.

Temperature: A temperature in the range of 20 ° C to 80 ° C can be used and a temperature range of 30 ° C to 60 ° C is preferred.

Fat / adsorbent ratio: 0.001 g fat / g adsorbent to 0.11 g fat / g adsorbent.

Moisture content of the adsorbent material: 0.2% w / w to 5.0% w / w. It is preferred that the moisture content is as low as possible. Similarly, high-pressure carbon dioxide should be kept as dry as possible.

Methods of contacting the liquid with the adsorbent:

Any method suitable for contacting the two phases may be used, and is not necessarily limited to passing the high pressure liquid onto a static column or bed of the adsorbent material. For example, the high-pressure fluid may be passed through a nozzle through which the finely powdered adsorbent material passes, or a finely powdered adsorbent material may be added to the high-pressure fluid and may be mixed in a reaction vessel or added to the high-pressure liquid and pumped with the high-pressure liquid into a solvent. / solute into the separation section where it collects and the sediment of the adsorbent material upon which the cholesterol is adsorbed can then be separated by suitable physical action, such as filtration, hydrocyclone or possibly centrifugation. In any case, it is preferred to use the crushed or granulated adsorbent material in a fixed bed to avoid abrasion reactions due to the transfer of the finely divided material in the apparatus with high pressure carbon dioxide.

The present invention is now illustrated by the description of experimental examples. In Example A, cholesterol is separated from the butter using a calcium hydroxide adsorbent, and 100% of the cholesterol is bound to the adsorbent within the limits of the experimental error.

and 80% of triglycerides in color, and there is no change in the control of the test value used).

Examples B and E of the cholesterol from cooking fat samples have been rationally grown) by fractionation of cholesterol butter. There is no change in the iodine value (this is an omission of fat fat unsaturated fat fat samples (i. and can be used to increase the concentration of low molecular weight triglycerides in order to obtain better spreadable cholesterol-free butter without changing the other food-related characteristics of the butter.

In Examples A, B and D, magnesium and calcium hydroxides are used as the adsorbent material, while in Example E the oxides of calcium and magnesium are used as well as the oxides, hydroxides, carbonates, sulfates and other oxygen-containing salts of the various base metals listed above.

Example:

Removal of cholesterol from butter using calcium oxide adsorbent.

Experiment number: 197.1

Adsorbent Data:

mass = 45 g particle size distribution = 45 - 125 μτη.

type = calcium hydroxide

Experimental Conditions:

pressure = 220 bar temperature = 45 ° C

Animal fat sample:

sample type = salt of unsalted butter = 0.50 g composition = 242 mg cholesterol / 100 g (wet matter)% moisture

lipid Bed retention getting Triacylglycerols 20.0% 80.0% cholesterol 100.0% 0.0% Comparison Raw material Grease recovered color yellow yellow iodine value value 33.0 32.1

X-ray diffraction analysis of the calcium hydroxide used in Example A after the experiment shows that a substantial portion of the bed has been converted to calcite, followed by calcium carbonate (Example E), indicating that it is a suitable and even preferred adsorbent material for carbon. when using carbon dioxide.

Example B:

Removal of cholesterol from stitched tallow using calcium hydroxide adsorbent.

Experiment number: 193.1

Adsorbent Data:

mass = 40 g particle size distribution = 45 - 125 µm type = calcium hydroxide

Experimental Conditions:

pressure = 220 bar temperature

35 ° C * ♦ »

- 20 Animal Fat Samples:

sample weight = 0.50 g sample type = staple cooking fat (cattle fat) = 990.7 mg cholesterol / 100 g (= 10x normal level), equilibrium triglycerides.

lipid

Bed retention

getting

Triacylglycerols

2.3

97.7%

cholesterol

100.0

0.0% £ example:

Removal of cholesterol from staple fat sample using calcium carbonate adsorbent.

Experiment number: 204.1

Adsorbent Data:

weight g

125 μιτι particle size distribution

type = calcium carbonate Experimental conditions: pressure = 220 bar

temperature = 45 ° C

Animal fat sample:

as in experiment 193.1 (Example B).

lipid

Bed retention

getting

Triacylglycerols

0.0%

100.0%

cholesterol

99.7%

0.3%

- Example 21 D:

Removal of cholesterol from butter and fractional (molecular weight) fractionation of triglycerides using magnesium hydroxide adsorbent.

Experiment number: 189.1

Adsorbent Data:

mass = 45 g particle size distribution = 45 - 125 pm type = magnesium oxide

Experimental Conditions:

pressure = 220 bar temperature = 35'C

Animal fat sample:

sample type = weight of unsalted butter = 2.04 g composition = 242 mg cholesterol / 100 g (wet matter)% moisture

lipid

Bed retention

getting

triglycerides

40.3%

59.7%

cholesterol

100.0%

0.0%

The triglycerides are obtained in the following weight percentages.

(The number of carbon atoms beside C does not include the carbon atoms of the glycerol chain.) * »·· ·

- 22 Triglyceride Composition

carbon number feed On the bed retrieve triglycerides triglycerides triglycerides C34 3.96 2.90 4.64 C36 11.60 4.46 16.22 C38 17.46 6, 71 24.35 C40 11.87 4.13 16, 83 C44 8.93 5.74 10.96 C46 9.09 10.03 8.49 C48 12.71 16.69 10, 17 C50 11.45 21.08 5.29 C52 12.89 28.24 3.06

The concentration of lower molecular weight triglycerides was significantly increased in the regenerated butterfat, the triglycerides of higher molecular weight decreased, and the butter fat was completely cholesterol free. The recovered butter oil also has a lower melting point, which makes it even more lubricant at a lower storage temperature.

The resulting butter fat is yellow and the ratio of saturated fats to unsaturated has changed.

variations:

Although the foregoing examples relate to the removal of cholesterol from butter or tallow, it is to be understood that the method of the invention may also be used to separate a wide variety of other steroids from lipid raw materials, so that the process of the invention is advantageously used for medical use. ·· ♦ ··

- 23 to concentrate harsh steroids, such as hormones, steroids and D-series vitamins.

Other steroids listed below may be further exemplified for materials obtainable by the extraction process of the present invention:

stigmastrin, beta-systerrin, brassicaester, campesterol, spinasterin, zymosterin, various forms of steroids in marine algae and invertebrates, steroids, especially cholesterol autooxidation products, lanosterol, ergosterol,

D ₂ -vítamin (calciferin),

Vitamin D ^ (cholecalciferin).

Similar steroids and hormones can be purified and concentrated using the method of the present invention, and it is understood that the separation of steroids from lipids is a general term for the separation of steroids and hormones of similar structure.

Finally, it is to be understood that many changes and modifications may be made to the foregoing without departing from the spirit and scope of the invention.

• ·· • ···

Claims

f. A method of separating steroids from lipids, characterized in that

i) dissolving the steroid / lipid mixture in a high pressure physiologically acceptable liquid (or high pressure liquid or high pressure sub- or supercritical gas);

ii) selectively adsorbing the steroids on the adsorbent material by contacting the resulting high-pressure liquid mixture with an adsorbent comprising or containing base metals containing oxygen, such as oxides, hydroxides, carbonates, sulfates or the like; and ili) recovering substantially steroid-free lipids from the high pressure liquid.

2. The method of separating steroids according to claim 1, wherein the steroids are selectively removed from the adsorbent material to the adsorbent material.

a) the same physiologically acceptable high pressure liquid as described in claim 1 used for dissolution; or

b) with other high pressure liquids; or

c) washing with an organic solvent.

3. The method of claim 2, wherein the adsorbent is calcium hydroxide, calcium oxide, calcium carbonate, magnesium carbonate or magnesium hydroxide.

Process according to claim 3, characterized in that sub-or supercritical carbon dioxide is used as a high-pressure physiologically acceptable liquid in the range of 50 to 400 bar