CS241285B1 - pumpable fat with increased oxidative stability based on rapeseed oil - Google Patents

Abstract

The solution is a pumpable fat with increased oxidative stability based on rapeseed oil by defining it as a product of selective hydrogenation and isomerization of rapeseed oil, containing a specific amount of fatty acids in the triacylglycerol molecule with a certain total content of their trans isomers, or further modified by controlled crystallization and tempering.

Description

pumpable fat with increased oxidation stability based on rapeseed oil

The solution is a pumpable fat with increased oxidative stability based on rapeseed oil by defining it as a product of the selective hydrogenation and isomerization of rapeseed oil containing a specific amount of fatty acids in a triacylglycerol molecule at a certain total content of their transisomers, respectively. further controlled crystallization and tempering.

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The subject of the invention is an oil with increased stability against oxidation based on rapeseed oil for the food industry.

For industrial frying of food products and heat treatment of food and meals, as well as for the preparation of meat and fish products, vegetable oils are used which do not contain trinenasycene fatty acids. These include palm oil, preferably its liquid fraction, peanut, cotton and, in particular, olive oil for the treatment of fish products.

Worldwide consumption of vegetable oils is increasing and consumption growth is offset by an increase in rapeseed production, mainly by cultivation of low erucoic acid varieties, namely 0.1 wt. % to 5.0 wt. % in the triacylglycerol molecule, respectively with an average erucic acid content in the triacylglycerol molecule, namely 6 wt. % to 15 wt. %.

The degree of oxidative stability of the oil or fat is the time in hours at which they are heated to 180 ° C, and the acid number increases from 0.10 to 0.16 mg KOH / g to 2.5 mg KOH / g, or when oxidized fatty acids are formed up to 0.7 wt. %, or when their smoke point drops below 170 ° C.

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The accompanying phenomenon of decomposition of triglycerides under thermal stress is the formation of volatile compounds such as aldehydes, ketones, low molecular weight fatty acids, as well as the formation of non-volatile compounds such as hydroxy, epoxy, ketoacids and polymer compounds which are insoluble in light petroleum and as oxyacids. Decomposition of triglycerides decreases iodine value, increases free fatty acid content and decreases the fat or oil smoke point ·

The fat smoking point is the temperature at which a continuous trickle of smoke appears on its surface.

The analytical methodology determines the parameters of theoretical oxidation stability, which must be distinguished from practical oxidation stability, which is dependent on the frying temperature, the method of heating the oil, the quality of the frying apparatus material and significantly on the material being fried or otherwise heat treated. Practical oxidation stability is generally lower than theoretical but is always proportional. A similar proportionality of practical oxidation stability is also apparent in relation to the relative oxidation disposition coefficient, which is a value calculated from the fatty acid composition of triacylglycerols as determined by gas chromatography in mass. % and the known coefficients of relative oxidation disposition, valid for individual groups of fatty acids or fatty acids themselves, the value of which is as follows:

Type or group of fatty acids

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Coefficient of relative oxidation disposition

Saturated 1.0 Trans-acids 1.0 Oleic acid C 18: 1 1.8 Linoleic acid C 18: 2 3.0 Linoleic acid C 18: 3 4.6 C 22: 1 erucic acid 2,0

Oils used for frying and cooking have the following theoretical oxidation stability and relative oxidation disposition coefficient:

Oil type Theoretical oxide. Coefficient of relative stability in hour oxide. Disposition

Palm 75 <* 80 1,5 4 » 1.6 Olive 60 « 65 1.8 «£ 1.85 Underground 50 « 55 1.8 «r 2,0 Cotton 45 « 50 2,0 2.2

On the other hand, rapeseed oil with a low or reduced erucic acid content in the triacylglycerol molecule is characterized by a reduced oxidation stability as compared to said oils, due to a content of 6.0 wt. to 14.0 wt. % of tri-unsaturated fatty acids in the C 18: 3 triacylglycerol molecule, linolenic acid.

Oxidative stability of low and medium erucic acid rapeseed oil in the triacylglycerol molecule with a fatty acid composition of 4 241 285:

wt.

C 16 • • 0 2.5 to 6.0 C 18 E • 0 0.9 to 2.1 C 18 • • 1 45.0 to 66.0 C 18 • • 2 12.5 to 30.0 C 18 • • 3 6.0 to 14.0 C 22nd • 1 0.1 to 15.0

was determined by heating to 180 ° C and showed a value of 30 to 35 hours and a relative oxidation disposition coefficient of 2.26-2.40.

Increased oxidation stability of polyene-type oils is achieved by addition of synthetic organic substances, antioxidants, BHA - butylhydroxianisole, BHT - butylhydroxitoluene, alkyl gallates, ascorbilpalmitate, (phyto-tocopherol, or their combination with natural phospholipids. 100 to 200 mg / kg of oil. Increasing the oxidative stability of oils using organic antioxidants is effective at normal oil temperature, but their effect is greatly reduced when the oil is subjected to thermal stress in the range of 170 ° to 200 ° C and therefore In addition, their presence impairs the organoleptic properties of the oil and, for health reasons, their addition to oils is limited.

When it is reported in the literature to increase the stability of polyene-type oils by partial hydrogenation, this is done exclusively using copper catalysts, mixed catalysts of copper oxide, chromium, manganese,

241 285 optionally using precious metals of silver, platinum and palladium. The use of copper catalysts leads to increased labor and material costs, since the traces of copper pass into the oil and their removal requires further operation using special adsorbents. The noble metal mixed catalysts are not industrially produced for this purpose and their potential application would significantly increase production costs.

Attempts to produce rapeseed oil with increased oxidation stability have not yet produced the desired result, due to the high melting point of 34 to 36 ° C, which is not satisfactory for this purpose, since the fat does not meet the desired functional properties after cooling product undesirable solid incrust, which deteriorates its organoleptic properties.

In addition, the fat of said melting point does not satisfy the pumpability, fluidity and dosability requirements in the temperature range of 15 ° to 28 ° C.

It has now been found that the pumpable fat with increased oxidation stability for use in the food industry, based on low or medium erucic acid rapeseed oil according to the invention, which is a product of selective hydrogenation and isomerization of rapeseed oil containing 0, 1 wt. % to 15.0 wt. % erucic acid and 6.0 wt.% to 14.0 wt. % of linolenic acid, in the presence of a nickel catalyst, containing mainly in the triacylglycerol molecule

4.0 to 11.5 wt. % fatty acid C 16: 0

1.5 to 8.0 wt.% C18: 0 to 79.5 wt. % C 18: 1

- 6 241 285 to 19.0 game. % 0.1 to 3.0 game. % 0.1 to 15.0% by weight

C 18: 2 C 18: 3 C 22: 1 with a total content of their transisors ranging from 8 to 64% by weight. %. In addition to these main fatty acids, the fat in the triecylglycerol molecule contains an additional amount of 3.0 to 5.5 wt. % of the mixture of the remaining fatty acids in repeating, almost standard compositions, which do not substantially affect the desired product quality parameters.

An increase in the fat scavengability in the range of 15 ° to 28 ° C without heating with the required fluidity can be achieved by using the product of the present invention modified by crystallization and temparation. The pumpable fat according to the invention is basically treated either by laminar tempering and subsequent crystallization, or by rapid cooling by dynamic crystallization and subsequent laminar tamparation.

The fat with increased oxidation stability having a melting point of max. 25 ° C according to the invention contains 0.3 wt. % to 10.0 wt. % of solids at 20 ° C, which is formed either by partial selective hydrogenation or by the addition of 1.0 to 5.0 wt. % high-strength iodine value of 2.0 to 6.0.

The main tachnic-economic effect in the production and application of the fat according to the invention is to achieve the same and higher oxidation stability compared to the 8 oils used to date, while maintaining its fluidity and scavengability in the range 15 ° to 28 ° C, using economically advantageous rapeseed oil varieties with low or moderate erucic acid content in the triacylglycerol molecule.

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The achievement of an unexpected effect, a considerable increase in the oxidation stability, fluidity and pumpability of the fat according to the invention can be demonstrated in the following examples.

Example 1

The droplet oil of 5 t weight was selectively hydrogenated in the presence of 20.0 kg of catalyst containing 15 wt. % Ni, for 1.5 hours, at a temperature of 18 ° C and a hydrogen pressure of 0.04 MPa. After reaching linolenic acid content

2.5 wt. As determined refractometrically, from the correlation between the iodine value and the concentration of linolenic acid, the fat was filtered and refined in the usual manner, and before the deodorization, 1 wt. % of the high-strength iodine number tallow 5, after which the fat blend was subjected to a dynamic controlled crystallization consisting of rapid cooling to 12 ° C and laminar continuous tempering, which was controlled by tempering the raffinate to 22 ° C.

A pumpable fat was obtained at 15 ° C with a linolenic acid content of 2.5 wt. erucic acid 3.5 wt. having an iodine value of 100, with a high oxidation stability of 50 hours and a transisomer content of 18 wt.

Example 2

Rape oil of 5 t weight was selectively hydrogenated and isomerized in the presence of 120.0 kg of catalyst containing 15 wt. Ni, for 1 hour, at a temperature of 180 ° C and a hydrogen pressure of 0.04 MPa. After the linolenic acid content reached 0.5 wt. as found in Example 1, the fat was filtered, refined and deodorized, after which the fat was subjected to laminar continuous tempering

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followed by crystallization, which was controlled by tempering the raffinate to 23 ° C followed by crystallization at the same temperature ·

A pumpable fat was obtained at 24 ° C with a linolenic acid content of 0.5 wt. %, erucic acid 0.5 wt. % with an iodine value of 87.4 with a high oxidation stability of 80 hours and a transisomer content of 40.0 wt. % ·

Example 3

Rape oil of 5 t weight was selectively hydrogenated in the presence of 27.0 kg of catalyst containing 15.0 wt. % Ni, over a period of 1.5 hours, at a temperature of 195 ° C and a hydrogen pressure of 0.30 MPa. After the linolenic acid content reached 2.4 wt. %, as found in Example 1, the fat was filtered and refined in the usual manner, and 4.0 wt.% of a high-strength iodine value of 2.0 was added to the fat prior to deodorization, after which the fat blend was subjected to dynamic controlled crystallization which consisted of rapid cooling to 10 ° C and laminar continuous temperature control, which was controlled temperature control of the raffinate to 24 ° C.

A pumpable fat was obtained at 16 ° C with a linolenic acid content of 2.4 wt. %, erucic acid 3.4 wt. %, with an iodine value of 94, with a high oxidation stability of 65 hours and a content of 17.0 wt. % ·

Example 4

Rape oil of 5 t weight was selectively hydrogenated and isomerized in the presence of 100.0 kg of catalyst containing 12 wt. % Ni, for 1 hour at a temperature of 190 ° C and a hydrogen pressure of 1 bar. After the linolenic acid content reached 1.5 wt. %, as found in Example 1, the fat was filtered and refined

241 285 in the usual manner and before deodorization, 2 wt.% Of high-strength iodine-4 palmstearin was added to the fat, after which the fat blend was subjected to dynamic controlled crystallization consisting of rapid cooling to 15 ° C and laminar continuous tempering which was controlled tempering at 26 ° C.

A pumpable fat was obtained at 19 ° C, with a linolenic acid content of 1.5 wt. erucic acid 6.9 wt. % with an iodine value of 92.9, with a high oxidation stability of 70 hours and a transisomer content of 30.0 wt. %.

Example 5

The 5 tons of rapeseed oil were selectively hydrogenated and isomerized in the presence of 130.0 kg of catalyst containing 12 wt. % Ni, for 1.0 hour, at 200 ° C and 50 psi of hydrogen. After the linolenic acid content reached 1.0 wt. %, as found in Example 1, the fat was filtered, refined and deodorized, then subjected to laminar annealing followed by crystallization, which was controlled by tempering the raffinate to 20 ° C, followed by crystallization at the same temperature.

A pumpable fat was obtained at 21 ° C with a linolenic acid content of 1.0 wt. %, erucic acid 11.9 wt.% having an iodine value of 88.4 with a high oxidation stability of hours and a transisomer content of 35.0 wt. %.

Example 6

Rape oil of 5 t weight was selectively hydrogenated and isomerized in the presence of 60.0 kg of catalyst containing 15 wt. % Ni, for 3 hours, at a temperature of 210 ° C and a hydrogen pressure of 1 bar. After the linolenic acid content reached 0.2 wt. %, which was found, as in Example 1, that the fat was filtered, refined, deodorized and then pumped to the tank for dispatch.

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A pumpable fat was obtained at a temperature of 27 ° C β with a linolenic acid content of 0.2 wt. % of erucic acid 13.8 wt.% with an iodine value of 80.5, a high oxidation stability of 85 hours and a transisomer content of 60 wt. %.

Example 7

Rape oil of 5 t weight was selectively hydrogenated in the presence of 17 kg of catalyst containing 15 wt. % Ni, for 2 hours, at a temperature of 205 ° C and a hydrogen pressure of 0.15 MPa. After the linolenic acid content reached 2.8 wt. %, as found in Example 1, the fat was filtered, refined and deodorized, and then subjected to controlled crystallization consisting of rapid cooling to 8 ° C and controlled tempering, which was the diacontinuous tempering of the raffinate to 21 ° C.

A pumpable fat was obtained at 15 ° C with a linolonic acid content of 2.8 wt. %, erucic acid 1.5 g /% having an iodine value of 105.0, with a high oxidation stability of 58 hours and a content of trans isomer A of 11 wt. %.

Claims (5)

OBJECT OF THE INVENTION 1.5 to 8.0 wt. % -. '- C 18: 0 55 to 79.5 wt. % - ^M - C 18: 1 6.0 to 19.0 wt. C 18: 2 0.1 to 3.0 wt. % - ”- C 18: 3 0.1 to 15.0 wt. % - - C 22: 1 with a total content of their transisomers ranging from 8 to 64% by weight. %. A pumpable fat having increased oxidative stability based on rapeseed oil, characterized in that it is a product of selective hydrogenation and isomerization of rapeseed oil containing 0.1 to 15 wt. % erucic acid and 6.0 to 14.0 wt. ^l of linolenic acid, in the presence of a nickel catalyst, containing in the triacylglycsrole molecule mainly 2. Pumpable fat according to claim 1, characterized in that it is a product further modified by controlled crystallization and temparation. 3. A pumpable fat according to claim 2, characterized in that it comprises a product further treated by laminar tempering followed by crystallization. 4. The pumpable fat according to claim 2, characterized in that it comprises a product further treated by rapid cooling with dynamic crystallization and subsequent laminar tempering. 4.0 to 11.5 wt. % fatty acid C 16: 0 5. A pumpable fat as claimed in claim 1, characterized in that it consists of a pre-quenched product produced by tempering with crystallization by the addition of 0 to 5% by weight of iodine target 2 to 6. Corrections in printed descriptions of inventions In the printed description of the invention for author's certificate No. 241 285 (PV 7949-84), the definition in the subject matter of the invention has been additionally modified on page 13, line 6a? Above, in line 6, the expression "molecule" is deleted and in the same line and subsequent is modified to in triglycerides. The same adjustments apply to the title of the page. 5 lines, page 1. 9 rows, tranches 3, 3 rows from below, page 5 4 and 5 rows from below, and row 6 from the top.