WO2006109340A1

WO2006109340A1 - Enrichment and integration of single-seed and multi- seed vegetable oils, and palm coconut, argan and other oils, with organic antioxidants and process for the production thereof

Info

Publication number: WO2006109340A1
Application number: PCT/IT2006/000235
Authority: WO
Inventors: Franco Francesco Vincieri; Annalisa Romani; Nadia Mulinacci
Original assignee: Goya Holding S.A.
Priority date: 2005-04-13
Filing date: 2006-04-07
Publication date: 2006-10-19
Also published as: ITFI20050070A1

Abstract

The product is enriched and integrated with natural extracts and organic additives comprising organic antioxidants composed of biophenols fractions of vegetable origin through dehydration of the natural extracts and solubilization thereof in glycerol/water in a ratio of 1 :1.

Description

"ENRICHMENT AND INTEGRATION OF SINGLE-SEED AND MULTI- SEED VEGETABLE OILS, AND PALM COCONUT, ARGAN AND OTHER OILS, WITH ORGANIC ANTIOXIDANTS AND PROCESS FOR THE PRODUCTION THEREOF" DESCRIPTION

The present invention relates to an improved process to obtain a product based on vegetable oils and a method for enrichment and integration of single-seed and multi-seed oils (sesame, safflower, peanut, sunflower, com, rapeseed, soybean, grape seed, palm kernel) and coconut, palm, argan, wheat germ and rice oils, by boosting their antioxidant and health beneficial properties.

The present invention also relates to products obtained with said process, and to a system for implementation of said process.

The process in question substantially comprises the steps of dehydration of the extracts and solubilization thereof in glycerol/water in a ratio of 1 :1 , mixing advantageously using ultrasound; and adding, in two subsequent steps, the antioxidant fraction composed of vegetable biophenols to the oil under stirring and in the presence of streams of inert gases, especially a countercurrent stream of nitrogen. The finished product thus obtained is composed of a homogeneous and limpid system which, compared with the initial oil, has a high antioxidant capacity efficacious both for stabilizing the product and for its potential health beneficial effects on humans.

The added fractions are composed of biophenols of vegetable origin.

The choice of the new carrier composed of glycerol/water allows a dissolution, in one liter of oil, of 300 mg of biophenol extract from green tea to be obtained.

These compounds, only slightly soluble or even insoluble in oil, allow an increase in the antioxidant power and health beneficial properties of the oil considering that green tea gallocatechins, in particular epigallocatechin gallate - the most abundant compound in the extract considered - is described in the literature as the most active antioxidant molecule among the natural polyphenols compounds studied to date.

It would also be possible to add ascorbyl-6-palmitate (vitamin C palmitate) both as antioxidant and as adjuvant in solubilization of biophenol extracts. Moreover, it would be possible also to add mixtures of fatty acids of the omega 3 series.

More specifically, the treatment process of the oil enriched with vegetable biophenol extracts as above, comprises the steps of.

> drying the biophenol fractions for 24 hours in a dryer, in order to guarantee fine dispersion of the powder forming the extract; > dissolving the phenol fraction in a dispersant mixture composed of glycerol/water in a ratio of 1 :1 V/V, said dissolution/dispersion of the biophenols being implemented with the aid of ultrasound for approximately 10 minutes in the presence of inert atmosphere, at temperatures ranging from 25° to 35°C, as a function of the chosen formulation;

> providing, in a temperature-controlled stainless steel container, equipped with mixer and with a suitable nitrogen sparger, a suitable quantity of oil to sustain a dispersion of the enrichment substances up to 100 times greater than the concentration to be obtained in the finished product;

> switching on the mixer and simultaneously transferring the glycerol/water solution enriched in biophenols into the oil by pouring, at the same time adding approximately 0.3% of monoesters of glycerol with fatty acids, such as oleic, palmitic or stearic acid; > optimizing the mixing speed up to the maximum speed established according to type of formulation and maintaining this speed for 20-25 minutes to obtain a fine emulsion; (to guarantee sufficient homogeneity of the product, the stirring process will also be applied during the subsequent step); > transferring the fine emulsion as above to a third and final container of large capacity, where the final concentration to be obtained will be reached; this product will be maintained under mechanical stirring both during and after addition of the premixture (fine emulsion as above) for at least 20-25 minutes under temperature controlled conditions and in the presence of nitrogen sparger.

The accompanying drawing schematically shows a system for implementation of the process above.

In the drawing, 3 indicates a reactor and 5 and 7 indicate two containers. Feed of the oil to be treated, to the two containers 5 and 7 with suitable control valves, is indicated with 1. Feed of nitrogen (or another inert gas) for the reactor 3 and the containers 5 and 7, is indicated with 2.

The vegetable biophenol extracts as above, previously dried, are dissolved in the reactor 3 in the dispersant mixture composed of glycerol/water in a ratio of 1 :1 VA/, contained in the reactor 3. Dissolution- dispersion is implemented in the reactor 3 with the aid of ultrasound for approximately 10 minutes, in an inert atmosphere at temperature ranging from 25°C to 35°C, as a function of the formulation chosen. In the container 5 - with a volume of around 50 liters and equipped with mixer 5A - the mixture from the reactor 3 is introduced by pouring slowly. A suitable quantity of filtered oil is fed to the container 5, to obtain dispersion of the enrichment substances up to 100 times greater than the concentration to be obtained in the finished product; nitrogen is made to bubble with a sparger 5B. The oil is then transferred - through the line 13 with pump 13A - from the container 5 to the temperature-controlled stainless steel container 7, equipped with mixer 7A and sparger 7B to bubble nitrogen, to guarantee homogeneous dispersion of the gas in the oil to be treated. The oil treated in 5 is fed into the top part of the container 7. The oil treated in the container 7 is then sent with a line 20 and a pump 22 to a storage system. Simultaneously to feed of the mixture from the reactor 3 to the container 5 (poured from above), approximately 0.3% of monoesters of glycerol with fatty acids such as oleic, palmitic or stearic acid, can optionally be added. The mixing speed is accelerated to maximum speed - established according to the type of formulation and maintained for 20-25 minutes to obtain a fine emulsion, in order to obtain and guarantee adequate product homogeneity.

It is advantageous to specify that optimization of the production process provides for: - rapid biophenol dissolution times in the dispersant, with the aid of ultrasound in inert atmosphere in order to guarantee maximum integrity of the antioxidant molecules added;

- the choice of solubilizing mixture and further simultaneous addition of natural emulsifying agents such as: monoglycerides of fatty acids (such as palmitic acid, oleic acid and stearic acid) in quantities of no more than 0.3% of the finished product, to obtain a finished product which is limpid and stable (the product has no sediment through time);

- the use of inert gas dispersed homogeneously in a countercurrent stream in the containers during the process steps, to allow the stability of all the antioxidants added to be further preserved guaranteeing, with respect to normal production and storage conditions of the oil, almost total removal of oxygen, the oxidizing agent that endangers chemical and organoleptic properties and stability of the oil. To better clarify the aspects and results of the present invention, a description of the components forming the new formulations is provided hereunder. Base oils

The production of vegetable oils has increased considerably from the 1950s onwards, above all due to the fact that populations require an increasing number of vegetable sources of food lipids. The current trend, both for religious and above all for health reasons, is to replace the majority of animal fats in the diet with lipids of vegetable origin.

Different types of oils have different compositions from one another. Seed oils, compared to olive oil, contain much higher percentages of polyunsaturated fatty acids with 18 carbon atoms, in particular linoleic and linolenic essential and parent fatty acids of the Omega 6 and Omega 3 families respectively. Above all, fatty acids of the Omega 3 series are particularly important from the point of view of health benefits(Siddiqui RA, Shaikh SR, Sech LA, Yount HR, Stillwell W, Zaloga GP Omega 3-fatty acids: health benefits and cellular mechanism of action. Mini Rev Med Chem. 2004; 4(8): 859-71 ; Ruxton CH, Reed SC, Simpson MJ, Millington KJ. The health benefits of omega-3 polyunsaturated fatty acids: a review of the evidence. J Hum Nutr Diet. 2004; 17(5): 449-59).

With regard to this considerable biological interest for these molecules, they are particularly susceptible to oxidative processes and this must be taken into due account both during industrial preparation of the product and for its use in the domestic environment. It must also be pointed out that the presence of phenol molecules with anti-oxidant and health beneficial action has not previously been highlighted in appreciable quantities in these oils, in contrast to what has been widely demonstrated for extra virgin olive oil. The possibility of adding suitably carried vegetable antioxidants, which can reduce the susceptibility to oxidation and increase stability through time, to these oils improves the quality of the oil and its health beneficial potentials for humans. Phenol compounds Numerous plants such as: Vitis vinifera, Camellia sinensis, Cynara scolymus, Origanum vulgaris, Origanum majorana, Menta piperita, Olea europaea L, Rosmarinus officinalis, Salvia officinalis, Rosa canina, Thymus vulgaris, Glycine soja and Glycine max, Pinus pinaster or Pinus maritima are utilized to prepare natural extracts containing phenol compounds with high antioxidant powers.

Recently, in the food and dietary field the extracts most commonly utilized as source of phenol compounds have been: procyanidin extract from the leaves of Camellia sinensis (green tea), grape seed procyanidin extract from vitis vinifera, polyphenol extract from fruits of the Citrus family, extract from leaves of Cynara scolymus and bark extract from Pinus pinaster or Pinus maritima, etc..

Many studies have demonstrated that procyanidins, and in particular procyanidins esterified with gallic acid, are the phenol compounds that exhibit a greater antioxidant and anti-free radical activity. Natural extracts containing polyphenol molecules of this kind are those of Vitis vinifera and in particular those of Camellia sinensis (green tea) which contain procyanidin esterified with gallic acid in larger quantities. The main catechins present in green tea extract are epigallocatechin 3-O- gallate, epigallocatechin and epicatechin 3-0-gallate. Many in vitro studies and also in vivo studies on animals have provided good experimental proof of the protective role exerted by green tea catechins in reducing the risk of development of pathologies such as hepatopathies, breast cancer, disorders of the cardiovascular system [ Crespy V and Williamson G., A review of the health effects of green tea catechins in in vivo animal models, J Nutr., 134(12):3431 S-3440S, 2004].

Recent data show that green tea catechins act as inhibiting agents of various growth factors involved in the development of arteriosclerosis exerting an antiproliferative effect. [Gouni-Berthold I e Sachinidis Molecular mechanisms explaining the preventive effects of catechins on the development of proliferative diseases, Curr Pharm Des.;10(11):1261- 71 , 2004]. Research carried out on animals show that green tea catechins are capable of inhibiting one or more stages of the tumor development process [Chung-Fung-Lung et al., Tea and cancer prevention: studies in animals and human J. Nutr., 133, 3268s-3274s, 2003]. The National Cancer Institute has chosen green tea catechins among the most promising bioactive components present in foods, to develop clinical trials targeted at assessing their effect in the reducing the risk of breast cancer [Greenwald P., Clinical trials in cancer prevention: current results and perspectives for the future. J Nutr. ; 134(12):3507S- 3512S, 2004.].

Finally, some authors have pointed out how the daily intake of green tea both as a beverage and as a food supplement has led to an increase, which although not high is significant, of the total plasmatic antioxidant capacity in humans [Henning S. M. et al., Bioavailability and antioxidant activity of tea flavanols after consumption of green tea, black tea, or a green tea extract supplement Am J Clin Nutr. 80(6): 1558-64, 2004]. Ascorbyl-6-palmitate The use of ascorbyl 6-palmitate (vitamin C palmitate) represents an innovative element since it guarantees improved stability of the product by contributing towards optimizing the solubilization of the biophenols in the oil, thanks to its surfactant properties, and towards providing the oil with a water-soluble vitamin known for its antioxidant actions (vitamin C). Vitamin C palmitate is present in the list of antioxidants permitted for use in the food sector (Ministerial Decree 209 dated 27/02/1996 in implementation of EC Directives) The production process The process according to the invention is further clarified hereunder. It comprises the following steps, with reference to the products that are utilized in the various formulations according to the invention:

> drying the polyphenols for 24 hours in a dryer, in order to guarantee fine dispersion of the powder forming the biophenol extract;

> solubilizing the dried polyphenols in glycerol/water in a ratio of 1 :1 V/V, with a first small mixer, maintaining the product under a homogeneously distributed stream of inert gas in an ultrasound bath for approximately 10 minutes at a suitable temperature, as a function of the chosen formulation and in any case never above 30⁰C;

> providing a suitable quantity of oil to sustain a dispersion of the enriching substances 100 times greater than the concentration to be obtained in the final product;

> transferring the above mentioned mixed product (biophenols in glycerol/water) by pouring through a duct which feeds the concentrated mixture into the top part of a tank containing the above mentioned suitable quantity of oil, and provided with: temperature control, two mixing blades with reverse rotation, which rotate at increasing speed up to 90/120 revolutions per minute for at least 20- 25 minutes, nitrogen sparger, where a concentration equal to at least

100 times the final concentration to be obtained will be reached in a homogeneous mixture;

> providing a suitable quantity of oil in a further temperature-controlled tank, equipped with inert gas (nitrogen) sparger, two mixing blades with reverse rotation, which rotate at increasing speed up to 90/120 revolutions per minute;

> approximately 15 minutes after the biophenol mixture has been added to the first tank containing the oil, transferring the pre-mixed product as above - through a duct and a pump - into the top part of - B -

the further tank containing oil, where the final concentration to be obtained will be reached, and switching on the mixer to rotate at a low rotation speed, then gradually increasing the mixing speed to the maximum speed required (increasing up to 90/120 revolutions per minute for at least 20-25 minutes) according to the type of formulation, in temperature-controlled conditions and in the presence of nitrogen spargers, until complete homogenization of the product, and continuing the countercurrent stream of nitrogen for approximately 20 minutes after termination of the process in order to reduce the concentration of oxygen present to a minimum.

Example of preparation of a base formula with some possible variants thereof

The following antioxidants were added to samples of oil:

> dry procyanidin extracts from green tea > standardized procyanidin extracts from grapes

> standardized extracts in phenol products deriving from Olea europaea L.

> standardized biophenol extracts from the bark of Pinus pinaster L or Pinus maritima L > standardized soybean extracts and the like

> ascorbyl-6-pa Imitate (vitamin C palmitate)

> standardized extracts of fatty acids of the omega 3 series.

The glycerol/water 1 :1 V/V mixture was utilized as technological adjuvant for accelerated solubilization of compounds that are poorly or not liposoluble.

The base formulation was prepared in the following way: the decaffeinated procyanidin extract from green tea was maintained in the dryer for 24 hours; 300 mg of this extract were solubilized in 1.0 ml_ of glycerol/water in the ratio 1:1 v/v, with the aid of an ultrasound bath at ambient temperature for approximately 10 minutes in an inert gas (nitrogen) current until obtaining a limpid solution. This solution was added to 1 liter of oil, previously filtered, with the addition of ascorbyl 6- palmitate (from 10 to 50 mg/l) and maintained, at suitable temperature (25-3O⁰C) under mechanical stirring until obtaining a homogeneous mixture.

Different samples containing procyanidin extract from green tea in concentrations ranging from 100 to 300 mg/l of oil were prepared. The tests carried out both on the base formulation and on formulations 1 , 2, 3, 4 and 5 hereunder were carried out in analogous conditions both with single-seed and multi-seed oils.

Example of preparation of Formulation 1

A standardized dry phenol extract from Olea europaea L. (pre- dried) was added to the base formulation in concentrations ranging from 20 to 40 mg/L. The extract was added to the glycerol/water solution of the procyanidin extract from green tea and this mixture was subsequently added to the oil sample.

Example of preparation of Formulation 2

A standardized procyanidin extract from bark of Pinus pinaster or Pinus maritima L. was added to the base formulation in quantities ranging from 20 to 30 mg/L. This extract was added to the glycerol/water solution together with the procyanidin extract from green tea and this mixture was subsequently added to the oil sample.

Example of preparation of Formulation 3 A commercial dry procyanidin extract from the tegument of grape seeds, pre-dried, was added to the base formulation in concentrations ranging from 20 to 30 mg/L. This extract was added to the glycerol/water solution together with the procyanidin extract from the tea and this mixture was subsequently added to the oil sample. Example of preparation of Formulation 4

The dry polyphenol extract from bark of Cynara scolymus was added to the base formulation in concentrations ranging from 20 to 40 mg/L. This extract was added to the glycerol/water solution together with the procyanidin extract from the tea and this mixture was subsequently added to the oil sample.

Example of preparation of Formulation 5

The standardized commercial dry extract from soybeans, pre-dried was added to the base formulation in concentrations ranging from 20 to

30 mg/L. This extract was added to the glycerol/water solution together with the procyanidin extract from the tea and this mixture was subsequently added to the oil sample.

To summarize, the invention in question reaches - with respect to prior art techniques - a plurality of objects and advantages such as: - rapid efficacious dispersion and solubilization of the polyphenols; optional addition of fatty acids of the omega 3 series; substantial decrease in the presence of oxygen (and of the risk of oxidation) for the predominant action of nitrogen; substantial increase in the final concentration of polyphenols, having antioxidant activity; prolonged preservation of the polyphenols of the oil, without any appreciable change in the organoleptic properties of the final product; prolonged preservation of the unsaturated acids of the oil, with reference to their oxidative processes.

Claims

1. Process to enrich and integrate single-seed and multi-seed oils and the like, with natural extracts and organic additives, characterized in that it comprises dehydration of said extracts and solubilization thereof in glycerol/water in a ratio of 1:1 v/v.

2. Process to enrich and integrate vegetable oils with natural extracts and organic additives comprising organic antioxidants composed of biophenol fractions of vegetable origin, characterized in that it comprises the steps of dehydration of the extracts and solubilization thereof in a carrier based on glycerol/water in a ratio of 1 :1 , mixing, and adding, in two subsequent steps, the antioxidant fraction composed of vegetable biophenols to the oil maintained under stirring.

3. Process as claimed in claim 2, characterized in that the mixture is obtained under use of ultrasound.

4. Process as claimed in claim 2 or 3, characterized in that, at least in said mixing and adding steps, the product is subjected to the action of streams of nitrogen.

5. Process as claimed in claim 2, characterized in that dissolution in oil of 300 mg of biophenol extract from green tea in one liter of oil is implemented in said carrier, thereby obtaining approximately a 50% increase in an oil of average type, with increase in the antioxidant power and in the health beneficial properties of said oil.

6. Process as claimed in any one of the previous claims, characterized by the addition of ascorbyl-6-palmitate (vitamin C palmitate) both as antioxidant and as adjuvant in the solubilization of the biophenol extracts.

7. Process as claimed in any one of the previous claims, characterized by the addition of mixtures of fatty acids of the omega 3 series.

8. Process as claimed in any one of the previous claims, characterized in that it comprises the steps of:

- drying the biophenol fractions for 24 hours in a dryer;

- dissolving the phenol fraction in a dispersant composed of glycerol/water in a ratio of 1 :1 V/V, in a first tank; - dissolution and dispersion of the biophenols in the dispersant with the aid of ultrasound for approximately 10 minutes in the presence of inert atmosphere at temperatures ranging from 25° to 35°C;

- providing a limited quantity of oil, such as to obtain a dispersion of the enrichment substances up to 100 times greater than the concentration to be obtained in the finished product;

- placing the oil in a temperature-controlled stainless steel tank, equipped with mixer and with a suitable nitrogen sparger which guarantees homogeneous dispersion of the gas in the oil, - mixing and simultaneously transferring the glycerol/water solution enriched in biophenols into the oil by pouring;

- optimizing the mixing speed up to a maximum pre-set speed and maintaining for 20-25 minutes to obtain a fine emulsion;

- transferring the fine emulsion, again by pouring, into a further tank, where the final concentration to be obtained in the final product will be reached under mechanical stirring both during and after addition of said fine emulsion, for at least 20-25 minutes under temperature controlled conditions and in the presence of nitrogen sparger.

9. Process as claimed in claim 8, characterized in that said final transferring step is performed under stirring.

10. Process as claimed in claim 8 or 9, characterized by the addition of approximately 0.3% of monoesters of glycerol with fatty acids such as oleic, palmitic or stearic acid.

11. A system for implementing the process as claimed in any one of claims 1 to 10, comprising: a reactor (3) of limited volume, associated with a mechanical mixer and with an ultrasound dissolution system for treatment of the glycerol, water and polyphenol components; a second tank (5) of intermediate volume, for mixing a first quantity of oil with the mixture fed from said reactor, and with a stirring (5A) and nitrogen bubbling (5B) system; a third tank (7) of larger volume, with further nitrogen bubbling system (7B) and mechanical mixer (7A), to mix a second quantity of oil with the mixture fed from said second tank (5); and a storage container in nitrogen environment.