TW201642751A - Preparation method of blended oil containing fat-soluble functional ingredient - Google Patents

Abstract

A method for preparing blended oil containing fat-soluble functional ingredient comprises the steps: a) mixing a granular plant feedstock (e.g., algae feedstock) with an edible oil to obtain a first mixture; b) ultrasonic vibrating the first mixture in an ultrasonic device at 0-25 DEG C and under inert gas atmosphere to extract the fat-soluble functional ingredient contained in the plant feedstock into the edible oil to obtain a second mixture; and c) solid-liquid separating the second mixture to obtain the edible blended oil containing the fat-soluble functional ingredient, wherein the fat-soluble functional ingredient is an unsaturated fatty acid, such as docosahexaenoic acid (DHA).

Description

Preparation method of blending oil containing fat-soluble functional ingredients

The present invention relates to a method for producing an edible blending oil containing a fat-soluble functional ingredient, wherein ultrasonic vibration is directly used using an edible oil without using an organic solvent.

In the extraction and purification technology of fat-soluble functional ingredients, conventionally, solvent extraction or high-temperature water extraction is used, and there are problems of solvent residue and organic structure destruction. In recent years, under the concept of sustainable development, reducing the dependence on petrochemical raw materials and developing environmentally friendly and safe processes is the current direction of the industry and academic circles.

The use of edible oil as the organic phase solvent for ultrasonic extraction is a potential green process, which saves the traditional edible oil processing, first extracts the functional ingredients with a petrochemical solvent, removes the solvent and then dissolves the ingredients. In the oil step, not only ultrasonic extraction improves extraction efficiency, but also saves solvent removal steps and greatly reduces processing time.

Ying Li, et al., Green ultrasound-assisted extraction of carotenoids based on the bio-refinery concept using sunflower oil as an alternative solvent , Ultrasonics Sonochemistry, Volume 20, Issue 1, January 2013, Pages 12-18, ISSN 1350-4177 Revealing the use of sunflower oil as a solvent to extract functional ingredients from carrot pieces by ultrasonic extraction: carotenoids, and compared with solvents. Ultrasonic oil phase extraction gave a sunflower oil mixture containing 334.75 mg/l beta carotene in 20 minutes, while solvent extraction with n-hexane took 60 minutes to obtain a close yield (321.35 mg/l). The operating variables are processing time, power density, and operating temperature, using a probe-type ultrasonic source. The method of this paper does not take into account that the extracted components and oils may be degraded by oxidative rancidity due to oxygen in the air, and the oil has a large change in specific heat, and the non-temperature-controlled water bath can be cooled down, which is not conducive to the conformity of the finished product to the edible oil standard.

SébastienVeillet, ValérieTomao, FaridChemat, Ultrasound assisted maceration: An original procedure for direct aromatisation of olive oil with basil , Food Chemistry, Volume 123, Issue 3, 1 December 2010, Pages 905-911, ISSN 0308-8146, revealing the use of olive oil As a solvent, the aromatic oil-containing essential oil is extracted from the basil leaf pieces by ultrasonic extraction to form a value-added blending oil. Aromatized olive oil is a new trend in the Mediterranean region, and it can enhance sensory and nutritional value. This process can omit the use of organic solvent extraction essential oils to add olive oil after refining, which can save process time and linalool. ) and eugenol (eugenol) as the standard of aromatic essential oils. The method of this paper also does not take into account that the extracted components and oils may be degraded by oxidative rancidity due to oxygen in the air, and the oil has a large change in specific heat, and the non-temperature-controlled water bath can be cooled, which is not conducive to the conformity of the finished product to the edible oil standard.

Farid Chemat, SandrinePe ' rino-Issartier, Lynda Loucif, Mohamed Elmaataoui and Timothy J. Mason, Enrichment of edible oil with sea buckthornby-products using ultrasound-assisted extraction , Eur. J. Lipid Sci. Technol. 2012,114, 453- 460, revealing that the carotenoids of seabuckthorn pomace are directly added to the edible oil by ultrasonic assisted extraction, and the unit power (per gram of oil), the operating temperature and the operation time are used as variables, and are obtained at 0.67 W/g oil, 35. At °C, the edible oil containing 51.64mg/L carotenoid can be obtained within 20 minutes, which is not only more time-saving than the solvent extraction, but also has higher efficiency. The method of this paper also does not take into account that the extracted components and oils may be degraded by oxidative rancidity due to oxygen in the air, and the oil has a large change in specific heat, and the non-temperature-controlled water bath can be cooled, which is not conducive to the conformity of the finished product to the edible oil standard.

Fanny Adam, MarylineAbert-Vian, Gilles Peltier, FaridChemat, Solvent-free ultrasound-assisted extraction of lipids from fresh microalgae cells: A green, clean and scalable process , Bioresource Technology, Volume 114, June 2012, Pages 457-465, ISSN 0960 -8524 uses the "solvent-free" ultrasonic assisted extraction process for lipid extraction of microalgae cells, and optimizes the ultrasonic power, operating temperature, solid-liquid ratio and operating time as variables. The solvent is replaced by water instead of n-hexane, and the original cell breaking, impregnation, and extraction are integrated into one step, and the step of removing the solvent in the solvent method is omitted, and the FAME (fatty acid methyl ester) extracted per gram of dry weight is omitted. As an indicator, the results were obtained under the condition that the 5% algae dry weight solution was treated with 1000 W ultrasonic waves at 35 ° C for 30 minutes. In the previous case, water was used as a solvent, and the separation problem of water and oil emulsification had to be dealt with. The demulsifier (containing a little organic solvent) was added to centrifuge, and the process design did not consider the use of edible oil containing unsaturated fatty acids. The problem of rancidity deterioration, as well as the functional oxidative cracking of the functional components through the oxygen in the ultrasonic air, may require a refined process to be used as a food grade material.

The microalgae oil production process is mainly divided into five steps: algae selection, culture, harvesting, concentration and extraction and purification. The algae oil extraction method is divided into three parts: wall breaking, pressing and solvent extraction and separation. Internationally, the US Energy Agency's Aquatic Species Program (ASP) program is the study of microalgae biomass energy. Martek Bioscience Corporation has a number of related patented technologies for algae oil production, and its market for algae oil DHA products is quite mature (Martek Bioscience Corporation website).

In the value-added application of algae oil or fat-soluble ingredients, edible oils containing fat-soluble functional ingredients are currently mostly used as health or oil as their selling point. The added ingredients are mainly medium-chain fatty acids, omega-3 fatty acids (ALA, EPA, DHA), carotenoids, vitamin E, polyphenols and phytosterols. In Taiwan, Taishan Enterprise has a number of related commodities, such as plant sterol sunflower oil, polyphenol healthy essence blending oil and OMEGA-3 unsaturated healthy blending oil, which are added with fat-soluble nutrients. Uni-President, Fushou, Weidan and other companies also have similar commodities, and the relevant market potential is huge. In mainland China, there is a blend of DHA blending oil (content 0.05%), and the United States has Martek (now DSM) algae DHA (Life's DHA), Flora.Udo 369 DHA formula (content 0.76%) Wait.

The blending oil and process of the fat-soluble functional component prepared by the invention have the following advantages, including the higher content of the fat-soluble functional component compared with the commercially available product, which is characterized in that the edible oil is used as the extraction medium in the process and Ultrasonic oscillatory extraction under low temperature deoxidation environment, and no organic solvent is used in the process, and several energy-consuming separation steps are omitted, while maintaining high extraction rate and cell breaking rate, which is a green process. In addition to directly competing with the market for healthy blending oils with similar functional ingredients, the subsequent value-added applications can be processed into powdered oils, microemulsions, or multiple emulsions. Applications include formula, health foods, and animals. Other functional foods, cosmetics, and skin care products such as health care products.

The vegetable raw materials used in the process of the present invention may include algae, Chinese herbal medicine, mushroom raw materials and the like. Ultrasonic oscillatory extraction in the process of the present invention is preferably carried out using intermittent ultrasonic wave oscillation extraction.

Fig. 1 shows the results of fluorescence microscopic observation of DHA algal flour: (a) 0 minute (no ultrasonic wave oscillation treatment); (b) ultrasonic wave oscillation treatment for 120 seconds (preparation example 1).

2(a), 2(b) and 2(c) are SEM images of the original sample of DHA algal flour, wherein (a) is a single algal body with a magnification of 5000 times; (b) is an aggregated algae body, The magnification is 5000 times; and (c) is a single algae with a magnification of 8000 times.

3(a), 3(b), 3(c) and 3(d) are SEM images of DHA algal flour after ultrasonic vibration treatment for 120 seconds (Preparation Example 1), wherein (a) is agglomerated Body, magnification of 5000 times; (b) is a cluster of algae, magnification 500 times; (c) and (d) are single algae with magnifications of 5000 and 8000 times, respectively.

Fig. 4 is a block flow chart showing the preparation method of the ultrasonic wave extraction in the deoxidizing environment in the first embodiment of the present invention while cooling (cooling by a cooling device).

Fig. 5 is a view showing the DHA content (%) of the product obtained by ultrasonic wave extraction for 1 hour to 5 hours at two solid-liquid ratios in Example 1 of the present invention, and the upper curve is a solid-liquid ratio of 1:2, and the lower portion is shown below. The curve is the result of a 1:45 solid-liquid ratio.

Preferred embodiments of the invention include, but are not limited to, the following items:

A method for preparing a blending oil containing a fat-soluble functional ingredient, comprising the steps of: a) mixing a particulate vegetable material with an oil to obtain a first mixture; b) at an ultrasonic device, 0-25 ° C Ultrasonic oscillation of the first mixture under a temperature and an inert gas atmosphere, such that the fat-soluble functional component contained in the vegetable material is extracted into the oil to obtain a second mixture; and c) solid-liquid separation The mixture is obtained, and the blending oil containing the fat-soluble functional component is obtained, wherein the ratio of the vegetable material to the oil is 0.1-0.7 g/ml; the oscillation frequency of the ultrasonic oscillation is 10 kHz~1 MHz, and the operating power is 0.1~ 10W / cm ³ oil.

2. The method of item 1, wherein the oil is Miglyol 812, sunflower oil, olive oil, canola oil, soybean oil or a mixture thereof.

3. The method of item 1, wherein the vegetable material is an algae material.

4. The method of item 1, wherein the fat-soluble functional ingredient is an unsaturated fatty acid.

5. The method of item 1, wherein the fat soluble functional ingredient comprises docosahexaenoic acid (DHA).

6. The method of item 1, wherein the inert gas is nitrogen.

7. The method of item 1, wherein the ultrasonic oscillation of step b) is intermittent ultrasonic oscillation, for each continuous oscillation operation for 20 to 60 seconds, the oscillation operation is stopped for a period of time, and the time for stopping the oscillation operation is continuous oscillation. The ratio of operating time is 0.1~1.

8. The method of item 1, wherein step b) comprises maintaining a portion of the first mixture being extracted by the ultrasonic device while the ultrasonic oscillation is being performed, being cooled by an external cooling device, and then being returned to the ultrasonic device. .

9. The method of item 8, wherein the external cooling device simultaneously agitates and mixes the passed first mixture.

10. The method of item 8, wherein the ultrasonic device is provided with a cooling jacket to cool the first mixture.

The present invention can be further understood by the following preparation examples and examples.

The following preparation examples and examples were carried out using the following materials and instruments.

Algae raw materials:

The algae raw material is DHA-rich dry algal flour, which is purchased from Weidan Biotech Co., Ltd. as a fine powder, and the algae species is Schizochytrium Sp. Table 1 shows the fatty acid composition specifications of dried algal flour.

Ultrasonic extraction equipment:

The ultrasonic extraction device used in the present invention is a probe type cell crusher of the Misonix, Inc. (Farmingdale, New York, US) model Sonicator S-4000, and the adjustable amplitude intensity is between 0 and 100 (controllable operation time and Operating mode, recording total energy consumption and temperature), the frequency is 20kHz.

Types of edible oil:

Miglyol 812 (Sasol Germany GmbH)

Sunflower oil (Taishan Enterprise Co., Ltd., Taishan 100% pure sunflower oil)

Olive oil (Taiwan Jiage Food Co., Ltd., Quaker 100% olive oil a day)

Canola oil (Dongtongyi Co., Ltd., gourmet 100% Canadian import canola oil)

Preparation example 1 Preparation of edible blending oil containing DHA with different solid-liquid ratio (algae/fat)

30 ml of Miglyol 812 oil was separately mixed with 9 g of DHA algal flour, 12 g and 15 g in a 50 ml centrifuge tube for 60 seconds. The obtained oil powder mixture was cooled in an ice bath to 15 ° C, and the probe of the ultrasonic extraction apparatus was placed in the oil powder mixture for intermittent ultrasonic extraction under the following conditions:

Amplitude 60, 80 and 100)

Total time 120 seconds

Intermittent ratio (ratio of stop oscillation time to ultrasonic oscillation time): 20 seconds of oscillation, 10 seconds of pause, and a pause ratio of 0.5.

In the intermittent ultrasonic wave oscillation extraction operation, the oil powder mixture is placed in an ice water bath (0-5 ° C), and the temperature of the oil powder mixture can be up to 60 ° C under intermittent operation, and the temperature of the mixture after the operation is stopped. The mixture was cooled to about 20 ° C, and then subjected to solid-liquid separation by centrifugation (10000 rpm, 10 min) to obtain DHA-containing Miglyol 812 oil.

Analysis index of edible blend oil containing fat-soluble ingredients:

Analytical indicators include raw material breaking rate, component extraction rate and fat-soluble content. The rate of breaking the raw material was taken by microscopy. (1) Fluorescence microscope was used to separate the algae from the oil and then added to the water/oil containing the fluorescent dye Nile Red. The solution was evenly mixed, and the degree of breakage of the algae was observed by the degree of oil leakage. (2) Scanning electron microscope (SEM) was used to observe the broken cells of the algae.

The extraction rate of the components was calculated by weight, and the dry matter of the algae was extracted by washing with n-hexane to calculate the algal oil extraction rate and the total oil extraction rate (unsaturated fatty acid content). The calculation method is as follows: after the solid-liquid separation of the algal powder and the oil product, the algal powder is washed with an organic solvent (n-hexane), and the surface is decomposed under reduced pressure to remove the solvent, and the dry weight of the algae is weighed. The dry weight of the algae and the oil product were combined and the weight of the raw material (Miglyol 812 oil 30m and 1DHA algae powder 9g) was weighed. The content of Docosahexaenoic Acid (DHA) was determined by HPLC (High Performance Liquid Chromatography).

Algal oil extraction rate: algal oil weight / algal powder (9 g)

Unsaturated fatty acid content: algal oil weight / total oil (algae oil + Miglyol 812) weight

Total DHA content: DHA content / total fat weight (algae oil + Miglyol 812)

result:

Table 2 lists the results of the extraction rate of the components of the ultrasonic extraction and the DHA content of the fat-soluble component.

In the preparation example 1, the highest algae oil extraction rate was 27.56% at a solid-liquid ratio of 0.5, and the total oil weight was 27.56%/49.26%=55.95% oil extraction rate, of which 49.26% was the total fatty acid of the raw algae powder ( TFA) (see Table 1).

Fig. 1 shows the results of fluorescence microscopic observation of DHA algal flour: (a) 0 minute (no ultrasonic wave oscillation treatment); (b) ultrasonic wave oscillation treatment for 120 seconds (preparation example 1). It can be seen from Fig. 1 that most of the algae have broken cells after 120 seconds of ultrasonic vibration treatment (in the dark).

2(a), 2(b) and 2(c) are SEM images of the original sample of DHA algal flour, wherein (a) is a single algal body with a magnification of 5000 times; (b) is an aggregated algae body, The magnification is 5000 times; and (c) is a single algae with a magnification of 8000 times. Figures 3(a), 3(b), 3(c) and 3(d) show the DHA algae powder undergoing ultrasonic oscillation SEM image after 120 seconds (Preparation Example 1), wherein (a) is agglomerated algae body, the magnification is 5000 times, the surface of the algae body is obviously broken (black pores); (b) is an agglomerated algae body The magnification is 500 times, and there are obvious holes of different sizes on the surface of the algae; (c) and (d) are single algae bodies, the magnifications are 5000 and 8000 times, respectively, and the algae body shrinks.

Preparation example 2 Preparation of edible blending oil containing DHA in different operation time

The procedure of Preparation Example 1 was repeated except that only 15 grams of DHA algal flour was used for intermittent ultrasonic extraction, and four different total times of 120 seconds, 240 seconds, 360 seconds, and 480 seconds were used.

The results showed that the highest algal oil extraction rate was 35.97% at 480 seconds, the oil extraction rate was 73.02% and the total DHA content was 4.30%.

Preparation Example 3 Preparation of edible blending oil with different edible oil types containing DHA

The procedure of Preparation Example 1 was repeated except that only 15 grams of DHA algal flour was used for intermittent ultrasonic extraction, and four different edible oil types were used: Miglyol 812, sunflower oil, olive oil, and canola oil.

The results are listed in Table 3.

The results in Table 3 show that Miglyol 812 has the best performance.

The above preparation examples 1 to 3 were all carried out in an ice bath cooled but not deoxidized environment, because these preparation examples were mainly used to investigate the effects of solid-liquid ratio, operation time and type of edible oil on the effect of intermittent ultrasonic extraction. .

The inventor of the present invention repeated the steps of preparing the steps of Example 1 but not providing ice bath cooling, and the extracted oil after treatment has a marked burnt smell, which is a result of severe browning of the extracted oil product, and the temperature of the extracted oil is also Increase to 90-100 °C. The acid value of the extraction oil of the comparative example was tested with a test paper, and the acid value was >3.0 (the test paper identification range was only up to >3.0).

Preparation Example 1-3 was not operated in a deoxygenated environment, resulting in an acid value of the extracted oil product of >3.0 (Preparation Example 1 has a test acid value, Preparation 2 and 3 did not test the acid value), but the temperature of the mixture after ultrasonic extraction At about 20 ° C, the extracted oil product did not brown.

Example 1 Trial production process of edible blending oil containing DHA

In this embodiment, ultrasonic extraction is performed while cooling (cooling by a cooling device) and in a deoxidizing environment. The detailed flow is shown in Fig. 4, and the circulating reflux flow rates are 1.8, 3, 4.2, and 7.7 ml/s.

The circulating reflux flow rate of 3 ml/s is the best result of the DHA extraction amount in all circulating reflux flow rates. Figure 5 shows the DHA content (%) of the product obtained by performing different operating times at two solid-liquid ratios. The upper curve is the solid-liquid ratio 1:2, and the lower curve is the solid-liquid ratio 1:5. As the operating time increases from 1 hour to 5 hours, the DHA content of the product also increases.

The acid value of all products obtained under the above different operating conditions is less than 2, wherein the solid-liquid ratio of 1:5 and the circulating reflux flow rate of 3 ml / s and the operating time of 2 hours of product acid value of about <0.5; solid-liquid ratio 1: 2 The acid value of the product with a circulating reflux flow rate of 3 ml/s and an operation time of 5 hours is about <1.5.

Claims (10)

A method for preparing a blending oil containing a fat-soluble functional ingredient, comprising the steps of: a) mixing a particulate vegetable material with an oil to obtain a first mixture; b) at an ultrasonic device, at a temperature of 0-25 ° C And ultrasonically oscillating the first mixture under an inert gas atmosphere, such that the fat-soluble functional component contained in the vegetable material is extracted into the oil to obtain a second mixture; and c) solid-liquid separation of the second mixture And obtaining a blending oil containing the fat-soluble functional component, wherein the ratio of the vegetable material to the oil is 0.1 to 0.7 g/ml; the oscillation frequency of the ultrasonic oscillation is 10 kHz to 1 MHz, and the operating power is 0.1 to 10 W/ Cm ³ oil. The method of claim 1, wherein the oil is Miglyol 812, sunflower oil, olive oil, canola oil, soybean oil or a mixture thereof. The method of claim 1, wherein the vegetable material is an algae material. The method of claim 1, wherein the fat-soluble functional ingredient is an unsaturated fatty acid. The method of claim 1, wherein the fat-soluble functional component comprises docosahexaenoic acid (DHA). The method of claim 1, wherein the inert gas is nitrogen. The method of claim 1, wherein the ultrasonic oscillation of step b) is intermittent ultrasonic oscillation, for each continuous oscillation operation for 20 to 60 seconds, the oscillation operation is stopped for a period of time, and the time for stopping the oscillation operation is continuous oscillation operation. The ratio of time is 0.1~1. The method of claim 1, wherein the step b) comprises maintaining a portion of the first mixture while the ultrasonic oscillation is being carried out by the ultrasonic device to be cooled by an external cooling device and then returned to the ultrasonic device. The method of claim 8, wherein the external cooling device simultaneously agitates and mixes the passed first mixture. The method of claim 8, wherein the ultrasonic device is provided with a cooling jacket to cool the first mixture.