KR101854993B1 - Method for preparing amorphous granular starch using ethanol - Google Patents

Abstract

The present invention discloses amorphous starch particles using ethanol. A method for preparing amorphous starch particles according to an embodiment of the present invention includes: preparing a starch suspension by dispersing starch in an ethanol solution; Heat treating the starch suspension; Adding alcohol to the heat-treated starch suspension and centrifuging the starch to wash the starch; And drying and pulverizing the washed starch to obtain an amorphous particle starch.

Description

TECHNICAL FIELD [0001] The present invention relates to a method for preparing amorphous starch particles using ethanol,

The present invention relates to a process for preparing amorphous starch particles using ethanol.

Starch is a renewable biodegradable natural polymer material that is synthesized and stored as an energy storage medium in most plants and provides 70% to 80% of the energy intake for humans. Starch is the second most abundant carbon source in the natural world found in crops such as stem, root, seed and rice, corn, wheat, potato, cassava, tapioca and sweet potato.

Globally, corn (82%), wheat (8%), potatoes (5%) and cassava (5%) are the major starch sources. In the 2000s, the world starch market was estimated to be 48.5 million tons of natural starch and modified starch, and the economic scale of production was estimated to reach 15 billion euros per year. This indirectly implies that industry and academia are constantly pursuing new characteristics of starch and high-value-added applications.

In the starch industry, starch is extracted and purified through immersion, grinding, filtration and drying processes through a wet milling process. However, the natural starch present in the natural state is hardly soluble in water, making it difficult to apply to the food industry.

To overcome this problem, Jane et al. (1986) proposed an alcohol-alkali treatment method to make cold-water soluble starch (GCWSS). In order to swell the starch particles, they treated starch with a mixture of ethanol and alkali, then used hydrochloric acid to neutralize, washed with alcohol and dried.

The GCWSS thus produced exhibited a higher viscosity and a smoother texture, and the quality of the dough was reported to be better when processed compared to pre-gelatinized starch. However, in the case of GCWSS, sodium hydroxide (NaOH) is used to produce the product, which has a disadvantage in application to the food industry, and when it is dispersed in water, it is completely dissolved and difficult to use.

Physical deformation methods include drum drying, extrusion, and high hydrostatic pressure (HHP). In the case of drum drying and extrusion methods, the starch particles are lost after the denaturation and the pasting quality is reduced, and the HHP method is difficult to mass-produce commercially because of difficulty in continuous processing .

However, amorphous granular starch (AGS) is prepared by controlling the content of ethanol and the heating temperature, so that the starch particles are retained like natural starch but the birefringence disappears, and the pre- gelatinized starch).

On the other hand, Liu et al. (2010), who produced noncrystalline granular starch (NCGS) in the same form as AGS, may have many advantages such as the fact that the new type of starch may promote physical and chemical reactions And NCGS should be considered as a new raw material for preparing various modified starches and products.

In order to overcome the problems of the prior art, the inventors of the present invention have studied an improved gelatinization method of starch. When preparing amorphous starch using ethanol and heat treatment, they have a particle structure similar to that of natural starch, And the present invention has been completed upon confirming that the destroyed starch can be produced.

Korean Patent Registration No. 10-1610653 (Apr. 26, 2014), " Method for producing amorphous particle starch using ultrahigh pressure &

An embodiment of the present invention is to provide a method for producing amorphous starch particles.

A method for preparing amorphous starch particles according to an embodiment of the present invention includes: preparing a starch suspension by dispersing starch in an ethanol solution; Heat treating the starch suspension; Adding alcohol to the heat-treated starch suspension and centrifuging the starch to wash the starch; And drying and pulverizing the washed starch to obtain an amorphous particle starch.

The ethanol solution may include 40 to 70 parts by weight of ethanol relative to 100 parts by weight of the ethanol solution.

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The ethanol may be hydrated ethanol.

The temperature of the heat treatment may be 80 ° C to 100 ° C.

The time of the heat treatment may be 5 minutes to 60 minutes.

The alcohol may be methanol, ethanol or propanol.

The amorphous starch may be a starch which is lost in crystalline regions of the starch but retains its particle structure.

The starch may be a natural starch obtained from a plant.

The starch may be a potato starch.

The viscosity enhancer according to an embodiment of the present invention includes the amorphous particle starch prepared by the above-described production method.

The food composition according to an embodiment of the present invention includes the amorphous particle starch prepared by the above-described method.

According to the embodiment of the present invention, it is possible to prepare amorphous starch, which is amorphous but has a granular structure, that is, a starch, which is a starch which is lost in crystal region but retains its grain structure.

In addition, according to the embodiment of the present invention, the swelling of starch is suppressed by using ethanol, and the phenomenon of starch gelification is caused by heat treatment to produce amorphous starch particles which can be edible without using a chemical method can do.

1 shows a method for producing amorphous starch particles of the present invention.
Figs. 2A to 2G are microscope images of amorphous particle starches of Examples 1 to 7. Fig.
3 is a graph showing the thermodynamic characteristics of the amorphous particle starch of Example 7 and the natural potato starch of Comparative Example 1 by DSC analysis.
4 is a graph showing the X-ray diffraction characteristics of the amorphous particle starch of Example 7 and the natural potato starch of Comparative Example 1. Fig.

Hereinafter, a method for preparing amorphous starch particles according to an embodiment of the present invention will be described.

According to the present invention,

Dispersing the starch in an ethanol solution to prepare a starch suspension,

Heat treating the starch suspension,

Adding alcohol to the heat-treated starch suspension and centrifuging the starch to wash the starch;

Drying and pulverizing the washed starch to obtain an amorphous particle starch

To a process for producing amorphous starch particles.

The present invention also relates to amorphous starch particles prepared according to the process for preparing amorphous starch particles according to an embodiment of the present invention.

Hereinafter, a method for producing amorphous starch particles according to an embodiment of the present invention will be described in detail with reference to FIG.

1 shows a method for producing amorphous starch particles of the present invention.

S110: Preparation of starch suspension by dispersing starch in ethanol solution

Referring to FIG. 1, in step S110, a starch suspension is prepared by dispersing starch in an ethanol solution.

In step S110, the starch is ungrown starch.

The starch is natural starch obtained from a plant, but the starch may be, but not limited to, corn starch, tapioca starch, rice starch, potato starch, sweet potato starch, rice starch, cassava starch, wheat starch and barley starch. According to the embodiment, the starch may be a potato starch, and the potato starch may be a potato starch produced by a conventional method.

The ethanol solution is a mixture of water and ethanol. Here, it is preferable to use distilled water as the water.

The ethanol solution may contain 40 to 70 parts by weight of ethanol with respect to 100 parts by weight of the ethanol solution, and may preferably include 48 to 62 parts by weight of ethanol.

When ethanol is contained in the ethanol solution in the above-mentioned range, the starch particles are well preserved and the birefringence disappears. Specifically, when the content of ethanol is less than 40 parts by weight with respect to 100 parts by weight of the ethanol solution, the starch does not maintain the particle shape when heat-treated, and when the ethanol content is more than 70 parts by weight, There is a need for an appropriate range of ethanol.

Ethanol can be hydrated ethanol. Because ethanol is not a luxury, it is possible to use hydrated ethanol mixed with ethanol and water, and hydrated ethanol may have the same meaning as an ethanol solution.

Generally, when starch is hydrolyzed by high temperature and moisture, swelling of starch occurs at the same time. When starch is swollen, starch molecular crystals are tensed and tend to distort the crystals. This causes the double helix to loosen and separate, resulting in the collapse of the crystal region and the collapse of the arrangement. For example, amylose and amylopectin intertwine in the potato starch to maintain the particle shape of the potato starch.

In step S110, ethanol causes a change in the surface of starch by ethanol treatment. For example, in the case of corn and tapioca, wrinkles appear on the surface of starch particles, and cracks are formed in the case of potatoes. Such surface changes of the starch particles can be attributed to differences in the molecular structure of the starch.

In addition, ethanol can help to maintain the particle structure by inhibiting the swelling of starch particles.

The starch suspension may comprise 5 to 50 parts by weight of starch, preferably 20 to 40 parts by weight, based on 100 parts by weight of the starch suspension.

When the starch content in the starch suspension is less than 5 parts by weight, the concentration of the starch suspension is so low that the efficiency is low. When the starch content is more than 50 parts by weight, the amount of water is too low compared to the starch content, It is difficult to make amorphous starch.

S120: Heat treatment of starch suspension

Referring to FIG. 1, step S120 heat-treats the starch suspension prepared in step S110.

In step S110, the heat treatment can be performed at a temperature condition ranging from 80 占 폚 to 100 占 폚, and preferably, a temperature condition ranging from 88 占 폚 to 96 占 폚.

When the temperature of the heat treatment is less than 80 캜, sufficient heat energy is not transmitted and the full enhancement is not achieved. When the temperature of the heat treatment exceeds 100 캜, the loss of the starch particles is relatively large, .

The heat treatment can be performed at a time condition ranging from 5 minutes to 60 minutes, preferably at a time ranging from 10 minutes to 30 minutes.

When the heat treatment time is less than 5 minutes, complete liquefaction is not achieved, and when the heat treatment time exceeds 60 minutes, the loss of the starch particles is relatively large, which makes it difficult to produce amorphous starch particles. Without heat treatment, starch can not be luxuriously produced, making it impossible to produce amorphous starch.

According to the embodiment of the present invention, amorphous starch particles that can be edible even without using a chemical method can be produced by generating a phenomenon of starch gelification by heat treatment.

In addition, according to the embodiment of the present invention, the ethanol solution for suppressing moisture, heat, and swelling for swelling starch causes the starch to lose its birefringence while maintaining its particle shape.

S130: Starch wash

1, in step S130, alcohol is added to the starch suspension heat-treated in step S120, and the starch is washed by centrifugation.

Specifically, the starch suspension is heat-treated and then washed with alcohol. It is preferable to use centrifugation. In step S130, dehydration of the starch suspension is performed by washing with water, and by using centrifugation, rapid precipitation can be obtained.

Washing may be repeated a plurality of times. The number of times of rinsing and the rpm, temperature and time conditions of the centrifugal separator can be appropriately adjusted depending on the amount of alcohol used and the like.

The alcohol is preferably a lower alcohol having 3 or less carbon atoms such as methanol, ethanol or propanol, and ethanol is particularly preferable, and it may be anhydrous ethanol.

S140: Acquisition of amorphous particle starch

Referring to FIG. 1, step S140 is a step of drying and pulverizing the starch washed in step S130 to obtain amorphous starch particles.

In step S140, if drying is sufficient to remove water and alcohol inside the starch particles, various drying methods known in the art may be used.

Drying can be carried out by, for example, a vacuum drying method, a freeze drying method, a buried drying method, a hot air drying method, or a reduced pressure drying method.

The drying can be carried out, for example, at temperature conditions ranging from 20 ° C to 60 ° C, and preferably at 40 ° C.

The pulverization may be carried out by various known pulverizing methods. The pulverization can be carried out by, for example, a ball mill, a jet mill, homogenization, microfluidisation or ultrasonication.

In consideration of the denaturation by heat, it is preferable to crush at room temperature as possible. The pulverization process is a simple pulverization process, in which the amorphous particle starch must not be damaged.

Amorphous particle starch

The amorphous starch according to an embodiment of the present invention refers to a starch having a crystalline structure of starch but having a grain structure. Specifically, the amorphous particle starch according to an embodiment of the present invention is a processed starch in which the outer shape of the natural starch is maintained, but the crystalline region inside the starch particle is lost.

The term "amorphous" indicates that the crystalline region of the starch is lost, and the starch no longer contains the crystalline region, and the birefringence is lost. The "particle structure" refers to the outline of the granule, that is, the granule. The amorphous particle starch according to the embodiment of the present invention maintains the outer shape, that is, the particle structure, of the granule like the natural starch.

The amorphous starch particles according to the embodiments of the present invention have a particle shape, that is, a particle structure substantially the same as that of natural starch, but the solubility, swelling power and gelatinization property are different from natural starch. In addition, by producing the amorphous starch particles using the manufacturing method according to the embodiment of the present invention, microbial sterilization effect and enzyme inactivation effect can be obtained at the same time, and the change and loss of flavor, taste, .

Viscosity enhancer

The viscosity enhancer according to an embodiment of the present invention includes amorphous particle starch according to an embodiment of the present invention. The viscosity enhancer according to the embodiment of the present invention can be widely used in foods, chemical fields, industrial fields, and the like.

Food composition

The food composition according to an embodiment of the present invention comprises amorphous particle starch according to an embodiment of the present invention. The food according to the embodiment of the present invention may be a health supplement food, a health functional food, a functional food and the like, but is not limited thereto. The amorphous particle starch of the present invention may be added to natural foods, processed foods, patient foods, .

There is no particular limitation on the kind of the food. The food composition may be used in the form of tablets, hard or soft capsules, liquids, suspensions, and the like, which may contain conventional excipients, such as excipients in the case of oral preparations, Binders, disintegrators, lubricants, solubilizers, suspending agents, preservatives or extenders.

BRIEF DESCRIPTION OF THE DRAWINGS The advantages and features of the present invention, and the manner of achieving them, will be apparent from and elucidated with reference to the embodiments described hereinafter in conjunction with the accompanying drawings. It should be understood, however, that the invention is not limited to the disclosed embodiments, but is capable of many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, To fully disclose the scope of the invention to those skilled in the art, and the invention is only defined by the scope of the claims.

Example  One

10 g of natural potato starch (dry basis, db) was well dispersed in 100 mL of a hydrated ethanol solution (50 wt%), and the mixture was stirred in a water bath set at 90 캜 for 20 minutes with stirring. The boiling point of ethanol is 78 ℃, it may cause ethanol loss when heated to 90 ℃. Therefore, to minimize the loss of ethanol, put the sample in a 50 mL conical tube, close the lid, cover the gap with parafilm . As soon as the bath was finished, 50 mL of anhydrous ethanol was added to prevent gel formation, dehydrated and centrifuged. The centrifugation was performed at 3,000 rpm at 4 ° C for 5 minutes. This procedure was repeated three times. The dehydrated potato starch was pulverized by drying in a 40 ° C dry oven for 24 hours and then passed through a 100 mesh sieve and used as a sample.

Example  2

10 g of natural potato starch (dry basis, d.b) was well dispersed in 100 mL of a hydrated ethanol solution (50 wt%), and the mixture was stirred in a water bath set at 95 캜 for 20 minutes with stirring. The subsequent procedure was carried out in the same manner as in Example 1 above.

Example  3

10 g of natural potato starch (dry basis, d.b) was well dispersed in 100 mL of a hydrated ethanol solution (55 wt%), and the mixture was stirred in a water bath set at 88.3 캜 for 20 minutes with stirring. The subsequent procedure was carried out in the same manner as in Example 1 above.

Example  4

10 g of natural potato starch (dry basis, d.b) was well dispersed in 100 mL of a hydrated ethanol solution (55% by weight), and the mixture was stirred in a water bath set at 92.5 캜 for 20 minutes with stirring. The subsequent procedure was carried out in the same manner as in Example 1 above.

Example  5

10 g of natural potato starch (dry basis, d.b) was well dispersed in 100 mL of a hydrated ethanol solution (60% by weight), and the mixture was stirred in a water bath set at 90 캜 for 20 minutes. The subsequent procedure was carried out in the same manner as in Example 1 above.

Example  6

10 g of natural potato starch (dry basis, d.b) was well dispersed in 100 mL of a hydrated ethanol solution (60 wt%), and the mixture was stirred in a water bath set at 95 캜 for 20 minutes with stirring. The subsequent procedure was carried out in the same manner as in Example 1 above.

Example  7

10 g of natural potato starch (dry basis, d.b) was well dispersed in 100 mL of a hydrated ethanol solution (53% by weight), and the mixture was stirred in a water bath set at 94 캜 for 20 minutes with stirring. The subsequent procedure was carried out in the same manner as in Example 1 above.

Comparative Example  One

A natural potato starch was prepared and used as the starch of Comparative Example 1.

Examples 1 to 7 and Comparative Example 1 are briefly summarized in Table 1 below.

Starch raw material Ethanol content (% by weight) Heat treatment temperature (캜) Example One Potato starch 50 90 2 Potato starch 50 95 3 Potato starch 55 88.3 4 Potato starch 55 92.5 5 Potato starch 60 90 6 Potato starch 60 95 7 Potato starch 53 94 Comparative Example One Potato starch - -

Microscopic analysis of starch

Microscopic analysis of the amorphous particle starches of Examples 1 to 7 was performed.

A small amount of distilled water was dispersed in natural starch (Comparative Example 1) and amorphous starch particles (Examples 1 to 7), and then one drop was dropped on a slide glass and covered with a cover glass to prepare a sample for general microscope and polarization microscope analysis.

Microscopic analysis was performed using the sample. Specifically, the outline was observed using light which was not polarized by a general microscope analysis, and the presence of birefringence observed through a polarization microscope was observed. The results are shown in Figs. 2A to 2G.

Figs. 2A to 2G are microscope images of amorphous particle starches of Examples 1 to 7. Fig. In FIGS. 2A to 2G, the image A on the left is a result of observation with a general microscope, and the image B on the right is a result of observation with a polarization microscope.

Referring to Figs. 2A-2F, it can be seen from the general microscope image of A in each of the figures that amorphous particle starches (Examples 1 to 6) retained their particle morphology, Microscopic images showed that the birefringence disappeared and that the birefringence disappeared.

The potato starches (Examples 1 and 2) treated with an ethanol content of 50% by weight exhibited a phenomenon that the starch particles swelled to become somewhat larger, so that some starch particles were broken and potato starches treated with an ethanol content of 55% 3 and 4) showed similar particle shape and birefringence due to the difference of heating temperature.

In the case of the potato starch treated with the ethanol content of 60% by weight (Examples 5 and 6), the ethanol content was so high that the gelation did not proceed completely and the birefringence was not lost much. However, it was confirmed that the shape of the starch particles was slightly bulky, and maintained the shape well without any distortion.

Referring to FIG. 2G, it was confirmed from the general microscope image of A in the figure that the amorphous particle starch (Example 7) was slightly larger in size compared with the particle shape of the natural potato starch, In the figure, it was confirmed that the birefringence completely disappeared through the polarizing microscope image of B, and it was found that the enhancement was proceeded by the disappearance of birefringence.

Thermodynamic Properties of Starch in Luxury

Differential scanning calorimetry (DSC) analysis was performed to investigate the thermodynamic properties of amorphous starch particles (Example 7) and natural potato starch (Comparative Example 1). This was measured using a differential scanning calorimeter (DSC 4000, Perkin Elmar, Inc., Waltham, MA, USA) with a sealed blank pan as a reference.

A sample of 75% moisture content was immersed in an aluminum pan at a concentration of about 20 mg and allowed to stand at room temperature (25 ° C) for 1 hour to stabilize it. ℃ for 1 minute and then 25 ℃ to 120 ℃ for 5 minutes. / Min to obtain a thermodynamic characteristic curve (DSC thermogram).

3 is a graph showing the thermodynamic characteristics of the amorphous particle starch of Example 7 and the natural potato starch of Comparative Example 1 by DSC analysis.

Referring to FIG. 3, it can be seen from the graph obtained from the DSC thermogram that a peak appears when starch is enamelled between 57 ° C and 72 ° C in the case of natural potato starch (Comparative Example 1). However, in the case of amorphous starch particles (Example 7), peaks were not observed and it was confirmed that the crystal region inside the particles was destroyed due to the progress of the gelation.

X-ray diffraction diagram

The X-ray diffraction characteristics of amorphous starch particles (Example 7) and natural potato starch (Comparative Example 1) were measured.

The X-ray diffraction pattern was measured by using an X-ray diffractometer (D8 Advance, Bruker AXS GmbH, Karlsruhe, Germany) under conditions of 40 kV and 300 mA using Cu-Kα as an X- To an X-ray diffraction pattern at 3 DEG / min.

4 is a graph showing the X-ray diffraction characteristics of the amorphous particle starch of Example 7 and the natural potato starch of Comparative Example 1. Fig.

Referring to FIG. 4, in the case of the natural potato starch (Comparative Example 1), the crystal form shows a pattern of B-type and a peak appears at 7 °, 17 °, 22 ° and 24 ° there was. However, in the case of amorphous starch particles (Example 7), peaks at 7 °, 17 °, 22 ° and 24 ° were disappeared, and a new peak appeared at around 13 °. In addition, it showed a gentle curve similar to that of the V-type pattern observed in amorphous starch particles.

Accordingly, when the XT ray diffraction patterns of the natural potato starch (Comparative Example 1) and the amorphous starch (Example 7) were compared, the crystal form changed from the B-type pattern to the V-type pattern. And it was confirmed that the crystal region was destroyed.

While the invention has been shown and described with reference to certain preferred embodiments thereof, it will be understood by those of ordinary skill in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims. This is possible. Therefore, the scope of the present invention should not be limited to the described embodiments, but should be determined by the equivalents of the claims, as well as the claims.

Claims (11)

Preparing a starch suspension by dispersing starch in the ethanol solution containing 40 to 70 parts by weight of ethanol per 100 parts by weight of the ethanol solution;
Heat treating the starch suspension for 5 minutes to 60 minutes;
Adding alcohol to the heat-treated starch suspension and centrifuging the starch to wash the starch; And
Drying and pulverizing the washed starch to obtain an amorphous particle starch
Lt; / RTI >
Wherein the amorphous particle starch is a starch starch which has lost the crystal region of the starch but retains its particle structure.
delete The method according to claim 1,
Wherein the ethanol is hydrated ethanol.
The method according to claim 1,
Wherein the temperature of the heat treatment is in the range of 80 ° C to 100 ° C.
delete The method according to claim 1,
Wherein the alcohol is methanol, ethanol or propanol.
delete The method according to claim 1,
Wherein the starch is a natural starch obtained from a plant.
9. The method of claim 8,
Wherein the starch is a potato starch.
The amorphous particle starch produced by the method of any one of claims 1, 3, 4, 6, 8 and 9,
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The amorphous particle starch produced by the method of any one of claims 1, 3, 4, 6, 8 and 9,
≪ / RTI >

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