JPH0673467B2 - Method for manufacturing starch hydrolyzate - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a starch hydrolyzate and a method for producing the same.

It is known that starch can be hydrolyzed with an acid or an enzyme to produce a hydrolyzed product containing sugar and useful in foods.
The sweetness properties of starch hydrolysates depend in large part on the degree of conversion, ie the degree of hydrolysis of the starch molecules. A very common method of classifying starch hydrolysates is to measure the degree of hydrolysis by dextrose equivalent (DE), which is calculated as dextrose and is expressed as a percentage of total dry matter. It is a measure of the reducing sugar content of a product. Starch hydrolyzate
DE value is "Jounnal of Biological Chemistry" 160,6
It is convenient to measure by the method of Smogyi, M. described in 1 (1945), which method is referred to herein as DE
The method used to measure the value.

The use of enzymes to hydrolyze starch has become widespread in recent years, and enzymes are used to commercially manufacture certain products. Enzymes have the advantage of acid catalysis which exhibits specificity for certain bonds, α-amylase has the property of splitting all 1-4 bonds of the starch molecule in a somewhat random manner, with almost no 1-6 bond. Has no effect. Note that α-amylase is 1-4 of maltose and maltotriose.
The bond is not easily hydrolyzed or split. When substantially complete starch conversion is achieved by α-amylase, maltose and small amounts of trisaccharides and other low molecular weight polysaccharides, especially those containing 1-6 bonds, are present in the final hydrolyzate.

Low DE starch hydrolyzate is widely used in the food industry as a bodying agent and a carrier for food flavors. In many applications, the functionality or adaptability is enhanced when the hydrolyzate has a relatively low DE. Low DE starch hydrolysates generally exhibit viscous, film forming and low sweetness properties, which are particularly preferred for some applications. D. less than 10.
Although the advantages of hydrolyzates with E. values have been previously recognized in food factories, previous attempts to produce purified hydrolysates of this DE range of non-waxy starch have been hampered by the inability of the hydrolysates to filter. Was given. The unusual difficulty of filtering such low DE products has been a serious problem in the past. Non-waxy low-DE products are crude hydrolysates,
Although produced as an unfiltered product, such products have been determined for use due to their incomplete solubility and their strong tendency to give rise to lancets with off-flavors during storage.

The main object of the present invention is to provide a novel low DE starch hydrolyzate from non-waxy starch.

Another object of the present invention is to provide a palatable, colorless, water-soluble, non-waxy starch hydrolyzate having a DE value of up to about 6.

It is also an object of the present invention to provide a non-waxy starch hydrolyzate having a DE value of up to about 6 which is easily filterable and which can be treated with carbon to recover a high yield of purified product.

Yet another object of the present invention is to provide a low DE non-waxy starch hydrolyzate that yields an aqueous solution of relatively high viscosity, improved emulsion stability, improved film strength and good clarity stability.

Another object of the present invention is to provide a method for producing a novel low DE starch hydrolyzate from non-waxy starch.

Another object of the present invention is to provide a method for producing a palatable, colorless, water-soluble, non-waxy starch hydrolyzate having a DE value of up to about 6.

An additional object of the present invention is a low DE hydrolyzate which is easily filtered and yields an aqueous solution of relatively high viscosity, improved emulsion stability, improved film strength and good clarity stability, non-waxy starch. It is to provide a method of manufacturing from.

The present invention also provides a method for producing a non-waxy starch hydrolyzate having a DE value of up to about 6, which allows easy filtration and recovery of the carbon-treated purified product in high yield.
Has one purpose.

The present invention provides a low DE starch hydrolyzate having a DE value of about 6,
Includes findings that can be produced, filtered and purified by prolonged treatment of α-amylase at temperatures of 95 ° C and above. According to a preferred embodiment of the present invention,
Dispersing non-waxy starch in water at a proportion of 10 to 40% solids, preferably in the range of 20 to 30% solids and heating with acid or a liquefying enzyme as described in US Pat. No. 3,663,369. Liquefy by. Whichever liquefaction method is used, it is important to carry out the liquefaction so as to provide complete gelatinization with essentially no residual starch particles and a liquefied starch having a DE of substantially less than 3. The pH of the liquefied starch is about 6.5 to 8.0, preferably 6.8 to 7.5.
Adjust to the pH value of. Bacterial α-amylase is added to the liquefied starch and it is added at a temperature of about 95 ° C or higher, preferably about
Adjust the temperature to 95-100 ° C and hold for 10-60 minutes.
Upon reaching the desired DE, preferably 3.5 to 4.0, the hydrolyzate has a pH of less than 4.5, preferably a pH of 3.5 to 4.0.
Acidify to deactivate the enzyme and collect the hydrolyzate by filtration. The hydrolyzate can then be treated with carbon and dried using methods conventional in the art.

The use of long-term treatment with α-amylase at temperatures of at least about 95 ° C is a critical feature of the invention.
The prior art shows that α-amylase is used for a short time at a temperature of 93 ° C or higher to achieve liquefaction, but in a normal practice, the temperature after liquefaction is reduced to 85 ° C or lower, and it is measured by the increase of DE. Maximize the hydrolysis rate. Under these conditions, the hydrolyzate is essentially unfilterable until the DE reaches a value of 8 or higher. It has been found that treating liquefied starch with α-amylase at temperatures above 95 ° C. results in an unexpected improvement in filterability with little increase in DE. By increasing the time of amylase treatment at 95 ° C or higher, the filterability of hydrolyzate of 6D.E.
E. Decreasing rate of increase This finding is a feature of the present invention, which allows the recovery of purified low DE hydrolysates of non-waxy starch previously unavailable.

For example, various non-waxy starches or starchy substances such as garlic and potatoes, white sweet potatoes, corn, tapioca, wheat, rice, sago etc. can be used according to the present invention. Corn starch is the preferred material.

The types of α-amylases suitable for practicing the present invention are well known in the art and are described in Biocon Canalpha 180, Miles Tenas
e, or under the name Novo BAN. These are bacterial enzymes produced by Bacillus subtilis. Another type of bacterial α-amylase that can be used is produced by culturing Bacillus licheniformis and is commercially available under the names Novo Termamyl and Miles Taka-Therm. Amylases derived from Bacillus licheniformis have higher saccharification activity above 95 ° C than amylases derived from Bacillus subtilis, so there are more difficulties to control to provide a final DE of 6 or less.

When using commercially available enzyme products such as those listed above, the proportion of α-amylase suitable for carrying out the method is generally in the range of 0.1 to 0.6% based on starch solids. The exact usage depends on the desired final DE, enzyme activity and reaction temperature and pH. When the desired final DE is in the range of 3 to 4, it is preferable to use a slightly higher temperature and pH, ie 97 ° C, pH 7.5, in order to provide the best filtration performance, lower temperature and pH should be used. , 95 ℃, pH
A higher proportion of α-amylase is required than is needed to obtain the 6D.E. product at 7.0. Usually 4 to 6
For the production of hydrolyzates in the DE range, it has been found that 0.2 to 0.4% of α-amylase showing 3,000 to 4.000 skB units per gram give satisfactory results.

The reaction time and temperature are closely related. That is, within the relatively narrow temperature range in which the present invention can be practiced, increasing the temperature will reduce the time to obtain maximum filtration capacity. The reaction time can be as short as 5 minutes or as long as 40 minutes in order to produce a product having a DE of less than 6, but the reaction time is usually 95 ° C./20 minutes to provide a filterable hydrolyzate. Is enough.

With a comparable DE value of less than 6, the hydrolyzate of the invention is superior to the prior art non-waxy starch hydrolysates in terms of better solubility and clarity of aqueous solutions. Prior art 6D.
E. The following non-waxy products are largely non-filterable,
The novel low DE hydrolyzate of the present invention is easily filterable and treated with carbon to provide a product that is substantially completely soluble in water and is an essentially colorless, odorless, tasteless solution. You can The hydrolyzate of the invention has a very low proportion of oligosaccharides, as shown in the data of Example 5. As the data in Example 4 shows,
The transparency stability is better than that of products manufactured by the prior art method.
Has been substantially improved. The novel low DE starch hydrolyzate can be characterized as follows.

(1) Low D.E. of 6 or less.

(2) It is completely soluble in water at a total solid content concentration of less than 35%.

(3) The transparency of a 30% solution at 80 ° C. exceeds 60% with respect to 600 mμ of water in a 19 mm cell, and the light transmittance is measured.

(4) Less than 1% monosaccharide and less than 1.5% disaccharide and D
Includes the Descriptive Ratio calculated by dividing the total amount of sugars from P1 to DP6 by the DE less than 2.

(5) It can be filtered at a good filtration rate, that is, at a rate of 100 ml / min or more. Example 1 The invention and its advantages are further illustrated by the following example.

Example 1 Two samples of 3 of acid liquefied waxy corn starch
Obtained with an industrial jet type cooker. Liquefied starch containing 25% solids had a pH of 7.2 and a DE of 2.2. One of the samples was kept at 80 ° C and the other at 96 ° C. Bacterial α-amylase (Canalpha 180) based on starch solids
It was added to both samples at a rate of 0.2%. This ratio is 1
This corresponds to 800 skB units of α-amylase per 00 grams of starch. Samples of 200 ml were taken every 5, 10, 20, 30 and 40 minutes, acidified to pH 3.5 to 4.0 and tested for filterability by the following test: (This test method is used throughout this specification. To).

A # 1 Whatman paper was attached to a filter funnel heated by circulating hot water at 80 ° C. with a 9 cm jacket and fitted with a suction device. 2 grams of filter aid (Cela
tom) is added to 200 ml of crude hydrolyzate at 75 ° C to 77 ° C,
Pour into the funnel. A stopwatch was used to measure the time to filter all samples or the amount filtered in 5 minutes. Filtration time was used to calculate the filtration rate in ml per minute.

The results of a comparison of α-amylase treatment at 80 ° C and 96 ° C are shown below. It is easily seen that the filtration rate is much higher after amylase treatment at 96 ° C than at 80 ° C, but the rate of DE increase is much higher at 80 ° C than at 96 ° C.

Example 2 Six samples of acid liquefied starch with a solids content of 23.3% were prepared by a jet cooker and shown below in the Biocon Can.
Alpha180 α-amylase treatment was performed and divided into two 3-samples. One sample was kept at 80 ° C and the other at 95 ° C. After adjusting the pH from 3.5 to 4.0 to inactivate the enzyme, samples were taken out periodically for DE and filterability measurements.

Test results show that DE increased fastest in the sample at 80 ° C, while filtration rate increased faster at 95 ° C.

Example 3 A dispersion of non-waxy starch was treated with α-amylase and liquefied in an industrial jet cooker. Two samples of liquefied starch were adjusted to pH 7.0 and heated to 80 ° C and 95 ° C for treatment with α-amylase as follows: Filtration rate for low DE products (<6) is 95 above 80 ° C
It is faster to use the reaction temperature of ℃, but the DE is 95 ℃.
It increased faster at 80 ℃. For example, at 80 ℃, DE is 5
After minutes, 5.88 was reached, providing a filtration rate of 81 ml / min. 95 ° C
The DE reached 5.6 in 30 minutes and had a filtration rate of 160 ml / min.

Example 4 Four, 3-samples of acid-liquefied starch were taken from an industrial steam jet cooker. The liquefied starch is 22
% Solids and had a DE of 2.2. The pH was adjusted to 7.2 and the temperatures were held at 85, 90, 95 and 99 ° C as shown below. α-Amylase (Biocon Canalpha 180) was added at a rate of 0.3% based on solids. Samples were taken periodically, acidified to pH 4 with hydrochloric acid and tested for filterability using the standard filtration test method described above. Part of the filtrate is D.
Used to measure E., heated to 80 ° C., then cooled to 60 ° C. and checked for clarity. Spectronic 20 Colorimete
Clarity was determined by measuring the light transmission to 600 mμ of water using an r 19 ml B & L test tube.

The results are shown in the table below. A filterable product at 85 ° C has a DE of 6
The data show that treatment with α-amylase at temperatures of 95 ° or 99 ° C yields a filterable hydrolyzate in the DE range of 3 to 5, although not obtained until or 7 is reached. Clarity data show that increasing the temperature of amylase treatment from 85 ° C to 99 ° C substantially improves the stability of permeability in samples in the DE range of 3 to 6.

Example 5 Several samples of non-waxy hydrolyzate with DE of 4 to 6 were prepared by the method of the present invention, as shown in the following table, D.
E. and sugar profiles were analyzed.

Example 6 Acid-heated starch paste 3, prepared in a steam jet cooker, was adjusted to pH 7.0 with sodium carbonate and cooled to 96 ° C. 48 ml of diluted Biocon Canalpha bacterial α-amylase (equal to 0.4% starch dry matter) was added and the solution was kept at 95-96 ° C for 27 minutes. PH by adding hydrochloric acid
Adjusted to 4.2 and added 2.5 grams of carbon. After holding at 95 ° C for 10 minutes, the solution was cooled to 85 ° C and filtered through a filter aid. The filtrate is clear like water at temperatures above 75 ° C, 4.
It had a DE of 3.

Modifications and equivalents of the invention that come within the spirit of the invention are considered part of the invention.

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Claims (11)

[Claims] 1. An aqueous slurry of non-waxish starch is treated with an acid or an enzyme to liquefy the starch and substantially free of residual starch particles having a measurable DE value of substantially 3 or less. A dispersion is provided, which is then treated with 0.1-0.6% of bacterial α-amylase based on starch solids at a temperature of at least about 95 ° C. and has a measurable DE value of substantially 10 or less. A process for the preparation of a starch hydrolyzate, which comprises obtaining a filterable hydrolyzate, stopping the enzymatic action and recovering the hydrolyzate obtained having a descriptive ratio of not more than about 1.5. 2. A process according to claim 1, wherein the treatment with the bacterial α-amylase is carried out at a temperature in the range of about 95 to 100 ° C.
The method described in the section. 3. The method according to claim 1, wherein the treatment with the bacterial α-amylase is carried out at a pH of about 6.5 to 8. 4. Treatment with bacterial α-amylase at a temperature of about 95 to 100 ° C. and a pH of about 6.5 to 8,
The method according to claim 1. 5. The method according to claim 1, wherein the treatment with the bacterial α-amylase is carried out at a temperature of about 95 to 100 ° C. and a pH of about 6.8 to 7.5. 6. The method according to claim 1, wherein the starch hydrolyzate having a measurable DE value of not more than 6 is recovered. 7. The method according to claim 6, wherein the starch hydrolyzate is recovered by filtration. 8. The method according to claim 6, wherein the starch hydrolyzate is recovered by filtration and then treated with carbon to obtain a purified starch hydrolyzate. 9. The method of claim 1 wherein the starch hydrolyzate having a measurable DE value of about 3 to about 6 is recovered. 10. A starch hydrolyzate is recovered by filtration.
A method according to claim 9. 11. The method according to claim 9, wherein the starch hydrolyzate is recovered by filtration and then treated with carbon to obtain a purified starch hydrolyzate.