CN110372802B - Citrate starch and preparation method thereof - Google Patents
Citrate starch and preparation method thereof Download PDFInfo
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- CN110372802B CN110372802B CN201910827858.8A CN201910827858A CN110372802B CN 110372802 B CN110372802 B CN 110372802B CN 201910827858 A CN201910827858 A CN 201910827858A CN 110372802 B CN110372802 B CN 110372802B
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- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B31/00—Preparation of derivatives of starch
- C08B31/02—Esters
- C08B31/04—Esters of organic acids, e.g. alkenyl-succinated starch
Abstract
The invention relates to citrate starch and a preparation method thereof, wherein the preparation method of the citrate starch comprises the following steps: mixing starch and citric acid, adding deionized water and an alkaline catalyst, uniformly mixing, sealing, placing in subcritical extrusion equipment, drying, crushing, sieving, washing with alcohol, and removing impurities to obtain citrate starch with substitution degree of not less than 0.01. The method for preparing the citrate starch by subcritical water extrusion has the advantages of achieving the substitution value of more than 0.01, being convenient to operate, simple in process, capable of realizing continuous preparation, solving the technical problem of the existing citrate starch preparation, greatly promoting the industrial production of the citrate starch, and having wide market space.
Description
Technical Field
The invention relates to the technical field of starch modification, in particular to citrate starch and a preparation method thereof.
Background
Citric acid and Starch used as an acidulant, an antioxidant, a pH adjuster, and the like of food can be esterified into Citrate Starch (SC) under certain conditions. SC is added into food such as bread, crisp cake, flour food and extruded product to improve product quality.
However, compared with other modified starches, the existing citrate starch modification process has the characteristics of complex preparation process, long period, high energy consumption, low yield and the like, and seriously restricts the development of SC industrialization and the application of SC in food, so that a continuous production technology with high modification efficiency is needed to be developed to improve the SC yield. At present, SC products sold in the market are not used as food additives or auxiliary materials, and if the preparation method is deeply researched and developed, the commercial development value of the SC products can be greatly improved.
In 1978, Klaushofer et al reported that SC was prepared by a high temperature dry process (Klaushofer process for short), by mixing an alkalized citric acid solution into starch, standing (16h), drying at medium temperature (about 50 ℃) to about 10% moisture content, and heating at high temperature (about 130 ℃) for 3-12h, citrate starch was prepared. Most of the dry-process citrate starch preparation methods reported at home and abroad hereafter basically adopt the Klaushofer method directly or indirectly.
For example, chinese patent application 105348400a discloses a citrate starch and its preparation process, wherein the preparation process comprises the steps of firstly, taking a certain amount of citric acid, adding distilled water, continuously stirring with a stirrer to dissolve the citric acid in the water, then pouring a certain amount of NaOH solution, adjusting the PH value of the solution to 3-4, continuously stirring, adding water chestnut starch, standing for reaction for a period of time, drying in a drying oven, taking out the dried product after drying, grinding, further reacting the ground powder in a high temperature environment, washing with acetone solution, finally washing with water and drying to obtain the citrate starch. The method has the disadvantages of complex preparation process, long time, high temperature, high energy consumption and other costs, and difficult continuous preparation.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide the citrate starch and the preparation method thereof, which adopt subcritical extrusion equipment, have high production efficiency and can be continuously produced, the prepared citrate starch has a substitution value of more than 0.01, and can be added into foods such as bread, crackers, wheaten food, extruded products and the like to improve the product quality.
The degree of substitution of citrate starch refers to the amount of material in which the active hydroxyl groups on each D-glucose unit of the starch are esterified with citric acid.
One of the technical difficulties of the invention is the proportion of the raw materials, wherein the sum of the addition amount of the deionized water and the water content of the starch is 15 wt% -35 wt% of the dry basis of the starch, and the water can not reach the subcritical state if the deionized water is not in the range. All the raw materials are required to be sealed and kept stand after being mixed, because the deionized water and the starch are uniformly mixed, the standing time is less than 4 hours, and the water distribution is not uniform.
The second technical difficulty of the invention is the parameter control of the subcritical extrusion equipment, the setting temperature is 100-. The temperature of less than 100 ℃ can cause that water can not reach a subcritical state, but the temperature of more than 180 ℃ causes that starch is seriously degraded, which is not beneficial to the improvement of the later starch property. The principle of the invention for completing the reaction by using subcritical extrusion equipment is that in the extrusion process of the material, because the material is heated, extruded and rubbed to form subcritical conditions, the polarity of the material is reduced, the collision probability of chemical groups is increased, the modification activity is increased, and because of the good dissolution and migration effects of subcritical water, the modifier is infiltrated into the interior of the starch granules, so that the problem that the traditional chemical modification is concentrated on the surface of the starch granules is avoided, and more starch hydroxyl groups are replaced. By means of reasonably controlling the heating temperature, the rotating speed of the screw rod and the like, the substitution degree of the product as large as possible can be realized. For example, the mass ratio of the starch dry basis to the citric acid is within the range of 2.5:1-6:1, the heating temperature is controlled within the range of 120-150 ℃, the rotation speed of a screw is controlled within the range of 15-20r/min, and the degree of substitution of the citrate starch is not lower than 0.2 under the condition.
The specific scheme is as follows:
a method for preparing citrate starch comprises the following steps: mixing starch and citric acid, adding deionized water and an alkaline catalyst, uniformly mixing, sealing, placing in subcritical extrusion equipment, drying, crushing, sieving, washing with alcohol, and removing impurities to obtain citrate starch with substitution degree of not less than 0.01.
Further, the degree of substitution of the citrate starch is more than or equal to 0.2;
optionally, the starch is dried starch, and the mass ratio of the dry basis of the dried starch to the citric acid is 2.5:1-10: 1.
Furthermore, the sum of the addition amount of the deionized water and the water content of the starch is 15-35 wt% of the dry basis of the starch.
Further, the alkaline catalyst is sodium hydroxide, potassium hydroxide or sodium carbonate, and the addition amount of the alkaline catalyst is 0.5-9 wt% of the dry basis of the starch.
Further, the sealed placement is standing for 4-12h at room temperature.
Further, the temperature of the subcritical extrusion equipment is set to be 100-180 ℃, and the rotating speed of a screw is 10-25 r/min; the preferred temperature is 120-150 ℃.
Further, the drying temperature of the extrusion product is 50-100 ℃, and the drying time is 1-12 h; the preferred temperature is 65-100 ℃.
Further, the extruded product is crushed and sieved by a sieve of 80-120 meshes.
Further, ethanol is adopted in the alcohol washing.
The invention also protects the citrate starch prepared by using the preparation method of the citrate starch.
Has the advantages that:
the method adopts subcritical water extrusion equipment to prepare the citrate starch with the substitution value of more than or equal to 0.01, even reaches more than 0.2, is convenient to operate, has simple process, can realize continuous preparation, solves the technical problem of the conventional SC preparation, can greatly promote the industrial production of SC, and has wide market space.
Drawings
In order to illustrate the technical solution of the present invention more clearly, the drawings will be briefly described below, and it is apparent that the drawings in the following description relate only to some embodiments of the present invention and are not intended to limit the present invention.
FIG. 1 is an infrared spectrum provided in accordance with an embodiment 1 of the present invention.
Detailed Description
Preferred embodiments of the present invention will be described in more detail below. While the following describes preferred embodiments of the present invention, it should be understood that the present invention may be embodied in various forms and should not be limited by the embodiments set forth herein. The examples do not specify particular techniques or conditions, and are performed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available. In the following examples, "%" means weight percent, unless otherwise specified.
The subcritical extrusion equipment used in the examples was supplied by jonan heshun machinery, model number G32. It should be noted that the manufacturer and model of the device are merely examples and should not be construed as limiting the invention.
Example 1
And mixing the dried starch dry basis with citric acid according to the mass ratio of 4:1, adding deionized water and NaOH, and uniformly blending. Wherein the sum of the addition of the deionized water and the water content of the starch is 20 wt% of the dry mass of the starch, and the sodium hydroxide accounts for 3 wt% of the dry mass of the starch. Mixing the raw materials, sealing, keeping for 6 hours, and opening to obtain the premix. Adding the premix into a feeding hopper of subcritical extrusion equipment, continuously extruding at the set temperature of 120 ℃ at the screw rotating speed of 20r/min to prepare modified starch, cutting the obtained long-strip material, drying at the temperature of 70 ℃ for 10 hours, crushing, sieving by a 100-mesh sieve to obtain powder modified starch, eluting unreacted citric acid by ethanol to obtain citrate starch, and measuring the substitution degree of the citrate starch to be 0.23. The sample is scanned and analyzed by an infrared spectrometer, the result is shown in figure 1, and an ester group characteristic peak 1730cm is found-1The peak is obvious, and the continuous preparation of the starch by the subcritical water extrusion method is proved to be successfully esterified by the citric acid.
Example 2
Drying the dried starch withMixing citric acid according to the mass ratio of 8:1, adding deionized water and sodium carbonate, and uniformly blending. Wherein the sum of the addition amount of the deionized water and the water content of the starch is 15 wt% of the dry mass of the starch, the sodium carbonate accounts for 9 wt% of the dry mass of the starch, the raw materials are uniformly mixed and then sealed, and the bag is opened after the mixture is kept for 4 hours to obtain the premix. Adding the premix into a feeding hopper of subcritical extrusion equipment, continuously extruding and preparing modified starch at the temperature of 110 ℃ and the screw rotating speed of 15r/min by the subcritical extrusion equipment, cutting the obtained long-strip material, drying at the temperature of 80 ℃ for 3 hours, crushing, sieving by a 100-mesh sieve to obtain powder modified starch, eluting unreacted citric acid by ethanol to obtain citrate starch, and measuring the substitution degree of the citrate starch to be 0.07. The sample is scanned and analyzed by an infrared spectrometer, and the characteristic peak 1730cm of the ester group is found-1The peak is obvious, and the continuous preparation of the starch by the subcritical water extrusion method is proved to be successfully esterified by the citric acid.
Example 3
And mixing the dried starch dry basis with citric acid according to the mass ratio of 6:1, adding deionized water and KOH, and uniformly blending. Wherein the sum of the addition amount of the deionized water and the water content of the starch is 30 wt% of the dry mass of the starch, the KOH accounts for 0.5 wt% of the dry mass of the starch, the raw materials are uniformly mixed and then sealed, and the bag is opened after the raw materials are kept for 4 hours to obtain the premix. Adding the premix into a feeding hopper of subcritical extrusion equipment, continuously extruding and preparing modified starch at the temperature of 130 ℃ and the screw rotating speed of 25r/min by the subcritical extrusion equipment, cutting the obtained long-strip material, drying at the temperature of 50 ℃ for 12 hours, crushing, sieving by a 80-mesh sieve to obtain powder modified starch, eluting unreacted citric acid by ethanol to obtain citrate starch, and measuring the substitution degree of the citrate starch to be 0.21. The sample is scanned and analyzed by an infrared spectrometer, and the characteristic peak 1730cm of the ester group is found-1The peak is obvious, and the continuous preparation of the starch by the subcritical water extrusion method is proved to be successfully esterified by the citric acid.
Example 4
And mixing the dried starch dry basis with citric acid according to the mass ratio of 2.5:1, adding deionized water and NaOH, and uniformly blending. Wherein the sum of the addition of the deionized water and the water content of the starch is 35 wt% of the dry basis weight of the starch, NaOH accounts for 6 wt% of the dry basis weight of the starch, the raw materials are uniformly mixed and sealed, the bag is opened after the mixture is kept for 10 hours,a premix was obtained. Adding the premix into a feeding hopper of subcritical extrusion equipment, continuously extruding and preparing modified starch at the temperature of 140 ℃ and the screw rotating speed of 10r/min by the subcritical extrusion equipment, cutting the obtained long-strip material, drying at the temperature of 100 ℃ for 1h, crushing, sieving by a 120-mesh sieve to obtain powder modified starch, eluting unreacted citric acid by ethanol to obtain citrate starch, and measuring the substitution degree of the citrate starch to be 0.38. The sample is scanned and analyzed by an infrared spectrometer, and the characteristic peak 1730cm of the ester group is found-1The peak is obvious, and the continuous preparation of the starch by the subcritical water extrusion method is proved to be successfully esterified by the citric acid.
Example 5
And mixing the dried starch dry basis with citric acid according to the mass ratio of 10:1, adding deionized water and KOH, and uniformly blending. Wherein the sum of the addition amount of the deionized water and the water content of the starch is 25 percent of the mass of the dry base of the starch, KOH accounts for 2 percent of the weight of the dry base of the starch, the raw materials are uniformly mixed and then sealed, and the bag is opened after the raw materials are kept for 12 hours to obtain the premix. Adding the premix into a feeding hopper of subcritical extrusion equipment, continuously extruding and preparing modified starch at the temperature of 150 ℃ and the screw rotating speed of 15r/min by the subcritical extrusion equipment, cutting the obtained long-strip material, drying for 3 hours at the temperature of 60 ℃, crushing, sieving by a 120-mesh sieve to obtain powder modified starch, eluting unreacted citric acid by ethanol to obtain citrate starch, and measuring the substitution degree of the citrate starch to be 0.02. The sample is scanned and analyzed by an infrared spectrometer, and the characteristic peak 1730cm of the ester group is found-1The peak is obvious, and the continuous preparation of the starch by the subcritical water extrusion method is proved to be successfully esterified by the citric acid.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various features described in the above embodiments may be combined in any suitable manner without departing from the scope of the invention. The invention is not described in detail in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (9)
1. A method for preparing citrate starch is characterized in that: the method comprises the following steps: mixing starch and citric acid, adding deionized water and an alkaline catalyst, uniformly mixing, sealing and placing, wherein the sum of the addition amount of the deionized water and the water content of the starch is 15 wt% -35 wt% of the dry basis of the starch, standing for 4-12h at room temperature, then putting into subcritical extrusion equipment, setting the temperature of the subcritical extrusion equipment to be 100-180 ℃, drying, crushing and screening the obtained extrusion product, and washing with alcohol to remove impurities to obtain the citrate starch with the substitution degree of more than or equal to 0.01.
2. The method of preparing a citrate starch according to claim 1, wherein: the degree of substitution of the citrate starch is more than or equal to 0.2.
3. The method of preparing a citrate starch according to claim 1, wherein: the starch is dried starch, and the mass ratio of the dry basis of the dried starch to the citric acid is 2.5:1-10: 1.
4. The method of preparing a citrate starch according to claim 1, wherein: the alkaline catalyst is sodium hydroxide, potassium hydroxide or sodium carbonate, and the addition amount of the alkaline catalyst is 0.5-9 wt% of the dry basis of the starch.
5. Process for the preparation of citrate starch according to any of the claims 1 to 4, characterized in that: the temperature of the subcritical extrusion equipment is set to be 120-150 ℃, and the rotating speed of the screw is 10-25 r/min.
6. Process for the preparation of citrate starch according to any of the claims 1 to 4, characterized in that: the drying temperature of the extrusion product is 50-100 ℃, and the drying time is 1-12 h.
7. The method of preparing a citrate starch according to claim 6, wherein: the temperature at which the extruded product is dried is 65-100 ℃.
8. Process for the preparation of citrate starch according to any of the claims 1 to 4, characterized in that: and crushing the extruded product and sieving the crushed product with a sieve of 80 to 120 meshes.
9. Process for the preparation of citrate starch according to any of the claims 1 to 4, characterized in that: the alcohol washing is performed by using ethanol.
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