CN113907332A - Efficient preparation method and application of crystal form-controllable starch-lipid compound - Google Patents
Efficient preparation method and application of crystal form-controllable starch-lipid compound Download PDFInfo
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- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
- A23L29/00—Foods or foodstuffs containing additives; Preparation or treatment thereof
- A23L29/30—Foods or foodstuffs containing additives; Preparation or treatment thereof containing carbohydrate syrups; containing sugars; containing sugar alcohols, e.g. xylitol; containing starch hydrolysates, e.g. dextrin
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- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
- A23L33/00—Modifying nutritive qualities of foods; Dietetic products; Preparation or treatment thereof
- A23L33/10—Modifying nutritive qualities of foods; Dietetic products; Preparation or treatment thereof using additives
- A23L33/115—Fatty acids or derivatives thereof; Fats or oils
- A23L33/12—Fatty acids or derivatives thereof
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- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23P—SHAPING OR WORKING OF FOODSTUFFS, NOT FULLY COVERED BY A SINGLE OTHER SUBCLASS
- A23P30/00—Shaping or working of foodstuffs characterised by the process or apparatus
- A23P30/20—Extruding
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- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23V—INDEXING SCHEME RELATING TO FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES AND LACTIC OR PROPIONIC ACID BACTERIA USED IN FOODSTUFFS OR FOOD PREPARATION
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Abstract
The invention discloses a high-efficiency preparation method of a crystal form-controllable starch-lipid compound, which comprises the following steps: (1) premixing raw materials, (2) preparing a starch-lipid compound, (3) drying, crushing and sieving. The invention has the advantages that the starch-lipid compound with controllable crystal forms can be efficiently produced by using an extrusion cooking method, and the formation of the starch-lipid compound with different crystal forms can have different influences on the functional characteristics of starch, such as texture, viscosity, retrogradation and nutrient digestion characteristics, so the starch-lipid compound has wide application prospect in the fields of food processing and food nutrition. Meanwhile, the fusion temperature of the compounds with different crystal forms is different, so that the potential application of the starch as a degradable material can be further widened.
Description
Technical Field
The invention belongs to the field of food processing, and particularly relates to an efficient preparation method and application of a crystal form controllable starch-lipid compound.
Background
The main ingredients of raw materials for producing food are starch, protein, fiber and lipid, etc. The interaction of these components greatly affects the nutritional and quality characteristics of processed foods, so it is important to understand the changes of these substances in food processing engineering. Currently, there are many conventional thermal processing methods in the production of cereals, such as hot air baking, extrusion cooking, etc. And innovative methods such as radio frequency, infrared, microwave heating, vacuum baking and the like also exist. Starch and lipid are two main components in food, and the interaction between the two components has very important influence on the quality of the food, particularly plays an important role in the texture and functional characteristics of the food.
Starch is a mixture of two different polymers, amylose being a predominantly linear glucose polymer and amylopectin being a branched glucose polymer. Amylose can be thermally processed or added with a certain solvent to form a single helical structure which is susceptible to forming complexes with iodine, monoglycerides, lysophospholipids, fatty acids, alcohols and the like. Amylose can form starch-lipid complexes with lipids through hydrophobic interactions. Starch-lipid complexes are classified into type i and type ii depending on the type of crystallization and the melting temperature. The melting point of the type I complex is generally between 94 and 104 ℃ and the melting point of the type II complex is generally between 115 and 121 ℃, the type I complex is composed of a partially ordered structure without distinct crystalline regions, and the type II complex is composed of a distinct crystalline/semi-crystalline structure. The current research mainly focuses on the preparation and crystal structure characterization of the starch-lipid complex, and the efficient preparation of the complex with controllable crystal form and the application of related products are not reported in documents.
Disclosure of Invention
Extrusion cooking technology is now widely used in the food processing industry, and has been used to produce many different processed foods, particularly cereal foods. Generally, the shear energy generated by the rotating screw and the additional heat energy provided by the extruder heat the feedstock to the melting point of the biopolymer, such as starch. In this rheological state, the food product is conveyed through the die under high pressure and the product expands to its final shape. The processing parameters of the extruder (such as material moisture, processing temperature, screw rotation speed, etc.) all affect the system parameters of mechanical energy, heat energy, material residence time, etc. provided by the extruder, thereby changing the structure of the starch and further affecting the functional properties of the starch.
Related studies have reported that starch and lipid are broken down during extrusion cooking process due to mechanical and thermal energy provided by screw extruder, resulting in release of amylose and binding of lipid to form starch-lipid complex. Different processing conditions can generate different influences on the formation of the starch-lipid compound in the processing process, and the efficient preparation of the I-type compound or the II-type compound with controllable crystal forms by using a double-screw extruder does not have related research reports.
Starch-lipid complexes of different crystalline forms have different effects on the organoleptic quality, storage characteristics and nutritional digestion (viscosity, texture, retrogradation, digestion and fermentation characteristics, etc.) of starch-based foods due to their different structural and functional properties. The type I complex is more beneficial to the sensory quality of food than the type II complex, and the type II complex has better nutritional and health functions, so that the two complexes have distinct applications in the food field. By adjusting the processing conditions, the controllable preparation of the compound I and the compound II can be better used for developing nutritional health foods with different characteristics. In order to obtain two compounds with different crystal forms simultaneously, the invention provides the following technical scheme:
a high-efficiency preparation method of a starch-lipid complex with controllable crystal form comprises the following steps:
(1) premixing raw materials:
mixing starch and fatty acid to prepare a sample with the water content of 15% -55%, mixing and stirring for 5min, placing in a sealed bag at room temperature, balancing for 24h, and then processing;
(2) preparation of starch-lipid complexes:
and (2) extruding and cooking the prepared starch-fatty acid mixture containing different water contents by using a double-screw extruder to obtain a starch-lipid compound, wherein the parameters of the extruder are as follows: the diameter of the screw is 2cm, the length-diameter ratio L/D is 40: 1, the feeding speed is 20kg/h, the set temperatures of the first three temperature zones are 40 ℃, 60 ℃ and 90 ℃, and the set temperature ranges of the last three temperature zones are 80-160 ℃; the rotating speed range of the screw is 100-500 rpm;
(3) drying, crushing and sieving:
and (3) cutting the starch-lipid complex sample obtained in the step (2) into fine strips by using scissors, loading the fine strips by using a glass plate, drying the fine strips in an oven at 45 ℃ for 24 hours, grinding the fine strips, and sieving the fine strips by using a 60-mesh sieve to obtain the starch-lipid complex.
Preferably, corn starch and lauric acid are mixed according to the mass ratio of 24:1 to prepare samples with different water contents.
Preferably, in the step (2), the corn starch and the fatty acid are mixed according to a mass ratio of 24:1 to prepare samples with moisture contents of 15%, 25%, 35%, 45% and 55%.
Preferably, the temperature of the three temperature zones after setting in step (2) is adjusted to 80 ℃, 100 ℃, 120 ℃, 140 ℃ or 160 ℃.
Preferably, the screw rotation speed of step (2) is adjusted to 100rpm, 200rpm, 300rpm, 400rpm or 500 rpm.
A starch-lipid complex with controllable crystal form comprises the following steps:
(1) premixing raw materials:
mixing corn starch and lauric acid according to a mass ratio of 24:1 to prepare a sample with the water content of 27%, mixing and stirring for 5min, placing in a sealed bag at room temperature, balancing for 24h, and then processing;
(2) preparation of starch-lipid complexes:
carrying out extrusion treatment by using a double-screw extruder, wherein the extruder consists of six temperature zones, the diameter of a screw is 2cm, and the length-diameter ratio L/D is 40: 1, the feeding speed is 20kg/h, and the processing temperatures of the first three temperature areas of six temperature areas of an extruder are set to be 40 ℃, 60 ℃ and 90 ℃ and the processing temperatures of the other three temperature areas of the other processing areas are uniformly set to be 120 ℃; the screw speed was set to 303 rpm;
(3) drying, crushing and sieving:
and (3) cutting the starch-lipid complex sample obtained in the step (2) into fine strips by using scissors, loading the fine strips by using a glass plate, drying the fine strips in an oven at 45 ℃ for 24 hours, and grinding and sieving the fine strips by using a 60-mesh sieve to obtain the I-type starch-lipid complex.
A starch-lipid complex with controllable crystal form comprises the following steps:
(1) premixing raw materials:
mixing corn starch and lauric acid according to a mass ratio of 24:1 to prepare a sample with the water content of 39%, mixing and stirring for 5min, placing in a sealed bag at room temperature for 24h, and processing;
(2) preparation of starch-lipid complexes:
carrying out extrusion treatment by using a double-screw extruder, wherein the extruder consists of six temperature zones, the diameter of a screw is 2cm, and the length-diameter ratio L/D is 40: 1, setting the feeding speed to be 20kg/h, setting the processing temperatures of the first three temperature zones to be 40 ℃, 60 ℃ and 90 ℃ and setting the processing temperatures of the subsequent processing three temperature zones to be 125 ℃; the screw speed was set to 290 rpm; (3) drying, crushing and sieving:
and (3) cutting the starch-lipid complex sample obtained in the step (2) into fine strips by using scissors, loading the fine strips by using a glass plate, drying the fine strips in an oven at 45 ℃ for 24 hours, and grinding and sieving the fine strips by using a 60-mesh sieve to obtain the II-type starch-lipid complex.
A starch-lipid complex prepared by the efficient preparation method of a crystal form-controllable starch-lipid complex is used in the field of food.
The starch-lipid complex with different crystal forms prepared by the efficient preparation method of the starch-lipid complex with controllable crystal forms has different influences on the sensory quality, the storage property and the nutrient digestion function of starch-based food. The prepared starch-lipid complex with different crystal forms can be added into food according to the requirements of product characteristics.
The starch-lipid complex with different crystal forms is divided into I type and II type according to the type of crystallization and the melting temperature. Type I complexes consist of partially ordered structures with no distinct crystalline regions, while type II complexes consist of distinct crystalline/semi-crystalline structures. The melting point of the type I compound is generally between 94 and 104 ℃ and the melting point of the type II compound is generally between 115 and 121 ℃. These differences in structural properties have different effects on the functional properties of starch, which in turn determine the applications of the complexes in the food field, for example: improving the sensory and storage qualities of food, as fat substitute, as resistant starch, etc.
Starch-lipid complexes of different crystal forms influence the digestibility of starch-based food due to their own crystal order, and thus influence the utilization of the starch-based food by microorganisms in the intestinal tract. Compared with the II type compound, the I type compound is easier to digest by human bodies due to lower crystalline order of the I type compound, and is difficult to control postprandial blood sugar well, however, compared with the II type compound, the I type compound is more beneficial to improving the texture and color of starch-based food and improving the sensory quality of the starch-based food. The prepared starch-lipid complex with different crystal forms can purposefully change the mixture ratio of the two according to the required sensory quality, storage property and nutritional property of the product, and can be better applied to the product.
The invention has the advantages that:
1. the starch-lipid complex with different crystal forms can be continuously and efficiently prepared by changing the extrusion processing conditions, and has potential wide application in the field of food.
2. The starch-lipid complexes with different crystal forms can generate different influences on the sensory quality, the storage characteristic and the nutritional characteristic of starch-based food, and the health food which can keep good sensory and storage quality and improve the nutritional value can be developed by changing the adding proportion of the two different crystal form complexes, so the starch-lipid complexes with different crystal forms have wide application prospects in the fields of food processing and nutrition.
3. Starch and lipid are common nutrient substances in food, the interaction of the starch and the lipid in the processing process has very important influence on the texture and the functional characteristics of the food, and the invention can provide reference for the influence of the component interaction on the functional characteristics of the food under the conditions of heat and shearing force in the processing process of the food.
Drawings
FIG. 1: DSC (differential scanning calorimetry) map under different processing temperature conditions of 25% moisture and 200rpm rotating speed
FIG. 2: DSC (differential scanning calorimetry) spectrum under different material moisture conditions of temperature of 120 ℃ and rotating speed of 200rpm
FIG. 3: DSC (differential scanning calorimetry) spectrum under different screw rotation speeds of 120 ℃ and 45% of water
FIG. 4: x-ray diffraction pattern under different processing temperature conditions of 25% moisture and 200rpm rotation speed
FIG. 5: x-ray diffraction pattern under different material moisture conditions of 120 ℃ temperature and 200rpm rotating speed
FIG. 6: x-ray diffraction pattern under different screw rotation speed conditions of 120 ℃ of temperature and 45% of water
FIG. 7: response surface diagram and contour line of processing temperature and material moisture to type I starch-lipid complex
FIG. 8: response surface diagram and contour line of processing temperature and screw rotation speed to type I starch-lipid complex
FIG. 9: response surface diagram and contour line of material moisture and screw rotation speed to type I starch-lipid complex
FIG. 10: response surface diagram and contour line of processing temperature and material moisture to type II starch-lipid complex
FIG. 11: response surface diagram and contour line of processing temperature and material moisture to type II starch-lipid complex
FIG. 12: response surface diagram and contour line of processing temperature and material moisture to type II starch-lipid complex
Detailed Description
Example 1: preparation of starch-lipid complexes under different material moisture
(1) Premixing raw materials:
corn starch and lauric acid are mixed according to the proportion of 24:1 to prepare samples with the water content of 15%, 25%, 35%, 45% and 55%. Mixing, stirring for 5min, storing in a sealed bag at room temperature for 24 hr, and processing.
(2) Preparation of starch-lipid complexes
The twin-screw extruder used in the experiment was an SHJ-20 co-rotating parallel twin-screw extruder constructed in tokyo-jeya, which consisted of six temperature zones, with a screw diameter of 2cm and a length-diameter ratio L/D of 40: 1. the feed rate was 20 kg/h. The first three temperature zones are set to be 40 ℃, 60 ℃ and 90 ℃ and the processing temperature of the subsequent processing three temperature zones is set to be 120 ℃, and the rotating speed of the screw is set to be 200 rpm.
(3) Drying, pulverizing and sieving
And (3) cutting the starch-lipid complex sample obtained in the step (2) into fine strips by using scissors, loading the fine strips by using a glass plate, drying the fine strips in an oven at 45 ℃ for 24 hours, grinding the fine strips, and sieving the fine strips by using a 60-mesh sieve for subsequent determination.
Example 2: preparation of starch-lipid complexes at different processing temperatures
(1) Premixing raw materials
Corn starch and lauric acid are mixed according to the proportion of 24:1 to prepare a sample with the water content of 25%. Mixing, stirring for 5min, storing in a sealed bag at room temperature for 24 hr, and processing.
(2) Preparation of starch-lipid complexes
The twin-screw extruder used in the experiment was an SHJ-20 co-rotating parallel twin-screw extruder constructed in tokyo-jeya, which consisted of six temperature zones, with a screw diameter of 2cm and a length-diameter ratio L/D of 40: 1. the feed rate was 20 kg/h. The first three temperature zones are set to be at 40 ℃, 60 ℃ and 90 ℃ and the temperature gradient is uniformly set to be at 80 ℃, 100 ℃, 120 ℃, 140 ℃ and 160 ℃ according to the experimental requirements, and the rotating speed of the screw is set to be 200 rpm.
(3) Drying, pulverizing and sieving
And (3) cutting the starch-lipid complex sample obtained in the step (2) into fine strips by using scissors, loading the fine strips by using a glass plate, drying the fine strips in an oven at 45 ℃ for 24 hours, grinding the fine strips, and sieving the fine strips by using a 60-mesh sieve for subsequent determination.
Example 3: preparation of starch-lipid complexes at different screw speeds
(1) Premixing raw materials
Corn starch and lauric acid are mixed according to the proportion of 24:1 to prepare a sample with the water content of 25%. Mixing, stirring for 5min, storing in a sealed bag at room temperature for 24 hr, and processing.
(2) Preparation of starch-lipid complexes
The twin-screw extruder used in the experiment was an SHJ-20 co-rotating parallel twin-screw extruder constructed in tokyo-jeya, which consisted of six temperature zones, with a screw diameter of 2cm and a length-diameter ratio L/D of 40: 1. the feed rate was 20 kg/h. The processing temperatures of the first three temperature zones are set to be 40 ℃, 60 ℃ and 90 ℃ and the processing temperatures of the subsequent processing three temperature zones are uniformly set to be 120 ℃, and the rotating speed of a screw is respectively set to be 100rpm, 200rpm, 300rpm, 400rpm or 500 rpm.
(3) Drying, pulverizing and sieving
And (3) cutting the starch-lipid complex sample obtained in the step (2) into fine strips by using scissors, loading the fine strips by using a glass plate, drying the fine strips in an oven at 45 ℃ for 24 hours, grinding the fine strips, and sieving the fine strips by using a 60-mesh sieve for subsequent determination.
Example 4: effect of different processing conditions on the thermodynamic Properties of starch-lipid complexes
DSC is adopted to detect the enthalpy value of the starch-lipid complex under different processing conditions, and the quantity of the starch-lipid complex can be represented by the size of the melting enthalpy value.
(1) Effect of different Material moisture on starch-lipid Complex formation
TABLE 1 influence of different material moisture on the thermodynamic properties of starch-lipid complexes
It can be seen from the observation of the enthalpy changes in FIG. 1 and Table 1 that the moisture content does not have much influence on the total amount of starch-lipid complex formation, and that type I complex. DELTA.H increases with the moisture content1Enthalpy value delta H of gradually decreasing type II compound2At a gradual increase, however Δ H1+△H2The unchanged total enthalpy value indicates that the water content of the material is mainly concentrated on the conversion between the type I and the type II complex for the formation of the starch-lipid complex.
(2) Effect of different processing temperatures on starch-lipid Complex formation
TABLE 2 Effect of different processing temperatures on starch-lipid Complex formation
By observing the change in enthalpy in table 2 and figure 2, it can be seen that increasing the temperature favours the flow of the starch chains so that amylose binds better to the fatty acids favouring the formation of the starch-lipid complex. The compound is converted from the type I compound to the type II compound when the processing temperature is higher than 120 ℃.
(3) Effect of different screw speeds on starch-lipid Complex formation
By observing the enthalpy changes in table 3 and figure 3, it can be seen that too high or too low a screw speed is not prone to the formation of starch-lipid complexes. Higher screw speeds provide greater shear forces, making the starch granules more completely destructed and more susceptible to the formation of starch-lipid complexes. However, faster screw speeds result in shorter material residence times and easier formation of type I compounds. When the screw rotation speed is too low, the gelatinization degree of starch is incomplete, amylose is difficult to release and combine with fatty acid, and a II type compound with stable structure is difficult to form.
TABLE 3 influence of screw speed on starch-lipid Complex formation
Example 5: effect of different processing conditions on the Crystal Structure of starch-lipid complexes
The effect of different processing conditions on the long-range crystalline order of the starch-lipid complexes was determined by means of an X-ray diffractometer (D8 Advance, Bruker, Germany). During detection, scanning is carried out within the scanning range of 5-30 degrees (2 theta) at the scanning speed of 2 DEG/min and the step size of 0.02 deg.
(1) Influence of different material moisture on the crystal structure of starch-lipid complex
It can be seen from fig. 4 that the intensity of the diffraction peak of the crystal increases first and then decreases as the moisture content increases. Moisture acts as a plasticizer and reduces the shear strength provided by the extruder, and as the moisture content increases, it also increases the degree of gelatinization of the starch, which better combines with the fatty acids to form the crystalline structure of the starch-lipid complex with peak order.
(2) Effect of different processing temperatures on the Crystal Structure of starch-lipid complexes
It can be seen from fig. 5 that the diffraction peak of the crystal increases with increasing temperature. Indicating that increasing the temperature is more favorable for forming an ordered crystal structure. When the temperature is increased, the composite can be fully accumulated to form a good crystal structure.
(3) Effect of different screw rotation speeds on the Crystal Structure of starch-lipid complexes
According to fig. 6, it can be seen that the peak intensity of the diffraction peak increases and then decreases with the increasing of the screw rotation speed, and an unstable i-type compound is easily formed when the material stays in the extruder for too short time due to too high screw rotation speed, however, the starch particles are not completely damaged when the screw rotation speed is low, amylose cannot be completely released, and an ordered crystal structure is not easily formed.
Example 6: processing conditions for efficiently preparing I-type compound by double-screw extruder
The optimal processing conditions for forming the enthalpy value of the single-factor I-type compound are taken as the basis (the processing temperature is 80 ℃, the moisture content is 25 percent, and the screw rotating speed is 300rpm), the interaction among the three factors is considered, and the processing conditions for preparing the I-type compound with the highest content are optimized by a response surface method.
TABLE 4 test factors and levels
The processing temperature (A), the material moisture (B) and the screw rotating speed (C) are selected as test factors, and the enthalpy value of the I-type compound in DSC measurement is taken as a response value. Three-factor three-level response surface test Design is carried out according to the Box-Benhnken Design (BBD) test Design principle, and 17 groups of experiments are total.
TABLE 5Box-Benhnken Design test Design and response results
Performing regression fitting on the data in the table 5 by using Design-expert 8.0.6 software to obtain a quadratic polynomial regression equation with the enthalpy value (Y) of the type I starch-lipid complex as an objective function: y ═ 2.09+0.099A +0.091B +0.051C-0.049AB +0.11AC-0.29BC-0.46A2-0.23B2-0.22C2
As can be seen from the ANOVA analysis (see table 6 for details), the model F is 25.22 and P is 0.0002, the established model is very significant (P < 0.01); the mismatching term P value of 0.2237 is not significant when being larger than 0.05, which indicates that the selected quadratic polynomial model has good fitting degree. Model R20.9701, indicating that the regression equation is well correlated, RAdj20.9316, indicating that 93.16% variability in experimental data can be explained with this regression model. And judging the influence sequence of the 3 single factors on the type I starch-lipid complex according to the P value, wherein the influence sequence is that the processing temperature (A) is higher than the material moisture (B) is higher than the screw rotating speed (C). I.e., the processing temperature (a) has the most significant effect on the formation of type i starch-lipid complexes.
TABLE 6 results of ANOVA analysis of response surface
The influence of the interaction of each factor on the response value can be intuitively reflected according to the response surface diagram and the contour diagram, the shape of the contour line reflects the strength of the interaction between different factors, the circle shows that the interaction of the two factors is not obvious and has no promotion effect, and the ellipse shows that the interaction has promotion effect obviously.
From FIG. 7, the effect of material moisture (A) and processing temperature (B) on the formation of type I complexes can be seen. The slope of the curved surface corresponding to the processing temperature is steeper than that of the liquid-material ratio, which indicates that the influence degree of the processing temperature on the I-type compound is larger than the moisture of the material. The contour lines are circular, the interaction between the material moisture and the processing temperature is not obvious in the processing process, and no promotion effect exists between the two factors, so that the contour lines are in positive accordance with the analysis result of the AB term variance in the regression equation.
From FIG. 8, the effect of processing temperature (A) and screw speed (C) on the formation of type I composite is evident. The slope of the curved surface corresponding to the processing temperature is steeper than that of the liquid-material ratio, which shows that the influence degree of the processing temperature on the I-type compound is larger than the rotation speed of the screw. The contour line is elliptic, the interaction between the screw rotation speed and the processing temperature is obvious in the processing process, and the promotion effect between the two factors is in positive accordance with the analysis result of the variance of the AC term in the regression equation.
From FIG. 9, the effect of material moisture (B) and screw speed (C) on the formation of type I complexes can be seen. The slope of the curved surface corresponding to the moisture of the material is steeper than that of the liquid-material ratio, which shows that the influence degree of the moisture of the material on the I-type compound is larger than the rotating speed of the screw. The contour line is elliptic, the interaction between the screw rotation speed and the material moisture is obvious in the processing process, and the promotion effect between the two factors is in positive accordance with the BC term variance analysis result in the regression equation.
And (3) verification experiment: the optimal processing conditions for efficiently preparing the I-type compound by the double-screw extruder are that the optimal processing temperature is 92.1 ℃, the material moisture is 26.6 percent, and the screw rotating speed is 303 rpm. The enthalpy value of the compound I is 2.01J/kg. In consideration of practical operability, the test conditions were adjusted to a processing temperature of 92 ℃, a material moisture of 27%, and a screw rotation speed of 303 rpm. In order to test the reliability of the optimal process condition obtained by the response surface method, the test is repeated for 3 times, the average enthalpy value of the obtained I-type compound is 1.98J/kg, the result is close to the theoretical maximum value, and the obtained optimal process parameter is accurate and reliable.
EXAMPLE 7 processing conditions for efficient preparation of type II composites by twin screw extruder
The optimal processing conditions for forming enthalpy value of the single-factor II-type compound are taken as the basis (the processing temperature is 120 ℃, the moisture content is 45 percent, and the screw rotating speed is 300rpm) to consider the interaction among the three factors, and the processing conditions for preparing the II-type compound with the highest content are optimized by a response surface method.
TABLE 7 test factors and levels
The processing temperature (A), the material moisture (B) and the screw rotating speed (C) are selected as test factors, and the enthalpy value of the I-type compound in DSC measurement is taken as a response value. Three-factor three-level response surface test Design is carried out according to the Box-Benhnken Design (BBD) test Design principle, and 17 groups of experiments are total.
Table 8: Box-Benhnken Design test Design and response results
And (3) performing regression fitting on the data of the table 8 by using Design-expert 8.0.6 software to obtain a quadratic polynomial regression equation with the enthalpy value (Y) of the type II starch-lipid complex as an objective function: y ═ 3.29+0.14A-0.10B +0.0041C-0.25AB-0.19AC-0.039BC-0.39A2-0.72B2-0.19C2
Table 9: results of response surface ANOVA analysis
As can be seen from the ANOVA analysis (see table 9 for details), the model F is 29.05 and P is 0.0007, the established model is significant (P < 0.01); the mismatching term P value of 0.2237 is not significant above 0.05. The fitting degree of the selected quadratic polynomial model is good. Model R20.9618, indicating that the regression equation is well correlated, RAdj20.9627, indicating that the variability of 96.27% of the experimental data can be explained by this regression model. Judging the influence sequence of 3 single factors on the type II starch-lipid complex according to the P value, wherein the influence sequence is (B) > processing temperature (A) > screw rotating speed (C). I.e., the moisture content of the material has the most significant effect on the formation of type ii starch-lipid complexes.
From FIG. 10, the effect of material moisture (A) and processing temperature (B) on the formation of type II complexes is evident. The slope of the curved surface corresponding to the moisture of the material is steeper than that of the liquid-material ratio, which shows that the influence degree of the moisture of the material on the II-type compound is larger than that of the moisture of the material. The contour line is elliptic, the interaction between the material moisture and the processing temperature is obvious in the processing process, and the promotion effect between the two factors is in positive accordance with the analysis result of the AB term variance in the regression equation.
FIG. 11 shows the effect of type II compound formation on the processing temperature (A) and screw speed (C). The slope of the curved surface corresponding to the processing temperature is steeper than the liquid-material ratio, which indicates that the influence degree of the processing temperature on the II-type compound is larger than the screw rotation speed. The contour line is elliptic, the interaction between the screw rotation speed and the processing temperature is obvious in the processing process, and the promotion effect between the two factors is in positive accordance with the analysis result of the AC term variance in the regression equation.
FIG. 12 shows the effect of formation of type II compounds on the moisture content of the material (B) and the screw speed (C). The slope of the curved surface corresponding to the processing temperature is steeper than the liquid-material ratio, which indicates that the influence degree of the processing temperature on the II-type compound is larger than the screw rotation speed. The contour line is circular, the interaction between the screw rotation speed and the processing temperature is not obvious in the processing process, no promotion effect exists between the two factors, and the contour line is in positive accordance with the BC term variance analysis result in the regression equation.
And (3) verification experiment: the optimal processing conditions for efficiently preparing the II type compound by the double-screw extruder are that the optimal processing temperature is 124.7 ℃, the material moisture is 38.9 percent, and the screw rotating speed is 290 rpm. The enthalpy value of the compound II is 3.31J/kg. In consideration of practical operability, the test conditions were adjusted to a processing temperature of 125 ℃, a material moisture of 39%, and a screw rotation speed of 290 rpm. In order to test the reliability of the optimal process condition obtained by the response surface method, the test is repeated for 3 times, the average enthalpy value of the II-type compound is 3.41J/kg, the result is close to the theoretical maximum value, and the obtained optimal process parameter is accurate and reliable.
The method can prepare the compounds with different crystal forms according to requirements by using extrusion cooking equipment through adjusting the water content, the screw rotation speed and the processing temperature of the raw materials. There is no relevant research that can regulate the formation of starch-lipid complexes of different crystal forms by changing the processing conditions.
Claims (8)
1. A high-efficiency preparation method of a starch-lipid complex with controllable crystal form is characterized by comprising the following steps:
(1) premixing raw materials:
mixing starch and fatty acid to prepare a sample with the water content of 15% -55%, mixing and stirring for 5min, and placing the sample in a sealed bag at room temperature for balancing for 24h and then processing;
(2) preparation of starch-lipid complexes:
and (2) extruding and cooking the prepared starch-fatty acid mixture containing different water contents by using a double-screw extruder to obtain a starch-lipid compound, wherein the parameters of the extruder are as follows: the diameter of the screw is 2cm, the length-diameter ratio L/D is 40: 1, the feeding speed is 20kg/h, the set temperatures of the first three temperature zones are 40 ℃, 60 ℃ and 90 ℃, and the set temperature ranges of the last three temperature zones are 80-160 ℃; the rotating speed range of the screw is 100-500 rpm;
(3) drying, crushing and sieving:
and (3) cutting the starch-lipid complex sample obtained in the step (2) into fine strips by using scissors, loading the fine strips by using a glass plate, drying the fine strips in an oven at 45 ℃ for 24 hours, grinding the fine strips, and sieving the fine strips by using a 60-mesh sieve to obtain the starch-lipid complex.
2. The method for preparing the starch-lipid complex with the controlled crystal form according to claim 1, wherein the corn starch and the lauric acid are mixed according to a mass ratio of 24:1 to prepare samples with different water contents.
3. The method for preparing the starch-lipid complex with the controlled crystal form according to claim 1, wherein the corn starch and the lauric acid are mixed according to a mass ratio of 24:1 in the step (2) to prepare the sample with the moisture content of 15%, 25%, 27%, 35%, 39%, 45% and 55%.
4. The method for preparing starch-lipid complex with controlled crystal form according to claim 1, wherein the temperature of the three temperature zones after setting in step (2) is adjusted to 80 ℃, 92 ℃, 100 ℃, 120 ℃, 125 ℃, 140 ℃ or 160 ℃.
5. The controllable preparation method of starch-lipid complex in different crystal forms according to claim 1, characterized in that the screw rotation speed of step (2) is adjusted to 100rpm, 200rpm, 290rpm, 300rpm, 303rpm, 400rpm or 500 rpm.
6. The method for preparing the starch-lipid complex with the controlled crystal form according to claim 1, is characterized by comprising the following steps:
(1) premixing raw materials:
mixing corn starch and lauric acid according to a mass ratio of 24:1 to prepare a sample with water content of 27%, mixing and stirring for 5min, placing the mixture in a sealed bag at room temperature for balancing for 24h, and then processing;
(2) preparation of starch-lipid complexes:
carrying out extrusion treatment by using a double-screw extruder, wherein the extruder consists of six temperature zones, the diameter of a screw is 2cm, and the length-diameter ratio L/D is 40: 1, the feeding speed is 20kg/h, and the processing temperatures of the first three temperature areas of six temperature areas of an extruder are set to be 40 ℃, 60 ℃ and 90 ℃ and the processing temperatures of the other three temperature areas of the other processing areas are uniformly set to be 120 ℃; the screw speed was set to 303 rpm;
(3) drying, crushing and sieving:
and (3) cutting the starch-lipid complex sample obtained in the step (2) into fine strips by using scissors, loading the fine strips by using a glass plate, drying the fine strips in an oven at 45 ℃ for 24 hours, and grinding and sieving the fine strips by using a 60-mesh sieve to obtain the I-type starch-lipid complex.
7. The method for preparing the crystal-controlled starch-lipid complex according to claim 1, comprising the following steps:
(1) premixing raw materials:
mixing corn starch and lauric acid according to a mass ratio of 24:1 to prepare a sample with the water content of 39%, mixing and stirring for 5min, placing in a sealed bag at room temperature for 24h, and then processing;
(2) preparation of starch-lipid complexes:
carrying out extrusion treatment by using a double-screw extruder, wherein the extruder consists of six temperature zones, the diameter of a screw is 2cm, and the length-diameter ratio L/D is 40: 1, setting the feeding speed to be 20kg/h, setting the processing temperatures of the first three temperature zones to be 40 ℃, 60 ℃ and 90 ℃ and setting the processing temperatures of the subsequent processing three temperature zones to be 125 ℃; the screw speed was set to 290 rpm;
(3) drying, crushing and sieving:
and (3) cutting the starch-lipid complex sample obtained in the step (2) into fine strips by using scissors, loading the fine strips by using a glass plate, drying the fine strips in an oven at 45 ℃ for 24 hours, and grinding and sieving the fine strips by using a 60-mesh sieve to obtain the II-type starch-lipid complex.
8. The starch-lipid complex prepared by the efficient preparation method of the starch-lipid complex with controlled crystal form of claim 6 or 7, which is used in the field of food.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20190373938A1 (en) * | 2018-07-19 | 2019-12-12 | Jiangnan University | Preparation of Recombinant Rice with Low Glycemic Index from a Raw Material of Resistant Starch |
| US20200291137A1 (en) * | 2019-03-15 | 2020-09-17 | Green Dot Bioplastics Inc. | Thermoplastic starch and method for preparing the same |
| CN112544955A (en) * | 2020-11-25 | 2021-03-26 | 华南理工大学 | Food raw material rich in slowly digestible and resistant starch and preparation method and application thereof |
| CN113061193A (en) * | 2021-03-31 | 2021-07-02 | 齐鲁工业大学 | Method for preparing RS-5 type resistant starch by melt extrusion method |
-
2021
- 2021-09-10 CN CN202111060164.XA patent/CN113907332B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20190373938A1 (en) * | 2018-07-19 | 2019-12-12 | Jiangnan University | Preparation of Recombinant Rice with Low Glycemic Index from a Raw Material of Resistant Starch |
| US20200291137A1 (en) * | 2019-03-15 | 2020-09-17 | Green Dot Bioplastics Inc. | Thermoplastic starch and method for preparing the same |
| CN112544955A (en) * | 2020-11-25 | 2021-03-26 | 华南理工大学 | Food raw material rich in slowly digestible and resistant starch and preparation method and application thereof |
| CN113061193A (en) * | 2021-03-31 | 2021-07-02 | 齐鲁工业大学 | Method for preparing RS-5 type resistant starch by melt extrusion method |
Non-Patent Citations (4)
| Title |
|---|
| JUAN E. CERVANTES-RAMÍREZ等: "Amylose-lipid complex formation from extruded maize starch mixed with fatty acids", CARBOHYDRATE POLYMERS, vol. 246, pages 1 - 10 * |
| 史苗苗等: "直链淀粉复合物制备及表征的研究进展", 食品工业, vol. 39, no. 9, pages 245 - 249 * |
| 褚绍言等: "淀粉-脂质复合物的形成及其性质的研究进展", 食品研究与开发, vol. 42, no. 12, pages 206 - 211 * |
| 贾祥泽;陈秉彦;赵蓓蓓;郑宝东;郭泽镔;: "直链淀粉-脂质复合物的形成及其结构性质研究进展", 食品与发酵工业, vol. 43, no. 03, pages 276 - 284 * |
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