CN101698710B - Method for producing modified starch - Google Patents

Method for producing modified starch Download PDF

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Publication number
CN101698710B
CN101698710B CN2009102369626A CN200910236962A CN101698710B CN 101698710 B CN101698710 B CN 101698710B CN 2009102369626 A CN2009102369626 A CN 2009102369626A CN 200910236962 A CN200910236962 A CN 200910236962A CN 101698710 B CN101698710 B CN 101698710B
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starch
quality
reaction
acetic anhydride
slurry
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CN101698710A (en
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刘族安
古碧
岑喜
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Guangxi Wuming Anning Starch Co Ltd
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Guangxi Wuming Anning Starch Co Ltd
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Abstract

The invention discloses a method for producing modified starch. The method provided by the invention comprises the following steps: (1) mixing starch mixture with water for obtaining starch slurry, wherein the weight percent of the starch mixture is 30-50%, and the starch mixture consists of 5-95 parts by weight of waxy corn starch and 95-5 parts by weight of cassava starch; (2) adding sodium sulfate and acetic anhydride in the starch slurry and carrying out the reaction at the temperature of 20-35 DEG C and the pH value of 8.0-10.0 for 15-180 minutes, wherein the weight of the sodium sulfate accounts for 1-7% of the weight of the starch mixture, and the weight of the acetic anhydride accounts for 2-10% of the weight of the starch mixture; and (3) carrying out the post-treatment on a reaction product for obtaining the modified starch. The method has the following advantages: the comprehensive performance of the product is better than that of cassava esterified starch or waxy corn esterified starch, which has good thickening property and good gelation property, and can meet the market demands, reduce the production cost to the maximum extent, fully utilize the superior resource of the cassava starch in Guangxi on the use of raw materials and be conductive to deep processing and value adding of renewable resources in Guangxi. The method has broad development prospects, and the further promotion of the method can play the role of promoting food production enterprises to reduce the production cost and improve the economic benefits.

Description

A kind of method of producing modified starch
Technical field
The present invention relates to a kind of method of producing modified starch.
Background technology
For the performance of improving starch, enlarge its range of application, utilize physics, chemistry or enzymatic treatment, on starch molecule, introduce new functional group or change starch molecule size and starch granules character, thereby change the natural characteristic (as gelatinization point, thermoviscosity and stability thereof, freeze-thaw stability, gel force, film-forming properties, the transparency etc.) of starch, make it be more suitable for requirement in certain application.This through secondary processing, the starch that changes character is referred to as modified starch.The purpose of sex change: (1) is in order to adapt to various industrial application requirements; As, high-temperature technology (sterilization of canned food) requires starch high temperature viscosity good stability, and frozen product requires starch freeze thawing good stability, and jelly foodstuff requires that the transparency is good, good film-forming property etc.; (2) in order to open up the new purposes of starch, broadened application scope.As: the modified starch that textile sizing uses; Hydroxyethylamyle, hydroxypropylated starch replace blood plasma; High cross-linking starch replaces surgical glove with talcum powder etc.The development of modified starch has wide sight.
The domestic modified starch of using in food service industry at present, its raw materials for production are 100% single raw starch, the W-Gum as 100%, 100% waxy corn starch, 100% yam starch, 100% tapioca (flour) etc.These modified starches are in application process, because excellent, the shortcoming of its raw material itself are difficult to reach the requirement of " comprehensive ".Such as: (about 4200 yuan of price/T) is the modified starch of raw material production, is difficult to capture the more market share because of its price makes it with 100% waxy corn starch; (about 2800 yuan of price/T) is the modified starch of raw material production, and its application performance has some limitation again with 100% tapioca (flour).Study carefully its major cause, be the chemical structure difference of different material starch, the shared ratio of contained amylose starch and amylopectin is different.Also,, when producing a certain modified starch, need to adopt different technology for different material starch just because of this reason.
2008, China's modified starch output was about about 1,200,000 tons, and 165920 tons of Guangxi cassava modified starch output account for 19.46% of ultimate production, occupied the whole nation second.The Guangxi Wuming County is maximum cassava industrial base, the whole nation, and whole county cassava cultivated area reaches 380,000 mu.Clearly proposing tapioca (flour) processing in " Guangxi farming industry development program (2003-2010) " (No. (2003) 29, Gui Zhengfa) that in June, 2003, autonomous regional government issued is the emphasis that I distinguish the characteristic farming industry.Planning is accelerated development deep processed product with high content of technology, that added value is high based on the high-grade modified starch of development cassava, high added value alcohol, improves the cassava Industrial economic benefit.
Summary of the invention
The purpose of this invention is to provide a kind of method of producing modified starch.
The method of production modified starch provided by the invention comprises the steps:
(1) starch mixture is mixed with water, obtain starch slurry; The quality percentage composition of starch mixture is 30-50% in the described starch slurry; Described starch mixture is made up of the waxy corn starch of 5-95 mass parts and the tapioca (flour) of 95-5 mass parts;
(2) in the starch slurry that step (1) obtains, add sodium sulfate and acetic anhydride, 20-35 ℃, pH8.0-10.0 reaction 15-180 minute; Wherein, the quality of the sodium sulfate that is added is the 1-7% of starch mixture quality in the described starch slurry, and the quality of the acetic anhydride that is added is the 2-10% of starch mixture quality in the described starch slurry;
(3) reaction product of step (2) is carried out aftertreatment, obtain modified starch.
In the described step (1), described starch mixture specifically can be made up of the waxy corn starch of 5-20 mass parts and the tapioca (flour) of 95-80 mass parts.
Described step (2) specifically can be: 25-28 ℃, pH8.5-9.0 reaction 50-70 minute; Wherein, the quality of the sodium sulfate that is added specifically can be the 2.0-3.5% of starch mixture quality in the described starch slurry.
Described step (2) most preferably is, 28 ℃, pH9.0 reaction 60 minutes; Wherein, the optimal quality of the sodium sulfate that is added is elected 2.0% of starch mixture quality in the described starch slurry as.、
In the step (2), the adding speed of described acetic anhydride can be 4.0-6.5Kg/ hour, and the adding speed of described acetic anhydride is preferably 4.0Kg/ hour.
In the step (2), what be used to regulate pH specifically can be aqueous sodium hydroxide solution.
After step (2) reaction finished, it was 6.5~8.0 that available hydrochloric acid is transferred pH.
The purpose of described aftertreatment is to remove impurity and drying, and ordinary method all can adopt, as washing, drying etc.
The water content of described modified starch specifically can be below 14% (the quality percentage composition).
More than the modified starch for preparing of arbitrary described method also belong to protection scope of the present invention.
Application Areas of the present invention is as follows:
(1) the natural difficult composition of removing of starch mainly is protein and lipid, the existence of these two kinds of compositions not only can reduce the transparency of starch paste and the quality guaranteed period of starchbased product, and can produce unpleasant odor, the present invention utilizes the low protein of tapioca (flour) and lipid and the high amylopection content of waxy corn starch, composite raw material carries out reaction of degeneration, and this just makes its product have better applicability.
(2) utilize the transparency characteristics higher of tapioca (flour) than waxy corn starch, through carrying out the esterification of raw material after composite with waxy corn starch, its product also shows well in fruit filling material Application Areas, acid resistance, freeze-thaw stability and high temperature that it can improve the fruit filling material cure performance, and bring extremely transparent visual effect.
(3) utilize waxy corn starch to have high thickening property, through carrying out the esterification of raw material after composite with tapioca (flour), its product has possessed the thickening property of height, and good transparency and low gelatinization point, thereby the application in soup stock and material has a lot of advantages.Even its fabulous thickening stabilities reduces the prescription of used starch, do not influence the mouthfeel and the viscosity of product at all yet.The starch gelatinization temperature that it is lower is even make the intimate perfection that the fast food soup stock of its goods also shows in the lower water temperature of automatic water-drinking machine.
(4) owing to made full use of the advantage of tapioca (flour) and waxy corn starch, product can satisfy the various conditions of various manufacturerss technology, pays close attention to the human consumer simultaneously.Through adjusting the compound proportion and the adjusting process parameter of raw material, the fabrication process condition of the applicable various complexity of product of producing, from high temperature, highly compressed processing condition, handle vapo(u)r blasting, pyroprocessing from freezing, refrigeration, multigelation, and the performance of high-shear and anti-low pH value, salt tolerant is good, and product of the present invention can both provide good performance.
(5) in the snackfoods field, the present invention utilizes the advantage of the high side chain of waxy corn starch, high expansion and crisp performance can be provided, the feature of unique " be melted in mouthful " can be provided for its product, for the exploitation of snackfoods brings the brand-new interesting variation that is full of.
The present invention adopts the wet method esterification reaction tech of independent research, the mixture that adopts tapioca (flour) and waxy corn starch is as raw material, adopt acetic anhydride as esterifying catalyst, adopt sodium sulfate as antiswelling agent, grope the suitableeest additive capacity and each reaction parameter, produced novel esterification starch.The result shows, after the starch granules of tapioca (flour) and waxy corn starch mixture was activated, its pars amorpha obviously increased to some extent, and the structure of two kinds of starch materials reaches unanimity, help the reactive material molecule and react, this is the key that increases substantially the tapioca (flour) consumption.Modified starch advantage of the present invention is as follows: (1) The comprehensive performance is better than cassava esterification starch and Glutinous Semen Maydis esterification starch, and existing good thickening property has good gelation again, can satisfy the requirement in market; (2) reduced production cost to greatest extent; (3) on raw material uses, make full use of Guangxi superior resources tapioca (flour), helped the deep processing increment of area, Guangxi renewable resources.Foodstuffs industry is sunrise industry, and inseparable with the people's standard of living raising, the present invention has vast potential for future development, and its further popularization also can reduce production costs for foodstuff production enterprise, increase economic efficiency and play promoter action.
The present invention is by production practice, having broken through modified starch production all is single variety ative starch (as tapioca (flour)) carries out reaction of degeneration for raw material limitation, for the new raw material mix of modified starch production developing, produce the new product that has various raw starch performances concurrently.The present invention is a developing and innovation to the modified starch implication, will play for the development of China's modified starch industry to promote and promoted effect.The present invention will prolong the production cycle of factory under the situation that does not increase facility investment, increase output, increases income, and this meaning to the starch industry in whole Guangxi is fairly obvious.The present invention has vast potential for future development, and its further popularization also can reduce production costs for foodstuff production enterprise, increase economic efficiency and play promoter action.
Description of drawings
Fig. 1 is the industrial flow chart of the modified starch preparation among the embodiment 2.
Fig. 2 is the relation of acetyl content in temperature of reaction and the modified starch.
Fig. 3 is the relation of acetyl content in reaction pH and the modified starch.
Fig. 4 is the relation of acetyl content in reaction times and the modified starch.
Fig. 5 is the relation of acetyl content in the addition of acetic anhydride and the modified starch.
Fig. 6 is the relation of acetyl content in adding speed (flow) and the modified starch of acetic anhydride.
Fig. 7 is the relation of acetyl content in the addition of sodium sulfate and the modified starch.
Fig. 8 is the rheological characteristics of cassava esterification starch (first, second, third, fourth).
Fig. 9 is the rheological characteristics of Glutinous Semen Maydis esterification starch (first, second, third, fourth).
Figure 10 is the rheological characteristics of modified starch (first, second, third, fourth).
Embodiment
Following embodiment is convenient to understand better the present invention, but does not limit the present invention.Experimental technique among the following embodiment if no special instructions, is ordinary method.Used test materials among the following embodiment if no special instructions, is to buy from routine biochemistry reagent shop and obtains.In following examples, three repetitions, results averaged are all established in experiment.In following examples, adopt the GB/20373-2006 standard method to detect acetyl content (%) in the modified starch.Tapioca (flour) is available from the Guangxi Wuming County Anning Starch Co. Co., Ltd, and product reaches: NY/T875-2004 " edible tapioca (flour) " standard.Waxy corn starch is " the emerging trade board of Heilungkiang phoenix corn development corporation, Ltd. " starch.
The parameter of embodiment 1, material performance analysis and production technique is selected
One, material performance analysis
For different raw materials, as potato, cassava, corn, Glutinous Semen Maydis, wheat etc., the character of its starch granules degree, relative molecular weight, gelatinization point, paste etc. are all different, and pH, temperature of reaction, reagent addition, reaction times are controlled also different in process of production.Use different material to produce similar modified starch, it is to the requirement of raw material, and the addition of reagent is all different, and manufacturing requirements is higher.Because the performance difference of different starch molecules, intramolecularly frictional force varies in size, viscosity and stability are different, the graininess difference, significant difference appears in starch structure, crystallization and non-crystalline state ratio, all these, all requirement to reach the unified quality index of product (with and the intrinsic characteristic), then to use different production technique at different material.
The performance perameter of tapioca (flour), waxy corn starch sees Table 1.
The performance of table 1 tapioca (flour), waxy corn starch
Tapioca (flour) Waxy corn starch
Amylose starch 17% 0
Amylopectin 83% 100%
Starch granules size/μ m 5-35 10-25
Gelatinization temperature range/℃ 52-64 63-67
The amylose starch polymerization degree/DP 2600 0
The chain length of the amylopectin polymerization degree 23AGU 22AGU
Aging resistance Low High
Anti-shearing Difference Difference
Freeze-stable Poor slightly Good
The film transparency Very high High
Film toughness High High
The film snappiness High High
The transparency of sticking with paste 18.99% 15.54%
Humidity expands 25% 30%
Lipid 0.10% 0.15%
The boiling complexity Rapidly Rapidly
The viscosity peak value High And it is high
Boiling stability Well Excellent
Reverse in the cooling Higher High
Cold paste consistence Adhesivity is not solidified Adhesivity is not solidified
Two, the parameter of production technique is selected
Wet processing is that starch is scattered in the aqueous media, is made into certain density suspension, reacts with chemical reagent under certain temperature and pH condition.Wash after the reaction, dewater and drying.Starch still keeps graininess in the reaction process, and water plays carrier function, and the reagent porous is reacted to granule interior.This kind technological reaction efficient height, the product purity height of acquisition is the particularly main mode of production of modified food starch of suitability for industrialized production.In the production process of acetic acid esterification starch, factors such as temperature of reaction, reaction pH, acetic anhydride consumption and adding speed, ative starch kind will directly influence indexs such as the substitution value, viscosity, gelatinization point of esterification starch, thus the quality of decision esterification starch quality.
Below keeping reactant concn, ative starch kind and chemicals usage, stirring velocity, liquid caustic soda to add under the identical condition of speed, carried out the starch acetic anhydride esterification under a series of differential responses conditions: starch and water are mixed in the adding reactor, start stirring, pH value in reaction, temperature of reaction and acetic anhydride add speed control at desired conditions; Slowly add 3% (quality percentage composition) sodium hydroxide solution within the specific limits with the control of pH value; From under meter, slowly add acetic anhydride; Control reaction temperature in the reaction process is controlled the pH value in constant scope all the time with sodium hydroxide solution, till acetic anhydride all adds; After waiting to add acetic anhydride, be 6.5, stop to stir with the hydrochloric acid adjust pH; With starch milk washing, filtration, be dried to moisture less than 14% (quality percentage composition), grinding and sieving, packing promptly get product, carry out the test of every physical and chemical index then.
1, the selection of temperature of reaction
Composite raw material, pH are 8.5~9.0, and the acetic anhydride consumption is 5%, and the reaction times is 60 minutes.The results are shown in Table 2 and Fig. 2.
Acetyl content under the table 2 differential responses temperature in the product
Temperature of reaction (℃) Acetyl content (%)
5 1.49
10 1.52
15 1.57
20 1.61
25 1.65
28 1.72
30 1.64
35 1.59
40 1.53
When temperature of reaction was 25-28 ℃, the starch acetate acetyl content increased along with the rising of temperature of reaction; When temperature of reaction during greater than 30 ℃, the starch acetate acetyl content descends along with the rising of temperature of reaction, and this is because under higher temperature, due to the hydrolysis reaction speed of starch acetate and acetic anhydride increased, therefore, suitable temperature of reaction was 28 ℃.
2, the selection of pH value
Composite raw material, acetic anhydride consumption are 5%, and the reaction times is 60 minutes, 25~28 ℃ of temperature of reaction.The results are shown in Table 3 and Fig. 3.
Acetyl content under the table 3 differential responses pH in the product
The pH value Acetyl content (%)
7.0~7.5 1.35
7.5~8.0 1.49
8.0~8.5 1.53
8.5~9.0 1.64
9.0~9.5 1.58
9.5~10.0 1.50
10.0~11.0 1.21
In pH value<9.0 o'clock, the acetyl content of starch acetate increases with the rising of pH value; When the pH value was 9.0, it is maximum that the acetyl content of starch acetate reaches; And after pH value>9.0, because the starch acetate amount of hydrolysis increases, then with the increase of pH value, the acetyl content of starch acetate reduces, so suitable reaction pH value is 9.0.
3, the reaction times is to the influence of starch acetate acetyl content
Composite raw material, acetic anhydride consumption are 5%, pH value 9.0,25~28 ℃ of temperature of reaction.The results are shown in Table 4 and Fig. 4.
Acetyl content in the table 4 differential responses time product
Reaction times (minute) Acetyl content (%)
15 1.12
30 1.51
45 1.63
60 1.72
75 1.68
90 1.63
100 1.59
120 1.55
180 1.51
Reaction times, the acetyl content of starch acetate increased with the increase in reaction times during less than 60 minutes; Reaction times, the acetyl content maximum of starch acetate was finished in reaction substantially when reaching 60 minutes; After this continue to prolong the reaction times, the acetyl content of starch acetate descends gradually.So the suitable reaction times is 60 minutes.
4, the acetic anhydride consumption is to the influence of starch acetate acetyl content and reaction efficiency
Composite raw material, the reaction times is 60 minutes, pH value 9.0,25~28 ℃ of temperature of reaction.The results are shown in Table 5 and Fig. 5.
Acetyl content in the different acetic anhydride consumption of table 5 product
Acetic anhydride (%) Acetyl content (%) Reaction efficiency (%)
2.0 1.02 84
3.0 1.12 90
4.0 1.32 76
5.0 1.53 70
6.0 1.64 63
7.0 1.81 60
8.0 1.84 58
10.0 1.89 53
As seen from the figure, along with the increase of acetic anhydride consumption, the acetyl content of starch acetate increases, and reaction efficiency descends.The increase of acetic anhydride consumption, the collision probability of starch molecule and acetic anhydride molecule increases, and acetyl content increases, but acetic anhydride hydrolysis probability also increases, thus reaction efficiency descends.When the starch acetate acetyl content reached certain value, along with the increase of acetic anhydride consumption, acetyl content increased slowly, and reaction efficiency but descends very fast, so the acetic anhydride consumption can be selected according to product requirement.
5, the acetic anhydride flow is to the influence of starch acetate acetyl content
Composite raw material, acetic anhydride consumption 5%, the reaction times is 60 minutes, pH value 9.0,25~28 ℃ of temperature of reaction.The results are shown in Table 6 and Fig. 6.
Acetyl content in the different acetic anhydride flow of table 6 product
Acetic anhydride flow (Kg/ hour) Acetyl content (%)
6.5 1.62
6.0 1.75
5.5 1.74
5.0 1.76
4.5 1.75
4.0 1.70
When acetic anhydride adds speed when 6.5Kg/ hour reduces to 6.0Kg/ hour; acetyl content is increased to 1.73% from 1.60%; acetic anhydride adding speed continues from reduced to 4.5Kg/ hour process in 6.0Kg/ hour; acetyl content does not have considerable change, and acetyl content slightly reduces when acetic anhydride adding speed is reduced to 4.0Kg/ hour.This explanation adds too fast then its concentration height in starch milk of speed as the acetic anhydride of reactant, be beneficial to the generation of the hydrolysis reaction of acetic anhydride, make it to form acetic acid, acetic acid changes acetate into and is unfavorable for the generation of esterification starch under alkaline condition, thereby acetyl content is on the low side; Too slowly, then its concentration in starch milk is also low if acetic anhydride adds speed, and the generating rate of esterification starch slows down, and is unfavorable for the generation of esterification starch equally, thereby acetyl content reduces.Comprehensive acetic acid acid anhydrides adds speed to the influence of acetyl content, peak viscosity and gelatinization point and to the considering of the output of esterification starch production, and determines that the best acetic anhydride adding speed of starch esterification reaction is 4.0Kg/ hour.
6, sodium sulfate is to the influence of starch acetate acetyl content
The effect of sodium sulfate has two, and the one, suppress starch granules and expand, reaction process is carried out smoothly, the 2nd, the hydration layer of destruction starch particle surface, the esterification of promotion acetic anhydride molecule and starch molecule.Composite raw material, acetic anhydride consumption are 5%, pH value 9.0, and 25~28 ℃ of temperature of reaction, the reaction times is 60 minutes.The results are shown in Table 7 and Fig. 7.
Acetyl content in the different sodium sulfate consumption of table 7 product
Sodium sulfate consumption (%) Acetyl content (%)
1.0 1.57
1.5 1.63
2.0 1.69
4.0 1.65
5.0 1.61
7.0 1.59
When the sodium sulfate consumption was lower than 2%, the acetyl content of starch acetate raise along with the increase of sodium sulfate consumption; At the sodium sulfate consumption is 2.0%~3.5% o'clock, and the acetyl content of starch acetate is along with the increase of sodium sulfate consumption changes little; When the sodium sulfate consumption greater than 3.5% the time, the acetyl content of starch acetate reduces gradually along with the increase of sodium sulfate consumption.Therefore, the consumption of sodium sulfate is advisable with 2%.
7, the influence of the compound proportion of ative starch and starch acetate acetyl content
The results are shown in Table 8 and Fig. 8.
Acetyl content in the composite product of the different ative starchs of table 8
A∶B Acetyl content (%) 1# Acetyl content (%) 2#
5∶95 1.57 1.70
10∶90 1.61 1.69
20∶80 1.63 1.71
30∶70 1.60 1.68
40∶60 1.58 1.70
50∶50 1.62 1.71
60∶40 1.59 1.71
80∶20 1.58 1.69
90∶10 1.63 1.70
Annotate: 1, " acetyl content (%) 1 in the table #" data are products of under same manufacturing condition, producing, the result that same detection method is measured; " acetyl content (%) 2 in the table #" data be to adjust the product that manufacturing condition is produced, the result that same detection method is carried out; 2, " A " is the representative waxy corn starch in the table, and " B " represents tapioca (flour).
From different material combination can be under same reaction conditions go out different product specifications.Different material combination can be in the basic identical product specification of adjusting under the reaction conditions of producing.Like this, fully can be according to the purpose that user's difference requires and reasonably economic benefit reach doulbe-sides' victory.
The preparation of embodiment 2, modified starch and performance measurement
One, the preparation of modified starch
1, the preparation of modified starch first and contrast thereof
(1) preparation of modified starch first
1. starch mixture and water are added in the reactor, start stirring, mix, obtain starch slurry; The quality percentage composition of starch mixture is 30% in the described starch slurry; Described starch mixture is made up of the waxy corn starch of 5 mass parts and the tapioca (flour) of 95 mass parts;
2. in the starch slurry that 1. step obtains, add sodium sulfate (quality of the sodium sulfate that is added be in the described starch slurry starch mixture quality 1%) and acetic anhydride (quality of the acetic anhydride that is added be in the described starch slurry starch mixture quality 2%; Acetic anhydride adopts under meter slowly to add, and adding speed is 6.5Kg/ hour), 20 ℃, pH8.0 reaction 180 minutes; Transferring the pH solutions employed is the aqueous sodium hydroxide solution of 3% (quality percentage composition); After reaction finished, transferring pH with hydrochloric acid was 6.5;
3. with 2. reaction product dilution, washing of step, concentrate, obtain the modified starch first of water ratio after the dehydration, drying less than 14% (quality percentage composition).
(2) preparation of cassava esterification starch first
1. tapioca (flour) is mixed with water, obtain starch slurry; The quality percentage composition of tapioca (flour) is 30% in the described starch slurry;
2. in the starch slurry that 1. step obtains, add sodium sulfate (quality of the sodium sulfate that is added be in the described starch slurry starch quality 1%) and acetic anhydride (quality of the acetic anhydride that is added be in the described starch slurry starch quality 2%; Acetic anhydride adopts under meter slowly to add, and adding speed is 6.5Kg/ hour), 20 ℃, pH8.0 reaction 180 minutes; Transferring the pH solutions employed is the aqueous sodium hydroxide solution of 3% (quality percentage composition); After reaction finished, transferring pH with hydrochloric acid was 6.5;
3. with 2. reaction product dilution, washing of step, concentrate, obtain the cassava esterification starch first of water ratio after the dehydration, drying less than 14% (quality percentage composition).
(3) preparation of Glutinous Semen Maydis esterification starch first
1. waxy corn starch is mixed with water, obtain starch slurry; Waxy corn starch quality percentage composition is 30% in the described starch slurry;
2. in the starch slurry that 1. step obtains, add sodium sulfate (quality of the sodium sulfate that is added be in the described starch slurry starch quality 1%) and acetic anhydride (quality of the acetic anhydride that is added be in the described starch slurry starch quality 2%; Acetic anhydride adopts under meter slowly to add, and adding speed is 6.5Kg/ hour), 20 ℃, pH8.0 reaction 180 minutes; Transferring the pH solutions employed is the aqueous sodium hydroxide solution of 3% (quality percentage composition); After reaction finished, transferring pH with hydrochloric acid was 6.5;
3. with 2. reaction product dilution, washing of step, concentrate, obtain the Glutinous Semen Maydis esterification starch first of water ratio after the dehydration, drying less than 14% (quality percentage composition).
2, the preparation of modified starch second and contrast thereof
(1) preparation of modified starch second
1. starch mixture is mixed with water, obtain starch slurry; The quality percentage composition of starch mixture is 50% in the described starch slurry; Described starch mixture is made up of the waxy corn starch of 95 mass parts and the tapioca (flour) of 5 mass parts;
2. in the starch slurry that 1. step obtains, add sodium sulfate (quality of the sodium sulfate that is added be in the described starch slurry starch mixture quality 7%) and acetic anhydride (quality of the acetic anhydride that is added be in the described starch slurry starch mixture quality 10%; Acetic anhydride adopts under meter slowly to add, and adding speed is 5.0Kg/ hour), 35 ℃, pH10.0 reaction 15 minutes; After reaction finished, transferring pH with hydrochloric acid was 8.0;
3. with 2. reaction product dilution, washing of step, concentrate, obtain the modified starch second of water ratio after the dehydration, drying less than 14% (quality percentage composition).
(2) preparation of cassava esterification starch second
1. tapioca (flour) is mixed with water, obtain starch slurry; The quality percentage composition of tapioca (flour) is 50% in the described starch slurry;
2. in the starch slurry that 1. step obtains, add sodium sulfate (quality of the sodium sulfate that is added be in the described starch slurry starch quality 7%) and acetic anhydride (quality of the acetic anhydride that is added be in the described starch slurry starch quality 10%; Acetic anhydride adopts under meter slowly to add, and adding speed is 5.0Kg/ hour), 35 ℃, pH10.0 reaction 15 minutes; After reaction finished, transferring pH with hydrochloric acid was 8.0;
3. with 2. reaction product dilution, washing of step, concentrate, obtain the cassava esterification starch second of water ratio after the dehydration, drying less than 14% (quality percentage composition).
(3) preparation of Glutinous Semen Maydis esterification starch second
1. waxy corn starch is mixed with water, obtain starch slurry; The quality percentage composition of waxy corn starch is 50% in the described starch slurry.
2. in the starch slurry that 1. step obtains, add sodium sulfate (quality of the sodium sulfate that is added be in the described starch slurry starch quality 7%) and acetic anhydride (quality of the acetic anhydride that is added be in the described starch slurry starch quality 10%; Acetic anhydride adopts under meter slowly to add, and adding speed is 5.0Kg/ hour), 35 ℃, pH10.0 reaction 15 minutes; After reaction finished, transferring pH with hydrochloric acid was 8.0;
3. with 2. reaction product dilution, washing of step, concentrate, obtain the Glutinous Semen Maydis esterification starch second of water ratio after the dehydration, drying less than 14% (quality percentage composition).
3, the preparation of modified starch third and contrast thereof
(1) preparation of modified starch third
1. starch mixture is mixed with water, obtain starch slurry; The quality percentage composition of starch mixture is 40% in the described starch slurry; Described starch mixture is made up of the waxy corn starch of 10 mass parts and the tapioca (flour) of 90 mass parts;
2. in the starch slurry that 1. step obtains, add sodium sulfate (quality of the sodium sulfate that is added be in the described starch slurry starch mixture quality 2%) and acetic anhydride (quality of the acetic anhydride that is added be in the described starch slurry starch mixture quality 5%; Acetic anhydride adopts under meter slowly to add, and adding speed is 4.0Kg/ hour), 28 ℃, pH9.0 reaction 60 minutes; After reaction finished, transferring pH with hydrochloric acid was 7.0;
3. with 2. reaction product dilution, washing of step, concentrate, obtain the modified starch third of water ratio after the dehydration, drying less than 14% (quality percentage composition).
(2) preparation of cassava esterification starch third
1. tapioca (flour) is mixed with water, obtain starch slurry; The quality percentage composition of tapioca (flour) is 40% in the described starch slurry;
2. in the starch slurry that 1. step obtains, add sodium sulfate (quality of the sodium sulfate that is added be in the described starch slurry starch quality 2%) and acetic anhydride (quality of the acetic anhydride that is added be in the described starch slurry starch quality 7%; Acetic anhydride adopts under meter slowly to add, and adding speed is 8.0Kg/ hour), 30 ℃, pH10.0 reaction 150 minutes; After reaction finished, transferring pH with hydrochloric acid was 6.5;
3. with 2. reaction product dilution, washing of step, concentrate, obtain the cassava esterification starch third of water ratio after the dehydration, drying less than 14% (quality percentage composition).
(3) preparation of Glutinous Semen Maydis esterification starch third
1. waxy corn starch is mixed with water, obtain starch slurry; Waxy corn starch quality percentage composition is 40% in the described starch slurry;
2. in the starch slurry that 1. step obtains, add sodium sulfate (quality of the sodium sulfate that is added be in the described starch slurry starch quality 6%) and acetic anhydride (quality of the acetic anhydride that is added be in the described starch slurry starch quality 6%; Acetic anhydride adopts under meter slowly to add, and adding speed is 6.5Kg/ hour), 30 ℃, pH10.0 reaction 120 minutes; After reaction finished, transferring pH with hydrochloric acid was 6.5;
3. with 2. reaction product dilution, washing of step, concentrate, obtain the Glutinous Semen Maydis esterification starch third of water ratio after the dehydration, drying less than 14% (quality percentage composition).
4, the preparation of modified starch fourth and contrast thereof
(1) preparation of modified starch fourth
1. starch mixture is mixed with water, obtain starch slurry; The quality percentage composition of starch mixture is 40% in the described starch slurry; Described starch mixture is made up of the waxy corn starch of 20 mass parts and the tapioca (flour) of 80 mass parts;
2. in the starch slurry that 1. step obtains, add sodium sulfate (quality of the sodium sulfate that is added be in the described starch slurry starch mixture quality 3.5%) and acetic anhydride (quality of the acetic anhydride that is added be in the described starch slurry starch mixture quality 4%; Acetic anhydride adopts under meter slowly to add, and adding speed is 4.0Kg/ hour), 25 ℃, pH8.5 reaction 50 minutes; After reaction finished, transferring pH with hydrochloric acid was 6.5;
3. with 2. reaction product dilution, washing of step, concentrate, obtain the modified starch fourth of water ratio after the dehydration, drying less than 14% (quality percentage composition).
(2) preparation of cassava esterification starch fourth
1. the tapioca (flour) mixture is mixed with water, obtain starch slurry; The quality percentage composition of tapioca (flour) is 40% in the described starch slurry;
2. in the starch slurry that 1. step obtains, add sodium sulfate (quality of the sodium sulfate that is added be in the described starch slurry starch quality 3.5%) and acetic anhydride (quality of the acetic anhydride that is added be in the described starch slurry starch quality 4%; Acetic anhydride adopts under meter slowly to add, and adding speed is 4.0Kg/ hour), 25 ℃, pH8.5 reaction 50 minutes; After reaction finished, transferring pH with hydrochloric acid was 6.5;
3. with 2. reaction product dilution, washing of step, concentrate, obtain the cassava esterification starch fourth of water ratio after the dehydration, drying less than 14% (quality percentage composition).
(3) preparation of Glutinous Semen Maydis esterification starch fourth
1. the waxy corn starch mixture is mixed with water, obtain starch slurry; The quality percentage composition of waxy corn starch is 40% in the described starch slurry;
2. in the starch slurry that 1. step obtains, add sodium sulfate (quality of the sodium sulfate that is added be in the described starch slurry starch quality 3.5%) and acetic anhydride (quality of the acetic anhydride that is added be in the described starch slurry starch quality 4%; Acetic anhydride adopts under meter slowly to add, and adding speed is 4.0Kg/ hour), 25 ℃, pH8.5 reaction 50 minutes; After reaction finished, transferring pH with hydrochloric acid was 6.5;
3. with 2. reaction product dilution, washing of step, concentrate, obtain the Glutinous Semen Maydis esterification starch fourth of water ratio after the dehydration, drying less than 14% (quality percentage composition).
Two, the performance of product
1, viscograph eigenwert
With the various modified starches of step 1 preparation and contrast water-solublely, be made into the solution of 5% (quality percentage composition) respectively, adopt the Brabender viscometer to detect.The results are shown in Table 9.
Table 9 viscograph eigenwert
The modified starch first Cassava esterification starch first Glutinous Semen Maydis esterification starch first Modified starch second Cassava esterification starch second Glutinous Semen Maydis esterification starch second
Acetyl content % 1.63 1.48 1.58 1.65 1.59 1.60
GT(℃) 54.78 60.32 58.71 55.01 61.3 59.8
PT(℃) 66.59 65.21 673 67.21 65.3 66.03
PK(BU) 1009 897 998 1100 987 1087
A(BU) 476 441 456 487 412 477
B(BU) 289 219 275 298 241 256
C(BU) 587 521 565 599 518 543
D(BU) 566 498 503 578 521 551
B-A(BU) 288 245 367 295 233 284
D-C(BU) -42 -38 -39 -43 -39 -41
C-B(BU) 289 277 281 298 256 288
Acetyl content % Modified starch third Cassava esterification starch third Glutinous Semen Maydis esterification starch third The modified starch fourth Cassava esterification starch fourth Glutinous Semen Maydis esterification starch fourth
GT(℃) 1.68 1.68 1.68 1.64 1.59 1.63
PT(℃) 59.07 60.3 60.01 58.9 61.3 60.2
PK(BU) 69.57 68.9 69.89 70.1 73.4 70.5
A(BU) 1202 1159 1298 1125 1098 1103
B(BU) 512 493 563 631 587 601
C(BU) 311 281 369 487 492 499
D(BU) 645 562 697 712 698 701
B-A(BU) 611 515 643 709 723 711
D-C(BU) 301 212 315 418 423 426
C-B(BU) -49 -46 -53 -51 -49 -53
In the table: GT: rise and stick with paste temperature;
PK: peak viscosity, heat up and 95 ℃ of soaks between the high viscosity value that reaches;
PT: peak temperature, the temperature when starch is in peak viscosity;
A: the viscosity number when being warmed up to 95 ℃, the difference of this value and PK is represented the difficulty or ease of gelatinization, difference represents that greatly then starch is easy to gelatinization;
B: stick with paste the viscosity number of liquid behind 95 ℃ of insulation 45min, the difference of it and A viscosity number reflects the thermoviscosity stability of paste; (B-A) value is big more, and then the thermostability of Huing is poor more;
C: stick with paste the viscosity number of temperature when being reduced to 50 ℃, the difference of the viscosity number that this value and B are ordered represents to cool off the power of the gelation of formation, and the big more then gelation of value (C-B) is strong more;
D: stick with paste the viscosity number behind 50 ℃ of insulations of liquid 45min, the difference of the viscosity number that this value and C are ordered is represented the cold bonding degree stability of sticking with paste, and the cold bonding degree stability that difference is greatly then stuck with paste is low;
The result shows: between modified starch, cassava esterification starch and Glutinous Semen Maydis esterification starch that employing same process parameter prepares, modified starch has higher gamma value (seeing modified starch first and contrast thereof, modified starch second and contrast thereof and modified starch fourth and contrast thereof); Prepare the modified starch with identical gamma value, tapioca (flour) with 100% or 100% waxy corn starch be as raw material, and the pharmaceutical chemicals add-on of its production is big, the production time is long, production cost high (particularly waxy corn starch, raw materials cost is just very high); Adopt the modified starch of method preparation of the present invention, compare with the Glutinous Semen Maydis esterification starch with the cassava esterification starch with identical gamma value, performance is higher than the cassava esterification starch, and cost is significantly less than Glutinous Semen Maydis esterification starch (seeing modified starch third and contrast thereof).
Data adopt in the modified starch of method preparation of the present invention performance the best of sample third as can be seen from table 9.Compare with the Glutinous Semen Maydis esterification starch with the cassava esterification starch of identical gamma value, the performance of sample third is better than the cassava esterification starch, can reach the performance of Glutinous Semen Maydis esterification starch, because employing tapioca (flour) and waxy corn starch are composite, the cost of sample third is far below the Glutinous Semen Maydis esterification starch.
2, the transmittance of product
When product is used for candy, beverage and can as thickening material, require it transparent as far as possible, and can not influence the color and luster of food product bodies.Water is made into the various starch waters of step 1 preparation the starch milk of 1% (quality percentage composition) respectively, boiling water heating 20 minutes is cooled to room temperature, with 722 type grating spectrophotometers, the 1cm cuvette is surveyed transmittance (distilled water is blank) at wavelength 650mm place.The results are shown in Table 10.
The transmittance of table 10 product
The modified starch first Cassava esterification starch first Glutinous Semen Maydis esterification starch first Modified starch second Cassava esterification starch second Glutinous Semen Maydis esterification starch second
Acetyl content % 1.63 1.48 1.58 1.65 1.59 1.60
Transmittance % 68.5 61.1 65.7 70.3.3 67.1 69.7
Modified starch third Cassava esterification starch third Glutinous Semen Maydis esterification starch third The modified starch fourth Cassava esterification starch fourth Glutinous Semen Maydis esterification starch fourth
Acetyl content % 1.68 1.68 1.68 1.64 1.59 1.63
Transmittance % 69.3 60.1 63.7 61.9 58.7 61.7
Modified starch first and contrast thereof: as can be seen from the table, under same processing condition, the modified starch first substitution value of producing is the highest, the transmittance of modified starch first is than other height, this is because the transparency of the transmittance of tapioca (flour) itself is big, through composite with a certain proportion of waxy corn starch, and the production of thing appropriate processing condition, the transmittance of the product that makes is higher.
Modified starch second and contrast thereof: under same processing condition, the modified starch second substitution value of producing is the highest, the transmittance of modified starch second is than other height, this be because, the transparency of the transmittance of tapioca (flour) itself is big, through composite with a certain proportion of waxy corn starch, and appropriate processing condition production, the transmittance of the product that makes is higher.
Modified starch third and contrast thereof: at same substitution value product, the transmittance of modified starch third is than other height, this be because, the transparency of the transmittance of tapioca (flour) itself is big, through composite with a certain proportion of waxy corn starch, and appropriate processing condition production, the transmittance of the product that makes is higher.
Modified starch fourth and contrast thereof: under same processing condition, the modified starch first substitution value of producing is the highest, the transmittance of modified starch fourth is than other height, this be because, the transparency of the transmittance of tapioca (flour) itself is big, through composite with a certain proportion of waxy corn starch, and appropriate processing condition production, the transmittance of the product that makes is higher.
3, the rheological characteristics of product
Starch paste in use mostly will pass through the mechanical shearing effect of operations such as conveying, stirring, homogeneous, and the rheological characteristics of paste is to the key that plays a part of this class operation.The rheological characteristics of product can adopt the Brabender instrumentation to the results are shown in Figure 8 surely to Figure 10 by the starch sample water being mixed with the solution of 5% (quality percentage composition).
As seen from the figure, compared with the control, the temperature reduction is stuck with paste in rising of modified starch first, second, third, fourth, and the peak value viscosity increases, and thermostability, cold stability descend the retrogradation enhancing.The result shows: after introducing ethanoyl; the shear shinning phenomenon of starch is more obvious; wherein composite raw material esterification starch is more far better than the anti-shearing of Glutinous Semen Maydis esterification starch and tapioca (flour) esterification, and this character is having important meaning in the modern production technology at present.
4, the freeze-thaw stability of product
The starch paste of in frozen product, using, need freezing at low temperatures, perhaps through repeatedly freezing, melt, food still can keep original matter structure.The number of freezing and thawing of starch paste is many more, and its freeze-thaw stability is good more, is suitable for the usefulness of low temperature thickening more.Freeze-thaw stability detects: sample is added the starch milk that water is made into 3% (quality percentage composition), boiling water heating 20 minutes, fully gelatinization, cooling, get wherein that 30ml is added in the plastic cup, add a cover, place-18 ℃ of refrigerator and cooled to freeze 24 hours, take out under room temperature and thaw naturally, observe the situation of sticking with paste, repeat then repeatedly, destroy until the colloidal structure of sticking with paste, have clear water to separate out to become spongy till, the moving sub-quantity that melts of record.The freeze-thaw stability number of times of product is many more, and it is good more as the application performance in the food thickener.
The freeze-thaw stability of table 11 product
The modified starch first Cassava esterification starch first Glutinous Semen Maydis esterification starch first Modified starch second Cassava esterification starch second Glutinous Semen Maydis esterification starch second
Acetyl content % 1.63 1.48 1.58 1.65 1.59 1.60
Number of freezing and thawing 9 7 8 10 8 9
Modified starch third Cassava esterification starch third Glutinous Semen Maydis esterification starch third The modified starch fourth Cassava esterification starch fourth Glutinous Semen Maydis esterification starch fourth
Acetyl content % 1.68 1.68 1.68 1.64 1.59 1.63
Number of freezing and thawing 12 10 12 9 8 9
Modified starch first and contrast thereof: under same processing condition, the modified starch first substitution value of producing is the highest, the freeze thawing of modified starch first is than other height, this be because, the freeze thawing of tapioca (flour) itself is good, through composite with a certain proportion of waxy corn starch, and appropriate processing condition production, the freeze thawing of the product that makes is higher.
Modified starch second and contrast thereof: under same processing condition, the substitution value of the modified starch second of producing is the highest, the freeze thawing of modified starch second is than other height, this be because, the freeze thawing of tapioca (flour) itself is good, through composite with a certain proportion of waxy corn starch, and appropriate processing condition production, the freeze thawing of the product that makes is higher.
Modified starch third and contrast thereof: for the modified starch third and the contrast thereof of identical gamma value, the freeze thawing of modified starch third is than other height, this is because the freeze thawing of tapioca (flour) itself is good, through composite with a certain proportion of waxy corn starch, and appropriate processing condition production, the freeze thawing of the product that makes is higher.
Modified starch fourth and contrast thereof: under same processing condition, the substitution value of the modified starch fourth of producing is the highest, the freeze thawing of modified starch fourth is than other height, this be because, the freeze thawing of tapioca (flour) itself is good, through composite with a certain proportion of waxy corn starch, and appropriate processing condition production, the freeze thawing of the product that makes is higher.

Claims (9)

1. a method of producing modified starch comprises the steps:
(1) starch mixture is mixed with water, obtain starch slurry; The quality percentage composition of starch mixture is 30-50% in the described starch slurry; Described starch mixture is made up of the waxy corn starch of 5-20 mass parts and the tapioca (flour) of 95-80 mass parts;
(2) in the starch slurry that step (1) obtains, add sodium sulfate and acetic anhydride, 20-35 ℃, pH8.0-10.0 reaction 15-180 minute; Wherein, the quality of the sodium sulfate that is added is the 1-7% of starch mixture quality in the described starch slurry, and the quality of the acetic anhydride that is added is the 2-10% of starch mixture quality in the described starch slurry; The adding speed of described acetic anhydride is 4.0-6.5Kg/ hour;
(3) reaction product of step (2) is carried out aftertreatment, obtain modified starch.
2. the method for claim 1 is characterized in that: in the described step (2), and 25-28 ℃, pH8.5-9.0 reaction 50-70 minute; Wherein, the quality of the sodium sulfate that is added is the 2.0-3.5% of starch mixture quality in the described starch slurry.
3. method as claimed in claim 2 is characterized in that: in the described step (2), and 28 ℃, pH9.0 reaction 60 minutes; Wherein, the quality of the sodium sulfate that is added be in the described starch slurry starch mixture quality 2.0%.
4. as arbitrary described method in the claim 1 to 3, it is characterized in that: in the step (2), the adding speed of described acetic anhydride is 4.0Kg/ hour.
5. as arbitrary described method in the claim 1 to 3, it is characterized in that: in the step (2), be used to regulate the aqueous sodium hydroxide solution that is of pH.
6. as arbitrary described method in the claim 1 to 3, it is characterized in that: after step (2) reaction finished, transferring pH with hydrochloric acid was 6.5~8.0.
7. as arbitrary described method in the claim 1 to 3, it is characterized in that: described aftertreatment is for removing impurity and drying with the reaction product of step (2).
8. method as claimed in claim 7 is characterized in that: after the described drying, the water content of described modified starch is below 14% (the quality percentage composition).
9. the modified starch that arbitrary described method prepares in the claim 1 to 8.
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