CN113773405B - Acetylated distarch phosphate modified starch and preparation method and application thereof - Google Patents
Acetylated distarch phosphate modified starch and preparation method and application thereof Download PDFInfo
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- 235000013804 distarch phosphate Nutrition 0.000 title claims abstract description 65
- 239000001245 distarch phosphate Substances 0.000 title claims abstract description 51
- 229920000881 Modified starch Polymers 0.000 title claims abstract description 36
- 239000004368 Modified starch Substances 0.000 title claims abstract description 36
- 235000019426 modified starch Nutrition 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title abstract description 13
- 229920002472 Starch Polymers 0.000 claims abstract description 158
- 239000008107 starch Substances 0.000 claims abstract description 158
- 235000019698 starch Nutrition 0.000 claims abstract description 158
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 43
- 235000013336 milk Nutrition 0.000 claims abstract description 37
- 239000008267 milk Substances 0.000 claims abstract description 37
- 210000004080 milk Anatomy 0.000 claims abstract description 37
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims abstract description 36
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 33
- 238000004132 cross linking Methods 0.000 claims abstract description 26
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 19
- 239000000843 powder Substances 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims abstract description 12
- 239000012043 crude product Substances 0.000 claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 9
- 235000021056 liquid food Nutrition 0.000 claims abstract description 9
- 239000007788 liquid Substances 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims description 51
- 238000005507 spraying Methods 0.000 claims description 34
- 238000005886 esterification reaction Methods 0.000 claims description 23
- 238000001035 drying Methods 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 18
- 239000000047 product Substances 0.000 claims description 17
- 229910019142 PO4 Inorganic materials 0.000 claims description 14
- 230000032050 esterification Effects 0.000 claims description 14
- 239000010452 phosphate Substances 0.000 claims description 14
- 238000007670 refining Methods 0.000 claims description 14
- -1 phosphate ester Chemical class 0.000 claims description 12
- 229920002261 Corn starch Polymers 0.000 claims description 10
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 10
- 239000008120 corn starch Substances 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 7
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 5
- 235000013361 beverage Nutrition 0.000 claims description 3
- 239000000203 mixture Substances 0.000 abstract description 10
- 238000004062 sedimentation Methods 0.000 abstract description 8
- 239000007791 liquid phase Substances 0.000 abstract description 6
- 238000006467 substitution reaction Methods 0.000 abstract description 6
- 230000015271 coagulation Effects 0.000 abstract description 5
- 238000005345 coagulation Methods 0.000 abstract description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 235000021317 phosphate Nutrition 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 229920000856 Amylose Polymers 0.000 description 8
- 239000000243 solution Substances 0.000 description 6
- 239000012153 distilled water Substances 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 238000005096 rolling process Methods 0.000 description 5
- 239000006228 supernatant Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 230000001276 controlling effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 235000013618 yogurt Nutrition 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- 229920000945 Amylopectin Polymers 0.000 description 2
- 241000237502 Ostreidae Species 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 235000020636 oyster Nutrition 0.000 description 2
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 235000015067 sauces Nutrition 0.000 description 2
- 239000012086 standard solution Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000010257 thawing Methods 0.000 description 2
- 241001411320 Eriogonum inflatum Species 0.000 description 1
- 206010016807 Fluid retention Diseases 0.000 description 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 1
- 230000000397 acetylating effect Effects 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 239000008186 active pharmaceutical agent Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 239000012374 esterification agent Substances 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B31/00—Preparation of derivatives of starch
- C08B31/02—Esters
- C08B31/06—Esters of inorganic acids
- C08B31/066—Starch phosphates, e.g. phosphorylated starch
-
- 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
- A23L2/00—Non-alcoholic beverages; Dry compositions or concentrates therefor; Their preparation
- A23L2/52—Adding ingredients
- A23L2/62—Clouding agents; Agents to improve the cloud-stability
-
- 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
- A23L29/20—Foods or foodstuffs containing additives; Preparation or treatment thereof containing gelling or thickening agents
- A23L29/206—Foods or foodstuffs containing additives; Preparation or treatment thereof containing gelling or thickening agents of vegetable origin
- A23L29/212—Starch; Modified starch; Starch derivatives, e.g. esters or ethers
- A23L29/219—Chemically modified starch; Reaction or complexation products of starch with other chemicals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B30/00—Preparation of starch, degraded or non-chemically modified starch, amylose, or amylopectin
- C08B30/12—Degraded, destructured or non-chemically modified starch, e.g. mechanically, enzymatically or by irradiation; Bleaching of starch
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B31/00—Preparation of derivatives of starch
- C08B31/003—Crosslinking of starch
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B31/00—Preparation of derivatives of starch
- C08B31/02—Esters
- C08B31/04—Esters of organic acids, e.g. alkenyl-succinated starch
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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
- A23V2002/00—Food compositions, function of food ingredients or processes for food or foodstuffs
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A40/00—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
- Y02A40/90—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in food processing or handling, e.g. food conservation
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- Medicinal Chemistry (AREA)
- Biochemistry (AREA)
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- Nutrition Science (AREA)
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Abstract
The invention discloses an acetylated distarch phosphate modified starch and a preparation method and application thereof, hydrochloric acid is sprayed into starch with the water content less than or equal to 1 percent, the mixture is stirred and reacted, then the mixture is kept stand until the powder is expanded, the mixture is dried for 40-90min at 50-120 ℃ to obtain pretreated starch, anhydrous sodium sulfate and sodium carbonate are added, phosphorus oxychloride is sprayed, the sodium carbonate is added again after the mixture is stirred uniformly, the mixture is kept stand until the powder is expanded, the temperature is kept for 30-50min at 40-50 ℃ to obtain phosphate crosslinked starch, the mixture is added with water to prepare starch milk, the pH is adjusted to 9-10, a catalyst is added after the temperature is raised to 33-35 ℃, acetic anhydride is dripped to keep the pH of the system to be 8.4-8.6, the reaction is carried out for 30-40min after the dripping is finished, and acetylated distarch phosphate crude product is obtained and refined. The invention improves the crosslinking degree and the substitution degree by pretreating, crosslinking and esterifying the starch, obviously improves the physicochemical property of the modified starch, simultaneously ensures that the modified starch has special gel coagulation property, has stable solid-liquid phase and difficult sedimentation, does not have layering of the liquid phase and the like, and can be applied to liquid foods such as drinks, oral liquid and the like.
Description
Technical Field
The invention belongs to the technical field of modified starch preparation, and particularly relates to acetylated distarch phosphate modified starch and a preparation method and application thereof.
Background
Starch molecules are polymers formed by connecting glucose units, including amylose and amylopectin, which are composed of alpha-D-1, 4-glycosidic bond and alpha-D-1, 6-glycosidic bond, and the C2, C3 and C6 bonds of each unit have free hydroxyl groups as active reaction units, and the active reaction units can react with a plurality of compounds, such as the possibility of forming cross-links with hydroxyl groups on the same molecule or different molecules when some compounds contain two or more groups capable of reacting with the hydroxyl groups, and the active reaction units on the starch molecules are activated under alkaline conditions, and can be replaced by esterification agents and connected together through hydrogen bonds, thereby improving the performance of the starch. The acetylated distarch phosphate modified starch is esterified and crosslinked composite modified starch obtained by acetylating and reacting original starch with phosphate, and has the characteristics of good film forming property, good fluidity, high thermal stability, strong acid resistance and the like.
Chinese patent CN 109400723A discloses a preparation process of acetylated distarch phosphate, which adopts ultrasonic treatment of starch milk to improve the specific surface area of starch, generate micropores on the surface of starch and improve the crosslinking and esterification efficiency of starch, thereby improving the properties of freeze-thaw stability, crosslinking degree and the like of modified starch. Chinese patent CN 107163152A discloses a preparation method of acetylated starch phosphate used in oil consumption, which can effectively avoid the phenomenon of water layering of oyster sauce during storage by improving the water retention of acetylated distarch phosphate to oyster sauce. Chinese patent CN 111732670A discloses an acetylated distarch phosphate for yoghourt, which is applied to yoghourt and can obviously enhance the apparent viscosity, water holding capacity and storage stability of the yoghourt.
Due to different preparation process conditions, the obtained modified starch has different properties, and has certain advantages and disadvantages when being applied to different foods, such as meatballs or yoghourt products, and the effect is different. In addition, in the prior art, the preparation method of the modified starch mostly adopts wet crosslinking, and the starch is hydrolyzed in an aqueous solution, so that the bonding property of the crosslinking is influenced, and the application performance in food is further influenced.
Disclosure of Invention
Aiming at the problem of low esterification and crosslinking degree in the preparation process of acetylated distarch phosphate modified starch in the prior art, the invention provides acetylated distarch phosphate modified starch and a preparation method and application thereof.
The invention is realized by the following technical scheme:
an acetylated distarch phosphate modified starch is prepared by the following method:
(1) Pretreatment: spraying hydrochloric acid with a mass of 0.5-2% of the dry mass of the starch into the starch, continuously stirring for reaction for 20-30 min, standing until the powder expands, and then drying at 50-120 ℃ for 40-90min to obtain pretreated starch;
(2) And (3) crosslinking: adding anhydrous sodium sulfate and sodium carbonate into pretreated starch, uniformly stirring, spraying phosphorus oxychloride with the concentration of 0.05-0.1% of the dry starch basis, uniformly stirring, adding the sodium carbonate again, uniformly stirring, standing until the powder expands, and keeping the temperature at 40-50 ℃ for 30-50 min to obtain phosphate ester crosslinked starch;
(3) Esterification: preparing phosphate crosslinked starch and water into starch milk, adjusting the pH value to 9-10, stirring and heating to 33-35 ℃, adding a catalyst, then dropwise adding acetic anhydride accounting for 3-7% of the dry weight of the starch, and keeping the pH value of a reaction system to 8.4-8.6; after the dropwise addition is finished, controlling the pH value to be 8.4-8.6, and continuously reacting for 30-40min to obtain an acetylated distarch phosphate crude product;
(4) And (5) refining.
Further, the starch in the step (1) is corn starch which is dried until the moisture content is less than or equal to 1%; the concentration of the hydrochloric acid is 1 percent.
Further, stirring starch all the time in the spraying process of the step (1) and the step (2); the dripping time of the acetic anhydride in the step (3) is 60-70min.
Further, the adding amount of the anhydrous sodium sulfate and the sodium carbonate in the step (2) is 0.5-1% and 1-2% of the dry weight of the starch respectively, and the adding amount of the sodium carbonate is 0.5-1% of the dry weight of the starch again.
Further, the catalyst in the step (3) is pyridine, and the adding amount of the pyridine is 0.01 percent of the dry weight of the starch.
Further, the weight ratio of the phosphate ester cross-linked starch to the water in the step (3) is 1:2-3.
Further, the refining method in the step (3) is as follows: adjusting the pH value of the starch milk of the acetylated distarch phosphate crude product to 4.2-4.5, stopping the esterification reaction, and filtering, washing, drying at low temperature and crushing to obtain an acetylated distarch phosphate finished product.
In the invention, the preparation method of the acetylated distarch phosphate modified starch comprises the following steps:
(1) Pretreatment: spraying hydrochloric acid with the mass of 0.5-2% of the dry mass of the starch into the starch, continuously stirring for reacting for 20-30 min, standing until the powder expands, and then drying for 40-90min at 50-120 ℃ to obtain pretreated starch;
(2) And (3) crosslinking: adding anhydrous sodium sulfate and sodium carbonate into pretreated starch, uniformly stirring, spraying phosphorus oxychloride with the content of 0.05-0.1% of the dry starch, uniformly stirring, adding sodium carbonate again, uniformly stirring, standing until the powder expands, and keeping the temperature at 40-50 ℃ for 30-50 min to obtain phosphate ester crosslinked starch;
(3) Esterification: preparing phosphate crosslinked starch and water into starch milk, adjusting the pH value to 9-10, stirring and heating to 33-35 ℃, adding a catalyst, then dropwise adding acetic anhydride accounting for 3-7% of the dry weight of the starch, and keeping the pH value of a reaction system to 8.4-8.6; after the dropwise addition is finished, controlling the pH value to be 8.4-8.6, and continuously reacting for 30-40min to obtain an acetylated distarch phosphate crude product;
(4) And (4) refining.
In the invention, the acetylated distarch phosphate modified starch is applied to liquid food.
In the invention, the acetylated distarch phosphate modified starch is applied to liquid food, and the liquid food is beverage or oral liquid.
The starch molecule is composed of amylose and amylopectin, and during the hydrolysis process of the starch, a proper amount of acid can firstly cause the hydrolysis of alpha-1.6 glycosidic bonds in certain molecules, so that the amylose content in the starch is increased, the hydroxyl activity on the amylose molecule is improved, the starch is easy to activate, and further the starch is easy to crosslink and esterify. By pretreating starch, i.e. drying the starch to below 1% moisture, amylose hydrolysis can be reduced; after the starch is sprayed with acid, high-temperature treatment can cause hydrolysis of alpha-1, 6 glycosidic bonds, so that the content of amylose in the starch is increased, and simultaneously, the activity of hydroxyl groups on amylose molecules is improved, so that the amylose molecules are easy to activate, and further, the crosslinking degree and the substitution degree are improved; the influence of the substitution degree and the crosslinking degree of the starch after esterification and crosslinking obviously improves the physicochemical property of the modified starch, simultaneously ensures that the modified starch has special gel coagulation property, ensures that a solid-liquid phase is stable and not easy to settle, does not cause layering of a stable liquid phase and the like, and can be applied to liquid foods such as drinks, oral liquid and the like
Advantageous effects
The acetylated distarch phosphate modified starch prepared by the invention has the advantages that the starch is pretreated, and is crosslinked and esterified, so that the crosslinking degree and the substitution degree are improved, the physicochemical property of the modified starch is obviously improved, meanwhile, the modified starch has special gel coagulation property, the solid-liquid phase is stable and is not easy to settle, the stable liquid phase is not layered, and the like, and the acetylated distarch phosphate modified starch can be applied to liquid foods such as drinks, oral liquids, and the like.
Detailed Description
The following examples are given for the detailed implementation and specific operation of the present invention, but the scope of the present invention is not limited to the following examples.
The starch in the embodiment of the invention is corn starch with 14% of moisture content.
Example 1
(1) Pretreatment: drying corn starch to water content of 0.8%, then uniformly spraying hydrochloric acid (hydrochloric acid concentration of 1%) with a mass of 0.5% of dry mass of starch into the starch, stirring the starch all the time in the spraying process, continuously stirring for 30 minutes after spraying is finished, standing the starch until the powder expands, and then drying for 90 minutes at 70 ℃ to obtain pretreated starch;
(2) And (3) crosslinking: adding anhydrous sodium sulfate accounting for 0.5 percent of the dry mass of the starch and anhydrous sodium carbonate accounting for 1.5 percent of the dry mass of the starch into the pretreated starch, uniformly stirring, spraying phosphorus oxychloride accounting for 0.1 percent of the dry mass of the starch, stirring the starch all the time in the spraying process, and continuously stirring until the mixture is completely uniform after the spraying is finished; then adding anhydrous sodium carbonate with 0.8% of dry basis again, stirring uniformly, standing the starch until the powder expands, and then rolling and preserving the temperature for 40min at 45 ℃ to obtain phosphate ester crosslinked starch;
(3) Esterification: preparing phosphate crosslinked starch and water into starch milk according to the proportion of 1;
(4) Refining: regulating the pH value of the crude starch milk to 4.5, terminating the esterification reaction, and obtaining the finished product of the acetylated distarch phosphate after filtering, washing, drying at low temperature and crushing.
Example 2
(1) Pretreatment: drying corn starch to water content of 0.7%, then uniformly spraying hydrochloric acid (hydrochloric acid concentration of 1%) with a mass of 1% of dry basis of starch into the starch, stirring the starch all the time in the spraying process, continuously stirring for 20 minutes after spraying is finished, standing the starch until the powder expands, and then drying for 80 minutes at 80 ℃ to obtain pretreated starch;
(2) And (3) crosslinking: adding anhydrous sodium sulfate and sodium carbonate which are 0.6 percent and 2 percent of the dry mass of the starch into the pretreated starch, and uniformly stirring; spraying phosphorus oxychloride with 0.1% of dry starch basis, stirring the starch all the time in the spraying process, continuously stirring until the starch is completely uniform after the spraying is finished, then adding sodium carbonate with 0.6% of dry starch basis again, stirring uniformly, standing the starch until the powder expands, and then rolling and preserving the temperature for 50min at 40 ℃ to obtain phosphate ester crosslinked starch;
(3) Esterification: preparing phosphate crosslinked starch and water into starch milk according to the proportion of 1;
(4) Refining: adjusting the pH value of the crude starch milk to 4.2, terminating the esterification reaction, and obtaining the finished product of the acetylated distarch phosphate after filtering, washing, drying at low temperature and crushing.
Example 3
(1) Pretreatment: drying corn starch to water content of 0.9%, then uniformly spraying hydrochloric acid (hydrochloric acid concentration of 1%) with a mass of 2% of dry basis mass of the starch into the starch, stirring the starch all the time in the spraying process, continuously stirring for 25 minutes after spraying is finished, standing the starch until the powder expands, and then drying for 50 minutes at 120 ℃ to obtain pretreated starch;
(2) And (3) crosslinking: adding anhydrous sodium sulfate accounting for 1 percent of the dry basis mass of the starch and sodium carbonate accounting for 1 percent of the dry basis mass of the starch into the pretreated starch, and uniformly stirring; spraying phosphorus oxychloride with 0.1% of dry starch basis, stirring the starch all the time in the spraying process, and continuously stirring until the starch is completely uniform after the spraying is finished; then adding sodium carbonate with the starch dry basis of 1 percent again, stirring uniformly, standing the starch until the powder expands, and then rolling and preserving the temperature for 35min with the temperature of 50 ℃ to obtain phosphate ester crosslinked starch;
(3) Esterification: preparing phosphate crosslinked starch and water into starch milk according to the proportion of 1:2.5, adding alkali to adjust the pH of the starch milk to 9.8, stirring and heating to 33 ℃, adding 0.01% of pyridine as a catalyst into the starch milk on a dry basis, then dropwise adding acetic anhydride with the mass of 4.5% of the dry basis of the starch into the starch milk, wherein the dropwise adding time is 60min, the pH of a reaction system is kept to be 8.4-8.6 all the time in the process of dropwise adding the acetic anhydride, after the dropwise adding is finished, controlling the pH to be 8.4-8.6, and continuously reacting for 35min to obtain an acetylated distarch phosphate crude product;
(4) Refining: adjusting the pH value of the crude starch milk to 4.4, terminating the esterification reaction, and obtaining the finished product of the acetylated distarch phosphate after filtering, washing, drying at low temperature and crushing.
Comparative example 1
(1) And (3) crosslinking: drying corn starch to water content of 0.8%, adding anhydrous sodium sulfate 0.5% of dry mass of the starch and anhydrous sodium carbonate 1.5%, stirring uniformly, spraying phosphorus oxychloride 0.1% of dry mass of the starch, stirring the starch all the time in the spraying process, and continuously stirring to be completely uniform after the spraying is finished; then adding anhydrous sodium carbonate with the dry basis of 0.8 percent again, uniformly stirring, standing the starch until the powder expands, and then rolling and preserving the temperature for 40min at 45 ℃ to obtain phosphate ester crosslinked starch;
(2) Esterification: preparing phosphate crosslinked starch and water into starch milk according to the proportion of 1;
(3) Refining: regulating the pH value of the crude starch milk to 4.5, terminating the esterification reaction, and obtaining the finished product of the acetylated distarch phosphate after filtering, washing, drying at low temperature and crushing.
Comparative example 2
(1) And (3) crosslinking: adding anhydrous sodium sulfate accounting for 0.5 percent of the dry mass of the starch and sodium carbonate accounting for 1.5 percent of the dry mass of the starch into the original corn starch, uniformly stirring, spraying phosphorus oxychloride accounting for 0.1 percent of the dry mass of the starch, stirring the starch all the time in the spraying process, and continuously stirring until the mixture is completely uniform after the spraying is finished; then adding anhydrous sodium carbonate with the dry basis of 0.8 percent again, uniformly stirring, standing the starch until the powder expands, and then rolling and preserving the temperature for 40min at 45 ℃ to obtain phosphate ester crosslinked starch;
(2) Esterification: preparing phosphate crosslinked starch and water into starch milk according to the proportion of 1;
(3) Refining: adjusting the pH value of the crude starch milk to 4.5, terminating the esterification reaction, and obtaining the finished product of the acetylated distarch phosphate after filtering, washing, drying at low temperature and crushing.
Comparative example 3
(1) And (3) crosslinking: preparing raw corn starch and water into starch milk according to the proportion of 1;
(2) Esterification: adjusting the pH value of phosphate ester cross-linked starch milk to 9.5, stirring and heating to 35 ℃, then dropwise adding acetic anhydride with the mass of 5% of the dry mass of the starch into the starch milk, wherein the dropwise adding time is 60min, the pH value of a reaction system is kept between 8.4 and 8.6 all the time in the process of dropwise adding the acetic anhydride, after the dropwise adding is finished, the pH value is controlled between 8.4 and 8.6, and the reaction is continued for 40min to obtain a crude product of acetylated distarch phosphate;
(3) Refining: adjusting the pH value of the crude starch milk to 4.5, terminating the esterification reaction, and obtaining the finished product of the acetylated distarch phosphate after filtering, washing, drying at low temperature and crushing.
Comparative example 4
(1) And (3) crosslinking: preparing raw corn starch and water into starch milk according to the proportion of 1;
(2) Esterification: adjusting the pH value of the phosphate ester cross-linked starch milk to 9-10, stirring and heating to 35 ℃, adding 0.01% of pyridine serving as a catalyst on a dry basis into the starch milk, dropwise adding acetic anhydride with the mass of 5% of the dry basis of the starch into the starch milk for 60min, and keeping the pH value of a reaction system to 8.4-8.6 all the time in the process of dropwise adding the acid anhydride; after the dropwise addition is finished, controlling the pH value to be 8.4-8.6, and continuously reacting for 40min to obtain an acetylated distarch phosphate crude product;
(3) Refining: adjusting the pH value of the crude starch milk to 4.5, terminating the esterification reaction, and obtaining the finished product of the acetylated distarch phosphate after filtering, washing, drying at low temperature and crushing.
Test examples
EXAMPLES 1-3, COMPARATIVE EXAMPLES 1-3, properties of acetylated distarch phosphate prepared
(1) And (3) testing the transmittance:
acetylated distarch phosphate prepared in examples 1-3 and comparative examples 1-3 was prepared into 6% starch milk, the starch milk was heated to 95 ℃ with stirring, the temperature was maintained for 15min, the starch milk was cooled, the zero point was adjusted with distilled water at 620nm, and the transmittance was measured, and the results are shown in the following table.
(2) And (3) testing the freeze-thaw stability:
the acetylated distarch phosphate prepared in examples 1-3 and comparative examples 1-3 was prepared into 3% starch milk, which was gelatinized in boiling water for 20min to fully gelatinize the starch milk, taken out and naturally cooled to room temperature, then placed in a refrigerator at-18 ℃ for freezing for a day and night, taken out and naturally thawed at room temperature for 6h, observed for a plurality of times, freeze thawing was repeated until the colloidal structure of the starch paste was destroyed and clear water was precipitated or changed into a spongy form, and the number of freeze thawing times was recorded, with the results shown in the following table.
(3) Viscosity:
the acetylated distarch phosphates prepared in examples 1-3 and comparative examples 1-3 were prepared into 6% starch milk, and the gelatinization temperature and peak viscosity of the starch milk were measured by a brabender viscometer, and the results are shown in the following table.
(4) Coagulation property:
3g of each of the acetylated distarch phosphates prepared in examples 1-3 and comparative examples 1-3 was weighed in a 500ml beaker, 280ml of water was added, the mixture was stirred for 30min in a magnetic stirrer, gelatinized in a 90-100 ℃ water bath for 15min until the solution became milky transparent, cooled to 60 ℃ and kept at a constant temperature, dropped to pH8.5-9.0 with 0.1mol/L NaOH solution, and maintained for 5min, and recordedThe required NaOH volume. Then taking out the rotor, adding water to total amount of solution of 300g, centrifuging at 4800r/min for 15min, taking distilled water as reference, collecting supernatant, and measuring absorbance A at 650nm 1 Refining the rest solution at 4 deg.C for 72 hr, centrifuging at 4800r/min for 15min, collecting supernatant, and measuring absorbance A at 650nm 2 . The formula for calculating the coagulation value is as follows:
retrogradation value = (10) -A2 -10 -A1 ）*100%。
(5) Sedimentation product:
the crosslinking degree of the crosslinked starch is in a linear and negative correlation with the sedimentation product, and the sedimentation product is used for expressing the crosslinking degree.
0.5g of each of the acetylated distarch phosphate prepared in examples 1-3 and comparative examples 1-3 was weighed, prepared into a starch emulsion with a mass fraction of 2% with distilled water, heated in a water bath at 82-85 ℃ for 2min, taken out, left to cool at room temperature, 10ml of the paste was placed in each of two centrifuge tubes, centrifuged at 4000r/min for 2min, the centrifuged supernatant was poured into centrifuge tubes of the same volume, the volume of the supernatant was read, the sedimentation product was calculated, and each sample was subjected to 3 parallel determinations;
sedimentation volume (ml) = 10-supernatant volume.
(6) And (3) measuring the degree of substitution:
5g of each of the acetylated distarch phosphates prepared in examples 1 to 3 and comparative examples 1 to 3 was accurately weighed in a 250ml iodine flask, 50ml of distilled water was added and mixed, 2 drops of 1% phenolphthalein indicator were added dropwise, after mixing, 0.1mol/L NaOH solution was added dropwise until reddish color did not disappear, 25ml of 0.5mol/L sodium hydroxide standard solution was added, and the mixture was placed on a constant temperature water bath speed-regulating oscillator and mechanically oscillated for 30min for saponification. Washing the bottle stopper and the inner wall of the iodine measuring bottle with a small amount of distilled water, dripping the saponified solution with 0.5mol/L hydrochloric acid standard solution until the red color disappears to obtain the end point, and recording the volume of the consumed hydrochloric acid. Taking native starch as a blank control test;
acetyl content W ac （%）=
V2: volume of hydrochloric acid consumed for the blank (ml); v1: sample consumption hydrochloric acid volume (ml);
c: the concentration of hydrochloric acid (mol/L); m: sample weight (g)
Degree of substitution DS = esterified starch
The results are shown in Table 1 below
TABLE 1 modified starch Properties test results for acetylated distarch phosphate
As can be seen from the results in Table 1, the acetylated distarch phosphate obtained by the preparation method of the present invention, due to the addition of the pretreatment step and the subsequent dry crosslinking step, reduces the average molecular weight and chain length of the resulting modified starch as a whole, so that the obtained product has high transmittance and freeze-thaw stability, high crosslinking degree due to sedimentation value, a relatively moderate viscosity value, and a high sedimentation value, and is suitable for application to liquid beverages.
Claims (10)
1. The acetylated distarch phosphate modified starch is characterized by being prepared by the following method:
(1) Pretreatment: spraying hydrochloric acid with a mass of 0.5-2% of the dry mass of the starch into the starch, continuously stirring for reaction for 20-30 min, standing until the powder expands, and drying at 70-120 ℃ for 40-90min to obtain pretreated starch;
(2) And (3) crosslinking: adding anhydrous sodium sulfate and sodium carbonate into pretreated starch, uniformly stirring, spraying phosphorus oxychloride with the content of 0.05-0.1% of the dry starch, uniformly stirring, adding sodium carbonate again, uniformly stirring, standing until the powder expands, and keeping the temperature at 40-50 ℃ for 30-50 min to obtain phosphate ester crosslinked starch;
(3) Esterification: preparing phosphate crosslinked starch and water into starch milk, adjusting the pH value to 9-10, stirring and heating to 33-35 ℃, adding a catalyst, then dropwise adding acetic anhydride accounting for 3-7% of the dry weight of the starch, and keeping the pH value of a reaction system to 8.4-8.6; after the dropwise addition is finished, controlling the pH value to be 8.4-8.6, and continuously reacting for 30-40min to obtain an acetylated distarch phosphate crude product;
(4) Refining;
the starch in the step (1) is corn starch which is dried until the moisture content is less than or equal to 1 percent.
2. The acetylated distarch phosphate modified starch according to claim 1, wherein the hydrochloric acid concentration in step (1) is 1%.
3. The acetylated distarch phosphate modified starch of claim 1 wherein the spraying of steps (1) and (2) agitates the starch throughout; the dripping time of the acetic anhydride in the step (3) is 60-70min.
4. The acetylated distarch phosphate modified starch of claim 1, wherein the anhydrous sodium sulfate and sodium carbonate are added in step (2) in an amount of 0.5-1% and 1-2% by weight of the starch on a dry basis, respectively, and the sodium carbonate is added again in an amount of 0.5-1% by weight of the starch on a dry basis.
5. The acetylated distarch phosphate modified starch according to claim 1, wherein the catalyst in step (3) is pyridine added in an amount of 0.01% by weight of the starch on a dry basis.
6. The acetylated distarch phosphate modified starch of claim 1, wherein the weight ratio of phosphate cross-linked starch to water in step (3) is 1:2-3.
7. The acetylated distarch phosphate modified starch of claim 1, wherein the refining process in step (3) is: adjusting the pH value of the starch milk of the acetylated distarch phosphate crude product to 4.2-4.5, stopping the esterification reaction, and filtering, washing, drying at low temperature and crushing to obtain an acetylated distarch phosphate finished product.
8. A method for preparing the acetylated distarch phosphate modified starch of any one of claims 1 to 7, comprising the steps of:
(1) Pretreatment: spraying hydrochloric acid with a mass of 0.5-2% of the dry mass of the starch into the starch, continuously stirring for reaction for 20-30 min, standing until the powder expands, and drying at 70-120 ℃ for 40-90min to obtain pretreated starch;
(2) And (3) crosslinking: adding anhydrous sodium sulfate and sodium carbonate into pretreated starch, uniformly stirring, spraying phosphorus oxychloride with the concentration of 0.05-0.1% of the dry starch basis, uniformly stirring, adding the sodium carbonate again, uniformly stirring, standing until the powder expands, and keeping the temperature at 40-50 ℃ for 30-50 min to obtain phosphate ester crosslinked starch;
(3) Esterification: preparing phosphate crosslinked starch and water into starch milk, adjusting the pH value to 9-10, stirring and heating to 33-35 ℃, adding a catalyst, then dropwise adding acetic anhydride accounting for 3-7% of the dry weight of the starch, and keeping the pH value of a reaction system to 8.4-8.6; after the dropwise addition is finished, controlling the pH value to be 8.4-8.6, and continuously reacting for 30-40min to obtain an acetylated distarch phosphate crude product;
(4) And (5) refining.
9. Use of the acetylated distarch phosphate modified starch of any one of claims 1 to 7 in liquid food.
10. The use of acetylated distarch phosphate modified starch according to claim 9 in a liquid food product, said liquid food product being a beverage or an oral liquid.
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