CN104086661A - Acid-heat degradation preparation method of low-viscosity octenyl succinic anhydride modified starch - Google Patents

Abstract

The invention discloses a method for preparing a low-viscosity water-soluble starch octenyl succinate product through acid-heat degradation. The steps include mixing raw starch, adding lye, and adding octene under the starch gelatinization temperature. base succinic anhydride, esterified for more than 8 hours, then neutralized, deliquified, washed with pure water and refined. Add water to filter cake to adjust slurry, adjust pH with oxalic acid solution, acid hydrolysis reaction, high temperature acid heat treatment with continuous spraying of water heater at 125~130°C, laminar flow heat preservation, cooling, add calcium hydroxide saturated solution, or add calcium carbonate milk Turbid liquid and sodium carbonate solution, stirred and neutralized, added activated carbon, press-filtered, the filtrate was concentrated in vacuum, fine-filtered, spray-dried, cooled, packaged to obtain a low-viscosity water-soluble starch alkenyl succinate product, suitable for use in It can be used as emulsifier or microcapsule embedding material for food and daily chemical industry. The invention can produce and prepare low-viscosity, water-soluble starch octenyl succinate products, and achieve better economic benefits.

Description

A kind of acid-thermal degradation preparation method of low-viscosity octenyl succinic acid starch ester

technical field

The invention relates to a process method of acid-heat degradation to prepare low-viscosity water-soluble starch octenyl succinate, which can be used as an emulsification stabilizer for food and daily chemical industry or as an embedding material for microcapsules.

Background technique

Starch alkenyl succinate is a kind of starch ester product obtained by esterification reaction of raw starch or starch derivatives with alkenyl succinic anhydrides containing carbon chains of different lengths under alkaline conditions. Alkenyl succinic anhydride Decenyl succinic anhydride, dodecenyl succinic anhydride and hexadecenyl succinic anhydride, currently only octenyl succinic anhydride is allowed to be used for food starch modification.

Octenyl Succinic Anhydride Modified Starch (OSA-Starch for short) is a modified starch product developed by Caldwell and Wurzburg in the United States. It applied for a patent in 1953. The U.S. Food and Drug Administration (FDA) classified OSA starch as a product generally recognized as safe (GRAS), which was listed in the Food Chemicals Handbook published in the United States in 1972. my country approved the use of this modified starch as a food additive in 1997, and in 2001 approved the expansion of the scope of use of this product in food, and the dosage can be added according to demand without control.

Starch octenyl succinate is different from other traditional modified starches. It has surface activity and emulsifying thickener, and has a large molecular weight. It can play an important and efficient role especially in oil-in-water emulsions. Due to its special function and good use effect, it is widely used in various food and daily chemical products, such as emulsified essence, microcapsule powder products, powder oil, soft drinks, yogurt and cheese, canned food and cosmetics. It is also used in textiles, papermaking, pharmaceuticals, and latex coatings. It is a high-end modified starch product with a high market price. Starch octenyl succinate products mainly fall into two categories:

(1) One type is a modified starch product prepared from raw starch, which is mainly used as a thickener and has a certain surface activity. It is suitable for use in some high-viscosity and high-concentration food or chemical products. Such high-concentration modified starch products are generally monomodified, with fewer varieties, easier production, relatively low technical requirements, and no obvious difference in quality between domestic and foreign products.

(2) The other type is low-viscosity octenyl succinic acid starch ester obtained through moderate degradation of (original) starch octenyl succinate, which is generally soluble in cold water or insoluble in cold water, and is mainly used as Emulsion stabilizer or microcapsule material. Low viscosity starch octenyl succinate products that are cold water inert generally require gelatinization during use. This type of octenyl succinic acid starch ester is a compound modified starch product. Different degradation methods and degrees can produce a series of products with different qualities. There are many varieties. The manufacturing steps and processes are relatively complicated, and the requirements for production technology are high. Domestic The quality of the product is far from that of foreign countries.

After the starch is esterified with octenyl succinic anhydride, a long carbon chain is introduced, which increases the paste viscosity of the esterified starch, and the modified starch has a high viscosity, which limits its application. In order to solve this problem, the method of degradation is usually adopted to reduce the relative molecular weight of starch, such as making it dextrinized, which can achieve the purpose of reducing viscosity. The low-viscosity octenyl succinic acid starch ester obtained through moderate degradation can be used as a microcapsule wall material to embed water-insoluble and non-volatile component substances, and traditional Compared with Bi material, the comprehensive effect is better from many aspects.

The technical route for preparing low-viscosity starch octenyl succinate mainly includes synthesizing starch ester and then degrading it, or degrading the original starch and then esterifying it. Degradation methods include thermal degradation, sodium hypochlorite oxidation, acid hydrolysis and enzymatic hydrolysis, and acid hydrolysis and enzymatic hydrolysis are the most commonly used methods. Acid hydrolysis is adding acid to hydrolyze starch milk at high temperature. The DE value of the product is usually less than 10, and it has more linear side chains than the original starch. The enzyme used for enzymolysis is α-amylase or β-amylase. When using α-amylase, the DE value of the product is required to be less than 20, and it needs to be pre-heated and gelatinized before enzymatic hydrolysis. The molecular structure of the product obtained by using β-amylase is similar to β-limited dextrin, and has good emulsifying properties. Yang Yuan'e et al. used α-amylase and glucoamylase to degrade it, and prepared a low-viscosity octenyl succinic acid starch ester with a DE value of 30 and a fluidity of 80. People such as Richards in the United States, Trzasko, etc., and Kato in Japan have carried out systematic research on the degradation of starch octenyl succinate. The results show that the use of enzymes to treat starch octenyl succinate can form part of branched chain oligosaccharides, It can effectively reduce the viscosity of modified starch, and also improve other properties, such as enhanced paste transparency, improved freeze-thaw stability, increased solubility, enhanced stability in water, etc., expanding its application range. Blue et al. used different amylases to degrade starch octenyl succinate to obtain products with different glucose values (19.8-45). They studied their application in microcapsule wall materials and found that they had better embedding effects.

Different degradation methods and process conditions can be used to prepare starch octenyl succinate products with different low viscosity or DE values, which can meet different application requirements.

Contents of the invention

According to the existing production method and technology, the invention provides a process method of acid-thermal degradation to prepare low-viscosity water-soluble starch octenyl succinate product.

A method of preparing low-viscosity water-soluble octenyl succinic acid starch ester by adopting acid-thermal degradation process means proposed by the present invention, including starch size adjustment, esterification reaction, neutralization, dehydration and washing, size adjustment and acid adjustment, The steps of acidolysis reaction, continuous jet high temperature treatment, heat preservation treatment, neutralization, decolorization, filtration, vacuum concentration, spray drying, cooling and packaging are as follows:

(1) Sizing and esterification reaction: Add water to starch and stir to obtain a slurry. The dry solids concentration of the slurry is 40% to 45% (w/w). The temperature is raised to 40°C to 50°C, and the concentration is 10% (w/w). w) sodium carbonate solution to adjust the pH of the starch milk to 8.5~9.5, maintain the temperature and pH of the starch milk, add 1%~8% octenyl succinic anhydride relative to the starch mass for reaction, and the esterification time is 6~24 hours , and then use a 10% (v/v) hydrochloric acid solution to neutralize the pH of the starch milk to 6.0~6.5.

The starch used in the above steps can be common cornstarch, or waxy cornstarch, high-chain cornstarch, or common raw starches such as cassava, wheat, and potato. When the low-viscosity starch octenyl succinate product is used in the food field, the amount of octenyl succinic anhydride cannot exceed 3.0% of the starch mass, preferably 2.8% to 3.0%. As an auxiliary agent for pesticides and daily chemicals, the higher the proportion of octenyl succinic anhydride, the better the application effect.

(2) Deliquification and washing, slurry adjustment and acidification, acidification reaction: remove the waste liquid from the neutralized emulsion by pressure filtration or centrifugation, wash with water and then deliquify, add water to the filter cake, use a concentration of 10% (w /w) oxalic acid solution to adjust the pH of the emulsion to 2.0~2.8, the dry solids concentration of the emulsion is 15%~25% (w/w), heat up to 45°C~50°C, stir for 2.0~4.0 hours for acidolysis reaction , to obtain acid-hydrolyzed modified starch milk;

The preferred pH range in the above steps is 2.0-2.4, and the acid hydrolysis reaction takes 3.5-4.0 hours. The lower the pH of the system, the higher the acid hydrolysis temperature and the longer the time, the greater the degree of starch degradation.

(3) Continuous spray high temperature treatment, heat preservation treatment, neutralization: use a water heater to perform continuous spray high temperature treatment on the acid-hydrolyzed modified starch milk at 125°C~130°C for 3~5 minutes, and laminar flow at 90°C~99°C Keep warm for 1.0~2.5 hours, cool down to 80°C~82°C, add saturated calcium hydroxide solution ground by colloid mill, or calcium carbonate emulsion ground by colloid mill and a small amount of 10% (w/w) Sodium carbonate solution, stirred and neutralized until the pH is 5.2~5.6, and solids such as calcium oxalate are precipitated;

(4) Decolorization and filtration: add activated carbon with a relative starch mass of 1.5%~2.0%, stir and decolorize at 80°C for 0.5 hours, press filter to obtain filtrate, and filter at a temperature above 60°C;

(5) Concentration, spray drying, cooling, and packaging: vacuum concentrate the filtrate to a concentration of 40%~50% (w/w), fine filter, and dry the filtrate with a spray dryer, and then pass the material through 20°C~25°C , Cooling with cold air with a relative humidity of about 50%, to 38°C or below, and packing to obtain a low-viscosity starch octenyl succinate product.

In the above-mentioned method, before carrying out the treatment of continuous spraying high temperature, oxalic acid is used as the acidolysis catalyst, and at the gelatinization temperature of starch, the octenyl succinic acid (original) starch ester is first carried out to a certain degree of acidolysis, preferably The pH range is 2.0~2.4.

In the above method, oxalic acid is used as a catalyst for the acid hydrolysis and hydrolysis of the modified starch, and a water heater is used to continuously spray high-temperature treatment on the acid-hydrolyzed modified starch milk.

In the above method, the material after continuous spraying high-temperature treatment is kept at 90° C. to 99° C. for 1.0 to 2.5 hours in laminar flow to continue further degradation.

In the above method, oxalic acid is used as a catalyst for the acid hydrolysis and hydrolysis of modified starch, and the saturated solution of calcium hydroxide or calcium carbonate emulsion ground by a colloid mill is used for neutralization to form insoluble substances such as calcium oxalate.

In the above method, the concentrated solution is decolorized and filtered.

In the above method, the filtrate is dried with a spray dryer to obtain a low-viscosity starch octenyl succinate product.

Compared with the prior art, the present invention has the following advantages:

(1) On the basis of the original solid maltodextrin production line, the present invention can add some production equipment such as reaction kettle, feeding tank, batching tank and storage tank, and carry out certain technical transformations such as equipment and pipelines, and then it can Production and preparation of low-viscosity, water-soluble starch octenyl succinate products to achieve better economic benefits.

(2) The octenyl succinic acid (original) starch ester obtained in the previous steps of the present invention is first subjected to a certain degree of acidolysis at starch gelatinization temperature and acidic conditions, which can be used for the next step of continuous spraying high-temperature acid heat treatment, Make a certain contribution to the viscosity reduction of the system process.

(3) The present invention uses a water heater for starch liquefaction to carry out continuous jet high-temperature acid heat treatment, so that the system can quickly pass through the high-viscosity stage caused by the gelatinization process of starch or modified starch, and then pass through the laminar flow heat preservation at 90°C~99°C As a result, the modified starch is gradually degraded. According to the pH of acid heat action and the time of laminar flow insulation, the octenyl succinic acid starch ester product of low viscosity can be regulated to obtain certain DE value or fluidity range (DE is glucose value, DE value of starch is 0, glucose is 100, DE is 1 or more starch or modified starch hydrolyzate, its viscosity value will be greatly reduced compared with the original starch).

(4) The present invention uses oxalic acid as a catalyst for acid heat high temperature treatment and hydrolysis, and neutralizes with calcium hydroxide or calcium carbonate to form insoluble calcium oxalate substances, which can be removed together with activated carbon after decolorization and filtration.

(5) Vacuum concentration of the neutralized solution increases the concentration of the system, which can further solidify and precipitate solids such as calcium oxalate, and also create favorable conditions for improving the performance of the spray drying equipment.

the

Detailed ways

The present invention is implemented through the following processes:

Raw starch→add water to make slurry→raise temperature to adjust pH→add octenyl succinic anhydride for esterification reaction→neutralization→deliquoring→washing→add water to make size→add oxalic acid to adjust pH to 2.0~2.8→acidolysis reaction→hydrothermal Continuous injection of high-temperature acid heat treatment → laminar flow heat preservation → cooling → neutralization → activated carbon decolorization → pressure filtration → vacuum concentration → spray drying → cooling → packaging → low-viscosity octenyl succinic acid starch ester products.

Example 1

(1) Sizing and esterification reaction: mix 1000 dry weight parts of cornstarch with water, the milk concentration is 40.0% (w/w), the temperature is raised to 50°C, and the concentration is 10% (w/w) sodium carbonate solution Adjust the pH of the starch milk to 9.5, maintain the temperature and pH of the starch milk, add 1% (to the starch) octenyl succinic anhydride for esterification reaction for 6 hours, and neutralize the starch with a 10% (v/v) hydrochloric acid solution Milk pH to 6.0.

(2) Deliquification and washing, slurry adjustment and acidification, acidification reaction: the neutralized starch emulsion is used to remove the waste liquid with a filter press, washed with water until the conductivity of the lotion is not greater than 100μs/cm, and the filter cake is adjusted with water. Use 10% (w/w) oxalic acid solution to adjust the pH of the emulsion to 2.0, and the dry solids concentration of the emulsion to 25% (w/w), raise the temperature to 50°C, and stir for 4.0 hours to carry out acidolysis reaction.

(3) Continuous spray high temperature treatment, heat preservation treatment, and neutralization: use a water heater to perform continuous spray high temperature treatment on acid-thinned starch milk at 130°C for 5 minutes, keep it at 97°C~99°C for 2.5 hours in laminar flow, and cool down to 80°C ℃, add the calcium carbonate emulsion ground with a colloid mill, stir for 0.5 hours, then add a part of the concentration of 5.0% (w/w) sodium carbonate solution, neutralize to pH 5.6, and precipitate solid colloids such as calcium oxalate .

(4) Decolorization and filtration: add 2.0% (to starch) activated carbon, stir and decolorize at 80°C for 0.5 hour, press filter to obtain the filtrate.

(5) Concentration, spray drying, cooling, and packaging: Concentrate the solution in vacuum to a concentration of 50% (w/w), fine filter, and dry the filtrate with a spray dryer; The cold air is cooled to 35 ℃, packs, and obtains the octenyl succinic acid starch ester product of DE value 28.2.

Example 2

(1) Sizing and esterification reaction: mix 1000 dry weight parts of cornstarch with water, the milk concentration is 42.0% (w/w), the temperature is raised to 45°C, and the concentration is 10% (w/w) of sodium carbonate solution Adjust the pH of the starch milk to 9.0, maintain the temperature and pH of the starch milk, add 3% (to the starch) octenyl succinic anhydride for esterification reaction for 14 hours, and neutralize the starch with a 10% (v/v) hydrochloric acid solution Milk pH to 6.0.

(2) Deliquification and washing, slurry adjustment and acidification, acidification reaction: the neutralized starch emulsion is used to remove the waste liquid with a filter press, washed with water until the conductivity of the lotion is not greater than 100μs/cm, and the filter cake is adjusted with water. Use 10% (w/w) oxalic acid solution to adjust the pH of the emulsion to 2.5, the dry solids concentration of the emulsion is 20% (w/w), raise the temperature to 45°C, and stir for 2.0 hours for acidolysis reaction.

(3) Continuous spray high temperature treatment, heat preservation treatment, and neutralization: use a water heater to conduct continuous spray high temperature treatment on acid-thinned starch milk at 125°C for 3 minutes, keep it at 90°C~94°C for 1.0 hour in laminar flow, and cool down to 80°C ℃, add the saturated solution of calcium hydroxide ground with a colloid mill, stir, and gradually neutralize to a pH of 5.4, and precipitate solid colloids such as calcium oxalate.

(4) Decolorization and filtration: Add 1.5% (to starch) activated carbon, stir and decolorize at 80°C for 0.5 hour, press filter to obtain the filtrate.

(5) Concentration, spray drying, cooling, and packaging: Concentrate the solution in vacuum to a concentration of 43% (w/w), fine filter, and dry the filtrate with a spray dryer; The cold air is cooled to 38 ℃, packs, and obtains the octenyl succinic acid starch ester product of DE value 6.3.

Example 3

(1) Sizing and esterification reaction: mix 1000 dry weight parts of cornstarch with water, the milk concentration is 42.0% (w/w), the temperature is raised to 45°C, and the concentration is 10% (w/w) of sodium carbonate solution Adjust the pH of the starch milk to 9.0, maintain the temperature and pH of the starch milk, add 3% (to the starch) octenyl succinic anhydride for esterification reaction for 14 hours, and neutralize the starch with a 10% (v/v) hydrochloric acid solution Milk pH to 6.0.

(2) Deliquification and washing, slurry adjustment and acidification, acidification reaction: the neutralized starch emulsion is used to remove the waste liquid with a filter press, washed with water until the conductivity of the lotion is not greater than 100μs/cm, and the filter cake is adjusted with water. Use 10% (w/w) oxalic acid solution to adjust the pH of the emulsion to 2.5, the dry solids concentration of the emulsion is 20% (w/w), raise the temperature to 45°C, and stir for 2.0 hours for acidolysis reaction.

(3) Continuous spray high temperature treatment, heat preservation treatment, and neutralization: use a water heater to perform continuous spray high temperature treatment on acid-thinned starch milk at 125°C for 3 minutes, keep it at 90°C~94°C for 2.5 hours in laminar flow, and cool down to 80°C ℃, add the saturated solution of calcium hydroxide ground with a colloid mill, stir, and gradually neutralize to a pH of 5.4, and precipitate solid colloids such as calcium oxalate.

(4) Decolorization and filtration: Add 1.5% (to starch) activated carbon, stir and decolorize at 80°C for 0.5 hour, press filter to obtain the filtrate.

(5) Concentration, spray drying, cooling, and packaging: Concentrate the solution in vacuum to a concentration of 45% (w/w), fine filter, and dry the filtrate with a spray dryer; The cold air is cooled to 37 ℃, packs, and obtains the octenyl succinic acid starch ester product of DE value 9.4.

Example 4

(1) Sizing and esterification reaction: mix 1000 dry weight parts of cornstarch with water, the milk concentration is 42.0% (w/w), the temperature is raised to 45°C, and the concentration is 10% (w/w) of sodium carbonate solution Adjust the pH of the starch milk to 9.0, maintain the temperature and pH of the starch milk, add 3% (to the starch) octenyl succinic anhydride for esterification reaction for 14 hours, and neutralize the starch with a 10% (v/v) hydrochloric acid solution Milk pH to 6.0.

(2) Deliquification and washing, slurry adjustment and acidification, acidification reaction: the neutralized starch emulsion is used to remove the waste liquid with a filter press, washed with water until the conductivity of the lotion is not greater than 100μs/cm, and the filter cake is adjusted with water. Use 10% (w/w) oxalic acid solution to adjust the pH of the emulsion to 2.2, the dry solids concentration of the emulsion is 20% (w/w), raise the temperature to 45°C, and stir for 2.0 hours for acidolysis reaction.

(3) Continuous spray high temperature treatment, heat preservation treatment, neutralization: use a water heater to conduct continuous spray high temperature treatment on acid-thinned starch milk at 125°C for 5 minutes, keep it at 90°C~94°C for 2.5 hours in laminar flow, and cool down to 80°C ℃, add the saturated solution of calcium hydroxide ground with a colloid mill, stir, and gradually neutralize to a pH of 5.4, and precipitate solid colloids such as calcium oxalate.

(4) Decolorization and filtration: Add 1.5% (to starch) activated carbon, stir and decolorize at 80°C for 0.5 hour, press filter to obtain the filtrate.

(5) Concentration, spray drying, cooling, and packaging: Concentrate the solution in vacuum to a concentration of 45% (w/w), fine filter, and dry the filtrate with a spray dryer; The cold air is cooled to 36 ℃, packs, and obtains the octenyl succinic acid starch ester product of DE value 15.7.

Example 5

(1) Sizing and esterification reaction: mix 1000 dry weight parts of cornstarch with water, the milk concentration is 42.0% (w/w), the temperature is raised to 45°C, and the concentration is 10% (w/w) of sodium carbonate solution Adjust the pH of the starch milk to 9.0, maintain the temperature and pH of the starch milk, add 3% (to the starch) octenyl succinic anhydride for esterification reaction for 14 hours, and neutralize the starch with a 10% (v/v) hydrochloric acid solution Milk pH to 6.0.

(2) Deliquification and washing, slurry adjustment and acidification, acidification reaction: the neutralized starch emulsion is used to remove the waste liquid with a filter press, washed with water until the conductivity of the lotion is not greater than 100μs/cm, and the filter cake is adjusted with water. Use 10% (w/w) oxalic acid solution to adjust the pH of the emulsion to 2.0, and the dry solids concentration of the emulsion is 25% (w/w), raise the temperature to 50°C, and stir for 3.5 hours for acidolysis reaction.

(3) Continuous spray high temperature treatment, heat preservation treatment, and neutralization: use a water heater to perform continuous spray high temperature treatment on acid-thinned starch milk at 130°C for 5 minutes, keep it at 97°C~99°C for 2.5 hours in laminar flow, and cool down to 80°C ℃, add calcium percarbonate emulsion with a colloid mill, stir for 0.5 hours, and finally add part of 5.0% (w/w) sodium carbonate solution, gradually neutralize to pH 5.6, and precipitate solid colloids such as calcium oxalate.

(4) Decolorization and filtration: add 2.0% (to starch) activated carbon, stir and decolorize at 80°C for 0.5 hour, press filter to obtain the filtrate.

(5) Concentration, spray drying, cooling, and packaging: Concentrate the solution in vacuum to a concentration of 50% (w/w), fine filter, and dry the filtrate with a spray dryer; The cold air is cooled to 37 ℃, packs, and obtains the octenyl succinic acid starch ester product of DE value 26.2.

Example 6

(1) Sizing and esterification reaction: mix 1000 dry weight parts of cornstarch with water, the milk concentration is 45.0% (w/w), the temperature is raised to 40°C, and the concentration is 10% (w/w) of sodium carbonate solution Adjust the pH of the starch milk to 8.5, maintain the temperature and pH of the starch milk, add 8% (to the starch) octenyl succinic anhydride to react for 24 hours, and neutralize the starch with a 10% (v/v) hydrochloric acid solution Milk pH to 6.5.

(2) Deliquification and washing, sizing and acidification, acidification reaction: use a centrifuge to remove the waste liquid from the neutralized starch emulsion, wash with water until the conductivity of the lotion is not greater than 100μs/cm, add water to the filter cake, and use The oxalic acid solution with a concentration of 10% (w/w) adjusted the pH of the emulsion to 2.8, and the dry solid content of the emulsion was 15% (w/w). The temperature was raised to 48°C, and the acid hydrolysis reaction was carried out with stirring for 2.0 hours.

(3) Continuous spray high temperature treatment, heat preservation treatment, and neutralization: use a water heater to perform continuous spray high temperature treatment on acid-thinned starch milk at 130°C for 5 minutes, keep it at 97°C~99°C for 1.5 hours in laminar flow, and cool down to 82 ℃, add a saturated solution of calcium hydroxide ground with a colloid mill, stir, and neutralize to a pH of 5.2, and precipitate solid colloids such as calcium oxalate.

(4) Decolorization and filtration: Add 1.5% (to starch) activated carbon, stir and decolorize at 80°C for 0.5 hour, press filter to obtain the filtrate.

(5) Concentration, spray drying, cooling, and packaging: vacuum concentrate the filtrate to a concentration of 40% (w/w), fine filter, and dry the filtrate with a spray dryer; the material is passed through 25°C and a relative humidity of about 50%. The cold air is cooled to 38 ℃, packs, obtains the octenyl succinic acid starch ester product of DE value 3.1.

Example 7

(1) Sizing and esterification reaction: mix 1000 dry weight parts of cornstarch with water, the milk concentration is 45.0% (w/w), the temperature is raised to 40°C, and the concentration is 10% (w/w) of sodium carbonate solution Adjust the pH of the starch milk to 8.5, maintain the temperature and pH of the starch milk, add 8% (to the starch) octenyl succinic anhydride to react for 24 hours, and neutralize the starch with a 10% (v/v) hydrochloric acid solution Milk pH to 6.5.

(2) Deliquification and washing, sizing and acidification, acidification reaction: use a centrifuge to remove the waste liquid from the neutralized starch emulsion, wash with water until the conductivity of the lotion is not greater than 100μs/cm, add water to the filter cake, and use The oxalic acid solution with a concentration of 10% (w/w) adjusted the pH of the emulsion to 2.4, and the dry solid content of the emulsion was 15% (w/w). The temperature was raised to 48°C, and the acid hydrolysis reaction was carried out with stirring for 2.0 hours.

(3) Continuous spray high temperature treatment, heat preservation treatment, and neutralization: use a water heater to conduct continuous spray high temperature treatment on acid-thinned starch milk at 125°C for 5 minutes, keep it at 97°C~99°C for 1.5 hours in laminar flow, and cool down to 82 ℃, add calcium percarbonate emulsion with a colloid mill, stir, and gradually neutralize to pH 5.4, and precipitate solid colloids such as calcium oxalate.

(4) Decolorization and filtration: add 1.6% (to starch) activated carbon, stir and decolorize at 80°C for 0.5 hour, press filter to obtain the filtrate.

(5) Concentration, spray drying, cooling, and packaging: Concentrate the solution in vacuum to a concentration of 40% (w/w), fine filter, and dry the filtrate with a spray dryer; The cold air is cooled to 35 ℃, packs, and obtains the octenyl succinic acid starch ester product of DE value 7.6.

Example 8

(1) Sizing and esterification reaction: mix 1000 dry weight parts of cornstarch with water, the milk concentration is 45.0% (w/w), the temperature is raised to 40°C, and the concentration is 10% (w/w) of sodium carbonate solution Adjust the pH of the starch milk to 8.5, maintain the temperature and pH of the starch milk, add 8% (to the starch) octenyl succinic anhydride to react for 24 hours, and neutralize the starch with a 10% (v/v) hydrochloric acid solution Milk pH to 6.5.

(2) Deliquification and washing, sizing and acidification, acidification reaction: use a centrifuge to remove the waste liquid from the neutralized starch emulsion, wash with water until the conductivity of the lotion is not greater than 100μs/cm, add water to the filter cake, and use The oxalic acid solution with a concentration of 10% (w/w) adjusted the pH of the emulsion to 2.2, and the dry solid content of the emulsion was 15% (w/w). The temperature was raised to 48°C, and the acid hydrolysis reaction was carried out with stirring for 2.0 hours.

(3) Continuous spray high temperature treatment, heat preservation treatment, and neutralization: use a water heater to conduct continuous spray high temperature treatment on acid-thinned starch milk at 125°C for 3 minutes, keep it at 95°C~99°C for 1.0 hour in laminar flow, and cool down to 82 ℃, add and grind the calcium perhydroxide emulsion with a colloid mill, stir, and gradually neutralize to a pH of 5.4, and precipitate solid colloids such as calcium oxalate.

(4) Decolorization and filtration: add 1.6% (to starch) activated carbon, stir and decolorize at 80°C for 0.5 hour, press filter to obtain the filtrate.

(5) Concentration, spray drying, cooling, and packaging: Concentrate the solution in vacuum to a concentration of 45% (w/w), fine filter, and dry the filtrate with a spray dryer; The cold air is cooled to 38 ℃, packs, obtains the octenyl succinic acid starch ester product of DE value 12.5.

the

The technological process of using raw starch raw materials such as cassava and wheat to prepare is the same as that of corn starch raw materials, so it is omitted. The above example is a preferred embodiment of the present invention, but the embodiment of the present invention is not limited by the above embodiment, and any other changes, modifications, substitutions, combinations or simplifications that do not deviate from the spirit and principles of the present invention , all should be equivalent replacement methods, and are all included in the protection scope of the present invention.

Claims (8)

1. the acid heat of low-viscosity octenyl succinic anhydride modified starch degraded preparation method, it is characterized in that, comprise that starch is sized mixing, esterification, neutralization, de-liquid washing, the acid adjustment of sizing mixing, acidolysis reaction, continuous injection pyroprocessing, be incubated processing, neutralization, decolouring, filtration, vacuum concentration, spraying is dry, cooling and packaging step, concrete steps are as follows:

(1) size mixing, esterification: starch adds water, stirring obtains slurries, the dry substance mass concentration of slurries is 40%～45%(w/w), heat up 40 ℃ ~ 50 ℃, use concentration 10%(w/w) sodium carbonate solution to regulate the pH of starch milk be 8.5 ~ 9.5, keep temperature and the pH of starch milk, the octenyl succinic acid anhydride that stream adds relative starch quality 1% ~ 8% reacts, esterification time 6 ~ 24 hours, then uses concentration 10%(v/v) hydrochloric acid soln in and pH to 6.0 ~ 6.5 of starch milk;

(2) de-liquid washing, the acid adjustment of sizing mixing, acidification reaction: the emulsion after neutralization removes waste liquid by press filtration or centrifugal method, wash again de-liquid with water, filter cake adds water and sizes mixing, use concentration 10%(w/w) oxalic acid solution regulate ph value of emulsion, the dry substance mass concentration of emulsion is 15%～25%(w/w), be warming up to 45 ℃ ~ 50 ℃, stir and carry out acidolysis reaction, obtain the modified starch breast of acidolysis;

(3) continuous injection pyroprocessing, insulation are processed, are neutralized: with water heater, at 125 ℃ ~ 130 ℃ modified starch breasts to acidolysis, carry out the continuous injection pyroprocessing of 3 ~ 5 minutes, 90 ℃ ~ 99 ℃ underflow insulations 1.0 ~ 2.5 hours, be cooled to 80 ℃ ~ 82 ℃, the calcium hydroxide saturated solution that interpolation was ground with colloidal mill, or the calcium carbonate emulsion grinding with colloidal mill and a small amount of 10%(w/w) sodium carbonate solution, it is 5.2 ~ 5.6 that stirring is neutralized to pH, separates out caoxalate solids;

(4) decolouring, filtration: add the gac of relative starch quality 1.5% ~ 2.0%, stir decolouring 0.5 hour at 80 ℃, press filtration obtains cleaner liquid, and temperature during filtration is more than 60 ℃;

(5) concentrated, spraying is dry, cooling, pack: by filtrate vacuum concentration to concentration 40% ~ 50%(w/w), essence filter, cleaner liquid is dried with spray-dryer, material again through 20 ℃ ~ 25 ℃, the freezing air of relative humidity approximately 50% cooling, to 38 ℃ or following, packing, obtains low viscous starch octenyl succinate anhydride product.

2. the acid heat of low-viscosity octenyl succinic anhydride modified starch according to claim 1 degraded preparation method, it is characterized in that, described starch comprises W-Gum, cassava, wheat or potato ative starch, described W-Gum comprises conventional corn starch, more than one in waxy corn starch and high amylose corn starch.

3. the acid heat of low-viscosity octenyl succinic anhydride modified starch according to claim 1 and 2 degraded preparation method, it is characterized in that, when described low viscous starch octenyl succinate anhydride product application is during in field of food, the usage ratio of octenyl succinic acid anhydride can not surpass 3.0% of starch quality.

4. the acid heat of low-viscosity octenyl succinic anhydride modified starch according to claim 1 and 2 degraded preparation method, it is characterized in that, when described low viscous starch octenyl succinate anhydride product application is during in field of food, the usage ratio of octenyl succinic acid anhydride is starch quality 2.8% ~ 3.0%.

5. the acid heat of low-viscosity octenyl succinic anhydride modified starch according to claim 1 degraded preparation method, is characterized in that, in step (2), described pH value is 2.0 ~ 2.8; The described acidolysis reaction time is 2.0 ~ 4.0 hours.

6. the acid heat of low-viscosity octenyl succinic anhydride modified starch according to claim 1 degraded preparation method, is characterized in that, in step (2), described pH value is 2.0 ~ 2.4; The described acidolysis reaction time is 3.5 ~ 4.0 hours.

7. the acid heat of low-viscosity octenyl succinic anhydride modified starch according to claim 1 degraded preparation method, it is characterized in that, the catalyzer that the oxalic acid of usining is hydrolyzed as modified starch acidolysis, adopts water heater the modified starch breast of acidolysis to be carried out to the processing of continuous injection high temperature.

8. the acid heat of low-viscosity octenyl succinic anhydride modified starch according to claim 1 degraded preparation method, it is characterized in that, the catalyzer that the oxalic acid of usining is hydrolyzed as modified starch acidolysis, the calcium hydroxide saturated solution grinding with colloidal mill or the neutralization of calcium carbonate emulsion, form caoxalate indissoluble thing.