WO2023213241A1 - Hydroxypropyl starch resistant dextrin and preparation method therefor - Google Patents

Hydroxypropyl starch resistant dextrin and preparation method therefor Download PDF

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WO2023213241A1
WO2023213241A1 PCT/CN2023/091623 CN2023091623W WO2023213241A1 WO 2023213241 A1 WO2023213241 A1 WO 2023213241A1 CN 2023091623 W CN2023091623 W CN 2023091623W WO 2023213241 A1 WO2023213241 A1 WO 2023213241A1
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hydroxypropyl starch
resistant dextrin
alcohol
preparation
reaction
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PCT/CN2023/091623
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French (fr)
Chinese (zh)
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姜雄
尹忠洲
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深圳市悠阳天颂科技发展有限公司
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Publication of WO2023213241A1 publication Critical patent/WO2023213241A1/en

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    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P19/00—Preparation of compounds containing saccharide radicals
    • C12P19/04—Polysaccharides, i.e. compounds containing more than five saccharide radicals attached to each other by glycosidic bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B11/00—Preparation of cellulose ethers
    • C08B11/20—Post-etherification treatments of chemical or physical type, e.g. mixed etherification in two steps, including purification
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P19/00—Preparation of compounds containing saccharide radicals
    • C12P19/14—Preparation of compounds containing saccharide radicals produced by the action of a carbohydrase (EC 3.2.x), e.g. by alpha-amylase, e.g. by cellulase, hemicellulase
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P19/00—Preparation of compounds containing saccharide radicals
    • C12P19/20—Preparation of compounds containing saccharide radicals produced by the action of an exo-1,4 alpha-glucosidase, e.g. dextrose

Definitions

  • the invention belongs to the field of resistant dextrin preparation, and specifically relates to a hydroxypropyl starch resistant dextrin and a preparation method thereof.
  • Resistant dextrin is a non-viscous dietary fiber that cannot be digested in the small intestine, but is fermented by colon bacteria in the colon, thereby increasing the production of short-chain fatty acids and therefore beneficial to the human body.
  • Resistant dextrin fermented in the colon has a variety of benefits, such as weight control, lowering blood sugar, lowering triacylglycerols, and regulating appetite.
  • Resistant dextrin has a bland taste and non-stick texture, and has good development in health foods and beverages. potential.
  • the preparation and industrial production methods of resistant dextrin are mostly acid-thermal methods, that is, starch molecules are decomposed into pyrodextrin under the catalysis of acid, and then enzymatically digested by liquefaction enzyme and glucoamylase, and finally refined to obtain resistant dextrin.
  • this method is a random conversion mechanism, and it is difficult to control the polymerization of the product.
  • the whiteness of the obtained pyrodextrin is low.
  • the light transmittance of the material liquid is poor, and a lot of carbon is used in the refining process. The loss is large and the cost is high.
  • Chinese patent application 201210588555.3 discloses a method for co-producing resistant dextrin, ⁇ -cyclodextrin and F42 fructose syrup with high yield.
  • This process uses corn starch as raw material, and converts digestible dextrin into ⁇ -cyclodextrin through pyrogelatinization, liquefaction, and addition of cyclodextrin glycosyltransferase. It is compounded with toluene to obtain composite insoluble matter, and the toluene is filtered and recovered to obtain ⁇ -cyclodextrin; the remaining solution is saccharified by complex saccharification enzyme, separated by chromatography, and refined to obtain resistant dextrin and glucose syrup.
  • This invention can produce high-purity resistant dextrin, expand the application field of resistant dextrin, and Effectively utilizing the remaining digestible mother liquor to produce ⁇ -cyclodextrin and F42 fructose syrup greatly reduces production costs and significantly improves the utilization rate and yield of raw materials.
  • the existing technology discloses the use of microwave radiation-enzyme method to prepare resistant dextrin, which is to pretreat starch with microwave to improve the sensitivity of starch to enzymes, and then prepare resistant dextrin through enzymatic method, as shown in Chinese patent application 201911215052.
  • Resistant dextrin sugar is prepared by filtration and spray drying.
  • This invention uses a microwave method to prepare resistant dextrin. Although it improves the problem of uneven heating of the traditional acid-heat pre-processed product and improves product quality, the resistant dextrin prepared in this application has poor transparency and cannot be better fulfil requirements.
  • the patent application discloses a preparation method of hydroxypropyl starch resistant dextrin.
  • the invention uses hydroxypropyl starch as raw material, so that the prepared starch paste has high transparency, strong fluidity, weak retrogradation, high stability, It has good freeze-thaw stability.
  • Adding ⁇ -amylase for hydrolysis can effectively increase the resistant dextrin content.
  • Adding starch branching enzyme can increase the digestibility of the starch paste, thereby more effectively increasing the resistant dextrin content.
  • the resistant dextrin prepared by the present invention is tested according to the national food safety standard GB 5009.88-2014 method. Although the resistant dextrin content reaches more than 80%, there is still room for improvement.
  • the present invention aims to provide a method for preparing hydroxypropyl starch resistant dextrin with higher resistant dextrin content and high transparency.
  • the present invention proposes the following technical solutions:
  • a preparation method of hydroxypropyl starch resistant dextrin including the following steps:
  • step (2) subjecting the hydroxypropyl starch raw material treated with alcohol in step (1) to high-temperature heating to obtain char gelatinized powder of hydroxypropyl starch;
  • step (3) Cool the gelatinized powder obtained in step (2), then add water and stir, filter and wash to remove alcohol until there is no alcohol smell, and obtain an emulsion;
  • step (3) Add water to the emulsion obtained in step (3) to form an emulsion, adjust the pH to 5.5-6.5, add ⁇ -amylase, adjust the pH to 4.5-5.0 after the reaction, add glucoamylase, and continue the reaction. Sterilize after the reaction is completed to obtain the hydroxypropyl starch resistant dextrin semi-finished product;
  • step (3) The hydroxypropyl starch resistant dextrin semi-finished product obtained in step (3) is decolorized, desalted, alcohol precipitated, and then dried to obtain the hydroxypropyl starch resistant dextrin.
  • the mass fraction of hydrochloric acid described in the above step (1) is 1-2%, preferably 1.2-1.8%, more preferably 1.4-1.6%, even more preferably 1.5%.
  • the added amount of hydrochloric acid is 8-12% of the dry weight of hydroxypropyl starch; preferably 9-10%, and more preferably 10%.
  • the alcohol described in the above step (1) is one or more of monohydric alcohols or polyhydric alcohols;
  • the alcohol is selected from one or more of ethanol, ethylene glycol, 1,2-propanediol, 1,3-propanediol and glycerol.
  • the alcohol is selected from a mixture of any two of ethanol, ethylene glycol, 1,2-propanediol and glycerin.
  • the alcohol is a mixture of ethanol and 1,2-propanediol, and the volume ratio of the two is 1:1.
  • the added amount of alcohol is 20-100% of the dry weight of hydroxypropyl starch; preferably, the added amount of alcohol is hydroxypropyl starch 30-50% of the dry weight of starch; more preferably, the addition amount of the alcohol is 40% of the dry weight of hydroxypropyl starch.
  • the alcohols mentioned are all alcohols after drying treatment.
  • acid serves as a catalyst in acid-thermal reactions and can catalyze the degradation of ⁇ -1,4 glycosidic bonds of starch molecules to generate monosaccharides, disaccharides, oligosaccharides and small molecule dextrins, and the degraded small molecules are It will repolymerize at high temperatures to form ⁇ -1,4, ⁇ -1,6 or ⁇ -2,3, ⁇ -3,3, ⁇ -2,4, ⁇ -3,6, ⁇ -2,6, ⁇ -4,6 and other glycosidic bonds formed by ⁇ -2,3, ⁇ -3,3, ⁇ -2,4, ⁇ -3,6, ⁇ -2,6, ⁇ -4,6 and other glycosidic bonds It cannot be enzymatically decomposed by ⁇ -amylase and glucoamylase, so it cannot be digested and absorbed in the human small intestine, but it can be decomposed and utilized by beneficial microorganisms in the intestine, thereby having the function
  • the reducing end can further open the ring to form an aldehyde group, and the linear aldehyde group configuration and the cyclic hemiacetal configuration are Constantly switch between times to achieve balance.
  • the added post-alcohol hydroxyl group can also form an acetal or hemiacetal with the aldehyde group, shifting the above balance toward the ring-opening direction, thus reducing the number of ⁇ -1,4 glycosidic bonds and ⁇ -1,6 glycosidic bonds that can be digested. formation, thus increasing the resistant dextrin content and yield.
  • the heating temperature in the above step (2) is 150-180°C; preferably, the heating temperature is 160-175°C; further preferably, the heating temperature is 175°C.
  • the heating time is 20-120min; preferably, the heating time is 30-50min; further preferably, the heating time is 40min.
  • the heating method is steam heating, electric heating or microwave heating.
  • the temperature and time of the high-temperature reaction will significantly affect the yield and purity of resistant dextrin.
  • Starch forms small molecules after acidolysis.
  • High-temperature conditions are conducive to the repolymerization of small molecules, thereby increasing the resistance.
  • the content and yield of resistant dextrin but if the temperature is too high, the color of resistant dextrin will deepen, thus affecting the quality of resistant dextrin; in addition, the heating time will also affect the quality of resistant dextrin, and the heating time is short for small molecules.
  • the polymerization is incomplete, thereby reducing the content and yield of resistant dextrin; heating for too long will increase the content of reaction by-products, thus affecting the yield of resistant dextrin.
  • the heating temperature is controlled to 150-180°C, heating time of 30-50min significantly improves the yield and yield of resistant dextrin.
  • the cooling treatment described in the above step (3) is to cool to 30-45°C, preferably 40°C; the volume-to-mass ratio of the amount of water added to dissolve the water and the coke gelatinized powder is 3-6:1mL/mg; Preferably it is 4-5:1mL/mg; more preferably it is 5:1mL/mg.
  • the purpose of this operation is to remove alcohol for the next step of enzymatic hydrolysis.
  • the above step (3) also includes an acid-base adjustment step, that is, using sodium hydroxide to adjust the pH value to 6.5-7.
  • the volume-to-mass ratio of the amount of water added to the gelatinized powder described in the above step (4) is 2-4:1 mL/mg, preferably 3:1 mL/mg.
  • alcohol is added in the acid heat treatment step, so that the degraded small molecules can polymerize at high temperature, mainly forming ⁇ -2,3, ⁇ -3,3, ⁇ -2,4, ⁇ -3,6,
  • ⁇ -2,6 and ⁇ -4,6 There are relatively few glycosidic bonds such as ⁇ -2,6 and ⁇ -4,6, but there are relatively few ⁇ -1,4 and ⁇ -1,6 glycosidic bonds, so the content of enzymes that need to be added later and the reaction time are significantly shortened.
  • the addition amount of ⁇ -amylase described in the above step (3) is 0.05-0.08% of the dry weight of hydroxypropyl starch, the reaction temperature is 60-95°C, and the reaction time is 0.5-1h;
  • the amount of glucoamylase described in the above step (3) is 0.05-0.08% of the dry weight of hydroxypropyl starch, the reaction temperature is 50-60°C, and the reaction time is 0.25-0.5h.
  • activated carbon or large-pore resin is used for decolorization; ion exchange resin is used for desalination; alcohol precipitation is used for desugaring, and then concentrated and dried to obtain resistant dextrin with a moisture content of less than 5%.
  • the present invention first mixes hydroxypropyl starch with acid, and then performs ethanol treatment on hydroxypropyl starch. Unexpectedly, it is found that this operation can significantly increase the content and yield of resistant dextrin. increase, the quality of the finally obtained resistant dextrin is significantly higher than the effect of acid heat treatment using hydrochloric acid alone;
  • the existing resistant dextrin preparation process generally has problems such as long reaction time and dark color of the reaction product, which makes decolorization difficult.
  • uneven heating causes a large amount of starch to remain in the preparation process of reaction resistant dextrin.
  • Starch forms small molecules after acidolysis, and high temperature conditions are beneficial to small molecules.
  • a repolymerization reaction occurs, which can increase the content and yield of resistant dextrin.
  • the temperature is too high, the color of the resistant dextrin will deepen, thus affecting the quality of the resistant dextrin.
  • the heating time will also affect the resistance.
  • the quality of dextrin the polymerization of small molecules during the heating period is incomplete, thus reducing the content and yield of resistant dextrin; heating for too long will increase the content of reaction by-products, thus affecting the yield of resistant dextrin.
  • the heating temperature is controlled to 150-180°C and the heating time is 30-50 min, which significantly improves the yield and yield of resistant dextrin;
  • the method provided by the invention has high production efficiency, short overall reaction time, and is more energy-saving and environmentally friendly.
  • step (2) The hydroxypropyl starch raw material treated with alcohol in step (1) is subjected to high-temperature heating (150°C, 50 min) to obtain hydroxypropyl starch gelatinized powder;
  • step (3) Cool the gelatinized powder obtained in step (2) (30°C), then add water (mass to volume ratio: 1:3mg/mL), stir, filter and wash to remove alcohol until there is no alcohol smell, and obtain a milky form thing;
  • step (3) Add water to the emulsion obtained in step (3) to form an emulsion (mass to volume ratio is 1:2 mg/mL), adjust the pH to 5.5, and add hydroxypropyl starch dry weight 0.05% ⁇ -amylase , react at 60°C for 0.5h, adjust the pH value to 4.5 after the reaction, add hydroxypropyl starch dry weight 0.05% glucoamylase, 0.25h at 50°C, sterilize after the reaction is completed, and obtain hydroxypropyl starch resistant Sex dextrin semi-finished products;
  • step (3) The hydroxypropyl starch resistant dextrin semi-finished product obtained in step (3) is decolorized, desalted, alcohol precipitated, and then dried to obtain the hydroxypropyl starch resistant dextrin.
  • step (1) The hydroxypropyl starch raw material treated with ethanol in step (1) is subjected to high-temperature heating (180°C, 30 min) to obtain hydroxypropyl starch gelatinized powder;
  • step (3) Cool the gelatinized powder obtained in step (2) (45°C), then add water (mass to volume ratio: 1:6mg/mL), stir, filter and wash to remove alcohol until there is no alcohol smell, and obtain a milky form thing;
  • step (3) Add water to the emulsion obtained in step (3) to form an emulsion (mass to volume ratio is 1:4 mg/mL), adjust the pH to 5.5, and add 0.08% ⁇ -amylase by dry weight of hydroxypropyl starch. , react at 95°C for 1 hour, adjust the pH after the reaction When the value is 4.5, add 0.08% glucoamylase by dry weight of hydroxypropyl starch and incubate at 60°C for 0.5 hours. Sterilize after the reaction is completed to obtain the hydroxypropyl starch resistant dextrin semi-finished product;
  • step (3) The hydroxypropyl starch resistant dextrin semi-finished product obtained in step (3) is sterilized, decolorized, desalted, alcohol precipitated, and then dried to obtain the hydroxypropyl starch resistant dextrin.
  • step (2) The hydroxypropyl starch raw material treated with alcohol in step (1) is subjected to high-temperature heating (175°C, 40 min) to obtain hydroxypropyl starch gelatinized powder;
  • step (3) Cool the gelatinized powder obtained in step (2) (40°C), then add water (mass to volume ratio: 1:5 mg/mL), stir, filter and wash to remove alcohol until there is no alcohol smell, and obtain a milky form thing;
  • step (3) Add water to the emulsion obtained in step (3) to form an emulsion (mass to volume ratio is 1:3 mg/mL), adjust the pH to 5.5, and add 0.06% ⁇ -amylase by dry weight of hydroxypropyl starch. , react at 85°C for 1 hour, adjust the pH value to 4.5 after the reaction, add hydroxypropyl starch dry weight 0.06% glucoamylase, 0.3h at 60°C, sterilize after the reaction is completed, and obtain hydroxypropyl starch resistance Dextrin semi-finished products;
  • step (3) The hydroxypropyl starch resistant dextrin semi-finished product obtained in step (3) is sterilized, decolorized, desalted, alcohol precipitated, and then dried to obtain the hydroxypropyl starch resistant dextrin.
  • step (1) only hydrochloric acid with a mass fraction of 1.5% is used for treatment, and no pentanol treatment is performed.
  • Other operating steps are the same as Example 3.
  • Embodiment 2 of the prior art CN 110117628 A.
  • Embodiment 1 of the prior art CN 105543311 A.
  • the performance of the hydroxypropyl starch resistant dextrin obtained in the present invention is tested, and the water-soluble dietary fiber content and transparency are mainly tested.
  • Example 3 by controlling each The hydroxypropyl starch resistant dextrin obtained with the optimal parameters has the highest content of water-soluble dietary fiber, which can reach 93.8%.
  • Comparative Example 1 uses only one acid as a catalyst to catalyze acidolysis of starch.
  • the content of water-soluble dietary fiber in the obtained hydroxypropyl starch resistant dextrin is significantly lower than that of the Example, so that the content of resistant dextrin is reduced; Comparative Example 3 and Comparative Example 4 adopt methods disclosed in the prior art, and the content of the resistant dextrin obtained is significantly lower than that in the Examples.
  • Detection method The transmittance of resistant dextrin is detected according to the method disclosed in the TGDL1-2019 standard. The specific calculation results are shown in Table 2 below.
  • the resistant dextrin prepared in Examples 1-3 of the present invention has high transparency, indicating that the resistant dextrin prepared by the method provided by the present invention has high purity and good solubility.
  • the transparency of the resistant dextrin obtained by changing the preparation method is significantly reduced. Therefore, the performance of the resistant dextrin obtained by using the preparation method disclosed in the present invention is better.

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Abstract

The present invention belongs to the field of preparation of resistant dextrin. Provided are a hydroxypropyl starch resistant dextrin and a preparation method therefor. In the implementation process of the present invention, hydrochloric acid and alcohol are mixed to perform acid heat treatment on hydroxypropyl starch, so that the decomposition rate can be obviously increased, leading to an obvious increase in the content and yield of the resistant dextrin. In the implementation process of the present invention, it is found that the use of a mixture of 1,2-propylene glycol and ethanol, with the volume ratio of the 1,2-propylene glycol to the ethanol controlled to be 1:1, is more conducive to the re-polymerization of degraded small molecules at a high temperature to formα-2,3, α-3,3, α-2,4, α-3,6, α-2,6, α-4,6 and the like as main glycosidic bonds, thereby increasing the content of water-soluble dietary fibers in the resistant dextrin and reducing the content of small molecule sugars.

Description

一种羟丙基淀粉抗性糊精及其制备方法A kind of hydroxypropyl starch resistant dextrin and preparation method thereof 技术领域Technical field
本发明属于抗性糊精制备领域，具体涉及一种羟丙基淀粉抗性糊精及其制备方法。The invention belongs to the field of resistant dextrin preparation, and specifically relates to a hydroxypropyl starch resistant dextrin and a preparation method thereof.
背景技术Background technique
抗性糊精是一种非粘性膳食纤维，在小肠中不能消化，但是在结肠中被结肠细菌发酵，从而增加短链脂肪酸的产生，因此对人体有利。抗性糊精在结肠中发酵具有多种好处，如控制体重、降低血糖、降低三酰甘油和调节食欲等，抗性糊精口感平淡、质地不粘，在健康食品和饮料中具有良好的发展潜力。Resistant dextrin is a non-viscous dietary fiber that cannot be digested in the small intestine, but is fermented by colon bacteria in the colon, thereby increasing the production of short-chain fatty acids and therefore beneficial to the human body. Resistant dextrin fermented in the colon has a variety of benefits, such as weight control, lowering blood sugar, lowering triacylglycerols, and regulating appetite. Resistant dextrin has a bland taste and non-stick texture, and has good development in health foods and beverages. potential.
目前，抗性糊精的制备及工业化生产方法多为酸热法，即淀粉分子在酸的催化下分解成焦糊精，然后经液化酶和糖化酶酶解，最后经精制得到抗性糊精，该方法是一种随机转化机制，对产品的聚合情况不易控制，且经高温热解，所得焦糊精白度较低，经液化糖化后料液透光性较差，精制过程用碳多，损失大，成本较高，如中国专利申请201210588555.3中公开了一种高收率联产抗性糊精、β-环糊精与F42果葡糖浆的方法。该工艺以玉米淀粉为原料，经焦糊化、液化、加环糊精葡糖基转移酶将可消化糊精转化为β-环糊精，经甲苯复合得复合不溶物，过滤、回收甲苯得到β-环糊精；剩余溶液经复合糖化酶糖化、色谱分离、精制得抗性糊精和葡萄糖浆，该发明可生产出高纯度的抗性糊精，扩大抗性糊精的应用领域，并有效利用剩余的可消化母液生产β-环糊精和F42果葡糖浆，大大降低了生产成本，显著提高了原料的利用率和产率。At present, the preparation and industrial production methods of resistant dextrin are mostly acid-thermal methods, that is, starch molecules are decomposed into pyrodextrin under the catalysis of acid, and then enzymatically digested by liquefaction enzyme and glucoamylase, and finally refined to obtain resistant dextrin. , this method is a random conversion mechanism, and it is difficult to control the polymerization of the product. Moreover, after high-temperature pyrolysis, the whiteness of the obtained pyrodextrin is low. After liquefaction and saccharification, the light transmittance of the material liquid is poor, and a lot of carbon is used in the refining process. The loss is large and the cost is high. For example, Chinese patent application 201210588555.3 discloses a method for co-producing resistant dextrin, β-cyclodextrin and F42 fructose syrup with high yield. This process uses corn starch as raw material, and converts digestible dextrin into β-cyclodextrin through pyrogelatinization, liquefaction, and addition of cyclodextrin glycosyltransferase. It is compounded with toluene to obtain composite insoluble matter, and the toluene is filtered and recovered to obtain β-cyclodextrin; the remaining solution is saccharified by complex saccharification enzyme, separated by chromatography, and refined to obtain resistant dextrin and glucose syrup. This invention can produce high-purity resistant dextrin, expand the application field of resistant dextrin, and Effectively utilizing the remaining digestible mother liquor to produce β-cyclodextrin and F42 fructose syrup greatly reduces production costs and significantly improves the utilization rate and yield of raw materials.
为了提高聚合情况，现有技术公开采用微波辐射-酶法制备抗性糊精，是通过微波预处理淀粉，提高淀粉对酶的敏感性，然后经酶法制备抗性糊精，如中国专利申请201911215052.X中公开了一种利用微波制备抗性糊精的方法，包括如下步骤：(1)向淀粉干粉中加入酸溶液，搅拌均匀，制得淀粉酸处理样品；(2)淀粉酸处理样品在微波装置中进行处理，制得抗性糊精粗品；(3)将抗性糊精粗品溶解于水中，经α-耐高温淀粉酶和复合糖化酶酶解，然后经脱色、离交、纳滤、喷雾干燥制得抗性糊精糖。该发明通过采用微波法制备抗性糊精，虽然改善了传统酸热法前处理产品受热不均的问题，提高了产品品质，但是该申请制备的抗性糊精透明度不佳，不能更好地满足要求。In order to improve the polymerization, the existing technology discloses the use of microwave radiation-enzyme method to prepare resistant dextrin, which is to pretreat starch with microwave to improve the sensitivity of starch to enzymes, and then prepare resistant dextrin through enzymatic method, as shown in Chinese patent application 201911215052. Process it in a microwave device to obtain crude resistant dextrin; (3) Dissolve the crude resistant dextrin in water, enzymatically hydrolyze it with α-high temperature-resistant amylase and complex glucoamylase, and then undergo decolorization, cleaving, and sodium hydration. Resistant dextrin sugar is prepared by filtration and spray drying. This invention uses a microwave method to prepare resistant dextrin. Although it improves the problem of uneven heating of the traditional acid-heat pre-processed product and improves product quality, the resistant dextrin prepared in this application has poor transparency and cannot be better fulfil requirements.
但是现有的抗性糊精大多采用玉米淀粉、马铃薯淀粉或木薯淀粉为原料，而采用变性淀粉为原料制备抗性糊精的报道确很少，申请人2019年提交了申请号为201910383563.6的专 利申请公开了一种羟丙基淀粉抗性糊精的制备方法，该发明使用羟丙基淀粉为原料，使制得的淀粉糊透明度高、流动性强、凝沉性弱、稳定性高、冻融稳定性好，再加入α-淀粉酶进行水解，可有效提高抗性糊精含量；再加入淀粉分支酶，增加淀粉糊的耐消化性，从而更加有效提高了抗性糊精含量。本发明制备得到的抗性糊精，按食品安全国家标准GB 5009.88-2014方法检测，虽抗性糊精含量达80％以上，但依然有改进的空间。However, most of the existing resistant dextrins use corn starch, potato starch or tapioca starch as raw materials, and there are very few reports on using modified starch as raw materials to prepare resistant dextrins. The applicant submitted an application number 201910383563.6 in 2019. The patent application discloses a preparation method of hydroxypropyl starch resistant dextrin. The invention uses hydroxypropyl starch as raw material, so that the prepared starch paste has high transparency, strong fluidity, weak retrogradation, high stability, It has good freeze-thaw stability. Adding α-amylase for hydrolysis can effectively increase the resistant dextrin content. Adding starch branching enzyme can increase the digestibility of the starch paste, thereby more effectively increasing the resistant dextrin content. The resistant dextrin prepared by the present invention is tested according to the national food safety standard GB 5009.88-2014 method. Although the resistant dextrin content reaches more than 80%, there is still room for improvement.
因此，需要提供一种具有更好抗性糊精含量的羟丙基淀粉抗性糊精的制备方法。Therefore, there is a need to provide a method for preparing hydroxypropyl starch resistant dextrin with better resistant dextrin content.
发明内容Contents of the invention
基于现有技术中存在的问题，本发明旨在提供一种具有更高抗性糊精含量，透明度高的羟丙基淀粉抗性糊精的制备方法。Based on the problems existing in the prior art, the present invention aims to provide a method for preparing hydroxypropyl starch resistant dextrin with higher resistant dextrin content and high transparency.
为了解决上述问题，本发明提出以下技术方案：In order to solve the above problems, the present invention proposes the following technical solutions:
一种羟丙基淀粉抗性糊精的制备方法，包括以下步骤：A preparation method of hydroxypropyl starch resistant dextrin, including the following steps:
(1)称取羟丙基淀粉用盐酸对其进行酸处理之后，干燥至含水量为5-10％，然后对其喷洒醇，得到喷醇处理后的羟丙基淀粉原料；(1) Weigh the hydroxypropyl starch and acid-treat it with hydrochloric acid, dry it until the moisture content is 5-10%, and then spray it with alcohol to obtain the alcohol-sprayed hydroxypropyl starch raw material;
(2)将步骤(1)中喷醇处理后的羟丙基淀粉原料进行高温加热处理，得到羟丙基淀粉的焦糊化粉；(2) subjecting the hydroxypropyl starch raw material treated with alcohol in step (1) to high-temperature heating to obtain char gelatinized powder of hydroxypropyl starch;
(3)将步骤(2)中得到的焦糊化粉进行降温处理，然后加水搅拌，过滤、洗涤除醇至无醇味，得到乳状物；(3) Cool the gelatinized powder obtained in step (2), then add water and stir, filter and wash to remove alcohol until there is no alcohol smell, and obtain an emulsion;
(4)向步骤(3)中得到的乳状物加水配置成乳状液，并调整pH为5.5-6.5，加入α-淀粉酶，反应后调节pH值为4.5-5.0，加入糖化酶，继续反应，反应结束后灭菌，得到羟丙基淀粉抗性糊精半成品；(4) Add water to the emulsion obtained in step (3) to form an emulsion, adjust the pH to 5.5-6.5, add α-amylase, adjust the pH to 4.5-5.0 after the reaction, add glucoamylase, and continue the reaction. Sterilize after the reaction is completed to obtain the hydroxypropyl starch resistant dextrin semi-finished product;
(5)将步骤(3)中得到的羟丙基淀粉抗性糊精半成品进行脱色、脱盐、醇沉，然后干燥，得到所述的羟丙基淀粉抗性糊精。(5) The hydroxypropyl starch resistant dextrin semi-finished product obtained in step (3) is decolorized, desalted, alcohol precipitated, and then dried to obtain the hydroxypropyl starch resistant dextrin.
上述步骤(1)中所述的盐酸的质量分数为1-2％，优选为1.2-1.8％，再优选为1.4-1.6％，进一步优选为1.5％。The mass fraction of hydrochloric acid described in the above step (1) is 1-2%, preferably 1.2-1.8%, more preferably 1.4-1.6%, even more preferably 1.5%.
所述的盐酸的加入量为羟丙基淀粉干重的8-12％；优选为9-10％，再优选为10％。The added amount of hydrochloric acid is 8-12% of the dry weight of hydroxypropyl starch; preferably 9-10%, and more preferably 10%.
上述步骤(1)中所述的醇为一元醇或多元醇中的一种或几种；The alcohol described in the above step (1) is one or more of monohydric alcohols or polyhydric alcohols;
优选地，所述的醇选自乙醇、乙二醇、1,2-丙二醇、1,3-丙二醇和丙三醇中的一种或几种。Preferably, the alcohol is selected from one or more of ethanol, ethylene glycol, 1,2-propanediol, 1,3-propanediol and glycerol.
再优选地，所述的醇选自乙醇、乙二醇、1,2-丙二醇和丙三醇中的任意两种混合。Preferably, the alcohol is selected from a mixture of any two of ethanol, ethylene glycol, 1,2-propanediol and glycerin.
进一步优选地，所述的醇为乙醇和1,2-丙二醇的混合物，两者的体积比为1:1。Further preferably, the alcohol is a mixture of ethanol and 1,2-propanediol, and the volume ratio of the two is 1:1.
所述的醇的加入量为羟丙基淀粉干重的20-100％；优选地，所述的醇的加入量为羟丙基 淀粉干重的30-50％；再优选地，所述的醇的加入量为羟丙基淀粉干重的40％。The added amount of alcohol is 20-100% of the dry weight of hydroxypropyl starch; preferably, the added amount of alcohol is hydroxypropyl starch 30-50% of the dry weight of starch; more preferably, the addition amount of the alcohol is 40% of the dry weight of hydroxypropyl starch.
所述的醇均为经干燥处理后的醇。The alcohols mentioned are all alcohols after drying treatment.
本领域技术人员公知在酸热反应中酸作为催化剂，能够催化淀粉分子α-1,4糖苷键降解，生成单糖、双糖、低聚糖以及小分子糊精，而降解后的小分子在高温下会重新聚合，形成α-1,4、α-1,6或者α-2,3、α-3,3、α-2,4、α-3,6、α-2,6、α-4,6等其它糖苷键，形成的α-2,3、α-3,3、α-2,4、α-3,6、α-2,6、α-4,6等其它糖苷键不能被α-淀粉酶和糖化酶酶解，因此不能在人体小肠内消化吸收，但是可以被肠道内有益微生物分解利用，从而具备膳食纤维的功能；本发明在实施过程中意外地发现采用盐酸和醇对羟丙基淀粉进行酸解，能够明显提升分解和聚合速率，因而使抗性糊精含量和产率明显提高。It is well known to those skilled in the art that acid serves as a catalyst in acid-thermal reactions and can catalyze the degradation of α-1,4 glycosidic bonds of starch molecules to generate monosaccharides, disaccharides, oligosaccharides and small molecule dextrins, and the degraded small molecules are It will repolymerize at high temperatures to form α-1,4, α-1,6 or α-2,3, α-3,3, α-2,4, α-3,6, α-2,6, α -4,6 and other glycosidic bonds formed by α-2,3, α-3,3, α-2,4, α-3,6, α-2,6, α-4,6 and other glycosidic bonds It cannot be enzymatically decomposed by α-amylase and glucoamylase, so it cannot be digested and absorbed in the human small intestine, but it can be decomposed and utilized by beneficial microorganisms in the intestine, thereby having the function of dietary fiber; during the implementation of the present invention, it was unexpectedly discovered that hydrochloric acid and The acidolysis of hydroxypropyl starch by alcohol can significantly increase the decomposition and polymerization rate, thus significantly increasing the content and yield of resistant dextrin.
推测其原理为：形成的α-1,4、α-1,6糖苷键降解后，还原端可进一步开环形成醛基，并在线性的醛基构型和环形的半缩醛构型之间不断转换，达成平衡。加入的醇后羟基也可与醛基形成缩醛或半缩醛，使上述平衡朝开环方向移动，因此可减少能被消化的α-1,4糖苷键和α-1,6糖苷键的形成，从而提高了抗性糊精含量和产率。It is speculated that the principle is: after the formed α-1,4 and α-1,6 glycosidic bonds are degraded, the reducing end can further open the ring to form an aldehyde group, and the linear aldehyde group configuration and the cyclic hemiacetal configuration are Constantly switch between times to achieve balance. The added post-alcohol hydroxyl group can also form an acetal or hemiacetal with the aldehyde group, shifting the above balance toward the ring-opening direction, thus reducing the number of α-1,4 glycosidic bonds and α-1,6 glycosidic bonds that can be digested. formation, thus increasing the resistant dextrin content and yield.
上述步骤(2)中所述的加热为温度为150-180℃；优选地，所述的加热温度为160-175℃；再优选地，所述的加热温度为175℃。The heating temperature in the above step (2) is 150-180°C; preferably, the heating temperature is 160-175°C; further preferably, the heating temperature is 175°C.
所述的加热时间为20-120min；优选地，所述的加热时间为30-50min；再优选地，所述的加热时间为40min。The heating time is 20-120min; preferably, the heating time is 30-50min; further preferably, the heating time is 40min.
所述的加热方式为蒸汽加热、电加热或微波加热。The heating method is steam heating, electric heating or microwave heating.
本发明在实施过程中发现高温反应的温度和时间会明显影响抗性糊精的产率和纯度，淀粉酸解后形成小分子，高温条件下有利于小分子发生重聚反应，从而可以增加抗性糊精的含量和产率，但是温度过高会使抗性糊精的颜色加深，从而影响抗性糊精的品质；另外，加热时间也会影响抗性糊精的品质，加热时间短小分子聚合不完全，从而使抗性糊精的含量和产率降低；加热时间过长，会使反应副产物含量增加，从而影响抗性糊精的产率，本发明在实施过程中控制加热温度为150-180℃，加热时间为30-50min明显提高了抗性糊精的产率和收率。During the implementation of the present invention, it was found that the temperature and time of the high-temperature reaction will significantly affect the yield and purity of resistant dextrin. Starch forms small molecules after acidolysis. High-temperature conditions are conducive to the repolymerization of small molecules, thereby increasing the resistance. The content and yield of resistant dextrin, but if the temperature is too high, the color of resistant dextrin will deepen, thus affecting the quality of resistant dextrin; in addition, the heating time will also affect the quality of resistant dextrin, and the heating time is short for small molecules. The polymerization is incomplete, thereby reducing the content and yield of resistant dextrin; heating for too long will increase the content of reaction by-products, thus affecting the yield of resistant dextrin. During the implementation of the present invention, the heating temperature is controlled to 150-180℃, heating time of 30-50min significantly improves the yield and yield of resistant dextrin.
上述步骤(3)中所述的降温处理是降温至30-45℃，优选为40℃；所述的加水溶解的加水量与焦糊化粉的体积质量比为3-6:1mL/mg；优选为4-5:1mL/mg；再优选为5:1mL/mg。The cooling treatment described in the above step (3) is to cool to 30-45°C, preferably 40°C; the volume-to-mass ratio of the amount of water added to dissolve the water and the coke gelatinized powder is 3-6:1mL/mg; Preferably it is 4-5:1mL/mg; more preferably it is 5:1mL/mg.
此操作的目的是为了将醇除去，以便进行下一步酶解操作。The purpose of this operation is to remove alcohol for the next step of enzymatic hydrolysis.
上述步骤(3)中还包括酸碱调节步骤，即使用氢氧化钠调节pH值为6.5-7。The above step (3) also includes an acid-base adjustment step, that is, using sodium hydroxide to adjust the pH value to 6.5-7.
上述步骤(4)中所述的加水量与焦糊化粉的体积质量比为2-4:1mL/mg，优选为3:1mL/mg。 The volume-to-mass ratio of the amount of water added to the gelatinized powder described in the above step (4) is 2-4:1 mL/mg, preferably 3:1 mL/mg.
本发明在酸热处理步骤中加入了醇，可以使降解后的小分子在高温下发生聚合，主要形成α-2,3、α-3,3、α-2,4、α-3,6、α-2,6、α-4,6等糖苷键，α-1,4、α-1,6糖苷键比较少，因此后期需要加入的酶的含量以及反应时间均明显缩短。In the present invention, alcohol is added in the acid heat treatment step, so that the degraded small molecules can polymerize at high temperature, mainly forming α-2,3, α-3,3, α-2,4, α-3,6, There are relatively few glycosidic bonds such as α-2,6 and α-4,6, but there are relatively few α-1,4 and α-1,6 glycosidic bonds, so the content of enzymes that need to be added later and the reaction time are significantly shortened.
上述步骤(3)中所述的α-淀粉酶的加入量为羟丙基淀粉干重的0.05-0.08％，其反应温度为60-95℃，反应时间为0.5-1h；The addition amount of α-amylase described in the above step (3) is 0.05-0.08% of the dry weight of hydroxypropyl starch, the reaction temperature is 60-95°C, and the reaction time is 0.5-1h;
上述步骤(3)中所述的糖化酶得加入量为羟丙基淀粉干重的0.05-0.08％，其反应温度为50-60℃，反应时间为0.25-0.5h。The amount of glucoamylase described in the above step (3) is 0.05-0.08% of the dry weight of hydroxypropyl starch, the reaction temperature is 50-60°C, and the reaction time is 0.25-0.5h.
上述步骤(5)中所述的灭菌、脱色、脱盐、醇沉、浓缩干燥，均为本领域常规操作。The sterilization, decolorization, desalination, alcohol precipitation, concentration and drying described in the above step (5) are all routine operations in this field.
即采用活性炭或大孔径树脂进行脱色；采用离子交换树脂进行脱盐；采用酒精沉淀进行脱糖，然后浓缩干燥得到含水量小于5％的抗性糊精。That is, activated carbon or large-pore resin is used for decolorization; ion exchange resin is used for desalination; alcohol precipitation is used for desugaring, and then concentrated and dried to obtain resistant dextrin with a moisture content of less than 5%.
与现有技术相比，本发明的有益效果在于：Compared with the prior art, the beneficial effects of the present invention are:
(1)本发明在酸热处理步骤中先将羟丙基淀粉与酸混合后，然后又对羟丙基淀粉进行了喷醇处理，意外地发现该操作能够使抗性糊精含量和产率明显增加，最终得到的抗性糊精的质量明显高于单独使用盐酸进行酸热处理的效果；(1) In the acid heat treatment step, the present invention first mixes hydroxypropyl starch with acid, and then performs ethanol treatment on hydroxypropyl starch. Unexpectedly, it is found that this operation can significantly increase the content and yield of resistant dextrin. increase, the quality of the finally obtained resistant dextrin is significantly higher than the effect of acid heat treatment using hydrochloric acid alone;
(2)本发明在实施过程中发现使用1,2-丙二醇和乙二醇的混合物，且控制两者的体积比为1:1，更有利于降解后的小分子在高温下会重新聚合，形成α-2,3、α-3,3、α-2,4、α-3,6、α-2,6、α-4,6等其它糖苷键，从而提高抗性糊精中水溶性膳食纤维含量，本发明公开的制备方法得到的抗性糊精颗粒比较小，颗粒的比表面积，水溶性好，从而使得抗性糊精的透明度提高；(2) During the implementation of the present invention, it was found that using a mixture of 1,2-propanediol and ethylene glycol, and controlling the volume ratio of the two to 1:1, is more conducive to the repolymerization of degraded small molecules at high temperatures. Form other glycosidic bonds such as α-2,3, α-3,3, α-2,4, α-3,6, α-2,6, α-4,6, etc., thereby improving the water solubility of resistant dextrin Dietary fiber content, the resistant dextrin particles obtained by the preparation method disclosed in the present invention are relatively small, the specific surface area of the particles, and water solubility are good, thereby improving the transparency of the resistant dextrin;
(3)现有的抗性糊精制备工艺普遍存在反应时间较长，反应产物颜色深导致脱色困难的问题，并且还会由于加热不均匀导致反应抗性糊精制备过程中残留大量的淀粉，从而影响产品在食品中的使用；本发明在实施过程中发现高温反应的温度和时间会明显影响抗性糊精的产率和纯度，淀粉酸解后形成小分子，高温条件下有利于小分子发生重聚反应，从而可以增加抗性糊精的含量和产率，但是温度过高会使抗性糊精的颜色加深，从而影响抗性糊精的品质；同时，加热时间也会影响抗性糊精的品质，加热时间段小分子聚合不完全，从而使抗性糊精的含量和产率降低；加热时间过长，会使反应副产物含量增加，从而影响抗性糊精的产率，本发明在实施过程中控制加热温度为150-180℃，加热时间为30-50min明显提高了抗性糊精的产率和收率；(3) The existing resistant dextrin preparation process generally has problems such as long reaction time and dark color of the reaction product, which makes decolorization difficult. In addition, uneven heating causes a large amount of starch to remain in the preparation process of reaction resistant dextrin. Thereby affecting the use of the product in food; during the implementation of the present invention, it was found that the temperature and time of the high-temperature reaction will significantly affect the yield and purity of resistant dextrin. Starch forms small molecules after acidolysis, and high temperature conditions are beneficial to small molecules. A repolymerization reaction occurs, which can increase the content and yield of resistant dextrin. However, if the temperature is too high, the color of the resistant dextrin will deepen, thus affecting the quality of the resistant dextrin. At the same time, the heating time will also affect the resistance. Regarding the quality of dextrin, the polymerization of small molecules during the heating period is incomplete, thus reducing the content and yield of resistant dextrin; heating for too long will increase the content of reaction by-products, thus affecting the yield of resistant dextrin. During the implementation process of the present invention, the heating temperature is controlled to 150-180°C and the heating time is 30-50 min, which significantly improves the yield and yield of resistant dextrin;
(4)本发明提供的方法，生产效率高，整体反应时间短，更加节能环保。(4) The method provided by the invention has high production efficiency, short overall reaction time, and is more energy-saving and environmentally friendly.
具体实施方式 Detailed ways
下面结合具体实施例，对本发明作进一步详细的阐述，下述实施例不用于限制本发明，仅用于说明本发明。以下实施例中所使用的实验方法如无特殊说明，实施例中未注明具体条件的实验方法，通常按照常规条件，下述实施例中所使用的材料、试剂等，如无特殊说明，均可从商业途径得到。The present invention will be further described in detail below with reference to specific examples. The following examples are not used to limit the present invention, but are only used to illustrate the present invention. Unless otherwise specified, the experimental methods used in the following examples are generally in accordance with conventional conditions. Unless otherwise specified, the experimental methods used in the examples are generally in accordance with conventional conditions. Unless otherwise specified, the materials, reagents, etc. used in the following examples are all Available commercially.
实施例1一种羟丙基淀粉抗性糊精的制备方法Example 1 Preparation method of hydroxypropyl starch resistant dextrin
包括以下步骤：Includes the following steps:
(1)称取羟丙基淀粉用1％盐酸对其进行酸处理(加入量为羟丙基淀粉干重的8％)之后，干燥至含水量为5％，然后对其喷洒干燥后的乙醇(加入量为羟丙基淀粉干重的30％)，得到喷醇处理后的羟丙基淀粉原料；(1) Weigh the hydroxypropyl starch and acid-treat it with 1% hydrochloric acid (the addition amount is 8% of the dry weight of hydroxypropyl starch), dry it until the moisture content is 5%, and then spray it with dried ethanol. (The addition amount is 30% of the dry weight of hydroxypropyl starch) to obtain the pentanol-treated hydroxypropyl starch raw material;
(2)将步骤(1)中喷醇处理后的羟丙基淀粉原料进行高温加热(150℃，50min)处理，得到羟丙基淀粉的焦糊化粉；(2) The hydroxypropyl starch raw material treated with alcohol in step (1) is subjected to high-temperature heating (150°C, 50 min) to obtain hydroxypropyl starch gelatinized powder;
(3)将步骤(2)中得到的焦糊化粉进行降温(30℃)处理，然后加水(质量体积比为1:3mg/mL)搅拌，过滤、洗涤除醇至无醇味，得到乳状物；(3) Cool the gelatinized powder obtained in step (2) (30°C), then add water (mass to volume ratio: 1:3mg/mL), stir, filter and wash to remove alcohol until there is no alcohol smell, and obtain a milky form thing;
(4)向步骤(3)中得到的乳状物加水配置成乳状液(质量体积比为1:2mg/mL)，并调整pH为5.5，加入羟丙基淀粉干重0.05％的α-淀粉酶，60℃条件下反应0.5h，反应后调节pH值为4.5，加入羟丙基淀粉干重0.05％的糖化酶，50℃条件下应0.25h，反应结束后灭菌，得到羟丙基淀粉抗性糊精半成品；(4) Add water to the emulsion obtained in step (3) to form an emulsion (mass to volume ratio is 1:2 mg/mL), adjust the pH to 5.5, and add hydroxypropyl starch dry weight 0.05% α-amylase , react at 60°C for 0.5h, adjust the pH value to 4.5 after the reaction, add hydroxypropyl starch dry weight 0.05% glucoamylase, 0.25h at 50°C, sterilize after the reaction is completed, and obtain hydroxypropyl starch resistant Sex dextrin semi-finished products;
(5)将步骤(3)中得到的羟丙基淀粉抗性糊精半成品进行脱色、脱盐、醇沉，然后干燥，得到所述的羟丙基淀粉抗性糊精。(5) The hydroxypropyl starch resistant dextrin semi-finished product obtained in step (3) is decolorized, desalted, alcohol precipitated, and then dried to obtain the hydroxypropyl starch resistant dextrin.
实施例2一种羟丙基淀粉抗性糊精的制备方法Example 2 Preparation method of hydroxypropyl starch resistant dextrin
包括以下步骤：Includes the following steps:
(1)称取羟丙基淀粉用2％盐酸对其进行酸处理(加入量为羟丙基淀粉干重的12％)之后，干燥至含水量为5％，然后对其喷洒干燥后的1,2-丙二醇(加入量为羟丙基淀粉干重的100％)，得到喷醇处理后的羟丙基淀粉原料；(1) Weigh the hydroxypropyl starch and acid-treat it with 2% hydrochloric acid (the amount added is 12% of the dry weight of hydroxypropyl starch), dry it until the moisture content is 5%, and then spray the dried 1 , 2-propanediol (the amount added is 100% of the dry weight of hydroxypropyl starch) to obtain the hydroxypropyl starch raw material after pentanol treatment;
(2)将步骤(1)中喷醇处理后的羟丙基淀粉原料进行高温加热(180℃，30min)处理，得到羟丙基淀粉的焦糊化粉；(2) The hydroxypropyl starch raw material treated with ethanol in step (1) is subjected to high-temperature heating (180°C, 30 min) to obtain hydroxypropyl starch gelatinized powder;
(3)将步骤(2)中得到的焦糊化粉进行降温(45℃)处理，然后加水(质量体积比为1:6mg/mL)搅拌，过滤、洗涤除醇至无醇味，得到乳状物；(3) Cool the gelatinized powder obtained in step (2) (45°C), then add water (mass to volume ratio: 1:6mg/mL), stir, filter and wash to remove alcohol until there is no alcohol smell, and obtain a milky form thing;
(4)向步骤(3)中得到的乳状物加水配置成乳状液(质量体积比为1:4mg/mL)，并调整pH为5.5，加入羟丙基淀粉干重0.08％的α-淀粉酶，95℃条件下反应1h，反应后调节pH 值为4.5，加入羟丙基淀粉干重0.08％的糖化酶，60℃条件下应0.5h，反应结束后灭菌，得到羟丙基淀粉抗性糊精半成品；(4) Add water to the emulsion obtained in step (3) to form an emulsion (mass to volume ratio is 1:4 mg/mL), adjust the pH to 5.5, and add 0.08% α-amylase by dry weight of hydroxypropyl starch. , react at 95°C for 1 hour, adjust the pH after the reaction When the value is 4.5, add 0.08% glucoamylase by dry weight of hydroxypropyl starch and incubate at 60°C for 0.5 hours. Sterilize after the reaction is completed to obtain the hydroxypropyl starch resistant dextrin semi-finished product;
(5)将步骤(3)中得到的羟丙基淀粉抗性糊精半成品进行灭菌、脱色、脱盐、醇沉，然后干燥，得到所述的羟丙基淀粉抗性糊精。(5) The hydroxypropyl starch resistant dextrin semi-finished product obtained in step (3) is sterilized, decolorized, desalted, alcohol precipitated, and then dried to obtain the hydroxypropyl starch resistant dextrin.
实施例3一种羟丙基淀粉抗性糊精的制备方法Example 3 Preparation method of hydroxypropyl starch resistant dextrin
包括以下步骤：Includes the following steps:
(1)称取羟丙基淀粉用1.5％盐酸对其进行酸处理(加入量为羟丙基淀粉干重的10％)之后，干燥至含水量为5％，然后对其喷洒干燥后的1,2-丙二醇和乙醇的混合物(两者体积比为1:1，加入量为羟丙基淀粉干重的40％)，得到喷醇处理后的羟丙基淀粉原料；(1) Weigh the hydroxypropyl starch and acid-treat it with 1.5% hydrochloric acid (the addition amount is 10% of the dry weight of hydroxypropyl starch), dry it until the moisture content is 5%, and then spray the dried 1 , a mixture of 2-propanediol and ethanol (the volume ratio of the two is 1:1, the addition amount is 40% of the dry weight of hydroxypropyl starch), and the hydroxypropyl starch raw material after pentanol treatment is obtained;
(2)将步骤(1)中喷醇处理后的羟丙基淀粉原料进行高温加热(175℃，40min)处理，得到羟丙基淀粉的焦糊化粉；(2) The hydroxypropyl starch raw material treated with alcohol in step (1) is subjected to high-temperature heating (175°C, 40 min) to obtain hydroxypropyl starch gelatinized powder;
(3)将步骤(2)中得到的焦糊化粉进行降温(40℃)处理，然后加水(质量体积比为1:5mg/mL)搅拌，过滤、洗涤除醇至无醇味，得到乳状物；(3) Cool the gelatinized powder obtained in step (2) (40°C), then add water (mass to volume ratio: 1:5 mg/mL), stir, filter and wash to remove alcohol until there is no alcohol smell, and obtain a milky form thing;
(4)向步骤(3)中得到的乳状物加水配置成乳状液(质量体积比为1:3mg/mL)，并调整pH为5.5，加入羟丙基淀粉干重0.06％的α-淀粉酶，85℃条件下反应1h，反应后调节pH值为4.5，加入羟丙基淀粉干重0.06％的糖化酶，60℃条件下应0.3h，反应结束后灭菌，得到羟丙基淀粉抗性糊精半成品；(4) Add water to the emulsion obtained in step (3) to form an emulsion (mass to volume ratio is 1:3 mg/mL), adjust the pH to 5.5, and add 0.06% α-amylase by dry weight of hydroxypropyl starch. , react at 85°C for 1 hour, adjust the pH value to 4.5 after the reaction, add hydroxypropyl starch dry weight 0.06% glucoamylase, 0.3h at 60°C, sterilize after the reaction is completed, and obtain hydroxypropyl starch resistance Dextrin semi-finished products;
(5)将步骤(3)中得到的羟丙基淀粉抗性糊精半成品进行灭菌、脱色、脱盐、醇沉，然后干燥，得到所述的羟丙基淀粉抗性糊精。(5) The hydroxypropyl starch resistant dextrin semi-finished product obtained in step (3) is sterilized, decolorized, desalted, alcohol precipitated, and then dried to obtain the hydroxypropyl starch resistant dextrin.
对比例1Comparative example 1
与实施例3的区别在于：步骤(1)中仅使用质量分数为1.5％的盐酸处理，不进行喷醇处理，其他操作步骤与实施例3相同。The difference from Example 3 is that in step (1), only hydrochloric acid with a mass fraction of 1.5% is used for treatment, and no pentanol treatment is performed. Other operating steps are the same as Example 3.
对比例2Comparative example 2
现有技术CN 110117628 A中实施例2公开的方法。The method disclosed in Embodiment 2 of the prior art CN 110117628 A.
对比例3Comparative example 3
现有技术CN 105543311 A中实施例1公开的方法。The method disclosed in Embodiment 1 of the prior art CN 105543311 A.
对本发明得到的羟丙基淀粉抗性糊精进行性能检测，主要对水溶性膳食纤维含量以及透明度进行检测。The performance of the hydroxypropyl starch resistant dextrin obtained in the present invention is tested, and the water-soluble dietary fiber content and transparency are mainly tested.
试验例1抗性糊精的含量检测Test Example 1 Content Detection of Resistant Dextrin
根据GB 5009.88-2014中公开的方法对实施例1-3以及对比例1-3制备的羟丙基淀粉抗性 糊精样品进行检测，检测结果见下表1。Resistance of hydroxypropyl starch prepared according to the method disclosed in GB 5009.88-2014 in Examples 1-3 and Comparative Examples 1-3 Dextrin samples were tested, and the test results are shown in Table 1 below.
表1
Table 1
根据上表1的检测结果可以看出，本发明实施例1-3制备的羟丙基淀粉抗性糊精中水溶性膳食纤维的含量较高，均在92％以上，实施例3通过控制各个参数为最优值得到的羟丙基淀粉抗性糊精中水溶性膳食纤维的含量最高，可以达到93.8％。对比例1仅使用一种酸作为催化剂对淀粉进行催化酸解，得到的羟丙基淀粉抗性糊精中水溶性膳食纤维的含量将实施例显著降低，使抗性糊精含量降低；对比例3和对比例4采用现有技术中公开的方法，得到的抗性糊精的含量较实施例出现明显降低。According to the test results in Table 1 above, it can be seen that the content of water-soluble dietary fiber in the hydroxypropyl starch resistant dextrin prepared in Examples 1-3 of the present invention is relatively high, all above 92%. In Example 3, by controlling each The hydroxypropyl starch resistant dextrin obtained with the optimal parameters has the highest content of water-soluble dietary fiber, which can reach 93.8%. Comparative Example 1 uses only one acid as a catalyst to catalyze acidolysis of starch. The content of water-soluble dietary fiber in the obtained hydroxypropyl starch resistant dextrin is significantly lower than that of the Example, so that the content of resistant dextrin is reduced; Comparative Example 3 and Comparative Example 4 adopt methods disclosed in the prior art, and the content of the resistant dextrin obtained is significantly lower than that in the Examples.
试验例2抗性糊精的透光率检测Test Example 2 Light transmittance detection of resistant dextrin
检测方法：按照TGDL1-2019标准中公开的方法对抗性糊精的透光度进行检测，具体计算结果见下表2。Detection method: The transmittance of resistant dextrin is detected according to the method disclosed in the TGDL1-2019 standard. The specific calculation results are shown in Table 2 below.
表2
Table 2
根据上表2的检测数据可以看出本发明实施例1-3中制备的抗性糊精具有较高的透明度，说明通过本发明提供的方法制备的抗性糊精纯度高、溶解性好，而对比例1-3改变制备方法得到的抗性糊精的透明度明显降低，因此采用本发明公开的制备方法得到的抗性糊精性能更优异。According to the test data in Table 2 above, it can be seen that the resistant dextrin prepared in Examples 1-3 of the present invention has high transparency, indicating that the resistant dextrin prepared by the method provided by the present invention has high purity and good solubility. In Comparative Examples 1-3, the transparency of the resistant dextrin obtained by changing the preparation method is significantly reduced. Therefore, the performance of the resistant dextrin obtained by using the preparation method disclosed in the present invention is better.
以上所述，为本发明的具体实施方式，但本发明的保护范围并不局限于此，任何熟悉本技术领域的技术人员在本发明揭露的技术范围内，可轻易想到各种等效的修改或替换，这些修改或替换都应涵盖在本发明的保护范围之内。因此，本发明的保护范围应以权利要求的保护范围为准。 The above are specific embodiments of the present invention, but the protection scope of the present invention is not limited thereto. Any person familiar with the technical field can easily think of various equivalent modifications within the technical scope disclosed in the present invention. Or replacement, these modifications or replacements should be covered by the protection scope of the present invention. Therefore, the protection scope of the present invention should be subject to the protection scope of the claims.

Claims (10)

  1. 一种羟丙基淀粉抗性糊精的制备方法，其特征在于：包括以下步骤：A method for preparing hydroxypropyl starch resistant dextrin, which is characterized in that it includes the following steps:
    (1)称取羟丙基淀粉用盐酸对其进行酸处理之后，干燥至含水量为5-10％，然后对其喷洒醇，得到喷醇处理后的羟丙基淀粉原料；(1) Weigh the hydroxypropyl starch and acid-treat it with hydrochloric acid, dry it until the moisture content is 5-10%, and then spray it with alcohol to obtain the alcohol-sprayed hydroxypropyl starch raw material;
    (2)将步骤(1)中喷醇处理后的羟丙基淀粉原料进行高温加热处理，得到羟丙基淀粉的焦糊化粉；(2) subjecting the hydroxypropyl starch raw material treated with alcohol in step (1) to high-temperature heating to obtain char gelatinized powder of hydroxypropyl starch;
    (3)将步骤(2)中得到的焦糊化粉进行降温处理，然后加水搅拌，过滤、洗涤除醇至无醇味，得到乳状物；(3) Cool the gelatinized powder obtained in step (2), then add water and stir, filter and wash to remove alcohol until there is no alcohol smell, and obtain an emulsion;
    (4)向步骤(3)中得到的乳状物加水配置成乳状液，并调整pH为5.5-6.5，加入α-淀粉酶，反应后调节pH值为4.5-5.0，加入糖化酶，继续反应，反应结束后灭菌，得到羟丙基淀粉抗性糊精半成品；(4) Add water to the emulsion obtained in step (3) to form an emulsion, adjust the pH to 5.5-6.5, add α-amylase, adjust the pH to 4.5-5.0 after the reaction, add glucoamylase, and continue the reaction. Sterilize after the reaction is completed to obtain the hydroxypropyl starch resistant dextrin semi-finished product;
    (5)将步骤(3)中得到的羟丙基淀粉抗性糊精半成品进行脱色、脱盐、醇沉，然后干燥，得到所述的羟丙基淀粉抗性糊精。(5) The hydroxypropyl starch resistant dextrin semi-finished product obtained in step (3) is decolorized, desalted, alcohol precipitated, and then dried to obtain the hydroxypropyl starch resistant dextrin.
  2. 根据权利要求1所述的制备方法，其特征在于：步骤(1)中所述的盐酸的质量分数为1-2％；所述的盐酸的加入量为羟丙基淀粉干重的8-12％。The preparation method according to claim 1, characterized in that: the mass fraction of hydrochloric acid described in step (1) is 1-2%; the added amount of hydrochloric acid is 8-12% of the dry weight of hydroxypropyl starch %.
  3. 根据权利要求1所述的制备方法，其特征在于：步骤(1)中所述的醇为一元醇或多元醇中的一种或几种。The preparation method according to claim 1, characterized in that: the alcohol described in step (1) is one or more of monohydric alcohols or polyhydric alcohols.
  4. 根据权利要求3所述的制备方法，其特征在于：所述的醇选自乙醇、乙二醇、1,2-丙二醇、1,3-丙二醇和丙三醇中的任意两种混合。The preparation method according to claim 3, characterized in that the alcohol is selected from a mixture of any two of ethanol, ethylene glycol, 1,2-propanediol, 1,3-propanediol and glycerin.
  5. 根据权利要求4所述的制备方法，其特征在于：所述的醇为1,2-丙二醇和乙醇的混合物，两者的体积比为1:1。The preparation method according to claim 4, characterized in that: the alcohol is a mixture of 1,2-propanediol and ethanol, and the volume ratio of the two is 1:1.
  6. 根据权利要求1所述的制备方法，其特征在于：所述的醇的加入量为羟丙基淀粉干重的20-100％。The preparation method according to claim 1, characterized in that: the addition amount of the alcohol is 20-100% of the dry weight of hydroxypropyl starch.
  7. 根据权利要求1所述的制备方法，其特征在于：步骤(2)中所述的加热为温度为150-180℃；所述的加热时间为20-120min。The preparation method according to claim 1, characterized in that: the heating temperature in step (2) is 150-180°C; the heating time is 20-120 min.
  8. 根据权利要求1所述的制备方法，其特征在于：步骤(3)中所述的降温处理是降温至30-45℃；所述的加水溶解的加水量与焦糊化粉的体积质量比为3-6:1mL/mg。The preparation method according to claim 1, characterized in that: the cooling treatment in step (3) is to cool to 30-45°C; the volume-to-mass ratio of the amount of water added to dissolve the water and the coke gelatinized powder is 3-6:1mL/mg.
  9. 根据权利要求1所述的制备方法，其特征在于：步骤(4)中所述的加水量与焦糊化粉的体积质量比为2-4:1mL/mg。 The preparation method according to claim 1, characterized in that: the volume-to-mass ratio of the amount of water added in step (4) to the char gelatinized powder is 2-4:1 mL/mg.
  10. 根据权利要求1所述的制备方法，其特征在于：步骤(3)中所述的α-淀粉酶的加入量为羟丙基淀粉干重的0.05-0.08％，其反应温度为60-95℃，反应时间为0.5-1h；所述的糖化酶得加入量为羟丙基淀粉干重的0.05-0.08％，其反应温度为50-60℃，反应时间为0.25-0.5h。 The preparation method according to claim 1, characterized in that: the addition amount of α-amylase in step (3) is 0.05-0.08% of the dry weight of hydroxypropyl starch, and the reaction temperature is 60-95°C , the reaction time is 0.5-1h; the added amount of the glucoamylase is 0.05-0.08% of the dry weight of hydroxypropyl starch, the reaction temperature is 50-60°C, and the reaction time is 0.25-0.5h.
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