阅读说明：本技术 一种β-环糊精的制备工艺 (Preparation process of beta-cyclodextrin ) 是由 楼志华 周立 张培东 丁红辉 于 2020-07-27 设计创作，主要内容包括：本发明公开了一种β-环糊精的制备工艺,本申请先将淀粉与水混合成淀粉乳,再添加耐高温的α-淀粉酶进行液化,将淀粉转化为糊精和低聚糖,增加淀粉的可溶性；在液化过程中,本申请采用喷射蒸煮的方式进行,该方法大大降低了能耗,淀粉的水解效率也大大提高。在液化后,本申请又采取了层流的方式进行组分分离,将水解过程中产生的蛋白作为固形物分离,同时还能进一步促进淀粉转化,提高淀粉转化率,降低液化液中含有的杂质；本申请以连续高温喷射和闪蒸层流相结合的方式、并控制DE值,能够使淀粉有效液化,与常规加工工艺相比,淀粉转化率得到提高；液化步骤可连续进行,有利于连续规模化生产。(The invention discloses a preparation process of beta-cyclodextrin, which comprises the steps of mixing starch and water into starch milk, adding high-temperature-resistant alpha-amylase for liquefaction, converting the starch into dextrin and oligosaccharide, and increasing the solubility of the starch; in the liquefaction process, the method is carried out in a jet cooking mode, the energy consumption is greatly reduced, and the hydrolysis efficiency of starch is also greatly improved. After liquefaction, the method adopts a laminar flow mode to separate components, separates proteins generated in the hydrolysis process as solid matters, and can further promote starch conversion, improve the starch conversion rate and reduce impurities contained in the liquefied liquid; the method combines the continuous high-temperature injection and the flash evaporation laminar flow, and controls the DE value, so that the starch can be effectively liquefied, and compared with the conventional processing technology, the starch conversion rate is improved; the liquefaction step can be continuously carried out, which is beneficial to continuous large-scale production.)

1. A preparation process of beta-cyclodextrin is characterized by comprising the following steps: the method comprises the following steps:

1) starch liquefaction;

2) converting with invertase;

3) converting compound enzyme;

4) decolorizing and filtering;

5) electrodialysis separation;

6) evaporating, concentrating, crystallizing, centrifuging and drying to obtain the beta-cyclodextrin.

2. The process according to claim 1, wherein the beta-cyclodextrin is prepared by the following steps: the method comprises the following steps:

1) starch liquefaction: mixing starch and water, preparing starch slurry, adjusting pH to 5.4-5.8, adding alpha-amylase, mixing, liquefying, controlling DE value to 2-4, and inactivating enzyme to obtain liquefied solution;

2) converting with invertase: cooling the liquefied liquid to 55-60 ℃, adding branch chain amylase and beta-CGTase, adding cyclohexane, fully reacting for 12-15h, heating to 95-100 ℃, and distilling and recovering the cyclohexane to obtain a conversion liquid;

3) compound enzyme conversion: taking the conversion solution, adding complex enzyme and saccharifying enzyme, converting for 3-6h, and inactivating enzyme to obtain mixed solution;

4) and (3) decoloring and filtering: adding activated carbon into the mixed solution, stirring and decolorizing, and filtering with a plate frame to obtain a decolorized solution;

5) electrodialysis separation: taking the decolorized solution, performing electrodialysis, and separating to obtain a weak solution containing beta-cyclodextrin and a thick solution containing gluconic acid;

6) taking the light liquid containing the beta-cyclodextrin, evaporating, concentrating, crystallizing, centrifuging and drying to obtain the beta-cyclodextrin.

3. The process for preparing beta-cyclodextrin according to claim 2, wherein: the method comprises the following steps:

1) starch liquefaction: taking starch and water, mixing uniformly, preparing starch slurry, adjusting the pH value to 5.4-5.8, adding alpha-amylase, mixing uniformly, heating to 105-;

2) converting with invertase: cooling the liquefied liquid to 55-60 ℃, adding branch chain amylase and beta-CGTase, adding cyclohexane, fully reacting for 12-15h, heating to 95-100 ℃, and distilling and recovering the cyclohexane to obtain a conversion liquid;

3) compound enzyme conversion: adding catalase, glucose oxidase and glucoamylase into the conversion solution, converting the pH value to 5.5-6.5, converting the temperature to 45-55 ℃, converting for 3-6h, and inactivating the enzyme to obtain a mixed solution;

4) and (3) decoloring and filtering: adding activated carbon into the mixed solution, decolorizing for 60-80min, and filtering with plate frame to obtain decolorized solution;

5) electrodialysis separation: taking a decolorized solution, performing electrodialysis until the conductance value of an electrodialysis weak solution is less than or equal to 1000us/cm, and separating to obtain a weak solution containing beta-cyclodextrin and a concentrated solution containing gluconic acid;

6) taking the light liquid containing the beta-cyclodextrin, evaporating and concentrating at 68-75 ℃, stopping concentrating when the concentration is carried out until the dry matter content is 50-60%, crystallizing, and centrifugally drying to obtain the beta-cyclodextrin.

4. The process according to claim 3, wherein the beta-cyclodextrin is prepared by the following steps: in the step 3), the adding amount of the saccharifying enzyme is 0.1-0.3% of the mass of the starch, the adding amount of the glucose oxidase is 1-1.5% of the mass of the starch, and the adding amount of the catalase is 1.5-3% of the mass of the starch.

5. The process according to claim 3, wherein the beta-cyclodextrin is prepared by the following steps: and 5), concentrating the concentrated solution containing the gluconic acid to 50% -60% to obtain a finished product of the gluconic acid.

6. The process according to claim 3, wherein the beta-cyclodextrin is prepared by the following steps: in the step 2), the branch chain amylase is pullulanase and isoamylase; the addition amount of the branch chain amylase is 2.5-3.0% of the mass of the starch.

7. The process according to claim 3, wherein the beta-cyclodextrin is prepared by the following steps: in the step 2), the addition amount of the beta-CGT enzyme is 2.5-5% of the mass of the starch; the addition amount of the cyclohexane is 3-10% of the mass of the starch.

8. The process according to claim 3, wherein the beta-cyclodextrin is prepared by the following steps: in the step 1), the addition amount of the alpha-amylase is 0.02-0.04% of the starch.

9. The process according to claim 3, wherein the beta-cyclodextrin is prepared by the following steps: in the step 1), the starch is any one or mixture of corn starch, potato starch and cassava starch.

Technical Field

The invention relates to the technical field of cyclodextrin production, in particular to a preparation process of beta-cyclodextrin.

Background

Cyclodextrin (beta-cyclodextrin, beta-CD for short) is a product generated by acidolysis and cyclization of starch. The beta-cyclodextrin is a cyclic substance which is prepared by extracting starch after the action of microbial enzyme and is formed by combining 7 glucose residues with beta-1, 4-glycosidic bonds, and has relative molecular mass 1135.

The current preparation process of beta-cyclodextrin has the following disadvantages: aiming at the problems of high preparation cost, low yield and low purity of the prepared beta-cyclodextrin and low overall conversion rate of starch, the applicant finds that the application number 201210588555.3 applies for a Chinese patent application of a publication number CN103045701A named 'a method for co-producing resistant dextrin, beta-cyclodextrin and F42 fructose syrup with high yield', the high-purity resistant dextrin can be produced, the residual digestible mother liquor is effectively utilized to produce the beta-cyclodextrin and the F42 fructose syrup, and the utilization rate and the yield of raw materials are improved. However, the main purpose of this solution is to produce high purity resistant dextrin, not specifically for the production of β -cyclodextrin, and the above prior art problems cannot be solved.

Disclosure of Invention

The invention aims to provide a preparation process of beta-cyclodextrin, which improves the starch conversion rate, ensures that the obtained beta-cyclodextrin has high purity, has high market value of byproduct gluconic acid obtained by co-production, saves energy and consumption of the process, greatly shortens the process flow time and solves the problems in the prior art.

In order to achieve the purpose, the invention provides the following technical scheme:

a preparation process of beta-cyclodextrin comprises the following steps:

1) starch liquefaction;

2) converting with invertase;

3) converting compound enzyme;

4) decolorizing and filtering;

5) electrodialysis separation;

6) evaporating, concentrating, crystallizing, centrifuging and drying to obtain the beta-cyclodextrin.

The optimized scheme comprises the following steps:

1) starch liquefaction: mixing starch and water, preparing starch slurry, adjusting pH to 5.4-5.8, adding alpha-amylase, mixing, liquefying, controlling DE value to 2-4, and inactivating enzyme to obtain liquefied solution;

2) converting with invertase: cooling the liquefied liquid to 55-60 ℃, adding branch chain amylase and beta-CGTase, adding cyclohexane, fully reacting for 12-15h, heating to 95-100 ℃, and distilling and recovering the cyclohexane to obtain a conversion liquid;

3) compound enzyme conversion: taking the conversion solution, adding complex enzyme and saccharifying enzyme, converting for 3-6h, and inactivating enzyme to obtain mixed solution;

4) and (3) decoloring and filtering: adding activated carbon into the mixed solution, stirring and decolorizing, and filtering with a plate frame to obtain a decolorized solution;

5) electrodialysis separation: taking the decolorized solution, performing electrodialysis, and separating to obtain a weak solution containing beta-cyclodextrin and a thick solution containing gluconic acid;

6) taking the light liquid containing the beta-cyclodextrin, evaporating, concentrating, crystallizing, centrifuging and drying to obtain the beta-cyclodextrin.

The optimized scheme comprises the following steps:

1) starch liquefaction: taking starch and water, mixing uniformly, preparing starch slurry, adjusting the pH value to 5.4-5.8, adding alpha-amylase, mixing uniformly, heating to 105-;

2) converting with invertase: cooling the liquefied liquid to 55-60 ℃, adding branch chain amylase and beta-CGTase, adding cyclohexane, fully reacting for 12-15h, heating to 95-100 ℃, and distilling and recovering the cyclohexane to obtain a conversion liquid;

3) compound enzyme conversion: adding catalase, glucose oxidase and glucoamylase into the conversion solution, converting the pH value to 5.5-6.5, converting the temperature to 45-55 ℃, converting for 3-6h, and inactivating the enzyme to obtain a mixed solution;

4) and (3) decoloring and filtering: adding activated carbon into the mixed solution, decolorizing for 60-80min, and filtering with plate frame to obtain decolorized solution;

5) electrodialysis separation: taking a decolorized solution, performing electrodialysis until the conductance value of an electrodialysis weak solution is less than or equal to 1000us/cm, and separating to obtain a weak solution containing beta-cyclodextrin and a concentrated solution containing gluconic acid;

6) taking the light liquid containing the beta-cyclodextrin, evaporating and concentrating at 68-75 ℃, stopping concentrating when the concentration is carried out until the dry matter content is 50-60%, crystallizing, and centrifugally drying to obtain the beta-cyclodextrin.

In an optimized scheme, in the step 3), the adding amount of the saccharifying enzyme is 0.1-0.3% of the mass of the starch, the adding amount of the glucose oxidase is 1-1.5% of the mass of the starch, and the adding amount of the catalase is 1.5-3% of the mass of the starch.

In an optimized scheme, in the step 5), the concentrated solution containing the gluconic acid is concentrated to 50% -60%, and a finished product of the gluconic acid is obtained.

In an optimized scheme, in the step 2), the branch chain amylase is pullulanase and isoamylase; the addition amount of the branch chain amylase is 2.5-3.0% of the mass of the starch.

In an optimized scheme, in the step 2), the addition amount of the beta-CGTase is 2.5-5% of the mass of the starch; the addition amount of the cyclohexane is 3-10% of the mass of the starch.

In an optimized scheme, in the step 1), the addition amount of the alpha-amylase is 0.02-0.04% of the starch.

In an optimized scheme, in the step 1), the starch is any one or a mixture of more of corn starch, potato starch and cassava starch.

In the step 1), starch and water are mixed to obtain starch milk, and then high-temperature-resistant alpha-amylase is added for liquefaction to convert the starch into dextrin and oligosaccharide, so that the solubility of the starch is increased; at present can generally stir the liquefaction in the liquefaction technology, but this technology operation energy consumption is big, and the stirring degree of difficulty is higher, and starch hydrolysis is efficient, to this problem, this application adopts the mode of jet cooking to go on in the liquefaction process, has not only reduced the energy consumption, has reduced the processing degree of difficulty, and the hydrolysis efficiency of starch also improves greatly simultaneously.

Subsequently, the component separation is carried out in a laminar flow mode, and the protein generated in the hydrolysis process is separated as a solid, so that the starch liquefaction is further promoted, the starch conversion rate is improved, and the impurities in the liquefied liquid are reduced; the DE value, at which the starch conversion is at a maximum, is controlled in the present application to be in the range of 2 to 4, and is determined by the Applicant after a number of tests.

Adding branched chain amylase and beta-CGT enzyme in the step 2), wherein the branched chain amylase comprises pullulanase and isoamylase, and amylopectin is removed by utilizing the synergistic action of the branched chain amylase and the beta-CGT enzyme and is hydrolyzed into glucose; and then adding a complex enzyme and a saccharifying enzyme in the step 3), wherein the complex enzyme comprises catalase and glucose oxidase, and the saccharifying enzyme and the complex enzyme are mutually synergistic to oxidize glucose and generate a byproduct gluconic acid, so that the process flow and the reaction time are greatly saved, and the preparation cost is reduced.

In the conventional treatment step, unconverted dextrine in a system is converted into maltose or glucose, but the operation is high in difficulty in subsequent impurity removal and separation, and the purity of the obtained beta-cyclodextrin is reduced, so that the complex enzyme is added to oxidize the glucose into gluconic acid, the gluconic acid can be used as a byproduct, the market value is high, the gluconic acid has charges, the beta-cyclodextrin is uncharged, and the electrodialysis separation is adopted in the subsequent step based on the property difference between the gluconic acid and the beta-cyclodextrin, so that the beta-cyclodextrin can be separated more thoroughly, and the purity and the yield are greatly improved.

In the step 3), the complex enzyme and the saccharifying enzyme are added to carry out enzyme conversion in a coordinated manner, so that the production speed and the working efficiency can be greatly improved, and the problem of over-slow production speed caused by batch addition of various enzymes is solved; based on the properties of the saccharifying enzyme, the compound enzyme and the enzyme in the step 2), the whole enzyme conversion temperature is controlled to be 45-55 ℃, so that the production energy consumption can be reduced under the condition of ensuring the enzyme activity, the conversion temperature change caused by different enzyme types in the production process is avoided, the unnecessary energy consumption caused by heating, cooling and other operations is reduced, and the production cost is reduced.

Activated carbon is added for decoloring in the step 4), electrodialysis is adopted for desalting separation in the step 5), the electrodialysis is stopped until the conductance value of a dilute solution is less than or equal to 1000us/cm, the dilute solution containing beta-cyclodextrin and a concentrated solution containing gluconic acid are obtained, then the dilute solution containing beta-cyclodextrin is evaporated, concentrated and recrystallized, and material extraction is generally carried out through cooling crystallization in the conventional processing process.

When this application carries out evaporative concentration, control evaporative concentration's temperature through control vacuum, temperature control is more accurate effective when evaporative concentration, the energy saving consumption.

Compared with the prior art, the invention has the beneficial effects that:

1. the method combines the continuous high-temperature injection and the flash evaporation laminar flow, and controls the DE value, so that the starch can be effectively liquefied, and compared with the conventional processing technology, the starch conversion rate is improved; meanwhile, the liquefaction step can be continuously carried out, which is beneficial to continuous large-scale production.

2. According to the method, the branch chain amylase and the beta-CGTase are used for carrying out cooperative transformation, the beta-CGTase is only needed to be added once, catalase, glucose oxidase and glucoamylase are added in the subsequent process for synchronous transformation, and the residual unconverted starch and glucose are transformed into gluconic acid.

3. The method has the advantages that the gluconic acid and the beta-cyclodextrin are separated by electrodialysis, the separation difficulty is low, the obtained product is high in purity, the subsequent evaporation concentration, crystallization and centrifugal drying modes are adopted, the crystallization concentration is greatly improved, the purity is improved before crystallization, the high-purity product can be obtained without leaching or only with a little leaching, the crystallization yield is obviously improved, and meanwhile, the purity of the product is further improved.

Drawings

In order that the present invention may be more readily and clearly understood, a more particular description of the invention briefly described above will be rendered by reference to specific embodiments that are illustrated in the appended drawings.

FIG. 1 is a schematic view of a process flow of a preparation process of beta-cyclodextrin of the present invention.

FIG. 2 is a liquid chromatogram of a beta-cyclodextrin sample prepared in example 1 of the present invention;

FIG. 3 is a liquid chromatogram of a standard beta-cyclodextrin sample in example 1 of the present invention;

FIG. 4 is a liquid chromatogram of a beta-cyclodextrin sample prepared in example 2 of the present invention;

FIG. 5 is a liquid chromatogram of a standard beta-cyclodextrin sample in example 2 of the present invention.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

A preparation process of beta-cyclodextrin specifically comprises the following steps:

s1: starch liquefaction: taking starch and water, mixing uniformly, preparing starch slurry, adjusting the pH value to 5.4-5.8, adding alpha-amylase, mixing uniformly, heating to 105-; the addition amount of the alpha-amylase is 0.02-0.04% of the starch. The starch is any one of corn starch, potato starch and cassava starch.

S2: converting with invertase: cooling the liquefied liquid to 55-60 ℃, adding branch chain amylase and beta-CGTase, adding cyclohexane, fully reacting for 12-15h, heating to 95-100 ℃, and distilling and recovering the cyclohexane to obtain a conversion liquid; the branch chain amylase is pullulanase and isoamylase; the addition amount of the branch chain amylase is 2.5-3.0% of the mass of the starch. The addition amount of the beta-CGTase is 2.5-5% of the mass of the starch; the addition amount of the cyclohexane is 3-10% of the mass of the starch.

S3: compound enzyme conversion: adding catalase, glucose oxidase and glucoamylase into the conversion solution, converting the pH value to 5.5-6.5, converting the temperature to 45-55 ℃, converting for 3-6h, and inactivating the enzyme to obtain a mixed solution; the adding amount of the saccharifying enzyme is 0.1-0.3% of the mass of the starch, the adding amount of the glucose oxidase is 1-1.5% of the mass of the starch, and the adding amount of the catalase is 1.5-3% of the mass of the starch.

S4: and (3) decoloring and filtering: adding activated carbon into the mixed solution, decolorizing for 60-80min, and filtering with plate frame to obtain decolorized solution;

s5: electrodialysis separation: taking a decolorized solution, performing electrodialysis until the conductance value of an electrodialysis weak solution is less than or equal to 1000us/cm, and separating to obtain a weak solution containing beta-cyclodextrin and a concentrated solution containing gluconic acid; concentrating the concentrated solution containing gluconic acid to 50% -60% to obtain a finished product of the gluconic acid.

S6: taking the light liquid containing the beta-cyclodextrin, evaporating and concentrating at 68-75 ℃, stopping concentrating when the concentration is carried out until the dry matter content is 50-60%, crystallizing, and centrifugally drying to obtain the beta-cyclodextrin.