CN111850069A - Production and preparation process of trehalose - Google Patents
Production and preparation process of trehalose Download PDFInfo
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Abstract
The invention discloses a production and preparation process of trehalose, which adopts high-temperature-resistant alpha-amylase, combines a continuous high-temperature injection and flash laminar flow mode, and simultaneously controls a DE value, so that starch can be effectively liquefied, and the conversion rate is favorably improved; in addition, the step can be continuously carried out, batch operation is not needed, and continuous large-scale production is facilitated; according to the invention, high-purity trehalose and gluconic acid are obtained through multi-part conversion, the trehalose as a main product is easy to separate, the purity of the trehalose can reach 99.81%, and the gluconic acid as a byproduct is obtained through co-production, so that the market value is high; the method has the advantages of high utilization rate of raw materials, coherent process and high product yield, reduces sewage discharge while improving the yield of enterprises, is energy-saving and environment-friendly, and is beneficial to industrial production of high-purity trehalose.
Description
Technical Field
The invention relates to the technical field of trehalose preparation, and particularly relates to a production and preparation process of trehalose.
Background
Trehalose is also called rhaponticum and mycose, and is a non-reducing disaccharide composed of two glucose molecules. Trehalose is a typical stress metabolite, can form a unique protective film on the surface of cells under severe environmental conditions such as high temperature, high cold, high osmotic pressure, dry dehydration and the like, and effectively protects a biological molecular structure from being damaged, so that the life process and biological characteristics of a living body are maintained.
Trehalose production is aimed at obtaining high purity trehalose products and related enzyme products. There are three main methods for preparing trehalose: firstly, extracting from biological cells; secondly, adopting microbial fermentation production; thirdly, relevant trehalose synthetase is extracted by adopting microbial fermentation, and trehalose is synthesized by adopting an enzyme method.
At present, for the improvement of the content of trehalose, methods of ion exchange desalination and chromatographic separation and purification are generally adopted, and the content of the prepared trehalose is about 98 percent; or refining by adopting alcoholization separation, but some chemical reagents, such as alcohol substances, are required to be used in the alcoholization separation, and certain amount of the chemical reagents are remained in the trehalose product and cannot be completely removed, so that although the content of the trehalose in the product is increased, the application range of the trehalose product is limited to a certain extent, and the trehalose product with the alcohol substances remained cannot be used in cosmetics.
Aiming at the problem, a production and preparation process of trehalose is provided, which is one of the technical problems to be solved urgently.
Disclosure of Invention
The invention aims to provide a production and preparation process of trehalose, which improves the starch conversion rate, ensures that the obtained trehalose has high purity, and ensures that a byproduct gluconic acid obtained by co-production has high market value, simple and smooth process and high production efficiency so as to solve the problems in the prior art.
In order to achieve the purpose, the invention provides the following technical scheme:
a production and preparation process of trehalose comprises the following steps:
1) starch liquefaction;
2) converting trehalose invertase;
3) converting compound enzyme;
4) decolorizing and filtering;
5) desalting by electrodialysis;
6) ion exchange treatment;
7) evaporating, concentrating and crystallizing;
8) and drying to obtain the trehalose.
The optimized scheme comprises the following steps:
1) starch liquefaction: mixing starch and water, stirring to obtain starch slurry, adjusting pH of the starch slurry to 5.4-5.8, adding alpha-amylase, mixing, liquefying, controlling DE value to 2-4, and inactivating enzyme to obtain liquefied solution;
2) trehalase conversion: adding starch debranching enzyme and trehalose converting enzyme into the liquefied solution, and performing enzymolysis at 45-55 deg.C and pH of 5.5-6.5 for 24-48 hr to obtain trehalose converting solution;
3) compound enzyme conversion: adding saccharifying enzyme and complex enzyme into trehalose conversion solution, converting pH to 5.5-6.5, converting at 45-55 deg.C for 3-6 hr, and inactivating enzyme to obtain mixed solution;
4) and (3) decoloring and filtering: adding activated carbon into the mixed solution, decolorizing at 60-80 deg.C for 30-120min, and filtering to obtain decolorized solution;
5) electrodialysis desalination: taking the decolorized solution, and performing electrodialysis to obtain a light solution containing trehalose and a concentrated solution containing gluconic acid;
6) ion exchange treatment: taking a light solution containing trehalose, and carrying out ion exchange to obtain a purified solution;
7) taking the purified liquid, carrying out evaporation concentration, cooling and crystallizing, and obtaining cooled crystal mush when the temperature of the cooled and crystallized liquid is reduced to 15-20 ℃;
8) and (3) taking the cooled crystal mush, carrying out centrifugal separation to obtain a wet product, and drying the wet product until the water content is less than 1% to obtain the trehalose.
The optimized scheme comprises the following steps:
1) starch liquefaction: mixing starch and water, stirring to obtain starch slurry, adjusting pH value of the starch slurry to 5.4-5.8, adding alpha-amylase, mixing, heating to 105-;
2) trehalase conversion: adding starch debranching enzyme and trehalose converting enzyme into the liquefied solution, and performing enzymolysis at 45-55 deg.C and pH of 5.5-6.5 for 24-48 hr to obtain trehalose converting solution;
3) compound enzyme conversion: adding saccharifying enzyme and complex enzyme into trehalose conversion solution, converting pH to 5.5-6.5, converting at 45-55 deg.C for 3-6 hr, and inactivating enzyme to obtain mixed solution; wherein the complex enzyme comprises catalase and glucose oxidase;
4) and (3) decoloring and filtering: adding activated carbon into the mixed solution, decolorizing at 60-80 deg.C for 30-120min, and circularly filtering until the light transmittance of the filtrate reaches above 95% to obtain decolorized solution;
5) electrodialysis desalination: taking a decolorized solution, performing electrodialysis until the conductance value of an electrodialysis diluted solution is less than or equal to 1000us/cm to obtain a diluted solution containing trehalose and a concentrated solution containing gluconic acid;
6) ion exchange treatment: taking a light solution containing trehalose, and carrying out ion exchange until the conductivity value is less than or equal to 50us/cm to obtain a purified solution;
7) taking the purified liquid, carrying out evaporation concentration at the evaporation temperature of 68-75 ℃, carrying out cooling crystallization when the concentration of solid matters in the evaporation concentrated liquid is 60-70%, and obtaining cooling crystal mush when the temperature of the cooling crystallization is reduced to 15-20 ℃;
8) and (3) taking the cooled crystal mush, carrying out centrifugal separation to obtain a wet product, and drying the wet product until the water content is less than 1% to obtain the trehalose.
In an optimized scheme, in the step 5), the concentrated solution containing the gluconic acid is concentrated and dehydrated to obtain the gluconic acid.
In an optimized scheme, in the step 3), the addition amount of the complex enzyme is 1-3% of the mass of the starch.
According to an optimized scheme, the enzyme activity mixing ratio of catalase to glucose oxidase is (1-20): 1.
in an optimized scheme, in the step 2), the trehalose converting enzyme comprises trehalose hydrolase and trehalose synthase; the mass of the trehalose invertase is 1-3% of the mass of starch.
In an optimized scheme, in the step 3), the mass of the saccharifying enzyme is 0.1-0.3% of the mass of starch; in the step 4), the mass of the activated carbon is 0.1-0.5% of the mass of the mixed solution.
In an optimized scheme, in the step 1), the addition amount of the alpha-amylase is 0.02-0.04% of the mass of the starch.
In an optimized scheme, in the step 1), the starch is any one of corn starch, potato starch and cassava starch; the mass concentration of the starch slurry is 20-30%.
In the step 1), starch and water are mixed and gelatinized, and then high-temperature-resistant alpha-amylase is added for liquefaction, so that the starch is converted into dextrin and oligosaccharide, and the solubility of the starch is increased; because the conventional stirring liquefaction process has large operation energy consumption, is difficult to stir and has low starch hydrolysis efficiency, in the liquefaction process, the method is carried out by adopting a jet cooking mode, the energy consumption is greatly reduced, the treatment difficulty is reduced, and the starch hydrolysis efficiency 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, further promotes starch conversion, improves the starch conversion rate, and reduces impurities contained in the liquefied liquid; in the present application, the DE value is controlled to be 2-4, and is determined by the applicant after a plurality of experiments, and at the DE value, the conversion rate of starch is maximized, and the yield of trehalose is further improved.
Adding starch debranching enzyme and trehalose converting enzyme in the step 2), removing amylopectin by using the starch debranching enzyme, and generating trehalose by using the synergistic action of trehalose hydrolase and trehalose synthase; in the step 3), saccharifying enzyme and complex enzyme are added simultaneously, and the saccharifying enzyme is utilized to convert amylopectin and heterosaccharide (such as monosaccharide, disaccharide, trisaccharide, macromolecular saccharide and other heterosaccharide) in the trehalose conversion solution into glucose, so that the influence of impurities is reduced, the yield and purity of byproducts are improved, and the purity of trehalose is improved; meanwhile, the complex enzyme can oxidize glucose in the process and generate a byproduct gluconic acid.
After the complex enzyme treatment, 99% of components in the obtained conversion solution are trehalose and gluconic acid. Generally, glucose in a system is converted into maltose in a conventional treatment step, but because the similarity of the properties of maltose and trehalose is too high, the difficulty is higher during subsequent impurity removal and separation, and the purity of trehalose is also reduced, complex enzyme is added to oxidize the glucose into gluconic acid, the gluconic acid can exist as a byproduct, the market value is high, meanwhile, the gluconic acid has charges, and the trehalose is not charged.
In the method, the complex enzyme and the saccharifying enzyme are added simultaneously for conversion, so that the production speed and the working efficiency are improved to a great extent, and the problem of over-low production speed caused by adding of multiple enzymes is avoided; meanwhile, based on the properties of saccharifying enzyme, compound enzyme and trehalose converting enzyme, the overall conversion temperature is controlled to be 45-55 ℃, and the overall conversion temperature is in the same region as the treatment temperature of the trehalose converting enzyme in the step 2), so that the production energy consumption is reduced under the condition of ensuring the activity of the enzyme, the conversion temperature change caused by different enzyme types in the production process is avoided, unnecessary energy consumption caused by heating, cooling and other operations is reduced, and the production cost is reduced.
Activated carbon is added in the step 4) of the method for decoloring, electrodialysis is adopted in the step 5) for desalting separation, the electrodialysis is stopped until the conductivity value of the dilute solution is less than or equal to 1000us/cm, the dilute solution containing trehalose and the concentrated solution containing gluconic acid are obtained, and based on parameter control and process improvement of the steps 1) -3), redundant impurities do not exist in the prepared decolored solution, so that the electrodialysis step is easier to process, high-purity gluconic acid slurry and trehalose slurry can be obtained, the trehalose slurry is further subjected to ion exchange, the purification is carried out again, recrystallization is carried out after evaporation concentration, centrifugal drying is carried out, trehalose products are obtained, and the gluconic acid is concentrated to obtain the gluconic acid products.
Compared with the prior art, the invention has the beneficial effects that:
1. the method adopts high-temperature-resistant alpha-amylase, combines a continuous high-temperature injection mode and a flash laminar flow mode, and simultaneously controls the DE value to be 2-4, so that the starch can be effectively liquefied, and the conversion rate is favorably improved; in addition, the step can be continuously carried out, batch operation is not needed, and continuous large-scale production is facilitated.
2. According to the method, the glucoamylase is added to convert both amylopectin and heterosaccharide in the material into glucose, and the complex enzyme is used for oxidation, so that the material impurities can be further reduced; the synergistic cooperation of the saccharifying enzyme and the complex enzyme can effectively improve the purity of the glucose and the gluconic acid and can also improve the yield of the byproduct gluconic acid.
3. This application adopts the electrodialysis to separate gluconic acid thick liquid and trehalose thick liquid, compares with conventional simulated moving bed separation method, and its separation effect is light more excellent, can make the separation of trehalose and byproduct gluconic acid more thorough, and the electrodialysis is handled further to carry out ion exchange after the step and is handled simultaneously, further improves the purity of trehalose, gluconic acid, and the yield of trehalose also obtains promoting.
4. According to the invention, high-purity trehalose and gluconic acid are obtained through multi-part conversion, the trehalose as a main product is easy to separate, the purity of the trehalose can reach more than 99.8%, and the gluconic acid as a byproduct is obtained through co-production, so that the market value is high; the method has the advantages of high utilization rate of raw materials, coherent process and high product yield, reduces sewage discharge while improving the yield of enterprises, is energy-saving and environment-friendly, and is beneficial to industrial production of high-purity trehalose.
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 trehalose production and preparation process of the present invention.
FIG. 2 is a first schematic liquid chromatography diagram of trehalose prepared in example 1 of the present invention;
FIG. 3 is a second schematic liquid chromatography diagram of trehalose prepared in example 1 of the present invention;
FIG. 4 is a schematic liquid chromatography diagram of trehalose prepared 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.
Example 1:
s1: starch liquefaction: mixing starch and water, stirring to obtain starch slurry, adjusting pH of the starch slurry to 5.4, adding alpha-amylase, mixing, heating to 105 deg.C, jet-cooking for 5min, flash-evaporating to 94 deg.C, laminar-flowing for 60min, controlling DE value to 2, and inactivating enzyme to obtain liquefied solution; the starch is 84.3% corn starch; the mass concentration of the starch slurry is 20%; the addition amount of the alpha-amylase is 0.02 percent of the mass of the starch.
S2: trehalase conversion: adding starch debranching enzyme and trehalose converting enzyme into the liquefied solution, and performing enzymolysis at 45 deg.C and pH of 5.5 for 24 hr to obtain trehalose converting solution. The trehalose converting enzyme comprises trehalose hydrolase and trehalose synthase; the mass of the trehalose converting enzyme is 1% of the mass of starch.
S3: compound enzyme conversion: adding saccharifying enzyme and complex enzyme into trehalose conversion solution, converting pH to 5.5, saccharifying at 45 deg.C for 3 hr, and inactivating enzyme to obtain mixed solution; the mass of the saccharifying enzyme is 0.1% of that of starch; the adding amount of the complex enzyme is 1 percent of the mass of the starch; wherein the complex enzyme comprises catalase and glucose oxidase; the enzyme activity mixing ratio of the catalase to the glucose oxidase is 1: 1.
s4: and (3) decoloring and filtering: and (3) adding activated carbon into the mixed solution, decoloring for 30min at the temperature of 60 ℃, and circularly filtering until the light transmittance value of the filtrate reaches over 95% to obtain a decolored solution, wherein the mass of the activated carbon is 0.1% of the mass of the mixed solution.
S5: electrodialysis desalination: taking a decolorized solution, performing electrodialysis until the conductance value of an electrodialysis diluted solution is less than or equal to 1000us/cm to obtain a diluted solution containing trehalose and a concentrated solution containing gluconic acid; and concentrating and dehydrating the concentrated solution containing the gluconic acid to obtain the gluconic acid.
S6: ion exchange treatment: taking the light liquid containing trehalose, and carrying out ion exchange until the conductivity value is less than or equal to 50us/cm to obtain a purified liquid.
S7: taking the purified liquid, carrying out evaporation concentration at the evaporation temperature of 68 ℃, carrying out cooling crystallization when the concentration of solid matters in the evaporation concentrated liquid is 60 percent, and obtaining cooling crystal mush when the temperature of the cooling crystallization is reduced to 15 ℃;
s8: and (3) taking the cooled crystal mush, carrying out centrifugal separation to obtain a wet product, and drying the wet product until the water content is less than 1% to obtain the trehalose.
Example 2:
s1: starch liquefaction: mixing starch and water, stirring to obtain starch slurry, adjusting pH of the starch slurry to 5.6, adding alpha-amylase, mixing, heating to 108 deg.C, jet-cooking for 6min, flash-evaporating to 97 deg.C, laminar-flowing for 75min, controlling DE value to 3, and inactivating enzyme to obtain liquefied solution; the starch is 85.9% potato starch; the mass concentration of the starch slurry is 25%; the addition amount of the alpha-amylase is 0.03 percent of the mass of the starch.
S2: trehalase conversion: adding starch debranching enzyme and trehalose converting enzyme into the liquefied solution, and performing enzymolysis at 50 deg.C and pH 6 for 36h to obtain trehalose converting solution. The trehalose converting enzyme comprises trehalose hydrolase and trehalose synthase; the mass of the trehalose converting enzyme is 2% of the mass of starch.
S3: compound enzyme conversion: adding saccharifying enzyme and complex enzyme into trehalose conversion solution, converting pH to 6, saccharifying at 50 deg.C for 5 hr, and inactivating enzyme to obtain mixed solution; the mass of the saccharifying enzyme is 0.2% of that of starch; the addition amount of the complex enzyme is 2 percent of the mass of the starch; wherein the complex enzyme comprises catalase and glucose oxidase; the enzyme activity mixing ratio of the catalase to the glucose oxidase is 10: 1.
s4: and (3) decoloring and filtering: and (3) adding activated carbon into the mixed solution, decoloring for 80min at the temperature of 70 ℃, and circularly filtering until the light transmittance value of the filtrate reaches over 95% to obtain a decolored solution, wherein the mass of the activated carbon is 0.3% of the mass of the mixed solution.
S5: electrodialysis desalination: taking a decolorized solution, performing electrodialysis until the conductance value of an electrodialysis diluted solution is less than or equal to 1000us/cm to obtain a diluted solution containing trehalose and a concentrated solution containing gluconic acid; and concentrating and dehydrating the concentrated solution containing the gluconic acid to obtain the gluconic acid.
S6: ion exchange treatment: taking the light liquid containing trehalose, and carrying out ion exchange until the conductivity value is less than or equal to 50us/cm to obtain a purified liquid.
S7: taking the purified liquid, carrying out evaporation concentration at the evaporation temperature of 70 ℃, carrying out cooling crystallization when the concentration of solid matters in the evaporation concentrated liquid is 65 percent, and obtaining cooling crystal mush when the temperature of the cooling crystallization is reduced to 18 ℃;
s8: and (3) taking the cooled crystal mush, carrying out centrifugal separation to obtain a wet product, and drying the wet product until the water content is less than 1% to obtain the trehalose.
Example 3:
s1: starch liquefaction: mixing starch and water, stirring to obtain starch slurry, adjusting pH of the starch slurry to 5.8, adding alpha-amylase, mixing, heating to 110 deg.C, jet-cooking for 8min, flash-evaporating to 99 deg.C, laminar-flowing for 90min, controlling DE value to 4, and inactivating enzyme to obtain liquefied solution; the starch is cassava starch; the mass concentration of the starch slurry is 30%; the addition amount of the alpha-amylase is 0.04 percent of the mass of the starch.
S2: trehalase conversion: adding starch debranching enzyme and trehalose converting enzyme into the liquefied solution, and performing enzymolysis at 55 deg.C and pH of 6.5 for 48 hr to obtain trehalose converting solution. The trehalose converting enzyme comprises trehalose hydrolase and trehalose synthase; the mass of the trehalose converting enzyme is 3% of the mass of starch.
S3: compound enzyme conversion: adding saccharifying enzyme and complex enzyme into trehalose conversion solution, converting pH to 6.5, converting at 55 deg.C for 6 hr, and inactivating enzyme to obtain mixed solution; the mass of the saccharifying enzyme is 0.3 percent of that of starch; the addition amount of the complex enzyme is 3 percent of the mass of the starch; wherein the complex enzyme comprises catalase and glucose oxidase; the enzyme activity mixing ratio of the catalase to the glucose oxidase is 20: 1.
s4: and (3) decoloring and filtering: and (3) adding activated carbon into the mixed solution, decoloring for 120min at the temperature of 80 ℃, and circularly filtering until the light transmittance value of the filtrate reaches over 95% to obtain a decolored solution, wherein the mass of the activated carbon is 0.5% of the mass of the mixed solution.
S5: electrodialysis desalination: taking a decolorized solution, performing electrodialysis until the conductance value of an electrodialysis diluted solution is less than or equal to 1000us/cm to obtain a diluted solution containing trehalose and a concentrated solution containing gluconic acid; and concentrating and dehydrating the concentrated solution containing the gluconic acid to obtain the gluconic acid.
S6: ion exchange treatment: taking the light liquid containing trehalose, and carrying out ion exchange until the conductivity value is less than or equal to 50us/cm to obtain a purified liquid.
S7: taking the purified liquid, carrying out evaporation concentration at the evaporation temperature of 75 ℃, carrying out cooling crystallization when the concentration of solid matters in the evaporation concentrated liquid is 70 percent, and obtaining cooling crystal mush when the temperature of the cooling crystallization is reduced to 20 ℃;
s9: and (3) taking the cooled crystal mush, carrying out centrifugal separation to obtain a wet product, and drying the wet product until the water content is less than 1% to obtain the trehalose.
Example 4:
in this example, the DE value was controlled to be 2.54 in step S1, and the parameters of the remaining steps were the same as those in example 3.
Example 5:
in this example, the DE value was controlled to be 3.25 in step S1, and the parameters of the remaining steps were the same as those in example 3.
Detection experiment 1:
in examples 1 to 5, trehalose is prepared according to the technical scheme disclosed in the present application, and the obtained material is detected, and the specific calculation method is as follows:
1. calculating the yield of trehalose: dividing the quality of the trehalose finished product by the oven-dried quality of the added starch; the trehalose purity is as follows: diluting 1g of the sample by 100 times, and feeding the sample into a liquid chromatography column to obtain the trehalose purity;
2. yield of gluconic acid: gluconic acid product quality:gluconicacid content/total amount of gluconic acid in the conversion solution. Purity of gluconic acid: diluting 1g of the sample by 100 times, and feeding the sample into a liquid chromatography column to obtain the purity of the gluconic acid.
3. Starch conversion rate: (the oven-dried quality of the trehalose finished product + the oven-dried quality of the gluconic acid finished product)/the oven-dried total amount of the starch.
The measurement was performed 2 times, and the average value was obtained, and the obtained measurement data are shown in the following table:
and (4) conclusion: from the data obtained in the above table, it can be seen that the following data are shown in the accompanying drawings (fig. 2 and 3 are schematic diagrams of two tests on the purity of trehalose prepared in example 1; fig. 4 is a schematic diagram of a test on the purity of trehalose prepared in example 2):
examples 1 to 5 are all produced according to the scheme disclosed in the present application, and the purity of the obtained trehalose can reach as high as 99.81%, the yield of trehalose can reach 71.4%, the yield of a byproduct gluconic acid can reach as high as 99.6%, and the purity of gluconic acid can reach as high as 99.8%; the starch conversion rate in the whole production process can reach 90.3 percent.
The scheme disclosed by the application can improve the starch conversion rate, the obtained trehalose is high in yield and purity, and the byproduct gluconic acid obtained by co-production is high in yield and purity.
Comparative example 1:
in this example, the DE value was controlled to be 8 in step S1, and the remaining step parameters were the same as in example 3.
Comparative example 2:
in this example, the DE value was controlled to 13 in step S1, and the remaining step parameters were the same as in example 3.
Comparative example 3:
in this example S1, after addition of alpha-amylase, the mixture was liquefied at 110 ℃ for 90min (under normal stirring), and the parameters of the remaining steps were the same as those in example 3.
Comparative example 4:
in this example S1, after adding alpha-amylase, the mixture was liquefied at 110 ℃ for 90min, and the DE value was controlled to 13, and the parameters of the remaining steps were the same as those of example 3.
Comparative example 5:
in the step S3 of this example, firstly, saccharifying enzyme is added at 60 ℃ and pH 4.5, the temperature is adjusted to 40 ℃ after reaction for 3 hours, catalase and glucose oxidase are added at pH 6.0, reaction is carried out for 3 hours, and enzyme deactivation is carried out.
The remaining process parameters were the same as in example 3.
Comparative example 6:
in this example, the step S6 was separated by a simulated moving bed, and ion exchange was performed after the simulated moving bed separation, and the remaining parameters were the same as in example 3.
Comparative example 7:
in the step S6, a simulated moving bed is adopted to separate trehalose and gluconic acid, the ion exchange in the step S7 is lacked, and the parameters of the rest steps are the same as those in the step 3.
Comparative example 8:
in this example, the ion exchange removal was performed in the step S6, and then the separation of trehalose and gluconic acid was performed using a simulated moving bed, and the parameters of the remaining steps were the same as those in example 3.
Comparative example 9:
in this embodiment, in S7, evaporation concentration is performed until the concentration of the solid content in the evaporation concentrated solution reaches 75%, and the parameters of the remaining steps are the same as those in embodiment 2.
Comparative example 10:
in this embodiment, in S7, evaporation concentration is performed until the concentration percentage of the solid in the evaporation concentrated solution is 55%, and the parameters of the remaining steps are the same as those in embodiment 2.
Comparative example 11:
in this example, in S7, the evaporation temperature was 85 ℃ and the other process parameters were the same as in example 2.
Detection experiment 2:
comparative examples 1 to 11 are comparative experiments to example 3, and the test data are as follows:
and (4) conclusion: as can be seen from the above table, comparative examples 1 to 11 are comparative experiments of example 3, in which the yield of trehalose in example 3 reaches 70.4%, the purity reaches 99.78%, the yield of the byproduct gluconic acid reaches 99.6%, the purity of gluconic acid reaches 99.8%, and the conversion rate of starch reaches 90.3%.
1. Comparative example 1 the DE value was controlled to 8 in the starch liquefaction step, and the trehalose yield reached only 64.2% in the process; comparative example 2 the DE value was controlled to 13 in the starch liquefaction step and the trehalose yield reached only 58.4% in the process.
The trehalose yields of comparative examples 1 and 2 are greatly reduced compared to example 3, which fully illustrates that the present application controls the DE value of 2-4 in the starch liquefaction step, at which the yield of trehalose can be greatly increased.
2. Comparative example 3 the conventional agitation liquefaction treatment was used in the starch liquefaction step, and in the process, the yield of trehalose only reached 65.7%, the purity of trehalose only reached 99.63%, and the yield of the by-product gluconic acid also showed a decreasing trend.
Compared with the embodiment 3, the trehalose yield and the trehalose purity of the comparative example 3 are greatly reduced, which fully shows that the starch can be effectively liquefied by adopting a mode of combining continuous high-temperature spraying and flash laminar flow in the starch liquefying step, the trehalose conversion rate is improved, and the trehalose yield and the yield of a byproduct gluconic acid are greatly improved; meanwhile, solid-liquid separation and impurity removal are carried out on the materials in the flash evaporation laminar flow process, so that the purity of the trehalose is greatly improved.
3. Comparative example 4 in the starch liquefaction step, the conventional stirring liquefaction treatment is adopted, the DE value is controlled to be 13, the yield of the trehalose in the process reaches only 55.2%, the purity of the trehalose reaches only 99.57%, and the purity of the byproduct gluconic acid also shows a reduction trend.
Comparative example 4 compared to example 3, the trehalose yield and purity of comparative example 4 were both greatly reduced; comparative example 4 compared with comparative examples 2 and 3, the trehalose yield and the starch conversion rate of comparative example 4 are both reduced;
this fully demonstrates that the present application adopts a combination of continuous high temperature spraying and flash laminar flow in the starch liquefaction step, and controls the DE value to be 2-4, and under the operation step, the conversion rate of trehalose is greatly improved, and the yield and purity of trehalose are also obviously improved.
4. In comparative example 5, the temperature and the pH were frequently adjusted, but the performance data of the obtained product was slightly different from that of example 3, and the energy consumption generated by adopting the scheme in actual production was large, the process was long, the operation was complicated, and the practicability was not high.
5. In comparative example 6, the separation was carried out using a simulated moving bed, and the purity of trehalose in the process was only 99.34%, and the purity of gluconic acid as a byproduct was only 99.1%.
In comparative example 7, the material separation is carried out by adopting a simulated moving bed and the ion exchange treatment is lacked, in the process, because of the existence of a large amount of ions, the trehalose crystallization production is inhibited, the crystallization is fine, the crystallization yield of the trehalose is reduced, the final yield of the trehalose is reduced to 65.7 percent, the purity of the trehalose is only 96.82 percent, the conversion rate of starch is also influenced and is reduced to 86.7 percent, and the purity of the byproduct gluconic acid is only 91 percent.
Compared with the example 3, the trehalose purity and the purity of the byproduct gluconic acid in the comparative examples 6 and 7 are obviously reduced; compared with the comparative example 6, the trehalose purity and the gluconic acid purity of the byproduct of the comparative example 7 are obviously reduced.
The method fully shows that the electrodialysis is adopted for treatment in the material purification process, so that the separation of the trehalose and the byproduct gluconic acid can be more thorough, and meanwhile, the ion exchange treatment is further carried out after the electrodialysis treatment step, so that the purity of the trehalose and the gluconic acid is further improved.
6. In comparative example 8, the trehalose purity only reaches 97.79% and the purity of the byproduct gluconic acid only reaches 89.5% in the process of separation by ion exchange treatment and simulated moving bed.
Compared with the embodiment 3, in the comparative example 8, the gluconic acid is adsorbed by the ion exchange resin through ion exchange, the loss is large, the conversion rate of the gluconic acid and the starch is greatly reduced, and other ion exchanges are insufficient due to the adsorption of the gluconic acid, the removal is incomplete, and the crystallization effect is influenced.
Compared with comparative examples 6 and 7, the trehalose purity and the purity of the byproduct gluconic acid in the comparative example 8 are reduced, which fully indicates that the application carries out electrodialysis firstly in the material purification process to separate trehalose and the byproduct gluconic acid, then carries out ion exchange treatment to remove impurities and filter the trehalose, and the operation sequence can effectively reduce the influence of materials such as the gluconic acid on the trehalose, so that the trehalose is further removed in the ion exchange step to improve the trehalose purity.
7. In the comparative example 9, the yield of cyclodextrin, the conversion rate of starch and the parameters of byproducts obtained after evaporation until the concentration percentage of solid matters in the evaporation concentrated solution is more than or equal to 70 percent (actually 75 percent) are smaller than those in the example 3, but the energy consumption generated by adopting the scheme in the actual production is larger, the generated crystals are too much, the fluidity is sharply reduced, the crystal mush is difficult to remove from a crystallization tank, and the concentration ratio is high, so that the impurity concentration in the mother solution is high, more leaching is needed, the crystal purity is slightly reduced, and the production practicability is poor.
In the comparative example 10, the concentration percentage content of the solid matters in the evaporation concentrated solution is less than or equal to 60 percent (actually 55 percent), the feed liquid obtained after evaporation concentration is thinner, the crystal crystals are fine, the crystallization yield is low, the yield of the product after centrifugation and drying is low, and the production efficiency is not high.
In comparative example 11, the evaporation concentration temperature was set to 85 ℃, and in actual operation, the product obtained at a higher concentration temperature was yellow in color and poor in practical effect.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.
Claims (10)
1. A production and preparation process of trehalose is characterized by comprising the following steps: the method comprises the following steps:
1) starch liquefaction;
2) converting trehalose invertase;
3) converting compound enzyme;
4) decolorizing and filtering;
5) desalting by electrodialysis;
6) ion exchange treatment;
7) evaporating, concentrating and crystallizing;
8) and drying to obtain the trehalose.
2. The process for preparing trehalose according to claim 1, wherein the process comprises the following steps: the method comprises the following steps:
1) starch liquefaction: mixing starch and water, stirring to obtain starch slurry, adjusting pH of the starch slurry to 5.4-5.8, adding alpha-amylase, mixing, liquefying, controlling DE value to 2-4, and inactivating enzyme to obtain liquefied solution;
2) trehalase conversion: adding starch debranching enzyme and trehalose converting enzyme into the liquefied solution, and performing enzymolysis at 45-55 deg.C and pH of 5.5-6.5 for 24-48 hr to obtain trehalose converting solution;
3) compound enzyme conversion: adding saccharifying enzyme and complex enzyme into trehalose conversion solution, converting pH to 5.5-6.5, converting at 45-55 deg.C for 3-6 hr, and inactivating enzyme to obtain mixed solution;
4) and (3) decoloring and filtering: adding activated carbon into the mixed solution, decolorizing at 60-80 deg.C for 30-120min, and filtering to obtain decolorized solution;
5) electrodialysis desalination: taking the decolorized solution, and performing electrodialysis to obtain a light solution containing trehalose and a concentrated solution containing gluconic acid;
6) ion exchange treatment: taking a light solution containing trehalose, and carrying out ion exchange to obtain a purified solution;
7) taking the purified liquid, carrying out evaporation concentration, cooling and crystallizing, and obtaining cooled crystal mush when the temperature of the cooled and crystallized liquid is reduced to 15-20 ℃;
8) and (3) taking the cooled crystal mush, carrying out centrifugal separation to obtain a wet product, and drying the wet product until the water content is less than 1% to obtain the trehalose.
3. The process for preparing trehalose according to claim 2, wherein the process comprises the following steps: the method comprises the following steps:
1) starch liquefaction: mixing starch and water, stirring to obtain starch slurry, adjusting pH value of the starch slurry to 5.4-5.8, adding alpha-amylase, mixing, heating to 105-;
2) trehalase conversion: adding starch debranching enzyme and trehalose converting enzyme into the liquefied solution, and performing enzymolysis at 45-55 deg.C and pH of 5.5-6.5 for 24-48 hr to obtain trehalose converting solution;
3) compound enzyme conversion: adding saccharifying enzyme and complex enzyme into trehalose conversion solution, converting pH to 5.5-6.5, converting at 45-55 deg.C for 3-6 hr, and inactivating enzyme to obtain mixed solution; wherein the complex enzyme comprises catalase and glucose oxidase;
4) and (3) decoloring and filtering: adding activated carbon into the mixed solution, decolorizing at 60-80 deg.C for 30-120min, and circularly filtering until the light transmittance of the filtrate reaches above 95% to obtain decolorized solution;
5) electrodialysis desalination: taking a decolorized solution, performing electrodialysis until the conductance value of an electrodialysis diluted solution is less than or equal to 1000us/cm to obtain a diluted solution containing trehalose and a concentrated solution containing gluconic acid;
6) ion exchange treatment: taking a light solution containing trehalose, and carrying out ion exchange until the conductivity value is less than or equal to 50us/cm to obtain a purified solution;
7) taking the purified liquid, carrying out evaporation concentration at the evaporation temperature of 68-75 ℃, carrying out cooling crystallization when the concentration of solid matters in the evaporation concentrated liquid is 60-70%, and obtaining cooling crystal mush when the temperature of the cooling crystallization is reduced to 15-20 ℃;
8) and (3) taking the cooled crystal mush, carrying out centrifugal separation to obtain a wet product, and drying the wet product until the water content is less than 1% to obtain the trehalose.
4. The process for preparing trehalose according to claim 3, wherein the process comprises the following steps: and in the step 5), concentrating and dehydrating the concentrated solution containing the gluconic acid to obtain the gluconic acid.
5. The process for preparing trehalose according to claim 3, wherein the process comprises the following steps: in the step 3), the addition amount of the complex enzyme is 1-3% of the mass of the starch.
6. The process for preparing trehalose according to claim 3, wherein the process comprises the following steps: the enzyme activity mixing ratio of the catalase to the glucose oxidase is (1-20): 1.
7. the process for preparing trehalose according to claim 3, wherein the process comprises the following steps: in the step 2), the trehalose converting enzyme comprises trehalose hydrolase and trehalose synthase; the mass of the trehalose invertase is 1-3% of the mass of starch.
8. The process for preparing trehalose according to claim 3, wherein the process comprises the following steps: in the step 3), the mass of the saccharifying enzyme is 0.1-0.3% of that of starch; in the step 4), the mass of the activated carbon is 0.1-0.5% of the mass of the mixed solution.
9. The process for preparing trehalose according to claim 3, wherein the process comprises the following steps: in the step 1), the addition amount of the alpha-amylase is 0.02-0.04% of the mass of the starch.
10. The process for preparing trehalose according to claim 3, wherein the process comprises the following steps: in the step 1), the starch is any one of corn starch, potato starch and cassava starch; the mass concentration of the starch slurry is 20-30%.
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