Method for efficiently crystallizing psicose
By stirring the paclitaxel concentrate at room temperature and adding ethanol solution dropwise, the problems of long crystallization time and low yield in the prior art are solved, and efficient and uniform paclitaxel crystallization is achieved. , simplifies the process flow and reduces costs, and is suitable for industrial production.
Patent Information
- Application Number
- CN202411385184.8
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-09-30
- Publication Date
- 2025-01-07
AI Technical Summary
The existing paclitaxel crystallization technology has problems such as long crystallization time, low yield, uneven particle size, and easy to agglomerate. The traditional methods and equipment are complex and costly, making it difficult to meet the needs of industrial production.
The paclitaxel concentrate solution was stirred at room temperature in medium speed and added seeds. The ethanol solution was slowly added dropwise until the crystal precipitated. Then, the crystallization was stirred and cultivated at low speed. The crystallized paclitaxel was obtained by solid-liquid separation and vacuum drying. The concentration was controlled. The liquid concentration is between 70% and 90%, the ethanol dosage is between 30% and 80%, and the stirring speed and drop acceleration are appropriately adjusted to achieve efficient crystallization.
Achieves paclitol crystals with high crystal yield, short time, uniform and uneven grains, simplify the process flow, reduce costs, are suitable for industrial production, and do not require strict purity of concentrate, and can be smoother than 95%. crystallization.
Smart Images
Figure CN119264197A_ABST
Abstract
Description
Technical Field
[0001] The invention belongs to the technical field of psicose crystallization, and particularly relates to a method for efficient crystallization of psicose. Background Art
[0002] D-Allulose is a rare six-carbon ketose and the diastereomer corresponding to the carbon number 3 of D-fructose. It exists in nature but in very small amounts. D-Allulose is difficult to digest and absorb and provides almost no energy for life activities, so it is a very useful low-calorie sweetener. In the field of medicine and health, D-allulose can inhibit lipase and intestinal α-glucosidase, thereby reducing the accumulation of body fat and inhibiting the rise in blood sugar concentration. Therefore, allulose may help control body weight and blood sugar levels, and has certain preventive and therapeutic potential for type 2 diabetes. As an emerging sweetener, allulose is gradually attracting market attention, especially in today's increasingly health-conscious world. Its low calories and small impact on blood sugar make it a potential sucrose substitute.
[0003] Allulose is highly water-soluble and difficult to crystallize. It is easily hygroscopic when spray-dried and has poor appearance. Therefore, developing a suitable crystallization process is very important for the development of the allulose industry.
[0004] The commonly used crystallization technology for allulose is aqueous crystallization, and a few companies also use ethanol crystallization. There are generally three technical ideas for aqueous crystallization. The first is to adjust the supersaturation in the crystallization liquid by adjusting the relationship between temperature and solubility; the second is to continuously reduce the water content in the crystallization mother liquor by evaporation to increase the crystallization yield; the third is to crystallize in two steps, first by concentration crystallization, and then cool down and crystallize when the concentration of the concentrated crystallization mother liquor is high. However, the above three aqueous crystallization methods all have many disadvantages, such as high liquid viscosity, crystallization time of about 120 hours, and difficult to control crystallization rate, resulting in uneven product particle size, easy agglomeration, low yield, and other problems. Although a few companies use ethanol crystallization, the concentrated solution needs to be of higher purity, the amount of ethanol used is large, and ultrasonic assistance is required, etc. The process is relatively cumbersome and increases labor costs.
[0005] Therefore, it is necessary to develop a method for crystallizing allulose with high crystallization yield, relatively short crystallization time, uniform product particles that are not easy to form agglomerates, simple and safe preparation process, low cost, and environmental friendliness. Summary of the invention
[0006] In order to solve the problems of the prior art, the object of the present invention is to provide a method for efficient crystallization of psicose, which has low preparation cost, is environmentally friendly, has high crystallization yield, short crystallization time, and the product particles are uniform and not easy to form agglomerates.
[0007] In order to achieve the above object, the present invention provides a method for efficient crystallization of psicose, which mainly comprises the following steps:
[0008] S1. Take a D-psicose concentrate, stir the concentrate at room temperature at a medium speed, and add seed crystals while stirring until the concentrate is evenly stirred;
[0009] S2, continue stirring at a medium speed, and slowly add ethanol solution while stirring until crystals precipitate; after the crystals precipitate, increase the ethanol addition speed;
[0010] S3, after the ethanol addition is completed, the stirring is changed to low speed, and crystals are grown to obtain a slurry;
[0011] S4, performing solid-liquid separation on the slurry to obtain wet Psicose product and mother liquor;
[0012] S5. Drying the wet psicose product to obtain crystalline psicose.
[0013] In the above-mentioned method for efficient crystallization of psicose, the concentration of the psicose concentrate in step S1 is 70%-90%.
[0014] In the above-mentioned method for efficient crystallization of psicose, the psicose concentrate in step S1 is obtained by concentrating a psicose solution after purification.
[0015] In the above-mentioned method for efficient crystallization of psicose, the speed of medium-speed stirring in step S1 is 750-800 r / h; and the amount of seed crystals added is 1‰-10‰ of the mass of the psicose concentrate.
[0016] In the above-mentioned method for efficient crystallization of psicose, the amount of ethanol used in step S2 is 30%-80% of the mass of the psicose concentrate.
[0017] In the above-mentioned method for efficient crystallization of psicose, the speed of slowly adding the ethanol solution dropwise in step S2 is 3% / h-8% / h, and the speed of ethanol dropping after the crystals are precipitated is 8% / h-15% / h.
[0018] In the above-mentioned method for efficient crystallization of allulose, the crystal growing time in step S3 is 8-15 hours.
[0019] In the above-mentioned method for efficient crystallization of allulose, the speed of low-speed stirring in step S3 is 300-500 r / h.
[0020] In the above-mentioned method for efficient crystallization of psicose, filtration or centrifugation is used for solid-liquid separation in step S4.
[0021] In the above-mentioned method for efficient crystallization of allulose, in step S5, the wet allulose product is dried by vacuum drying, the drying temperature is 20-40° C., and the vacuum degree is 0.7-1 MPa.
[0022] The beneficial effects of the technical solution of the present invention are:
[0023] 1. The method for efficiently crystallizing allulose of the present invention can control the crystal size according to product requirements and can meet different product requirements.
[0024] 2. The method for efficient crystallization of allulose of the present invention is simpler and can obtain allulose crystals with higher yield and purity in a shorter time, and the crystal particles are uniform, and the product is dispersed without agglomeration.
[0025] 3. The method for efficiently crystallizing allulose of the present invention can obtain allulose crystals at room temperature, and the preparation process has mild conditions, simple operation, simple equipment, low cost, and is easy for industrial production.
[0026] 4. Compared with the traditional process that requires the concentrate to have a purity of about 98% for successful crystallization, the method for efficient crystallization of allulose in the present invention does not have strict requirements on the purity of the concentrate, and crystallization can be successfully achieved when the purity reaches 95% or above. BRIEF DESCRIPTION OF THE DRAWINGS
[0027] Figure 1 It is a schematic diagram of the process flow of the present invention. DETAILED DESCRIPTION
[0028] The technical solution of the present invention will be clearly and completely described below in conjunction with specific embodiments and test examples. However, it should be understood by those skilled in the art that the embodiments are only used to illustrate the technical solution of the present invention and should not be regarded as limiting the scope of protection of the present invention. Based on the following embodiments, all other implementation schemes obtained by ordinary technicians in the field without making creative work, such as modification, deformation or simple replacement, should belong to the scope of protection of the present invention.
[0029] Example 1: This example uses the amount of anhydrous ethanol added as a single variable, and sets up multiple experimental groups to verify the effect of the amount of ethanol added on the crystallization yield and purity of allulose. The concentration of the allulose concentrate used in each group is 85%, the amount of seed crystals used is 1‰ of the concentrate, the ethanol drop rate before crystallization is 5% / h, and the stirring speed is 800r / h; the ethanol drop rate after crystallization is 10% / h, the stirring speed is 400r / h, the crystal growing time is 12h, the crystal is grown at room temperature, and the vacuum degree of vacuum drying at room temperature is 0.7MPa. The crystallization yield and purity of allulose in different experimental groups were measured, and the results are shown in Table 1 below.
[0030] Table 1 Effect of different ethanol dosages on the crystallization yield and purity of psicose
[0031]
[0032] It can be seen from Table 1 that, under the same other conditions, with the gradual increase in the amount of anhydrous ethanol added, the yield and purity of allulose gradually increased, but after the amount of ethanol added exceeded 80%, the yield and purity did not change significantly.
[0033] Example 2: This example uses the concentration of the allulose concentrate as a single variable, and sets up multiple experimental groups to verify the effect of the concentration of the allulose concentrate on the crystallization yield and purity of allulose. The amount of seed crystals used in each group is 1‰ of the concentrate, the amount of ethanol added is 80%, the ethanol drop rate before crystallization is 5% / h, and the stirring speed is 800r / h; the ethanol drop rate after crystallization is 10% / h, the stirring speed is 400r / h, the crystal is grown at room temperature, the crystal growing time is 10h, and the vacuum degree of vacuum drying at room temperature is 0.7MPa. The crystallization yield and purity of allulose in different experimental groups were measured, and the results are shown in Table 2 below.
[0034] Table 2 Effect of concentration of allulose concentrate on crystallization yield and purity
[0035]
[0036] It can be seen from Table 2 that, under the same other conditions, with the gradual increase in the concentration of the concentrate, the yield and purity of allulose gradually increased, but after the concentration of the concentrate exceeded 85%, the yield and purity did not change significantly.
[0037] Example 3: This example uses crystal growing time as a single variable, and sets up multiple experimental groups to verify the effect of crystal growing time on the crystal yield and purity of allulose. The concentration of the allulose concentrate used in each group is 85%, the amount of seed crystals used is 1‰ of the concentrate, the amount of ethanol added is 80%, the ethanol drop rate before crystallization is 5% / h, and the stirring speed is 800r / h; the ethanol drop rate after crystallization is 10% / h, the stirring speed is 400r / h, the crystal is grown at room temperature, and the vacuum degree of vacuum drying at room temperature is 0.7MPa. The crystal yield and purity of allulose in different experimental groups were measured, and the results are shown in Table 3 below.
[0038] Table 3 Effect of crystal growth time on the yield and purity of allulose
[0039]
[0040]
[0041] It can be seen from Table 3 that, under the same other conditions, the yield and purity of allulose show an upward trend with the increase of crystal culturing time, but too long crystal culturing time may increase the risk of crystals sticking to the wall, which is not conducive to improving the yield and purity.
[0042] Example 4: In this example, different purities of allulose concentrate were set, and the purity of the allulose concentrate was used as a single variable. Multiple experimental groups were set to verify the effect of the purity of the allulose concentrate on the crystallization yield and purity of allulose. The amount of seed crystals used in each group was 1‰ of the mass of the concentrate, the ethanol drop rate before crystallization was 5% / h, and the stirring speed was 800r / h; the ethanol drop rate after crystallization was 10% / h, the stirring speed was 400r / h, the crystal growing time was 12h, the crystal was grown at room temperature, and the vacuum degree of vacuum drying at room temperature was 0.7MPa. The crystallization yield and purity of allulose in different experimental groups were measured, and the results are shown in Table 4 below.
[0043] Table 4 Crystallization of allulose concentrates with different purities
[0044] Group Purity of Allulose Concentrate % Crystallization yield% Crystal purity % Experiment 1 94.0 68.2 98.2 Experiment 2 95.0 74.5 99.3 Experiment 3 95.5 75.1 99.4 Experiment 4 96.0 74.8 99.3 Experiment 5 96.5 75.5 99.5
[0045] It can be seen from Table 4 that with the increase of the purity of the allulose concentrate, the yield and purity of allulose show an upward trend. At the same time, it can also be seen that efficient crystallization can be completed when the purity of the allulose concentrate reaches 95.0%. Compared with other methods that require a purity of more than 98% for crystallization, it can effectively reduce energy consumption and reduce production costs.
[0046] Example 5: This example uses the stirring speed after crystallization as a single variable, and sets up multiple experimental groups to verify the effect of stirring speed on the crystallization yield and purity of allulose. The concentration of the allulose concentrate used in each group is 85%, the amount of seed crystals is 1‰ of the concentrate, the amount of ethanol added is 80%, the ethanol dropping speed before crystallization is 5% / h, and the stirring speed is 800r / h; the ethanol dropping speed after crystallization is 10% / h, the crystal growing time is 12h, the crystal is grown at room temperature, and the vacuum degree of vacuum drying at room temperature is 0.7MPa. The crystallization yield and purity of allulose in different experimental groups were measured, and the results are shown in Table 5 below.
[0047] Table 5 Effect of different stirring speeds on the crystallization yield and purity of allulose
[0048]
[0049] It can be seen from Table 5 that the stirring speed after crystallization has a greater influence on the particle size of allulose crystals. In specific production, the stirring speed is determined according to the particle size of the required product. If the product requires a smaller particle size, the stirring speed will be reduced less after crystallization; if the product requires a larger particle size, the stirring speed will be reduced more after crystallization, but the stirring must be guaranteed to operate normally throughout the process without any jamming.
[0050] Example 6: This example uses crystal growth temperature as a single variable, and sets up multiple experimental groups to verify the effect of crystal growth temperature on the crystallization yield and purity of allulose. The concentration of the allulose concentrate used in each group is 85%, the amount of seed crystals used is 1‰ of the concentrate, the amount of ethanol added is 80%, the ethanol drop rate before crystallization is 5% / h, and the stirring speed is 800r / h; the ethanol drop rate after crystallization is 10% / h, the stirring speed is 400r / h, the crystal growth time is 12h, and the vacuum degree of vacuum drying at room temperature is 0.7MPa. The crystallization yield and purity of allulose in different experimental groups were measured, and the results are shown in Table 6 below.
[0051] Table 6 Effect of different crystal growth temperatures on the yield and purity of allulose
[0052] Group Temperature ℃ Yield % purity% Experiment 1 40 65 99.2 Experiment 2 30 71 99.1 Experiment 3 20 75 99.4 Experiment 4 10 76 99.3 Experiment 5 0 76 99.3
[0053] It can be seen from Table 6 that the lower the crystal growth temperature, the greater the yield, but the effect of room temperature and low temperature on the yield and purity is not much different, so there is no need to deliberately control the crystallization below room temperature, because controlling the low temperature will increase the cost, and it is sufficient to maintain the crystallization at room temperature.
[0054] Example 7: This example provides a method for efficient crystallization of psicose, comprising the following steps:
[0055] S1. Taking a purified allulose solution with a purity of 95.5%, and concentrating it to a concentration of 84% to obtain a psicose concentrated solution;
[0056] S2. Take 20 kg of allulose concentrate and stir it at a speed of 800 r / h at room temperature, add 20 g of seed crystals while stirring until the mixture is evenly stirred, and slowly add 8 kg of anhydrous ethanol solution dropwise thereto after stirring for 10 min at a dropping speed of 5% / h; after crystals are precipitated, increase the ethanol dropping speed to 10% / h until the ethanol dropping is completed;
[0057] S3, after the ethanol addition is completed, the rotation speed is adjusted to 400r / h, and the crystals are grown at room temperature for 10h to obtain a slurry;
[0058] S4, centrifuging the slurry to separate the solid and the liquid to obtain a wet Allulose product and a mother liquor;
[0059] S5. Drying the wet psicose under vacuum at room temperature to obtain crystalline psicose, wherein the vacuum degree is 0.8 MPa; the purity of the crystalline psicose after drying is 99.4%, and the yield is 76%.
[0060] Example 8: This example provides a method for efficient crystallization of psicose, comprising the following steps:
[0061] S1. Taking a purified allulose solution with a purity of 95.5%, and concentrating it to a concentration of 85% to obtain a allulose concentrated solution;
[0062] S2. Take 20 kg of allulose concentrate and stir it at a speed of 800 r / h at room temperature, add 20 g of seed crystals while stirring until the mixture is evenly stirred, and slowly add 9 kg of anhydrous ethanol solution dropwise thereto after stirring for 10 min at a dropping rate of 5% / h; after crystals are precipitated, increase the ethanol dropping rate to 10% / h until the ethanol addition is completed;
[0063] S3, after the ethanol addition is completed, the rotation speed is adjusted to 400r / h, and the crystals are grown at room temperature for 12h to obtain a slurry;
[0064] S4, centrifuging the slurry to separate the solid and the liquid to obtain a wet Allulose product and a mother liquor;
[0065] S5. Drying the wet psicose under vacuum at room temperature to obtain crystalline psicose, wherein the vacuum degree is 1 MPa; the purity of the crystalline psicose after drying is 99.3%, and the yield is 81%.
[0066] The above is a detailed introduction to a method for efficient crystallization of psicose provided by the present invention. The same and similar parts between the various embodiments of the specification can be referred to each other. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made to the present invention without departing from the principle of the present invention, and these improvements and modifications also fall within the scope of protection of the claims of the present invention.
Claims
1. A method for efficient crystallization of psicose, characterized by: The following steps are involved: S1. Take a D-psicose concentrate, stir the concentrate at room temperature at a medium speed, and add seed crystals while stirring until the concentrate is evenly stirred; S2, continue stirring at a medium speed, and slowly add ethanol solution while stirring until crystals precipitate; after the crystals precipitate, increase the ethanol addition speed; S3, after the ethanol addition is completed, the stirring is changed to low speed, and crystals are grown to obtain a slurry; S4, performing solid-liquid separation on the slurry to obtain wet Psicose product and mother liquor; S5. Drying the wet psicose product to obtain crystalline psicose.
2. The method for efficient crystallization of psicose according to claim 1, characterized in that: The concentration of the D-psicose concentrate in step S1 is 70%-90%.
3. The method for efficient crystallization of psicose according to claim 1, characterized in that: The psicose concentrate in step S1 is obtained by concentrating a psicose solution after purification.
4. The method for efficient crystallization of psicose according to claim 1, characterized in that: The speed of medium-speed stirring in step S1 is 750-800 r / h; the amount of seed crystal added is 1‰-10‰ of the mass of the allulose concentrate.
5. The method for efficient crystallization of D-psicose according to claim 1, wherein: In step S2, the amount of ethanol used is 30%-80% of the mass of the psicose concentrated solution.
6. The method for efficient crystallization of D-psicose according to claim 1, wherein: The speed of slowly adding the ethanol solution dropwise in step S2 is 3% / h-8% / h, and the speed of slowly adding the ethanol solution dropwise after the crystals are precipitated is 8% / h-15% / h.
7. The method for efficient crystallization of D-psicose according to claim 1, wherein: The crystal growing time in step S3 is 8-15 hours.
8. The method for efficient crystallization of psicose according to claim 1, characterized in that: The speed of low-speed stirring in step S3 is 300-500 r / h.
9. The method for efficient crystallization of psicose according to claim 1, characterized in that: In step S4, solid-liquid separation is performed by filtration or centrifugation.
10. The method for efficient crystallization of D-psicose according to claim 1, characterized in that: In step S5, the wet allulose product is dried by vacuum drying, the drying temperature is 20-40° C., and the vacuum degree is 0.7-1 MPa.