CN115385776B - Erythritol crystal and preparation method and application thereof - Google Patents
Erythritol crystal and preparation method and application thereof Download PDFInfo
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- CN115385776B CN115385776B CN202210948104.XA CN202210948104A CN115385776B CN 115385776 B CN115385776 B CN 115385776B CN 202210948104 A CN202210948104 A CN 202210948104A CN 115385776 B CN115385776 B CN 115385776B
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- 239000013078 crystal Substances 0.000 title claims abstract description 193
- UNXHWFMMPAWVPI-ZXZARUISSA-N erythritol Chemical compound OC[C@H](O)[C@H](O)CO UNXHWFMMPAWVPI-ZXZARUISSA-N 0.000 title claims abstract description 124
- 239000004386 Erythritol Substances 0.000 title claims abstract description 123
- UNXHWFMMPAWVPI-UHFFFAOYSA-N Erythritol Natural products OCC(O)C(O)CO UNXHWFMMPAWVPI-UHFFFAOYSA-N 0.000 title claims abstract description 123
- 235000019414 erythritol Nutrition 0.000 title claims abstract description 123
- 229940009714 erythritol Drugs 0.000 title claims abstract description 123
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 30
- 238000001816 cooling Methods 0.000 claims description 48
- 238000002425 crystallisation Methods 0.000 claims description 27
- 230000008025 crystallization Effects 0.000 claims description 27
- 239000000243 solution Substances 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 17
- 238000001704 evaporation Methods 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 8
- 239000012141 concentrate Substances 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 4
- 230000009471 action Effects 0.000 claims description 2
- 238000005119 centrifugation Methods 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 239000002356 single layer Substances 0.000 claims description 2
- 238000007738 vacuum evaporation Methods 0.000 claims description 2
- 230000008020 evaporation Effects 0.000 claims 2
- 238000005406 washing Methods 0.000 claims 1
- 239000002245 particle Substances 0.000 abstract description 70
- 238000004090 dissolution Methods 0.000 abstract description 29
- 230000002776 aggregation Effects 0.000 abstract description 15
- 238000005054 agglomeration Methods 0.000 abstract description 14
- 239000006185 dispersion Substances 0.000 abstract description 5
- 239000003960 organic solvent Substances 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 5
- 239000007864 aqueous solution Substances 0.000 abstract 1
- 238000009826 distribution Methods 0.000 description 42
- 230000000052 comparative effect Effects 0.000 description 29
- 238000000399 optical microscopy Methods 0.000 description 9
- 235000013361 beverage Nutrition 0.000 description 8
- 235000013305 food Nutrition 0.000 description 8
- 239000010410 layer Substances 0.000 description 8
- 230000003287 optical effect Effects 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 6
- 150000005846 sugar alcohols Chemical class 0.000 description 5
- 238000010899 nucleation Methods 0.000 description 4
- 230000006911 nucleation Effects 0.000 description 4
- 238000010900 secondary nucleation Methods 0.000 description 4
- 238000004581 coalescence Methods 0.000 description 3
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- 208000008589 Obesity Diseases 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- TVXBFESIOXBWNM-UHFFFAOYSA-N Xylitol Natural products OCCC(O)C(O)C(O)CCO TVXBFESIOXBWNM-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
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- 239000012530 fluid Substances 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 229940095686 granule product Drugs 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 235000021070 high sugar diet Nutrition 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000007561 laser diffraction method Methods 0.000 description 1
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- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 description 1
- 230000002503 metabolic effect Effects 0.000 description 1
- 210000000214 mouth Anatomy 0.000 description 1
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- 235000020824 obesity Nutrition 0.000 description 1
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- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
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- 239000007858 starting material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 235000021092 sugar substitutes Nutrition 0.000 description 1
- 239000003765 sweetening agent Substances 0.000 description 1
- 239000006188 syrup Substances 0.000 description 1
- 235000020357 syrup Nutrition 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 210000002700 urine Anatomy 0.000 description 1
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 description 1
- 235000010447 xylitol Nutrition 0.000 description 1
- 239000000811 xylitol Substances 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
- C07C29/78—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by condensation or crystallisation
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
- A23L2/00—Non-alcoholic beverages; Dry compositions or concentrates therefor; Their preparation
- A23L2/52—Adding ingredients
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
- A23L29/00—Foods or foodstuffs containing additives; Preparation or treatment thereof
- A23L29/30—Foods or foodstuffs containing additives; Preparation or treatment thereof containing carbohydrate syrups; containing sugars; containing sugar alcohols, e.g. xylitol; containing starch hydrolysates, e.g. dextrin
- A23L29/37—Sugar alcohols
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23V—INDEXING SCHEME RELATING TO FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES AND LACTIC OR PROPIONIC ACID BACTERIA USED IN FOODSTUFFS OR FOOD PREPARATION
- A23V2002/00—Food compositions, function of food ingredients or processes for food or foodstuffs
Abstract
The application provides an erythritol crystal, a preparation method and application thereof, wherein when the erythritol crystal is cooled and crystallized, aiming at the agglomeration phenomenon caused by the adhesion work of the erythritol crystal in an aqueous solution, the erythritol crystal is subjected to adjustable agglomeration by adjusting and controlling the dispersion work of the erythritol crystal in the wet agglomeration process in a system, so that a highly-uniform crystal product is prepared by utilizing micro seed crystals. The erythritol crystals have uniform particle size, more than 89.2 weight percent of 20-40 meshes, more than 97.0 weight percent of 20-60 meshes, high dissolution rate and good fluidity. The preparation method is simple, easy to realize, environment-friendly, capable of realizing industrialization and low in economic investment, and does not use any organic solvent.
Description
Technical Field
The application belongs to the technical field of crystallization in chemical engineering industry, in particular relates to an erythritol crystal, a preparation method and application thereof, and particularly relates to a method for producing erythritol crystals with uniform particle size and high dissolution rate by utilizing wet agglomeration regulation.
Background
High-sugar diets are considered to be a significant cause of obesity and various diseases. As people's pursue of health has become stronger, more and more consumers use new sugar substitutes as a source of sweet taste in foods, which has led to the vigorous development of the sugar alcohol industry. Erythritol (CAS: 149-32-6) English name erythrotol, formula C 4 H 10 O 4 Molecular weight 122.12. Usually white crystalline powder, has a refreshing sweet taste, and its sweetness is 60-80% of that of sucrose. According to European food additive guidelines (2008/100/EC), erythritol has a caloric value of 0kcal kg -1 Therefore, in recent years, more and more emphasis has been placed on the formulation of erythritol-containing foods, which also results in a dramatic increase in erythritol production, and according to the thaliana forecast, the production scale is expected to reach a market scale of 35 ten thousand tons in the next five years. Currently erythritol is mainly produced by a biological fermentation process. The metabolic behavior of the microbial preparation is different from that of other polyols, and the microbial preparation is mainly discharged through urine, so that no digestive dysfunction is caused. Tolerance in humans is 2-3 times that of xylitol and therefore there is hardly any laxative compared to other sugar alcohols. Erythritol has strong heat absorption when being dissolved in water, the dissolution heat absorption is 97.4kJ/kg, and the granular compound food can be constructed in the oral cavityA cool and refreshing taste. Since erythritol has many unique advantages, it is widely used in sugarless beverages and other low-sugar food formulations.
CN103709007a mentions a method of refining erythritol crystals by using cooling crystallization coupled with dialysis crystallization, but this method requires the use of an organic solvent for auxiliary production, which is not environmentally friendly. CN113912475a proposes a method for preparing erythritol large-particle crystals with a size of 50 mesh or more with high yield by using cooling crystallization, in order to further confirm the technical advantages, the method is adopted to prepare erythritol crystals, and the obtained crystals have larger particles, good fluidity and lower dissolution rate. CN112479820a proposes a continuous oscillating flow membrane crystallization device for erythritol, but the operation of the device is complex, and industrialization is difficult to realize.
Therefore, finding a preparation method of erythritol crystals which does not use any organic solvent, has the advantages of high uniformity of product particle size and good dissolution performance and can realize industrialization is still an unsolvable technical problem in the prior art.
Disclosure of Invention
The food industry has very strict requirements on the dissolution rate, flowability and anti-caking performance of the sugar granule powder, so that the granularity control of sugar alcohol crystals is always a research difficulty and a hot spot in the field of functional sugar, and the flowability and the anti-caking performance of the sugar alcohol crystals can be obviously improved due to the narrow granularity distribution. Currently, erythritol is mainly applied to the field of sugarless beverages, has higher requirements on the particle size distribution of erythritol, and also has higher requirements on the particle size distribution of erythritol in consideration of the requirements on dissolution rate, flowability and anti-caking property, and the erythritol crystals with different particle size distribution ranges show different physical properties. For example: under the condition of constant-temperature water bath at 25 ℃,30g of erythritol crystals with different particle size ranges are dissolved in water, the time required for dissolving the erythritol crystals with the particle size distribution of 16-40 meshes is approximately 180-240 s, the time required for dissolving the erythritol crystals with the particle size distribution of 20-60 meshes is approximately 140-200 s, and the time required for dissolving the erythritol crystals with the particle size distribution of 30-80 meshes is 100-150 s. The dissolution rate directly relates to the degree of cooling sensation in the oral cavity when the sugar alcohol of the sugarless beverage is dissolved in man-hours and when erythritol is used as a compound granule product. Flowability is another important property of granular products in beverage dissolution and granular products, usually measured by angle of repose, and is significantly improved when the particle size becomes larger or uniform, and otherwise reduced. Balancing the factors, it is generally desirable that the crystal size is not too large or too small, and in the marketplace, crystals of 20-60 mesh are more popular for beverage production and granule food compounding. However, in industrial production, erythritol crystals undergo wet agglomeration and scaling during solution crystallization, and the cooling curve is unreasonably designed, so that the particle size distribution of the product is out of control, wherein large particles above 20 meshes and crushed crystals below 60 meshes have higher mass ratio. Currently, grinding is generally adopted for large-particle treatment modes, which increases energy consumption and damages crystal morphology, and a large amount of fine powder generated during grinding can significantly increase caking risk. In order to overcome the defects of the existing product preparation method and utilize the characteristic that erythritol crystals have larger adhesion work in solution so as to be agglomerated, the application provides a method for preparing erythritol crystals with high dissolution rate, which has uniform granularity (20-60 meshes) by using micro-seed crystals to influence the dispersion force in wet agglomeration by utilizing a regulating flow field and further regulating the number of agglomeration layers by changing the dispersion work to resist the adhesion work, and the prepared granular product has good fluidity, adjustable granularity distribution, and small seed crystal amount used in the process, thereby being beneficial to amplification. The process does not use any organic solvent, and is environment-friendly.
One of the purposes of the application is to provide a preparation method of erythritol crystals, which comprises the following steps:
adding erythritol seed crystals into erythritol concentrated solution with the temperature of 60-70 ℃, and cooling and crystallizing in four sections under the flow field and stirring action to obtain erythritol crystals;
preferably, the preparation method of the erythritol concentrated solution with the temperature of 60-70 ℃ comprises the following steps: evaporating and concentrating erythritol solution with concentration of 10-20wt% at constant temperature of 60-70deg.C to 50-70wt%;
preferably, the preparation method of the erythritol concentrated solution with the temperature of 60-70 ℃ comprises the following steps: evaporating and concentrating erythritol solution with concentration of 10-20wt% at constant temperature of 60-70deg.C to 61-68wt%;
preferably, the preparation of the erythritol concentrate is achieved in a sugar boiling tank or a vacuum evaporation crystallizer;
preferably, the erythritol seed particle size is 250-325 mesh.
In the present application, the seed crystal particle size is required to be uniform (the mesh size is not more than 0.02mm, for example, 250 to 300 mesh, 300 to 325 mesh). The adding amount of the seed crystal needs to be controlled properly, and the particle size of the crystal product is not out of control due to excessively large or excessively small seed crystal;
preferably, the erythritol seed crystals are added in an amount of 0.2 to 1wt%, preferably 0.3 to 0.6wt%, of the erythritol dry matter content in the erythritol concentrate;
preferably, the flow field is a flow field with the z-axis direction and the tangential direction simultaneously;
preferably, the z-axis flow field is applied through a flow guide;
preferably, the tangential direction of the flow field is applied by a single layer three-bladed propeller;
preferably, the stirring power during the cooling crystallization is 0.37-2.64kW/m 3 。
Preferably, the cooling crystallization comprises four steps, wherein the first step is to cool from 70-60 ℃ to 64-54 ℃ at a cooling rate of 0.5-1.5 ℃/h, the second step is to cool from 64-54 ℃ to 54-39 ℃ at a cooling rate of 1-2.5 ℃/h, the third step is to cool from 54-39 ℃ to 39-25 ℃ at a cooling rate of 2-4 ℃/h, and the third step is to cool from 39-25 ℃ to 25-20 ℃ at a cooling rate of 4.5-5.5 ℃/h;
preferably, the cooling crystallization is achieved in a vertical cooling crystallizer with a guide cylinder, a cooling crystallizer with a guide cylinder or a cooling crystallizer with a guide cylinder.
In the application, a cooling crystallizer with a guide cylinder is needed, and a z-axial flow field is needed to be provided to avoid excessive coalescence of crystals. And avoid the great linear velocity difference of each point of fluid when the tangential flow field exists alone to cause different crystal growth rates, influence the grain size distribution of the product;
preferably, the preparation method further comprises the steps of sequentially carrying out solid-liquid separation, cleaning and drying on the mixed solution obtained by cooling crystallization.
Preferably, the solid-liquid separation mode is centrifugation;
preferably, the drying mode is normal pressure drying, the drying temperature is 45-55 ℃, and the drying time is 6-12h.
The second purpose of the application is to prepare erythritol crystals according to the preparation method of the first purpose;
preferably, the erythritol crystals have a uniform particle size, wherein 89.2wt% or more of the crystals have a size of 20 to 40 mesh and 97wt% or more of the crystals have a size of 20 to 60 mesh;
preferably, the erythritol crystals have an angle of repose of 21.3-22.6 °;
preferably, the erythritol crystals have a dissolution rate of 96-105s in 100g of water of 30g of the product in a constant temperature water bath at 25 ℃ which is significantly faster than the erythritol crystals in the same field for the preparation of proprietary products.
The particle size particle distinguishing method is a vibrating screen sieving method;
preferably, 100g of the same batch of products are placed in the uppermost layers of screens with different meshes, the screens are laminated in a vibrating screen bed, the vibrating time is adjusted to be 5min, and the amplitude of the vibration is 1mm/g to screen the erythritol particle size.
The third object of the present application is the use of erythritol crystals according to the second object for the preparation of a sugarless beverage and for enhancing the cooling taste of a granular product.
The application has the technical characteristics and beneficial effects that:
1. the erythritol crystals are prepared by adopting a cooling crystallization technology, multiple times of temperature return are not needed, and the process is simple; no organic solvent is needed, the cost is low, and the environment is protected; the obtained product has high uniformity of particle size.
2. According to the application, the crystal homogenization and coalescence caused by the flow field are utilized to obviously reduce the adding amount of the crystal seeds, so that less crystal seeds can finish the homogenization of the particle size, the crystal particle size distribution range of the crystal seeds can be regulated and controlled by adjusting the adding and stirring rate of the crystal seeds, and the precise control of the particle size distribution of the product is realized.
3. According to molecular thermodynamics and crystal growth kinetic parameters of erythritol, different cooling rates are designed in different temperature intervals. In a higher temperature range (above 55 ℃), the nucleation of erythritol is obviously inhibited, and the growth is promoted. Under reasonable cooling rate, secondary nucleation can be restrained by adding trace seed crystal, and under the condition of 55 ℃, although nucleation is promoted, under the same supersaturation degree, the system is easier to nucleate, but the seed crystal added in the earlier stage is obviously grown up, and more crystal faces are used for bearing the supersaturation degree consumption, so that the cooling rate can be gradually accelerated. By reasonably designing the cooling curve, the broad particle size distribution caused by secondary nucleation can be significantly suppressed.
4. After crystallization is finished according to the preparation method provided by the application, the obtained erythritol crystals have uniform particle size, the crystal size of more than 89.2 weight percent can be 20-40 meshes, and the crystal size of more than 97.0 weight percent can be 20-60 meshes. The dissolution time of 30g of the product in 100g of water at the constant temperature of 25 ℃ is 96-105s, and the dissolution rate is obviously faster than that of erythritol crystals in the same field to prepare the patent product. And the repose angle is 21.3-22.6 degrees, and the fluidity is good. Has wide application in the fields of food chemical industry such as sugar-free beverage production, granule food compounding and the like.
Drawings
Fig. 1: solubility versus metastable zone curve for erythritol;
fig. 2: optical microscopy pictures of erythritol crystals of example 1;
fig. 3: optical microscopy pictures of erythritol crystals of example 2;
fig. 4: optical microscopy pictures of erythritol crystals of example 3;
fig. 5: optical microscopy pictures of erythritol crystals of comparative example 1;
fig. 6: optical microscopy pictures of erythritol crystals of comparative example 2;
fig. 7: optical microscopy pictures of erythritol crystals of comparative example 3;
fig. 8: optical microscopy pictures of erythritol crystals of comparative example 4;
fig. 9: optical microscopy pictures of erythritol crystals of comparative example 5;
fig. 10: optical microscopy pictures of erythritol crystals of comparative example 6;
fig. 11: XRD contrast patterns of erythritol crystals of example 1 and comparative example 6;
fig. 12: a method for testing dissolution rate;
fig. 13: the angle of repose is measured.
Detailed Description
The technical scheme of the application is further described by the following specific embodiments. It should be apparent to those skilled in the art that the examples are merely provided to aid in understanding the present application and should not be construed as limiting the application in any way.
In order to enable those skilled in the art to more clearly understand the technical scheme of the present application, the technical scheme of the present application will be described in detail with reference to specific embodiments. If experimental details are not specified in the examples, the conditions are generally conventional or recommended by the reagent company; the erythritol starting material used in the examples described below was purchased from Fuyang Biotechnology Co., ltd. Shandong, and the dry matter purity of the erythritol syrup was 99.6% by weight or more, and other reagents, consumables, etc. used, unless otherwise specified, were commercially available.
Example 1:
(1) And (3) evaporating and concentrating: taking a certain amount of erythritol sugar solution (10wt%) and evaporating and concentrating to 65wt% under the vacuum degree of 0.04MPa, maintaining the temperature at 65deg.C and stirring power of 0.1kW/m 3 ；
(2) Seed crystal is added: injecting the solution into crystallizer with guide cylinder, cooling to 65deg.C, maintaining stability, adding 3.36g300-325 mesh seed crystal (solute mass fraction 0.2 wt%) for 1 hr, and stirring at 1.16kW/m 3 ；
(3) Cooling and crystallizing: the cooling rate is 1.0 ℃ per hour in the range of 65-60 ℃,2 ℃ per hour in the range of 60.0-54.0 ℃, 3.0 ℃ per hour in the range of 54-39 ℃,5 ℃ per hour in the range of 39-25 ℃ and the crystallization is stopped when the temperature is reduced to 25 ℃.
(4) And (3) product treatment: the centrifugal speed was 1000rpm,2000rpm,3000rpm each for 1min and the drying was carried out at 50℃for 9 hours.
The solubility and supersaturation liquid concentration of erythritol are shown in figure 1, the integral optical microscope picture of the product is shown in figure 2, the crystal size is highly uniform, and each crystal is formed by stacking 2-3 layers of small crystals. Erythritol crystals were detected in a yield of 71.07wt% and the resulting crystal size distribution is shown in the following table (table 1), wherein 90wt% of the crystals were between 20 and 40 mesh and 97.8wt% were between 20 and 60 mesh.
TABLE 1 Crystal size distribution of example 1
Example 2:
(1) And (3) evaporating and concentrating: taking a certain amount of erythritol sugar solution (15 wt%) with vacuum degree of 0.01MPa, evaporating and concentrating to 68wt%, maintaining temperature at 70deg.C and stirring power of 0.05kW/m 3 ；
(2) Seed crystal is added: injecting the solution into a crystallizer with a guide cylinder, cooling the solution to 70deg.C, maintaining stability, adding 6.72g 250-325 mesh seed crystal (solute mass fraction 0.6wt%) for 1 hr, and stirring with stirring power of 0.37kW/m 3 ；
(3) Cooling and crystallizing: the cooling rate is 1.5 ℃ per hour in the range of 70-60 ℃, 2.5 ℃ per hour in the range of 60-54 ℃,4 ℃ per hour in the range of 54.0-39.0 ℃, 5.5 ℃ per hour in the range of 39-25 ℃ and the crystallization is stopped when the temperature is reduced to 25 ℃.
(4) And (3) product treatment: the centrifugal speed was 1000rpm,2000rpm,3000rpm each for 1min and dried at 45℃for 12h.
The integral optical microscope picture of the product is shown in fig. 3, the crystal size is highly uniform, and each crystal is formed by polymerizing 2-3 layers of small crystals. The erythritol crystals were detected to have a yield of 72.46wt% and the resulting crystal size distribution is shown in the following table (table 2), wherein 89.8wt% of the crystals were between 20 and 40 mesh and 98.2wt% were between 20 and 60 mesh.
TABLE 2 Crystal size distribution of example 2
Example 3:
(1) And (3) evaporating and concentrating: taking a certain amount of erythritol sugar solution (20 wt%) with vacuum degree of 0.08MPa, evaporating and concentrating to 61wt%, maintaining temperature at 60deg.C and stirring power at 5kW/m 3 ；
(2) Seed crystal is added: injecting the solution into a crystallizer with a guide cylinder, cooling the solution to 60 ℃, adding 4.48g of 250-325 mesh seed crystal (solute mass fraction 0.4 wt%) for 1h, and stirring with stirring power of 2.64kW/m 3 ；
(3) Cooling and crystallizing: the cooling rate is 0.5 ℃ per hour in the range of 60-54 ℃,1 ℃ per hour in the range of 60-54 ℃,2 ℃ per hour in the range of 54-39 ℃, 4.5 ℃ per hour in the range of 39-25 ℃ and the crystallization is stopped when the temperature is reduced to 25 ℃.
(4) And (3) product treatment: the centrifugal speed was 1000rpm,2000rpm,3000rpm each for 1min and dried at 55℃for 6h.
The integral optical microscope picture of the product is shown in fig. 4, the crystal size is highly uniform, and each crystal is formed by polymerizing 2-3 layers of small crystals. The erythritol crystals were detected to have a yield of 65.78wt% and the resulting crystal size distribution is shown in the following table (table 3), wherein 89.8wt% of the crystals were between 20 and 40 mesh and 97.4wt% were between 20 and 60 mesh.
TABLE 3 Crystal size distribution of example 3
The above embodiments are preferred embodiments of the present application, but the embodiments of the present application are not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present application should be made in the equivalent manner, and the embodiments are included in the protection scope of the present application.
Comparative example 1:
erythritol crystals were prepared as in example 1, except that erythritol crystals were seeded at 6g of 150-180 mesh crystals (solute mass fraction 0.54 wt%) and the procedure was the same as in example 1.
After the crystallization is completed, as shown in fig. 5, the crystals are still more uniform, but the number of crystal faces of the seed crystals is insufficient, a certain degree of secondary nucleation occurs, and as the size of the seed crystals increases, the particle size distribution is as shown in the following table (table 4), 27.5wt% of the product is larger than 20 mesh, the particle size is mainly distributed between 4-20 mesh and 20-30 mesh, and 27.7wt% exceeds the effective particle size range of erythritol crystals.
TABLE 4 Crystal size distribution of comparative example 1
Comparative example 2:
erythritol crystals were prepared according to the method of example 1, except that the flow guide cylinder was not used to apply the z-axis flow field, instead of a double-layer propeller to promote back mixing, and the other steps and operations were the same as in example 1.
After the crystallization is finished, as shown in fig. 6, the bulk optical microscope photograph of the obtained crystal shows that the wet agglomeration of erythritol cannot be effectively controlled because a z-axis flow field is not applied, and then 1-4 layers of unequal small crystals are agglomerated, a large amount of scaling bodies are generated, and the particle size distribution is widened. The particle size distribution is shown in Table 5 below, with 18.3wt% product larger than 20 mesh and 23.5wt% outside the effective particle size range of erythritol crystals.
TABLE 5 Crystal size distribution of comparative example 2
Comparative example 3:
erythritol crystals were prepared as in example 2The difference from example 1 is that the stirring power was 4.98kW/m 3 Other steps and operations were the same as in example 1.
After the crystallization is finished, the integral optical microscope photograph of the obtained crystal is shown in fig. 7, the grain size of the crystal is not uniform, the phenomenon of coexistence of agglomeration and non-agglomeration occurs, and more fine crystals exist. The particle size distribution is shown in Table 6 below, with 11wt% product smaller than 60 mesh and 11.8wt% outside the erythritol effective particle size range.
TABLE 6 Crystal size distribution of comparative example 3
Comparative example 4:
erythritol crystals were prepared as in example 2, except that the cooling rate was set to a constant cooling rate of 2.5 c per hour, and the other steps and operations were the same as in example 1.
After the completion of crystallization, the bulk optical micrograph of the obtained crystals was as shown in FIG. 8, and the crystal grain size was not uniform and had a large number of fine crystals. The partial agglomeration phenomenon tends to adhere to fine crystals. The particle size distribution is shown in Table 7 below, with 13.2wt% product particle size greater than 20 mesh and 22.4wt% outside the erythritol effective particle size range.
TABLE 7 Crystal size distribution of comparative example 4
Comparative example 5:
erythritol crystals were prepared according to the method of example 3, differing from example 3 in that the cooling rate was divided into two steps, cooling to 3℃per hour in the interval of 60 to 45℃and cooling to 5℃per hour in the interval of 45 to 25℃and stopping crystallization. Other steps and operations were the same as in example 3.
After the crystallization is completed, as shown in fig. 9, the bulk optical microscope photograph of the obtained crystal is that the crystal particle size is not uniform, more fine crystals exist, and the phenomenon of partial agglomeration tends to adhere to the fine crystals. The particle size distribution is shown in Table 8 below, with 8.4wt% product particle size greater than 20 mesh and 19.0wt% outside the erythritol effective particle size range.
TABLE 8 Crystal size distribution of comparative example 5
Comparative example 6:
erythritol crystals were prepared according to the method of patent CN113912475A, and after crystallization was completed, the bulk optical microscope photograph of the obtained crystals was as shown in fig. 10, and the obtained product was consistent with the crystal morphology obtained in patent CN113912475A, and exists mostly in single crystal morphology. The particle size distribution is shown in Table 9 below, with 85.9wt% of the product having a particle size between 20 and 40 mesh. 98.6wt% of the crystals are larger than 40 mesh, which meets the standard that the majority of the particle size is above 50 mesh.
TABLE 9 Crystal size distribution of comparative example 6
The crystal form refers to the arrangement mode of crystal molecules in the crystal, is important physicochemical properties of the crystal, and for polymorphic substances, certain physicochemical properties (such as melting point, solubility and stability) may be different due to different crystal forms; under different conditions, the crystal forms may be mutually converted, and the crystal transformation phenomenon occurs. In order to verify whether the erythritol agglomerated crystal has a crystal form difference compared with the erythritol common crystal, XRD characterization is performed on the erythritol agglomerated crystal in example 1 and the erythritol large-particle crystal in comparative example 6, diffraction peak positions are shown in fig. 11, and according to the specification of P372 in 2015 of Chinese pharmacopoeia, if the two crystalline sample crystal forms are judged to be identical, the error range of the diffraction peak positions of the two crystalline sample crystal forms is within +/-0.2 degrees. In fig. 11, the peak positions of two erythritol crystals with different morphologies correspond to the same diffraction angle, so that the erythritol agglomerated crystals in the patent are considered to be consistent compared with the conventional product in crystal form, and no crystal transformation phenomenon occurs in the crystallization process.
In addition, the angle of repose and dissolution rates of the different examples and comparative examples were tested to evaluate their potential for use in beverages. The dissolution rate test method adopts a laser diffraction method, specifically, 30g of erythritol crystal product is poured into 100g of pure water at 25 ℃ and 300rpm, signal intensity of a signal receiver is gradually reduced along with dissolution of the crystal, when the signal receiver shows that the value is lower than a certain value and is kept unchanged, the dissolution end of the crystal is judged, and the required time is the dissolution time, as shown in fig. 12, and the repose angle test method is according to the repose angle measurement method provided by patent CN113412266a, as shown in fig. 13, and the repose angles and the dissolution rates of different examples and comparative examples are shown in the following table (table 10).
Table 10 dissolution rates and angle of repose of the crystalline products obtained in the different examples and comparative examples.
As is clear from a comparison of example 1 and comparative example 1, when the seed crystal addition amount is out of the limit of the present application, the particle size distribution of the product is significantly large because the seed crystals having a larger particle size grow into larger crystals, and these larger crystals further coalesce to form large crystals, which cause the particle size distribution to be out of control, and furthermore, the number of large-particle seed crystals is smaller at the same mass, and the consumption capacity for supersaturation is insufficient, resulting in secondary nucleation of erythritol. These factors lead to a broad distribution of erythritol crystal particle size distribution, and a significant portion of the crystals are outside the range of particle sizes in which erythritol is suitable for sale, and because of the larger particle size, the dissolution rate is lower, and because of the uneven particle size distribution, the fluidity is reduced, and the angle of repose is increased.
As can be seen from the comparison between the example 1 and the comparative example 2, when the x-axis and y-axis flow fields are the same, and when the whole z-axis flow field is applied without using the guide cylinder and the propeller, the local z-axis back mixing is performed by means of double-layer stirring, the aggregation of erythritol cannot be controlled, dead zones are formed locally, scaling occurs in the crystallizer, and non-aggregated large blocks are formed when the scaling falls off, and these factors make the product particle size of erythritol bigger and cannot meet the product requirement. The dissolution rate is low due to the larger particle size, the fluidity is reduced due to the uneven particle size distribution, and the repose angle is increased.
As is evident from a comparison of example 2 and comparative example 3, when the stirring rate is too high, a large shearing force and dispersion work are brought about, and when the dispersion work of the crystals in the solution is smaller than the adhesion work to a certain extent, a part of the crystals do not participate in coalescence. In addition, too much shearing force can break up a considerable part of crystals, so that broken crystals are more, the particle size distribution is out of control, the morphology of the crystals is reduced, and the agglomeration risk of subsequent products is increased. Thus, although the dissolution rate is faster due to the fact that the particle size is smaller, the particle size distribution is uneven, the particles are more broken, the fluidity is reduced, and the repose angle is increased.
It is known from example 2 and comparative example 4 that when the cooling rate is reduced at a constant speed, the seed crystal cannot consume a sufficient amount of supersaturation in a part of the cooling interval, so that burst nucleation caused by accumulation of supersaturation occurs, the particle size distribution is widened, the fluidity is poor, the repose angle is large, and the overall dissolution rate is low due to the significant increase of the large crystal content, so that the requirement of the application field on the product cannot be met.
It is known from example 3 and comparative example 5 that when the cooling rate is two-stage cooling instead of four-stage cooling, the seed crystal still cannot consume enough supersaturation in a part of the cooling interval, so that burst nucleation occurs, the particle size distribution is widened, the fluidity is poor, the repose angle is large, and the overall dissolution rate is low due to the significant increase of the large crystal content, so that the requirement of the application field on the product cannot be met.
As is evident from example 3 and comparative example 6 (patent CN 113912475A), the dissolution rate of erythritol single crystal particles is significantly lower than that of the agglomerated crystals prepared by the present method, because the agglomerated crystals have a significantly larger surface area than the single crystal particles at the same volume, and the agglomerated flower-like structure can significantly reduce the dissolution radius as compared with the single crystal having the same particle size, thereby greatly improving the dissolution rate of the agglomerated crystals. On the basis, the particle size is uniform and the agglomeration degree is effectively controlled, so that the particle size can still keep similar fluidity compared with single crystals.
The application discloses and provides an erythritol crystal, a preparation method and application thereof, and a person skilled in the art can properly change part of links by referring to the content of the erythritol crystal. While the method of the present application has been described in terms of preferred embodiments, it will be apparent to those skilled in the relevant art that variations and combinations of the methods and products described herein can be made to practice the present technology without departing from the spirit or scope of the application. It is expressly noted that all such similar substitutes and modifications apparent to those skilled in the art are deemed to be included within the spirit, scope and content of the application.
Claims (11)
1. A method for preparing erythritol crystals, comprising the steps of:
adding erythritol seed crystal into erythritol concentrated solution with temperature of 60-70 ℃, and cooling and crystallizing in four sections under the flow field and stirring action to obtain erythritol crystals;
the flow field is a flow field with the z-axis direction and the tangential direction simultaneously; the z-axis flow field is applied through a guide cylinder; the tangential direction of the flow field is applied by a single-layer three-blade propulsion propeller; the stirring power during cooling crystallization is 0.37-2.64kW/m 3 ；
The cooling crystallization comprises four steps, namely, the temperature is reduced from 70-60 ℃ to 64-54 ℃ at the temperature reduction rate of 0.5-1.5 ℃/h, the temperature is reduced from 64-54 ℃ to 54-39 ℃ at the temperature reduction rate of 1-2.5 ℃/h, the temperature is reduced from 54-39 ℃ to 39-25 ℃ at the temperature reduction rate of 2-4 ℃/h, and the temperature is reduced from 39-25 ℃ to 25-20 ℃ at the temperature reduction rate of 4.5-6 ℃/h;
the grain diameter of the erythritol seed crystal is 250-325 meshes;
the adding amount of the erythritol seed crystal is 0.2-1wt% of the dry matter content of the erythritol in the erythritol concentrated solution.
2. The method according to claim 1, wherein the method for preparing the erythritol concentrate having a temperature of 60 to 70 ℃ comprises: and evaporating and concentrating the erythritol solution with the concentration of 10-20wt% to 50-70wt% at the constant temperature of 60-70deg.C.
3. The preparation method according to claim 2, wherein the preparation method of the erythritol concentrate at a temperature of 60-70 ℃ comprises: and evaporating and concentrating the erythritol solution with the concentration of 10-15wt% at the constant temperature of 60-70 ℃ to 61-68wt%.
4. The method according to claim 2, wherein the constant temperature evaporation has a vacuum degree of 0.01 to 0.08MPa.
5. The method according to claim 2, wherein the constant temperature evaporation has a stirring power of 0.05-5kW/m 3 。
6. The method according to claim 1, wherein the erythritol concentrate is prepared in a vacuum evaporation crystallizer.
7. The preparation method according to claim 1, wherein the erythritol seed crystal is added in an amount of 0.3 to 0.6wt% of the dry matter content of erythritol in the erythritol concentrate.
8. The method of claim 1, wherein the cooling crystallization is performed in a cooling crystallizer with a guide shell.
9. The method according to claim 1, further comprising subjecting the mixed solution obtained by cooling crystallization to solid-liquid separation, washing and drying in this order.
10. The method according to claim 9, wherein the solid-liquid separation is performed by centrifugation.
11. The method according to claim 9, wherein the drying is performed at a temperature of 25 to 55 ℃ for 6 to 48 hours under normal pressure.
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