A method for the production of a refined honey

Abstract

This invention belongs to the field of food technology, specifically relating to a method for preparing refined honey. A composite treatment agent of strontium oxide and silicon oxide doped with carbon is prepared. The strontium-based treatment agent is mixed with honey and treated at 40-60°C for 1-4 hours. The honey and the strontium-based treatment agent are then separated to obtain refined honey. This method can regulate the proportion of sugar components in honey, significantly reduce glucose supersaturation, achieve long-term non-crystallization storage of honey, and significantly slow down the formation rate of high-methanesulfonic acid (HMF) during storage.

Description

Technical Field

[0001] This invention belongs to the field of food technology, specifically relating to a method for preparing refined honey. Background Technology

[0002] Honey contains a large amount of glucose and fructose. Due to the low solubility of glucose, honey is prone to crystallization during storage. This is a natural phenomenon, but incomplete crystallization causes honey to separate into layers. This can easily give unsuspecting consumers a bad impression, leading to the misconception that the honey is adulterated, resulting in food waste and even disrupting the market order for natural honey. Furthermore, the non-crystallized portion of crystallized honey contains a high water content, making it more susceptible to microbial growth and affecting its shelf life.

[0003] Besides containing a large amount of sugars, honey also contains various antioxidants such as polyphenols, phenolic acids, and ketones. Therefore, honey has antioxidant activity and broad application prospects in health products, food additives, and cosmetics. However, the antioxidant properties vary considerably among different types of honey. Differences in processing and storage methods, especially temperature changes during the process, can significantly affect its antioxidant activity, promoting the formation of the harmful substance 5-hydroxymethylfurfural (HMF). 5-hydroxymethylfurfural is mainly produced by the dehydration of glucose or fructose and is an indicator for evaluating storage conditions and honey aging; its content directly reflects the quality of the honey. Summary of the Invention

[0004] To address the problems in existing technologies where honey easily crystallizes during storage and the reduced antioxidant activity leading to the formation of 5-hydroxymethylfurfural, which shortens the shelf life of honey, this invention primarily provides a method for preparing refined honey that reduces the probability of crystallization while preserving its antioxidant activity.

[0005] A method for preparing refined honey includes the following steps: mixing a strontium-based treatment agent with honey and treating it at 40-60°C for 1-4 hours; separating the honey from the strontium-based treatment agent to obtain refined honey.

[0006] Furthermore, the mass of the strontium-based treatment agent is 5-20% of the mass of the honey.

[0007] Furthermore, before mixing with the strontium-based treatment agent, the honey is diluted with water to a water content of 30-70%; the treated honey is then concentrated at low temperature to reduce the water content to less than 25%.

[0008] Furthermore, the preparation of the strontium-based treatment agent includes the following steps:

[0009] a. Add the carbon source, silicon source, strontium source, and template agent to water and stir to dissolve;

[0010] b. Adjust the pH to weakly alkaline with stirring, continue stirring and aging to obtain a gel; form the gel into spherical particles, and dry to obtain microspheres;

[0011] c. Under a protective atmosphere, heat the microspheres to 500~700℃ and then calcine for 1~3 hours.

[0012] Furthermore, in step a, the mass ratio of the carbon source to the silicon source is 1:10~20; the molar ratio of silicon to strontium in the silicon source to the strontium source is 7~9:1; and the template agent accounts for 5~15% of the mass of the silicon source.

[0013] Furthermore, the diameter of the microspheres in step b is 0.5~5mm; and the pH of the weakly alkaline solution is 8~10.

[0014] Furthermore, in step c, the temperature is increased to 150-250°C at a rate of 2-5°C / min, and then increased to 500-700°C at a rate of 5-10°C.

[0015] Furthermore, the carbon source includes one or more of starch, sucrose, glucose, or lignin; the silicon source includes one or more of tetraethoxysilane, tetramethoxysilane, tetran-propoxysilane, and tetraisopropoxysilane; and the strontium source includes one or more of strontium chloride, strontium acetate, or strontium nitrate.

[0016] Furthermore, the gel is injected onto a mold with a groove array, the surface is scraped clean after vacuum degassing, and the coated mold is dried at 40~70℃ to obtain microspheres after demolding.

[0017] Furthermore, after washing the strontium-based treatment agent with water, it is heat-treated at 450~600℃ for 1~2 hours to complete the regeneration.

[0018] By adopting the above scheme, the method of the present invention has the following advantages:

[0019] 1. The Lewis basic sites in the treatment agent of this invention can efficiently catalyze the isomerization of glucose into fructose; at the same time, the preferential adsorption and enrichment effect of glucose by the carbon support can pull the reaction equilibrium towards the direction of fructose production, breaking through the thermodynamic equilibrium limitation of traditional isomerization reactions, realizing the conversion of glucose at high sugar concentrations, and increasing the ratio of fructose to glucose in natural honey.

[0020] 2. This invention significantly reduces the supersaturation of glucose by regulating the proportion of sugar components in honey, thereby inhibiting the homogeneous nucleation and crystal growth of glucose molecules from the source, achieving long-term non-crystallization storage of honey. No crystallization occurs after 12 months of storage at room temperature, completely solving the problem of easy crystallization in natural honey.

[0021] 3. The weakly alkaline sites in the treatment agent of this invention can combine with the hydrogen ions of some free organic acids in honey, slightly increasing the pH of honey and significantly reducing the reaction rate of fructose dehydration to form HMF. At the same time, the reaction process is carried out under low temperature conditions, avoiding the problem of high temperature induction of HMF formation in traditional pyrolysis crystallization processes. During treatment and long-term storage, the HMF formation rate is significantly reduced compared to untreated honey, far below the national standard limit, eliminating the need for external antioxidants and not affecting the flavor of honey.

[0022] 4. The inert silicon-based framework of the treatment agent of the present invention has no significant effect on the active nutrients such as phenolic antioxidants, organic acids, and vitamins in honey. The retention rate of nutrients is high during the treatment process, thus preserving the natural flavor and nutritional effects of honey.

[0023] 5. The treatment agent of this invention is a structured microsphere at the millimeter-scale macroscopic level. After the reaction is completed, it can be completely separated by simple procedures such as gravity sedimentation without the need for additional precision filtration equipment. At the same time, the strontium silicate framework has extremely high structural stability, with a leaching rate of <0.008% in a weakly acidic environment, and no significant decrease in catalytic activity after 25 cycles of use. The deactivated catalyst can be regenerated through simple operations, which greatly reduces the processing cost.

[0024] 6. The carbon doping in the treatment agent of the present invention significantly improves the mass transfer efficiency in high viscosity and high sugar concentration systems, which can be adapted to the high sugar concentration environment of honey, avoids the loss of nutrients and the generation of harmful oxidizing substances such as HMF caused by large-scale concentration, and has low process complexity and energy consumption. Attached Figure Description

[0025] Figure 1 This is a comparison chart of the 5-hydroxymethylfurfural content of each embodiment and the comparative example after being stored at 60°C for 30 days. Detailed Implementation

[0026] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0027] Example 1: (1) Starch, tetraethoxysilane, and strontium chloride hexahydrate were added to deionized water at a mass ratio of 0.5:6:1, stirred and dissolved, and hexadecyltrimethylammonium bromide was added at 10% of the mass of tetraethoxysilane.

[0028] (2) While stirring, adjust the pH to 9 and continue stirring to age to obtain a gel; pour the gel into a mold with a groove array, vacuum degas the surface and scrape it clean, then dry the coated mold at 60°C and demold to obtain microspheres with a diameter of 2 mm.

[0029] (3) Under a protective atmosphere, the microspheres were heated to 200°C at a rate of 3°C / min, and then heated to 600°C at a rate of 8°C. The microspheres were calcined for 2 hours. The resulting product was thoroughly washed with water and dried to obtain the strontium-based treatment agent.

[0030] (4) Dilute the honey with water to a water content of 40%, mix 10% of the honey mass of strontium-based treatment agent with the diluted honey, and treat at 50°C for 2 hours; separate the honey from the strontium-based treatment agent, and concentrate the treated honey at low temperature to obtain refined honey with a water content of less than 20%.

[0031] Example 2: The difference from Example 1 is as follows:

[0032] (1) Take starch, tetraethoxysilane and strontium chloride hexahydrate in a mass ratio of 0.5:8:1 and add them to deionized water. Stir to dissolve and add hexadecyltrimethylammonium bromide, which accounts for 10% of the mass of tetraethoxysilane.

[0033] Example 3: The difference from Example 1 is as follows:

[0034] (1) Take starch, tetraethoxysilane and strontium chloride hexahydrate in a mass ratio of 0.5:5:1 and add them to deionized water. Stir to dissolve and add hexadecyltrimethylammonium bromide, which accounts for 10% of the mass of tetraethoxysilane.

[0035] Example 4: The difference from Example 1 is as follows:

[0036] (2) While stirring, adjust the pH to 9 and continue stirring to age to obtain a gel; pour the gel into a mold with a groove array, vacuum degas the surface and scrape it clean, then dry the coated mold at 60°C and demold to obtain microspheres with a diameter of 1 mm.

[0037] Example 5: The difference from Example 1 is as follows:

[0038] (2) While stirring, adjust the pH to 9 and continue stirring to age to obtain a gel; pour the gel into a mold with a groove array, vacuum degas the surface and scrape it clean, then dry the coated mold at 60°C and demold to obtain microspheres with a diameter of 5 mm.

[0039] Comparative Example 1: The difference from Example 1 is that:

[0040] (1) Take tetraethoxysilane and strontium chloride hexahydrate in a mass ratio of 6:1 and add them to deionized water. Stir to dissolve and add hexadecyltrimethylammonium bromide, which accounts for 10% of the mass of tetraethoxysilane.

[0041] Comparative Example 2: The difference from Example 1 is that:

[0042] (3) Under a protective atmosphere, the microspheres were heated to 600°C at a rate of 5°C and calcined for 2 hours. The resulting product was thoroughly washed with water and dried to obtain the strontium-based treatment agent.

[0043] Example Sample Testing:

[0044] The honey used in each embodiment and comparative example had a fructose / glucose ratio of 1.07, a fructose content of 36.94 g / 100 g, and a glucose content of 34.52 g / 100 g. The changes in fructose and glucose content of the honey after treatment in each embodiment and comparative example were detected, and the fructose / glucose ratio was calculated.

[0045] Table 1:

[0046] Fructose (g / 100g) Glucose (g / 100g) Fructose / Glucose Example 1 40.63 28.61 1.42 Example 2 39.57 30.01 1.32 Example 3 41.07 28.19 1.45 Example 4 42.15 27.73 1.52 Example 5 41.06 30.42 1.35 Comparative Example 1 39.46 31.57 1.25 Comparative Example 2 39.95 31.45 1.27

[0047] As shown in the table above, compared to Example 1, Example 2 shows an increased tetraethoxysilane content and a relatively decreased strontium content, resulting in a weakened catalytic effect. In Example 3, the strontium content was relatively increased, leading to a relatively lower fructose conversion efficiency. The microspheres of the treatment agent in Example 4 have a smaller diameter, resulting in lower internal mass transfer resistance and higher utilization of active sites. The fructose to glucose ratio is significantly increased, but excessive changes in this ratio can affect the flavor of honey, so it needs to be controlled within a suitable range. Meanwhile, the microspheres of the treatment agent in Example 5 have a larger diameter, and the significantly increased mass transfer resistance affects the fructose conversion efficiency. Comparative Example 1 uses an undoped carbon treatment agent, which increases mass transfer resistance, weakens the catalytic effect, and reduces the fructose conversion efficiency. Comparative Example 2 uses a rapid one-stage heating process, which easily leads to agglomeration of the catalyst's active sites, resulting in a decrease in fructose conversion rate.

[0048] The treated honey was stored in a 60℃ incubator for 30 days, with the initial honey without treatment as a control. 50g of honey was accurately weighed and added to a 500mL Erlenmeyer flask, then diluted with water to 200mL to obtain a honey solution of 0.25g / mL. A standard solution of 5-hydroxymethylfurfural was prepared, and the 5-hydroxymethylfurfural content of the sample was determined by high performance liquid chromatography to evaluate the antioxidant level.

[0049] Depend on Figure 1It can be seen that, compared with the untreated control, the 5-hydroxymethylfurfural content in each example and comparative example remained at a low level after storage at 60°C for 30 days. This indicates that the method of the present invention can significantly reduce the oxidation of honey and extend its shelf life. Among them, Comparative Example 1, treated with an undoped carbon-based treatment agent, showed a decrease in catalytic activity and mass transfer efficiency, resulting in a weakened pH regulation effect and an increase in 5-hydroxymethylfurfural content. Furthermore, Comparative Example 2, which used a faster one-stage heating method, also showed a greater increase in 5-hydroxymethylfurfural content during storage than the examples, indicating that this heating method affects the formation of active sites in the treatment agent, thereby affecting its pH regulation effect.

[0050] For those skilled in the art, various other corresponding changes and modifications can be made based on the technical solutions and concepts described above, and all such changes and modifications should fall within the protection scope of the claims of this invention.

Claims

1. A method for preparing refined honey, characterized in that, Includes the following steps: Mix the strontium-based treatment agent with honey and treat at 40-60℃ for 1-4 hours; separate the honey from the strontium-based treatment agent to obtain refined honey.

2. The method for preparing refined honey according to claim 1, characterized in that, The mass of the strontium-based treatment agent is 5-20% of the mass of the honey.

3. The method for preparing refined honey according to claim 1, characterized in that, Before mixing with the strontium-based treatment agent, the honey is diluted with water to a water content of 30-70%; the treated honey is then concentrated at low temperature to reduce the water content to less than 25%.

4. The method for preparing refined honey according to claim 1, characterized in that, The preparation of the strontium-based treatment agent includes the following steps: a. Add the carbon source, silicon source, strontium source, and template agent to water and stir to dissolve; b. Adjust the pH to weakly alkaline with stirring, continue stirring and aging to obtain a gel; form the gel into spherical particles, and dry to obtain microspheres; c. Under a protective atmosphere, heat the microspheres to 500~700℃ and then calcine for 1~3 hours.

5. The method for preparing refined honey according to claim 4, characterized in that, The mass ratio of carbon source to silicon source in step a is 1:10~20; the molar ratio of silicon to strontium in silicon source to strontium source is 7~9:1; and the template agent accounts for 5~15% of the mass of silicon source.

6. The method for preparing refined honey according to claim 4, characterized in that, The diameter of the microspheres in step b is 0.5~5mm; the pH of the weakly alkaline solution is 8~10.

7. The method for preparing refined honey according to claim 4, characterized in that, The temperature rise in step c is to increase the temperature to 150-250°C at a rate of 2-5°C / min, and then to 500-700°C at a rate of 5-10°C.

8. The method for preparing refined honey according to claim 1, characterized in that, The carbon source includes one or more of starch, sucrose, glucose, or lignin; the silicon source includes one or more of tetraethoxysilane, tetramethoxysilane, tetran-propoxysilane, and tetraisopropoxysilane; and the strontium source includes one or more of strontium chloride, strontium acetate, or strontium nitrate.

9. The method for preparing refined honey according to claim 1, characterized in that, The gel is injected into a mold with a groove array, the surface is scraped clean after vacuum degassing, and the coated mold is dried at 40~70℃. The microspheres are then demolded.

10. The method for preparing refined honey according to claim 1, characterized in that, After washing the strontium-based treatment agent with water, it is heat-treated at 450~600℃ for 1~2 hours to complete the regeneration.

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