A processing, extraction, and purification method for natural ferulic acid vanillin.

Abstract

This invention relates to the field of vanillin production and processing technology, and discloses a method for processing, extracting, and purifying natural ferulic acid vanillin, comprising the following steps: Raw material pretreatment: After drying and pulverizing the plant raw materials, they are extracted by reflux extraction with 40%-60% ethanol to remove fat-soluble impurities, and the filter residue is collected. By using a eutectic solvent coupled with ultrasound-assisted extraction, the solvent has good biocompatibility and no toxic residue. The ultrasonic cavitation effect and the hydrogen bonding effect of the eutectic solvent synergistically promote the efficient dissolution of the two active ingredients, increasing the extraction rate by 30%-40% compared with traditional methods; Non-ionic microemulsion extraction is used to achieve fractional separation of ferulic acid and vanillin, with a separation efficiency of over 95%, avoiding cross-contamination and simplifying the subsequent purification process; Combined with chromatographic purification and recrystallization technology, the product purity is high: meeting pharmaceutical grade standards; The integrated process design realizes the comprehensive utilization of plant raw materials, with a solvent recovery rate of ≥90% and a reduction in energy consumption of 25%-30%, making it suitable for large-scale industrial production.

Description

Technical Field

[0001] This invention relates to the field of vanillin production and processing technology, specifically a method for processing, extracting, and purifying natural ferulic acid vanillin. Background Technology

[0002] Ferulic acid and vanillin are both natural active ingredients with significant medicinal value and promising industrial applications. Ferulic acid possesses pharmacological effects such as antioxidant, anti-inflammatory, and lipid-regulating properties. Vanillin, as a natural fragrance and pharmaceutical intermediate, can be used in many daily chemical fragrance formulations, but is primarily used in food flavorings. It is widely used, especially in candies, chocolates, beverages, ice cream, and alcoholic beverages, and also has significant applications in tobacco flavorings; it is often used as a base fragrance and can be widely used in almost all fragrance types, such as violet, orchid, sunflower, and oriental scents. It can also be used as a fixative and is a major raw material for formulating vanilla-type flavorings. It can also be directly used to flavor biscuits, pastries, candies, beverages, and other foods. In existing technologies, the extraction of ferulic acid and vanillin are mostly carried out through independent processes: ferulic acid extraction often employs alkaline hydrolysis or enzymatic hydrolysis, but these methods suffer from cumbersome purification processes and residual organic solvents; vanillin preparation largely relies on chemical synthesis or single microbial transformation, resulting in low extraction efficiency of natural vanillin and difficulty in simultaneously enriching both components. Furthermore, traditional extraction methods suffer from drawbacks such as high solvent toxicity, high energy consumption, and easy degradation of active ingredients. For example, chemical synthesis methods use toxic solvents such as pyridine and toluene, which do not conform to the concept of green production; and single extraction processes lead to low utilization of plant resources and high production costs.

[0003] Therefore, developing a green and efficient integrated method that can simultaneously extract and purify natural ferulic acid and vanillin to achieve comprehensive resource utilization and high-purity product output has become a technical problem that needs to be solved in this field. Summary of the Invention

[0004] This invention provides a method for processing, extracting, and purifying natural ferulic acid vanillin, achieving simultaneous extraction, efficient separation, and high-purity purification of the two active ingredients, while taking into account the greenness of the process, ease of operation, and industrial feasibility, thus solving the problems mentioned in the background art.

[0005] This invention provides the following technical solution: a method for processing, extracting, and purifying natural ferulic acid vanillin, comprising the following steps: (1) Raw material pretreatment: After drying and pulverizing the plant raw materials, they are extracted by reflux extraction with 40%-60% ethanol to remove fat-soluble impurities and the filter residue is collected; The specific steps are as follows: Select plant raw materials rich in ferulic acid and vanillin precursors, dry them and pulverize them to 60-80 mesh, add 10-15 times the volume of 40%-60% ethanol solution, reflux extract at 70-80℃ for 0.5-2 hours, filter to remove fat-soluble impurities, and collect the filter residue for later use. Synergistic extraction: The filter residue is mixed with a eutectic solvent and subjected to ultrasonic-assisted, constant-temperature stirring for synergistic extraction. The crude extract is then filtered. The specific steps are as follows: The pretreated filter residue is mixed with a eutectic solvent at a mass-to-volume ratio of 1:(10-30). The eutectic solvent is composed of choline chloride and glycerol in a molar ratio of 1:2. 15%-20% (v / v) deionized water is added to adjust the viscosity. The mixture is then ultrasonically extracted at 40-60℃ and 30-50kHz for 20-40 minutes, followed by heating to 70-85℃ and stirring for 1-2 hours. The crude extract is then obtained by filtration. Fractional separation: Adjust the pH of the crude extract to 2-3, perform non-ionic microemulsion extraction to separate the layers, and collect the organic phase containing vanillin and the aqueous phase containing ferulic acid separately; The specific steps are as follows: Adjust the pH of the crude extract to 2-3, add a non-ionic microemulsion system (Tween 80-n-hexane-sodium dihydrogen phosphate, mass ratio 5:4:1), stir and extract at 30-40℃ for 30 min, collect the organic components containing vanillin and ferulic acid after standing and separating the layers; recover the solvent by vacuum distillation to obtain crude vanillin; filter the aqueous phase through a 0.22μm ceramic membrane to remove macromolecular impurities to obtain crude ferulic acid extract; Purification and refining: The organic phase was purified by macroporous resin chromatography-crystallization to obtain high-quality vanillin, and the aqueous phase was purified by gel column chromatography-recrystallization to obtain high-quality ferulic acid. The specific content is as follows: Vanillin purification: Crude vanillin was dissolved in a 50%-70% (v / v) aqueous ethanol solution, and adsorption chromatography was performed using macroporous resin AB-8. The solution was eluted with a gradient of 30%-50% ethanol solution. The target eluent was collected, concentrated under reduced pressure, and crystallized at 4-8℃ for 12 hours. The purified vanillin was then obtained by filtration and drying. Ferulic acid purification: The crude extract of ferulic acid was subjected to polyamide gel column chromatography and eluted with 20%-40% ethanol solution. The eluent was collected and recrystallized by adding an organic alcohol aqueous solution (ethanol:water = 1:1). The eluent was dried in a forced-air environment at 40-65℃ to obtain the purified ferulic acid.

[0006] The selected plant materials are wheat bran, rice bran, Dendrobium officinale, or vanilla pods.

[0007] Preferably, the eutectic solvent can be replaced with a choline chloride-malic acid molar ratio of 1:1 or a choline chloride-glycerol-urea molar ratio of 1:1:1.

[0008] Specifically, the ultrasonic extraction power is 150-200W, and the stirring speed is 200-300r / min.

[0009] The preferred adsorption conditions for the macroporous resin AB-8 are: flow rate 1-2 BV / h, sample concentration 5-10 mg / mL; and elution flow rate for polyamide gel column chromatography is 0.5-1 BV / h.

[0010] The present invention has the following beneficial effects: This invention employs ultrasonic-assisted extraction coupled with a eutectic solvent. The solvent exhibits good biocompatibility and leaves no toxic residues. The synergistic effect of ultrasonic cavitation and hydrogen bonding in the eutectic solvent promotes the efficient dissolution of the two active ingredients, increasing the extraction rate by 30%-40% compared to traditional methods. Nonionic microemulsion extraction achieves fractional separation of ferulic acid and vanillin with a separation efficiency exceeding 95%, avoiding cross-contamination and simplifying subsequent purification processes. Combined with chromatographic purification and recrystallization techniques, the product boasts high purity: ferulic acid purity ≥98.5% and vanillin purity ≥99.0%, meeting pharmaceutical-grade standards. The integrated process design enables comprehensive utilization of plant raw materials, achieving a solvent recovery rate ≥90% and reducing energy consumption by 25%-30%, making it suitable for large-scale industrial production. Detailed Implementation

[0011] The technical solutions in the embodiments of this invention are clearly and completely described. Obviously, the described embodiments are only a part of the embodiments of this invention, and not all of them. Based on the embodiments of this invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of this invention.

[0012] A method for processing, extracting, and purifying natural ferulic acid vanillin, characterized by the following steps: (1) Raw material pretreatment: After drying and pulverizing the plant raw materials, they are extracted by reflux extraction with 40%-60% ethanol to remove fat-soluble impurities and the filter residue is collected; The specific steps are as follows: Select plant raw materials rich in ferulic acid and vanillin precursors, dry them and pulverize them to 60-80 mesh, add 10-15 times the volume of 40%-60% ethanol solution, reflux extract at 70-80℃ for 0.5-2 hours, filter to remove fat-soluble impurities, and collect the filter residue for later use. Synergistic extraction: The filter residue is mixed with a eutectic solvent and subjected to ultrasonic-assisted, constant-temperature stirring for synergistic extraction. The crude extract is then filtered. The specific steps are as follows: The pretreated filter residue is mixed with a eutectic solvent at a mass-to-volume ratio of 1:(10-30). The eutectic solvent is composed of choline chloride and glycerol in a molar ratio of 1:2. 15%-20% (v / v) deionized water is added to adjust the viscosity. The mixture is then ultrasonically extracted at 40-60℃ and 30-50kHz for 20-40 minutes, followed by heating to 70-85℃ and stirring for 1-2 hours. The crude extract is then obtained by filtration. Fractional separation: Adjust the pH of the crude extract to 2-3, perform non-ionic microemulsion extraction to separate the layers, and collect the organic phase containing vanillin and the aqueous phase containing ferulic acid separately; The specific steps are as follows: Adjust the pH of the crude extract to 2-3, add a non-ionic microemulsion system (Tween 80-n-hexane-sodium dihydrogen phosphate, mass ratio 5:4:1), stir and extract at 30-40℃ for 30 min, collect the organic components containing vanillin and ferulic acid after standing and separating the layers; recover the solvent by vacuum distillation to obtain crude vanillin; filter the aqueous phase through a 0.22μm ceramic membrane to remove macromolecular impurities to obtain crude ferulic acid extract; Purification and refining: The organic phase was purified by macroporous resin chromatography-crystallization to obtain high-quality vanillin, and the aqueous phase was purified by gel column chromatography-recrystallization to obtain high-quality ferulic acid. The specific content is as follows: Vanillin purification: Crude vanillin was dissolved in a 50%-70% (v / v) aqueous ethanol solution, and adsorption chromatography was performed using macroporous resin AB-8. The solution was eluted with a gradient of 30%-50% ethanol solution. The target eluent was collected, concentrated under reduced pressure, and crystallized at 4-8℃ for 12 hours. The purified vanillin was then obtained by filtration and drying. Ferulic acid purification: The crude extract of ferulic acid was subjected to polyamide gel column chromatography and eluted with 20%-40% ethanol solution. The eluent was collected and recrystallized by adding an organic alcohol aqueous solution (ethanol:water = 1:1). The eluent was dried in a forced-air environment at 40-65℃ to obtain the purified ferulic acid.

[0013] The plant-based raw materials include wheat bran, rice bran, Dendrobium officinale, or vanilla pods.

[0014] The eutectic solvent can be replaced with a choline chloride-malic acid molar ratio of 1:1 or a choline chloride-glycerol-urea molar ratio of 1:1:1.

[0015] The ultrasonic extraction power is 150-200W, and the stirring speed is 200-300r / min.

[0016] The adsorption conditions for macroporous resin AB-8 were: flow rate 1-2 BV / h, sample concentration 5-10 mg / mL; and the elution flow rate for polyamide gel column chromatography was 0.5-1 BV / h. Example

[0017] 1. Raw material pretreatment: Take 100g of wheat bran raw material, dry it with hot air at 60℃ to constant weight, grind it to 70 mesh, add 1200mL of 50% ethanol solution, reflux extract at 75℃ for 1h, filter and collect the residue. 2. Synergistic extraction: The filter residue was mixed with choline chloride-glycerol eutectic solvent (molar ratio 1:2) at a ratio of 1:20 (m / v), and 18% deionized water was added to adjust the viscosity. The mixture was ultrasonically extracted at 50℃, 40kHz, and 180W for 30 min, and then heated to 80℃ and stirred at 250r / min for 1.5 h. The crude extract was obtained by filtration. 3. Fractional separation: Adjust the pH of the crude extract to 2.5, add a non-ionic microemulsion system (Tween80-n-hexane-sodium dihydrogen phosphate = 5:4:1), stir and extract at 35℃ for 30 min, after separation, distill the organic phase under reduced pressure to obtain crude vanillin (purity 68.3%), and filter the aqueous phase through a membrane to obtain crude ferulic acid extract (purity 52.7%). 4. Purification and refining: Vanillin: The crude product was dissolved in a 60% ethanol aqueous solution, and eluted with AB-8 macroporous resin (flow rate 1.5 BV / h) using a 40% ethanol gradient. After concentration, crystallization was carried out at 4°C for 12 h, and dried to obtain the pure vanillin (purity 99.2%). Ferulic acid: The crude extract was subjected to polyamide gel column chromatography (flow rate 0.8 BV / h), eluted with 30% ethanol, and the collected solution was recrystallized with ethanol-water (1:1) and dried at 50°C to obtain high-purity ferulic acid (purity 98.7%). Example

[0018] 1. Raw material pretreatment: Take 100g of rice bran raw material, dry it with hot air at 60℃ to constant weight, pulverize it to 70 mesh, add 1200mL of 50% ethanol solution, reflux extract at 75℃ for 1h, filter and collect the residue. 2. Synergistic extraction: The filter residue was mixed with choline chloride-malic acid (molar ratio 1:1 at 1:20 (m / v), 18% deionized water was added to adjust the viscosity, and ultrasonic extraction was performed at 45℃, 35kHz, and 180W for 30min. Then the temperature was raised to 80℃ and stirred at 250r / min for 1.5h. The crude extract was obtained by filtration. 3. Fractional separation: Adjust the pH of the crude extract to 2.5, add a non-ionic microemulsion system (Tween80-n-hexane-sodium dihydrogen phosphate = 5:4:1), stir and extract at 35℃ for 30 min, after separation, distill the organic phase under reduced pressure to obtain crude vanillin (purity 68.3%), and filter the aqueous phase through a membrane to obtain crude ferulic acid extract (purity 52.7%). 4. Purification and refining: Vanillin: The crude product was dissolved in 60% ethanol aqueous solution, and eluted by AB-8 macroporous resin chromatography (flow rate 1.5 BV / h), with a 40% ethanol gradient. After concentration, crystallization was carried out at 4℃ for 12 h, and dried to obtain pure vanillin (purity 99%). Ferulic acid: The crude extract was subjected to polyamide gel column chromatography (flow rate 0.8 BV / h), eluted with 30% ethanol, and the collected solution was recrystallized with ethanol-water (1:1) and dried at 50℃ to obtain high-purity ferulic acid (purity 98.6%).

[0019] Although embodiments of the invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the appended claims and their equivalents.

Claims

1. A method for processing, extracting, and purifying natural ferulic acid vanillin, characterized in that: Includes the following steps: (1) Raw material pretreatment: After drying and pulverizing the plant raw materials, they are extracted by reflux extraction with 40%-60% ethanol to remove fat-soluble impurities and the filter residue is collected; The specific steps are as follows: Select plant raw materials rich in ferulic acid and vanillin precursors, dry them and pulverize them to 60-80 mesh, add 10-15 times the volume of 40%-60% ethanol solution, reflux extract at 70-80℃ for 0.5-2 hours, filter to remove fat-soluble impurities, and collect the filter residue for later use. Synergistic extraction: The filter residue is mixed with a eutectic solvent and subjected to ultrasonic-assisted, constant-temperature stirring for synergistic extraction. The crude extract is then filtered. The specific steps are as follows: The pretreated filter residue is mixed with a eutectic solvent at a mass-to-volume ratio of 1:(10-30). The eutectic solvent is composed of choline chloride and glycerol in a molar ratio of 1:

2. 15%-20% (v / v) deionized water is added to adjust the viscosity. The mixture is then ultrasonically extracted at 40-60℃ and 30-50kHz for 20-40 minutes, followed by heating to 70-85℃ and stirring for 1-2 hours. The crude extract is then obtained by filtration. Fractional separation: Adjust the pH of the crude extract to 2-3, perform non-ionic microemulsion extraction to separate the layers, and collect the organic phase containing vanillin and the aqueous phase containing ferulic acid separately; The specific steps are as follows: Adjust the pH of the crude extract to 2-3, add a non-ionic microemulsion system (Tween 80-n-hexane-sodium dihydrogen phosphate, mass ratio 5:4:1), stir and extract at 30-40℃ for 30 min, collect the organic components containing vanillin and ferulic acid after standing and separating the layers; recover the solvent by vacuum distillation to obtain crude vanillin; filter the aqueous phase through a 0.22μm ceramic membrane to remove macromolecular impurities to obtain crude ferulic acid extract; Purification and refining: The organic phase was purified by macroporous resin chromatography-crystallization to obtain high-quality vanillin, and the aqueous phase was purified by gel column chromatography-recrystallization to obtain high-quality ferulic acid. The specific content is as follows: Vanillin purification: Crude vanillin was dissolved in a 50%-70% (v / v) aqueous ethanol solution, and adsorption chromatography was performed using macroporous resin AB-8. The solution was eluted with a gradient of 30%-50% ethanol solution. The target eluent was collected, concentrated under reduced pressure, and crystallized at 4-8℃ for 12 hours. The purified vanillin was then obtained by filtration and drying. Ferulic acid purification: The crude extract of ferulic acid was subjected to polyamide gel column chromatography and eluted with 20%-40% ethanol solution. The eluent was collected and recrystallized by adding an organic alcohol aqueous solution (ethanol:water = 1:1). The eluent was dried in a forced-air environment at 40-65℃ to obtain the purified ferulic acid.

2. The method for processing, extracting, and purifying natural ferulic acid vanillin according to claim 1, characterized in that: The plant materials are wheat bran, rice bran, Dendrobium officinale, or vanilla pods.

3. The method for processing, extracting, and purifying natural ferulic acid vanillin according to claim 1, characterized in that: The eutectic solvent can be replaced with a choline chloride-malic acid molar ratio of 1:1 or a choline chloride-glycerol-urea molar ratio of 1:1:

1.

4. The method for processing, extracting, and purifying natural ferulic acid vanillin according to claim 1, characterized in that: The ultrasonic extraction power is 150-200W, and the stirring speed is 200-300r / min.

5. The method for processing, extracting, and purifying natural ferulic acid vanillin according to claim 1, characterized in that: The adsorption conditions for the macroporous resin AB-8 are: flow rate 1-2 BV / h, sample concentration 5-10 mg / mL; and the elution flow rate for polyamide gel column chromatography is 0.5-1 BV / h.