CN116903461A - Method for separating monoglyceride and diglyceride by ultrasonic-enhanced solvent extraction - Google Patents

Method for separating monoglyceride and diglyceride by ultrasonic-enhanced solvent extraction Download PDF

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CN116903461A
CN116903461A CN202310654429.1A CN202310654429A CN116903461A CN 116903461 A CN116903461 A CN 116903461A CN 202310654429 A CN202310654429 A CN 202310654429A CN 116903461 A CN116903461 A CN 116903461A
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ultrasonic
monoglyceride
diglyceride
solvent
separating
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陆向红
丁金霞
计建炳
邱梦琪
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Zhejiang University of Technology ZJUT
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Zhejiang University of Technology ZJUT
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Abstract

The invention discloses a method for extracting and separating monoglyceride and diglyceride by using an ultrasonic reinforced solvent. The invention adopts the ultrasonic cell grinder to carry out ultrasonic treatment on the substances, and utilizes cavitation effect generated by strong ultrasonic in the liquid to accelerate the extraction process. The method adopts the technology of solvent extraction and coupling ultrasonic separation, can obtain the monoglyceride and diglyceride with higher content, has the advantages of low energy consumption, fast mass transfer, simple operation, low production cost and the like, and is suitable for commercial production.

Description

Method for separating monoglyceride and diglyceride by ultrasonic-enhanced solvent extraction
Technical Field
The invention relates to the technical field of grease purification and ultrasonic, in particular to a method for extracting and separating monoglyceride and diglyceride by using an ultrasonic reinforced solvent.
Background
Monoglyceride is a high-efficiency surfactant with good emulsifying, dispersing and stabilizing effects, and is widely applied to industries such as food, plastics, medicines, daily chemicals and the like, and particularly in the food industry, the use amount of monoglyceride exceeds 70% of the total amount of food emulsifying agents. The diglycolide can play roles in reducing blood fat, reducing body fat and the like by regulating the expression of enzyme genes related to lipid metabolism, and has important roles in preventing and treating cardiovascular and cerebrovascular diseases. In the existing industrial production, the monoglyceride is prepared by a direct esterification method or an ester exchange method, and the diglyceride is mainly treated as a byproduct of monoglyceride production, wherein the content of monoglyceride is 40-60%, and the content of diglyceride is 30-45%, so that the market is difficult to meet the purity requirement of the monoglyceride and the diglyceride, and therefore the method has important significance in purifying the monoglyceride and the diglyceride from a crude ester mixture respectively. The usual separation and purification methods include column chromatography, solvent crystallization, molecular distillation, thin layer chromatography, and the like. Although the above separation methods can effectively obtain the monoglyceride and the diglyceride with higher content, the effect is not ideal by means of a single separation method, repeated separation is sometimes required, and even a plurality of methods are combined for application, so that a plurality of limitations exist in practical industrial application.
Cavitation by ultrasound is commonly used for chemical process enhancement. Ultrasonic wave and solid-liquid extraction are combined, and cavitation effect of ultrasonic wave in liquid is utilized to collapse a large number of bubbles and form shock waves, so that solid particles are broken, the solid surface area is increased, mixing is enhanced, and solute diffusion from a solid phase is facilitated. The invention provides a method for extracting and separating monoglyceride and diglyceride by utilizing ultrasonic strengthening solvent, which is characterized in that ultrasonic is used for carrying out mixing strengthening, and the diffusion of solute from a solid oil phase into an extraction phase is enhanced at low temperature, so that references are provided for the separation and purification of monoglyceride and diglyceride in the future.
Disclosure of Invention
Aiming at the defects of the prior art for separating monoglyceride and diglyceride, the invention aims to provide a method for separating monoglyceride and diglyceride by ultrasonic reinforced solvent extraction, which adopts the technology of solvent extraction and coupling ultrasonic separation, uses n-hexane or ethanol water solution as an extractant, and strengthens the mass transfer process by ultrasonic waves, thereby obtaining monoglyceride and diglyceride with higher content in lower energy consumption and shorter time.
The method for extracting and separating the monoglyceride and the diglyceride by using the ultrasonic-enhanced solvent comprises the following steps of:
1) The method comprises the steps of (1) taking layered upper-layer grease obtained after transesterification reaction of triglyceride and glycerol under base catalysis as a crude ester raw material to be separated and purified, mixing the crude ester and an extractant in a centrifuge tube, inserting the centrifuge tube into a beaker filled with crushed ice, fixing the position, vertically suspending a variable spoke rod in the center of the centrifuge tube, placing the bottom end of the variable spoke rod in the middle position of a solution in the centrifuge tube, and placing a temperature probe in an ice water bath;
2) Carrying out ultrasonic treatment on the centrifuge tube by an ultrasonic cell grinder, and centrifuging after ultrasonic extraction to obtain layered solid phase and liquid phase;
3) Drying the solid phase obtained in the step 2), decompressing and evaporating the liquid phase, and removing the solvent to obtain the corresponding solid products of the monoglyceride and the diglyceride.
Further, the triglyceride in the step 1) is one or a mixture of more than one of stearic acid triglyceride, palmitic acid triglyceride, lauric acid triglyceride and myristic acid triglyceride.
Further, in the crude ester in the step 1), the content of monoglyceride is 40-60%, the content of diglyceride is 30-50% and the content of triglyceride is 5-10% by weight.
Further, the extractant in the step 1) is a low-polarity solvent, a high-polarity solvent or a mixed solvent of a low-polarity solvent and a high-polarity solvent with a volume ratio of 1:2-4, the low-polarity solvent is one or more of n-hexane, n-heptane and petroleum ether, the high-polarity solvent is methanol aqueous solution or ethanol aqueous solution, and the volume concentrations of the methanol aqueous solution and the ethanol aqueous solution are 50-100%.
Further, the ratio of the mass of the crude ester raw material to the volume of the extractant is 1 g:1-8 mL, preferably 1 g:2-6 mL.
Further, the total working time of the ultrasonic treatment in the step 2) is 5-30 min, preferably 20min, and the ultrasonic program is as follows: every 10s is an ultrasonic period, and after each ultrasonic period, the ultrasonic period is stopped for a period of time, the ultrasonic period is 2-8 s, the stopping time is 8-2 s, the preferable ultrasonic period is 5s, the stopping time is 5s, and the ultrasonic power is 100-900W, and the preferable ultrasonic power is 500W.
Compared with the prior art, the invention has the beneficial effects that: compared with the traditional heat treatment or mechanical stirring, the cavitation effect of the ultrasonic wave can obviously strengthen the mass transfer process between two phases, reduce the energy consumption, shorten the extraction time, reduce the dosage of the extractant, and has the advantages of high mass transfer rate, simple operation, low production cost and the like, thereby being a separation technology with development prospect.
Detailed Description
The invention will be further illustrated with reference to specific examples, but the scope of the invention is not limited thereto.
Example 1
1) Preparation of crude esters
Adding glycerol and stearic acid triglyceride in a molar ratio of 9:1 into a four-neck flask, introducing nitrogen for protection, heating until the solid is basically dissolved (about 70 ℃), then opening stirring, continuously heating to a reaction temperature of 250 ℃, adding CaO catalyst (the CaO catalyst dosage is 0.4% of the mass of the triglyceride), and reacting for 30min at the temperature of 250 ℃. After the completion, cooling to room temperature, recovering the glycerin at the lower layer, and taking the oil at the upper layer as a crude ester mixture for separation and purification. The crude ester mixture had a monoglyceride content of 50.5%, a diglyceride content of 40.2% and a triglyceride content of 9.3%.
2) Ultrasonic enhanced n-hexane extraction
5g of the crude ester mixture of step 1) was placed in a 50ml centrifuge tube, 30ml of n-hexane solvent was added, the centrifuge tube was inserted into a beaker filled with crushed ice (new ice cubes were replaced before the next sample treatment to ensure ice bath conditions for the next sample treatment), and fixed in place, a spoke-changing rod was suspended vertically in the center of the centrifuge tube, its bottom end was placed in the middle of the solution, the shaft was kept at a substantially equal distance from the inner wall around the tube, and placed in a temperature probe. The ultrasonic condition is set at the ultrasonic generator for 20min, the ultrasonic program is that every 10s is an ultrasonic period, every ultrasonic period is stopped for a period of time, the ultrasonic period is circularly reciprocated, the interval time/ultrasonic time is 5s/5s, and the ultrasonic power is 500W. The power change is concerned at the moment in the ultrasonic process, and the ultrasonic power is ensured to be 500W through the adjusting knob. And taking out the centrifuge tube after the ultrasonic treatment, and centrifuging at 8000rpm for 10min to obtain solid-liquid two phases. The upper n-hexane phase was evaporated under reduced pressure, the solvent was removed to give 2.61g of a milky solid, which was analyzed by high performance liquid chromatography to give a fraction having a glycylglycol content of 67.55% and a yield of 87.71%. The lower solid was dried to give 2.28g of a white powdery solid, which was analyzed by high performance liquid chromatography to give a monoglyceride content of 87.32% and a yield of 78.85%.
Examples 2 to 9
The crude product was isolated and purified in the same manner as in example 1, and experimental conditions were changed to obtain experimental results shown in table 1.
TABLE 1 Experimental conditions and results for examples 1-9
Example 10
1) Preparation of crude esters
The desired crude ester starting material was prepared by transesterification, see example 1.
2) Ultrasonic enhanced double solvent extraction
5g of the crude ester mixture from step 1) was placed in a 50ml centrifuge tube, 7.5ml of n-hexane and 22.5ml of 80% ethanol aqueous solution were added, the tube was inserted into a beaker filled with crushed ice (new ice cubes were replaced before the next sample treatment to ensure the ice bath conditions for the next sample treatment), and the position was fixed, the variable spoke was suspended vertically in the center of the tube, its bottom end was placed in the middle of the solution, the shaft was kept at a substantially equal distance from the inner wall around the tube, and a temperature probe was placed. The ultrasonic conditions were set at the ultrasonic generator for a total operating time of 20min, a gap time/ultrasonic time of 5s/5s in one ultrasonic cycle, and ultrasonic power of 500W. The power change is concerned at the moment in the ultrasonic process, and the ultrasonic power is ensured to be 500W through the adjusting knob. And after the ultrasonic treatment is finished, taking out the centrifuge tube, transferring all the products in the centrifuge tube into a separating funnel, standing for 3 hours, and observing the system to be in a liquid-solid-liquid three-phase state. The n-hexane phase, the white solid, and the ethanol-water phase are sequentially arranged from top to bottom. The lower ethanol-water phase is decompressed and evaporated, the ethanol water solution is removed, the obtained white solid is monoglyceride, the quality of monoglyceride is 2.48g, the monoglyceride is analyzed by high performance liquid chromatography, the monoglyceride content is 87.59%, and the yield is 86.03%. The intermediate solid is subjected to coherent drying, the obtained white powdery solid is the glycylglycine, the mass of the glycylglycine is 0.86g, the glycylglycine is formed by high performance liquid chromatography, the content of the glycylglycine is 88.85%, and the yield is 38.02%. The upper layer phase contains more diglycolide, triglyceride and a certain amount of monoglyceride, and can be recycled as a reaction raw material.
Comparative example 1
1) Preparation of crude esters
Adding glycerol and stearic acid triglyceride in a ratio of 9:1 (molar ratio) into a four-neck flask, introducing nitrogen for protection, heating until the solid is basically dissolved (about 70 ℃), then opening stirring, continuously heating to the reaction temperature of 250 ℃, adding CaO catalyst (the CaO catalyst dosage is 0.4% of the mass of the triglyceride), waiting until the temperature reaches the designated temperature again, and reacting for 30min. After the completion, the mixture is cooled to room temperature rapidly, the glycerin at the lower layer is recovered, and the grease at the upper layer is used as a crude ester mixture for separation and purification. The crude ester mixture had a monoglyceride content of 50.5%, a diglyceride content of 40.2% and a triglyceride content of 9.3%.
2) N-hexane extraction at room temperature
Taking 5g of the crude ester mixture obtained in the step 1), adding 20ml of normal hexane solvent into a 50ml centrifuge tube, stirring for 5min at room temperature, and centrifuging at 8000rpm for 10min to obtain solid-liquid two phases. The upper n-hexane phase is evaporated under reduced pressure, and the solvent is removed to obtain a white solid, and the white solid is formed by high performance liquid chromatography analysis, wherein the content of the N-phosphonomethyl iminodiacetic acid is 25.73%, and the yield is 40.13%. The lower layer solid is dried to obtain white solid, and the white solid is formed by high performance liquid chromatography analysis, wherein the content of monoglyceride is 46.27%, and the yield is 23.92%.
Comparative example 2
1) Preparation of crude esters
The desired crude ester starting material was prepared by transesterification, see comparative example 1.
2) Ethanol extraction at room temperature
Taking 5g of the crude ester mixture obtained in the step 1), adding 30ml of ethanol solvent into a 50ml centrifuge tube, shaking for 5min at room temperature, and centrifuging at 8000rpm for 10min to obtain solid-liquid two phases. The upper ethanol aqueous phase is decompressed and evaporated, the solvent is removed to obtain white solid, the white solid is formed by high performance liquid chromatography analysis, the monoglyceride content is 40.55%, and the yield is 95.75%. The lower layer solid is dried to obtain white solid, and the white solid is analyzed by high performance liquid chromatography to obtain the product with the content of the diglycolide of 55.50 percent and the yield of 13.64 percent.
Comparative example 3
1) Preparation of crude esters
The desired crude ester starting material was prepared by transesterification, see comparative example 1.
2) Extraction of n-hexane under thermal reflux
Taking 5g of the crude ester mixture obtained in the step 1), adding 30ml of normal hexane solvent into a 100ml three-neck flask, heating and refluxing under the water bath condition of 65 ℃, stirring, extracting for 20min, pouring into a 50ml centrifuge tube, standing and crystallizing at room temperature for 20min, and centrifuging at 8000rpm for 10min to obtain solid-liquid two phases. The upper n-hexane phase was evaporated under reduced pressure and the solvent was removed to give 2.01g of a milky solid, which was analyzed by high performance liquid chromatography to give a fraction containing 73.68% of N-glycylglycol with a yield of 64.49%. The lower solid was dried to give 2.74g of a white powdery solid, which was analyzed by high performance liquid chromatography to give a monoglyceride content of 76.56% and a yield of 88.32%.
Comparative example 4
1) Preparation of crude esters
The desired crude ester starting material was prepared by transesterification, see comparative example 1.
2) Extraction with 80% ethanol under thermal reflux
Taking 5g of the crude ester mixture obtained in the step 1), putting the crude ester mixture into a 100ml three-neck flask, adding 30ml of 80% ethanol water solution, heating and refluxing under the water bath condition of 65 ℃, stirring, extracting for 20min, pouring the mixture into a 50ml centrifuge tube, standing and crystallizing for 20min at room temperature, and centrifuging at 8000rpm for 10min to obtain solid-liquid two phases. The upper ethanol aqueous phase is evaporated under reduced pressure, the solvent is removed, 1.64g of milky solid is obtained, the composition is analyzed by high performance liquid chromatography, the monoglyceride content is 90.66%, and the yield is 62.48%. The lower solid was dried to give 2.82g of a white powdery solid, which was analyzed by high performance liquid chromatography to give a composition having a glycylglycol content of 62.68% and a yield of 83.02%.
Comparative example 5
1) Preparation of crude esters
The desired crude ester starting material was prepared by transesterification, see comparative example 1.
2) Taking 5g of the crude ester mixture obtained in the step 1) in a 100ml three-neck flask, adding 7.5ml of normal hexane and 22.5ml of 80% ethanol water solution, stirring at 65 ℃ and extracting for 20min, transferring all products in the three-neck flask into a separating funnel, standing and crystallizing for 3 hours at room temperature, and observing that a system is in a liquid-solid-liquid three-phase state. The n-hexane phase, the white solid, and the ethanol-water phase are sequentially arranged from top to bottom. The lower ethanol-water phase is decompressed and evaporated, the ethanol water solution is removed, the obtained white solid is monoglyceride, the quality of monoglyceride is 2.55g, the monoglyceride is analyzed by high performance liquid chromatography, the monoglyceride content is 88.56%, and the yield is 89.30%. The intermediate solid is subjected to coherent drying, the obtained white powdery solid is the glycylglycine, the mass of the glycylglycine is 1.03g, the glycylglycine is analyzed by high performance liquid chromatography, the content of the glycylglycine is 89.14%, and the yield is 45.17%.
The invention discovers that the ten examples and the five comparative examples have low extraction efficiency under the condition of room temperature, the diffusion rate of components in solids is low, and the extraction effect is poor; compared with the traditional heat treatment method, the ultrasonic extraction method can achieve similar effects, the ultrasonic enhanced extraction can be operated at low temperature, a large amount of solvent reflux is avoided, the energy consumption is low, and the method has the advantages of simplicity and convenience in operation, good repeatability, low technical and equipment requirements, low production cost and the like, and provides reference value for separation and purification of monoglyceride and diglyceride in the future.
What has been described in this specification is merely an enumeration of possible forms of implementation for the inventive concept and may not be considered limiting of the scope of the present invention to the specific forms set forth in the examples.

Claims (6)

1. The method for separating the monoglyceride and the diglyceride by ultrasonic enhanced solvent extraction is characterized by comprising the following steps of:
1) The method comprises the steps of (1) taking layered upper-layer grease obtained after transesterification reaction of triglyceride and glycerol under base catalysis as a crude ester raw material to be separated and purified, mixing the crude ester and an extractant in a centrifuge tube, inserting the centrifuge tube into a beaker filled with crushed ice, fixing the position, vertically suspending a variable spoke rod in the center of the centrifuge tube, placing the bottom end of the variable spoke rod in the middle position of a solution in the centrifuge tube, and placing a temperature probe in an ice water bath;
2) Carrying out ultrasonic treatment on the centrifuge tube by an ultrasonic cell grinder, and centrifuging after ultrasonic extraction to obtain layered solid phase and liquid phase;
3) Drying the solid phase obtained in the step 2), decompressing and evaporating the liquid phase, and removing the solvent to obtain the corresponding solid products of the monoglyceride and the diglyceride.
2. The method for separating monoglyceride and diglyceride by ultrasonic-enhanced solvent extraction according to claim 1, wherein said triglyceride in step 1) is one or more of the group consisting of stearic acid triglyceride, palmitic acid triglyceride, lauric acid triglyceride, and myristic acid triglyceride.
3. The method for separating monoglyceride and diglyceride by ultrasonic-enhanced solvent extraction according to claim 1, wherein the monoglyceride content is 40-60%, the diglyceride content is 30-50%, and the triglyceride content is 5-10% in terms of weight fraction in the crude ester in step 1).
4. The method for extracting and separating monoglyceride and diglyceride by using an ultrasonic-enhanced solvent according to claim 1, wherein in the step 1), the extracting agent is a low-polarity solvent, a high-polarity solvent or a mixed solvent of a low-polarity solvent and a high-polarity solvent with a volume ratio of 1:2-4, the low-polarity solvent is one or more of n-hexane, n-heptane and petroleum ether, the high-polarity solvent is a methanol aqueous solution or an ethanol aqueous solution, and the volume concentrations of the methanol aqueous solution and the ethanol aqueous solution are 50-100%.
5. The method for separating monoglyceride and diglyceride by ultrasonic-enhanced solvent extraction according to claim 4, wherein the ratio of the mass of the raw material of the crude ester to the volume of the extractant is 1g to 8ml, preferably 1g to 2 to 6ml.
6. The method for separating monoglyceride and diglyceride by ultrasonic-enhanced solvent extraction according to claim 1, wherein the total working time of the ultrasonic treatment in step 2) is 5 to 30min, preferably 20min, and the ultrasonic procedure is as follows: and according to the ultrasonic power measuring method, the ultrasonic power measuring method comprises the steps of taking the ultrasonic power measuring method as a ultrasonic period every 10s, stopping for a period of time after each ultrasonic period in one ultrasonic period, wherein the ultrasonic time in one ultrasonic period is 2-8 s, the stopping time is 8-2 s, the optimal ultrasonic time is 5s, the stopping time is 5s, and the ultrasonic power is 100-900W, and the optimal ultrasonic power is 500W.
CN202310654429.1A 2023-06-05 2023-06-05 Method for separating monoglyceride and diglyceride by ultrasonic-enhanced solvent extraction Pending CN116903461A (en)

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