CN109265478B - Method for preparing glycerophosphatidylcholine based on egg shells - Google Patents
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- CN109265478B CN109265478B CN201811279199.0A CN201811279199A CN109265478B CN 109265478 B CN109265478 B CN 109265478B CN 201811279199 A CN201811279199 A CN 201811279199A CN 109265478 B CN109265478 B CN 109265478B
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- 210000003278 egg shell Anatomy 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title claims abstract description 26
- SUHOQUVVVLNYQR-MRVPVSSYSA-N choline alfoscerate Chemical compound C[N+](C)(C)CCOP([O-])(=O)OC[C@H](O)CO SUHOQUVVVLNYQR-MRVPVSSYSA-N 0.000 title claims abstract description 25
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 63
- 239000000047 product Substances 0.000 claims abstract description 43
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000003054 catalyst Substances 0.000 claims abstract description 33
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 28
- IIZPXYDJLKNOIY-JXPKJXOSSA-N 1-palmitoyl-2-arachidonoyl-sn-glycero-3-phosphocholine Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@H](COP([O-])(=O)OCC[N+](C)(C)C)OC(=O)CCC\C=C/C\C=C/C\C=C/C\C=C/CCCCC IIZPXYDJLKNOIY-JXPKJXOSSA-N 0.000 claims abstract description 19
- 235000010445 lecithin Nutrition 0.000 claims abstract description 19
- 239000000787 lecithin Substances 0.000 claims abstract description 19
- 229940067606 lecithin Drugs 0.000 claims abstract description 19
- 150000003904 phospholipids Chemical class 0.000 claims abstract description 14
- 239000000126 substance Substances 0.000 claims abstract description 13
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- 238000001914 filtration Methods 0.000 claims abstract description 11
- 239000011259 mixed solution Substances 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 10
- 239000000243 solution Substances 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 9
- 239000006228 supernatant Substances 0.000 claims abstract description 8
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- 238000001556 precipitation Methods 0.000 claims abstract description 4
- 230000001476 alcoholic effect Effects 0.000 claims abstract description 3
- 238000001704 evaporation Methods 0.000 claims abstract description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 31
- WTJKGGKOPKCXLL-RRHRGVEJSA-N phosphatidylcholine Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@H](COP([O-])(=O)OCC[N+](C)(C)C)OC(=O)CCCCCCCC=CCCCCCCCC WTJKGGKOPKCXLL-RRHRGVEJSA-N 0.000 claims description 14
- JLPULHDHAOZNQI-ZTIMHPMXSA-N 1-hexadecanoyl-2-(9Z,12Z-octadecadienoyl)-sn-glycero-3-phosphocholine Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@H](COP([O-])(=O)OCC[N+](C)(C)C)OC(=O)CCCCCCC\C=C/C\C=C/CCCCC JLPULHDHAOZNQI-ZTIMHPMXSA-N 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 7
- 229940083466 soybean lecithin Drugs 0.000 claims description 7
- JQWAHKMIYCERGA-UHFFFAOYSA-N (2-nonanoyloxy-3-octadeca-9,12-dienoyloxypropoxy)-[2-(trimethylazaniumyl)ethyl]phosphinate Chemical compound CCCCCCCCC(=O)OC(COP([O-])(=O)CC[N+](C)(C)C)COC(=O)CCCCCCCC=CCC=CCCCCC JQWAHKMIYCERGA-UHFFFAOYSA-N 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 5
- 102000002322 Egg Proteins Human genes 0.000 claims description 4
- 108010000912 Egg Proteins Proteins 0.000 claims description 4
- JZNWSCPGTDBMEW-UHFFFAOYSA-N glycerophosphatidylethanolamine Chemical compound NCCOP(O)(=O)OCC(O)CO JZNWSCPGTDBMEW-UHFFFAOYSA-N 0.000 claims description 4
- 239000012528 membrane Substances 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000005909 Kieselgur Substances 0.000 claims description 2
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- 239000000463 material Substances 0.000 claims 1
- 238000000926 separation method Methods 0.000 abstract description 9
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- 235000019441 ethanol Nutrition 0.000 description 12
- 239000002699 waste material Substances 0.000 description 7
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- 238000001354 calcination Methods 0.000 description 4
- 230000036541 health Effects 0.000 description 4
- 229940042880 natural phospholipid Drugs 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- 210000004556 brain Anatomy 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- -1 mercury ions Chemical class 0.000 description 3
- 230000008569 process Effects 0.000 description 3
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- 239000002904 solvent Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- TZCPCKNHXULUIY-RGULYWFUSA-N 1,2-distearoyl-sn-glycero-3-phosphoserine Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC[C@H](COP(O)(=O)OC[C@H](N)C(O)=O)OC(=O)CCCCCCCCCCCCCCCCC TZCPCKNHXULUIY-RGULYWFUSA-N 0.000 description 2
- ZWZWYGMENQVNFU-UHFFFAOYSA-N Glycerophosphorylserin Natural products OC(=O)C(N)COP(O)(=O)OCC(O)CO ZWZWYGMENQVNFU-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 230000002490 cerebral effect Effects 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
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- 239000008399 tap water Substances 0.000 description 2
- 235000020679 tap water Nutrition 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- 150000003751 zinc Chemical class 0.000 description 2
- CTKINSOISVBQLD-VKHMYHEASA-N (S)-Glycidol Chemical compound OC[C@H]1CO1 CTKINSOISVBQLD-VKHMYHEASA-N 0.000 description 1
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- HEHOPCBAIAIYSP-UHFFFAOYSA-N 6-oxa-2-phosphabicyclo[3.1.0]hexane Chemical compound P1CCC2OC21 HEHOPCBAIAIYSP-UHFFFAOYSA-N 0.000 description 1
- 208000024827 Alzheimer disease Diseases 0.000 description 1
- 208000000044 Amnesia Diseases 0.000 description 1
- 208000031091 Amnestic disease Diseases 0.000 description 1
- 241000283690 Bos taurus Species 0.000 description 1
- 206010008190 Cerebrovascular accident Diseases 0.000 description 1
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 1
- 206010039966 Senile dementia Diseases 0.000 description 1
- 208000006011 Stroke Diseases 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000003811 acetone extraction Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 230000006986 amnesia Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000003925 brain function Effects 0.000 description 1
- OEYIOHPDSNJKLS-UHFFFAOYSA-N choline Chemical compound C[N+](C)(C)CCO OEYIOHPDSNJKLS-UHFFFAOYSA-N 0.000 description 1
- 229960001231 choline Drugs 0.000 description 1
- 230000019771 cognition Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005947 deacylation reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000009982 effect on human Effects 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 235000013376 functional food Nutrition 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 229960002523 mercuric chloride Drugs 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- LWJROJCJINYWOX-UHFFFAOYSA-L mercury dichloride Chemical compound Cl[Hg]Cl LWJROJCJINYWOX-UHFFFAOYSA-L 0.000 description 1
- 239000002207 metabolite Substances 0.000 description 1
- 239000002858 neurotransmitter agent Substances 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 210000000496 pancreas Anatomy 0.000 description 1
- 229950004354 phosphorylcholine Drugs 0.000 description 1
- PYJNAPOPMIJKJZ-UHFFFAOYSA-N phosphorylcholine chloride Chemical compound [Cl-].C[N+](C)(C)CCOP(O)(O)=O PYJNAPOPMIJKJZ-UHFFFAOYSA-N 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 description 1
- IWISVGQUKNSOCC-UHFFFAOYSA-K tetramethylazanium;phosphate Chemical compound C[N+](C)(C)C.C[N+](C)(C)C.C[N+](C)(C)C.[O-]P([O-])([O-])=O IWISVGQUKNSOCC-UHFFFAOYSA-K 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/09—Esters of phosphoric acids
- C07F9/10—Phosphatides, e.g. lecithin
- C07F9/103—Extraction or purification by physical or chemical treatment of natural phosphatides; Preparation of compositions containing phosphatides of unknown structure
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Fats And Perfumes (AREA)
Abstract
The invention provides a method for preparing glycerophosphatidylcholine based on egg shells, which comprises the following steps: step 1, heating an alcohol solution of lecithin to 20-70 ℃; step 2, adding a catalyst into the alcoholic solution obtained in the step 1, and stirring and reacting for 2-8 hours to obtain a mixed solution; the catalyst is prepared by crushing and roasting eggshells; step 3, filtering the mixed solution obtained in the step 2, and evaporating the filtrate to obtain an oily product; dissolving the oily product with methanol to obtain methanol dissolved product, precipitating with diethyl ether, discarding supernatant after precipitation is complete, and repeating the above steps for several times; and 4, drying the oily product obtained in the step 3 to obtain the phospholipid deacylated substance containing the glycerophosphatidylcholine. The catalyst adopted by the invention is a solid catalyst, and the separation can be realized only by filtering, so that the separation and purification process of the product is simple.
Description
Technical Field
The invention relates to the technical field of medical health products and food processing, in particular to a method for preparing glycerophosphatidylcholine based on egg shells.
Background
Glycerol Phosphatidylcholine (GPC) is a water-soluble phospholipid metabolite naturally occurring in human body, is also an important neurotransmitter and phospholipid precursor, and has an unrivaled effect on human body. GPC has positive effects on various crowds including healthy young people, can protect cerebral vessels, improve memory, and especially has obvious curative effect on crowds with brain circulation problems such as cerebral apoplexy patients and senile dementia patients. GPC can effectively improve cognition, not only can repair damaged brains and improve brain functions, but also can inhibit or even eliminate pain caused by amnesia, and plays an important role in protecting the brains. GPC supports human health through various mechanisms, and is widely used in the healthcare industry and the functional food industry.
Early GPC was obtained mainly from bovine pancreas by a biological extraction method, and some GPC was obtained from egg yolk lecithin or soybean lecithin by hydrolysis extraction, but to obtain high purity GPC, the process was complicated and the cost was extremely high. With the advance of chemical technology, researchers have proposed the synthesis of GPC using chemical methods. EP0486100 discloses a method for preparing GPC by ring-opening condensation of D-isopropylidene glycerol with 2-oxo-2-chloro-1, 3, 2-epoxyphospholane and trimethylamine. EP0502357 discloses the preparation of GPC by condensation of D-isopropylidene glycerol p-toluenesulfonate with choline tetramethylammonium phosphate. CN101544667A discloses a scheme of preparing (2R) -glycidol p-toluenesulfonate ester from (S) -glycidol, condensing the ester with tetraethylammonium choline phosphate, and purifying to obtain GPC. The preparation methods all belong to chemical synthesis methods, and the domestic industrial production of GPC is mainly based on the chemical method at present, so that the method has the defects that a high-purity product is difficult to obtain and the food-grade requirement cannot be met. The proposal disclosed in US2864848A is to hydrolyze phospholipid with mercuric chloride as a catalyst to prepare GPC, but the separation and purification process is very complicated, and the product inevitably has residual mercury ions, so that the safety of the product is threatened. The scheme disclosed in EP0217765a2 is that under the presence of sodium salts of lower alcohols such as methanol, ethanol and isopropanol, the soybean lecithin after acetone extraction is subjected to deacylation reaction, after the reaction is completed, halide of zinc is added to the reaction solution, organic base such as pyrimidine is added to compound with zinc salt, and finally ion exchange resin is used to separate the zinc salt.
Compared with biological extraction and chemical synthesis methods, the preparation of GPC by using natural raw materials such as soybean lecithin or egg yolk lecithin is a more favorable approach for being used as a medical health product.
However, in the literature reports, a homogeneous catalyst is mostly used in the GPC reaction process prepared from natural raw materials such as soybean lecithin or egg yolk lecithin, the disadvantages of difficult catalyst separation, serious waste, complex whole product preparation and purification process and high cost exist, and heavy metal ions can be introduced in some separation processes, so that the safety of the product when the product is used as a medical health product is directly threatened. Therefore, an effective heterogeneous catalyst is developed for catalyzing ester exchange reaction to prepare GPC, which not only can simplify the product separation process, but also can recycle the catalyst, thereby reducing the production cost.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a method for preparing glycerophosphatidylcholine based on egg shells, which is relatively simple in process and overcomes the problems of complex process and difficult product separation in the prior art.
The invention is realized by the following technical scheme:
a method for preparing glycerophosphatidylcholine based on egg shells comprises the following steps:
step 1, heating an alcohol solution of lecithin to 20-70 ℃;
step 2, adding a catalyst into the alcoholic solution obtained in the step 1, and stirring and reacting for 2-8 hours to obtain a mixed solution; the catalyst is prepared by crushing and roasting eggshells;
step 3, filtering the mixed solution obtained in the step 2, and evaporating the filtrate to obtain an oily product; dissolving the oily product with methanol to obtain methanol dissolved product, precipitating with diethyl ether, discarding supernatant after precipitation is complete, and repeating the above steps for several times;
and 4, drying the oily product obtained in the step 3 to obtain the phospholipid deacylated substance containing the glycerophosphatidylcholine.
Preferably, in step 2, the specific preparation steps of the catalyst are as follows:
step a, cleaning an egg shell, removing an inner membrane and drying;
b, crushing the eggshells obtained in the step a to obtain powder;
and c, roasting the powder obtained in the step b at the temperature of 750-950 ℃ for 2-5 hours.
Further, in step b, the eggshell is pulverized to 120-.
Preferably, in the step 1, the alcohol is methanol or ethanol, and the concentration of lecithin in the alcohol is 10-30 g/L.
Preferably, in step 1, the lecithin is soybean lecithin or egg yolk lecithin, wherein the content of phosphatidylcholine is 20% to 95%.
Preferably, in the step 2, the content of the catalyst in the alcohol solution is 15-40 g/L.
Preferably, in the step 3, in the operation of precipitating with diethyl ether, the volume ratio of diethyl ether to methanol dissolved product is (5-10): 1.
preferably, in step 4, the phospholipid deacylate obtained comprises glycerol phosphatidylcholine, glycerol phosphatidylethanolamine and glycerol phosphatidylserine.
Furthermore, the content of the glycerol phosphatidylcholine in the phospholipid deacylated substance is 33.5% -68.5%.
Preferably, in step 4, the obtained phospholipid deacylated product containing glycerophosphatidylcholine is subjected to a crystallization operation using a mixed solution of absolute ethanol and diethyl ether in the presence of diatomaceous earth, thereby obtaining glycerophosphatidylcholine.
Compared with the prior art, the invention has the following beneficial technical effects:
the invention provides a method for preparing glycerophosphatidylcholine by using waste egg shells, which is characterized in that a catalyst is prepared by using the waste egg shells as raw materials, and the glycerol phosphatidylcholine is obtained by catalyzing natural lecithin and alcohol to perform ester exchange reaction. The catalyst adopted by the invention is a solid catalyst, and can be separated only by filtering, so that the separation and purification process of the product is simple, the reaction condition is mild, the reaction process is simple, and the catalyst can be recycled after being filtered and recovered. Meanwhile, the catalyst is prepared by adopting the waste egg shells as the raw material, so that the reasonable utilization of resources is facilitated, waste is turned into wealth, the separation process is simplified, and the production cost is reduced.
Detailed Description
The present invention will now be described in further detail with reference to specific examples, which are intended to be illustrative, but not limiting, of the invention.
The method for preparing the glycerol phosphatidylcholine based on the waste egg shells comprises the following steps:
step (1): adding the alcohol solution of lecithin with the formula ratio into a three-neck flask with condensation reflux, and heating the three-neck flask to 20-70 ℃ in a heat collection type constant temperature heating magnetic stirrer;
step (2): after the temperature of the reaction liquid in the three-neck flask is constant, adding a catalyst and magnetons in a formula amount, and stirring for reaction for 2-8 hours; the catalyst is prepared from waste egg shells;
and (3): filtering the mixed solution reacted in the step (2), recovering the catalyst, performing vacuum rotary evaporation on the filtrate, dissolving the obtained oily product with methanol, precipitating with diethyl ether with the volume 5-10 times that of the methanol dissolved product, discarding the supernatant after the precipitate is completely dissolved, and repeating the operation for multiple times;
and (4): the resulting oily product was dried under vacuum to remove the residual solvent, thereby obtaining GPC or a phospholipid deacylated product mainly containing GPC.
In the step (1), the solvent alcohol is methanol or ethanol, and the concentration of lecithin in the solvent alcohol is 10-30 g/L.
In the step (1), the lecithin is soybean lecithin or egg yolk lecithin, wherein the content of phosphatidylcholine is 20-95%.
In the step (1), the stirring speed of the heat collection type constant temperature heating magnetic stirrer is controlled to be 200-800 r/min.
In the step (2), the content of the catalyst in the reaction liquid is 15-40 g/L; the specific preparation steps of the catalyst are as follows:
step (a): repeatedly soaking and cleaning the collected egg shells with tap water, removing the inner membranes and drying;
step (b): crushing the eggshell obtained in the step (a) to 120-;
step (c): and (c) placing the powder obtained in the step (b) into a muffle furnace to be roasted for 2-5 hours at the temperature of 750-950 ℃.
Cleaning the eggshells by an ultrasonic cleaning instrument in the step (a); and drying the processed egg shells by adopting an air-blast drying box.
In the step (3), the methanol obtained by vacuum rotary evaporation can be recycled, so that the cost is saved;
in the step (4), the phospholipid deacylates include glycerophosphatidylcholine, glycerophosphatidylethanolamine and glycerophosphatidylserine.
The invention is further illustrated by the following examples:
example 1:
repeatedly soaking and cleaning the collected egg shells with tap water, removing the inner membranes and drying; crushing the dried egg shells by a high-speed crusher to obtain powder of 120-200 meshes; finally, roasting the catalyst for 3 hours at 850 ℃ in a muffle furnace to obtain the required catalyst.
Dissolving 5g of lecithin with phosphatidylcholine content of 20% in 167mL of methanol, filtering out insoluble substances, adding the lecithin into a three-neck flask with condensation reflux, placing the lecithin into a heat collection type constant-temperature heating magnetic stirrer for heating, adding 2.505g of the prepared catalyst and magneton when the temperature is raised to 50 ℃, starting stirring, and reacting for 5 hours under the condition that the stirring speed is 200 r/min. Filtering the mixed solution after the reaction is finished, recovering the catalyst, performing vacuum rotary evaporation on the filtrate, dissolving the obtained oily product by using 4mL of anhydrous methanol, precipitating by using 20mL of diethyl ether, completely precipitating, removing the supernatant, repeating the operation for 3 times, and finally performing vacuum drying on the obtained oily product to obtain 0.986g of natural phospholipid deacylated substance which is light yellow in appearance and mainly contains GPC, wherein the natural phospholipid deacylated substance comprises glycerol phosphatidylcholine, glycerol phosphatidylethanolamine and glycerol phosphatidylserine through detection, and the content of GPC accounts for 33.5% of the total mass of the product.
Example 2
This example differs from example 1 in that the catalyst obtained has a calcination temperature of 950 ℃ and a calcination time of 2 hours. Dissolving 2g of lecithin with 60% of phosphatidylcholine content in 200mL of absolute ethyl alcohol, filtering insoluble substances, adding the lecithin into a three-neck flask with condensation reflux, heating the lecithin in a heat collection type constant-temperature heating magnetic stirrer, adding 5g of the prepared catalyst and magnetons when the temperature is raised to 70 ℃, starting stirring, and reacting for 8 hours at the stirring speed of 500 r/min. Filtering the mixed solution after the reaction is finished, recovering the catalyst, carrying out vacuum rotary evaporation on the filtrate, dissolving the obtained oily product by using 2mL of anhydrous methanol, precipitating by using 20mL of diethyl ether, completely precipitating, removing the supernatant, repeating the operation for 3 times, and finally carrying out vacuum drying on the obtained oily product to obtain 0.533g of natural phospholipid deacylated substance which is light yellow in appearance and mainly contains GPC, wherein the content of GPC accounts for 68.5% of the total mass of the product.
Example 3
This example differs from example 2 only in that the phosphatidylcholine content in the lecithin was 95% and the reaction time was 2 h. After the reaction, dissolving the oily precipitate at the bottom with 2mL of anhydrous methanol, adding 10mL of diethyl ether for precipitation, completely precipitating, removing the supernatant, repeating the operation for 2 times, and finally performing vacuum drying on the obtained oily product in the presence of diatomite by using a solvent with a volume ratio of 6: 4 was crystallized from a mixture of absolute ethyl alcohol and diethyl ether at 4 ℃ to obtain 0.421g of GPC crystals. The melting point is 132 ℃,
(10% aqueous solution), elemental analysis results were: c, 37.2%; h, 7.8%; and N, 5.3 percent.
Example 4
This example differs from example 2 in that the catalyst obtained has a calcination temperature of 750 ℃ and a calcination time of 5 hours. 2g of lecithin containing 60% phosphatidylcholine were dissolved in 100mL of anhydrous methanol at 20 ℃ with 4g of catalyst. Filtering the mixed solution after the reaction is finished, recovering the catalyst, carrying out vacuum rotary evaporation on the filtrate, dissolving the obtained oily product by using 2mL of anhydrous methanol, precipitating by using 15mL of diethyl ether, completely precipitating, removing the supernatant, repeating the operation for 3 times, and finally carrying out vacuum drying on the obtained oily product to obtain 0.485g of natural phospholipid deacylated substance which is light yellow in appearance and mainly contains GPC, wherein the content of GPC accounts for 62.3% of the total mass of the product.
Claims (9)
1. A method for preparing glycerol phosphatidylcholine based on egg shells is characterized by comprising the following steps:
step 1, heating an alcohol solution of lecithin to 20-70 ℃;
step 2, adding a catalyst into the alcoholic solution obtained in the step 1, and stirring and reacting for 2-8 hours to obtain a mixed solution; the catalyst is prepared by crushing and roasting eggshells;
step 3, filtering the mixed solution obtained in the step 2, and evaporating the filtrate to obtain an oily product; dissolving the oily product with methanol to obtain methanol dissolved product, precipitating with diethyl ether, discarding supernatant after precipitation is complete, and repeating the above steps for several times;
step 4, drying the oily product obtained in the step 3 to obtain a phospholipid deacylated substance containing the glycerophosphatidylcholine;
in step 2, the specific preparation steps of the catalyst are as follows:
step a, cleaning an egg shell, removing an inner membrane and drying;
b, crushing the eggshells obtained in the step a to obtain powder;
and c, roasting the powder obtained in the step b at the temperature of 750-950 ℃ for 2-5 hours.
2. The method for preparing glycerophosphatidylcholine based on egg shells according to claim 1, wherein in step b, the egg shells are pulverized to 120-200 mesh.
3. The method for preparing glycerophosphatidylcholine based on egg shells according to claim 1, wherein in step 1, the alcohol is methanol or ethanol, and the concentration of lecithin in the alcohol is 10-30 g/L.
4. The method for preparing glycerophosphatidylcholine based on egg shells according to claim 1, wherein in step 1, the lecithin is soybean lecithin or egg yolk lecithin, wherein the content of phosphatidylcholine is 20% to 95%.
5. The method for preparing glycerophosphatidylcholine based on egg shells according to claim 1, wherein in step 2, the content of the catalyst in the alcohol solution is 15-40 g/L.
6. The method for preparing glycerophosphatidylcholine based on egg shells according to claim 1, wherein in the step 3, the volume ratio of the ether to the methanol dissolved product is (5-10): 1.
7. the method for preparing glycerophosphatidylcholine based on egg shells according to claim 1, wherein in step 4, the obtained phospholipid deacylates comprise glycerophosphatidylcholine, glycerophosphatidylethanolamine and glycerophosphatidylserine.
8. The method for preparing glycerophosphatidylcholine based on egg shells according to claim 7, wherein the content of glycerophosphatidylcholine in the phospholipid deacylated material is 33.5% to 68.5%.
9. The method for preparing glycerophosphatidylcholine based on egg shells of claim 1, wherein in step 4, the obtained phospholipid deacylated product containing glycerophosphatidylcholine is subjected to a crystallization operation using a mixture of absolute ethanol and diethyl ether in the presence of diatomaceous earth, thereby obtaining glycerophosphatidylcholine.
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| CN102964377A (en) * | 2012-11-30 | 2013-03-13 | 西北大学 | Method for preparing natural L-alpha-glycerol phosphatidylcholine |
| CN108516989A (en) * | 2018-05-18 | 2018-09-11 | 榆林学院 | A kind of preparation method of phosphatide deacylation substratess |
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| CN108516989A (en) * | 2018-05-18 | 2018-09-11 | 榆林学院 | A kind of preparation method of phosphatide deacylation substratess |
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