CN109265478A - A method of glycerolphosphocholine is prepared based on egg shell - Google Patents
A method of glycerolphosphocholine is prepared based on egg shell Download PDFInfo
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- CN109265478A CN109265478A CN201811279199.0A CN201811279199A CN109265478A CN 109265478 A CN109265478 A CN 109265478A CN 201811279199 A CN201811279199 A CN 201811279199A CN 109265478 A CN109265478 A CN 109265478A
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- glycerolphosphocholine
- egg shell
- preparing
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- lecithin
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- 102000002322 Egg Proteins Human genes 0.000 title claims abstract description 37
- 108010000912 Egg Proteins Proteins 0.000 title claims abstract description 37
- 210000003278 egg shell Anatomy 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 title claims abstract description 29
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 60
- 239000000047 product Substances 0.000 claims abstract description 35
- 239000003054 catalyst Substances 0.000 claims abstract description 32
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 30
- 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 15
- 229940067606 lecithin Drugs 0.000 claims abstract description 15
- 239000000787 lecithin Substances 0.000 claims abstract description 15
- 235000010445 lecithin Nutrition 0.000 claims abstract description 15
- 230000020176 deacylation Effects 0.000 claims abstract description 13
- 238000005947 deacylation reaction Methods 0.000 claims abstract description 13
- 230000001476 alcoholic effect Effects 0.000 claims abstract description 9
- 239000007788 liquid Substances 0.000 claims abstract description 9
- 230000001376 precipitating effect Effects 0.000 claims abstract description 8
- 239000006228 supernatant Substances 0.000 claims abstract description 8
- 239000000706 filtrate Substances 0.000 claims abstract description 7
- 239000006166 lysate Substances 0.000 claims abstract description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 19
- 235000019441 ethanol Nutrition 0.000 claims description 12
- 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 8
- 239000000843 powder Substances 0.000 claims description 8
- 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
- 238000002360 preparation method Methods 0.000 claims description 6
- 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 5
- 229940083466 soybean lecithin Drugs 0.000 claims description 5
- MTCFGRXMJLQNBG-UHFFFAOYSA-N Serine Natural products OCC(N)C(O)=O MTCFGRXMJLQNBG-UHFFFAOYSA-N 0.000 claims description 4
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 4
- 229960004756 ethanol Drugs 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000002425 crystallisation Methods 0.000 claims description 2
- 230000008025 crystallization Effects 0.000 claims description 2
- 125000002252 acyl group Chemical group 0.000 claims 1
- 238000000926 separation method Methods 0.000 abstract description 9
- 238000001914 filtration Methods 0.000 abstract description 3
- 239000011949 solid catalyst Substances 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 14
- 239000000243 solution Substances 0.000 description 8
- 238000004064 recycling Methods 0.000 description 6
- 230000036541 health Effects 0.000 description 5
- 238000009833 condensation Methods 0.000 description 4
- 230000005494 condensation Effects 0.000 description 4
- 229940079593 drug Drugs 0.000 description 4
- 239000003814 drug Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000003760 magnetic stirring Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000002390 rotary evaporation Methods 0.000 description 4
- 210000004556 brain Anatomy 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229940042880 natural phospholipid Drugs 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 235000010469 Glycine max Nutrition 0.000 description 2
- 244000068988 Glycine max Species 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- RNVYQYLELCKWAN-RXMQYKEDSA-N [(4r)-2,2-dimethyl-1,3-dioxolan-4-yl]methanol Chemical compound CC1(C)OC[C@@H](CO)O1 RNVYQYLELCKWAN-RXMQYKEDSA-N 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 230000006870 function Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 150000003904 phospholipids Chemical class 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 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
- 239000002699 waste material Substances 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
- 208000024827 Alzheimer disease Diseases 0.000 description 1
- 208000000044 Amnesia Diseases 0.000 description 1
- 208000031091 Amnestic disease Diseases 0.000 description 1
- MJJLPVTVJUMSCE-UHFFFAOYSA-N CCCCC.[P] Chemical compound CCCCC.[P] MJJLPVTVJUMSCE-UHFFFAOYSA-N 0.000 description 1
- YAKKUGCYZAVNHY-UHFFFAOYSA-M CC[N+](CC)(CC)CC.C[N+](C)(C)CCOP([O-])([O-])=O Chemical compound CC[N+](CC)(CC)CC.C[N+](C)(C)CCOP([O-])([O-])=O YAKKUGCYZAVNHY-UHFFFAOYSA-M 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 206010054949 Metaplasia 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
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000003811 acetone extraction Methods 0.000 description 1
- 230000006986 amnesia Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000002490 cerebral effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- RCTYPNKXASFOBE-UHFFFAOYSA-M chloromercury Chemical compound [Hg]Cl RCTYPNKXASFOBE-UHFFFAOYSA-M 0.000 description 1
- SUHOQUVVVLNYQR-MRVPVSSYSA-N choline alfoscerate Chemical compound C[N+](C)(C)CCOP([O-])(=O)OC[C@H](O)CO SUHOQUVVVLNYQR-MRVPVSSYSA-N 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
- 238000004090 dissolution Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 235000013376 functional food Nutrition 0.000 description 1
- 229960004956 glycerylphosphorylcholine Drugs 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 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
- 230000003301 hydrolyzing effect Effects 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
- BQPIGGFYSBELGY-UHFFFAOYSA-N mercury(2+) Chemical compound [Hg+2] BQPIGGFYSBELGY-UHFFFAOYSA-N 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 230000015689 metaplastic ossification Effects 0.000 description 1
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002858 neurotransmitter agent Substances 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 210000004681 ovum Anatomy 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 210000000496 pancreas Anatomy 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- WHJKYJBKWZOMMW-UHFFFAOYSA-M tetramethylazanium;2-(trimethylazaniumyl)ethyl phosphate Chemical compound C[N+](C)(C)C.C[N+](C)(C)CCOP([O-])([O-])=O WHJKYJBKWZOMMW-UHFFFAOYSA-M 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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 present invention provides a kind of method for preparing glycerolphosphocholine based on egg shell, comprising the following steps: step 1, the alcoholic solution of lecithin is heated to 20 DEG C~70 DEG C；Step 2, catalyst is added into the alcoholic solution of step 1, is stirred to react 2h~8h, obtain mixed liquor；Catalyst is crushed using egg shell and roasting is prepared；Step 3, mixed liquor step 2 obtained is filtered, and filtrate is evaporated operation and obtains oil product；Oil product is dissolved with methanol, obtains methanol lysate, then precipitated with ether, liquid is discarded supernatant after precipitating is complete, operates repeatedly several times；Step 4, oil product step 3 obtained is dried, and obtains the phosphatide deacylation substratess containing glycerolphosphocholine.The catalyst that the present invention uses is solid catalyst, it is only necessary to which separation can be realized in filtering, so that the separation purifying technique of product is simple.
Description
Technical field
The present invention relates to Medicines and Health Product and food processing technology fields, are prepared in particular to one kind based on egg shell
The method of glycerolphosphocholine.
Background technique
Glycerolphosphocholine (Glycerophosphocholine, abbreviation GPC) is naturally occurring a kind of water in human body
Dissolubility phospholipid metabolism product, and a kind of important neurotransmitter and phospholipid precursor, have impayable effect to human body.
GPC has the function of the young man that various people include health positive, it can protect the cerebrovascular, improve memory, especially
It is that the crowd to go wrong to the Brain circlulations such as headstroke person and senile dementia person has more significant curative effect.GPC can effectively change
Kind cognition, can not only be such that the brain of damage is repaired, and improve cerebral function, can also inhibit even to be eliminated amnesia bring
Pain plays important protective effect to brain.GPC supports the health of the mankind by various mechanism, is widely used in curing
Medicine healthcare industry and functional food industry.
The GPC of early stage is mainly obtained from Pancreas Bovis seu Bubali by biological extraction method, is also had from egg yolk lecithin or soybean ovum
Phosphatide is extracted through hydrolysis, but to obtain the GPC of purity is high, complex process, and cost is high.With the progress of chemical technology, section
The worker of grinding, which proposes to utilize, is chemically synthesized GPC.Scheme disclosed in EP0486100 is with D- acetone glycerol and 2-
Chloro- 1,3,2- epoxy phosphorus pentane of oxygen -2-, then GPC is condensed to yield with trimethylamine open loop.Scheme disclosed in EP0502357 is to use D-
Acetone glycerol p-methyl benzenesulfonic acid ester and phosphocholine tetramethyl ammonium carry out condensation preparation GPC.CN101544667A is disclosed
Scheme be that (S)-glycidol is made to (2R)-glycidol p-methyl benzenesulfonic acid ester, then with phosphocholine tetraethyl ammonium salt
Condensation, then purified GPC.The above preparation method belongs to chemical synthesis, at present domestic industry metaplasia produce GPC also with
Based on chemical method, this method has the drawback that the product for being difficult to obtain high-purity, and the requirement of food-grade is not achieved.
Scheme disclosed in US2864848A is GPC to be made using mercury chloride as catalyst hydrolytic phosphatide, but separation purifying technique is very numerous
It is trivial, and inevitably remain mercury ion in product, so that the safety of product is on the hazard.Disclosed in EP0217765A2
It, will be through acetone extraction treated soybean under the conditions of scheme is existing for the sodium salt of the low-carbon alcohols such as methanol, ethyl alcohol and isopropanol
Lecithin carries out de-acyl reaction, and the halide of zinc is added into reaction solution after reaction, adds the organic bases such as pyrimidine and zinc
Salt is compound, finally ion exchange resin is recycled to make its separation, which produces a large amount of waste water during separating zinc salt,
And affect the final yield of product and purity.
With biological extraction method and chemical synthesis comparatively, passing through the natural materials such as soybean lecithin or egg yolk lecithin
Preparing GPC is its more favorable approach as Medicines and Health Product.
But it is more by the natural materials such as soybean lecithin or egg yolk lecithin preparation GPC reaction process in document report
Using homogeneous catalyst, there are catalyst separation difficulties, and waste is serious, and entire product prepares purifying process complexity, at high cost
Drawback, and heavy metal ion can be also introduced in the separation process having, when directly threatening product and being used as Medicines and Health Product
Safety.Therefore it develops a kind of effective heterogeneous catalysis and prepares GPC for catalyzed transesterification, can not only simplify
Product separating technique, and catalyst can reduce production cost with recycling and reusing.
Summary of the invention
Aiming at the problems existing in the prior art, the present invention, which provides, a kind of prepares glycerolphosphocholine based on egg shell
Method, process is relatively easy, overcomes the problem that complex process, product separation are difficult in the prior art.
The present invention is to be achieved through the following technical solutions:
A method of glycerolphosphocholine is prepared based on egg shell, comprising the following steps:
Step 1, the alcoholic solution of lecithin is heated to 20~70 DEG C；
Step 2, catalyst is added into the alcoholic solution of step 1, is stirred to react 2~8h, obtain mixed liquor；Catalyst uses
Egg shell is crushed and roasting is prepared；
Step 3, mixed liquor step 2 obtained is filtered, and filtrate is evaporated operation and obtains oil product；Use methanol
Oil product is dissolved, obtains methanol lysate, then precipitated with ether, discards supernatant liquid after precipitating is complete, repeatedly
Operation is several times；
Step 4, oil product step 3 obtained is dried, and obtains the phosphatide deacylation base containing glycerolphosphocholine
Object.
Preferably, in step 2, specific preparation process is as follows for catalyst:
Step a, egg shell is cleaned, and removes drying after inner membrance；
Step b crushes the obtained egg shell of step a to obtain powder；
Step c, the powder that step b is obtained roast 2~5 hours at 750~950 DEG C.
Further, in stepb, egg shell powder is broken to 120-200 mesh.
Preferably, in step 1, the alcohol is methanol or ethyl alcohol, and concentration of the lecithin in alcohol is 10~30g/L.
Preferably, in step 1, the lecithin is soybean lecithin or egg yolk lecithin, wherein phosphatidyl choline
Content be 20%~95%.
Preferably, in step 2, content of the catalyst in alcoholic solution is 15~40g/L.
Preferably, in step 3, in the operation precipitated with ether, the volume ratio of ether and methanol lysate is
(5~10): 1.
Preferably, in step 4, gained phosphatide deacylation substratess include glycerolphosphocholine, L-ALPHA-GPE
With glycerophosphatide acyl serine.
Further, the content of glycerolphosphocholine is 33.5%-68.5% in phosphatide deacylation substratess.
Preferably, in step 4, by the obtained phosphatide deacylation substratess containing glycerolphosphocholine existing for the diatomite
Under the conditions of, crystallization operation is carried out using the mixed liquor of dehydrated alcohol and ether, obtains glycerolphosphocholine.
Compared with prior art, the invention has the following beneficial technical effects:
The method provided by the invention for preparing glycerolphosphocholine using discarded egg shell is with discarded egg shell for original
Catalyst is prepared in material, carries out ester exchange reaction by catalysis natural phosphatidyl choline and alcohol and obtains glycerolphosphocholine.This hair
The bright catalyst used is solid catalyst, it is only necessary to and separation can be realized in filtering, so that the separation purifying technique of product is simple,
And reaction condition of the present invention is mild, reaction process is simple, can be recycled after catalyst filtration recycling.Simultaneously using discarded egg
Shell is that catalyst is prepared in raw material, not only contributes to the reasonable utilization of resource, turns waste into wealth, also simplify separating technology, drops
Low production cost.
Specific embodiment
Below with reference to specific embodiment, the present invention is described in further detail, it is described be explanation of the invention and
It is not to limit.
The method of the present invention that glycerolphosphocholine is prepared based on discarded egg shell, comprising the following steps:
Step (1): the alcoholic solution of the lecithin of formula ratio is added in the three-necked flask being condensed back, heat collecting type is placed in
20~70 DEG C are heated in constant-temperature heating magnetic stirring apparatus；
Step (2): after reacting liquid temperature in three-necked flask is constant, the catalyst and magneton of formula ratio is added, stirring is anti-
Answer 2~8h；Catalyst is prepared using discarded egg shell；
Step (3): the mixed liquor after step (2) reaction is filtered, and catalyst recycling, filtrate carries out vacuum rotating steaming
Hair, obtained oil product is dissolved with methanol, then is precipitated with the ether relative to 5~10 times of volumes of methanol lysate,
Liquid is discarded supernatant after precipitating is complete, operation is multiple repeatedly；
Step (4): obtained oil product is subjected to vacuum drying and removes remaining solvent, GPC is obtained or is with GPC
Main phosphatide deacylation substratess.
In step (1), the solvent alcohol is methanol or ethyl alcohol, and concentration of the lecithin in solvent alcohol is 10~30g/
L。
In step (1), the lecithin is soybean lecithin or egg yolk lecithin, the wherein content of phosphatidyl choline
It is 20%~95%.
In step (1), the mixing speed of the heat collecting type constant-temperature heating magnetic stirring apparatus is controlled in 200~800r/
min。
In step (2), content of the catalyst in reaction solution is 15~40g/L；The specific preparation step of its catalyst
It is as follows:
Step (a): will collect the egg shell tap water soaking and washing repeatedly come, and remove dry after inner membrance；
Step (b): 120-200 mesh is crushed to by high speed disintegrator to the egg shell that step (a) obtains；
Step (c): the powder that step (b) is obtained is put into Muffle furnace to be roasted 2~5 hours at 750~950 DEG C.
Egg shell is cleaned using ultrasonic washing instrument in step (a)；It is clean to handling using air dry oven
Egg shell be dried.
In step (3), the methanol that rotary evaporation in vacuo obtains is recyclable, with save the cost；
In step (4), phosphatide deacylation substratess include glycerolphosphocholine, L-ALPHA-GPE and glycerophosphatide acyl
Serine.
The present invention is further detailed below with reference to embodiment:
Embodiment 1:
The egg shell tap water soaking and washing repeatedly come will be collected, will be removed dry after inner membrance；To the egg shell after drying
It is crushed by high speed disintegrator, obtains 120-200 mesh powder；3 hours are finally roasted at 850 DEG C in Muffle furnace to obtain the final product
To required catalyst.
The lecithin that 5g phosphatidylcholine content is 20% is dissolved in 167mL methanol, insoluble matter is filtered off, band condensation is added
It in the three-necked flask of reflux, is placed in heat collecting type constant-temperature heating magnetic stirring apparatus and heats, when temperature rises to 50 DEG C, be added
The catalyst and magneton that 2.505g is prepared, open stirring, and low whipping speed reacts 5h under conditions of being 200r/min.Reaction
After mixed liquor be filtered, catalyst recycling, filtrate carry out rotary evaporation in vacuo, obtained oil product with 4mL without
Water methanol dissolution, then is precipitated with 20mL ether, precipitating completely after discard supernatant liquid, operate 3 times repeatedly, finally will
To oil product be dried in vacuo, obtain 0.986g appearance be the flaxen natural phospholipid deacylation substratess based on GPC,
It is detected, including glycerolphosphocholine, L-ALPHA-GPE and glycerophosphatide acyl serine, wherein the content of GPC accounts for
The 33.5% of product gross mass.
Embodiment 2
The present embodiment the difference from embodiment 1 is that, it is 950 DEG C that made catalyst, which obtains maturing temperature, and calcining time is 2 small
When.The lecithin that 2g phosphatidylcholine content is 60% is dissolved in 200mL dehydrated alcohol, insoluble matter is filtered off, band condensation is added
It in the three-necked flask of reflux, is placed in heat collecting type constant-temperature heating magnetic stirring apparatus and heats, when temperature rises to 70 DEG C, 5g system is added
Standby obtained catalyst and magneton, opens stirring, and low whipping speed reacts 8h under conditions of being 500r/min.After reaction
Mixed liquor is filtered, and catalyst recycling, filtrate carries out rotary evaporation in vacuo, and obtained oil product is molten with 2mL anhydrous methanol
Solution, then precipitated with 20mL ether, liquid is discarded supernatant after precipitating is complete, is operated 3 times repeatedly, the oily that will finally obtain
Product is dried in vacuo, and obtaining 0.533g appearance is the flaxen natural phospholipid deacylation substratess based on GPC, wherein GPC
Content account for the 68.5% of product gross mass.
Embodiment 3
The present embodiment and the difference of embodiment 2 are only that phosphatidylcholine content is 95% in lecithin, the reaction time
2h.Oily sediment 2mL anhydrous methanol in bottom is dissolved after reaction, 10mL ether is added and is precipitated, after precipitating is complete
Liquid is discarded supernatant, operates 2 times, is finally dried in vacuo obtained oil product repeatedly, and existing for the diatomite
Under the conditions of, it is crystallized at 4 DEG C using the mixed liquor of dehydrated alcohol and ether that volume ratio is 6:4, obtains GPC crystal
0.421g.132 DEG C of fusing point,(10% aqueous solution), elemental analysis result are as follows: C, 37.2%；H, 7.8%；N,
5.3%.
Embodiment 4
The present embodiment the difference from example 2 is that, it is 750 DEG C that made catalyst, which obtains maturing temperature, and calcining time is 5 small
When.The lecithin that 2g phosphatidylcholine content is 60% is dissolved in 100mL anhydrous methanol, reaction temperature is 20 DEG C, catalyst
Dosage is 4g.Mixed liquor after reaction is filtered, and catalyst recycling, filtrate carries out rotary evaporation in vacuo, obtains
Oil product 2mL anhydrous methanol dissolves, then is precipitated with 15mL ether, discards supernatant liquid after precipitating is complete, repeatedly
Obtained oil product, is finally dried in vacuo by operation 3 times, and it is flaxen based on GPC for obtaining 0.485g appearance
Natural phospholipid deacylation substratess, wherein the content of GPC accounts for the 62.3% of product gross mass.
Claims (10)
1. a kind of method for preparing glycerolphosphocholine based on egg shell, which comprises the following steps:
Step 1, the alcoholic solution of lecithin is heated to 20~70 DEG C；
Step 2, catalyst is added into the alcoholic solution of step 1, is stirred to react 2~8h, obtain mixed liquor；Catalyst uses egg
Shell is crushed and roasting is prepared；
Step 3, mixed liquor step 2 obtained is filtered, and filtrate is evaporated operation and obtains oil product；It is dissolved with methanol
Oil product obtains methanol lysate, then is precipitated with ether, discards supernatant liquid after precipitating is complete, operates repeatedly
Several times；
Step 4, oil product step 3 obtained is dried, and obtains the phosphatide deacylation substratess containing glycerolphosphocholine.
2. the method according to claim 1 for preparing glycerolphosphocholine based on egg shell, which is characterized in that step 2
In, specific preparation process is as follows for catalyst:
Step a, egg shell is cleaned, and removes drying after inner membrance；
Step b crushes the obtained egg shell of step a to obtain powder；
Step c, the powder that step b is obtained roast 2~5 hours at 750~950 DEG C.
3. the method according to claim 2 for preparing glycerolphosphocholine based on egg shell, which is characterized in that in step
In b, egg shell powder is broken to 120-200 mesh.
4. the method according to claim 1 for preparing glycerolphosphocholine based on egg shell, which is characterized in that in step
In 1, the alcohol is methanol or ethyl alcohol, and concentration of the lecithin in alcohol is 10~30g/L.
5. the method according to claim 1 for preparing glycerolphosphocholine based on egg shell, which is characterized in that in step
In 1, the lecithin is soybean lecithin or egg yolk lecithin, and wherein the content of phosphatidyl choline is 20%~95%.
6. the method according to claim 1 for preparing glycerolphosphocholine based on egg shell, which is characterized in that in step
In 2, content of the catalyst in alcoholic solution is 15~40g/L.
7. the method according to claim 1 for preparing glycerolphosphocholine based on egg shell, which is characterized in that in step
In 3, in the operation that is precipitated with ether, the volume ratio of ether and methanol lysate is (5~10): 1.
8. the method according to claim 1 for preparing glycerolphosphocholine based on egg shell, which is characterized in that in step
In 4, gained phosphatide deacylation substratess include glycerolphosphocholine, L-ALPHA-GPE and glycerophosphatide acyl serine.
9. the method according to claim 8 for preparing glycerolphosphocholine based on egg shell, which is characterized in that phosphatide is de-
The content of glycerolphosphocholine is 33.5%-68.5% in acyl group object.
10. the method according to claim 1 for preparing glycerolphosphocholine based on egg shell, which is characterized in that in step
In rapid 4, under the conditions of by the obtained phosphatide deacylation substratess containing glycerolphosphocholine existing for the diatomite, dehydrated alcohol is utilized
Crystallization operation is carried out with the mixed liquor of ether, obtains glycerolphosphocholine.
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