CN108822146A - The production method of high-purity hydrogenated soy phosphatidyl choline - Google Patents
The production method of high-purity hydrogenated soy phosphatidyl choline Download PDFInfo
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- CN108822146A CN108822146A CN201810720902.0A CN201810720902A CN108822146A CN 108822146 A CN108822146 A CN 108822146A CN 201810720902 A CN201810720902 A CN 201810720902A CN 108822146 A CN108822146 A CN 108822146A
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- 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 title claims abstract description 25
- 238000004519 manufacturing process Methods 0.000 title abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 47
- 239000003054 catalyst Substances 0.000 claims abstract description 37
- 239000002904 solvent Substances 0.000 claims abstract description 29
- 235000010469 Glycine max Nutrition 0.000 claims abstract description 28
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000001257 hydrogen Substances 0.000 claims abstract description 28
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 28
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 19
- 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 abstract description 15
- 229940083466 soybean lecithin Drugs 0.000 claims abstract description 14
- 238000009903 catalytic hydrogenation reaction Methods 0.000 claims abstract description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 9
- 238000002360 preparation method Methods 0.000 claims abstract description 9
- 238000001953 recrystallisation Methods 0.000 claims abstract description 8
- 229910001220 stainless steel Inorganic materials 0.000 claims abstract description 5
- 239000010935 stainless steel Substances 0.000 claims abstract description 5
- 238000001914 filtration Methods 0.000 claims abstract description 4
- 238000005360 mashing Methods 0.000 claims abstract description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 40
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 28
- 235000019441 ethanol Nutrition 0.000 claims description 16
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 7
- 238000000926 separation method Methods 0.000 claims description 3
- 239000006227 byproduct Substances 0.000 claims 1
- 239000003814 drug Substances 0.000 abstract description 5
- 238000005516 engineering process Methods 0.000 abstract description 3
- 238000002347 injection Methods 0.000 abstract 1
- 239000007924 injection Substances 0.000 abstract 1
- 239000000546 pharmaceutical excipient Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 27
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 22
- 239000011630 iodine Substances 0.000 description 22
- 229910052740 iodine Inorganic materials 0.000 description 22
- 238000005984 hydrogenation reaction Methods 0.000 description 17
- 239000000787 lecithin Substances 0.000 description 16
- 235000010445 lecithin Nutrition 0.000 description 16
- 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 description 15
- 229940067606 lecithin Drugs 0.000 description 15
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- 229910052763 palladium Inorganic materials 0.000 description 8
- 244000068988 Glycine max Species 0.000 description 7
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 7
- 230000000694 effects Effects 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000010828 elution Methods 0.000 description 4
- 238000004128 high performance liquid chromatography Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 229910002056 binary alloy Inorganic materials 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000004440 column chromatography Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 2
- 108090000790 Enzymes Proteins 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 235000010627 Phaseolus vulgaris Nutrition 0.000 description 2
- 244000046052 Phaseolus vulgaris Species 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910018879 Pt—Pd Inorganic materials 0.000 description 2
- 229910000564 Raney nickel Inorganic materials 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000006911 enzymatic reaction Methods 0.000 description 2
- XTLNYNMNUCLWEZ-UHFFFAOYSA-N ethanol;propan-2-one Chemical compound CCO.CC(C)=O XTLNYNMNUCLWEZ-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 2
- 235000019345 sodium thiosulphate Nutrition 0.000 description 2
- 238000000638 solvent extraction Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 240000007124 Brassica oleracea Species 0.000 description 1
- 235000003899 Brassica oleracea var acephala Nutrition 0.000 description 1
- 235000011301 Brassica oleracea var capitata Nutrition 0.000 description 1
- 235000001169 Brassica oleracea var oleracea Nutrition 0.000 description 1
- ZKQDCIXGCQPQNV-UHFFFAOYSA-N Calcium hypochlorite Chemical compound [Ca+2].Cl[O-].Cl[O-] ZKQDCIXGCQPQNV-UHFFFAOYSA-N 0.000 description 1
- 230000005526 G1 to G0 transition Effects 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000007868 Raney catalyst Substances 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- OGACPMYMNGHHCL-UHFFFAOYSA-N [Ni].[Mo].[Re] Chemical compound [Ni].[Mo].[Re] OGACPMYMNGHHCL-UHFFFAOYSA-N 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Inorganic materials [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- WORJEOGGNQDSOE-UHFFFAOYSA-N chloroform;methanol Chemical compound OC.ClC(Cl)Cl WORJEOGGNQDSOE-UHFFFAOYSA-N 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- GVJHHUAWPYXKBD-UHFFFAOYSA-N d-alpha-tocopherol Natural products OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-UHFFFAOYSA-N 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- FHHZOYXKOICLGH-UHFFFAOYSA-N dichloromethane;ethanol Chemical compound CCO.ClCCl FHHZOYXKOICLGH-UHFFFAOYSA-N 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 125000005909 ethyl alcohol group Chemical group 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-N formic acid Substances OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 229940099578 hydrogenated soybean lecithin Drugs 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000014759 maintenance of location 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
- 239000000203 mixture Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- YTJSFYQNRXLOIC-UHFFFAOYSA-N octadecylsilane Chemical compound CCCCCCCCCCCCCCCCCC[SiH3] YTJSFYQNRXLOIC-UHFFFAOYSA-N 0.000 description 1
- 150000003904 phospholipids Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 230000007420 reactivation Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 238000004808 supercritical fluid chromatography Methods 0.000 description 1
- 238000000194 supercritical-fluid extraction Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000012085 test solution Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 235000010384 tocopherol Nutrition 0.000 description 1
- 229960001295 tocopherol Drugs 0.000 description 1
- 229930003799 tocopherol Natural products 0.000 description 1
- 239000011732 tocopherol Substances 0.000 description 1
- GVJHHUAWPYXKBD-IEOSBIPESA-N α-tocopherol Chemical compound OC1=C(C)C(C)=C2O[C@@](CCC[C@H](C)CCC[C@H](C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-IEOSBIPESA-N 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)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
The present invention provides the preparation method of a kind of soybean lecithin catalytic hydrogenation and purifying, and concrete technology is as follows：(1) soybean lecithin, catalysts and solvents are added in stainless steel cauldron, seal reaction kettle.It is passed through air in nitrogen replacement reaction kettle, then is passed through nitrogen in hydrogen replacement reaction kettle, finally keeps certain Hydrogen Vapor Pressure isothermal reaction in reaction kettle.(2) after completion of the reaction, product is separated with catalyst, active carbon decoloring is added, solvent is removed after filtering, recrystallization, mashing obtain high-purity hydrogenated soy phosphatidyl choline.Method of the present invention can obtain high-purity hydrogenated soy phosphatidyl choline, and in pharmaceuticals industry as injection pharmaceutic adjuvant, reaction condition is mild, easily controllable, be suitble to industrial-scale production.
Description
Technical field
The present invention relates to a kind of production methods of high-purity hydrogenated soy phosphatidyl choline, belong to field of medicine and chemical technology.
Background technique
Catalytic hydrogenation
Hydrogenated soy phosphatidyl choline through catalytic hydrogenation, is after purification made using high iodine number soybean lecithin as raw material.The product
Appearance claims into faint yellow or white powdery solids.Soybean lecithin keeps the unsaturation in molecular structure double after catalytic hydrogenation
Key adds hydrogen to open, and removes peculiar smell, and the stability and chemical property (stability, dispersibility, emulsibility) of product significantly improve,
It is saved suitable for the long period of low temperature or room temperature.Hydrogenated soy phosphatidyl choline is in food, health care product, superior cosmetics, medicine system
It makes, be widely used in light industry.
Since technique limits, similar product is there are iodine number height currently on the market, and purity is lower, and stability is poor, and peculiar smell is difficult to
The problems such as removing, limits it in high-end market, the especially application of medical manufacture industry.In consideration of it, the present invention is added by catalysis
Hydrogen technique, unsaturated double-bond hydrogenates completely substantially in molecule, effectively removes product peculiar smell, significantly reduces iodine number, then pass through purifying
Means reduce impurity content, product purity are greatly improved, to make the stability and chemical property (stability, dispersion of product
Property, emulsibility) it significantly improves, its application range is widened, meets the needs of pharmaceuticals industry is to high purity lecithin, fills up city
Field blank.
1966, the trials such as Sokol'Skii Pt/Pd BaSO4As catalyst, the mixing Pt-Pd with 10% is found
The hydrogenation rate of catalyst is less than pure 10%Pd catalyst.Use Pt-Pd/BaSO again later4Catalyst investigates different solvents pair
Lecithin adds the influence of hydrogen.Be carried on the noble metal catalyst of active carbon, as Pd, Pt with its hydrogenation temperature low, catalyst amount
Less, it is gradually taken seriously the advantages that good reaction selectivity.This method there are catalyst efficiencies low, higher problem of product iodine number.
He Fengying etc. to palladium, Raney's nickel, copper-chromated oxide, nickel-molybdenum-rhenium/silica-alumina catalyst, carries out screening and assessment respectively,
The experimental results showed that only palladium catalyst has preferable hydrogenation activity.Hydrogen Vapor Pressure 0.490MPa, 50~60 DEG C of reaction temperature, palladium
Catalyst amount is that soybean lecithin weighs 5%, and using methylene chloride or dichloromethane-ethanol mixture as solvent, isothermal reaction 3h is obtained
Nitrogen content 0.62% is arrived, iodine value is 20~30, phosphorus content 3.2%, flaxen hydrogenated soya phosphatide product, and yield is
80%.The product iodine number that the technique obtains is still higher, is unable to satisfy demand to be used.
Japan Patent JP0403629 report makees solvent using mixed solvent normal heptane and lower alcohol, and Pt is as catalyst, instead
80 DEG C of temperature are answered, pressure 20kg/cm3, obtained 90% hydrolecithin, iodine number 4.3.The product iodine number that the technique obtains compared with
It is low, but reaction temperature is higher, and pressure is larger, and energy consumption is high, low efficiency.
Cao Liang in CN103130829 using amorphous state NiB/diatomite-Pd/ diatomite as catalyst, Hydrogen Vapor Pressure 1MPa,
Reaction time 1h, 70 DEG C of reaction temperature, ethyl alcohol obtains hydrolecithin product, iodine number 15 as solvent, through column chromatographic purifying.Column layer
The method efficiency of analysis is lower, and energy consumption is high, limits its large-scale production.
Zhang Feitong crosses the iodine number investigated in the case of different solvents, temperature, pressure, catalyst and different time, final selected
Hydrogenation conditions are raw material 10g, and the palladium charcoal (water content 63.25%) that catalyst is 5%, dosage is the 5% of material quality, solvent
Use methylene chloride: alcohol mixed solvent (V: V=3: 1) dosage is 160mL, and reaction temperature is 50 ± 2 DEG C, reaction pressure
0.5MPa, reaction time 3.5h obtain iodine number 10 hereinafter, the hydrolecithin of PC purity 65%.
It is palladium, platinum, nickel that lecithin hydrogenation catalysts, which are applied at most,.The Raney nickel more early used, due to itself plus
Hydrogen activity is low, is not easy to regenerate, and Hydrogen Vapor Pressure requirement is larger, is unfavorable for industrialized production.Platinum, palladium are used as hydrogenation reaction catalysis
Agent, their hydrogenation activities are high, and precious metal catalyst scarcity of resources is expensive, but due to being disperse type catalyzer, dosage
Fewer, for the hydrolecithin product of high added value, the price of catalyst can receive.Palladium charcoal is catalytic hydrogenation
One of most common catalyst, since active carbon has bigger surface area, palladium, which is carried on wherein it is possible to greatly improve, adds hydrogen
Efficiency.
Purifying
1 solvent extraction
Zhang Weinong etc. by soybean oil residue with ethanol in proper amount extract dehydration de-oiling after, through vacuum concentration remove ethyl alcohol, after use second
Ether dissolution obtains suspension and solid impurity is removed by centrifugation, and acetone precipitation is added in supernatant liquor, and obtaining PC content is 65.8%
Thick soybeans phosphatide product.Solvent extraction is mainly used for pretreatment and the initial concentration of raw material.
2 column chromatographies
Li Wei etc. is tested by type of elution and gradient difference, show that gradient difference is using chloroform-methanol (2: 1, V/V)~nothing
The gradient elution mode gradient elution of water methanol is the conclusion of best type of elution, and eluting agent is 5-6 times of column volume, is washed
The de- time is 6h or so, can obtain purer P C product.Column chromatography consume quantity of solvent is big, and yield is low or stationary phase is expensive,
Adsorbent reactivation difficulty and solvent were difficult in place of the deficiencies of recycling.
3 supercritical fluid extractions
In patent US5616352, when pressure is 10~100bar, temperature is 30~50 DEG C, with propane: carbon dioxide
(70: 30, w/w), is extracted, and the product that content of phospholipid is 85% is obtained.More common in supercritical fluid method is overcritical
CO2, its molten oily ability ability that is relatively strong and dissolving phosphatide is weaker, and cost of equipment is more expensive.
4 enzymatic method for refining
Lekh et al. improves the content of phosphatidyl choline in phosphatide using enzyme process, and used enzyme is from cabbage
In phosphatidase, result of study rises to the phosphatidylcholine content of soybean lecithin for being 80% containing phosphatidyl choline
95%.Although lecithin content can be improved in enzymatic method for refining, but method is still immature up to now, and industrial application is less.
5 membrane separation process
In US6140519, first crude lecithin is mixed with n-hexane, remove grease, then (molecular weight is with pvdf membrane
10000~50000) it is separated, film retention part obtains phosphatide (the acetone insoluble matter content of de-oiling rouge>90%)；Then
Phosphatide is decolourized with bleaching powder, while a small amount of tocopherol or other antioxidants are added；Finally use at a suitable temperature
Fluidized bed dryer removes solvent.The cost of equipment of membrane separation process is also higher, and it is close that film function is still not completely separated molecular weight
Component, gained lecithin content is unable to reach medicinal requirements.
In conclusion obtaining, a simple production process, at low cost, yield is high, hydrogenation with high purity and environmental-friendly is big
The preparation method of beans lecithin becomes current urgent need.
Market is big to high-end lecithin demand gap, but the open method products obtained therefrom quality reported is still lower at present,
Iodine number, purity are unable to satisfy the demand of domestic market.The present invention focuses on solving the critical process problem such as catalytic hydrogenation and purifying, leads to
Screening catalytic hydrogenation conditions and purifying process are crossed, suitable industrialized production is found, meets life of the market to high-end lecithin demand
Production. art.
Summary of the invention
Present invention firstly discloses soybean lecithins under Pd/C catalytic condition, catalytic hydrogenation, with lower Hydrogen Vapor Pressure,
Higher suction hydrogen speed, shorter reaction time and higher conversion ratio obtain high-purity hydrogenated soy phosphatidyl choline.It is of the invention public
The method and process opened is simple, mild condition, economical environment-protective, product purity are high, is suitble to industrial-scale production.
The purpose of the present invention is to solve the existing hydrogenated soy phosphatidyl choline catalytic hydrogenation activity for preparing is low, hydrogenate not thorough
Bottom, the problem of product purity is low, provide a kind of preparation method of high-purity hydrogenated soy phosphatidyl choline.
The present invention provides a kind of catalytic hydrogenation of soybean lecithin and the method for purifying, concrete technology are as follows：It will be big
Beans lecithin, catalysts and solvents are added in stainless steel cauldron, seal reaction kettle.It is passed through in nitrogen replacement reaction kettle empty
Gas, then it is passed through nitrogen in hydrogen replacement reaction kettle, finally keep certain Hydrogen Vapor Pressure isothermal reaction in reaction kettle；End of reaction
Afterwards, product is separated with catalyst, active carbon decoloring is added, removes solvent after filtering, is recrystallized to give high-purity hydrogenated soybean
Lecithin.
Specifically, the catalytic hydrogenation of soybean lecithin of the present invention and purification process are as follows：Weigh soybean lecithin and 0.05-25
Weight %Pd/C catalyst is added in stainless steel cauldron, and ethyl alcohol is added and makes it dissolve, closed reactor, nitrogen displacement reaction
In kettle after air, then with hydrogen in hydrogen replacement reaction kettle, Hydrogen Vapor Pressure 0.05-25MPa in reaction kettle is finally maintained, in 20-
Isothermal reaction 1-8 hours under the conditions of 200 DEG C.After completion of the reaction, product is separated with catalyst, active carbon decoloring, filtering is added
After remove solvent, ethanol-acetone recrystallization, normal heptane is beaten to obtain high-purity hydrogenated soy phosphatidyl choline.
Further, in step of the present invention solvent be selected from methanol, ethyl alcohol, methylene chloride, propyl alcohol, isopropanol or they
Mixed solvent.
Further, the pressure of hydrogen is 0.1-12.5MPa in step of the present invention.
Further, the step reaction time of the present invention is 1-4 hours.
Further, reaction temperature is 20-100 DEG C in step of the present invention.
Further, recrystallization solvent is acetone in step of the present invention.
Further, it is normal heptane that solvent is beaten in step of the present invention.
Further, catalyst is Pd/C, dosage 2% in step of the present invention.
Further, solvent is ethyl alcohol in step of the present invention.
Further, Hydrogen Vapor Pressure is 0.8MPa in step of the present invention.
Further, the reaction time is 2.0 hours in step of the present invention.
Further, reaction temperature is 45 DEG C in step of the present invention.
Further, it is acetone-ethanol that solvent for use is recrystallized in step of the present invention.
The soya bean lecithin hydrogenation catalysis resulting hydrogenated soy phosphatidyl choline of preparation method is used for medical industry medicine in the present invention
Use auxiliary material.
Compared with prior art, the invention has the advantages that：
1. used catalyst of the present invention is Pd/C, under working condition disclosed above, high catalytic efficiency, hydrogenation is thorough, table
Reveal preferable catalytic activity and catalytic selectivity, significantly reduces reaction temperature, reaction time and hydrogenation pressure.
2. catalyst Pd/C property used in the present invention is stablized, it is suitable for continuous process, is reused after recyclable, shown
Writing reduces production cost, increases economic efficiency.
3. the hydrogenated soy phosphatidyl choline that in the present invention prepared by catalytic hydrogenation is purified using the method for recrystallization, easy to operate easy
Row, impurity-eliminating effect is excellent, avoids the highly energy-consumings, cumbersome method such as column chromatography.
4. the small polar impurity of embedding, simple and effective are removed in the present invention using normal heptane mashing.
5. the hydrogenated soy phosphatidyl choline purity is high prepared in the present invention, iodine number is low, and free from extraneous odour can satisfy high-end market
The broad mass market demand of high purity lecithin.
6. the high-purity hydrogenated soy phosphatidyl choline property prepared in the present invention is stablized, it is white powdery solids, is suitable for
Long-term room-temperature saves, and reduces product carrying cost, significantly improves product economy benefit and the scope of application.
Specific embodiment
Embodiment 1
Soya bean lecithin hydrogenation
It weighs 100g soybean lecithin to be added in hydrogenation reaction cauldron, 1L ethyl alcohol is added, catalyst Pd/C 2g, sealing is added
Reaction kettle, air in nitrogen replacement reaction kettle, then with nitrogen in hydrogen replacement reaction kettle, hydrogen is passed through to 0.8MPa after last.
45 DEG C of constant temperature stir 2 hours in reaction kettle.
Hydrogenated soy phosphatidyl choline purifying
It is above-mentioned after reaction to separate product catalyst, it is filtered to remove after active carbon decoloring, removes solvent.With acetone-
Ethyl alcohol binary system recrystallization purifying, ratio 8: 1 (volume ratio).Solvent is removed, is beaten after dry with normal heptane, solvent is removed
Hydrogenated soy phosphatidyl choline 90g, HPLC purity can be obtained after drying afterwards：98.2%, iodine number：1.60.
Embodiment 2
Soya bean lecithin hydrogenation
It weighs 100g soybean lecithin to be added in hydrogenation reaction cauldron, 1L ethyl alcohol is added, catalyst Pd/C 4.0g is added, it is close
Reaction kettle is sealed, air in nitrogen replacement reaction kettle, then with nitrogen in hydrogen replacement reaction kettle, hydrogen is finally passed through to 1.6MPa.
55 DEG C of constant temperature stir 4 hours in reaction kettle.
Hydrogenated soy phosphatidyl choline purifying
It is above-mentioned after reaction to separate product catalyst, it is filtered to remove after active carbon decoloring, removes solvent.With acetone-
Ethyl alcohol binary system recrystallization purifying, ratio 8: 1 (volume ratio).Solvent is removed, is beaten after dry with normal heptane, solvent is removed
Drying can obtain hydrogenated soy phosphatidyl choline 88g, HPLC purity afterwards：98.0%, iodine number：1.58.
Embodiment 3
Soya bean lecithin hydrogenation
It weighs 100g soybean lecithin to be added in hydrogenation reaction cauldron, 1L ethyl alcohol is added, catalyst Pd/C 1.0g is added, it is close
Reaction kettle is sealed, air in nitrogen replacement reaction kettle, then with nitrogen in hydrogen replacement reaction kettle, hydrogen is finally passed through to 0.6MPa.
60 DEG C of constant temperature stir 3 hours in reaction kettle.
Hydrogenated soy phosphatidyl choline purifying
It is above-mentioned after reaction to separate product catalyst, it is filtered to remove after active carbon decoloring, removes solvent.With acetone-
Ethyl alcohol binary system recrystallization purifying, ratio 8: 1 (volume ratio).Solvent is removed, is beaten after dry with normal heptane, solvent is removed
Hydrogenated soy phosphatidyl choline 85g, HPLC purity can be obtained after drying afterwards：93.0%, iodine number：4.00.
Embodiment 4
Purity analysis, HPLC：
Chromatographic column：Octadecylsilane chemically bonded silica column (ODS column)
Mobile phase：Methanol-tetrahydrofuran-formic acid (45: 3: 2) is mobile phase
Column temperature：35℃
Detector：Differential refraction detector
Detect temperature：40℃
Flow velocity：1.0ml/ minute
Embodiment 5
Determination of iodine value
This product 0.5g is taken, it is accurately weighed, it is placed in the drying iodine flask of 250ml, adds chloroform 4ml, after dissolution, precision adds
Enter bromination iodine solution 10ml, close plug shakes up, and places 30 minutes in the dark.The potassium iodide test solution 4ml and water 40ml of brand-new is added,
It shakes up, titrates remaining iodine with sodium thiosulfate titrating solution (0.1mol/L), when titration pays attention to shake well, the palm fibre of liquid to be mixed
Discoloration be it is faint yellow, add starch indicator solution 8 drip, continue to be titrated to blue disappearance；Blank test is done simultaneously.Sulphur is consumed with test sample
The volume (ml) of sodium thiosulfate titrating solution (0.1mol/L) is A, and the volume (ml) of blank test consumption is B, the weight of test sample
It is W for (g), calculates iodine number according to following formula, as a result should be not more than 2.0.(four general rules 0713 of Chinese Pharmacopoeia version in 2015)
The iodine number of test sample=(B-A) × 1.269/W.
Claims (5)
1. a kind of soybean lecithin catalytic hydrogenation and the preparation method of purifying, it is characterised in that following methods：
It weighs soybean lecithin and 0.1-10 weight %Pd/C catalyst is added in stainless steel cauldron, ethyl alcohol, which is added, keeps its molten
Solution, closed stainless steel cauldron are finally kept in nitrogen replacement reaction kettle after air, then with hydrogen in hydrogen replacement reaction kettle
Hydrogen Vapor Pressure 0.8MPa in reaction kettle maintains temperature to react 1-5 hours under the conditions of 40-50 DEG C.After completion of the reaction, by product with
Active carbon decoloring is added in catalyst separation, and solvent is removed after filtering, and recrystallization, mashing obtain high-purity hydrogenated soy phosphatidyl choline.
2. preparation method according to claim 1, wherein catalyst is Pd/C in the step, dosage is 0.5-5 weight
Measure %.
3. preparation method according to claim 2, wherein catalyst is Pd/C in the step, dosage is 2 weight %.
4. preparation method according to claim 1, wherein the reaction time is 2.0 hours in the step.
5. preparation method according to claim 1, wherein purifying is recrystallized with ethanol/acetone in the step, normal heptane
Mashing.
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| CN112142777A (en) * | 2020-10-22 | 2020-12-29 | 广州善合化工有限公司 | Preparation method and application of hydrogenated lecithin |
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