CN102757988B - Preparation method of 1,3-dioleoyl-2-palmitoyl triglyceride - Google Patents
Preparation method of 1,3-dioleoyl-2-palmitoyl triglyceride Download PDFInfo
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Abstract
The invention discloses a preparation method of 1,3-dioleoyl-2-palmitoyl triglyceride, which comprises the following steps: carrying out esterification reaction on glycerol and palmitinic acid under the action of a catalyst to obtain tripalmitin; carrying out ester exchange reaction on the tripalmitin and oleic acid or oleate under the action of 1,3-specific lipase until the ester exchange rate reaches 30-60%, and removing free fatty acids or fatty acid esters in the reaction system; and adding oleic acid or oleate into the reaction system, continuing the reaction until the ester exchange rate reaches 60-90%, and separating and purifying the 1,3-dioleoyl-2-palmitoyl triglyceride from the reaction products. The method disclosed by the invention has the advantages of wide raw material sources, high economy, high safety, mild technological conditions, short reaction time, low energy consumption and low enzyme consumption; and the method can be used for preparing high-yield high-purity 1,3-dioleoyl-2-palmitoyl triglyceride, and can be used as a food nutrient reinforcer for blending infant formula milk powder.
Description
Technical field
The present invention relates to human milk fat substituted product field, particularly relate to a kind of preparation method of OPO.
Background technology
1,3-bis-oleic acid-2-palmitic acid three ester (1,3-Dioleoyl-2-palmitoyl triglyceride, OPO) be a kind of nutrition-fortifying agent that China's newly approval in 2008 uses, be mainly used in infant formula, larger baby and baby formula.As everyone knows, breast milk is the optimal food of baby, but due to some special reason cause carrying out normal breast-feeding time, infant formula powder is then a kind of more satisfactory selection.Butterfat is the important component part in breast milk, and it only accounts for 3.6%-4.5% in breast milk, but for baby provides the energy of 50%.In butterfat composition, the palmitinic acid of about 70% is positioned at the Sn-2 position of triglyceride level, and Sn-1 and Sn-3 position mainly oleic acid; And the grease many employings vegetables oil in current infant formula powder is in harmonious proportion obtained, in vegetables oil, palmitinic acid great majority are all distributed in Sn-1,3.Research in recent years shows, mineral substance in the baby intestinal that difference on this lipid acid position can cause baby formula milk powder to feed and Sn-1, the palmitinic acid that 3 hydrolysis are got off combines and generates insoluble salt and run off, energy absorption can be reduced simultaneously, cause constipation and stomachache, even also may cause intestinal obstruction.
1, the early stage research of 3-bis-oleic acid-2-palmitic acid three ester preparation method adopts lard to be raw material more, how river etc. utilizes lard under Lipozyme RM IM makes catalyzer, synthesize breast milk Structure grease (2003, the research of enzyme process modified lard human milk substitute, the 28th volume the 1st phase).Publication number is that also to disclose a kind of be raw material with lard in the application for a patent for invention of CN102229866A, through after cholesterol with oleic acid 1, prepare the production method of 1,3 two oleic acid-2-palmitic acid three esters under 3 specific lipase effects.But lard component is complicated, unsaturated fatty acids is more oxidizable, very easily produces mda, and its application is subject to nationality, religious restriction.
Except lard, the production being used for OPO using plam oil as raw material also has research.Loders Croklaan company of Holland discloses a kind of method preparing triglyceride level in the patent of invention of notification number CN101287819B, the ethyl oleate mainly utilizing the vegetables oil alcoholysis containing high gas oil ratio to get off and plam oil Reactive Synthesis OPO under specific lipase catalysis.The method adopting oleic acid or its ester and plam oil catalyzed reaction to synthesize OPO is disclosed in the publication number CN101273118A application for a patent for invention of the said firm's application.The application for a patent for invention of publication number CN101258230A disclose a kind of utilize iodine number between 2-12 palm oil stearin and the ester of oleic acid or its nonglyceride carry out the method that enzymatic transesterification synthesizes OPO.The application for a patent for invention of publication number CN101679909A discloses carries out random transesterify by one or more iodine numbers in the palm oil stearin fractions of 18-40, and the product obtained, 1, synthesizes OPO under the effect of 3 specificity enzymes.Take plam oil as the different impact of the various physical and chemical index of palmitinic acid that OPO prepared by raw material is easily subject to causing due to raw material batch difference; Meanwhile, easily produce trans fatty acid in the process of hydrogenation reduction iodine number, the product containing high level trans fatty acid can not add infant formula.
Also have research first to prepare tripalmitin (tripalmitin, PPP) by chemical process or enzyme process, then with the OPO of oleic acid ester permutoid reaction synthesis of high purity.Adopt in the OPO research of the method synthesis of high purity, in order to obtain higher purity, generally adopting the mol ratio of raising oleic acid and PPP, extending the reaction times or first prepare the methods such as Sn-2 palmitinic acid Tegin 55G resynthesis OPO.The application for a patent for invention disclosed a kind of 1 of publication number CN102126950A, the preparation method of 3-bis-oleic acid-2-palmitic acid three ester, the method utilizes PPP to prepare Sn-2 position palmitinic acid Tegin 55G under specific lipase hydrolysis, and Sn-2 position palmitinic acid Tegin 55G and oleic acid synthesize OPO under specific lipase catalysis.The OPO content that this method obtains can reach 60%, but the production cycle is long, and with PPP being the substrate production OPO stage needs 24-36 hour.The people such as U.Schmid also adopt similar approach to produce highly purified OPO, but technique is more complicated is not easy to suitability for industrialized production (U.Schmid, 1999, Highly Selective Synthesis of 1,3-Oleoyl-2-Palmitoylglycerol by Lipase Catalysis.SCHMID ET AL.678-684).Also having document to disclose with PPP is the research that substrate synthesizes OPO, OPO content reaches the 74% needs reaction times of 24 hours (Ming-Lung Chen, 2004, Synthesis of the Structured Lipid 1,3-Dioleoyl-2-palmitoylglycerol from Palm Oil.JAOCS, Vol.81, no.6,525-532).
Summary of the invention
The invention provides a kind of 1, the preparation method of 3-bis-oleic acid-2-palmitic acid three ester, processing condition are gentle, and the reaction times is short, and energy consumption is little, few by enzyme amount, high yield pulp1, highly purified OPO can be prepared, solve the prior art production cycle long, energy consumption is large, by the problem that enzyme amount is large.
A preparation method for OPO, comprising:
(1) glycerine and palmitinic acid are carried out esterification under catalyst action, obtained tripalmitin;
(2) by tripalmitin and oleic acid or oleic acid ester 1, carry out transesterification reaction under 3 specific lipase effects, when to react to ester exchange rate be 30-60%, the free fatty acids in removing reaction system or fatty acid ester;
(3) in reaction system, add oleic acid or oleic acid ester, when continuation reaction is 60-90% to ester exchange rate, from reaction product, separation and purification obtains OPO.
1, under 3 specific lipase catalysis, highly purified tripalmitin (tripalmitin, PPP) can react with oleic acid or oleic acid ester, free fatty acids after certain hour in removing system or fatty acid ester, then fill into a small amount of oleic acid or oleic acid ester continuation reaction, can ester exchange rate be improved, prepare high yield pulp1, highly purified OPO (OPO).
In step (1), the purity of described palmitinic acid is preferably more than 95%.
In order to reduce grease oxidation at high temperature, preferably, described esterification is carried out under protection of inert gas or under the vacuum being less than 90mmHg in air residual voltage; Described rare gas element can be nitrogen, and low price is easy to operate.
Described catalyzer can be chemical catalyst; Be preferably sodium hydroxide, sulfuric acid, phosphoric acid, sodium methylate or tosic acid.Chemical catalyst catalytic efficiency is high, effectively can accelerate the esterification rate of glycerine and palmitinic acid.
Described catalyzer can also for the microbe-derived lipase with esterification activity; Commercial goods can be adopted, as Novozym 435 (being purchased from Novozymes Company of Denmark).Microbe-derived lipase abundance, it is convenient to obtain, and gentleer as catalyst reaction condition using it, security is better.
The reaction conditions of described esterification can be determined according to concrete catalyst type used.When adopting chemical catalyst, the mol ratio of glycerine and palmitinic acid is preferably 1: 3-1: 8, and the consumption of chemical catalyst is preferably the 0-2% of reaction substrate gross weight, and temperature of reaction is preferably 160-250 DEG C, and the reaction times is preferably 1-5 hour; When adopt microbe-derived there is the lipase of esterification activity time, the mol ratio of glycerine and palmitinic acid is preferably 1: 4-1: 10, the microbe-derived consumption with the lipase of esterification activity is preferably the 5-20% of reaction substrate gross weight, temperature of reaction is preferably 35 DEG C-65 DEG C, and the reaction times is preferably 1-10 hour.
After esterification completes, purification process can be carried out to product, make the content of tripalmitin in product more than 80%; Be preferably more than 90%; Be more preferably more than 95%.Described purification process can adopt acid-base neutralisation, underpressure distillation or molecular distillation method.Using the substrate that the product that tripalmitin content is higher reacts as next step, the content of OPO in next step building-up reactions can be improved.
In step (2), the purity of described oleic acid is preferably more than 75%.
Described oleic acid ester can be oleic acid nonglyceride, is preferably Witconol 2301 or ethyl oleate.
The mol ratio of described tripalmitin and oleic acid or oleic acid ester is preferably 1: 4-1: 12.The content of product OPO increases along with the increase of oleic acid or oleic acid ester consumption, but when adding oleic acid or the oleic acid ester of volume, non-oleic acid content wherein can the carrying out of inhibited reaction, causes the waste of the energy and resource simultaneously.
Described 1,3 specific lipases are location specific lipase, derive from microorganism, can act preferentially on triacylglycerol Sn-1, the lipid acid of 3.Microbe-derived 1,3 specific lipase wide material sources, in non-aqueous system, the esterification activity of lipase is high.Described 1, 3 specific lipases can be geotrichum candidum lipase, lipase from Aspergillus Niger, fold lipase from candida sp, antarctic candidia lipase, to dismiss from office lipase from candida sp, Candida parapsilosis lipase, look bacillus lipase, Mucor javanicus lipase, oat lipase, penicillium cammenberti lipase, penicillum requeforti lipase, dodge and close man's lipase, Pseudomonas lipase, mucormycosis lipase, Dai Shi rizolipase, melon rizolipase, Japan's rizolipase, Rhizopus niveus lipase, Rhizopus oryzae lipase, one or more in rhizopus arrhizus lipase and cotton like thermophilic silk robe bacterium lipase, commercial goods can be adopted, as Lipozyme TL IM, Lipozyme RM IM (being all purchased from Novozymes Company of Denmark) or Lpase DF (being purchased from Japanese Amano company).
Described 1, the consumption of 3 specific lipases is preferably the 6-12% of tripalmitin and oleic acid or oleic acid ester gross weight.The more reactions of enzyme concentration are faster, but can cause more acyl migration when enzyme concentration is too much, and namely Sn-2 position palmitinic acid is substituted by other lipid acid, cause the reduction of product OPO content.
Described transesterification reaction can be carried out in organic solvent or solvent-free system; Preferably carry out in organic solvent; More preferably, organic solvent is normal hexane, and the consumption of normal hexane is 0-20mL/g reaction substrate total amount.Because the fusing point of tripalmitin higher (about 67 DEG C), so solvent-free system can only carry out (>=55 DEG C) at a higher temperature, and solvent system can carry out (40 DEG C ~ 65 DEG C) at a lower temperature, lower temperature is conducive to the vigor of protective enzyme, reduces the generation of acyl migration simultaneously; And normal hexane is non-polar organic solvent, can not produce destruction, and boiling point is low to lipase, reaction terminates rear easy removal.
The temperature of reaction of described transesterification reaction is preferably 40-65 DEG C, and this temperature of reaction is the suitable range of reaction temperature of 1,3 specific lipases, and concrete temperature of reaction can be determined according to concrete enzyme class.
The reaction times of described transesterification reaction is preferably 2-10 hour; Be more preferably 4-5 hour.Increase the reaction times, transesterification reaction can be made more abundant, but along with the prolongation in reaction times, product OPO builds up, and can hinder the carrying out of transesterification reaction on the contrary, even acyl migration occurs when reaching a certain amount of, makes Sn-2 position palmitinic acid replaced.Adopt preferred reaction times condition, the ester exchange rate of reaction can be made to reach 30-60%, and now efficiency of pcr product is the highest.
Described ester exchange rate can characterize transesterification reaction degree, is obtained by following formulae discovery: ester exchange rate (%)=(after 1-transesterification reaction in triglyceride level before palmitic acid residues content/transesterification reaction in triglyceride level palmitic acid residues content) × 100%.
When ester exchange rate is too low, show that reaction not exclusively, product OPO yield is lower, and reactant utilization ratio is not high; When ester exchange rate is too high, acyl migration can occur, Sn-2 position palmitic acid content in product is reduced, and OPO yield can reduce on the contrary.When ester exchange rate is 30-60%, OPO yield is the highest, now removes free fatty acids or fatty acid ester, is conducive to reaction and continues to carry out to positive reaction direction, thus effectively can improve the yield of OPO.Preferably, when ester exchange rate is 45-60%, the free fatty acids in removing reaction system or fatty acid ester.
Free fatty acids in described removing reaction system or fatty acid ester can carry out as follows: from reaction system, isolate 1,3 specific lipases, then the free fatty acids in reaction system or fatty acid ester is removed, being returned by isolated 1,3 specific lipase is added in reaction system again; Wherein, isolate 1,3 specific lipases can adopt filtration or centrifugal treating method; Removing free fatty acids or fatty acid ester can adopt underpressure distillation, acid-base neutralisation or molecular distillation method.
Or the free fatty acids in described removing reaction system or fatty acid ester also can carry out as follows: adopt the free fatty acids in distillation under vacuum removing reaction system or fatty acid ester.Can save like this enzyme separation and return add step.
In step (3), the purity of described oleic acid is preferably more than 75%.
Described oleic acid ester can be oleic acid nonglyceride, is preferably Witconol 2301 or ethyl oleate.
In the tripalmitin in every mole of step (2), described oleic acid or the add-on of oleic acid ester are preferably 2-6mol.Under this dosage condition, oleic acid or oleic acid ester fully can react to positive reaction direction with remaining tripalmitin, make ester exchange rate reach 60-90%.
The temperature of reaction continuing reaction can keep identical with the temperature in step (2), and now the katalysis of 1,3 specific lipases is the strongest.
The reaction times of continuing reaction is preferably 0.5-5h; Be more preferably 1-4h.Adopt this reaction times, ester exchange rate can be made to reach 60-90%, be conducive to the accumulation of product OPO most.
The method of calculation of described ester exchange rate can with reference to the formula in step (2).
Transesterify degree is when certain limit, and OPO content can reach peak value.When ester exchange rate is 60-90%, product OPO yield is higher, now carries out separation and purification to reaction product, can obtain the OPO of high-content.Preferably, when ester exchange rate is 70-90%, from reaction product, separation and purification obtains OPO.
In order to improve product purity further, described separation and purification can be: reaction product is carried out molecular distillation, column chromatography or preparative liquid chromatography and be separated, obtained OPO.
In the present invention, when ester exchange rate reaches 60-90%, the free fatty acids in reaction system or fatty acid ester can be removed, again add oleic acid or oleic acid ester proceeds esterification, so repeatedly capable of circulation, can not only enzyme dosage be saved, and more highly purified OPO can be obtained.
The free fatty acids removed from reaction system in reaction process is recyclable recycling after purifying.
The present invention with glycerine and plant origin lipid acid (palmitinic acid, oleic acid) for raw material, first reacted by chemical process or enzyme law catalysis glycerine and palmitinic acid and generate highly purified PPP, then by twice ester-interchange method, under suitable processing condition, high yield pulp1, highly purified OPO has been prepared.
Adopt the inventive method, there is following beneficial effect:
(1) raw material sources are wide, economic security, reusable edible.
(2) compare the method for existing synthesis of high purity OPO, the inventive method has that the reaction times is short, energy consumption is little, by features such as enzyme amount are few.
(3) when PPP and oleic acid or oleic acid ester carry out transesterification reaction; compare a transesterification reaction of same condition; adopt twice ester-interchange method of the present invention can significantly improve transesterify degree between reactant; reduce acyl migration; thus effectively improve yield and the content in the product thereof of OPO; and product purity is higher, can as food enrichment for allocating baby formula milk powder.
Accompanying drawing explanation
Fig. 1 compares in the different methods synthesis product purity of OPO and reaction times, and wherein, method 1 is method disclosed in the application for a patent for invention of employing publication number CN102126950A; Method 2 is for adopting method disclosed in Ming-Lung Chen; Method 3 is for adopting method disclosed in the people such as U.Schmid; Method 4 is the method for in the employing embodiment of the present invention 5 No. 3.
Embodiment
Unless otherwise indicated, the technique means used in the present invention is the method for well known to a person skilled in the art, following embodiment object is to understand the present invention better, but not limits the scope of the invention, and the spirit and scope of the invention limited by claims.To those skilled in the art, under the prerequisite not deviating from essence of the present invention and scope, the various change carry out the reaction conditions in these embodiments, separation and Extraction condition or change also belong to protection scope of the present invention.
Embodiment 1 prepares OPO
(1) reaction substrate glycerine 0.1mol, palmitinic acid 0.6mol are mixed, add catalyst n aOH (accounting for 0.5% of reaction substrate gross weight), be placed in four mouthfuls of round-bottomed flasks; Round-bottomed flask is placed in constant-temperature heating sleeve, adds stirring rake, stirring velocity 150 revs/min, temperature of reaction 200 DEG C, reaction 2h, uninterruptedly passes into nitrogen as shielding gas between the reaction period; After having reacted, with the free fatty acids in KOH-water-alcohol solution removing reaction product;
Detect through gas phase (fid detector, high temperature capillary post), in reaction product, tripalmitin content is 92.2%, and glycerol-1,3-dipalmitate content is 6.6%.
(2) reaction product (containing 92.2% tripalmitin), 0.03mol oleic acid (oleic acid content 85.8%) and immobilization 1 that 0.005mol step (1) prepares is got, 3 specific lipase Lipozyme TL IM (being purchased from Novozymes Company of Denmark) (accounting for 10% of reaction substrate gross weight), add in 3mL normal hexane, be placed in the magnetic stirring apparatus of 50 DEG C, rotating speed 150 revs/min, reaction 4h; Reaction mixture adopts KOH-water-alcohol solution removing free fatty acids, and now use GC (fid detector) to measure palmitic acid content 45.6% in total fatty acids, palmitic acid content 99% in former substrate, ester exchange rate is 53.9%;
(3) in reaction system, add 0.01mol oleic acid, continue reaction 1h, ester exchange rate reaches 70.8%;
The product obtained measures through HPLC-ELSD (C18 post), and OPO content is 58.8%, and recording Sn-2 fatty acid content in reaction product by GC (fid detector) is 90.2%.
Embodiment 2 prepares OPO
(1) reaction substrate glycerine 1mol, palmitinic acid 5mol are mixed, add catalyzer tosic acid (accounting for 0.5% of reaction substrate gross weight), be placed in four mouthfuls of round-bottomed flasks; Round-bottomed flask is placed in constant-temperature heating sleeve, adds stirring rake, stirring velocity 160 revs/min, temperature of reaction 240 DEG C, reaction 1h, uninterruptedly passes into nitrogen as shielding gas between the reaction period; After having reacted, with the tripalmitin in molecular distillation method purified product;
Detect through HPLC (ELSD detector, strong polar ion exchange column), in product, the content of tripalmitin is 98.7%.
(2) reaction product (containing 98.7% tripalmitin), 0.3mol oleic acid (oleic acid content 95.6%) and immobilization 1 that 0.05mol step (1) prepares is got, 3 specific lipase Lipozyme R IM (being purchased from Novozymes Company of Denmark) (accounting for 10% of reaction substrate gross weight), add in 6mL normal hexane, be placed in 50 DEG C of shaking baths, rotating speed 200 revs/min, reaction 4h; Centrifugal, draw upper strata reaction mixture, be added back in reaction system after adopting KOH-water-alcohol solution removing free fatty acids, mixing, now use GC (fid detector) to measure palmitic acid content 50.1% in total fatty acids, palmitic acid content 99% in former substrate, ester exchange rate is 49.4%;
(3) in reaction system, add 3ml normal hexane, 0.3mol oleic acid, continue reaction 4h, ester exchange rate reaches 88.3%;
The product obtained detects through HPLC, and OPO content is 78.5%, and recording Sn-2 fatty acid content in reaction product by GC (fid detector) is 83.9%.
Embodiment 3 prepares OPO
(1) by reaction substrate glycerine 0.1mol, palmitinic acid 0.8mol, Novozym 435 (Novozymes Company of Denmark) (accounting for 12% of reaction substrate gross weight) mixes, and adds in 1L normal hexane, temperature of reaction 50 DEG C, reaction 8h; After having reacted, with KOH-water-alcohol solution removing free fatty acids;
Detect through GC (fid detector, high temperature capillary post), in product, the content of tripalmitin is 89.4%.
(2) get reaction product (containing 89.4% tripalmitin), 0.03mol oleic acid (oleic acid content 95.6%) and Lpase DF (Japanese Amano company) (accounting for 10% of reaction substrate gross weight) that 0.005mol step (1) prepares, in 40 DEG C of enzyme reactors, react 5h; Centrifugation reaction mixture, get supernatant liquor removing free fatty acids after with bottom enzyme together add-back reactor.Now use GC (fid detector) to measure palmitic acid content 43.2% in total fatty acids, palmitic acid content 99% in former substrate, ester exchange rate is 56.4%;
(3) in reaction system, add 0.02mol oleic acid, continue reaction 1h, ester exchange rate reaches 80.0%;
Reaction product is through HPLC (ELSD detector, strong polar ion exchange column) detect, OPO content is 60.1%, and recording Sn-2 fatty acid content in reaction product by GC (fid detector) is 92.0%.
Embodiment 4 prepares OPO
(1) reaction substrate glycerine 10mol and palmitinic acid 60mol is mixed in 25L pyroreaction still, add catalyst n aOH (accounting for 0.5% of reaction substrate gross weight), temperature of reaction 220 DEG C, rotating speed of agitator 180 revs/min, logical nitrogen protection, reaction 2h; After having reacted, vacuumize, extract unreacted palmitinic acid;
Detect through HPLC (ELSD detector, strong polar ion exchange column), in reactant, tripalmitin content is 96.7%.
(2) reaction product (containing 96.7% tripalmitin), 6mol oleic acid (oleic acid content 90.2%) and Lipozyme RM IM (Japanese Amano company) (accounting for 11% of reaction substrate gross weight) that 1mol step (1) prepares is got, reaction 4h in 55 DEG C of enzyme reactors (25L); Underpressure distillation goes out free fatty acids.Now use GC (fid detector) to measure palmitic acid content 39.0% in total fatty acids, palmitic acid content 99% in former substrate, ester exchange rate is 59.6%;
(3) in reaction system, add 2mol oleic acid, continue reaction 4h, ester exchange rate reaches 89.5%; Underpressure distillation extracts free fatty acids again;
Reaction product detects through HPLC-ELSD, and OPO content is 73.8%, and recording Sn-2 fatty acid content in reaction product by GC (fid detector) is 88.0%.
Embodiment 5 esterifications prepare comparing of OPO with twice esterification
In the present embodiment, reaction conditions: PPP (content 95%) is 1: 8 with the mol ratio of total oleic acid (content 96%), immobilized lipase Novi letter Lipozyme TL IM add-on is 10%, and solvent system is normal hexane, and temperature of reaction is 50 DEG C.
Wherein, No. 1 is PPP and oleic acid mol ratio 1: 8, reacts 8 hours; No. 2 is that PPP and oleic acid ratio 1: 6 are reacted 6 hours, removing free fatty acids, then add with PPP ratio be 1: 2 oleic acid continue reaction 2 hours; No. 3 for PPP and oleic acid ratio be 1: 4 react remove free fatty acids after 4 hours after to add with PPP ratio be the oleic acid of 1: 4 again, continuation reaction 4 hours.
The product obtained carries out GC (fid detector) and HPLC-ELSD and analyzes, and the results are shown in Table 1.As can be seen from the table, although the reaction times 1,2, No. 3 are all 8 hours, Sn-1, and 3 oleic acid contents can be different, and OPO content also has larger difference.In 3 groups, No. 3 effects are best.
Result shows, under the same reaction conditions, twice esterification process, compared to other aspects, significantly improves OPO (OPO) content.
The esterification next time of table 1 same reaction conditions and secondary esterification results contrast
Product purity and the reaction times of embodiment 6 different methods synthesis OPO compare
Relatively different methods synthesizes product purity and the reaction times of OPO, the results are shown in Figure 1, and wherein, method 1 is method disclosed in the application for a patent for invention of employing publication number CN102126950A; Method 2 is for adopting method (Ming-Lung Chen, 2004, Synthesis of the Structured Lipid 1 disclosed in Ming-Lung Chen, 3-Dioleoyl-2-palmitoylglycerol from Palm Oil.JAOCS, Vol.81, no.6,525-532); Method 3 is for adopting method (U.Schmid disclosed in the people such as U.Schmid, 1999, Highly Selective Synthesis of 1,3-Oleoyl-2-Palmitoylglycerol by Lipase Catalysis.SCHMID ET AL.678-684); Method 4 is the method for in the employing embodiment of the present invention 5 No. 3.
As seen from the figure, in synthesis of high content OPO, the OPO purity adopting the inventive method to obtain is higher, does not have marked difference with existing method; But in the reaction times, adopt the inventive method can obvious Reaction time shorten (foreshortening to 8h by 23-24h), be significantly better than existing method.
Claims (1)
1. a preparation method for OPO, comprising:
(1) glycerine and palmitinic acid are carried out esterification under catalyst action, obtained tripalmitin;
(2) by tripalmitin and oleic acid or oleic acid ester 1, carry out transesterification reaction under 3 specific lipase effects, when to react to ester exchange rate be 45-60%, the free fatty acids in removing reaction system or fatty acid ester; The mol ratio of described tripalmitin and oleic acid or oleic acid ester is 1:4-1:12, and the consumption of 1,3 specific lipases is the 6-12% of tripalmitin and oleic acid or oleic acid ester gross weight; The temperature of reaction of described transesterification reaction is 40-65 DEG C;
(3) in reaction system, add oleic acid or oleic acid ester, when continuation reaction is 70-90% to ester exchange rate, from reaction product, separation and purification obtains OPO; In the tripalmitin in every mole of step (2), described oleic acid or the add-on of oleic acid ester are 2-6mol;
In step (1), described catalyzer is chemical catalyst, and the mol ratio of glycerine and palmitinic acid is 1:3-1:8, and the consumption of chemical catalyst is the 0-2% of reaction substrate gross weight; Wherein, chemical catalyst is sodium hydroxide, sulfuric acid, phosphoric acid, sodium methylate or tosic acid; Or, in step (1), described catalyzer is the microbe-derived lipase with esterification activity, and the mol ratio of glycerine and palmitinic acid is 1:4-1:10, and the microbe-derived consumption with the lipase of esterification activity is the 5-20% of reaction substrate gross weight;
In step (1), described esterification is carried out under protection of inert gas or under the vacuum being less than 90mm Hg in air residual voltage;
Described transesterification reaction is carried out in organic solvent or solvent-free system, and organic solvent is normal hexane.
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| CN103305332B (en) * | 2013-06-27 | 2015-08-05 | 江南大学 | Dry method coupling solvent method divides the method carrying enrichment OPO |
| CN104561145A (en) * | 2013-10-17 | 2015-04-29 | 常州骏石生物技术有限公司 | Preparation method of 1, 3-dioleoyl-2-palmitoyl triglyceride |
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