CN102863470A - Method for coproducing egg yolk lecithin, cephalin, yolk oil and low-denatured protein flour - Google Patents
Method for coproducing egg yolk lecithin, cephalin, yolk oil and low-denatured protein flour Download PDFInfo
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Abstract
The invention discloses a method for coproducing soybean germ oil, soybean germ protein concentrate, soybean oligosaccharides, soyasaponins and soy isoflavones by using soybean germs and relates to the grain deep-processing field. The method comprises the following steps: performing online stabilizing treatment on soybean germs; then with sub-critical fluid as the lyase, carrying out normal-temperature extraction and low-temperature desolventizing to produce soybean germ oil; and extracting polar components such as soybean oligosaccharides from the nonfat soybean germs by using sub-critical liquid ammonia and the like as the lyase and finally separating and purifying oligosaccharides, isoflavones and saponins in the extract; and finally separating soybean germ protein concentrate from the liquid ammonia raffinate, namely low temperature soybean germ meal. By adopting the co-production method, five products such as germ oil, oligosaccharides and soybean germ protein concentrate can be obtained simultaneously, the full utilization of soybean germs can be realized and the production cost is low; two-step extraction can be completed in different extraction sections of one leaching equipment, the investment is low; and zero emission is realized, and the method is green and environmentally friendly.
Description
Technical field
The present invention relates to food, medicine batching production field, refer in particular to a kind of take yolk as raw material, adopt pulse ultrasonic wave auxiliary extraction technology, subcritical fluid extraction technology and magnetic Nano isolation technique to produce high-purity egg yolk lecithin, and realized synchronously the coproduction exploitation of yolk cephalin, Oil of egg yolk and low sex change yolk powder.
Background technology
Egg is one of shared food in a few whole world, its mesolecithal is the abundantest part of nutritive value in the egg, and protein content is not only high, and its amino acid forms very similar to human body protein, be the high-quality complete protein that is only second to cow's milk, its biological value is up to 96%; Secondly, be enriched in the lipid in the yolk, not only contain abundant unsaturated fatty acids, and suitable linoleic acid content, contain simultaneously human at phospholipid compositions such as brain and neural system indispensable Yelkin TTS (PC), kephalins (PE), therefore, the exploitation of the bioactive ingredients such as the protein in the egg yolk, lipid and PC, PE is the study hotspot of Chinese scholars always.
Because the yolk moiety is complicated, is difficult to accomplish to make the best use of everything.At present research mainly concentrates on the separation and Extraction aspect of bioactive ingredients in the yolk, seldom the comprehensive utilization of yolk is studied.The present invention is intended to realize simultaneously coproduction of high-purity egg yolk PC separation and purification PE, Oil of egg yolk and low sex change yolk powder, set up that a cover PC extraction efficiency is high, purity is high, the egg product production technique for deep processing of workable and high-valued, complete utilization, for the yolk comprehensive utilization provides technical support.
High purity PC and PE refer to that content is greater than 95% phospholipid prod.Its preparation mainly comprises two steps of purifying, and at present, that has reported mainly includes machine solvent extration, the composite salt precipitator method, enzyme catalysis method, supercritical CO about the phosphatide extracting method
2Extraction process and column chromatography etc. wherein are most widely used, and apply for a patent maximum organic solvent extractionprocess and supercritical COs of surely belonging to
2Extraction process.
Chinese patent CN201110090211.5, CN97118167.5, CN02160786.9, CN200510060250.2, CN200910181427.5, CN201010291041.2 disclose the organic solvent extractionprocess of egg phospholipids, although this method output is large, but the organic solvent consumption is large, the process time is long, extraction yield is low, and the organic solvent majority that adopts does not meet environmental requirement, and the part organic solvent residual can cause food safety hidden danger in phosphatide.In order to improve the percentage extraction of this method, eliminate issuable food safety hidden danger, the researchist adopts the ethanol that allows on the food to use as solvent, adopt the means assisted extraction egg phospholipidss such as ultrasonic, as CN99808033.0, the disclosed Ovum Gallus domesticus Flavus lecithin of CN200610123974.4 ultrasonic-the ethanol assisted Extraction follows the example of, yet the single-frequency ultrasonic intensity is stronger, easily causes the serious sex change of egg yolk protein, reduces its use value.
Key problem in technology problem for above-mentioned organic solvent extractionprocess existence, the present invention introduces pulse ultrasonic wave Assisted Ethanol extractive technique, the impulse ultrasound wave technology is compared with the ultrasonic technology of the constant sound intensity of tradition, destruction to cell walls is stronger, extraction efficiency is high, extraction temperature is lower simultaneously, and is all less on the denaturation degrees impact of PC and egg yolk protein.
Supercritical CO
2Extraction preparation lecithin also receives much concern, Chinese patent CN02149172.0, CN99124381.1, CN02150144.0, CN02160786.9, CN03140389.1, CN94102372.9, CN96120082.0, CN200710067279.5, CN200910136630.0 disclose the supercritical liquid extraction technique of Ovum Gallus domesticus Flavus lecithin, however supercritical CO
2Extraction process exists the problems such as treatment capacity is little, equipment investment large, product cost is higher all the time, has restricted its large-scale promotion in the phosphatide production technique.
The subcritical fluid extraction technology is a novel extraction and isolation technique, has nontoxic, environmental protection, the activeconstituents of non-hot-work, reservation extract does not destroy, production capacity is large, can carry out large-scale industrialization production, the advantages such as energy-conservation, running cost is low are for the extraction of yolk mesolecithal oil provides new approaches.The people such as Zhang Min have reported the research of sub-Critical Extraction of Egg Yolk Oil by Propane, and this method employing drip washing technique, required solvent are easy to get, the Oil of egg yolk yield is higher.But its deficiency point is: (1) extraction efficiency is lower, extraction time is longer; (2) solvent-oil ratio is large thereby consume energy high, and easily residual.And the present invention to select propane or butane be extraction solvent, the adverse current that adopts stirring and leaching formula technique to carry out Oil of egg yolk repeats to extract, and greatly improves extraction efficiency, has shortened extraction time.
In addition, in the preparation process of high purity lecithin, report maximum column chromatographies that surely belongs to both at home and abroad.Lv Xiuyang discloses the concrete grammar of mixed-bed ion exchange resin refined lecithin in its patent of invention CN1634940, key step is that yolk is through the acetone degreasing, then use 95% extraction using alcohol, cross the chromatography column of pretreated strong acid type resin and strong base mixed with resin, after vacuum concentration, freeze-drying, can obtain respectively purity greater than 92% Yelkin TTS and purity greater than 80% PC.Although column chromatography can obtain content greater than 90% high purity lecithin, but treatment capacity is very limited, cycle is long, complex steps, the difficult continuous operation of realizing, and to use many organic solvents that certain toxicity is arranged in the treating processes, dissolvent residual has also limited this technology applying at food, field of medicaments.
Adopt Complex precipitation with inorganic salts, also can realize the purifying of PC.The Japanese Patent report mixes with thick egg phospholipids with 95% ethanol, then uses ZnCl
2After the precipitation and centrifugal separation, collect ZnCl
2Phospholipid complex adds the acetone that cools off again, steams desolventizing after the agitation and filtration under nitrogen protection, can obtain purity and reach 99.6% Yelkin TTS.Complex precipitation with inorganic salts utilizes inorganic salt to the selectivity of phospholipid molecule, although can greatly improve the content of Yelkin TTS, can introduce in operation metal ion, affects quality product, causes metal ion pollution.
Therefore, develop and be fit to preparation method China's national situation, low-cost, high purity PC and PE, and realize that simultaneously the coproduction exploitation of Oil of egg yolk, de-fatted egg yolk protein powder has important economy and social value.
This patent adopts pulse ultrasonic wave Assisted Ethanol extractive technique, not only can greatly improve the extraction yield of neutral lipid, also can reduce the denaturation degrees of yolk protein simultaneously, improves its following process, utility value; In addition, in the subtractive process of Oil of egg yolk, introduced the subcritical fluid extraction technology, a kind of novel extraction of subcritical fluid extraction technology and isolation technique, activeconstituents with nontoxic, environmental protection, reservation extract does not destroy, production capacity is large, can carry out the advantage such as large-scale industrialization production, and this technology provides new approaches for the efficient extraction of egg phospholipids; At last, in the phosphatide purification step, adopt first magnetic nanoparticle specific adsorption yolk PE, realize high efficiency separation, the purifying of yolk PC and PE.
Summary of the invention
Make the best use of everything for egg yolk is reached, the invention provides a kind of suitable China's national situation, low-cost, high purity PC preparation method, and realize simultaneously the coproduction working method of PE, Oil of egg yolk and low sex change yolk powder.
The technical solution adopted for the present invention to solve the technical problems is: at first carry out egg white, yolk separation after the Fresh Egg inspection sterilization, egg yolk liquid is placed extractor and add ethanol with the pulse ultrasonic wave assisted extraction, alcohol extract obtains the egg phospholipids crude extract after concentrated, alcohol insoluble solids is the yolk protein product, then adopt the subcritical fluid extraction technology to isolate Oil of egg yolk, be further purified with the magnetic Nano isolation technique at last, prepare high-purity egg yolk PC and PE.
Method of the present invention, carry out according to following step:
(1) yolk, egg white separate:At first to Fresh Egg inspection, cleaning and sterilization, after the broken shell yolk, egg white are separated, after yolk stirs, obtain the fresh-laid egg yellow liquor; The condition of sterilization is in 95～100 ℃ the boiling water, soaks 5～7 s.
(2) extraction of neutral lipid:Fresh-laid egg yellow liquor and water are joined in the ultrasonic extraction tank by weight 1:1～1:3 dilution and after stirring, and the massfraction that adds 1～9 times of volume in the extractor is 80～95% ethanolic solns, adopt subsequently pulse ultrasonic wave to carry out assisted extraction, extract behind 0.1～1 h mixture through centrifugal or filtering separation, repeatedly extract 1～5 time, merge alcohol extract and be yolk neutral lipid extracting solution (including egg phospholipids), impulse ultrasound wave frequency 20～200 KHz wherein, preferred 20～80 KHz; Extract 20～70 ℃ of temperature, wherein preferred 45～60 ℃; Extraction times 10～60 min, recurrent interval 1～5 s.
(3) concentrated, drying:The yolk neutral lipid extracting solution of step (2) gained is evaporated to the thick paste shape under 40～50 ℃, reclaims solvent, the thick paste of gained in 50～65 ℃ of lower vacuum-dryings, is namely got light yellow egg phospholipids crude extract.
(4) preparation of de-fatted egg yolk protein powder:Collect the alcohol-insoluble substance after massfraction is 80～95% extraction using alcohols in the step (2), then carry out (60～63 ℃ of pasteurizes, 180～240 s), by spraying drying, drying conditions is 175～185 ℃ of inlet temperature, 75～80 ℃ of air outlet temperatures cool off after the powder delivery, process through the vibratory screening apparatus classification.
(5) subcritical fluids is separated Oil of egg yolk:Will be through the Ovum Gallus domesticus Flavus lecithin crude extract that step (3) the obtains extraction kettle of packing into, extraction kettle is vacuumized, utilize pressure difference that subcritical solvent in the solvent tank (propane or butane) is injected in the extraction kettle and carry out the stirring-type countercurrent leaching, whole extraction process is finished under the processing condition of complete closed; Wherein extraction conditions is: extracting times 1～5 time, solid-liquid ratio 1:1～1:6, extraction time 10～120 min, stirring velocity 35～100 r/min, 10～90 ℃ of extraction temperature, wherein preferred 40～60 ℃, pressure 0.2～1.0 Mpa; After extracting end, from extract, collect and obtain Oil of egg yolk, from extract remainder, obtain de-oiling egg phospholipids mixture (mainly comprising PC and PE).
(6) egg phospholipids mixture precipitation:At first adopt steam (or hot water) that extractor is heated, and stir, 10～110 ℃ of Heating temperatures, stirring velocity 30～100 r/min, treat that extraction kettle pressure drops to 0.01MPa, enable vacuum pump and carry out negative pressure evaporation, until pressure is down to below – 0.09 MPa, open extractor, discharge low temperature de-oiling egg phospholipids mixture; Butane after the gasification is compressed, behind the condensation liquefaction, get back in the solvent tank recycling.
(7) preparation of Oil of egg yolk:Collect step (5) gained Oil of egg yolk, adopting massfraction is 80～95% alcohol solvent extractions, and then NaOH alkali refining method is carried out the depickling processing to high acid value Oil of egg yolk crude product; Wherein, the parameter of alcohol solvent extraction method is: solid-liquid ratio: 1:1～1:8 (g:mL), extraction time 10～60 min, extraction times 1～5; The processing condition of NaOH alkali refining method are: the alkali lye mass concentration is 1～10%, and initial temperature is 20～60 ℃, and final temperature is 50～65 ℃, and the reaction times is 10～60 min.
(8) preparation of magnetic Nano carrier of separating:Adopt chemical coprecipitation: iron vitriol and the Iron trichloride hexahydrate of solubility are dissolved in the aqueous solution, and the two mol ratio is 1:2～2:1, and total iron concentration is 0.01～0.5 mol/L; The mechanical stirring revolution is 200～800 r/min; Then add polyethylene glycol 6000 (PEG 6000), wherein add-on is 1/10 of total weight of iron; The control temperature is 40～70 ℃, deoxygenation 30 min; Afterwards under the mechanical stirring state, add fast 25% ammoniacal liquor or sodium hydroxide alkaline solution, make the pH of reaction soln〉10, slowly adding mass concentration behind stirring reaction 10 min under the vigorous stirring state is cm-chitosan (CM-CTS) solution of 5 %, the add-on of CM-CTS solution is 1/10 of total reaction liquor capacity, after application of sample is complete temperature is elevated to rapidly 70～90 ℃ and reacts 30～120 min; After reaction finished, sharp separation went out magnetic-particle under the effect of externally-applied magnetic field, with washed with de-ionized water for several times to remove completely chemical substance of unreacted, until the pH of last solution is about 7; The magnetic cm-chitosan nano particle of collecting at last black (is abbreviated as Fe
3O
4And carry out lyophilize and process (PEG+CM-CTS)); Then adopt Ca
2+To Fe
3O
4(PEG+CM-CTS) surface is further modified, and processing condition are as follows: the Fe of 1 mg/mL
3O
4(PEG+CM-CTS) nano particle respectively with the Ca of 2 mg/mL
2+Solution mixes, the pH value to 5.0 of adjusting mixing solutions～8.0, and under the lasting whipped state of 200～800 r/min, dynamic adsorption 30～120 min make it reach adsorption equilibrium under 25～50 ℃ constant temperature, prepare Ca
2+The affine magnetic nanoparticle of immobilized metal of modifying is abbreviated as Fe
3O
4(PEG+CM-CTS)@Ca
2+, Ca wherein is provided
2+May be the combination of a kind of in calcium chloride, calcium carbonate, calcium phosphate, caoxalate, the calcium acetate or two kinds.
(9) separation and purification of PC, PE:Adopting massfraction is the precipitation egg phospholipids mixture of 80～95% dissolve with ethanol solution step (6) gained, adds afterwards Fe
3O
4(PEG+CM-CTS)@Ca
2+Magnetic nanoparticle at 0～37 ℃ of stirring reaction 10～180 min, makes the PE in the phospholipid complex solution specifically be adsorbed on Fe
3O
4(PEG+CM-CTS)@Ca
2+The magnetic nanoparticle surface, under the effect of externally-applied magnetic field, there is the magnetic nanoparticle of PE from reaction soln, to separate absorption, as eluent its magnetic carrier is carried out wash-out with any in EDTA-2Na or 1～25% ammonia soln, collect elutriant, dialysis, concentrated, prepare high-purity PE; Carrier can utilize Ca behind wash-out
2+Solution is regenerated, and realizes the recycling of magnetic carrier.
(10) decolouring of yolk PC:The adsorption liquid of collection after step (9) is processed, and adopt neutral activated carbon decolorizing to process, 25～45 ℃ of bleaching temperatures, discoloring agent addition 2.0～5.0%, bleaching time are 30～90 min.
Advantage of the present invention:
(1) the present invention adopts pulse ultrasonic wave extractive technique, subcritical fluid extraction technology and magnetic Nano isolation technique, obtain simultaneously high-purity PC, high-purity PE, high-quality Oil of egg yolk and 4 products of de-fatted egg yolk protein powder, realized the high-valued complete utilization of yolk.
When (2) the present invention carries out yolk PC extraction, take harmless edible ethanol as solvent, adopt the pulse ultrasonic wave Assisted Ethanol to extract, accelerated the egg phospholipids dissolution rate, shorten the production cycle, can reduce again the denaturation degrees of leaching process mesolecithal protein simultaneously.
(3) the present invention adopts the subcritical fluid extraction technology to remove Oil of egg yolk, for supercritical extraction technique, the device fabrication cost is low, shortened the production cycle, extraction process all is to finish under the processing condition of complete closed, realized zero release, nothing " three-waste pollution " in the production can be to environment.
(4) the present invention adopts the magnetic Nano isolation technique that the egg phospholipids mixture is carried out refinement treatment, has realized the high efficiency separation of PC and PE, and simple to operate, separation cycle is shorter, the specific adsorption of PE is good, and reaction conditions is gentle, has preferably industrial applications prospect.
Embodiment
Below in conjunction with embodiment the present invention is further elaborated.
Embodiment 1
100.0 kg Fresh Eggs are through choosing egg, washing egg by sterilization (in 95～100 ℃ the boiling water, soaking 5～7 s), air-dry, with egg white, yolk separating device egg white is separated with yolk after the broken shell, obtain 28.0 kg egg yolk liquids.After adding the dilution of 28 L water in the egg yolk liquid and stirring, this yolk diluent is added in the extractor, the massfraction that adds subsequently 56 L is 80% ethanolic soln, at 20 KHz, 45 ℃ of lower lixiviate 10 min, recurrent interval 1 s, vat liquor filters after extracting, filtrate standing over night under room temperature discards precipitation and obtains yolk neutral fat vat liquor (including egg phospholipids), and under 45 ℃, be evaporated to the thick paste shape, reclaim solvent, the thick paste of gained in 55 ℃ of lower vacuum-dryings, is obtained lurid Ovum Gallus domesticus Flavus lecithin crude extract 4.1 kg; Collect alcohol-insoluble substance, reduction vaporization residual ethanol solvent by pasteurize, spraying drying, cooling, sieve powder, gets de-fatted egg yolk protein powder 8.8 kg.
4.1 kg Ovum Gallus domesticus Flavus lecithin crude extracts are placed the subcritical abstraction still, extraction kettle is vacuumized, utilize pressure difference that subcritical butane in the 4.1 L solvent tanks is injected in the extraction kettle; Extraction process is finished under the processing condition of complete closed, stirring velocity is 35 r/min, 40 ℃ of extraction temperature, pressure-controlling is at 0.2 Mpa, extract 120 min after, mixing oil enters evaporating pot, under decompression state, 50 ℃ of hot water heating precipitations after the compressed machine compression of the butane of gasification, are got back in the solvent tank after the liquefaction in condenser; At last the Ovum Gallus domesticus Flavus lecithin in the extraction kettle is carried out the reduction vaporization precipitation: in chuck and agitating vane, pass into steam heating and stir precipitation, stirring velocity 30 r/min, the precipitation temperature is controlled at 50 ℃, below Ya Li – 0.09 MPa, the butane compression condensation liquefaction cycle of gasification is used to the extraction kettle; Finally obtain egg phospholipids mixture 1.1 kg, Oil of egg yolk 2.8 kg.
Collected Oil of egg yolk acid value is higher, needs to process through depickling, and at first adopting massfraction is that 95% ethanol carries out solvent extract deacidification, and experiment condition is: Oil of egg yolk 2.8 kg, ethanol volume 2.8 L at room temperature extract 120 min.With this understanding, the acid value of Oil of egg yolk is reduced to 19.4 mg KOH/g by 30.6 mg KOH/g.Further adopt afterwards alkali-refining deacidification, processing condition are: the alkali lye mass concentration is 1%, and initial temperature is 20 ℃, and final temperature is 50 ℃, and the reaction times is 10 min.With this understanding, the acid value of Oil of egg yolk is reduced to 8.2 mgKOH/g by 19.4 mg KOH/g.
Carry out subsequently the carrier preparation, adopt chemical coprecipitation: 9.3 g iron vitriols and 18 g Iron trichloride hexahydrates are dissolved in the 10 L aqueous solution; The mechanical stirring revolution is 800 r/min; Then add 2.73 g PEG 6000, the control temperature is 40 ℃, deoxygenation 30 min; Afterwards under the mechanical stirring state, add fast 25% ammonia soln, make the pH of reaction soln〉10, under the vigorous stirring state, slowly add 1L concentration behind stirring reaction 10 min and be 5% CM-CTS, after application of sample is complete temperature is elevated to rapidly 70 ℃ of reaction 30 min; After reaction finished, sharp separation went out magnetic-particle under the effect of externally-applied magnetic field, with washed with de-ionized water for several times to remove completely chemical substance of unreacted, until the pH of last solution is about 7; The magnetic cm-chitosan nano particle of collecting at last black (is abbreviated as Fe
3O
4And carry out lyophilize and process (PEG+CM-CTS)).Then adopt Ca
2+To Fe
3O
4(PEG+CM-CTS) surface is further modified, processing condition are as follows: 1mg/mL Fe3O4 (PEG+CM-CTS) nano particle fully mixes with 2 mg/mL calcium chloride metal ion solutions, regulate the pH value to 5.0 of metal ion solution, and under the lasting whipped state of 200 r/min, dynamic adsorption 30 min under 25 ℃ constant temperature, make it reach adsorption equilibrium, prepare Ca
2+The affine magnetic nanoparticle of immobilized metal of modifying is abbreviated as Fe
3O
4(PEG+CM-CTS)@Ca
2+, at last the egg phospholipids that obtains is further adopted Fe
3O
4(PEG+CM-CTS)@Ca (II) magnetic nanoparticle carries out separation and purification, and take the processing (25 ℃ of bleaching temperatures, application of sample amount 2.0%, bleaching time are as 30 min) of decolouring of neutral gac, finally obtain high-purity PC 0.7 kg, high-purity PE 0.2 kg, PC purity〉95%, PE purity〉98%.
Embodiment 2
100.0 kg Fresh Eggs are through choosing egg, washing egg by sterilization (in 95～100 ℃ the boiling water, soaking 5～7 s), air-dry, with egg white, yolk separating device egg white is separated with yolk after the broken shell, obtain 28.0 kg egg yolk liquids.After adding the dilution of 28 L water in the gained egg yolk liquid and stirring, this yolk diluent is added in the extractor, adding subsequently 504 L massfractions is 95 % ethanolic solns, at 80 KHz, 60 ℃ of lower lixiviates 5 times, each 60 min, recurrent intervals 5 s, vat liquor filters after extracting, filtrate standing over night under room temperature discards precipitation and obtains yolk neutral fat vat liquor (including egg phospholipids), and under 50 ℃, be evaporated to the thick paste shape, reclaim solvent, the thick paste of gained in 65 ℃ of lower vacuum-dryings, is obtained lurid Ovum Gallus domesticus Flavus lecithin crude extract 8.1 kg; Collect alcohol-insoluble substance, reduction vaporization residual ethanol solvent by pasteurize, spraying drying, cooling, sieve powder, gets de-fatted egg yolk protein powder 4.7 kg.
8.1 kg Ovum Gallus domesticus Flavus lecithin crude extracts are placed the subcritical abstraction still, extraction kettle is vacuumized, utilize pressure difference that Propane in the 48.6 L solvent tanks is injected in the extraction kettle; Extraction process is finished under the processing condition of complete closed, stirring velocity is 100 r/min, 60 ℃ of extraction temperature, and pressure-controlling is at 1 Mpa, repeat lixiviate 5 times, each 10 min, after extraction finished, mixing oil entered evaporating pot, under decompression state, 70 ℃ of hot water heating precipitations after the compressed machine compression of the propane of gasification, are got back in the solvent tank after the liquefaction in condenser; At last the Ovum Gallus domesticus Flavus lecithin in the extraction kettle is carried out the reduction vaporization precipitation: in chuck and agitating vane, pass into steam heating and stir precipitation, stirring velocity 35 r/min, the precipitation temperature is controlled at 70 ℃, below the Ya Li – 0.09MPa, the propane compression condensation liquefaction cycle of gasification is used to the extraction kettle; Finally obtain egg phospholipids mixture 2.1 kg, Oil of egg yolk 5.8 kg.
Collected Oil of egg yolk acid value is higher, needs to process through depickling, and at first adopting massfraction is that 95% ethanol carries out solvent extract deacidification, and experiment condition is: Oil of egg yolk 5.8 kg, ethanol volume 46.4 L at room temperature extract 5 times, extract 60 min at every turn.With this understanding, the acid value of Oil of egg yolk is reduced to 4.5mg KOH/g by 31.6 mg KOH/g.Further adopt afterwards alkali-refining deacidification, processing condition are: the alkali lye mass concentration is 10%, and initial temperature is 60 ℃, and final temperature is 65 ℃, and the reaction times is 60 min.With this understanding, the acid value of Oil of egg yolk is reduced to 0.2 mg KOH/g by 4.5 mg KOH/g.
Carry out subsequently the carrier preparation, adopt chemical coprecipitation: 926.7 g aqueous ferrous sulfates and 450 g Iron trichloride hexahydrates are dissolved in the 10L aqueous solution; The mechanical stirring revolution is 200 r/min; Then add 137.67 g PEG 6000, the control temperature is 70 ℃, deoxygenation 30 min; Afterwards under the mechanical stirring state, add fast 25% ammonia soln, make the pH of reaction soln〉10, under the vigorous stirring state, slowly add 1L concentration behind stirring reaction 10 min and be 5% CM-CTS, after application of sample is complete temperature is elevated to rapidly 90 ℃ of reaction 120 min; After reaction finished, sharp separation went out magnetic-particle under the effect of externally-applied magnetic field, with washed with de-ionized water for several times to remove completely chemical substance of unreacted, until the pH of last solution is about 7; The magnetic cm-chitosan nano particle of collecting at last black (is abbreviated as Fe
3O
4And carry out lyophilize and process (PEG+CM-CTS)).Then adopt Ca
2+To Fe
3O
4(PEG+CM-CTS) surface is further modified, and processing condition are as follows: 1mg/mL Fe
3O
4(PEG+CM-CTS) nano particle fully mixes with 2 mg/mL calcium chloride metal ion solutions, regulate the pH value to 8.0 of metal ion solution, and under the lasting whipped state of 800 r/min, dynamic adsorption 120 min under 50 ℃ constant temperature, make it reach adsorption equilibrium, prepare Ca
2+The affine magnetic nanoparticle of immobilized metal of modifying is abbreviated as Fe
3O
4(PEG+CM-CTS)@Ca
2+At last the egg phospholipids that obtains is further adopted Fe
3O
4(PEG+CM-CTS)@Ca (II) magnetic nanoparticle carries out separation and purification, and take the processing (45 ℃ of bleaching temperatures, application of sample amount 5.0%, bleaching time are as 90min) of decolouring of neutral gac, finally obtain high-purity PC 1.4 kg, high-purity PE 0.3 kg, PC purity 〉=95%, PE purity〉95%.
Embodiment 3
100.0 kg Fresh Eggs are through choosing egg, washing egg by sterilization (in 95～100 ℃ the boiling water, soaking 5～7 s), air-dry, with egg white, yolk separating device egg white is separated with yolk after the broken shell, obtain 28.0 kg egg yolk liquids.After adding the dilution of 56 L water in the gained egg yolk liquid and stirring, this yolk diluent is added in the ultrasonic extraction tank, add subsequently 126 L massfractions, 90% ethanolic soln, at 40 KHz, 55 ℃ of lower lixiviates 2 times, each 30 min, recurrent intervals 2 s, vat liquor filters after extracting, filtrate standing over night under room temperature discards precipitation and obtains yolk neutral fat vat liquor (including egg phospholipids), and under 50 ℃, be evaporated to the thick paste shape, reclaim solvent, the thick paste of gained in 55 ℃ of lower vacuum-dryings, is obtained lurid Ovum Gallus domesticus Flavus lecithin crude extract 7.5 kg; Collect alcohol-insoluble substance, reduction vaporization residual ethanol solvent by pasteurize, spraying drying, cooling, sieve powder, gets de-fatted egg yolk protein powder 5.3 kg.
7.5 kg Ovum Gallus domesticus Flavus lecithin crude extracts are placed the subcritical abstraction still, extraction kettle is vacuumized, utilize pressure difference that subcritical butane in the 15 L solvent tanks is injected in the extraction kettle; Extraction process is finished under the processing condition of complete closed, stirring velocity is 80 r/min, 40 ℃ of extraction temperature, and pressure-controlling is at 0.3 Mpa, repeat lixiviate 3 times, each 40 min, after extraction finished, mixing oil entered evaporating pot, under decompression state, 60 ℃ of hot water heating precipitations after the compressed machine compression of the butane of gasification, are got back in the solvent tank after the liquefaction in condenser; At last the Ovum Gallus domesticus Flavus lecithin in the extraction kettle is carried out the reduction vaporization precipitation: in chuck and agitating vane, pass into steam heating and stir precipitation, stirring velocity 60 r/min, the precipitation temperature is controlled at 60 ℃, below Ya Li – 0.09 MPa, the butane compression condensation liquefaction cycle of gasification is used to the extraction kettle; Finally obtain egg phospholipids mixture 1.8 kg, Oil of egg yolk 5.4 kg.
Collected Oil of egg yolk acid value is higher, needs to process through depickling, and at first adopting massfraction is that 90% ethanol carries out solvent extract deacidification, and experiment condition is: Oil of egg yolk 5.4 kg, ethanol volume 21.6 L at room temperature extract 4 times, extract 10 min at every turn.With this understanding, the acid value of Oil of egg yolk is reduced to 7.5 mg KOH/g by 31.6 mg KOH/g.Further adopt afterwards alkali-refining deacidification, processing condition are: the alkali lye mass concentration is 8%, and initial temperature is 55 ℃, and final temperature is 65 ℃, and the reaction times is 30 min.With this understanding, the acid value of Oil of egg yolk is reduced to 0.1 mg KOH/g by 7.5 mg KOH/g.
Carry out subsequently the carrier preparation, adopt chemical coprecipitation: 111.2g iron vitriol and 162g Iron trichloride hexahydrate are dissolved in the 10 L aqueous solution, and the mechanical stirring revolution is 800 r/min; Then add 27.3 g PEG 6000, the control temperature is 60 ℃, deoxygenation 30 min; Afterwards under the mechanical stirring state, add fast sodium hydroxide solution, make the pH of reaction soln〉10, under the vigorous stirring state, slowly add 1L concentration behind stirring reaction 10 min and be 5% CM-CTS, after application of sample is complete temperature is elevated to rapidly 80 ℃ of reaction 60 min; After reaction finished, sharp separation went out magnetic-particle under the effect of externally-applied magnetic field, with washed with de-ionized water for several times to remove completely chemical substance of unreacted, until the pH of last solution is about 7; The magnetic cm-chitosan nano particle of collecting at last black (is abbreviated as Fe
3O
4And carry out lyophilize and process (PEG+CM-CTS)).Then adopt Ca
2+To Fe
3O
4(PEG+CM-CTS) surface is further modified, and processing condition are as follows: 1mg/mL Fe
3O
4(PEG+CM-CTS) nano particle fully mixes with 2 mg/mL calcium chloride metal ion solutions, regulate the pH value to 6.0 of metal ion solution, and under the lasting whipped state of 400 r/min, dynamic adsorption 90 min under 37 ℃ constant temperature, make it reach adsorption equilibrium, prepare Ca
2+The affine magnetic nanoparticle of immobilized metal of modifying is abbreviated as Fe
3O
4(PEG+CM-CTS)@Ca
2+At last the egg phospholipids that obtains is further adopted Fe
3O
4(PEG+CM-CTS)@Ca (II) magnetic nanoparticle carries out separation and purification, and take the processing (35 ℃ of bleaching temperatures, application of sample amount 4.0%, bleaching time are as 60 min) of decolouring of neutral gac, finally obtain high-purity PC 1.2 kg, high-purity PE 0.2 kg, PC purity〉95%, PE purity〉97%.
Claims (2)
1. Ovum Gallus domesticus Flavus lecithin, kephalin, Oil of egg yolk reach the co-production of low metaprotein powder, it is characterized in that carrying out according to following step:
(1) yolk, egg white separate:At first to Fresh Egg inspection, cleaning and sterilization, after the broken shell yolk, egg white are separated, after yolk stirs, obtain the fresh-laid egg yellow liquor; The condition of sterilization is in 95～100 ℃ the boiling water, soaks 5～7 s;
(2) extraction of neutral lipid:Fresh-laid egg yellow liquor and water are joined in the ultrasonic extraction tank by weight 1:1～1:3 dilution and after stirring, and the massfraction that adds 1～9 times of volume in the extractor is 80～95% ethanolic solns, adopt subsequently pulse ultrasonic wave to carry out assisted extraction, extract behind 0.1～1 h mixture through centrifugal or filtering separation, repeatedly extract 1～5 time, merge alcohol extract and be yolk neutral lipid extracting solution, impulse ultrasound wave frequency 20～200 KHz wherein, extract 20～70 ℃ of temperature, extraction times 10～60 min, recurrent interval 1～5 s;
(3) concentrated, drying:The yolk neutral lipid extracting solution of step (2) gained is evaporated to the thick paste shape under 40～50 ℃, reclaims solvent, the thick paste of gained in 50～65 ℃ of lower vacuum-dryings, is namely got light yellow egg phospholipids crude extract;
(4) preparation of de-fatted egg yolk protein powder:Collect the alcohol-insoluble substance after massfraction is 80～95% extraction using alcohols in the step (2), then 60～63 ℃, 180～240 s carry out pasteurize, by spraying drying, drying conditions is 175～185 ℃ of inlet temperature, 75～80 ℃ of air outlet temperatures cool off after the powder delivery, process through the vibratory screening apparatus classification;
(5) subcritical fluids is separated Oil of egg yolk:Will be through the Ovum Gallus domesticus Flavus lecithin crude extract that step (3) the obtains extraction kettle of packing into, extraction kettle is vacuumized, utilize pressure difference to carry out the stirring-type countercurrent leaching in Propane in the solvent tank or the subcritical butane injection extraction kettle, whole extraction process is finished under the processing condition of complete closed; Wherein extraction conditions is: extracting times 1～5 time, solid-liquid ratio 1:1～1:6, extraction time 10～120 min, stirring velocity 35～100 r/min, 10～90 ℃ of extraction temperature, wherein preferred 40～60 ℃, pressure 0.2～1.0 Mpa; After extracting end, from extract, collect and obtain Oil of egg yolk, from extract remainder, obtain de-oiling egg phospholipids mixture (mainly comprising PC and PE);
(6) egg phospholipids mixture precipitation:At first adopt steam or hot water that extractor is heated, and stir, 10～110 ℃ of Heating temperatures, stirring velocity 30～100 r/min, treat that extraction kettle pressure drops to 0.01MPa, enable vacuum pump and carry out negative pressure evaporation, until pressure is down to below – 0.09 MPa, open extractor, discharge low temperature de-oiling egg phospholipids mixture; Butane after the gasification is compressed, behind the condensation liquefaction, get back in the solvent tank recycling;
(7) preparation of Oil of egg yolk:Collect step (5) gained Oil of egg yolk, adopting massfraction is 80～95% alcohol solvent extractions, and then NaOH alkali refining method is carried out the depickling processing to high acid value Oil of egg yolk crude product; Wherein, the parameter of alcohol solvent extraction method is: solid-liquid ratio: 1:1～1:8 (g:mL), extraction time 10～60 min, extraction times 1～5; The processing condition of NaOH alkali refining method are: the alkali lye mass concentration is 1～10%, and initial temperature is 20～60 ℃, and final temperature is 50～65 ℃, and the reaction times is 10～60 min;
(8) preparation of magnetic Nano carrier of separating:Adopt chemical coprecipitation: iron vitriol and the Iron trichloride hexahydrate of solubility are dissolved in the aqueous solution, and the two mol ratio is 1:2～2:1, and total iron concentration is 0.01～0.5 mol/L; The mechanical stirring revolution is 200～800 r/min; Then add polyethylene glycol 6000, its add-on is 1/10 of total weight of iron; The control temperature is 40～70 ℃, deoxygenation 30 min; Afterwards under the mechanical stirring state, add fast 25% ammoniacal liquor or sodium hydroxide alkaline solution, make the pH of reaction soln〉10, slowly adding mass concentration behind stirring reaction 10 min under the vigorous stirring state is the carboxymethyl chitosan sugar soln of 5 %, the add-on of carboxymethyl chitosan sugar soln is 1/10 of total reaction liquor capacity, after application of sample is complete temperature is elevated to rapidly 70～90 ℃ and reacts 30～120 min; After reaction finished, sharp separation went out magnetic-particle under the effect of externally-applied magnetic field, with washed with de-ionized water for several times to remove completely chemical substance of unreacted, until the pH of last solution is about 7; Collect at last the magnetic cm-chitosan nano particle of black, and carry out lyophilize and process; Then adopt Ca
2+Magnetic cm-chitosan nano grain surface is further modified, and processing condition are as follows: the magnetic cm-chitosan nano particle of 1 mg/mL respectively with the Ca of 2 mg/mL
2+Solution mixes, the pH value to 5.0 of adjusting mixing solutions～8.0, and under the lasting whipped state of 200～800 r/min, dynamic adsorption 30～120 min make it reach adsorption equilibrium under 25～50 ℃ constant temperature, prepare Ca
2+The affine magnetic nanoparticle of immobilized metal of modifying,, Ca wherein is provided
2+Be the combination of a kind of in calcium chloride, calcium carbonate, calcium phosphate, caoxalate, the calcium acetate or two kinds;
(9) separation and purification of PC, PE:Adopting massfraction is the precipitation egg phospholipids mixture of 80～95% dissolve with ethanol solution step (6) gained, adds afterwards Ca
2+The affine magnetic nanoparticle of immobilized metal of modifying at 0～37 ℃ of stirring reaction 10～180 min, makes the PE in the phospholipid complex solution specifically be adsorbed on Ca
2+The affine magnetic nanoparticle of the immobilized metal of modifying is surperficial, under the effect of externally-applied magnetic field, there is the magnetic nanoparticle of PE from reaction soln, to separate absorption, as eluent its magnetic carrier is carried out wash-out with any in EDTA-2Na or 1～25% ammonia soln, collect elutriant, dialysis, concentrated, prepare high-purity PE; Carrier can utilize Ca behind wash-out
2+Solution is regenerated, and realizes the recycling of magnetic carrier;
(10) decolouring of yolk PC:The adsorption liquid of collection after step (9) is processed, and adopt neutral activated carbon decolorizing to process, 25～45 ℃ of bleaching temperatures, discoloring agent addition 2.0～5.0%, bleaching time are 30～90 min.
2. the co-production of Ovum Gallus domesticus Flavus lecithin according to claim 1, kephalin, Oil of egg yolk and low metaprotein powder is characterized in that impulse ultrasound wave frequency 20～80 KHz in the step (2); Extract 45～60 ℃ of temperature; Extraction times 10～60 min, extraction temperature is 30～45 ℃ in the step (5).
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| CN109971538A (en) * | 2019-04-16 | 2019-07-05 | 江南大学 | A method of egg oil is prepared using Propane abstraction technique |
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| CN109971538A (en) * | 2019-04-16 | 2019-07-05 | 江南大学 | A method of egg oil is prepared using Propane abstraction technique |
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