CN101293895B - Fine purification technique for phospholipid - Google Patents
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Abstract
The invention relates to a refining process of phospholipid, belonging to the technology field of oil production and comprehensive utilization. The refining process of phospholipid comprises the following steps of: (1) mixing a mixture containing phospholipid with pentane, hexane, heptane, ethyl ether or petroleum ether to obtain a layered emulsion system; (2) separating the emulsion system obtained in the step (1), and collecting the supernatant emulsion; and (3) removing the solvent and water in the supernatant emulsion obtained in the step (2). Compared with the prior phospholipid refining process, the inventive phospholipid refining process has the advantages of low equipment requirements, low operation cost, and applicability to large scale production. The obtained product has good quality, and can be used in fields with high requirement for the phospholipid quality, such as food processing.
Description
Technical field
The invention belongs to grease production and comprehensive utilization technique field, relate to process for refining phospholipid.
Background technology
Chinese oil industry is obtaining the development of advancing by leaps and bounds over past ten years, system fuel oil meter mould, complete processings such as soybean, vegetable seed, peanut have all reached higher level, for satisfy domestic growing albumen, the grease demand provides assurance.At present, the bottleneck of restriction China oil prodution industry level raising is making in the byproduct comprehensive utilization that produces in the oily process.Wherein, hydrated phospholipid is one of main byproduct that produces in the processes such as soybean processing, vegetable seed, peanut, and at present China all is in relatively backward level to research and development, the processing of phosphatide.
The main source of natural phospholipid is a soybean, contains the phosphatide of 0.3-0.6% in the soybean, contains the phosphatide of 1.0-3.0% in the soybean oil.In addition, Semen Brassicae campestris, peanut, yolk etc. also are the important sources of phosphatide." Yelkin TTS " (Lecithin) speech is the biochemist to being commonly called as of phosphatidylcholine (phosphatidylcholine), but " Yelkin TTS " of commercial indication then is the common name of various phospholipid prods, its accurately title be commodity phosphatide just.People's Republic of China's Yelkin TTS industry standard is at present general be " the phosphatide general technical specifications " implemented on issue on June 27th, 1994, December 1 (SB/T10206-94).This standard is clear and definite " phosphatide " is meant yellow or the brown phosphorous lipoid that are insoluble in acetone." hydrated phospholipid " is meant that the filter plant crude oil is through aquation, separation, the yellow thick liquid that obtains.Hydrated phospholipid is commonly called as " hydrated oil foot " or oil foot in grease processing industry.It mainly consists of water, triglyceride level, impurity and phosphatide.By chemical structure, phosphatide is lipid acid, the derivative of compound such as triglyceride level and phosphoric acid is the mixture of compositions such as phosphatidylcholine, phosphatidylethanolamine, phosphatidylinositols, phosphatidic acid, phosphatidylserine, lyso-phosphatidylcholine, hemolytic phosphatidyl inositol, haemolysis acyl Serine, Ultrapole L, phytoglycolipid.The hydrated phospholipid drying and dehydrating to water content below 1%, is promptly obtained concentrated phosphatide." concentrated phosphatide " hydrated phospholipid through vacuum hydro-extraction, operation such as concentrate and make mould shape or thick product.
The purposes of phosphatide is very extensive, is mainly used in fields such as food, medicine, chemical industry, feed breed.Phosphatide because have emulsification, splashproof, instant, wetting, dispersion, the demoulding separates, improves multiple functional performances such as viscosity and nutrition source, make it can be used for field of food ideally, and, be subjected to the human consumer and generally accept as a kind of natural product.As in oleomargarine, phosphatide can be used as antispattering agent and emulsifying agent; In chocolate, caramel, coating, phosphatide can be controlled viscosity, reduce and be clamminess and crystallization control; In instant food such as cocoa powder, breakfast drink, milk-substitute, phosphatide can be used as emulsifying agent and wetting agent; In bakeries such as bread, volume cake, doughnut, cake, cooky, face system cake, pie, phosphatide is as emulsifying agent, wetting agent and releasing agent; In milk-product such as infant formula, milk-substitute, ice-creams and local flavor product, phosphatide can be used as emulsifying agent, wetting agent, antispattering agent and releasing agent.All contain phosphatide in nearly all animal body, human nutrition needs phosphatide, and phosphatidylcholine provides indispensable fatty acid and choline source for people in the meals.Phosphatide is regulated the serum lipid effect in addition, regulates the serum lipid level and means energy reducing cholesterol level, protection liver.Phosphatide also has certain memory of improving, effects such as booster immunization power.Phosphatide can also be as bulk drug of target body medicine etc.In addition, phosphatide also has use widely in fields such as coating, paint, plastics, glass reinforced plastic, rubber, papermaking, printing ink, metal processing, feed, weaving and mrts.
Phosphatide is produced so far only year history surplus in the of 80 from commercialization, according to statistics, and about 140,000 tons of world soybean phosphatide in 1992 annual production, the U.S. and West Europe account for 60% of world soybean phosphatide ultimate production.The main manufacturer of phosphatide raw material is Jia Ji (Cargill) company (having annexed the phosphatide business of German Degussa (Degussa) company), ADM company (Archer Daniels MidlandCompany) in the world, Shu Lai (Solae) company, German Nattermann phosphatide company, U.S. Yelkin TTS company (American Lecithin Company) etc.At present, the phosphatide processing technology of these offshore companies is to be in blockage state to China basically, and there are bigger gap in the manufacturing enterprise of domestic phosphatide and these phosphatide well-established business in the world on state of the art.The main dependence on import of the present high-grade concentrated phosphatide of China, about 10,000 tons of year import volume.China has abundant phosphatide resource as main in the world soybean, Semen Brassicae campestris, peanut processing base, but can not produce high-quality phospholipid prod.And along with the phosphatide Application Areas progressively enlarges, the consumption of Chinese phosphatide will progressively rise.So the production of high-quality phosphatide is for the present food service industry of China, pharmaceutical industries, oils industry, especially soyabean processing enterprise shows important especially.
China's phosphatide industry is owing to fully utilize problems such as poor, that technical study is not enough, slower development always.Domestic existing concentrated phosphatide manufacturer produces phosphatide and mainly adopts the hydrated phospholipid direct drying method.Have following problem in this technology: the impurity in the crude oil is after process aquation, centrifugation, and most of impurity is transferred in the hydrated phospholipid.These impurity are dry with hydrated phospholipid, and impurity content is very high in the finished product, has limited the use of phosphatide in food, medicine and other fields.
The natural concentrated phosphatide standard of one-level of the highest ranking of " phosphatide general technical specifications " (SB/T 10206-94) regulation is as follows: ingredient requirement be raw materials used must be fresh hydrated phospholipid or qualified concentrated phosphatide, must not be mixed with non-edible plant oil in the raw material.The Oranoleptic indicator for color and luster be pale brown look or brown, be and mould shape or thick; Quality is even, and nothing is gone mouldy, and has phosphatide inherent smell, free from extraneous odour.Quality index is: ether insolubles≤0.3%; Acetone insoluble matter 〉=65.0%; Moisture content and volatile matter≤1.0%; Acid value≤30.0mgKOH/g; Color and luster≤12Gardner; Hydration test: not stratified.Edible concentrated phosphatide sanitary index: peroxide value≤12meq/kg; Residual solvent amount≤50mg/kg; Arsenic (in As)≤0.1mg/kg.36 tons of/day concentrated phosphatide production lines that three rivers remittance good fortune grain and oil group went into operation in 2007 take directly to concentrate the concentrated soybean phospholipid that hydrated phospholipid is produced.The standard of product meets the regulation of national standard for one-level food grade concentrated phosphatide substantially, but compare with external high-grade concentrated phosphatide product standard and also to have a certain distance, wherein topmost gap is ether insolubles index: the external product majority is controlled at the ether insolubles below 0.1%, and domestic industry index height is 0.3%.The too high levels of ether insolubles all can have a negative impact for the outward appearance of phosphatide, transparency etc., has limited the application of phosphatide in fields such as food service industrys.The another one gap is that the phosphatide color and luster is deeper than the high-grade phospholipid prod of import slightly.
Domestic oil research mechanism, enterprise have carried out the years of researches exploitation to refining concentrated phosphatide, have obtained certain progress.As having at present before crude oil glue phosphatide, the technology by filtered crude oil or mixing oil reduces impurity content.Theoretically, the crude oil that impurity content is low makes the low phosphatide of impurity content easily.But in fact, because when removing phosphatide, the small amount of impurities of filtering the back crude oil still can major part be transferred in the hydrated phospholipid, influences phosphatide impurity content index.And crude oil viscosity is higher during owing to filtration, and the phosphatide that contains in its crude oil is filtered agent absorption easily, and the filter pressure of requirement is higher, and filtration velocity is slow.A large amount of phosphatide of filtering medium absorption also are taken as waste disposal usually, have caused a large amount of wastes.Because crude oil will increase large-scale filter plant and be undoubtedly a kind of filtration that repeats for final finished oil in advance through the residual neat soap of filtering and removing, micelle, pigment etc. when refining.And phospholipids content removes to filter a large amount of crude oils for obtaining a spot of phosphatide in the crude oil about 1.0-3.0%, and facility investment, power consumption all can increase a lot.Also have at present to adopt to filter and leach the technical scheme that mixing oil is produced high-quality phosphatide.Because soybean has water to enter mixing oil in the oily process of system, the phosphatide with good emulsifying can form soya-bean oil, solvent, water the very big micelle of molecular weight, and then stop up a whole set of filtering system.In addition, the phospholipids content in the mixing oil is lower, filters a large amount of mixing oils for obtaining the low phosphatide of impurity content merely, needs to increase large-scale filter plant, and operation is inconvenience very.
What also have is that raw material carries out processing and refining food grade phosphatide with feed grade phosphatide, announced a kind of production method of food-level concentrated soybean phospholipid as number of patent application 200710019614.4, adopt mineral membrane (comprising inorganic ceramic film and stainless steel membrane) filtering technique, the product transparency will be influenced in the phosphatide, the material of ether insolubles removes. but just there is defective in the employed feed grade phospholipid prod of this technology raw material. in production feed grade phosphatide process, because foreign matter content is higher in the hydrated phospholipid, the more high reason of vaporization temperature, make that feed grade phosphatide color and luster is dark, sex change is serious. and, because phosphatide forms the higher micella of apparent molecular weight in hexane, flux is little during inorganic membrane filtration, clean difficulty, continuous large-scale production acquires a certain degree of difficulty.
Soybean comprehensive utilization project is an extremely promising agriculture industrialization project.It not only can drive the adjustment of the structure of agricultural production, and aquaculture, foodstuffs industry, healthcare products industry, medicine industry etc. are all had an immense impact on.It not only has great economic benefit, and has brought great social benefit.Soybean comprehensive utilization project has more realistic meaning to China, and it will improve the private foster level of Chinese people, promotes relevant industrial and agricultural development and plays an important role, and becomes to have one of project of agriculture industrialization future now most.
Summary of the invention
The object of the present invention is to provide a kind of process for purification of phosphatide, it is primarily aimed at is that the hydrated phospholipid product dehydration temperaturre height, the phospholipid prod color and luster that run in the existing phosphatide industry are dark, the production status and the technical barrier of domestic phosphatide such as phospholipid prod impurity content height, concentrated phosphatide product poor transparency.The present invention can make the byproduct in the oil plant preparation process obtain to utilize, and reduces the foreign matter content of phospholipid prod, improves the color and luster of phosphatide, improves the quality of phosphatide.According to said method final product processed be enough to be used in food-processing etc. to the requirement of phospholipid prod class than higher field, realize the comprehensive utilization of raw material, avoided waste.
Above-mentioned purpose of the present invention is achieved in that
Process for refining phospholipid provided by the invention comprises the steps:
1) mixture that contains phosphatide mixes the emulsification system of score layer with pentane, hexane, heptane, ether or sherwood oil;
2) emulsification system to the step 1) preparation separates, and gets the upper strata emulsion;
3) to step 2) the upper strata emulsion of preparation removes solvent and water.
As preferably, the above-mentioned mixture that contains phosphatide is meant raw phospholipid or hydrated phospholipid.
Specifically, above-mentioned raw phospholipid is meant the mixture of phospholipids that contains of ether insolubles 〉=0.1%, comprise according to China's Yelkin TTS industry standard " phosphatide general technical specifications " (SB/T10206-94) in the regulation one-level, secondary, three grades of concentrated phosphatides.One-level concentrated phosphatide ether insolubles≤0.3% wherein, secondary concentrated phosphatide ether insolubles≤1.0%, three grade of concentrated phosphatide ether insolubles≤3.0%.Though raw phospholipid can satisfy the demand of certain fields, since ether insolubles 〉=0.1%, the foreign matter content height, and transparency is very poor, can not be applied to the fields such as foodstuffs industry that quality product is had relatively high expectations.
Specifically, above-mentioned hydrated phospholipid prepares with the following method: the crude oil that will contain phosphatide adds water hydratable, obtains hydrated phospholipid through settlement separate or centrifugation.The used crude oil that contains phosphatide is optional from soybean crude oil, vegetable seed crude oil or crude peanut oil.
As optimization, above-mentioned steps 1) in, the mixture and pentane, hexane, heptane, ether or the sherwood oil blended mass ratio that contain phosphatide are 1: 1-1: 10, and the blended temperature is 1-60 ℃.
As optimization, above-mentioned steps 2) be separated into settlement separate or centrifugation in.Specifically, the centrifugal condition be 700-12000 (* g), 5 seconds to 25 minutes time; The standing sedimentation condition is 10 minutes to 24 hours, settling temperature 1-60 ℃.
As optimization, above-mentioned steps 3) is at absolute pressure 0.001-0.03MPa, is lower than and carries out under 105 ℃ of conditions.
As optimization, above-mentioned steps 3) before removing solvent, filters as permeating medium with in diatomite, polynite, wilkinite, perlite, atlapulgite and the attapulgite one or more.
The present invention also provides a kind of phosphatide process for refining of accommodation: with the raw phospholipid is raw material, filters as permeating medium with in diatomite, polynite, wilkinite, perlite, atlapulgite and the attapulgite one or more.
Above-mentioned is to carry out under the filter pressure condition of 0-40 ℃ temperature condition and 0.02-1.5MPa with one or more filtrations carried out as permeating medium in diatomite, polynite, wilkinite, perlite, atlapulgite and the attapulgite.
Generally, process for refining phospholipid provided by the present invention is: with hydrated phospholipid and the emulsification of hexane equal solvent high-speed mixing, form the binary emulsification system.The coating systems evaporation will be gone up after settlement separate, elementary refining concentrated phosphatide product can be obtained.Again this product is carried out miscible, filtration, evaporation, precipitation, can obtain high-quality concentrated phosphatide.
The extraction process of phosphatide provided by the present invention, more existing phosphatide extraction process is compared, and this technology is low for equipment requirements, and running cost is low, is easy to large-scale production.The superior product quality that makes can be used for the fields higher to the phospholipid prod quality requirements such as food-processing.The finished product foreign matter content is lower than 0.05%, and transparency is better, lighter color, and other indexs all meet the regulation in the GB.
Description of drawings
Fig. 1: the technological process of production figure of refined phosphatide.
Embodiment
In conjunction with the technological process of production figure of refined phosphatide shown in Figure 1, the preferred embodiment of phosphatide process for refining provided by the invention is described in detail.But this description only is used for the present invention's technology is further specified, and should not be considered as the restriction to the technology of the present invention.Under the situation that does not break away from marrow of the present invention, all change methods all should be treated as in the present invention.
Step 1: the preparation of crude oil:
The quality index of phosphatide such as impurity, color and luster, smell, peroxide value etc. are subjected to the influence of oil plant quality and complete processing.Therefore, for guaranteeing the quality of phospholipid prod, need begin control from raw material.Oil plant is cleared up the back strip plate, rolls good base sheet and enters leacher, uses the hexane extraction grease.Hexane and the evaporation of greasy mixed solution obtain crude oil.Before extraction, also can press in advance oil plant, directly obtain crude oil.Soybean can directly carry out cold press, but it is lower to contain the phosphatide amount in the cold press crude oil.Peanut, the contour oil-containing oil plant of vegetable seed can directly be produced the crude oil that contains phosphatide by hot moulding.
Embodiment 1: 5400 tons of selected soybean through latter stage of ripening, and oleaginousness 19%, foreign matter content 0.5%, moisture content 13%, cotyledon metachromatic granule 5%, unsound grain total amount 10%, wherein moldy kernel 2%, and the color and luster smell is normal.Through dedusting, impurity elimination, remove stone, remove shoulder to shoulder cleaning technology such as mud, de-iron after, soybean is peeled.80 ℃ of decortication temperature, peeling rate 90%.To peel soybean fragmentation, strip plate, base sheet thickness is 0.25-0.35mm behind the strip plate, base sheet moisture content 11%.Then the base sheet is sent into leacher.The extraction of employing industrial hexane, 55 ℃ of extraction temperature.Obtain the mixing liquid of crude oil and hexane after the extraction, the industrial mixing oil that is commonly called as.Miscella evaporation adopts double evaporation-cooling, temperature is controlled to be 58 ℃-60 ℃ during single vaporization, and miscella concentration is controlled to be 38-42%, and temperature is controlled to be 90-105 ℃ during double evaporation-cooling, miscella concentration is controlled at 96-99%, and the evaporation vacuum degree control is at absolute pressure 0.02-0.03MPa.So promptly obtain quality crude oil preferably, about 1000 tons.According to producing needs, crude oil is carried out stripping precipitation and drying treatment after can being chosen in double evaporation-cooling.
Embodiment 2: 100 tons of selected Semen Brassicae campestris through latter stage of ripening, oleaginousness 38%, foreign matter content 1%, moisture content 7%, the color and luster smell is normal. through impurity elimination, remove stone, cleaning technologies such as de-iron, vegetable seed is carried out strip plate, base sheet thickness is 0.25-0.35mm, steam stir-fry, the pre-press for extracting juice, collect the vegetable seed pre-pressed crude oil. the vegetable seed after pre-the press for extracting juice carries out the industrial hexane extraction, 55 ℃ of extraction temperature. obtain mixing oil after the extraction. miscella evaporation adopts double evaporation-cooling, temperature is controlled to be 58 ℃-60 ℃ during single vaporization, miscella concentration is controlled to be 38-42%, and temperature is controlled to be 100-105 ℃ during double evaporation-cooling, and miscella concentration is controlled at 96-99%, the evaporation vacuum degree control so promptly obtains quality vegetable seed crude oil preferably at absolute pressure 0.02-0.04MPa.. according to producing needs, after can being chosen in double evaporation-cooling crude oil is carried out stripping precipitation and drying treatment. with above-mentioned leaching, crude oil after the evaporation and pre-pressed crude oil merge, and amount to about 37 tons, promptly obtain being used to further process the vegetable seed crude oil that phosphatide is used.
Step 2: the preparation of hydrated phospholipid: the crude oil that will contain phosphatide adds water hydratable, obtains hydrated phospholipid (being commonly called as oil foot or hydrated oil foot) and comes unstuck crude oil through settlement separate or centrifugation.Come unstuck crude oil again through removing the back refined vegetable oils that promptly obtain such as free fatty acids, pigment, stink substance.
Embodiment 1: get 1000 tons of crude oil of soybean that obtain according to the foregoing description 1, be warming up to 70 ℃, with 10 tons of pure water uniform mixing.Crude oil and water mix contact after, phosphatide begins to flocculate, flocculation time is 20-40 minute.Separate through disk centrifugal separator then, relative centrifugal force 3000-6000 (* g), centrifugation time 5-10 second, the whizzer light phase export is the crude oil that removes hydrated phospholipid, heavy out is a hydrated phospholipid, is about 20 tons.By analysis, the hydrated phospholipid feed composition is: moisture content 50.15%, acetone insoluble matter 32.32%, fat content 17.38%, ether insolubles 0.15%.
Embodiment 2: get 100 tons of vegetable seed crude oils that obtain according to the foregoing description 2, be warming up to 90 ℃, evenly add 1.5 tons of pure water.After the full and uniform mixing, make phosphatide, water flocculation, 8 hours time.Pass through standing separation then, lower floor's material is hydrated phospholipid, about altogether 3 tons.By analysis, the hydrated phospholipid feed composition is: moisture content 51.00%, acetone insoluble matter 30.20%, fat content 18.65%, ether insolubles 0.15%.
Embodiment 3: get the crude peanut oil that 10 tons of commerce are purchased, by analysis, phospholipids content 1% in the crude oil.Be warming up to 60 ℃, evenly add 0.1 ton of pure water.After the full and uniform mixing, make phosphatide, water flocculation, 4 hours time.Pass through standing separation then, lower floor's material is hydrated phospholipid, about altogether 185 kilograms.By analysis, the hydrated phospholipid feed composition is: moisture content 54.00%, acetone insoluble matter 29.30%, fat content 16.50%, ether insolubles 0.20%.
Embodiment 4: get the crude oil of soybean that 100 tons of commerce are purchased, experiment records phospholipids content 1.5%.Adding has in the slurry tank of mechanical stirring device, is warming up to 70 ℃, evenly adds 2 tons of pure water.Slowly stir (being lower than 60 rev/mins), make phosphatide, water flocculation, 24 hours time.Pass through standing separation then, lower floor's material is hydrated phospholipid, and about 3.8 tons, by analysis, the hydrated phospholipid feed composition is: moisture content 53.00%, acetone insoluble matter 28.04%, fat content 18.74%, ether insolubles 0.22%.
The main component of the hydrated phospholipid that obtains after in general, the aforesaid method process is separated is:
| Moisture content | Grease | Phosphatide | Impurity |
| 37-55％ | 16-28％ | 22-34％ | Change (0.05-0.5) with raw material |
" senior oil man must be read " that the preparation technology of hydrated phospholipid also can write with reference to grease branch of Zhejiang Province's grain employer's organization and Zhejiang food industry and trade school, Chinese agriculture science and technology press, in June, 1999.The technology that this book chapter 2 to chapter 5 has been narrated the cleaning technology of oil plant, milling process, hexane extraction extract technology in the actual industrial production in more detail and removed hydrated phospholipid.
Step 3: hydrated phospholipid and solvent:
Hydrated phospholipid viscosity is higher, and viscosity is subjected to phospholipids content, water content, condition influence such as temperature are bigger. and the impurity in the hydrated phospholipid (0.05-0.5%) is one of principal element of the final phospholipid prod of influence, ordinary method is difficult to these impurity are separated from full-bodied hydrated phospholipid. for separating impurity from high viscosity aquation phosphatide better, employing adds low viscosity solvent in hydrated phospholipid, mix according to a certain percentage, overall viscosity is reduced, produce the system that is easy to separating impurity. utilize that contained phosphatide has hydrophilic simultaneously in the hydrated phospholipid, oleophilic characteristics, form emulsification system. through the test of many times screening, got rid of benzene, toluene, aromatic hydrocarbon solvents such as dimethylbenzene, methyl alcohol, ethanol, Virahol, alcoholic solvents such as propyl carbinol, acetone, espeleton, ketones solvent and phenol such as mibk, acetonitrile or the like is finally selected pentane, hexane, heptane, ether, sherwood oil is best.
Also can before hydrated phospholipid and solvent, under the prerequisite of the color and luster that guarantees the finished product, under lesser temps, higher vacuum condition, remove the portion water of hydrated phospholipid.
Can be raw material also, mix with above-mentioned pentane equal solvent with raw phospholipid.Contain a spot of water, impurity in the raw phospholipid, in the raw phospholipid system, introduce pentane, hexane equal solvent after, through stirring, phosphatide still can be with a spot of water and solvent, vegetables oil emulsification as emulsifying agent, formation milk sap.But because hydrated phospholipid product dehydration temperaturre height during the preparation raw phospholipid in the existing phosphatide industry, phospholipid prod color and luster are dark, phospholipid prod impurity content height, at high temperature the chemical reaction of many complexity takes place in these impurity and phosphatide, produces the compound of many complexity.Even also has partially carbonized black particle under the situation about having.Test confirms, after raw phospholipid and solvent form emulsification system, handles according to subsequent step, only can be significantly increased, make moderate progress for transparency its impurity content index.But, very little for the influence of indexs such as the color and luster of product, acid value.The refined phosphatide product applications that it finally makes also is subjected to certain restriction.
Embodiment 1: get 10 tons of hydrated phospholipid that obtain according to step 2 embodiment 1, be warming up to 45 ℃.According to hydrated phospholipid: hexane is that 1: 5 mass ratio mixes hydrated phospholipid with hexane, promptly evenly adds 50 tons of hexanes.Behind hydrated phospholipid and the hexane mixing and emulsifying, form the emulsification system of hexane, phosphatide, grease, water, impurity, amount to 60 tons.
Embodiment 2: get 2 tons of hydrated phospholipid that obtain according to step 2 embodiment 1, mix with 2 tons of ether, 20 ± 5 ℃ of temperature, 60 rev/mins of stirring velocitys, churning time 2 hours, substantially the hydrated phospholipid that does not have the thickness state in whole system can obtain the emulsification system of ether, phosphatide, grease, water, impurity, amounts to 4 tons.
Embodiment 3: get 100 kilograms of hydrated phospholipid that obtain according to step 2 embodiment 2, mix with 300 kilograms of pentanes, 10 ± 5 ℃ of temperature, 40 rev/mins of stirring velocitys, churning time 3 hours, substantially the hydrated phospholipid that does not have the thickness state in whole system can obtain the emulsification system of pentane, phosphatide, grease, water, impurity, amounts to 400 kilograms.
Embodiment 4: get 100 kilograms of hydrated phospholipid that obtain according to step 2 embodiment 3, mix with 1000 kilograms of heptane, 50 ± 5 ℃ of temperature, 70 rev/mins of stirring velocitys, churning time 1.5 hours, substantially the hydrated phospholipid that does not have the thickness state in whole system can obtain the emulsification system of heptane, phosphatide, grease, water, impurity, amounts to 1100 kilograms.
Embodiment 5: get 10 tons of hydrated phospholipid that obtain according to step 2 embodiment 3, at 60 ℃, under the absolute pressure 0.01-0.015MPa condition, dewater in advance, 30 seconds-2 minutes time.After the dehydration, recording hydrated phospholipid moisture is 21%, 5.8 tons of quality, 70 ℃ of temperature.According to pre-dehydration hydrated phospholipid: heptane is that 1: 4 the mass ratio hydrated phospholipid of will dewatering is in advance mixed with heptane.Behind pre-dehydration hydrated phospholipid and the heptane mixing and emulsifying, form the emulsification system of heptane, phosphatide, grease, water, impurity, amount to 29 tons.
Embodiment 6: get 2 tons of hydrated phospholipid that obtain according to step 2 embodiment 1, at 70 ℃, under the absolute pressure 0.01-0.015MPa condition, dewater in advance, time 20-60 minute.After the dehydration, recording hydrated phospholipid moisture is 5%, 1.05 tons of quality, 65 ℃ of temperature.According to pre-dehydration hydrated phospholipid: sherwood oil is that 1: 6 the mass ratio hydrated phospholipid of will dewatering is in advance mixed with sherwood oil.Mixing condition is: 40 ± 5 ℃ of solution temperatures, 20 rev/mins of stirring velocitys, churning time 2 hours does not have the hydrated phospholipid of thickness state substantially in whole system, can obtain the emulsification system of sherwood oil, phosphatide, grease, water, impurity, amount to 7.35 tons.
Embodiment 7: water intaking part 0.7%, 1 ton of the raw phospholipid of ether insolubles 0.5%. according to raw phospholipid: sherwood oil is that 1: 3 mass ratio mixes raw phospholipid with sherwood oil. confirm through test, 30 ± 5 ℃ of solution temperatures, 60 rev/mins of stirring velocitys, churning time can mix under the condition in 20 minutes, can obtain the emulsification system of sherwood oil, phosphatide, grease, less water, impurity, amount to 4 tons.
Step 4: mixed solution is settlement separate:
The emulsification system of the phosphatide of above-mentioned formation, grease, solvent, water, impurity is a kind of unsettled system.Contained phosphatide mainly is divided into two kinds in the hydrated phospholipid, and a kind of hydrophilic characteristics is stronger, is representative with the phosphatidylcholine; A kind of oil-wet behavior is stronger, is representative with the phosphatidylethanolamine.Utilize the solution of the formed different qualities of complexing action of contained dissimilar phosphatide in the hydrated phospholipid, can separate emulsification system.Find after the test of many times that emulsification system will be divided into after by standing sedimentation or centrifugal settling two-layer up and down.The upper strata is the emulsification system of water-in-oil-type (W/O), the formation of this water-in-oil dispersed system, and the polar group that mainly is phospholipid molecule forms ball-like structure towards aqueous medulla, and a spot of water is enclosed in wherein.This structure has certain stability, and outward appearance presents the oil sample state.Lower floor is the emulsification system of oil-in-water-type (O/W), and the formation of this oil-in-water dispersed system is because the non-polar group of phospholipid molecule towards the butyraceous medulla, forms ball-like structure, and a spot of oil is enclosed in wherein.This structure has certain stability, and outward appearance presents the water sample state.After forming two kinds of different emulsification systems, by standing sedimentation or centrifugal settling, two-layer emulsification system further separates up and down.The impurity that contains in hydrated phospholipid major part in mixed system is transferred to lower floor's emulsification system, realizes the initial gross separation of impurity in the hydrated phospholipid.
Embodiment 1: get the emulsification system of the hexane that obtains according to step 3 embodiment 1, phosphatide, grease, water, impurity, 60 tons of total masses.By regulating heating medium the mixed system bulk temperature is controlled at 25-27 ℃, relative centrifugal force 6000-9000 (* g), centrifugal settling under centrifugation time 4-30 condition second is isolated 54 tons of upper strata emulsification system solution from light phase export, is the material solution that next step is processed.Isolate 6 tons of lower floor's emulsification system solution that contain most of impurity from heavy out, can be used as the raw material of producing raw phospholipid, also can further reclaim phosphatide.
Embodiment 2: get 4 tons altogether of the emulsification systems of the ether that obtains according to step 3 embodiment 2, phosphatide, grease, water, impurity, carry out standing sedimentation and separate.Experiment confirm, 20 ± 5 ℃ of temperature.The sedimentation layered effect of standing sedimentation time about 24 hours is better.Form two-layer emulsification system up and down behind the standing sedimentation.Lower floor is the liquid that contains most of impurity, 1.25 tons of total masses.Upper solution is the material solution that next step is processed for 2.75 tons.
Embodiment 3: get the 500 gram hydrated phospholipid, the sherwood oil that obtain according to step 3 embodiment 6 and form mixing solutions, put into the 1000ml separating funnel, sedimentation is 1 hour under the room temperature condition, tells lower floor's sedimentation liquid.Then the lower floor sedimentation liquid is added in the centrifuge tube, experiment confirm, relative centrifugal force 1500-2700 (* g), the centrifugal settling condition is better under the centrifugation time 10-25 minute condition.After centrifugal the settled oil-in-water type emulsion sediment of lower floor in the centrifuge tube is discarded, amount to 20 grams.Keep the clarifying water-in-oil-type liquid in upper strata, and with separating funnel in after the sedimentation supernatant liquid merge, merge the back and amount to 480 grams, be the stock liquid that next step is processed.
Embodiment 4: get the 1500 gram hydrated phospholipid, the pentane that obtain according to step 3 embodiment 3 and form mixing solutions.Experiment confirm, relative centrifugal force 2500-3700 (* g), the centrifugal settling condition is better under the centrifugation time 5-10 minute condition.After centrifugal the settled oil-in-water type emulsion sediment of lower floor is discarded, amount to 468 grams.Keep the clarifying water-in-oil-type liquid in upper strata, amount to 1032 grams, be the stock liquid that next step is processed.
Embodiment 5: get the get 1100 kilograms of hydrated phospholipid, heptane that obtain according to step 3 embodiment 4 and form mixing solutions, carry out centrifugation.Centrifugal condition be relative centrifugal force 3500-6200 (* g), centrifugation time 7-60 second.After centrifugal the settled oil-in-water type emulsion sediment of lower floor is discharged, amount to 60 kilograms.Keep the clarifying water-in-oil-type liquid in upper strata, amount to 1040 kilograms, be the stock liquid that next step is processed.
Embodiment 6: the emulsification system of getting 7.35 tons of sherwood oils obtaining according to step 3 embodiment 6, phosphatide, grease, water, impurity, carry out centrifugation. centrifugal condition be relative centrifugal force 4500-8000 (* g), centrifugation time 7-40 second. after centrifugal the settled oil-in-water type emulsion sediment of lower floor is discharged, amount to 0.4 ton. keep the clarifying water-in-oil-type liquid in upper strata, amount to 6.95 tons, be the stock liquid that next step is processed.
Embodiment 7: get the emulsification system of getting 4 tons of sherwood oils, phosphatide, grease, less water, impurity that obtains according to step 3 embodiment 7, carry out centrifugation.Centrifugal condition be relative centrifugal force 7000-12000 (* g), centrifugation time 3-20 second.After centrifugal the settled oil-in-water type emulsion sediment of lower floor is discharged, amount to 0.4 ton.Keep the clarifying water-in-oil-type liquid in upper strata, amount to 3.6 tons, be the stock liquid that next step is processed.
Step 5: low-temperature evaporation:
The boiling point of hexane equal solvent, water is much smaller than the boiling point of phosphatide and Vegetable oil lipoprotein, can realize further separating of phosphatide and water, solvent by evaporation.The purpose of traditional hydrated phospholipid evaporation technology is single vaporize water, requires that the water of 37-55% content is evaporated to below 1% from hydrated phospholipid, evaporates condition such as temperature required, vacuum tightness and need guarantee and the water sepn in the high viscosity systems can gone out.The soybean hydrated phospholipid is moisture 19.3%, and the vegetable seed hydrated phospholipid is moisture at 12.2% o'clock, total system viscosity maximum.In the time of 70 ℃, the high viscosity of the hydrated phospholipid of moisture 5-10% can reach 9000mPas, and the rising of viscosity not only can reduce heat transfer coefficient, and " pot overflows " phenomenon because full-bodied material is created in the bubble that produces in the evaporative process and gathers easily, takes place easily.When traditional hydrated phospholipid removed water, phosphatide raise with temperature easily sex change takes place.Can guarantee to remove moisture under high viscosity, guarantee the color and luster of phospholipid prod again, this is the big technical barrier in the present phosphatide industrial production.
Step 3 of the present invention is introduced the pentane equal solvent in hydrated phospholipid another purpose is to reduce vaporization temperature, to guarantee the color and luster of phosphatide.Phosphatide is heat-sensitive material, soybean phospholipid especially, and color and luster can be deepened gradually when surpassing more than 60 ℃.If temperature rises too fast too highly, phosphatide will coking, can produce the black particle of carbonization in the product.In order to guarantee that convection drying phosphatide removes moisture under cold condition, in whole system, introduce low boiling point solvents such as pentane, hexane.The boiling point of these solvents is lower than the boiling point of water, in evaporative process because the effect of solvent partial pressure, integral body requires vacuum tightness, vaporization temperature condition relatively gentle, make whole vaporization temperature than 10-30 ℃ of conventional primary drying temperature decline, significant for the indexs such as color and luster that guarantee phosphatide.And, the present invention since in step 4 by the settlement separate water of having removed in time coating systems, make that the total amount of vaporize water significantly reduces in the whole evaporation process.This provides assurance more reliably for obtaining the more shallow phosphatide of color and luster undoubtedly.
After evaporation is finished,, only residual solvent need be removed and to obtain the standard that every index all can reach state food level phosphatide if only need obtain elementary refined phosphatide product.If improve the quality of products, increase indexs such as transparency of products, can select to filter further refining.Need to filter the purified phospholipid prod, can be directly with evaporating the volatile content that makes phospholipid prod less than 2%, and needn't be through carrying out precipitation treatment.
Embodiment 1: get 54 tons of obtaining according to step 4 embodiment 1 and form through the upper strata hydrated phospholipid after the centrifugation, hexane and mix milky solution, adopt double evaporation-cooling to remove water, hexane.Vaporization temperature is 66-68 ℃ when evaporating for the first time, and vacuum degree control is at absolute pressure 0.01-0.03MPa, and exit concentration is controlled at 50%.Vaporization temperature is 70-80 ℃ when evaporating for the second time, and the evaporation vacuum degree control is at absolute pressure 0.01-0.015MPa, and exit concentration is controlled at 99.9%.Carry out carrying out precipitation treatment at last, the precipitation condition is 65 ℃ of temperature, vacuum tightness absolute pressure 0.002-0.003MPa, and 3 hours precipitation time, remove residual solvent, can obtain elementary refined phosphatide, its elementary refined phosphatide yield specific targets are: ether insolubles 0.09%; Acetone insoluble matter 65%; Moisture content and volatile matter 0.5%; Acid value 25mgKOH/g; Color and luster 11Gardner; Hydration test is not stratified.4.4 tons of elementary refined phosphatide amounts, with respect to the phospholipids content in the hydrated phospholipid, first refined yield 88.5%.With respect to the foreign matter content in the hydrated phospholipid, refining for the first time removal of impurity 74%.
By analysis, the quality index of this product and as follows with the contrast of additive method products obtained therefrom index:
Same hydrated phospholipid raw material,
Decolour this handicraft product of the natural GB one-level of project GB one-level adopts a convection drying
The technology products obtained therefrom
The ether insolubles, %≤0.3≤0.3 0.09 0.3
Acetone insoluble matter, % 〉=65.0 〉=65.0 65 65.8
Moisture content and volatile matter, %≤1.0≤1.0 0.5 0.9
Acid value, mgKOH/g≤30.0≤30.0 25 25
Color and luster, Gardner≤12≤7 11 13
Hydration test is not stratified
Embodiment 2: get the upper solution of 2.75 tons of processes that obtain according to step 4 embodiment 2 after settlement separate.Adopt the vertical luwa evaporator evaporation of secondary, vaporization temperature is 40-65 ℃ for the first time, and vacuum degree control is at absolute pressure 0.01-0.03MPa, and exit concentration is controlled at 80%.88-93 ℃ of double evaporation-cooling temperature, vacuum degree control is at absolute pressure 0.01-0.015MPa, and exit concentration is controlled at 98%.Carry out carrying out precipitation treatment at last, the precipitation condition is 85 ℃ of temperature, vacuum tightness absolute pressure 0.002-0.003MPa, and 1 hour precipitation time, remove residual solvent, can obtain elementary refined phosphatide, amount to 0.83 ton.By analysis, the quality index of this product is as follows: ether insolubles 0.1%, acetone insoluble matter 65%, moisture content and volatile matter 0.6%, acid value 25mgKOH/g, color and luster 11Gardner, hydration test: not stratified.Elementary refined phosphatide amount is with respect to the phospholipids content in the hydrated phospholipid, first refined yield 84%.With respect to the foreign matter content in the hydrated phospholipid, refining for the first time removal of impurity 72%.
Embodiment 3: get the upper strata clarifying water-in-oil-type liquid of 1032 grams after centrifugal that obtains according to step 4 embodiment 4, put into the ground flask of 5000ml, 80-84 ℃ of water-bath, speed of rotation 20-40 rev/min, vacuum absolute pressure 0.001-0.002MPa in the flask container, rotational time 5 hours is removed residual solvent, obtain elementary refined phosphatide product, amount to 125 grams.By analysis, the product quality indicator that makes according to this method is as follows: ether insolubles 0.09%, acetone insoluble matter 61%, moisture content and volatile matter 0.4%, acid value 29mgKOH/g, color and luster 12Gardner, hydration test: not stratified.Elementary refined phosphatide amount is with respect to the phospholipids content in the hydrated phospholipid, first refined yield 84%.With respect to the foreign matter content in the hydrated phospholipid, refining for the first time removal of impurity 88%.
Embodiment 4: get the upper solution of 6.95 tons of processes that obtain according to step 4 embodiment 6 after settlement separate.Adopt the high vacuum double evaporation-cooling, vaporization temperature is 65-70 ℃ for the first time, and vacuum degree control is at absolute pressure 0.02-0.03MPa, and exit concentration is controlled at 70%.88-99 ℃ of double evaporation-cooling temperature, vacuum degree control is at absolute pressure 0.01-0.015MPa, and exit concentration is controlled at 99%.Carry out carrying out precipitation treatment at last, the precipitation condition is 82 ℃ of temperature, vacuum tightness absolute pressure 0.002-0.003MPa, and 1.5 hours precipitation time, remove residual solvent, can obtain elementary refined phosphatide, amount to 0.94 ton.By analysis, the quality index of this product is as follows: ether insolubles 0.07%, acetone insoluble matter 65%, moisture content and volatile matter 0.3%, acid value 25mgKOH/g, color and luster 11Gardner, hydration test: not stratified.Elementary refined phosphatide amount is with respect to the phospholipids content in the hydrated phospholipid, first refined yield 95%.With respect to the foreign matter content in the hydrated phospholipid, refining for the first time removal of impurity 77%.
Embodiment 5: get the upper solution of 3.6 tons of processes that obtain according to step 4 embodiment 7 after settlement separate. adopt double evaporation-cooling, vaporization temperature is 70-75 ℃ for the first time, vacuum degree control is at absolute pressure 0.02-0.03MPa, exit concentration is controlled at 90-105 ℃ of 75%. double evaporation-cooling temperature, vacuum degree control is at absolute pressure 0.01-0.015MPa, exit concentration is controlled at 99%. and carries out carrying out precipitation treatment at last, the precipitation condition is 88 ℃ of temperature, vacuum tightness absolute pressure 0.002-0.003MPa, 2 hours precipitation time, remove residual solvent, can obtain elementary refined phosphatide, amount to 0.92 ton. by analysis, the quality index of this product is as follows: ether insolubles 0.095%, the elementary refined phosphatide amount of moisture content and volatile matter 0.3%. is with respect to the phospholipids content in the hydrated phospholipid, and first refined yield 92%. is made with extra care removal of impurity 96%. for the first time with respect to the foreign matter content in the hydrated phospholipid
6: filter:
As need the quality of the phospholipid prod of step 5 gained is further improved, need before carrying out precipitation, to mix with the low boiling point solvent that hexane dissolves each other fully with pentane, hexane, heptane, ether etc., reduce the viscosity of phosphatide, again to more trickle impurity of the further filtering and removing of low viscosity mixed solution and the complex compound that influences the phosphatide quality.Filtering method can adopt the mixed solution filtration method.Find through screening experiment, select for use diatomite, polynite, wilkinite, perlite, atlapulgite or attapulgite better as filtration medium.Filtration mediums such as gac, quartz sand, silicon-dioxide, manganese sand are then then not too suitable for the filtration of phospholipid solution.
General points of view thinks that filtering accuracy is high more, and its finished product impurity content is low more.But this viewpoint also is applicable to that not exclusively phosphatide filters.Why select above-mentioned media filtration form, be to sum up the back through test of many times to find: (1) phosphatide can not remove water totally in dehydration fully, national Specification concentrated phosphatide moisture content and volatile matter are smaller or equal to 1%, this a spot of moisture content influences whole solution system to be filtered just.Because these a spot of water in whole solvent liquid system, by the effect of phosphatide, form emulsification particulate (reversed micelle).The medulla of reversed micelle is a water molecules, the polar group of phosphatide points to medulla, the non-polar group of phosphatide points in the solution, form ball-like structure, therefore the apparent molecular weight of reversed micelle is bigger, when adopting the filtered version of higher form, aperture flux must allow by this micella, and pore size filter very easily is obstructed.When being lower than 0.6 μ m in the mineral membrane membrane pore size, under 30 ℃ of conditions, the 0.2MPa filter pressure is poor, concentration be 30% phosphatide hexane solution by mineral membrane after yield only be about 60%.When (2) adopting bigger pore size filter, emulsified particle can pass through filtering micropore, the finished product impurity content height, poor transparency.By experimental study, even use the direct filtration forms such as bag type filtering, bar type filtration of 1 μ m, for improving almost not influence through the product quality of above-mentioned settlement separate purified phosphatide.
Raw phospholipid can also mix with the low boiling point solvent that hexane dissolves each other fully with pentane, hexane, heptane, ether etc., carries out filter media.But because hydrated phospholipid product dehydration temperaturre height during the preparation raw phospholipid in the existing phosphatide industry, phospholipid prod color and luster are dark, phospholipid prod impurity content height, at high temperature the chemical reaction of many complexity takes place in these impurity and phosphatide, produces the compound of many complexity.Even also has partially carbonized black particle under the situation about having.Direct filtration raw phospholipid solution, because foreign matter content is big, the filtering system lifting capacity is big, filtration velocity is comparatively slow.Because filtration medium such as atlapulgite has certain adsorpting pigment function, can play certain improvement effect for the color and luster of product.But because the relatively poor factors of index such as the acid value of raw phospholipid product itself, color and luster, impurity, these indexs of final filtering product also are subjected to influence to a certain degree, and the refined phosphatide product applications that it finally makes also is subjected to certain restriction.
Embodiment 1: get 4.4 tons of dry phosphatide producing according to step 5 embodiment 1, specific targets are ether insolubles 0.09%, acetone insoluble matter 65%, moisture content and volatile matter 0.5%, acid value 25mgKOH/g, color and luster 11Gardner, hydration test: not stratified. at room temperature mixing with 13.2 tons of hexanes, to there not being block thick material. in mixing liquid, add the diatomite of liquid total mass 0.5% again, the attapulgite that adds liquid total mass 0.1% again, stir. this mixing liquid is delivered to leaf-type filter, circulation 2-10 minute, until outlet liquid clear. the filter operation pressure-controlling is at 0.02-0.2MPa, temperature maintenance is at 15-40 ℃. along with diatomite, the attapulgite amount progresses into leaf-type filter, filter pressure raises gradually, when being increased to 0.3MPa, stop filter operation, open the leaf-type filter blow-off valve, discharge diatomite, the attapulgite filter cake. after will clarifying the dry precipitation of after-filtration liquid, obtain 4.2 tons of refined phosphatide products, it is as follows that filtration yield 95%. records the finished product index: ether insolubles 0.04%, acetone insoluble matter 65%, moisture content and volatile matter 0.3%, acid value 25mgKOH/g, color and luster 11Gardner, hydration test: not stratified. and the overall appearance state that is translucent, have phosphatide inherent smell.
This method is filtered with traditional crude oil and is filtered and hybrid oil filter contrast index following (calculating with refining 1 ton of phosphatide):
Phosphatide solvent liquid
The project crude oil filters and leaches hybrid oil filter
Filter
Filter liquide total amount (t) 2.5 50 160
Filtration medium consumes (kg) 15 250 400
Hexane consumes (kg) 10 0 100
Filtration pump power consumption (KWh) 25 400 500
Tooling cost is (according to 1 yuan/kg of filtration medium, hexane 6.5
92.5 450 1300
Unit/kilogram, 0.5 yuan/kwh of electric power calculate unit: unit)
In fact, crude oil filtration and leaching hybrid oil filter prepare the required filter plant of phosphatide and must be stainless steel equipment, invest bigger.In addition, final phospholipid prod quality instability, the especially transparency that crude oil filters and hybrid oil filter makes is far below filter the phospholipid prod that makes by phosphatide solvent liquid.In actual industrial production, because filtered crude oil is when removing phosphatide, filters small amount of impurities in the crude oil of back and still can most ofly concentrate and be transferred in the hydrated phospholipid, influence phosphatide impurity content index.And because crude oil viscosity is higher, the phosphatide that contains in its crude oil is filtered agent absorption easily during filtration, and the filter pressure of requirement is higher, and filtration velocity is slow.A large amount of phosphatide of filtering medium absorption also are taken as waste disposal usually, have caused a large amount of wastes.Because crude oil will filter through atlapulgite when refining, increase large-scale filter plant in advance and for final finished oil, be undoubtedly a kind of filtration that repeats.
Embodiment 2: get 20 tons of raw phospholipids, specific targets are ether insolubles 0.3%, acetone insoluble matter 63%, moisture content and volatile matter 0.8%, acid value 29mgKOH/g, color and luster 13Gardner, hydration test: not stratified.Add 20 tons of pentanes, mix in the at room temperature airtight mixing tank, to there not being block thick material.This mixing liquid is delivered in the leaf-type filter that installs filtration medium in advance.The filtration medium that adopts is the mixture of atlapulgite, attapulgite, and the mixing quality ratio is 1: 1.This mixing liquid is delivered to leaf-type filter, circulation 2-10 minute, until outlet liquid clear.Evidence, filter operation pressure-controlling are at 0.1-0.8MPa, and temperature maintenance filter effect under 20-30 ℃ of condition is better.Along with the fine impurity in the solution constantly enters cake layer, filter pressure raises gradually, when being increased to 1.0MPa, stops filter operation, opens the leaf-type filter blow-off valve, discharges filtration medium.After will clarifying the dry precipitation of after-filtration liquid, obtain 18.4 tons of refined phosphatide products, filter yield 92%.It is as follows to record the finished product index: ether insolubles 0.07%, acetone insoluble matter 62%, moisture content and volatile matter 0.7%, acid value 29mgKOH/g, color and luster 13Gardner, hydration test: not stratified.And the overall appearance state that is translucent.
Embodiment 3: get 0.83 ton of elementary refined phosphatide producing according to step 5 embodiment 2, index is: phospholipid ether insolubles 0.1%, acetone insoluble matter 65%, moisture content and volatile matter 0.6%, acid value 25mgKOH/g, color and luster 11Gardner, hydration test: not stratified., according to phosphatide: the mass ratio of ether=1: 9 mixes with ether, mixing temperature is controlled at 0-25 ℃. with this mixing solutions by being equipped with according to polynite: diatomite: perlite equals in the Depth Filtration tank body of 1: 5: 1 mixed. with this mixing liquid by Depth Filtration jar circulation, until outlet liquid clear. evidence, the filter operation pressure-controlling is at 0.3-0.7MPa, temperature maintenance is better at 15-30 ℃ of filter effect. along with the fine impurity in the mixed solution progresses into the Depth Filtration jar, resistance of filter cake increases gradually, hay tank pressure raises gradually, when being increased to 0.7MPa, stop filter operation, change the tank body inner filter media. after will clarifying the dry precipitation of after-filtration liquid, obtain 0.77 ton of refined phosphatide product, it is as follows to filter yield 93%. the finished product indexs: ether insolubles 0.06%, acetone insoluble matter 65%, moisture content and volatile matter 0.5%, acid value 25mgKOH/g, color and luster 11Gardner, hydration test: not stratified. and the overall appearance state that is translucent, have phosphatide inherent smell.
Embodiment 4: get 0.97 ton of elementary refined phosphatide producing according to step 5 embodiment 4.The quality index of this product is as follows: ether insolubles 0.07%, acetone insoluble matter 65%, moisture content and volatile matter 0.3%, acid value 25mgKOH/g, color and luster 11Gardner, hydration test: not stratified.According to phosphatide: the mass ratio of heptane=9: 1 mixes, and mixing temperature is controlled at 20-35 ℃.This mixing liquid is delivered to coat in advance in the diatomaceous leaf-type filter filters.Evidence, filter operation pressure-controlling are at 0.5-1.5MPa, and temperature maintenance is better at 30-50 ℃ of filter effect.Along with the fine impurity in the mixed solution progresses into the Depth Filtration jar, resistance of filter cake increases gradually, and hay tank pressure raises gradually, when being increased to 2.0MPa, stops filter operation.After will clarifying the dry precipitation of after-filtration liquid, obtain 0.95 ton of refined phosphatide product, filter yield 98%.The finished product index is as follows: ether insolubles 0.03%, acetone insoluble matter 65%, moisture content and volatile matter 0.2%, acid value 25mgKOH/g, color and luster 11Gardner, hydration test: not stratified.And the overall appearance state that is translucent has phosphatide inherent smell.
Those skilled in the art as can be known, the filtration process of this step can directly be that raw material carries out with the raw phospholipid.Directly be the food grade phosphatide that filtration step that raw material the invention provides also can obtain to meet national standard, therefore, also belong to the equivalent technologies that the present invention advocates the technology protected with the raw phospholipid.
7: sum up: main settlement separate by preparation, preparation, hydrated phospholipid and the solvent of hydrated phospholipid, the mixed solution of crude oil, low-temperature evaporation, six steps of filtration of above-mentioned technology are formed.Its step 1, step 2 are for making high-quality initial feed---hydrated phospholipid, and step 3 is removed impurity to the viscosity of step 6 for the reduction hydrated phospholipid, and low-temperature evaporation is to guarantee the high-quality of the finished product.
According to the order processing of step 1 to step 6, can make high-quality concentrated phosphatide, its ether insolubles can be less than 0.05% high level, need not to adopt discoloring agent, and its color and luster can reach 11Gardner.And the overall appearance state that is translucent has phosphatide inherent smell.Other indexs all can reach or be better than the like product that offshore company produces.
For the crude oil that contains phosphatide, can be from the preparation of step 2 hydrated phospholipid, carry out the operation of step 3 to step 5, can obtain meeting the phospholipid prod of state food level phosphatide standard, if add the operation of step 6 again, the ether insolubles of its product then can be less than 0.07% level, and its integrated quality is apparently higher than the standard of state food level phosphatide.
Claims (3)
1. process for refining phospholipid comprises the steps:
1) mixture that contains phosphatide mixes the emulsification system of score layer with pentane, hexane, heptane, ether or sherwood oil;
2) emulsification system to the step 1) preparation separates, and gets the upper strata emulsion;
3) removal step 2) solvent and the water in the upper strata emulsion of preparation;
The described mixture that contains phosphatide is raw phospholipid or hydrated phospholipid;
Described raw phospholipid is meant the mixture of phospholipids that contains of ether insolubles 〉=0.1%;
The preparation method of described hydrated phospholipid is as follows: the crude oil that will contain phosphatide adds water hydratable, obtains hydrated phospholipid through settlement separate or centrifugation;
The described crude oil that contains phosphatide is crude oil of soybean, vegetable seed crude oil or crude peanut oil;
Described processing step 1) mixture and pentane, hexane, heptane, ether or the sherwood oil blended mass ratio that contain phosphatide in are 1: 1-1: 10, and the blended temperature is 1-60 ℃;
Described processing step 2) be separated into settlement separate or centrifugation in;
The centrifugal condition is 700-12000 * g, and the time is 5 seconds to 25 minutes; The standing sedimentation condition is 10 minutes to 24 hours, settling temperature 1-60 ℃;
Described processing step 3) at absolute pressure 0.001-0.03MPa, temperature is lower than under 105 ℃ of conditions carries out.
2. according to the described process for refining phospholipid of claim 1, it is characterized in that the step 3) of described technology was filtered as permeating medium with in diatomite, polynite, wilkinite, perlite, atlapulgite and the attapulgite one or more before removing solvent.
3. according to the described process for refining phospholipid of claim 2, it is characterized in that described filtration is carried out under the filter pressure condition of 0-40 ℃ temperature condition and 0.02-1.5MPa.
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| CN1958728A (en) * | 2006-10-30 | 2007-05-09 | 华中科技大学 | Method for refining biologic diesel oil, phospholipid and glycerin by using leftovers of vegetable oil |
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| CN1214340A (en) * | 1997-10-15 | 1999-04-21 | 齐齐哈尔大学工学院 | Fine separation of high-purity phospholipid |
| CN1958728A (en) * | 2006-10-30 | 2007-05-09 | 华中科技大学 | Method for refining biologic diesel oil, phospholipid and glycerin by using leftovers of vegetable oil |
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