CN101139289A - Technique for producing alpha-linolenic acid ethyl with 90 percent more purity - Google Patents
Technique for producing alpha-linolenic acid ethyl with 90 percent more purity Download PDFInfo
- Publication number
- CN101139289A CN101139289A CNA2007100550124A CN200710055012A CN101139289A CN 101139289 A CN101139289 A CN 101139289A CN A2007100550124 A CNA2007100550124 A CN A2007100550124A CN 200710055012 A CN200710055012 A CN 200710055012A CN 101139289 A CN101139289 A CN 101139289A
- Authority
- CN
- China
- Prior art keywords
- nitrogen protection
- reduced
- acid
- omnidistance
- gained
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Fats And Perfumes (AREA)
Abstract
The present invention relates to a production process of using the Perilla as the raw material to produce an alpha-flax ethyl ester with the purity more than 90 percent. The alpha-flax ethyl ester with the purity more than 90 percent can be got after the oil squeezing, filtration, saponification, acidification, water washing, twice urea complexes, freezing, compression and filtration, heating, extraction, esterification, water washing, dehydration and molecular distillation. The present invention has the advantages of the high purity, the low cost and the long security period.
Description
Technical field
The present invention relates to a kind of is the purity that goes out of raw material production with the perilla seed greater than the production technique of 90% Alpha-ethyl linolenate.
Background technology
Alpha-linolenic acid mainly is present in the various plants grease with the triglyceride level form, comprise linseed oil, Purple Perilla Seed Oil, rape seed oil, Oleum Gossypii semen, soybean wet goods, wherein content is up to 50%～60% in linseed oil, the Purple Perilla Seed Oil, and content is all below 10% in other oil.To unsaturated fatty acids famine, particularly alpha-linolenic acid, need to replenish among the crowd from other approach.Many as adding use in medicine, food service industry, because alpha-linolenic acid purity is lower in the nature species, the interpolation that has influenced alpha-linolenic acid is used, the existence form of ethyl ester is stable than free acid, be convenient to scale operation and use, and the domestic technology of still not having production purity greater than 90% Alpha-ethyl linolenate.
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art and the production technique of a kind of purity greater than 90% Alpha-ethyl linolenate is provided; on traditional technical foundation; improve complexing purification techniques and substep Refrigeration Technique; and molecular distillation technique; emphasis is captured the isolation technique between the unsaturated straight chain fatty acid and the system protection problem of the easy oxidation of superelevation degree of unsaturation lipid acid; guarantee the quality and the commercialization of superelevation degree of unsaturation fatty acid product; the Alpha-ethyl linolenate product purity of producing reaches 90%, has filled up domestic blank.
The object of the present invention is achieved like this:
Carry out according to following technology:
The first step: oil expression: adopt mechanical cold pressing process to squeeze perilla oil perilla seed,
Second step: filter: the solid impurity in the perilla oil is leached,
The 3rd step: saponification: the second step gained perilla oil and deionized water, enzyme catalyst lipolase100L are added in the container according to the ratio of weight ratio 1: 0.5～4: 0.01～0.1; stir and heating; the control temperature of charge is between 40 ℃～70 ℃; control material pH value is 7; reaction times, sample thief was analyzed acid number at 20～40 hours, and reaction finishes when acid number reaches 120～210mgKOH/g; the omnidistance logical nitrogen protection of this process
The 4th step: acidifying: be in the material after 10%～90% sulfuric acid slowly adds the saponification of the 3rd step gained with concentration and stir, control material reaction temperature is between 40 ℃～95 ℃, when the pH value of material is stopping to add sulfuric acid less than 4 the time, when the pH value of material greater than 4 the time, continue slowly to add sulfuric acid; When the pH value of material less than 4 keep 2 hours constant after, reaction finishes, the omnidistance logical nitrogen protection of this process,
The 5th step: washing: the 4th step gained material was left standstill 1～6 hour; emit lower aqueous solution; the deionized water that adds 0.5～4 times in remaining upper strata lipid acid stirs, and leaves standstill 1～6 hour; emit lower aqueous solution again; until the lower aqueous solution pH value of emitting is 7, and upper strata lipid acid enters next procedure, this end of processing; the omnidistance logical nitrogen protection of this process
The 6th step: urea complexation: with the lipid acid of the 5th step output, 70%～99.9% edible ethanol, urea by weight 1: (1～8): the ratio of (1～8) adds container and stirs; controlled temperature is between 60 ℃～100 ℃; 0.5～8 hour hold-time; then material is cooled to 20 ℃～60 ℃; this operation finishes; the omnidistance logical nitrogen protection of this operation
The 7th step: freezing: the material in the 6th step is carried out the stage cooling; fs is reduced to 0 ℃ from original temperature; subordinate phase is reduced to-5～-10 ℃ from 0 ℃; phase III is reduced to-10～-20 ℃ from-5～-10 ℃; the quadravalence section is reduced to-20～-30 ℃ from-10～-20 ℃; five-stage is reduced to-30～-40 ℃ from-20～-30 ℃; the 6th stage was reduced to-40～-50 ℃ from-30～-40 ℃; per stage need be incubated 0.5～8 hour; the uninterrupted stirring, when temperature reached requirement, this operation finished; the omnidistance logical nitrogen protection of this operation
The 8th step: press filtration: the 7th step gained material is realized solid-liquid separation with pressure and filtering net under 0 ℃～-50 ℃ states, liquid enters next procedure,
The 9th step: heat up: the material of the 8th step gained is warming up to 10 ℃～30 ℃, the omnidistance nitrogen protection of this operation,
The tenth goes on foot: extraction: with the material and deionized water 1: 0.5～4 the mixed and the stirring by weight of the 9th step gained, standing demix is emitted lower aqueous solution, and upper strata lipid acid enters next procedure, the omnidistance nitrogen protection of this operation,
The 11 step: secondary urea complexation: the lipid acid of the tenth step output, 70%～99.9% edible ethanol, urea are added the container stirring by weight 1: 3～10: 3～10 ratio; controlled temperature is between 60 ℃～100 ℃; 0.5～8 hour hold-time; then material is cooled to 20 ℃～60 ℃; this operation finishes; the omnidistance logical nitrogen protection of this operation
The 12 step: freezing: the material in the 11 step is carried out the stage cooling; fs is reduced to 0 ℃ from original temperature; subordinate phase is reduced to-5～-10 ℃ from 0 ℃; phase III is reduced to-10～-20 ℃ from-5～-10 ℃; the quadravalence section is reduced to-20～-30 ℃ from-10～-20 ℃; five-stage is reduced to-30～-40 ℃ from-20～-30 ℃; the 6th stage was reduced to-40～-50 ℃ from-30～-40 ℃; per stage need be incubated 0.5～8 hour; the uninterrupted stirring, when temperature reached requirement, this operation finished; the omnidistance logical nitrogen protection of this operation
The 13 step: press filtration: the 12 step gained material is realized solid-liquid separation with pressure and filtering net under 0 ℃～-50 ℃ states, liquid enters next procedure,
The 14 step: heat up: the material of the 13 step gained is warming up to 10 ℃～30 ℃, the omnidistance nitrogen protection of this operation,
The 15 goes on foot: extraction: with the material and deionized water 1: 0.5～4 the mixed and the stirring by weight of the 14 step gained, standing demix is emitted lower aqueous solution, and upper strata lipid acid enters next procedure, the omnidistance nitrogen protection of this operation,
The 16 step: esterification: the lipid acid of the 15 step gained, 85%～99.9% edible ethanol, 50%～98% sulfuric acid amount are added in the container than the mixed by 1: 0.2～2: 0.05～0.1, between 70 ℃～100 ℃ of the control reaction temperature, 4～20 hours time, emit lower floor's solution after the cooling, repeat aforesaid operations, analyze acid number less than 10mgKOH/g until upper strata fatty-acid ethyl ester sample thief, this operation finishes, the upper strata fatty-acid ethyl ester enters next procedure
The 17 step: washing: the 16 step fatty-acid ethyl ester of gained and the deionized water ratio by weight 1: 0.5～4 entered mix in the container; standing demix; discharge lower layer of water; repeat aforesaid operations; until the lower layer of water pH value is 7; the upper strata fatty-acid ethyl ester enters next procedure, the omnidistance nitrogen protection of this operation
The 18 step: dehydration: the fatty-acid ethyl ester of the 17 step gained was distilled 1～4 hour under the condition of 20 ℃～80 ℃ of vacuum 400～700mmHg, temperature,
The 19 step: molecular distillation: the fatty-acid ethyl ester of the 18 step gained is entered complete molecular distillation apparatus, control pressure is between 0.1～5Pa, 80 ℃～150 ℃ of temperature, decolouring flavor is handled, and produces purity greater than 90% Alpha-ethyl linolenate product.
The present invention has following positively effect:
The first, the present invention has successfully realized the production of purity greater than 90% Alpha-ethyl linolenate product.
The second, on traditional technical foundation, improve complexing purification techniques and substep Refrigeration Technique, and molecular distillation technique.Emphasis is captured the isolation technique between the unsaturated straight chain fatty acid and the system protection problem of the easy oxidation of superelevation degree of unsaturation lipid acid, guarantees the quality and the commercialization of superelevation degree of unsaturation fatty acid product
Three, make the interpolation approach of alpha-linolenic acid more extensive.
Four, make the crowd better replenish alpha-linolenic acid, promoted that effectively the crowd is healthy.
Five, the quality product prepared of the present invention meets the provisions of the relevant regulations issued by the State, and fills the domestic gaps.
The every index of product is as follows
The Oranoleptic indicator
| Project | Requirement |
| Color and luster | Colourless-faint yellow |
| Impurity | The visible tramp material of no naked eyes |
| Transparency | Allow little turbid |
Physical and chemical index
| Alpha-linolenic acid second fat % 〉= | 90 |
| Linolic acid % 〉= | 8* |
| Oleic acid %≤ | 0.5* |
| Stearic acid %≤ | 0.02* |
| Acid value mgKOH/g≤ | 10 |
| Moisture %≤ | 0.1 |
| Peroxide value %≤ | 0.15 |
Annotate: " * " is the production controlling index.
Microbiological indicator
| Project | Index |
| Total number of bacterial colony, cfu/g≤ | 1000 |
| Coliform, MPN/100g≤ | 40 |
| Mould, cfu/g≤ | 25 |
| Yeast, cfu/g≤ | 25 |
| Salmonellas | Must not detect |
| Shigellae | Must not detect |
| Streptococcus aureus | Must not detect |
| Hemolytic streptococcus | Must not detect |
Embodiment
Embodiment 1:
The first step: oil expression: perilla seed 300Kg, adopt mechanical cold pressing process to squeeze perilla oil,
Second step: filter: the solid impurity in the perilla oil is leached, get perilla oil 100Kg,
The 3rd step: saponification: get perilla oil 100Kg; deionized water 80Kg; enzyme catalyst (lipolase100L) 1Kg adds in the container; stir and heating, 40 ℃ of control temperature of charge, control material pH value is 7; reaction times was at 2 hours; sample thief is analyzed acid number, and reaction finishes when acid number reaches 120～210mgKOH/g, the omnidistance logical nitrogen protection of this process.
The 4th step: acidifying: be in the material after 10% sulfuric acid slowly adds the saponification of the 3rd step gained with concentration and stir; 40 ℃ of control material reaction temperature; when the pH value of material is stopping to add sulfuric acid less than 4 the time; when the pH value of material greater than 4 the time; continue slowly to add sulfuric acid, repeat aforesaid operations, when the pH value of material less than 4 keep 2 hours constant after; reaction finishes, the omnidistance logical nitrogen protection of this process.
The 5th step: washing: the 4th step gained material was left standstill 1 hour; emit lower aqueous solution, get lipid acid 60Kg, in lipid acid, add the deionized water of 30Kg; stir; left standstill 1 hour, and emitted lower aqueous solution again, repeat aforesaid operations; until the lower aqueous solution pH value of emitting is 7; get upper strata lipid acid 58Kg and enter next procedure, this end of processing, the omnidistance logical nitrogen protection of this process.
The 6th step: urea complexation: with the lipid acid 58Kg of the 5th step output, 70% edible ethanol 58Kg, urea 58Kg add container and stir; controlled temperature 0.5 hour hold-time, is cooled to 20 ℃ to material then at 60 ℃; this operation finishes, the omnidistance logical nitrogen protection of this operation.
The 7th step: freezing: the material in the 6th step is carried out the stage cooling; fs is reduced to 0 ℃ from original temperature, and subordinate phase is reduced to-5 ℃ from 0 ℃, and the phase III is reduced to-10 ℃ from-5 ℃; the quadravalence section is reduced to-20 ℃ from-10 ℃; five-stage is reduced to-30 ℃ from-20 ℃, and the 6th stage was reduced to-40 ℃, per stage insulation 0.5 hour from-30 ℃; the uninterrupted stirring; when temperature reached requirement, this operation finished, the omnidistance logical nitrogen protection of this operation.
The 8th step: press filtration: the 7th step gained material is realized solid-liquid separation with pressure and filtering net under 0 ℃ of state, get liquid material 80Kg, liquid material enters next procedure,
The 9th step: heat up: the material of the 8th step gained is warming up to 10 ℃, the omnidistance nitrogen protection of this operation.
The tenth goes on foot: extraction: with material and the deionized water 21Kg mixing and the stirring of the 9th step gained, standing demix is emitted lower aqueous solution, gets upper strata lipid acid 16Kg and enters next procedure, the omnidistance nitrogen protection of this operation.
The 11 step: secondary urea complexation: with lipid acid 16Kg, 80% the edible ethanol 48Kg of the tenth step output, the urea ratio of 48Kg by weight; adding container stirs; controlled temperature is between 70 ℃; 1 hour hold-time; then material is cooled to 20 ℃; this operation finishes, the omnidistance logical nitrogen protection of this operation.
The 12 step: freezing: the material in the 11 step is carried out the stage cooling; fs is reduced to 0 ℃ from original temperature, and subordinate phase is reduced to-5 ℃ from 0 ℃, and the phase III is reduced to 15 ℃ from-5 ℃; the quadravalence section is reduced to-25 ℃ from-15 ℃; five-stage is reduced to-35 ℃ from-25 ℃, and the 6th stage was reduced to-45 ℃ from-35 ℃, and per stage need be incubated 1 hour; the uninterrupted stirring; when temperature reached requirement, this operation finished, the omnidistance logical nitrogen protection of this operation.
The 13 step: press filtration: the 12 step gained material is realized solid-liquid separation with pressure and filtering net under-20 ℃ of states, get liquid material 50Kg, liquid material enters next procedure,
The 14 step: heat up: the material of the 13 step gained is warming up to 5 ℃, the omnidistance nitrogen protection of this operation.
The 15 goes on foot: extraction: with material and the deionized water 25Kg mixing and the stirring of the 14 step gained, standing demix is emitted lower aqueous solution, gets upper strata lipid acid 5Kg and enters next procedure, the omnidistance nitrogen protection of this operation.
The 16 step: esterification: the lipid acid 5Kg of the 15 step gained, 85% edible ethanol 1Kg, 50% sulfuric acid 0.25Kg are mixed in the adding container, 70 ℃ of control reaction temperature, 4 hours time, emit lower floor's solution after the cooling, repeat aforesaid operations, analyze acid number less than 10mgKOH/g until upper strata fatty-acid ethyl ester sample thief, this operation finishes.Get upper strata fatty-acid ethyl ester 5Kg and enter next procedure.
The 17 step: washing: the fatty-acid ethyl ester of the 16 step gained being added deionized water 3Kg mixing, leave standstill, discharge lower layer of water, repeat aforesaid operations, is 7 until the lower layer of water pH value, and the upper strata fatty-acid ethyl ester enters next procedure, the omnidistance nitrogen protection of this operation.
The 18 step: dehydration: with the distillation 1 hour under the condition of 20 ℃ of vacuum 400mmHg, temperature of the fatty-acid ethyl ester of the 17 step gained,
The 19 step: molecular distillation: the fatty-acid ethyl ester of the 18 step gained is entered international advanced complete molecular distillation apparatus, control pressure is at 0.1Pa, 80 ℃ of temperature, the flavor that decolours is handled, and produces the product 2Kg of purity greater than 90% Alpha-ethyl linolenate.
Embodiment 2:
The first step: oil expression: perilla seed 300Kg, adopt mechanical cold pressing process to squeeze perilla oil,
Second step: filter: the solid impurity in the perilla oil is leached, get perilla oil 100Kg,
The 3rd step: saponification: with perilla oil 100Kg; deionized water 400Kg; enzyme catalyst (lipolase100L) 10Kg adds in the container; stir and heating, the control temperature of charge is between 70 ℃, and control material pH value is 7; reaction times was at 20 hours; sample thief is analyzed acid number, and reaction finishes when acid number reaches 120～210mgKOH/g, the omnidistance logical nitrogen protection of this process.
The 4th step: acidifying: be in the material after 90% sulfuric acid slowly adds the saponification of the 3rd step gained with concentration and stir; control material reaction temperature is at 95 ℃; when the pH value of material is stopping to add sulfuric acid less than 4 the time; when the pH value of material greater than 4 the time; continue slowly to add sulfuric acid, repeat aforesaid operations, when the pH value of material less than 4 keep 2 hours constant after; reaction finishes, the omnidistance logical nitrogen protection of this process.
The 5th step: washing: the 4th step gained material was left standstill 6 hours; emit lower aqueous solution, get lipid acid 70Kg, in lipid acid, add the deionized water of 280Kg; stir; left standstill 6 hours, and emitted lower aqueous solution again, repeat aforesaid operations; until the lower aqueous solution pH value of emitting is 7; upper strata lipid acid enters next procedure, this end of processing, the omnidistance logical nitrogen protection of this process.
The 6th step: urea complexation: the lipid acid 68Kg of the 5th step output, 99.9% edible ethanol 544Kg, urea 544Kg are added the container stirring; controlled temperature 8 hours hold-times, is cooled to 60 ℃ to material then at 100 ℃; this operation finishes, the omnidistance logical nitrogen protection of this operation.
The 7th step: freezing: the material in the 6th step is carried out the stage cooling; fs is reduced to 0 ℃ from original temperature, and subordinate phase is reduced to-10 ℃ from 0 ℃, and the phase III is reduced to-20 ℃ from-10 ℃; the quadravalence section is reduced to-30 ℃ from-20 ℃; five-stage is reduced to-40 ℃ from-30 ℃, and the 6th stage was reduced to-50 ℃, per stage insulation 8 hours from-40 ℃; the uninterrupted stirring; when temperature reached requirement, this operation finished, the omnidistance logical nitrogen protection of this operation.
The 8th step: press filtration: the 7th step gained material is realized solid-liquid separation with pressure and filtering net under-50 ℃ of states, get liquid material 500Kg, liquid material enters next procedure,
The 9th step: heat up: the material of the 8th step gained is warming up to 30 ℃, the omnidistance nitrogen protection of this operation.
The tenth goes on foot: extraction: with material and the deionized water 2000Kg mixing and the stirring of the 9th step gained, standing demix is emitted lower aqueous solution, gets upper strata lipid acid 11Kg and enters next procedure, the omnidistance nitrogen protection of this operation.
The 11 step: secondary urea complexation: with lipid acid 11Kg, 90% the edible ethanol 55Kg of the tenth step output, the urea ratio of 55Kg by weight; adding container stirs; controlled temperature is at 60 ℃; 1 hour hold-time; then material is cooled to 25 ℃; this operation finishes, the omnidistance logical nitrogen protection of this operation.
The 12 step: freezing: the material in the 11 step is carried out the stage cooling; fs is reduced to 0 ℃ from original temperature, and subordinate phase is reduced to-5 ℃ from 0 ℃, and the phase III is reduced to 15 ℃ from-5 ℃; the quadravalence section is reduced to-25 ℃ from-15 ℃; five-stage is reduced to-35 ℃ from-25 ℃, and the 6th stage was reduced to-45 ℃ from-35 ℃, and per stage need be incubated 1 hour; the uninterrupted stirring; when temperature reached requirement, this operation finished, the omnidistance logical nitrogen protection of this operation.
The 13 step: press filtration: the 12 step gained material is realized solid-liquid separation with pressure and filtering net under-10 ℃ of states, get liquid material 56Kg, liquid material enters next procedure,
The 14 step: heat up: the material of the 13 step gained is warming up to 5 ℃, the omnidistance nitrogen protection of this operation.
The 15 goes on foot: extraction: with material and the deionized water 25Kg mixing and the stirring of the 14 step gained, standing demix is emitted lower aqueous solution, gets upper strata lipid acid 11Kg and enters next procedure, the omnidistance nitrogen protection of this operation.
The 16 step: esterification: the lipid acid 11Kg of the 15 step gained, 99.9% edible ethanol 22Kg, 98% sulfuric acid 1.1Kg are mixed in the adding container, 100 ℃ of control reaction temperature, 20 hours time, emit lower floor's solution after the cooling, repeat aforesaid operations, analyze acid number less than 10mgKOH/g until upper strata fatty-acid ethyl ester sample thief, this operation finishes.Get upper strata fatty-acid ethyl ester 11Kg and enter next procedure.
The 17 step: washing: the fatty-acid ethyl ester of the 16 step gained is added deionized water 44Kg mixing, and standing demix is discharged lower layer of water, repeats aforesaid operations, is 7 until the lower layer of water pH value, and the upper strata fatty-acid ethyl ester enters next procedure, the omnidistance nitrogen protection of this operation.
The 18 step: dehydration: with the distillation 4 hours under the condition of 80 ℃ of vacuum 700mmHg, temperature of the fatty-acid ethyl ester of the 17 step gained,
The 19 step: molecular distillation: the fatty-acid ethyl ester of the 18 step gained is entered international advanced complete molecular distillation apparatus, control pressure is between 5Pa, 150 ℃ of temperature, decolouring flavor is handled, and produces purity greater than 90% alpha-linolenic acid product 9Kg.
Embodiment 3:
The first step: oil expression: perilla seed 300Kg, adopt mechanical cold pressing process to squeeze perilla oil,
Second step: filter: the solid impurity in the perilla oil is leached, get perilla oil 100Kg,
The 3rd step: saponification: with perilla oil 100Kg; deionized water 120Kg, enzyme catalyst (lipolase100L) 8Kg add in the container; stir and heating; the control temperature of charge is between 55 ℃; control material pH value is 7, and the reaction times, sample thief was analyzed acid number at 12 hours; reaction finishes when acid number reaches 120～210mgKOH/g, the omnidistance logical nitrogen protection of this process.
The 4th step: acidifying: be in the material after 80% sulfuric acid slowly adds the saponification of the 3rd step gained with concentration and stir; control material reaction temperature is between 75 ℃; when the pH value of material is stopping to add sulfuric acid less than 4 the time; when the pH value of material greater than 4 the time; continue slowly to add sulfuric acid, repeat aforesaid operations, when the pH value of material less than 4 keep 2 hours constant after; reaction finishes, the omnidistance logical nitrogen protection of this process.
The 5th step: washing: the 4th step gained material was left standstill 3 hours; emit lower aqueous solution, get upper strata lipid acid 68Kg, add the deionized water of 50Kg; stir; left standstill 5 hours, and emitted lower aqueous solution again, repeat aforesaid operations; until the lower aqueous solution pH value is 7; upper strata lipid acid enters next procedure, this end of processing, the omnidistance logical nitrogen protection of this process.
The 6th step: urea complexation: the lipid acid 68Kg of the 5th step output, 90% edible ethanol 100Kg, urea 150Kg are added the container stirring; controlled temperature 3 hours hold-times, is cooled to 55 ℃ to material then at 90 ℃; this operation finishes, the omnidistance logical nitrogen protection of this operation.
The 7th step: freezing: the material in the 6th step is carried out the stage cooling; fs is reduced to 0 ℃ from original temperature, and subordinate phase is reduced to-6 ℃ from 0 ℃, and the phase III is reduced to-18 ℃ from-6 ℃; the quadravalence section is reduced to-21 ℃ from-18 ℃; five-stage is reduced to-33 ℃ from-21 ℃, and the 6th stage was reduced to-49 ℃, per stage insulation 2 hours from-33 ℃; the uninterrupted stirring; when temperature reached requirement, this operation finished, the omnidistance logical nitrogen protection of this operation.
The 8th step: press filtration: make the 7th step gained material realize solid-liquid separation with pressure and filtering net under-15 ℃ of states, get liquid material 90Kg, liquid material enters next procedure,
The 9th step: heat up: the material of the 8th step gained is warming up to 25 ℃, the omnidistance nitrogen protection of this operation.
The tenth goes on foot: extraction: the material 90Kg of the 9th step gained is added deionized water 165Kg mixing and stirring, and standing demix is emitted lower aqueous solution, gets upper strata lipid acid 10Kg and enters next procedure, the omnidistance nitrogen protection of this operation.
The 11 step: secondary urea complexation: with lipid acid 10Kg, 90% the edible ethanol 80Kg of the tenth step output, the urea ratio of 110Kg by weight; adding container stirs; controlled temperature is at 60 ℃; 1 hour hold-time; then material is cooled to 25 ℃; this operation finishes, the omnidistance logical nitrogen protection of this operation.
The 12 step: freezing: the material in the 11 step is carried out the stage cooling; fs is reduced to 0 ℃ from original temperature, and subordinate phase is reduced to-10 ℃ from 0 ℃, and the phase III is reduced to-20 ℃ from-10 ℃; the quadravalence section is reduced to-30 ℃ from-20 ℃; five-stage is reduced to-40 ℃ from-30 ℃, and the 6th stage was reduced to-50 ℃ from-40 ℃, and per stage need be incubated 1.5 hours; the uninterrupted stirring; when temperature reached requirement, this operation finished, the omnidistance logical nitrogen protection of this operation.
The 13 step: press filtration: the 12 step gained material is realized solid-liquid separation with pressure and filtering net under-5 ℃ of states, get liquid material 52Kg, liquid material enters next procedure,
The 14 step: heat up: the material of the 13 step gained is warming up to 5 ℃, the omnidistance nitrogen protection of this operation.
The 15 goes on foot: extraction: with material and the deionized water 30Kg mixing and the stirring of the 14 step gained, standing demix is emitted lower aqueous solution, gets upper strata lipid acid 10Kg and enters next procedure, the omnidistance nitrogen protection of this operation.
The 16 step: esterification: the lipid acid 10Kg of the 15 step gained, 90% edible ethanol 10Kg, 80% sulfuric acid 0.06Kg are mixed in the adding container, 95 ℃ of control reaction temperature, 10 hours time, emit lower floor's solution after the cooling, repeat aforesaid operations, analyze acid number less than 10mgKOH/g until upper strata fatty-acid ethyl ester sample thief, this operation finishes.Upper strata fatty-acid ethyl ester 10Kg enters next procedure.
The 17 step: washing: the fatty-acid ethyl ester 10Kg of the 16 step gained is added deionized water 10Kg mixing, and standing demix is discharged lower layer of water; repeat aforesaid operations; until the lower layer of water pH value is 7, and the upper strata fatty-acid ethyl ester enters next procedure, the omnidistance nitrogen protection of this operation.
The 18 step: dehydration: with the distillation 2 hours under the condition of 65 ℃ of vacuum 550mmHg, temperature of the fatty-acid ethyl ester of the 17 step gained,
The 19 step: molecular distillation: the fatty-acid ethyl ester of the 18 step gained is entered international advanced complete molecular distillation apparatus, control pressure is at 2Pa, 100 ℃ of temperature, the flavor that decolours is handled, and produces the product 8.5Kg of purity greater than 90% Alpha-ethyl linolenate.
Claims (1)
1. a purity is characterized in that: carry out according to following technology greater than the production technique of 90% Alpha-ethyl linolenate:
The first step: oil expression: adopt mechanical cold pressing process to squeeze perilla oil perilla seed,
Second step: filter: the solid impurity in the perilla oil is leached,
The 3rd step: saponification: the second step gained perilla oil and deionized water, enzyme catalyst lipolase100L are added in the container according to the ratio of weight ratio 1: 0.5～4: 0.01～0.1; stir and heating; the control temperature of charge is between 40 ℃～70 ℃; control material pH value is 7; reaction times, sample thief was analyzed acid number at 20～40 hours, and reaction finishes when acid number reaches 120～210mgKOH/g; the omnidistance logical nitrogen protection of this process
The 4th step: acidifying: be in the material after 10%～90% sulfuric acid slowly adds the saponification of the 3rd step gained with concentration and stir, control material reaction temperature is between 40 ℃～95 ℃, when the pH value of material is stopping to add sulfuric acid less than 4 the time, when the pH value of material greater than 4 the time, continue slowly to add sulfuric acid; When the pH value of material less than 4 keep 2 hours constant after, reaction finishes, the omnidistance logical nitrogen protection of this process,
The 5th step: washing: the 4th step gained material was left standstill 1～6 hour; emit lower aqueous solution; the deionized water that adds 0.5～4 times in remaining upper strata lipid acid stirs, and leaves standstill 1～6 hour; emit lower aqueous solution again; until the lower aqueous solution pH value of emitting is 7, and upper strata lipid acid enters next procedure, this end of processing; the omnidistance logical nitrogen protection of this process
The 6th step: urea complexation: with the lipid acid of the 5th step output, 70%～99.9% edible ethanol, urea by weight 1: (1～8): the ratio of (1～8) adds container and stirs; controlled temperature is between 60 ℃～100 ℃; 0.5～8 hour hold-time; then material is cooled to 20 ℃～60 ℃; this operation finishes; the omnidistance logical nitrogen protection of this operation
The 7th step: freezing: the material in the 6th step is carried out the stage cooling; fs is reduced to 0 ℃ from original temperature; subordinate phase is reduced to-5～-10 ℃ from 0 ℃; phase III is reduced to-10～-20 ℃ from-5～-10 ℃; the quadravalence section is reduced to-20～-30 ℃ from-10～-20 ℃; five-stage is reduced to-30～-40 ℃ from-20～-30 ℃; the 6th stage was reduced to-40～-50 ℃ from-30～-40 ℃; per stage need be incubated 0.5～8 hour; the uninterrupted stirring, when temperature reached requirement, this operation finished; the omnidistance logical nitrogen protection of this operation
The 8th step: press filtration: the 7th step gained material is realized solid-liquid separation with pressure and filtering net under 0 ℃～-50 ℃ states, liquid enters next procedure,
The 9th step: heat up: the material of the 8th step gained is warming up to 10 ℃～30 ℃, the omnidistance nitrogen protection of this operation,
The tenth goes on foot: extraction: with the material and deionized water 1: 0.5～4 the mixed and the stirring by weight of the 9th step gained, standing demix is emitted lower aqueous solution, and upper strata lipid acid enters next procedure, the omnidistance nitrogen protection of this operation,
The 11 step: secondary urea complexation: the lipid acid of the tenth step output, 70%～99.9% edible ethanol, urea are added the container stirring by weight 1: 3～10: 3～10 ratio; controlled temperature is between 60 ℃～100 ℃; 0.5～8 hour hold-time; then material is cooled to 20 ℃～60 ℃; this operation finishes; the omnidistance logical nitrogen protection of this operation
The 12 step: freezing: the material in the 11 step is carried out the stage cooling; fs is reduced to 0 ℃ from original temperature; subordinate phase is reduced to-5～-10 ℃ from 0 ℃; phase III is reduced to-10～-20 ℃ from-5～-10 ℃; the quadravalence section is reduced to-20～-30 ℃ from-10～-20 ℃; five-stage is reduced to-30～-40 ℃ from-20～-30 ℃; the 6th stage was reduced to-40～-50 ℃ from-30～-40 ℃; per stage need be incubated 0.5～8 hour; the uninterrupted stirring, when temperature reached requirement, this operation finished; the omnidistance logical nitrogen protection of this operation
The 13 step: press filtration: the 12 step gained material is realized solid-liquid separation with pressure and filtering net under 0 ℃～-50 ℃ states, liquid enters next procedure,
The 14 step: heat up: the material of the 13 step gained is warming up to 10 ℃～30 ℃, the omnidistance nitrogen protection of this operation,
The 15 goes on foot: extraction: with the material and deionized water 1: 0.5～4 the mixed and the stirring by weight of the 14 step gained, standing demix is emitted lower aqueous solution, and upper strata lipid acid enters next procedure, the omnidistance nitrogen protection of this operation,
The 16 step: esterification: the lipid acid of the 15 step gained, 85%～99.9% edible ethanol, 50%～98% sulfuric acid amount are added in the container than the mixed by 1: 0.2～2: 0.05～0.1, between 70 ℃～100 ℃ of the control reaction temperature, 4～20 hours time, emit lower floor's solution after the cooling, repeat aforesaid operations, analyze acid number less than 10mgKOH/g until upper strata fatty-acid ethyl ester sample thief, this operation finishes, the upper strata fatty-acid ethyl ester enters next procedure
The 17 step: washing: the 16 step fatty-acid ethyl ester of gained and the deionized water ratio by weight 1: 0.5～4 entered mix in the container; standing demix; discharge lower layer of water; repeat aforesaid operations; until the lower layer of water pH value is 7; the upper strata fatty-acid ethyl ester enters next procedure, the omnidistance nitrogen protection of this operation
The 18 step: dehydration: the fatty-acid ethyl ester of the 17 step gained was distilled 1～4 hour under the condition of 20 ℃～80 ℃ of vacuum 400～700mmHg, temperature,
The 19 step: molecular distillation: the fatty-acid ethyl ester of the 18 step gained is entered complete molecular distillation apparatus, control pressure is between 0.1～5Pa, 80 ℃～150 ℃ of temperature, decolouring flavor is handled, and produces purity greater than 90% Alpha-ethyl linolenate product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007100550124A CN101139289A (en) | 2007-08-22 | 2007-08-22 | Technique for producing alpha-linolenic acid ethyl with 90 percent more purity |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007100550124A CN101139289A (en) | 2007-08-22 | 2007-08-22 | Technique for producing alpha-linolenic acid ethyl with 90 percent more purity |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101139289A true CN101139289A (en) | 2008-03-12 |
Family
ID=39191420
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2007100550124A Pending CN101139289A (en) | 2007-08-22 | 2007-08-22 | Technique for producing alpha-linolenic acid ethyl with 90 percent more purity |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101139289A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102993011A (en) * | 2011-09-13 | 2013-03-27 | 丰宁京北第一草原原生态食品科技开发有限公司 | Method for preparing alpha-ethyl linolenate through using Fructus Perillae oil |
| CN104693032A (en) * | 2014-09-28 | 2015-06-10 | 河南利诺生化有限责任公司 | Process for manufacturing high-purity alpha-ethyl linolenate |
| CN104693033A (en) * | 2014-09-28 | 2015-06-10 | 河南利诺生化有限责任公司 | Production process of high-purity alpha-ethyl linolenate |
| CN104974029A (en) * | 2015-07-15 | 2015-10-14 | 上海亿康生物医药科技有限公司 | Method for extracting linolenic acid from perilla seeds |
| CN106350233A (en) * | 2016-08-24 | 2017-01-25 | 哈尔滨普润油脂有限公司 | Preparation method of high-quality ethyl linolenate |
| CN107459456A (en) * | 2016-06-02 | 2017-12-12 | 中国石化扬子石油化工有限公司 | A kind of method that methyl stearate is extracted in the benzoyl methane raffinate from stearic acid |
-
2007
- 2007-08-22 CN CNA2007100550124A patent/CN101139289A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102993011A (en) * | 2011-09-13 | 2013-03-27 | 丰宁京北第一草原原生态食品科技开发有限公司 | Method for preparing alpha-ethyl linolenate through using Fructus Perillae oil |
| CN102993011B (en) * | 2011-09-13 | 2015-01-14 | 丰宁京北第一草原原生态食品科技开发有限公司 | Method for preparing alpha-ethyl linolenate through using Fructus Perillae oil |
| CN104693032A (en) * | 2014-09-28 | 2015-06-10 | 河南利诺生化有限责任公司 | Process for manufacturing high-purity alpha-ethyl linolenate |
| CN104693033A (en) * | 2014-09-28 | 2015-06-10 | 河南利诺生化有限责任公司 | Production process of high-purity alpha-ethyl linolenate |
| CN104693033B (en) * | 2014-09-28 | 2016-08-31 | 河南利诺生化有限责任公司 | The production technology of highly purified a-ethyl linolenate |
| CN104974029A (en) * | 2015-07-15 | 2015-10-14 | 上海亿康生物医药科技有限公司 | Method for extracting linolenic acid from perilla seeds |
| CN107459456A (en) * | 2016-06-02 | 2017-12-12 | 中国石化扬子石油化工有限公司 | A kind of method that methyl stearate is extracted in the benzoyl methane raffinate from stearic acid |
| CN106350233A (en) * | 2016-08-24 | 2017-01-25 | 哈尔滨普润油脂有限公司 | Preparation method of high-quality ethyl linolenate |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101139289A (en) | Technique for producing alpha-linolenic acid ethyl with 90 percent more purity | |
| CN101805666B (en) | Process for extracting high-grade rice bran oil by physical method | |
| CN101717689B (en) | Method for preparing first-level tea oil by alcohol extraction and deacidification | |
| CN101691520B (en) | Walnut oil refining method | |
| CN103045356A (en) | Production method for linseed oil | |
| CN102224854A (en) | Method for producing flaxseed oil under nitrogen protection | |
| CN106755151B (en) | Method for producing ARA by utilizing microbial fermentation | |
| CN105087140A (en) | Production process of snakegourd fruit seed oil | |
| CN100363326C (en) | Process for preparing alpha-linolenic acid with purity more than 80% | |
| CN100366601C (en) | Process for preparing alpha-ethyl linolenate with purity more than 80% | |
| CN112159706A (en) | Efficient perilla seed oil preparation process | |
| CN105062661A (en) | Production technology of sunflower oil | |
| ES2184118T3 (en) | PROCEDURE FOR THE PRODUCTION OF GLYCERED OIL WITH LOW CONTENT OF NON-HYDRATABLE PHOSFATIDES. | |
| CN104693033B (en) | The production technology of highly purified a-ethyl linolenate | |
| CN105166088A (en) | Production technology of linseed oil | |
| CN111346112A (en) | Method for extracting Brazilian green propolis with ethanol at low temperature | |
| CN107858203A (en) | A kind of high alpha linolenic acid peanut ready-mixed oil and preparation method thereof | |
| CN114196474A (en) | Method for synchronously refining camellia seed oil and preparing liposome | |
| CN105038952A (en) | Juglans cathayensis oil and production process thereof | |
| CN105038958A (en) | Rice oil production technology | |
| CN107927200A (en) | Low acid number corn sunflower ready-mixed oil of a kind of high oleic acid and preparation method thereof | |
| CN1737094A (en) | Edible oil continuous filtration fining process | |
| CN107324883A (en) | A kind of method that vegetable oil residue prepares quality improver for fruit | |
| CN107129865A (en) | A kind of method that pumpkin phylloquinone is extracted based on subcritical fluids and molecular distillation | |
| SU1763460A1 (en) | Method for production of food dye from marc |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Open date: 20080312 |