CN1580030A - Method for synthesizing conjugated linoleic acid - Google Patents
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Abstract
The invention discloses a kind of method to compound the conjugated linoleic acid. The method saponifies and hydrolyzes the vegetable oil with linoleic acid in aqueous alkali (including the alkaline alcosol and alkaline aqueous solution) and at high temperature to produce the linoleate; transform the linoleate into the conjugated linoleate with the catalysis of alkali at high temperature; then transform the dissoluble linoleate into the non soluble linoleate to deposit; acidify the deposit with acid to produce the conjugated linoleic acid; the components of the filtrate are mainly alkali, solvent (the solvent added at the beginning) and glycerin and can be reused in the nest round. The method enriches the linoleic acid before and after the saponification to increase the content of the linoleic acid and then carries out the next reaction, which makes it more convenient to make the products with high content of linoleic acid from the cheep vegetable oil with low content of linoleic acid.
Description
Technical field the present invention relates to a kind of synthetic method of lipid acid, specifically relates to the method for a kind of synthesis of conjugated linoleic acid (CLA).
Background technology conjugated linolic acid (CLA) is to contain the positional isomers of octadecadienoic acid of two conjugated double bonds and the mixture of conjugated isomers.Since the researchist of the hot university of University of Wisconsin-Madison in 1978 finds conjugated linolic acid, through years of researches, it is found that conjugated linolic acid has many physiologically actives, as: enhancing immunity, suppress fatty deposits, reduce cholesterol in blood and the liver, anti-oxidant, anticancer and promote effect such as growth.Natural conjugated linolic acid mainly is present in the butterfat and meat product thereof of ruminating animal ox, sheep etc., but content is very little.And the recommendation daily ingested dose of conjugated linolic acid is 7-45mg/kg body weight (U.S. Pat 6432453).According to recommending intake, even be the western countries of staple food with milk-product and animal food, the conjugated linolic acid intake is also less than 1/3rd of recommended amounts per capita.So be necessary additionally to replenish conjugated linolic acid from other approach.
But it is too high to extract the conjugated linolic acid cost in the natural goods, and output is too low, does not satisfy on the market demand to conjugated linolic acid.So in recent years, use the chemical process synthesis of conjugated linoleic acid to become the focus of domestic and international research.U.S. Pat 2389260, US 2242230 and US 2343644 have introduced the method for using highly basic catalysis synthesis of conjugated linoleic acid, these methods all are to make glyceryl linoleate hydrolysis saponification under highly basic generate linoleate earlier, use the highly basic that is dissolved in the alcoholic solvents such as glycerine, ethylene glycol and propylene glycol to make catalyzer then and at high temperature be converted into conjugate linoleate, add acid again conjugate linoleate is converted into conjugated linolic acid by linoleate.U.S. Pat 2350583,4164505 of US have introduced the use water to replace organic solvent, and highly basic is dissolved in wherein as catalyzer, prepare the method for conjugated linolic acid under High Temperature High Pressure.It is raw material that U.S. Pat 5719301 has then been introduced with the oleum lini, and closing ruthenium, iridic compound etc. with chromium carbonyl, ferrocene, ten dicarbapentaborane is catalyzer, is auxiliary with formic acid and phase acidoid, the linolic acid isomery is turned to the method for conjugated linolic acid.It is raw material that Chinese patent CN1356386A (application number 011434026) has introduced with synourin oil, is rich in c-9, t-11, t-10, the method for the conjugated linolic acid of c-12 isomer through inducing isomerization, hydrolysis and multistep the operation preparation of three steps such as to separate.
The method of above-mentioned synthesis of conjugated linoleic acid respectively has its relative merits.The method that U.S. Pat 5719301 is introduced is too loaded down with trivial details, and step is more, and production cost is too high.The method that Chinese patent CN1356386A (application number 011434026), U.S. Pat 2350583, US 4164505, US 2389260, US 2350583 introduce, all be to use base catalysis to prepare conjugate linoleate, prepare conjugated linolic acid with acid and conjugated linolic acid reactant salt then, alkali all is can not be reusable in these technologies, and in the above-mentioned method, be to use the solvent of alcoholic solvent as alkali more, but according to above-mentioned method, after reaction finishes, alcoholic solvent and a large amount of water mix, and are difficult to reclaim.According to statistics, according to above-mentioned method, the conjugated linolic acid that every generation is a ton needs to consume (method of introducing with U.S. Pat 2389260 are an example) such as the ethylene glycol, propylene glycol of the monobasic highly basic (is example with KOH) of equal quality and 1.5 times of quality approximately.
What the method for above-mentioned synthesis of conjugated linoleic acid adopted all is the working system that directly feeds intake, and promptly vegetables oil, alkali and alcoholic solvent are not treated, and the production conjugated linolic acid directly feeds intake.But vegetables oil is as a kind of natural products, and its linoleic content is more unsettled, if use its production conjugated linolic acid that directly feeds intake, it is stable that the quality of conjugated linolic acid also is difficult to keep.And according to above method, want to improve the content of the conjugated linolic acid in the product, just must adopt high as far as possible vegetables oil of linoleic acid content such as Thistle oil, sunflower seeds wet goods, but safflower and Sunflower Receptacle are wideless in the cultivated area of China, Thistle oil, sunflower seeds wet goods are little in China's output, cost an arm and a leg, improved the production cost of conjugated linolic acid greatly.
Based on these above reasons, the cost of synthesis of conjugated linoleic acid is that quite high, too high cost makes the market value of conjugated linolic acid high at present, and content is at the conjugated linolic acid market value Yue Wei $200 more than 80% at present, 000-$500,000/ ton.
Summary of the invention the objective of the invention is to overcome the shortcoming of prior art, and a kind of method of synthesis of conjugated linoleic acid is provided, to reduce the production cost of conjugated linolic acid.
The present invention improves from the aspects such as production technique of raw material, conjugated linolic acid, thereby reaches the purpose of the production cost that reduces conjugated linolic acid.It is realized by following several process modification, wherein in technology 1 described synthesis technique, by the form that generates insoluble salt conjugated linolic acid is precipitated out, with acid resolution of precipitate is prepared conjugated linolic acid again, alcoholic solvent in the reaction solution and alkali then can recycle.Technology 2 has been introduced and has been used the low-temperature sludge method to remove most of saturated and monounsaturated fatty acids in the vegetables oil, the method for refabrication conjugated linolic acid behind the raising content of polyunsaturated fatty acid.Technology 3 has been introduced the method with refabrication conjugated linolic acid behind the urea adduct method enrichment linolic acid.
Introduce each technology below in detail: technology 1. (1) but. add alkali and alcoholic solvent under the room temperature in the encloses container, slowly heating makes alkali dissolution among alcoholic solvent; (2). in container, feed nitrogen, wait to estimate all to be full of in the container after the nitrogen, in container, add the raw material that is rich in linolic acid or linoleate, container is airtight, while stirring temperature is raised to 130 ℃-270 ℃, keeps this temperature and continue to stir 2h-12h; (3). in container, add the soluble salt of calcium hydroxide, calcium oxide or calcium, magnesium, iron, manganese, zinc, copper, aluminium etc. or the mixture of forming by two or more above-mentioned substances, stirring forwards reaction solution in one centrifuge tube to after allowing it fully react 0.5h-2h, with the centrifugal 15min of the speed of 2000 commentaries on classics/min; (4). the main component of supernatant liquor is alkali, alcoholic solvent and glycerine, can forward step (1) to and reuse as saponification reaction agent and conjugation catalyzer.(5). in (3), add hydrochloric acid in the precipitation of centrifugal gained, fully stir and all dissolve until solid; (6). use petroleum ether extraction three times, the consumption of each sherwood oil is about 1/3 of (5) middle reaction solution volume; (7). merge petroleum ether layer and wash petroleum ether layer to neutral; (8). remove sherwood oil at 0.01MPa-0.1MPa, 25 ℃ of-40 ℃ of following concentrating under reduced pressure, promptly get the crude product of conjugated linolic acid.
Said molten antalkaline alcoholic solvent in this specification sheets, comprise that ethylene glycol, propylene glycol (comprise 1,2-propylene glycol and 1, ammediol), (polyoxyethylene glycol that comprises the various polymerization degree is as PEG100 for glycerine and polyoxyethylene glycol, PEG200, PEG300, PEG400, PEG600, PEG1000, PEG6000 etc.) etc.The mass percent of alcoholic solvent in total reactant is about 30%-60%.Also can replace above-mentioned said alcoholic solvent for water, will under high pressure finish reaction this moment.
The said alkali of this specification sheets can be oxide compound, oxyhydroxide, salt of weak acid of basic metal, alkaline-earth metal and solubility thereof etc.Especially refer to potassium hydroxide, sodium hydroxide, yellow soda ash and salt of wormwood etc.The mass percent of alkali in total reactant is about 20%-50%.
This specification sheets is said to contain linoleic raw material, refer to the abundant vegetables oil (linoleic quality percentage composition is greater than 30%) of natural linoleic acid content, as: Thistle oil, sunflower seed oil, common seepweed seeds oil, oriental wormwood seed oil, extra large fluffy seed oil, sesame oil, Semen Maydis oil, soybean oil, Oenothera oil, raisin seed oil, Oleum Gossypii semen, water white gourd oil, Semen Cucumidis sativi oil, linseed oil, English walnut wet goods.It can also be the raw material that is rich in linoleate.The said raw material that is rich in linoleate refers to the quality percentage composition of linoleate in this raw material greater than 40%.The raw material shared mass percent in total reactant that is rich in linolic acid or linoleate is about 20%-60%.
If employing mol ratio, then alkali (monoatomic base) in the total reactant: alcohol: the raw material (being converted into linoleic mole number) that is rich in linolic acid or linoleate is preferably 3-8: 4-8: 1.
(2) the feeding amount that feeds nitrogen in is decided according to the volume of container, and the amount that generally will feed nitrogen is about about 4 times of vessel volume.
(2) temperature of said heating can be 130 ℃-270 ℃ in, is preferably 170 ℃-185 ℃, and the reaction times changes according to the temperature of reaction difference, is preferably 2h-6h. 170 ℃-185 ℃ scope internal reaction times.
Usually add calcium hydroxide, calcium oxide or its mixture in the step (3), but also can add the soluble salt of calcium, magnesium, iron, manganese, zinc, copper, aluminium etc. or the mixture of two or more above-mentioned substance.
(5) except that using hydrochloric acid, also can use organic acids such as mineral acid such as phosphoric acid, sulfuric acid and formic acid, oxalic acid, acetate, citric acid in.The concentration of the acid that adds should be greater than 0.01mol/L.The acid (is example with monoprotic acid) that adds should be greater than 2 with the ratio of the mole number of the solid (it is all regarded as calcium conjugated linoleic acid calculates) that filters gained.
From solution, extract conjugated linolic acid in this specification sheets, can use the sherwood oil of various boiling ranges, as the sherwood oil of boiling range at 30 ℃-60 ℃ or 60 ℃-90 ℃.In addition, except that sherwood oil, non-polar solvents such as also available normal hexane, hexanaphthene, normal heptane, ethyl acetate extract.
Conjugated linolic acid crude product described in this specification sheets can be further refining again with the higher product of preparation cla levels.Technology 2. (1). get and contain linoleic vegetables oil and slowly cool to 4 ℃--10 ℃, and under this temperature, leave standstill (2) more than the 12h. above-mentioned vegetables oil with the centrifugal 10min of the speed of 2000 commentaries on classics/min, is taken out upper solution; (3) but. add alkali and alcoholic solvent under the room temperature in the encloses container, slowly heating makes alkali dissolution among alcoholic solvent; (4). in container, feed nitrogen, wait to estimate all to be full of in the container after the nitrogen, add the filtrate of gained in (2) to container, container is airtight, while stirring temperature is raised to 130 ℃-270 ℃, and keeps this temperature 2.5h-12h; (5). reaction solution is taken out and adding acid, fully stir 15min-45min; (6). use sherwood oil with the extraction of the reaction solution in (5) three times, the consumption of each sherwood oil is 1/3 of (5) middle reaction solution volume; (7). merge petroleum ether layer and wash petroleum ether layer to neutral; (8). remove sherwood oil at 0.01MPa-0.1MPa, 25 ℃ of-40 ℃ of following concentrating under reduced pressure, promptly get the crude product of conjugated linolic acid.
(2) upper solution of gained also can replace the linoleic vegetables oil that contains described in the technology 1 in, according to the step synthesis of conjugated linoleic acid of technology 1.
The temperature of freezing precipitation can be 4 ℃--and 10 ℃, preferable temperature is-5 ℃--10 ℃.
Technology 3 (1) but. at room temperature add the aqueous solution that contains linoleic vegetables oil and alkali in the encloses container, container be full of behind the nitrogen container is airtight, be warmed up to 50 ℃-100 ℃ then; (2). keep this temperature and stir 0.5h-2h; (3). reaction solution is returned to room temperature, it is changed in the centrifuge tube, with the centrifugal 15min of 2000 rev/mins speed; (4). lower floor's solution that will be rich in linoleate is transferred in another container, adds the alcoholic solution of urea, behind the about 30min of backflow temperature is slowly dropped to 4 ℃ down at 60 ℃-100 ℃--and 15 ℃; (5). under this temperature, place 8h-32h, filter, most of saturated fatty acid and monounsaturated fatty acids can be removed; (6) but. add alkali and alcoholic solvent under the room temperature in the encloses container, slowly heating makes alkali dissolution among alcoholic solvent; (7). in container, feed nitrogen, wait to estimate all to be full of in the container after the nitrogen, add the filtrate of gained in (5) to container, container is airtight, temperature is raised to 130 ℃ while stirring--270 ℃, and keep this temperature 1-8h; (8). reaction solution is taken out and adding acid, fully stir 15min-45min; (9). use sherwood oil with the extraction of the reaction solution in (8) three times, the consumption of each sherwood oil is 1/3 of (8) middle reaction solution volume; (10). merge petroleum ether layer and wash petroleum ether layer to neutral; (11). remove sherwood oil at 0.01MPa-0.1MPa, 25-40 ℃ of following concentrating under reduced pressure, promptly get the crude product of conjugated linolic acid.
(1) also can use the solvent of alcohol (comprising ethylene glycol, propylene glycol, glycerine, polyoxyethylene glycol etc.) as alkali in, step this moment (3) can be omitted, and direct solution after saponification adds the alcoholic solution of urea, and all the other steps are constant.
(4) soap in: urea: the mass ratio of alcohol should be 1: 1-8: 4-12, preferable mass ratio are 1: 2-4: 6-10; The temperature of urea clathration can be 4 ℃--and 15 ℃, the temperature of preferable urea clathration is-6 ℃--12 ℃; The time of urea clathration can be 8h-32h, and the preferable urea clathration time is 12h-24h; The alcohol that is adopted can be ethylene glycol, propylene glycol, glycerine, preferred ethylene glycol.
(5) filtrate of gained also can be according to the step synthesis of conjugated linoleic acid of technology 1 in.
The present invention compares with existing technology of producing conjugated linolic acid, and following advantage is arranged:
1. as described in the technology 1, after finishing, the conjugation reaction adopt the form that generates insoluble salt that conjugated linolic acid is precipitated out, precipitation adds acid dissolving preparation conjugated linolic acid, and the main component of filtrate is alcoholic solvent, alkali and glycerine, can forward initial step to directly recycles, and needn't greatly reduce the production cost of conjugated linolic acid through complicated recovery, purge process.
2. as described in the technology 2, before vegetables oil is carried out saponification, if contained linoleic acid content low excessively (the quality percentage composition is less than 40% in all fatty acids) in the vegetables oil can separate and purifying vegetables oil earlier, enriching polyunsaturated fatty acid is to improve its linoleic content.
3. as described in the technology 3, after the saponification hydrolysis, if the content of linoleate is still low excessively among the soap stock of gained, can carry out separation and purification to it again, with further enrichment linolic acid.
Technology 3 and technology 4 makes that to utilize the not really high cheap vegetables oil production of linoleic acid content to contain the conjugated linolic acid high product more convenient, and can produce byproducts such as saturated fatty acid and phosphatide simultaneously, thereby can reduce the production cost of conjugated linolic acid greatly.
With concrete example embodiments of the present invention are described below the embodiment
Embodiment 1
(1). with 1, ammediol 62.35g places in the reactor, adds KOH 30.12g again, feeds nitrogen protection and be heated to 120 ℃ under mechanical stirring; (2). treat that KOH all after the dissolving adds the 56.56g Thistle oil, continue to stir, under nitrogen protection, be warming up to 140 ℃, container is airtight, under this temperature, stir 8h; (3). add calcium hydroxide 12.14g, stir 45min; (4). reaction solution is forwarded in the centrifuge tube, with the centrifugal 15min of the speed of 2000 commentaries on classics/min; (5). be rich in 1 in the supernatant liquor, ammediol and KOH can return step (1) and recycle; (6). add 200 milliliters of 5% hydrochloric acid to the lower floor solid, slowly be warmed up to 70 ℃ while stirring, treat solid all after the dissolving, reaction solution is left standstill be cooled to room temperature; (7). reaction solution is forwarded in the separating funnel, add petroleum ether extraction three times, the volume of each sherwood oil is 1/3 of a reaction solution cumulative volume;
(8). merge petroleum ether layer and wash petroleum ether layer to neutral; (9). remove sherwood oil at 0.01MPa-0.1MPa, 60 ℃ of following concentrating under reduced pressure, promptly get the crude product of conjugated linolic acid.
Detect:
1. the esterification of lipid acid
The 60mg that materialses splashes in the 20ml volumetric flask, adds 2ml BF
3Methanol solution boils 2min with mixture in 70 ℃ of water-baths.Cooling adds the 2ml normal hexane, and jolting makes methyl esters change the normal hexane layer over to, adds saturated NaCl solution 12ml, extracts the normal hexane layer out with syringe, puts into clean bottle and adds more than the dry 24h of anhydrous sodium sulfate dehydration about 5g.Carry out stratographic analysis then
2. instrument: Tianjin, island GC-9AM gas chromatograph; Detector is a flame ionization ditector; Capillary column: CP-Sil88TM (100m * 0.25mm * 0.20 μ m).
3. heating schedule: with 80 ℃ of beginnings, the speed with 10 ℃/min rises to 220 ℃ with temperature then, keeps this temperature 10min.
4. carrier gas: nitrogen
5. other parameters: press before the post to be 100kPa; Injector temperature is 240 ℃; Detector temperature is 280 ℃; Air pressure is 50kPa; Hydrogen pressure is 60kPa; Nitrogen pressure is 400kPa;
Component content adopts area normalization method to calculate, and the result charges to table 1.
Embodiment 2
(1). glycerine 150.56g is placed in the reactor, add NaOH80.12g again, under mechanical stirring, feed nitrogen protection and be heated to 130 ℃; (2). treat that KOH all after the dissolving adds the 92.56g sunflower seed oil, feeding volume is that container is airtight behind the nitrogen of container volume more than 4 times, continues to stir, and is warming up to 250 ℃, stirs 2.5h under this temperature; (3). add calcium hydroxide 8g, calcium oxide 6g stirs 45min.
All the other steps are with embodiment 1, and just the hydrochloric acid that will implement in 1 changes phosphoric acid into, and the result charges to table 1.
Embodiment 3:
1). ethylene glycol 54.76g is placed in the reactor, add KOH30.12g again, under mechanical stirring, feed nitrogen protection and be heated to 120 ℃; (2). treat that KOH all after the dissolving adds the 36.46g common seepweed seeds oil, continue to stir, under nitrogen protection, be warming up to 175 ℃, container is airtight, under this temperature, stir 3.5h; (3). add magnesium chloride 10.21g, stir 45min;
All the other steps just change the hydrochloric acid among the embodiment 1 into citric acid with embodiment 1, and the result charges to table 1
Embodiment 4
With 1 among the embodiment 1, ammediol is changed to PEG100, and Thistle oil is changed to raisin seed oil, and the temperature of conjugation reaction changes 140 ℃ into, and the time changes 3h into, and calcium hydroxide changes the mixture of calcium hydroxide and zinc chloride into.
All the other just change the hydrochloric acid among the embodiment 1 into sodium pyrosulfate with embodiment 1, and the result charges to table 1.
Embodiment 5
(1) but. at room temperature add NaOH and the 54.15ml water of 25.45g in the encloses container, slowly be warming up to 80 ℃ and stir and allow NaOH be dissolved in the water; (2). add raisin seed oil 90.64g, feed behind the nitrogen that is equivalent to 10 times of volumes of container container is airtight, be warmed up to 210 ℃ then, keep this temperature and stir 6h;
Remaining step is with (3)-(9) of embodiment 1, and the result charges to table 1.
Embodiment 6
(1). get oriental wormwood seed oil 120g, slowly cool to-4 ℃, and under this temperature, leave standstill 24h, again with 2000 rev/mins the centrifugal 10min of speed constant temperature (4 ℃), take out supernatant liquor (2). PEG400 62.35g is placed in the reactor, add KOH 30.12g again, under mechanical stirring, feed nitrogen protection and be heated to 120 ℃; (3). treat that KOH all after the dissolving adds the supernatant liquor in (1), continue to stir, under nitrogen protection, be warming up to 260 ℃, container is airtight, under this temperature, stir 2h; (4). reaction solution is cooled to adds 200 milliliters of 5% hydrochloric acid after the room temperature, stir 15min; (5). reaction solution is forwarded in the separating funnel, add petroleum ether extraction three times, the volume of each sherwood oil is 1/3 of a reaction solution cumulative volume; (6). merge petroleum ether layer and wash petroleum ether layer to neutral; (7). remove sherwood oil at 0.01MPa-0.1MPa, 60 ℃ of following concentrating under reduced pressure, promptly get the crude product of conjugated linolic acid.
Detection method is with embodiment 1, and the result charges to table 1
Implement 7
Get soybean oil 120g, slowly cool to-8 ℃, and under this temperature, leave standstill 24h,, take out supernatant liquor, replace the Thistle oil among the embodiment 1 with 2000 rev/mins the centrifugal 10min of speed constant temperature (4 ℃)
All the other steps are with the step 1-9 among the embodiment 1, and the result charges to table 1.
Example example 8
(1) but. at room temperature add 56.25g Semen Maydis oil in the encloses container, and be preheating to the aqueous solution of 80 ℃ 100ml 20%NaOH, feed nitrogen and also fully stir 2h down at 80 ℃.(2). change in the centrifuge tube after reacted solution is cooled to room temperature, with the centrifugal 10min of the speed of 2000 commentaries on classics/min.(3). in lower floor's solution, add the ethylene glycol solution of the urea of 400ml 30%, after stirring mixing solutions is placed 24h under-10 ℃ of environment.(4). mixed reaction solution is filtered, and filtrate is again with the centrifugal 10min of 1000 rev/mins speed.(5). lower floor's filtrate is taken out, and the content that records linoleate wherein is 85.16%; (7) but. lower floor's filtrate is gone in another encloses container, adds the NaOH of the 15g be preheating to 130 ℃ and the PEG600 of 30.54g, feed nitrogen simultaneously, temperature is risen to 140 ℃, and under this temperature, stir 8h.All the other steps are with the step among the embodiment 1 (3)-(9), and also with embodiment 1, the result charges to table 1 to detection method.
Embodiment 9
(1) but. at room temperature add 56.25g Semen Maydis oil in the encloses container, and be preheating to the propylene glycol solution 100ml of 80 ℃ 20% NaOH, feed nitrogen and also fully stir 2h down at 80 ℃.(3). in above-mentioned reaction solution, add the propylene glycol solution of the urea of 400ml 30%, after stirring mixing solutions is placed 24h under-4 ℃ of environment.(4). mixed reaction solution is filtered., the content that records the linoleate in the filtrate is 80.16%; (7) but. filtrate is gone in another encloses container, adds the NaOH of the 20g be preheating to 130 ℃, feed nitrogen simultaneously, temperature is risen to 160 ℃, and under this temperature, stir 6h.All the other steps are with the step among the embodiment 6 (4)-(9), and also with embodiment 1, the result charges to table 1 to detection method.
Embodiment 10
Change the Semen Maydis oil among the embodiment 9 into Oleum Gossypii semen, 20%NaOH solution changes 35% Na into
2CO
3, urine bag temperature changes 0 ℃ into, and all the other are with embodiment 9, and the result charges to table 1.
Detection method is with embodiment 1, and the result charges to table 1.
Table 1 conjugated linolic acid synthetic result
Implement
Example 1 example 2 examples 3 examples 4 examples 5 examples 6 examples 7 examples 8 examples 9 examples 10
CLA total content (%) * 83.88 76.24 77.21 68.0 72.61 82.32 70.22 86.51 72.74 62.83
Transformation efficiency (%)
*95.43 99.69 99.86 88.64 82.06 98.36 94.61 90.72 97.46 96.95
C9, the t11 isomer contains 36.51 15.62 35.51 28.30 10.87 17.51 33.73 33.73 31.64 30.42
Amount (%)
* *
T10, c12 isomer 37.16 12.75 34.16 30.47 16.00 12.16 35.10 35.10 30.16 27.94
Content (%)
*Content in this table all is to adopt area normalization method to calculate, and the CLA total content has comprised the total content of conjugated linolic acid in the conjugated linolic acid crude product of all configurations.
*Transformation efficiency is reaction back conjugated linolic acid and the ratio that reacts preceding linoleic chromatographic integration area.
* *C9, the t11 content of isomer refers to c9, t11 isomer shared per-cent in the conjugated linolic acid crude product.
Claims (11)
1. the method for a synthesis of conjugated linoleic acid contains following steps:
(1) with alkali in the polar solvent of non-water such as water-soluble or ethylene glycol, propylene glycol, glycerine, again with contain linoleic vegetables oil and mix and carry out saponification reaction, generate linoleate, linoleate is conjugation under the catalysis of 130 ℃-270 ℃ and alkali, generates conjugate linoleate; Described alkali refers to the salt of weak acid of alkali-metal oxyhydroxide or their solubility;
(2) add acid in the reaction solution in (1), conjugate linoleate is converted into conjugated linolic acid;
It is characterized in that after linoleate is converted into conjugate linoleate, not directly to add acid-respons, but add earlier a kind of material in the soluble salt of calcium hydroxide or calcium oxide or calcium, magnesium, iron, manganese, zinc, copper, aluminium etc., or add the mixture of forming by two or more above-mentioned substances, thereby the conjugate linoleate of solubility is converted into insoluble conjugate linoleate, and then insoluble conjugate linoleate is added acid dissolving generation conjugated linolic acid.
Synthesis of conjugated linoleic acid according to claim 1 method, it is characterized in that after linoleate is converted into conjugate linoleate, not directly to add acid-respons, but add earlier calcium hydroxide or calcium oxide or both mixtures the conjugate linoleate of solubility is converted into insoluble calcium conjugated linoleic acid, carries out acidifying again and prepare conjugated linolic acid.
3. the method for a synthesis of conjugated linoleic acid contains following steps:
(1) with alkali in the polar solvent of non-water such as water-soluble or ethylene glycol, propylene glycol, glycerine, again with contain linoleic vegetables oil and mix and carry out saponification reaction, generate linoleate, linoleate is conjugation under the catalysis of 130 ℃-270 ℃ and alkali, generates conjugate linoleate;
(2) in the reaction solution of (1), add acid, conjugate linoleate is converted into conjugated linolic acid;
It is characterized in that before saponification or earlier linolic acid is carried out carrying out next step reaction again after the enrichment after the saponification.
4. according to the method for each described synthesis of conjugated linoleic acid in the claim 1,2 or 3, it is characterized in that the polar solvent of non-water refers to polyoxyethylene glycol.
5. according to the method for each described synthesis of conjugated linoleic acid in the claim 1,2 or 3, it is characterized in that described acid, comprise mineral acid, as: hydrochloric acid, sulfuric acid, phosphoric acid etc. also comprise PK
aValue is less than 4 organic acid, as citric acid, oxalic acid, formic acid, acetate etc., also comprises the acid salt such as dihydrogen phosphate, hydrosulfate of solubility.
6. according to the method for each described synthesis of conjugated linoleic acid in the claim 1,2 or 3, it is characterized in that described alkali refers to sodium hydroxide or potassium hydroxide.
7. according to claim 1, the method of each described synthesis of conjugated linoleic acid in 2 or 3, it is characterized in that describedly containing linoleic vegetables oil and referring to linolic acid quality percentage composition, comprise Thistle oil, sunflower seed oil, common seepweed seeds oil, oriental wormwood seed oil, glasswort oil, sesame oil, Semen Maydis oil, soybean oil, Oenothera oil, raisin seed oil, Oleum Gossypii semen, water white gourd oil, Semen Cucumidis sativi oil, linseed oil, English walnut wet goods greater than 30% vegetables oil.
8. according to the method for each described synthesis of conjugated linoleic acid in the claim 1,2 or 3, the temperature that it is characterized in that conjugation is 170 ℃-185 ℃.
9. the method for synthesis of conjugated linoleic acid according to claim 3, what it is characterized in that the enrichment linolic acid adopts before the saponification is the low-temperature sludge method, the temperature that is adopted is 4 ℃--10 ℃.
10. the method for synthesis of conjugated linoleic acid according to claim 3, what it is characterized in that the enrichment linolic acid adopts after the saponification is urea adduct method, urine bag temperature is 4 ℃--15 ℃.
11. the method for synthesis of conjugated linoleic acid according to claim 10 is characterized in that the solvent that described urea adduct method adopts is ethylene glycol, propylene glycol or glycerine.
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| CNA031400485A CN1580030A (en) | 2003-08-04 | 2003-08-04 | Method for synthesizing conjugated linoleic acid |
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| CNA031400485A CN1580030A (en) | 2003-08-04 | 2003-08-04 | Method for synthesizing conjugated linoleic acid |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102086427A (en) * | 2011-01-17 | 2011-06-08 | 海南省粮油科学研究所 | Process for producing conjugated linoleic acid by using rubber seed oil |
| CN103012109A (en) * | 2012-12-12 | 2013-04-03 | 南京工业大学 | Preparation method for metal oleate |
| CN104672088A (en) * | 2015-02-12 | 2015-06-03 | 湖北华龙生物制药有限公司 | Method for preparing conjugated ethyl linoleate from Chinese tallow kernel oil |
| CN104673499A (en) * | 2013-11-28 | 2015-06-03 | 丰益(上海)生物技术研发中心有限公司 | Method for preparing conjugated linoleic acid |
| CN106565454A (en) * | 2016-10-20 | 2017-04-19 | 武汉藤欣生物工程有限公司 | Preparation method for conjugated linoleic acid |
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| CN110857270A (en) * | 2018-08-22 | 2020-03-03 | 大连医诺生物股份有限公司 | High-content conjugated linoleic acid triglyceride and preparation method thereof |
| CN113121332A (en) * | 2021-03-29 | 2021-07-16 | 湖南万象生物科技有限公司 | Method for reducing content of unsaponifiable matters in high-purity oleic acid |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102086427A (en) * | 2011-01-17 | 2011-06-08 | 海南省粮油科学研究所 | Process for producing conjugated linoleic acid by using rubber seed oil |
| CN102086427B (en) * | 2011-01-17 | 2013-11-13 | 海南省粮油科学研究所 | Process for producing conjugated linoleic acid by using rubber seed oil |
| CN103012109A (en) * | 2012-12-12 | 2013-04-03 | 南京工业大学 | Preparation method for metal oleate |
| CN103012109B (en) * | 2012-12-12 | 2015-06-03 | 南京工业大学 | Preparation method for metal oleate |
| CN104673499A (en) * | 2013-11-28 | 2015-06-03 | 丰益(上海)生物技术研发中心有限公司 | Method for preparing conjugated linoleic acid |
| CN104672088A (en) * | 2015-02-12 | 2015-06-03 | 湖北华龙生物制药有限公司 | Method for preparing conjugated ethyl linoleate from Chinese tallow kernel oil |
| CN106565454A (en) * | 2016-10-20 | 2017-04-19 | 武汉藤欣生物工程有限公司 | Preparation method for conjugated linoleic acid |
| CN108892609A (en) * | 2018-06-29 | 2018-11-27 | 菏泽中禾健元生物科技有限公司 | It is a kind of to prepare the linoleic method of high-purity using safflower seed oil |
| CN110857270A (en) * | 2018-08-22 | 2020-03-03 | 大连医诺生物股份有限公司 | High-content conjugated linoleic acid triglyceride and preparation method thereof |
| CN110257175A (en) * | 2019-06-20 | 2019-09-20 | 深圳市仙迪化妆品有限公司 | It is a kind of to prepare linoleic method and linoleic application using rose hip oil |
| CN113121332A (en) * | 2021-03-29 | 2021-07-16 | 湖南万象生物科技有限公司 | Method for reducing content of unsaponifiable matters in high-purity oleic acid |
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