CN107216249A - A kind of preparation method of high-quality CLA - Google Patents
A kind of preparation method of high-quality CLA Download PDFInfo
- Publication number
- CN107216249A CN107216249A CN201610164578.XA CN201610164578A CN107216249A CN 107216249 A CN107216249 A CN 107216249A CN 201610164578 A CN201610164578 A CN 201610164578A CN 107216249 A CN107216249 A CN 107216249A
- Authority
- CN
- China
- Prior art keywords
- cla
- preparation
- short
- chain alcohol
- alcohol ester
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/02—Preparation of carboxylic acids or their salts, halides or anhydrides from salts of carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C57/00—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms
- C07C57/02—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms with only carbon-to-carbon double bonds as unsaturation
- C07C57/03—Monocarboxylic acids
- C07C57/12—Straight chain carboxylic acids containing eighteen carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/03—Preparation of carboxylic acid esters by reacting an ester group with a hydroxy group
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Fats And Perfumes (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a kind of preparation method of high-quality CLA, the preparation method comprises the following steps：1) preparation and purification of aliphatic acid short-chain alcohol ester；2) base catalyst stirring under nitrogen protection, is added into aliphatic acid short-chain alcohol ester and carries out catalytic isomerization reaction, CLA short-chain alcohol ester is obtained；3) CLA short-chain alcohol ester is added to progress saponification in aqueous alkali and obtains CLA soap；4) acidification reaction is carried out using phosphoric acid；And 5) the molecular distillation after low temperature crystallization, obtain the CLA of high-quality.The present invention solves the problem of existing process is present, and the CLA product content produced is high, and trans body ratio is low, and acid number is high, lighter color, stable storing, without undesirable substance generation.
Description
Technical field
The present invention relates to the preparation method of CLA, especially a kind of dependence to raw material
Low, trans body ratio is low, acid number is high, lighter color, stable storing, the Gao Pin without bad component
The preparation method of matter CLA.
Background technology
CLA (Conjugated Linoleic Acid, abbreviation CLA) is the sub- oil of a class
The position of acid and the conjugated diene isomers in space, 9 is suitable, 11 trans- CLAs (9c,
11t-CLA) anti-with 10,12 cis- CLAs (10t, 12c-CLA) are its two kinds of masters
The active component wanted, with anticancer, prevents artery sclerosis, fat-reducing, strengthen immunity and increasing
Strong cell is to physiological functions such as the resistances of free radical.
Current CLA is main with different by base catalysis rich in linoleic crude vegetal
Prepared by structure method, safflower seed oil is high due to linoleic acid content, is to realize that industrialized production is total at present
The unique raw material of conjugated linoleic acid.It can be divided mainly into the technique that safflower seed oil prepares CLA
Two classes, a class be using safflower seed oil as raw material, using single hydroxyl alcohol or polyhydroxy-alcohol as solvent,
Isomerization and saponification are carried out simultaneously under the catalysis of the alkali such as NaOH or KOH, must be conjugated after acidifying
Linoleic acid；Another kind of is first to carry out isomerization reaction after safflower seed oil alcoholysis, then must be total to through hydrolyzing
Conjugated linoleic acid, this two classes method has the advantages that certain, but there is also certain deficiency.Safflower
Seed oil fatty acid composition is as follows：
No. 12 bulletin approval CLA of Ministry of Health of the People's Republic of China 2009 year is new
Resource food, has carried out detailed regulation, it is desirable in product to the quality requirement of CLA
Cla levels 78-84%, wherein 9c, 11t and 10t, two kinds of content of isomer of 12c will
Reach 37.5%-42%, C18:2,9c, 12c are less than 3%, and all trans isomer content is less than 1%.
The production technology reported at present is difficult to reach whole requirements, in addition the product of existing process production
The indexs such as acid number, color and luster, low-temperature storage state are even more that Cen can not joined.
US6822104 discloses a kind of preparation method of CLA, and method is with rich in sub- oil
The vegetable oil of acid is raw material, using high-boiling point alcohols such as polyethylene glycol, propane diols as solvent, in highly basic
Catalysis under saponification isomerization synchronously carry out, after acidifying CLA.This method technique stream
Journey is fairly simple, but there is certain defect, such as using glyceride as raw material, it is difficult to purify
Its linoleic acid content is improved, causes the content of CLA in final products to be determined completely by raw material
It is fixed, and the content of conventional Linoleic Acid in Safflower Oil is generally below 80%, add conjugation conversion ratio,
The influence of the factors such as other isomer proportions, the CLA obtained by the technique is difficult to reach matter
The requirement of amount standard；Only once it is acidified after the other technique isomerization, gained free acid
In will certainly be mingled with and be necessarily acidified incomplete soap, influence the acid number of product.
US0225142 is utilized and methyl linoleate is prepared after alcoholysis rich in linoleic vegetable oil
Or ethyl ester, then prepare acidifying water after conjugate linoleate, saponification after potassium alcoholate or sodium alkoxide catalysis
Wash, obtain CLA product.The technique can be by the short chain alcohol that is produced to vegetable oil alcoholysis
Ester purifies to improve linoleic content, solves the problem of product purity is completely dependent on raw material.
Though the product that the technique productions go out can meet basic quality requirement, to the saturation in product
Fatty acid component is not handled, and these saturation component fusing points are higher, and product is in storage duration
Time will certainly produce solid precipitation, cause product muddy, influence product sensory quality.It is identical
The problem of in the patents such as CN101565373, CN102605013, CN104725217
In the presence of.
In the linoleic preparation technology that CN101438740 is mentioned, reaction temperature reaches
More than 160 DEG C, high temperature can cause increasing for the trans body of CLA, and product is unsatisfactory for quality
It is required that in " trans body content be less than 1% " requirement.Further, since having few in reaction system
Measure glycerine to exist, trimethoxypropane gave had under the process conditions or triethoxy propane is produced,
There is potential quality safety risk.
To being acidified after linoleic acid isomerization in the patents such as US7241910 and US0189817,
Degassing is washed after layering, later-stage utilization decrease temperature crystalline improves the purity of product.Although the technique
Yield is higher, and single acidifying can not be acidified soap therein completely, and product acid number is not high, Er Qiedan
The content effect that net income improves CLA with decrease temperature crystalline is limited, and product content is difficult to reach
To quality requirement, finished product is not refined in addition, the peroxide produced in isomerization process
Compound, condensate etc. cause product color deeper.
All in all, the preparation technology of current CLA has certain deficiency, raw
Or the CLA of production is difficult to reach quality requirement, lack or product quality has certain
Fall into, be mainly manifested in the following aspects：1) raw material dependence is strong.Directly with containing linoleic acid
Vegetable oil be raw material, it is difficult to linoleic acid content therein is improved by conventional means of purification,
Cla levels do not reach quality requirement in finished product, can only rely on linoleic acid content high
Vegetable oil is produced.2) trans-isomer content is high.Because isomerization reaction temperature is higher,
Alltrans CLA is easily produced, trans body content exceedes the 1% of quality criteria requirements.3)
Acid number is low.Containing incomplete soap is acidified in product, cause product acid number low.4) color and luster is deep.
Without by refining in finished product, the component such as soap, condensate that isomerization is produced remains in product
In, cause product color deeper.5) store unstable.When being stored under cryogenic conditions, fusing point
Higher aliphatic acid can crystallize precipitation and form precipitation, and product is in cloudy state.6) bad group is contained
Point.Without the removal glycerol derivatives such as glycerine or glyceride, isomerization completely before isomerization
Trimethoxypropane gave is had in reaction or triethoxy propane is produced, there is potential quality safety wind
Danger.
The content of the invention
The technical problems to be solved by the invention are to overcome what above-mentioned prior art was present to lack
It is sunken that there is provided cla levels prepared by a kind of preparation method of CLA, this method
It is high and to the dependence of raw material is low, trans body ratio is low, acid number is high, lighter color, stable storing,
Without bad component.
The technical problem to be solved in the present invention is to provide for a kind of high-quality CLA
Preparation method, the preparation method comprises the following steps：1) preparation of aliphatic acid short-chain alcohol ester
And purifying；2) its quality 2~10% under nitrogen protection, is added into aliphatic acid short-chain alcohol ester
Base catalyst, stirring carries out catalytic isomerization reaction at 90-120 DEG C, obtains CLA
Short-chain alcohol ester；3) CLA short-chain alcohol ester is added in aqueous alkali in saponification
Saponification is carried out at 50-90 DEG C of temperature and obtains CLA soap；4) entered using phosphoric acid
Row acidification reaction, is acidified 70-90 DEG C of washing temperature, and being acidified to pH=6-7 and being layered immediately prevents
Resterification, discards lower floor, and oil layer utilizes sour water and pure water successively；And 5) through low
Molecular distillation after temperature crystallization, obtains the CLA of high-quality.
In the preferred technical solution of the present invention, it is preferable that step 1) described in aliphatic acid short chain
Alcohol ester is urged by vegetable oil of the linoleic acid weight/mass percentage composition more than 40% with short chain alcohol in alkalescence
It is made under agent effect by ester exchange reaction.
In the preferred technical solution of the present invention, it is preferable that step 1) described in short chain alcohol be
C1~C6 monohydric alcohols, the aliphatic acid short-chain alcohol ester is fatty acid methyl ester and/or fatty-acid ethyl ester.
In the preferred technical solution of the present invention, it is preferable that step 1) described in aliphatic acid short chain
The purifying of alcohol ester includes molecular distillation or rectifying.
In the preferred technical solution of the present invention, it is preferable that step 2) in the stirring reaction time be
Isomerisation conversion is surveyed in 3-5h, sampling, and linoleic acid content stops reaction when being less than 1%, obtained
CLA short-chain alcohol ester.
In the preferred technical solution of the present invention, it is preferable that the base catalyst include sodium methoxide,
Potassium methoxide, caustic alcohol, potassium ethoxide, sodium tert-butoxide, potassium tert-butoxide.
In the preferred technical solution of the present invention, it is preferable that step 2) described in CLA
Short-chain alcohol ester is CLA methyl esters and/or conjugated linoleic acid ethyl ester.
In the preferred technical solution of the present invention, it is preferable that the aqueous alkali is that quality percentage contains
Measure the NaOH aqueous solution or the KOH aqueous solution for 10-40%.
In the preferred technical solution of the present invention, it is preferable that step 3) in saponification time 1-4
The mol ratio of h, alkali and CLA short-chain ester is 1:1-2:1.
In the preferred technical solution of the present invention, it is preferable that step 4) in utilize phosphate aqueous solution
Repeated washing twice, pH=6-7 is washed till when being less than 5 to pH with pure water again.
In the preferred technical solution of the present invention, it is preferable that step 5) in crystallize when use gradient
Cooling, 1-1.5 DEG C/h is cooled to filtering after 5 DEG C, crystallization 24h and removes filter cake.
In the preferred technical solution of the present invention, it is preferable that step 5) in molecular distillation include two
Level, temperature is respectively less than 150 DEG C and 160-180 DEG C, vacuum 1-5Pa.
In the preferred technical solution of the present invention, it is preferable that the CLA tool of gained high-quality
There are following characteristics：Cla levels more than 80%, predominantly 9c, 11t-CLA and
Two kinds of configurations of 10t, 12c-CLA；Trans body content is less than 1%；Acid number is 195-205
mgKOH/g；Color and luster value is no more than 2；Cryopreservation is clarified, and no solid is separated out.
The problem of existing in view of prior art, the present invention will be enriched in linoleic vegetable oil first
Methyl esters or ethyl ester form are converted into by glyceride, the means such as molecular distillation or rectifying are then utilized
Raw material Linoleic acid content is improved, cla levels are solved in product to raw material dependence
Strong the problem of, while it also avoid glycerine and its derivative presence causes in later stage isomerization process
Produce the possibility of trimethoxypropane gave or triethoxy propane；The sub- oil of strong base catalyst is utilized afterwards
Acid esters is converted into conjugate linoleate, and reaction temperature is relatively low, and alltrans is reduced to greatest extent
The generation of body；And after be repeatedly acidified after saponification, it is to avoid be once acidified and do not remain thoroughly
The problem of soap, improve the acid number of product；Filter, eliminate wherein after low temperature crystallization again
The higher component of fusing point, improves stability during product storage, it was unexpected that passing through processing
The content of CLA has also obtained further raising in product afterwards；Finally steamed using molecule
Evaporate, further increase the organoleptic attributes such as smell, the color and luster of product.
What the present invention had has the prominent advantages that：1. it can be prepared according to different quality requirements higher
The CLA product of content, it is to avoid cla levels are merely determined by raw material in product
The problem of determining, gives birth to while the raw material after purified avoids undesirable substance in later stage isomerization process
Into possibility；2. isomerisation conditions are relatively mild, the generation of all trans isomer is greatly reduced；
3. many acidifyings, more completely improve product acid by saponified conversion for free fatty
Value；4. have passed through the processes such as crystallization, distillation, product storage stability and organoleptic attribute are improved.
Embodiment
The present invention is further illustrated with embodiment below, embodiments of the invention are merely to illustrate
Technical scheme, and the non-limiting present invention.
Embodiment 1
Linoleic acid content 78wt.% safflower seed oil 200g is taken, with 80 under the catalysis of sodium methoxide
The reaction of mL methanol prepares safflower seed oil methyl esters, and low boiling impurity is removed using common molecular distillation
After must refine safflower seed oil methyl esters be used for isomerization reaction.
Under the protection of nitrogen, 6g sodium methoxides, 110 DEG C are added into 100g safflower seed oil methyl esters
The content of linoleate is 0.8% after stirring reaction 3h, and CLA first is reacted to obtain in stopping
Ester.The NaOH aqueous solution that weight/mass percentage composition is 30% is added into CLA methyl esters
54g, 90 DEG C of stirring reaction 1h, add certain water regulation system viscosity, and phosphoric acid is added dropwise to body
It is that pH value is 6-7, stratification, discards and phosphoric acid water washing two is used at lower floor, 70 DEG C immediately
It is secondary to obtain CLA thick to system pH=6-7 less than 5, then with pure water to system pH
Product.
CLA crude product is down to 5 DEG C by normal temperature with 1 DEG C/h speed, 24 are stood still for crystals
H, filtering removes solid precipitation, and filtrate enters molecular distillation apparatus, vacuum 2Pa, 140 DEG C
Under steam light component, heavy constituent carries out second distillation at 170 DEG C, and distillate is that conjugation is sub-
Oleic acid product.
Products obtained therefrom CLA total content 82%, wherein all trans isomer content 0.7%,
The requirement that quality standard is less than 1% is met, product acid number 195mgKOH/g, product clarification is saturating
It is bright, close to colourless, place still clear and bright after one week at normal temperatures, nodeless mesh is separated out.
Embodiment 2
The sunflower oil 1000g of linoleic acid content 60% is taken, with 300 under the catalysis of caustic alcohol
ML ethanol synthesis prepares sunflower oil ethyl ester, is removed and is obtained after low boiling impurity using molecular distillation
Refined sunflower oil ethyl ester is used for isomerization reaction.
Under the protection of nitrogen, 10g caustic alcohols, 120 DEG C are added into 500g sunflower oil ethyl esters
The content of linoleate is 0.7% after stirring reaction 4h, and CLA second is reacted to obtain in stopping
Ester.The NaOH aqueous solution that weight/mass percentage composition is 10% is added into conjugated linoleic acid ethyl ester
1300g, 50 DEG C of stirring reaction 3h, it is 6-7 that phosphoric acid to system pH, which is added dropwise, is stood immediately
Layering, discards and is washed twice at lower floor, 80 DEG C with phosphoric acid water to system pH less than 5, then use
Pure water obtains CLA crude product to system pH=6-7.
CLA crude product is down to 5 DEG C by normal temperature with 1.5 DEG C/h speed, knot is stood
Brilliant 24h, filtering removes solid precipitation, and filtrate enters molecular distillation apparatus, vacuum 5Pa,
Light component is steamed at 150 DEG C, heavy constituent carries out second distillation at 180 DEG C, and distillate is
CLA product.
Products obtained therefrom CLA total content 80%, wherein all trans isomer content 0.8%,
The requirement that quality standard is less than 1% is met, product acid number 198mgKOH/g, product clarification is saturating
Bright, color and luster value is 2, places still clear and bright after one week at normal temperatures, and nodeless mesh is separated out.
Embodiment 3
The corn oil 2000g of linoleic acid content 50% is taken, with 700mL under the catalysis of potassium methoxide
Methanol reaction prepares methyl esters, is removed using rectifying and refined maize oil first is obtained after low boiling and height boiling impurity
Ester is used for isomerization reaction.
Under the protection of nitrogen, 40g potassium methoxides, 100 DEG C are added into 1000g corn oil methyl esters
The content of linoleate is 0.5% after stirring reaction 5h, and CLA first is reacted to obtain in stopping
Ester.The KOH aqueous solution 952 that weight/mass percentage composition is 40% is added into CLA methyl esters
G, 70 DEG C of stirring reaction 2h, add certain water regulation system viscosity, and phosphoric acid is added dropwise to body
It is that pH value is 6-7, stratification, discards and phosphoric acid water washing two is used at lower floor, 90 DEG C immediately
It is secondary to obtain CLA thick to system pH=6-7 less than 5, then with pure water to system pH
Product.
CLA crude product is down to 5 DEG C by normal temperature with 1 DEG C/h speed, 24 are stood still for crystals
H, filtering removes solid precipitation, and filtrate enters molecular distillation apparatus, vacuum 1-2Pa, 140 DEG C
Under steam light component, heavy constituent carries out second distillation at 160 DEG C, and distillate is that conjugation is sub-
Oleic acid product.
Products obtained therefrom CLA total content 83%, wherein all trans isomer content 0.8%,
The requirement that quality standard is less than 1% is met, product acid number 199mgKOH/g, product clarification is saturating
Bright, color and luster value is 2, and refrigeration places still clear and bright after 48h in refrigerator, and nodeless mesh is separated out.
Embodiment 4
The soybean oil 1000g of linoleic acid content 40% is taken, with 400mL under the catalysis of potassium ethoxide
Ethanol synthesis prepares soybean oil ethyl ester, is gone using some means of purification including rectifying after the removal of impurity
Obtaining refined soybean oil ethyl ester is used for isomerization reaction.
Under the protection of nitrogen, 100g potassium ethoxides, 90 DEG C are added into 1000g soybean oil ethyl esters
The content of linoleate is 0.3% after stirring reaction 5h, and CLA second is reacted to obtain in stopping
Ester.The KOH aqueous solution 909 that weight/mass percentage composition is 40% is added into conjugated linoleic acid ethyl ester
G, 50 DEG C of stirring reaction 4h, add certain water regulation system viscosity, and phosphoric acid is added dropwise to body
It is that pH value is 6-7, stratification, discards and phosphoric acid water washing two is used at lower floor, 70 DEG C immediately
It is secondary to obtain CLA thick to system pH=6-7 less than 5, then with pure water to system pH
Product.
CLA crude product is down to 5 DEG C by normal temperature with 1-1.5 DEG C/h speed, knot is stood
Brilliant 24h, filtering removes solid precipitation, and filtrate enters molecular distillation apparatus, vacuum 5Pa,
Light component is steamed at 150 DEG C, heavy constituent carries out second distillation at 180 DEG C, and distillate is
CLA product.
Products obtained therefrom CLA total content 80%, wherein all trans isomer content 0.2%,
The requirement that quality standard is less than 1% is met, product acid number 205mgKOH/g, product clarification is saturating
Bright, color and luster value is 2, and refrigeration places still clear and bright after 48h in refrigerator, and nodeless mesh is separated out.
Embodiment 5
The soybean oil 2000g of linoleic acid content 40% is taken, with 700 under the catalysis of sodium tert-butoxide
ML ethanol synthesis prepares soybean oil ethyl ester, and removal of impurities is gone using some means of purification including rectifying
Refined soybean oil ethyl ester is obtained after matter is used for isomerization reaction.
Under the protection of nitrogen, 30g sodium tert-butoxides are added into 1000g soybean oil ethyl esters,
The content of linoleate is 0.4% after 100 DEG C of stirring reaction 4h, and stopping, which is reacted, must be conjugated sub- oil
Acetoacetic ester.
The NaOH aqueous solution that weight/mass percentage composition is 30% is added into conjugated linoleic acid ethyl ester
500g, 60 DEG C of stirring reaction 3h, add certain water regulation system viscosity, and phosphoric acid is added dropwise
It is 6-7 to system pH, stratification, discards and washed at lower floor, 70 DEG C with phosphoric acid immediately
Wash and be less than 5 to system pH twice, then with pure water to system pH=6-7, sub- oil must be conjugated
Acid crude.
CLA crude product is down to 5 DEG C by normal temperature with 1-1.5 DEG C/h speed, knot is stood
Brilliant 24h, filtering removes solid precipitation, and filtrate enters molecular distillation apparatus, vacuum 3Pa,
Light component is steamed at 150 DEG C, heavy constituent carries out second distillation at 170 DEG C, and distillate is
CLA product.
Products obtained therefrom CLA total content 82%, wherein all trans isomer content 0.3%,
The requirement that quality standard is less than 1% is met, product acid number 197mgKOH/g, product clarification is saturating
Bright, color and luster value is 2, and refrigeration places still clear and bright after 48h in refrigerator, and nodeless mesh is separated out.
Embodiment 6
The soybean oil 2000g of linoleic acid content 50% is taken, with 900 under the catalysis of potassium tert-butoxide
ML ethanol synthesis prepares soybean oil ethyl ester, and removal of impurities is gone using some means of purification including rectifying
Refined soybean oil ethyl ester is obtained after matter is used for isomerization reaction.
Under the protection of nitrogen, 20g potassium tert-butoxides are added into 1000g soybean oil ethyl esters,
The content of linoleate is 0.2% after 90 DEG C of stirring reaction 3h, and stopping, which is reacted, must be conjugated sub- oil
Acetoacetic ester.
The KOH aqueous solution that weight/mass percentage composition is 40% is added into conjugated linoleic acid ethyl ester
460g, 80 DEG C of stirring reaction 2h, add certain water regulation system viscosity, and phosphoric acid is added dropwise extremely
System pH is 6-7, immediately stratification, discards and uses phosphoric acid water washing at lower floor, 80 DEG C
It is less than 5 to system pH twice, then CLA is obtained to system pH=6-7 with pure water
Crude product.
CLA crude product is down to 5 DEG C by normal temperature with 1-1.5 DEG C/h speed, knot is stood
Brilliant 24h, filtering removes solid precipitation, and filtrate enters molecular distillation apparatus, vacuum 3Pa,
Light component is steamed at 150 DEG C, heavy constituent carries out second distillation at 180 DEG C, and distillate is
CLA product.
Products obtained therefrom CLA total content 83%, wherein all trans isomer content 0.5%,
The requirement that quality standard is less than 1% is met, product acid number 200mgKOH/g, product clarification is saturating
Bright, color and luster value is 2, and refrigeration places still clear and bright after 48h in refrigerator, and nodeless mesh is separated out.
Embodiment 7
According to " the method progress check experiment of embodiment 6 ", the preparation of soybean oil ethyl ester,
Isomerization, saponification process are all and " embodiment 6 " is identical, when to saponified acidifying, utilizes
Phosphoric acid is neutralized to pH value and washed for direct layering after 6-7, is no longer repeated to wash with phosphate aqueous solution
Wash twice.
Into molecular distillation apparatus, vacuum 3Pa steams light component at 150 DEG C, recombinated
Divide and second distillation is carried out at 180 DEG C, distillate is CLA product.With embodiment
The Comparative result of CLA product such as table 1 below in 6：
Table 1
| Acid number (mgKOH/g) | Content | Color and luster value | Refrigerate 48h | |
| Embodiment 6 | 200 | 83% | 2 | It is clear and bright |
| Embodiment 7 | 185 | 82% | 3 | It is muddy |
As can be seen from Table 1, the CLA product acid prepared fully according to the present invention
Value is higher, stores more stable, quality is higher.
The present invention is illustrated by above embodiment, it is understood, however, that this hair
It is bright to be not limited to particular example as described herein and embodiment.It is special comprising these herein
The purpose of example and embodiment is to help the those of skill in the art practice present invention.Appoint
What those of skill in the art is easy to without departing from the spirit and scope of the present invention
It is further improved and perfect, therefore the present invention is only by the content of the claims in the present invention
With the limitation of scope, its intention covers all this hairs for being included in and being limited by appendix claim
Alternative and equivalent in bright spirit and scope.
Claims (13)
1. a kind of preparation method of high-quality CLA, the preparation method includes following
Step：
1) preparation and purification of aliphatic acid short-chain alcohol ester；
2) alkali of its quality 2~10% under nitrogen protection, is added into aliphatic acid short-chain alcohol ester
Property catalyst, stirring carries out catalytic isomerization reaction at 90-120 DEG C, obtains CLA short chain
Alcohol ester；
3) CLA short-chain alcohol ester is added in aqueous alkali in saponification temperature
Saponification is carried out at 50-90 DEG C and obtains CLA soap；
4) acidification reaction is carried out using phosphoric acid, is acidified 70-90 DEG C of washing temperature, is acidified to
PH=6-7 is layered immediately prevents resterification, discards lower floor, and oil layer utilizes sour water and pure successively
Water washing；And
5) molecular distillation after low temperature crystallization, obtains the CLA of high-quality.
2. preparation method as claimed in claim 1, wherein, step 1) described in fat
Sour short-chain alcohol ester is existed by vegetable oil of the linoleic acid weight/mass percentage composition more than 40% with short chain alcohol
It is made under base catalyst effect by ester exchange reaction.
3. preparation method as claimed in claim 1, wherein, step 1) described in short chain
Alcohol is C1~C6 monohydric alcohols, and the aliphatic acid short-chain alcohol ester is fatty acid methyl ester and/or aliphatic acid
Ethyl ester.
4. preparation method as claimed in claim 1, wherein, step 1) described in fat
The purifying of sour short-chain alcohol ester includes molecular distillation or rectifying.
5. preparation method as claimed in claim 1, wherein, step 2) in stirring reaction
Time is 3-5h, and isomerisation conversion is surveyed in sampling, and linoleic acid content stops reaction when being less than 1%,
Obtain CLA short-chain alcohol ester.
6. preparation method as claimed in claim 1, wherein, the base catalyst includes
Sodium methoxide, potassium methoxide, caustic alcohol, potassium ethoxide, sodium tert-butoxide, potassium tert-butoxide.
7. preparation method as claimed in claim 1, wherein, step 2) described in be conjugated
Linoleic acid short-chain alcohol ester is CLA methyl esters and/or conjugated linoleic acid ethyl ester.
8. preparation method as claimed in claim 1, wherein, the aqueous alkali is quality
Percentage composition is the 10-40% NaOH aqueous solution or the KOH aqueous solution.
9. preparation method as claimed in claim 1, wherein, step 3) in saponification
The mol ratio of time 1-4h, alkali and CLA short-chain ester is 1:1-2:1.
10. preparation method as claimed in claim 1, wherein, step 4) in utilize phosphoric acid
Aqueous solution repeated washing twice, pH=6-7 is washed till when being less than 5 to pH with pure water again.
11. preparation method as claimed in claim 1, wherein, step 5) in adopt when crystallizing
With gradient cooling, 1-1.5 DEG C/h is cooled to filtering after 5 DEG C, crystallization 24h and removes filter cake.
12. preparation method as claimed in claim 1, wherein, step 5) in molecular distillation
Including two-stage, temperature is respectively less than 150 DEG C and 160-180 DEG C, vacuum 1-5Pa.
13. preparation method as claimed in claim 1, wherein, the conjugation of gained high-quality is sub-
Oleic acid has following characteristics：Cla levels more than 80%, predominantly 9c, 11t-CLA and
Two kinds of configurations of 10t, 12c-CLA；Trans body content is less than 1%；Acid number is 195-205
mgKOH/g；Color and luster value is no more than 2；Cryopreservation is clarified, and no solid is separated out.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610164578.XA CN107216249A (en) | 2016-03-22 | 2016-03-22 | A kind of preparation method of high-quality CLA |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610164578.XA CN107216249A (en) | 2016-03-22 | 2016-03-22 | A kind of preparation method of high-quality CLA |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107216249A true CN107216249A (en) | 2017-09-29 |
Family
ID=59927269
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610164578.XA Pending CN107216249A (en) | 2016-03-22 | 2016-03-22 | A kind of preparation method of high-quality CLA |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107216249A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109134237A (en) * | 2018-04-18 | 2019-01-04 | 邯郸晨光珍品油脂有限公司 | A kind of production method of conjugated linoleic acid |
| CN109516623A (en) * | 2018-11-16 | 2019-03-26 | 浙江万盛股份有限公司 | A kind of method of comprehensive utilization of tri butylethyl phosphate waste water |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101032278A (en) * | 2007-02-08 | 2007-09-12 | 大连医诺生物有限公司 | Combination including calcium conjugated linoleic acid and producing method thereof |
| CN104725217A (en) * | 2015-02-27 | 2015-06-24 | 蓬莱市海洋生物有限公司 | Production process of conjugated linoleic acids |
-
2016
- 2016-03-22 CN CN201610164578.XA patent/CN107216249A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101032278A (en) * | 2007-02-08 | 2007-09-12 | 大连医诺生物有限公司 | Combination including calcium conjugated linoleic acid and producing method thereof |
| CN104725217A (en) * | 2015-02-27 | 2015-06-24 | 蓬莱市海洋生物有限公司 | Production process of conjugated linoleic acids |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109134237A (en) * | 2018-04-18 | 2019-01-04 | 邯郸晨光珍品油脂有限公司 | A kind of production method of conjugated linoleic acid |
| CN109134237B (en) * | 2018-04-18 | 2021-07-06 | 邯郸晨光珍品油脂有限公司 | Production method of conjugated linoleic acid |
| CN109516623A (en) * | 2018-11-16 | 2019-03-26 | 浙江万盛股份有限公司 | A kind of method of comprehensive utilization of tri butylethyl phosphate waste water |
| CN109516623B (en) * | 2018-11-16 | 2021-06-01 | 浙江万盛股份有限公司 | Comprehensive utilization method of tributoxyethyl phosphate wastewater |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP2011527319A (en) | Extraction method of squalene, sterol and vitamin E contained in physically refined condensate and / or deodorized distillate of vegetable oil | |
| TW200920840A (en) | Method of fractionating 1, 3-disaturated-2-unsaturated triglyceride | |
| CN101591586A (en) | Secondary fractionation product of palm oil and preparation method thereof | |
| CN105001297B (en) | A kind of method extracting plant sterol from plant asphalt | |
| CN103238846B (en) | Alpha-linolenic acid soft capsule | |
| CN102224854A (en) | Method for producing flaxseed oil under nitrogen protection | |
| CN109574826A (en) | A kind of preparation method of high-purity oleic acid | |
| CN107216249A (en) | A kind of preparation method of high-quality CLA | |
| JP2002542161A (en) | How to recover plant sterols | |
| CN102559394A (en) | Low-calorie edible vegetable oil preparation technology | |
| CN105638932B (en) | Low-antiform acid basic oil of one species butter characteristic and preparation method thereof | |
| CN105779140A (en) | Preparation method of ethyl ester type fish oil with high EPA content | |
| CN110668945B (en) | Method for extracting DHA and EPA in fish oil by combining supercritical fluid | |
| CN101125845A (en) | Method for separating and preparing tocopherol from cottonseed oil deordorization distillate | |
| CN101538306A (en) | Preparation method of phytosterin ester rich in oleic acid | |
| CN104711112A (en) | Method for realization of combined production of high quality rice bran oil and ferulic acid from rice bran | |
| CN104151282A (en) | Method for preparing natural vitamin E and phytosterol with resin absorption method | |
| CN106565454A (en) | Preparation method for conjugated linoleic acid | |
| CN100516188C (en) | Method for preparing fatty acid | |
| CN104529746A (en) | Method for synthesizing dimer acid by compounding catalyst | |
| US11781088B2 (en) | Process for the production and purification of sterols | |
| CN1830993A (en) | Method for producing mixture of phytosterol and vitamin E | |
| CN105132153A (en) | Method for preparing squid liver oil | |
| CN102605013B (en) | Preparation method of conjugated linoleic acid short-chain alcohol ester | |
| CN105861162A (en) | Preparation method of aliphatic ester by using solid catalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20170929 |
|
| RJ01 | Rejection of invention patent application after publication |