CN109609285A - A kind of preparation method of fatty acid mixed - Google Patents
A kind of preparation method of fatty acid mixed Download PDFInfo
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- CN109609285A CN109609285A CN201811526464.0A CN201811526464A CN109609285A CN 109609285 A CN109609285 A CN 109609285A CN 201811526464 A CN201811526464 A CN 201811526464A CN 109609285 A CN109609285 A CN 109609285A
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- oil
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- fatty acid
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Classifications
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
- C11C1/00—Preparation of fatty acids from fats, fatty oils, or waxes; Refining the fatty acids
- C11C1/02—Preparation of fatty acids from fats, fatty oils, or waxes; Refining the fatty acids from fats or fatty oils
- C11C1/04—Preparation of fatty acids from fats, fatty oils, or waxes; Refining the fatty acids from fats or fatty oils by hydrolysis
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
- C11C1/00—Preparation of fatty acids from fats, fatty oils, or waxes; Refining the fatty acids
- C11C1/08—Refining
Abstract
The present invention relates to the preparation technical fields of fatty acid, and in particular to a kind of preparation method of fatty acid mixed.The present invention provides a kind of preparation methods of fatty acid mixed, comprising the following steps: reaction is hydrolyzed in grease under neopelex, pyrrolidonium ionic liquids and water existence condition, obtains fatty acid mixed.The present invention is played the effect of enhancing oil-water emulsion, is reduced the temperature of hydrolysis, promote the progress of hydrolysis using neopelex as emulsifier.The present invention is using pyrrolidonium ionic liquids as catalyst, and catalytic activity is high, at low cost, toxicity is low and can recycle.Preparation method of the invention is easy to operate, suitable for scale production.Embodiment test result shows the percent hydrolysis of preparation method grease provided by the invention up to 97.11%；After pyrrolidonium ionic liquids are catalyzed rapeseed oil hydrolysis recycling 6 times, for percent hydrolysis still 94% or more, reusing is good.
Description
Technical field
The present invention relates to the preparation technical fields of fatty acid, and in particular to a kind of preparation method of fatty acid mixed.
Background technique
Fatty acid is essential raw chemical material in oil chemical industry.The trip generated by animal and plant fat hydrolysis
Soap, surfactant, lubricant, paint, food, cosmetics, drug etc. are commonly used for preparing from fatty acid.Biodiesel
It can be obtained by fatty acid and short chain alcohol through esterification, carbon chain length distribution is similar to fossil diesel fuel fuel.These lifes
Object fuel is the ideal substitute of petroleum based fuels and chemicals.
Animal and plant fat is hydrolyzed into fatty acid and chemical method or biological method is generally used to carry out.Wherein, biological method master
If through Lipase catalyzed hydrolysis.The hydrolysis of lipase-catalyzed animal and plant fat can carry out in a mild condition, generally in normal pressure
Lower progress, reaction temperature 308K.But the higher cost of enzyme, it is not applied for commercial process.
For chemical method, Colgate-Emery technique be produce fatty acid common industrial technique, operating condition compared with
For harshness, usually require that operating temperature is 250 DEG C, reaction pressure 5MPa, and under high temperature and pressure, triglycerides and by
They, which crack the fatty acid generated, can occur the side reactions such as oxidation, dehydration and transesterification, cause product fatty acid rotten.
Twitchell lipolysis process be by Twitchell reagent under the conditions of relatively mild (373K and 1atm) into
Capable catalytic reaction process, still, Twitchell reagent are mainly made of hydrocarbon, oleic acid and the concentrated sulfuric acid, and use is this
Strong inorganic acid catalyst will increase the corrosion of equipment, and generate a large amount of industrial wastewater.
Currently, solid super acid catalyst is successfully used for grease hydrolysis into free fatty acid, such as Ngaosuwan
Deng (referring to Ngaosuwan, K., Lotero, E., Suwannakarn, K., Goodwin Jr, J.G., Praserthdam, P.
(2009).Hydrolysis of triglycerides using solid acid
Catalysts.Ind.Eng.Chem.Res., 48 (10), 4757-4767.doi:10.1021/ie8013988.) it reports
The solid acid catalyst that the tungsten wire array and nanometer Nafion resin particle loaded on mesoporous silicon oxide is constituted, it is pungent for hydrolyzing three
Acid glyceride；The reaction process carries out in semibatch reactor, normal pressing operation, and reaction temperature is 110~150 DEG C, water
It is continuously added in a manner of low flow velocity.Satyarthi etc. (referring to Satyarthi, J.K., Srinivas, D., Ratnasamy,
P.(2011).Hydrolysis of vegetable oils and fats to fatty acids over solid acid
catalysts.Appl.Catal.A-Gen. 391(1-2),427-435.doi:10.1016/
J.apcata.2010.03.047.) using solid Fe-Zn double metal cyanide (DMC) complex as vegetable oil and animal oil
The catalyst of rouge hydrolysis, in normal pressure, temperature is 190 DEG C, under the conditions of catalyst amount is the 5% of grease weight, catalyst choice
Property is up to 73% or more.However, above-mentioned solid acid catalyst is easy inactivation, and regeneration is extremely difficult.
Ionic liquid (Ionic liquids, ILs) is due to good thermal stability, outstanding dissolubility, reliable
Fixedness, adjustable physics and chemical property, and it is widely used as green solvent and catalyst.In the prior art for urging
The ionic liquid for changing grease hydrolysis is mainly caprolactam, pyridine, imidazoles, triethylamine class ionic liquid, such as 1- (4- sulfonic group)
Butyl caprolactam disulfate ([HSO3-bCPL][HSO4]), 1- (4- sulfonic group) butyl-pyridinium disulfate ([HSO3-
bPy][HSO4]), 1- (4- sulfonic group) butyl -3- methylimidazolium hydrogen sulphate salt ([HSO3-bMIM][HSO4]), 1- (4- sulfonic acid
Base) butyl triethylamine disulfate ([HSO3-bTEA][HSO4]).But the synthesis material of these ionic liquids is at high cost, and
And reaction temperature is high, it is higher to equipment requirement and energy consumption.
Summary of the invention
The purpose of the present invention is to provide a kind of low reaction temperatures, low cost and it can be realized pyrrolidonium ionic liquids weight
The preparation method of the fatty acid mixed utilized again.
In order to achieve the above-mentioned object of the invention, the present invention the following technical schemes are provided:
The present invention provides a kind of preparation methods of fatty acid mixed, comprising the following steps: neopelex,
Reaction is hydrolyzed in grease under pyrrolidonium ionic liquids and water existence condition, obtains fatty acid mixed.
Preferably, the grease includes rapeseed oil, jatropha curcas oil, palm oil, cottonseed oil, soybean oil, peanut oil, walnut
One of oil, lard, butter, vegetable seed acidification oil, soybean acidified oil, palm acidification oil, cottonseed acidification oil and waste cooking oil or
It is several.
Preferably, the pyrrolidonium ionic liquids include n-methyl-2-pyrrolidone disulfate, N- methyl -2- pyrrole
Pyrrolidone methane sulfonates, 2-Pyrrolidone disulfate, 2-Pyrrolidone methane sulfonates, 1- (3- sulfonic group) propyl -1-
N-methyl-2-2-pyrrolidone N disulfate or 1- (3- sulfonic group) propyl -2- pyrrolidones disulfate.
Preferably, the mass ratio of the pyrrolidonium ionic liquids and grease is (0.1~0.2): 1.
Preferably, the mass ratio of the neopelex and grease is (0.02~0.04): 1.
Preferably, the mass ratio of the water and grease is (1.5~2.5): 1.
Preferably, the hydrolysis carries out in atmospheric conditions, and the temperature of the hydrolysis is 90~120 DEG C.
Preferably, after the hydrolysis further include: gained system is cooled to room temperature after terminating the hydrolysis, into
Row layering, obtains upper and lower phase；Wherein, the upper phase includes fatty acid mixed, and the lower phase includes glycerol, water, dodecane
Base benzene sulfonic acid sodium salt and pyrrolidonium ionic liquids.
Preferably, after obtaining the upper phase further include: the upper phase is successively carried out hot water washing and drying, is mixed
Fatty acid.
Preferably, after obtaining the lower phase further include: the lower phase is successively carried out air-distillation and vacuum distillation, is obtained
Pyrrolidonium ionic liquids.
The present invention provides a kind of preparation methods of fatty acid mixed, comprising the following steps: neopelex,
Reaction is hydrolyzed in grease under pyrrolidonium ionic liquids and water existence condition, obtains fatty acid mixed.The present invention is with 12
Sodium alkyl benzene sulfonate plays the effect of enhancing oil-water emulsion as emulsifier, reduces the temperature of hydrolysis, promotes hydrolysis
The progress of reaction, and neopelex is anionic surfactant, containing phenyl and sulfonate functional groups, in oil
The catalytic efficiency that acid catalyst can be enhanced in rouge hydrolytic process makes it play synergistic effect in the reaction.The present invention adopts
Use pyrrolidonium ionic liquids as catalyst, catalytic activity is high, at low cost, toxicity is low and can recycle.Of the invention
Preparation method is easy to operate, suitable for scale production.Embodiment test result shows preparation method grease provided by the invention
Percent hydrolysis is up to 97.11%；After pyrrolidonium ionic liquids are catalyzed rapeseed oil hydrolysis recycling 6 times, percent hydrolysis still exists
94% or more, reusing is good.
Specific embodiment
The present invention provides a kind of preparation methods of fatty acid mixed, comprising the following steps: neopelex,
Reaction is hydrolyzed in grease under pyrrolidonium ionic liquids and water existence condition, obtains fatty acid mixed.
In the present invention, the preparation method of the fatty acid mixed is preferably specifically includes the following steps: by detergent alkylate
Sodium sulfonate, pyrrolidonium ionic liquids, water and grease mixing, are hydrolyzed reaction, until gained reaction system under agitation
Acid value it is constant, hydrolysis terminate, obtain fatty acid mixed.
In the present invention, the grease is any animal and plant fat and waste grease, preferably includes rapeseed oil, Jatropha curcas
Oil, palm oil, cottonseed oil, soybean oil, peanut oil, walnut oil, lard, butter, vegetable seed acidification oil, soybean acidified oil, palmitinic acid
One or more of carburetion, cottonseed acidification oil and waste cooking oil.
In the present invention, the mass ratio of the water and grease is preferably (1.5~2.5): 1, more preferably (1.7~
2.3): 1, most preferably (1.9~2.1): 1.
In the present invention, the pyrrolidonium ionic liquids preferably include n-methyl-2-pyrrolidone disulfate
([HNMP]HSO4), n-methyl-2-pyrrolidone methane sulfonates ([HNMP]CH3SO3), 2-Pyrrolidone disulfate
([Hnhp]HSO4), 2-Pyrrolidone methane sulfonates ([Hnhp] CH3SO3), 1- (3- sulfonic group) propyl -1- methyl -2- pyrrole
Pyrrolidone disulfate ([C3SO3HNMP]HSO4) or 1- (3- sulfonic group) propyl -2-Pyrrolidone disulfate
([C3SO3Hnhp]HSO4).In the present invention, the mass ratio of the pyrrolidonium ionic liquids and grease be preferably (0.1~
0.2): 1, more preferably (0.12~0.18): 1, most preferably (0.14~0.16): 1.The present invention is with pyrrolidones ionic liquid
Body is catalyst, and catalytic activity is high, at low cost, toxicity is low and can recycle.
In the present invention, the mass ratio of the grease and neopelex is preferably 1:(0.02~0.04), more
Preferably 1:(0.025~0.035), most preferably 1:(0.028~0.033).In the present invention, by adding detergent alkylate
The effect of oil-water emulsion can be enhanced in sodium sulfonate emulsifier, reduces the temperature of hydrolysis, promotes the progress of hydrolysis.
The stirring is not particularly limited in the present invention, using agitating mode well known in the art, specifically such as
Using magnetic agitation mode, the revolving speed of the stirring is preferably 300-600r/min, more preferably 350-500r/min.
In the present invention, the hydrolysis preferably carries out in atmospheric conditions, and the temperature of the hydrolysis is preferably
90~120 DEG C, more preferably 95~115 DEG C, most preferably 100~110 DEG C；The present invention, which preferably passes through oil bath heating, makes reactant
System reaches the temperature of hydrolysis.
The present invention preferably terminates the hydrolysis when the acid value of reaction system is constant, and the acid value of reaction system is at this time
For the acid value of the product fatty acid mixed of hydrolysis, the acid value is preferably 140~210 mgKOH/g, more preferably 150~
200mgKOH/g, most preferably 160~190mgKOH/g.In the present invention, the method for the acid value measuring is GB/T 5530-
Method specified in 2005/ISO 660:1996, after obtaining the acid value, for calculating the percent hydrolysis of the grease, the water
The calculation formula of solution rate are as follows:
In formula, AV1: the initial acid value of raw material, mgKOH/g；
AV2: the acid value of product, mgKOH/g；
SV: the saponification number of raw material, mgKOH/g.
After hydrolysis terminates, system obtained by hydrolysis is preferably cooled to room temperature by the present invention, is layered, is obtained
Phase and lower phase.In the present invention, the upper phase preferably includes fatty acid mixed, and the lower phase preferably includes glycerol, water, dodecane
Base benzene sulfonic acid sodium salt and pyrrolidonium ionic liquids.
After obtaining the upper phase, the present invention it is also preferable to include: the upper phase is successively subjected to hot water washing and drying, is obtained
Fatty acid mixed.In the present invention, the hot water washing preferably includes to wash Xiang Sanci with the deionized water of heat, and removal is remaining
Catalyst and glycerol；The purity of fatty acid mixed can be improved using the deionized water washing of heat by the present invention.In the present invention for
The drying is not particularly limited, specific as dry using anhydrous sodium sulfate using drying mode well known in the art.
After obtaining the lower phase, present invention preferably comprises the lower phase is successively carried out air-distillation and vacuum distillation, obtain
To pyrrolidonium ionic liquids.In the present invention, the air-distillation preferably carries out under conditions of pressure is 1.01KPa, institute
Stating air-distillation is to remove extra water；In the present invention, system obtained by the air-distillation is carried out vacuum distillation is
In order to remove the glycerol of hydrolysis generation, pyrrolidonium ionic liquids are obtained, gained pyrrolidonium ionic liquids can repeat
It utilizes.The pressure of the vacuum distillation is preferably 0.3~0.5kPa, more preferably 0.4kPa, and temperature is preferably 150~170 DEG C,
More preferably 160 DEG C.
The present invention provides a kind of preparation methods of fatty acid mixed, comprising the following steps: neopelex,
Reaction is hydrolyzed in grease under pyrrolidonium ionic liquids and water existence condition, obtains fatty acid mixed.The present invention is with 12
Sodium alkyl benzene sulfonate plays the effect of enhancing oil-water emulsion, promotes the progress of hydrolysis, and dodecane as emulsifier
Base benzene sulfonic acid sodium salt is anionic surfactant, can play synergistic effect with pyrrolidonium ionic liquids in the reaction.
The present invention is using pyrrolidonium ionic liquids as catalyst, and catalytic activity is high, at low cost, toxicity is low and can recycle.
The present invention takes water as a solvent, and avoids the use of organic solvent, clean and environmental protection.Preparation method reaction condition of the invention is mild, right
The requirement of consersion unit is low, consumes energy low；And easy to operate, clean and environmental protection, it is suitable for scale production.Embodiment test result table
Bright, for the percent hydrolysis of preparation method grease provided by the invention up to 97.11%, pyrrolidonium ionic liquids are catalyzed vegetable seed grease
After recycling 6 times of solution, for percent hydrolysis still 94% or more, reusing is good.
Below in conjunction with the embodiment in the present invention, the technical solution in the present invention is clearly and completely described.It is aobvious
So, described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.Based on the reality in the present invention
Example is applied, every other embodiment obtained by those of ordinary skill in the art without making creative efforts all belongs to
In the scope of protection of the invention.
Embodiment 1
By 100g rapeseed oil, 200g deionized water, 4g neopelex, 10g n-methyl-2-pyrrolidone sulphur
Sour hydrogen salt ([HNMP]HSO4) be stirred, atmospheric pressure reflux 30h, the reaction terminating (acid of system are carried out in 100 DEG C of constant temperature oil baths
Value is 189.3mgKOH/g)；Gained system is cooled to room temperature, is layered, obtain include fatty acid mixed upper phase and packet
Include glycerol, water, neopelex and [HNMP]HSO4The lower phase of ionic liquid；The upper phase liquid is successively subjected to heat
Water washing is dry with anhydrous sodium sulfate three times, obtains fatty acid mixed；The lower phase liquid is successively subjected to air-distillation removal
Then extra water carries out the glycerol that vacuum distillation removal reaction obtains under the conditions of 0.4kPa, 160 DEG C, obtains [HNMP]HSO4
Ionic liquid.
The percent hydrolysis that rapeseed oil is calculated according to the acid value of system when reaction terminating, the results show that the hydrolysis of the rapeseed oil
Rate is 97.11%.
Embodiment 2
By 100g rapeseed oil, 150g deionized water, 4g neopelex, 15g 2-Pyrrolidone disulfate
([Hnhp]HSO4) be stirred, 48 h of atmospheric pressure reflux is carried out in 90 DEG C of constant temperature oil baths, (acid value of system is reaction terminating
167.14mgKOH/g)；Gained system is cooled to room temperature, is layered, obtains including the upper phase of fatty acid mixed and including sweet
Oil, water, neopelex and [Hnhp]HSO4The lower phase of ionic liquid；The supernatant liquid is successively subjected to hot water wash
It washs three times with anhydrous sodium sulfate drying, obtains fatty acid mixed；It is extra that the lower phase liquid is successively subjected to air-distillation removal
Water, vacuum distillation removal reaction obtained glycerol is then carried out under the conditions of 0.4kPa, 160 DEG C, obtains [Hnhp]HSO4Ion
Liquid, obtained [Hnhp]HSO4Ionic liquid can reuse.
The percent hydrolysis that rapeseed oil is calculated according to the acid value of system when reaction terminating, the results show that the hydrolysis of the rapeseed oil
Rate is 85.66%.
Embodiment 3
By 100g rapeseed oil, 200g deionized water, 3g neopelex, 20g 1- (3- sulfonic group) propyl -2-
Pyrrolidones disulfate ([C3SO3Hnhp]HSO4) be stirred, atmospheric pressure reflux 48h is carried out in 110 DEG C of constant temperature oil baths, instead
(acid value of system is 168.33mgKOH/g) should be terminated；Gained system is cooled to room temperature, is layered, obtains including mixing
The upper phase of fatty acid and including glycerol, water, neopelex and [C3SO3Hnhp]HSO4The lower phase of ionic liquid；By institute
It states supernatant liquid and successively carries out hot water washing three times with anhydrous sodium sulfate drying, obtain fatty acid mixed；By the lower phase liquid
It successively carries out air-distillation and removes extra water, it is sweet that vacuum distillation removal reaction is then carried out under the conditions of 0.4kPa, 160 DEG C
Oil obtains [C3SO3Hnhp]HSO4Ionic liquid, obtained [C3SO3Hnhp]HSO4Ionic liquid can reuse.
The percent hydrolysis that rapeseed oil is calculated according to the acid value of system when reaction terminating, the results show that the hydrolysis of the rapeseed oil
Rate is 86.28%.
Embodiment 4
By 100g curcas oil and palm oil, 180g deionized water, 2.5g neopelex, 12g N- methyl-
2-Pyrrolidone methane sulfonates ([HNMP]CH3SO3) be stirred, atmospheric pressure reflux 60h is carried out in 115 DEG C of constant temperature oil baths, instead
(acid value of system is 189.1mgKOH/g) should be terminated；Gained system is cooled to room temperature, is layered, obtains including mixing rouge
The upper phase of fat acid and including glycerol, water, neopelex and [HNMP]CH3SO3The lower phase of ionic liquid；By the upper phase
Liquid successively carries out hot water washing three times with anhydrous sodium sulfate drying, obtains fatty acid mixed；By the lower phase liquid successively into
Row air-distillation removes extra water, then carried out under the conditions of 0.4kPa, 160 DEG C vacuum distillation removal reaction obtain it is sweet
Oil obtains [HNMP]CH3SO3Ionic liquid, obtained [HNMP]CH3SO3Ionic liquid can reuse.
The percent hydrolysis that rapeseed oil is calculated according to the acid value of system when reaction terminating, the results show that the hydrolysis of the miscella
Rate is 92.3%.
Embodiment 5
By 100g lard, butter and soybean acidified oil, 180g deionized water, 2.8g neopelex, 17g 2-
Pyrrolidones methane sulfonates ([Hnhp]CH3SO3) be stirred, atmospheric pressure reflux 45h, reaction are carried out in 105 DEG C of constant temperature oil baths
Terminate (acid value of system is 172.3mgKOH/g)；Gained system is cooled to room temperature, is layered, obtains including mixing-in fat
Acid upper phase and including glycerol, water, neopelex and [Hnhp]CH3SO3The lower phase of ionic liquid；By the upper phase liquid
Body successively carries out hot water washing three times with anhydrous sodium sulfate drying, obtains fatty acid mixed；The lower phase liquid is successively carried out
Air-distillation removes extra water, and the glycerol that vacuum distillation removal reaction obtains then is carried out under the conditions of 0.4kPa, 160 DEG C,
Obtain [Hnhp]CH3SO3Ionic liquid, obtained [[Hnhp]CH3SO3Ionic liquid can reuse.
The percent hydrolysis that rapeseed oil is calculated according to the acid value of system when reaction terminating, the results show that the hydrolysis of the miscella
Rate is 88.5%.
Embodiment 6
By 100g peanut oil and walnut oil, 200g deionized water, 4g neopelex, 10g N- methyl -2- pyrrole
Pyrrolidone disulfate ([HNMP]HSO4) be stirred, atmospheric pressure reflux 30h, reaction terminating are carried out in 100 DEG C of constant temperature oil baths
(acid value of system is 184.7mgKOH/g)；Gained system is cooled to room temperature, is layered, obtains including fatty acid mixed
Upper phase and including glycerol, water, neopelex and [HNMP]HSO4The lower phase of ionic liquid；By the upper phase liquid according to
Secondary progress hot water washing is dry with anhydrous sodium sulfate three times, obtains fatty acid mixed；The lower phase liquid is successively subjected to normal pressure
Distillation removes extra water, and the glycerol that vacuum distillation removal reaction obtains then is carried out under the conditions of 0.4kPa, 160 DEG C, is obtained
[HNMP]HSO4Ionic liquid.
The percent hydrolysis that rapeseed oil is calculated according to the acid value of system when reaction terminating, the results show that the hydrolysis of the miscella
Rate is 94.7%.
Embodiment 7
Pyrrolidonium ionic liquids [the H that embodiment 1 is obtainedNMP]HSO4It is reused, catalysis rapeseed oil hydrolysis
Recycling effectiveness results are shown in Table 1.
1 [H of tableNMP]HSO4It is catalyzed the recycling number and effect of rapeseed oil hydrolysis
| Number of repetition | Acid value (mgKOH/g) | Percent hydrolysis (%) |
| 1 | 188.4 | 96.63 |
| 2 | 187.3 | 96.07 |
| 3 | 186.0 | 95.39 |
| 4 | 185.3 | 95.03 |
| 5 | 183.9 | 94.32 |
As shown in Table 1, after the pyrrolidonium ionic liquids that embodiment obtains reuse 5 times, the percent hydrolysis of rapeseed oil
Still 94% or more, the pyrrolidonium ionic liquids recycling rate of waterused for illustrating that the present invention uses is good, and pyrrolidones ion
The preparation of liquid is easy, toxicity is lower, and preparation method provided by the invention has more practical application value.
Reference examples 1
By 100g rapeseed oil, 200g deionized water, neopelex (respectively 0g, 1g, 2g, 3g, 4g and
5g), 10g n-methyl-2-pyrrolidone disulfate ([HNMP]HSO4) be stirred, it is carried out in 100 DEG C of constant temperature oil baths normal
Push back 6~60h of stream, reaction terminating.Respectively 6h, 12 h, 18h, for 24 hours, 30h, 36h, 42h, 48h, 54h and 60h be sampled
Analysis, sample is cooled to room temperature, is layered, and obtains including the upper phase of fatty acid mixed and including glycerol, water, detergent alkylate
Sodium sulfonate and [HNMP]HSO4The lower phase of ionic liquid；The upper phase liquid is successively subjected to hot water washing three times and anhydrous slufuric acid
Sodium is dry, obtains fatty acid mixed；The lower phase liquid is successively subjected to air-distillation and removes extra water, is then existed
0.4kPa, the glycerol that vacuum distillation removal reaction obtains is carried out under the conditions of 160 DEG C, obtain [HNMP]HSO4Ionic liquid.
Then, measure respectively 6h, 12h, 18h, for 24 hours, the differential responses time of 30h, 36h, 42h, 48h, 54h and 60h
Under hydrolysate acid value, and the percent hydrolysis of rapeseed oil is calculated according to the acid value of system under the return time, as a result such as table 2 and table
Shown in 3.
The hydrolysate acid value of 2 differential responses time of table rapeseed oil
The percent hydrolysis of 3 differential responses time of table rapeseed oil
By table 2 and table 3 it is found that when dodecyl benzene sulfonic acid emulsifier from the 1% of oil quality increase to 5% feelings
Under condition, before reaction carries out 6h, the percent hydrolysis of rapeseed oil does not have notable difference.However, rapeseed oil percent hydrolysis is poor after reacting 12h
It is different to become apparent from, and percent hydrolysis does not increase with the increase of emulsifier.When emulsifier is less than 4%
When, the percent hydrolysis of rapeseed oil increases with the increase of emulsifier.But when the amount of emulsifier is more than 4%, percent hydrolysis drops instead
It is low.This is because surfactant solution forms single-phase, two-phase, three-phase in its ratio when the concentration of surfactant is lower.With
The increase of surfactant concentration, surfactant solution form viscosity solution, gel or layered liquid crystal.Therefore, it obtains most
The concentration of the neopelex of big product acid value is the plyability of the surfactant solution by oil-containing and ionic liquid
What matter determined.Emulsifier additive amount is excessive, and after the completion of reaction, reaction mixture is not layered significantly.But meanwhile percent hydrolysis
Increase with the increase of hydrolysis time, when emulsifier is 2~4%, percent hydrolysis is almost constant after about 30h
Value, when emulsifier is 1% or 5%, percent hydrolysis also increase with time, but needs longer reaction time (54 h) ability
Reach reaction balance.The phenomenon that hydrolysis, illustrates, under conditions of normal pressure and reaction temperature lower (100 DEG C), hydrolysis
It may be since lower reaction temperature leads to lower reaction rate up to the reason of balance.In addition, this phenomenon also indicates that cream
The additional amount of agent dodecyl benzene sulfonic acid is very little or is all unfavorable for hydrolysis too much.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of preparation method of fatty acid mixed, comprising the following steps: in neopelex, pyrrolidones ionic liquid
Reaction is hydrolyzed in grease under body and water existence condition, obtains fatty acid mixed.
2. preparation method according to claim 1, which is characterized in that the grease includes rapeseed oil, jatropha curcas oil, palm
Oil, cottonseed oil, soybean oil, peanut oil, walnut oil, lard, butter, vegetable seed acidification oil, soybean acidified oil, palm acidification oil, cotton
One or more of seed acidification oil and waste cooking oil.
3. preparation method according to claim 1, which is characterized in that the pyrrolidonium ionic liquids include N- methyl-
2-Pyrrolidone disulfate, n-methyl-2-pyrrolidone methane sulfonates, 2-Pyrrolidone disulfate, 2-Pyrrolidone
Methane sulfonates, 1- (3- sulfonic group) propyl -1-Methyl-2-Pyrrolidone disulfate or 1- (3- sulfonic group) propyl -2- pyrrole
Pyrrolidone disulfate.
4. preparation method according to claim 1,2 or 3, which is characterized in that the pyrrolidonium ionic liquids and grease
Mass ratio be (0.1~0.2): 1.
5. preparation method according to claim 1 or 2, which is characterized in that the neopelex and grease
Mass ratio is (0.02~0.04): 1.
6. preparation method according to claim 1, which is characterized in that the mass ratio of the water and grease be (1.5~
2.5): 1.
7. preparation method according to claim 1, which is characterized in that the hydrolysis carries out in atmospheric conditions, institute
The temperature for stating hydrolysis is 90~120 DEG C.
8. preparation method according to claim 1, which is characterized in that after the hydrolysis further include: by the hydrolysis
Gained system is cooled to room temperature after reaction terminating, is layered, obtains upper and lower phase；Wherein, the upper phase includes mixing rouge
Fat acid, the lower phase includes glycerol, water, neopelex and pyrrolidonium ionic liquids.
9. preparation method according to claim 8, which is characterized in that after obtaining the upper phase further include: by the upper layer
Liquid successively carries out hot water washing and drying, obtains fatty acid mixed.
10. preparation method according to claim 8, which is characterized in that after obtaining the lower phase further include: by the lower phase
Air-distillation and vacuum distillation are successively carried out, pyrrolidonium ionic liquids are obtained.
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| CN201811526464.0A CN109609285A (en) | 2018-12-13 | 2018-12-13 | A kind of preparation method of fatty acid mixed |
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| CN112625803A (en) * | 2020-12-16 | 2021-04-09 | 正大国际科技(常德)集团有限公司 | Method for preparing higher fatty acid ester by using illegal cooking oil |
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| CN101024625A (en) * | 2007-03-23 | 2007-08-29 | 广东工业大学 | Ketopyrrolidine sulfurate in liquid and its prpearing method |
| CN101462938A (en) * | 2008-12-12 | 2009-06-24 | 中南大学 | Method for preparing mixed fatty acid from hogwash oil and use method of mixed fatty acid |
| CN102872911A (en) * | 2012-10-23 | 2013-01-16 | 吴峰 | Ion liquid catalyst and fatty acid preparation method |
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| CN101024625A (en) * | 2007-03-23 | 2007-08-29 | 广东工业大学 | Ketopyrrolidine sulfurate in liquid and its prpearing method |
| CN101462938A (en) * | 2008-12-12 | 2009-06-24 | 中南大学 | Method for preparing mixed fatty acid from hogwash oil and use method of mixed fatty acid |
| CN102872911A (en) * | 2012-10-23 | 2013-01-16 | 吴峰 | Ion liquid catalyst and fatty acid preparation method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112625803A (en) * | 2020-12-16 | 2021-04-09 | 正大国际科技(常德)集团有限公司 | Method for preparing higher fatty acid ester by using illegal cooking oil |
| CN112625803B (en) * | 2020-12-16 | 2022-06-03 | 正大国际科技(常德)集团有限公司 | Preparation method of environment-friendly bio-based lubricating grease |
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