CN108658767A - A kind of preparation method of methyl oleate - Google Patents
A kind of preparation method of methyl oleate Download PDFInfo
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- CN108658767A CN108658767A CN201810761891.0A CN201810761891A CN108658767A CN 108658767 A CN108658767 A CN 108658767A CN 201810761891 A CN201810761891 A CN 201810761891A CN 108658767 A CN108658767 A CN 108658767A
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
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Abstract
The invention discloses a kind of preparation methods of methyl oleate, and this approach includes the following steps：Step 1 is that oleic acid and methanol are added in pressure reaction still, then adds pyrovinic acid catalyst, an esterification is carried out in the case where temperature is 140 DEG C, pressure is 0.7MPa；Step 2 is that methanol is added in pressure reaction still after step 1 pressure release, secondary esterification is carried out in the case where temperature is 140 DEG C, pressure is 0.7MPa, then pass through centrifuge, thick methyl oleate and pyrovinic acid catalyst are detached, upper layer is thick methyl oleate, and lower layer is pyrovinic acid catalyst, and the acid value of thick methyl oleate is less than 2, thick methyl oleate is distilled, oelic acid methyl esters is obtained；The method reaction time that the present invention prepares methyl oleate is short, can be applied mechanically repeatedly after catalyst separation, and after applying mechanically repeatedly repeatedly catalytic efficiency without being substantially reduced.
Description
Technical field
The present invention relates to oil prodution industry technical field, the preparation method of specifically a kind of methyl oleate.
Background technology
Methyl oleate is a kind of unsaturated high-grade fatty acid ester, is important industrial chemicals, is widely used as preparing surface work
The property basic material of agent, the softening agent of leather and rubber, the plasticizer of plastics and water repellent agent, the tough agent of resin, oil exploration
Lubricant, textile auxiliary and desinsection agent aid of unstressed configuration mud etc..At present prepare methyl oleate method be：By oleic acid and
Methanol is added in round-bottomed flask, adds the catalyst concentrated sulfuric acid or p-methyl benzenesulfonic acid, after mixing, is heated to reflux 10h, instead
It being cooled to room temperature after answering, the pH value of solution is 8.0-9.0 after adjusting reaction with sodium methoxide, is then washed with water to neutrality,
It is evaporated under reduced pressure to get methyl oleate after anhydrous calcium chloride is dried.The catalytic efficiency of catalyst is relatively low in this method, instead
It is longer between seasonable, a large amount of waste acid water and waste residue are generated in reaction process, are unfavorable for realizing that the industrialization of methyl oleate is advised greatly
Mould produces.
Invention content
The purpose of the present invention is to provide a kind of preparation methods of methyl oleate, to solve the problems of the prior art.
To achieve the above object, the present invention provides the following technical solutions：A kind of preparation method of methyl oleate, this method
Include the following steps：
(1) oleic acid and methanol are added in pressure reaction still, then add pyrovinic acid catalyst, be 140 in temperature
DEG C, pressure be 0.7MPa under carry out an esterification, after reaction, to the direct pressure release of pressure reaction still, in pressure leak process
In, water generated in the esterification is detached from reaction system with methanol, and the mass ratio of oleic acid and methanol is 1:0.2-
0.3, the dosage of pyrovinic acid catalyst is the 0.1-0.3% of reactant gross mass；
(2) methanol is added into the pressure reaction still after step (1) pressure release, methanol and the pressure after step (1) pressure release are anti-
It is 0.15-0.2 to answer the mass ratio of surplus material in kettle:1, carry out secondary esterification in the case where temperature is 140 DEG C, pressure is 0.7MPa
Reaction, after reaction, to the direct pressure release of the pressure reaction still, in pressure leak process, generated in the esterification
Water is detached from reaction system with methanol, then passes through centrifuge, thick methyl oleate and pyrovinic acid catalyst are divided
From upper layer is thick methyl oleate, and lower layer is pyrovinic acid catalyst, is distilled to thick methyl oleate, obtains oelic acid first
Ester.
As an optimization, after determination step (1) reaction in reaction system pyrovinic acid catalyst content, loss part is used
Pure pyrovinic acid substitutes, and is applied in the ratio of pure pyrovinic acid in the esterification that step (2) synthesizes methyl oleate.
As an optimization, an esterification and secondary esterification are homogeneous reaction, and the reaction time is 5min.
As an optimization, the acid value of thick methyl oleate is less than 2.Acid value is smaller, illustrates that the quality of methyl oleate is better, fresh
Degree and refinement are better.
Compared with prior art, the beneficial effects of the invention are as follows：First, the method that the present invention prepares methyl oleate is oleic acid
Esterification is carried out in the pressure reaction still that temperature is 140 DEG C, pressure is 0.7MPa with methanol, the esterification is using high
The condition of warm high pressure, improves the rate of reaction, only needs 10min reactions that can complete, and prepares the side of methyl oleate at present
Method needs 10h, the method that the present invention prepares methyl oleate to substantially reduce the time of reaction；Second is that the present invention prepares oleic acid first
In the method for ester after esterification, to the direct pressure release of pressure reaction still, in pressure leak process, institute in the esterification
The water of generation is detached from reaction system with methanol, eliminates processing waste water this step, greatly reduces and prepare methyl oleate
Cost；Third, the present invention is prepared in the method for methyl oleate, catalyst pyrovinic acid, can be in the case where that need not handle
It is directly applied in the esterification for preparing methyl oleate in next step, applies mechanically the catalytic efficiency of multiple rear catalyst repeatedly without bright
It is aobvious to reduce, it is advantageously implemented the industrialization large-scale production of methyl oleate.
Specific implementation mode
The following is a clear and complete description of the technical scheme in the embodiments of the invention, it is clear that described implementation
Example is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, this field is general
The every other embodiment that logical technical staff is obtained without making creative work, belongs to protection of the present invention
Range.
Embodiment 1：
A kind of preparation method of methyl oleate, this approach includes the following steps：
(1) oleic acid 500g and methanol 125g are added in pressure reaction still, then add 1g pyrovinic acid catalyst,
Carry out an esterification in the case where temperature is 140 DEG C, pressure is 0.7MPa, which is homogeneous reaction, and the reaction time is
5min, after reaction, to the direct pressure release of pressure reaction still, in pressure leak process, water generated in the esterification with
Methanol is detached from reaction system together；
(2) methanol is added into the pressure reaction still after step (1) pressure release, methanol and the pressure after step (1) pressure release are anti-
It is 0.15 to answer the mass ratio of surplus material in kettle:1, secondary esterification is carried out in the case where temperature is 140 DEG C, pressure is 0.7MPa,
The esterification is homogeneous reaction, reaction time 5min, after reaction, to the direct pressure release of pressure reaction still, in pressure release
In the process, the water generated in the esterification is detached from reaction system with methanol, then passes through centrifuge, by crude oil acid
Methyl esters and pyrovinic acid catalyst are detached, and upper layer is thick methyl oleate, and lower layer is pyrovinic acid catalyst, measures crude oil
The acid value of sour methyl esters is 1.45, is distilled to thick methyl oleate, obtains oelic acid methyl esters, obtains 1.3g reuse pyrovinic acids.
Embodiment 2：
A kind of preparation method of methyl oleate, this approach includes the following steps：
(1) oleic acid 500g and methanol 125g are added in pressure reaction still, then add the catalysis of 1.3g pyrovinic acids
Agent, carries out an esterification in the case where temperature is 140 DEG C, pressure is 0.7MPa, which is homogeneous reaction, when reaction
Between be 5min, after reaction, to the direct pressure release of pressure reaction still, in pressure leak process, generated in the esterification
Water is detached from reaction system with methanol；
(2) methanol is added into the pressure reaction still after step (1) pressure release, methanol and the pressure after step (1) pressure release are anti-
It is 0.16 to answer the mass ratio of surplus material in kettle:1, secondary esterification is carried out in the case where temperature is 140 DEG C, pressure is 0.7MPa,
The esterification is homogeneous reaction, reaction time 5min, after reaction, to the direct pressure release of pressure reaction still, in pressure release
In the process, the water generated in the esterification is detached from reaction system with methanol, then passes through centrifuge, by crude oil acid
Methyl esters and pyrovinic acid catalyst are detached, and upper layer is thick methyl oleate, and lower layer is pyrovinic acid catalyst, measures crude oil
The acid value of sour methyl esters is 1.58, is distilled to thick methyl oleate, obtains oelic acid methyl esters, obtains 1.1g reuse pyrovinic acids.
Embodiment 3：
A kind of preparation method of methyl oleate, this approach includes the following steps：
(1) oleic acid 500g and methanol 125g are added in pressure reaction still, then add the catalysis of 1.1g pyrovinic acids
Agent, carries out an esterification in the case where temperature is 140 DEG C, pressure is 0.7MPa, which is homogeneous reaction, when reaction
Between be 5min, after reaction, to the direct pressure release of pressure reaction still, in pressure leak process, generated in the esterification
Water is detached from reaction system with methanol；
(2) methanol is added into the pressure reaction still after step (1) pressure release, methanol and the pressure after step (1) pressure release are anti-
It is 0.17 to answer the mass ratio of surplus material in kettle:1, secondary esterification is carried out in the case where temperature is 140 DEG C, pressure is 0.7MPa,
The esterification is homogeneous reaction, reaction time 5min, after reaction, to the direct pressure release of pressure reaction still, in pressure release
In the process, the water generated in the esterification is detached from reaction system with methanol, then passes through centrifuge, by crude oil acid
Methyl esters and pyrovinic acid catalyst are detached, and upper layer is thick methyl oleate, and lower layer is pyrovinic acid catalyst, measures crude oil
The acid value of sour methyl esters is 1.65, is distilled to thick methyl oleate, obtains oelic acid methyl esters, obtains 1.2g reuse pyrovinic acids.
Embodiment 4：
A kind of preparation method of methyl oleate, this approach includes the following steps：
(1) oleic acid 500g and methanol 125g are added in pressure reaction still, then add the catalysis of 1.2g pyrovinic acids
Agent, carries out an esterification in the case where temperature is 140 DEG C, pressure is 0.7MPa, which is homogeneous reaction, when reaction
Between be 5min, after reaction, to the direct pressure release of pressure reaction still, in pressure leak process, generated in the esterification
Water is detached from reaction system with methanol；
(2) methanol is added into the pressure reaction still after step (1) pressure release, methanol and the pressure after step (1) pressure release are anti-
It is 0.18 to answer the mass ratio of surplus material in kettle:1, secondary esterification is carried out in the case where temperature is 140 DEG C, pressure is 0.7MPa,
The esterification is homogeneous reaction, reaction time 5min, after reaction, to the direct pressure release of pressure reaction still, in pressure release
In the process, the water generated in the esterification is detached from reaction system with methanol, then passes through centrifuge, by crude oil acid
Methyl esters and pyrovinic acid catalyst are detached, and upper layer is thick methyl oleate, and lower layer is pyrovinic acid catalyst, measures crude oil
The acid value of sour methyl esters is 1.44, is distilled to thick methyl oleate, obtains oelic acid methyl esters, obtains 0.9g reuse pyrovinic acids.
Embodiment 5：
A kind of preparation method of methyl oleate, this approach includes the following steps：
(1) oleic acid 500g and methanol 125g are added in pressure reaction still, then add the catalysis of 1.2g pyrovinic acids
Agent, carries out an esterification in the case where temperature is 140 DEG C, pressure is 0.7MPa, which is homogeneous reaction, when reaction
Between be 5min, after reaction, to the direct pressure release of pressure reaction still, in pressure leak process, generated in the esterification
Water is detached from reaction system with methanol；
(2) methanol is added into the pressure reaction still after step (1) pressure release, methanol and the pressure after step (1) pressure release are anti-
It is 0.19 to answer the mass ratio of surplus material in kettle:1, secondary esterification is carried out in the case where temperature is 140 DEG C, pressure is 0.7MPa,
The esterification is homogeneous reaction, reaction time 5min, after reaction, to the direct pressure release of pressure reaction still, in pressure release
In the process, the water generated in the esterification is detached from reaction system with methanol, then passes through centrifuge, by crude oil acid
Methyl esters and pyrovinic acid catalyst are detached, and upper layer is thick methyl oleate, and lower layer is pyrovinic acid catalyst, measures crude oil
The acid value of sour methyl esters is 1.58, is distilled to thick methyl oleate, obtains oelic acid methyl esters, obtains 0.6g reuse pyrovinic acids.
Embodiment 6：
A kind of preparation method of methyl oleate, this approach includes the following steps：
(1) oleic acid 500g and methanol 125g are added in pressure reaction still, then add the catalysis of 0.6g pyrovinic acids
Agent, carries out an esterification in the case where temperature is 140 DEG C, pressure is 0.7MPa, which is homogeneous reaction, when reaction
Between be 5min, after reaction, to the direct pressure release of pressure reaction still, in pressure leak process, generated in the esterification
Water is detached from reaction system with methanol；
(2) methanol is added into the pressure reaction still after step (1) pressure release, methanol and the pressure after step (1) pressure release are anti-
It is 2.0 to answer the mass ratio of surplus material in kettle:1, secondary esterification is carried out in the case where temperature is 140 DEG C, pressure is 0.7MPa,
The esterification is homogeneous reaction, reaction time 5min, after reaction, to the direct pressure release of pressure reaction still, in pressure release
In the process, the water generated in the esterification is detached from reaction system with methanol, then passes through centrifuge, by crude oil acid
Methyl esters and pyrovinic acid catalyst are detached, and upper layer is thick methyl oleate, and lower layer is pyrovinic acid catalyst, measures crude oil
The acid value of sour methyl esters is 1.7, is distilled to thick methyl oleate, obtains oelic acid methyl esters, obtains 1.0g reuse pyrovinic acids.
The present invention prepares the condition that methyl oleate uses high temperature and pressure, improves the rate of reaction, only 10min is needed to react
The method that can be completed, and prepare methyl oleate at present needs 10h, the method that the present invention prepares methyl oleate to substantially reduce
The time of reaction；When after reaction, to the direct pressure release of pressure reaction still, in pressure leak process, the water generated in reaction
It is detached from reaction system with methanol, processing waste water this step is eliminated, greatly reduces the cost for preparing methyl oleate；It urges
Agent pyrovinic acid can be directly applied in the case where that need not handle in the reaction for preparing methyl oleate in next step,
The catalytic efficiency of multiple rear catalyst is applied mechanically repeatedly without being substantially reduced, and the industrialization for being advantageously implemented methyl oleate is given birth on a large scale
Production.
It is obvious to a person skilled in the art that invention is not limited to the details of the above exemplary embodiments, Er Qie
In the case of without departing substantially from spirit or essential attributes of the invention, the present invention can be realized in other specific forms.Therefore, nothing
By from the point of view of which point, the present embodiments are to be considered as illustrative and not restrictive, and the scope of the present invention is by institute
Attached claim rather than above description limit, it is intended that will fall within the meaning and scope of the equivalent requirements of the claims
All changes be included within the present invention.
Claims (4)
1. a kind of preparation method of methyl oleate, which is characterized in that this approach includes the following steps：
(1) oleic acid and methanol are added in pressure reaction still, then add pyrovinic acid catalyst, be 140 DEG C, press in temperature
By force to carry out an esterification under 0.7MPa, after reaction, to the direct pressure release of the pressure reaction still, in pressure leak process
In, water generated in the esterification is detached from reaction system with methanol, and the mass ratio of the oleic acid and methanol is 1:
0.2-0.3, the dosage of the pyrovinic acid catalyst are the 0.1-0.3% of reactant gross mass；
(2) methanol is added into the pressure reaction still after step (1) pressure release, the methanol and the pressure after step (1) pressure release are anti-
It is 0.15-0.2 to answer the mass ratio of surplus material in kettle:1, it is anti-that secondary esterification is carried out in the case where temperature is 140 DEG C, pressure is 0.7MPa
Answer, after reaction, to the direct pressure release of the pressure reaction still, in pressure leak process, water generated in the esterification with
Methanol is detached from reaction system together, then passes through centrifuge, thick methyl oleate and pyrovinic acid catalyst is detached, upper layer
For thick methyl oleate, lower layer is pyrovinic acid catalyst, is distilled to the thick methyl oleate, obtains oelic acid methyl esters.
2. a kind of preparation method of methyl oleate according to claim 1, it is characterised in that：After determination step (1) reaction
The content of pyrovinic acid catalyst in reaction system, loss part is substituted with pure pyrovinic acid, in the ratio set of pure pyrovinic acid
With in the esterification for synthesizing methyl oleate to step (2).
3. a kind of preparation method of methyl oleate according to claim 1, it is characterised in that：Esterification and
Secondary esterification is homogeneous reaction, and the reaction time is 5min.
4. a kind of preparation method of methyl oleate according to claim 2, it is characterised in that：The acid of the thick methyl oleate
Valence is less than 2.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112159727A (en) * | 2020-09-09 | 2021-01-01 | 湖北天基生物能源科技发展有限公司 | Esterification method of waste oil |
| CN113755249A (en) * | 2021-10-08 | 2021-12-07 | 湖北天基生物能源科技发展有限公司 | Treatment method for reducing acid value of crude methyl ester |
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| CN113755249A (en) * | 2021-10-08 | 2021-12-07 | 湖北天基生物能源科技发展有限公司 | Treatment method for reducing acid value of crude methyl ester |
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