CN109942420A - A kind of method of reaction rectification method preparation high-purity propionic ester - Google Patents
A kind of method of reaction rectification method preparation high-purity propionic ester Download PDFInfo
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- CN109942420A CN109942420A CN201910304020.0A CN201910304020A CN109942420A CN 109942420 A CN109942420 A CN 109942420A CN 201910304020 A CN201910304020 A CN 201910304020A CN 109942420 A CN109942420 A CN 109942420A
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Abstract
The invention discloses a kind of methods of reaction rectification method preparation high-purity propionic ester, using reaction and rectification device, its structure includes: reactive distillation column, the efferent duct with sampling valve is provided at the top of reactive distillation column, efferent duct is connected with the input terminal of condenser, and the output end of condenser is connected with liquid separation tank and finished pot respectively, is provided with return pipe and drainpipe on liquid separation tank, it is connected at the top of return pipe and reactive distillation column, drainpipe is connected with recycling can；It uses propionic acid and monohydric alcohol is reaction raw materials, using disulfate as catalyst；It is sampled in the output end of condenser, when the content of propionic ester in fraction is lower than 99%, the fraction of reactive distillation column output enters in liquid separation tank through delivery pipe, condenser；When the content of propionic ester in fraction is more than or equal to 99%, the fraction of reactive distillation column output, which is then transported in finished pot, to be stored.The invention has the advantages that reaction, rectifying are integrated in one, reaction efficiency is high, and selectivity is good.
Description
Technical field
The present invention relates to the technical fields of propionic ester preparation.
Background technique
Propionic ester can be used as the solvent, various chemical reagent and lithium of food additives, natural resin and synthetic resin
Battery electrolyte solvent etc., with very extensive.The preparation method of propionic ester is relatively more, as heteropoly acid homogeneous catalysis method,
Solid acid H catalysis method etc., these preparation methods all using first reacting the process route separated afterwards, can refer to CN207944042U,
CN102976939B、CN106146302A。
Current, it using the preparation process for first reacting the propionic ester separated afterwards, has a disadvantage in that: energy consumption height, equipment investment
Greatly, reaction process kind poor selectivity, yield are low.
Summary of the invention
The object of the present invention is to provide a kind of method of reaction rectification method preparation high-purity propionic ester, high conversion rates, choosing
Selecting property is good, with high purity.
To achieve the above object, the technical solution adopted by the present invention is that: a kind of reaction rectification method prepares high-purity propionic ester
Method, using reaction and rectification device, structure includes: reactive distillation column, and efferent duct, institute are provided at the top of reactive distillation column
The efferent duct stated is connected with the input terminal of condenser, and the output end of condenser is connected with liquid separation tank and finished pot respectively, point
It is provided with return pipe and drainpipe on flow container, is connected at the top of return pipe and reactive distillation column, drainpipe is connected with recycling can
It connects；It using propionic acid and monohydric alcohol is reaction raw materials, using disulfate as catalyst, reaction temperature is controlled at 60 DEG C ~ 130 DEG C,
Middle propionic acid and disulfate are fed from the top feed of reactive distillation column, monohydric alcohol from the bottom of reactive distillation column；In condenser
Output end to fraction sample, when the mass fraction of propionic ester in fraction be lower than 99% when, reactive distillation column output fraction it is continuous
It is entered in liquid separation tank through delivery pipe, condenser, the organic phase in liquid separation tank is then constantly back to reactive distillation by return pipe
In tower, the water phase in liquid separation tank is then discharged into recycling can；When the mass fraction of propionic ester in fraction is more than or equal to 99%, instead
The fraction for answering rectifying column to export, which is then transported in finished pot, to be stored.
Further, a kind of method of reaction rectification method preparation high-purity propionic ester above-mentioned, wherein the hydrogen sulfate
Salt is sodium bisulfate, and the usage amount of sodium bisulfate is the 0.5% of propionic acid and monohydric alcohol quality summation.
Further, a kind of method of reaction rectification method preparation high-purity propionic ester above-mentioned, wherein disulfate configuration
It feeds intake after the aqueous solution for being 50% at mass fraction.
Further, the method for a kind of reaction rectification method preparation high-purity propionic ester above-mentioned, wherein propionic acid and monohydric alcohol
The molar ratio to feed intake be 1:(1 ~ 1.3).
Further, the method for a kind of reaction rectification method preparation high-purity propionic ester above-mentioned, wherein monohydric alcohol is in batches
Interval feeds intake.
Further, the method for a kind of reaction rectification method preparation high-purity propionic ester above-mentioned, wherein in reactive distillation column
Bottom be provided with blender, blender is for being stirred the material of reactive distillation tower bottom.
Further, a kind of method of reaction rectification method preparation high-purity propionic ester above-mentioned, wherein having in liquid separation tank
When machine is mutually back in reactive distillation column from return pipe, the flow-rate ratio in reactive distillation column efferent duct and return pipe is 1:1.
Further, a kind of method of reaction rectification method preparation high-purity propionic ester above-mentioned, wherein the output of condenser
End is provided with sampling valve.
The invention has the advantages that one, using disulfate as catalyst, especially using sodium bisulfate as catalyst,
It reacts mild, and by-product is few, acid low, small to the corrosivity of equipment.Two, monohydric alcohol is added in batches, carries out reaction forward,
Accelerate reaction process, higher efficiency obtains the propionic ester of high-content.Three, reaction, rectifying are integrated in one, and reaction efficiency is high, choosing
Selecting property is good.
Detailed description of the invention
Fig. 1 is that the structure of the reaction and rectification device used in the of the present invention kind of method for preparing high-purity propionic ester is shown
It is intended to.
Specific embodiment
It elaborates below to a kind of method of reaction rectification method preparation high-purity propionic ester.
A kind of method of reaction rectification method preparation high-purity propionic ester, using reaction and rectification device, using propionic acid and unitary
Alcohol is reaction raw materials, using disulfate as catalyst.
Reaction and rectification device includes: reactive distillation column 1, and reactive distillation column is the tower reactor for integrating reaction and rectifying, instead
The bottom in rectifying column 1 is answered to be provided with blender 11, blender 11 is for being stirred the material of 1 bottom of reactive distillation column.
Efferent duct 6 is arranged in the top of reactive distillation column 1, and the efferent duct 6 is connected with the input terminal of condenser 2, condenser 2 it is defeated
Outlet is connected with liquid separation tank 3 and finished pot 5 respectively, and for the ease of sampling, the output end of condenser 2 is additionally provided with sampling valve 7.Point
Return pipe 31 and drainpipe 32 are provided on flow container 3, return pipe 31 is connected with the top of reactive distillation column 1, drainpipe 32 with
Recycling can 4 is connected.
It uses propionic acid and monohydric alcohol is reaction raw materials, using disulfate as catalyst.Reaction temperature is controlled 60 DEG C ~ 130
℃.The molar ratio that propionic acid and monohydric alcohol feed intake is 1:(1 ~ 1.3), monohydric alcohol feeds intake in batches, generallys use three batches.Wherein,
Propionic acid and disulfate are fed from the top feed of reactive distillation column 1, monohydric alcohol from the bottom of reactive distillation column 1.Reaction process
Middle monohydric alcohol moves upwards, and propionic acid and disulfate move downward, and propionic acid and monohydric alcohol contact quickly react.Hydrogen sulfate
Salt is configured to the aqueous solution that mass fraction is 50% and feeds intake, and disulfate is preferably sodium bisulfate, the usage amount of sodium bisulfate
It is the 0.5% of propionic acid and monohydric alcohol quality summation.
Fraction is sampled at sampling valve 7, when the mass fraction of propionic ester in fraction is lower than 99%, reactive distillation column 1 is defeated
Fraction out enters in liquid separation tank 3 through efferent duct 6, condenser 2, and fraction is layered in liquid separation tank 3, organic in liquid separation tank 3
Phase is then constantly back in reactive distillation column 1 by return pipe 31, and reflux ratio is controlled in 1:1, the i.e. efferent duct of reactive distillation column 1
Flow-ratio control in 6 flow and return pipe 31 is in 1:1.Due to reaction system complexity, a variety of azeotropic mixtures can be generated, through detecting
If product content is lower in fraction, just the organic phase in fraction is recycled in reactive distillation column and is further reacted, this energy
So that reaction forward carries out, while reaction efficiency can be improved, reduce energy consumption of reaction.
Water phase in liquid separation tank 3 then passes through drainpipe 32 and is discharged into recycling can 4.When the mass fraction of propionic ester in fraction
When more than or equal to 99%, fraction is input in finished pot 5 and is stored.
Below by specific embodiment to reaction rectification method of the present invention preparation high-purity propionic ester method do into
One step explanation.
Embodiment 1.
By propionic acid (300 kg) and sodium bisulphate solution (2.34 kg of sulfur acid hydrogen sodium, mass fraction 50%) from
The top of the reactive distillation column 1 of 1000L feeds intake, and methanol (168.86 kg) is fed intake by the bottom of reactive distillation column 1, wherein methanol
It is secondary in three batches to feed intake.Reaction temperature control is at 76.5 DEG C ~ 80.5 DEG C, 4 h of reaction time, the blender of 1 bottom of reactive distillation column
11 mixing speed is 700 r/min.Fraction is monitored, when the mass fraction of propionic ester in fraction is lower than 99%, from reactive distillation
The fraction steamed at the top of tower 1 enters in liquid separation tank 3 through condenser 2, and water phase is separated in liquid separation tank 3 to recycling can 4, organic phase
It is back in reactive distillation column 1 that the reaction was continued, reflux ratio 1:1.The mass fraction for detecting propionic ester in fraction is 99.70%
When, by fraction collection to finished pot 5, obtain 350.01 kg of finished product, molar yield: 97.70%.
Embodiment 2.
By propionic acid (300 kg) and sodium bisulphate solution (2.71 kg of sulfur acid hydrogen sodium, mass fraction 50%) from
The top of the reactive distillation column 1 of 1000L feeds intake, and ethyl alcohol (242.56 kg) is fed intake by the bottom of reactive distillation column 1, wherein ethyl alcohol
It is secondary in three batches to feed intake.Reaction temperature control is at 98.6 DEG C ~ 100.8 DEG C, 5 h of reaction time, the blender of 1 bottom of reactive distillation column
11 mixing speed is 600 r/min.Fraction is monitored, when the mass fraction of propionic ester in fraction is lower than 99%, from reactive distillation
The fraction steamed at the top of tower 1 enters in liquid separation tank 3 through condenser 2, and the water phase in liquid separation tank 3 enters to recycling can 4, organic phase
It is back in reactive distillation column 1 that the reaction was continued, reflux ratio 1:1.The mass fraction for detecting propionic ester in fraction is 99.75%
When, by fraction collection to finished pot 5, obtain 406.05 kg of finished product, molar yield: 97.92%.
Embodiment 3.
By propionic acid (300 kg) and sodium bisulphate solution (3.08 kg of sulfur acid hydrogen sodium, mass fraction 50%) from
The top of the reactive distillation column 1 of 1000L feeds intake, and normal propyl alcohol (316.42 kg) is fed intake by the bottom of reactive distillation column 1, wherein just
Propyl alcohol is secondary in three batches to feed intake.Reaction temperature is controlled at 121.3 DEG C ~ 124.8 DEG C, 6 h of reaction time, 1 bottom of reactive distillation column
The mixing speed of blender is 500 r/min.Fraction is monitored, when the mass fraction of propionic ester in fraction is lower than 99%, from reaction
The fraction steamed at the top of rectifying column 1 enters in liquid separation tank 3 through condenser 2, and water phase is separated in liquid separation tank 3 to recycling can 4, is had
Machine is mutually back in reactive distillation column 1 that the reaction was continued, reflux ratio 1:1.The mass fraction for detecting propionic ester in fraction is
When 99.78%, by fraction collection to finished pot 5,462.95 kg of finished product, molar yield: 98.19% are obtained.
Embodiment 4.
By propionic acid (400 kg) and sodium bisulphate solution (3.62 kg of sulfur acid hydrogen sodium, mass fraction 50%) from
The top of the reactive distillation column 1 of 1000L feeds intake, and ethyl alcohol (323.74 kg) is fed intake by the bottom of reactive distillation column 1, wherein ethyl alcohol
It is secondary in three batches to feed intake.Reaction temperature is controlled at 98.6 DEG C ~ 100.8 DEG C, 4 h of reaction time, 1 bottom stirrer of reactive distillation column
Mixing speed is 800 r/min.Fraction is monitored, when the mass fraction of propionic ester in fraction is lower than 99%, from reactive distillation column 1
The fraction that top steams enters in liquid separation tank 3 through condenser 2, and the water phase in liquid separation tank 3 enters to recycling can 4, and organic phase is returned
It flow in reactive distillation column 1 that the reaction was continued, reflux ratio 1:1.When the mass fraction for detecting propionic ester in fraction is 99.8%,
By fraction collection to finished pot 5,542.29 kg of finished product, molar yield: 98.24% are obtained.
From the foregoing, it will be observed that the invention has the advantages that one, using disulfate, especially sodium bisulfate as catalyst, it is anti-
Should be mild, by-product is few, and it is acid low, it is small to the corrosivity of equipment.Two, monohydric alcohol is added in batches, carries out reaction forward, accelerates
Reaction process, higher efficiency obtain the propionic ester of high-content.Three, reaction, rectifying are integrated in one, and reaction efficiency is high, selectivity
It is good.
Claims (8)
1. a kind of method of reaction rectification method preparation high-purity propionic ester, it is characterised in that: use reaction and rectification device, structure
Include: reactive distillation column, efferent duct is provided at the top of reactive distillation column, efferent duct is connected with the input terminal of condenser, cold
The output end of condenser is connected with liquid separation tank and finished pot respectively, is provided with return pipe and drainpipe on liquid separation tank, return pipe with
It is connected at the top of reactive distillation column, drainpipe is connected with recycling can；Using propionic acid and monohydric alcohol is reaction raw materials, with sulfuric acid
Hydrogen salt is catalyst, and reaction temperature is controlled at 60 DEG C ~ 130 DEG C, wherein propionic acid and disulfate from the top of reactive distillation column into
Material, monohydric alcohol are fed from the bottom of reactive distillation column；Fraction is sampled in the output end of condenser, when the matter of propionic ester in fraction
When measuring score lower than 99%, the fraction of reactive distillation column output is constantly entered in liquid separation tank through delivery pipe, condenser, liquid separation tank
In organic phase be then constantly back in reactive distillation column by return pipe, the water phase in liquid separation tank is then discharged into recycling can；
When the mass fraction of propionic ester in fraction is more than or equal to 99%, the fraction of reactive distillation column output is then transported in finished pot
Storage.
2. a kind of method of reaction rectification method preparation high-purity propionic ester according to claim 1, it is characterised in that: described
Disulfate be sodium bisulfate, the usage amount of sodium bisulfate is the 0.5% of propionic acid and monohydric alcohol quality summation.
3. a kind of method of reaction rectification method preparation high-purity propionic ester according to claim 1, it is characterised in that: sulfuric acid
Hydrogen salt feeds intake after being configured to the aqueous solution that mass fraction is 50%.
4. a kind of method of reaction rectification method preparation high-purity propionic ester according to claim 1, it is characterised in that: propionic acid
The molar ratio to feed intake with monohydric alcohol is 1:(1 ~ 1.3).
5. a kind of method of reaction rectification method preparation high-purity propionic ester according to claim 1, it is characterised in that: unitary
Minor tick feeds intake alcohol in batches.
6. a kind of method of reaction rectification method preparation high-purity propionic ester according to claim 1, it is characterised in that: reaction
Bottom in rectifying column is provided with blender, and blender is for being stirred the material of reactive distillation tower bottom.
7. a kind of method of reaction rectification method preparation high-purity propionic ester according to claim 1, it is characterised in that: liquid separation
When organic phase in tank is back in reactive distillation column from return pipe, reactive distillation column efferent duct is with the flow-rate ratio in return pipe
1:1。
8. a kind of method of reaction rectification method preparation high-purity propionic ester according to claim 1, it is characterised in that: condensation
The output end of device is provided with sampling valve.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114644556A (en) * | 2020-12-21 | 2022-06-21 | 山东石大胜华化工集团股份有限公司 | Device and process method for preparing propionate |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102320962A (en) * | 2011-07-18 | 2012-01-18 | 邢台旭阳煤化工有限公司 | Method for catalytic synthesis of methyl propionate |
| CN207944042U (en) * | 2017-12-26 | 2018-10-09 | 东营市海科新源化工有限责任公司 | A kind of process system preparing propionic ester |
| CN108929221A (en) * | 2018-07-10 | 2018-12-04 | 天津科技大学 | A kind of preparation method of n propyl propionate |
-
2019
- 2019-04-16 CN CN201910304020.0A patent/CN109942420A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102320962A (en) * | 2011-07-18 | 2012-01-18 | 邢台旭阳煤化工有限公司 | Method for catalytic synthesis of methyl propionate |
| CN207944042U (en) * | 2017-12-26 | 2018-10-09 | 东营市海科新源化工有限责任公司 | A kind of process system preparing propionic ester |
| CN108929221A (en) * | 2018-07-10 | 2018-12-04 | 天津科技大学 | A kind of preparation method of n propyl propionate |
Non-Patent Citations (5)
| Title |
|---|
| CARSTEN BUCHALY等: "n-Propyl Propionate Synthesis via Catalytic Distillation-Experimental Investigation in Pilot-Scale", 《INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH》 * |
| 姚允斌等编: "《物理化学手册》", 31 December 1985, 上海科学技术出版社，第1版 * |
| 徐红等: "反应精馏合成丙酸丙酯模拟与动力学", 《石油学报（石油加工）》 * |
| 蔡述兰等: "硫酸氢钠在催化有机合成反应中的研究进展", 《化工时刊》 * |
| 钟桐生等: "硫酸氢钠催化合成丙酸酯", 《贵州师范大学学报（自然科学版）》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114644556A (en) * | 2020-12-21 | 2022-06-21 | 山东石大胜华化工集团股份有限公司 | Device and process method for preparing propionate |
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