CN110642692B - Device and method for purifying cyclopropyl methyl ketone by salt extraction and rectification - Google Patents
Device and method for purifying cyclopropyl methyl ketone by salt extraction and rectification Download PDFInfo
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- C07C45/78—Separation; Purification; Stabilisation; Use of additives
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- C07C45/78—Separation; Purification; Stabilisation; Use of additives
- C07C45/81—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
- C07C45/82—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
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Abstract
A device and a method for purifying cyclopropyl methyl ketone by salting extraction and rectification belong to the technical field of separation and purification, and aim to provide an energy-saving separation and purification process of cyclopropyl methyl ketone. The separation time is shortened, and the separation and purification cost of the cyclopropyl methyl ketone is reduced.
Description
Technical Field
The invention belongs to the technical field of separation and purification, and particularly relates to a device and a method for purifying cyclopropyl methyl ketone by salt extraction and rectification.
Background
Cyclopropyl methyl ketone is an important organic synthesis intermediate raw material, and is a drug intermediate for synthesizing efavirenz which is an anti-AIDS specific drug; is an indispensable intermediate for synthesizing 'green pesticide' cyprodinil; is the main component for synthesizing cyproconazole which is used for preventing and controlling pests in forest and animal husbandry and regulating the growth of plants. Cyclopropyl methyl ketone is increasingly showing its importance as an indispensable intermediate for the synthesis of these organic compounds.
At present, the main synthetic method of cyclopropyl methyl ketone is to take acetyl-n-propanol (CN 1994996), alpha-acetyl-gamma-butyrolactone (CN 101643397, CN102643179A, CN105622369A, and the research on synthetic process of niu feng, isoxaflutole [ D ]. university of china eastern physiology, 2013), pentachlorodipentanone (research on synthetic process of Liu Juan. cyclopropyl methyl ketone and product analysis method [ D ]. university of Shandong traditional Chinese medicine, 2012, and anyuan. synthesis process research and industrial design of cyprodinil [ D ]. Zhejiang industry university, 2017, Meshcherakov A P, Glukhovtsev V G, prepartive synthesis of cyclopropy methyl ketone [ J ]. 1959) as raw materials, and prepare crude organic phase cyclopropyl methyl ketone through distillation, standing, layering or refining.
The crude product of cyclopropyl methyl ketone generally contains cyclopropyl methyl ketone, water, unreacted pentachlorodipentanone, etc., and organic ether used for extracting water layer from the crude product. Most of the methods directly apply a rectification method to separate and purify, and calcium chloride or potassium carbonate or potassium hydroxide is adopted for drying and then distillation separation and purification are carried out respectively. The direct distillation separation is carried out, impurities and water are sequentially distilled out, and then the cyclopropyl methyl ketone is distilled out, so that the water content of a crude product of the cyclopropyl methyl ketone is high (about 15 percent), the yield of the cyclopropyl methyl ketone is low, the loss is large, and meanwhile, the cyclopropyl methyl ketone is also completely distilled out, so that the energy consumption is quite high; the calcium chloride or potassium carbonate or potassium hydroxide is used for drying and then is distilled, separated and purified, the energy consumption of rectification is reduced to a certain degree, but the cost of the drying agent is high and is still higher.
Disclosure of Invention
The invention aims to provide an energy-saving separation and purification process of cyclopropyl methyl ketone. Provides a device and a method for purifying cyclopropyl methyl ketone by salt extraction and rectification.
The invention adopts the following technical scheme:
the utility model provides a device of extraction and rectification purification cyclopropyl methyl ketone adds salt, including the extractor, the salt water phase jar, the centrifugal pump, hypergravity agitating unit, hypergravity rectifier unit, a condenser, the buffer tank, reboiler and storage tank, the salt water phase jar is connected through the discharge gate I of pipeline and extractor bottom, the discharge gate II of extractor bottom is connected through the feed inlet of centrifugal pump with hypergravity agitating unit, hypergravity agitating unit's discharge gate passes through the pipeline and is connected with the feed inlet of extractor, pipeline between hypergravity agitating unit's feed inlet and the centrifugal pump is connected with the feed inlet of one side of hypergravity rectifier unit, condenser and buffer tank and hypergravity rectifier unit top constitute circulation circuit, the reboiler constitutes circulation circuit with hypergravity rectifier unit bottom, the reboiler is connected with the storage tank.
Hypergravity agitating unit includes shell I, is equipped with rotor I in the shell I, is equipped with filler I in the rotor I, and one side of shell I is equipped with liquid inlet I, and the bottom is equipped with liquid outlet I, and I department of liquid inlet is equipped with liquid distributor, and I bottom of shell is equipped with motor I.
Hypergravity rectifier unit includes shell II, and one side of shell II is equipped with gas inlet, and the top is equipped with gas outlet, and the opposite side is equipped with liquid inlet II and backward flow import respectively, and the backward flow import is located the top of liquid inlet II, and II bottoms of shell are equipped with liquid outlet II, are equipped with rotor II in the shell II, are equipped with filler II in the rotor II, and II bottoms of shell are equipped with motor II.
A method for purifying cyclopropyl methyl ketone by salt extraction and rectification comprises the following steps:
firstly, extracting, namely adding a pre-separated and purified cyclopropyl methyl ketone crude product and an extracting agent into an extractor according to a ratio, stirring, mixing and dissolving the extracting agent, standing and layering, wherein the upper layer is an organic phase, the lower layer is a brine phase, and the brine phase enters a brine phase tank;
and secondly, rectifying, namely rectifying the organic phase to obtain distilled water and impurities, wherein the residue is rectified cyclopropyl methyl ketone.
The extraction in the first step comprises one-step extraction or two-step extraction, wherein the extraction and rectification in one step comprise the following steps: adding an extracting agent into the crude product of the cyclopropyl methyl ketone at normal temperature, stirring for 1-3min in a supergravity stirring device, standing for 0.5-1h, layering, wherein the upper layer is an organic phase, the lower layer is a brine phase, and rectifying and purifying the organic phase;
the extractant comprises one or more of anhydrous sodium chloride, magnesium chloride, potassium chloride, anhydrous calcium chloride, potassium fluoride, anhydrous sodium carbonate, anhydrous potassium carbonate and potassium hydroxide, and the mass ratio of the crude cyclopropyl methyl ketone to the extractant is 5.8-28: 1.
The two-step extraction and rectification comprises the following steps:
adding an extracting agent I into a crude product of cyclopropyl methyl ketone according to a proportion at normal temperature, stirring for 1-3min in a hypergravity stirring device, standing for 0.5-1h, and then layering, wherein the upper layer is an organic phase I, the lower layer is a brine phase I, and the brine phase I enters a brine phase tank; the extractant I comprises any one of anhydrous sodium chloride, potassium chloride, magnesium chloride, potassium fluoride, anhydrous sodium carbonate, magnesium carbonate and potassium carbonate, and the mass ratio of the crude cyclopropyl methyl ketone to the extractant I is 5.8-28: 1;
adding an extracting agent II into the organic phase I in proportion, stirring for 1min in a high-gravity stirring device, standing for 0.5-1h, and then layering, wherein the upper layer is the organic phase II, the lower layer is a brine phase II, and the brine phase II enters a brine phase tank; the extractant II comprises any one of calcium chloride, potassium hydroxide and potassium carbonate, and the mass ratio of the crude cyclopropyl methyl ketone to the extractant I is 15-35: 1;
and (3) pumping the organic phase II into a hypergravity rectifying device under the action of a centrifugal pump, heating the organic phase II to be gasified at the rectifying temperature of 80-114 ℃, refluxing for 5-10min at the reflux ratio of 3-10:1, and rectifying for 0.5-1h to obtain the pure cyclopropyl methyl ketone.
The invention has the following beneficial effects:
compared with the prior common rectification technology, the invention has the following advantages: firstly, the invention reduces the water content of the raw material from 15-22% to 1-6% because of selecting proper salt during the extraction by adding salt, and reduces the energy consumption required by rectification; and secondly, during extraction, part of impurities are retained in the water layer along with the extraction, so that the impurities in the organic layer are purified, and cyclopropyl methyl ketone does not need to be completely evaporated during rectification, thereby greatly reducing the rectification energy consumption. Thirdly, the operation is flexible. The supergravity rectification is adopted, the heat and mass transfer in the rectification process is enhanced, the purity of the cyclopropyl methyl ketone reaches 99.0-99.9%, and the water content is less than 0.5%. Meanwhile, the machine is convenient to start and stop. Fourthly, the stirring by the super-gravity is adopted, and the stirring time is shortened by 1 to 2 orders of magnitude compared with the traditional stirring time.
Drawings
FIG. 1 is a schematic diagram of a two-step extraction and rectification apparatus according to the present invention;
wherein: 1-an extractor; 2-a brine phase tank; 3-a centrifugal pump; 4-a super-gravity stirring device; 5-a hypergravity rectification device; 6-a condenser; 7-a buffer tank; 8-a reboiler; 9-storage tank.
FIG. 2 is a gas chromatogram of cyclopropyl methyl ketone after two-step extraction and rectification in example 2.
FIG. 3 is a graph showing a gas-liquid equilibrium of cyclopropylmethyl ketone with water.
FIG. 4 is a schematic structural diagram of the high-gravity stirring device of the present invention;
wherein: 10-shell I; 11-rotor I; 12-filler I; 13-liquid inlet I; 14-liquid outlet I; 15-a liquid distributor; 16-motor I.
FIG. 5 is a schematic structural diagram of a hypergravity rectifying apparatus according to the present invention;
wherein: 17-shell ii; 18-gas inlet; 19-a gas outlet; 20-liquid inlet II; 21-reflux inlet; 22-liquid outlet II; 23-rotor II; 24-filler ii; 25-motor II.
Detailed Description
The cyclopropyl methyl ketone crude product is prepared by taking acetyl-n-propanol and alpha-acetyl-gamma-butyrolactone as raw materials and carrying out acidification, alkalization, rectification or layering. Or the preparation method comprises the steps of alkalizing, rectifying or layering pentachlorodipentanone and 1-chloro-4 pentanone which are used as raw materials.
In the crude product of the cyclopropyl methyl ketone, the mass fraction of the cyclopropyl methyl ketone is as follows: 65-75%, and the mass fraction of water content is as follows: 15% -22%, and the mass fraction of other components: 8 to 13 percent.
The extractor is a commonly used vessel with a visual level gauge. The reboiler is a conventional reboiler.
The supergravity stirring device mainly comprises a shell, a rotor, a motor, a filler and a liquid distributor. And a liquid inlet pipe and a liquid outlet pipe are arranged.
The hypergravity rectifying device mainly comprises a shell, a rotor, a motor and a filler. Is provided with a raw material liquid inlet pipe, a reflux liquid inlet pipe, a gas inlet pipe and a gas outlet pipe.
Comparative example 1
And (2) performing one-step extraction, namely adding sodium chloride, magnesium chloride, potassium chloride, calcium chloride, potassium fluoride, sodium carbonate, potassium hydroxide and potassium carbonate into a crude product of cyclopropyl methyl ketone (the water content is 16%) respectively according to saturation at normal temperature, magnetically stirring, standing for layering, wherein the upper layer is an organic phase, and the water content and the cost of an extracting agent in the organic phase are measured by a water content titrator and shown in table 1.
TABLE 1 extraction effectiveness and cost of various kinds of extractants
The anhydrous calcium chloride and potassium hydroxide have the best extraction effect, but the cost is higher. And the stirring time and the extraction time of the anhydrous calcium chloride are longer, and impurities in the potassium hydroxide react with organic matters to cause the organic phase to turn yellow.
Example 1
The super-heavy machine is used as a stirrer, the processing capacity is 1000ml, and the extraction time is shown in Table 2.
TABLE 2 extraction time and standing time of various kinds of extractants
As shown in Table 2, compared with magnetic stirring, the high-gravity stirring time is shortened by 1-2 orders of magnitude, the extraction standing time is reduced by nearly one third, and the separation and purification time of the cyclopropyl methyl ketone is greatly shortened.
Example 2
Selecting low-cost sodium chloride, potassium chloride, sodium carbonate and magnesium chloride as first-step extractant, stirring, standing and layering to obtain organic phase
Then using calcium chloride as extractant to separate organic phase
Performing a second extraction to obtain an organic phase
. The extraction effect and cost are shown in table 3.
TABLE 3 two-step extraction results
As shown in Table 3, the first extraction with NaCl and then the second extraction with Ca chloride are superior to those with Ca chloride and the cost is low. Is the preferred method.
Mixing the organic phase
Or
Is pumped into a rectifying device under the action of a centrifugal pump, and the rectifying temperature is set to be 80-114 ℃; heating to gasify, and totally refluxing for 5-10 min; adjusting the reflux ratio to be 10:1, rectifying for 1h, and obtaining a cyclopropyl methyl ketone product at the bottom of the tower, wherein the purity is 99.0-99.9%, and the water content is less than 0.5%.
The rectification can adopt batch rectification or continuous rectification.
The cyclopropyl methyl ketone and water are partially miscible systems, and a partially miscible interval is formed between 20-80% of the volume content of the cyclopropyl methyl ketone. The vapor-liquid equilibrium curves of cyclopropylmethyl ketone and water at ranges of 0-20% and 80-100% measured by a boiling point measuring instrument under 94 kPa are shown in FIG. 3.
Claims (4)
1. A device for purifying cyclopropyl methyl ketone by salt extraction and rectification is characterized in that: comprises an extractor (1), a brine phase tank (2), a centrifugal pump (3), a hypergravity stirring device (4), a hypergravity rectifying device (5), a condenser (6), a buffer tank (7), a reboiler (8) and a storage tank (9), wherein the brine phase tank (2) is connected with a discharge port I at the bottom of the extractor (1) through a pipeline, a discharge port II at the bottom of the extractor (1) is connected with a feed port of the hypergravity stirring device (4) through the centrifugal pump (3), a discharge port of the hypergravity stirring device (4) is connected with a feed port of the extractor (1) through a pipeline, a pipeline between the feed port of the hypergravity stirring device (4) and the centrifugal pump (3) is connected with a feed port at one side of the hypergravity rectifying device (5), the condenser (6) and the buffer tank (7) form a circulation loop with the top end of the hypergravity rectifying device (5), the reboiler (8) and the bottom of the hypergravity rectifying device (5) form a circulation loop, the reboiler (8) is connected with the storage tank (9).
2. The device for extracting and rectifying cyclopropyl methyl ketone by adding salt according to claim 1, wherein: hypergravity agitating unit (4) are equipped with rotor I (11) including shell I (10) in shell I (10), are equipped with filler I (12) in rotor I (11), and one side of shell I (10) is equipped with liquid inlet I (13), and the bottom is equipped with liquid outlet I (14), and liquid inlet I (13) department is equipped with liquid distributor (15), and shell I (10) bottom is equipped with motor I (16).
3. The device for extracting and rectifying cyclopropyl methyl ketone by adding salt according to claim 1, wherein: hypergravity rectifier unit (5) are including shell II (17), one side of shell II (17) is equipped with gas inlet (18), the top is equipped with gas outlet (19), the opposite side is equipped with liquid inlet II (20) and reflux import (21) respectively, reflux import (21) are located the top of liquid inlet II (20), shell II (17) bottom is equipped with liquid outlet II (22), be equipped with rotor II (23) in shell II (17), be equipped with filler II (24) in rotor II (23), shell II (17) bottom is equipped with motor II (25).
4. The method for purifying cyclopropyl methyl ketone by salt-adding extraction and rectification by using the device for purifying cyclopropyl methyl ketone by salt-adding extraction and rectification as claimed in claim 1, 2 or 3, characterized in that: the method comprises the following steps:
firstly, extracting, namely adding a pre-separated and purified cyclopropyl methyl ketone crude product and an extracting agent into an extractor according to a ratio, stirring, mixing and dissolving the extracting agent, standing and layering, wherein the upper layer is an organic phase, the lower layer is a brine phase, and the brine phase enters a brine phase tank;
secondly, rectification, namely rectifying the organic phase to obtain distilled water and impurities, wherein the residue is rectified cyclopropyl methyl ketone;
the extraction in the first step comprises one-step extraction or two-step extraction, wherein the extraction and rectification in one step comprise the following steps: adding an extracting agent into the crude product of the cyclopropyl methyl ketone at normal temperature, stirring for 1-3min in a supergravity stirring device, standing for 0.5-1h, layering, wherein the upper layer is an organic phase, the lower layer is a brine phase, and rectifying and purifying the organic phase;
the extractant comprises one or more of anhydrous sodium chloride, magnesium chloride, potassium chloride, anhydrous calcium chloride, potassium fluoride, anhydrous sodium carbonate, anhydrous potassium carbonate and potassium hydroxide, and the mass ratio of the crude cyclopropyl methyl ketone to the extractant is 5.8-28: 1;
the two-step extraction and rectification comprises the following steps:
adding an extracting agent I into a crude product of cyclopropyl methyl ketone according to a proportion at normal temperature, stirring for 1-3min in a hypergravity stirring device, standing for 0.5-1h, and then layering, wherein the upper layer is an organic phase I, the lower layer is a brine phase I, and the brine phase I enters a brine phase tank; the extractant I comprises any one of anhydrous sodium chloride, potassium chloride, magnesium chloride, potassium fluoride, anhydrous sodium carbonate, magnesium carbonate and potassium carbonate, and the mass ratio of the crude cyclopropyl methyl ketone to the extractant I is 5.8-28: 1;
adding an extracting agent II into the organic phase I in proportion, stirring for 1min in a high-gravity stirring device, standing for 0.5-1h, and then layering, wherein the upper layer is the organic phase II, the lower layer is a brine phase II, and the brine phase II enters a brine phase tank; the extractant II comprises any one of calcium chloride, potassium hydroxide and potassium carbonate, and the mass ratio of the crude cyclopropyl methyl ketone to the extractant I is 15-35: 1;
and (3) pumping the organic phase II into a hypergravity rectifying device under the action of a centrifugal pump, heating the organic phase II to be gasified at the rectifying temperature of 80-114 ℃, refluxing for 5-10min at the reflux ratio of 3-10:1, and rectifying for 0.5-1h to obtain the pure cyclopropyl methyl ketone.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102485708A (en) * | 2010-12-03 | 2012-06-06 | 中国石油化工股份有限公司 | C5 fraction separation method employing hypergravity extractive distillation apparatus |
| CN102643179A (en) * | 2012-04-07 | 2012-08-22 | 安徽绩溪县徽煌化工有限公司 | Preparation method of cyclopropyl methyl ketone |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102485708A (en) * | 2010-12-03 | 2012-06-06 | 中国石油化工股份有限公司 | C5 fraction separation method employing hypergravity extractive distillation apparatus |
| CN102643179A (en) * | 2012-04-07 | 2012-08-22 | 安徽绩溪县徽煌化工有限公司 | Preparation method of cyclopropyl methyl ketone |
Non-Patent Citations (1)
| Title |
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| 环丙基甲基酮的合成新方法;武祥龙等;《应用化学》;20070930;第24卷(第9期);1077-1079 * |
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