CN114917602A - Device and process method for preparing propionate - Google Patents
Device and process method for preparing propionate Download PDFInfo
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- CN114917602A CN114917602A CN202210553612.8A CN202210553612A CN114917602A CN 114917602 A CN114917602 A CN 114917602A CN 202210553612 A CN202210553612 A CN 202210553612A CN 114917602 A CN114917602 A CN 114917602A
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/14—Fractional distillation or use of a fractionation or rectification column
- B01D3/143—Fractional distillation or use of a fractionation or rectification column by two or more of a fractionation, separation or rectification step
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/009—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping in combination with chemical reactions
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/34—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping with one or more auxiliary substances
- B01D3/40—Extractive distillation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
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- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/52—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
- C07C67/54—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
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Abstract
The application discloses a device, which comprises a first rectifying tower, a water separation tank and a second rectifying tower; the top of the first rectifying tower is connected with the water diversion tank so that the material flow at the top of the first rectifying tower is led into the water diversion tank; a propionic acid inlet is formed in the top of the first rectifying tower; an alcohol compound inlet is formed in the bottom of the first rectifying tower; the water separation tank is provided with an extracting agent inlet; the outlet of the water knockout drum is connected with the top of the second rectifying tower; and a product outlet is formed in the tower kettle of the second rectifying tower. According to the method, the excessive high alcohol content in the ternary azeotropic system of propionate, water and alcohol is eliminated by a large amount of excess propionic acid at the top of the first rectifying tower and a reaction-rectification technical means, so that the propionate content can be controlled to be more than 80% and the alcohol content can be controlled to be less than 3% by a single tower.
Description
Technical Field
The application relates to a device and a process method for preparing propionate, belonging to the technical field of propionate.
Background
The propionate is low in toxicity and can be applied to solvents of natural or synthetic resins; can be used as spice for blending apple essence, banana essence, plum essence, pineapple essence, butter, western wine and other edible essence, and can also be used as high-grade daily-use cosmetic essence; the ethyl propionate and the propyl propionate can promote the low-temperature performance of the lithium ion battery, improve the compatibility of the electrolyte with the anode material and the cathode graphite material, reduce the viscosity and the eutectic point of the electrolyte system, and are beneficial to the migration of lithium ions.
Taking ethyl propionate as an example, the traditional process adopts an esterification method, concentrated sulfuric acid, p-toluenesulfonic acid or sulfonic acid resin is used as a catalyst, and benzene, toluene or cyclohexane is used as an intermittent reaction process of a water-carrying agent. The water generated after the esterification of the propionic acid and the ethanol is separated out of the reaction system by the water-carrying agent, but because the azeotropic point of the ethanol and the water-carrying agent is lower, the ethanol, the water and the water at the top of the tower generally comprise 30% of ethanol, 10% of water and 60% of the water-carrying agent by mass, so that a large amount of ethanol is carried out of the reaction system, latent heat of a large amount of ethanol and the water-carrying agent is wasted in the rectification process, and the energy consumption is high; the reaction raw material ethanol is excessive in quantity, so that the conversion rate of the propionic acid is higher than 90 percent as much as possible, and the ethanol separated from the tower top can only be recovered by the azeotropic composition of 95 percent ethanol and 5 percent water; about 2% of propionic acid, 5% of ethanol, 2% of water and about 91% of ethyl propionate are remained in the tower bottom product, and the unreacted propionic acid and the catalyst are removed by alkali washing and then are rectified and separated, so that the yield of the propionic acid is low and is only about 95%, and the raw material waste is caused.
Disclosure of Invention
According to one aspect of the present application, there is provided an apparatus comprising a first rectification column, a knock-out drum, and a second rectification column; the top of the first rectifying tower is connected with the water diversion tank so that the material flow at the top of the first rectifying tower is led into the water diversion tank; a propionic acid inlet is formed in the top of the first rectifying tower; an alcohol compound inlet is formed in the bottom of the first rectifying tower; the water separation tank is provided with an extracting agent inlet; the outlet of the water knockout drum is connected with the top of the second rectifying tower; and a product outlet is formed in the tower kettle of the second rectifying tower. According to the method, the excessive propionic acid at the top of the first rectifying tower and the overhigh alcohol content in the ternary azeotropic system of propionate, water and alcohol are eliminated by a reaction-rectification technical means, so that the propionate content can be controlled to be more than 80% and the alcohol content can be controlled to be less than 3% by a single tower.
According to a first aspect of the present application, there is provided an apparatus comprising a first rectification column, a knock-out drum, and a second rectification column; the top of the first rectifying tower is connected with the water diversion tank so that the material flow at the top of the first rectifying tower is led into the water diversion tank;
a propionic acid inlet is formed in the top of the first rectifying tower; an alcohol compound inlet is formed at the bottom of the first rectifying tower;
the water separation tank is provided with an extracting agent inlet;
the outlet of the water knockout drum is connected with the top of the second rectifying tower;
and the tower kettle of the second rectifying tower is provided with a product outlet.
Optionally, the top of the second distillation column is connected to the inlet of the alcohol compound at the bottom of the first distillation column, so that the second distillation column top stream is passed to the bottom of the first distillation column.
Optionally, a propionic acid outlet is further arranged at the bottom of the first rectifying tower;
the propionic acid outlet is connected with the propionic acid inlet at the top of the first rectifying tower.
Optionally, the propionic acid inlet is positioned at a full tower height of 1/6-1/2 away from the top of the first rectifying tower;
the height from the alcohol compound inlet to the tower kettle of the first rectifying tower is 0-1/2 of the total tower height;
the propionic acid inlet is higher than the alcohol compound inlet.
Optionally, the propionic acid inlet is positioned at a full tower height of 1/5-1/3 away from the top of the first rectifying tower;
the height from the alcohol compound inlet to the first rectifying tower kettle is 1/10-1/4 of the total tower height.
Optionally, the number of the trays of the first rectifying tower is 40-80;
the number of the tower plates of the second rectifying tower is 20-80.
Optionally, the number of plates of the first rectifying tower is 45-60.
Optionally, the number of the plates of the second rectifying tower is 40-60.
Optionally, the apparatus further comprises a third rectification column;
the outlet of the water diversion tank is connected with the top of the third rectifying tower;
the top of the third rectifying tower is connected with an alcohol compound inlet at the bottom of the first rectifying tower, so that the material flow at the top of the third rectifying tower is introduced to the bottom of the first rectifying tower;
preferably, the number of the plates of the third rectifying tower is 20-80.
According to a second aspect of the present application, there is provided a process for the preparation of propanoates, characterized by the use of the above-described apparatus.
The process for preparing propionic acid esters provided in the present application comprises the following process steps: introducing a raw material containing propionic acid from the top of a first rectifying tower, introducing a raw material containing alcohol compounds from the bottom of the first rectifying tower, reacting in the first rectifying tower, mixing and layering a material flow obtained from the top of the first rectifying tower and an extracting agent, introducing a layered organic layer into a second rectifying tower, and obtaining the propionate in the kettle of the second rectifying tower; the first rectifying tower is filled with a catalyst or the raw material containing the propionic acid contains the catalyst. The process takes propionic acid and various alcohols as raw materials, concentrated sulfuric acid, p-toluenesulfonic acid and sulfonic acid resin as catalysts, and obtains products of methyl propionate, ethyl propionate, propyl propionate and butyl propionate including isomer propionate through the processes of reactive distillation, water addition, extraction separation and the like.
Optionally, the following process steps are included:
(a) introducing a raw material I containing propionic acid from the top of a first rectifying tower, introducing a raw material II containing alcohol compounds from the bottom of the first rectifying tower, reacting in the first rectifying tower, mixing a material flow obtained from the top of the first rectifying tower with an extracting agent, layering, introducing a layered organic layer into a second rectifying tower, and obtaining a product containing propionic ester in the bottom of the second rectifying tower;
filling a catalyst in the first rectifying tower or containing the catalyst in the raw material containing the propionic acid;
preferably, the step (a) includes: and the raw material I and the raw material II react in the first rectifying tower to generate a gas-phase azeotrope containing propionate, the gas-phase azeotrope flows towards the top of the first rectifying tower and continuously reacts with the raw material I introduced from the top of the first rectifying tower to generate a material flow containing propionate.
Optionally, in the step (a), the mass of the extractant is 10-20% of the mass of the stream obtained from the top of the first rectifying tower.
Optionally, the propionate is present in the product comprising the propionate in an amount of 99.0 to 100%.
Optionally, the organic layer after layering further contains a substance A;
the substance A comprises alcohol and/or water;
in the layered organic layer, the content of propionate is 95.0-100%;
the content of the substance A is 0-5%.
Optionally, the molar ratio of the propionic acid to the alcohol compound is 2: 1-10: 1.
optionally, the raw materials are propionic acid (with a purity of more than 99%) and a plurality of alcohols (with a purity of more than 99.5%) at a feed molar ratio of 4:1 to 6: 1.
The alcohol compound may be selected from any one of alcohol normal forms and isomers such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, and tert-butanol.
Optionally, the catalyst is selected from any one of homogeneous catalysts, heterogeneous catalysts.
Optionally, the homogeneous catalyst is selected from any one of concentrated sulfuric acid and p-toluenesulfonic acid;
the heterogeneous catalyst is selected from sulfonic acid resins.
Optionally, the mass content of the catalyst in the raw material containing propionic acid is 0.3-1.0%.
Optionally, the process operating conditions of the first rectification column are: the temperature of the top of the tower is 55-110 ℃; the temperature of the tower kettle is 135-150 ℃; the reflux ratio at the top of the tower is 1: 1-1: 2;
the technological operating conditions of the second rectifying tower are as follows: the temperature of the top of the tower is 62-90 ℃; the temperature of the tower kettle is 75-125 ℃; the reflux ratio at the top of the tower is 1: 1-1: 2.
optionally, the process operating conditions of the first rectification column are: the temperature of the tower top is 80-100 ℃; the temperature of the tower bottom is 142-146 ℃.
Optionally, the process operating conditions of the second rectification column are: the temperature of the tower top is 70-80 ℃; the temperature of the tower bottom is 80-100 ℃.
Optionally, in the step (a), the mass of the extractant is 3-50% of the mass of the stream obtained from the top of the first rectifying tower.
Optionally, the extractant is selected from water.
Optionally, in the step (a), the stream obtained from the top of the second rectifying tower is returned to the bottom of the first rectifying tower.
Optionally, the temperature in the knock out pot is-30-40 ℃, preferably-10-20 ℃.
Optionally, the following process steps are also included:
(b) and introducing the layered extractant layer into a third rectifying tower, and returning the material flow obtained at the top of the third rectifying tower to the bottom of the first rectifying tower.
Optionally, the process operating conditions of the third rectification column are: the temperature of the tower top is 60-90 ℃; the temperature of the tower kettle is 80-125 ℃; the reflux ratio of the tower top is 1:1-2: 1.
optionally, the process operating conditions of the third distillation column are: the temperature of the tower top is 80-88 ℃; the temperature of the tower bottom is 90-110 ℃.
Optionally, the number of the plates of the third rectifying tower is 20-80.
Optionally, the number of the plates of the third rectifying tower is 40-60.
Alternatively, the process flow for the preparation of propanoates herein comprises the steps of:
(1) raw material propionic acid carrying a homogeneous catalyst is fed from the top of the first rectifying tower, and various alcohol raw materials are fed from the bottom of the first rectifying tower; or the sulfonic acid resin catalyst is directly filled into the first rectifying tower, and the propionic acid raw material does not need to carry a homogeneous catalyst additionally;
(2) the flow mode of the propionic acid in the first rectifying tower is that a liquid phase flows from the top of the first rectifying tower to the bottom of the first rectifying tower; various alcohols flow from the bottom of the first rectifying tower to the top of the first rectifying tower in a gas phase state; the gas-liquid two phases are contacted in a first rectifying tower;
(3) the generated propionate, water and unreacted alcohol form binary or ternary azeotrope, and the binary or ternary azeotrope continuously moves to the top of the first rectifying tower in a gas phase;
(4) the closer to the top of the first rectifying tower, the higher the content of propionic acid, and the propionic acid continues to react with various alcohols; the tower top produced materials of the first rectifying tower are propionate and water, the content of alcohol is lower than 3 percent, and alcohol raw materials are consumed by means of reactive distillation and a large amount of excess propionic acid;
(5) adding a certain volume of water into the extracted substance at the top of the first rectifying tower, mixing and oscillating in a water separation tank, and standing for layering;
(6) the upper organic phase directly enters a second rectifying tower, qualified products are extracted from the bottom of the second rectifying tower, and a small amount of binary or ternary azeotrope at the top of the second rectifying tower returns to the bottom of the first rectifying tower;
(7) and introducing the lower water phase in the water knockout drum into a third rectifying tower, and rectifying and separating out alcohol-ester-water binary or ternary azeotrope to return to the tower kettle of the first rectifying tower.
The continuous process method for synthesizing propionate by the reaction-rectification technology comprises the following process steps: raw material propionic acid is fed from the lower part of the top of the first rectifying tower, various alcohol raw materials are fed from the bottom of the first rectifying tower, the raw materials and the alcohol raw materials are in reverse contact in the first rectifying tower and react under the action of a catalyst, excessive propionic acid on the top of the first rectifying tower continuously consumes the alcohol raw materials, and a binary or ternary azeotropic system of propionate-alcohol-water is broken; binary or ternary azeotropy of propionate-alcohol-water extracted from the top of the first rectifying tower is added with a small amount of water, and the materials are fully mixed and then are kept stand for layering; the content of alcohol and water in the organic layer is about 1 percent, the content of propionate is 98 percent, and after a small amount of azeotrope of the alcohol and the propionate is separated from the top of the second rectifying tower through the second rectifying tower, a propionate product with the purity higher than 99 percent is extracted from the top or the bottom of the second rectifying tower; the water layer enters a third rectifying tower, and binary or ternary azeotrope of propionate-alcohol-water is separated from the top of the third rectifying tower; the azeotrope at the top of the second rectifying tower and the azeotrope at the top of the third rectifying tower directly circulates to the alcohol raw material inlet at the bottom of the first rectifying tower;
optionally, the process in the present application includes key equipment such as a first rectification column, a knock-out drum, and a second rectification column.
Optionally, the second rectification column top or bottom draws propionate ester with purity higher than 99%.
The beneficial effects that this application can produce include:
1. excessive propionic acid at the top of a first rectifying tower and excessive alcohol content in a ternary azeotropic system of propionate, water and alcohol are eliminated by a reaction-rectification technical means, the content of propionate can be controlled to be more than 80 percent by a single tower, and the content of alcohol is controlled to be less than 3 percent;
2. a water-carrying agent is not needed, and the content of alcohol and propionate returned by the second rectifying tower is obviously reduced, so that the energy consumption is obviously reduced;
3. the method adopts water as an extracting agent, does not need to be added into the tower and is only needed to be added into the water separation tank, the energy consumption of the tower kettle is not increased, the process is simple, the energy consumption is obviously reduced, other extracting agents need to be added into the tower to be vaporized to the tower top and condensed into liquid, and the energy is consumed by the tower kettle;
4. the continuous process has stable product quality and high propionate yield.
Drawings
FIG. 1 is a schematic process flow diagram according to an embodiment of the present invention.
The reference numerals in the figures are illustrated as follows:
1, a first rectifying tower and 2, a water separation tank;
3 a second rectifying tower and 4 a third rectifying tower.
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples.
The invention takes propionic acid and various alcohols as raw materials, takes concentrated sulfuric acid, p-toluenesulfonic acid and sulfonic resin as catalysts, and obtains products of methyl propionate, ethyl propionate, propyl propionate and butyl propionate including isomers through processes of reactive distillation, reactive separation and the like.
The specific process of the invention comprises the following steps:
raw material propionic acid carries a certain amount of homogeneous catalyst and is fed from the top of the first rectifying tower 1, and various alcohol raw materials are fed from the bottom of the first rectifying tower 1. The temperature of the top of the first rectifying tower 1 is controlled between 55 ℃ and 110 ℃, and the temperature of the bottom of the first rectifying tower 1 is controlled between 135 ℃ and 145 ℃. Propionic acid flows from the top of the first rectifying tower 1 to the bottom of the first rectifying tower 1 in a liquid phase state in the first rectifying tower 1, various alcohols flow from the bottom of the first rectifying tower 1 to the top of the first rectifying tower 1 in a gas phase state, and a gas-liquid two phase contacts and reacts in the first rectifying tower 1. The generated propionate, water and unreacted alcohol form binary or ternary azeotrope, the binary or ternary azeotrope continuously moves to the top of the first rectifying tower 1 in a gas phase mode, the closer to the top of the first rectifying tower 1, the higher the content of propionic acid is, the continuous reaction with various alcohols is carried out, the produced substances at the top of the first rectifying tower 1 are propionate and water, the alcohol content is lower than 3%, and alcohol raw materials are consumed by means of reactive distillation and a large amount of excess propionic acid. The excessive propionic acid is in the bottom of the first rectifying tower 1 and directly circulates to the top of the first rectifying tower 1. Adding a small amount of water into light components extracted from the top of the first rectifying tower 1, shaking up the mixture, standing the mixture for layering, directly feeding an organic layer into a second rectifying tower 3 for separation, circulating components at the top of the second rectifying tower 3 to the bottom of the first rectifying tower 1, and extracting qualified products from the top of the second rectifying tower or the bottom of the second rectifying tower 3.
The process for preparing propanoates provided herein comprises:
(1) raw material propionic acid is fed from the lower part of the top of the first rectifying tower 1, various alcohol raw materials are fed from the bottom of the first rectifying tower 1, the raw materials and the alcohol raw materials are in reverse contact in the first rectifying tower 1 and react under the action of a catalyst, excessive propionic acid at the tower top continuously consumes the alcohol raw materials, and a binary or ternary azeotropic system of propionate-alcohol-water is broken;
(2) adding a small amount of water into binary or ternary azeotropic mixture of propionate-alcohol-water extracted from the top of the first rectifying tower 1, fully mixing in a water separation tank 2, and standing for layering;
(3) the content of alcohol and water in the organic layer is about 1-3%, the content of propionate is more than 95%, after a small amount of water and azeotrope of alcohol and propionate are separated from the top of the second rectifying tower 3 through the second rectifying tower 3, propionate products with the purity higher than 99% are extracted from the top or the bottom of the second rectifying tower 3;
(4) the water layer enters a third rectifying tower 4, and binary or ternary azeotrope of propionate-alcohol-water is separated from the top of the third rectifying tower 4;
(5) the azeotrope at the top of the second rectifying tower 3 and the azeotrope at the top of the third rectifying tower 4 directly circulate to the alcohol raw material inlet at the bottom of the first rectifying tower 1.
The model of the gas chromatograph used in the present application is shimadzu GC 2014C.
Example 1
As shown in figure 1, propionic acid and ethanol are used as raw materials to prepare ethyl propionate, the feeding molar ratio of the raw materials of the propionic acid to the ethanol is 4:1, the propionic acid is fed from the top of a first rectifying tower 1, a catalyst adopts p-toluenesulfonic acid, the content of the catalyst is 1% of the mass fraction of the propionic acid, and the catalyst is completely dissolved in the propionic acid. The propionic acid moves from the top of the first rectifying tower 1 to the bottom of the first rectifying tower 1 in a liquid phase state. Ethanol is fed from the bottom of the first rectifying tower 1, flows from the bottom of the first rectifying tower 1 to the top of the first rectifying tower 1 in a gas phase, and is contacted and reacted in the first rectifying tower 1 in a gas-liquid two-phase mode. The number of the tower plates of the first rectifying tower 1 is 60, the metal theta ring is filled, the height of the filler is 2m, the reflux ratio of the top of the first rectifying tower 1 is controlled to be 1:1-2:1, the temperature of the top of the first rectifying tower 1 is stabilized to be 80-85 ℃, the temperature of the bottom of the first rectifying tower 1 is 135-140 ℃, and the composition of ethyl propionate at the top of the first rectifying tower 1 is about 82.4%, 14.5% of water and 3.1% of ethanol through determination. Water with the content of 10% (namely 10% of the total mass formed at the top of the first rectifying tower 1) is additionally added, the mixture is shaken up in a water separation tank 2 and then is kept stand for layering, and an organic layer approximately contains 1.2% of water, 1.6% of ethanol and 97.2% of ethyl propionate. The ratio of ethanol to ethyl propionate in the aqueous layer was 3: 1. The organic layer mixture directly enters a second rectifying tower 3, the number of the tower plates of the second rectifying tower 3 is 42, metal theta ring packing is filled, the height of the packing is 1.5m, the reflux ratio of the top of the second rectifying tower 3 is controlled to be 1:1-2:1, the temperature of the top of the second rectifying tower 3 is stabilized to be 78-80 ℃, the temperature of the bottom of the second rectifying tower 3 is 99-103 ℃, the components at the top of the second rectifying tower 3 change along with the extraction time, the initial components are about 50% of ethanol, 36% of ethyl propionate and 14% of water, and then the components are changed into about 6% of ethanol, 72% of ethyl propionate and 22% of water which are directly recycled to the ethanol raw material. And the ethyl propionate product with the purity higher than 99 percent is extracted from the top or the bottom of the second rectifying tower 3. The water layer enters a third rectifying tower 4 for separation, the number of tower plates of the third rectifying tower 4 is 45, the height of a filler is 1.5m, the reflux ratio of the top of the third rectifying tower 4 is controlled to be 1:1-2:1, the temperature of the top of the third rectifying tower 4 is stabilized at 78 ℃, the temperature of the bottom of the third rectifying tower 4 is 100-.
Example 2
As shown in figure 1, methyl propionate is prepared by taking propionic acid and methanol as raw materials, the feeding molar ratio of the propionic acid to the methanol is 4:1, the propionic acid is fed from the top of a first rectifying tower 1, a catalyst adopts p-toluenesulfonic acid resin, the catalyst is filled in the first rectifying tower 1, and theta ring packing is filled in a mode of one layer of catalyst and one layer of packing, and the height of the theta ring packing is about 8 cm. The propionic acid moves from the top of the first rectifying tower 1 to the bottom of the first rectifying tower 1 in a liquid phase state. Methanol is fed from the bottom of the first rectifying tower 1, flows from the bottom of the first rectifying tower 1 to the top of the first rectifying tower 1 in a gas phase, and is contacted and reacted in the first rectifying tower 1 in a gas-liquid two-phase mode. The number of the tower plates of the first rectifying tower 1 is 60, the metal theta ring is filled, the height of the filler is 2m, the reflux ratio of the top of the first rectifying tower 1 is controlled to be 1:1-2:1, the temperature of the top of the first rectifying tower 1 is stabilized to be 67-73 ℃, the temperature of the bottom of the first rectifying tower 1 is 110-115 ℃, and the compositions of the top of the first rectifying tower 1 are about 95.5 percent of methyl propionate, 2.5 percent of water and 2 percent of methanol through determination. 30 percent of water is additionally added, the mixture is shaken up in a water separation tank 2 and then is kept stand for layering, and an organic layer contains about 0.8 percent of water, 1.1 percent of methanol and 98.1 percent of methyl propionate. The ratio of methanol to methyl propionate in the aqueous layer was about 2.5: 1. The organic layer mixture directly enters a second rectifying tower 3, the number of the rectifying tower plates of the second rectifying tower 3 is 45, the metal theta ring is filled, the height of the filler is 1.5m, the reflux ratio of the top of the second rectifying tower 3 is controlled to be 1:1-2:1, the temperature of the top of the second rectifying tower 3 is stabilized to be 62-63 ℃, and methanol with light component content of about 48 percent and methyl propionate with light component content of 52 percent are collected and directly circulated to a methanol raw material. And then controlling the temperature at the top of the second rectifying tower 3 to 79-81 ℃ to extract methyl propionate with the purity higher than 99%. The water layer enters a third rectifying tower 4 for separation, the number of the plates of the third rectifying tower 4 is 50, the height of a filler is 1.5m, the reflux ratio of the top of the third rectifying tower 4 is controlled to be 1:1-2:1, the temperature of the top of the third rectifying tower 4 is stabilized at 62-63 ℃, the temperature of the bottom of the third rectifying tower 4 is 100-.
Example 3
As shown in fig. 1, propyl propionate is prepared by using propionic acid and n-propanol as raw materials, the feeding molar ratio of the propionic acid to the n-propanol is 4:1, the propionic acid is fed from the position 1/4 below the top of the first rectifying tower 1, the catalyst adopts p-toluenesulfonic acid, the content of the catalyst is 1% of the mass fraction of the propionic acid, the catalyst is completely dissolved in the propionic acid, and the propionic acid moves from the top of the first rectifying tower 1 to the bottom of the first rectifying tower 1 in a liquid phase state. The n-propanol is fed from the bottom of the first rectifying tower 1, flows from the bottom of the first rectifying tower 1 to the top of the first rectifying tower 1 in a gas phase, and is contacted and reacted in the first rectifying tower 1 in a gas-liquid two-phase manner. The number of the tower plates of the first rectifying tower 1 is 60, the height of the filler is 2m, the reflux ratio at the top of the first rectifying tower 1 is controlled to be 1:1-2:1, the temperature at the top of the first rectifying tower 1 is stabilized to be 88-103 ℃, the temperature at the bottom of the first rectifying tower 1 is 140-145 ℃, and the composition at the top of the first rectifying tower 1 is determined to be about 83.5 percent of propyl propionate, 13 percent of water and 3.5 percent of n-propanol. An additional 20% of water was added, the mixture was shaken up in a knockout drum 2 and then allowed to stand for separation, and the organic layer contained about 1.3% of water, 2.5% of n-propanol and 96.2% of propyl propionate. The ratio of n-propanol to propyl propionate in the aqueous layer was about 4.5: 1. The organic layer mixture directly enters a second rectifying tower 3, the number of plates of the second rectifying tower 3 is 40, metal theta ring packing is adopted, the height of the packing is 1.5m, the reflux ratio of the top of the second rectifying tower 3 is controlled to be 1:1-2:1, the temperature of the top of the second rectifying tower 3 is stabilized to be 87-89 ℃, the temperature of the bottom of the second rectifying tower 3 is 120-125 ℃, the components of the top of the second rectifying tower 3 change along with the extraction time, the initial composition is about 28 percent of water and 72 percent of normal propyl alcohol, and the later composition is changed into about 23 percent of water and 77 percent of propyl propionate which are directly circulated to the normal propyl alcohol raw material. Then, a propyl propionate product with the purity higher than 99 percent is extracted from the top of the second rectifying tower 3. The water layer enters a third rectifying tower 4 for separation, the number of plates of the third rectifying tower 4 is 50, the height of metal theta ring packing is 1.5m, the reflux ratio of the top of the third rectifying tower 4 is controlled to be 1:1-2:1, the temperature of the top of the third rectifying tower 4 is stabilized to be 87-89 ℃, the temperature of the bottom of the third rectifying tower 4 is 100-105 ℃, the components of the top of the third rectifying tower 4 comprise about 70 percent of propyl propionate and about 30 percent of normal propyl alcohol and about 30 percent of water, and the components are directly returned to the feeding part of the normal propyl alcohol at the bottom of the first rectifying tower 1.
Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.
Claims (10)
1. The device is characterized by comprising a first rectifying tower, a water separation tank and a second rectifying tower; the top of the first rectifying tower is connected with the water separation tank so that the material flow at the top of the first rectifying tower is introduced into the water separation tank;
a propionic acid inlet is formed in the top of the first rectifying tower; an alcohol compound inlet is formed in the bottom of the first rectifying tower;
the water separation tank is provided with an extracting agent inlet;
the outlet of the water diversion tank is connected with the top of the second rectifying tower;
and a product outlet is formed in the tower kettle of the second rectifying tower.
2. The apparatus of claim 1, wherein the top of the second rectification column is connected to an alcohol compound inlet at the bottom of the first rectification column such that the second rectification column top stream passes to the bottom of the first rectification column.
3. The device according to claim 1, characterized in that a propionic acid outlet is further arranged at the bottom of the first rectifying tower;
the propionic acid outlet is connected with the propionic acid inlet at the top of the first rectifying tower.
4. The apparatus of claim 1, wherein the propionic acid inlet has a height from the top of the first rectification column of a full column height of 1/6-1/2;
the height from the alcohol compound inlet to the tower kettle of the first rectifying tower is 0-1/2 of the total tower height;
the propionic acid inlet is higher than the alcohol compound inlet.
5. The apparatus according to claim 1, wherein the number of plates of the first rectifying column is 40 to 80;
the number of the tower plates of the second rectifying tower is 20-80.
6. The apparatus of claim 1, further comprising a third rectification column;
the outlet of the water knockout drum is connected with the top of the third rectifying tower;
the top of the third rectifying tower is connected with an alcohol compound inlet at the bottom of the first rectifying tower, so that the material flow at the top of the third rectifying tower is introduced to the bottom of the first rectifying tower;
preferably, the number of the plates of the third rectifying tower is 20-80.
7. A process for the preparation of propanoates, characterized by the fact that it is carried out using the apparatus according to any one of claims 1 to 6.
8. The process according to claim 7, characterized by the process steps of:
(a) introducing a raw material I containing propionic acid from the top of a first rectifying tower, introducing a raw material II containing alcohol compounds from the bottom of the first rectifying tower, reacting in the first rectifying tower, mixing and layering a material flow obtained from the top of the first rectifying tower and an extracting agent, introducing a layered organic layer into a second rectifying tower, and obtaining a product containing propionic ester at the bottom of the second rectifying tower;
filling a catalyst in the first rectifying tower or containing the catalyst in the raw material containing the propionic acid;
preferably, the step (a) comprises: and the raw material I and the raw material II react in the first rectifying tower to generate a gas-phase azeotrope containing propionate, the gas-phase azeotrope flows towards the top of the first rectifying tower and continuously reacts with the raw material I introduced from the top of the first rectifying tower to generate a material flow containing propionate.
9. The process of claim 8, wherein the propionate is present in the product comprising propionate in an amount of 99.0-100%.
10. The process according to claim 8, wherein the organic layer after the delamination further comprises a substance A;
the substance A comprises alcohol and/or water;
in the layered organic layer, the content of propionate is 95.0-100%;
the content of the substance A is 0-5%;
preferably, the molar ratio of the propionic acid to the alcohol compound is 2: 1-10: 1;
preferably, the catalyst is selected from any one of homogeneous catalysts, heterogeneous catalysts;
preferably, in the raw material containing propionic acid, the mass content of the catalyst is 0.3-1.0%;
preferably, the process operating conditions of the first rectification column are: the temperature of the tower top is 55-110 ℃; the temperature of the tower kettle is 135-150 ℃; the reflux ratio of the tower top is 1: 1-1: 2;
the technological operating conditions of the second rectifying tower are as follows: the temperature of the top of the tower is 62-90 ℃; the temperature of the tower kettle is 75-125 ℃; the reflux ratio of the tower top is 1: 1-1: 2;
preferably, in the step (a), the mass of the extractant is 3 to 50 percent of the mass of the stream obtained from the top of the first rectifying tower;
preferably, the extractant is selected from water;
preferably, in the step (a), the stream obtained from the top of the second rectifying tower is returned to the bottom of the first rectifying tower;
preferably, the method also comprises the following process steps:
(b) introducing the layered extractant layer into a third rectifying tower, and returning the material flow obtained at the top of the third rectifying tower to the bottom of the first rectifying tower;
preferably, the process operating conditions of the third rectifying tower are as follows: the temperature of the tower top is 60-90 ℃; the temperature of the tower kettle is 80-125 ℃; the reflux ratio at the top of the tower is 1:1-2: 1.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1182189A2 (en) * | 1995-12-15 | 2002-02-27 | Rohm And Haas Company | Process for recovering butyl acrylate substantially free from acrylic acid |
| CN103483192A (en) * | 2013-01-16 | 2014-01-01 | 南通大学 | High-yield separation method of methyl propionate-methanol-water system |
| CN104649902A (en) * | 2013-11-19 | 2015-05-27 | 中国石油天然气股份有限公司 | Production method of sec-butyl acetate |
| 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 |
| CN109851496A (en) * | 2019-01-09 | 2019-06-07 | 沈阳化工大学 | It is a kind of by ester alcohol exchange system for the heterogeneous catalysis rectification process of propionic ester |
-
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1182189A2 (en) * | 1995-12-15 | 2002-02-27 | Rohm And Haas Company | Process for recovering butyl acrylate substantially free from acrylic acid |
| CN103483192A (en) * | 2013-01-16 | 2014-01-01 | 南通大学 | High-yield separation method of methyl propionate-methanol-water system |
| CN104649902A (en) * | 2013-11-19 | 2015-05-27 | 中国石油天然气股份有限公司 | Production method of sec-butyl acetate |
| 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 |
| CN109851496A (en) * | 2019-01-09 | 2019-06-07 | 沈阳化工大学 | It is a kind of by ester alcohol exchange system for the heterogeneous catalysis rectification process of propionic ester |
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