CN114917602B - Device and technological method for preparing propionate - Google Patents
Device and technological method for preparing propionate Download PDFInfo
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- CN114917602B CN114917602B CN202210553612.8A CN202210553612A CN114917602B CN 114917602 B CN114917602 B CN 114917602B CN 202210553612 A CN202210553612 A CN 202210553612A CN 114917602 B CN114917602 B CN 114917602B
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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
- B01D3/14—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
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/42—Regulation; Control
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- C—CHEMISTRY; METALLURGY
- 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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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- 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
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/58—Separation; Purification; Stabilisation; Use of additives by liquid-liquid treatment
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Abstract
The application discloses a device, which comprises a first rectifying tower, a water distributing tank and a second rectifying tower; the top of the first rectifying tower is connected with the water diversion tank so that the top material flow of the first rectifying tower is led into the water diversion tank; the top of the first rectifying tower is provided with a propionic acid inlet; an alcohol compound inlet is formed in the bottom of the first rectifying tower; the water diversion tank is provided with an extractant inlet; the outlet of the water diversion tank is connected with the top of the second rectifying tower; and a product outlet is arranged at the bottom of the second rectifying tower. According to the application, excessive propionic acid in the tower top of the 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, so that the content of propionate 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, and belongs to the technical field of propionate.
Background
The propionate is low in toxicity and can be applied to solvents of natural or synthetic resins; the spice can be used for blending apple aroma, banana aroma, plum aroma, pineapple aroma, butter, american wine and other various edible essence, and also can be used as a high-grade daily 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 favorable for the migration of lithium ions.
By taking ethyl propionate synthesis as an example, the traditional process adopts an esterification method, concentrated sulfuric acid, p-toluenesulfonic acid or sulfonic acid resin as a catalyst, and benzene, toluene or cyclohexane as a water carrying agent. The water generated after the esterification of the propionic acid and the ethanol is separated from a reaction system by a water carrying agent, but because the azeotropic point of the ethanol and the water carrying agent is lower, the mass composition of the ethanol, the water and the water carrying agent at the top of the tower is 30 percent of ethanol, 10 percent of water and 60 percent of water carrying agent generally, so that a large amount of ethanol is carried out of the reaction system, a large amount of ethanol and the latent heat of the water carrying agent are wasted in the rectification process, and the energy consumption is high; the ethanol which is a reaction raw material is excessive, so that the conversion rate of propionic acid is higher than 90% as much as possible, and the ethanol separated from the top of the tower can be recovered only by azeotropic composition of 95% ethanol and 5% water; the residue of the tower bottom product is about 2 percent of propionic acid, 5 percent of ethanol, 2 percent of water and about 91 percent of ethyl propionate, and unreacted propionic acid and catalyst are removed by alkali washing and then are rectified and separated, so that the yield of propionic acid is low, and only about 95 percent of propionic acid is needed, thereby wasting raw materials.
Disclosure of Invention
According to one aspect of the present application, there is provided an apparatus comprising a first rectifying column, a water dividing tank and a second rectifying column; the top of the first rectifying tower is connected with the water diversion tank so that the top material flow of the first rectifying tower is led into the water diversion tank; the top of the first rectifying tower is provided with a propionic acid inlet; an alcohol compound inlet is formed in the bottom of the first rectifying tower; the water diversion tank is provided with an extractant inlet; the outlet of the water diversion tank is connected with the top of the second rectifying tower; and a product outlet is arranged at the bottom of the second rectifying tower. According to the application, excessive propionic acid in the tower top of the 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, so that the content of propionate 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 rectifying column, a water dividing tank and a second rectifying column; the top of the first rectifying tower is connected with the water diversion tank so that the top material flow of the first rectifying tower is led into the water diversion tank;
the top of the first rectifying tower is provided with a propionic acid inlet; an alcohol compound inlet is formed in the bottom of the first rectifying tower;
the water diversion tank is provided with an extractant inlet;
the outlet of the water diversion tank is connected with the top of the second rectifying tower;
and a product outlet is arranged at the bottom of the second rectifying tower.
Optionally, the top of the second rectifying tower is connected with an alcohol compound inlet at the bottom of the first rectifying tower, so that the top stream of the second rectifying tower is led to the bottom of the first rectifying tower.
Optionally, a propionic acid outlet is further arranged at the bottom of the first rectifying tower;
the propionic acid outlet is connected with a propionic acid inlet at the top of the first rectifying tower.
Optionally, the height of the propionic acid inlet from the top of the first rectifying tower is 1/6-1/2 of the total tower height;
the height of the alcohol compound inlet from the tower bottom 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 height of the propionic acid inlet from the top of the first rectifying tower is 1/5-1/3 of the total tower height;
the height of the alcohol compound inlet from the tower bottom of the first rectifying tower is 1/10-1/4 of the total tower height.
Optionally, the number of the tower plates 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 the tower plates of the first rectifying tower is 45-60.
Optionally, the number of the tower plates of the second rectifying tower is 40-60.
Optionally, the apparatus further comprises a third rectifying 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 as to enable the top stream of the third rectifying tower to flow through the bottom of the first rectifying tower;
preferably, the third rectifying tower has a tray number of 20 to 80.
According to a second aspect of the present application there is provided a process for the preparation of a propionate, characterised in that it is carried out using the apparatus described above.
The process for preparing the propionate provided by the application comprises the following process steps: introducing raw materials containing propionic acid from the top of a first rectifying tower, introducing raw materials 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 the layered organic layer into a second rectifying tower, and obtaining the propionate at the bottom of the second rectifying tower; the first rectifying tower is filled with a catalyst or the raw material containing propionic acid contains the catalyst. The process takes propionic acid and various alcohols as raw materials, takes 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 reaction rectification, water adding extraction separation and the like.
Optionally, the method comprises the following process steps:
(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 extractant, layering, introducing a layered organic layer into a second rectifying tower, and obtaining a product containing propionate at the bottom of the second rectifying tower;
the first rectifying tower is filled with a catalyst or the raw material containing propionic acid contains the catalyst;
preferably, the step (a) includes: the raw materials I and II react in the first rectifying tower to generate a gas-phase azeotrope containing propionate, and 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 at the top of the first rectifying column.
Optionally, in the product containing the propionate, the content of the propionate is 99.0-100%.
Optionally, the layered organic layer further comprises a substance A;
the substance a comprises an 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 to 10:1.
alternatively, the raw materials are propionic acid (purity more than 99%) and a plurality of alcohols (purity more than 99.5%), and the feeding molar ratio is 4:1-6:1.
Optionally, the alcohol compound is selected from any one of alcohol normal forms and isomers such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol and the like.
Alternatively, the catalyst is selected from any one of a homogeneous catalyst and a heterogeneous catalyst.
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, in the raw material containing propionic acid, the mass content of the catalyst is 0.3-1.0%.
Optionally, the process operating conditions of the first rectifying tower are: the temperature of the tower top is 55-110 ℃; the temperature of the tower kettle is 135-150 ℃; the overhead reflux ratio was 1:1 to 1:2;
the process operation conditions of the second rectifying tower are as follows: the temperature of the tower top is 62-90 ℃; the temperature of the tower kettle is 75-125 ℃; the overhead reflux ratio was 1:1 to 1:2.
optionally, the process operating conditions of the first rectifying tower are: the temperature of the tower top is 80-100 ℃; the temperature of the tower kettle is 142-146 ℃.
Optionally, the process operating conditions of the second rectifying tower are: the temperature of the tower top is 70-80 ℃; the temperature of the tower kettle is 80-100 ℃.
Optionally, in the step (a), the mass of the extractant is 3-50% of the mass of the stream obtained at the top of the first rectifying column.
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.
Alternatively, the temperature in the knock out drum is-30-40 ℃, preferably-10-20 ℃.
Optionally, the method further comprises the following process steps:
(b) And (3) 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 rectifying tower are as follows: the temperature of the tower top is 60-90 ℃; the temperature of the tower kettle is 80-125 ℃; the overhead reflux ratio was 1:1-2: 1.
optionally, the process operating conditions of the third rectifying tower are as follows: the temperature of the tower top is 80-88 ℃; the temperature of the tower kettle is 90-110 ℃.
Optionally, the number of the tower plates of the third rectifying tower is 20-80.
Optionally, the number of the tower plates of the third rectifying tower is 40-60.
Optionally, the process flow for preparing the propionate comprises the following steps:
(1) Raw material propionic acid carries a homogeneous catalyst and is fed from the top of a 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 adopted to be directly filled into the first rectifying tower, and the propionic acid raw material does not need to additionally carry a homogeneous catalyst;
(2) The flow mode of the propionic acid in the first rectifying tower is that the propionic acid flows from the top of the first rectifying tower to the bottom of the first rectifying tower in a liquid phase; the 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 and water and unreacted alcohols form binary or ternary azeotrope which continuously moves towards 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 propionic acid content, and the more the propionic acid content reacts with various alcohols; the top extract of the first rectifying tower is propionate and water, the alcohol content is lower than 3%, and alcohol raw materials are consumed by means of reactive rectification and a large amount of excess propionic acid;
(5) Adding a certain volume of water into the tower top extract of the first rectifying tower, mixing and vibrating in a water distributing 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 the lower water in the water separating tank is led into a third rectifying tower, and the alcohol-ester-water binary or ternary azeotrope is rectified and separated and returned to the tower bottom of the first rectifying tower.
The continuous process for synthesizing the 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 material propionic acid and the first rectifying tower 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 material, and a binary or ternary azeotropic system of propionate-alcohol-water is broken; adding a small amount of water into binary or ternary azeotropy of propionate-alcohol-water extracted from the top of the first rectifying tower, fully mixing, standing and layering; alcohol and water content in the organic layer is about 1%, propionate content is 98%, after a small amount of water and azeotrope of alcohol and propionate are separated from the top of the second rectifying tower through the second rectifying tower, the top or bottom of the second rectifying tower is used for extracting propionate products with purity higher than 99%; the water layer enters a third rectifying tower, and a 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 top of the third rectifying tower is directly circulated to an alcohol raw material inlet at the bottom of the first rectifying tower;
optionally, the process comprises a first rectifying tower, a water distributing tank, a second rectifying tower and other key equipment.
Optionally, the second rectification column top or column bottom produces propionate with a purity higher than 99%.
The application has the beneficial effects that:
1. the excessive propionic acid at the top of the first rectifying tower and the excessive alcohol content in a ternary azeotropic system of propionate, water and alcohol are eliminated by a reaction-rectification technical means, so that the content of propionate can be controlled to be more than 80% by a single tower, and the alcohol content is controlled to be less than 3%;
2. the water carrying agent is not needed, the content of alcohol and propionate returned by the second rectifying tower is obviously reduced, and the energy consumption is obviously reduced;
3. the application adopts water as the extractant, the extractant is not required to be added into a tower and added into a water distribution tank, the energy consumption of a tower kettle is not increased, the process is simple, the energy consumption is obviously reduced, and other extractants are required to be added into the tower and vaporized to the tower top to be condensed into liquid, and the energy consumption of the tower kettle is required;
4. continuous process, stable product quality and high propionate yield.
Drawings
FIG. 1 is a schematic process flow diagram of an embodiment of the present application.
Reference numerals in the drawings are explained as follows:
1 a first rectifying tower and 2 a water separating tank;
3 a second rectifying tower and 4 a third rectifying tower.
Detailed Description
The present application is described in detail below with reference to examples, but the present application is not limited to these examples.
The application takes propionic acid and various alcohols as raw materials, takes 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 isomers through the processes of reactive distillation, reactive separation and the like.
The specific technical process of the application is as follows:
the raw material propionic acid carries a certain amount of homogeneous catalyst to be 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 in a liquid phase state from the top of the first rectifying tower 1 to the bottom of the first rectifying tower 1 in the first rectifying tower 1, various alcohols flow in a gas phase state from the bottom of the first rectifying tower 1 to the top of the first rectifying tower 1, and gas-liquid two phases are contacted and reacted in the first rectifying tower 1. The binary or ternary azeotrope composed of the generated propionate, water and unreacted alcohols continuously moves towards the top of the first rectifying tower 1 in a gas phase, the closer to the top of the first rectifying tower 1, the higher the propionic acid content is, the continuously reacts with various alcohols, the propionate and water are extracted from the top of the first rectifying tower 1, the alcohol content is lower than 3%, and alcohol raw materials are consumed by means of reactive rectification and a large amount of propionic acid excess. The excessive propionic acid is directly circulated to the top of the first rectifying tower 1. Adding a small amount of water into the light component extracted from the top of the first rectifying tower 1, shaking uniformly, standing for layering, directly separating an organic layer into a second rectifying tower 3, recycling the component at the top of the second rectifying tower 3 to the bottom of the first rectifying tower 1, and extracting a qualified product from the top of the second rectifying tower or the bottom of the second rectifying tower 3.
The technical method for preparing the propionate provided by the application comprises the following steps:
(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 material propionic acid and the first rectifying tower are in reverse contact in the first rectifying tower 1, the raw material propionic acid react under the action of a catalyst, excessive propionic acid on the top of the tower continuously consumes the alcohol raw material, and a binary or ternary azeotropic system of propionate-alcohol-water is broken;
(2) Adding a small amount of water into binary or ternary azeotropy of propionate-alcohol-water extracted from the top of the first rectifying tower 1, fully mixing in a water diversion tank 2, and standing for layering;
(3) The alcohol and water content in the organic layer is about 1-3%, the propionate content 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, the top or bottom of the second rectifying tower 3 is used for extracting propionate products with purity higher than 99%;
(4) The water layer enters a third rectifying tower 4, and a 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 top of the third rectifying tower 4 is directly recycled to the alcohol raw material inlet at the bottom of the first rectifying tower 1.
The gas chromatograph used in the present application is model number shimadzu GC2014C.
Example 1
As shown in figure 1, ethyl propionate is prepared by taking propionic acid and ethanol as raw materials, the feed molar ratio of the raw materials of propionic acid to ethanol is 4:1, the propionic acid is fed from the top of the first rectifying tower 1, the catalyst adopts p-toluenesulfonic acid, the catalyst content 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 contacts and reacts with gas-liquid two phases in the first rectifying tower 1. The number of the tower plates of the first rectifying tower 1 is 60, the height of the metal theta ring filler is 2m, the reflux ratio of the tower top of the first rectifying tower 1 is controlled between 1:1 and 2:1, the temperature of the tower top of the first rectifying tower 1 is stabilized between 80 and 85 ℃, the temperature of the tower bottom of the first rectifying tower 1 is 135 to 140 ℃, and the tower top of the first rectifying tower 1 is determined to be about 82.4 percent of ethyl propionate, 14.5 percent of water and 3.1 percent of ethanol. 10% of water (i.e., 10% of the total mass of the first rectifying tower 1 overhead composition) was additionally added, and the mixture was shaken well in a knock-out tank 2, and then allowed to stand still for delamination, and an organic layer containing about 1.2% of water, 1.6% of ethanol and 97.2% of ethyl propionate was formed. 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 tower plate number of the second rectifying tower 3 is 42, the metal theta ring filler is 1.5m, the reflux ratio of the top of the second rectifying tower 3 is controlled between 1:1 and 2:1, the temperature of the top of the second rectifying tower 3 is stabilized between 78 ℃ and 80 ℃, the temperature of the bottom of the second rectifying tower 3 is between 99 ℃ and 103 ℃, the top components of the second rectifying tower 3 change along with the extraction time, the initial composition is about 50 percent of ethanol, 36 percent of ethyl propionate and 14 percent of water, the composition is changed into about 6 percent of ethanol, 72 percent of ethyl propionate and 22 percent of water, and the components are all directly circulated back to the ethanol raw material. The top or bottom of the second rectifying tower 3 is used for extracting ethyl propionate products with purity higher than 99 percent. 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 metal theta ring filler is 1.5m, the reflux ratio of the top of the third rectifying tower 4 is controlled between 1:1 and 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 100-105 ℃, the top of the third rectifying tower 4 is composed of about 68 percent ethanol, 20 percent ethyl propionate and 12 percent water, and the mixture also directly returns to the ethanol feeding position at the bottom of the first rectifying tower 1.
Example 2
As shown in FIG. 1, methyl propionate is prepared by taking propionic acid and methanol as raw materials, the feed molar ratio of the raw materials of propionic acid to methanol is 4:1, propionic acid is fed from the top of the first rectifying tower 1, p-toluenesulfonic acid resin is adopted as a catalyst, the catalyst is filled into the first rectifying tower 1, and the theta-ring filler is filled in a manner of one layer of catalyst and one layer of filler, and the height 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 contacts and reacts with gas-liquid two phases in the first rectifying tower 1. The number of the tower plates of the first rectifying tower 1 is 60, the height of the metal theta ring filler is 2m, the reflux ratio of the tower top of the first rectifying tower 1 is controlled between 1:1 and 2:1, the temperature of the tower top of the first rectifying tower 1 is stabilized between 67 and 73 ℃, the temperature of the tower bottom of the first rectifying tower 1 is 110 to 115 ℃, and the tower top of the first rectifying tower 1 is determined to be about 95.5 percent of methyl propionate, 2.5 percent of water and 2 percent of methanol. An additional 30% water content was added and the mixture was shaken in a knock-out pot 2 and allowed to stand for delamination, the organic layer containing approximately 0.8% water, 1.1% methanol and 98.1% methyl propionate. The ratio of methanol to methyl propionate in the aqueous layer was about 2.5:1. The mixture of the organic layers directly enters a second rectifying tower 3, the number of tower plates of the second rectifying tower 3 is 45, the height of metal theta ring packing is 1.5m, the reflux ratio of the top of the second rectifying tower 3 is controlled between 1:1 and 2:1, the temperature of the top of the second rectifying tower 3 is stabilized between 62 ℃ and 63 ℃, and methanol with the light component content of about 48 percent and methyl propionate with the light component content of 52 percent are collected and directly circulated to a methanol raw material. And then controlling the temperature of the top of the second rectifying tower 3 to be 79-81 ℃ to produce methyl propionate with purity higher than 99%. The water layer enters a third rectifying tower 4 for separation, the number of tower plates of the third rectifying tower 4 is 50, the metal theta ring filler is 1.5m, the reflux ratio of the top of the third rectifying tower 4 is controlled between 1:1 and 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 100-105 ℃, the top of the third rectifying tower 4 is composed of about 48 percent of methanol and 52 percent of methyl propionate, and the methanol is directly returned to the methanol feeding position at the bottom of the first rectifying tower 1.
Example 3
As shown in figure 1, propionic acid and n-propanol are used as raw materials to prepare propyl propionate, the feeding mole ratio of the raw materials of propionic acid and n-propanol is 4:1, the propionic acid is fed from the position 1/4 below the top of the first rectifying tower 1, p-toluenesulfonic acid is adopted as a catalyst, the catalyst content 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. 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 gas-liquid two phases in the first rectifying tower 1. The number of the tower plates of the first rectifying tower 1 is 60, the height of the metal theta ring filler is 2m, the reflux ratio of the tower top of the first rectifying tower 1 is controlled between 1:1 and 2:1, the temperature of the tower top of the first rectifying tower 1 is stabilized between 88 ℃ and 103 ℃, the temperature of the tower bottom of the first rectifying tower 1 is 140 ℃ to 145 ℃, and the tower 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% water content was added and the mixture was shaken in a knock-out pot 2 and allowed to stand for delamination, the organic layer containing approximately 1.3% water, 2.5% n-propanol and 96.2% 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 tower plates of the second rectifying tower 3 is 40, the metal theta ring filler is 1.5m, the reflux ratio of the top of the second rectifying tower 3 is controlled between 1:1 and 2:1, the temperature of the top of the second rectifying tower 3 is stabilized between 87 ℃ and 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% of water and 72% of n-propanol, the composition is changed into about 23% of water and 77% of propyl propionate, and the components are directly circulated to the n-propanol raw material. Thereafter, propyl propionate product with purity higher than 99% 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 tower plates of the third rectifying tower 4 is 50, the metal theta ring filler is 1.5m, the reflux ratio of the top of the third rectifying tower 4 is controlled between 1:1 and 2:1, the temperature of the top of the third rectifying tower 4 is stabilized between 87 ℃ and 89 ℃, the temperature of the bottom of the third rectifying tower 4 is 100 ℃ to 105 ℃, and the top of the third rectifying tower 4 is composed of propyl propionate, n-propanol and water with the content of about 70 percent, and the water with the content of about 30 percent, and the water is directly returned to the feeding position of the n-propanol at the bottom of the first rectifying tower 1.
While the application has been described in terms of preferred embodiments, it will be understood by those skilled in the art that various changes and modifications can be made without departing from the scope of the application, and it is intended that the application is not limited to the specific embodiments disclosed.
Claims (20)
1. The technical method for preparing the propionate is carried out by adopting a device and is characterized by comprising the following technical steps:
(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 extractant, layering, introducing a layered organic layer into a second rectifying tower, and obtaining a product containing propionate at the bottom of the second rectifying tower;
the first rectifying tower is filled with a catalyst or the raw material containing propionic acid contains the catalyst.
2. The process of claim 1, wherein the apparatus comprises a first rectifying column, a water knockout drum, and a second rectifying column; the top of the first rectifying tower is connected with the water diversion tank so that the top material flow of the first rectifying tower is led into the water diversion tank;
the top of the first rectifying tower is provided with a propionic acid inlet; an alcohol compound inlet is formed in the bottom of the first rectifying tower;
the water diversion tank is provided with an extractant inlet;
the outlet of the water diversion tank is connected with the top of the second rectifying tower;
and a product outlet is arranged at the bottom of the second rectifying tower.
3. The process of claim 2, wherein the second rectifying column top is connected to an alcohol compound inlet at the bottom of the first rectifying column to allow the second rectifying column top stream to pass into the bottom of the first rectifying column.
4. The process according to claim 2, wherein a propionic acid outlet is further provided at the bottom of the first rectifying column;
the propionic acid outlet is connected with a propionic acid inlet at the top of the first rectifying tower.
5. The process of claim 4, wherein the propionic acid inlet has a total column height from the top of the first rectifying column of 1/6 to 1/2;
the height of the alcohol compound inlet from the tower bottom 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.
6. The process according to claim 2, wherein the number of trays of the first rectifying column is 40 to 80;
the number of the tower plates of the second rectifying tower is 20-80.
7. The process of claim 2, wherein 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 top stream of the third rectifying tower flows through the bottom of the first rectifying tower.
8. The process according to claim 7, wherein the third rectifying column has a tray number of 20 to 80.
9. The process of claim 1, wherein step (a) comprises: the raw materials I and II react in the first rectifying tower to generate a gas-phase azeotrope containing propionate, and 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.
10. Process according to claim 9, characterized in that the content of propionate in the product containing propionate is 99.0-100%.
11. The process according to claim 9, wherein the layered organic layer further comprises a substance a;
the substance a comprises an 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%.
12. The process of claim 11, wherein the molar ratio of propionic acid to the alcohol compound is 2:1 to 10:1.
13. the process of claim 1, wherein the catalyst is selected from any one of a homogeneous catalyst and a heterogeneous catalyst.
14. The process according to claim 12, wherein the mass content of the catalyst in the propionic acid-containing raw material is 0.3 to 1.0%.
15. The process of claim 9, wherein 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 overhead reflux ratio was 1:1 to 1:2;
the process operation conditions of the second rectifying tower are as follows: the temperature of the tower top is 62-90 ℃; the temperature of the tower kettle is 75-125 ℃; the overhead reflux ratio was 1:1 to 1:2.
16. the process according to claim 1, wherein in step (a), the mass of the extractant is 3-50% of the mass of the stream obtained at the top of the first rectifying column.
17. The process according to claim 1, wherein the extractant is selected from water.
18. The process of claim 1, wherein in step (a) the stream obtained from the top of the second rectification column is returned to the bottom of the first rectification column.
19. The process according to claim 1, further comprising the process steps of:
(b) And (3) 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.
20. The process of claim 19, wherein 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 overhead reflux ratio was 1:1-2: 1.
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| 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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| 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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