CN108947774B - Method and device for separating isopropanol - Google Patents
Method and device for separating isopropanol Download PDFInfo
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- CN108947774B CN108947774B CN201810793708.5A CN201810793708A CN108947774B CN 108947774 B CN108947774 B CN 108947774B CN 201810793708 A CN201810793708 A CN 201810793708A CN 108947774 B CN108947774 B CN 108947774B
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Abstract
The invention discloses a method for separating isopropanol from a mixture obtained after reaction of isopropyl acetate and low-carbon alcohol, which comprises the steps of feeding the mixture obtained after reaction of isopropyl acetate and low-carbon alcohol into a crude isopropanol tower, carrying out primary separation on the mixture obtained after reaction in the crude isopropanol tower to obtain crude isopropanol mainly comprising isopropanol, isopropyl acetate and methanol/ethanol, feeding the crude isopropanol into an isopropanol refining tower, carrying out full refining separation in the isopropanol refining tower, and finally separating to obtain the isopropanol with the purity of more than or equal to 99.9 wt%. The method has the advantages of simple process flow, low separation energy consumption and high product purity. Meanwhile, the invention also discloses a separation device suitable for the method, and the device has simple structure and less investment.
Description
Technical Field
The invention relates to a method and a device for separating isopropanol, in particular to a method and a device for separating isopropanol from a mixture obtained after reaction of isopropyl acetate and low-carbon alcohol.
Background
Isopropyl alcohol, also known as 2-propanol, is an important chemical product and raw material, is mainly used as a solvent and a synthetic intermediate, and has wide application in the fields of pesticides, electronic industry, medicines, coatings, daily chemical industry and organic synthesis.
At present, the industrial production method of isopropanol mainly comprises two processes of a propylene hydration method and an acetone hydrogenation method. The propylene hydration method comprises a gas phase hydration method (Viba method) developed by Viba of Germany, a liquid phase hydration method (solution catalysis method) of Deshan Caoda of Japan, a gas-liquid mixed phase hydration method (ion exchange resin method) of Texaco of America and the like, the single-pass conversion rate of the propylene hydration method is only about 10%, the reaction is carried out under the pressure condition of 2.0-6.0 MPa, a dehydrating agent needs to be introduced in the separation process of a product, a large amount of sewage is generated, the separation process flow is complex, and adverse effects are brought to the environment. Although the acetone hydrogenation method has the advantages of high acetone conversion rate, high isopropanol selectivity, few reaction byproducts and the like, the reaction needs to be carried out under the harsh conditions of 150-300 ℃ and 4.0-10.0 MPa, the product can be separated only through a complex process flow, and the energy consumption is high.
In recent years, a new method for preparing isopropanol by an ester exchange reaction between isopropyl acetate and methanol/ethanol is widely concerned and researched, and the method has the characteristics of mild reaction conditions, high reaction conversion rate and selectivity, no pollution and the like. The post-reaction mixture included isopropanol, methyl acetate/ethyl acetate, unreacted isopropyl acetate, and methanol/ethanol.
Chinese patents CN102718628A and CN102850185A disclose a method for producing isopropyl alcohol by using isopropyl acetate and methanol as raw materials and using sodium methoxide or cation exchange resin as basic catalysts for catalytic reaction, wherein the reaction is performed at 25-60 ℃ and normal pressure, and the reaction conversion rate reaches 50-80%. Chinese patents CN102755759B and CN102976894B further illustrate a catalytic rectification process for producing isopropanol by an ester exchange reaction between isopropyl acetate and methanol, wherein CN102755759B uses sodium methoxide as a catalyst to catalyze the reaction between isopropyl acetate and methanol in a catalytic rectification tower, and materials at the top and bottom of the catalytic rectification tower are separated and purified by a methyl ester rectification tower, a methanol rectification tower, an evaporator and an isopropanol rectification tower to obtain the product isopropanol, and unreacted raw materials and the catalyst are recovered at the same time; on the basis of the process of patent CN102755759B, patent CN102976894B replaces homogeneous catalyst sodium methoxide with heterogeneous catalyst cation exchange resin, and places the resin in a catalytic rectification tower, thereby avoiding the problems of recycling alkali salt catalyst, easy crystallization and separation of catalyst in the tower, and the like, and the materials at the top and bottom of the catalytic rectification tower are separated and purified by a methyl ester rectification tower, a methanol rectification tower and an isopropanol rectification tower to obtain the product isopropanol, and meanwhile, the unreacted raw materials are recycled, and the quality purity of the isopropanol product is more than 99%.
Chinese patent CN105061148A discloses an extractive distillation method for separating isopropyl alcohol and isopropyl acetate based on ionic liquid mixed solvent as extractant, which uses ionic liquid 1-ethyl-3-methylimidazole tetrafluoroborate ([ Emim ] [ BF4]) and 1-butyl-3-methylimidazole hexafluorophosphate ([ Emim ] [ PF6]) mixed solvent to separate isopropyl alcohol and isopropyl acetate through 2 distillation towers, but the cost of the mixed solvent is very high. The literature, iso-pressure vapor-liquid phase equilibrium and extractive distillation simulation of isopropyl acetate-isopropanol-DMSO, uses dimethyl sulfoxide (DMSO) with relatively low cost as an extractant to separate isopropanol and isopropyl acetate, but the process has high energy consumption. The document "isopropyl acetate-isopropanol system heat integration pressure swing distillation separation simulation" adopts a combination mode of pressure swing distillation technology and heat pump technology to separate isopropanol and isopropyl acetate, the process adopts heat pump technology, can effectively save energy by 28.5%, but the process conditions of a high pressure tower and a vacuum tower are harsh, and the equipment investment is large.
In summary, the existing process technology for separating the mixed system of the reaction products of isopropyl acetate and low-carbon alcohol has one or more problems of complex process flow, harsh process conditions, large equipment investment, low product purity, influence on product quality by using an extractant, increase in production cost and the like. For the process for producing isopropanol by isopropyl acetate and low-carbon alcohol, the process flow needs to be simplified, the investment cost is saved, and the operation energy consumption is reduced.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide the isopropanol separation method which has simple process flow, low separation energy consumption and high product purity for separating the mixed system of the reaction products of the isopropyl acetate and the low-carbon alcohol; meanwhile, the invention also provides an isopropanol separating device which is simple in structure and low in investment.
In order to achieve the purpose, the invention adopts the technical scheme that:
a process for separating isopropanol from a mixture after the reaction of isopropyl acetate with a lower alcohol, said process comprising the steps of;
(1) sending a mixture obtained after reaction of isopropyl acetate and low-carbon alcohol into a crude isopropanol tower, wherein the mixture obtained after reaction mainly comprises isopropanol, methyl acetate/ethyl acetate, isopropyl acetate and methanol/ethanol, wherein an azeotrope formed by methyl acetate/ethyl acetate and methanol/ethanol is evaporated from the top of the tower, part of the mixture is refluxed to the crude isopropanol tower after condensation, and the other part of the mixture is extracted as crude methyl acetate/ethyl acetate; wherein the crude isopropanol is extracted from a crude isopropanol tower kettle, and the crude isopropanol mainly comprises isopropanol, isopropyl acetate and methanol/ethanol;
(2) feeding the crude isopropanol extracted from the crude isopropanol tower kettle in the step (1) into an isopropanol refining tower, simultaneously supplementing an entrainer methanol/ethanol into the isopropanol refining tower, forming an azeotrope by the isopropyl acetate and the methanol/ethanol, evaporating out from the tower top of the isopropanol refining tower, condensing, refluxing a part of the condensed azeotrope to the isopropanol refining tower, conveying the other part of the condensed azeotrope to a reaction system of the isopropyl acetate and the lower alcohol, and extracting the isopropanol from the tower kettle of the isopropanol refining tower.
In the method for separating the isopropanol from the mixture after the reaction of the isopropyl acetate and the lower alcohol, the mixture after the reaction of the isopropyl acetate and the lower alcohol is sent into a crude isopropanol tower for separation treatment, in the crude isopropanol tower, an azeotrope formed by methyl acetate/ethyl acetate and methanol/ethanol is removed from the top of the tower, after condensation, one part of the azeotrope flows back to the crude isopropanol tower, and the other part of the azeotrope is taken as crude methyl acetate/ethyl acetate for other use; extracting crude isopropanol mainly comprising isopropanol, isopropyl acetate and methanol/ethanol from a tower kettle after separation in the crude isopropanol tower, and then feeding the crude isopropanol into an isopropanol refining tower for refining and separation; in the isopropanol refining tower, an entrainer methanol/ethanol is fed simultaneously with crude isopropanol, in the isopropanol refining tower, an azeotrope formed by isopropyl acetate and methanol/ethanol is evaporated from the top of the isopropanol refining tower, after condensation, one part of the condensed azeotrope flows back to the isopropanol refining tower, and the other part of the condensed azeotrope is conveyed to a feeding system of a reaction system of isopropyl acetate and low-carbon alcohol, and the refined and separated isopropanol can be obtained in a tower kettle of the isopropanol refining tower and can be directly extracted. The inventor of the application detects that the purity of the isopropanol extracted from the tower kettle of the isopropanol refining tower can reach more than 99.9 wt%.
As a preferred embodiment of the method for separating isopropanol from a mixture after the reaction of isopropyl acetate with a lower alcohol according to the present invention, the method further comprises the steps of:
(3) and (2) conveying the crude methyl acetate/ethyl acetate extracted from the top of the crude isopropanol tower in the step (1) to an acetate refining tower, performing high-pressure rectification separation, extracting a methyl acetate/ethyl acetate product from a tower kettle of the acetate refining tower, evaporating a high-pressure azeotropic mixture formed by methyl acetate/ethyl acetate and methanol/ethanol from the top of the acetate refining tower, condensing, refluxing a part of the condensed mixture to the acetate refining tower, and conveying the other part of the condensed mixture to a feeding material of a reaction system of isopropyl acetate and low-carbon alcohol.
Preferably, the method of the invention further comprises a step of conveying crude methyl acetate/ethyl acetate extracted from the top of the crude isopropanol tower to an acetate refining tower for rectification separation, wherein after the crude methyl acetate/ethyl acetate is subjected to high-pressure rectification separation in the acetate refining tower, a methyl acetate/ethyl acetate product can be extracted from the tower bottom of the acetate refining tower, and meanwhile, after a high-pressure azeotropic mixture formed by methyl acetate/ethyl acetate and methanol/ethanol is evaporated and condensed, a part of the high-pressure azeotropic mixture flows back to the acetate refining tower, and the other part of the high-pressure azeotropic mixture can be conveyed to a system feeding material for reacting isopropyl acetate and lower alcohol. Can make full use of various materials obtained in the separation process.
As a preferred embodiment of the method for separating isopropanol from a mixture after the reaction of isopropyl acetate with a lower alcohol according to the present invention, the method further comprises the steps of:
(3) conveying the crude methyl acetate/ethyl acetate extracted from the top of the crude isopropanol tower in the step (1) to an acetate refining tower, adopting high-pressure rectification separation, extracting a methyl acetate/ethyl acetate product from a tower kettle of the acetate refining tower, evaporating a high-pressure azeotropic mixture formed by methyl acetate/ethyl acetate and methanol/ethanol from the top of the acetate refining tower, condensing, refluxing a part of the condensed product to the acetate refining tower, and conveying the other part of the condensed product to a low-carbon alcohol recovery tower;
(4) and (4) operating the low-carbon alcohol recovery tower in the step (3) at normal pressure, recovering a low-carbon alcohol product from a tower kettle of the low-carbon alcohol recovery tower, condensing an azeotropic mixture formed by methyl acetate/ethyl acetate and methanol/ethanol at the tower top of the low-carbon alcohol recovery tower, refluxing a part of the condensed azeotropic mixture to the low-carbon alcohol recovery tower, and conveying the other part of the condensed azeotropic mixture to an acetate refining tower for cyclic rectification.
More preferably, the method of the invention further comprises a step of recovering the lower alcohol, specifically, the crude methyl acetate/ethyl acetate extracted from the tower top of the crude isopropanol tower is subjected to high-pressure rectification separation in an acetate refining tower, a methyl acetate/ethyl acetate product is extracted from the tower bottom, and after a high-pressure azeotropic mixture formed by the methyl acetate/ethyl acetate and methanol/ethanol formed at the tower top is condensed, one part of the condensed product flows back to the acetate refining tower, and the other part of the condensed product is conveyed to a lower alcohol recovery tower to recover the lower alcohol; in the low carbon alcohol recovery tower, normal pressure operation is adopted, the low carbon alcohol product is obtained by recovering the tower bottom of the low carbon alcohol, an azeotropic mixture of methyl acetate/ethyl acetate and methanol/ethanol is formed at the tower top of the low carbon alcohol, after condensation, one part of the mixture flows back to the low carbon alcohol recovery tower, and the other part of the mixture can be conveyed to an acetate refining tower for circular rectification. The method can fully utilize various substances obtained in the isopropanol separation process.
As a preferred embodiment of the method for separating isopropanol from the mixture after the reaction of isopropyl acetate and lower alcohol, the operation conditions of the crude isopropanol tower in the step (1) are as follows: the pressure is 0.1-0.3 MPa, the reflux ratio is 1.0-5.0, the tower top temperature is 55-90 ℃, and the tower kettle temperature is 82-115 ℃. Through a great deal of experimental research, the present inventors found that the operation conditions of the crude isopropanol tower are very important for the separation of isopropanol in the present application, and only when the crude isopropanol tower adopts the operation conditions as described above, the mixture after the reaction of the isopropyl acetate and the lower alcohol can be subjected to crude separation in the crude isopropanol tower, so as to obtain crude isopropanol mainly comprising isopropanol, isopropyl acetate, methanol/ethanol.
As a preferred embodiment of the method for separating isopropanol from a mixture after the reaction of isopropyl acetate and a lower alcohol according to the present invention, the operating conditions of the isopropanol purification column in the step (2) are as follows: the pressure is 0.10-0.15 MPa, the reflux ratio is 1.0-5.0, the tower top temperature is 64-75 ℃, and the tower kettle temperature is 82-94 ℃. Through a large amount of experimental researches, the inventor of the application finds that the operation condition of the isopropanol refining tower is important for whether the isopropanol with the required purity can be separated, and through repeated experimental trials, the inventor finally finds that the crude isopropanol after the crude separation in the step (1) can be fully refined and separated in the isopropanol refining tower only by adopting the operation condition, and the purity of the isopropanol finally separated can reach more than 99.9 wt%.
In a preferred embodiment of the method for separating isopropanol from a mixture obtained by reacting isopropyl acetate with a lower alcohol, the mass ratio of isopropyl acetate to methanol/ethanol as a boiling agent in the step (2) is 1:2 to 1: 5.
As a preferred embodiment of the method for separating isopropanol from the mixture after the reaction of isopropyl acetate and the lower alcohol, the reaction condition of the reaction of isopropyl acetate and the lower alcohol in the step (1) is a heterogeneous catalyst reaction; preferably, in the step (1), the reaction condition of the reaction of the isopropyl acetate and the lower alcohol is a cation exchange resin catalyst reaction, the reaction temperature is 70-80 ℃, the reaction pressure is 150-300 KPa, and the molar ratio of the alcohol ester is 1.5-3.5;
the concentration of the crude methyl acetate/ethyl acetate product extracted from the top of the crude isopropanol tower in the step (1) is 72-81 wt%.
As a preferred embodiment of the method for separating the isopropanol from the mixture after the reaction of the isopropyl acetate and the lower alcohol, the purity of the isopropanol extracted in the tower kettle of the isopropanol refining tower in the step (2) is more than or equal to 99.9 wt%.
As a preferred embodiment of the method for separating isopropanol from a mixture after the reaction of isopropyl acetate and a lower alcohol according to the present invention, the operating conditions of the acetate refining column in the step (3) are as follows: the pressure is 0.9-1.3 MPa, the reflux ratio is controlled to be 1.0-5.0, the temperature at the top of the tower is controlled to be 110-150 ℃, and the temperature at the bottom of the tower is controlled to be 145-180 ℃;
the product concentration of the methyl acetate/ethyl acetate extracted from the tower kettle of the acetate refining tower is 99.0-99.5 wt%.
As a preferred embodiment of the method for separating isopropanol from the mixture after the reaction of isopropyl acetate and lower alcohol, in the step (4), the operating conditions of the lower alcohol recovery tower are as follows: the pressure is 0.1-0.2 MPa, the reflux ratio is 1.0-5.0, the tower top temperature is 55-85 ℃, and the tower kettle temperature is 64-95 ℃;
the concentration of the low-carbon alcohol product recovered from the tower kettle of the low-carbon alcohol recovery tower is 99.0-99.5 wt%.
In addition, another purpose of the present invention is to provide a simple and low-investment apparatus for separating isopropyl alcohol from a mixture of isopropyl acetate and lower alcohol after reaction, and to achieve the purpose, the technical scheme adopted by the present invention is as follows: an apparatus for separating isopropanol from a mixture after isopropyl acetate reacts with a lower alcohol, the apparatus comprising a crude isopropanol column and an isopropanol refining column;
the crude isopropanol tower comprises a rectifying section and a stripping section, the number of theoretical plates of the rectifying section is 30-60, the number of theoretical plates of the stripping section is 10-30, a feed inlet is formed in the middle of the crude isopropanol tower, a condenser and a reflux tank are sequentially connected to the top of the crude isopropanol tower, a reflux pump is connected to an outlet of the reflux tank, an overhead product extraction pipe and a reflux pipe are respectively connected to an outlet of the reflux pump, and the reflux pipe is connected to the top of the crude isopropanol tower; a tower kettle of the crude isopropanol tower is provided with a tower kettle extraction outlet, the tower kettle extraction outlet is respectively connected with a tower kettle reboiler and a tower kettle pump, the outlet of the tower kettle reboiler is communicated with the tower kettle of the crude isopropanol tower through a pipeline, and the tower kettle pump is connected to a feeding pipe of the isopropanol refining tower;
the isopropanol refining tower comprises a rectifying section and a stripping section, the number of theoretical plates of the rectifying section is 40-70, the number of theoretical plates of the stripping section is 20-30, a feed inlet is formed in the middle of the isopropanol refining tower, the feed inlet is respectively connected with a tower kettle pump and an entrainer feed pipe of the crude isopropanol tower, the top of the isopropanol refining tower is sequentially connected with a condenser and a reflux tank, an outlet of the reflux tank is connected with a reflux pump, an outlet of the reflux pump is respectively connected with a tower top product extraction pipe and a reflux pipe, and the reflux pipe is connected with the tower top of the isopropanol refining tower; the tower kettle of the isopropanol refining tower is provided with a tower kettle extraction outlet, the tower kettle extraction outlet is respectively connected with a tower kettle reboiler and an isopropanol product extraction pipe, and the outlet of the tower kettle reboiler is communicated with the tower kettle of the isopropanol refining tower through a pipeline.
In the device for separating the isopropanol from the mixture after the reaction of the isopropyl acetate and the lower alcohol, the device comprises a crude isopropanol tower and an isopropanol refining tower;
the crude isopropanol tower comprises a rectification section and a stripping section, wherein a mixture feeding pipe for reacting isopropyl acetate and low-carbon alcohol is arranged in the middle of the crude isopropanol tower, a tower top outlet of the crude isopropanol tower is connected with a tower top condenser and then is connected with a tower top reflux tank of the crude isopropanol tower, a reflux pump is connected with an outlet of the reflux tank, an outlet of the reflux pump is divided into two paths, one path is extracted to be used as a crude acetate product, the other path is connected with the tower top of the crude isopropanol tower through a reflux pipeline, a tower kettle extraction outlet of the crude isopropanol tower is divided into two paths, one path is returned to the crude isopropanol tower kettle after passing through a reboiler of the tower kettle of the crude isopropanol tower, and the other path is connected with a feeding pipe in the middle of an isopropanol refining tower after being;
the isopropanol refining tower comprises a rectifying section and a stripping section, a crude isopropanol feeding pipe and an entrainer low-carbon alcohol feeding pipe are arranged at the part of the isopropanol refining tower, a tower top outlet of the isopropanol refining tower is connected with a tower top condenser and then is connected with a tower top reflux tank of the isopropanol refining tower, a reflux tank outlet is connected with a reflux pump, a reflux pump outlet is divided into two paths, one path of the reflux pump outlet is used as a reaction system for feeding isopropyl acetate and low-carbon alcohol after being produced, the other path of the reflux pump outlet is connected with the top of the isopropanol refining tower through a reflux pipe, the tower kettle of the isopropanol refining tower is extracted into two paths, one path of the reflux pump outlet returns to the bottom of the isopropanol refining tower after passing through a reboiler of the bottom of the isopropanol refining tower, and the other.
As a preferred embodiment of the apparatus for separating isopropyl alcohol from a mixture after the reaction of isopropyl acetate with a lower alcohol according to the present invention, the apparatus further comprises an acetate refining column;
the feeding hole of the acetate refining tower is connected with a product extraction pipe at the top of the crude isopropanol tower, the top of the acetate refining tower is sequentially connected with a condenser and a reflux tank, the outlet of the reflux tank is connected with a reflux pump, the outlet of the reflux pump is respectively connected with a product extraction pipe at the top of the tower and a reflux pipe, and the reflux pipe is connected with the top of the acetate refining tower; the tower kettle of the acetate refining tower is provided with a tower kettle extraction outlet, the tower kettle extraction outlet is respectively connected with a tower kettle reboiler and a tower kettle product extraction pipe, and the outlet of the tower kettle reboiler is communicated with the tower kettle of the acetate refining tower through a pipeline.
As a more preferred embodiment of the apparatus for separating isopropyl alcohol from a mixture after the reaction of isopropyl acetate with a lower alcohol according to the present invention, the apparatus further comprises a lower alcohol recovery column;
the feeding hole of the low-carbon alcohol recovery tower is connected with a product extraction pipe at the top of the acetate refining tower, the top of the low-carbon alcohol recovery tower is sequentially connected with a condenser and a reflux tank, the outlet of the reflux tank is connected with a reflux pump, the outlet of the reflux pump is respectively connected with a product extraction pipe at the top of the tower and a reflux pipe, and the reflux pipe is connected with the top of the low-carbon alcohol recovery tower; the tower kettle of the low-carbon alcohol recovery tower is provided with a tower kettle extraction outlet, the tower kettle extraction outlet is respectively connected with a tower kettle reboiler and a tower kettle product extraction pipe, and the outlet of the tower kettle reboiler is communicated with the tower kettle of the low-carbon alcohol recovery tower through a pipeline.
The method for separating isopropanol from a mixture obtained after reaction of isopropyl acetate and low-carbon alcohol comprises the steps of firstly feeding the mixture obtained after reaction of isopropyl acetate and low-carbon alcohol into a crude isopropanol tower, preliminarily separating the mixture obtained after reaction in the crude isopropanol tower to obtain crude isopropanol mainly comprising isopropanol, isopropyl acetate and methanol/ethanol, then feeding the crude isopropanol into an isopropanol refining tower, sufficiently refining and separating in the isopropanol refining tower, and finally separating to obtain the isopropanol with the purity of more than or equal to 99.9 wt%. The device for separating the isopropanol from the mixture after the reaction of the isopropyl acetate and the low-carbon alcohol has the advantages of simple structure, less investment and contribution to wide popularization and application.
Drawings
FIG. 1 is a schematic flow diagram of one embodiment of the process for separating isopropanol of the present invention;
FIG. 2 is a schematic flow chart of another embodiment of the method for separating isopropanol according to the present invention;
FIG. 3 is a schematic structural diagram of an embodiment of the apparatus for separating isopropanol according to the present invention.
In the figure, 1 is a crude isopropanol tower, 2 is an isopropanol refining tower, 3 is an acetate refining tower, 4 is a low-carbon alcohol recovery tower, 5 is a crude isopropanol tower top condenser, 6 is a crude isopropanol tower top reflux tank, 7 is a crude isopropanol tower kettle reboiler, 8 is an isopropanol refining tower top condenser, 9 is an isopropanol refining tower top reflux tank, 10 is an isopropanol refining tower kettle reboiler, P1 is a crude isopropanol tower reflux pump, P2 is a crude isopropanol tower kettle pump, P1 is an isopropanol refining tower reflux pump, 11 is a reaction mixture feed line, 12 is a crude isopropanol tower top reflux line, 13 is a crude acetate extraction line, 14 is a crude isopropanol extraction line, 21 is an entrainer feed line, 22 is an isopropanol refining tower feed line, 23 is an isopropanol refining tower top reflux line, 24 is an isopropanol refining tower top reflux line, 25 is an isopropanol product extraction line, 31 is an acetate product extraction line, 32 is an acetate refining tower top return line, 33 is a lower alcohol recovery tower feed line, 34 is an acetate refining tower top extraction line, 41 is a lower alcohol product extraction line, 42 is a lower alcohol recovery tower top return line, and 43 is a lower alcohol recovery tower top extraction line.
Detailed Description
To better illustrate the objects, aspects and advantages of the present invention, the present invention will be further described with reference to the accompanying drawings and specific embodiments.
Example 1
The method comprises the following step of separating isopropanol from a mixture obtained after reaction of isopropyl acetate and lower alcohol, wherein a process flow schematic diagram of the method is shown in figure 1, the lower alcohol in the embodiment is methanol, the isopropyl acetate and the methanol are subjected to ester exchange reaction under the action of an acidic cation exchange resin catalyst, the reaction temperature is 70-80 ℃, the reaction pressure is 150-300 KPa, and the molar ratio of alcohol ester is 1.5-3.5. After the reaction, the mixture was mainly isopropanol, isopropyl acetate, methyl acetate and methanol.
The method in this embodiment includes the following steps:
(1) feeding the reacted mixture into a crude isopropanol tower, forming an azeotrope by methyl acetate and methanol, evaporating the azeotrope from the tower top, condensing, refluxing a part of the condensed mixture to the crude isopropanol tower, extracting the other part of the condensed mixture as crude methyl acetate, and extracting crude isopropanol from a tower kettle;
(2) conveying the crude isopropanol extracted in the step (1) to an isopropanol refining tower, supplementing an entrainer methanol into the isopropanol refining tower, controlling the mass ratio of isopropyl acetate to methanol to be 1:5 in feeding materials, forming an azeotrope by the isopropyl acetate and the methanol, evaporating out from the tower top, condensing, refluxing a part of the azeotrope to the isopropanol refining tower, extracting the other part of the azeotrope to serve as feeding materials of an ester exchange reaction system, and extracting an isopropanol product from the side line of the tower bottom.
In the method of this example, the crude isopropanol column and the isopropanol purification column in step (1) and step (2) were respectively provided with three different sets of operating conditions, and the operating conditions of each set and the purity of the separated isopropanol product are shown in table 1.
TABLE 1 separation results for different operating conditions
Example 2
On the basis of example 1, the crude methyl acetate obtained in example 1 was further purified and separated to obtain a high-purity methyl acetate product and a methanol product.
The process flow diagram of the method of the embodiment is shown in fig. 2, and the specific operations in the embodiment are as follows:
the crude methyl acetate extracted from the top of the crude isopropanol tower in the test group 1, the test group 2 and the test group 3 in the example 1 is respectively conveyed to an acetate refining tower for refining, the acetate refining tower adopts high-pressure operation because the azeotropic mass ratio of the methyl acetate and methanol is reduced under the high-pressure operation condition, a methyl acetate product is extracted from a tower kettle, an azeotropic mixture formed by the methyl acetate and the methanol is evaporated from the top of the tower, a part of the azeotropic mixture is refluxed to the acetate refining tower after condensation, and the other part of the azeotropic mixture is extracted as a reaction system feed or conveyed to a low-carbon alcohol recovery tower;
the low-carbon alcohol recovery tower adopts normal-pressure operation, the tower bottom recovers a low-carbon alcohol product, an azeotropic mixture formed by methyl acetate and methanol at the tower top is condensed, one part of the azeotropic mixture flows back to the low-carbon alcohol recovery tower, and the other part of the azeotropic mixture is conveyed to an acetate refining tower for circular rectification.
In the method of this example, the acetate refining column and the lower alcohol recovery column were set with three different sets of operating conditions, and the operating conditions of each set, the purity of the methyl acetate product and the purity of the methanol product obtained by separation are shown in table 2.
TABLE 2 separation results for different operating conditions
Example 3
The method comprises the following step of separating isopropanol from a mixture obtained after reaction of isopropyl acetate and lower alcohol, wherein a process flow schematic diagram of the method is shown in figure 1, the lower alcohol in the embodiment is ethanol, the isopropyl acetate and the ethanol perform ester exchange reaction under the action of an acidic cation exchange resin catalyst at 70-80 ℃, the reaction pressure is 150-300 KPa, and the molar ratio of alcohol ester is 1.5-3.5. After the reaction, the mixture is mainly isopropanol, isopropyl acetate, ethyl acetate and ethanol.
The method in this embodiment includes the following steps:
(1) feeding the reacted mixture into a crude isopropanol tower, forming an azeotrope by ethyl acetate and ethanol, evaporating from the top of the tower, condensing, refluxing a part of the condensed mixture to the crude isopropanol tower, extracting the other part of the condensed mixture as crude ethyl acetate, and extracting crude isopropanol from a tower kettle;
(2) conveying the crude isopropanol extracted in the step (1) to an isopropanol refining tower, supplementing an entrainer ethanol into the isopropanol refining tower, controlling the mass ratio of isopropyl acetate to ethanol in the feeding material to be 1:4, forming an azeotrope by the isopropyl acetate and the ethanol, evaporating out from the tower top, condensing, refluxing a part of the azeotrope to the isopropanol refining tower, extracting the other part of the azeotrope to serve as the feeding material of an ester exchange reaction system, and extracting an isopropanol product from the side line of the tower bottom.
In the method of this example, the crude isopropanol column and the isopropanol purification column in step (1) and step (2) were respectively provided with three different sets of operating conditions, and the operating conditions of each set and the purity of the separated isopropanol product are shown in table 3.
TABLE 3 separation results for different operating conditions
Example 4
On the basis of example 3, the crude ethyl acetate obtained in example 3 was further refined and separated to obtain a high-purity ethyl acetate product and an ethanol product.
The specific operations in this example are as follows:
the crude ethyl acetate extracted from the top of the crude isopropanol tower in test group 7, test group 8 and test group 9 of example 3 was fed to an acetate refining tower for refining, respectively, and since the azeotropic mass ratio of ethyl acetate and ethanol was significantly reduced under high-pressure operating conditions, the acetate refining tower was operated at high pressure, and the ethyl acetate product was extracted from the bottom of the tower, and the azeotropic mixture of ethyl acetate and ethanol was distilled off from the top of the tower, after condensation, a portion of the azeotropic mixture was refluxed to the acetate refining tower, and the other portion of the azeotropic mixture was fed to the reaction system as ethanol raw material.
In the method of this example, three different sets of operating conditions were set for the acetate refining column, and the operating conditions for each set, the purity of the ethyl acetate product and the purity of the ethanol product obtained by separation are shown in table 4.
TABLE 4 separation results for different operating conditions
Example 5
The invention relates to an embodiment of a device for separating isopropanol from a mixture after isopropyl acetate and low-carbon alcohol react, the structural schematic diagram of the device in the embodiment is shown in figure 3, as can be seen from figure 3, the device in the embodiment comprises a crude isopropanol tower and an isopropanol refining tower;
the crude isopropanol tower comprises a rectification section and a stripping section, the number of theoretical plates of the rectification section is 30-60, the number of theoretical plates of the stripping section is 10-30, a mixture feed inlet for reacting isopropyl acetate with low-carbon alcohol is formed in the middle of the crude isopropanol tower, the top of the crude isopropanol tower is sequentially connected with a condenser and a reflux tank, an outlet of the reflux tank is connected with a reflux pump, an outlet of the reflux pump is respectively connected with a product extraction pipe at the top of the tower and a reflux pipe, the reflux pipe is connected with the top of the crude isopropanol tower, the outlet of the reflux pump is divided into two paths, one path is extracted as a crude acetate product, and the other path is connected with the top of the crude isopropanol tower through a reflux pipeline; a tower kettle of the crude isopropanol tower is provided with a tower kettle extraction outlet, the tower kettle extraction outlet is respectively connected with a tower kettle reboiler and a tower kettle pump, the outlet of the tower kettle reboiler is communicated with the tower kettle of the crude isopropanol tower through a pipeline, and the tower kettle pump is connected to a feeding pipe of the isopropanol refining tower; the tower kettle extraction outlet of the crude isopropanol tower is divided into two paths, one path of the extraction outlet passes through a reboiler of the tower kettle of the crude isopropanol tower and then returns to the tower kettle of the crude isopropanol tower, and the other path of the extraction outlet is connected with a feeding pipe in the middle of an isopropanol refining tower after being extracted by a tower kettle pump;
the isopropanol refining tower comprises a rectifying section and a stripping section, the number of theoretical plates of the rectifying section is 40-70, the number of theoretical plates of the stripping section is 20-30, a feed inlet is formed in the middle of the isopropanol refining tower, the feed inlet is respectively connected with a tower kettle pump and an entrainer feed pipe of the crude isopropanol tower, the top of the isopropanol refining tower is sequentially connected with a condenser and a reflux tank, an outlet of the reflux tank is connected with a reflux pump, an outlet of the reflux pump is respectively connected with a tower top product extraction pipe and a reflux pipe, the reflux pipe is connected with the tower top of the isopropanol refining tower, an outlet of the reflux pump is divided into two paths, one path of extracted product is used as a reaction system for feeding isopropyl acetate and low-carbon alcohol, and the other path of extracted product is connected with the tower top of the isopropanol refining tower through the reflux pipe; a tower kettle of the isopropanol refining tower is provided with a tower kettle extraction outlet, the tower kettle extraction outlet is respectively connected with a tower kettle reboiler and an isopropanol product extraction pipe, and the outlet of the tower kettle reboiler is communicated with the tower kettle of the isopropanol refining tower through a pipeline; the tower kettle extraction of the isopropanol refining tower is divided into two paths, one path of the extraction is returned to the isopropanol refining tower kettle after passing through a reboiler of the isopropanol refining tower kettle, and the other path of the extraction is an isopropanol product extraction pipe.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (8)
1. A process for separating isopropyl alcohol from a mixture of isopropyl acetate reacted with a lower alcohol, comprising the steps of;
(1) sending a mixture obtained after reaction of isopropyl acetate and low-carbon alcohol into a crude isopropanol tower, wherein the mixture obtained after reaction mainly comprises isopropanol, methyl acetate/ethyl acetate, isopropyl acetate and methanol/ethanol, wherein an azeotrope formed by methyl acetate/ethyl acetate and methanol/ethanol is evaporated from the top of the tower, part of the mixture is refluxed to the crude isopropanol tower after condensation, and the other part of the mixture is extracted as crude methyl acetate/ethyl acetate; wherein the crude isopropanol is extracted from a crude isopropanol tower kettle, and the crude isopropanol mainly comprises isopropanol, isopropyl acetate and methanol/ethanol;
(2) feeding the crude isopropanol extracted from the crude isopropanol tower kettle in the step (1) into an isopropanol refining tower, simultaneously supplementing an entrainer methanol/ethanol into the isopropanol refining tower, forming an azeotrope by the isopropyl acetate and the methanol/ethanol, evaporating out the azeotrope from the tower top of the isopropanol refining tower, condensing, refluxing a part of the condensed azeotrope to the isopropanol refining tower, conveying the other part of the condensed azeotrope to a reaction system of the isopropyl acetate and the lower alcohol, and extracting the isopropanol from the tower kettle of the isopropanol refining tower;
the operation conditions of the crude isopropanol tower in the step (1) are as follows: the pressure is 0.1-0.3 MPa, the reflux ratio is 1.0-5.0, the tower top temperature is 55-90 ℃, and the tower kettle temperature is 82-115 ℃;
the operation conditions of the isopropanol refining tower in the step (2) are as follows: the pressure is 0.10-0.15 MPa, the reflux ratio is 1.0-5.0, the tower top temperature is 64-75 ℃, the tower bottom temperature is 82-94 ℃, and the mass ratio of isopropyl acetate to entrainer methanol/ethanol is 1: 2-1: 5.
2. The process for separating isopropyl alcohol from a mixture of isopropyl acetate reacted with a lower alcohol according to claim 1, further comprising the steps of:
(3) and (2) conveying the crude methyl acetate/ethyl acetate extracted from the top of the crude isopropanol tower in the step (1) to an acetate refining tower, performing high-pressure rectification separation, extracting a methyl acetate/ethyl acetate product from a tower kettle of the acetate refining tower, evaporating a high-pressure azeotropic mixture formed by methyl acetate/ethyl acetate and methanol/ethanol from the top of the acetate refining tower, condensing, refluxing a part of the condensed mixture to the acetate refining tower, and conveying the other part of the condensed mixture to a feeding material of a reaction system of isopropyl acetate and low-carbon alcohol.
3. The process for separating isopropyl alcohol from a mixture of isopropyl acetate reacted with a lower alcohol according to claim 1, further comprising the steps of:
(3) conveying the crude methyl acetate/ethyl acetate extracted from the top of the crude isopropanol tower in the step (1) to an acetate refining tower, adopting high-pressure rectification separation, extracting a methyl acetate/ethyl acetate product from a tower kettle of the acetate refining tower, evaporating a high-pressure azeotropic mixture formed by methyl acetate/ethyl acetate and methanol/ethanol from the top of the acetate refining tower, condensing, refluxing a part of the condensed product to the acetate refining tower, and conveying the other part of the condensed product to a low-carbon alcohol recovery tower;
(4) and (4) operating the low-carbon alcohol recovery tower in the step (3) at normal pressure, recovering a low-carbon alcohol product from a tower kettle of the low-carbon alcohol recovery tower, condensing an azeotropic mixture formed by methyl acetate/ethyl acetate and methanol/ethanol at the tower top of the low-carbon alcohol recovery tower, refluxing a part of the condensed azeotropic mixture to the low-carbon alcohol recovery tower, and conveying the other part of the condensed azeotropic mixture to an acetate refining tower for cyclic rectification.
4. The method for separating isopropanol from the mixture after the reaction of isopropyl acetate and the lower alcohol according to any one of claims 1 to 3, wherein the reaction condition in the step (1) is a heterogeneous catalyst reaction.
5. The method for separating isopropanol from the mixture obtained after the reaction of isopropyl acetate and lower alcohol according to claim 4, wherein the reaction conditions in the step (1) are that the isopropyl acetate and the lower alcohol react with each other by using a cation exchange resin catalyst, the reaction temperature is 70-80 ℃, the reaction pressure is 150-300 KPa, and the molar ratio of the alcohol ester is 1.5-3.5;
the concentration of the crude methyl acetate/ethyl acetate product extracted from the top of the crude isopropanol tower in the step (1) is 70-81 wt%.
6. The method for separating isopropanol from the mixture obtained after the reaction of isopropyl acetate and lower alcohol according to any one of claims 1 to 3, wherein the purity of the isopropanol extracted in the tower kettle of the isopropanol refining tower in the step (2) is not less than 99.9 wt%.
7. The process for separating isopropyl alcohol from a mixture after the reaction of isopropyl acetate with a lower alcohol according to claim 2 or 3, wherein the operating conditions of the acetate refining column in the step (3) are: the pressure is 0.9-1.3 MPa, the reflux ratio is controlled to be 1.0-5.0, the temperature at the top of the tower is controlled to be 110-150 ℃, and the temperature at the bottom of the tower is controlled to be 145-180 ℃;
the product concentration of the methyl acetate/ethyl acetate extracted from the tower kettle of the acetate refining tower is 99.0-99.5 wt%.
8. The method for separating isopropanol from the mixture after the reaction of isopropyl acetate and lower alcohol according to claim 3, wherein the operating conditions of the lower alcohol recovery column in the step (4) are as follows: the pressure is 0.1-0.2 MPa, the reflux ratio is 1.0-5.0, the tower top temperature is 55-85 ℃, and the tower kettle temperature is 64-95 ℃;
the concentration of the low-carbon alcohol product recovered from the tower kettle of the low-carbon alcohol recovery tower is 99.0-99.5 wt%.
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| CN111569791A (en) * | 2020-03-25 | 2020-08-25 | 南京延长反应技术研究院有限公司 | Enhanced reaction system and process for catalyzing propylene hydration by ionic liquid |
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| CN102755759A (en) * | 2012-07-27 | 2012-10-31 | 福州大学 | Continuous reaction rectification process and rectification equipment for synthesizing isopropyl alcohol |
| CN102850185A (en) * | 2012-09-20 | 2013-01-02 | 福州大学 | Method for synthesizing isopropanol by using cation exchange resin as catalyst |
| CN102942475A (en) * | 2012-11-23 | 2013-02-27 | 福建师范大学福清分校 | Variable-pressure rectification method for separating ethyl acetate and ethanol azeotropes and production device for azeotropes |
| CN102976894A (en) * | 2012-09-20 | 2013-03-20 | 福州大学 | Catalysis rectification process for isopropanol synthesis through transesterification method, and production equipment thereof |
| CN106631801A (en) * | 2015-10-31 | 2017-05-10 | 湖南中创化工股份有限公司 | Method and device for separating impurities in sec-butyl acetate by using methanol as azeotropic agent |
| CN107235824A (en) * | 2017-06-05 | 2017-10-10 | 惠州宇新化工有限责任公司 | A kind of method that isopropyl acetate prepares isopropanol with low-carbon alcohols reaction |
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| CN103755559B (en) * | 2014-01-08 | 2016-04-06 | 沈阳化工大学 | A kind of method of ion liquid abstraction rectifying separation ethyl acetate-isopropanol |
| CN107501042B (en) * | 2017-08-17 | 2020-08-11 | 惠州宇新化工有限责任公司 | Method for preparing isopropanol by hydrolyzing isopropyl acetate |
| CN108947774B (en) * | 2018-07-18 | 2020-12-08 | 惠州宇新化工有限责任公司 | Method and device for separating isopropanol |
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| CN102755759A (en) * | 2012-07-27 | 2012-10-31 | 福州大学 | Continuous reaction rectification process and rectification equipment for synthesizing isopropyl alcohol |
| CN102850185A (en) * | 2012-09-20 | 2013-01-02 | 福州大学 | Method for synthesizing isopropanol by using cation exchange resin as catalyst |
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