CN113262509B - Treatment system and treatment method for isobutanol recovered from diisobutyl ester preparation process - Google Patents
Treatment system and treatment method for isobutanol recovered from diisobutyl ester preparation process Download PDFInfo
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Abstract
The invention relates to the technical field of diisobutyl ester production, and discloses a treatment system and a treatment method of isobutanol for recovering isobutanol in the diisobutyl ester preparation process, aiming at the problem that the reuse of isobutanol is affected due to high content of color substances in the isobutanol recovered in the conventional diisobutyl ester preparation process. The treatment system and the treatment method can effectively purify the isobutanol recovered in the diisobutyl ester production, have high recovery rate and high purity, can achieve the sulfur test color of less than 15# and meet the production and application of the diisobutyl ester, and have simple process structure and positive economic benefit and environmental protection benefit.
Description
Technical Field
The invention relates to the technical field of diisobutyl ester production, in particular to a treatment system and a treatment method for isobutanol recovered from a diisobutyl ester preparation process.
Background
The diisobutyl ester is produced by using phthalic anhydride and isobutanol as raw materials, heating under the action of sulfuric acid catalyst to produce crude ester, performing neutralization reaction with sodium carbonate in a neutralization station after the crude ester is qualified by test, conveying the neutralized crude ester into a dealcoholization tower by a pump for vacuum dealcoholization operation, and conveying the dealcoholized semi-finished product into a filter press to remove impurity components and enter a finished product large tank. And (3) treating the wastewater generated by esterification and neutralization by a wastewater treatment tower, and then recovering the isobutanol, wherein the recovered isobutanol is used as a raw material again. The sulfur test color of the recovered alcohol produced by the esterification working section and the waste water recovery working section is very high, because under the reaction condition, the impurities in the recovered alcohol continuously generate thermal cracking and oxidation reaction to generate unsaturated matters, the unsaturated matters are further polymerized to form substances with color, the byproducts have bad influence on the color of the esterification crude ester, the sulfur test color of the recovered alcohol in the esterification phase separator and the recovered alcohol in the recovered phase separator is found to be more than 100# through periodic sampling detection of the isobutanol recovered by the esterification, dealcoholization and other working sections, the recycling accumulation of the recovered isobutanol is carried out along with the recycling and reusing of the recovered isobutanol, the content of the byproducts is increased, the components are increasingly complex, and the quality of the diisobutyl ester is seriously influenced. In addition, solid waste generated by the diisobutyl ester production system is mainly derived from low-boiling-point substances and high-boiling-point substances generated by treating and recycling alcohol. Therefore, how to treat the isobutanol recovered in the diisobutyl ester preparation and reduce the solid waste yield are of great significance to the production of the diisobutyl ester.
Disclosure of Invention
Aiming at the problem that the content of color substances in the isobutanol recovered in the existing diisobutyl ester preparation is high so as to influence the reuse of the isobutanol, the invention aims to provide a treatment system for the isobutanol recovered in the diisobutyl ester preparation process, which can effectively reduce the content of the color substances in the isobutanol, improve the purity of the isobutanol, and has the advantages of high purity and high recovery rate.
It is another object of the present invention to provide a process for the treatment of isobutanol recovered using the above-described treatment system.
The technical scheme provided by the invention is as follows:
the treatment system for the isobutanol recovered from the diisobutyl ester preparation process comprises a pretreatment kettle (1), a pretreatment tower (2), a pretreatment phase separator (4), a primary low-boiling tank (5), a second fraction tank (6), a front isobutanol tank (7), a low-boiling kettle (10), a low-boiling tower (11), a low-boiling phase separator (13), a rear isobutanol tank (14) and a secondary low-boiling tank (15) which are sequentially arranged along the material flow direction;
the top of the pretreatment kettle is provided with a first feed inlet (18), a first discharge outlet (19) and a second feed inlet (20), and the bottom of the pretreatment kettle is provided with a second discharge outlet (21);
the top of the pretreatment tower is provided with a third discharge port (23), the upper part of the pretreatment tower is provided with a fifth feed port (26), and the bottom of the pretreatment tower is provided with a fifth discharge port (27) and a third feed port (22);
the pretreatment phase separator is provided with a fourth feed inlet (24) and a fourth discharge outlet (25);
the first discharge port is communicated with the third feed port through a feed pipeline, the fifth discharge port is communicated with the second feed port through a discharge pipeline, the third discharge port is communicated with the fourth feed port through a feed pipeline, and the fourth discharge port is communicated with the fifth feed port through a return pipeline;
the fourth discharge port is also communicated with the front isobutanol tank, the second fraction tank and the primary low-boiling tank through a feed pipeline respectively;
the top of the low-boiling kettle is provided with a sixth feed inlet (28), a sixth discharge outlet (29) and a seventh feed inlet (30), and the bottom of the low-boiling kettle is provided with a seventh discharge outlet (31);
the lower part of the low-boiling tower is provided with an eighth feed inlet (32), the bottom of the low-boiling tower is provided with a tenth discharge outlet (37), the upper part of the low-boiling tower is provided with a tenth feed inlet (36), and the top of the low-boiling tower is provided with an eighth discharge outlet (33);
a ninth feeding port (34) and a ninth discharging port (35) are arranged on the low-boiling phase separator;
the primary low-boiling tank is provided with a low-boiling material outlet, and is communicated with a sixth feed inlet through a feed pipeline, a sixth discharge outlet is communicated with an eighth feed inlet through a feed pipeline, and the bottom of the tenth discharge outlet is communicated with a seventh feed inlet through a return pipeline;
the eighth discharge port is communicated with the ninth feed port through a discharge pipeline, and the ninth discharge port is communicated with the tenth feed port through a return pipeline;
the ninth discharging hole is also communicated with the rear isobutanol groove and the secondary low-boiling groove through a discharging pipeline.
The process for recovering isobutanol of the present invention is different from the process for purifying isobutanol in other cases, such as the process for preparing isobutanol by hydrogenation of isobutyraldehyde, mainly because of the difference in organic impurity components and content in isobutanol. The recovered isobutanol to be treated in the invention is derived from the preparation process of diisobutyl ester, such as esterification reaction and neutralization reaction, wherein the generated impurities continuously generate thermal cracking and oxidation reaction to generate unsaturated matters, the unsaturated matters are further polymerized to form substances with color, and the byproducts have bad influence on the color of the esterified crude ester. The inventor repeatedly tries to connect a rectifying still, a rectifying tower and a phase separator according to the impurity components and the content characteristics in the recovered isobutanol, and adopts a double rectifying mode to effectively treat the recovered isobutanol, the recovery rate of the isobutanol can reach 90 percent or even more than 96 percent, the purity is high, the color and impurity content is greatly reduced, the color number can reach below 15# and the raw material requirement of the diisobutyl production on the isobutanol is completely met.
Preferably, the temperature of the pretreatment kettle is 80-113 ℃; the temperature of the low-boiling kettle is 80-113 ℃. The pretreatment kettle carries out the first separation of the recovered isobutanol, the generated gas phase enters the subsequent separation process, and the high-boiling-point substances are separated from the pretreatment kettle as one of solid waste sources; the low-boiling kettle separates the components in the primary low-boiling tank, the generated gas phase enters the subsequent separation process, and the high-boiling matters are separated from the pretreatment kettle as one of solid waste sources.
Preferably, the number of trays in the pretreatment column is 28 to 32; the number of the tower plates of the low-boiling tower is 28-32. Controlling the proper number of trays is important to maintain the desired analytical results.
As a preferable mode of the invention, the first low boiling tank collects the front cut fraction when the top temperature of the pretreatment tower is 86-107 ℃, the second cut fraction tank collects the middle cut fraction when the top temperature of the pretreatment tower is 107-108 ℃, and the front isobutanol tank collects the rear cut fraction when the top temperature of the pretreatment tower is higher than 108 ℃. The isobutanol in the pre-isobutanol tank can be reused, the material in the primary low-boiling tank is a low-boiling material with sulfur test color more than 200# and isobutanol content of 50-60 wt% and needs further treatment, and the material in the second fraction tank is determined according to the isobutanol quality.
As a preferable mode of the invention, the secondary low-boiling tank collects the front fraction when the temperature of the top of the low-boiling column is 86-108 ℃, and the later isobutanol tank collects the rear fraction when the temperature of the top of the low-boiling column is higher than 108 ℃. The isobutanol in the post isobutanol tank can be reused, and the isobutanol content in the materials of the secondary low-boiling tank is 30-40% and is the main solid waste source.
As the preferable mode of the invention, the flow ratio of the material returned from the pretreatment phase separator to the pretreatment tower to the total material entering the pretreatment phase separator into the pre-isobutanol tank, the second fraction tank and the primary low-boiling tank is 1:1-1.2.
As the preferable flow ratio of the material which flows back from the low-boiling phase separator to the pretreatment tower and the total material which enters the isobutanol tank and the secondary low-boiling tank from the low-boiling phase separator is 1:1-1.2.
A method for treating isobutanol recovered from diisobutyl ester preparation process by using the above treatment system comprises the following steps:
(1) Isobutanol recovered from diisobutyl ester preparation is sent into a pretreatment kettle through a first feed port to be heated, generated gas phase is sent into a pretreatment tower through a first discharge port and a third feed port, and high-boiling substances generated in the pretreatment kettle are discharged from a second discharge port;
(2) The gas phase in the pretreatment tower enters a pretreatment phase separator from a third discharge port to separate a water phase and an organic phase, when the temperature of the top of the pretreatment tower is more than or equal to 86 ℃, part of the organic phase in the pretreatment phase separator flows back to the pretreatment tower from a fourth discharge port, and the other part of the organic phase is collected into a primary low-boiling tank, a second fraction tank or a pre-isobutanol tank, wherein the primary low-boiling tank collects a front fraction when the temperature of the top of the pretreatment tower is 86-107 ℃, and the isobutanol tank collects a rear fraction when the temperature of the top of the pretreatment tower is higher than 108 ℃;
(3) The organic phase collected in the primary low-boiling tank enters a low-boiling tank through a sixth feed inlet, the gas phase generated in the low-boiling tank enters a low-boiling tower through a sixth discharge outlet, the gas phase generated in the low-boiling tower enters a low-boiling phase separator through an eighth discharge outlet to separate the water phase and the organic phase, a part of the organic phase flows back to the low-boiling tower through a ninth discharge outlet, the other part of the organic phase is collected into a post isobutanol tank or a secondary low-boiling tank, the secondary low-boiling tank collects the front fraction when the tower top temperature of the low-boiling tower is 86-108 ℃, and the post isobutanol tank collects the rear fraction when the tower top temperature of the low-boiling tower is higher than 108 ℃;
(4) And collecting isobutanol in the front isobutanol tank and the rear isobutanol tank to obtain purified isobutanol, and collecting low-boiling substances in the secondary low-boiling tank and high-boiling substances in the treatment kettle and the low-boiling kettle to obtain solid wastes.
In the above process, since isobutanol is initially recovered to contain 10 to 15wt% of water, total reflux water separation is required for the organic phase in the pretreatment phase separator at an initial stage.
As a preferable mode of the method, the step (3) further comprises adding 10-15 wt% of water to the low-boiling kettle. As the isobutanol content of the materials in the primary low-boiling tank is reduced, the impurity content is increased (sulfur test color is more than 200 #), the moisture content is reduced to 1-5 wt percent, and the high-content impurities are extracted from the top of the tower to enter the secondary low-boiling tank after further water is added and azeotropy with the low-boiling impurities and ether is needed.
As a preferred embodiment of the process according to the invention, the treatment is ended when the temperature in the pretreatment tank or in the low-boiling tank is greater than 113 ℃.
The beneficial effects of the invention are as follows:
the treatment system and the treatment method can effectively purify the isobutanol recovered in the diisobutyl ester production, have high recovery rate and high purity, can achieve the sulfur test color of less than 15# and meet the production and application of the diisobutyl ester, and have simple process structure and positive economic benefit and environmental protection benefit.
Drawings
FIG. 1 is a process flow diagram of a processing system of the present invention.
In the figure: 1. a pretreatment tank 2, a pretreatment column 3, a column top condenser 4, a pretreatment phase separator 5, a primary low boiling tank 6, a second distillate tank 7, a front isobutanol tank 8, a recovery alcohol feed pump 9, a low boiling feed pump 10, a low boiling tank 11, a low boiling column 12, a low boiling column top condenser 13, a low boiling phase separator 14, a secondary low boiling tank 15, a rear isobutanol tank 18, a first feed port 19, a first feed port 20, a second feed port 21, a second feed port 22, a third feed port 23, a third feed port 24, a fourth feed port 25, a fourth feed port 26, a fifth feed port 27, a fifth feed port 28, a sixth feed port 29, a sixth feed port 30, a seventh feed port 31, a seventh feed port 32, an eighth feed port 33, an eighth feed port 34, a ninth feed port 35, a ninth feed port 36, a tenth feed port 37, a tenth feed port.
Detailed Description
The following is a further description of embodiments of the invention.
Unless otherwise indicated, all starting materials used in the present invention are commercially available or are commonly used in the art, and unless otherwise indicated, the methods in the examples below are all conventional in the art.
A treatment system for isobutanol recovered from diisobutyl ester production process, as shown in FIG. 1, comprises a pretreatment kettle 1, a pretreatment tower 2, a pretreatment phase separator 4, a primary low-boiling tank 5, a second fraction tank 6, a front isobutanol tank 7, a low-boiling kettle 10, a low-boiling tower 11, a low-boiling phase separator 13, a rear isobutanol tank 14 and a secondary low-boiling tank 15 which are sequentially arranged along the material flow direction.
The top of the pretreatment kettle is provided with a first feed inlet 18, a first discharge outlet 19 and a second feed inlet 20, the bottom of the pretreatment kettle is provided with a second discharge outlet 21, and the temperature of the pretreatment kettle is 80-113 ℃. The pretreatment tower is a packed tower, the number of tower plates is 28-32, the top of the pretreatment tower is provided with a third discharge hole 23, the upper part of the pretreatment tower is provided with a fifth feed hole 26, and the bottom of the pretreatment tower is provided with a fifth discharge hole 27 and a third feed hole 22; the pretreatment phase separator is provided with a fourth feed port 24 and a fourth discharge port 25.
The top of the low-boiling kettle is provided with a sixth feed inlet 28, a sixth discharge outlet 29 and a seventh feed inlet 30, the bottom of the low-boiling kettle is provided with a seventh discharge outlet 31, and the temperature of the low-boiling kettle is 80-113 ℃. The lower part of the low-boiling tower is provided with an eighth feed inlet 32, the bottom of the low-boiling tower is provided with a tenth discharge outlet 37, the upper part of the low-boiling tower is provided with a tenth feed inlet 36, and the top of the low-boiling tower is provided with an eighth discharge outlet 33; the low-boiling phase separator is provided with a ninth feed inlet 34 and a ninth discharge outlet 35.
The first feed inlet is communicated with a pipeline for conveying the recovered isobutanol, and the recovered isobutanol is fed into the pretreatment kettle through the first feed inlet by a recovered alcohol feed pump 8; the first discharge port is communicated with the third feed port through a feed pipeline, the fifth discharge port is communicated with the second feed port through a discharge pipeline, the third discharge port is communicated with the fourth feed port through a feed pipeline, a tower top condenser 3 is further arranged on a pipeline for communicating the third discharge port with the fourth feed port, and the fourth discharge port is communicated with the fifth feed port through a return pipeline; the fourth discharge port is also communicated with the front isobutanol tank, the second fraction tank and the primary low-boiling tank through a feed pipeline respectively.
The primary low-boiling tank is provided with a low-boiling material outlet which is communicated with a sixth feeding port through a feeding pipeline, and a low-boiling feeding pump 9 is arranged on the feeding pipeline; the sixth discharge port is communicated with the eighth feed port through a feed pipeline, and the tenth discharge port is communicated with the seventh feed port through a return pipeline; the eighth discharge port is communicated with the ninth feed port through a discharge pipeline, a low-boiling tower top condenser 12 is arranged on the discharge pipeline, and the ninth discharge port is communicated with the tenth feed port through a return pipeline; the ninth discharging hole is also communicated with the rear isobutanol groove and the secondary low-boiling groove through a discharging pipeline.
When the recovered isobutanol is treated, the recovered isobutanol enters a pretreatment kettle through a recovered alcohol feeding pump, gas phase generated in the pretreatment kettle enters a pretreatment tower, and high-boiling substances in the pretreatment kettle are treated from a bottom ladle. The heavy components at the bottom of the pretreatment tower flow back to the pretreatment kettle, the gas phase light components enter the pretreatment phase separator through the top condenser to separate the water phase from the organic phase, when the top temperature of the pretreatment tower is lower than 86 ℃, the organic phase in the pretreatment phase separator flows back completely, when the top temperature of the current treatment tower is higher than 86 ℃, the organic phase in the pretreatment phase separator flows back to the pretreatment tower partially, the isobutanol tank, the second fraction tank or the primary low-boiling tank is collected partially, and the flow ratio of the reflux to the extraction is controlled to be 1:1-1.2, specifically: the first low boiling tank collects the front cut fraction when the top temperature of the pretreatment tower is 86-107 ℃, the second cut fraction tank collects the middle cut fraction when the top temperature of the pretreatment tower is 107-108 ℃, and the front isobutanol tank collects the rear cut fraction when the top temperature of the pretreatment tower is higher than 108 ℃.
The low-boiling substances in the primary low-boiling tank enter a low-boiling kettle through a low-boiling feed pump, gas phase generated in the low-boiling kettle enters a low-boiling tower, the number of tower plates of the low-boiling tower is 28-32, and high-boiling substances in the low-boiling kettle are treated through a ladle from the bottom. The heavy components at the bottom of the low-boiling tower are refluxed to a low-boiling kettle, gas phase light components in the low-boiling tower enter a low-boiling phase splitter through an eighth discharge port and a low-boiling tower top condenser, the low-boiling phase splitter separates organic phases from water phases, water phases are discharged from the bottom, part of the organic phases are refluxed to the low-boiling tower, and the other part of the organic phases are extracted to a rear isobutanol tank or a secondary low-boiling tank, wherein the reflux and extraction flow ratio is 1:1-1.2, and the method specifically comprises the following steps: the secondary low-boiling tank collects the front fraction when the temperature of the top of the low-boiling tower is 86-108 ℃, the rear isobutanol tank collects the rear fraction when the temperature of the top of the low-boiling tower is higher than 108 ℃, and when the temperature of the current treatment kettle or the low-boiling kettle is higher than 113 ℃, the treatment is finished.
Specific application example 1 for treating isobutanol recovered from the diisobutyl ester production process using the above-described treatment system, the steps are as follows:
(1) Recovering isobutanol from the wastewater generated in the esterification stage and the neutralization stage of diisobutyl ester after being treated by a wastewater treatment tower, continuously feeding 147 tons of recovered isobutanol into a pretreatment kettle through a first feed port for heating, wherein the temperature of the pretreatment kettle is 80 ℃, the mass concentration of isobutanol in the recovered isobutanol is 85%, the balance of wastewater, color substances and solid waste are the sulfur test color is 150#, then feeding gas phase generated in the pretreatment kettle into the pretreatment tower through a first discharge port and a third feed port, the number of tower plates of the pretreatment tower is 30, and discharging high-boiling substances generated in the pretreatment kettle from a second discharge port;
(2) The gas phase in the pretreatment tower enters the pretreatment phase separator from the third discharge port to separate the water phase and the organic phase, when the temperature of the top of the pretreatment tower is less than 86 ℃, the organic phase in the pretreatment phase separator is totally refluxed to the pretreatment tower, when the temperature of the top of the current treatment tower is raised to 86 ℃, part of the organic phase in the pretreatment phase separator is refluxed to the pretreatment tower, and part of the organic phase is extracted, the flow ratio of the reflux to the extraction is 1:1, and the extraction method is as follows: the first low-boiling tank collects the front cut fraction when the top temperature of the pretreatment tower is 86-107 ℃, the isobutanol tank collects the rear cut fraction when the top temperature of the pretreatment tower is higher than 108 ℃, and the second cut fraction tank collects the cut fraction when the top temperature of the pretreatment tower is 107-108 ℃; when the temperature of the current treatment kettle is higher than 113 ℃, finishing the treatment;
(3) The organic phase collected in the primary low-boiling tank enters a low-boiling tank through a sixth feed inlet, the temperature of the low-boiling tank is 108 ℃,10 wt% of water of materials in the low-boiling tank is added into the low-boiling tank, gas phase generated in the low-boiling tank enters a low-boiling tower through a sixth discharge outlet, the gas phase generated in the low-boiling tower enters a low-boiling phase separator through an eighth discharge outlet to separate water phase and organic phase, part of the organic phase flows back to the low-boiling tower through a ninth discharge outlet, the other part of the organic phase is collected into a post isobutanol tank or a secondary low-boiling tank, the flow ratio of the reflux to the extraction is 1:1, and the extraction method is as follows: the secondary low-boiling tank collects the front fraction when the temperature of the top of the low-boiling tower is 86-108 ℃, and the rear isobutanol tank collects the rear fraction when the temperature of the top of the low-boiling tower is higher than 108 ℃; when the temperature in the low-boiling kettle is higher than 113 ℃, ending the treatment;
(4) And collecting isobutanol in the front isobutanol tank and the rear isobutanol tank to obtain purified isobutanol, and collecting low-boiling substances in the secondary low-boiling tank and high-boiling substances in the treatment kettle and the low-boiling kettle to obtain solid wastes.
In the application example, the recovery rate of the isobutanol is 96.5%, the purity is 98.8%, and the sulfur test color is less than or equal to 15#.
Specific application example 2 for treating isobutanol recovered from the diisobutyl ester production process using the above-described treatment system, the steps are as follows:
(1) Recovering isobutanol from the wastewater generated in the esterification stage and the neutralization stage of diisobutyl ester after being treated by a wastewater treatment tower, continuously feeding 147 tons of recovered isobutanol into a pretreatment kettle through a first feed port for heating, wherein the temperature of the pretreatment kettle is 112 ℃, the mass concentration of isobutanol in the recovered isobutanol is 85%, the balance of wastewater, color substances and solid waste are the sulfur test color is 150#, then feeding gas phase generated in the pretreatment kettle into the pretreatment tower through a first discharge port and a third feed port, the number of tower plates of the pretreatment tower is 30, and discharging high-boiling substances generated in the pretreatment kettle from a second discharge port;
(2) The gas phase in the pretreatment tower enters a pretreatment phase separator from a third discharge port to separate a water phase and an organic phase, when the top temperature of the pretreatment tower is lower than 86 ℃, the organic phase in the pretreatment phase separator is totally refluxed to the pretreatment tower, the top temperature of the current treatment tower is raised to 86 ℃, part of the organic phase in the pretreatment phase separator is refluxed to the pretreatment tower, part of the organic phase is extracted, the flow ratio of the reflux to the extraction is 1:1.1, and the extraction method is as follows: the first low-boiling tank collects the front cut fraction when the top temperature of the pretreatment tower is 86-107 ℃, the isobutanol tank collects the rear cut fraction when the top temperature of the pretreatment tower is higher than 108 ℃, and the second cut fraction tank collects the cut fraction when the top temperature of the pretreatment tower is 107-108 ℃; when the temperature of the current treatment kettle is higher than 113 ℃, finishing the treatment;
(3) The organic phase collected in the primary low-boiling tank enters a low-boiling tank through a sixth feed inlet, the temperature of the low-boiling tank is 112 ℃,15 wt% of water of materials in the low-boiling tank is added into the low-boiling tank, gas phase generated in the low-boiling tank enters a low-boiling tower through a sixth discharge outlet, gas phase generated in the low-boiling tower enters a low-boiling phase separator through an eighth discharge outlet to separate water phase and organic phase, part of the organic phase flows back to the low-boiling tower through a ninth discharge outlet, the other part of the organic phase is collected into a post isobutanol tank or a secondary low-boiling tank, the flow ratio of the reflux to the extraction is 1:1.1, and the method comprises the following steps: the secondary low-boiling tank collects the front fraction when the temperature of the top of the low-boiling tower is 86-108 ℃, and the rear isobutanol tank collects the rear fraction when the temperature of the top of the low-boiling tower is higher than 108 ℃; when the temperature in the low-boiling kettle is higher than 113 ℃, ending the treatment;
(4) And collecting isobutanol in the front isobutanol tank and the rear isobutanol tank to obtain purified isobutanol, and collecting low-boiling substances in the secondary low-boiling tank and high-boiling substances in the treatment kettle and the low-boiling kettle to obtain solid wastes.
In the application example, the recovery rate of the isobutanol is 96.2%, the purity is 99.1%, and the sulfur test color is less than or equal to 15#.
Specific application example 3 of the treatment of isobutanol recovered from the diisobutyl ester production process using the above-described treatment system is as follows:
(1) Recovering isobutanol from the wastewater generated in the esterification stage and the neutralization stage of diisobutyl ester after being treated by a wastewater treatment tower, continuously feeding 147 tons of recovered isobutanol into a pretreatment kettle through a first feed port for heating, wherein the temperature of the pretreatment kettle is 100 ℃, the mass concentration of isobutanol in the recovered isobutanol is 85%, the balance of wastewater, color substances and solid waste are the sulfur test color is 150#, then feeding gas phase generated in the pretreatment kettle into the pretreatment tower through a first discharge port and a third feed port, the number of tower plates of the pretreatment tower is 30, and discharging high-boiling substances generated in the pretreatment kettle from a second discharge port;
(2) The gas phase in the pretreatment tower enters a pretreatment phase separator from a third discharge port to separate a water phase and an organic phase, when the top temperature of the pretreatment tower is lower than 86 ℃, the organic phase in the pretreatment phase separator is totally refluxed to the pretreatment tower, the top temperature of the current treatment tower is raised to 86 ℃, part of the organic phase in the pretreatment phase separator is refluxed to the pretreatment tower, part of the organic phase is extracted, the flow ratio of the reflux to the extraction is 1:1.2, and the extraction method is as follows: the first low-boiling tank collects the front cut fraction when the top temperature of the pretreatment tower is 86-107 ℃, the isobutanol tank collects the rear cut fraction when the top temperature of the pretreatment tower is higher than 108 ℃, and the second cut fraction tank collects the cut fraction when the top temperature of the pretreatment tower is 107-108 ℃; when the temperature of the current treatment kettle is higher than 113 ℃, finishing the treatment;
(3) The organic phase collected in the primary low-boiling tank enters a low-boiling tank through a sixth feed inlet, the temperature of the low-boiling tank is 100 ℃,14 wt% of water of materials in the low-boiling tank is added into the low-boiling tank, gas phase generated in the low-boiling tank enters a low-boiling tower through a sixth discharge outlet, gas phase generated in the low-boiling tower enters a low-boiling phase separator through an eighth discharge outlet to separate water phase and organic phase, part of the organic phase flows back to the low-boiling tower through a ninth discharge outlet, the other part of the organic phase is collected into a post isobutanol tank or a secondary low-boiling tank, the flow ratio of the reflux to the extraction is 1:1-1.2, and the extraction method is as follows: the secondary low-boiling tank collects the front fraction when the temperature of the top of the low-boiling tower is 86-108 ℃, and the rear isobutanol tank collects the rear fraction when the temperature of the top of the low-boiling tower is higher than 108 ℃; when the temperature in the low-boiling kettle is higher than 113 ℃, ending the treatment;
(4) And collecting isobutanol in the front isobutanol tank and the rear isobutanol tank to obtain purified isobutanol, and collecting low-boiling substances in the secondary low-boiling tank and high-boiling substances in the treatment kettle and the low-boiling kettle to obtain solid wastes.
In the application example, the recovery rate of the isobutanol is 96.8%, the purity is 99.3%, and the sulfur test color is less than or equal to 10#.
Specific application example 4 of the treatment of isobutanol recovered from the diisobutyl ester production process using the above-described treatment system is as follows:
(1) Recovering isobutanol from the wastewater generated in the esterification stage and the neutralization stage of diisobutyl ester after being treated by a wastewater treatment tower, continuously feeding 147 tons of recovered isobutanol into a pretreatment kettle through a first feed port for heating, wherein the temperature of the pretreatment kettle is 80 ℃, the mass concentration of isobutanol in the recovered isobutanol is 85%, the balance of wastewater, color substances and solid waste are the sulfur test color is 150#, then feeding gas phase generated in the pretreatment kettle into the pretreatment tower through a first discharge port and a third feed port, the number of tower plates of the pretreatment tower is 30, and discharging high-boiling substances generated in the pretreatment kettle from a second discharge port;
(2) The gas phase in the pretreatment tower enters a pretreatment phase separator from a third discharge port to separate a water phase and an organic phase, when the top temperature of the pretreatment tower is lower than 86 ℃, the organic phase in the pretreatment phase separator is totally refluxed to the pretreatment tower, the top temperature of the current treatment tower is raised to 86 ℃, part of the organic phase in the pretreatment phase separator is refluxed to the pretreatment tower, part of the organic phase is extracted, the flow ratio of the reflux to the extraction is 1:1, and the extraction method is as follows: the first low-boiling tank collects the front cut fraction when the top temperature of the pretreatment tower is 86-107 ℃, the isobutanol tank collects the rear cut fraction when the top temperature of the pretreatment tower is higher than 108 ℃, and the second cut fraction tank collects the cut fraction when the top temperature of the pretreatment tower is 107-108 ℃; when the temperature of the current treatment kettle is higher than 113 ℃, finishing the treatment;
(3) The organic phase collected in the primary low-boiling tank enters a low-boiling tank through a sixth feed inlet, the temperature of the low-boiling tank is 108 ℃, gas phase generated in the low-boiling tank enters a low-boiling tower through a sixth discharge outlet, the gas phase generated in the low-boiling tower enters a low-boiling phase separator through an eighth discharge outlet to separate water phase and organic phase, a part of the organic phase flows back to the low-boiling tower through a ninth discharge outlet, the other part of the organic phase is collected in a rear isobutanol tank or a secondary low-boiling tank, the flow ratio of the reflux to the extraction is 1:1, and the extraction method is as follows: the secondary low-boiling tank collects the front fraction when the temperature of the top of the low-boiling tower is 86-108 ℃, and the rear isobutanol tank collects the rear fraction when the temperature of the top of the low-boiling tower is higher than 108 ℃; when the temperature in the low-boiling kettle is higher than 113 ℃, ending the treatment;
(4) And collecting isobutanol in the front isobutanol tank and the rear isobutanol tank to obtain purified isobutanol, and collecting low-boiling substances in the secondary low-boiling tank and high-boiling substances in the treatment kettle and the low-boiling kettle to obtain solid wastes.
In the application example, the recovery rate of the isobutanol is 90.5%, the purity is 91.8%, and the sulfur test color is less than or equal to 30#.
Claims (8)
1. A method for treating isobutanol recovered from a diisobutyl ester production process using a treatment system,
the treatment system comprises a pretreatment kettle (1), a pretreatment tower (2), a pretreatment phase separator (4), a primary low-boiling tank (5), a second fraction tank (6), a front isobutanol tank (7), a low-boiling kettle (10), a low-boiling tower (11), a low-boiling phase separator (13), a rear isobutanol tank (14) and a secondary low-boiling tank (15) which are sequentially arranged along the material flow direction;
the top of the pretreatment kettle is provided with a first feed inlet (18), a first discharge outlet (19) and a second feed inlet (20), and the bottom of the pretreatment kettle is provided with a second discharge outlet (21);
the top of the pretreatment tower is provided with a third discharge port (23), the upper part of the pretreatment tower is provided with a fifth feed port (26), and the bottom of the pretreatment tower is provided with a fifth discharge port (27) and a third feed port (22);
the treatment phase separator is provided with a fourth feed inlet (24) and a fourth discharge outlet (25);
the first discharge port is communicated with the third feed port through a feed pipeline, the fifth discharge port is communicated with the second feed port through a discharge pipeline, the third discharge port is communicated with the fourth feed port through a feed pipeline, and the fourth discharge port is communicated with the fifth feed port through a return pipeline;
the fourth discharge port is also communicated with the front isobutanol tank, the second fraction tank and the primary low-boiling tank through a feed pipeline respectively;
the top of the low-boiling kettle is provided with a sixth feed inlet (28), a sixth discharge outlet (29) and a seventh feed inlet (30), and the bottom of the low-boiling kettle is provided with a seventh discharge outlet (31);
the lower part of the low-boiling tower is provided with an eighth feed inlet (32), the bottom of the low-boiling tower is provided with a tenth discharge outlet (37), the upper part of the low-boiling tower is provided with a tenth feed inlet (36), and the top of the low-boiling tower is provided with an eighth discharge outlet (33);
a ninth feeding port (34) and a ninth discharging port (35) are arranged on the low-boiling phase separator;
the primary low-boiling tank is provided with a low-boiling material outlet, and is communicated with a sixth feed inlet through a feed pipeline, a sixth discharge outlet is communicated with an eighth feed inlet through a feed pipeline, and the bottom of the tenth discharge outlet is communicated with a seventh feed inlet through a return pipeline;
the eighth discharge port is communicated with the ninth feed port through a discharge pipeline, and the ninth discharge port is communicated with the tenth feed port through a return pipeline;
the ninth discharging port is also communicated with the rear isobutanol tank and the secondary low-boiling tank through a discharging pipeline;
the method is characterized by comprising the following steps of:
(1) Isobutanol recovered from diisobutyl ester preparation is sent into a pretreatment kettle through a first feed port to be heated, generated gas phase is sent into a pretreatment tower through a first discharge port and a third feed port, and high-boiling substances generated in the pretreatment kettle are discharged from a second discharge port;
(2) The gas phase in the pretreatment tower enters a pretreatment phase separator from a third discharge port to separate a water phase and an organic phase, when the temperature of the top of the pretreatment tower is more than or equal to 86 ℃, part of the organic phase in the pretreatment phase separator flows back to the pretreatment tower from a fourth discharge port, and the other part of the organic phase is collected into a primary low-boiling tank, a second fraction tank or a pre-isobutanol tank, wherein the primary low-boiling tank collects a front fraction when the temperature of the top of the pretreatment tower is 86-107 ℃, and the isobutanol tank collects a rear fraction when the temperature of the top of the pretreatment tower is higher than 108 ℃;
(3) The organic phase collected in the primary low-boiling tank enters a low-boiling tank through a sixth feed inlet, the gas phase generated in the low-boiling tank enters a low-boiling tower through a sixth discharge outlet, the gas phase generated in the low-boiling tower enters a low-boiling phase separator through an eighth discharge outlet to separate the water phase and the organic phase, a part of the organic phase flows back to the low-boiling tower through a ninth discharge outlet, the other part of the organic phase is collected into a post isobutanol tank or a secondary low-boiling tank, the secondary low-boiling tank collects the front fraction when the tower top temperature of the low-boiling tower is 86-108 ℃, and the post isobutanol tank collects the rear fraction when the tower top temperature of the low-boiling tower is higher than 108 ℃;
(4) Collecting isobutanol in the front isobutanol tank and the rear isobutanol tank to obtain purified isobutanol, and collecting low-boiling substances in the secondary low-boiling tank and high-boiling substances in the treatment kettle and the low-boiling kettle to obtain solid wastes;
and (3) adding 10-15 wt% of water into the low-boiling kettle.
2. The method for treating isobutanol recovered from the diisobutyl ester production process of claim 1, wherein the temperature of the pre-treatment tank is 80-113 ℃; the temperature of the low-boiling kettle is 80-113 ℃.
3. The method for treating isobutanol recovered from the production process of diisobutyl ester of claim 1, wherein the number of plates of said pretreatment column is 28 to 32; the number of the tower plates of the low-boiling tower is 28-32.
4. A method for treating isobutanol recovered from the production process of diisobutyl ester as claimed in claim 1 or 3, wherein the first low boiling tank collects a front cut at a top temperature of 86 to 107 ℃ in the pretreatment column, the second cut tank collects a middle cut at a top temperature of 107 to 108 ℃ in the pretreatment column, and the front isobutanol tank collects a rear cut at a top temperature of more than 108 ℃ in the pretreatment column.
5. A method for treating isobutanol recovered from the production process of diisobutyl ester according to claim 1 or 3, wherein the secondary low boiling tank collects a front cut at a low boiling column overhead temperature of 86 to 108 ℃ and the rear isobutanol tank collects a rear cut at a low boiling column overhead temperature of more than 108 ℃.
6. The method for treating isobutanol recovered from the production process of diisobutyl ester according to claim 1, wherein the flow ratio of the material refluxed from the pretreatment phase separator to the total material fed from the pretreatment phase separator into the pretreatment tank, the second distillation tank, and the primary low boiling tank is 1:1 to 1.2.
7. The method according to claim 1, wherein the flow ratio of the material returned from the low-boiling phase separator to the low-boiling column to the total material in the isobutanol tank and the secondary low-boiling tank after the material enters from the low-boiling phase separator is 1:1 to 1.2.
8. The method for treating isobutanol recovered from the production process of diisobutyl ester according to claim 1, wherein the treatment is completed when the temperature in the current treatment vessel or the low boiling vessel is greater than 113 ℃.
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