CN111138347B - Industrial method and device for water diversion of vinyl pyridine compounds - Google Patents
Industrial method and device for water diversion of vinyl pyridine compounds Download PDFInfo
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- CN111138347B CN111138347B CN201911405223.5A CN201911405223A CN111138347B CN 111138347 B CN111138347 B CN 111138347B CN 201911405223 A CN201911405223 A CN 201911405223A CN 111138347 B CN111138347 B CN 111138347B
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- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
- C07D213/16—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom containing only one pyridine ring
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Abstract
The invention discloses a water diversion industrialization method for vinyl pyridine compounds, which comprises the following steps: s1, extracting a crude product of the non-dehydrated vinylpyridine compound by adopting an extractant, and centrifugally separating to obtain a mixed organic phase and a water phase which contain the vinylpyridine compound, the extractant and a trace amount of water; s2, rectifying the mixed organic phase obtained in the step S1, collecting at the top of the tower to obtain mixed gas containing extractant and trace water, and collecting at the bottom of the tower to obtain a water-separated vinyl pyridine compound; s3, condensing the mixed gas obtained in the step S2 into liquid, and layering to obtain an extractant phase and a water phase. The invention has the advantages of less polymerization of products, high yield, low energy consumption, low waste water residue, high biodegradability and the like in the production process, and greatly reduces the manufacturing cost. On the basis, the invention also provides a water division industrialization device which can be completely suitable for the water division industrialization method of the vinylpyridine compounds.
Description
Technical Field
The invention belongs to the technical field of chemical production, and particularly relates to a water diversion industrialization method and device for a vinyl pyridine compound.
Background
2-vinylpyridine (2-vp) is an important pyridine derivative which is slightly soluble in water, very soluble in ethanol, diethyl ether and chloroform, soluble in benzene, acetone and the like, and is easily polymerized by heating.
One of the main synthesis methods at present is as follows: 2-methylpyridine and formaldehyde are used as raw materials, the raw materials are synthesized by a gas phase one-step method or a liquid phase two-step method, a gas phase one-step method synthesis technology is adopted, the reaction temperature is relatively high, the reaction pressure is high, the reaction tube is a pipeline type, the blockage is easy, the equipment needs pressure resistance and corrosion resistance, the requirement is high, and the product yield can only reach 60%. The liquid phase two-step method is that firstly, 2-hydroxyethyl pyridine is generated by addition condensation reaction, then, 2-hydroxyethyl pyridine is taken as a raw material, and a catalyst (such as sodium hydroxide, potassium hydroxide, sulfuric acid and phosphoric acid) is added for dehydration to generate a crude product of 2-vinyl pyridine. The 2-vinyl pyridine crude product is mixed with more reaction generated water, the water content is about 25%, and the existing industrialized dehydration method mainly comprises two methods: a process for preparing the 2-vinyl pyridine product includes such steps as separating the water from the reaction mixture by alkali separation (sodium hydroxide) to obtain the coarse 2-vinyl pyridine product with water content of 10-15%, rectifying, azeotropic dewatering, removing heavy components to obtain the 2-vinyl pyridine product with water content not greater than 0.5%, and returning the azeotropic light components to alkali separation step for continuous dewatering. The method has the main defects that the consumption of sodium hydroxide in the water separation process is large, the 2-vp content in the wastewater after water separation is high, the wastewater containing alkali is difficult to biochemically degrade, the wastewater containing alkali is distilled and concentrated, the dangerous waste is produced in a large amount and is difficult to treat, the water content of 2-vp and water azeotropic components produced at the top of the rectifying section is 75%, the 2-vp content is 25%, the process needs to be returned to the previous process to continue adding alkali for water separation, the retention time is kept for more than half an hour during heating and layering, the liquid holdup and the retention time of the 2-vp in a system are greatly increased, and the polymerization risk of the 2-vp is increased. Another method is a temperature rising water diversion method: the mixed solution of 2-vp and water contains 2-vp at about 55 ℃ at least, only 1.5-2% of water content is contained in the mixed solution, about 10% of waste water can be separated by a method of standing and layering in a layering tank when the water content of 2-vp is about 25%, then the residual water is continuously removed by azeotropic distillation, the azeotropic part is returned to the layering tank at 55 ℃ for standing and water diversion, the mixed solution is an improved version of the first method, compared with the first method, the pollution of alkali is saved, the problem that the 2-vp content in the waste water is too high to be biochemically treated is fundamentally not solved, meanwhile, the 2-vp needs to be stored at a low temperature, the increase of polymerization by a heating method is obvious, the method is a technology of relatively green technology with relatively sacrificing the yield, the 2-vp content in the tower top is azeotropy when the temperature is rectified, the water content of the azeotropic component is 75%, the retention time is more than half hour when the temperature is raised and the retention time is long, the retention time is high, and the polymerization is easy to be carried out when the temperature is high, so that a high-yield green technology capable of comprehensively solving the problems is needed.
4-vinylpyridine has similar properties to 2-vinylpyridine, and is produced by removing one molecule of water from 4-hydroxyethylpyridine, and the above-mentioned problems are also present in practical production, and therefore, there is a need for solving the problems.
Disclosure of Invention
The invention aims to provide a method and a device for industrialized water diversion of a vinyl pyridine compound, which solve the defects in the prior art.
The invention aims at realizing the following technical scheme:
a water diversion industrialization method of a vinyl pyridine compound comprises the following steps:
s1, extracting a crude product of the non-dehydrated vinylpyridine compound by adopting an extractant, and centrifugally separating to obtain a mixed organic phase and a water phase which contain the vinylpyridine compound, the extractant and a trace amount of water; the extractant is a solvent which is mutually insoluble with water and has a boiling point lower than that of the vinyl pyridine compound;
s2, rectifying the mixed organic phase obtained in the step S1, collecting at the top of a tower to obtain a mixture containing an extractant and a trace amount of water, and collecting at the bottom of the tower to obtain a split vinylpyridine compound;
s3, condensing the mixed gas obtained in the step S2 into liquid, and layering to obtain an extractant phase and a water phase, wherein the extractant phase is recycled to the step S1.
Preferably, the vinyl pyridine compound is 2-vinyl pyridine or 4-vinyl pyridine.
Preferably, the extractant is benzene, toluene, xylene or ethyl acetate.
Preferably, the volume ratio of the crude vinylpyridine compound product to the extractant in the step S1 is 1 (0.2-5).
Preferably, the rectification condition in the step S2 is that the temperature of the tower bottom is 95+/-5 ℃ and the pressure is-90+/-5 kpa; the temperature at the top of the column is 60+ -5 deg.C, and the pressure is 95+ -5 kpa.
The invention also provides a vinyl pyridine compound water diversion industrialization device which comprises a crude product conveying pipeline, an extraction centrifuge, a rectifying tower system, a condenser and a layering tank; the extraction centrifuge is provided with a crude product inlet, an extractant inlet, an organic phase outlet and a wastewater outlet, the rectifying tower system is provided with an inlet, an overhead extractant reflux port, an extractant extraction outlet and a tower bottom vinyl pyridine compound outlet, and the layering tank is provided with an extractant outlet and a wastewater outlet;
the extraction centrifuge is characterized in that a crude product inlet is connected with the crude product conveying pipeline, an extractant inlet is connected with an extractant outlet of the layering tank, and an organic phase outlet is connected with an inlet of the rectifying tower system and is used for carrying out water-based extraction on a crude product of the vinylpyridine compound by using an extractant, and the extracted extractant, the vinylpyridine compound and water mixed solution are discharged and conveyed to the rectifying tower system;
the tower top extractant extraction port of the rectifying tower system is connected with the inlet of the condenser and is used for rectifying and separating the extracted extractant and the mixed solution of the vinyl pyridine compounds, and the rectified extractant gas and water vapor are discharged from the tower top extractant extraction port and conveyed to the condenser; the tower top extractant reflux port of the rectifying tower system is connected with the extractant outlet of the layering tank;
the condenser is used for condensing extractant gas and vapor into liquid, the condensed liquid is discharged and conveyed to the layering tank, the layering tank is used for layering the condensed liquid into extractant phase and water phase, one part of the layered extractant is discharged and conveyed to the rectifying tower system for self-refluxing use, and the other part of the layered extractant is conveyed to the extraction centrifugal machine for recycling.
Preferably, the extraction centrifuge is two or more stages.
Preferably, the system further comprises a vinylpyridine compound crude product storage tank, and the crude product conveying pipeline is connected with the vinylpyridine compound crude product storage tank.
Preferably, the extraction device further comprises an extractant storage tank, wherein an inlet of the extractant storage tank is connected with an extractant outlet of the layering tank, and an outlet of the extractant storage tank is connected with an extractant inlet of the extraction centrifuge.
Preferably, the extraction centrifuges are two stages, namely a first extraction centrifuges and a second extraction centrifuges, the first extraction centrifuges are provided with a first coarse product inlet, a first extractant inlet, a first aqueous phase outlet and a first organic phase outlet, the second extraction centrifuges are provided with a second aqueous phase inlet, a second extractant inlet, a wastewater outlet and a second organic phase outlet, the first coarse product inlet of the first extraction centrifuges is connected with the coarse product conveying pipeline, the first extractant inlet is connected with the second organic phase outlet of the second extraction centrifuges, the first aqueous phase outlet is connected with the second aqueous phase inlet of the second extraction centrifuges, and the first organic phase outlet is connected with the inlet of the rectifying tower; and a second extractant inlet of the second extraction centrifuge is connected with an extractant outlet of the layering tank.
The invention adopts the extraction centrifugation and extraction rectification combined dehydration method to replace the two methods of alkali precipitation or salting out water analysis and heating dehydration in the prior art, thereby thoroughly solving the problem that the content of vinyl pyridine compounds such as 2-vinyl pyridine in the wastewater is high and the wastewater is difficult to biochemically treat; the generation of dangerous waste of catalysts such as sodium hydroxide is stopped; solves the problems of the prior art that the vinyl pyridine compounds such as 2-vinyl pyridine and water azeotropic components in the top of the tower are returned to the alkali-adding dehydration for reuse, has the advantages of less polymerization of products, high yield, low energy consumption, low waste water residue, high biodegradability and the like in the production process, and greatly reduces the manufacturing cost. On the basis, the invention also provides a water diversion industrialization device, wherein an extraction centrifuge is adopted to extract and separate 2-vinyl pyridine from water in a vinyl pyridine compound crude product, such as a 2-vinyl pyridine crude product, the 2-vinyl pyridine is transferred into an extracting agent, then the extracting agent and the water are rapidly separated by the extraction centrifuge, then the extracting agent and the 2-vinyl pyridine are separated by a rectifying tower, and finally the extracting agent is recycled by a condenser and a layering tank, so that the water diversion industrialization method for the vinyl pyridine compound can be completely applied to.
Drawings
FIG. 1 is a schematic diagram of a device for the industrial water diversion of vinylpyridine compounds;
fig. 2 is a schematic structural diagram of a device for industrialized water diversion of vinylpyridine compounds in a preferred embodiment provided by the invention.
Detailed description of the preferred embodiments
The invention provides a water diversion industrialization method of a vinyl pyridine compound, which comprises the following steps:
s1, extracting a coarse product of a non-dehydrated vinylpyridine compound, such as a coarse product of 2-vinylpyridine, by adopting an extractant, and centrifugally separating to obtain a mixed organic phase and a water phase which contain 2-vinylpyridine, the extractant and a trace amount of water; in order to improve the extraction efficiency, two-stage or multistage continuous extraction centrifugation can be adopted, the extractant is a solvent which is mutually insoluble in water and has a boiling point lower than that of 2-vinyl pyridine, and the solvent comprises but is not limited to benzene, toluene, xylene or cyclohexane, so that the 2-vinyl pyridine can be easily extracted and separated from an aqueous phase, can be easily separated from water, has a boiling point lower than that of 2-vinyl pyridine, and can be separated from the 2-vinyl pyridine through rectification; the unhydrogenated crude product of 2-vinylpyridine is a crude product produced by dehydration of 2-hydroxyethylpyridine and a catalyst, and the water content is about 25%; the extracted extractant phase and the water phase are separated by adopting centrifugation, so that the separation time is short, the separation is thorough, the content of 2-vinyl pyridine in the wastewater is low (0.05 percent, which is far lower than the content of 1.5 to 2 percent in alkali adding layering and heating layering); the step can be carried out in an extraction centrifuge, and the centrifugal speed is generally more than 1500r/m;
s2, rectifying the mixed organic phase obtained in the step S1, and collecting mixed gas containing the extractant and a small amount of water at the top of the tower to obtain 2-vinylpyridine after water separation because the boiling point of the extractant is lower than that of the 2-vinylpyridine; the water content of the 2-vinylpyridine after water division is less than 0.2 percent, and the 2-vinylpyridine can be further sent into a rectifying tower for heavy component removal and purification;
s3, condensing the mixed gas obtained in the step S2 into liquid, and layering to obtain an extractant phase and a water phase, wherein the extractant phase is recycled to the step S1.
The invention firstly adopts extractant to separate 2-vinyl pyridine from water in crude product, removes most of water in crude product, separates extractant phase and water phase rapidly and thoroughly by centrifugation, separates 2-vinyl pyridine from extractant by rectification, and the water content of 2-vinyl pyridine obtained after rectification is about 0.2% or less. In addition, the 2-vp of the two methods in the prior art is azeotroped at the top of the tower during rectification, the water content of the azeotropic component is 75%, the 2-vp content is 25%, the residence time during heating and layering is kept for more than half an hour, the 2-vp of the two methods has long residence time in the system and high temperature and is easy to polymerize, and the 2-vp is hardly contained at the top of the rectification tower through extraction and centrifugation, so that the residence time of the 2-vp in the system is reduced, and the polymerization in the production process is reduced.
Therefore, the invention adopts the extraction centrifugation and extraction rectification combined dehydration method to replace the two methods of alkali precipitation water diversion and temperature rising water diversion in the prior art, thoroughly solves the problems that the 2-vinyl pyridine content in the wastewater is high and difficult to biochemically treat, reduces the residence time of the product in a system, reduces the polymerization in the production process, and greatly reduces the cost. 4-vinylpyridine has similar properties to 2-vinylpyridine and the water splitting process is equally applicable to the above method.
Preferably, the volume ratio of the crude vinylpyridine compound product to the extractant in the step S1 is 1 (0.2-5), and in the dosage range, the 2-vinylpyridine or 4-vinylpyridine can be completely extracted, the dosage of the extractant is reduced as much as possible, and the production cost and the subsequent rectification separation time are saved.
Preferably, in the step S2, the bottom temperature is 95+/-5 ℃ and the pressure is-90+/-5 kpa; the temperature of the tower top is 60+/-5 ℃ and the pressure is 95+/-5 kpa, and under the rectification condition, the extractant can be completely separated from the 2-vinyl pyridine or the 4-vinyl pyridine.
It will be appreciated by those skilled in the art that the method of the present invention for the industrial application of water diversion provided by the present invention can be applied to other water diversion processes similar to vinyl pyridine compounds, in addition to 2-vinyl pyridine and 4-vinyl pyridine, and is not exemplified herein.
The invention also provides a vinyl pyridine compound water diversion industrialization device, which is shown in figure 1 and comprises a crude product conveying pipeline 1, an extraction centrifuge 2, a rectifying tower system 3, a condenser 4 and a layering tank 5; the extraction centrifuge 2 is provided with a crude product inlet 23, an extractant inlet 24, an organic phase outlet 25 and a wastewater outlet 26, the rectifying tower is provided with an inlet 31, an overhead extractant reflux port 32, an extractant extraction outlet 33 and a tower bottom vinyl pyridine compound outlet 34, and the layering tank 5 is provided with an extractant outlet 51 and a wastewater outlet 52;
the crude product inlet 23 of the extraction centrifuge 2 is connected with the crude product conveying pipeline 1, the extractant inlet 24 is connected with the extractant outlet 51 of the layering tank 5, the crude product of the vinylpyridine compound and the extractant are respectively introduced, the organic phase outlet 25 is connected with the inlet 31 of the rectifying tower system 3 and is used for separating and extracting the crude product of the vinylpyridine compound by adopting the extractant, then the crude product is centrifugally separated into a mixed organic phase containing the extractant, the vinylpyridine compound and water and a water phase, the organic phase is discharged and conveyed to the rectifying tower system, the water phase is wastewater containing trace vinylpyridine compound, and the wastewater can be conveyed to the wastewater treatment system 9 for subsequent treatment;
the tower top extractant extraction port 33 of the rectifying tower system 3 is connected with the inlet of the condenser 4 and is used for rectifying and separating the extracted extractant and the mixed solution of the vinyl pyridine compounds, and the rectified extractant gas and water vapor are discharged from the tower top extractant extraction port 33 and conveyed to the condenser 4; the vinyl pyridine compound can be collected at the bottom of the tower and can be sent to a rectifying tower for further heavy component removal, purification and refining; the tower top extractant reflux port 32 of the rectifying tower system 3 is connected with the extractant outlet 51 of the layering tank 5 for introducing extractant for self-reflux;
the condenser 4 is used for condensing extractant gas and water vapor into liquid, the condensed liquid is discharged and conveyed to the layering tank 5, the layering tank 5 is used for layering the condensed liquid into an extractant phase and a water phase, one part of the layered extractant is discharged and conveyed to the rectifying tower system 3 for self-reflux use, the other part of the layered extractant is conveyed to the extraction centrifuge 2 for recycling according to the extraction proportion of the vinylpyridine compounds, and the water phase can be conveyed to the wastewater treatment system 9 for subsequent treatment.
According to the water diversion industrialization device provided by the invention, an extraction centrifuge is adopted to extract and separate 2-vinyl pyridine from water in a vinyl pyridine compound crude product such as a 2-vinyl pyridine crude product, the 2-vinyl pyridine is transferred into an extracting agent, then the extracting agent and the water are rapidly separated by centrifugation through the extraction centrifuge, then the extracting agent and the 2-vinyl pyridine are separated by a rectifying tower, and finally the extracting agent is recycled through a condenser and a layering tank, so that the water diversion problem that the 2-vinyl pyridine content in the wastewater is high, the 2-vinyl pyridine and the water are rectified and azeotroped to and fro in the prior art is solved, the product yield is improved, the polymerization of the product in the production process is reduced, the cost is greatly reduced, and the water diversion industrialization method is completely applicable to the vinyl pyridine compound water diversion industrialization method provided by the invention.
Preferably, to increase extraction efficiency, the extraction centrifuge may employ two or more stages.
Preferably, as shown in fig. 1, the water diversion industrialization device provided by the invention further comprises a vinylpyridine compound crude product storage tank 8, wherein the crude product conveying pipeline 1 is connected with the vinylpyridine compound crude product storage tank 8, and can directly convey the vinylpyridine compound crude product to an extraction centrifuge.
Preferably, as shown in fig. 1, a reflux pump 7 is arranged on a conveying pipeline between the layering tank 5 and the extraction centrifuge 2, so that the conveying control of the extracting agent is facilitated.
Preferably, as shown in fig. 2, the water diversion industrialization device provided by the invention further comprises an extractant storage tank 6, wherein an inlet of the extractant storage tank 6 is connected with an extractant outlet 51 of the layering tank 5, and an outlet of the extractant storage tank 6 is connected with an extractant inlet of the extraction centrifuge. The extractant storage tank 6 is arranged to store the extractant, so that the use is convenient. The outlet of the extractant storage tank 6 can be connected with an extractant reflux port at the top of the rectifying tower system 3, and the rectifying tower reflux extractant is also led from the extractant storage tank, so that the recycling of the extractant is further realized.
According to certain embodiments of the present invention, as shown in fig. 2, the extraction centrifuges are a first extraction centrifuge 21 and a second extraction centrifuge 22, respectively, the first extraction centrifuge is provided with a first raw product inlet 211, a first extractant inlet 212, a first aqueous phase outlet 213, a first organic phase outlet 214, and the second extraction centrifuge 22 is provided with a second aqueous phase inlet 221, a second extractant inlet 222, a wastewater outlet 223, a second organic phase outlet 224; the first crude product inlet 211 of the first extraction centrifuge 21 is connected to the crude product feed line 1, the first extractant inlet 212 is connected to the second organic phase outlet 224 of the second extraction centrifuge 22, the first aqueous phase outlet 213 is connected to the second aqueous phase inlet 221 of the second extraction centrifuge 22, and the first organic phase outlet 214 is connected to the inlet 31 of the rectifying column 3; a second extractant inlet 222 of the second extraction centrifuge 22 is connected with the outlet of the extractant storage tank 6, and the layered extractant is introduced into the layering tank 5; namely, the crude product of the vinyl pyridine compound in the first extraction centrifuge is led from a crude product conveying pipeline, the extractant is led from a second extraction centrifuge, and the water phase after the primary centrifugal separation of the extraction enters the second extraction centrifuge for secondary extraction separation, so that the vinyl pyridine compound in the wastewater, such as 2-vinyl pyridine, is reduced to the minimum, the difficulty of wastewater treatment is reduced, and the yield of the 2-vinyl pyridine is improved.
Example 1
The method for industrialized water diversion of the vinyl pyridine compound provided in the embodiment, wherein the vinyl pyridine compound is 2-vinyl pyridine, adopts a water diversion device shown in fig. 2 to conduct water diversion, and comprises the following steps:
s1, a water separation procedure, namely, carrying out two-stage extraction on a crude product of the 2-vinyl pyridine which is not separated by toluene in an extraction centrifuge, and carrying out centrifugal separation to obtain a mixed organic phase and a water phase which contain the 2-vinyl pyridine, an extractant and a trace amount of water; the dosage volume ratio of the 2-vinyl pyridine crude product to the extractant is 1:0.6, and the centrifugal rotating speed is 1500r/m;
and S2, rectifying the mixed organic phase obtained in the step S1 in a rectifying tower under the following conditions: the temperature of the bottom of the tower is 95 ℃ and the pressure is-90 kpa; the temperature of the tower top is 60 ℃ and the pressure is 95kpa, and because the boiling point of the extractant is lower than that of the 2-vinyl pyridine, the mixed gas containing the extractant and trace water is collected at the tower top, and the 2-vinyl pyridine after water separation is collected at the tower bottom; the 2-vinyl pyridine after water diversion can be further sent into a rectifying tower for heavy component removal and purification;
s3, condensing the mixed gas obtained in the step S2 into liquid through a condenser, layering through a layering tank to obtain an extractant phase and a water phase, wherein a part of the extractant is fed back to a rectifying system, and the other part of the extractant is recycled to the step S1.
Example 2
The method for industrialized water diversion of the vinyl pyridine compound provided in the embodiment, wherein the vinyl pyridine compound is 4-vinyl pyridine, adopts a water diversion device shown in fig. 2 to conduct water diversion, and comprises the following steps:
s1, a water separation procedure, namely, performing two-stage extraction on a 4-vinyl pyridine crude product which is not separated by xylene in an extraction centrifuge, and performing centrifugal separation to obtain a mixed organic phase and a water phase which contain 4-vinyl pyridine, an extractant and a trace amount of water; the dosage volume ratio of the 4-vinyl pyridine crude product to the extractant is 1:2, and the centrifugal rotating speed is 1500r/m;
and S2, rectifying the mixed organic phase obtained in the step S1 in a rectifying tower under the following conditions: the temperature of the bottom of the tower is 95 ℃ and the pressure is-90 kpa; the temperature of the tower top is 60 ℃ and the pressure is 95kpa, and because the boiling point of the extractant is lower than that of the 4-vinyl pyridine, the mixed gas containing the extractant and trace water is collected at the tower top, and the 2-vinyl pyridine after water separation is collected at the tower bottom; the 4-vinyl pyridine after water diversion can be further sent into a rectifying tower for heavy component removal and purification;
s3, condensing the mixed gas obtained in the step S2 into liquid through a condenser, layering through a layering tank to obtain an extractant phase and a water phase, wherein a part of the extractant is fed back to a rectifying system, and the other part of the extractant is recycled to the step S1.
Experimental example
The crude 2-vinylpyridine product (water content 25%) was extracted and centrifuged with toluene and xylene as extractant, the amounts of toluene and xylene were shown in Table 1, and the other steps were compared with those of example 1 by alkali analysis and temperature rising methods of the prior art, and the water content of the organic phase and the 2-vp content of the aqueous phase in the water separation step in the preparation process, the water content of the top component 2-vp of the rectifying step and the water content of the bottom component of the rectifying step and the yield of the product 2-vp were measured, and the results are shown in Table 1.
TABLE 1
As can be seen from Table 1, in the method of the present invention, when toluene and xylene are used as extractants and the addition ratio of (2-vp: A) (v/v) is 1 (0.25-0.75), the content of 2-vp in the wastewater separated after extraction and centrifugation (0-0.36%) is significantly lower than that of the alkaline precipitation method (1.87%) and the heating method (2.12%), the content of 2-vp in the top of the column in the rectification process (0.08-2.15%) is significantly lower than that of the alkaline precipitation method (25% of 2-vp) and the heating method (75% of water), the water content (0.05-0.12%) in the 2-vp product obtained by the bottom collection is also significantly lower than that of the alkaline precipitation method (0.28%) and the heating method (0.38%), and the 2-vp yield (96.50-98.20%) is higher than that of the alkaline precipitation method (93.50%) and the heating method (92.30%). The invention has the advantages of low waste water residue and high 2-vp yield, and can further prove that the product has short system residence time and polymerization is reduced in the production process.
While preferred embodiments of the present invention have been described, additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. It is therefore intended that the following claims be interpreted as including the preferred embodiments and all such alterations and modifications as fall within the scope of the invention. It will be apparent to those skilled in the art that various modifications and variations can be made to the present invention without departing from the spirit or scope of the invention. Thus, it is intended that the present invention also include such modifications and alterations insofar as they come within the scope of the appended claims or the equivalents thereof.
Claims (5)
1. The method for industrialized water diversion of the vinylpyridine compound is characterized by comprising the step of using a water diversion industrialized device, wherein the water diversion industrialized device comprises a crude product conveying pipeline, an extraction centrifuge, a rectifying tower system, a condenser and a layering tank; the extraction centrifuge is provided with a crude product inlet, an extractant inlet, an organic phase outlet and a wastewater outlet, the rectifying tower system is provided with an inlet, an overhead extractant reflux port, an extractant extraction outlet and a tower bottom vinyl pyridine compound outlet, and the layering tank is provided with an extractant outlet and a wastewater outlet;
the extraction centrifuge is characterized in that a crude product inlet is connected with the crude product conveying pipeline, an extractant inlet is connected with an extractant outlet of the layering tank, and an organic phase outlet is connected with an inlet of the rectifying tower system and is used for carrying out water-based extraction on a crude product of the vinylpyridine compound by using an extractant, and the extracted extractant, the vinylpyridine compound and water mixed solution are discharged and conveyed to the rectifying tower system;
the tower top extractant extraction port of the rectifying tower system is connected with the inlet of the condenser and is used for rectifying and separating the extracted extractant and the mixed solution of the vinyl pyridine compounds, and the rectified extractant gas and water vapor are discharged from the tower top extractant extraction port and conveyed to the condenser; the tower top extractant reflux port of the rectifying tower system is connected with the extractant outlet of the layering tank;
the condenser is used for condensing the extractant gas and the water vapor into liquid, and the condensed liquid is discharged and conveyed to the layering tank;
the layering tank is used for layering condensed liquid into an extractant phase and a water phase, and part of the layered extractant is discharged and conveyed to the rectifying tower system for self-reflux use, and the other part of the layered extractant is conveyed to the extraction centrifuge for recycling;
the method comprises the following steps:
s1, extracting a crude product of the non-dehydrated vinylpyridine compound by adopting an extractant, and centrifugally separating to obtain a mixed organic phase and a water phase which contain the vinylpyridine compound, the extractant and a trace amount of water; the extractant is a solvent which is mutually insoluble with water and has a boiling point lower than that of the vinyl pyridine compound; the vinyl pyridine compound is 2-vinyl pyridine; the extractant is toluene or xylene; the dosage volume ratio of the crude vinylpyridine compound product to the extractant is 1 (0.5-0.75);
s2, rectifying the mixed organic phase obtained in the step S1, collecting at the top of a tower to obtain mixed gas containing extractant and trace water, and collecting at the bottom of the tower to obtain a water-separated vinyl pyridine compound; the rectification condition is that the temperature of the tower bottom is 95+/-5 ℃ and the pressure is-90+/-5 kpa; the temperature of the tower top is 60+/-5 ℃ and the pressure is 95+/-5 kpa;
s3, condensing the mixed gas obtained in the step S2 into liquid, and layering to obtain an extractant phase and a water phase, wherein the extractant phase is recycled to the step S1.
2. The method for the water division industrialization of vinylpyridines according to claim 1, characterized in that,
the extraction centrifugal machine is in two stages or multiple stages.
3. The method for the water division industrialization of vinylpyridines according to claim 1, characterized in that,
the device also comprises a vinyl pyridine compound crude product storage tank, and the crude product conveying pipeline is connected with the vinyl pyridine compound crude product storage tank.
4. The method for the water division industrialization of vinylpyridines according to claim 1, characterized in that,
the device also comprises an extractant storage tank, wherein an inlet of the extractant storage tank is connected with an extractant outlet of the layering tank, and an outlet of the extractant storage tank is connected with an extractant inlet of the extraction centrifuge.
5. A method for the water division industrialization of vinylpyridines according to claim 2,
the extraction centrifuges are two stages, namely a first extraction centrifuges and a second extraction centrifuges, wherein the first extraction centrifuges are provided with a first coarse product inlet, a first extractant inlet, a first aqueous phase outlet and a first organic phase outlet, the second extraction centrifuges are provided with a second aqueous phase inlet, a second extractant inlet, a wastewater outlet and a second organic phase outlet, the first coarse product inlet of the first extraction centrifuges is connected with the coarse product conveying pipeline, the first extractant inlet is connected with the second organic phase outlet of the second extraction centrifuges, the first aqueous phase outlet is connected with the second aqueous phase inlet of the second extraction centrifuges, and the first organic phase outlet is connected with the inlet of the rectifying tower; and a second extractant inlet of the second extraction centrifuge is connected with an extractant outlet of the layering tank.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101511788A (en) * | 2006-09-12 | 2009-08-19 | 朱比兰特奥甘诺斯有限公司 | Eco-friendly process for recovery of pyridine and/or its derivatives |
| CN104130182A (en) * | 2014-07-17 | 2014-11-05 | 东南大学 | High-efficiency environment-friendly 2-vinyl pyridine preparation method |
| CN106748978A (en) * | 2016-12-02 | 2017-05-31 | 山东海昆化工技术有限公司 | It is a kind of to extract the method for being coupled with rectifying and realizing the dehydration of 2 picolines |
| CN207294650U (en) * | 2017-09-14 | 2018-05-01 | 山东天说橡胶有限公司 | Dehydration device in 2- vinylpyridine production processes |
| CN110003053A (en) * | 2019-03-26 | 2019-07-12 | 经纬精细化工(南通)有限公司 | A kind of method of purification and device of acetonitrile |
-
2019
- 2019-12-31 CN CN201911405223.5A patent/CN111138347B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101511788A (en) * | 2006-09-12 | 2009-08-19 | 朱比兰特奥甘诺斯有限公司 | Eco-friendly process for recovery of pyridine and/or its derivatives |
| CN104130182A (en) * | 2014-07-17 | 2014-11-05 | 东南大学 | High-efficiency environment-friendly 2-vinyl pyridine preparation method |
| CN106748978A (en) * | 2016-12-02 | 2017-05-31 | 山东海昆化工技术有限公司 | It is a kind of to extract the method for being coupled with rectifying and realizing the dehydration of 2 picolines |
| CN207294650U (en) * | 2017-09-14 | 2018-05-01 | 山东天说橡胶有限公司 | Dehydration device in 2- vinylpyridine production processes |
| CN110003053A (en) * | 2019-03-26 | 2019-07-12 | 经纬精细化工(南通)有限公司 | A kind of method of purification and device of acetonitrile |
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