CN113548967A - Device and method for producing high-purity dimethyl carbonate by heterogeneous catalytic reaction rectification - Google Patents
Device and method for producing high-purity dimethyl carbonate by heterogeneous catalytic reaction rectification Download PDFInfo
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- C07C68/06—Preparation of esters of carbonic or haloformic acids from organic carbonates
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Abstract
The invention belongs to the technical field of chemical industry, and particularly relates to a device and a method for producing high-purity dimethyl carbonate by heterogeneous catalytic reaction rectification. In order to solve the problems of poor product stability, low yield, high energy consumption, low purity and the like in the prior art, ethylene carbonate and methanol respectively pass through an azeotropic distillation tower, an azeotrope cooler, a liquid-liquid separator, a solvent recovery tower, a DMC refining tower, an ethylene glycol light component removal tower and an ethylene glycol refining tower after the heterogeneous catalytic reaction distillation process of the reaction distillation tower to obtain high-purity dimethyl carbonate and ethylene glycol products. The method can effectively improve the yield of the dimethyl carbonate and the ethylene glycol, has good product stability, avoids the problem of catalyst separation in the homogeneous catalytic reaction process, and has low material consumption and energy consumption of the process, and the whole process is economic and environment-friendly.
Description
Technical Field
The invention belongs to the technical field of chemical industry, and particularly relates to a device and a method for producing high-purity dimethyl carbonate by heterogeneous catalytic reaction rectification.
Background
Dimethyl carbonate (DMC) is widely used in the fields of pesticides, medicines, dyes, fine chemicals, electronic industry, etc., and is called "green" chemical product and "new base block" for chemical synthesis. The DMC synthesis method mainly comprises a phosgene method, an ester exchange method, a methanol liquid-phase oxidation carbonylation method, a methanol gas-phase oxidation carbonylation method, a direct synthesis method of methanol and CO2, and a urea and methanol alcoholysis method. The transesterification method is widely applied due to rich raw material sources, mild reaction conditions, easy industrialization and environmental friendliness, and the byproduct glycol of the process is also an important chemical raw material.
The process for producing DMC by ester exchange method is that ethylene oxide and CO are used2Ethylene carbonate generated by cycloaddition is combined by methanol to obtain a crude DMC product, and then industrial grade DMC is obtained through a series of separation measures. The process mainly has two technical problems: 1) the ester exchange reaction is limited by thermodynamics, and the single-pass conversion rate is low; 2) the methanol is in excess in the reaction to ensure conversion of the feedstock, while methanol forms a minimum azeotrope with the DMC, resulting in difficulties in DMC purification. The problem is solved by adopting reaction rectification in industry, but a homogeneous liquid base catalyst (US4181676, EP499924) is generally adopted, so that the problems of difficult subsequent separation and catalyst loss exist, and metal ions inevitably exist in a product, so that the product quality is influenced. In comparison, the heterogeneous catalyst is easy to separate, the product quality is controllable, and the method is favored by researchers. The heterogeneous catalysts developed at present mainly comprise resin catalysts, zeolite catalysts and metal oxide catalysts, but the catalytic activity and stability of the heterogeneous catalysts are different from those of the catalysts developed in the industrialization (for example, JP6336461 adopts Amb-26 at 100 ℃, 5MPa, N2Under the protection, the yield of DMC after 3h of reaction is 78.5%; JP 648993 adopts calcium oxide as catalyst, reacts for 2h at 100 ℃, and DMC yield is 37.8%). CN202010944229.6 discloses a metal oxide type solid base catalyst, the DMC yield can reach 79.2%, but a fixed bed reactor is adopted, and the DMC yield is influenced. Aiming at the problem 2), the separation and purification of the methanol and DMC azeotrope are generally realized by methods of extractive distillation, pressure swing distillation, azeotropic distillation, melt crystallization and the like in industry. The gold powerful bit adopts ethylene glycol as an extractant, and DMC purity is 99.78% by double-tower extraction and rectification (2015, 16(4):39-43) in the fine petrochemical industry), but the extraction and rectification have the problems of high energy consumption and DMC decomposition. CN101381309B purification of DMC by pressure swing distillation coupled with decompression and pressurization, the method has limited DMC purity and high energy consumption. CN111704545B discloses a method for separating DMC-methanol azeotrope by a melt crystallization method, which can obtain electronic grade DMC with the purity of 99.9-99.99%, but the method still has the problem of high energy consumption.
Based on the analysis, the development of a stable, high-yield, environment-friendly and high-purity dimethyl carbonate production method has important value.
Disclosure of Invention
The invention provides a device and a method for producing high-purity dimethyl carbonate and co-producing ethylene glycol by heterogeneous catalytic reaction rectification coupled with azeotropic rectification, aiming at overcoming the defects of the prior art, and solving the problems of poor product stability, low yield, high energy consumption, low purity and the like in the prior art. The DMC disclosed by the invention can achieve the electronic grade standard purity of more than or equal to 99.99 wt% and the ethylene glycol purity of more than or equal to 99.5 wt%.
In order to achieve the purpose, the invention adopts the following technical scheme:
a device for producing high-purity dimethyl carbonate by heterogeneous catalytic reaction rectification comprises a reaction rectification tower, an azeotropic rectification tower, a liquid-liquid separator, a solvent recovery tower, an ethylene glycol lightness-removing tower, an ethylene glycol refining tower, a first cooler, a second cooler, a third cooler, a fourth cooler, a fifth cooler, a sixth cooler, a first azeotrope former, a second azeotrope former, a third azeotrope former, a fourth azeotrope former and a fifth azeotrope former;
the reaction rectifying tower is provided with a vinyl carbonate feeding hole and a methanol feeding hole, and is respectively positioned at the upper part and the lower part of the reaction rectifying tower, the top outlet of the reaction rectifying tower is divided into two paths through a first cooler, one path of the outlet flows back to the top of the reaction rectifying tower, the other path of the outlet is connected with the feeding hole arranged at the lower part of the reaction rectifying tower, the top outlet of the azeotropic rectifying tower is divided into two paths through a second cooler, one path of the outlet flows back to the top of the azeotropic rectifying tower, the other path of the outlet is connected with the feeding hole of a liquid-liquid separator through a third cooler, the alcohol phase discharging hole of the liquid-liquid separator is connected with the alcohol phase feeding hole of a solvent recovery tower, the outlet of the solvent recovery tower is divided into two paths, one path of the outlet flows back to the tower kettle of the solvent recovery tower through the third azeotropic device, the other path of the outlet is connected with the methanol feeding hole, the top outlet of the solvent recovery tower is divided into two paths through a fourth cooler, and flows back to the top of the solvent recovery tower, the other path of the mixed gas enters a total boiling agent feeding hole arranged at the upper part of an azeotropic distillation tower after being converged with an oil phase outlet of a liquid-liquid separator and a fresh entrainer, the outlet of a tower kettle of the azeotropic distillation tower is divided into two paths, one path of the mixed gas flows back to the tower kettle of the azeotropic distillation tower through a second azeotrope device, the other path of the mixed gas is extracted from a DMC product with industrial grade purity, the outlet of the tower kettle of the reactive distillation tower is divided into two paths, the other path of the mixed gas flows back to the tower kettle of the reactive distillation tower through a first azeotrope device, the other path of the mixed gas is connected with a feeding hole of an ethylene glycol lightness-removing tower, the outlet of the tower top of the ethylene glycol lightness-removing tower is divided into two paths through a fifth azeotrope device, the one path of the mixed gas flows back to the tower kettle of the ethylene glycol lightness-removing tower, the other path of the mixed gas is connected with the feeding hole of the ethylene glycol refining tower, the outlet of the tower top of the ethylene glycol refining tower is divided into two paths through a sixth cooler, one path of the heavy component reflux liquid flows to the top of the ethylene glycol refining tower, the other path of the ethylene glycol product is extracted, the outlet of the tower kettle of the ethylene glycol refining tower is divided into two paths, one path of the heavy component reflux liquid flows to the tower kettle of the ethylene glycol refining tower through a fifth azeotropic device, and the other path of the heavy component product is extracted. The technical scheme adopts a method combining heterogeneous catalytic reaction rectification and azeotropic rectification, solves the problems of difficult separation and recovery of the catalyst in the conventional homogeneous catalytic reaction rectification and high energy consumption in the pressure swing rectification and extractive rectification methods, and can obtain high-purity dimethyl carbonate and ethylene glycol products with high efficiency, environmental protection and low cost.
The device further comprises a DMC refining tower, a seventh cooler and a sixth azeotrope vessel, the DMC product with industrial-grade purity enters the DMC refining tower, the top of the DMC refining tower is divided into two paths by the seventh cooler, one path of DMC product reflows to the top of the DMC refining tower, the other path of DMC product is extracted by the component product, the outlet of the tower kettle of the DMC refining tower is divided into two paths, one path of DMC product reflows to the tower kettle of the DMC refining tower by the sixth azeotrope vessel, and the other path of DMC product is extracted by the electronic-grade DMC product. The technical scheme utilizes the characteristic that methanol and DMC form the lowest azeotrope, obtains the electronic grade DMC product with higher added value by losing a small amount of industrial grade DMC product, and has high economical efficiency.
The method for producing high-purity dimethyl carbonate by utilizing the device for heterogeneous catalytic reaction rectification comprises the following steps:
step 1, vinyl carbonate and methanol enter a reaction rectifying tower from a vinyl carbonate feeding hole and a methanol feeding hole of the reaction rectifying tower respectively, an azeotropic mixture of methanol and DMC obtained at the top of the reaction rectifying tower enters the lower part of an azeotropic rectifying tower, the top material flow of the azeotropic rectifying tower contains methanol, an entrainer and a small amount of DMC, part of the methanol flows back to the azeotropic rectifying tower, the rest of the mixture is cooled by a third cooler and then enters a liquid-liquid separator, the liquid-liquid separator clearly divides the mixture into an oil phase and an alcohol phase, the oil phase serves as a circulating solvent, the alcohol phase enters a solvent recovery tower, the top of the solvent recovery tower serves as the entrainer and the methanol mixture, the oil phase of the liquid-liquid separator and the top product of the solvent recovery tower supplement fresh entrainer and serve as the total entrainer to enter the upper part of the azeotropic rectifying tower, and the bottom of the solvent recovery tower serves as high-purity methanol to circulate to the lower part of the reaction rectifying tower;
and 3, obtaining the DMC product with industrial-grade purity at the tower kettle of the azeotropic distillation tower.
Further, the method comprises the following steps: and the DMC product with industrial-grade purity obtained at the tower bottom of the azeotropic distillation tower enters a DMC refining tower, a component product is obtained at the tower top of the DMC refining tower, and an electronic-grade DMC product is obtained at the tower bottom of the DMC refining tower.
Further, the molar ratio of the vinyl carbonate to the methanol in the step 1 is 5-20.
Further, the total theoretical plate number of the reactive distillation column is 60-100, wherein the theoretical plate number of a stripping section of the reactive distillation column is 20-30, the theoretical plate number of a rectifying section of the reactive distillation column is 20-30, the height ratio of the reactive section of the reactive distillation column is 0.1-0.5, a heterogeneous solid catalyst is filled in the reactive section of the reactive distillation column, the top operating pressure of the reactive distillation column is 1bar, the top operating temperature of the reactive distillation column is 62.5-64 ℃, the bottom operating temperature of the reactive distillation column is 65-95 ℃, and the reflux ratio of the reactive distillation column is 1-5;
the total theoretical plate number of the azeotropic distillation tower is 40-70, the operation pressure at the top of the azeotropic distillation tower is 1bar, the operation temperature at the top of the azeotropic distillation tower is 48-51 ℃, the operation temperature at the bottom of the azeotropic distillation tower is 88-91 ℃, and the reflux ratio of the azeotropic distillation tower is 0.1-2;
the total theoretical plate number of the solvent recovery tower is 20-40, the operation pressure of the top of the solvent recovery tower is 1bar, the operation temperature of the top of the solvent recovery tower is 48-52 ℃, the operation temperature of the bottom of the solvent recovery tower is 64-65 ℃, and the reflux ratio of the solvent recovery tower is 0.5-5.
The total theoretical plate number of the ethylene glycol lightness-removing tower is 20-40, the operation pressure at the top of the ethylene glycol lightness-removing tower is 1bar, the operation temperature at the top of the ethylene glycol lightness-removing tower is 60-80 ℃, the operation temperature at the bottom of the ethylene glycol lightness-removing tower is 150-200 ℃, and the reflux ratio of the ethylene glycol lightness-removing tower is 0.5-5;
the total theoretical plate number of the ethylene glycol refining tower is 20-40, the operation pressure at the top of the ethylene glycol refining tower is 0.1bar, the operation temperature at the top of the ethylene glycol refining tower is 130-135 ℃, the operation temperature at the bottom of the ethylene glycol refining tower is 150-200 ℃, and the reflux ratio of the ethylene glycol refining tower is 0.5-5.
Further, the height ratio of the reaction section of the reaction rectifying tower is 0.2-0.3, the heterogeneous solid catalyst is made into a cylinder or a cloverleaf shape by sheet beating or strip extruding, the height-diameter ratio of the heterogeneous solid catalyst is 0.1-5, and the hydraulic diameter is 1-5 mm.
Further, the operating pressure of the third cooler is 1bar, and the operating temperature is 25-30 ℃.
Further, the total theoretical plate number of the DMC refining tower is 20-30, the operation pressure of the top of the DMC refining tower is 1bar, the operation temperature of the top of the DMC refining tower is 75-85 ℃, the operation temperature of the bottom of the DMC refining tower is 90-91 ℃, and the reflux ratio of the DMC refining tower is 0.5-5.
Further, the ratio of the total mass flow of the total boiling agent in the upper part of the azeotropic distillation tower to the mass flow of the azeotropic mixture of methanol and DMC in the lower part is 2-4, and the azeotropic agent in the azeotropic distillation tower is normal alkane which forms an azeotrope with the methanol. Preferably, the entrainer is n-hexane.
Compared with the prior art, the invention has the following advantages:
1. by adopting a heterogeneous catalytic reaction rectification technology, the yield of dimethyl carbonate and ethylene glycol is effectively improved, the product stability is good, and the problem of catalyst separation in the homogeneous catalytic reaction process is avoided.
2. The n-hexane is used as an entrainer, and a solvent recovery system is adopted to obtain high-purity DMC and glycol products, so that the process material consumption and the energy consumption are low, and the whole process is economic and environment-friendly.
3. The conversion rate of the ethylene carbonate of the reactive distillation tower is 95-99.9%, the DMC selectivity is 90-99%, and the ethylene glycol selectivity is 90-99%.
Drawings
FIG. 1 is a schematic diagram of an apparatus for producing high-purity dimethyl carbonate and co-producing ethylene glycol by rectification according to the present invention;
wherein, the reaction rectifying tower-1, the azeotropic rectifying tower-2, the liquid-liquid separator-3, the solvent recovery tower-4, the ethylene glycol lightness-removing tower-5, the ethylene glycol refining tower-6, the first cooler-7, the second cooler-8, the third cooler-9, the fourth cooler-10, the fifth cooler-11, the sixth cooler-12, the first azeotrope-13, the second azeotrope-14, the third azeotrope-15, the fourth azeotrope-16, the fifth azeotrope-17, the seventh cooler-18, the sixth azeotrope-19 and the DMC refining tower-20.
Detailed Description
Example 1
As shown in fig. 1, the apparatus for producing high-purity dimethyl carbonate (industrial grade) and co-producing ethylene glycol by heterogeneous catalytic reaction rectification comprises a reaction rectification tower 1, an azeotropic rectification tower 2, a liquid-liquid separator 3, a solvent recovery tower 4, an ethylene glycol lightness-removing tower 5, an ethylene glycol refining tower 6, a first cooler 7, a second cooler 8, a third cooler 9, a fourth cooler 10, a fifth cooler 11, a sixth cooler 12, a first reboiler 13, a second reboiler 14, a third reboiler 15, a fourth reboiler 16 and a fifth reboiler 17;
the reaction rectifying tower 1 is provided with a ethylene carbonate feeding port and a methanol feeding port, and is respectively positioned at the upper part and the lower part of the reaction rectifying tower 1, the outlet at the top of the reaction rectifying tower 1 is divided into two paths through a first cooler 7, one path of the outlet flows back to the top of the reaction rectifying tower 1, the other path of the outlet is connected with the feeding port arranged at the lower part of an azeotropic rectifying tower 2, the outlet at the top of the azeotropic rectifying tower 2 is divided into two paths through a second cooler 8, one path of the outlet flows back to the top of the azeotropic rectifying tower 2, the other path of the outlet is connected with the feeding port of a liquid-liquid separator 3 through a third cooler 9, the alcohol phase discharging port of the liquid-liquid separator 3 is connected with the alcohol phase feeding port of a solvent recovery tower 4, the outlet at the tower bottom of the solvent recovery tower 4 is divided into two paths, one path of the outlet at the tower bottom of the solvent recovery tower 4 flows back to the tower bottom of the solvent recovery tower 4 through a third reboiler 15, the other path of the outlet at the tower bottom of the methanol feeding port is connected with the methanol feeding port, the outlet at the tower bottom of the solvent recovery tower 4 is divided into two paths through a fourth cooler 10, one path of the DMC reflux to the top of a solvent recovery tower 4, the other path of the DMC reflux to a total boiling agent feeding hole arranged at the upper part of an azeotropic rectification tower 2 after being converged with an oil phase outlet of a liquid-liquid separator 3 and a fresh entrainer, the outlet of a tower kettle of the azeotropic rectification tower 2 is divided into two paths, the other path of the DMC reflux to a tower kettle of the azeotropic rectification tower 2 is divided into two paths through a second entrainer 14, the other path of DMC product with industrial grade purity is extracted, the outlet of a tower kettle of a reaction rectification tower 1 is divided into two paths, the other path of the reflux to a tower kettle of the reaction rectification tower 1 is connected with a feeding hole of an ethylene glycol lightness-removing tower 5, the outlet of the tower top of the ethylene glycol lightness-removing tower 5 is divided into two paths through a fifth cooler 11, the other path of the reflux to the tower top of an ethylene glycol lightness-removing tower 5, the other path of the light component product is extracted, the outlet of the tower kettle of the tower bottom of the ethylene glycol lightness-removing tower 5 is divided into two paths through a fourth entrainer 16, the other path of the reflux to the kettle of the ethylene glycol lightness-removing tower 5, the other path is connected with a feed inlet of the ethylene glycol refining tower 6, an outlet at the top of the ethylene glycol refining tower 6 is divided into two paths through a sixth cooler 12, one path of the two paths of the heavy component products are extracted.
A method for producing high-purity dimethyl carbonate and co-producing ethylene glycol by using the device comprises the following steps:
step 1, ethylene carbonate and methanol enter a reaction rectifying tower 1 from an ethylene carbonate feeding hole and a methanol feeding hole of the reaction rectifying tower 1 respectively, an azeotropic mixture of methanol and DMC obtained from the top of the reaction rectifying tower 1 enters the lower part of an azeotropic rectifying tower 2, a material flow at the top of the azeotropic rectifying tower 2 contains methanol, an azeotropic agent and a small amount of DMC, part of the material flow flows back to the azeotropic rectifying tower 2, cooling the rest mixture by a third cooler 9, then feeding the cooled mixture into a liquid-liquid separator 3, clearly dividing the mixture into an oil phase and an alcohol phase by the liquid-liquid separator 3, taking the oil phase as a circulating solvent, feeding the alcohol phase into a solvent recovery tower 4, taking an entrainer and methanol mixture at the top of the solvent recovery tower 4, integrating the oil phase of the liquid-liquid separator 3 and a product at the top of the solvent recovery tower 4, supplementing a fresh entrainer as a total entrainer, feeding the mixture into the upper part of an azeotropic distillation tower 2, and circulating the methanol at the bottom of the solvent recovery tower 4 to the lower part of a reactive distillation tower 1;
and 3, obtaining the DMC product with industrial-grade purity by using the tower kettle of the azeotropic distillation tower 2.
Example 2
A device for producing high-purity dimethyl carbonate (electronic grade) and co-producing ethylene glycol by heterogeneous catalytic reaction rectification comprises a reaction rectifying tower 1, an azeotropic rectifying tower 2, a liquid-liquid separator 3, a solvent recovery tower 4, an ethylene glycol lightness-removing tower 5, an ethylene glycol refining tower 6, a first cooler 7, a second cooler 8, a third cooler 9, a fourth cooler 10, a fifth cooler 11, a sixth cooler 12, a first reboiler 13, a second reboiler 14, a third reboiler 15, a fourth reboiler 16, a fifth reboiler 17, a DMC refining tower 20, a seventh cooler 18 and a sixth reboiler 19;
the reaction rectifying tower 1 is provided with a ethylene carbonate feeding port and a methanol feeding port, and is respectively positioned at the upper part and the lower part of the reaction rectifying tower 1, the outlet at the top of the reaction rectifying tower 1 is divided into two paths through a first cooler 7, one path of the outlet flows back to the top of the reaction rectifying tower 1, the other path of the outlet is connected with the feeding port arranged at the lower part of an azeotropic rectifying tower 2, the outlet at the top of the azeotropic rectifying tower 2 is divided into two paths through a second cooler 8, one path of the outlet flows back to the top of the azeotropic rectifying tower 2, the other path of the outlet is connected with the feeding port of a liquid-liquid separator 3 through a third cooler 9, the alcohol phase discharging port of the liquid-liquid separator 3 is connected with the alcohol phase feeding port of a solvent recovery tower 4, the outlet at the tower bottom of the solvent recovery tower 4 is divided into two paths, one path of the outlet at the tower bottom of the solvent recovery tower 4 flows back to the tower bottom of the solvent recovery tower 4 through a third reboiler 15, the other path of the outlet at the tower bottom of the methanol feeding port is connected with the methanol feeding port, the outlet at the tower bottom of the solvent recovery tower 4 is divided into two paths through a fourth cooler 10, one path of the DMC reflux to the top of a solvent recovery tower 4, the other path of the DMC reflux to a total boiling agent feeding hole arranged at the upper part of an azeotropic rectification tower 2 after being converged with an oil phase outlet of a liquid-liquid separator 3 and a fresh entrainer, the outlet of a tower kettle of the azeotropic rectification tower 2 is divided into two paths, the other path of the DMC reflux to a tower kettle of the azeotropic rectification tower 2 is divided into two paths through a second entrainer 14, the other path of DMC product with industrial grade purity is extracted, the outlet of a tower kettle of a reaction rectification tower 1 is divided into two paths, the other path of the reflux to a tower kettle of the reaction rectification tower 1 is connected with a feeding hole of an ethylene glycol lightness-removing tower 5, the outlet of the tower top of the ethylene glycol lightness-removing tower 5 is divided into two paths through a fifth cooler 11, the other path of the reflux to the tower top of an ethylene glycol lightness-removing tower 5, the other path of the light component product is extracted, the outlet of the tower kettle of the tower bottom of the ethylene glycol lightness-removing tower 5 is divided into two paths through a fourth entrainer 16, the other path of the reflux to the kettle of the ethylene glycol lightness-removing tower 5, the other path is connected with a feed inlet of the ethylene glycol refining tower 6, an outlet at the top of the ethylene glycol refining tower 6 is divided into two paths through a sixth cooler 12, one path of the two paths of the heavy component products are extracted. The DMC product with the industrial grade purity enters a DMC refining tower 20, the top of the DMC refining tower 20 is divided into two paths through a seventh cooler 18, one path of DMC product flows back to the top of the DMC refining tower 20, the other path of DMC product is extracted through component products, the outlet of the tower kettle of the DMC refining tower 20 is divided into two paths, one path of DMC product flows back to the tower kettle of the DMC refining tower 20 through a sixth azeotrope 19, and the other path of DMC product is extracted through an electronic grade DMC product.
A method for producing high-purity dimethyl carbonate and co-producing ethylene glycol by using the device comprises the following steps:
step 1, ethylene carbonate and methanol enter a reaction rectifying tower 1 from an ethylene carbonate feeding hole and a methanol feeding hole of the reaction rectifying tower 1 respectively, an azeotropic mixture of methanol and DMC obtained from the top of the reaction rectifying tower 1 enters the lower part of an azeotropic rectifying tower 2, a material flow at the top of the azeotropic rectifying tower 2 contains methanol, an azeotropic agent and a small amount of DMC, part of the material flow flows back to the azeotropic rectifying tower 2, cooling the rest mixture by a third cooler 9, then feeding the cooled mixture into a liquid-liquid separator 3, clearly dividing the mixture into an oil phase and an alcohol phase by the liquid-liquid separator 3, taking the oil phase as a circulating solvent, feeding the alcohol phase into a solvent recovery tower 4, taking an entrainer and methanol mixture at the top of the solvent recovery tower 4, integrating the oil phase of the liquid-liquid separator 3 and a product at the top of the solvent recovery tower 4, supplementing a fresh entrainer as a total entrainer, feeding the mixture into the upper part of an azeotropic distillation tower 2, and circulating the methanol at the bottom of the solvent recovery tower 4 to the lower part of a reactive distillation tower 1;
and 4, feeding the industrial grade DMC product obtained from the tower bottom of the azeotropic distillation tower 2 into a DMC refining tower 20, obtaining a component product from the tower top of the DMC refining tower 20, and obtaining an electronic grade DMC product from the tower bottom of the DMC refining tower 20.
Example 3
By using the apparatus and process as in example 1, the ethylene carbonate feed rate was 371kg/h, fresh methanol 441kg/h, fresh n-hexane 3kg/h, the n-hexane amount was 2700kg/h at the time of start-up, the ratio of the total mass flow rate of the boiling agent in the upper part of the azeotropic distillation column to the mass flow rate of the azeotropic mixture of methanol and DMC in the lower part was 2.38, the heterogeneous solid catalyst loading was 20 vol%, the catalyst was formed into a cylindrical body by flaking, the aspect ratio was 0.1, and the hydraulic diameter was 2 mm.
The total theoretical plate number of the reaction rectifying tower is 80, wherein the theoretical plate number of the stripping section is 25, and the theoretical plate number of the rectifying section is 25. The operation pressure at the top of the tower is 1bar, the operation temperature at the top of the tower is 63.5 ℃, the operation temperature at the bottom of the tower is 70 ℃, and the reflux ratio is 5.
The total theoretical plate number of the azeotropic distillation tower is 60, the operation pressure at the top of the tower is 1bar, the operation temperature at the top of the tower is 50.5 ℃, the operation temperature at the bottom of the tower is 88.5 ℃, and the reflux ratio is 0.5.
The third cooler was operated at 1bar and 25 ℃ at an operating pressure.
The total theoretical plate number of the solvent recovery tower is 30, the operation pressure at the top of the tower is 1bar, the operation temperature at the top of the tower is 50.5 ℃, the operation temperature at the bottom of the tower is 64.5 ℃, and the reflux ratio is 2.
The total theoretical plate number of the ethylene glycol lightness-removing tower is 40, the operation pressure at the top of the tower is 1bar, the operation temperature at the top of the tower is 70 ℃, the operation temperature at the bottom of the tower is 175 ℃, and the reflux ratio is 5.
The total theoretical plate number of the ethylene glycol refining tower is 40, the operation pressure at the top of the tower is 0.1bar, the operation temperature at the top of the tower is 134 ℃, the operation temperature at the bottom of the tower is 170 ℃, and the reflux ratio is 3.
By the technical scheme, the conversion rate of the ethylene carbonate in the reactive distillation tower is 99.8%, the DMC selectivity is 97.5%, the ethylene glycol selectivity is 98.8%, the yield of 99.5 wt% of the obtained industrial grade DMC product is 367kg/h, and the yield of 99.5 wt% of the high-purity ethylene glycol product is 258 kg/h.
Example 4
By using the apparatus and method as in example 2, the ethylene carbonate feed rate was 371kg/h, fresh methanol 441kg/h, fresh n-hexane 3kg/h, n-hexane usage was 2700kg/h at start-up, the ratio of the total boiling agent mass flow rate at the upper part of the azeotropic distillation column to the mass flow rate of the azeotropic mixture of methanol and DMC at the lower part was 2.38, the heterogeneous solid catalyst loading was 20 vol%, the mixture was formed into clover type by extrusion, the aspect ratio was 5, and the hydrodynamic diameter was 1 mm.
The total theoretical plate number of the reaction rectifying tower is 80, wherein the theoretical plate number of the stripping section is 25, and the theoretical plate number of the rectifying section is 25. The operation pressure at the top of the tower is 1bar, the operation temperature at the top of the tower is 63.8 ℃, the operation temperature at the bottom of the tower is 70 ℃, and the reflux ratio is 5.
The total theoretical plate number of the azeotropic distillation tower is 60, the operation pressure at the top of the tower is 1bar, the operation temperature at the top of the tower is 50.5 ℃, the operation temperature at the bottom of the tower is 88.5 ℃, and the reflux ratio is 0.5.
The operating pressure of the azeotrope cooler was 1bar and the operating temperature was 25 ℃.
The total theoretical plate number of the solvent recovery tower is 30, the operation pressure at the top of the tower is 1bar, the operation temperature at the top of the tower is 50.5 ℃, the operation temperature at the bottom of the tower is 64.5 ℃, and the reflux ratio is 2.
The total theoretical plate number of the DMC refining tower is 30, the operation pressure at the top of the tower is 1bar, the operation temperature at the top of the tower is 80 ℃, the operation temperature at the bottom of the tower is 90.5 ℃, and the reflux ratio is 2.
The total theoretical plate number of the ethylene glycol lightness-removing tower is 40, the operation pressure at the top of the tower is 1bar, the operation temperature at the top of the tower is 70 ℃, the operation temperature at the bottom of the tower is 175 ℃, and the reflux ratio is 5.
The total theoretical plate number of the ethylene glycol refining tower is 40, the operation pressure at the top of the tower is 0.1bar, the operation temperature at the top of the tower is 134 ℃, the operation temperature at the bottom of the tower is 170 ℃, and the reflux ratio is 3.
By the technical scheme, the conversion rate of the ethylene carbonate in the reactive distillation tower is 99.5%, the DMC selectivity is 97.8%, the ethylene glycol selectivity is 98.5%, the yield of the obtained electronic grade DMC product is 99.99 wt% and is 335kg/h, and the yield of the high-purity ethylene glycol product is 99.5 wt% and is 262 kg/h.
Example 5
By using the apparatus and method as in example 2, the ethylene carbonate feed rate was 371kg/h, fresh methanol 441kg/h, fresh n-hexane 3kg/h, n-hexane usage was 2700kg/h at start-up, the ratio of the total boiling agent mass flow rate at the upper part of the azeotropic distillation column to the mass flow rate of the azeotropic mixture of methanol and DMC at the lower part was 2.38, the heterogeneous solid catalyst loading was 20 vol%, the mixture was sheeted or extruded into clover type, the aspect ratio was 2, and the hydraulic diameter was 3 mm.
The total theoretical plate number of the reaction rectifying tower is 60, wherein the theoretical plate number of the stripping section is 20, and the theoretical plate number of the rectifying section is 20. The operation pressure at the top of the tower is 1bar, the operation temperature at the top of the tower is 62.5 ℃, the operation temperature at the bottom of the tower is 65 ℃, and the reflux ratio is 1.
The total theoretical plate number of the azeotropic distillation tower is 40, the operation pressure at the top of the tower is 1bar, the operation temperature at the top of the tower is 49 ℃, the operation temperature at the bottom of the tower is 88 ℃, and the reflux ratio is 0.1.
The operating pressure of the azeotrope cooler was 1bar and the operating temperature was 28 ℃.
The total theoretical plate number of the solvent recovery tower is 20, the operation pressure at the top of the tower is 1bar, the operation temperature at the top of the tower is 48 ℃, the operation temperature at the bottom of the tower is 64 ℃, and the reflux ratio is 0.5.
The total theoretical plate number of the DMC refining tower is 20, the operation pressure at the top of the tower is 1bar, the operation temperature at the top of the tower is 75 ℃, the operation temperature at the bottom of the tower is 90 ℃, and the reflux ratio is 0.5.
The total theoretical plate number of the ethylene glycol lightness-removing tower is 20, the operation pressure at the top of the tower is 1bar, the operation temperature at the top of the tower is 60 ℃, the operation temperature at the bottom of the tower is 150 ℃, and the reflux ratio is 0.5.
The total theoretical plate number of the ethylene glycol refining tower is 20, the operation pressure at the top of the tower is 0.1bar, the operation temperature at the top of the tower is 130 ℃, the operation temperature at the bottom of the tower is 150 ℃, and the reflux ratio is 3.
By the technical scheme, the conversion rate of the ethylene carbonate in the reactive distillation tower is 95.5%, the DMC selectivity is 93%, the ethylene glycol selectivity is 95.5%, the 99.5 wt% yield of the industrial grade DMC product is 321kg/h, and the 99.5 wt% yield of the high-purity ethylene glycol product is 245 kg/h.
Example 6
By using the apparatus and method as in example 2, the ethylene carbonate feed rate was 371kg/h, fresh methanol 441kg/h, fresh n-hexane 3kg/h, n-hexane usage was 2700kg/h at start-up, the ratio of the total boiling agent mass flow rate at the upper part of the azeotropic distillation column to the mass flow rate of the azeotropic mixture of methanol and DMC at the lower part was 2.38, the heterogeneous solid catalyst loading was 20 vol%, the mixture was sheeted or extruded into clover type, the aspect ratio was 2, and the hydraulic diameter was 3 mm.
The total theoretical plate number of the reaction rectifying tower is 100, wherein the theoretical plate number of the stripping section is 30, and the theoretical plate number of the rectifying section is 30. The operation pressure at the top of the tower is 1bar, the operation temperature at the top of the tower is 64 ℃, the operation temperature at the bottom of the tower is 95 ℃, and the reflux ratio is 3.
The total theoretical plate number of the azeotropic distillation tower is 70, the operation pressure at the top of the tower is 1bar, the operation temperature at the top of the tower is 51 ℃, the operation temperature at the bottom of the tower is 91 ℃, and the reflux ratio is 2.
The operating pressure of the azeotrope cooler was 1bar and the operating temperature was 30 ℃.
The total theoretical plate number of the solvent recovery tower is 20, the operation pressure at the top of the tower is 1bar, the operation temperature at the top of the tower is 52 ℃, the operation temperature at the bottom of the tower is 65 ℃, and the reflux ratio is 5.
The total theoretical plate number of the DMC refining tower is 25, the operation pressure at the top of the tower is 1bar, the operation temperature at the top of the tower is 85 ℃, the operation temperature at the bottom of the tower is 91 ℃, and the reflux ratio is 5.
The total theoretical plate number of the ethylene glycol lightness-removing tower is 30, the operation pressure at the top of the tower is 1bar, the operation temperature at the top of the tower is 80 ℃, the operation temperature at the bottom of the tower is 200 ℃, and the reflux ratio is 2.
The total theoretical plate number of the ethylene glycol refining tower is 30, the operation pressure at the top of the tower is 0.1bar, the operation temperature at the top of the tower is 135 ℃, the operation temperature at the bottom of the tower is 1200 ℃, and the reflux ratio is 3.
By the technical scheme, the conversion rate of the ethylene carbonate in the reactive distillation tower is 99.9 percent, the DMC selectivity is 98.2 percent, the ethylene glycol selectivity is 98.9 percent, 99.5 weight percent yield of the obtained industrial grade DMC product is 375kg/h, and 99.5 weight percent yield of the high-purity ethylene glycol product is 268 kg/h.
Claims (10)
1. A device for producing high-purity dimethyl carbonate by heterogeneous catalytic reaction rectification is characterized by comprising a reaction rectifying tower (1), an azeotropic rectifying tower (2), a liquid-liquid separator (3), a solvent recovery tower (4), an ethylene glycol lightness-removing tower (5), an ethylene glycol refining tower (6), a first cooler (7), a second cooler (8), a third cooler (9), a fourth cooler (10), a fifth cooler (11), a sixth cooler (12), a first azeotrope (13), a second azeotrope (14), a third azeotrope (15), a fourth azeotrope (16) and a fifth azeotrope (17);
the reaction rectifying tower (1) is provided with a ethylene carbonate feeding hole and a methanol feeding hole, and is respectively positioned at the upper part and the lower part of the reaction rectifying tower (1), the outlet at the top of the reaction rectifying tower (1) is divided into two paths through a first cooler (7), one path of the outlet flows back to the top of the reaction rectifying tower (1), the other path of the outlet is connected with the feeding hole arranged at the lower part of an azeotropic rectifying tower (2), the outlet at the top of the azeotropic rectifying tower (2) is divided into two paths through a second cooler (8), the other path of the outlet flows back to the top of the azeotropic rectifying tower (2), the other path of the outlet is connected with the feeding hole of a liquid-liquid separator (3) through a third cooler (9), the alcohol phase discharging hole of the liquid-liquid separator (3) is connected with the alcohol phase feeding hole of a solvent recovery tower (4), the outlet at the bottom of the solvent recovery tower (4) is divided into two paths, and the other path of the outlet flows back to the bottom of the solvent recovery tower (4) through a third cooler (15), the other path is connected with a methanol feed inlet, the outlet at the top of the solvent recovery tower (4) is divided into two paths through a fourth cooler (10), one path reflows to the top of the solvent recovery tower (4), the other path reflows to the bottom of the azeotropic distillation tower (2) through a second entrainer (14) after converging with an oil phase outlet of a liquid-liquid separator (3) and a fresh entrainer and then enters a total entrainer feed inlet arranged at the upper part of the azeotropic distillation tower (2), the outlet at the bottom of the azeotropic distillation tower (2) is divided into two paths, the other path reflows to the bottom of the azeotropic distillation tower (2) through a second entrainer (14), the DMC product with industrial grade purity is extracted, the outlet at the bottom of the reactive distillation tower (1) is divided into two paths, the other path reflows to the bottom of the reactive distillation tower (1) through a first entrainer (13), the other path is connected with the feed inlet of an ethylene glycol light-removing tower (5), the outlet at the top of the ethylene glycol light-removing tower (5) is divided into two paths through a fifth cooler (11), and the other path reflows to the top of the ethylene glycol light-removing tower (5), another way light component product is extracted, the export of ethylene glycol lightness-removing tower (5) tower cauldron is divided into two ways through fourth azeotrope ware (16), flows back to ethylene glycol lightness-removing tower (5) tower cauldron all the way, and another way is connected with the feed inlet of ethylene glycol refining tower (6), the export of ethylene glycol refining tower (6) tower top is divided into two ways through sixth cooler (12), flows back to ethylene glycol refining tower (6) top all the way, and another way ethylene glycol product is extracted, the export of ethylene glycol refining tower (6) tower cauldron is divided into two ways, flows back to ethylene glycol refining tower (6) tower cauldron through fifth azeotrope ware (17) all the way, and another way heavy component product is extracted.
2. The device for producing the high-purity dimethyl carbonate by the heterogeneous catalytic reaction rectification is characterized by further comprising a DMC refining tower (20), a seventh cooler (18) and a sixth azeotrope device (19), wherein the DMC product with the industrial-grade purity enters the DMC refining tower (20), the top of the DMC refining tower (20) is divided into two paths by the seventh cooler (18), one path of DMC product flows back to the top of the DMC refining tower (20), the other path of DMC product is extracted by the component product, the outlet of the tower kettle of the DMC refining tower (20) is divided into two paths, one path of DMC product flows back to the tower kettle of the DMC refining tower (20) by the sixth azeotrope device (19), and the other path of DMC product is extracted by the electronic-grade DMC product.
3. A method for producing high-purity dimethyl carbonate by heterogeneous catalytic reaction rectification by using the device of claim 2, which is characterized by comprising the following steps:
step 1, vinyl carbonate and methanol enter a reaction rectifying tower (1) from a vinyl carbonate feed inlet and a methanol feed inlet of the reaction rectifying tower (1), azeotropic mixture of methanol and DMC obtained from the top of the reaction rectifying tower (1) enters the lower part of an azeotropic rectifying tower (2), the top material flow of the azeotropic rectifying tower (2) contains methanol, entrainer and a small amount of DMC, part of the methanol, the entrainer and the small amount of DMC flow back to the azeotropic rectifying tower (2), the rest of the mixture is cooled by a third cooler (9) and then enters a liquid-liquid separator (3), the liquid-liquid separator (3) clearly divides the mixture into an oil phase and an alcohol phase, the oil phase is used as a circulating solvent, the alcohol phase enters a solvent recovery tower (4), the top of the solvent recovery tower (4) is the mixture of the entrainer and the methanol, the oil phase of the integration liquid-liquid separator (3) and the top product of the solvent recovery tower (4) supplement fresh entrainer and serve as the total entrainer to enter the upper part of the azeotropic rectifying tower (2), the bottom of the solvent recovery tower (4) is high-purity methanol and is circulated to the lower part of the reaction rectifying tower (1);
step 2, feeding a mixed material flow containing methanol, ethylene glycol monomethyl ether, ethylene glycol, diethylene glycol and triethylene glycol into a reactive distillation tower (1) at the tower bottom, feeding a light component containing methanol and ethylene glycol monomethyl ether at the tower top of the ethylene glycol lightness-removing tower (5), feeding a heavy component containing ethylene glycol, diethylene glycol and triethylene glycol at the tower bottom of the ethylene glycol lightness-removing tower (5), feeding a material flow at the tower bottom of the ethylene glycol lightness-removing tower (5) into an ethylene glycol refining tower (6), obtaining a high-purity ethylene glycol product at the tower top of the ethylene glycol refining tower (6), and feeding a heavy component at the tower bottom of the ethylene glycol refining tower (6);
and 3, obtaining the DMC product with industrial-grade purity by the tower kettle of the azeotropic distillation tower (2).
4. The method for producing high-purity dimethyl carbonate by heterogeneous catalytic reaction rectification as claimed in claim 3, further comprising the steps of:
the DMC product with industrial-grade purity obtained at the tower bottom of the azeotropic distillation tower (2) enters a DMC refining tower (20), a component product is obtained at the tower top of the DMC refining tower (20), and an electronic-grade DMC product is obtained at the tower bottom of the DMC refining tower (20).
5. The method for producing high-purity dimethyl carbonate through heterogeneous catalytic reaction rectification according to claim 3, wherein the molar ratio of the ethylene carbonate to the methanol in the step 1 is 5-20.
6. The method for producing high-purity dimethyl carbonate through heterogeneous catalytic reaction rectification according to claim 3, characterized in that the total theoretical plate number of the reactive rectification tower (1) is 60-100, wherein the theoretical plate number of the stripping section of the reactive rectification tower (1) is 20-30, the theoretical plate number of the rectification section of the reactive rectification tower (1) is 20-30, the height ratio of the reaction section of the reactive rectification tower (1) is 0.1-0.5, heterogeneous solid catalyst is filled in the reaction section of the reactive rectification tower (1), the top operating pressure of the reactive rectification tower (1) is 1bar, the top operating temperature of the reactive rectification tower (1) is 62.5-64 ℃, the bottom operating temperature of the reactive rectification tower (1) is 65-95 ℃, and the reflux ratio of the reactive rectification tower (1) is 1-5;
the total theoretical plate number of the azeotropic distillation tower (2) is 40-70, the operation pressure at the top of the azeotropic distillation tower (2) is 1bar, the operation temperature at the top of the azeotropic distillation tower (2) is 48-51 ℃, the operation temperature at the bottom of the azeotropic distillation tower (2) is 88-91 ℃, and the reflux ratio of the azeotropic distillation tower (2) is 0.1-2;
the total theoretical plate number of the solvent recovery tower (4) is 20-40, the operation pressure of the top of the solvent recovery tower (4) is 1bar, the operation temperature of the top of the solvent recovery tower (4) is 48-52 ℃, the operation temperature of the bottom of the solvent recovery tower (4) is 64-65 ℃, and the reflux ratio of the solvent recovery tower (4) is 0.5-5;
the total theoretical plate number of the ethylene glycol lightness-removing tower (5) is 20-40, the operation pressure at the top of the ethylene glycol lightness-removing tower (5) is 1bar, the operation temperature at the top of the ethylene glycol lightness-removing tower (5) is 60-80 ℃, the operation temperature at the bottom of the ethylene glycol lightness-removing tower (5) is 150-200 ℃, and the reflux ratio of the ethylene glycol lightness-removing tower (5) is 0.5-5;
the total theoretical plate number of the ethylene glycol refining tower (6) is 20-40, the operation pressure at the top of the ethylene glycol refining tower (6) is 0.1bar, the operation temperature at the top of the ethylene glycol refining tower (6) is 130-135 ℃, the operation temperature at the bottom of the ethylene glycol refining tower (6) is 150-200 ℃, and the reflux ratio of the ethylene glycol refining tower (6) is 0.5-5.
7. The method for producing high-purity dimethyl carbonate through heterogeneous catalytic reaction rectification as claimed in claim 6, wherein the height ratio of the reaction section of the reaction rectification tower (1) is 0.2-0.3, the heterogeneous solid catalyst is made into a cylinder or a cloverleaf shape through sheet beating or strip extrusion, the height ratio of the heterogeneous solid catalyst is 0.1-5, and the hydraulic diameter is 1-5 mm.
8. The method for producing high-purity dimethyl carbonate through heterogeneous catalytic reaction rectification according to claim 3, wherein the operating pressure of the third cooler (9) is 1bar, and the operating temperature is 25-30 ℃.
9. The method for producing the high-purity dimethyl carbonate through the heterogeneous catalytic reaction rectification as claimed in claim 4, wherein the total theoretical plate number of the DMC refining tower (20) is 20-30, the operation pressure at the top of the DMC refining tower (20) is 1bar, the operation temperature at the top of the DMC refining tower (20) is 75-85 ℃, the operation temperature at the bottom of the DMC refining tower (20) is 90-91 ℃, and the reflux ratio of the DMC refining tower (20) is 0.5-5.
10. The method for producing high-purity dimethyl carbonate through heterogeneous catalytic reactive distillation is characterized in that the ratio of the total mass flow of the boiling agent at the upper part of the azeotropic distillation tower (2) to the mass flow of the azeotropic mixture of methanol and DMC at the lower part is 2-4, and the azeotropic agent in the azeotropic distillation tower (2) is normal alkane which forms an azeotrope with methanol.
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